WO2022164868A1 - Process for making heavy grade base oil products - Google Patents
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- WO2022164868A1 WO2022164868A1 PCT/US2022/013855 US2022013855W WO2022164868A1 WO 2022164868 A1 WO2022164868 A1 WO 2022164868A1 US 2022013855 W US2022013855 W US 2022013855W WO 2022164868 A1 WO2022164868 A1 WO 2022164868A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/02—Specified values of viscosity or viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/308—Gravity, density, e.g. API
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/015—Distillation range
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/017—Specific gravity or density
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
Definitions
- Group III base oils and finished motor oils has usually required the use of expensive and supply-limited viscosity index improvers such as polyalphaolefins, or other expensive processing techniques, such as the use of gas-to-liquid (GTL) feedstocks or, e.g., through multihydrocracking processing of mineral oils.
- GTL gas-to-liquid
- the production of Group III base oils also generally requires high quality feedstock(s) and processing at high conversion to meet VI targets at the expense of product yield.
- a comparatively inexpensive and suitable feedstock, and a simplified process for making such products remains to be developed and commercialized.
- a first process according to the invention comprises making a base oil by providing an atmospheric resid feedstock, optionally combined with a conventional base oil feedstock, as a base oil feedstream; contacting the base oil feedstream with a hydrocracking catalyst under hydrocracking conditions to form a hydrocracked product; separating the hydrocracked product into a gaseous fraction and a liquid fraction; contacting the liquid fraction with a hydrodewaxing catalyst under hydroisomerization conditions, to produce a dewaxed product; and, optionally, contacting the dewaxed product with a hydrofinishing catalyst under hydrofinishing conditions to produce a hydrofinished dewaxed product.
- the modified base oil process comprises combining an atmospheric resid feedstock and a base oil feedstock to form a base oil feedstream; contacting the base oil feedstream with a hydrocracking catalyst under hydrocracking conditions to form a hydrocracked product; separating the hydrocracked product into at least a gaseous fraction and a liquid fraction; contacting the liquid fraction with a hydrodewaxing catalyst under hydroisomerization conditions, to produce a dewaxed product; and, optionally, contacting the dewaxed product with a hydrofinishing catalyst under hydrofinishing conditions to produce a hydrofinished dewaxed product.
- the invention further relates to a process for making a heavy base oil having a viscosity of at least about 13 cSt at 100°C by separating a base oil feedstream comprising an atmospheric resid feedstock, and, optionally, a base oil feedstock into a vacuum gas oil having a front end cut point of about 700°F or greater and a back end cut point of about 900°F or less to form a medium vacuum gas oil MVGO fraction and a heavy vacuum gas oil HVGO; contacting the HVGO fraction with a hydrocracking catalyst under hydrocracking conditions to form a hydrocracked product; separating the hydrocracked product into a gaseous fraction and a liquid fraction; hydrodewaxing the liquid fraction to produce a dewaxed product; and optionally, hydrofinishing of the dewaxed product to produce a hydrofinished dewaxed product.
- the process produces at least one base oil product comprising a heavy base oil product having a viscosity of at least about 12.7 cSt, or at least about 13 cSt, or at least about 13.3 cSt at 100°C as compared with the use of a feedstock that does not include an atmospheric resid feedstock component.
- the invention further provides a process for making a base oil product from the medium vacuum gas oil MVGO fraction by contacting the MVGO fraction with a hydrocracking catalyst under hydrocracking conditions to form a hydrocracked product; separating the hydrocracked product into a gaseous fraction and a liquid fraction; contacting the liquid fraction with a dewaxing catalyst under hydroisomerization conditions, to produce a dewaxed product; and, optionally, contacting the dewaxed product with a hydrofinishing catalyst under hydrofinishing conditions to produce a hydrofinished dewaxed product; wherein, the dewaxed product and/or the hydrofinished dewaxed product has a viscosity index of 120 or greater after dewaxing.
- FIG. 1 is a general block diagram schematic illustration of a prior art process to make a base oil product.
- FIG. 2b is a general block diagram schematic illustration of an embodiment of a process to make a Group III/III+ base oil product using a medium vacuum gas oil (MVGO) fraction from an atmospheric resid and a heavy base oil product using a heavy vacuum gas oil (HVGO) residual fraction from an atmospheric resid or a blend of VGO and HVGO (VGO/HVGO) according to the invention.
- MVGO medium vacuum gas oil
- HVGO heavy vacuum gas oil
- API gravity refers to the gravity of a petroleum feedstock or product relative to water, as determined by ASTM D4052-11 or ASTM D1298, typically performed using commercially available petroleum analysis equipment.
- ISO-VG refers to the viscosity classification that is recommended for industrial applications, as defined by IS03448:1992.
- Viscosity index (VI) represents the temperature dependency of a lubricant, as determined by ASTM D2270-10(E2011) , typically performed using commercially available petroleum analysis equipment.
- VGO vacuum gas oil
- MVGO intermediate vacuum gas oil
- MVGO vacuum gas oil
- a vacuum gas oil, or a portion thereof including, e.g., wherein the MVGO is a vacuum gas oil, or a portion thereof, having a front end cut point of about 700°F or greater and a back end cut point of about 900°F or less.
- DAO Deasphalted oil
- solvent deasphalting in a refinery is described in J. Speight, Synthetic Fuels Handbook, ISBN 007149023X, 2008, pages 64, 85-85, and 121.
- “Treatment,” “treated,” “upgrade,” “upgrading” and “upgraded,” when used in conjunction with an oil feedstock, describes a feedstock that is being or has been subjected to hydroprocessing, or a resulting material or crude product, having a reduction in the molecular weight of the feedstock, a reduction in the boiling point range of the feedstock, a reduction in the concentration of asphaltenes, a reduction in the concentration of hydrocarbon free radicals, and/or a reduction in the quantity of impurities, such as sulfur, nitrogen, oxygen, halides, and metals.
- Solvent Dewaxing is a process of dewaxing by crystallization of paraffins at low temperatures and separation by filtration. Solvent dewaxing produces a dewaxed oil and slack wax. The dewaxed oil can be further hydrofinished to produce base oil.
- Hydroprocessing refers to a process in which a carbonaceous feedstock is brought into contact with hydrogen and a catalyst, at a higher temperature and pressure, for the purpose of removing undesirable impurities and/or converting the feedstock to a desired product. Examples of hydroprocessing processes include hydrocracking, hydrotreating, catalytic dewaxing, and hydrofinishing.
- Hydroracking refers to a process in which hydrogenation and dehydrogenation accompanies the cracking/fragmentation of hydrocarbons, e.g., converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatics and/or cycloparaffins (naphthenes) into non-cyclic branched paraffins.
- Hydrorotreating refers to a process that converts sulfur and/or nitrogen-containing hydrocarbon feeds into hydrocarbon products with reduced sulfur and/or nitrogen content, typically in conjunction with hydrocracking, and which generates hydrogen sulfide and/or ammonia (respectively) as byproducts.
- Catalytic dewaxing refers to a process in which normal paraffins are isomerized to their more branched counterparts in the presence of hydrogen and over a catalyst.
- Hydrofinishing refers to a process that is intended to improve the oxidation stability, UV stability, and appearance of the hydrofinished product by removing traces of aromatics, olefins, color bodies, and solvents.
- UV stability refers to the stability of the hydrocarbon being tested when exposed to UV light and oxygen. Instability is indicated when a visible precipitate forms, usually seen as Hoc or cloudiness, or a darker color develops upon exposure to ultraviolet light and air.
- a general description of hydrofinishing may be found in U.S. Patent Nos. 3,852,207 and 4,673,487.
- Hydrogen refers to hydrogen itself, and/or a compound or compounds that provide a source of hydrogen.
- Cut point refers to the temperature on a True Boiling Point (TBP) curve at which a predetermined degree of separation is reached.
- Group II B or “Group II B metal” refers to zinc (Zn), cadmium (Cd), mercury (Hg), and combinations thereof in any of elemental, compound, or ionic form.
- Group IVA or “Group IVA metal” refers to germanium (Ge), tin (Sn) or lead (Pb), and combinations thereof in any of elemental, compound, or ionic form.
- Group V metal refers to vanadium (V), niobium (Nb), tantalum (Ta), and combinations thereof in their elemental, compound, or ionic form.
- Group VIB or “Group VIB metal” refers to chromium (Cr), molybdenum (Mo), tungsten (W), and combinations thereof in any of elemental, compound, or ionic form.
- Group VIII or Group VIII metal refers to iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhenium (Rh), rhodium (Ro), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt), and combinations thereof in any of elemental, compound, or ionic form.
- Molecular sieve refers to a material having uniform pores of molecular dimensions within a framework structure, such that only certain molecules, depending on the type of molecular sieve, have access to the pore structure of the molecular sieve, while other molecules are excluded, e.g., due to molecular size and/or reactivity. Zeolites, crystalline aluminophosphates and crystalline silicoaluminophosphates are representative examples of molecular sieves.
- W220 and W600 refer to waxy medium and heavy Group II base oil product grades, with
- W220 referring to a waxy medium base oil product having a nominal viscosity of about 6 cSt at 100°C
- W600 referring to a waxy heavy base oil product having a nominal viscosity of about 12 cSt at 100°C.
- wax content in the range of 5-90 wt.% or 5-80 wt.% or 5-70 wt.% or 5-60 wt.% or 5-50 wt.% or 5-40 wt.% or 5-30 wt.% or 10-25 wt.%, or at least 5 wt.% or at least 10 wt.%, or at least 15 wt.%, or, optionally, less than the wax content of the atmospheric resid feedstock; nitrogen content of less than 2500 ppm or less than 2000 ppm or less than 1500 ppm or less than 1000 ppm, or in the range of 1000-5000 ppm, or 2000-5000 ppm, or 1000-4000 ppm, or 1000-3000 ppm; sulfur content of less than 40000 ppm, or less than 35000 ppm, or less than 30000 ppm, or less than 25000 ppm, or less than 20000 ppm, or less than 15000
- the base oil feedstock has a nitrogen content of less than 2500 ppm or less than 2000 ppm or less than 1500 ppm or less than 1000 ppm, or in the range of 1000-5000 ppm, or 2000-5000 ppm, or 1000-4000 ppm, or 1000-3000 ppm; or a sulfur content of less than 40000 ppm, or less than 35000 ppm, or less than 30000 ppm, or less than 25000 ppm, or less than 20000 ppm, or less than 15000 ppm, or less than 10000 ppm, or in the range of 1000-40000 ppm or 1000-35000 ppm or 1000-30000 ppm or 1000-25000 ppm or 1000-15000 ppm or 1000-10000 ppm; or a 1050+°F content of less than 10 wt.%, or less than 8 wt.%, or less than 7 wt.%, or less than 6 wt.%, or less than 5 wt
- the atmospheric resid feedstock has a hot 07 asphaltene content in the range of less than about 0.3 wt. %, or less than about 0.2 wt.%, or less than about 0.1 wt.%; and a nitrogen content of less than 2500 ppm, or less than 2000 ppm, or less than 1500 ppm, or less than 1000 ppm, or less than 800 ppm, or less than 500 ppm, or less than 200 ppm, or less than 100 ppm.
- the atmospheric resid feedstock may also have a hot 07 asphaltene content in the range of less than about 0.3 wt.
- the AR feedstock may also meet the following conditions: the atmospheric resid feedstock meets the following conditions: viscosity at 100°C of less than lOcSt, or in the range of
- hot 07 asphaltene content of less than about 0.1 wt.%, or in the range of about 0.01-0.1 wt.%; MCRT of less than 2 wt.%; nitrogen content of less than 800 ppm; sulfur content of less than 3000 ppm; Nickel content of less than 5 ppm; Vanadium content of less than 3 ppm; and Iron content of less than 4 ppm.
- Both the base oil feedstock and the atmospheric resid feedstock may have any of the foregoing properties within any of the noted broad and narrower ranges and combinations of such ranges.
- the base oil feedstream generally comprises 5-95 wt.% atmospheric resid feedstock and 95-5 wt.% base oil feedstock, or 10-90 wt.% atmospheric resid feedstock and 90-10 wt.% base oil feedstock, or 10-80 wt.% atmospheric resid feedstock and 90-20 wt.% base oil feedstock, or 10-60 wt.% atmospheric resid feedstock and 90-40 wt.% base oil feedstock, or 10-50 wt.% atmospheric resid feedstock and 50-90 wt.% base oil feedstock, or 10-40 wt.% atmospheric resid feedstock and 90-60 wt.% base oil feedstock, or 10-30 wt.% atmospheric resid feedstock and 90-70 wt.% base oil feedstock, or 30-60 wt.% atmospheric resid feedstock and 70-40 wt.% base oil feedstock, or 40-60 wt.% atmospheric re
- the base oil feedstream does not contain an added whole crude oil feedstock, and/or does not contain a vacuum residue feedstock, and/or does not contain a deasphalted oil feedstock component, and/or contains only atmospheric resid feedstock and base oil feedstock. While some of the particular property characteristics of the base oil feedstock and the AR feedstock may have similar or overlapping property values or ranges of values, the base oil feedstock and the AR feedstock are not the same since typically one or more property characteristics will be significantly different. For example, in some cases, the atmospheric resid feedstock and the base oil feedstock differ in their respective nitrogen content, sulfur content, 1050+°F content, or a combination thereof.
- the process need not include recycle of a liquid feedstock as part of the base oil feedstream or as either or both of the atmospheric resid feedstock and the base oil feedstock.
- recycle of one or more intermediate streams may be used, however.
- the base oil feedstock may comprise vacuum gas oil, or consist essentially of vacuum gas oil, or consist of vacuum gas oil, including whole uncut feedstocks and cut feedstocks.
- the vacuum gas oil may be a heavy vacuum gas oil obtained from vacuum gas oil that is cut into a light fraction and a heavy fraction, with the heavy fraction having a cut point temperature range of about 950-1050°F.
- the VGO may be a blend derived from various feedstocks, as well, and may include defined boiling point range components in differing amounts. For example, one component of the VGO derived from a particular feedstock may have a higher 1050+°F content while other VGO components contribute lower 1050+°F content to the VGO.
- the dewaxed product and/or the hydrofinished dewaxed product is typically obtained as a light base oil product and a heavy base oil product.
- the light base oil product generally has a nominal viscosity in the range of about 3-9 cSt, or 4-8 cSt or 5-7 cSt at 100°C and/or with the heavy base oil product generally having a nominal viscosity in the range of 13-24 cSt or 13-21 cSt or 13-18 cSt at 100°C.
- the dewaxed product may be further separated into at least a light product having a nominal viscosity of about 6 cSt at 100°C, and/or at least a heavy product having a nominal viscosity of 13 cSt or greater at 100°C, or 13-16.5 cSt at 100°C, or about 13-23 cSt at 100°C, or a combination thereof.
- the yield of the heavy base oil product relative to the light base oil product may be increased by at least about 0.5 liquid volume % (Lvol.%), or at least about 1 Lvol.%, or at least about 2 Lvol.%, or at least about 5 Lvol.% compared with the same process that does not include the atmospheric resid feedstock in the lubricating oil feedstream.
- Lvol.% liquid volume %
- the yield of the heavy base oil product may be increased by at least about 0.5 Lvol.%, or at least about 1 Lvol.%, or at least about 2 Lvol.%, or at least about 5 Lvol.%, or at least about 10 Lvol.%, or at least about 20 Lvol.%, compared with the same process that does not include the atmospheric resid feedstock in the base oil feedstream.
- the total waxy yield may also be increased by at least about 0.5 Lvol.%, or at least about 1 Lvol.%, or at least about 2 Lvol.%, or at least about 5 Lvol.% compared with the same process that does not include the atmospheric resid feedstock in the base oil feedstream.
- the invention concerns a method for modifying a conventional or existing base oil process to produce a heavy base oil product, particularly a heavy base oil having a viscosity of at least about 12.7 cSt, or at least about 13 cSt, or at least about 13.3 cSt at 100°C.
- a base oil process that comprises subjecting a base oil feedstream to hydrocracking and dewaxing steps to form a dewaxed product comprising a lighter product and a heavier product may be modified according to the invention by subjecting a base oil feedstock comprising atmospheric resid feedstock to the hydrocracking and dewaxing steps of the base oil process to produce a dewaxed product.
- the dewaxed product may be optionally further contacted with a hydrofinishing catalyst under hydrofinishing conditions to produce a hydrofinished dewaxed product.
- the invention further relates to a process for making a heavy base oil having a viscosity of at least about 12.7 cSt, or at least about 13 cSt, or at least about 13.3 cSt at 100°C from a base oil feedstream, or a fraction thereof, comprising providing a base oil feedstream comprising an atmospheric resid feedstock, and, optionally, a base oil feedstock separating the base oil feedstream into a vacuum gas oil having a front end cut point of about 700°F or greater and a back end cut point of about 900°F or less to form a medium vacuum gas oil MVGO fraction and a heavy vacuum gas oil HVGO fraction; contacting the HVGO fraction with a hydrocracking catalyst under hydrocracking conditions to form a hydrocracked product; separating the hydrocracked product into a gaseous fraction
- a vacuum gas oil having a front end cut point of about 700°F or greater and a back end cut point of about 900°F or less herein referred to as a medium vacuum gas oil (MVGO) provides an improved waxy product yield at a Group III or Group 111+ viscosity of 4cSt 100°C of the MVGO that is at least about 0.5 lvol.%, or 1 lvol.%, or 2 lvol.%, or 3 lvol.%, or 5 lvol.% greater than the same process that does not include the MVGO as the base oil feedstock.
- MVGO medium vacuum gas oil
- the fractionation of the AR feedstock into MVGO and HVGO fractions provides the ability to produce Group III/III+ base oil product while still allowing the HVGO fraction to be used with a conventional VGO base oil feedstock to produce a heavy grade base oil product, particularly a heavy base oil product having a viscosity of at least about 12.7 cSt, or at least about 13 cSt, or at least about 13.3 cSt at 100°C.
- Group III/III+ products that may be produced include a base oil product having a viscosity of about 4 cSt at 100°C (e.g., 3-5 cSt at 100°C).
- the use of MVGO to produce Group III/III+ base oil product results in greater yields of such products.
- Catalysts suitable for hydrocracking comprise materials having hydrogenationdehydrogenation activity, together with an active cracking component support.
- Such catalysts are well described in many patent and literature references.
- Exemplary cracking component supports include silica-alumina, silica- oxide zirconia composites, acid-treated clays, crystalline aluminosilicate zeolitic molecular sieves such as zeolite A, faujasite, zeolite X, and zeolite Y, and combinations thereof.
- Hydrogenation-dehydrogenation components of the catalyst preferably comprise a metal selected from Group VIII metals and compounds thereof and Group VIB metals and compounds thereof.
- Typical hydrocracking reaction conditions include, for example, a temperature of from 450°F to 900°F (232°C to 482°C), e.g., from 650°F to 850°F (343°C to 454°C); a pressure of from 500 psig to 5000 psig (3.5 MPa to 34.5 MPa gauge), e.g., from 1500 psig to 3500 psig (10.4 MPa to 24.2 MPa gauge); a liquid reactant feed rate, in terms of liquid hourly space velocity (LHSV) of from 0.1 hr 1 to 15 hr 1 (v/v), e.g., from 0.25 hr 1 to 2.5 hr 1 ; a hydrogen feed rate, in terms of Hz/hydrocarbon ratio, of from 500 SCF/bbl to 5000 SCF/bbl (89 to 890 m 3 Hz/m 3 feedstock) of liquid base oil (lubricating) feedstock, and/or a hydrogen partial pressure of greater than
- Dewaxing generally includes processing the dewaxer feedstock by hydroisomerization to convert at least the n-paraffins and to form an isomerized product comprising isoparaffins.
- Suitable isomerization catalysts for use in the dewaxing step can include, but are not limited to, Pt and/or Pd on a support.
- Waxy products W220 and W600 may be dewaxed to form 220N and 600N neutral products that may be suitable (or better suited) for use as a lubricating base oil or in a lubricant formulation.
- the dewaxed product may be mixed or admixed with existing lubricating base oils in order to create new base oils or to modify the properties of existing base oils, e.g., to meet particular target conditions, such as viscometric or Noack target conditions, for particular base oil grades like 220N and 600N.
- Isomerization and blending can be used to modulate and maintain pour point and cloud point of the base oil at suitable values.
- Normal paraffins may also be blended with other base oil components prior to undergoing catalytic isomerization, including blending normal paraffins with the isomerized product.
- Lubricating base oils that may be produced in the dewaxing step may be treated in a separation step to remove light product.
- the lubricating base oil may be further treated by distillation, using atmospheric distillation and optionally vacuum distillation to produce a lubricating base oil.
- layered catalyst systems may be used comprising hydrotreating (HDT, HDM, DEMET, etc.), hydrocracking (HCR), hydrodewaxing (HDW), and hydrofinishing (HFN) catalysts to produce intermediate and/or finished base oils using single or multireactor systems.
- a typical configuration includes two reactors with the first reactor comprising layered catalysts providing DEMET, HDT pretreatment, HCR, and/or HDW activity. Differing catalysts performing similar functions, e.g., different levels of hydrocracking activity, may be used as well, e.g., in different layers within a single reactor or in separate reactors.
- API gravity in the range of 20-60 or 20-45 or 25-45, or at least 20, or at least 22, or, optionally, greater than the API of the base oil feedstock;
- MCRT of less than 2 wt.%; nitrogen content of less than 800 ppm; sulfur content of less than 3000 ppm;
- API gravity in the range of 15-40 or 15-30 or 15-25, or at least 15, or at least 17, optionally, less than the atmospheric resid feedstock
- VI in the range of 30-90 or 40-90 or 50-90 or 50-80, optionally, less than the VI of the atmospheric resid feedstock; viscosity at 100°C in the range of 3-30 cSt or 3-25 cSt or 3-20 cSt, or at least 3 cSt, or at least 4 cSt; viscosity at 70°C in the range of 5-50 cSt or 5-80 wt.% or 5-70 wt.% or 5-60 wt.% or 5-50 wt.% or 5-40 wt.% or 5-30 wt.% or 5-20 cSt or 5-15 cSt, or at least 5cSt, or at least 6 cSt; hot C7 asphaltene content in the range of 0.01-0.3 wt.% or 0.01-0.2 wt.% or 0.02-0.15 wt.%, or less than 0.3 wt.
- wax content in the range of 5-90 wt.% or 5-80 wt.% or 5-70 wt.% or 5-60 wt.% or 5-50 wt.% or 5-40 wt.% or 5-30 wt.% or 10-25 wt.%, or at least 5 wt.% or at least 10 wt.%, or at least 15 wt.%, or, optionally, less than the wax content of the atmospheric resid feedstock; nitrogen content of less than 2500 ppm or less than 2000 ppm or less than 1500 ppm or less than 1000 ppm, or in the range of 1000-5000 ppm, or 2000-5000 ppm, or 1000-4000 ppm, or 1000-3000 ppm; sulfur content of less than 40000 ppm, or less than 35000 ppm, or less than 30000 ppm, or less than 25000 ppm, or less than 20000 ppm, or less than 15000
- the base oil feedstream comprises 5-95 wt.% atmospheric resid feedstock and 95-5 wt.% base oil feedstock, or 10-90 wt.% atmospheric resid feedstock and 90-10 wt.% base oil feedstock, or 10-80 wt.% atmospheric resid feedstock and 90-20 wt.% base oil feedstock, or 10-60 wt.% atmospheric resid feedstock and 90-40 wt.% base oil feedstock, or 10-50 wt.% atmospheric resid feedstock and 50-90 wt.% base oil feedstock, or 10-40 wt.% atmospheric resid feedstock and 90-60 wt.% base oil feedstock, or 10-30 wt.% atmospheric resid feedstock and 90-70 wt.% base oil feedstock, or 30-60 wt.% atmospheric resid feedstock and 70-40 wt.% base oil feedstock, or 40
- the base oil feedstock comprises vacuum gas oil or is vacuum gas oil, or consists essentially of vacuum gas oil, or consists of vacuum gas oil.
- VGO vacuum gas oil
- AR atmospheric resid
- VGO Vacuum Gas Oil
- VGO feedstock A sample of vacuum gas oil (VGO) feedstock from a commercially available source used to produce base oil products was obtained and analyzed as a comparative base case.
- the VGO feedstock was used in the following examples according to the process configurations shown in FIG's 1 and 2a.
- the properties of this VGO feedstock are shown in Table 1.
- VGO Vacuum Gas Oil
- Table 2A provides properties for a comparative conventional AR base oil process feedstock component. As may be noted, the AR's shown in Table 2 differ significantly from ARO shown in Table 2A.
- the blend feedstock sample of the atmospheric resid AR3 with vacuum gas oil (VGO) of example 3 was evaluated for heavy base oil production according to the process represented by FIG 2a.
- the base oil total is 56 wt.% of the liquid product.
- the individual base oils had the following properties:
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Abstract
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Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023544763A JP2024506820A (en) | 2021-01-26 | 2022-01-26 | Process for manufacturing heavy grade base oil products |
| US18/263,119 US20240117256A1 (en) | 2021-01-26 | 2022-01-26 | Process for making heavy grade base oil products |
| BR112023014888A BR112023014888A2 (en) | 2021-01-26 | 2022-01-26 | PROCESS FOR PRODUCING HEAVY GRADE BASE OIL PRODUCTS |
| KR1020237028371A KR20230133367A (en) | 2021-01-26 | 2022-01-26 | Heavy grade base oil product manufacturing process |
| CA3209475A CA3209475A1 (en) | 2021-01-26 | 2022-01-26 | Process for making heavy grade base oil products |
| EP22704173.8A EP4284900A1 (en) | 2021-01-26 | 2022-01-26 | Process for making heavy grade base oil products |
| CN202280015466.1A CN116888244A (en) | 2021-01-26 | 2022-01-26 | Process used to manufacture heavy grade base oil products |
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| US202163141955P | 2021-01-26 | 2021-01-26 | |
| US63/141,955 | 2021-01-26 |
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| EP (1) | EP4284900A1 (en) |
| JP (1) | JP2024506820A (en) |
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| CN (1) | CN116888244A (en) |
| BR (1) | BR112023014888A2 (en) |
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| US20240117256A1 (en) | 2024-04-11 |
| BR112023014888A2 (en) | 2023-10-10 |
| TW202246473A (en) | 2022-12-01 |
| EP4284900A1 (en) | 2023-12-06 |
| KR20230133367A (en) | 2023-09-19 |
| JP2024506820A (en) | 2024-02-15 |
| CN116888244A (en) | 2023-10-13 |
| CA3209475A1 (en) | 2022-08-04 |
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