WO2012170153A2 - Conversion of fatty acids to base oils and transportation fuels - Google Patents
Conversion of fatty acids to base oils and transportation fuels Download PDFInfo
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- WO2012170153A2 WO2012170153A2 PCT/US2012/037767 US2012037767W WO2012170153A2 WO 2012170153 A2 WO2012170153 A2 WO 2012170153A2 US 2012037767 W US2012037767 W US 2012037767W WO 2012170153 A2 WO2012170153 A2 WO 2012170153A2
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
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- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
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- 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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- 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
- C10G45/60—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 characterised by the catalyst used
- C10G45/62—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 characterised by the catalyst used containing platinum group metals or compounds thereof
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- 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
- C10G45/60—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 characterised by the catalyst used
- C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- 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
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
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- 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
- C10G2300/1011—Biomass
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- 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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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- 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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- 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
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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- 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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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/011—Cloud point
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- 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
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- C10N2020/065—Saturated Compounds
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- C10N2070/00—Specific manufacturing methods for lubricant compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- the invention relates generally to lubricants and fuels derived from renewable resources, and specifically to methods for efficiently making base oils and transportation fuels from fatty acids.
- renewable resources e.g., biomass
- Fatty acids are a readily available renewable resource.
- the invention relates to a method comprising: contacting a fatty acid feed with a decarboxylation-coupling dimerization catalyst in a decarboxylation-coupling dimerization zone under decarboxylation-coupling dimerization conditions to yield a dimer ketone; hydrocracking the dimer ketone with a hydrocracking catalyst in a hydrocracking zone under hydrocracking conditions to yield a mixture of paraffins comprising a heavy waxy oil component and a diesel fuel component; and distilling the mixture to yield a heavy waxy oil and a diesel fuel.
- the invention in another aspect, relates to a method comprising: contacting a fatty acid feed with a decarboxylation-coupling dimerization catalyst in a decarboxylation-coupling dimerization zone under decarboxylation-coupling dimerization conditions to yield a dimer ketone; and hydroisomerization dewaxing the dimer ketone with a hydroisomerization dewaxing catalyst in a catalytic hydroisomerization zone under hydroisomerization dewaxing conditions to yield a lubricating base oil.
- FIG. 1 is an FT-IR spectrum of a dimer ketone of Example 2.
- bio refers to an association with a renewable resource of biological origin, such resources generally being exclusive of fossil fuels.
- Fatty acid refers to an aliphatic mono-carboxylic acid having at least 4 carbon atoms.
- the fatty acid can be saturated or unsaturated, branched or unbranched.
- Decarboxylation-coupling dimerization refers to a chemical reaction in which two molecules, each having a carboxylic acid functional group, combine to form one single molecule having a ketone functional group, with concurrent loss of carbon dioxide and water.
- Diesel fuel refers to hydrocarbons having boiling points in the range of from 250°F to 700°F (121°C to 371°C).
- Base oil refers to a hydrocarbon fluid to which other oils or substances are added to produce a lubricant.
- Group III base oil refers to a base oil which contains greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity index greater than or equal to 120 using the ASTM methods specified in Table E-1 of American Petroleum Institute Publication 1509.
- Viscosity index (VI) is an empirical, unit-less number indicating the effect of temperature change on the kinematic viscosity of the oil. The higher the VI of an oil, the lower its tendency to change viscosity with temperature. Viscosity index is measured according to ASTM D 2270-10.
- “Pour point” is a measurement of the temperature at which a sample will begin to flow under certain carefully controlled conditions, which can be determined as described in ASTM D 5950-02 (reapproved 2007).
- “Cloud point” represents the temperature at which a fluid begins to phase separate due to crystal formation, which can be determined as described in ASTM D 5771-10.
- Periodic Table of Elements referred to herein is the Table approved by IUPAC and the U.S. National Bureau of Standards, an example of which is the Periodic Table of the Elements by Los Alamos National Laboratory's Chemistry Division of October 2001.
- the fatty acid feed can be from a bio-based source (e.g., biomass) or can be derived from Fischer-Tropsch alcohols via oxidation.
- the fatty acid feed can be a bio-derived fatty acid formed by hydrolysis of one or more triglyceride-containing vegetable oils such as, but not limited to, coconut oil, corn oil, linseed oil, olive oil, palm oil, palm kernel oil, rapeseed oil, safflower oil, soybean oil, sunflower oil, and the like.
- Other sources of triglycerides, for which hydrolysis can yield fatty acids include, but are not limited to, algae, animal tallow, and zooplankton.
- hydrolyzed triglyceride sources contain mixtures of saturated fatty acids, mono-unsaturated fatty acids, and
- one or more techniques may be employed to isolate, concentrate, or otherwise separate the desired fatty acids from the other fatty acids in the mixture (see, e.g., U. S. Patent Application Publication No. 2009/0285728).
- the fatty acid feed comprises at least 50 wt. % saturated fatty acids, typically at least 75 wt. % saturated fatty acids, and more typically at least 90 wt. % saturated fatty acids.
- Non-limiting examples of suitable saturated fatty acids include caproic acid (C 6 ), caprylic acid (C 8 ), capric acid (Ci 0 ), lauric acid (Ci 2 ), myristic acid (Ci 4 ), palmitic acid (Ci 6 ), stearic acid (Cig), arachidic acid (C 2 o), palm kernel oil acid (a mixture of Cg to C 22 fatty acids, primarily lauric acid and myristic acid), coconut oil acid (a mixture of Cg to C 22 fatty acids, primarily lauric acid and myristic acid), and any combination of the foregoing.
- Dimer ketones may be prepared by decarboxylation-coupling of fatty acids.
- a ketone is formed in the decarboxylation- coupling process from two moles of fatty acid. Carbon dioxide and water are produced as by- products.
- the following reaction scheme illustrates this proposed scheme for a single fatty acid source:
- the fatty acid raw material, together with a diluent, when used, is contacted with a catalyst in a so-called reaction zone.
- a reaction zone may, for example, be contained within a fixed bed reactor, a fluid bed reactor, or a slurry reactor.
- the decarboxylation-coupling processes can also be conducted in a glass-lined stainless steel or similar type reaction equipment.
- the reaction zone may be fitted with one or more internal and/or external heat exchangers in order to control the temperature.
- Suitable decarboxylation-coupling dimerization conditions comprise generally a temperature in the range between 437°F and 932°F (225°C and 500°C), typically between 572°F and 752°F (300°C and 400°C); a pressure in the range between 10 and 3000 psig (0.07 and 20.7 MPa), typically between 100 and 2500 psig (0.7 and 17.2 MPa); a liquid hourly space velocity (LHSV) of from 0.1 to 50 h "1 , typically from 0.5 to 10 h "1 .
- LHSV liquid hourly space velocity
- the decarboxylation-coupling dimerization reaction can be conducted in the presence of at least one inert liquid diluent. Dilution can help minimize the corrosivity of the fatty acid feed.
- the liquid diluent should be a good solvent for the starting materials and easily separable from the ketone product. Suitable diluents include, but are not limited to, hydrocarbon solvents (e.g., benzene, toluene, xylene, ethylbenzene, heptane, octane, nonane, decane, dodecane, tridecane, and the like) and oxygenated solvents such as alcohols, ethers and ketones. When liquid diluents are used, the feed comprises generally between 1 and 95 wt. % of fatty acid, or between 5 and 50 wt. % of fatty acid.
- Suitable catalysts for fatty acid decarboxylation-coupling dimerization include alumina, silica, silica-alumina, titania, zirconia, and combinations thereof, and supported metal carbonates or hydroxides. Typical metals include Mg, Ca, Sr, Ba, and Mn.
- the support for metal carbonates or hydroxides can be chosen from any refractory material such as alumina, silica, silica-alumina, titania, zirconia, zinc oxide, magnesium oxide, and combinations thereof, or even naturally-occurring materials such as pumice.
- the decarboxylation-coupling dimerization catalyst is alumina.
- the decarboxylation-coupling dimerization process can be carried out in batch or continuous mode, with recycling of unconsumed starting materials if required.
- Dimer ketones derived by the above-described process can be separated from byproducts (such as oligomeric or polymeric species and low molecular weight "fragments" from the fatty acid chains) by distillation.
- byproducts such as oligomeric or polymeric species and low molecular weight "fragments" from the fatty acid chains
- the crude reaction product can be subjected to a distillation-separation at atmospheric or reduced pressure through a packed distillation column.
- the decarboxylation-coupling dimerization product is generally a wax at room temperature and pressure. In order to prevent clogging of the apparatus in which
- decarboxylation-coupling dimerization it may be necessary to heat those tubes by which the decarboxylation-coupling dimerization product is removed from the reaction zone and any vessel into which the dimer ketone is to be collected.
- Hydrocracking is generally accomplished by contacting, in a hydrocracking reactor or reaction zone, the feedstock to be treated with a suitable hydrocracking catalyst under conditions of elevated temperature and pressure. Hydrocracking reactions reduce the overall molecular weight of the heavy feedstock to yield upgraded (that is, higher value) products including transportation fuels (e.g., diesel fuel), kerosene, and naphtha. These upgraded products that are converted in the hydrocracking reaction zone are typically separated from the total hydrocracker effluent as lower boiling fractions, using one or more separation and/or distillation operations.
- transportation fuels e.g., diesel fuel
- kerosene kerosene
- naphtha kerosene
- These upgraded products that are converted in the hydrocracking reaction zone are typically separated from the total hydrocracker effluent as lower boiling fractions, using one or more separation and/or distillation operations.
- a remaining higher boiling fraction, containing heavy waxy feedstocks (referred herein as a "heavy hydrocarbon intermediate” or a “heavy waxy oil”) suitable for upgrading to lubricating base oils by hydroisomerization to improve its cold flow properties, is always generated in the fractionators.
- the heavy waxy oil has a boiling range of approximately 650°F to 1300°F (343°C to 704°C).
- the temperature in the hydrocracking zone is within the range of from 500°F to
- 900°F 260°C to 482°C
- 600°F to 800°F typically within the range of from 600°F to 800°F (316°C to 427°C), more often with 650°F to 750°F (343°C to 399°C).
- a total pressure above 1000 psig (6.89 MPa) is used.
- the total pressure can be above 1500 psig (10.34 MPa), or above 2000 psig (13.79 MPa).
- greater maximum pressures have been reported in the literature and may be operable, the maximum practical total pressure generally will not exceed 3000 psig (20.68 MPa).
- more severe hydrocracking conditions such as higher temperature or pressure will result in producing an original base oil product with a higher viscosity index.
- the LHSV generally falls within the range of from 0.1 to 50 h “1 , typically from 0.2 to 10 h “1 , more often from 0.5 to 5 h “1 .
- the supply of hydrogen (both make-up and recycle) is preferably in excess of the stoichiometric amount needed to crack the target molecules and generally falls within the range of from 500 to 10000 standard cubic feet (SCF)/barrel, typically from 1000 to 5000 SCF/barrel. Note that a feed rate of 10000 SCF/barrel is equivalent to 1781 L H2 /L feed.
- hydrocracking conditions are sufficient to convert the dimer ketone to hydrocarbon.
- the catalysts used in the hydrocracking zone are composed of natural and synthetic materials having hydrogenation and dehydrogenation activity and cracking activity. These catalysts are well known in the art and are pre-selected to crack the target molecules and produce the desired product slate.
- Exemplary commercial cracking catalysts generally contain a support consisting of alumina, silica, silica-alumina composites, silica-alumina-zirconia composites, silica-alumina-titania composites, acid treated clays, crystalline aluminosilicate zeolitic molecular sieve (e.g., zeolite A, faujasite-Y, zeolite beta), and various combinations of the above.
- the hydrogenation/dehydrogenation components generally consist of a metal or metal compound of Group VIII or Group VIB of the Periodic Table of the Elements. Metals and their compounds such as, for example, Co, Ni, Mo, W, Pt, Pd and combinations thereof are known hydrogenation components of hydrocracking catalysts.
- the step of distilling employs a distillation column (unit) to separate the heavy waxy oil and the diesel fuel into individual fractions.
- the heavy waxy oil is collected in a high-boiling fraction and the diesel fuel is collected in a low-boiling fraction.
- a fractional bifurcation occurs at or around 650°F (343°C), in which case the diesel fuel is largely contained within a 650°F- fraction (boiling below 650°F) and the heavy waxy oil is contained within a 650°F+ fraction (boiling above 650°F).
- the diesel fuel has a cetane index of at least 65, or at least 70, as determined by ASTM D 4737-10. In some or other such embodiments, the diesel fuel has a pour point of less than 0°C.
- Heavy intermediate feedstocks are characterized by high pour points and high cloud points.
- the pour point and cloud point In order to prepare commercially useful lubricating base oils from heavy intermediate feedstocks, the pour point and cloud point must be lowered without compromising the desired viscosity characteristics.
- Hydroisomerization dewaxing is intended to improve the cold flow properties of the heavy intermediate feedstocks by the selective addition of branching into the molecular structure. Hydroisomerization dewaxing ideally will achieve high conversion levels of the waxy oil to non-waxy iso-paraffins while at the same time minimizing cracking.
- the hydroisomerization catalyst preferably comprises a shape selective intermediate pore size molecular sieve, a noble metal hydrogenation component, and at least a refractory oxide support.
- the shape selective intermediate pore size molecular sieve is preferably selected from the group consisting of SAPO-11, SAPO-31, SAPO-41, SM-3, SM-7, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32, ferrierite, and combinations thereof.
- SAPO-11, SM-3, SM-7, SSZ-32, ZSM-23, and combinations thereof are often used.
- the noble metal hydrogenation component can be Pt, Pd, or combinations thereof.
- hydroisomerization dewaxing conditions depend on the feed used, the hydroisomerization dewaxing catalyst used, whether or not the catalyst is sulfided, the desired yield, and the desired properties of the product.
- Preferred hydroisomerization dewaxing conditions useful in the current invention include temperatures of 260°C to 413°C (500°F to 775°F); a total pressure of 15 to 3000 psig (0.10 to 20.68 MPa); a LHSV of 0.25 to 20 IT 1 ; and a hydrogen to feed ratio from about 200 to 30000 SCF/barrel.
- the hydrogen to feed ratio can be from 500 to 10000 SCF/barrel, in others from 1000 to 5000 SCF/barrel, and in still others from 2000 to 4000 SCF/barrel.
- hydrogen will be separated from the product and recycled to the hydroisomerization zone.
- hydroisomerization dewaxing conditions are sufficient to convert dimer ketones to hydrocarbon.
- the base oil has a viscosity index of at least 140, typically at least 170, and often at least 200. In some embodiments, the base oil is a Group III base oil. In some embodiments, the base oil produced has a pour point of less than 0°C.
- Hydrofinishing may be used as a step following hydroisomerization in the process of this invention to make base oils with improved properties. This step is intended to improve the oxidation stability, UV stability, and appearance of the product by removing traces of olefins and color bodies. A general description of hydrofinishing may be found in U.S. Pat. Nos. 3,852,207 and 4,673,487.
- the isomerized product from the hydroisomerization reactor passes directly to the hydrofinishing reactor.
- UV stability refers to the stability of the lubricating base oil when exposed to ultraviolet light and oxygen. Instability is indicated when the lubricating base oil forms a visible precipitate or darker color upon exposure to ultraviolet light and air which results in a cloudiness or floe in the product.
- lubricating base oils prepared by hydrocracking followed by hydroisomerization require UV stabilization before they are suitable for use in the manufacture of commercial lubricating oils.
- Table 2 shows that the TAN was reduced from 12.7 mg-KOH/g of the diluted coconut fatty acid feed to about 1 mg-KOH/g of the decarboxylated product at catalyst temperature (CAT) of 680°F and 0.5 h "1 LHSV and further reduced to about 0.3 mg-KOH/g at conditions of 730°F CAT and 0.5 h "1 LHSV, indicating catalytic conversion of fatty acid on alumina catalyst.
- Simulated Distillation or SimDis data indicate the formation of a heavy product with a boiling point of about 800°F+, much higher than the boiling point of the coconut fatty acid (590°F).
- Table 3 sets forth the concentration of CO and C0 2 in the off-gas of the decarboxylation-coupling dimerization process. The results demonstrate that carbon dioxide and water are the major side products, supporting ketone formation via decarboxylation-coupling dimerization.
- Table 4 shows reduced TAN of the stearic acid solution from 10.2 to less than 0.05 - 3.0 mg-KOH/g after contact with the alumina catalyst at conditions of about 1 - 2 h "1 LHSV and 680°F/730°F CAT.
- the major product via decarboxylation-coupling dimerization showed a boiling point of about 900°F+, slightly higher than that in Example 2. This is consistent with the higher molecular weight of stearic acid in comparison to coconut fatty acid.
- Table 6 sets forth a comparison of the activity, yields and product properties in stearic acid decarboxylation-coupling dimerization over the alumina catalyst of Example 3 and the Ti-modified SIRAL®-30 catalyst of Example 4. As shown, the acidic sites on the SIRAL®-30 lead to cracking resulting in the formation of 1.0 to 1.5 wt. % C 5 -250 o F, higher than 0.5 tol .0 wt. % with the pure alumina catalyst of Example 2 at comparable decarboxylation-coupling dimerization conditions.
- Hydrocracking of the dimerized product was performed using a commercial hydrocracking catalyst under the following conditions: 7000 SCF/barrel hydrogen, 1.0 h "1 LHSV and 2000 psig unit pressure.
- An online stripper operated at a cut point of about 700°F to generate a stripper overhead product or STO (700°F-, diesel fuel) and a stripper bottoms product or STB (700°F+, heavy waxy oil).
- Table 8 sets forth the activity, yields and product properties for the hydrocracked dimer ketone from stearic acid.
Abstract
Description
Claims
Priority Applications (3)
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BR112013027158A BR112013027158A2 (en) | 2011-06-10 | 2012-05-14 | conversion of fatty acids to base oils and transport fuels |
CA2835843A CA2835843C (en) | 2011-06-10 | 2012-05-14 | Conversion of fatty acids to base oils and transportation fuels |
SG2013085030A SG195010A1 (en) | 2011-06-10 | 2012-05-14 | Conversion of fatty acids to base oils and transportation fuels |
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US13/157,921 | 2011-06-10 | ||
US13/157,921 US20120316093A1 (en) | 2011-06-10 | 2011-06-10 | Conversion of fatty acids to base oils and transportation fuels |
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BR (1) | BR112013027158A2 (en) |
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WO2011011537A2 (en) | 2009-07-23 | 2011-01-27 | Ceramatec, Inc. | Method of producing coupled radical products from biomass |
US9051656B2 (en) * | 2009-07-23 | 2015-06-09 | Ceramatec, Inc. | Electrochemical synthesis of aryl-alkyl surfacant precursor |
US9957622B2 (en) | 2009-07-23 | 2018-05-01 | Field Upgrading Limited | Device and method of obtaining diols and other chemicals using decarboxylation |
US9206515B2 (en) | 2009-07-23 | 2015-12-08 | Ceramatec, Inc. | Method of producing coupled radical products via desulfoxylation |
US9493882B2 (en) | 2010-07-21 | 2016-11-15 | Ceramatec, Inc. | Custom ionic liquid electrolytes for electrolytic decarboxylation |
WO2012018418A2 (en) | 2010-08-05 | 2012-02-09 | Ceramatec, Inc. | Method and device for carboxylic acid production |
WO2012103135A2 (en) | 2011-01-25 | 2012-08-02 | Ceramatec, Inc. | Production of fuel from chemicals derived from biomass |
US9221725B2 (en) * | 2012-07-18 | 2015-12-29 | Exxonmobil Research And Engineering Company | Production of lubricant base oils from biomass |
US8927796B2 (en) | 2012-09-13 | 2015-01-06 | Chevron U.S.A. Inc. | Base oil upgrading by co-feeding a ketone or beta-keto-ester feedstock |
EP2935520B1 (en) | 2012-12-18 | 2020-05-20 | ExxonMobil Research and Engineering Company | Process for making a lube basestock from renewable feeds |
SG11201502700YA (en) * | 2012-12-18 | 2015-05-28 | Exxonmobil Res & Eng Co | Process for making lube base stocks from renewable feeds |
WO2014099373A1 (en) * | 2012-12-18 | 2014-06-26 | Exxonmobil Research And Engineering Company | Process for making lube base stocks from renewable feeds |
WO2014144432A1 (en) * | 2013-03-15 | 2014-09-18 | Ceramatec, Inc. | Device and method for aryl-alkyl coupling using decarboxylation |
US9314785B1 (en) | 2014-11-13 | 2016-04-19 | Chevron U.S.A. Inc. | Ketonization process using oxidative catalyst regeneration |
US9193650B1 (en) | 2014-11-13 | 2015-11-24 | Chevron U.S.A. Inc. | Long chain secondary alcohols from fatty acids and fatty oils |
US11267781B2 (en) | 2016-11-08 | 2022-03-08 | Rhodia Operations | Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives |
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WO2006075057A2 (en) * | 2005-01-14 | 2006-07-20 | Neste Oil Oyj | Method for the manufacture of hydrocarbons |
US7282134B2 (en) * | 2003-12-23 | 2007-10-16 | Chevron Usa, Inc. | Process for manufacturing lubricating base oil with high monocycloparaffins and low multicycloparaffins |
US7781619B2 (en) * | 2006-03-20 | 2010-08-24 | Albemarle Netherlands B.V. | Process for the decarboxylation of fatty acids |
US7928273B2 (en) * | 2005-08-29 | 2011-04-19 | David Bradin | Process for producing a renewable fuel in the gasoline or jet fuel range |
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US3365390A (en) * | 1966-08-23 | 1968-01-23 | Chevron Res | Lubricating oil production |
US8048290B2 (en) * | 2007-06-11 | 2011-11-01 | Neste Oil Oyj | Process for producing branched hydrocarbons |
-
2011
- 2011-06-10 US US13/157,921 patent/US20120316093A1/en not_active Abandoned
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2012
- 2012-05-14 CA CA2835843A patent/CA2835843C/en not_active Expired - Fee Related
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- 2012-05-14 WO PCT/US2012/037767 patent/WO2012170153A2/en active Application Filing
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US7282134B2 (en) * | 2003-12-23 | 2007-10-16 | Chevron Usa, Inc. | Process for manufacturing lubricating base oil with high monocycloparaffins and low multicycloparaffins |
WO2006075057A2 (en) * | 2005-01-14 | 2006-07-20 | Neste Oil Oyj | Method for the manufacture of hydrocarbons |
US7928273B2 (en) * | 2005-08-29 | 2011-04-19 | David Bradin | Process for producing a renewable fuel in the gasoline or jet fuel range |
US7781619B2 (en) * | 2006-03-20 | 2010-08-24 | Albemarle Netherlands B.V. | Process for the decarboxylation of fatty acids |
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CA2835843C (en) | 2017-03-14 |
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WO2012170153A3 (en) | 2013-06-13 |
WO2012170153A8 (en) | 2013-11-21 |
US20120316093A1 (en) | 2012-12-13 |
SG195010A1 (en) | 2013-12-30 |
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