WO2019165582A1 - Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition - Google Patents

Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition Download PDF

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Publication number
WO2019165582A1
WO2019165582A1 PCT/CN2018/077461 CN2018077461W WO2019165582A1 WO 2019165582 A1 WO2019165582 A1 WO 2019165582A1 CN 2018077461 W CN2018077461 W CN 2018077461W WO 2019165582 A1 WO2019165582 A1 WO 2019165582A1
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Prior art keywords
composition
acid
weight
composition according
iron
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PCT/CN2018/077461
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French (fr)
Inventor
Fengyang LI
Yan Xu
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Kemira Asia Co Ltd
Kemira Oyj
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Kemira Asia Co Ltd
Kemira Oyj
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Application filed by Kemira Asia Co Ltd, Kemira Oyj filed Critical Kemira Asia Co Ltd
Priority to EP18907545.0A priority Critical patent/EP3759050B1/en
Priority to BR112020014560-2A priority patent/BR112020014560B1/en
Priority to PCT/CN2018/077461 priority patent/WO2019165582A1/en
Priority to FIEP18907545.0T priority patent/FI3759050T3/en
Priority to RU2020127916A priority patent/RU2757475C1/en
Priority to CA3088453A priority patent/CA3088453C/en
Priority to CN201880090326.4A priority patent/CN111770895A/en
Priority to ES18907545T priority patent/ES2942584T3/en
Priority to US16/963,272 priority patent/US11498859B2/en
Publication of WO2019165582A1 publication Critical patent/WO2019165582A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/04—Ferrous oxide [FeO]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the invention relates to a composition and a method for stabilizing iron compounds in an aqueous environment.
  • the invention also relates to the use of said composition as iron dispersant or iron chelating agent.
  • Dispersant for iron which may disperse iron compound, is typically employed in water treatment industry. The most suitable dispersants can be chosen on the grounds of the requirements. Different dispersants have effect on different chemicals, such as iron, manganese, calcium carbonate or calcium sulfate.
  • diethylenetriamine penta methylene phosphonic acid
  • DTPMPA diethylenetriamine penta
  • a high phosphorus content of DTPMPA may have negative impact on environment.
  • the pulp properties such as brightness result and viscosity are measured.
  • the residual hydrogen peroxide after bleaching is informative.
  • Phosphonates are typically used as efficient chelating agents in those steps.
  • the effectiveness of phosphonates might be insufficient, and the hydrogen peroxide consumption cannot be reduced remarkably.
  • iron and manganese may be deactivated by complexing them with monomeric or polymeric complexing agents. This is done to prevent these metal ions from catalyzing the decomposition of hydrogen peroxide.
  • DTPMPA is also used as iron chelating agent in pulp and paper industry.
  • An object of this invention is to minimise or even totally eliminate the disadvantages existing in the prior art.
  • An object of the invention is to provide a stable composition for stabilizing iron compounds in an aqueous environment. Especially, an object of the invention is to provide a composition suitable for use as iron dispersant in water treatment for controlling, preventing and/or reducing the formation of iron deposit.
  • a typical composition according to the invention for stabilizing iron compounds in an aqueous environment comprises
  • Figure 1 shows the results obtained in Example 1 of the present application.
  • the composition for stabilizing iron compounds in an aqueous environment is typically used for controlling and preventing the formation of iron deposit and/or dissolving iron deposits in an aqueous system, especially in water treatment processes. Further, the composition according to the present invention is also used for stabilizing hydrogen peroxide in pulp bleaching process, since adding the composition according to the present invention in oxidation could efficiently prevent hydrogen peroxide degradation due to iron catalysis. Therefore, iron chelation by using the composition according to the present invention in pulp bleaching may decrease H 2 O 2 consumption.
  • Typical method according to the present invention for stabilizing iron compound in an aqueous system comprises adding the composition according to the present invention to an aqueous system.
  • composition according to the present invention provides synergetic effect and so the composition according to the present invention is able to provide several advantages simultaneously compared to the commonly used DTPMPA, such as high temperature tolerance and high efficiency even at low dosage amounts of the composition.
  • the composition according to the present invention provides cost effective iron dispersant composition with high efficiency for use as water treatment systems or iron chelating agent composition for use in pulp bleaching processes.
  • the composition according to the present invention has also remarkably less phosphorus content than the commonly used DTPMPA, and so the present invention also reduces negative impact on environment.
  • Iron dispersant composition refers in this description to a composition to prevent or reducing fouling of iron oxides/hydroxides in process equipment in water treatment processes.
  • the mechanism of the iron dispersant may be based on dispersing of the iron deposits, or preventing iron compounds to settle, precipitate or agglomerate.
  • Iron dispersant according to the present invention is not only effective for iron, but also have efficiency in calcium carbonate deposit control. Therefore, especially in water treatment industry, it provides multi-function on deposit control.
  • peroxide consumption speed in bleaching may be decreased greatly by using the composition according to the present invention as iron chelating agent.
  • composition according to the present invention in oxidation, it could efficiently stabilize hydrogen peroxide and prevent hydrogen peroxide degradation due to iron catalyzing.
  • the composition according to the invention comprises at least one monomeric or polymeric phosphonate comprising at least one phosphonic acid group.
  • the phosphonate may also comprise any suitable salt (s) thereof.
  • the phosphonate may be selected from hydroxyethylene diphosphonic acid (HEDP) , amino tris (methylenephosphonic acid) (ATMP) , 2-phosphonobutane-1, 2, 4, -tricarboxylic acid (PBTC) , diethylenetriamine penta (methylene phosphonic acid) (DTPMPA) , hexamethylenediamine tetramethylene phosphonic acid (BHMTPMPA) , polyamino polyether methylene phosphonic acid (PAPEMP) or any combination of them.
  • HEDP hydroxyethylene diphosphonic acid
  • ATMP amino tris
  • PBTC 2-phosphonobutane-1, 2, 4, -tricarboxylic acid
  • DTPMPA diethylenetriamine penta
  • BHMTPMPA hexamethylened
  • the phosphonate is polyamino polyether methylene phosphonic acid (PAPEMP) due to its good chelation characteristics.
  • PAPEMP polyamino polyether methylene phosphonic acid
  • the total amount of the monomeric or polymeric phosphonate (s) may be in the range of 10 -90 weight-%, preferably 60 -90 weight-%, and more preferably 70 -80 weight-%, calculated from the total weight of the constituents in the composition, as dry.
  • the composition of the invention further comprises a polycarboxylic acid or its salt (s) for providing high temperature tolerant performance and good dispersant performance.
  • the polycarboxylic acid is selected from poly (meth) acrylic acid, or a copolymer of (meth) acrylic acid and maleic acid, itaconic acid or lactic acid.
  • the polycarboxylic acid is poly (meth) acrylic acid.
  • the polycarboxylic acid may have a weight average molecular weight MW less than 5000 g/mol, preferably in a range of 1000 -5000 g/mol. The molecular weights are determined by using gel permeation chromatography (GPC) .
  • the amount of the polycarboxylic acid is in the range of 5 -80 weight-%, preferably 20 -50 weight-%and more preferably 20 -30 weight-%, calculated from the total weight of the constituents in the composition, as dry.
  • the composition according to the present invention comprises at least one corrosion inhibitor comprising amino groups.
  • the amount of the corrosion inhibitor may be in the range of 2 -10 weight-%, calculated from the total weight of the active constituents in the composition, as dry.
  • the corrosion, the inhibitor is selected from diethyl hydroxylamine (DEHA) , octadecylamine, hexadecylamine, cyclohexylamine, methoxypropylamine, other fatty alcohol amines, or any combination of them.
  • the corrosion inhibitor is diethyl hydroxylamine (DEHA) due to its excellent iron corrosion inhibition performance and efficiency even at small dosage amount.
  • the composition according to the present invention comprises also polycitric acid or a copolymer of citric acid with polyols or glycerol.
  • the composition comprises polycitric acid, which is obtained by polymerization using citric acid as raw material. Therefore, the composition according to the invention includes two kinds of carboxylic acid, i.e. polycitric acid and polycarboxylic acid or its salt (s) as defined above.
  • the amount of polycitric acid or a copolymer of citric acid with polyols or glycerol may be in the range of 1 -15 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry.
  • the amount of polycitric acid or a copolymer of citric acid with polyols or glycerol is less than 15 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry. In some preferred embodiments, the amount of polycitric acid or a copolymer of citric acid with polyols or glycerol is in the range of 5 -10 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry, when optimising the effect and total costs of the composition.
  • the composition according to the present invention comprises polycitric acid in an amount of 1 -15 weight-%or 5 -10 weight-%, calculated from the total weight of the constituents in the composition, as dry, and this amount is not included to the amount of the polycarboxylic acid or its salt (s) defined separately in the present application.
  • a copolymer of citric acid with polyols or glycerol may be poly (citric acid-glycol) ester, poly (citric acid-ethylene glycol) ester, poly (citric acid-propylene glycol) ester, poly (citric acid-glycerol) ester or poly (citric acid-triethanolamine) ester prepared by subjecting a raw material selected from the group consisting of a mixture of citric acid and glycol, a mixture of citric acid and ethylene glycol, a mixture of citric acid and propylene glycol, a mixture of citric acid and glycerol and a mixture of citric acid and triethanolamine to condensation polymerization.
  • the synthetization of polycitric acid or a copolymer of citric acid with polyols or glycerol applicable to be used in the composition of the present invention is described e.g. in the patent publication CN104030461.
  • polycitric acid may be synthesized by condensation polymerization by using citric acid as raw material.
  • Tetrahydrofuran is used as a solvent, wherein the solvent and citric acid are added in a reactor and the solution is obtained by mixing.
  • Concentrated sulfuric acid is used as a catalyst and added to the solution of the solvent and citric acid and heated to the reflux state to perform condensation polymerization for 4 -24 h to obtain the reaction solution.
  • the reaction solution is further neutralized, transferred to extraction and rotary evaporation steps.
  • Organic solvent is removed by rotary evaporation and the obtained polycitric acid is dark brown slime having substantially 100 %content of polycitric acid.
  • the composition comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA, and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry. More preferably, the composition comprises 60 -90 weight-%or 70 -80 weight-%of PAPEMP in combination with poly (meth) acrylic acid, DEHA and polycitric acid.
  • the composition comprises 60 -90 weight-%or 70 -80 weight-%of PAPEMP, 20 -50 weight-%or 20 -30 weight-%of poly (meth) acrylic acid, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.
  • the composition according to the invention tolerates high temperatures, i.e. it is effective also in high temperatures, and so it may be added to the industrial aqueous systems having temperature of the aqueous phase higher than 100 °C.
  • the temperature of the aqueous phase in the aqueous system, where the composition is dosed may be over 100 °C, or over 120 °C, or even over 200 °C.
  • the composition is added to an aqueous system.
  • the composition according to the invention may be used in desired dose, depending on the nature of the iron compounds to be stabilized and/or other conditions in the aqueous system where it is used.
  • the composition may be added in an amount of 5 -100 ppm, preferably 5 -70 ppm, and more preferably 5 -50 ppm to an aqueous system.
  • composition according to the present invention may be used at any process stage of suitable application, where there is a risk for iron deposit formation. According to one embodiment of the invention, the composition according to the present invention may be used for reducing or eliminating the formation of iron deposit in the water treatment systems.
  • composition according to the present invention may be used at bleaching process for stabilizing hydrogen peroxide. It may be added to the pulp prior to bleaching stages.
  • Solution A cationic CaCl 2 liquid, Ca 2+ concentration is 300 ppm;
  • Solution B Selected scale inhibitor is diluted according to a certain concentration
  • Solution C 5 g (FeSO 4 ⁇ 7H 2 O) /l, fresh;
  • Solution D 500 ppm Na 2 B 4 O 2 liquid.
  • Blank test 50 ml solution A + 12 ml deionized water +1 ml solution C + 37 ml solution D.
  • Scale inhibition test sample 50 ml solution A + 12 ml deionized water + selected solution B + 1 ml solution C + 37 ml solution D, pH about 8.7.
  • the bottles are stirred for 15 min. Then, the bottles are put into the water bath and heated for 20 h. The bottles are taken out from the water bath and stood for 1 hour. The solution from each bottle is filtered and Ca 2+ concentration in the filtrates are determined using inductively coupled plasma (ICP) instrument. Fe content is analyzed from the supernatant by using ICP.
  • ICP inductively coupled plasma
  • X1 Iron concentration (mg/l) in blank sample before treatment
  • X2 Iron concentration (mg/l) after treatment
  • the performance evaluation is carried out by using the following scale inhibitors: the composition according to the present invention (ND) , commercial iron dispersant products Kemguard 5876 (Acrylic acid terpolymer, sodium salt) and Kemguard 5042 (Polycarboxylate, sodium salt) from Kemira, PBTC, BHMPTMPA, HPMA, POCA and DTPMPA as solution B.
  • the ND composition according to the present invention comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.
  • the performance of the dispersant compositions is tested at two different temperatures 50 °C and 90 °C. Also, two different concentrations, namely 10 ppm and 20 ppm, are tested. The results are shown in Table 1 and Table 2.
  • Example 2 The effect of stabilizer on alkaline H 2 O 2 bleaching
  • the peroxide stability test is used to determine the peroxide content in a water solution containing specific amount of Fe ions and monitor the peroxide decomposition rate.
  • the test is performed in Erlenmeyer flasks.
  • the dilution water is heated to 90 °C before adding 11 ppm Fe ions and the 100 ppm stabilizer composition to be tested.
  • the pH is adjusted with NaOH to pH 10 before adding peroxide (initial peroxide content 3 g/l) .
  • the residual peroxide (g/l) in the sample is titrated after 5, 10, 15, 30, 60 and 90 min.
  • the following stabilizers are used in the tests: the composition according to the present invention (ND) , commercial stabilizer products Fennobrite FB590 from Kemira and CF2025 from Kemira, which comprise phosphonates.
  • the ND composition according to the present invention comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.

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  • Engineering & Computer Science (AREA)
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  • Hydrology & Water Resources (AREA)
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Abstract

Composition for stabilizing iron compounds in an aqueous environment, which comprises a polycarboxylic acid or its salt (s), at least one monomeric or polymeric phosphonate comprising at least one phosphonic acid group, or its salt (s), at least one corrosion inhibitor comprising amino groups, and 1 -15 weight-%of polycitric acid or a copolymer of citric acid with polyols or glycerol, calculated as active ingredient from the total weight of the constituents in the composition, as dry.

Description

COMPOSITION AND METHOD FOR STABILIZING IRON COMPOUNDS IN AN AQUEOUS ENVIRONMENT, AND USE OF COMPOSITION TECHNICAL FIELD
The invention relates to a composition and a method for stabilizing iron compounds in an aqueous environment. The invention also relates to the use of said composition as iron dispersant or iron chelating agent.
BACKGROUND ART
Iron is always existing in water and it could form deposit in the equipment and pipeline. The deposited iron may result in corrosion of metal pipes or equipment. Therefore, deposition of iron is a problem especially in water treatment industry. Dispersant for iron, which may disperse iron compound, is typically employed in water treatment industry. The most suitable dispersants can be chosen on the grounds of the requirements. Different dispersants have effect on different chemicals, such as iron, manganese, calcium carbonate or calcium sulfate. For water treatment industry, diethylenetriamine penta (methylene phosphonic acid) (DTPMPA) is one of typically used dispersants. However, a high phosphorus content of DTPMPA may have negative impact on environment.
In pulp and paper manufacturing, iron coming from wood and from the process equipment is a problem in pulp bleaching. Hydrogen peroxide is widely used as a bleaching agent for different mechanical and chemi-mechanical pulps. Using hydrogen peroxide it is possible to improve pulp brightness. Iron and manganese are the main catalysts for the decomposition of hydrogen peroxide. The decomposition of hydrogen peroxide results in deterioration of fibers, lower whiteness and brightness, and increased consumption of hydrogen peroxide. To reach the required ISO brightness, higher peroxide consumption is needed when iron exists in bleaching process. Therefore, specific chelating steps are included into the chemical pulp process, usually prior to bleaching stages, for eliminating effects of iron and manganese. To detect the efficiency of the deactivation of the metals, usually the pulp properties such as brightness result and viscosity are measured. Also, the residual hydrogen peroxide after bleaching is informative.  Phosphonates are typically used as efficient chelating agents in those steps. However, the effectiveness of phosphonates might be insufficient, and the hydrogen peroxide consumption cannot be reduced remarkably. In the case of mechanical pulp, iron and manganese may be deactivated by complexing them with monomeric or polymeric complexing agents. This is done to prevent these metal ions from catalyzing the decomposition of hydrogen peroxide. Commonly, DTPMPA is also used as iron chelating agent in pulp and paper industry.
However, there is a constant need for cost effective and environmentally benign compositions for stabilizing iron compounds in water treatment and/or in pulp bleaching processes.
SUMMARY OF INVENTION
An object of this invention is to minimise or even totally eliminate the disadvantages existing in the prior art.
An object of the invention is to provide a stable composition for stabilizing iron compounds in an aqueous environment. Especially, an object of the invention is to provide a composition suitable for use as iron dispersant in water treatment for controlling, preventing and/or reducing the formation of iron deposit.
Further, it is an object of the present invention to provide a composition suitable for use as iron chelating agent in pulp bleaching for stabilizing hydrogen peroxide and so providing a cost-effective method for preventing hydrogen peroxide degradation due to iron catalysis in bleaching processes.
In order to achieve among others the objects presented above, the invention is characterized by what is presented in the characterizing parts of the enclosed independent claims.
Some preferred embodiments of the invention will be described in the other dependent claims.
The embodiments and advantages mentioned in this text relate, where  applicable, both to the composition, the method as well as to the uses according to the invention, even though it is not always specifically mentioned.
A typical composition according to the invention for stabilizing iron compounds in an aqueous environment comprises
-a polycarboxylic acid or its salt (s) ,
-at least one monomeric or polymeric phosphonate comprising at least one phosphonic acid group, or its salt (s) ,
-at least one corrosion inhibitor comprising amino groups, and
-1 -15 weight-%of polycitric acid or a copolymer of citric acid with polyols or glycerol, calculated as active ingredient from the total weight of the constituents in the composition, as dry.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows the results obtained in Example 1 of the present application.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, the composition for stabilizing iron compounds in an aqueous environment is typically used for controlling and preventing the formation of iron deposit and/or dissolving iron deposits in an aqueous system, especially in water treatment processes. Further, the composition according to the present invention is also used for stabilizing hydrogen peroxide in pulp bleaching process, since adding the composition according to the present invention in oxidation could efficiently prevent hydrogen peroxide degradation due to iron catalysis. Therefore, iron chelation by using the composition according to the present invention in pulp bleaching may decrease H 2O 2 consumption.
Typical method according to the present invention for stabilizing iron compound in an aqueous system comprises adding the composition according to the present invention to an aqueous system.
Now, it has been surprisingly found that polycitric acid or a copolymer of citric acid with polyols or glycerol in combination with monomeric or polymeric  phosphonate, such as PAPEMP, provides synergetic effect and so the composition according to the present invention is able to provide several advantages simultaneously compared to the commonly used DTPMPA, such as high temperature tolerance and high efficiency even at low dosage amounts of the composition. Thus, the composition according to the present invention provides cost effective iron dispersant composition with high efficiency for use as water treatment systems or iron chelating agent composition for use in pulp bleaching processes. The composition according to the present invention has also remarkably less phosphorus content than the commonly used DTPMPA, and so the present invention also reduces negative impact on environment.
Iron dispersant composition refers in this description to a composition to prevent or reducing fouling of iron oxides/hydroxides in process equipment in water treatment processes. The mechanism of the iron dispersant may be based on dispersing of the iron deposits, or preventing iron compounds to settle, precipitate or agglomerate. Iron dispersant according to the present invention is not only effective for iron, but also have efficiency in calcium carbonate deposit control. Therefore, especially in water treatment industry, it provides multi-function on deposit control.
In paper and pulp industry, peroxide consumption speed in bleaching may be decreased greatly by using the composition according to the present invention as iron chelating agent. When adding composition according to the present invention in oxidation, it could efficiently stabilize hydrogen peroxide and prevent hydrogen peroxide degradation due to iron catalyzing.
The composition according to the invention comprises at least one monomeric or polymeric phosphonate comprising at least one phosphonic acid group. The phosphonate may also comprise any suitable salt (s) thereof. The phosphonate may be selected from hydroxyethylene diphosphonic acid (HEDP) , amino tris (methylenephosphonic acid) (ATMP) , 2-phosphonobutane-1, 2, 4, -tricarboxylic acid (PBTC) , diethylenetriamine penta (methylene phosphonic acid) (DTPMPA) , hexamethylenediamine tetramethylene phosphonic acid (BHMTPMPA) , polyamino polyether methylene phosphonic acid (PAPEMP) or any combination of them. According to one preferable embodiment, the phosphonate is polyamino  polyether methylene phosphonic acid (PAPEMP) due to its good chelation characteristics. The total amount of the monomeric or polymeric phosphonate (s) , such as PAPEMP, may be in the range of 10 -90 weight-%, preferably 60 -90 weight-%, and more preferably 70 -80 weight-%, calculated from the total weight of the constituents in the composition, as dry.
The composition of the invention further comprises a polycarboxylic acid or its salt (s) for providing high temperature tolerant performance and good dispersant performance. According to one embodiment of the invention, the polycarboxylic acid is selected from poly (meth) acrylic acid, or a copolymer of (meth) acrylic acid and maleic acid, itaconic acid or lactic acid. According to one preferred embodiment of the invention, the polycarboxylic acid is poly (meth) acrylic acid. The polycarboxylic acid may have a weight average molecular weight MW less than 5000 g/mol, preferably in a range of 1000 -5000 g/mol. The molecular weights are determined by using gel permeation chromatography (GPC) . According to one embodiment of the invention, the amount of the polycarboxylic acid is in the range of 5 -80 weight-%, preferably 20 -50 weight-%and more preferably 20 -30 weight-%, calculated from the total weight of the constituents in the composition, as dry.
Further, the composition according to the present invention comprises at least one corrosion inhibitor comprising amino groups. The amount of the corrosion inhibitor may be in the range of 2 -10 weight-%, calculated from the total weight of the active constituents in the composition, as dry. According to an embodiment of the invention the corrosion, the inhibitor is selected from diethyl hydroxylamine (DEHA) , octadecylamine, hexadecylamine, cyclohexylamine, methoxypropylamine, other fatty alcohol amines, or any combination of them. According to one preferred embodiment, the corrosion inhibitor is diethyl hydroxylamine (DEHA) due to its excellent iron corrosion inhibition performance and efficiency even at small dosage amount.
The composition according to the present invention comprises also polycitric acid or a copolymer of citric acid with polyols or glycerol. According to a preferred embodiment of the invention, the composition comprises polycitric acid, which is obtained by polymerization using citric acid as raw material. Therefore, the composition according to the invention includes two kinds of  carboxylic acid, i.e. polycitric acid and polycarboxylic acid or its salt (s) as defined above. The amount of polycitric acid or a copolymer of citric acid with polyols or glycerol may be in the range of 1 -15 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry. According to one preferred embodiment of the invention, the amount of polycitric acid or a copolymer of citric acid with polyols or glycerol is less than 15 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry. In some preferred embodiments, the amount of polycitric acid or a copolymer of citric acid with polyols or glycerol is in the range of 5 -10 weight-%, calculated as active ingredient from the total weight of the constituents in the composition, as dry, when optimising the effect and total costs of the composition. Preferably, the composition according to the present invention comprises polycitric acid in an amount of 1 -15 weight-%or 5 -10 weight-%, calculated from the total weight of the constituents in the composition, as dry, and this amount is not included to the amount of the polycarboxylic acid or its salt (s) defined separately in the present application.
According to an embodiment of the invention, a copolymer of citric acid with polyols or glycerol may be poly (citric acid-glycol) ester, poly (citric acid-ethylene glycol) ester, poly (citric acid-propylene glycol) ester, poly (citric acid-glycerol) ester or poly (citric acid-triethanolamine) ester prepared by subjecting a raw material selected from the group consisting of a mixture of citric acid and glycol, a mixture of citric acid and ethylene glycol, a mixture of citric acid and propylene glycol, a mixture of citric acid and glycerol and a mixture of citric acid and triethanolamine to condensation polymerization. The synthetization of polycitric acid or a copolymer of citric acid with polyols or glycerol applicable to be used in the composition of the present invention is described e.g. in the patent publication CN104030461.
As also disclosed in CN104030461, polycitric acid may be synthesized by condensation polymerization by using citric acid as raw material. Tetrahydrofuran is used as a solvent, wherein the solvent and citric acid are added in a reactor and the solution is obtained by mixing. Concentrated sulfuric acid is used as a catalyst and added to the solution of the solvent and citric acid and heated to the reflux state to perform condensation polymerization for 4 -24 h to obtain the reaction solution. The reaction  solution is further neutralized, transferred to extraction and rotary evaporation steps. Organic solvent is removed by rotary evaporation and the obtained polycitric acid is dark brown slime having substantially 100 %content of polycitric acid.
According to one preferred embodiment, the composition comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA, and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry. More preferably, the composition comprises 60 -90 weight-%or 70 -80 weight-%of PAPEMP in combination with poly (meth) acrylic acid, DEHA and polycitric acid. In one preferred embodiment, the composition comprises 60 -90 weight-%or 70 -80 weight-%of PAPEMP, 20 -50 weight-%or 20 -30 weight-%of poly (meth) acrylic acid, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.
The composition according to the invention tolerates high temperatures, i.e. it is effective also in high temperatures, and so it may be added to the industrial aqueous systems having temperature of the aqueous phase higher than 100 ℃. The temperature of the aqueous phase in the aqueous system, where the composition is dosed, may be over 100 ℃, or over 120 ℃, or even over 200 ℃.
According to the invention, the composition is added to an aqueous system. The composition according to the invention may be used in desired dose, depending on the nature of the iron compounds to be stabilized and/or other conditions in the aqueous system where it is used. For example, according to one embodiment of the invention the composition may be added in an amount of 5 -100 ppm, preferably 5 -70 ppm, and more preferably 5 -50 ppm to an aqueous system.
The composition according to the present invention may be used at any process stage of suitable application, where there is a risk for iron deposit formation. According to one embodiment of the invention, the composition according to the present invention may be used for reducing or eliminating the formation of iron deposit in the water treatment systems.
The composition according to the present invention may be used at bleaching process for stabilizing hydrogen peroxide. It may be added to the pulp prior to bleaching stages.
EXPERIMENTAL
Example 1: Iron dispersion performance evaluation in water
Solution A: cationic CaCl 2 liquid, Ca 2+ concentration is 300 ppm;
Solution B: Selected scale inhibitor is diluted according to a certain concentration;
Solution C: 5 g (FeSO 4·7H 2O) /l, fresh;
Solution D: 500 ppm Na 2B 4O 2 liquid.
Blank test: 50 ml solution A + 12 ml deionized water +1 ml solution C + 37 ml solution D.
Scale inhibition test sample: 50 ml solution A + 12 ml deionized water + selected solution B + 1 ml solution C + 37 ml solution D, pH about 8.7.
After all the chemicals of each sample are added into the bottle, the bottles are stirred for 15 min. Then, the bottles are put into the water bath and heated for 20 h. The bottles are taken out from the water bath and stood for 1 hour. The solution from each bottle is filtered and Ca 2+ concentration in the filtrates are determined using inductively coupled plasma (ICP) instrument. Fe content is analyzed from the supernatant by using ICP.
Iron dispersant capability calculation (%) :
Figure PCTCN2018077461-appb-000001
wherein
X1 is Iron concentration (mg/l) in blank sample before treatment,
X2 is Iron concentration (mg/l) after treatment,
10 is Iron preliminary concentration (mg/l) .
The performance evaluation is carried out by using the following scale inhibitors: the composition according to the present invention (ND) , commercial iron dispersant products Kemguard 5876 (Acrylic acid terpolymer, sodium salt) and Kemguard 5042 (Polycarboxylate, sodium salt) from Kemira, PBTC, BHMPTMPA, HPMA, POCA and DTPMPA as solution B. The ND composition according to the present invention comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.
The performance of the dispersant compositions is tested at two different temperatures 50 ℃ and 90 ℃. Also, two different concentrations, namely 10 ppm and 20 ppm, are tested. The results are shown in Table 1 and Table 2.
Table 1. The results of Iron dispersion performance at 50 ℃
Figure PCTCN2018077461-appb-000002
Table 2. The results of Iron dispersion performance at 90 ℃
Figure PCTCN2018077461-appb-000003
Figure PCTCN2018077461-appb-000004
From the experiment results, it can be seen that the ND material efficiency is much better than other compositions.
Example 2: The effect of stabilizer on alkaline H 2O 2 bleaching
The peroxide stability test is used to determine the peroxide content in a water solution containing specific amount of Fe ions and monitor the peroxide decomposition rate. The test is performed in Erlenmeyer flasks. The dilution water is heated to 90 ℃ before adding 11 ppm Fe ions and the 100 ppm stabilizer composition to be tested. The pH is adjusted with NaOH to pH 10 before adding peroxide (initial peroxide content 3 g/l) . The residual peroxide (g/l) in the sample is titrated after 5, 10, 15, 30, 60 and 90 min.
The following stabilizers are used in the tests: the composition according to the present invention (ND) , commercial stabilizer products Fennobrite FB590 from Kemira and CF2025 from Kemira, which comprise phosphonates. The ND composition according to the present invention comprises 5 -80 weight-%of poly (meth) acrylic acid, 10 -90 weight-%of PAPEMP, 2 -10 weight-%of DEHA and 1 -15 weight-%of polycitric acid, calculated from the total weight of the constituents in the composition, as dry.
The results are shown in Figure 1. Compared with FB 590 and CF 2025, the ND composition according to the present invention has better performance in H 2O 2 stabilizing.
Even if the invention was described with reference to what at present seems to be the most practical and preferred embodiments, it is appreciated that the invention shall not be limited to the embodiments described above, but the invention is intended to cover also different modifications and equivalent technical solutions within the scope of the enclosed claims.

Claims (14)

  1. Composition for stabilizing iron compounds in an aqueous environment, characterized in that the composition comprises
    - a polycarboxylic acid or its salt (s) ,
    - at least one monomeric or polymeric phosphonate comprising at least one phosphonic acid group, or its salt (s) ,
    - at least one corrosion inhibitor comprising amino groups, and
    - 1-15 weight-%of polycitric acid or a copolymer of citric with polyols or glycerol, calculated as active ingredient from the total weight of the constituents in the composition, as dry.
  2. The composition according to claim 1, characterized in that the polycarboxylic acid is selected from poly (meth) acrylic acid, or a copolymer of (meth) acrylic acid and maleic acid, itaconic acid or lactic acid, preferably a poly (meth) acrylic acid.
  3. The composition according to claim 1 or 2, characterized in that the polycarboxylic acid has a weight average molecular weight MW less than 5000 g/mol, preferably in the range of 1000-5000 g/mol, determined by using gel permeation chromatography (GPC) .
  4. The composition according to any of the preceding claims, characterized in that the phosphonate is selected from hydroxyethylene diphosphonic acid (HEDP) , amino tris (methylenephosphonic acid) (ATMP) , 2-phosphonobutane-1, 2, 4, -tricarboxylic acid (PBTC) , diethylenetriamine penta (methylene phosphonic acid) (DTPMPA) , hexamethylenediamine tetramethylene phosphonic acid (BHMTPMPA) , polyamino polyether methylene phosphonic acid (PAPEMP) or any combination of them, preferably polyamino polyether methylene phosphonic acid (PAPEMP) .
  5. The composition according to any of the preceding claims, characterized in that the corrosion inhibitor is selected from diethyl hydroxylamine (DEHA) , octadecylamine, hexadecylamine, cyclohexylamine, methoxypropylamine, other fatty alcohol amines or any combination of them, preferably diethyl hydroxylamine (DEHA) .
  6. The composition according to any of the preceding claims, characterized in that the amount of the polycarboxylic acid is in the range of 5-80 weight-%, preferably 20-50 weight-%and more preferably 20-30 weight-%, calculated from the total weight of the constituents in the composition, as dry.
  7. The composition according to any of the preceding claims, characterized in that the amount of the monomeric or polymeric phosphonate (s) is in the range of 10-90 weight-%, preferably 60-90 weight-%and more preferably 70-80 weight-%, calculated from the total weight of the constituents in the composition, as dry.
  8. The composition according to any of the preceding claims, characterized in that the amount of the corrosion inhibitor is in the range of 2-10 weight-%, calculated from the total weight of the constituents in the composition, as dry.
  9. Use of composition according to any of preceding claims 1 to 8 for stabilizing iron compounds in an aqueous environment.
  10. Use of composition according to claim 9, characterized in that the aqueous system is the water treatment process and the composition is used as iron dispersant for controlling and preventing the formation of iron deposit and/or dissolving iron deposits in an aqueous system.
  11. Use of composition according to claim 9, characterized in that the composition is used as iron chelating agent for stabilizing hydrogen peroxide in pulp bleaching process.
  12. A method for stabilizing iron compounds in an aqueous system, characterized in that the method comprises adding the composition according to any of claims 1 to 8 to an aqueous system.
  13. The method according to claim 12, characterized in that the composition is added in an amount of 5-100 ppm, preferably 5-70 ppm, and more preferably 5-50 ppm.
  14. The method according to claim 12 or 13, characterized in that the aqueous system is water treatment system or pulp bleaching process.
PCT/CN2018/077461 2018-02-27 2018-02-27 Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition Ceased WO2019165582A1 (en)

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EP18907545.0A EP3759050B1 (en) 2018-02-27 2018-02-27 Method for stabilizing iron compounds in an aqueous environment
BR112020014560-2A BR112020014560B1 (en) 2018-02-27 METHOD FOR STABILIZING IRON COMPOUNDS IN AN AQUEOUS ENVIRONMENT
PCT/CN2018/077461 WO2019165582A1 (en) 2018-02-27 2018-02-27 Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition
FIEP18907545.0T FI3759050T3 (en) 2018-02-27 2018-02-27 Method for stabilizing iron compounds in an aqueous environment
RU2020127916A RU2757475C1 (en) 2018-02-27 2018-02-27 Composition and method for stabilizing iron compounds in an aqueous medium and application of the composition
CA3088453A CA3088453C (en) 2018-02-27 2018-02-27 Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition
CN201880090326.4A CN111770895A (en) 2018-02-27 2018-02-27 Compositions and methods for stabilizing iron compounds in aqueous environments and uses of the compositions
ES18907545T ES2942584T3 (en) 2018-02-27 2018-02-27 Method for stabilizing iron compounds in an aqueous environment
US16/963,272 US11498859B2 (en) 2018-02-27 2018-02-27 Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition

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CN113388456B (en) * 2021-06-08 2023-04-07 安徽省复和利泰节能环保科技有限公司 Medium-high pressure boiler anti-corrosion and scale-inhibiting cleaning agent and preparation method thereof

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CA3088453A1 (en) 2019-09-06
US11498859B2 (en) 2022-11-15
RU2757475C1 (en) 2021-10-18
EP3759050A4 (en) 2021-10-06
CA3088453C (en) 2024-01-02
EP3759050A1 (en) 2021-01-06
EP3759050B1 (en) 2023-02-15
FI3759050T3 (en) 2023-05-08
ES2942584T3 (en) 2023-06-02
BR112020014560A2 (en) 2020-12-08
US20200354248A1 (en) 2020-11-12

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