WO2026008603A1 - Carbon black from particulate feedstock materials and fluid carbon-containing feedstock - Google Patents

Carbon black from particulate feedstock materials and fluid carbon-containing feedstock

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Publication number
WO2026008603A1
WO2026008603A1 PCT/EP2025/068641 EP2025068641W WO2026008603A1 WO 2026008603 A1 WO2026008603 A1 WO 2026008603A1 EP 2025068641 W EP2025068641 W EP 2025068641W WO 2026008603 A1 WO2026008603 A1 WO 2026008603A1
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WO
WIPO (PCT)
Prior art keywords
carbon
carbon black
containing feedstock
feedstock
particulate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/068641
Other languages
French (fr)
Inventor
David DETERS
Arndt-Peter Schinkel
Eddy TIMMERMANS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orion Engineered Carbons GmbH
Original Assignee
Orion Engineered Carbons GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP24186957.7A external-priority patent/EP4674916A1/en
Application filed by Orion Engineered Carbons GmbH filed Critical Orion Engineered Carbons GmbH
Publication of WO2026008603A1 publication Critical patent/WO2026008603A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04Compounds of zinc
    • C09C1/043Zinc oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44Carbon
    • C09C1/48Carbon black
    • C09C1/50Furnace black ; Preparation thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/19Oil-absorption capacity, e.g. DBP values

Definitions

  • the present invention relates to a process for the production of carbon black in an entrained flow reactor by using particulate carbon-containing feedstock and fluid carbon- containing feedstock.
  • the production of carbon black entails the cracking or thermal decomposition of a carbon-containing feedstock in a reaction chamber at temperatures such as 800°C and above (e.g. in the temperature range of 1100 °C to 2000 °C). These high temperatures are obtained by the combustion of a mixture comprising oxygen-containing gas and a combustion fuel (i.e. fuel).
  • the carbon black (CB) entrained in the gases (hot gas flow) exiting the reaction chamber are then cooled in a quenching operation and then collected by any suitable means conventionally used in the art.
  • Carbon blacks have numerous uses such as a reinforcing agent or filler for the rubber and tire industries. Moreover, carbon black has seen increased use in other areas such as coloring agents and reprographic toners for copying machines. The various applications of carbon black necessitate a diverse range of carbon black characteristics such as particle size, structure, yield, surface area, and stain.
  • the carbon black formation can be separated into different process steps including raising the temperature of the feedstock up to pyrolysis temperature, pyrolysis of the feedstock to unsaturated species such as acetylene and aromatic containing intermediate products, nuclei formation, surface growing, and aggregation.
  • liquid carbon-containing feedstocks are for example liquid hydrocarbons, such as cracker oil like oils derived from steam cracker or fluidized catalytic cracker.
  • the particulate carbon-containing feedstock such as tires can be pyrolyzed in a pyrolysis reactor.
  • the pyrolysis is carried out at low temperatures such as 500 °C and a liquid, a gaseous, and a solid fraction is obtained.
  • the liquid fraction can then be used to produce new or virgin carbon black (nCB) in an entrained flow reactor such as a furnace reactor.
  • US 2002/0117388 A1 relates to the aforementioned pyrolysis of scrap rubber materials including old tires.
  • the aim of US 2002/0117388 A1 is to recover the components in the scrap rubber materials such as carbon black. After the pyrolysis, carbon black can be recovered from the pyrolysis gas (recovered carbon black (rCB)).
  • the solid yield of the pyrolysis at low temperatures is low and a subsequent manufacturing process is required to obtain carbon black from the liquid fraction of the pyrolysis. Additionally, the coke content and ash content of recovered carbon black after pyrolysis is undesirable.
  • particulate carbon-containing feedstock as well as a fluid carbon-containing feedstock can be used in an entrained flow reactor to manufacture carbon black.
  • the objective is achieved by a method for producing carbon black in an entrained flow reactor comprising: (a) providing a hot gas flow, (b) providing a particulate carbon- containing feedstock, (c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and (d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
  • carbon black comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9- 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • carbon black is provided, preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m 2 /g, preferably a STSA surface area of 116 to 145 m 2 /g, more preferably a STSA surface area of 117 to 140 m 2 /g, and most preferably a STSA surface area of 120 to 135 m 2 /g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21.
  • composition comprising (A) an elastomeric polymer material, and (B) carbon black according to the invention.
  • a rubber article comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than
  • particulate carbon-containing feedstock and a fluid carbon-containing feedstock are used for the manufacturing of carbon black in an entrained flow reactor.
  • Figure 1 Section of a furnace reactor
  • Figure 6 The top (a) and the underside (b) of an exemplary vulcanizate sheet specimen coated with conductive silver.
  • the diameter always refers to the inner diameter of an object unless otherwise indicated.
  • the diameter of a tubular conduit refers to the inner diameter of the tubular conduit.
  • hot gas flow refers to a carrier gas in the entrained flow reactor, such as a furnace reactor that brings the reaction mixture (comprising the particulate carbon-containing feedstock) to the required temperature for the pyrolysis reaction.
  • the “hot gas flow” is the gas stream after the combustion of fuel in a furnace reactor.
  • Carbon black as referred to herein means a material composed substantially, e.g. to more than 80 wt.%, or more than 90 wt.% or more than 95 wt.%, based on its total weight of carbon that is produced by pyrolysis or radical driven abstraction of not carbon atoms of a carbon-containing feedstock.
  • Different industrial processes are known for the production of carbon blacks such as the furnace process, gas black process, acetylene black process, thermal black process or lamp black process.
  • the production of carbon blacks is per se well known in the art and for example outlined in J.-B. Donnet et al., “Carbon Black:Science and Technology”, 2 nd edition, therefore being not described herein in more detail.
  • the reaction volume of the reactor is the volume of the reactor between the position of the injection of the particulate carbon-containing feedstock and the position of the quench.
  • the present invention relates to a method for producing carbon black in an entrained flow reactor comprising: (a) providing a hot gas flow, (b) providing a particulate carbon-containing feedstock, (c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and (d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
  • the heating rate of particulate carbon-containing feedstock is lower compared to liquid carbon-containing feedstock so that it is desired that of particulate carbon-containing feedstock can be injected in the hot gas flow of an entrained flow reactor at a suitable temperature of 800 °C or even higher.
  • the temperature of the hot gas flow can be at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, at least 1600 °C.
  • the desired minimum temperature can be determined by measuring the transmittance of the produced carbon black. If the transmittance is low, the temperature of the hot gas flow can be increased.
  • the hot gas flow can be obtained by electrical preheating, plasma heating and combustion of a fuel and oxygen-containing gas.
  • the hot gas flow can be provided by (a 1 ) supplying fuel and oxygen-containing gas into a combustion chamber of the reactor, (b2) combusting fuel in the combustion chamber to produce the hot gas flow.
  • the particulate carbon-containing feedstock can comprise inert compounds, coke, C,H-containing compounds, and/or carbon black, preferably carbon black and C,H- containing compounds.
  • the particulate carbon-containing feedstock are particles and generally agglomerated particles.
  • a liquid carbon-containing feedstock means that the feedstock is liquid at 20 °C and 1 atm.
  • the particulate feedstock can comprise up to 10 wt.-% of an oil (extender oil).
  • oil extender oil
  • rubber granulates often comprise up to 10 wt.-% of an oil (extender oil).
  • Said oil or extender oil is generally an aliphatic or aromatic oil.
  • the particulate carbon-containing feedstock is a feedstock that is suitable to produce carbon black, i.e. new carbon black.
  • the particulate carbon-containing feedstock comprises materials that can be pyrolyzed.
  • the C,H-containing compound can be used to produce the carbon black, i.e. the new carbon black (nCB) or virgin carbon black (vCB).
  • the C, Flcontaining compounds refers to a compounds that each comprise C and H.
  • the C,H containing compounds are hydrocarbon compounds that can comprise heteroatoms such as O or S.
  • the particulate carbon-containing feedstock can comprise 10 to 100 wt.-% of C, Flcontaining compounds, preferably 20 to 99 wt.-% of C,H-containing compounds, more preferably 30 to 90 wt.-% of C,H-containing compounds, and most preferably 40 to 70 wt.-% of C,H-containing compounds, based on the total weight of the particulate carbon- containing feedstock.
  • the particulate carbon-containing feedstock can comprise inert compounds, and the inert compounds can comprise metals, metal compounds, silicon, silica. Metals can be zinc, silicon, calcium, aluminium, and/or iron.
  • the particulate carbon-containing feedstock can comprise 1 to 40 wt.-% inert compounds, preferably 3 to 30 wt.-% inert compounds, more preferably 4 to 20 wt.-% inert compounds, and most preferably 5 to 15 wt.-% inert compounds, based on the total weight of the particulate carbon-containing feedstock.
  • the particulate carbon-containing feedstock can in addition comprise carbon black, i.e. recovered carbon black. Said carbon black is typically present in tires and thus, can be recovered.
  • the particulate carbon-containing feedstock should comprise 1 to 70 wt.-% of carbon black, preferably 5 to 60 wt.-% of carbon black, more preferably 10 to 50 wt.-% of carbon black, and most preferably 15 to 40 wt.-% of carbon black, based on the total weight of the particulate carbon-containing feedstock.
  • the particulate carbon-containing feedstock is free of recovered carbon black.
  • recovered carbon black means carbon black that can be recovered in the process. In other words, carbon black that is present in the feedstock and not produced in the inventive process.
  • the C,H-containing compound are for example rubber, plastics and/or biomassbased materials.
  • the particulate carbon-containing feedstock is preferably provided as granulate (i.e. carbon-containing granulate feedstock).
  • the particulate carbon-containing feedstock may comprise or is rubber granulate, plastic granulate, and/or biomass-based granulate.
  • the particulate carbon-containing feedstock can be particulate rubber feedstock, particulate plastic feedstock, and/or particulate biomass-based feedstock. It is preferred that the particulate carbon containing feedstock comprises rubber granulate, wherein the rubber granulate comprising carbon black.
  • a biomass-based feedstock can be distinguished from fossil-based feedstock by measuring the C14 content ( 14 C content) in the feedstock (Radiocarbon dating).
  • the relative amount of C14 atoms compared to C12 (C14 to C12 ratio 1 14 C/ 12 C ratio) is lower in a fossil-based feedstock in comparison to a biomass-based feedstock.
  • fossil-based feedstock is feedstock that has relative amount of C14 atoms compared to C12 that is lower than the naturally occurring (or bio-based) relative amount of C14 atoms compared to C12.
  • the amount of particulate biomass-based feedstock in the particulate carbon-containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 60 to 80 wt.-% based on the total weight of the particulate carbon- containing feedstock.
  • the amount of particulate rubber granulate in the particulate carbon- containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-% based on the total weight of the particulate carbon-containing feedstock.
  • the amount of particulate plastic feedstock in the particulate carbon- containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-% based on the total weight of the particulate carbon-containing feedstock.
  • the particulate biomass-based carbon black feedstock can comprise a plantbased feedstock, preferably a non-edible plant-based feedstock and/or a waste plantbased feedstock.
  • a plantbased feedstock preferably a non-edible plant-based feedstock and/or a waste plantbased feedstock.
  • non-edible refers to materials that are unsuitable for human consumption.
  • waste refers to materials that are discarded or disposed of as unsuitable or no longer useful for the intended purpose, e.g., after use.
  • the particulate biomass-based carbon black feedstock can comprise wood, grass, cellulose, hemicellulose, lignin and/or natural rubber.
  • wood refers to porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. Suitable examples of wood include, but are not limited to, pine, spruce, larch, juniper, ash, hornbeam, birch, alder, beech, oak, pines, chestnut, mulberry or mixtures thereof. Suitable examples of grass include, but are not limited to, cereal grass, such as maize, wheat, rice, barley or millet; bamboos and grass of natural grassland and species cultivated in lawns and pasture. Suitable examples of lignin may include, but are not limited to, lignin removed by Kraft process and lignosulfonates.
  • the rubber granulate can comprise natural rubber and/or synthetic rubber.
  • the particulate carbon-containing feedstock can comprise rubber granulate comprising carbon black.
  • Natural rubber may be derived from rubber trees (Helvea brasiliensis), guayule, and dandelion.
  • the rubber granulate or the particulate carbon-containing feedstock can be derived from tires, cable sheaths, tubes, conveyor belts, shoe soles, hoses or mixtures thereof.
  • Synthetic rubber may include styrene-butadiene rubber such as emulsion-styrene- butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinylacetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber or a mixture or combinations of any of the foregoing.
  • ESBR emulsion-styrene- butadiene rubber
  • SSBR solution-styrene-buta
  • the plastic granulate or particulate plastic feedstock can be any plastic know in the art.
  • acrylics such as poly(acrylic acid), or poly(methyl methacrylate)
  • polyesters such as polyethylene terephthalate, or polyethylene glycol
  • polyurethanes such as derived from toluene diisocyanate (TDI) or methylene diphenyl diisocyanate
  • polyolefins such as polypropene, or polyethylene, or polystyrene.
  • thermoplastics and thermosets can be used.
  • the plastic granulate are preferably derived from waste materials of households. For instance, plastic bags, plastic containers, plastic packaging etc.
  • the particulate carbon-containing feedstock is provided as a particulate. This can be done by milling to the desired particle or granulate size. For instance, tires can be milled to obtain a particulate rubber granulate as the feedstock.
  • At least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, most preferably at least 80 wt.-%, of the particulate carbon-containing feedstock has a particle size of 125 pm to 2 mm, preferably 125 pm to 1 mm, more preferably 250 pm to 1 mm, and most preferably 500 pm to 1000 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • At least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, most preferably at least 80 wt.-%, of the particulate carbon-containing feedstock has a particle size of more than 250 pm to 2 mm, preferably 300 pm to 1 mm, more preferably 300 pm to 1 mm, and most preferably 400 pm to 1000 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • At least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • At least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 500 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • At least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 1 mm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • At least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • less than 1 wt.-%, preferably at least 0.5 wt.-%, more preferably less than 0.1 wt.-%, most preferably less than 0.01 wt.-%, of the particulate carbon- containing feedstock has a particle size of more than 2 mm, preferably more than 1 mm, more preferably more than 500 pm, and most preferably more than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • the particle size of the feedstock can be controlled by classify the particulate carbon-containing feedstock before the particulate carbon-containing feedstock is injected into the reactor. Accordingly, it is preferred that the particulate carbon-containing feedstock is classified before injecting into the reactor or before injecting into the mixing and feeding unit.
  • the classification can be done by any means known in the art such as sieving or other classifications. Classification can be done using vibratory screeners, rotary screeners, cyclones, elutriation classifiers, air jet sieve and/or dynamic air classifiers. Any of the aforementioned combinations can be used. Said classification can be used in order to obtain a maximum or minimum desired particle size as described in the specification.
  • the particle size of the feedstock can be controlled by sieving the particulate carbon-containing feedstock before the particulate carbon-containing feedstock is injected into the reactor.
  • the sieves sizes as described in ASTM D 1511-12 (2017) can be used. For instance, a sieve having openings of 2000 pm, 1000 pm, 500 pm, 250 pm, or 125 pm, preferably 500 pm, 250 pm, or 125 pm, can be used.
  • the sieve can have openings with a size that restrains particles with a size of more than 2000 pm, more than 1000 pm, more than 500 pm, more than 250 pm, or more than 125 pm, preferably more than 500 pm, more than 250 pm, or more than 125 pm.
  • No more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon- containing feedstock should have a particle size of over 4 mm, preferably over 2 mm, more preferably over 1 mm, and most preferably over 0.5 mm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • No more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon- containing feedstock should have a particle size of less than 150 pm, preferably less than 125 pm, more preferably less than 110 pm, and most preferably less than 100 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • None of the particles of the particulate carbon-containing feedstock should have a particle size of 1 mm or more, preferably of 500 pm or more, more preferably of 250 pm or more, and most preferably of 125 pm or more, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • the particle size distribution of the particulate carbon-containing feedstock can be measured according to ASTM D 1511-12 (2017) and (a) Sieve No. 10 retains 1 to 0 to 10 wt.-%, preferably 1 to 8 wt.-%, more preferably 1 to 5 wt.-%, and most preferably 1 to 3 wt.-% of the particulate carbon-containing feedstock, and/or (b) Sieve No. 18 retains 1 to 25 wt.-%, preferably 2 to 20 wt.-%, more preferably 4 to 15 wt.-%, and most preferably 5 to 12 wt.-% of the particulate carbon-containing feedstock, and/or (c) Sieve No.
  • 35 retains 10 to 80 wt.-%, preferably 15 to 70 wt.-%, more preferably 20 to 60 wt.-%, and most preferably 25 to 55 wt.-% of the particulate carbon-containing feedstock, and/or (d) Sieve No. 60 retains 5 to 70 wt.-%, preferably 10 to 60 wt.-%, more preferably 15 to 50 wt.-%, and most preferably 20 to 45 wt.-% of the particulate carbon-containing feedstock, and/or (e) Sieve No.
  • Bottom receive pan comprises less than 4 wt.-%, preferably less than 3 wt.-%, more preferably 0 to 2 wt.-%, and most preferably 0.01 to 1 wt.-% of the particulate carbon-containing feedstock. It is desirable to choose the desired range for each sieve independently.
  • the 50 wt.-% cumulative particle size of the particulate carbon-containing feedstock should be from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the 50 wt.-% cumulative particle size is measured according to ASTM D 1511-12 (2017).
  • the 50 wt.-% cumulative particle size can be interpolated using standard techniques know in the art. It is particularly, preferred that the Rosin-Rammler-Sperling-Bennett distribution (RRSB distribution) is used to interpolate the 50 wt.-% cumulative particle size.
  • the weight average particle size Dw50 of the particulate carbon-containing feedstock can be from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the weight average particle size Dw50 is measured according to ASTM D 1511-12 (2017).
  • the particle size distribution Dw10 of the particulate carbon-containing feedstock can be from 100 pm to 250 pm preferably 110 pm to 220 pm, more preferably 120 pm to 210 pm, and most preferably 130 pm to 200 pm, wherein the particle size distribution Dw10 is measured according to ASTM D 1511-12 (2017).
  • the particle size distribution of the particulate carbon-containing feedstock Dw90 can be from 400 pm to 4 mm preferably 500 pm to 3 mm, more preferably 600 pm to 2 mm, and most preferably 700 pm to 500 pm, wherein the particle size distribution Dw90 is measured according to ASTM D 1511-12 (2017).
  • the span of the particle size distributions of the particulate carbon-containing feedstock (Dw90-Dw10) I Dw50 can be 0.2 to 1.8, preferably 0.3 to 1.3, more preferably 0.4 to 1.1, most preferably 0.4 to 1.0, wherein the particle size distributions Dw10, Dw50, and Dw90 are measured according to ASTM D 1511-12 (2017).
  • the Dw50, Dw10, and Dw90 can be interpolated using standard techniques know in the art. It is particularly, preferred that the Rosin-Rammler-Sperling-Bennett distribution (RRSB distribution) is used to interpolate the Dw50, Dw10, and Dw90.
  • RTSB distribution Rosin-Rammler-Sperling-Bennett distribution
  • the particle or granulate size has an influence of the heating rate of the feedstock in the reactor. Smaller granulates or particles have a higher specific surface area so that the heating rate is higher. A fast-heating rate is beneficial so that the particulate feedstock can evaporate and then pyrolyzed. It is believed that the pyrolysis is significantly faster than the evaporation of the particulate feedstock.
  • the heating rate can also be increased by a higher temperature of the hot gas flow.
  • the carbon black produced according to the present invention can have a pMC (percent of modern carbon) of 1% or more, determined according to ASTM D6866-20 Methode B (AMS), such as 2 % or more, or 5 % or more, or 7 % or more, or 10 % or more, or 12 % or more, or 15 % or more, or 17 % or more, or 20 % or more, or 22 % or more, or 25 % or more, or 27 % or more, or 30 % or more, or 32 % or more, or 35 % or more, or 37 % or more, or 40 % or more, or 42 % or more, or 45 % or more, or 47 % or more, or 50 % or more, or 52 % or more, or 55 % or more, or 57 % or more, or 60 % or more, or 62 % or more, 65 % or more, or
  • the carbon black of the present invention can have a pMC (percent of modern carbon) of 5% or more, determined according to ASTM D6866-20 Methode B (AMS), preferably of 10 % or more, particularly preferably of 15 % or more, more preferably of 50 % or more, even more preferably of 85 % or more, most preferably of 90 % or more.
  • the carbon black of the present invention can have a pMC (percent of modern carbon) of 100%, determined according to ASTM D6866-20 Methode B (AMS).
  • the obtained carbon black typically comprises recovered carbon black and new carbon black.
  • Recovered carbon black is generally obtained if the particulate carbon-containing feedstock comprises carbon black.
  • the new carbon black is obtained by pyrolysis, i.e. the method according to the invention.
  • the mass flow of the particulate carbon-containing feedstock should be adjusted so that particulate carbon-containing feedstock can be uniformly heated.
  • the particulate carbon-containing feedstock should be injected into the reactor with a mass flow of 2 to 50 kg/h per 130 L of the reaction volume of the reactor, preferably 5 to 40 kg/h per 130 L of the reaction volume of the reactor, more preferably 8 to 30 kg/h per 130 L of the reaction volume of the reactor, and most preferably 10 to 20 kg/h per 130 L of the reaction volume of the reactor.
  • the fluid carbon-containing feedstock can comprise or can be a liquid carbon- containing feedstock. It is particularly preferred that the fluid carbon-containing feedstock is a liquid carbon-containing feedstock.
  • the fluid carbon-containing feedstock can comprise aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar distillates, residual oils which are produced during the catalytic cracking of petroleum fractions, residual oils which are produced during olefin production through cracking of naphtha or gas oil, natural gas, sustainable carbon black feedstock, renewable carbon black feedstock and/or a bio-based feedstock, pyrolysis oil, or a mixture or combination of any of the foregoing.
  • the fluid carbon-containing feedstock can comprise or can be coal tar distillates.
  • the aliphatic feedstock comprises aliphatic materials of 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-%, based on the total weight of the fluid carbon-containing feedstock.
  • Sustainable feedstock, renewable carbon black feedstock and/or a bio-based feedstock often comprise a high content of aliphatic feedstock as mentioned above.
  • Sustainable carbon black feedstocks refer to feedstocks that have generally a high content of aliphatic C-C bonding and preferably a low content of aromatic C-C bonding.
  • Sustainable carbon black feedstocks can include aliphatic oils, renewable carbon black feedstock, and biomass-based feedstocks.
  • Biomass-based feedstocks, sustainable carbon black and/or renewable carbon black feedstock can be distinguished from fossil-based feedstock by measuring the C14 content in the feedstock (Radiocarbon dating). The relative amount of C14 atoms compared to C12 (C14 to C12 ratio) is lower in fossil-based feedstock in comparison to biomass-based feedstocks.
  • the renewable carbon black feedstock can comprise a plant-based feedstock, preferably a non-edible plant-based feedstock and/or a waste plant-based feedstock.
  • a plant-based feedstock preferably a non-edible plant-based feedstock and/or a waste plant-based feedstock.
  • non-edible refers to materials that are suitable for human consumption.
  • waste refers to materials that are discarded or disposed of as unsuitable or no longer useful for the intended purpose, e.g., after use.
  • edible oils i.e. , cooking oils
  • used cooking oils are considered waste.
  • the renewable carbon black feedstock preferably may comprise plant-based oils and more preferably non-edible plant-based oils and/or waste plant-based oils.
  • the renewable carbon black feedstock according to the present invention may comprise black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, cooking oil, distillation residues from biodiesel plants or a mixture or combination of any of the foregoing.
  • cooking oil refers to edible oils used in food preparation, such as in frying, baking and other types of cooking.
  • cooking oils may comprise rice bran oil, rapeseed oil, linseed oil, palm oil, coconut oil, canola oil, soybean oil, sunflower oil, cotton seed oil, pine seed oil, olive oil, corn oil, grape seed oil, safflower oil, acai palm oil, jambu oil, sesame oil, chia seed oil, hemp oil, perilla oil, peanut oil, stillingia oil, cashew nut oil, brazil nut oil, macadamia nut oil, walnut oil, almond oil, hazel nut oil, beechnut oil, candlenut oil, chestnut oil or a mixture or combination of any of the foregoing.
  • the cooking oil of the present invention may be used cooking oil.
  • used cooking oil refers to oils originating from commercial or industrial food processing operations, such as restaurants, that have
  • the fluid carbon-containing feedstock can comprise or can be liquid components that may be selected from, but are not limited to, black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, cooking oil, distillation residues from biodiesel plants or a mixture or combination of any of the foregoing.
  • Some oils may be solid at room temperature, e.g., at temperatures of 25 °C, but liquid at elevated temperatures, such as temperatures above 25 °C, e.g., temperatures in a range of 25 to 100 °C.
  • black liquor refers to a by-product from the Kraft process which comes from the sulfate and soda processes of making cellulosic pulp.
  • liquid with respect to the fluid carbon-containing feedstock means that the respective component is liquid during the injection in the reactor.
  • Non-edible plant-based feedstock may comprise, but is not limited to, black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, distillation residues from biodiesel plants, or a mixture or combination of any of the foregoing.
  • the fluid carbon-containing feedstock may comprise tall oil.
  • tall oil and “crude tall oil” may be used interchangeably throughout this description unless otherwise stated.
  • Tall oil is derived from the chemical pulping of woods. Typically, tall oil is a mixture comprising resin acids, fatty acids, sterols, alcohols and further alkyl hydrocarbon derivatives.
  • Tall oil may be a natural unrefined product or a refined product. Refined tall oil may include tall oil fatty acid, tall oil fatty rosin, distilled tall oil and tall oil pitch. Tall oil can be distilled to obtain tall oil resin acids containing more than 10 wt.-% of resin acid content.
  • Tall oil may also be refined to tall oil fatty acids, where the resin acid content is typically less than 10 wt.-%.
  • suitable examples of tall oil may include, but are not limited to, SYLFATTM products, SYLVATALTM products, SYLVABLENDTM products and SYLVAROSTM products, all available from Kraton Corporation (USA), as well as tall oil products, such as crude tall oils and Tall Oil 1, available from UCY Energy (Germany).
  • the fluid carbon-containing feedstock may in particular comprise tall oil pitch.
  • Tall oil pitch is obtained as a nonvolatile residue from refining by distillation of tall oil and may be mixed with fore-runs of tall oil refining.
  • the yield of tall oil pitch in the refining process may range from about 15 to 50 wt.-%, depending for example on the quality and composition of the tall oil.
  • Tall oil pitch typically comprises neutral substances, free acids including resin acids and fatty acids, fatty acid esters, bound and free sterols, and polymeric compounds.
  • metals, metal cations, inorganic and organic compounds including metal resinates and salts of fatty acids can be found in tall oil pitch. Said metal cations typically originate from wood and fertilizers.
  • tall oil pitch examples include, but are not limited to, SYLVABLENDTM products, such as SYLVABLEND FA7002, SYLVABLEND PF 40, SYLVABLEND PF 60 and SYLVABLEND SF75 all available from Kraton Corporation (USA) as well as Tall Oil 1, UCY-TOF40 and UCY- TOF60 all available from UCY Energy (Germany).
  • SYLVABLENDTM products such as SYLVABLEND FA7002, SYLVABLEND PF 40, SYLVABLEND PF 60 and SYLVABLEND SF75 all available from Kraton Corporation (USA) as well as Tall Oil 1, UCY-TOF40 and UCY- TOF60 all available from UCY Energy (Germany).
  • the fluid carbon-containing feedstock can be a mixture of renewable carbon black feedstock and conventional carbon black feedstock.
  • Conventional carbon black feedstock may be aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar distillates, residual oils which are produced during the catalytic cracking of petroleum fractions, residual oils which are produced during olefin production through cracking of naphtha or gas oil, natural gas or a mixture or combination of any of the foregoing.
  • the fluid carbon-containing feedstock can be a liquid as well as a gas. It is preferred that the fluid carbon-containing feedstock is a liquid.
  • gaseous carbon black feedstock can be an aliphatic feedstock, such as methane, ethane, acetylene, ethylene, ethane, propyne, propane propene, butadiene, butane, pentane, or a mixture thereof.
  • aliphatic feedstock such as methane, ethane, acetylene, ethylene, ethane, propyne, propane propene, butadiene, butane, pentane, or a mixture thereof.
  • the fluid carbon-containing feedstock of the present invention may comprise the renewable carbon black feedstock in an amount greater than or equal to 10 wt.% based on the total weight of the carbon black feedstock.
  • the fluid carbon- containing feedstock can comprise the renewable carbon black feedstock in an amount greater than or equal to 15 wt.%, or in an amount greater than or equal to 20 wt.%, or in an amount greater than or equal to 25 wt.%, or in an amount greater than or equal to 30 wt.%, or in an amount greater than or equal to 35 wt.%, or in an amount greater than or equal to 40 wt.%, or in an amount greater than or equal to 45 wt.%, or in an amount greater than or equal to 50 wt.%, or in an amount greater than or equal to 55 wt.%, or in an amount greater than or equal to 60 wt.%, or in an amount greater than or equal to 65 wt.%, or in an amount greater than or equal to 70
  • the fluid carbon-containing feedstock may comprise the renewable carbon black feedstock in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 99 wt.-%, the weight percent being based on the total weight of the carbon black feedstock.
  • the fluid carbon-containing feedstock can consist of the renewable carbon black feedstock.
  • the fluid carbon-containing feedstock may comprise tall oil pitch in an amount of greater than or equal to 5 wt.-%, such as greater than or equal to 10 wt.-%, or greater than or equal to 15 wt.-%, or greater than or equal to 20 wt.-%, or greater than or equal to 25 wt.-%, or greater than or equal to 30 wt.-%, or greater than or equal to 35 wt.-%, greater than or equal to 40 wt.-%, or greater than or equal to 45 wt.-%, or greater than or equal to 50 wt.-%, or greater than or equal to 55 wt.-%, or greater than or equal to 60 wt- %, or greater than or equal to 65 wt.-%, or greater than or equal to 70 wt.-%, or greater than or equal to 75 wt.-%, or greater than or equal to 80 wt.-%, or greater than or equal to 85 wt.-
  • the fluid carbon-containing feedstock may comprise tall oil pitch in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the fluid carbon-containing feedstock.
  • the fluid carbon-containing feedstock can consist of tall oil pitch.
  • the renewable carbon black feedstock may comprise tall oil pitch in an amount of greater than or equal to 5 wt.-%, such as greater than or equal to 10 wt.-%, or greater than or equal to 15 wt.-%, or greater than or equal to 20 wt.-%, or greater than or equal to 25 wt.-%, or greater than or equal to 30 wt.-%, or greater than or equal to 35 wt.-%, or greater than or equal to 40 wt.-%, or greater than or equal to 45 wt.-%, or greater than or equal to 50 wt.-%, or greater than or equal to 55 wt.-%, or greater than or equal to 60 wt- %, or greater than or equal to 65 wt.-%, or greater than or equal to 70 wt.-%, or greater than or equal to 75 wt.-%, or greater than or equal to 80 wt.-%, or greater than or equal to 85 wt.-
  • the renewable carbon black feedstock may comprise tall oil pitch in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the renewable carbon black feedstock.
  • the renewable carbon black feedstock may consist of tall oil pitch.
  • the pyrolysis oil is usually obtained after pyrolysis of end-of-life products, such as scrap tires (waste tires) or rubber. Pyrolysis is usually carried out at low temperatures and produces a liquid, gaseous and solid fractions. The liquid fraction can then be used to produce new or virgin carbon black in an entrained flow reactor such as a furnace reactor. This means that the liquid fraction after the pyrolysis of rubber materials can be used as pyrolysis oil. In other words, pyrolysis oil is preferably the liquid fraction of the pyrolysis of waste tires.
  • the fluid carbon-containing feedstock can comprise or can be a liquid carbon- containing feedstock. It is preferred that the fluid carbon-containing feedstock is a liquid carbon-containing feedstock.
  • the mass ratio of particulate carbon-containing feedstock to fluid carbon- containing feedstock can be 0.5:1 to 1 :0.05, preferably 1 :1 to 1:0.1, more preferably 1.1:1 to 1:0.1, and most preferably 1.2:1 to 1 :0.2.
  • the mass flow rate of the fluid carbon-containing feedstock can be 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h.
  • the mass flow rate of the particulate carbon-containing feedstock can be 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1 ,000 kg/h, most preferably 30 to 500 kg/h.
  • the entrained flow reactor is a furnace reactor and the particulate carbon-containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means.
  • the entrained flow reactor is a furnace reactor and the fluid carbon-containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means.
  • the distance between the injection of the particulate carbon-containing feedstock and the fluid carbon-containing feedstock is 15 to 350 mm, and/or 850 mm to 5 m.
  • particulate carbon-containing feedstock is injected downstream of the injection of the fluid carbon-containing feedstock.
  • particulate carbon-containing feedstock is injected upstream of the injection of the fluid carbon-containing feedstock.
  • the fuel can comprise a gaseous or liquid hydrocarbons, preferably natural gas, a fuel oil or H2.
  • Hydrogen can be used as carrier gas and/or fuel for producing carbon black. It is preferred that the hydrogen is used as carrier gas and fuel for producing carbon black. Hydrogen will be used as a carrier gas if the hydrogen is present in the combustion mixture in molar excess with respect to oxygen. Thus, hydrogen should be present in the hot combustion gases and the hot reaction mixture.
  • the hot gas flow should have a temperature of 900 to 3500 °C, preferably 950 to 3000 °C, more preferably 1000 to 2000 °C, and most preferably 1200 to 1900 °C.
  • the hot gas flow can be obtained by electrical preheating, plasma and combustion of a fuel and oxygen containing gas.
  • the combustion of a fuel and oxygen containing gas is preferably done in a furnace reactor.
  • other means to provide the desired temperature of the hot gas flow are possible as mentioned above.
  • the entrained flow reactor can be a furnace reactor.
  • the furnace reactor can have a flow passage along a central longitudinal axis of the reactor.
  • the reactor generally comprises in the following order from upstream to downstream (flow direction) a combustion chamber, a choke, and a tunnel comprising quenching means. These components define a flow passage along the central longitudinal axis of the reactor for the hot gas flow, such as the hot combustion gases.
  • the components should be in fluid connection, particularly along a central longitudinal axis of the reactor.
  • a tubular conduit can be connected to the combustion chamber for supplying oxygen-containing gas that is necessary for the combustion of the fuel (or combustion fuel).
  • the tubular conduit can be also arranged along the central longitudinal axis of the reactor so that the supplement of the oxygen-containing gas occurs along the above- mentioned flow passage.
  • the reactor can comprise fuel injection means for injecting the fuel into the combustion chamber.
  • a fuel lance is used to supply the fuel into the combustion chamber.
  • the combustion chamber can be connected to the tubular conduit in the downstream to upstream direction so that the oxygen-containing gas can be supplied to the combustion chamber.
  • the combustion chamber is arranged along the central longitudinal axis of the reactor.
  • the combustion chamber is preferably formed of an internal refractory lining covered by a gas tight e.g. metallic covering.
  • the material forming the refractory, and outer lining can be those found conventionally in the art such as the castable refractory Kaocrete® 32-cm which is 70% alumina (AI2O3) and has a melting point of about 1870 °C.
  • a brick refractory can be relied upon such as RUBY SR (sold by Harrison- Walker Refractories, Pittsburg, PA.) brick refractory which is 84.5% alumina along with 9.8% chromic oxide (C ⁇ Ch) and has a melting point of about 2050 °C.
  • the shell or lining is preferably formed of carbon steel except for any piping in contact with hot process air. In those areas, the piping is formed of "316 Stainless Steel".
  • the combustion chamber is preferably dimensioned as a cylinder.
  • a constricting section (choke) can be provided downstream of the combustion chamber.
  • the constriction section has a tapering passageway and converges in an upstream to downstream direction.
  • these constriction sections are in the form of a frustoconical passageway.
  • the combustion chamber can also have a tapered in the downstream to upstream direction. Accordingly, the combustion chamber can comprise a zone that is tapered towards the reaction chamber and/or towards the tubular conduit.
  • the oxygen-containing gas is preheated to a temperature between 200 to 1600 °C, preferably 350 to 1400 °C, more preferably 500 to 1200 °C, and most preferably 450 to 950 °C.
  • the fuel is preheated to a temperature between 50 to 750 °C, preferably 100 to 700 °C, more preferably 300 to 700 °C, and most preferably 450 to 650 °C.
  • the preheating of the oxygen-containing gas and fuel can be done electrically or using a heat exchanger.
  • Water has an influence of the surface properties of the produced carbon black. Accordingly, it is possible that the amount of oxygen-containing gas, such as O2, in the combustion mixture is used to control the amount of water in the hot combustion mixture and/or hot reaction mixture and thus, preferably control the surface properties of the produced carbon black.
  • oxygen-containing gas such as O2
  • the tunnel is connected with the combustion chamber so that the hot combustion gases obtained in the combustion chamber can flow into the tunnel.
  • the tunnel can be arranged along the central longitudinal axis of the reactor.
  • the diameter of the reaction chamber can be higher than the diameter of the constriction section of the combustion chamber so that the hot combustion gas is able to expand.
  • the expansion section is preferably dimensioned as a cylinder and in communication with the combustion chamber, preferably in the communication with the constriction section (choke) of the combustion chamber.
  • the particulate carbon-containing feedstock can be injected in the combustion chamber, in the choke, and/or in the tunnel of the furnace reactor.
  • the particulate carbon- containing feedstock is typically injected in the choke (constriction section).
  • the particulate carbon-containing feedstock or the carrier gas comprising said feedstock should have a desirable pressure. This means that the pressure of the particulate carbon-containing feedstock or the carrier gas comprising said feedstock should be higher than the pressure in the combustion chamber. Accordingly, a suitable feeding and mixing device should be used that is configured to operate in pressurized conditions.
  • the particulate carbon-containing feedstock should be injected via multiply inlets, preferably radial and perpendicular to the central longitudinal axis of the reactor.
  • the concentration of O2 in the hot gas flow should be less than 5 vol.-%, preferably less than 4 vol.-%, more preferably 0.01 to 3 vol.-%, and most preferably 0.1 to 2 vol.-%.
  • the obtained carbon black generally comprises recovered carbon black and new carbon black.
  • the particulate carbon-containing feedstock may be injected to the reactor via means to inject the feedstock.
  • the means to inject the feedstock can comprise a plurality of injection nozzles or lances that are preferably arranged circumferentially with respect to the central longitudinal axis. The circumferential arrangement further improves the uniform characteristics of the carbon black since the feedstock for the carbon black can be homogenously mixed with the hot gas flow.
  • the particulate carbon-containing feedstock can be introduced through a plurality of means to inject the feedstock.
  • an axially extending feedstock lance and a radially extending feedstock injectors with nozzles capable of producing a variety of cone shaped sprays e.g., 15, 30, 45 and 60 degrees cone spray angles
  • radially extending feedstock injectors can be provided with shut off valves such that feedstock is only introduced through certain of the feedstock injectors or the flow rate is varied for the feedstock flowing in the injectors.
  • the tunnel can comprise means for injecting a quenching medium into the flow passage along the central longitudinal axis of the reactor.
  • the means for injecting a quenching medium are located subsequent with respect to the flow direction to the means to inject a feedstock for the carbon black.
  • the quenching medium is generally H 2 O.
  • the means for injecting a quenching medium can extend into the tunnel.
  • a cooling fluid conduit or a plurality of radial cooling fluid conduits can be used.
  • the quenching medium such as a cooling fluid (e.g. water), can be sprayed within the tunnel to stop the carbon black reaction at the appropriate time and location.
  • the reactor can further comprise a tubular conduit for supplying oxygencontaining gas to the combustion chamber.
  • the oxygen-containing gas O 2 containing gas or O 2 containing gas mixture
  • the tubular conduit can be in connection with the combustion chamber so that the oxygen-containing gas is able to flow through the tubular conduit in the combustion chamber.
  • the tubular conduit can be arranged along the central longitudinal axis of the reactor. It is desirable that the central longitudinal axis of the tubular conduit is coaxial to the central longitudinal axis of the reactor. Thus, the tubular conduit can be arranged coaxial along the central longitudinal axis of the reactor.
  • the wt.-% of oxygen that is present in the oxygen-containing gas should be 20 to 100 wt.-%, preferably 50 to 99 wt.-%, more preferably 60 to 95 wt.-% and most preferably 70 to 90 wt.-%, wherein the wt.-% is based on the total weight of the oxygen-containing gas.
  • the tubular conduit can have a cylindrical shape that extents along the central longitudinal axis of the reactor without curvatures.
  • the inner diameter of the tubular conduit for supplying oxygen-containing gas can be from 5 cm to 3 m, such as 10 cm to 3 m, 20 cm to 3 m, 9 cm to 2.5 m, 13 cm to 1.5 m, 0.1 m to 2 m, 20 cm to 1 m, 30 cm to 1.5 m, 15 cm to 60 cm, or 15 cm to 90 cm.
  • the fuel injection means for introducing any suitable combustion fuel e.g., natural gas, fuel oil or other gaseous or liquid hydrocarbons, preferably natural gas or a fuel oil, or H2
  • the injection means can be arranged at the end of the tubular conduit, where the tubular conduit is connected to the combustion chamber.
  • the injection means are tubular injection pipes arranged circumferentially with respect to the central longitudinal axis of the tubular conduit so that the injection angle of the fuel is substantially orthogonal to the flow direction of the oxygen-containing gas.
  • the oxygen-containing gas is generally supplied in an amount yielding an excess of oxygen with respect to the amount of oxygen for a complete combustion of the fuel, and/or wherein the oxygen-containing gas is supplied in an amount that the k-value is in a range of 0.01 to 10, preferably 0.1 to 5, more preferably 0.5 to 2, and most preferably 0.7 to 1.
  • the k value is defined by the ratio of stoichiometric O2 amount that is necessary for the complete stoichiometric combustion of the fuel to the supplied O2 amount.
  • Fuel and oxygen-containing gas flow rates can be adjusted to give high temperatures and normally fall close to stoichiometric ratios. Ratios must be adjusted to prevent melting the refractory.
  • the range of oxygen-containing flow is quite broad, going, for instance, from a low of approximately 1000 Nm 3 /h to a high of approximately 100 kNm 3 /h, such as 1000 Nm 3 /h to 100 kNm 3 /h, 1000 Nm 3 /h to 10 kNm 3 /h, 2000 Nm 3 /h to 3000 Nm 3 /h, or 1000 Nm 3 /h to 2000 Nm 3 /h.
  • the invention is not restricted to those dimensions; for larger reactors higher air flows are needed and for smaller reactors lower air flows are needed.
  • the desired temperature of the hot gas flow can also be achieved by plasma heating the gas flow.
  • the gas flow can be preheating as mentioned above.
  • a plasma torch can provide the plasma for the aforementioned heating.
  • a plasma torch design is described in WO 1993/012633 A1.
  • any means known in the art to produce a plasma can be used.
  • the plasma can be formed by means of a plasma carrier gas which is heated by an electric arc which burns between electrodes. In a plasma zone of high temperatures are reached, from 2500°C to 20,000°C, and it is in this zone that the plasma treatment can be achieved.
  • the plasma carrier gas can be oxygen or hydrogen. Hydrogen as plasma carrier gas is particularly preferred.
  • a microwave plasma can also provide the plasma for the aforementioned treatment.
  • a microwave generator can be used that provide microwave radiation inside the reaction chamber. Microwave radiation having 1 to 300 GHz can be used.
  • a plasma can be generated using a radio frequency power source (RF generator).
  • RF generator radio frequency power source
  • the residence time between the time of the injection of the particulate carbon- containing feedstock in the reactor and the time of the quench of product mixture should be from 150 ms to 4 sec, preferably 200 ms to 3 sec, more preferably 250 ms to 2 sec, and most preferably 250 ms to 1 sec.
  • the residence time of the particulate carbon- containing feedstock means the time in that the particulate carbon-containing feedstock is evaporated and pyrolyzed.
  • the quench of the product mixture stops the pyrolysis of the particulate carbon-containing feedstock.
  • the heating rate of particulate carbon-containing feedstock is lower compared to liquid feedstocks so that the evaporation and pyrolysis of the particulate carbon-containing feedstock generally requires more time.
  • the residence time is selected in such a way that the C,H-containing material in the particulate carbon-containing feedstock is completely pyrolyzed.
  • the formation of carbon black is generally terminated by the quench of the hot gas flow.
  • the method may further comprise (e) quenching the hot gas flow after the injection according to step (d).
  • the transmittance can be an indicator whether the residence time is sufficient for the feedstock for a complete pyrolysis of e.g. the C,H-containing material in the feedstock.
  • the particulate carbon-containing feedstock is deagglomerated before the injection into the reactor. It is believed that the evaporation time is decreased by using deagglomerated particles.
  • step (b) further comprises deagglomerating the particulate carbon containing feedstock and in step (d), the deagglomerated particulate carbon-containing feedstock is injected in the hot gas flow to form carbon black.
  • the deagglomeration can be achieved by (i) accelerating the particulate carbon- containing feedstock, and/or (ii) applying shear forces, preferably using an extruder.
  • the deagglomeration can be carried out in (i) a feeding and mixing device, preferably comprising a nozzle, and/or (ii) an extruder.
  • the feeding and mixing device is preferably a device according to the invention.
  • Accelerating of the particulate carbon-containing feedstock results in the deagglomeration of the particles.
  • a carrier gas such as N2 or air (nitrogen is preferred)
  • the particles are injected into the accelerated carrier gas.
  • the deagglomeration can be carried out by subjecting the particulate carbon-containing feedstock into a carrier gas jet.
  • the deagglomeration can be carried out in (i) a feeding and mixing device comprising a Laval nozzle.
  • the carrier gas and/or the particulate carbon-containing feedstock is preferably accelerated to over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma.
  • a Mach number of over 1 can be achieved with a jet nozzle such as a Laval nozzle. Ma is the Mach number. Accordingly, it is desired that the particulate carbon-containing feedstock is injected into the reactor at over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma.
  • flow velocities from 0.01 Ma to 3 Ma preferably 0.1 Ma to 2 Ma, more preferably 0.2 to 1.8 Ma, and most preferably 0.3 to less than 1 Ma, are also desirable.
  • the deagglomeration is also achieved by the impact of the accelerated particulate carbon-containing feedstock with an object, such as two particles of the particulate carbon-containing feedstock, or by the impact of particles of the particulate carbon- containing feedstock and a surface such as the inner surface of a deagglomeration conduit.
  • the deagglomerated particulate carbon-containing feedstock (or the carrier gas comprising the deagglomerated particulate carbon-containing feedstock) can be injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1 .5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar.
  • the pressure should be adjusted according to the injection position of the feedstock. For instance, the pressure in a combustion chamber is higher than the pressure in the choke so that the deagglomerated particulate carbon-containing feedstock or the carrier gas comprising the deagglomerated particulate carbon-containing feedstock should be injected at higher pressures in the combustion chamber.
  • the deagglomerated particulate carbon-containing feedstock can be comprised in a carrier gas and the carrier gas further comprises H2O and/or additives. H2O can prevent the re-agglomeration of the particles in the carrier gas.
  • the deagglomerated particulate carbon-containing feedstock should be comprised in a carrier gas and the carrier gas can further comprise H2O in an amount of 1 to 10 vol.-%, preferably 2 to 8 vol.-%, more preferably 3 to 7 vol.-%, based on the total volume of the carrier gas comprising the the deagglomerated particulate carbon-containing feedstock.
  • the particulate carbon-containing feedstock and/or the deagglomerated carbon- containing feedstock is generally comprised in a carrier gas.
  • the deagglomeration can be carried out in a feeding and mixing device for particles into a reactor comprising: (i) a carrier gas passage extending through said feeding and mixing device, (ii) at least one carrier gas inlet, which is in fluid communication with said carrier gas passage, (iii) at least one particle inlet, (iv) a mixing chamber which is in fluid communication with said at least one particle inlet and with said carrier gas inlet, (v) a deagglomeration conduit which is in fluid communication with said mixing chamber, (vi) at least one outlet for said carrier gas entraining particles which have been fed into said mixing chamber, wherein said at least one outlet for is in fluid communication with said deagglomeration conduit, and (vii) means for accelerating and injecting a stream of carrier gas into said mixing chamber.
  • Said gas passage should extend along a longitudinal axis through said feeding and mixing device and preferably said at least one inlet, said mixing chamber, said deagglomeration conduit and said outlet are aligned with said longitudinal axis.
  • Said particle inlet should be configured to feed particles into said mixing chamber at an angle relative to a carrier gas jet discharged into said mixing chamber, preferably perpendicularly to the carrier gas jet.
  • the angle is not particularly limited for the present invention.
  • Said means for accelerating and injecting the stream of carrier gas may include at least one jet nozzle (nozzle).
  • the jet nozzle is configurated to accelerate the stream of carrier gas. This means that the nozzle (or jet nozzle) is positions so that the nozzle convergent in a flow direction so that the gas stream is accelerated after exiting the nozzle and entering the mixing chamber.
  • said means for accelerating and injecting said stream of the carrier gas is preferably convergent in a flow direction extending from said at least one carrier gas inlet towards said at least one outlet.
  • Said jet nozzle can be a Laval-nozzle.
  • a Laval nozzle (or nozzle) may comprise (in the following order) a convergent section, a throat and a divergent section.
  • the convergent section reduces the diameter of the nozzle so that the gas flow is accelerated.
  • the divergent section increases the diameter in this section.
  • the diameter increased by the divergent section is still lower than the diameter before the convergent section. Accordingly, a nozzle comprising in the following order a convergent section, a throat and a divergent section, the gas flow is accelerated.
  • the cross-sectional area is usually circular or elliptical at each point of the jet nozzle.
  • Said jet nozzle may comprise a divergent section and the angle of divergent section can be from 2 to 30°, preferably 3 to 20°, more preferably 4 to 15°, and most preferably 5 to 10°.
  • the jet nozzle may comprise a convergent section and the maximum inner diameter of the convergent section can be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
  • the minimum inner diameter of the convergent section, divergent section and/or the inner diameter of the throat can be from 0.6 to 30 mm, preferably 1.2 to 18 mm, more preferably 1.9 to 12 mm, and most preferably 3 to 9 mm.
  • the minimum inner diameter of convergent section, divergent section and the inner diameter of the throat should be the same. In other words, the convergent, the throat and the divergent section are generally directly connected with each other.
  • the jet nozzle may comprise a divergent section and the maximum inner diameter of the divergent section can be from 0.3 to 11 mm, preferably 0.5 to 7 mm, more preferably 0.9 to 5 mm, and most preferably 1.1 to 4 mm.
  • the minimum inner diameter of the convergent section should be higher than the maximum inner diameter of the convergent section, preferably the difference of the maximum inner diameters of the convergent section and the divergent section is from 5 to 30 mm, preferably 8 to 20 mm, more preferably 9 to 18 min, and most preferably 10 to 15 mm.
  • the maximum inner diameter of the convergent section may be higher than the maximum inner diameter of the divergent section.
  • the distance between the means for accelerating and injecting and the conduit having a constant inner diameter can be from 2 to 20 mm, preferably 2.5 to 15 mm, more preferably 3 to 10 mm, and most preferably 3.5 to 7 mm.
  • a specific distance between the aforementioned components improves the deagglomeration of the particles since the jet stream flows directly into the deagglomeration conduit. Accordingly, turbulences can be avoided and a loss of the velocity of the jet stream is minimised.
  • the means for accelerating and injecting the carrier gas (or nozzle) is positioned in such a way that the means for accelerating and injecting the carrier gas protrudes into the cavity of the inlet funnel of the deagglomeration conduit.
  • Said deagglomeration conduit normally comprises a conduit having a constant inner diameter.
  • Said deagglomeration conduit can be configured as a diffuser.
  • Said deagglomeration conduit can comprise from downstream to upstream an inlet funnel, a conduit having a constant inner diameter and a diffuser nozzle diverging in said flow direction.
  • the nozzle for diverging should continuously increase the inner diameter of the deagglomeration conduit. Accordingly, the carrier gas flow is not interrupted and turbulences are avoided.
  • the angle of said diffuser nozzle can be from 1 to 30°, preferably 2 to 20°, more preferably 3 to 15°, and most preferably 4 to 8°.
  • the angle of said inlet funnel can be from 20 to 80°, preferably 30 to 75°, more preferably 40 to 70°, and most preferably 50 to 65°.
  • the longitudinal axis of said deagglomeration conduit could coaxial to the longitudinal axis of the feeding and mixing device.
  • the coaxial arrangement improves the overall acceleration as well as deagglomeration.
  • the inner diameter of the conduit having a constant inner diameter can be from 1 to 20 mm, preferably 2 to 10 mm, more preferably 3 to 7 mm and most preferably 4 to 6 mm.
  • the inner diameter can have an influence of the deagglomeration. Accordingly, the diameter should be selected for the specific particulate feedstock and preferably for the mass flow.
  • the maximum inner diameter of the diffuser nozzle is higher than the inner diameter of the conduit having a constant inner diameter.
  • the maximum inner diameter of the diffuser nozzle should be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
  • the diffuser nozzle and the convergent section of the jet nozzle can have the same maximum inner diameter.
  • the maximum inner diameter of said diffuser nozzle can be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
  • the length of the conduit having a constant inner diameter can be between 3 to 500 mm, preferably 5 to 200 mm, more preferably 10 to 50 mm and most preferably 13 to 30 mm.
  • the length of said conduit can have a beneficial influence of the deagglomeration of the particles (particulate carbon-containing feedstock). A longer conduit generally results in a better deagglomeration.
  • the length of the diffuser nozzle can be between 10 to 300 mm, preferably 20 to 200 mm, more preferably 25 to 150 mm and most preferably 30 to 100 mm.
  • the inner diameter of the conduit having a constant inner diameter should be higher than the maximum inner diameter of the outlet of the means for accelerating and injecting a stream of the carrier gas.
  • the means for accelerating and injecting a stream of carrier gas, the mixing chamber and the deagglomeration conduit should be configured so that the carrier gas jet is discharged in the deagglomeration conduit.
  • Feeding and mixing device can further comprise at least one hopper upstream said at least one particle inlet.
  • At least one screw conveyor such as a screw conveyor
  • the screw conveyor should be configured to provide a constant amount of particles such (or particulate carbon-containing feedstock) into the mixing chamber. Accordingly, the supply of the particles can be controlled by the screw conveyor.
  • the particles mentioned for the feeding and mixing device are the particulate carbon containing feedstock and said reactor is typically an entrained flow reactor for the manufacturing of carbon black.
  • the feeding and mixing often further comprise a pressure tank for the particles, wherein the pressure tank is in fluid communication with said at least one particle inlet and optionally with said at least one screw conveyor.
  • a pressure tank for the particles
  • the pressure tank is in fluid communication with said at least one particle inlet and optionally with said at least one screw conveyor.
  • two pressure tanks are present, wherein a first pressure tank connected to a second pressure tank. Both pressure tanks can be connected via a valve.
  • a reactor system comprising an entrained flow reactor and a feeding and mixing device, wherein said feeding and mixing device is in fluid communication with said reactor.
  • Said feeding and mixing device should be connected to a plurality of inlets of said reactor, preferably by injection lances.
  • Said feeding and mixing device can be in fluid connection with a choke, a combustion chamber and/or a tunnel upstream a quenching area of an entrained flow reactor.
  • Said reactor can be an entrained flow reactor, preferably a furnace reactor.
  • a method for injecting a particulate material into a reactor comprises the steps of (a) deagglomerating and entraining particles in a carrier gas stream, preferably by using a feeding and mixing device, (b) injecting the carrier gas stream comprising deagglomerated particles obtained in step (a) into said reactor.
  • the method can be a method for the manufacturing of carbon black and the particulate material is particulate carbon-containing feedstock and the reactor is an entrained flow reactor for the manufacturing of carbon black, preferably a furnace reactor.
  • Said particulate carbon-containing feedstock can be injected to said entrained flow reactor by a plurality of inlets, preferably by a plurality of injection lances.
  • the carrier gas stream can be accelerated and flows through a mixing chamber into a deagglomeration conduit.
  • the deagglomeration can be done by accelerating the particles in a carrier gas stream and collisions of the particles with the inner surface of a deagglomeration conduit.
  • the carrier gas is generally accelerated to over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma.
  • the particles can be subjected in the carrier gas jet, perpendicularly to the carrier gas jet.
  • the carrier gas stream comprising deagglomerated particles can be injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1.5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar.
  • the carrier gas further can further comprise H2O and/or additives.
  • the carrier gas can comprise H2O in an amount of 1 to 10 vol.-%.
  • the H2O can prevent the reagglomeration of the particles.
  • the feeding and mixing device can be used to deagglomerate particles, preferably a particulate carbon-containing feedstock.
  • carbon black is provided that is produced according to the inventive method.
  • Said carbon black may comprise new carbon black as well as recovered carbon black.
  • Carbon blacks are included in many polymer compositions, for example for modifying their color, mechanical, electrical, and/or processing properties. Carbon blacks are for instance commonly added to rubber compositions used to fabricate tires or components thereof to impart electrically dissipative properties to the insulating matrix. At the same time, carbon black additives affect the mechanical and elastic properties, such as stiffness, abrasion resistance and hysteresis, which affect to a great extent the performance of the resulting tire, e.g. in terms of its rolling resistance and durability.
  • Carbon black (produced carbon black) is provided, comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • the volume resistivity can be determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the examples, such as under item “Measuring the volume resistivity”.
  • ESBR emulsion-styrene-butadiene rubber
  • the cured emulsion-styrene-butadiene rubber (ESBR) containing 50 phr carbon black as prepared under items “Preparation of vulcanizable rubber compositions” and “Curing of the vulcanizable rubber compositions” can be used to measure the volume resistivity.
  • the emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black can consist the following components:
  • the volume resistivity can be determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black based on DIN EN ISO 3915:2022. The measurement of the volume resistivity is further described in full detail in the examples.
  • ESBR emulsion-styrene-butadiene rubber
  • carbon black (produced carbon black) is provided, preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m 2 /g, preferably a STSA surface area of 116 to 145 m 2 /g, more preferably a STSA surface area of 117 to 140 m 2 /g, and most preferably a STSA surface area of 120 to 135 m 2 /g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21.
  • the carbon black (produced carbon black) can have a BET surface area of 120 to 160 m 2 /g, preferably a BET surface area of 125 to 155 m 2 /g, more preferably a BET surface area of 127 to 150 m 2 /g, and most preferably a BET surface area of 130 to 145 m 2 /g, wherein the BET surface area is measured according to ASTM D6556-21.
  • the carbon black (produced carbon black) can have a compressed oil absorption number of 100 to 150 mL/100 g, preferably a compressed oil absorption number of 110 to 145 mL/100 g, more preferably a compressed oil absorption number of 115 to 140 mL/100 g, and most preferably a compressed oil absorption number of 117 to 135 mL/100 g, wherein the compressed oil absorption number is measured according to ASTM D3493-20 using paraffinic oil.
  • the carbon black (produced carbon black) can have volatiles of 1.0 to 4.5 wt.-%, preferably volatiles of 1.3 to 4.0 wt.-%, more preferably volatiles of 1.5 to 3.5 wt.-%, and most preferably volatiles of 1.7 to 3.0 wt.-%, wherein the volatiles are measured at 950 °C for 7 min as described in the specification.
  • the carbon black (produced carbon black) can have an iodine adsorption of 150 to 300 mg/g, preferably 160 to 280, more preferably 180 to 270 mg/g, and most preferably 190 to 260 mg/g, wherein the Iodine adsorption number is measured according to ASTM D1510-21.
  • the carbon black (produced carbon black) can have an ash content of at least 3 wt.-%, preferably at least 5 wt.-%, and most preferably at least 10 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • the carbon black (produced carbon black) can have an ash content of 3 to 25 wt.- %, preferably 5 to 20 wt.-%, and most preferably 8 to 18 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • the carbon black (produced carbon black) has a volume resistivity of less than 7.9'10 5 Q cm, preferably less than 1.0-10 5 Q cm, more preferably less than 1.0-10 4 Q cm, and most preferably less than 1.0-10 4 Q cm, as determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
  • ESBR emulsion-styrene- butadiene rubber
  • the carbon black (produced carbon black) can have resistivity of 10.0-Q cm to 7.9 10 5 Q cm, preferably 1.0- 10 2 Q cm to 1.0- 10 5 Q cm, more preferably 2.0 10 2 Q cm to 5.0 10 4 Q cm, and most preferably 2.0 10 2 Q- a volume cm to 1.0- 10 4 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
  • ESBR emulsion-styrene-butadiene rubber
  • composition comprising (A) an elastomeric polymer material, and (B) carbon black obtained according to the present invention. It should be noted that the provided article derived from said composition can also be used as a feedstock material.
  • composition refers to a material composed of multiple constituent chemical species or components.
  • An "elastomeric polymer material” is understood as a material essentially consisting of an elastomeric polymer.
  • polymer is used herein in its common meaning in the art, referring to macromolecular compounds, i.e. compounds having a relatively high molecular mass (e.g. 500 Da or more), the structure of which comprises multiple repetition units (also referred to as “mers”) derived, actually or conceptually, from chemical species of relatively lower molecular mass.
  • the term “elastomeric polymer” is used herein in its common meaning in the art, referring to a polymer which is elastic.
  • elastomeric polymeric materials for the practice of this invention are elastomers such as rubber materials.
  • the elastomeric polymer material (A) of the composition according to the present invention can comprise one or more than one rubber.
  • the terms “rubber”, “rubber material” and “elastomer” may be used interchangeably throughout this description unless otherwise stated. Rubbers that can be used according to the present invention include those containing olefinic unsaturation, i.e. diene-based rubber materials, as well as non-diene- based rubber materials.
  • the term “diene-based rubber materials” is intended to include both natural and synthetic rubbers or mixtures thereof.
  • the elastomeric polymer material (a) can consist of synthetic rubber.
  • the elastomeric polymer material (A) of the composition according to the present invention can comprise natural and/or synthetic rubber.
  • Natural rubber can be used in its raw form and in various processed forms conventionally known in the art of rubber processing. Natural rubber can for example be obtained from rubber trees (Helvea brasiliensis), guayule, and dandelion. Accordingly, the elastomeric polymer material (a) can comprise or consist of natural rubber.
  • Synthetic rubber can comprise styrene-butadiene rubber such as emulsion- styrene-butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylenepropylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinylacetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber or mixture of combinations of any of the foregoing.
  • the synthetic rubber can also be obtained from a renewable source material.
  • polybutadiene can be produced from alcohol obtained through fermentation
  • Suitable rubbers may also include functionalized rubbers and rubbers coupled to silicon or tin.
  • rubbers can be functionalized with functional groups like amine, alkoxy, silyl, thiols, thioesters, thioether, sulfanyl, mercapto, sulfide or combinations thereof.
  • the one or more functionalities can be primary, secondary or tertiary and can be located at one or both chain ends (e.g. a,w-functionalization), pendant from the polymer backbone and/or provided within the chain of the polymer backbone.
  • the rubber according to the invention can also be partially cross-linked. Thus, prior to use in the composition of the present invention, part of the polymer chains of the rubber material can be cross-linked either by means of a coupling agent or without.
  • the composition according to the invention can in particular be a curable composition, such as for example a vulcanizable rubber composition.
  • vulcanizable rubber composition refers to a composition of a rubber component optionally with various further ingredients conventionally used in the art of rubber compounding that can be cured by vulcanization under formation of a vulcanizate.
  • curable and vulcanizable are used interchangeably throughout this description unless otherwise stated and refer to a chemical reaction linking polymer chains to each other by means of a cross-linker or vulcanizing agent. The curing reaction can be induced by any means known in the art such as by light, moisture, heat and/or addition of a crosslinker.
  • the elastomeric polymer material (A) according to the invention may comprise a natural rubber.
  • the natural rubber can comprise natural rubber obtained from rubber trees (Helvea brasiliensis), guayule, dandelion or mixtures of combinations of any of the foregoing.
  • the natural rubber can comprise natural rubber obtained from guayule and/or dandelion.
  • the elastomeric polymer material (A) can comprise 5 phr or more of natural rubber, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more.
  • the term "phr” refers to parts by weight of the recited respective material per 100 parts by weight of rubber or elastomer.
  • the elastomeric polymer material (A) can comprise 100 phr or less of natural rubber, such as 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr, or less 70 phr or less, or 65 phr or less, or 60 phr or less.
  • the elastomeric polymer material (A) can comprise natural rubber in a range between any of the recited lower and upper limits.
  • the elastomeric polymer material (A) can comprise natural rubber in a range of 5 to 95 phr, such as in a range of 10 to 90 phr, or in a range of 20 to 80 phr, or in a range of 30 to 70 phr, or in a range of 40 to 60 phr.
  • the elastomeric polymer material (A) can consist of natural rubber.
  • the elastomeric polymer material (A) according to the invention may comprise a synthetic rubber.
  • the synthetic rubber can comprise synthetic rubber obtained from a renewable source material.
  • the renewable source material according to the present invention can be alcohol obtained through fermentation of plant biomass.
  • the synthetic rubber may comprise polybutadiene obtained from alcohol obtained through fermentation of plant biomass.
  • the elastomeric polymer material (A) can comprise 5 phr or more of synthetic rubber, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more.
  • the term "phr” refers to parts by weight of the recited respective material per 100 parts by weight of rubber or elastomer.
  • the elastomeric polymer material (A) can comprise 100 phr or less of synthetic rubber, such as 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr, or less 70 phr or less, or 65 phr or less, or 60 phr or less.
  • the elastomeric polymer material (A) can comprise synthetic rubber in a range between any of the recited lower and upper limits.
  • the elastomeric polymer material (A) can comprise synthetic rubber in a range of 5 to 95 phr, such as in a range of 10 to
  • the elastomeric polymer material (A) can consist of synthetic rubber.
  • the elastomeric polymer material (A) may comprise a mixture of natural rubber and synthetic rubber.
  • the elastomeric polymer material (A) can comprise from 5 to 100 phr of natural rubber and from 5 to 100 phr of synthetic rubber, such as from 10 to 90 phr of natural rubber and from 10 to 90 phr of synthetic rubber, or from 20 to 80 phr of natural rubber and from 20 to 80 phr of synthetic rubber, or from 30 to 70 phr of natural rubber and from 30 to 70 phr of synthetic rubber, or from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, or from 40 to 100 phr of natural rubber and from 5 to 60 phr of synthetic rubber, or from 50 to 95 phr of natural rubber and from 5 to 50 phr of synthetic rubber, or from 60 to 90 phr of natural rubber and from 10 to 50 phr of synthetic rubber, or from 5 to 40 p
  • the elastomeric polymer material (A) may comprise 50 phr of natural rubber and 50 phr of synthetic rubber or the elastomeric polymer material (A) may comprise 5 phr of natural rubber and 95 phr of synthetic rubber.
  • the synthetic rubber according to the present invention preferably comprises emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, more preferable polyisoprene and/or polybutadiene, even more preferably polybutadiene.
  • ESBR emulsion-styrene-butadiene rubber
  • polybutadiene polyisoprene
  • butyl rubber halogenated butyl rubber or mixture of combinations of any of the foregoing, more preferable polyisoprene and/or polybutadiene, even more preferably polybutadiene.
  • the synthetic rubber according to the present invention preferably consists of emulsion- styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, more preferable polyisoprene and/or polybutadiene, even more preferably polybutadiene.
  • the synthetic rubber can comprise emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene.
  • the synthetic rubber can comprise or consist polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene.
  • the synthetic rubber can comprise or consist polybutadiene, polyisoprene, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene.
  • the produced carbon black can also be pulverized before being added to the composition.
  • the composition can comprise pulverized carbon black.
  • the composition can comprise 3 to 200 phr of the carbon black obtained according to the present invention (B), preferably 5 to 190 phr of the carbon black obtained according to the present invention (B), more preferably 10 to 150 phr of the carbon black obtained according to the present invention (B), even more preferably 20 to 130 phr of the carbon black obtained according to the present invention (B), most preferably 30 to 100 phr of the carbon black (B) obtained according to the present invention.
  • the composition can comprise one or more additives selected from vulcanization agents, curing aids such as primary and secondary vulcanization accelerators, activators and pre-vulcanization inhibitors, processing additives such as oils, waxes, resins, plasticizers, softeners, rheology modifiers, pigments, peptizing agents, coupling agents, surfactants, biocides and anti-degradants, such as heat or light stabilizers, anti-oxidants and anti-ozonates, metal oxides, metal hydroxides, and filler materials such as silica, organo-silica, carbon nanotubes, carbon fibers, graphite and metal fibers.
  • curing aids such as primary and secondary vulcanization accelerators, activators and pre-vulcanization inhibitors
  • processing additives such as oils, waxes, resins, plasticizers, softeners, rheology modifiers, pigments, peptizing agents, coupling agents, surfactants, biocides and anti-degradants, such as heat or light stabilize
  • the composition of the present invention can be obtained and processed by common elastomer processing technology.
  • the composition according to the present invention can for example be obtained by combining the carbon black (B) of the present invention and any optional ingredients, if used, with the elastomeric polymer material (A) and mixing the same, e.g. to disperse the carbon black (B) and any optional ingredients, if used, in the elastomeric polymer material (A).
  • Dispersion can be achieved by any means known in the art such as by mixing, stirring, milling, kneading, ultrasound, a dissolver, a shaker mixer, rotor-stator dispersing assemblies, or high-pressure homogenizers or a combination thereof.
  • a lab mixer with intermeshing rotor geometry can be used.
  • the dispersing can for example be conducted until the carbon black (B) is homogeneously dispersed in the elastomeric polymer material (A) resulting in a dispersion index of larger than 95% or more, preferably 97% or more, or more than 99% according to the classification pursuant to ASTM D2663-88, test method B.
  • Preparation of the composition according to the present invention may for example be conducted in a multiple step process: At first, the carbon black (B) and optionally non-curative additives, if used, may be added to the elastomeric polymer material (A) concomitantly or successively.
  • the elastomeric polymer material (A), the carbon black (B) and the additives, if used, may then be mixed, typically at a temperature in a range from 40°C to 160°C for a total mixing time of less than 10 min, such as in a range from 2 to 8 min.
  • the obtained mixture may be blended with one or more curative additives for less than 5 min, typically less than 3 min, preferably for about 2.5 min, at a temperature of less than 115°C.
  • the process can comprise further steps such as extrusion or cooling down the product to room temperature and storing it for further processing.
  • the process can further comprise a curing step, which can for example be carried out by subjecting the composition to thermal curing conditions, e.g. a temperature of 120-200°C for a time of 5 minutes to 3 hours. Curing can for instance be carried out in a curing press for example at a temperature of 140-180°C for 5 to 60 minutes at a pressure between 100 and 150 bar.
  • compositions according to the invention can be utilized in various technical applications requiring polymer-based materials with carbon black filler, e.g. for imparting antistatic or electrically conductive properties, color, mechanical reinforcement and/or low hysteresis properties.
  • Mechanical properties that are of interest, particularly for the production of tires, include tear resistance, rebound and hysteresis.
  • the compositions according to the present invention provide cured compositions which have good and beneficial mechanical properties, especially for the production of tires.
  • Beneficial mechanical properties in accordance with the present invention are for example high tensile strength, high rebound and low hysteresis.
  • the composition according to the present invention provide cured compositions having mechanical properties which are comparable to rubber compositions comprising conventional carbon blacks.
  • the invention also relates to articles, such as rubber articles, and particularly tires made of or comprising the afore-mentioned composition according to the invention.
  • a rubber article comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • the tire can comprise a sidewall, wherein the sidewall is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, preferably from 50 to 60 phr of natural rubber and from 40 to 50 phr of synthetic rubber, more preferably 55 phr of natural rubber and 45 phr of synthetic rubber wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the comprise a tread, carcass, sidewall, inner liner, apex, shoulder, hump strip, chafer and/or a bead filler, wherein at least carbon black, preferably 50 phr of the carbon black.
  • the composition preferably comprises: (A) from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber
  • the tire can comprise a carcass, wherein the carcass is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 40 to 80 phr of natural rubber and from 20 to 60 phr of synthetic rubber, preferably from 50 to 70 phr of natural rubber and from 30 to 50 phr of synthetic rubber, more preferably 60 phr of natural rubber and from 40 phr of synthetic rubber wherein the synthetic rubber preferably comprises polybutadiene and emulsion-styrene-butadiene rubber (ESBR), more preferably comprises 20 phr of polybutadiene and 20 phr of emulsion-styrene- butadiene rubber (ESBR); and (B) from 5 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably 50 phr of the carbon black.
  • the synthetic rubber preferably comprises polybutadiene and emulsion-styrene-buta
  • the tire comprises a chafer, wherein the chafer is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 30 to 70 phr of natural rubber and from 30 to 70 phr of synthetic rubber, preferably from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, more preferably 50 phr of natural rubber and 50 phr of synthetic rubber, wherein the synthetic rubber preferably comprises emulsion-styrene-butadiene rubber (ESBR), more preferably consists of emulsion-styrene-butadiene rubber (ESBR); and (B) from 55 to 95 phr of the carbon black, preferably from 65 to 85 phr of the carbon black, preferably 75 phr of the carbon black.
  • ESBR emulsion-styrene-butadiene rubber
  • the tire can comprise a bead filler and/or an apex, wherein the bead filler and/or apex is/are made of the composition according to the invention, wherein the composition preferably comprises: (A) from 80 to 100 phr of natural rubber, preferably from 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 65 phr of the carbon black, more preferably from 55 phr of the carbon black.
  • the tire can comprise an inner liner, wherein the inner liner is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises a halogenated butyl rubber, more preferably consists of a halogenated butyl rubber; and (B) from 40 to 80 phr of the carbon black, preferably from 50 to 70 phr of the carbon black, more preferably from 60 phr of the carbon black.
  • the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises a halogenated butyl rubber, more preferably consists of a halogenated butyl rubber; and (B) from 40 to 80 phr of the carbon
  • the tire can comprise a tread, preferably a truck tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably from 80 phr of natural rubber and 20 phr of synthetic rubber, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably from 50 phr of the carbon black.
  • the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably from 80 phr of natural
  • the tire can comprise a tread, preferably a passenger car tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprises 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 65 phr of the carbon black, more preferably 55 phr of the carbon black.
  • the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises solution-s
  • the tire can comprise a tread, preferably a passenger car tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprises 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; and (B) from 3 to 25 phr of the carbon black, preferably from 5 to 15 phr of the carbon black, more preferably 5 phr of the carbon black; and (C) from 60 to 100 phr of silica, preferably from 70 to 90 phr of silica, more preferably 80 phr of silica.
  • the composition preferably comprises (A) from 80 to 100
  • the tire can comprise a tread, preferably an Off-the-road (OTR) tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of natural rubber, preferably from 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 75 phr of the carbon black, more preferably from 55 phr of the carbon black.
  • OTR Off-the-road
  • the rubber article can be a cable sheath, a tube, a drive belt, a conveyor belt, a roll covering, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating or a colored or printed article.
  • the rubber article can be a conveyor belt, wherein the conveyor belt is made of the composition according to the invention, wherein the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably 80 phr of natural rubber and from 20 phr of synthetic rubber, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably from 50 phr of the carbon black.
  • the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably 80 phr of natural rubber and from 20
  • the present invention relates to the use of the aforementioned composition according to the present invention for producing a tire, preferably a pneumatic tire, a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, inner liner, apex, shoulder, hump strip, chafer, a bead filler, a cable sheath, a tube, a drive belt, a conveyor belt, a roll covering, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating or a colored or printed article.
  • a tire preferably a pneumatic tire, a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, inner liner, apex, shoulder, hump strip, chafer, a bead filler, a cable sheath, a tube, a drive belt, a conveyor belt, a roll covering, a shoe sole
  • the rubber article can have an abrasion of less than 110 mm 3 , preferably less than 106 mm 3 , more preferably 50 to 10 5 mm 3 , and most preferably 90 to 10 5 mm 3 , as measured at 23 °C DIN ISO 4649:2014-03, 10 N.
  • the rubber article can have a tensile strength of 20.0 to 40.0 Mpa, preferably 23.0 to 35 Mpa, more preferably 24.0 to 32 Mpa, and most preferably 24.0 to 30 Mpa, as measured according to ISO 37 - 2012, S2.
  • the rubber article can have an elongation at break of more than 520 %, preferably 530 to 700 %, more preferably 550 to 650 %, even more preferably 570 to 630 %, and most preferably 580 to 620 %, as measured according to ISO 37 - 2012, S2.
  • the rubber article can have a Mooney viscosity of 40 to 80 Me, more preferably 50 to 76 Me, even more preferably 57 to 75 Me, and most preferably 65 to 74 Me, as measured according to ISO 289-1 :2015.
  • the present invention uses deagglomerated particulate carbon- containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor. Moreover, the present invention uses particulate carbon-containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor.
  • FIG. 1 a furnace reactor (100) is shown that comprises a combustion chamber (101), a choke (102) and a tunnel (103).
  • the reactor has an inner lining (106) as well as an outer lining (105).
  • the combustion chamber (101) comprises means to inject a fuel (101b) and oxygen-containing gas (101a).
  • the oxygen-containing gas is injected into the combustion chamber (101) tangential or radial via oxygen containing gas means (101a) and the fuel is injected into the combustion chamber (101) axial via fuel injection means (101b).
  • the oxygen-containing gas is preheated to a temperature described in the description. It is possible to adjust the temperature of the hot gas flow with the preheating of the oxygen-containing gas.
  • the fuel can be preheated.
  • the combustion chamber (101) the fuel is combusted in the presence of the oxygen-containing gas.
  • the temperature of the hot carrier gas can be above 800 °C to bring the particulate carbon-containing feedstock.
  • the particulate carbon-containing feedstock can be injected directly in the combustion chamber (101), in the choke (102) or in the tunnel (103).
  • the fluid carbon-containing feedstock can be injected directly in the combustion chamber (101), in the choke (102) or in the tunnel (103). It is preferred that the particulate carbon-containing feedstock is injected in the choke (102) and the fluid carbon-containing feedstock is injected in the tunnel (103).
  • the furnace reactor (100) comprises multiple positions for the quench (104a, 104b, 104c, 104d).
  • the quench medium that is usually water reduces the temperature of the hot gas flow (or the product mixture) so that the reaction for forming the carbon black is terminated.
  • the position of the quench has an influence of the residence time of the feedstock as well as the components derived from the feedstock.
  • residence time is increased if the quench position is adjusted further downstream the reactor.
  • a quench at a position (104a) near the choke (102) results in a low residence time
  • a quench at a position (104c) downstream the reactor results in a high residence time.
  • the reaction volume is the volume of the reactor between the injection of the feedstock and the position of the quench. If the feedstock is injected in the tunnel (103) and the distance between the position of the quench and the injection of the feedstock is 4200 mm, and the diameter of the tunnel is 200m, the resulting reaction volume is 132 L.
  • the feeding rate of the particulate carbon containing feedstock should be adjusted depending on the reaction volume as mentioned in the description.
  • a quench position at the back part of the tunnel is particularly preferred so that the particulate carbon containing feedstock has sufficient time for the evaporation or pyrolysis.
  • a feeding and mixing device 200
  • a carrier gas inlet 204
  • a particle inlet 201
  • means for accelerating and injecting a stream of carrier gas 207
  • a deagglomeration conduit 209
  • a mixing chamber 206
  • an outlet for said carrier gas entraining particles 210
  • the carrier gas passage 212
  • the carrier gas passage (212) extends along a longitudinal axis through said feeding and mixing device.
  • the carrier gas (203) enters the feeding and mixing device (200) through the carrier gas inlet (204) and is accelerated in the means for accelerating and injecting a stream of carrier gas (207).
  • the means for accelerating and injecting a stream of carrier gas (207) is configured as a Laval-nozzle.
  • the Laval-nozzle comprises a convergent area (207a) in the flow direction.
  • the resulting carrier gas jet is injected into the mixing chamber (206).
  • the particles such as the particulate carbon-containing feedstock (202) are perpendicularly injected into the mixing chamber (206). Accordingly, the particles will be entrained in the accelerated carrier gas.
  • the abrupt acceleration of the particles results in a deagglomeration of the particles.
  • the accelerated carrier gas comprising the particles are further injected into the deagglomeration conduit (209).
  • the particles collide with each other or the inner wall or inner surface of the deagglomeration conduit (209) thereby a further deagglomeration is achieved.
  • the means for accelerating and injecting a stream of carrier gas (207) is configured in such a way that the carrier gas jet is directly injected into the deagglomeration conduit (209). Accordingly, a loss of the velocity can be minimized.
  • the deagglomeration conduit (209) normally comprises from downstream to upstream (in the flow direction) an inlet funnel (209a), a conduit having a constant inner diameter (209b) and a diffuser nozzle diverging in said flow direction (209c).
  • the inlet funnel (209a) further allows an optimal flow behavior into the conduit having a constant inner diameter (209b).
  • the diffuser nozzle diverging in said flow direction (209c) is also beneficial for the flow behavior.
  • the outlet (406) can be connected to the means for injecting the feedstock into a reactor according to FIG.1. It is preferred that one feeding and mixing device (200) supplies the deagglomerated feedstock to multiple means for injecting the feedstock into the reactor.
  • the feeding and mixing device (200) comprises a screw conveyor that is connected with the particle inlet (201). The screw conveyor can provide a suitable amount or weight of particles into the mixing chamber (206). Furthermore, the feeding and mixing device (200) can be operated under pressure such as 1.5 bar or 2 bar.
  • a pressure tank for the particles e.g.
  • a pressure tank is in fluid connection with the particle inlet (201) and is preferably connected with the feeding and mixing device (200) via a valve.
  • a Laval-nozzle (300) for use in feeding and mixing device (200) is shown.
  • the carrier gas passage (306) extends along a longitudinal axis through said Laval-nozzle (300).
  • the carrier gas (304) enters the Laval-nozzle (300) and is accelerated.
  • the carrier gas jet (305) then leaves the Laval-nozzle (300).
  • the Laval- nozzle (300) comprises a section that has a constant diameter (301), a section that converges (302a) in the flow direction (302), a throat (303a) and a divergent section (303).
  • the carrier gas is accelerated to a velocity of over 1 Ma.
  • the deagglomeration conduit (400) for use in feeding and mixing device (200) is shown.
  • the carrier gas passage (407) extends along a longitudinal axis through said deagglomeration conduit (400).
  • the deagglomeration conduit (400) comprises an inlet funnel (401), a conduit having a constant inner diameter (402) and a diffuser nozzle (403) diverging in said flow direction (403a).
  • an outlet (404) is shown that can be connected to means to inject the deagglomerated particles (e.g. deagglomerated particulate carbon containing particles) (406) into the reactor.
  • the outlet (503) can be connected to a reactor. Similar to the feeding and mixing device (200), a screw conveyor and at least one pressure tank can be installed.
  • a method for producing carbon black in entrained flow reactor comprising:
  • Aspect 29 The method according to any one of aspects 22 to 28, wherein the supplied oxygen-containing gas is air, oxygen-enriched air or oxygen gas.
  • Aspect 30 The method according to any one of aspects 22 to 29, wherein the fuel comprises gaseous or liquid hydrocarbons, preferably natural gas, a fuel oil or H2.
  • Aspect 33 The method according to any one of the preceding aspects, wherein the concentration of O2 in the hot gas flow is less than 5 vol.-%, preferably less than 4 vol.-%, more preferably 0.01 to 3 vol.-%, and most preferably 0.1 to 2 vol.-%.
  • Aspect 34 The method according to any one of the preceding aspects, wherein the obtained carbon black comprises recovered carbon black and new carbon black.
  • Aspect 38 The method according to any one of aspects 2 to 37, wherein the deagglomeration is done by (i) accelerating the particulate carbon-containing feedstock, and/or (ii) applying shear forces, preferably using an extruder.
  • Aspect 39 The method according to any one of aspects 2 to 38, wherein the deagglomeration is carried out in (i) a feeding and mixing device, preferably comprising a nozzle, and/or (ii) an extruder.
  • Aspect 40 The method according to any one of aspects 2 to 39, wherein the deagglomeration is carried out in (i) a feeding and mixing device comprising a Laval nozzle.
  • Aspect 41 The method according to any one of aspects 2 to 40, wherein the deagglomeration is carried out by subjecting the particulate carbon-containing feedstock into a carrier gas jet.
  • Aspect 42 The method according to any one of aspects 2 to 41 , wherein the deagglomeration is carried out in a feeding and mixing device for particles into a reactor comprising:
  • Aspect 43 The method according to any one of aspects 2 to 42, wherein the deagglomerated particulate carbon-containing feedstock is injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1.5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar.
  • Aspect 44 The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is comprised in a carrier gas, preferably the carrier gas is nitrogen.
  • Aspect 45 The method according to any one of aspects 2 to 44, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas, preferably the carrier gas is nitrogen.
  • Aspect 46 The method according to any one of aspects 2 to 45, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas and the carrier gas further comprises H2O and/or additives.
  • Aspect 47 The method according to any one of aspects 2 to 46, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas and the carrier gas further comprises H2O in an amount of 1 to 10 vol.-%, based on the total volume of the carrier gas comprising the the deagglomerated particulate carbon- containing feedstock.
  • Aspect 48 The method according to any one of the preceding aspects, wherein said particulate carbon-containing feedstock is injected in said entrained flow reactor by a plurality of inlets, preferably by a plurality of injection lances.
  • Aspect 49 The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is classified, preferably sieved, before the particulate carbon-containing feedstock is injected into the reactor, preferably (a) the sieve has openings of 2000 pm, 1000 pm, 500 pm, 250 pm, or 125 pm, preferably 500 pm, 250 pm, or 125 pm, and/or (b) the sieve has openings with a size that restrains particles with a size of more than 2000 pm, more than 1000 pm, more than 500 pm, more than 250 pm, or more than 125 pm, preferably more than 500 pm, more than 250 pm, or more than 125 pm.
  • Aspect 50 The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • Aspect 51 Aspect 51.
  • Aspect 52 The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 1 mm, wherein the particle size is measured according to ASTM D 1511- 12 (2017).
  • Aspect 53 The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
  • Aspect 54 The method according to any one of the preceding aspects, wherein the method is for producing carbon black from a particulate carbon-containing feedstock and a fluid carbon-containing feedstock in entrained flow reactor having a flow passage along a central longitudinal axis of the reactor, wherein the hot gas flow has a temperature of at least 800 °C.
  • Aspect 55 The method according to any one of the preceding aspects, wherein the mass ratio of particulate carbon-containing feedstock to fluid carbon-containing feedstock 0.5:1 to 1 :0.05, preferably 1:1 to 1:0.1, more preferably 1.1:1 to 1 :0.1, and most preferably 1.2:1 to 1:0.2.
  • Aspect 56 The method according to any one of the preceding aspects, wherein the hot gas flow has a temperature of at least 800 °C, such as at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, or at least 1600 °C.
  • Aspect 57 Carbon black, comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9- 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • Carbon black preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m 2 /g, preferably a STSA surface area of 116 to 145 m 2 /g, more preferably a STSA surface area of 117 to 140 m 2 /g, and most preferably a STSA surface area of 120 to 135 m 2 /g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21.
  • Aspect 59 The carbon black according to aspects 57 or 58, wherein the carbon black has a BET surface area of 120 to 160 m 2 /g, preferably a BET surface area of 125 to 155 m 2 /g, more preferably a BET surface area of 127 to 150 m 2 /g, and most preferably a BET surface area of 130 to 145 m 2 /g, wherein the BET surface area is measured according to ASTM D6556-21 .
  • Aspect 60 The carbon black according to aspects 57 to 59, wherein the carbon black has a compressed oil absorption number of 100 to 150 mL/100 g, preferably a compressed oil absorption number of 110 to 145 mL/100 g, more preferably a compressed oil absorption number of 115 to 140 mL/100 g, and most preferably a compressed oil absorption number of 117 to 135 mL/100 g, wherein the compressed oil absorption number is measured according to ASTM D3493-20 using paraffinic oil.
  • Aspect 61 The carbon black according to aspects 57to 60, wherein the carbon black has volatiles of 1 .0 to 4.5 wt.-%, preferably volatiles of 1.3 to 4.0 wt.-%, more preferably volatiles of 1.5 to 3.5 wt.-%, and most preferably volatiles of 1.7 to 3.0 wt.-%, wherein the volatiles are measured at 950 °C for 7 min as described in the specification.
  • Aspect 62 The carbon black according to aspects 57to 61 , wherein the carbon black has an iodine adsorption of 150 to 300 mg/g, preferably 160 to 280, more preferably 180 to 270 mg/g, and most preferably 190 to 260 mg/g, wherein the Iodine adsorption number is measured according to ASTM D1510-21.
  • Aspect 63 The carbon black according to aspects 57to 62, wherein the carbon black has the ash content is at least 3 wt.-%, preferably 5 wt.-%, and most preferably 10 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • Aspect 64 The carbon black according to aspects 57to 63, wherein the carbon black has an ash content of 3 to 25 wt.-%, preferably 5 to 20 wt.-%, and most preferably 8 to 18 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • Aspect 65 The carbon black according to aspects 57to 64, wherein the carbon black has a volume resistivity of less than 7.9- 10 5 Q cm, preferably less than 1.0-10 5 Q cm, more preferably less than 1.0- 10 4 Q cm, and most preferably less than 1.0-10 4 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
  • ESBR emulsion-styrene-butadiene rubber
  • Aspect 66 The carbon black according to aspects 57to 65, wherein the carbon black has resistivity of 10.0 Q cm to 7.9- 10 5 Q cm, preferably 1.0 10 2 Q cm to 1.0-10 5 Q cm, more preferably 2.0 10 2 Q cm to 5.0 10 4 Q cm, and most preferably
  • ESBR emulsion-styrene-butadiene rubber
  • Aspect 68 The composition of aspect 67, wherein the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • a rubber article comprising carbon black preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 10 5 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • ESBR emulsion-styrene-butadiene rubber
  • Aspect 70 The rubber article according to aspect 69, wherein the rubber article has an abrasion of less than 110 mm 3 , preferably less than 106 mm 3 , more preferably 50 to 105 mm 3 , and most preferably 90 to 105 mm 3 , as measured at 23 °C DIN ISO 4649:2014-03, 10 N.
  • Aspect 71 The rubber article according to any one of aspects 69 or 70, wherein the rubber article comprises carbon black as defined in any one of aspects 57 to 68.
  • Aspect 72 The rubber article according to any one of aspects 69 to 71 , wherein the rubber article has a tensile strength of 20.0 to 40.0 Mpa, preferably 23.0 to 35 Mpa, more preferably 24.0 to 32 Mpa, and most preferably 24.0 to 30 Mpa, as measured according to ISO 37 - 2012, S2.
  • Aspect 73 The rubber article according to any one of aspects 69 to 72, wherein the rubber article has an elongation at break of more than 520 %, preferably 530 to 700 %, more preferably 550 to 650 %, even more preferably 570 to 630 %, and most preferably 580 to 620 %, as measured according to ISO 37 - 2012, S2.
  • Aspect 74 The rubber article according to any one of aspects 69 to 73, wherein the rubber article has a Mooney viscosity of 40 to 80 Me, more preferably 50 to 76 Me, even more preferably 57 to 75 Me, and most preferably 65 to 74 Me, as measured according to ISO 289-1:2015.
  • Aspect 75 Use of a particulate carbon-containing feedstock and a fluid carbon- containing feedstock for the manufacturing of carbon black in an entrained flow reactor.
  • Aspect 76 The use of aspect 75, wherein the use of a particulate carbon- containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor is defined as in any one of the previous aspects.
  • Example 1 Rubber granulate and liquid carbon-containing feedstock
  • Example 1 The experiments of Example 1 are performed on a small-scale furnace reactor as shown in FIG. 1.
  • the furnace reactor comprises a combustion chamber, a choke and a tunnel.
  • the choke reduces the diameter to 114 mm. Downstream of the choke a reactor tunnel is mounted having a diameter of 875 mm and has a length of 7820 mm.
  • Rubber granulate was injected to the furnace reactor in the choke via a feeding and mixing device having a nozzle similar as shown in FIG. 2.
  • the reaction volume of the reactor was about 4900 liters.
  • the reaction volume was the volume of the reactor between the position of the injection of the feedstock to the position of the quench.
  • the feeding and mixing device deagglomerated the rubber granulate by accelerating the particulate carbon-containing feedstock.
  • the present invention is not limited to the feeding and mixing device according to FIG. 1 so that other feeding and mixing device can be used.
  • a liquid carbon-containing feedstock was introduced in the choke of the reactor downstream the feeding and mixing device. The distance between the injection of the particulate carbon-containing feedstock and the injection of the fluid carbon-containing feedstock was 125 mm.
  • the liquid carbon-containing feedstock was a coal tar distillate “RuBrohstoff Typ K” from Rain Carbon Germany GmbH, Castrop-Rauxel.
  • the rubber granulate, i.e. Gummigranulat 0,0 - 0,5 mm (Article Nr. 005GLIM), used in the experiments was obtained from ESTATO reactor GmbH (ESTATO), Germany.
  • the rubber granulate was derived from old tires and comprises synthetic rubber (SBR) and natural rubber (NR).
  • SBR synthetic rubber
  • NR natural rubber
  • the particle fractions are shown in table 1.
  • the weight average particle diameter (Dw50) was about 400 pm, measured according to ASTM D 1511-12 (2017).
  • it is also possible to use different particulate carbon-containing feedstocks such as plastic granulates or biomass-based granulates.
  • Table 1 Particle distribution of rubber granulate from ESTATO, measured according to ASTM D 1511-12 (2017).
  • Table 2 Characterization of the rubber granulate from ESTATO.
  • the rubber granulate comprises several metals in a mass fraction of about 300 ppm. For instance, zinc, and iron.
  • the carbon mass fraction, hydrogen fraction mass, nitrogen mass fraction and sulfur mass fraction are measured using an elemental analyser with thermal conductivity and infrared detector.
  • the analyser is a device for the fully automatic and quantitative analysis of the above elements.
  • the combustion tube is brought to a temperature of 1100 °C and the reduction tube to 850 °C.
  • a blank measurement is conducted.
  • the carbon peak area should have a value ⁇ 50, the hydrogen peak area a value ⁇ 300, the nitrogen peak area a value ⁇ 50 and the sulphur peak area a value ⁇ 350. Otherwise, the individual adsorption columns are heated and then empty measurements are started again.
  • the blank measurement is calculated as follows: wherein b is the blank measurement, bj is the peak area of the respective blank measurement, n is the number of blank measurements, i is an index of 1 to n.
  • acomp. a - b, wherein acomp. Is the compensated peak area, a is the measured peak area, and b is the blank measurement value.
  • the daily factor is measured.
  • 3 mg of sulphanilamide and 3 mg of low-level standard e.g. carbon black standard
  • 3 mg of sulphanilamide and 3 mg of low-level standard are weighed into each of 8 tin capsules. After weighing out the respective sample, it is placed in the capsule press, overlaid with helium for 35 s and then cold-sealed. Subtracting the blank value, the known theoretical element concentration of the standard samples is put in relation to the actually calculated element concentration. This results in the daily factor, which must be between 0.9 - 1.1. If this is not the case, these measurements should be repeated with newly opened standards. Otherwise, a new calibration must be carried out according to the manufacturer's instructions.
  • the combustion tube is enriched with O2.
  • the elements C, H, N and S burn to form CO2, H2O, NOx, SO2 and SO3.
  • Halogen bound in the sample reacts to form volatile halogen compounds.
  • there are WO3 granules in the combustion tube that provide further O2 as a catalyst, prevent the formation of nonvolatile sulphates and bind interfering alkali and alkaline earth elements.
  • the carrier gas stream is fed into the reduction tube with Cu filling. Nitrogen oxides (NOx) are completely reduced to N2 at the copper contact. SO3 is reduced to SO2. Volatile halogen compounds are bound to the silver wool.
  • N2 is not adsorbed and enters the thermal conductivity detector as the first measuring component, CO2, H2O and SO2 are adsorbed on the respective adsorption columns.
  • the adsorption columns are brought to desorption temperature, so that CO2, then H2O as carrier gas enters the thermal conductivity detector and SO2 enters the infrared detector.
  • the detector delivers an electrical signal which is digitised and integrated.
  • the measurement signal is recorded as a function of time and displayed as an integral value.
  • the absolute element content of the sample is calculated from this integral value of the individual measurement peaks and the calibration factors.
  • an electrical signal is transmitted from the thermal conductivity detector (WLD) of the elemental analyser to a micro controller and then displayed as an integral value. From the integral value of the measurement peaks and the calibration factor, the absolute element content of the sample is concluded.
  • the pyrolysis tube is heated to a temperature of 1050°C.
  • a blank measurement is conducted. The oxygen peak area should have a maximum value of 200. If the blank value is not below 200, CO adsorption column should be heated up (260 °C, CO desorption 150 °C). After the blank values have been successfully measured, the mean value of the blank value areas is calculated.
  • the blank measurement is calculated as follows: wherein b is the blank measurement, bj is the peak area of the respective blank measurement, n is the number of blank measurements, i is an index of 1 to n.
  • the daily factor is measured.
  • 3 mg of acetanilide are weighed into each of 8 tin capsules. After weighing out the respective sample, it is placed in the capsule press, overlaid with helium for 35 s and then cold-sealed. Subtracting the blank value, the known theoretical element concentration of the standard samples is put in relation to the actually calculated element concentration. This results in the daily factor, which must be between 0.9 - 1.1. If this is not the case, these measurements should be repeated with newly opened standards. Otherwise, a new calibration must be carried out according to the manufacturer's instructions.
  • the daily factor is calculated as follows, f > Ctheor Cact wherein f is the daily factor, Ctheor. is the theoretical factor, c ac t. is the actual calculated elemental concentration.
  • the k value is defined by the ratio of stoichiometric O2 amount that is necessary for the complete stoichiometric combustion of the fuel to the supplied O2 amount [365]
  • the reaction is quenched with water and the obtained carbon black was dried and milled to obtain a volume average particle size of about 5 pm.
  • the obtained carbon black (see Experiments A1 and A2) were compared to carbon black N660, and a recovered carbon blacks rCB. rCB was recovered from a pyrolysis of rubber granulates.
  • the temperature in the combustion chamber i.e. the temperature of the hot combustion gases, was controlled by the temperature of the combustion air temperature upstream combustion chamber (i.e. temperature of the oxygen-containing gas).
  • the k value was controlled by the natural gas flow (fuel) into the combustion chamber.
  • the rubber granulate is used in an entrained flow reactor process, it is possible to not only recover carbon black but also to produce new carbon black derived from the rubber in addition, new carbon black is obtained from the liquid carbon- containing feedstock.
  • the ash content is lower compared to recovered carbon black from REOIL.
  • the ash content can be measured according to ASTM D 1506-15 at 550 °C, 16 h.
  • pH-value is measured according to ASTM D1512-21 , Test Method B - Sonic Slurry.
  • COAN Compressed oil absorption number
  • Oil absorption (OAN) number was measured according to ASTM D2414-19 (using paraffinic oil).
  • the ash content was determined according to ASTM D 1506-15 at 550 °C, 16 h.
  • a dispersion solution is prepared by adding 1 g of Tergitol-Type NP-40 (CAS-No. 9016-45-9) and 600 ml of demineralized water into a 1 I graduated flask. Stir until the surfactant has dissolved and fill up to the mark with demineralized water.
  • two spin fluids are prepared with 8 wt.% sucrose and 24 wt.% sucrose (CAS-No. 57-50-1).
  • 8% w/w solution Weigh 4.0 g of sucrose and 46.0 g of demineralized water into a glass beaker and stirred until complete dissolution.
  • 24% w/w solution Weigh 12.0 g of sucrose and 38.0 g of demineralized water into a glass beaker and stirred until complete dissolution.
  • SiO2 standard can be used.
  • the SiO2 standard is available from CPS Instruments, Inc. 41452 Bess Rd., Prairieville, LA 70769, USA. Standard particle diameter should be chosen in the range of the expected d mO de of the samples. SiO2 standards in the 150 nm diameter range can be used.
  • ITRB2 Industry Tint Reference Black
  • ITRB2 can be obtained from Balentine Enterprises Inc. 1410 South Cedar Street (STE 20) Borger, Texas 79007 USA.
  • a calibration carbon black sample was prepared by weighting 5 mg of ITRB2 into a titration glass and add 25 ml of the dispersion solution. If pelletized carbon black shall be tested, carefully crush and homogenize approximately 250 mg of the sample in an agate mortar. For carbon black in powder form, this step is not needed. Transfer the titration glass into a cooling bath and subject to ultrasonic radiation for 10 min at 100 % amplitude and 80 % pulse. If the standard carbon black is entirely dispersed, it will give a mean Stokes diameter (“mean”) of 95 nm ⁇ 4 nm for ITRB2.
  • a carbon black sample was prepared by weighting 5 mg of carbon black into a titration glass and add 25 ml of the dispersion solution. If pelletized carbon black shall be tested, carefully crush and homogenize approximately 250 mg of the sample in an agate mortar. For carbon black in powder form, this step is not needed. Transfer the titration glass into a cooling bath and subject to ultrasonic radiation for 10 min at 100 % amplitude and 80 % pulse. [379] Set-up of equipment and test parameters
  • Fluid parameters Fluid density: 1.051 g/ml, Fluid refractive index: 1.3612, Fluid viscosity: 1.28 cps.
  • Runtime options Calibration method: external. Samples per calibration: 1. Initial fill volume: 18 ml. Injected viscosity: 1 cps. Injected density: 1 g/ml. Injection timing: spacebar. Baseline drift display: no. Extra software noise filter: no. Speed ramping: fixed speed. Correct for non-Stokes: no. Force baseline: yes.
  • a rotational speed of 10 000 rpm is selected.
  • the rotational speed shall be 24 000 rpm.
  • Prepare the gradient of the spin fluid by following the next steps. Using a syringe, take up from the bottle with the 24 wt.% sucrose 1 .8 ml and inject this into the disc spinning at analysis speed. Next, the syringe is filled with only 1 .6 ml of the 24 wt.% sucrose solution and filled up with 0.2 ml of the 8 % solution.
  • the specific surface of a tested sample is available from aggregate size distribution measurement using CPS as described above.
  • thermogravimetric instrument of Fa. LEGO Instrumente GmbH (TGA-701) according to the following protocol: Pans were dried at 650°C for 30 min. The carbon black materials were stored in a desiccator equipped with desiccant prior to measurements. Baked-out pans were loaded in the instrument, fared and filled with between 0.5 g to 10 g carbon black material. Then, the oven of the TGA instrument loaded with the sample-filled pans was gradually heated up to 105°C by automated software control and the samples were dried until a constant mass was achieved. Subsequently, the pans were closed by lids, the oven was purged with nitrogen
  • the obtained carbon has desirable properties compared to standard carbon black products obtained from liquid carbon-containing feedstocks and obtained from only particulate carbon-containing feedstock.
  • the aggregate size is lower compared to aggregate size of the recovered carbon blacks and the carbon black obtained only from the particulate carbon black feedstock.
  • the STSA surface area of Experiment B4 is higher compared to the carbon black of Experiment B3 obtained only from the particulate carbon black feedstock.
  • the ash content of Experiment B4 is significantly lower compared to Experiment B3 obtained only from the particulate carbon black feedstock.
  • Example 2 Rubber compositions
  • the rubber compositions are mentioned in table 5.
  • the ESBR Buna SB 1500 was introduced to a laboratory mixer GK1.5E with an intermeshing PES5-rotor geometry made by Harburg Freudenberger and milled for 30 seconds at a chamber temperature of 40°C, a fill factor of 0.66 and a rotor speed of 45 rpm. Subsequently, half of the carbon black volume, ZnO and stearic acid were added under milling. After 90 seconds the other half of the carbon black volume and the 6PPD were added. After further 120 secs the ram was lifted and cleaned, and the batch was mixed for another 90 seconds. The total mixing time in the internal mixer was 5 minutes and afterwards the batch was dropped on an open mill for cooling down and additional distributive mixing. The batch temperature did not exceed 160°C in the first mixing step. The batch was allowed to rest overnight.
  • the prepared vulcanizable rubber compositions according to Table 5 were subjected to curing in a cure press at a temperature of 165°C. The applied pressure was 130 bar.
  • the cure kinetics were analyzed with a moving die rheometer Alpha Technologies Rheometer MDR 2000 at 165 °C and then the cure times were defined for the different compounds to assure optimized cure state.
  • the vulcanizable rubber compositions were cured in the cure press for a time, which allowed to reach the maximum torque in the respective measured torque-time curve to ensure full cure.
  • the cure times were between 11 and 15 minutes (C1: 15 min, C2: 12 min, C3: 5 min, C4: 11 min).
  • Respective vulcanizate sheets having a thickness of around 2 mm are provided.
  • the volume resistivity of the carbon blacks was determined in the thus prepared and cured emulsion-styrene-butadiene rubber (ESBR) containing 50 phr carbon black based on DIN EN ISO 3915:2022 using a resistance meter with a high Ohm measurement electrode and a high Ohm shield chamber (Milli-TO3 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany) with the guard ring electrode FE-50 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany) and the shield chamber TOM 300-2 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany)).
  • ESBR emulsion-styrene-butadiene rubber
  • Table 5 The rubber compositions using different carbon blacks as noted in table 6.
  • the rubber composition as mentioned in table 5 can be used to measure the volume resistivity of the respective carbon black.
  • the example reveal that the carbon blacks produced according to the invention can be beneficially used in a rubber composition.
  • the produced carbon blacks have improved tensile strength, tear and abrasion resistance, modulus 300% and electrical conductivity.

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Abstract

The present invention relates to a process for the production of carbon black in an entrained flow reactor by using particulate carbon-containing feedstock and fluid carbon-containing feedstock.

Description

CARBON BLACK FROM PARTICULATE FEEDSTOCK MATERIALS AND FLUID CARBON-CONTAINING FEEDSTOCK
TECHNICAL FIELD
[001] The present invention relates to a process for the production of carbon black in an entrained flow reactor by using particulate carbon-containing feedstock and fluid carbon- containing feedstock.
TECHNICAL BACKGROUND
[002] The production of carbon black entails the cracking or thermal decomposition of a carbon-containing feedstock in a reaction chamber at temperatures such as 800°C and above (e.g. in the temperature range of 1100 °C to 2000 °C). These high temperatures are obtained by the combustion of a mixture comprising oxygen-containing gas and a combustion fuel (i.e. fuel). The carbon black (CB) entrained in the gases (hot gas flow) exiting the reaction chamber are then cooled in a quenching operation and then collected by any suitable means conventionally used in the art.
[003] Carbon blacks have numerous uses such as a reinforcing agent or filler for the rubber and tire industries. Moreover, carbon black has seen increased use in other areas such as coloring agents and reprographic toners for copying machines. The various applications of carbon black necessitate a diverse range of carbon black characteristics such as particle size, structure, yield, surface area, and stain.
[004] The carbon black formation can be separated into different process steps including raising the temperature of the feedstock up to pyrolysis temperature, pyrolysis of the feedstock to unsaturated species such as acetylene and aromatic containing intermediate products, nuclei formation, surface growing, and aggregation.
[005] In the prior art, the feedstock for the production of carbon black in an entrained flow reactor, such as in a furnace reactor, is limited to liquid carbon-containing feedstocks. Liquid carbon-containing feedstocks are for example liquid hydrocarbons, such as cracker oil like oils derived from steam cracker or fluidized catalytic cracker.
[006] Immediately after the injection of liquid carbon-containing feedstocks into a carbon black reactor, the feedstock is evaporated and carbon black is formed. The transformation of particulate carbon-containing feedstocks to gaseous components is considerably slower compared to liquid carbon-containing feedstocks so that it is difficult to achieve a desirable pyrolysis of the particulate carbon-containing feedstocks.
[007] As an alternative approach, the particulate carbon-containing feedstock such as tires can be pyrolyzed in a pyrolysis reactor. The pyrolysis is carried out at low temperatures such as 500 °C and a liquid, a gaseous, and a solid fraction is obtained. The liquid fraction can then be used to produce new or virgin carbon black (nCB) in an entrained flow reactor such as a furnace reactor.
[008] US 2002/0117388 A1 relates to the aforementioned pyrolysis of scrap rubber materials including old tires. The aim of US 2002/0117388 A1 is to recover the components in the scrap rubber materials such as carbon black. After the pyrolysis, carbon black can be recovered from the pyrolysis gas (recovered carbon black (rCB)).
[009] However, the solid yield of the pyrolysis at low temperatures is low and a subsequent manufacturing process is required to obtain carbon black from the liquid fraction of the pyrolysis. Additionally, the coke content and ash content of recovered carbon black after pyrolysis is undesirable.
[010] Accordingly, a new method should be developed for the manufacturing carbon black that allows to utilize particulate carbon-containing feedstocks as well as liquid carbon-containing feedstocks.
[011] Surprisingly, it has been found that particulate carbon-containing feedstock as well as a fluid carbon-containing feedstock can be used in an entrained flow reactor to manufacture carbon black.
SUMMARY OF THE INVENTION
[012] The objective is achieved by a method for producing carbon black in an entrained flow reactor comprising: (a) providing a hot gas flow, (b) providing a particulate carbon- containing feedstock, (c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and (d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
[013] Moreover, carbon black, is provided comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h. Additionally, carbon black is provided, preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m2/g, preferably a STSA surface area of 116 to 145 m2/g, more preferably a STSA surface area of 117 to 140 m2/g, and most preferably a STSA surface area of 120 to 135 m2/g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21.
[014] Moreover, a composition is provided comprising (A) an elastomeric polymer material, and (B) carbon black according to the invention.
[015] Moreover, a rubber article is provided comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than
7.9 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[016] Additionally, particulate carbon-containing feedstock and a fluid carbon-containing feedstock are used for the manufacturing of carbon black in an entrained flow reactor.
BRIEF DESCRIPTION OF THE DRAWINGS
[017] Figure 1 : Section of a furnace reactor
[018] Figure 2: Feeding and mixing device comprising a nozzle
[019] Figure 3: Laval-nozzle for the feeding and mixing device
[020] Figure 4: Deagglomeration conduit for the feeding and mixing device
[021] Figure 5: Feeding and mixing device without a nozzle
[022] Figure 6: The top (a) and the underside (b) of an exemplary vulcanizate sheet specimen coated with conductive silver.
DETAILED DESCRIPTION
[023] It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an oxygen-containing gas” includes mixtures of oxygen-containing gases, reference to “a fuel” includes mixtures of two or more such fuels, and the like.
[024] The diameter always refers to the inner diameter of an object unless otherwise indicated. For example, the diameter of a tubular conduit refers to the inner diameter of the tubular conduit.
[025] The expression “hot gas flow” refers to a carrier gas in the entrained flow reactor, such as a furnace reactor that brings the reaction mixture (comprising the particulate carbon-containing feedstock) to the required temperature for the pyrolysis reaction. For example, the “hot gas flow” is the gas stream after the combustion of fuel in a furnace reactor.
[026] “Carbon black” as referred to herein means a material composed substantially, e.g. to more than 80 wt.%, or more than 90 wt.% or more than 95 wt.%, based on its total weight of carbon that is produced by pyrolysis or radical driven abstraction of not carbon atoms of a carbon-containing feedstock. Different industrial processes are known for the production of carbon blacks such as the furnace process, gas black process, acetylene black process, thermal black process or lamp black process. The production of carbon blacks is per se well known in the art and for example outlined in J.-B. Donnet et al., “Carbon Black:Science and Technology”, 2nd edition, therefore being not described herein in more detail.
[027] The reaction volume of the reactor is the volume of the reactor between the position of the injection of the particulate carbon-containing feedstock and the position of the quench.
[028] The present invention relates to a method for producing carbon black in an entrained flow reactor comprising: (a) providing a hot gas flow, (b) providing a particulate carbon-containing feedstock, (c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and (d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
[029] Without being bound by theory, it is believed that the heating rate of particulate carbon-containing feedstock is lower compared to liquid carbon-containing feedstock so that it is desired that of particulate carbon-containing feedstock can be injected in the hot gas flow of an entrained flow reactor at a suitable temperature of 800 °C or even higher. For instance, the temperature of the hot gas flow can be at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, at least 1600 °C. The desired minimum temperature can be determined by measuring the transmittance of the produced carbon black. If the transmittance is low, the temperature of the hot gas flow can be increased.
[030] The hot gas flow can be obtained by electrical preheating, plasma heating and combustion of a fuel and oxygen-containing gas. The hot gas flow can be provided by (a 1 ) supplying fuel and oxygen-containing gas into a combustion chamber of the reactor, (b2) combusting fuel in the combustion chamber to produce the hot gas flow.
[031] The particulate carbon-containing feedstock can comprise inert compounds, coke, C,H-containing compounds, and/or carbon black, preferably carbon black and C,H- containing compounds. The particulate carbon-containing feedstock are particles and generally agglomerated particles. In contrast, a liquid carbon-containing feedstock means that the feedstock is liquid at 20 °C and 1 atm.
[032] The particulate feedstock can comprise up to 10 wt.-% of an oil (extender oil). For instance, rubber granulates often comprise up to 10 wt.-% of an oil (extender oil). Said oil or extender oil is generally an aliphatic or aromatic oil.
[033] The particulate carbon-containing feedstock is a feedstock that is suitable to produce carbon black, i.e. new carbon black. Thus, the particulate carbon-containing feedstock comprises materials that can be pyrolyzed.
[034] The C,H-containing compound (hydrocarbon compound) can be used to produce the carbon black, i.e. the new carbon black (nCB) or virgin carbon black (vCB). The C, Flcontaining compounds refers to a compounds that each comprise C and H. For example, the C,H containing compounds are hydrocarbon compounds that can comprise heteroatoms such as O or S.
[035] The particulate carbon-containing feedstock can comprise 10 to 100 wt.-% of C, Flcontaining compounds, preferably 20 to 99 wt.-% of C,H-containing compounds, more preferably 30 to 90 wt.-% of C,H-containing compounds, and most preferably 40 to 70 wt.-% of C,H-containing compounds, based on the total weight of the particulate carbon- containing feedstock.
[036] The particulate carbon-containing feedstock can comprise inert compounds, and the inert compounds can comprise metals, metal compounds, silicon, silica. Metals can be zinc, silicon, calcium, aluminium, and/or iron.
[037] The particulate carbon-containing feedstock can comprise 1 to 40 wt.-% inert compounds, preferably 3 to 30 wt.-% inert compounds, more preferably 4 to 20 wt.-% inert compounds, and most preferably 5 to 15 wt.-% inert compounds, based on the total weight of the particulate carbon-containing feedstock.
[038] The particulate carbon-containing feedstock can in addition comprise carbon black, i.e. recovered carbon black. Said carbon black is typically present in tires and thus, can be recovered. The particulate carbon-containing feedstock should comprise 1 to 70 wt.-% of carbon black, preferably 5 to 60 wt.-% of carbon black, more preferably 10 to 50 wt.-% of carbon black, and most preferably 15 to 40 wt.-% of carbon black, based on the total weight of the particulate carbon-containing feedstock. Alternatively, the particulate carbon-containing feedstock is free of recovered carbon black. [039] In this context, recovered carbon black means carbon black that can be recovered in the process. In other words, carbon black that is present in the feedstock and not produced in the inventive process.
[040] The C,H-containing compound are for example rubber, plastics and/or biomassbased materials. The particulate carbon-containing feedstock is preferably provided as granulate (i.e. carbon-containing granulate feedstock). Accordingly, the particulate carbon-containing feedstock may comprise or is rubber granulate, plastic granulate, and/or biomass-based granulate. Accordingly, the particulate carbon-containing feedstock can be particulate rubber feedstock, particulate plastic feedstock, and/or particulate biomass-based feedstock. It is preferred that the particulate carbon containing feedstock comprises rubber granulate, wherein the rubber granulate comprising carbon black.
[041] A biomass-based feedstock can be distinguished from fossil-based feedstock by measuring the C14 content (14C content) in the feedstock (Radiocarbon dating). The relative amount of C14 atoms compared to C12 (C14 to C12 ratio 1 14C/12C ratio) is lower in a fossil-based feedstock in comparison to a biomass-based feedstock. Accordingly, fossil-based feedstock is feedstock that has relative amount of C14 atoms compared to C12 that is lower than the naturally occurring (or bio-based) relative amount of C14 atoms compared to C12.
[042] Preferably the amount of particulate biomass-based feedstock in the particulate carbon-containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 60 to 80 wt.-% based on the total weight of the particulate carbon- containing feedstock.
[043] Preferably the amount of particulate rubber granulate in the particulate carbon- containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-% based on the total weight of the particulate carbon-containing feedstock.
[044] Preferably the amount of particulate plastic feedstock in the particulate carbon- containing feedstock is 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-% based on the total weight of the particulate carbon-containing feedstock.
[045] The particulate biomass-based carbon black feedstock can comprise a plantbased feedstock, preferably a non-edible plant-based feedstock and/or a waste plantbased feedstock. As used herein, the term “non-edible” refers to materials that are unsuitable for human consumption. The term “waste” refers to materials that are discarded or disposed of as unsuitable or no longer useful for the intended purpose, e.g., after use.
[046] The particulate biomass-based carbon black feedstock can comprise wood, grass, cellulose, hemicellulose, lignin and/or natural rubber.
[047] As used herein, the term “wood” refers to porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. Suitable examples of wood include, but are not limited to, pine, spruce, larch, juniper, ash, hornbeam, birch, alder, beech, oak, pines, chestnut, mulberry or mixtures thereof. Suitable examples of grass include, but are not limited to, cereal grass, such as maize, wheat, rice, barley or millet; bamboos and grass of natural grassland and species cultivated in lawns and pasture. Suitable examples of lignin may include, but are not limited to, lignin removed by Kraft process and lignosulfonates.
[048] The rubber granulate can comprise natural rubber and/or synthetic rubber. The particulate carbon-containing feedstock can comprise rubber granulate comprising carbon black. Natural rubber may be derived from rubber trees (Helvea brasiliensis), guayule, and dandelion. The rubber granulate or the particulate carbon-containing feedstock can be derived from tires, cable sheaths, tubes, conveyor belts, shoe soles, hoses or mixtures thereof.
[049] Synthetic rubber may include styrene-butadiene rubber such as emulsion-styrene- butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinylacetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber or a mixture or combinations of any of the foregoing.
[050] The plastic granulate or particulate plastic feedstock can be any plastic know in the art. For instance, acrylics such as poly(acrylic acid), or poly(methyl methacrylate), polyesters such as polyethylene terephthalate, or polyethylene glycol, polyurethanes such as derived from toluene diisocyanate (TDI) or methylene diphenyl diisocyanate, polyolefins such as polypropene, or polyethylene, or polystyrene. Generally, thermoplastics and thermosets can be used.
[051] The plastic granulate are preferably derived from waste materials of households. For instance, plastic bags, plastic containers, plastic packaging etc. [052] The particulate carbon-containing feedstock is provided as a particulate. This can be done by milling to the desired particle or granulate size. For instance, tires can be milled to obtain a particulate rubber granulate as the feedstock.
[053] It is desired that at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, most preferably at least 80 wt.-%, of the particulate carbon-containing feedstock has a particle size of 125 pm to 2 mm, preferably 125 pm to 1 mm, more preferably 250 pm to 1 mm, and most preferably 500 pm to 1000 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[054] It is desired that at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, most preferably at least 80 wt.-%, of the particulate carbon-containing feedstock has a particle size of more than 250 pm to 2 mm, preferably 300 pm to 1 mm, more preferably 300 pm to 1 mm, and most preferably 400 pm to 1000 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[055] It is desired that at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[056] It is desired that at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 500 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[057] It is desired that at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 1 mm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[058] It is desired that at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[059] It is desired that less than 1 wt.-%, preferably at least 0.5 wt.-%, more preferably less than 0.1 wt.-%, most preferably less than 0.01 wt.-%, of the particulate carbon- containing feedstock has a particle size of more than 2 mm, preferably more than 1 mm, more preferably more than 500 pm, and most preferably more than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[060] It is particularly preferred that the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[061] The particle size of the feedstock can be controlled by classify the particulate carbon-containing feedstock before the particulate carbon-containing feedstock is injected into the reactor. Accordingly, it is preferred that the particulate carbon-containing feedstock is classified before injecting into the reactor or before injecting into the mixing and feeding unit.
[062] The classification can be done by any means known in the art such as sieving or other classifications. Classification can be done using vibratory screeners, rotary screeners, cyclones, elutriation classifiers, air jet sieve and/or dynamic air classifiers. Any of the aforementioned combinations can be used. Said classification can be used in order to obtain a maximum or minimum desired particle size as described in the specification.
[063] The particle size of the feedstock can be controlled by sieving the particulate carbon-containing feedstock before the particulate carbon-containing feedstock is injected into the reactor. The sieves sizes as described in ASTM D 1511-12 (2017) can be used. For instance, a sieve having openings of 2000 pm, 1000 pm, 500 pm, 250 pm, or 125 pm, preferably 500 pm, 250 pm, or 125 pm, can be used. Moreover, the sieve can have openings with a size that restrains particles with a size of more than 2000 pm, more than 1000 pm, more than 500 pm, more than 250 pm, or more than 125 pm, preferably more than 500 pm, more than 250 pm, or more than 125 pm.
[064] No more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon- containing feedstock should have a particle size of over 4 mm, preferably over 2 mm, more preferably over 1 mm, and most preferably over 0.5 mm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[065] No more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon- containing feedstock should have a particle size of less than 150 pm, preferably less than 125 pm, more preferably less than 110 pm, and most preferably less than 100 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017). [066] None of the particles of the particulate carbon-containing feedstock should have a particle size of 1 mm or more, preferably of 500 pm or more, more preferably of 250 pm or more, and most preferably of 125 pm or more, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[067] The particle size distribution of the particulate carbon-containing feedstock can be measured according to ASTM D 1511-12 (2017) and (a) Sieve No. 10 retains 1 to 0 to 10 wt.-%, preferably 1 to 8 wt.-%, more preferably 1 to 5 wt.-%, and most preferably 1 to 3 wt.-% of the particulate carbon-containing feedstock, and/or (b) Sieve No. 18 retains 1 to 25 wt.-%, preferably 2 to 20 wt.-%, more preferably 4 to 15 wt.-%, and most preferably 5 to 12 wt.-% of the particulate carbon-containing feedstock, and/or (c) Sieve No. 35 retains 10 to 80 wt.-%, preferably 15 to 70 wt.-%, more preferably 20 to 60 wt.-%, and most preferably 25 to 55 wt.-% of the particulate carbon-containing feedstock, and/or (d) Sieve No. 60 retains 5 to 70 wt.-%, preferably 10 to 60 wt.-%, more preferably 15 to 50 wt.-%, and most preferably 20 to 45 wt.-% of the particulate carbon-containing feedstock, and/or (e) Sieve No. 120 retains 1 to 80 wt.-%, preferably 7 to 70 wt.-%, more preferably 5 to 60 wt.-%, and most preferably 7 to 50 wt.-% of the particulate carbon-containing feedstock, and/or (f) Bottom receive pan comprises less than 4 wt.-%, preferably less than 3 wt.-%, more preferably 0 to 2 wt.-%, and most preferably 0.01 to 1 wt.-% of the particulate carbon-containing feedstock. It is desirable to choose the desired range for each sieve independently.
[068] The 50 wt.-% cumulative particle size of the particulate carbon-containing feedstock should be from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the 50 wt.-% cumulative particle size is measured according to ASTM D 1511-12 (2017). The 50 wt.-% cumulative particle size can be interpolated using standard techniques know in the art. It is particularly, preferred that the Rosin-Rammler-Sperling-Bennett distribution (RRSB distribution) is used to interpolate the 50 wt.-% cumulative particle size.
[069] The weight average particle size Dw50 of the particulate carbon-containing feedstock can be from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the weight average particle size Dw50 is measured according to ASTM D 1511-12 (2017).
[070] The particle size distribution Dw10 of the particulate carbon-containing feedstock can be from 100 pm to 250 pm preferably 110 pm to 220 pm, more preferably 120 pm to 210 pm, and most preferably 130 pm to 200 pm, wherein the particle size distribution Dw10 is measured according to ASTM D 1511-12 (2017). [071] The particle size distribution of the particulate carbon-containing feedstock Dw90 can be from 400 pm to 4 mm preferably 500 pm to 3 mm, more preferably 600 pm to 2 mm, and most preferably 700 pm to 500 pm, wherein the particle size distribution Dw90 is measured according to ASTM D 1511-12 (2017).
[072] The span of the particle size distributions of the particulate carbon-containing feedstock (Dw90-Dw10) I Dw50 can be 0.2 to 1.8, preferably 0.3 to 1.3, more preferably 0.4 to 1.1, most preferably 0.4 to 1.0, wherein the particle size distributions Dw10, Dw50, and Dw90 are measured according to ASTM D 1511-12 (2017).
[073] The Dw50, Dw10, and Dw90 can be interpolated using standard techniques know in the art. It is particularly, preferred that the Rosin-Rammler-Sperling-Bennett distribution (RRSB distribution) is used to interpolate the Dw50, Dw10, and Dw90.
[074] The particle or granulate size has an influence of the heating rate of the feedstock in the reactor. Smaller granulates or particles have a higher specific surface area so that the heating rate is higher. A fast-heating rate is beneficial so that the particulate feedstock can evaporate and then pyrolyzed. It is believed that the pyrolysis is significantly faster than the evaporation of the particulate feedstock. The heating rate can also be increased by a higher temperature of the hot gas flow.
[075] The carbon black produced according to the present invention (such as including the rCB) and/or the particulate carbon-containing feedstock can have a pMC (percent of modern carbon) of 1% or more, determined according to ASTM D6866-20 Methode B (AMS), such as 2 % or more, or 5 % or more, or 7 % or more, or 10 % or more, or 12 % or more, or 15 % or more, or 17 % or more, or 20 % or more, or 22 % or more, or 25 % or more, or 27 % or more, or 30 % or more, or 32 % or more, or 35 % or more, or 37 % or more, or 40 % or more, or 42 % or more, or 45 % or more, or 47 % or more, or 50 % or more, or 52 % or more, or 55 % or more, or 57 % or more, or 60 % or more, or 62 % or more, 65 % or more, or 67 % or more, or 70 % or more, or 72 % or more, or 75 % or more, or 77 % or more, or 80 % or more, or 82 % or more, or 85 % or more, or 87 % or more, or 90 % or more, or 92 % or more, or 95 % or more, or 97 % or more, or 99 % or more. For each sample, a ratio of 14C/13C is calculated and compared to measurements made on Oxalic Acid II standard (NIST-4990C). The measured values (pMC) are corrected by d13C measured using an isotope ratio mass spectrometer (I RMS). The carbon black of the present invention can have a pMC (percent of modern carbon) of 5% or more, determined according to ASTM D6866-20 Methode B (AMS), preferably of 10 % or more, particularly preferably of 15 % or more, more preferably of 50 % or more, even more preferably of 85 % or more, most preferably of 90 % or more. The carbon black of the present invention can have a pMC (percent of modern carbon) of 100%, determined according to ASTM D6866-20 Methode B (AMS).
[076] The obtained carbon black (i.e. produced according to the present invention) typically comprises recovered carbon black and new carbon black. Recovered carbon black is generally obtained if the particulate carbon-containing feedstock comprises carbon black. The new carbon black is obtained by pyrolysis, i.e. the method according to the invention.
[077] The mass flow of the particulate carbon-containing feedstock should be adjusted so that particulate carbon-containing feedstock can be uniformly heated. The particulate carbon-containing feedstock should be injected into the reactor with a mass flow of 2 to 50 kg/h per 130 L of the reaction volume of the reactor, preferably 5 to 40 kg/h per 130 L of the reaction volume of the reactor, more preferably 8 to 30 kg/h per 130 L of the reaction volume of the reactor, and most preferably 10 to 20 kg/h per 130 L of the reaction volume of the reactor.
[078] The fluid carbon-containing feedstock can comprise or can be a liquid carbon- containing feedstock. It is particularly preferred that the fluid carbon-containing feedstock is a liquid carbon-containing feedstock.
[079] The fluid carbon-containing feedstock can comprise aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar distillates, residual oils which are produced during the catalytic cracking of petroleum fractions, residual oils which are produced during olefin production through cracking of naphtha or gas oil, natural gas, sustainable carbon black feedstock, renewable carbon black feedstock and/or a bio-based feedstock, pyrolysis oil, or a mixture or combination of any of the foregoing.
[080] The fluid carbon-containing feedstock can comprise or can be coal tar distillates.
[081] Preferably the aliphatic feedstock comprises aliphatic materials of 20 to 100 wt.-%, such as 40 to 100 wt.-%, 50 to 99 wt.-%, 60 to 95 wt.-%, or 80 to 90 wt.-%, based on the total weight of the fluid carbon-containing feedstock. Sustainable feedstock, renewable carbon black feedstock and/or a bio-based feedstock often comprise a high content of aliphatic feedstock as mentioned above.
[082] Sustainable carbon black feedstocks refer to feedstocks that have generally a high content of aliphatic C-C bonding and preferably a low content of aromatic C-C bonding. Sustainable carbon black feedstocks can include aliphatic oils, renewable carbon black feedstock, and biomass-based feedstocks. Biomass-based feedstocks, sustainable carbon black and/or renewable carbon black feedstock can be distinguished from fossil-based feedstock by measuring the C14 content in the feedstock (Radiocarbon dating). The relative amount of C14 atoms compared to C12 (C14 to C12 ratio) is lower in fossil-based feedstock in comparison to biomass-based feedstocks.
[083] The renewable carbon black feedstock can comprise a plant-based feedstock, preferably a non-edible plant-based feedstock and/or a waste plant-based feedstock. As used herein, the term “non-edible” refers to materials that are suitable for human consumption. The term “waste” refers to materials that are discarded or disposed of as unsuitable or no longer useful for the intended purpose, e.g., after use. With respect to edible oils, i.e. , cooking oils, used cooking oils are considered waste. The renewable carbon black feedstock preferably may comprise plant-based oils and more preferably non-edible plant-based oils and/or waste plant-based oils.
[084] The renewable carbon black feedstock according to the present invention may comprise black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, cooking oil, distillation residues from biodiesel plants or a mixture or combination of any of the foregoing.
[085] As used herein, the term “cooking oil” refers to edible oils used in food preparation, such as in frying, baking and other types of cooking. According to the present invention, cooking oils may comprise rice bran oil, rapeseed oil, linseed oil, palm oil, coconut oil, canola oil, soybean oil, sunflower oil, cotton seed oil, pine seed oil, olive oil, corn oil, grape seed oil, safflower oil, acai palm oil, jambu oil, sesame oil, chia seed oil, hemp oil, perilla oil, peanut oil, stillingia oil, cashew nut oil, brazil nut oil, macadamia nut oil, walnut oil, almond oil, hazel nut oil, beechnut oil, candlenut oil, chestnut oil or a mixture or combination of any of the foregoing. The cooking oil of the present invention may be used cooking oil. As used herein, the term “used cooking oil” refers to oils originating from commercial or industrial food processing operations, such as restaurants, that have been used for food preparation, such as cooking or frying.
[086] The fluid carbon-containing feedstock can comprise or can be liquid components that may be selected from, but are not limited to, black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, cooking oil, distillation residues from biodiesel plants or a mixture or combination of any of the foregoing. Some oils may be solid at room temperature, e.g., at temperatures of 25 °C, but liquid at elevated temperatures, such as temperatures above 25 °C, e.g., temperatures in a range of 25 to 100 °C. As used herein, the term “black liquor” refers to a by-product from the Kraft process which comes from the sulfate and soda processes of making cellulosic pulp.
[087] It is intended that liquid with respect to the fluid carbon-containing feedstock means that the respective component is liquid during the injection in the reactor.
[088] Non-edible plant-based feedstock may comprise, but is not limited to, black liquor, tall oil, rubber seed oil, tobacco seed oil, castor oil, pongamia oil, crambe oil, neem oil, apricot kernel oil, rice bran oil, cashew nut shell oil, cyperus esculentus oil, distillation residues from biodiesel plants, or a mixture or combination of any of the foregoing.
[089] The fluid carbon-containing feedstock may comprise tall oil. The terms “tall oil” and “crude tall oil” may be used interchangeably throughout this description unless otherwise stated. Tall oil is derived from the chemical pulping of woods. Typically, tall oil is a mixture comprising resin acids, fatty acids, sterols, alcohols and further alkyl hydrocarbon derivatives. Tall oil may be a natural unrefined product or a refined product. Refined tall oil may include tall oil fatty acid, tall oil fatty rosin, distilled tall oil and tall oil pitch. Tall oil can be distilled to obtain tall oil resin acids containing more than 10 wt.-% of resin acid content. Tall oil may also be refined to tall oil fatty acids, where the resin acid content is typically less than 10 wt.-%. Suitable examples of tall oil may include, but are not limited to, SYLFAT™ products, SYLVATAL™ products, SYLVABLEND™ products and SYLVAROS™ products, all available from Kraton Corporation (USA), as well as tall oil products, such as crude tall oils and Tall Oil 1, available from UCY Energy (Germany).
[090] The fluid carbon-containing feedstock may in particular comprise tall oil pitch. Tall oil pitch is obtained as a nonvolatile residue from refining by distillation of tall oil and may be mixed with fore-runs of tall oil refining. The yield of tall oil pitch in the refining process may range from about 15 to 50 wt.-%, depending for example on the quality and composition of the tall oil. Tall oil pitch typically comprises neutral substances, free acids including resin acids and fatty acids, fatty acid esters, bound and free sterols, and polymeric compounds. Additionally, metals, metal cations, inorganic and organic compounds including metal resinates and salts of fatty acids can be found in tall oil pitch. Said metal cations typically originate from wood and fertilizers. Suitable examples of tall oil pitch include, but are not limited to, SYLVABLEND™ products, such as SYLVABLEND FA7002, SYLVABLEND PF 40, SYLVABLEND PF 60 and SYLVABLEND SF75 all available from Kraton Corporation (USA) as well as Tall Oil 1, UCY-TOF40 and UCY- TOF60 all available from UCY Energy (Germany).
[091] According to the present invention, the fluid carbon-containing feedstock can be a mixture of renewable carbon black feedstock and conventional carbon black feedstock. Conventional carbon black feedstock may be aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar distillates, residual oils which are produced during the catalytic cracking of petroleum fractions, residual oils which are produced during olefin production through cracking of naphtha or gas oil, natural gas or a mixture or combination of any of the foregoing. The fluid carbon-containing feedstock can be a liquid as well as a gas. It is preferred that the fluid carbon-containing feedstock is a liquid. For instance, gaseous carbon black feedstock can be an aliphatic feedstock, such as methane, ethane, acetylene, ethylene, ethane, propyne, propane propene, butadiene, butane, pentane, or a mixture thereof.
[092] The fluid carbon-containing feedstock of the present invention may comprise the renewable carbon black feedstock in an amount greater than or equal to 10 wt.% based on the total weight of the carbon black feedstock. For example, the fluid carbon- containing feedstock can comprise the renewable carbon black feedstock in an amount greater than or equal to 15 wt.%, or in an amount greater than or equal to 20 wt.%, or in an amount greater than or equal to 25 wt.%, or in an amount greater than or equal to 30 wt.%, or in an amount greater than or equal to 35 wt.%, or in an amount greater than or equal to 40 wt.%, or in an amount greater than or equal to 45 wt.%, or in an amount greater than or equal to 50 wt.%, or in an amount greater than or equal to 55 wt.%, or in an amount greater than or equal to 60 wt.%, or in an amount greater than or equal to 65 wt.%, or in an amount greater than or equal to 70 wt.%, or in an amount greater than or equal to 75 wt.%, or in an amount greater than or equal to 80 wt.%, or in an amount greater than or equal to 85 wt.%, or in an amount greater than or equal to 90 wt.%, or in an amount greater than or equal to 95 wt.%, the weight percentage being based on the total weight of the fluid carbon-containing feedstock. The fluid carbon-containing feedstock may comprise the renewable carbon black feedstock in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 99 wt.-%, the weight percent being based on the total weight of the carbon black feedstock. The fluid carbon-containing feedstock can consist of the renewable carbon black feedstock.
[093] The fluid carbon-containing feedstock may comprise tall oil pitch in an amount of greater than or equal to 5 wt.-%, such as greater than or equal to 10 wt.-%, or greater than or equal to 15 wt.-%, or greater than or equal to 20 wt.-%, or greater than or equal to 25 wt.-%, or greater than or equal to 30 wt.-%, or greater than or equal to 35 wt.-%, greater than or equal to 40 wt.-%, or greater than or equal to 45 wt.-%, or greater than or equal to 50 wt.-%, or greater than or equal to 55 wt.-%, or greater than or equal to 60 wt- %, or greater than or equal to 65 wt.-%, or greater than or equal to 70 wt.-%, or greater than or equal to 75 wt.-%, or greater than or equal to 80 wt.-%, or greater than or equal to 85 wt.-%, or greater than or equal to 90 wt.-%, or greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the fluid carbon-containing feedstock. The fluid carbon-containing feedstock may comprise tall oil pitch in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the fluid carbon-containing feedstock. The fluid carbon-containing feedstock can consist of tall oil pitch.
[094] The renewable carbon black feedstock may comprise tall oil pitch in an amount of greater than or equal to 5 wt.-%, such as greater than or equal to 10 wt.-%, or greater than or equal to 15 wt.-%, or greater than or equal to 20 wt.-%, or greater than or equal to 25 wt.-%, or greater than or equal to 30 wt.-%, or greater than or equal to 35 wt.-%, or greater than or equal to 40 wt.-%, or greater than or equal to 45 wt.-%, or greater than or equal to 50 wt.-%, or greater than or equal to 55 wt.-%, or greater than or equal to 60 wt- %, or greater than or equal to 65 wt.-%, or greater than or equal to 70 wt.-%, or greater than or equal to 75 wt.-%, or greater than or equal to 80 wt.-%, or greater than or equal to 85 wt.-%, or greater than or equal to 90 wt.-%, or greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the renewable carbon black feedstock. The renewable carbon black feedstock may comprise tall oil pitch in an amount greater than or equal to 10 wt.-%, preferably greater than or equal to 15 wt.-%, particularly preferably greater than or equal to 25 wt.-%, more preferably greater than or equal to 50 wt.-%, even more preferably greater than or equal to 85 wt.-%, most preferably greater than or equal to 95 wt.-%, the weight percent being based on the total weight of the renewable carbon black feedstock. The renewable carbon black feedstock may consist of tall oil pitch.
[095] The pyrolysis oil is usually obtained after pyrolysis of end-of-life products, such as scrap tires (waste tires) or rubber. Pyrolysis is usually carried out at low temperatures and produces a liquid, gaseous and solid fractions. The liquid fraction can then be used to produce new or virgin carbon black in an entrained flow reactor such as a furnace reactor. This means that the liquid fraction after the pyrolysis of rubber materials can be used as pyrolysis oil. In other words, pyrolysis oil is preferably the liquid fraction of the pyrolysis of waste tires. [096] The fluid carbon-containing feedstock can comprise or can be a liquid carbon- containing feedstock. It is preferred that the fluid carbon-containing feedstock is a liquid carbon-containing feedstock.
[097] The mass ratio of particulate carbon-containing feedstock to fluid carbon- containing feedstock can be 0.5:1 to 1 :0.05, preferably 1 :1 to 1:0.1, more preferably 1.1:1 to 1:0.1, and most preferably 1.2:1 to 1 :0.2.
[098] The mass flow rate of the fluid carbon-containing feedstock can be 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h.
[099] The mass flow rate of the particulate carbon-containing feedstock can be 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1 ,000 kg/h, most preferably 30 to 500 kg/h.
[100] It is possible to subject steam into the hot gas flow. Steam can selectively reduce the coke content with respect to the carbon black content of the carbon black-containing feedstock (gasification). For the gasification, H2O reacts with carbon of the carbon blackcontaining feedstock to CO and H2. It has been surprisingly found that the gasification can be used to selectively remove coke that is present in carbon black. Steam can be subjected into the hot gas flow, preferably at a mass flow of 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h.
[101] It is desired that the entrained flow reactor is a furnace reactor and the particulate carbon-containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means.
[102] It is desired that the entrained flow reactor is a furnace reactor and the fluid carbon-containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means.
[103] It is particularly desired that the distance between the injection of the particulate carbon-containing feedstock and the fluid carbon-containing feedstock is 15 to 350 mm, and/or 850 mm to 5 m.
[104] It is desired that the particulate carbon-containing feedstock is injected downstream of the injection of the fluid carbon-containing feedstock.
[105] It is desired that the particulate carbon-containing feedstock is injected upstream of the injection of the fluid carbon-containing feedstock.
[106] It is desired that the particulate carbon-containing feedstock is injected at the same position of the injection of the fluid carbon-containing feedstock. [107] The fuel can comprise a gaseous or liquid hydrocarbons, preferably natural gas, a fuel oil or H2.
[108] Hydrogen can be used as carrier gas and/or fuel for producing carbon black. It is preferred that the hydrogen is used as carrier gas and fuel for producing carbon black. Hydrogen will be used as a carrier gas if the hydrogen is present in the combustion mixture in molar excess with respect to oxygen. Thus, hydrogen should be present in the hot combustion gases and the hot reaction mixture.
[109] The hot gas flow should have a temperature of 900 to 3500 °C, preferably 950 to 3000 °C, more preferably 1000 to 2000 °C, and most preferably 1200 to 1900 °C.
[110] The hot gas flow can be obtained by electrical preheating, plasma and combustion of a fuel and oxygen containing gas. The combustion of a fuel and oxygen containing gas is preferably done in a furnace reactor. However, other means to provide the desired temperature of the hot gas flow are possible as mentioned above.
[111] The entrained flow reactor can be a furnace reactor. The furnace reactor can have a flow passage along a central longitudinal axis of the reactor. The reactor generally comprises in the following order from upstream to downstream (flow direction) a combustion chamber, a choke, and a tunnel comprising quenching means. These components define a flow passage along the central longitudinal axis of the reactor for the hot gas flow, such as the hot combustion gases. Thus, the components should be in fluid connection, particularly along a central longitudinal axis of the reactor.
[112] A tubular conduit can be connected to the combustion chamber for supplying oxygen-containing gas that is necessary for the combustion of the fuel (or combustion fuel). The tubular conduit can be also arranged along the central longitudinal axis of the reactor so that the supplement of the oxygen-containing gas occurs along the above- mentioned flow passage. Furthermore, the reactor can comprise fuel injection means for injecting the fuel into the combustion chamber.
[113] Generally, a fuel lance is used to supply the fuel into the combustion chamber. The combustion chamber can be connected to the tubular conduit in the downstream to upstream direction so that the oxygen-containing gas can be supplied to the combustion chamber. The combustion chamber is arranged along the central longitudinal axis of the reactor.
[114] The combustion chamber is preferably formed of an internal refractory lining covered by a gas tight e.g. metallic covering. The material forming the refractory, and outer lining can be those found conventionally in the art such as the castable refractory Kaocrete® 32-cm which is 70% alumina (AI2O3) and has a melting point of about 1870 °C. Additionally, a brick refractory can be relied upon such as RUBY SR (sold by Harrison- Walker Refractories, Pittsburg, PA.) brick refractory which is 84.5% alumina along with 9.8% chromic oxide (C^Ch) and has a melting point of about 2050 °C. The shell or lining is preferably formed of carbon steel except for any piping in contact with hot process air. In those areas, the piping is formed of "316 Stainless Steel".
[115] The combustion chamber is preferably dimensioned as a cylinder. A constricting section (choke) can be provided downstream of the combustion chamber. The constriction section has a tapering passageway and converges in an upstream to downstream direction. Preferably, these constriction sections are in the form of a frustoconical passageway. The combustion chamber can also have a tapered in the downstream to upstream direction. Accordingly, the combustion chamber can comprise a zone that is tapered towards the reaction chamber and/or towards the tubular conduit.
[116] Typically, the oxygen-containing gas is preheated to a temperature between 200 to 1600 °C, preferably 350 to 1400 °C, more preferably 500 to 1200 °C, and most preferably 450 to 950 °C.
[117] Typically, the fuel is preheated to a temperature between 50 to 750 °C, preferably 100 to 700 °C, more preferably 300 to 700 °C, and most preferably 450 to 650 °C.
[118] The preheating of the oxygen-containing gas and fuel can be done electrically or using a heat exchanger.
[119] Water has an influence of the surface properties of the produced carbon black. Accordingly, it is possible that the amount of oxygen-containing gas, such as O2, in the combustion mixture is used to control the amount of water in the hot combustion mixture and/or hot reaction mixture and thus, preferably control the surface properties of the produced carbon black.
[120] The tunnel is connected with the combustion chamber so that the hot combustion gases obtained in the combustion chamber can flow into the tunnel. The tunnel can be arranged along the central longitudinal axis of the reactor. The diameter of the reaction chamber can be higher than the diameter of the constriction section of the combustion chamber so that the hot combustion gas is able to expand. The expansion section is preferably dimensioned as a cylinder and in communication with the combustion chamber, preferably in the communication with the constriction section (choke) of the combustion chamber. [121] The particulate carbon-containing feedstock can be injected in the combustion chamber, in the choke, and/or in the tunnel of the furnace reactor. The particulate carbon- containing feedstock is typically injected in the choke (constriction section).
[122] If the particulate carbon-containing feedstock is injected for example in the combustion chamber, the particulate carbon-containing feedstock or the carrier gas comprising said feedstock should have a desirable pressure. This means that the pressure of the particulate carbon-containing feedstock or the carrier gas comprising said feedstock should be higher than the pressure in the combustion chamber. Accordingly, a suitable feeding and mixing device should be used that is configured to operate in pressurized conditions.
[123] The particulate carbon-containing feedstock should be injected via multiply inlets, preferably radial and perpendicular to the central longitudinal axis of the reactor.
[124] The concentration of O2 in the hot gas flow should be less than 5 vol.-%, preferably less than 4 vol.-%, more preferably 0.01 to 3 vol.-%, and most preferably 0.1 to 2 vol.-%.
[125] The obtained carbon black generally comprises recovered carbon black and new carbon black.
[126] The particulate carbon-containing feedstock may be injected to the reactor via means to inject the feedstock. The means to inject the feedstock can comprise a plurality of injection nozzles or lances that are preferably arranged circumferentially with respect to the central longitudinal axis. The circumferential arrangement further improves the uniform characteristics of the carbon black since the feedstock for the carbon black can be homogenously mixed with the hot gas flow. The particulate carbon-containing feedstock can be introduced through a plurality of means to inject the feedstock.
[127] For instance, an axially extending feedstock lance and a radially extending feedstock injectors with nozzles capable of producing a variety of cone shaped sprays (e.g., 15, 30, 45 and 60 degrees cone spray angles) can be implemented.
[128] For producing the desired carbon black characteristics, radially extending feedstock injectors can be provided with shut off valves such that feedstock is only introduced through certain of the feedstock injectors or the flow rate is varied for the feedstock flowing in the injectors.
[129] The means to inject the feedstock is preferably connected to feeding and mixing device. It is desired that one feeding and mixing device supplies multiply feedstock inlets. However, it is also possible that more than one feeding and mixing device is used. [130] The tunnel can further comprise means for injecting a quenching medium into the flow passage along the central longitudinal axis of the reactor located subsequent with respect to the flow direction to inject a feedstock for the carbon black. Alternatively, the quenching means can be a quench boiler or heat exchanger.
[131] The tunnel can comprise means for injecting a quenching medium into the flow passage along the central longitudinal axis of the reactor. The means for injecting a quenching medium are located subsequent with respect to the flow direction to the means to inject a feedstock for the carbon black. The quenching medium is generally H2O.
[132] The distance between the feedstock injection means and the means for injecting a quenching medium (the first means for injection a quenching medium) can be between 150 to 80,000 mm, preferably 900 to 50,000 mm, more preferably 1 ,500 to 30,000 mm, and most preferably 2,500 to 20,000 mm.
[133] The means for injecting a quenching medium can extend into the tunnel. For instance, a cooling fluid conduit or a plurality of radial cooling fluid conduits can be used. The quenching medium, such as a cooling fluid (e.g. water), can be sprayed within the tunnel to stop the carbon black reaction at the appropriate time and location.
[134] The reactor can further comprise a tubular conduit for supplying oxygencontaining gas to the combustion chamber. The oxygen-containing gas (O2 containing gas or O2 containing gas mixture) can be air, oxygen-enriched air, other oxygen containing gases and/or pure oxygen. Accordingly, the tubular conduit can be in connection with the combustion chamber so that the oxygen-containing gas is able to flow through the tubular conduit in the combustion chamber. The tubular conduit can be arranged along the central longitudinal axis of the reactor. It is desirable that the central longitudinal axis of the tubular conduit is coaxial to the central longitudinal axis of the reactor. Thus, the tubular conduit can be arranged coaxial along the central longitudinal axis of the reactor. The wt.-% of oxygen that is present in the oxygen-containing gas should be 20 to 100 wt.-%, preferably 50 to 99 wt.-%, more preferably 60 to 95 wt.-% and most preferably 70 to 90 wt.-%, wherein the wt.-% is based on the total weight of the oxygen-containing gas.
[135] The tubular conduit can have a cylindrical shape that extents along the central longitudinal axis of the reactor without curvatures.
[136] The inner diameter of the tubular conduit for supplying oxygen-containing gas can be from 5 cm to 3 m, such as 10 cm to 3 m, 20 cm to 3 m, 9 cm to 2.5 m, 13 cm to 1.5 m, 0.1 m to 2 m, 20 cm to 1 m, 30 cm to 1.5 m, 15 cm to 60 cm, or 15 cm to 90 cm. [137] The fuel injection means for introducing any suitable combustion fuel (e.g., natural gas, fuel oil or other gaseous or liquid hydrocarbons, preferably natural gas or a fuel oil, or H2) can be configured in different ways. For example, the injection means can be arranged at the end of the tubular conduit, where the tubular conduit is connected to the combustion chamber. For instance, the injection means are tubular injection pipes arranged circumferentially with respect to the central longitudinal axis of the tubular conduit so that the injection angle of the fuel is substantially orthogonal to the flow direction of the oxygen-containing gas.
[138] However, it is also possible to provide multiple fuel injection means in addition to the fuel lance. For instance, at the end of the tubular conduit additional fuel injection means are arranged rotationally symmetric with respect to the central longitudinal axis of the tubular conduit.
[139] The oxygen-containing gas is generally supplied in an amount yielding an excess of oxygen with respect to the amount of oxygen for a complete combustion of the fuel, and/or wherein the oxygen-containing gas is supplied in an amount that the k-value is in a range of 0.01 to 10, preferably 0.1 to 5, more preferably 0.5 to 2, and most preferably 0.7 to 1. Where the k value is defined by the ratio of stoichiometric O2 amount that is necessary for the complete stoichiometric combustion of the fuel to the supplied O2 amount.
[140] Fuel and oxygen-containing gas flow rates can be adjusted to give high temperatures and normally fall close to stoichiometric ratios. Ratios must be adjusted to prevent melting the refractory. The range of oxygen-containing flow is quite broad, going, for instance, from a low of approximately 1000 Nm3/h to a high of approximately 100 kNm3/h, such as 1000 Nm3/h to 100 kNm3/h, 1000 Nm3/h to 10 kNm3/h, 2000 Nm3/h to 3000 Nm3/h, or 1000 Nm3/h to 2000 Nm3/h. The invention, however, is not restricted to those dimensions; for larger reactors higher air flows are needed and for smaller reactors lower air flows are needed.
[141] The desired temperature of the hot gas flow can also be achieved by plasma heating the gas flow. The gas flow can be preheating as mentioned above.
[142] A plasma torch can provide the plasma for the aforementioned heating. A plasma torch design is described in WO 1993/012633 A1. However, any means known in the art to produce a plasma can be used. The plasma can be formed by means of a plasma carrier gas which is heated by an electric arc which burns between electrodes. In a plasma zone of high temperatures are reached, from 2500°C to 20,000°C, and it is in this zone that the plasma treatment can be achieved. The plasma carrier gas can be oxygen or hydrogen. Hydrogen as plasma carrier gas is particularly preferred.
[143] A microwave plasma can also provide the plasma for the aforementioned treatment. For instance, a microwave generator can be used that provide microwave radiation inside the reaction chamber. Microwave radiation having 1 to 300 GHz can be used. Alternative, a plasma can be generated using a radio frequency power source (RF generator).
[144] The residence time between the time of the injection of the particulate carbon- containing feedstock in the reactor and the time of the quench of product mixture should be from 150 ms to 4 sec, preferably 200 ms to 3 sec, more preferably 250 ms to 2 sec, and most preferably 250 ms to 1 sec. The residence time of the particulate carbon- containing feedstock means the time in that the particulate carbon-containing feedstock is evaporated and pyrolyzed. The quench of the product mixture stops the pyrolysis of the particulate carbon-containing feedstock. The heating rate of particulate carbon-containing feedstock is lower compared to liquid feedstocks so that the evaporation and pyrolysis of the particulate carbon-containing feedstock generally requires more time.
[145] In general, the residence time is selected in such a way that the C,H-containing material in the particulate carbon-containing feedstock is completely pyrolyzed.
[146] The formation of carbon black is generally terminated by the quench of the hot gas flow. Thus, the method may further comprise (e) quenching the hot gas flow after the injection according to step (d).
[147] The transmittance can be an indicator whether the residence time is sufficient for the feedstock for a complete pyrolysis of e.g. the C,H-containing material in the feedstock.
[148] It is particularly preferred that the particulate carbon-containing feedstock is deagglomerated before the injection into the reactor. It is believed that the evaporation time is decreased by using deagglomerated particles.
[149] Accordingly, it is desired that step (b) further comprises deagglomerating the particulate carbon containing feedstock and in step (d), the deagglomerated particulate carbon-containing feedstock is injected in the hot gas flow to form carbon black.
[150] The deagglomeration can be achieved by (i) accelerating the particulate carbon- containing feedstock, and/or (ii) applying shear forces, preferably using an extruder. The deagglomeration can be carried out in (i) a feeding and mixing device, preferably comprising a nozzle, and/or (ii) an extruder. The feeding and mixing device is preferably a device according to the invention.
[151] Accelerating of the particulate carbon-containing feedstock results in the deagglomeration of the particles. For example, a carrier gas, such as N2 or air (nitrogen is preferred), can be accelerated and the particles are injected into the accelerated carrier gas. In other words, the deagglomeration can be carried out by subjecting the particulate carbon-containing feedstock into a carrier gas jet.
[152] The deagglomeration can be carried out in (i) a feeding and mixing device comprising a Laval nozzle.
[153] The carrier gas and/or the particulate carbon-containing feedstock is preferably accelerated to over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma. A Mach number of over 1 can be achieved with a jet nozzle such as a Laval nozzle. Ma is the Mach number. Accordingly, it is desired that the particulate carbon-containing feedstock is injected into the reactor at over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma.
[154] However, flow velocities from 0.01 Ma to 3 Ma, preferably 0.1 Ma to 2 Ma, more preferably 0.2 to 1.8 Ma, and most preferably 0.3 to less than 1 Ma, are also desirable.
[155] The deagglomeration is also achieved by the impact of the accelerated particulate carbon-containing feedstock with an object, such as two particles of the particulate carbon-containing feedstock, or by the impact of particles of the particulate carbon- containing feedstock and a surface such as the inner surface of a deagglomeration conduit.
[156] The deagglomerated particulate carbon-containing feedstock (or the carrier gas comprising the deagglomerated particulate carbon-containing feedstock) can be injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1 .5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar. As mentioned above, the pressure should be adjusted according to the injection position of the feedstock. For instance, the pressure in a combustion chamber is higher than the pressure in the choke so that the deagglomerated particulate carbon-containing feedstock or the carrier gas comprising the deagglomerated particulate carbon-containing feedstock should be injected at higher pressures in the combustion chamber.
[157] The deagglomerated particulate carbon-containing feedstock can be comprised in a carrier gas and the carrier gas further comprises H2O and/or additives. H2O can prevent the re-agglomeration of the particles in the carrier gas. Thus, the deagglomerated particulate carbon-containing feedstock should be comprised in a carrier gas and the carrier gas can further comprise H2O in an amount of 1 to 10 vol.-%, preferably 2 to 8 vol.-%, more preferably 3 to 7 vol.-%, based on the total volume of the carrier gas comprising the the deagglomerated particulate carbon-containing feedstock.
[158] The particulate carbon-containing feedstock and/or the deagglomerated carbon- containing feedstock is generally comprised in a carrier gas.
[159] The deagglomeration can be carried out in a feeding and mixing device for particles into a reactor comprising: (i) a carrier gas passage extending through said feeding and mixing device, (ii) at least one carrier gas inlet, which is in fluid communication with said carrier gas passage, (iii) at least one particle inlet, (iv) a mixing chamber which is in fluid communication with said at least one particle inlet and with said carrier gas inlet, (v) a deagglomeration conduit which is in fluid communication with said mixing chamber, (vi) at least one outlet for said carrier gas entraining particles which have been fed into said mixing chamber, wherein said at least one outlet for is in fluid communication with said deagglomeration conduit, and (vii) means for accelerating and injecting a stream of carrier gas into said mixing chamber.
[160] Said gas passage should extend along a longitudinal axis through said feeding and mixing device and preferably said at least one inlet, said mixing chamber, said deagglomeration conduit and said outlet are aligned with said longitudinal axis.
[161] Said particle inlet should be configured to feed particles into said mixing chamber at an angle relative to a carrier gas jet discharged into said mixing chamber, preferably perpendicularly to the carrier gas jet. However, the angle is not particularly limited for the present invention.
[162] Said means for accelerating and injecting the stream of carrier gas may include at least one jet nozzle (nozzle). The jet nozzle is configurated to accelerate the stream of carrier gas. This means that the nozzle (or jet nozzle) is positions so that the nozzle convergent in a flow direction so that the gas stream is accelerated after exiting the nozzle and entering the mixing chamber. In other words, said means for accelerating and injecting said stream of the carrier gas is preferably convergent in a flow direction extending from said at least one carrier gas inlet towards said at least one outlet.
[163] Said jet nozzle can be a Laval-nozzle. Such a Laval nozzle (or nozzle) may comprise (in the following order) a convergent section, a throat and a divergent section. Typically, the convergent section reduces the diameter of the nozzle so that the gas flow is accelerated. The divergent section increases the diameter in this section. However, the diameter increased by the divergent section is still lower than the diameter before the convergent section. Accordingly, a nozzle comprising in the following order a convergent section, a throat and a divergent section, the gas flow is accelerated.
[164] The cross-sectional area is usually circular or elliptical at each point of the jet nozzle.
[165] Said jet nozzle may comprise a divergent section and the angle of divergent section can be from 2 to 30°, preferably 3 to 20°, more preferably 4 to 15°, and most preferably 5 to 10°.
[166] The jet nozzle may comprise a convergent section and the maximum inner diameter of the convergent section can be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
[167] The minimum inner diameter of the convergent section, divergent section and/or the inner diameter of the throat can be from 0.6 to 30 mm, preferably 1.2 to 18 mm, more preferably 1.9 to 12 mm, and most preferably 3 to 9 mm.
[168] The minimum inner diameter of convergent section, divergent section and the inner diameter of the throat should be the same. In other words, the convergent, the throat and the divergent section are generally directly connected with each other.
[169] The jet nozzle may comprise a divergent section and the maximum inner diameter of the divergent section can be from 0.3 to 11 mm, preferably 0.5 to 7 mm, more preferably 0.9 to 5 mm, and most preferably 1.1 to 4 mm.
[170] The minimum inner diameter of the convergent section should be higher than the maximum inner diameter of the convergent section, preferably the difference of the maximum inner diameters of the convergent section and the divergent section is from 5 to 30 mm, preferably 8 to 20 mm, more preferably 9 to 18 min, and most preferably 10 to 15 mm.
[171] The maximum inner diameter of the convergent section may be higher than the maximum inner diameter of the divergent section.
[172] The distance between the means for accelerating and injecting and the conduit having a constant inner diameter can be from 2 to 20 mm, preferably 2.5 to 15 mm, more preferably 3 to 10 mm, and most preferably 3.5 to 7 mm. A specific distance between the aforementioned components improves the deagglomeration of the particles since the jet stream flows directly into the deagglomeration conduit. Accordingly, turbulences can be avoided and a loss of the velocity of the jet stream is minimised. [173] It is possible that the means for accelerating and injecting the carrier gas (or nozzle) is positioned in such a way that the means for accelerating and injecting the carrier gas protrudes into the cavity of the inlet funnel of the deagglomeration conduit.
[174] Said deagglomeration conduit normally comprises a conduit having a constant inner diameter. In said conduit having a constant inner diameter the particles collide with each other or the particles collide with the wall of the conduit having a constant inner diameter to further deagglomerate. Said deagglomeration conduit can be configured as a diffuser.
[175] Said deagglomeration conduit can comprise from downstream to upstream an inlet funnel, a conduit having a constant inner diameter and a diffuser nozzle diverging in said flow direction. The nozzle for diverging should continuously increase the inner diameter of the deagglomeration conduit. Accordingly, the carrier gas flow is not interrupted and turbulences are avoided. The angle of said diffuser nozzle can be from 1 to 30°, preferably 2 to 20°, more preferably 3 to 15°, and most preferably 4 to 8°. The angle of said inlet funnel can be from 20 to 80°, preferably 30 to 75°, more preferably 40 to 70°, and most preferably 50 to 65°.
[176] The longitudinal axis of said deagglomeration conduit could coaxial to the longitudinal axis of the feeding and mixing device. The coaxial arrangement improves the overall acceleration as well as deagglomeration.
[177] The inner diameter of the conduit having a constant inner diameter can be from 1 to 20 mm, preferably 2 to 10 mm, more preferably 3 to 7 mm and most preferably 4 to 6 mm. The inner diameter can have an influence of the deagglomeration. Accordingly, the diameter should be selected for the specific particulate feedstock and preferably for the mass flow.
[178] The maximum inner diameter of the diffuser nozzle is higher than the inner diameter of the conduit having a constant inner diameter. The maximum inner diameter of the diffuser nozzle should be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
[179] The diffuser nozzle and the convergent section of the jet nozzle can have the same maximum inner diameter.
[180] The maximum inner diameter of said diffuser nozzle can be from 5 and 50 mm, preferably 8 to 40 mm, more preferably 10 to 30 mm, and most preferably 12 to 20 mm.
[181] The length of the conduit having a constant inner diameter can be between 3 to 500 mm, preferably 5 to 200 mm, more preferably 10 to 50 mm and most preferably 13 to 30 mm. The length of said conduit can have a beneficial influence of the deagglomeration of the particles (particulate carbon-containing feedstock). A longer conduit generally results in a better deagglomeration.
[182] The length of the diffuser nozzle can be between 10 to 300 mm, preferably 20 to 200 mm, more preferably 25 to 150 mm and most preferably 30 to 100 mm.
[183] The inner diameter of the conduit having a constant inner diameter should be higher than the maximum inner diameter of the outlet of the means for accelerating and injecting a stream of the carrier gas.
[184] The means for accelerating and injecting a stream of carrier gas, the mixing chamber and the deagglomeration conduit should be configured so that the carrier gas jet is discharged in the deagglomeration conduit.
[185] Feeding and mixing device can further comprise at least one hopper upstream said at least one particle inlet.
[186] At least one screw conveyor, such as a screw conveyor, is often present upstream said at least one particle inlet. The screw conveyor should be configured to provide a constant amount of particles such (or particulate carbon-containing feedstock) into the mixing chamber. Accordingly, the supply of the particles can be controlled by the screw conveyor.
[187] The particles mentioned for the feeding and mixing device are the particulate carbon containing feedstock and said reactor is typically an entrained flow reactor for the manufacturing of carbon black.
[188] The feeding and mixing often further comprise a pressure tank for the particles, wherein the pressure tank is in fluid communication with said at least one particle inlet and optionally with said at least one screw conveyor. Preferably two pressure tanks are present, wherein a first pressure tank connected to a second pressure tank. Both pressure tanks can be connected via a valve.
[189] A reactor system can be provided comprising an entrained flow reactor and a feeding and mixing device, wherein said feeding and mixing device is in fluid communication with said reactor. Said feeding and mixing device should be connected to a plurality of inlets of said reactor, preferably by injection lances.
[190] Said feeding and mixing device can be in fluid connection with a choke, a combustion chamber and/or a tunnel upstream a quenching area of an entrained flow reactor. Said reactor can be an entrained flow reactor, preferably a furnace reactor. [191] A method for injecting a particulate material into a reactor can be provided that comprises the steps of (a) deagglomerating and entraining particles in a carrier gas stream, preferably by using a feeding and mixing device, (b) injecting the carrier gas stream comprising deagglomerated particles obtained in step (a) into said reactor.
[192] The method can be a method for the manufacturing of carbon black and the particulate material is particulate carbon-containing feedstock and the reactor is an entrained flow reactor for the manufacturing of carbon black, preferably a furnace reactor.
[193] Said particulate carbon-containing feedstock can be injected to said entrained flow reactor by a plurality of inlets, preferably by a plurality of injection lances.
[194] The carrier gas stream can be accelerated and flows through a mixing chamber into a deagglomeration conduit.
[195] The deagglomeration can be done by accelerating the particles in a carrier gas stream and collisions of the particles with the inner surface of a deagglomeration conduit.
[196] The carrier gas is generally accelerated to over 1 Ma, preferably 1.01 Ma to 1.7 Ma, more preferably 1.1 Ma to 1.6 Ma, and most preferably 1.2 Ma to 1.5 Ma.
[197] The particles can be subjected in the carrier gas jet, perpendicularly to the carrier gas jet.
[198] The carrier gas stream comprising deagglomerated particles can be injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1.5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar.
[199] The carrier gas further can further comprise H2O and/or additives. The carrier gas can comprise H2O in an amount of 1 to 10 vol.-%. The H2O can prevent the reagglomeration of the particles.
[200] The feeding and mixing device can be used to deagglomerate particles, preferably a particulate carbon-containing feedstock.
[201] Furthermore, carbon black is provided that is produced according to the inventive method. Said carbon black may comprise new carbon black as well as recovered carbon black.
[202] Carbon blacks are included in many polymer compositions, for example for modifying their color, mechanical, electrical, and/or processing properties. Carbon blacks are for instance commonly added to rubber compositions used to fabricate tires or components thereof to impart electrically dissipative properties to the insulating matrix. At the same time, carbon black additives affect the mechanical and elastic properties, such as stiffness, abrasion resistance and hysteresis, which affect to a great extent the performance of the resulting tire, e.g. in terms of its rolling resistance and durability.
[203] Carbon black (produced carbon black) is provided, comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[204] Particularly, the volume resistivity can be determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the examples, such as under item “Measuring the volume resistivity”. Moreover, the cured emulsion-styrene-butadiene rubber (ESBR) containing 50 phr carbon black as prepared under items “Preparation of vulcanizable rubber compositions” and “Curing of the vulcanizable rubber compositions” can be used to measure the volume resistivity.
[205] The emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black can consist the following components:
[206] The volume resistivity can be determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black based on DIN EN ISO 3915:2022. The measurement of the volume resistivity is further described in full detail in the examples.
[207] In addition, carbon black (produced carbon black) is provided, preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m2/g, preferably a STSA surface area of 116 to 145 m2/g, more preferably a STSA surface area of 117 to 140 m2/g, and most preferably a STSA surface area of 120 to 135 m2/g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21. [208] The carbon black (produced carbon black) can have a BET surface area of 120 to 160 m2/g, preferably a BET surface area of 125 to 155 m2/g, more preferably a BET surface area of 127 to 150 m2/g, and most preferably a BET surface area of 130 to 145 m2/g, wherein the BET surface area is measured according to ASTM D6556-21.
[209] The carbon black (produced carbon black) can have a compressed oil absorption number of 100 to 150 mL/100 g, preferably a compressed oil absorption number of 110 to 145 mL/100 g, more preferably a compressed oil absorption number of 115 to 140 mL/100 g, and most preferably a compressed oil absorption number of 117 to 135 mL/100 g, wherein the compressed oil absorption number is measured according to ASTM D3493-20 using paraffinic oil.
[210] The carbon black (produced carbon black) can have volatiles of 1.0 to 4.5 wt.-%, preferably volatiles of 1.3 to 4.0 wt.-%, more preferably volatiles of 1.5 to 3.5 wt.-%, and most preferably volatiles of 1.7 to 3.0 wt.-%, wherein the volatiles are measured at 950 °C for 7 min as described in the specification.
[211] The carbon black (produced carbon black) can have an iodine adsorption of 150 to 300 mg/g, preferably 160 to 280, more preferably 180 to 270 mg/g, and most preferably 190 to 260 mg/g, wherein the Iodine adsorption number is measured according to ASTM D1510-21.
[212] The carbon black (produced carbon black) can have an ash content of at least 3 wt.-%, preferably at least 5 wt.-%, and most preferably at least 10 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[213] The carbon black (produced carbon black) can have an ash content of 3 to 25 wt.- %, preferably 5 to 20 wt.-%, and most preferably 8 to 18 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[214] The carbon black (produced carbon black) has a volume resistivity of less than 7.9'105 Q cm, preferably less than 1.0-105 Q cm, more preferably less than 1.0-104 Q cm, and most preferably less than 1.0-104 Q cm, as determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
[215] The carbon black (produced carbon black) can have resistivity of 10.0-Q cm to 7.9 105 Q cm, preferably 1.0- 102 Q cm to 1.0- 105 Q cm, more preferably 2.0 102 Q cm to 5.0 104 Q cm, and most preferably 2.0 102 Q- a volume cm to 1.0- 104 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
[216] According to the present invention, a composition is provided comprising (A) an elastomeric polymer material, and (B) carbon black obtained according to the present invention. It should be noted that the provided article derived from said composition can also be used as a feedstock material.
[217] The term "composition" as used herein refers to a material composed of multiple constituent chemical species or components. An "elastomeric polymer material" is understood as a material essentially consisting of an elastomeric polymer. The term "polymer" is used herein in its common meaning in the art, referring to macromolecular compounds, i.e. compounds having a relatively high molecular mass (e.g. 500 Da or more), the structure of which comprises multiple repetition units (also referred to as “mers”) derived, actually or conceptually, from chemical species of relatively lower molecular mass. The term “elastomeric polymer” is used herein in its common meaning in the art, referring to a polymer which is elastic.
[218] Particularly useful as elastomeric polymeric materials (or elastomeric polymer material) for the practice of this invention are elastomers such as rubber materials. The elastomeric polymer material (A) of the composition according to the present invention can comprise one or more than one rubber. The terms “rubber”, “rubber material” and “elastomer” may be used interchangeably throughout this description unless otherwise stated. Rubbers that can be used according to the present invention include those containing olefinic unsaturation, i.e. diene-based rubber materials, as well as non-diene- based rubber materials. The term “diene-based rubber materials” is intended to include both natural and synthetic rubbers or mixtures thereof. The elastomeric polymer material (a) can consist of synthetic rubber.
[219] The elastomeric polymer material (A) of the composition according to the present invention can comprise natural and/or synthetic rubber.
[220] Natural rubber can be used in its raw form and in various processed forms conventionally known in the art of rubber processing. Natural rubber can for example be obtained from rubber trees (Helvea brasiliensis), guayule, and dandelion. Accordingly, the elastomeric polymer material (a) can comprise or consist of natural rubber.
[221] Synthetic rubber can comprise styrene-butadiene rubber such as emulsion- styrene-butadiene rubber (ESBR) and solution-styrene-butadiene rubber (SSBR), polybutadiene, polyisoprene, ethylene-propylene-diene rubber (EPDM), ethylenepropylene rubber (EPM), butyl rubber, halogenated butyl rubber, chlorinated polyethylene, chlorosulfonated polyethylene, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, polychloroprene, acrylate rubber, ethylene-vinylacetate rubber, ethylene-acrylic rubber, epichlorohydrin rubber, silicone rubber, fluorosilicone rubber, fluorocarbon rubber or mixture of combinations of any of the foregoing. According to the invention, the synthetic rubber can also be obtained from a renewable source material. For example, polybutadiene can be produced from alcohol obtained through fermentation of plant biomass.
[222] Suitable rubbers may also include functionalized rubbers and rubbers coupled to silicon or tin. For example, rubbers can be functionalized with functional groups like amine, alkoxy, silyl, thiols, thioesters, thioether, sulfanyl, mercapto, sulfide or combinations thereof. The one or more functionalities can be primary, secondary or tertiary and can be located at one or both chain ends (e.g. a,w-functionalization), pendant from the polymer backbone and/or provided within the chain of the polymer backbone. The rubber according to the invention can also be partially cross-linked. Thus, prior to use in the composition of the present invention, part of the polymer chains of the rubber material can be cross-linked either by means of a coupling agent or without.
[223] The composition according to the invention can in particular be a curable composition, such as for example a vulcanizable rubber composition. The term "vulcanizable rubber composition" refers to a composition of a rubber component optionally with various further ingredients conventionally used in the art of rubber compounding that can be cured by vulcanization under formation of a vulcanizate. The terms “curable” and “vulcanizable” are used interchangeably throughout this description unless otherwise stated and refer to a chemical reaction linking polymer chains to each other by means of a cross-linker or vulcanizing agent. The curing reaction can be induced by any means known in the art such as by light, moisture, heat and/or addition of a crosslinker.
[224] The elastomeric polymer material (A) according to the invention may comprise a natural rubber. According to the invention, the natural rubber can comprise natural rubber obtained from rubber trees (Helvea brasiliensis), guayule, dandelion or mixtures of combinations of any of the foregoing. The natural rubber can comprise natural rubber obtained from guayule and/or dandelion. The elastomeric polymer material (A) can comprise 5 phr or more of natural rubber, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more. As used herein, the term "phr" refers to parts by weight of the recited respective material per 100 parts by weight of rubber or elastomer. The elastomeric polymer material (A) can comprise 100 phr or less of natural rubber, such as 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr, or less 70 phr or less, or 65 phr or less, or 60 phr or less. The elastomeric polymer material (A) can comprise natural rubber in a range between any of the recited lower and upper limits. For example, the elastomeric polymer material (A) can comprise natural rubber in a range of 5 to 95 phr, such as in a range of 10 to 90 phr, or in a range of 20 to 80 phr, or in a range of 30 to 70 phr, or in a range of 40 to 60 phr. According to the present invention, the elastomeric polymer material (A) can consist of natural rubber.
[225] The elastomeric polymer material (A) according to the invention may comprise a synthetic rubber. According to the invention, the synthetic rubber can comprise synthetic rubber obtained from a renewable source material. The renewable source material according to the present invention can be alcohol obtained through fermentation of plant biomass. For example, the synthetic rubber may comprise polybutadiene obtained from alcohol obtained through fermentation of plant biomass. The elastomeric polymer material (A) can comprise 5 phr or more of synthetic rubber, such as 10 phr or more, or 15 phr or more, or 20 phr or more, or 30 phr or more, or 40 phr or more, or 50 phr or more, or 60 phr or more, or 70 phr or more, or 80 phr or more. As used herein, the term "phr" refers to parts by weight of the recited respective material per 100 parts by weight of rubber or elastomer. The elastomeric polymer material (A) can comprise 100 phr or less of synthetic rubber, such as 95 phr or less, or 90 phr or less, or 85 phr or less, or 80 phr or less, or 75 phr, or less 70 phr or less, or 65 phr or less, or 60 phr or less. The elastomeric polymer material (A) can comprise synthetic rubber in a range between any of the recited lower and upper limits. For example, the elastomeric polymer material (A) can comprise synthetic rubber in a range of 5 to 95 phr, such as in a range of 10 to
90 phr, or in a range of 20 to 80 phr, or in a range of 30 to 70 phr, or in a range of 40 to 60 phr. According to the present invention, the elastomeric polymer material (A) can consist of synthetic rubber.
[226] According to the present invention, the elastomeric polymer material (A) may comprise a mixture of natural rubber and synthetic rubber. The elastomeric polymer material (A) can comprise from 5 to 100 phr of natural rubber and from 5 to 100 phr of synthetic rubber, such as from 10 to 90 phr of natural rubber and from 10 to 90 phr of synthetic rubber, or from 20 to 80 phr of natural rubber and from 20 to 80 phr of synthetic rubber, or from 30 to 70 phr of natural rubber and from 30 to 70 phr of synthetic rubber, or from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, or from 40 to 100 phr of natural rubber and from 5 to 60 phr of synthetic rubber, or from 50 to 95 phr of natural rubber and from 5 to 50 phr of synthetic rubber, or from 60 to 90 phr of natural rubber and from 10 to 50 phr of synthetic rubber, or from 5 to 40 phr of natural rubber and from 60 to 100 phr of synthetic rubber, or from 10 to 20 of natural rubber and from 80 to 90 phr. For example, the elastomeric polymer material (A) may comprise 50 phr of natural rubber and 50 phr of synthetic rubber or the elastomeric polymer material (A) may comprise 5 phr of natural rubber and 95 phr of synthetic rubber.
[227] The synthetic rubber according to the present invention preferably comprises emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, more preferable polyisoprene and/or polybutadiene, even more preferably polybutadiene. The synthetic rubber according to the present invention preferably consists of emulsion- styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, more preferable polyisoprene and/or polybutadiene, even more preferably polybutadiene. The synthetic rubber can comprise emulsion-styrene-butadiene rubber (ESBR), polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene. The synthetic rubber can comprise or consist polybutadiene, polyisoprene, butyl rubber, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene. The synthetic rubber can comprise or consist polybutadiene, polyisoprene, halogenated butyl rubber or mixture of combinations of any of the foregoing, preferably polyisoprene or polybutadiene, more preferably polybutadiene.
[228] The produced carbon black can also be pulverized before being added to the composition. Thus, the composition can comprise pulverized carbon black.
[229] The composition can comprise 3 to 200 phr of the carbon black obtained according to the present invention (B), preferably 5 to 190 phr of the carbon black obtained according to the present invention (B), more preferably 10 to 150 phr of the carbon black obtained according to the present invention (B), even more preferably 20 to 130 phr of the carbon black obtained according to the present invention (B), most preferably 30 to 100 phr of the carbon black (B) obtained according to the present invention.
[230] The composition can comprise one or more additives selected from vulcanization agents, curing aids such as primary and secondary vulcanization accelerators, activators and pre-vulcanization inhibitors, processing additives such as oils, waxes, resins, plasticizers, softeners, rheology modifiers, pigments, peptizing agents, coupling agents, surfactants, biocides and anti-degradants, such as heat or light stabilizers, anti-oxidants and anti-ozonates, metal oxides, metal hydroxides, and filler materials such as silica, organo-silica, carbon nanotubes, carbon fibers, graphite and metal fibers.
[231] The composition of the present invention can be obtained and processed by common elastomer processing technology. The composition according to the present invention can for example be obtained by combining the carbon black (B) of the present invention and any optional ingredients, if used, with the elastomeric polymer material (A) and mixing the same, e.g. to disperse the carbon black (B) and any optional ingredients, if used, in the elastomeric polymer material (A). Dispersion can be achieved by any means known in the art such as by mixing, stirring, milling, kneading, ultrasound, a dissolver, a shaker mixer, rotor-stator dispersing assemblies, or high-pressure homogenizers or a combination thereof. For example, a lab mixer with intermeshing rotor geometry can be used. The dispersing can for example be conducted until the carbon black (B) is homogeneously dispersed in the elastomeric polymer material (A) resulting in a dispersion index of larger than 95% or more, preferably 97% or more, or more than 99% according to the classification pursuant to ASTM D2663-88, test method B.
[232] Preparation of the composition according to the present invention may for example be conducted in a multiple step process: At first, the carbon black (B) and optionally non-curative additives, if used, may be added to the elastomeric polymer material (A) concomitantly or successively. The elastomeric polymer material (A), the carbon black (B) and the additives, if used, may then be mixed, typically at a temperature in a range from 40°C to 160°C for a total mixing time of less than 10 min, such as in a range from 2 to 8 min. Subsequently, the obtained mixture may be blended with one or more curative additives for less than 5 min, typically less than 3 min, preferably for about 2.5 min, at a temperature of less than 115°C.
[233] The process can comprise further steps such as extrusion or cooling down the product to room temperature and storing it for further processing. The process can further comprise a curing step, which can for example be carried out by subjecting the composition to thermal curing conditions, e.g. a temperature of 120-200°C for a time of 5 minutes to 3 hours. Curing can for instance be carried out in a curing press for example at a temperature of 140-180°C for 5 to 60 minutes at a pressure between 100 and 150 bar.
[234] As it will be appreciated, the compositions according to the invention can be utilized in various technical applications requiring polymer-based materials with carbon black filler, e.g. for imparting antistatic or electrically conductive properties, color, mechanical reinforcement and/or low hysteresis properties. Mechanical properties that are of interest, particularly for the production of tires, include tear resistance, rebound and hysteresis. The compositions according to the present invention provide cured compositions which have good and beneficial mechanical properties, especially for the production of tires. Beneficial mechanical properties in accordance with the present invention are for example high tensile strength, high rebound and low hysteresis. The composition according to the present invention provide cured compositions having mechanical properties which are comparable to rubber compositions comprising conventional carbon blacks.
[235] Accordingly, the invention also relates to articles, such as rubber articles, and particularly tires made of or comprising the afore-mentioned composition according to the invention.
[236] Thus, a rubber article is provided comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[237] The tire according to the present invention may comprise a tread, carcass, sidewall, inner liner, apex, shoulder, hump strip, chafer and/or a bead filler, wherein at least one of the foregoing is made of or comprises a composition according to the invention. Such tires include for example, without being limited thereto, truck tires, passenger tires, off-road tires, aircraft tires, agricultural tires, and earth-mover tires. The describes tires and/or components of the tire can also be used as the rubber granulate.
[238] The tire can comprise a sidewall, wherein the sidewall is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, preferably from 50 to 60 phr of natural rubber and from 40 to 50 phr of synthetic rubber, more preferably 55 phr of natural rubber and 45 phr of synthetic rubber wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the comprise a tread, carcass, sidewall, inner liner, apex, shoulder, hump strip, chafer and/or a bead filler, wherein at least carbon black, preferably 50 phr of the carbon black.
[239] The tire can comprise a carcass, wherein the carcass is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 40 to 80 phr of natural rubber and from 20 to 60 phr of synthetic rubber, preferably from 50 to 70 phr of natural rubber and from 30 to 50 phr of synthetic rubber, more preferably 60 phr of natural rubber and from 40 phr of synthetic rubber wherein the synthetic rubber preferably comprises polybutadiene and emulsion-styrene-butadiene rubber (ESBR), more preferably comprises 20 phr of polybutadiene and 20 phr of emulsion-styrene- butadiene rubber (ESBR); and (B) from 5 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably 50 phr of the carbon black.
[240] The tire comprises a chafer, wherein the chafer is made of the composition according to the invention, wherein the composition preferably comprises: (A) from 30 to 70 phr of natural rubber and from 30 to 70 phr of synthetic rubber, preferably from 40 to 60 phr of natural rubber and from 40 to 60 phr of synthetic rubber, more preferably 50 phr of natural rubber and 50 phr of synthetic rubber, wherein the synthetic rubber preferably comprises emulsion-styrene-butadiene rubber (ESBR), more preferably consists of emulsion-styrene-butadiene rubber (ESBR); and (B) from 55 to 95 phr of the carbon black, preferably from 65 to 85 phr of the carbon black, preferably 75 phr of the carbon black.
[241] The tire can comprise a bead filler and/or an apex, wherein the bead filler and/or apex is/are made of the composition according to the invention, wherein the composition preferably comprises: (A) from 80 to 100 phr of natural rubber, preferably from 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 65 phr of the carbon black, more preferably from 55 phr of the carbon black.
[242] The tire can comprise an inner liner, wherein the inner liner is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises a halogenated butyl rubber, more preferably consists of a halogenated butyl rubber; and (B) from 40 to 80 phr of the carbon black, preferably from 50 to 70 phr of the carbon black, more preferably from 60 phr of the carbon black.
[243] The tire can comprise a tread, preferably a truck tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably from 80 phr of natural rubber and 20 phr of synthetic rubber, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably from 50 phr of the carbon black.
[244] The tire can comprise a tread, preferably a passenger car tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprises 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 65 phr of the carbon black, more preferably 55 phr of the carbon black.
[245] The tire can comprise a tread, preferably a passenger car tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of synthetic rubber, preferably from 90 to 100 phr of synthetic rubber, more preferably 100 phr of synthetic rubber, wherein the synthetic rubber preferably comprises solution-styrene-butadiene rubber (SSBR) and polybutadiene, more preferably comprises 70 phr of solution-styrene-butadiene rubber (SSBR) and 30 phr of polybutadiene; and (B) from 3 to 25 phr of the carbon black, preferably from 5 to 15 phr of the carbon black, more preferably 5 phr of the carbon black; and (C) from 60 to 100 phr of silica, preferably from 70 to 90 phr of silica, more preferably 80 phr of silica.
[246] The tire can comprise a tread, preferably an Off-the-road (OTR) tire, wherein the tread is made of the composition according to the invention, wherein the composition preferably comprises (A) from 80 to 100 phr of natural rubber, preferably from 90 to 100 phr of natural rubber, more preferably 100 phr of natural rubber; and (B) from 35 to 75 phr of the carbon black, preferably from 45 to 75 phr of the carbon black, more preferably from 55 phr of the carbon black.
[247] The rubber article can be a cable sheath, a tube, a drive belt, a conveyor belt, a roll covering, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating or a colored or printed article.
[248] Moreover, the rubber article can be a conveyor belt, wherein the conveyor belt is made of the composition according to the invention, wherein the composition preferably comprises (A) from 60 to 95 phr of natural rubber and from 5 to 40 phr of synthetic rubber, preferably from 70 to 85 phr of natural rubber and from 15 to 30 phr of synthetic rubber, more preferably 80 phr of natural rubber and from 20 phr of synthetic rubber, wherein the synthetic rubber preferably comprises polybutadiene, more preferably consists of polybutadiene; and (B) from 30 to 70 phr of the carbon black, preferably from 40 to 60 phr of the carbon black, more preferably from 50 phr of the carbon black.
[249] Furthermore, the present invention relates to the use of the aforementioned composition according to the present invention for producing a tire, preferably a pneumatic tire, a tire tread, a belt, a belt reinforcement, a carcass, a carcass reinforcement, a sidewall, inner liner, apex, shoulder, hump strip, chafer, a bead filler, a cable sheath, a tube, a drive belt, a conveyor belt, a roll covering, a shoe sole, a hose, a sealing member, a profile, a damping element, a coating or a colored or printed article.
[250] The rubber article can have an abrasion of less than 110 mm3, preferably less than 106 mm3, more preferably 50 to 105 mm3, and most preferably 90 to 105 mm3, as measured at 23 °C DIN ISO 4649:2014-03, 10 N.
[251] The rubber article can have a tensile strength of 20.0 to 40.0 Mpa, preferably 23.0 to 35 Mpa, more preferably 24.0 to 32 Mpa, and most preferably 24.0 to 30 Mpa, as measured according to ISO 37 - 2012, S2.
[252] The rubber article can have an elongation at break of more than 520 %, preferably 530 to 700 %, more preferably 550 to 650 %, even more preferably 570 to 630 %, and most preferably 580 to 620 %, as measured according to ISO 37 - 2012, S2.
[253] The rubber article can have a Mooney viscosity of 40 to 80 Me, more preferably 50 to 76 Me, even more preferably 57 to 75 Me, and most preferably 65 to 74 Me, as measured according to ISO 289-1 :2015.
[254] Moreover, the present invention uses deagglomerated particulate carbon- containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor. Moreover, the present invention uses particulate carbon-containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor.
[255] The invention will now be described with reference to the accompanying figures which do not limit the scope and ambit of the invention. The description provided is purely by way of example and illustration. However, specific features exemplified in the figures can be used to further restrict the scope of the invention and claims.
[256] In FIG. 1 a furnace reactor (100) is shown that comprises a combustion chamber (101), a choke (102) and a tunnel (103). The reactor has an inner lining (106) as well as an outer lining (105). The combustion chamber (101) comprises means to inject a fuel (101b) and oxygen-containing gas (101a). In the figure, the oxygen-containing gas is injected into the combustion chamber (101) tangential or radial via oxygen containing gas means (101a) and the fuel is injected into the combustion chamber (101) axial via fuel injection means (101b). It is preferred that the oxygen-containing gas is preheated to a temperature described in the description. It is possible to adjust the temperature of the hot gas flow with the preheating of the oxygen-containing gas. Alternatively, the fuel can be preheated. In the combustion chamber (101) the fuel is combusted in the presence of the oxygen-containing gas. After the combustion, the temperature of the hot carrier gas can be above 800 °C to bring the particulate carbon-containing feedstock. The particulate carbon-containing feedstock can be injected directly in the combustion chamber (101), in the choke (102) or in the tunnel (103). The fluid carbon-containing feedstock can be injected directly in the combustion chamber (101), in the choke (102) or in the tunnel (103). It is preferred that the particulate carbon-containing feedstock is injected in the choke (102) and the fluid carbon-containing feedstock is injected in the tunnel (103). However, it is possible that the particulate carbon containing feedstock and the fluid carbon-containing feedstock can also be injected in any of the aforementioned combinations such as in the choke (102) as well as in the tunnel (103). The furnace reactor (100) comprises multiple positions for the quench (104a, 104b, 104c, 104d). The quench medium that is usually water reduces the temperature of the hot gas flow (or the product mixture) so that the reaction for forming the carbon black is terminated.
Accordingly, the position of the quench has an influence of the residence time of the feedstock as well as the components derived from the feedstock. This means that residence time is increased if the quench position is adjusted further downstream the reactor. For instance, a quench at a position (104a) near the choke (102) results in a low residence time and a quench at a position (104c) downstream the reactor results in a high residence time. The reaction volume is the volume of the reactor between the injection of the feedstock and the position of the quench. If the feedstock is injected in the tunnel (103) and the distance between the position of the quench and the injection of the feedstock is 4200 mm, and the diameter of the tunnel is 200m, the resulting reaction volume is 132 L. The feeding rate of the particulate carbon containing feedstock should be adjusted depending on the reaction volume as mentioned in the description. For the present invention, a quench position at the back part of the tunnel is particularly preferred so that the particulate carbon containing feedstock has sufficient time for the evaporation or pyrolysis.
[257] Referring to FIG. 2, a feeding and mixing device (200) is shown that comprises a carrier gas inlet (204), a particle inlet (201), means for accelerating and injecting a stream of carrier gas (207), a deagglomeration conduit (209), a mixing chamber (206) and an outlet for said carrier gas entraining particles (210). The carrier gas passage (212) is also indicated in FIG. 2. The carrier gas passage (212) extends along a longitudinal axis through said feeding and mixing device. The carrier gas (203) enters the feeding and mixing device (200) through the carrier gas inlet (204) and is accelerated in the means for accelerating and injecting a stream of carrier gas (207). In FIG. 2, the means for accelerating and injecting a stream of carrier gas (207) is configured as a Laval-nozzle. The Laval-nozzle comprises a convergent area (207a) in the flow direction. The resulting carrier gas jet is injected into the mixing chamber (206). The particles such as the particulate carbon-containing feedstock (202) are perpendicularly injected into the mixing chamber (206). Accordingly, the particles will be entrained in the accelerated carrier gas. The abrupt acceleration of the particles results in a deagglomeration of the particles. The accelerated carrier gas comprising the particles are further injected into the deagglomeration conduit (209). In the deagglomeration conduit (209) the particles collide with each other or the inner wall or inner surface of the deagglomeration conduit (209) thereby a further deagglomeration is achieved. It is desired that the means for accelerating and injecting a stream of carrier gas (207) is configured in such a way that the carrier gas jet is directly injected into the deagglomeration conduit (209). Accordingly, a loss of the velocity can be minimized. The deagglomeration conduit (209) normally comprises from downstream to upstream (in the flow direction) an inlet funnel (209a), a conduit having a constant inner diameter (209b) and a diffuser nozzle diverging in said flow direction (209c). The inlet funnel (209a) further allows an optimal flow behavior into the conduit having a constant inner diameter (209b). The diffuser nozzle diverging in said flow direction (209c) is also beneficial for the flow behavior. The outlet (406) can be connected to the means for injecting the feedstock into a reactor according to FIG.1. It is preferred that one feeding and mixing device (200) supplies the deagglomerated feedstock to multiple means for injecting the feedstock into the reactor. It is further desired that the feeding and mixing device (200) comprises a screw conveyor that is connected with the particle inlet (201). The screw conveyor can provide a suitable amount or weight of particles into the mixing chamber (206). Furthermore, the feeding and mixing device (200) can be operated under pressure such as 1.5 bar or 2 bar. A pressure tank for the particles (e.g. particulate carbon containing feedstock) can be installed. Such a pressure tank is in fluid connection with the particle inlet (201) and is preferably connected with the feeding and mixing device (200) via a valve. Preferably two pressure tanks are present, wherein a first pressure tank connected to a second pressure tank. Both pressure tanks can be connected via a valve. [258] In FIG. 3, a Laval-nozzle (300) for use in feeding and mixing device (200) is shown. The carrier gas passage (306) extends along a longitudinal axis through said Laval-nozzle (300). The carrier gas (304) enters the Laval-nozzle (300) and is accelerated. The carrier gas jet (305) then leaves the Laval-nozzle (300). The Laval- nozzle (300) comprises a section that has a constant diameter (301), a section that converges (302a) in the flow direction (302), a throat (303a) and a divergent section (303). In the Laval-nozzle (300) the carrier gas is accelerated to a velocity of over 1 Ma.
[259] In FIG. 4, the deagglomeration conduit (400) for use in feeding and mixing device (200) is shown. The carrier gas passage (407) extends along a longitudinal axis through said deagglomeration conduit (400). The deagglomeration conduit (400) comprises an inlet funnel (401), a conduit having a constant inner diameter (402) and a diffuser nozzle (403) diverging in said flow direction (403a). Furthermore, an outlet (404) is shown that can be connected to means to inject the deagglomerated particles (e.g. deagglomerated particulate carbon containing particles) (406) into the reactor.
[260] In FIG. 5, an alternative feeding and mixing device (500) is shown. The carrier gas passage (506) is also indicated in FIG. 5. The carrier gas passage (506) extends along a longitudinal axis through said feeding and mixing device. Said feeding and mixing device (500) comprises an inlet (504) for the carrier gas (501), a mixing chamber (505), an inlet for particles (502), and an outlet (503). A carrier gas (501) enters the feeding and mixing device (500). The carrier gas (501) should have a desirable velocity such as below 1 Ma or between 2 m/s to 1 Ma or between 20 m/s to 200 m/s. The particles such as the particulate carbon-containing feedstock (202) are perpendicularly injected into the mixing chamber (507). Accordingly, the particles will be entrained in the accelerated carrier gas. The abrupt acceleration of the particles results in a deagglomeration of the particles. The outlet (503) can be connected to a reactor. Similar to the feeding and mixing device (200), a screw conveyor and at least one pressure tank can be installed.
[261] In addition, the present invention will be described by means of the following aspects.
[262] Aspect 1. A method for producing carbon black in entrained flow reactor, comprising:
(a) providing a hot gas flow,
(b) providing a particulate carbon-containing feedstock,
(c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and (d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
[263] Aspect 2. The method according to aspect 1, wherein step (b) further comprises deagglomerating the particulate carbon-containing and in step (d), the deagglomerated particulate carbon-containing feedstock is injected in the hot gas flow to form carbon black.
[264] Aspect 3. A method for producing carbon black in entrained flow reactor, comprising:
(a) providing a hot gas flow,
(b) deagglomerating a particulate carbon-containing feedstock to provide deagglomerated a particulate carbon-containing feedstock,
(c) injecting the deagglomerated particulate carbon-containing feedstock in the hot gas flow to form carbon black, and
(d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
[265] Aspect 4. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises inert compounds, coke, C,H- containing compounds, and/or carbon black, preferably ash and carbon black.
[266] Aspect 5. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock further comprises inert compounds, wherein the inert compounds comprise zinc, silicon, calcium, aluminium, and/or iron.
[267] Aspect 6. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises 1 to 40 wt.-% inert compounds, preferably 3 to 30 wt.-% inert compounds, more preferably 4 to 20 wt.-% inert compounds, and most preferably 5 to 15 wt.-% inert compounds, based on the total weight of the particulate carbon-containing feedstock.
[268] Aspect 7. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock further comprises carbon black, wherein the carbon black is present in the particulate carbon-containing feedstock in an amount from
1 to 70 wt.-%, preferably 2 to 50 wt.-%, more preferably 5 to 40 wt.-%, and most preferably 10 to 30 wt.-%, based on the total weight of the particulate carbon-containing feedstock. [269] Aspect 8. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises 10 to 100 wt.-% of C,H-containing compounds, preferably 20 to 99 wt.-% of C,H-containing compounds, more preferably 30 to 90 wt.-% of C,H-containing compounds, and most preferably 40 to 70 wt.-% of C,H- containing compounds, based on the total weight of the particulate carbon-containing feedstock.
[270] Aspect 9. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises rubber granulate, plastic granulate, and/or biomass-based granulate.
[271] Aspect 10. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises rubber granulate, wherein the rubber granulate comprising carbon black.
[272] Aspect 11. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock comprises agglomerated feedstock.
[273] Aspect 12. The method according to any one of the preceding aspects, wherein at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, most preferably at least 80 wt.-%, of the particulate carbon-containing feedstock has a particle size of 125 pm to 2 mm, preferably 125 pm to 1 mm, more preferably 250 pm to 1 mm, and most preferably 500 pm to 1000 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[274] Aspect 13. The method according to any one of the preceding aspects, wherein the particle size distribution of the particulate carbon-containing feedstock is measured according to ASTM D 1511-12 (2017) and
(a) Sieve No. 10 retains 1 to 0 to 10 wt.-%, preferably 1 to 8 wt.-%, more preferably 1 to 5 wt.-%, and most preferably 1 to 3 wt.-% of the particulate carbon-containing feedstock, and/or
(b) Sieve No. 18 retains 1 to 25 wt.-%, preferably 2 to 20 wt.-%, more preferably 4 to 15 wt.-%, and most preferably 5 to 12 wt.-% of the particulate carbon-containing feedstock, and/or
(c) Sieve No. 35 retains 10 to 80 wt.-%, preferably 15 to 70 wt.-%, more preferably 20 to 60 wt.-%, and most preferably 25 to 55 wt.-% of the particulate carbon-containing feedstock, and/or
(d) Sieve No. 60 retains 5 to 70 wt.-%, preferably 10 to 60 wt.-%, more preferably 15 to 50 wt.-%, and most preferably 20 to 45 wt.-% of the particulate carbon-containing feedstock, and/or (e) Sieve No. 120 retains 1 to 80 wt.-%, preferably 7 to 70 wt.-%, more preferably 5 to 60 wt.-%, and most preferably 7 to 50 wt.-% of the particulate carbon-containing feedstock, and/or
(f) Bottom receive pan comprises less than 4 wt.-%, preferably less than 3 wt.-%, more preferably 0 to 2 wt.-%, and most preferably 0.01 to 1 wt.-% of the particulate carbon-containing feedstock.
[275] Aspect 14. The method according to any one of the preceding aspects, wherein no more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon-containing feedstock has a particle size of over 4 mm, preferably over 2 mm, more preferably over 1 mm, and most preferably over 0.5 mm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[276] Aspect 15. The method according to any one of the preceding aspects, wherein no more than 10 wt.-%, preferably no more than 5 wt.-%, more preferably no more than 4 wt.-%, and most preferably no more than 2 wt.-% of the particulate carbon-containing feedstock has a particle size of less than 150 pm, preferably less than 125 pm, more preferably less than 110 pm, and most preferably less than 100 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[277] Aspect 16. The method according to any one of the preceding aspects, wherein the 50 wt.-% cumulative particle size of the particulate carbon-containing feedstock is from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the 50 wt.-% cumulative particle size is measured according to ASTM D 1511-12 (2017).
[278] Aspect 17. The method according to any one of the preceding aspects, wherein the weight average particle size Dw50 of the particulate carbon-containing feedstock is from 100 pm to 4 mm preferably 100 pm to 3 mm, more preferably 100 pm to 2 mm, and most preferably 100 pm to 500 pm, wherein the weight average particle size Dw50 is measured according to ASTM D 1511-12 (2017).
[279] Aspect 18. The method according to any one of the preceding aspects, wherein the particle size distribution Dw10 of the particulate carbon-containing feedstock is from 100 pm to 250 pm preferably 110 pm to 220 pm, more preferably 120 pm to 210 pm, and most preferably 130 pm to 200 pm, wherein the particle size distribution Dw10 is measured according to ASTM D 1511-12 (2017).
[280] Aspect 19. The method according to any one of the preceding aspects, wherein the particle size distribution of the particulate carbon-containing feedstock Dw90 is from 400 m to 4 mm preferably 500 pm to 3 mm, more preferably 600 pm to 2 mm, and most preferably 700 pm to 500 pm, wherein the particle size distribution Dw90 is measured according to ASTM D 1511-12 (2017).
[281] Aspect 20. The method according to any one of the preceding aspects, wherein the span of the particle size distributions of the particulate carbon-containing feedstock (Dw90-Dw10) I Dw50 is 0.2 to 1.8, preferably 0.3 to 1.3, more preferably 0.4 to 1.1 , most preferably 0.4 to 1.0, wherein the particle size distributions Dw10, Dw50, and Dw90 are measured according to ASTM D 1511-12 (2017).
[282] Aspect 21. The method according to any one of the preceding aspects, wherein the mass flow rate of the fluid carbon-containing feedstock is 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h, and/or the mass flow rate of the particulate carbon-containing feedstock is 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h, and/or steam is subjected into the hot gas flow, preferably at a mass flow of 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1,000 kg/h, most preferably 30 to 500 kg/h.
[283] Aspect 22. The method according to any one of the preceding aspects, wherein the hot gas flow is obtained by electrical preheating, plasma heating and combustion of a fuel and oxygen-containing gas.
[284] Aspect 23. The method according to any one of the preceding aspects, wherein the hot gas flow is provided by
(a1) supplying fuel and oxygen-containing gas into a combustion chamber of the reactor,
(b2) combusting fuel in the combustion chamber to produce the hot gas flow.
[285] Aspect 24. The method according to any one of the preceding aspects, wherein the entrained flow reactor is a furnace reactor.
[286] Aspect 25. The method according to any one of aspects 22 to 24, wherein the particulate carbon-containing feedstock is injected in the combustion chamber, in the choke, and/or in the tunnel of the furnace reactor, preferably in the choke of the furnace reactor.
[287] Aspect 26. The method according to any one of the preceding aspects, wherein the hot gas flow has a temperature of 900 to 3500 °C, preferably 950 to 3000 °C, more preferably 1000 to 2000 °C, and most preferably 1200 to 1900 °C. [288] Aspect 27. The method according to any one of aspects 22 to 26, wherein the oxygen-containing gas is preheated to a temperature between 200 to 1600 °C, preferably 350 to 1400 °C, more preferably 500 to 1200 °C, and most preferably 450 to 950 °C.
[289] Aspect 28. The method according to any one of aspects 22 to 27, wherein the fuel is preheated to a temperature between 50 to 750 °C, preferably 100 to 700 °C, more preferably 300 to 700 °C, and most preferably 450 to 650 °C.
[290] Aspect 29. The method according to any one of aspects 22 to 28, wherein the supplied oxygen-containing gas is air, oxygen-enriched air or oxygen gas.
[291] Aspect 30. The method according to any one of aspects 22 to 29, wherein the fuel comprises gaseous or liquid hydrocarbons, preferably natural gas, a fuel oil or H2.
[292] Aspect 31. The method according to any one of aspects 22 to 30, wherein the oxygen-containing gas is supplied in an amount yielding an excess of oxygen with respect to the amount of oxygen for a complete combustion of the fuel, and/or wherein the oxygen-containing gas is supplied in an amount that the k-value is in a range of 0.01 to 10, preferably 0.1 to 5, more preferably 0.5 to 2, and most preferably 0.7 to below 1.
[293] Aspect 32. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is injected via multiply inlets, preferably radial and perpendicular to the central longitudinal axis of the reactor.
[294] Aspect 33. The method according to any one of the preceding aspects, wherein the concentration of O2 in the hot gas flow is less than 5 vol.-%, preferably less than 4 vol.-%, more preferably 0.01 to 3 vol.-%, and most preferably 0.1 to 2 vol.-%.
[295] Aspect 34. The method according to any one of the preceding aspects, wherein the obtained carbon black comprises recovered carbon black and new carbon black.
[296] Aspect 35. The method according to any one of the preceding aspects, wherein the residence time is the time between the of the injection of the particulate carbon- containing feedstock in the reactor and the time of the quench of product mixture and is 150 ms to 4 sec, preferably 200 ms to 3 sec, more preferably 250 ms to 2 sec, and most preferably 250 ms to 1 sec.
[297] Aspect 36. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is injected into the reactor with a mass flow of 2 to 50 kg/h per 130 L of the reaction volume of the reactor, preferably 5 to 40 kg/h per 130 L of the reaction volume of the reactor, more preferably 8 to 30 kg/h per 130 L of the reaction volume of the reactor, and most preferably 10 to 20 kg/h per 130 L of the reaction volume of the reactor. [298] Aspect 37. The method according to any one of the preceding aspects, wherein the reaction volume of the reactor is the volume of the reactor between the position of the injection of the particulate carbon-containing feedstock and the position of the quench.
[299] Aspect 38. The method according to any one of aspects 2 to 37, wherein the deagglomeration is done by (i) accelerating the particulate carbon-containing feedstock, and/or (ii) applying shear forces, preferably using an extruder.
[300] Aspect 39. The method according to any one of aspects 2 to 38, wherein the deagglomeration is carried out in (i) a feeding and mixing device, preferably comprising a nozzle, and/or (ii) an extruder.
[301] Aspect 40. The method according to any one of aspects 2 to 39, wherein the deagglomeration is carried out in (i) a feeding and mixing device comprising a Laval nozzle.
[302] Aspect 41. The method according to any one of aspects 2 to 40, wherein the deagglomeration is carried out by subjecting the particulate carbon-containing feedstock into a carrier gas jet.
[303] Aspect 42. The method according to any one of aspects 2 to 41 , wherein the deagglomeration is carried out in a feeding and mixing device for particles into a reactor comprising:
(i) a carrier gas passage extending through said feeding and mixing device,
(ii) at least one carrier gas inlet, which is in fluid communication with said carrier gas passage,
(iii) at least one particle inlet,
(iv) a mixing chamber which is in fluid communication with said at least one particle inlet and with said carrier gas inlet,
(v) a deagglomeration conduit which is in fluid communication with said mixing chamber,
(vi) at least one outlet for said carrier gas entraining particles which have been fed into said mixing chamber, wherein said at least one outlet for is in fluid communication with said deagglomeration conduit, and
(vii) means for accelerating and injecting a stream of carrier gas into said mixing chamber.
[304] Aspect 43. The method according to any one of aspects 2 to 42, wherein the deagglomerated particulate carbon-containing feedstock is injected into the reactor at a pressure from 0.5 bar to 2 bar, preferably 0.7 bar to 1.5 bar, more preferably 0.8 to 1.3 bar, and most preferably 0.8 to 1.2 bar.
[305] Aspect 44. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is comprised in a carrier gas, preferably the carrier gas is nitrogen.
[306] Aspect 45. The method according to any one of aspects 2 to 44, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas, preferably the carrier gas is nitrogen.
[307] Aspect 46. The method according to any one of aspects 2 to 45, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas and the carrier gas further comprises H2O and/or additives.
[308] Aspect 47. The method according to any one of aspects 2 to 46, wherein the deagglomerated particulate carbon-containing feedstock is comprised in a carrier gas and the carrier gas further comprises H2O in an amount of 1 to 10 vol.-%, based on the total volume of the carrier gas comprising the the deagglomerated particulate carbon- containing feedstock.
[309] Aspect 48. The method according to any one of the preceding aspects, wherein said particulate carbon-containing feedstock is injected in said entrained flow reactor by a plurality of inlets, preferably by a plurality of injection lances.
[310] Aspect 49. The method according to any one of the preceding aspects, wherein the particulate carbon-containing feedstock is classified, preferably sieved, before the particulate carbon-containing feedstock is injected into the reactor, preferably (a) the sieve has openings of 2000 pm, 1000 pm, 500 pm, 250 pm, or 125 pm, preferably 500 pm, 250 pm, or 125 pm, and/or (b) the sieve has openings with a size that restrains particles with a size of more than 2000 pm, more than 1000 pm, more than 500 pm, more than 250 pm, or more than 125 pm, preferably more than 500 pm, more than 250 pm, or more than 125 pm.
[311] Aspect 50. The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 1 mm, more preferably less than 500 pm, and most preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017). [312] Aspect 51. The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 500 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[313] Aspect 52. The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 1 mm, wherein the particle size is measured according to ASTM D 1511- 12 (2017).
[314] Aspect 53. The method according to any one of the preceding aspects, wherein at least 70 wt.-%, preferably at least 80 wt.-%, more preferably at least 90 wt.-%, most preferably at least 98 wt.-%, of the particulate carbon-containing feedstock has a particle size of less than 2 mm, preferably less than 250 pm, wherein the particle size is measured according to ASTM D 1511-12 (2017).
[315] Aspect 54. The method according to any one of the preceding aspects, wherein the method is for producing carbon black from a particulate carbon-containing feedstock and a fluid carbon-containing feedstock in entrained flow reactor having a flow passage along a central longitudinal axis of the reactor, wherein the hot gas flow has a temperature of at least 800 °C.
[316] Aspect 55. The method according to any one of the preceding aspects, wherein the mass ratio of particulate carbon-containing feedstock to fluid carbon-containing feedstock 0.5:1 to 1 :0.05, preferably 1:1 to 1:0.1, more preferably 1.1:1 to 1 :0.1, and most preferably 1.2:1 to 1:0.2.
[317] Aspect 56. The method according to any one of the preceding aspects, wherein the hot gas flow has a temperature of at least 800 °C, such as at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, or at least 1600 °C.
[318] Aspect 57. Carbon black, comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h. [319] Aspect 58. Carbon black, preferably comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m2/g, preferably a STSA surface area of 116 to 145 m2/g, more preferably a STSA surface area of 117 to 140 m2/g, and most preferably a STSA surface area of 120 to 135 m2/g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21.
[320] Aspect 59. The carbon black according to aspects 57 or 58, wherein the carbon black has a BET surface area of 120 to 160 m2/g, preferably a BET surface area of 125 to 155 m2/g, more preferably a BET surface area of 127 to 150 m2/g, and most preferably a BET surface area of 130 to 145 m2/g, wherein the BET surface area is measured according to ASTM D6556-21 .
[321] Aspect 60. The carbon black according to aspects 57 to 59, wherein the carbon black has a compressed oil absorption number of 100 to 150 mL/100 g, preferably a compressed oil absorption number of 110 to 145 mL/100 g, more preferably a compressed oil absorption number of 115 to 140 mL/100 g, and most preferably a compressed oil absorption number of 117 to 135 mL/100 g, wherein the compressed oil absorption number is measured according to ASTM D3493-20 using paraffinic oil.
[322] Aspect 61. The carbon black according to aspects 57to 60, wherein the carbon black has volatiles of 1 .0 to 4.5 wt.-%, preferably volatiles of 1.3 to 4.0 wt.-%, more preferably volatiles of 1.5 to 3.5 wt.-%, and most preferably volatiles of 1.7 to 3.0 wt.-%, wherein the volatiles are measured at 950 °C for 7 min as described in the specification.
[323] Aspect 62. The carbon black according to aspects 57to 61 , wherein the carbon black has an iodine adsorption of 150 to 300 mg/g, preferably 160 to 280, more preferably 180 to 270 mg/g, and most preferably 190 to 260 mg/g, wherein the Iodine adsorption number is measured according to ASTM D1510-21.
[324] Aspect 63. The carbon black according to aspects 57to 62, wherein the carbon black has the ash content is at least 3 wt.-%, preferably 5 wt.-%, and most preferably 10 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[325] Aspect 64. The carbon black according to aspects 57to 63, wherein the carbon black has an ash content of 3 to 25 wt.-%, preferably 5 to 20 wt.-%, and most preferably 8 to 18 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[326] Aspect 65. The carbon black according to aspects 57to 64, wherein the carbon black has a volume resistivity of less than 7.9- 105 Q cm, preferably less than 1.0-105 Q cm, more preferably less than 1.0- 104 Q cm, and most preferably less than 1.0-104 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
[327] Aspect 66. The carbon black according to aspects 57to 65, wherein the carbon black has resistivity of 10.0 Q cm to 7.9- 105 Q cm, preferably 1.0 102 Q cm to 1.0-105 Q cm, more preferably 2.0 102 Q cm to 5.0 104 Q cm, and most preferably
2.0' 102 Q- a volume cm to 1.0- 104 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
[328] Aspect 67. A composition comprising
(A) an elastomeric polymer material, and
(B) carbon black according to any one of aspects 1 to 66.
[329] Aspect 68. The composition of aspect 67, wherein the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[330] Aspect 69. A rubber article comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
[331] Aspect 70. The rubber article according to aspect 69, wherein the rubber article has an abrasion of less than 110 mm3, preferably less than 106 mm3, more preferably 50 to 105 mm3, and most preferably 90 to 105 mm3, as measured at 23 °C DIN ISO 4649:2014-03, 10 N.
[332] Aspect 71. The rubber article according to any one of aspects 69 or 70, wherein the rubber article comprises carbon black as defined in any one of aspects 57 to 68. [333] Aspect 72. The rubber article according to any one of aspects 69 to 71 , wherein the rubber article has a tensile strength of 20.0 to 40.0 Mpa, preferably 23.0 to 35 Mpa, more preferably 24.0 to 32 Mpa, and most preferably 24.0 to 30 Mpa, as measured according to ISO 37 - 2012, S2.
[334] Aspect 73. The rubber article according to any one of aspects 69 to 72, wherein the rubber article has an elongation at break of more than 520 %, preferably 530 to 700 %, more preferably 550 to 650 %, even more preferably 570 to 630 %, and most preferably 580 to 620 %, as measured according to ISO 37 - 2012, S2.
[335] Aspect 74. The rubber article according to any one of aspects 69 to 73, wherein the rubber article has a Mooney viscosity of 40 to 80 Me, more preferably 50 to 76 Me, even more preferably 57 to 75 Me, and most preferably 65 to 74 Me, as measured according to ISO 289-1:2015.
[336] Aspect 75. Use of a particulate carbon-containing feedstock and a fluid carbon- containing feedstock for the manufacturing of carbon black in an entrained flow reactor.
[337] Aspect 76. The use of aspect 75, wherein the use of a particulate carbon- containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor is defined as in any one of the previous aspects.
EXAMPLES
[338] Example 1 : Rubber granulate and liquid carbon-containing feedstock
[339] The experiments of Example 1 are performed on a small-scale furnace reactor as shown in FIG. 1. The furnace reactor comprises a combustion chamber, a choke and a tunnel. The choke reduces the diameter to 114 mm. Downstream of the choke a reactor tunnel is mounted having a diameter of 875 mm and has a length of 7820 mm.
[340] Rubber granulate was injected to the furnace reactor in the choke via a feeding and mixing device having a nozzle similar as shown in FIG. 2. The reaction volume of the reactor was about 4900 liters. The reaction volume was the volume of the reactor between the position of the injection of the feedstock to the position of the quench. The feeding and mixing device deagglomerated the rubber granulate by accelerating the particulate carbon-containing feedstock. However, the present invention is not limited to the feeding and mixing device according to FIG. 1 so that other feeding and mixing device can be used. In addition to the rubber granulate, a liquid carbon-containing feedstock was introduced in the choke of the reactor downstream the feeding and mixing device. The distance between the injection of the particulate carbon-containing feedstock and the injection of the fluid carbon-containing feedstock was 125 mm.
[341] The liquid carbon-containing feedstock was a coal tar distillate “RuBrohstoff Typ K” from Rain Carbon Germany GmbH, Castrop-Rauxel. [342] The rubber granulate, i.e. Gummigranulat 0,0 - 0,5 mm (Article Nr. 005GLIM), used in the experiments was obtained from ESTATO Umweltservice GmbH (ESTATO), Germany. The rubber granulate was derived from old tires and comprises synthetic rubber (SBR) and natural rubber (NR). The particle fractions are shown in table 1. Moreover, the weight average particle diameter (Dw50) was about 400 pm, measured according to ASTM D 1511-12 (2017). However, it is also possible to use different particulate carbon-containing feedstocks such as plastic granulates or biomass-based granulates.
[343] Table 1 : Particle distribution of rubber granulate from ESTATO, measured according to ASTM D 1511-12 (2017).
[344] The characterization of the rubber granulate from ESTATO is shown in table 2.
[345] Table 2: Characterization of the rubber granulate from ESTATO.
[346] In addition, the rubber granulate comprises several metals in a mass fraction of about 300 ppm. For instance, zinc, and iron.
[347] CHNS content determination by means of elemental analyser
The carbon mass fraction, hydrogen fraction mass, nitrogen mass fraction and sulfur mass fraction are measured using an elemental analyser with thermal conductivity and infrared detector. The analyser is a device for the fully automatic and quantitative analysis of the above elements. The combustion tube is brought to a temperature of 1100 °C and the reduction tube to 850 °C. First, a blank measurement is conducted. The carbon peak area should have a value < 50, the hydrogen peak area a value < 300, the nitrogen peak area a value < 50 and the sulphur peak area a value < 350. Otherwise, the individual adsorption columns are heated and then empty measurements are started again. The blank measurement is calculated as follows: wherein b is the blank measurement, bj is the peak area of the respective blank measurement, n is the number of blank measurements, i is an index of 1 to n.
[348] The compensation of the blank measurement is calculated as follows, acomp. = a - b, wherein acomp. Is the compensated peak area, a is the measured peak area, and b is the blank measurement value.
[349] Next, the daily factor is measured. For this purpose, 3 mg of sulphanilamide and 3 mg of low-level standard (e.g. carbon black standard) are weighed into each of 8 tin capsules. After weighing out the respective sample, it is placed in the capsule press, overlaid with helium for 35 s and then cold-sealed. Subtracting the blank value, the known theoretical element concentration of the standard samples is put in relation to the actually calculated element concentration. This results in the daily factor, which must be between 0.9 - 1.1. If this is not the case, these measurements should be repeated with newly opened standards. Otherwise, a new calibration must be carried out according to the manufacturer's instructions.
[350] The daily factor is calculated as follows, > Ctheor
Cact Wherein f is the daily factor, Ctheor. is the theoretical factor, cact. is the actual calculated elemental concentration.
[351] Then, 8 tin capsules each containing 5 mg ±1 mg of the desired measured component, such as rubber granulate, are weighed. After weighing the respective samples, they are placed in the capsule press, covered with helium for 35 s and then cold welded.
[352] For the measurement, the combustion tube is enriched with O2. The elements C, H, N and S burn to form CO2, H2O, NOx, SO2 and SO3. Halogen bound in the sample reacts to form volatile halogen compounds. In addition, there are WO3 granules in the combustion tube that provide further O2 as a catalyst, prevent the formation of nonvolatile sulphates and bind interfering alkali and alkaline earth elements. The carrier gas stream is fed into the reduction tube with Cu filling. Nitrogen oxides (NOx) are completely reduced to N2 at the copper contact. SO3 is reduced to SO2. Volatile halogen compounds are bound to the silver wool.
[353] N2 is not adsorbed and enters the thermal conductivity detector as the first measuring component, CO2, H2O and SO2 are adsorbed on the respective adsorption columns.
[354] Then, one after the other, the adsorption columns are brought to desorption temperature, so that CO2, then H2O as carrier gas enters the thermal conductivity detector and SO2 enters the infrared detector. Depending on the type and concentration of the components, the detector delivers an electrical signal which is digitised and integrated. The measurement signal is recorded as a function of time and displayed as an integral value. The absolute element content of the sample is calculated from this integral value of the individual measurement peaks and the calibration factors.
[355] The element concentration is calculated according to the following equation a*100 *f c = - w wherein c is the elemental concentration (in %), a is the absolute element content (in mg), f is the daily factor, and w is the actual amount of the sample.
[356] O content determination by means of elemental analyser
Depending on the oxygen concentration, an electrical signal is transmitted from the thermal conductivity detector (WLD) of the elemental analyser to a micro controller and then displayed as an integral value. From the integral value of the measurement peaks and the calibration factor, the absolute element content of the sample is concluded. The pyrolysis tube is heated to a temperature of 1050°C. First, a blank measurement is conducted. The oxygen peak area should have a maximum value of 200. If the blank value is not below 200, CO adsorption column should be heated up (260 °C, CO desorption 150 °C). After the blank values have been successfully measured, the mean value of the blank value areas is calculated.
[357] The blank measurement is calculated as follows: wherein b is the blank measurement, bj is the peak area of the respective blank measurement, n is the number of blank measurements, i is an index of 1 to n.
[358] Next, the daily factor is measured. For this purpose, 3 mg of acetanilide are weighed into each of 8 tin capsules. After weighing out the respective sample, it is placed in the capsule press, overlaid with helium for 35 s and then cold-sealed. Subtracting the blank value, the known theoretical element concentration of the standard samples is put in relation to the actually calculated element concentration. This results in the daily factor, which must be between 0.9 - 1.1. If this is not the case, these measurements should be repeated with newly opened standards. Otherwise, a new calibration must be carried out according to the manufacturer's instructions.
[359] The daily factor is calculated as follows, f > Ctheor Cact wherein f is the daily factor, Ctheor. is the theoretical factor, cact. is the actual calculated elemental concentration.
[360] Then, 8 tin capsules each containing 5 mg ±1 mg of the desired measured component, such as rubber granulate, are weighed. After weighing the respective samples, they are placed in the capsule press, covered with helium for 35 s and then cold welded. The samples are then measured.
[361] The element concentration is calculated according to the following equation a*100*f c = - w wherein c is the elemental concentration (in %), a is the absolute element content (in mg), f is the daily factor, and w is the actual amount of the sample.
[362] Reaction conditions in the furnace reactor [363] The reactions conditions for the manufacturing of the carbon black are shown in table 3. As mentioned above, the temperature (absolute temperature) can also be measured with a pyrometer.
[364] Table 3: Reaction conditions in the furnace reactor. 1273.15 K and 101325 Pa
2The k value is defined by the ratio of stoichiometric O2 amount that is necessary for the complete stoichiometric combustion of the fuel to the supplied O2 amount [365] After the injection of the rubber granulate feedstock and the liquid carbon- containing feedstock, the reaction is quenched with water and the obtained carbon black was dried and milled to obtain a volume average particle size of about 5 pm. The obtained carbon black (see Experiments A1 and A2) were compared to carbon black N660, and a recovered carbon blacks rCB. rCB was recovered from a pyrolysis of rubber granulates.
[366] The temperature in the combustion chamber, i.e. the temperature of the hot combustion gases, was controlled by the temperature of the combustion air temperature upstream combustion chamber (i.e. temperature of the oxygen-containing gas). The k value was controlled by the natural gas flow (fuel) into the combustion chamber.
[367] Since the rubber granulate is used in an entrained flow reactor process, it is possible to not only recover carbon black but also to produce new carbon black derived from the rubber in addition, new carbon black is obtained from the liquid carbon- containing feedstock. Thus, the ash content is lower compared to recovered carbon black from REOIL. The ash content can be measured according to ASTM D 1506-15 at 550 °C, 16 h.
[368] The carbon black obtained in each experiment was characterized and the results as shown in table 4.
[369] Table 4: Characterization of the obtained carbon black
4N660 carbon black obtained from liquid feedstock materials, Orion Engineered Carbons GmbH.
5rCB 2 recovered carbon black, REOIL S.P. Z O.O.
Aggregate size distribution was measured as described below.
7Specific surface was measured as described below.
8Volatiles were measured at 950 °C for 7 min as described below.
9BET surface area was measured according to ASTM D6556-21.
10STSA surface area was measured according to ASTM D6556-21.
11lodine adsorption number was measured according to ASTM D1510-21.
12pH-value is measured according to ASTM D1512-21 , Test Method B - Sonic Slurry.
13Compressed oil absorption number (COAN) was measured according to ASTM D3493- 20 (using paraffinic oil).
14Oil absorption (OAN) number was measured according to ASTM D2414-19 (using paraffinic oil).
15The ash content was determined according to ASTM D 1506-15 at 550 °C, 16 h.
[370] The aggregate size distribution
All test results are analyzed using CPS disc centrifuge DC24000UHR from CPS Instruments, Inc, Prairieville, LA 70769. Furthermore, an energy meter, capable of measuring the energy consumption (in kWh) of the probe-type sonicator is used. The energy meter is inserted between an electrical plug of the laboratory and the plug of the power supply cord of the sonicator. The actual energy consumption is indicated on a digital display. Moreover, probe-type sonicator with a nominal power of 200 W or more is used. Sonoplus 2220, equipped with Sonotrode UW 2200 and horn DH 13 G can be used and is available from BANDELIN electronic GmbH & Co. KG, HeinrichstraBe 3-4, D- 12207 Berlin. The norm ISO 15825:2016 can be used as a basis for the following procedure.
[371] First, a dispersion solution is prepared by adding 1 g of Tergitol-Type NP-40 (CAS-No. 9016-45-9) and 600 ml of demineralized water into a 1 I graduated flask. Stir until the surfactant has dissolved and fill up to the mark with demineralized water.
[372] Then, two spin fluids are prepared with 8 wt.% sucrose and 24 wt.% sucrose (CAS-No. 57-50-1). 8% w/w solution: Weigh 4.0 g of sucrose and 46.0 g of demineralized water into a glass beaker and stirred until complete dissolution. 24% w/w solution: Weigh 12.0 g of sucrose and 38.0 g of demineralized water into a glass beaker and stirred until complete dissolution.
[373] Moreover, a SiO2 standard can be used. The SiO2 standard is available from CPS Instruments, Inc. 41452 Bess Rd., Prairieville, LA 70769, USA. Standard particle diameter should be chosen in the range of the expected dmOde of the samples. SiO2 standards in the 150 nm diameter range can be used.
[374] A standard reference black ITRB2 (Industry Tint Reference Black) was used for the calibration. ITRB2 can be obtained from Balentine Enterprises Inc. 1410 South Cedar Street (STE 20) Borger, Texas 79007 USA.
[375] Calibration using a standard carbon black ITRB2
[376] A calibration carbon black sample was prepared by weighting 5 mg of ITRB2 into a titration glass and add 25 ml of the dispersion solution. If pelletized carbon black shall be tested, carefully crush and homogenize approximately 250 mg of the sample in an agate mortar. For carbon black in powder form, this step is not needed. Transfer the titration glass into a cooling bath and subject to ultrasonic radiation for 10 min at 100 % amplitude and 80 % pulse. If the standard carbon black is entirely dispersed, it will give a mean Stokes diameter (“mean”) of 95 nm ± 4 nm for ITRB2.
[377] Carbon black sample to be measured
[378] A carbon black sample was prepared by weighting 5 mg of carbon black into a titration glass and add 25 ml of the dispersion solution. If pelletized carbon black shall be tested, carefully crush and homogenize approximately 250 mg of the sample in an agate mortar. For carbon black in powder form, this step is not needed. Transfer the titration glass into a cooling bath and subject to ultrasonic radiation for 10 min at 100 % amplitude and 80 % pulse. [379] Set-up of equipment and test parameters
[380] Sample parameters: Maximum diameter: 2 pm, minimum diameter: 0.005 pm, particle refractive index: 1.98 g/mL, particle absorption: 0.85 K, non-sphericity factor: 1.
[381] Calibration standard parameters: Peak diameter: 0.145 pm, half height peak width: 0.011 pm, particle density: 2.05 g/ml.
[382] Fluid parameters: Fluid density: 1.051 g/ml, Fluid refractive index: 1.3612, Fluid viscosity: 1.28 cps.
[383] Runtime options: Calibration method: external. Samples per calibration: 1. Initial fill volume: 18 ml. Injected viscosity: 1 cps. Injected density: 1 g/ml. Injection timing: spacebar. Baseline drift display: no. Extra software noise filter: no. Speed ramping: fixed speed. Correct for non-Stokes: no. Force baseline: yes.
[384] Initiation of procedure
[385] For carbon blacks with a specific surface area smaller than 20 m2/g, a rotational speed of 10 000 rpm is selected. For carbon blacks with a specific surface area of 20 m2/g or higher, the rotational speed shall be 24 000 rpm. Prepare the gradient of the spin fluid by following the next steps. Using a syringe, take up from the bottle with the 24 wt.% sucrose 1 .8 ml and inject this into the disc spinning at analysis speed. Next, the syringe is filled with only 1 .6 ml of the 24 wt.% sucrose solution and filled up with 0.2 ml of the 8 % solution.
Continue by following the scheme below:
1 ,8 ml of the 24 % solution 0 ml of the 8 % solution; 1 ,6 ml of the 24 % solution 0,2 ml of the 8 % solution; 1 ,4 ml of the 24 % solution 0,4 ml of the 8 % solution; 1 ,2 ml of the 24 % solution 0,6 ml of the 8 % solution; 1 ,0 ml of the 24 % solution 0,8 ml of the 8 % solution; 0,8 ml of the 24 % solution 1 ,0 ml of the 8 % solution; 0,6 ml of the 24 % solution 1 ,2 ml of the 8 % solution; 0,4 ml of the 24 % solution 1 ,4 ml of the 8 % solution; 0,2 ml of the 24 % solution 1 ,6 ml of the 8 % solution; 0 ml of the 24 % solution 1 ,8 ml of the 8 % solution.
At the end, add a layer of 0,5 ml of dodecane above the spin fluid in the centrifuge. Let the system thermally stabilize for 45 min, then start the first measurement. When prompted, inject 100 pl of the appropriate calibration standard. When prompted, inject 100 pl of the sample to be tested. The weight (= volume) distribution is calculated from the raw data curve. For carbon blacks with a surface area of 20 m2/g and higher, restrict the evaluation to max. 1 pm particle size. For carbon blacks with a surface area below 20 m2/g, choose 3 pm for this parameter.
[386] Specific surface
The specific surface of a tested sample is available from aggregate size distribution measurement using CPS as described above.
[387] Volatiles at 950°C
Volatiles at 950°C were measured using a thermogravimetric instrument of Fa. LEGO Instrumente GmbH (TGA-701) according to the following protocol: Pans were dried at 650°C for 30 min. The carbon black materials were stored in a desiccator equipped with desiccant prior to measurements. Baked-out pans were loaded in the instrument, fared and filled with between 0.5 g to 10 g carbon black material. Then, the oven of the TGA instrument loaded with the sample-filled pans was gradually heated up to 105°C by automated software control and the samples were dried until a constant mass was achieved. Subsequently, the pans were closed by lids, the oven was purged with nitrogen
(99.9 vol% grade) and heated up to 950°C. The oven temperature was kept at 950°C for
7 min. The content of volatiles at 950°C was calculated using the following equation:
[388] Results
It has been surprisingly found, that it is possible to use particulate carbon-containing feedstock and a liquid carbon-containing feedstock in an entrained flow reactor process. As can be seen from table 4, the obtained carbon has desirable properties compared to standard carbon black products obtained from liquid carbon-containing feedstocks and obtained from only particulate carbon-containing feedstock.
[389] Moreover, the aggregate size is lower compared to aggregate size of the recovered carbon blacks and the carbon black obtained only from the particulate carbon black feedstock. Surprisingly, the STSA surface area of Experiment B4 is higher compared to the carbon black of Experiment B3 obtained only from the particulate carbon black feedstock. Furthermore, the ash content of Experiment B4 is significantly lower compared to Experiment B3 obtained only from the particulate carbon black feedstock.
[390] Example 2: Rubber compositions
[391] The preparation of the rubber compositions and the in rubber tests are described below. A general process for the production of rubber compounds and their vulcanisates is described in the book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994.
[392] Preparation of vulcanizable rubber compositions
The rubber compositions are mentioned in table 5. The ESBR Buna SB 1500 was introduced to a laboratory mixer GK1.5E with an intermeshing PES5-rotor geometry made by Harburg Freudenberger and milled for 30 seconds at a chamber temperature of 40°C, a fill factor of 0.66 and a rotor speed of 45 rpm. Subsequently, half of the carbon black volume, ZnO and stearic acid were added under milling. After 90 seconds the other half of the carbon black volume and the 6PPD were added. After further 120 secs the ram was lifted and cleaned, and the batch was mixed for another 90 seconds. The total mixing time in the internal mixer was 5 minutes and afterwards the batch was dropped on an open mill for cooling down and additional distributive mixing. The batch temperature did not exceed 160°C in the first mixing step. The batch was allowed to rest overnight.
[393] During the second and final mixing step the sulfur and the accelerator (Vulkacit CZ/EG-Z) were then added in the indicated amounts to the master batch obtained from the first mixing step. The resulting mixture was milled in the GK1.5E mixer with a chamber temperature of 40°C and a fill factor of 0.64 for 2 minutes. The rotor speed was 30 rpm and it was secured that the batch temperature did not exceed 110 °C. Finally, the mixture was dropped from the internal mixer processed again on an open mill. The two roll laboratory mill from company Troester was set to a roll temperature of 40 °C. The front roll was operated at 23 rpm and the back roll at 34 rpm. The compound was cut three times left and three times right and the 6 times rolled, turned 90 ° and transferred again through the nip.
[394] Curing of the vulcanizable rubber compositions
The prepared vulcanizable rubber compositions according to Table 5 were subjected to curing in a cure press at a temperature of 165°C. The applied pressure was 130 bar. The cure kinetics were analyzed with a moving die rheometer Alpha Technologies Rheometer MDR 2000 at 165 °C and then the cure times were defined for the different compounds to assure optimized cure state. The vulcanizable rubber compositions were cured in the cure press for a time, which allowed to reach the maximum torque in the respective measured torque-time curve to ensure full cure. The cure times were between 11 and 15 minutes (C1: 15 min, C2: 12 min, C3: 5 min, C4: 11 min). Respective vulcanizate sheets having a thickness of around 2 mm are provided.
[395] Measuring the volume resistivity
The volume resistivity of the carbon blacks was determined in the thus prepared and cured emulsion-styrene-butadiene rubber (ESBR) containing 50 phr carbon black based on DIN EN ISO 3915:2022 using a resistance meter with a high Ohm measurement electrode and a high Ohm shield chamber (Milli-TO3 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany) with the guard ring electrode FE-50 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany) and the shield chamber TOM 300-2 (H.-P. Fischer Elektronik GmbH & Co. Industrie- und Labortechnik KG (Germany)).
[396] The specimens were punched out of the respective vulcanizate sheets (having a thickness of around 2 mm) using a circular blade having a diameter of 82 mm. The respective specimens having a diameter of 82 mm and a thickness of around 2 mm were degreased with isopropyl alcohol. The thickness of the respective specimen was measured to an accuracy of 0.01 mm at several points using a thickness gauge having a diameter of 30 mm. The average sample thickness was used to calculate the volume resistivity.
[397] The respective specimens were coated with conductive silver (LS200N Silberleitlack (Hans Wolbring GmbH (Germany)) according to the dimensions of the FE-50 electrode. An area with a diameter of around 8.0 cm on the underside of the respective specimen was coated with the conductive silver (see Fig. 6 (b)). An area with a diameter of around 5.0 cm on the top of the respective specimen was coated with the conductive silver, an area of around 0.5 cm around the coated area (diameter of around 5.0 cm) was left blank and a further area of around 1 cm around the blank area was coated again with the conductive silver (see Fig. 6 (a)). After the conductive silver was applied, the respective specimen was dried for 24 hours. The respective specimen was placed in the measuring electrode device with the underside of the specimen facing downwards and volume resistivity of the respective specimen was measured at 100 V. The volume resistivities of the respective carbon blacks are displayed in Table 6.
[398] Table 5: The rubber compositions using different carbon blacks as noted in table 6.
16Rubber ESBR, Buna SB 1500, Resinex Deutschland GmbH
17Carbon black: N660, N550, rCB or of Experiments A3 to 5 and A8 to A10 (see table 6) 186PPD, VULKANOX 4020/LG, Brenntag GmbH
19Sulfur, MAHLSCHWEFEL 80/90° unbeblt, Avokal GmbH
20CBS, VULKACIT CZ/EG-C, Lanxess N.V.
21ZnO, ZNO RS RAL 844 C, Norkem B.V. 22Stearic Acid, Palmera B 1804, Caldic Deutschland GmbH
[399] The rubber composition as mentioned in table 5 can be used to measure the volume resistivity of the respective carbon black.
[400] The properties of the specimens were measured and the results are indicated in table 6. The results are compared with carbon blacks produced by using a liquid carbon black feedstock (N660 and N550), a recovered carbon blacks rCB and a particulate carbon black feedstock (C4).
[401] Table 6: Properties of the produced carbon black in rubber compositions.
23Tensile Strength was measured ISO 37 - 2012, S2.
24Elongation at Break was measured ISO 37 - 2012, S2.
25Abrasion was measured at 23 °C DIN ISO 4649:2014-03, 10 N.
26Modulus 300% was measured ISO 37 - 2012, S2.
27Tear Resistance GRAVES was measured DIN ISO 34-1 :2016-09, method B, variant (b).
28Hardness, Shore A was measured according to DIN 53 505
29Viscosity ML (1+4) 100 °C was measured according to ISO 289-1 :2015.
30MDR 165 °C - TC95% was determined as the time to 95% cure from the measurement of the torque as a function of the time at the used curing temperature of 165°C. A moving die rheometer Alpha Technologies Rheometer MDR 2000 was used.
31Complex modulus E* complex modulus E* were measured according to DIN 53 513 in strain-controlled mode (1 ± 0.5 mm) or force-controlled mode (50 N ± 25 N) on a cylindrical specimen (10 mm in height and 10 mm in diameter) at 60°C with a frequency of 16 Hz.
32Volume Resistivity of the carbon blacks was determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
[402] Results
The example reveal that the carbon blacks produced according to the invention can be beneficially used in a rubber composition. The produced carbon blacks have improved tensile strength, tear and abrasion resistance, modulus 300% and electrical conductivity.
[403] It will be appreciated that various modifications can be made, and that many changes can be made in the preferred embodiments without departing from the principle of the invention.

Claims

1. A method for producing carbon black in an entrained flow reactor comprising:
(a) providing a hot gas flow,
(b) providing a particulate carbon-containing feedstock,
(c) injecting the particulate carbon-containing feedstock in the hot gas flow to form carbon black, and
(d) injecting a fluid carbon-containing feedstock in the hot gas flow to form carbon black.
2. The method according to claim 1 , wherein the mass flow rate of the fluid carbon-containing feedstock is 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1 ,000 kg/h, most preferably 30 to 500 kg/h, and/or the mass flow rate of the particulate carbon-containing feedstock is 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1 ,000 kg/h, most preferably 30 to 500 kg/h, and/or steam is subjected into the hot gas flow, preferably at a mass flow of 10 to 2,000 kg/h, more preferably at a mass flow of 20 to 1 ,000 kg/h, most preferably 30 to 500 kg/h.
3. The method according to claims 1 or 2, wherein the mass ratio of particulate carbon-containing feedstock to fluid carbon-containing feedstock 0.5:1 to 1 :0.05, preferably 1 :1 to 1 :0.1 , more preferably 1.1 :1 to 1 :0.1 , and most preferably 1.2:1 to 1 :0.2, and/or wherein the hot gas flow has a temperature of at least 800 °C, such as at least 900 °C, at least 1000 °C, at least 1100 °C, at least 1200 °C, at least 1300 °C, at least 1400 °C, at least 1500 °C, or at least 1600 °C.
4. The method according to any one of the preceding claims, wherein the particulate carbon-containing feedstock comprises rubber granulate, plastic granulate, and/or biomass-based granulate, preferably the particulate carbon-containing feedstock comprises rubber granulate, wherein the rubber granulate comprising carbon black.
5. The method according to any one of the preceding claims, wherein the fluid carbon-containing feedstock comprises or is a liquid carbon-containing feedstock, and/or wherein the fluid carbon-containing feedstock comprises aliphatic or aromatic, saturated or unsaturated hydrocarbons or mixtures thereof, coal tar distillates, residual oils which are produced during the catalytic cracking of petroleum fractions, residual oils which are produced during olefin production through cracking of naphtha or gas oil, natural gas, sustainable carbon black feedstock, renewable carbon black feedstock and/or a bio-based feedstock, pyrolysis oil, or a mixture or combination of any of the foregoing.
6. The method according to any one of the preceding claims, wherein
(A) the entrained flow reactor is a furnace reactor and the particulate carbon- containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means, and/or
(B) the entrained flow reactor is a furnace reactor and the fluid carbon-containing feedstock is injected in the combustion chamber, in the choke and/or in a tunnel comprising quenching means, and/or
(C) the particulate carbon-containing feedstock is injected downstream of the injection of the fluid carbon-containing feedstock, and/or
(D) the particulate carbon-containing feedstock is injected upstream of the injection of the fluid carbon-containing feedstock, and/or
(E) the particulate carbon-containing feedstock is injected at the same position of the injection of the fluid carbon-containing feedstock.
7. The method according to any one of the preceding claims, wherein the particle size distribution of the particulate carbon-containing feedstock is measured according to ASTM D 1511-12 (2017) and
(a) Sieve No. 10 retains 1 to 0 to 10 wt.-%, preferably 1 to 8 wt.-%, more preferably 1 to 5 wt.-%, and most preferably 1 to 3 wt.-% of the particulate carbon-containing feedstock, and/or
(b) Sieve No. 18 retains 1 to 25 wt.-%, preferably 2 to 20 wt.-%, more preferably 4 to 15 wt.-%, and most preferably 5 to 12 wt.-% of the particulate carbon-containing feedstock, and/or (c) Sieve No. 35 retains 10 to 80 wt.-%, preferably 15 to 70 wt.-%, more preferably 20 to 60 wt.-%, and most preferably 25 to 55 wt.-% of the particulate carbon-containing feedstock, and/or
(d) Sieve No. 60 retains 5 to 70 wt.-%, preferably 10 to 60 wt.-%, more preferably 15 to 50 wt.-%, and most preferably 20 to 45 wt.-% of the particulate carbon-containing feedstock, and/or
(e) Sieve No. 120 retains 1 to 80 wt.-%, preferably 7 to 70 wt.-%, more preferably 5 to 60 wt.-%, and most preferably 7 to 50 wt.-% of the particulate carbon-containing feedstock, and/or
(f) Bottom receive pan comprises less than 4 wt.-%, preferably less than 3 wt.-%, more preferably 0 to 2 wt.-%, and most preferably 0.01 to 1 wt.-% of the particulate carbon-containing feedstock.
8. The method according to any one of the preceding claims, wherein the particulate carbon-containing feedstock is classified, preferably sieved, before the particulate carbon-containing feedstock is injected into the reactor, preferably (a) the sieve has openings of 2000 pm, 1000 pm, 500 pm, 250 pm, or 125 pm, preferably 500 pm, 250 pm, or 125 pm, and/or (b) the sieve has openings with a size that restrains particles with a size of more than 2000 pm, more than 1000 pm, more than 500 pm, more than 250 pm, or more than 125 pm, preferably more than 500 pm, more than 250 pm, or more than 125 pm.
9. The method according to any one of the preceding claims, wherein
(A) step (b) further comprises deagglomerating the particulate carbon- containing feedstock and in step (c), the deagglomerated particulate carbon- containing feedstock is injected in the hot gas flow to form carbon black, wherein the deagglomeration is done by (i) accelerating the particulate carbon-containing feedstock, and/or (ii) applying shear forces, preferably using an extruder; and/or
(B) step (b) further comprises deagglomerating the particulate carbon- containing feedstock and in step (c), the deagglomerated particulate carbon- containing feedstock is injected in the hot gas flow to form carbon black, wherein the deagglomeration is done by (i) accelerating the particulate carbon-containing feedstock using a carrier gas and the carrier gas is nitrogen.
10. Carbon black, comprising at least 1.5 wt.-% ash, based on the total weight of the carbon black, having a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
11 . Carbon black, preferably comprising at least 1 .5 wt.-% ash, based on the total weight of the carbon black, having an aggregate size weight mode of 10 to 60 nm, preferably 15 to 55 nm, more preferably 18 to 50 nm, even more preferably 20 to 45 nm, and most preferably 25 to 40 nm, and a STSA surface area of 112 to 150 m2/g, preferably a STSA surface area of 116 to 145 m2/g, more preferably a STSA surface area of 117 to 140 m2/g, and most preferably a STSA surface area of 120 to 135 m2/g, wherein the aggregate size distribution is measured as described in the specification, ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h and the STSA surface area is measured according to ASTM D6556-21 .
12. The carbon black according to claims 10 or 11 , wherein the carbon black has
(A) a BET surface area of 120 to 160 m2/g, preferably a BET surface area of 125 to 155 m2/g, more preferably a BET surface area of 127 to 150 m2/g, and most preferably a BET surface area of 130 to 145 m2/g, wherein the BET surface area is measured according to ASTM D6556-21 , and/or
(B) a compressed oil absorption number of 100 to 150 mL/100 g, preferably a compressed oil absorption number of 110 to 145 mL/100 g, more preferably a compressed oil absorption number of 115 to 140 mL/100 g, and most preferably a compressed oil absorption number of 117 to 135 mL/100 g, wherein the compressed oil absorption number is measured according to ASTM D3493-20 using paraffinic oil, and/or
(C) volatiles of 1.0 to 4.5 wt.-%, preferably volatiles of 1.3 to 4.0 wt.-%, more preferably volatiles of 1.5 to 3.5 wt.-%, and most preferably volatiles of 1.7 to 3.0 wt.-%, wherein the volatiles are measured at 950 °C for 7 min as described in the specification, and/or (D) an iodine adsorption of 150 to 300 mg/g, preferably 160 to 280, more preferably 180 to 270 mg/g, and most preferably 190 to 260 mg/g, wherein the Iodine adsorption number is measured according to ASTM D1510-21, and/or
(E) the ash content is at least 3 wt.-%, preferably 5 wt.-%, and most preferably 10 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h, and/or
(F) the ash content is 3 to 25 wt.-%, preferably 5 to 20 wt.-%, and most preferably 8 to 18 wt.-%, wherein the wt.-% is based on the total weight of the carbon black, and wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h, and/or
(G) a volume resistivity of less than 7.9- 105 Q cm, preferably less than 1.0-105 Q cm, more preferably less than 1.0- 104 Q cm, and most preferably less than 1.0-104 Q cm, as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, and/or
(H) a volume resistivity of 10.0-Q cm to 7.9- 105 Q cm, preferably 1.0 102 Q cm to 1.0-105 Q cm, more preferably 2.0 102 Q cm to 5.0 104 Q cm, and most preferably 2.0- 102 Q cm to 1.0- 104 Q cm, as determined in an emulsion-styrene- butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description.
13. A composition comprising
(A) an elastomeric polymer material, and
(B) carbon black obtained according to any one of claims 1 to 9 and/or carbon black according to claims 10 to 12.
14. A rubber article comprising carbon black, preferably the carbon black comprises at least 1.5 wt.-% ash determined according to ASTM D 1506-15 at 550 °C, 16 h, wherein the carbon black has a volume resistivity of less than 7.9- 105 Q cm as determined in an emulsion-styrene-butadiene rubber (ESBR) containing 50 phr of the carbon black as described in the description, wherein the ash content is determined according to ASTM D 1506-15 at 550 °C, 16 h.
15. Use of a particulate carbon-containing feedstock and a fluid carbon-containing feedstock for the manufacturing of carbon black in an entrained flow reactor.
PCT/EP2025/068641 2024-07-05 2025-07-01 Carbon black from particulate feedstock materials and fluid carbon-containing feedstock Pending WO2026008603A1 (en)

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