WO2023116168A1 - 一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料 - Google Patents

一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料 Download PDF

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WO2023116168A1
WO2023116168A1 PCT/CN2022/126731 CN2022126731W WO2023116168A1 WO 2023116168 A1 WO2023116168 A1 WO 2023116168A1 CN 2022126731 W CN2022126731 W CN 2022126731W WO 2023116168 A1 WO2023116168 A1 WO 2023116168A1
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liquid fuel
zsm
fatty acid
oil
long
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French (fr)
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张家仁
王旻烜
李金�
何皓
张佳
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • 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 to a method for preparing liquid fuel through selective catalytic deoxygenation of grease and the liquid fuel, belonging to the technical field of biomass energy.
  • Liquid fuels such as gasoline, diesel, aviation fuel, etc.
  • the long-term extensive use of fossil resources to prepare liquid fuels has had negative impacts on the environment such as the greenhouse effect.
  • the reserves of these non-renewable resources will decrease year by year with continuous consumption.
  • Deoxygenated liquid fuels prepared from renewable animal and vegetable oils have high calorific value, good combustion performance, similar composition to fossil fuels, and good compatibility, and have been widely valued. Therefore, countries all over the world pay more and more attention to the research on the technology of preparing deoxygenated liquid fuel from oil.
  • the oil can be hydrodeoxygenated into long-chain alkanes under the action of sulfurized NiMo/ ⁇ -Al 2 O 3 or CoMo/ ⁇ -Al 2 O 3 catalysts, and the long-chain alkanes can be loaded with Pt, Acidic molecular sieve catalysts such as Pd and other noble metals (such as Pt/ZSM-22) catalyze isomerization to prepare liquid fuels.
  • Pt Acidic molecular sieve catalysts
  • Pd and other noble metals
  • Canada s Canmet Energy Technology Center has developed a technology to produce high-cetane diesel by hydrogenation of oil, a technology of oil catalytic hydrodeoxygenation to produce diesel established in Porvoo by Finland’s Neste Oil Company, and a technology to prepare aviation kerosene from biomass developed by UOP.
  • Sulfurized hydrogenation catalysts reduce catalytic activity due to sulfur loss and thus generate sulfur pollution.
  • the use of hydrogenation metal catalysts such as nickel, palladium, platinum, and ruthenium can avoid sulfur-related problems.
  • Chinese patent CN 102876350A discloses a technology for preparing alkane fuels by catalyzing the hydrodeoxygenation of fats or fatty acids with Ru-based catalysts. Or it is also possible to directly use bifunctional catalysts to couple hydrodeoxygenation and cracking/isomerization in a single stage. For example, Herskowitz et al.
  • the oil is first hydrolyzed (or methylated) to release glycerol, and then the selective decarboxylation/carbonylation of fatty acid (or fatty acid methyl ester) is catalyzed to remove oxygen in the form of CO 2 /CO, which can significantly reduce hydrogen consumption.
  • Murzin et al. (Top Catal (2011) 54:460–466) reported that Al 2 O 3 or SiO 2 catalysts loaded with Pt and Pd noble metals can catalyze the decarboxylation of fatty acids with high selectivity. Under the conditions of 250-350°C and 0.1-2MPa, the conversion rate of stearic acid is greater than 80%, and the selectivity of n-heptadecane is about 93%.
  • Hydrodeoxygenation of oils to obtain alkanes, or selective decarboxylation/decarbonylation of fatty acids or their methyl esters to obtain alkanes, and then hydrocracking/isomerization of alkanes requires the use of noble metals such as Pt and Pd, which will significantly increase the cost of catalysts.
  • Chinese patent CN107987868A discloses a method for preparing liquid fuels through step-by-step deoxygenation of oils and fats. Construct fuel.
  • the water produced by catalytic deoxygenation of fatty alcohols usually leads to increased oxygen content of isomerized products and shortens catalyst life.
  • Chinese patent CN110066679A discloses a method for preparing liquid fuel from fatty alcohol, which is to continuously separate the water and cracked gas produced by the deoxygenation of fatty alcohol, and hydrogenate the reaction product to obtain fuel .
  • the object of the present invention is to provide a method for preparing liquid fuel through selective catalytic deoxygenation of oil and liquid fuel.
  • the present invention provides a method for preparing liquid fuel through selective catalytic deoxygenation of grease, wherein the method comprises:
  • liquid fuel is prepared by isomerizing long-chain hydrocarbons.
  • the fatty acid content of carbon chain length of C 12 -C 24 in the oil is greater than 80 wt%, fatty acid glyceride And the total content of free fatty acid is greater than 90wt%.
  • the fats include tallow, lard, chicken oil, rapeseed oil, soybean oil, cottonseed oil, palm oil, corn oil, rubber seed oil, catering industry Waste oil, gutter oil, acidified oil, rancid oil and other animal and vegetable oils, or low-quality oils such as frying oil and lubricating oil that have been used for other purposes but the main structure of fatty acids has not changed.
  • the content of impurities such as sulfur, phosphorus, nitrogen, chlorine and metals in the oil raw material should be appropriately reduced.
  • the content of impurities such as sulfur, phosphorus, nitrogen, chlorine and metals should be less than 100ppm, 200ppm, 300ppm, 400ppm and 1000ppm respectively.
  • the methyl esterification of the oil is to convert the oil into fatty acid methyl ester by reacting with methanol.
  • the grease and methanol are reacted under critical methanol conditions, under enzyme-catalyzed conditions, under homogeneous or heterogeneous acid-catalyzed conditions or homogeneous or Reaction conversion to fatty acid methyl esters under heterogeneous base-catalyzed conditions.
  • the present invention does not make specific requirements on the reactor, process conditions and catalysts used for methyl esterification of oils and fats in S1, and those skilled in the art can make reasonable choices according to actual operation needs, as long as it is guaranteed that the purpose of the present invention can be achieved. Can.
  • the process conditions for the methyl esterification of oil include: temperature 60-300°C , pressure 0.1-20MPa, mass space velocity 0.3-5h -1 , alcohol-oil molar ratio 3:1-16:1;
  • the reactor used may be a continuous reactor such as a tower reactor or a tubular reactor to improve reaction efficiency.
  • the mixture after methyl esterification of fats and oils can be further refined and separated or distilled under reduced pressure.
  • the content of fatty acid methyl ester in the obtained product is not less than 80 wt%.
  • the content of fatty acid methyl ester in the obtained product is not less than 85wt%.
  • the content of fatty acid methyl ester in the obtained product is 95-100 wt%.
  • the catalyst used for catalytic hydrogenation of fatty acid methyl esters into fatty alcohols is a supported catalyst
  • the hydrogenation active metal used by the supported catalyst includes platinum, One or more of palladium, gold, silver, cobalt, molybdenum, copper, nickel, zinc, iron, chromium, barium and manganese, etc.
  • the carrier is a high specific surface area carrier such as activated carbon, Al 2 O 3 or SiO 2 .
  • a supported catalyst with one or more non-precious metals such as copper, cobalt, molybdenum, nickel, iron, zinc and manganese as active centers is preferred.
  • the process conditions for catalytic hydrogenation of fatty acid methyl esters into fatty alcohols include: temperature 160-300°C, pressure 2-20MPa, mass space velocity 0.3-3h -1 .
  • the volume ratio of hydrogen to oil is 500:1-15000:1.
  • By-product methanol can be recycled.
  • the reactor used for catalytic hydrogenation of fatty acid methyl ester into fatty alcohol can be a reactor, a tower reactor and a fixed bed reactor, etc., preferably a tower reactors or fixed-bed tubular reactors.
  • the fatty alcohol content in the product obtained is greater than 86 wt%.
  • the content of fatty alcohol in the product obtained is 92-100 wt%.
  • high boiling point components can be separated by means of adsorption and distillation.
  • the catalyst used for intramolecular dehydration of fatty alcohols into long-chain hydrocarbons is an acid catalyst with a desorption temperature of 150-600°C after NH3 adsorption.
  • the acid catalyst can selectively catalyze the intramolecular dehydration of long-chain aliphatic alcohols into long-chain hydrocarbons under non-hydrogen atmosphere conditions.
  • the acid catalyst includes ⁇ -Al 2 O 3 , ZrO 2 , ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO One or more of -31, SAPO-11, ZSM-5, Y molecular sieve and ⁇ molecular sieve, etc.
  • the acid catalyst in S3, includes ⁇ -Al 2 O 3 and/or ZrO 2 , and ⁇ -Al 2 O 3 and/or ZrO 2 combined with ZSM-22, ZSM- 23.
  • ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y molecular sieve, and ⁇ molecular sieve is one or a combination of ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y molecular sieve, and ⁇ molecular sieve.
  • the reactions involved in the intramolecular dehydration conversion process of fatty alcohols include one or more of dehydration, cracking, isomerization, cyclization and other reactions.
  • the process conditions for intramolecular dehydration of fatty alcohols into long-chain hydrocarbons include: temperature 250-400°C, pressure -0.1MPa to 0.5MPa, mass space velocity is 0.2-4h -1 .
  • the oxygen content in the obtained long-chain hydrocarbon is less than 0.1 wt%.
  • the oxygen content in the obtained long-chain hydrocarbon is less than 0.05 wt%.
  • high boiling point components can be separated by means of adsorption and distillation.
  • the reactor used for the intramolecular dehydration conversion of fatty alcohol can be a reactor, a tower reactor and a fixed bed reactor, etc., preferably a tower reactor or fixed bed reactor.
  • the catalyst used for the isomerization of long-chain hydrocarbons to prepare liquid fuel is an acid catalyst with a desorption temperature of 150-600° C. after NH 3 adsorption.
  • the acid catalyst can selectively catalyze the isomerization of long-chain hydrocarbons under non-hydrogen atmosphere conditions to obtain liquid fuels.
  • the acid catalyst includes ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5 , EU-1, Y molecular sieve and ⁇ molecular sieve etc. one or more.
  • the reactions involved in the long-chain hydrocarbon isomerization process include one or more of cracking, isomerization, cyclization, superposition, and the like.
  • the process conditions for preparing liquid fuel by isomerization of long-chain hydrocarbons include: temperature 200-420°C, pressure -0.1MPa to 4MPa, mass space velocity 0.2- 3h -1 .
  • the reactor used for the preparation of liquid fuel by isomerization of long-chain hydrocarbons can be a reactor, a tower reactor and a fixed bed reactor, etc., preferably a tower reactor. reactor or fixed bed reactor.
  • the present invention also provides a liquid fuel, wherein the liquid fuel is prepared by the above-mentioned method for preparing liquid fuel through selective catalytic deoxygenation of grease.
  • the oxygen content of the liquid fuel is less than 0.05 wt%.
  • the main component of the engine liquid fuel obtained by the method for preparing liquid fuel by the selective catalytic deoxygenation of oil provided by the invention is C 6 -C 20 hydrocarbons, and can be obtained by changing the oil raw material The composition of fatty acids, catalysts and process conditions, etc., to adjust the composition of liquid fuels.
  • the liquid fuel can be further hydrorefined or rectified and separated to obtain target products of suitable fractions.
  • the method for preparing liquid fuel through selective catalytic deoxygenation of grease provided by the present invention has significant beneficial effects, including:
  • the method has strong adaptability to raw materials, and can directly process low-quality oil raw materials, which can significantly reduce raw material costs;
  • This method can also avoid problems related to sulfurized catalysts, and can significantly simplify the process flow
  • This method can also avoid the use of precious metal catalysts, and the catalysts used are cheap and easy to obtain, which reduces the cost of catalysts;
  • This method can also significantly reduce hydrogen consumption and material consumption
  • This method can also increase the production of glycerin with higher added value, and increase the production value
  • the reaction process of the method is highly controllable, the selectivity of the target product is good and the oxygen content is low;
  • the product composition can be flexibly adjusted to improve market adaptability.
  • ranges are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively.
  • a given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.
  • This embodiment provides a method for preparing liquid fuel through selective catalytic deoxygenation of grease, wherein the method includes the following specific steps:
  • Fatty acid methyl esters are subjected to catalytic hydrogenation in a tubular reactor filled with a 10-mesh copper-zinc-aluminum catalyst (the molar ratio of Cu:Zn:Al is 1:0.8:4, prepared by coprecipitation method).
  • the process conditions are: temperature 240°C, pressure 20MPa, volume ratio of hydrogen to fatty acid methyl ester 15000:1, mass space velocity 0.5h -1 .
  • the intramolecular dehydration of fatty alcohol is converted into long-chain hydrocarbons.
  • the reaction process conditions are: temperature 380°C, The pressure is 0.1MPa, the mass space velocity of the fatty alcohol is 3h -1 , the obtained reaction product is separated by distillation, the content of long-chain hydrocarbon is more than 98wt%, and the oxygen content in long-chain hydrocarbon is less than 0.04wt%.
  • long-chain hydrocarbons are isomerized to obtain isomerized liquid fuel, and the reaction process conditions are: temperature 300 °C, pressure 0.1MPa, mass space velocity of long-chain hydrocarbons is 1h -1 .
  • the liquid fuel prepared by refining soybean oil through a series of selective reaction deoxygenation is mainly a hydrocarbon fuel with a main component of C6 - C20 , the yield reaches 83.4wt%, and the oxygen content in the liquid fuel is 0.028wt% .
  • the liquid fuel obtained in this embodiment can also be divided according to the boiling range to obtain gasoline, diesel and aviation fuel components, and further hydrorefining can be used to improve the quality of the product.
  • This embodiment provides a method for preparing liquid fuel by selective catalytic deoxygenation of fats and oils, wherein the method comprises the following specific steps:
  • the rubber seed oil with an acid value of 30mgKOH/g was reacted with methanol at 300°C and 20MPa, the molar ratio of alcohol to oil was 16:1, and the mass space velocity was 5h -1 to esterify the rubber seed oil. After the reacted mixture was separated and recovered for methanol and glycerin (yield nearly 8 wt%), the content of fatty acid methyl ester was 95 wt%.
  • Fatty acid methyl esters are subjected to catalytic hydrogenation reaction through a tubular reactor filled with 20-mesh copper-nickel-aluminum catalyst (Cu:Ni:Al molar ratio is 1:0.3:4, prepared by co-precipitation method).
  • the process conditions are: temperature 200°C , pressure 6MPa, volume ratio of hydrogen to fatty acid methyl ester 8000:1, mass space velocity 2h -1 .
  • reaction process conditions are: temperature 380°C, pressure -0.08MPa, mass space velocity of fatty alcohol 1h - 1 .
  • reaction product is separated to obtain long-chain hydrocarbons with a content greater than 97 wt%, and the oxygen content in the long-chain hydrocarbons is less than 0.03 wt%.
  • long-chain hydrocarbons are isomerized under a nitrogen atmosphere to prepare isomerized liquid fuels.
  • the reaction process conditions are: The temperature is 320°C, the pressure is 2MPa, and the mass space velocity of long-chain hydrocarbons is 3h -1 .
  • the liquid fuel prepared by deoxygenating rubber seed oil through a series of selective reactions is mainly a hydrocarbon fuel with a main component of C 6 -C 20 , the yield reaches 81.3 wt%, and the oxygen content in the liquid fuel is 0.020 wt%.
  • the liquid fuel obtained in this embodiment can also be divided according to the boiling range to obtain gasoline, diesel and aviation fuel components, or further hydrorefining can improve the fuel quality.
  • This embodiment provides a method for preparing liquid fuel through selective catalytic deoxygenation of grease, wherein the method includes the following specific steps:
  • Fatty acid methyl esters are catalytically hydrogenated in a tubular reactor filled with a 20-mesh copper-nickel-iron-aluminum catalyst (the molar ratio of Cu:Ni:Fe:Al is 1:0.3:0.3:4, prepared by coprecipitation method).
  • the process conditions It is: temperature 180°C, pressure 10MPa, volume ratio of hydrogen to fatty acid methyl ester 600:1, mass space velocity 0.3h -1 .
  • the intramolecular dehydration of fatty alcohol is converted into long-chain hydrocarbons.
  • the reaction process conditions are: temperature 300°C , pressure 0.2MPa, mass space velocity of fatty alcohol 1h -1 .
  • the reaction product is separated by distillation to obtain long-chain hydrocarbons with a content greater than 98 wt%, and the oxygen content in the long-chain hydrocarbons is less than 0.035 wt%.
  • long-chain hydrocarbons are isomerized to prepare isomerized liquid fuels.
  • the reaction process conditions are: temperature 240 ° C, Pressure -0.05MPa, mass space velocity of long chain hydrocarbons 0.3h -1 .
  • the liquid fuel prepared by deoxygenating the waste oil of the catering industry through a series of selective reactions is mainly a hydrocarbon fuel with a main component of C6 - C20 , the yield reaches 81.3wt%, and the oxygen content in the liquid fuel is 0.023wt %.
  • the liquid fuel prepared in this embodiment can also be divided according to the boiling range to obtain gasoline, diesel and jet fuel components, or further hydrorefining can improve the fuel quality.
  • This embodiment provides a method for preparing liquid fuel through selective catalytic deoxygenation of grease, wherein the method includes the following specific steps:
  • Fatty acid methyl esters are catalytically hydrogenated through a tubular reactor filled with commercial copper-zinc-aluminum catalysts.
  • the process conditions are: temperature 230°C, pressure 16MPa, volume ratio of hydrogen to fatty acid methyl esters 6000:1, mass space velocity 1.2 h -1 .
  • the fatty alcohol content reaches 96 wt%.
  • the intramolecular dehydration of fatty alcohol is converted into long-chain hydrocarbons.
  • the reaction process conditions are: temperature 280 ° C, pressure -0.09MPa, mass space velocity of fatty alcohol 0.5h -1 .
  • the reaction product is separated to obtain long-chain hydrocarbons with a content greater than 97 wt%, and the oxygen content in the long-chain hydrocarbons is less than 0.04 wt%.
  • long-chain hydrocarbons are isomerized to prepare isomerized liquid fuels.
  • the reaction process conditions are: temperature 300°C , pressure 0.1MPa, mass space velocity of long-chain hydrocarbons 1h -1 .
  • the liquid fuel prepared by deoxygenating tallow through a series of selective reactions is mainly a hydrocarbon fuel with a main component of C6 - C20 , the yield reaches 82.5wt%, and the oxygen content in the liquid fuel is 0.024wt% .
  • the liquid fuel prepared in this embodiment can also be divided according to the boiling range to obtain gasoline, diesel and jet fuel components, or further hydrorefining can improve the fuel quality.
  • This embodiment provides a method for preparing liquid fuel through selective catalytic deoxygenation of grease, wherein the method includes the following specific steps:
  • Cottonseed oil is reacted with methanol at 210°C and 6MPa, and the molar ratio of alcohol to oil is controlled to be 9:1, and the mass space velocity is 0.5h -1 to esterify the cottonseed oil.
  • the content of fatty acid methyl ester was 96wt% after separation and recovery of methanol and glycerin (yield was about 9wt%).
  • Fatty acid methyl esters are catalytically hydrogenated through a tubular reactor filled with commercial copper-zinc-aluminum catalysts.
  • the process conditions are: temperature 250°C, pressure 10MPa, volume ratio of hydrogen to fatty acid methyl esters 2000:1, mass space velocity 0.5h -1 .
  • the fatty alcohol content reaches 97wt%.
  • the intramolecular dehydration of fatty alcohol is converted into long-chain hydrocarbons, and the reaction process conditions are: temperature 250 ° C , pressure 0.1MPa, mass space velocity of fatty alcohol 0.2h -1 .
  • the reaction product is separated, the long-chain hydrocarbon content obtained is greater than 96 wt%, and the oxygen content in the long-chain hydrocarbon is less than 0.04 wt%.
  • long-chain hydrocarbons are isomerized to prepare isomerized liquid fuels.
  • the reaction process conditions are: temperature 280°C , pressure -0.06MPa, mass space velocity of long chain hydrocarbons 0.5h -1 .
  • the liquid fuel prepared by deoxygenating cottonseed oil through a series of selective reactions is mainly a hydrocarbon fuel with a main component of C 6 -C 20 , with a yield of 82.3 wt % and an oxygen content of 0.021 wt % in the liquid fuel.
  • the liquid fuel prepared in this embodiment can also be divided according to the boiling range to obtain gasoline, diesel and aviation fuel components, or further hydrorefining can improve the fuel quality.
  • This comparative example provides a method for preparing liquid fuel by selective catalytic deoxygenation of grease, wherein the method comprises the following specific steps:
  • Fatty acid methyl esters are subjected to catalytic hydrogenation reaction through a tubular reactor filled with 20-mesh copper-nickel-aluminum catalyst (Cu:Ni:Al molar ratio is 1:0.3:4, prepared by co-precipitation method).
  • the process conditions are: temperature 200°C , pressure 6MPa, volume ratio of hydrogen to fatty acid methyl ester 8000:1, mass space velocity 2h -1 .
  • Fatty alcohols are directly passed through a tubular reactor packed with SAPO-31 and SAPO-11 (mass ratio: 1:1) catalysts, and the fatty alcohols are dehydrated and isomerized under the action of the catalyst in a nitrogen atmosphere to obtain isomerization
  • the process conditions for dehydration isomerization of liquid fuels are as follows: temperature 320°C, pressure 2MPa, mass space velocity of fatty alcohol 3h -1 .
  • Example 2 Comparing Example 2 and Comparative Example 1, it can be seen that in Example 2, the intramolecular dehydration of fatty alcohols is converted into long-chain hydrocarbons, specifically: in the tower reactor filled with ⁇ -Al 2 O 3 catalysts, the intramolecular dehydration of fatty alcohols Dehydration is converted into long-chain hydrocarbons.
  • the reaction process conditions are: temperature 380°C, pressure -0.08MPa, mass space velocity of fatty alcohol 1h -1 .
  • the reaction product is separated to obtain long-chain hydrocarbons with a content greater than 97 wt%, and the oxygen content in the long-chain hydrocarbons is less than 0.03 wt%.
  • the obtained long-chain hydrocarbons are mainly terminal olefins, the content of which is greater than 95 wt%. Then make this kind of high-purity long-chain terminal olefins in a tubular reactor filled with SAPO-31 and SAPO-11 (mass ratio is 1:1) catalysts, and carry out long-chain terminal olefin isolation under nitrogen atmosphere.
  • the isomerized liquid fuel is obtained through the formation reaction, and the specific reaction process conditions are: temperature 320°C, pressure 2MPa, mass space velocity of long-chain terminal olefins 3h -1 .
  • Example 2 the intramolecular dehydration of fatty alcohols into long-chain hydrocarbons and then the isomerization of long-chain hydrocarbons to prepare liquid fuels can suppress the generation of cracking reaction products, wherein the selectivity of C 12 -C 18 components is greater than 80%, and the oxygen content in the liquid fuel is almost zero; in comparison, in Comparative Example 1, the fatty alcohol obtained by catalytic hydrogenation conversion of fatty acid methyl ester is directly dehydrated and isomerized to prepare isomerized liquid fuel. The way of preparing liquid fuel cannot suppress the formation of cracking reaction products. Correspondingly, in Comparative Example 1, the selectivity of C 12 -C 18 components drops to 62%, and the oxygen content in liquid fuel is about 2.8wt%.
  • the method for preparing liquid fuel by selective catalytic deoxygenation of grease provided by the embodiment of the present invention first dehydrates fatty alcohols into long-chain hydrocarbons, and then isomerizes long-chain hydrocarbons to prepare liquid fuels, which can avoid
  • the water produced by alcohol catalytic deoxygenation leads to an increase in the oxygen content of isomer products, which can reduce the adverse effects of by-product water and prolong the service life of the catalyst; Isomerizing long-chain hydrocarbons to produce liquid fuels can also significantly reduce hydrogen consumption.

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Abstract

一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料，其中，所述方法包括：S1：先使油脂甲酯化转化为脂肪酸甲酯；S2：然后使脂肪酸甲酯催化加氢转化为脂肪醇；S3：再使脂肪醇分子内脱水转化为长链烃；S4：最后使长链烃异构化制备得到液体燃料。该油脂选择性催化脱氧制备液体燃料的方法具有原料适应性强、工艺流程简单、催化剂廉价易得、可显著降低氢耗、所得燃料产品选择性好、可增产甘油等优势。

Description

一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料 技术领域
本发明涉及一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料，属于生物质能源技术领域。
背景技术
液体燃料，如汽油、柴油、航空燃油等，是非常重要的动力燃料，是经济社会发展的重要物质基础。长期大量使用化石资源制备液体燃料，已对环境产生温室效应等负面影响。而且这些不可再生资源的储量会随着不断消耗而逐年减少。可再生的动植物油脂制备的脱氧液体燃料，具有热值高，燃烧性能好，与石化燃料组成相似、兼容性好等优异特点，受到广泛重视。因此，世界各国日益重视油脂制备脱氧液体燃料技术的研究。
油脂制备脱氧液体燃料，可以先使油脂在硫化NiMo/γ-Al 2O 3或CoMo/γ-Al 2O 3催化剂作用下加氢脱氧转化为长链烷烃，长链烷烃再经负载了Pt、Pd等贵金属的酸性分子筛催化剂(如Pt/ZSM-22)催化异构制备液体燃料。改变催化剂和异构化条件，可以选择性主产汽油、柴油或航空煤油燃料。例如，加拿大Canmet能源技术中心开发的油脂加氢制备高十六烷值柴油的技术，芬兰Neste Oil公司在Porvoo建立的油脂催化加氢脱氧制备柴油技术以及UOP开发的生物质制备航空煤油技术。
硫化的加氢催化剂会因为硫流失而降低催化活性，并因此产生硫污染。选用镍、钯、铂、钌等加氢金属催化剂，可以避免硫的相关问题。最近，中国专利CN 102876350A公开了Ru系催化剂催化油脂或脂肪酸加氢脱氧制备烷烃类燃料的技术。或者也可以直接用双功能催化剂将加氢脱氧和裂解/异构耦合在单段内完成，例如Herskowitz等(Earth and Environmental Science 93(2017)012003)用Pt/SAPO-11催化油脂在300-450℃、1-6MPa、0.5-5.0h -1的条件下一步反应得到凝点和冷滤点较低的柴油组分。
油脂直接加氢脱氧，氧元素完全以水的形式脱除，这不仅需要消耗大量的氢气，而且会损失甘油(加氢产生丙烷)，例如，每摩尔脂肪酸甘油酯加氢完全脱氧理论耗氢量不小于12摩尔。
将油脂先水解(或甲酯化)，释放甘油，然后催化脂肪酸(或脂肪酸甲酯)选择性脱羧/羰，使氧元素以CO 2/CO的形式脱除，可以显著减少氢气消耗。Murzin等(Top Catal(2011)54:460–466)报道了负载Pt、Pd贵金属的Al 2O 3或SiO 2催化剂能高选择性催化脂 肪酸脱羧。在250-350℃、0.1-2MPa的条件下，硬脂酸转化率大于80％，正十七烷选择性约为93％。与加氢脱氧反应相比，氢气消耗量下降70％-90％。脂肪酸酯选择性脱羧/羰的催化剂也已经报道，例如，Pt/Al 2O 3催化硬脂酸甲酯非加氢脱氧(Catal Lett(2009)130:9-18)。这些通过脱羧/羰的非加氢脱氧反应压力通常低于2MPa，几乎不消耗氢气，或极少消耗氢气。这些优势引起了研究人员的极大兴趣。
油脂加氢脱氧得到烷烃，或者经脂肪酸或其甲酯选择性脱羧/脱羰得到烷烃，烷烃再临氢裂解/异构，都需要使用Pt、Pd等贵金属，这会显著提高催化剂的成本。
为了减少甚至避免贵金属异构化催化剂的使用，降低催化剂成本、简化异构化过程，中国专利CN107987868A公开了一种油脂分步脱氧制备液体燃料的方法，其中，油脂经脂肪醇同步催化脱氧/异构制备燃料。但是脂肪醇催化脱氧产生的水通常会导致异构产物氧含量增加并缩短催化剂寿命。为减少副产水的不利影响，中国专利CN110066679A公开了一种脂肪醇制备液体燃料的方法，其是将脂肪醇脱氧产生的水和裂解气一起连续分出，并且对反应产物加氢精炼得到燃料。
为了进一步降低油脂脱氧的氢耗，避免使用硫化催化剂和贵金属催化剂，增产甘油，以期能为油脂制备脱氧液体燃料实现降耗增效，提供一种新型的油脂选择性催化脱氧制备液体燃料的方法及液体燃料已经成为本领域亟需解决的技术问题。
发明内容
为了解决上述的缺点和不足，本发明的目的在于提供一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料。
为了实现以上目的，一方面，本发明提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括：
S1：先使油脂甲酯化转化为脂肪酸甲酯；
S2：然后使脂肪酸甲酯催化加氢转化为脂肪醇；
S3：再使脂肪醇分子内脱水转化为长链烃；
S4：最后使长链烃异构化制备得到液体燃料。
作为本发明以上所述方法的一具体实施方式，其中，所述油脂为动物油脂和/或植物油脂，所述油脂中碳链长度为C 12-C 24的脂肪酸含量大于80wt％，脂肪酸甘油酯和游离脂肪酸的总含量大于90wt％。
作为本发明以上所述方法的一具体实施方式，其中，所述油脂包括牛油、猪油、鸡油、菜籽油、大豆油、棉籽油、棕榈油、玉米油、橡胶籽油、餐饮业废油、地沟油、酸 化油、酸败油等动植物油脂，或者经过其它用途，但是脂肪酸主体结构没有发生变化的煎炸油、油脂润滑油等劣质油脂。
为了提高液体燃料的质量，简化后续精炼工艺，并延长催化剂的寿命，应该适当降低油脂原料中硫、磷、氮、氯和金属等杂质的含量。在本发明一些实施例中，所用的油脂原料经过精制后，其中硫、磷、氮、氯和金属等杂质的含量应分别小于100ppm、200ppm、300ppm、400ppm和1000ppm。
作为本发明以上所述方法的一具体实施方式，其中，S1中，所述的油脂甲酯化为使油脂与甲醇反应转化为脂肪酸甲酯。
作为本发明以上所述方法的一具体实施方式，其中，S1中，使油脂与甲醇在临界甲醇条件下反应、酶催化条件下反应、均相或非均相酸催化条件下反应或者均相或非均相碱催化条件下反应转化为脂肪酸甲酯。
其中，本发明对S1中油脂甲酯化所用的反应器、工艺条件以及所用催化剂等均不做具体要求，本领域技术人员可以根据实际作业需要合理进行选择，只要保证可以实现本发明的目的即可。
在本发明一些实施例中，针对不同品质的油脂原料，需要选用不同催化剂催化油脂甲酯化，针对不同品质的油脂原料和不同的催化剂，油脂甲酯化的工艺条件包括：温度60-300℃、压力0.1-20MPa、质量空速0.3-5h -1、醇油摩尔比3:1-16:1；
所用反应器可为塔式反应器或管式反应器等连续反应器，以提高反应效率。
上述方法中，油脂甲酯化后的混合物可以进一步精炼分离或减压蒸馏。
作为本发明以上所述方法的一具体实施方式，其中，S1中，油脂甲酯化并精炼后，所得产物中脂肪酸甲酯含量不小于80wt％。
作为本发明以上所述方法的一具体实施方式，其中，S1中，油脂甲酯化并精炼后，所得产物中脂肪酸甲酯含量不小于85wt％。
作为本发明以上所述方法的一具体实施方式，其中，S1中，油脂甲酯化并精炼后，所得产物中脂肪酸甲酯含量为95-100wt％。
作为本发明以上所述方法的一具体实施方式，其中，S2中，脂肪酸甲酯催化加氢转化为脂肪醇所用的催化剂为负载型催化剂，所述负载型催化剂使用的加氢活性金属包括铂、钯、金、银、钴、钼、铜、镍、锌、铁、铬、钡及锰等中的一种或多种，载体为活性炭、Al 2O 3或者SiO 2等高比表面积载体。
综合考虑催化剂成本、活性和选择性，优选以铜、钴、钼、镍、铁、锌及锰等非贵金属中的一种或多种为活性中心的负载型催化剂。
作为本发明以上所述方法的一具体实施方式，其中，S2中，脂肪酸甲酯催化加氢转化为脂肪醇的工艺条件包括：温度160-300℃、压力2-20MPa、质量空速0.3-3h -1、氢油体积比500:1-15000:1。副产甲醇可以循环利用。
作为本发明以上所述方法的一具体实施方式，其中，S2中，脂肪酸甲酯催化加氢转化为脂肪醇所用的反应器可以是反应釜、塔式反应器和固定床反应器等，优选塔式反应器或固定床管式反应器。
作为本发明以上所述方法的一具体实施方式，其中，S2中，脂肪酸甲酯催化加氢转化并精炼后，所得产物中脂肪醇含量大于86wt％。
作为本发明以上所述方法的一具体实施方式，其中，S2中，脂肪酸甲酯催化加氢转化并精炼后，所得产物中脂肪醇含量为92-100wt％。为改善后续反应效果，可以通过吸附、蒸馏等方式分离高沸点组分。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化为长链烃所用的催化剂为NH 3吸附后的脱附温度为150-600℃的酸催化剂。其中，所述酸催化剂可在非氢气氛条件下选择性催化长链脂肪醇分子内脱水转化为长链烃。作为本发明以上所述方法的一具体实施方式，其中，S3中，所述酸催化剂包括γ-Al 2O 3、ZrO 2、ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、Y分子筛和β分子筛等中的一种或多种。
在本发明一些较为优选的实施方式中，S3中，所述酸催化剂包括γ-Al 2O 3和/或ZrO 2，以及γ-Al 2O 3和/或ZrO 2与ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、Y分子筛和β分子筛等中的一种或几种的组合。
作为本发明以上所述方法的一具体实施方式，其中，S3中，当将γ-Al 2O 3和/或ZrO 2与ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、Y分子筛和β分子筛等中的一种或几种的组合作为酸催化剂使用时，弱酸性的γ-Al 2O 3的含量大于20wt％，弱酸性的ZrO 2的含量大于20wt％。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化过程所涉及的反应包括脱水、裂解、异构、环化等反应中的一种或多种。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化为长链烃的工艺条件包括：温度250-400℃、压力-0.1MPa至0.5MPa、质量空速为0.2-4h -1。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化并精炼后，所得长链烃中氧含量小于0.1wt％。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化并精炼后，所得长链烃中氧含量小于0.05wt％。为改善后续反应效果，可以通过吸附、蒸馏等方式分离高沸点组分。
作为本发明以上所述方法的一具体实施方式，其中，S3中，脂肪醇分子内脱水转化所用的反应器可为反应釜、塔式反应器和固定床反应器等，优选塔式反应器或固定床反应器。
作为本发明以上所述方法的一具体实施方式，其中，S4中，长链烃异构化制备液体燃料所用的催化剂为NH 3吸附后的脱附温度为150-600℃的酸催化剂。其中，所述酸催化剂可在非氢气氛条件下选择性催化长链烃异构化得到液体燃料。
作为本发明以上所述方法的一具体实施方式，其中，S4中，所述酸催化剂包括ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、EU-1、Y分子筛和β分子筛等中的一种或多种。
作为本发明以上所述方法的一具体实施方式，其中，S4中，长链烃异构化过程所涉及的反应包括裂解、异构、环化、叠合等中的一种或多种。
作为本发明以上所述方法的一具体实施方式，其中，S4中，长链烃异构化制备液体燃料的工艺条件包括：温度200-420℃、压力-0.1MPa至4MPa、质量空速0.2-3h -1。
作为本发明以上所述方法的一具体实施方式，其中，S4中，长链烃异构化制备液体燃料所用的反应器可为反应釜、塔式反应器和固定床反应器等，优选塔式反应器或固定床反应器。
另一方面，本发明还提供了一种液体燃料，其中，所述液体燃料是由以上所述的油脂选择性催化脱氧制备液体燃料的方法制得。
作为本发明以上所述液体燃料的一具体实施方式，其中，所述液体燃料的氧含量小于0.05wt％。
根据油脂原料的组成、催化剂和工艺条件的差异，由本发明提供的油脂选择性催化脱氧制备液体燃料的方法得到的发动机液体燃料的主要成分为C 6-C 20的烃，并可以通过改变油脂原料的脂肪酸组成、催化剂和工艺条件等，调整液体燃料的组成。
为了得到适用于汽油、柴油或航空煤油的优质产品，该液体燃料可以进一步加氢精炼或精馏分离，以得到合适馏分的目标产品。
本发明提供的油脂选择性催化脱氧制备液体燃料的方法，具有显著的有益效果，包括：
1、该方法对原料适应性强，可以直接加工劣质油脂原料，可显著降低原料成本；
2、该方法还可避免硫化催化剂相关问题，可显著简化工艺流程；
3、该方法还可避免贵金属催化剂的使用，所使用的催化剂廉价易得，降低了催化剂成本；
4、该方法还可显著降低氢耗以及物耗；
5、该方法还可增产附加值较高的甘油，提高产值；
6、该方法的反应过程高度可控，目标产品选择性好并且氧含量较低；
7、另外，还可以通过改变该方法中的原料、催化剂和工艺条件，灵活调节产品组成，提高市场适应性。
具体实施方式
需要说明的是，本发明的说明书和权利要求书中的术语“包括”以及其任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
本发明所公开的“范围”以下限和上限的形式给出。可以分别为一个或多个下限，和一个或多个上限。给定的范围是通过选定一个下限和一个上限进行限定的。选定的下限和上限限定了特别范围的边界。所有以这种方式进行限定的范围是可组合的，即任何下限可以与任何上限组合形成一个范围。例如，针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是可以预料到的。此外，如果列出的最小范围值为1和2，列出的最大范围值为3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。
在本发明中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本发明中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。
在本发明中，如果没有特别的说明，本发明所提到的所有实施方式以及优选实施方式可以相互组合形成新的技术方案。
在本发明中，如果没有特别的说明，本发明所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领 域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。所使用的实验方法如无特殊说明，均为现有常规方法。
实施例1
本实施例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使用甲醇钠(用量为精炼大豆油质量的0.5％)催化精炼大豆油与甲醇在80℃、常压下反应，并控制醇油摩尔比为7:1，质量空速为0.7h -1，以将精炼大豆油甲酯化。经过分离甲醇和甘油(产率近10wt％)后，所得产物中脂肪酸甲酯的含量为97wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了10目的铜锌铝催化剂(Cu:Zn:Al的摩尔比为1:0.8:4，共沉淀法制备得到)的管式反应器进行催化加氢反应，工艺条件为：温度240℃、压力20MPa、氢气与脂肪酸甲酯的体积比15000:1、质量空速0.5h -1。脂肪酸甲酯催化加氢反应后，经过闪蒸后得到的脂肪醇含量达到98wt％。
脂肪醇分子内脱水转化为长链烃：
在装填了ZSM-22和γ-Al 2O 3(质量比为1:1)催化剂的管式反应器中，脂肪醇分子内脱水转化为长链烃，反应的工艺条件为：温度380℃、压力0.1MPa、脂肪醇的质量空速为3h -1，所得反应产物经过蒸馏分离，长链烃含量大于98wt％，长链烃中氧含量小于0.04wt％。
长链烃异构化制备得到液体燃料：
在装填了ZSM-48和ZSM-22(质量比为1:1)催化剂的管式反应器中，长链烃异构化制备得到异构化的液体燃料，其中反应的工艺条件为：温度300℃、压力0.1MPa、长链烃的质量空速为1h -1。
本实施例中，精炼大豆油经过系列选择性反应脱氧制备的液体燃料主要是主要成分为C 6-C 20的烃类燃料，产率达到83.4wt％，液体燃料中的氧含量为0.028wt％。另外，还可以根据沸程将本实施例所得到的液体燃料切分得到汽油、柴油和航煤组分，也可以进一步加氢精炼提高产品的质量。
实施例2
本实施例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包 括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使酸值为30mgKOH/g的橡胶籽油与甲醇在300℃、20MPa条件下反应，醇油摩尔比为16:1、质量空速为5h -1，以将橡胶籽油甲酯化。反应后的混合物分离回收甲醇和甘油(产率近8wt％)后，脂肪酸甲酯的含量为95wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了20目的铜镍铝催化剂(Cu:Ni:Al摩尔比为1:0.3:4，共沉淀法制备)的管式反应器进行催化加氢反应，工艺条件为：温度200℃、压力6MPa、氢气与脂肪酸甲酯的体积比8000:1、质量空速2h -1。脂肪酸甲酯选择性催化加氢反应结束后，对所得产品进行闪蒸后得到的脂肪醇含量达到94wt％。
脂肪醇分子内脱水转化为长链烃：
在装填了γ-Al 2O 3催化剂的塔式反应器中，脂肪醇分子内脱水转化为长链烃，反应工艺条件为：温度380℃、压力-0.08MPa、脂肪醇的质量空速1h -1。反应结束后，反应产物经过分离，得到长链烃含量大于97wt％，长链烃中氧含量小于0.03wt％。
长链烃异构化制备得到液体燃料：
在装填了SAPO-31和SAPO-11(质量比为1:1)催化剂的管式反应器中，氮气氛下长链烃异构化制备得到异构化的液体燃料，反应的工艺条件为：温度320℃、压力2MPa、长链烃的质量空速3h -1。
本实施例中，橡胶籽油经过系列选择性反应脱氧制备的液体燃料主要是主要成分为C 6-C 20的烃类燃料，产率达到81.3wt％，液体燃料中的氧含量为0.020wt％。另外，还可以根据沸程将本实施例所得到的液体燃料切分得到汽油、柴油和航煤组分，或者进一步加氢精炼提高燃油品质。
实施例3
本实施例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使ZSM-5酸性分子筛催化酸败的餐饮业废油与甲醇在160℃、1MPa下反应，并控制醇油摩尔比为7:1，质量空速为0.5h -1，以将餐饮业废油甲酯化。反应结束后，经过分离甲醇和甘油(产率约为5wt％)后，减压精馏得到精炼脂肪酸甲酯，其含量为99wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了20目的铜镍铁铝催化剂(Cu:Ni:Fe:Al摩尔比为1:0.3:0.3:4， 共沉淀法制备)的管式反应器进行催化加氢反应，工艺条件为：温度180℃、压力10MPa、氢气与脂肪酸甲酯的体积比600:1、质量空速0.3h -1。脂肪酸甲酯催化加氢反应结束后，对反应所得产物进行闪蒸后得到的脂肪醇含量达到97wt％。
脂肪醇分子内脱水转化为长链烃：
在装填了ZSM-35和γ-Al 2O 3(质量比为1:1)分子筛催化剂的管式反应器中，脂肪醇分子内脱水转化为长链烃，反应的工艺条件为：温度300℃、压力0.2MPa、脂肪醇的质量空速1h -1。反应产物经过蒸馏分离，得到长链烃含量大于98wt％，长链烃中氧含量小于0.035wt％。
长链烃异构化制备得到液体燃料：
在装填了ZSM-5和Y分子筛(质量比为1:1)催化剂的管式反应器中，长链烃异构化制备得到异构化的液体燃料，反应的工艺条件为：温度240℃、压力-0.05MPa、长链烃的质量空速0.3h -1。
本实施例中，餐饮业废油经过系列选择性反应脱氧制备的液体燃料主要是主要成分为C 6-C 20的烃类燃料，产率达到81.3wt％，液体燃料中的氧含量为0.023wt％。另外，还可以根据沸程将本实施例制得的液体燃料切分得到汽油、柴油和航煤组分，或者进一步加氢精炼提高燃油品质。
实施例4
本实施例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使牛油与甲醇在260℃、6MPa条件下反应，并控制醇油摩尔比为10:1，质量空速为0.5h -1，将牛油甲酯化。反应结束后，经过分离回收甲醇和甘油(甘油产率约为8wt％)后，脂肪酸甲酯的含量为97wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了商用的铜锌铝催化剂的管式反应器进行催化加氢反应，工艺条件为：温度230℃、压力16MPa、氢气与脂肪酸甲酯的体积比6000:1、质量空速1.2h -1。脂肪酸甲酯催化加氢反应得到的产物中，脂肪醇含量达到96wt％。
脂肪醇分子内脱水转化为长链烃：
在装填了ZSM-23和γ-Al 2O 3(质量比为1:1)催化剂的塔式反应器中，脂肪醇分子内脱水转化为长链烃，反应工艺条件为：温度280℃、压力-0.09MPa、脂肪醇的质量空速0.5h -1。反应产物经过分离，得到长链烃含量大于97wt％，长链烃中氧含量小于 0.04wt％。
长链烃异构化制备得到液体燃料：
在装填了ZSM-48和SAPO-11(质量比为1:1)催化剂的管式反应器中，长链烃异构化制备得到异构化的液体燃料，反应的工艺条件为：温度300℃、压力0.1MPa、长链烃的质量空速1h -1。
本发明实施例中，牛油经过系列选择性反应脱氧制备的液体燃料主要是主要成分为C 6-C 20的烃类燃料，产率达到82.5wt％，液体燃料中的氧含量为0.024wt％。另外，还可以根据沸程将本实施例制得的液体燃料切分得到汽油、柴油和航煤组分，或者进一步加氢精炼提高燃油品质。
实施例5
本实施例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使棉籽油与甲醇在210℃、6MPa条件下反应，并控制醇油摩尔比为9:1，质量空速为0.5h -1，以将棉籽油甲酯化。反应结束后，经过分离回收甲醇和甘油(产率约为9wt％)后，脂肪酸甲酯的含量为96wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了商用铜锌铝催化剂的管式反应器进行催化加氢反应，工艺条件为：温度250℃、压力10MPa、氢气与脂肪酸甲酯的体积比2000:1、质量空速0.5h -1。脂肪酸甲酯催化加氢反应得到的产物中，脂肪醇含量达到97wt％。
脂肪醇分子内脱水转化为长链烃：
在装填了ZrO 2和ZSM-22(二者按照质量比为1:1混合)分子筛催化剂的管式反应器中，脂肪醇分子内脱水转化为长链烃，反应的工艺条件为：温度250℃、压力0.1MPa、脂肪醇的质量空速0.2h -1。反应产物经过分离，得到的长链烃含量大于96wt％，长链烃中氧含量小于0.04wt％。
长链烃异构化制备得到液体燃料：
在装填了ZSM-48和ZSM-23(质量比为1:1)催化剂的管式反应器中，长链烃异构化制备得到异构化的液体燃料，反应的工艺条件为：温度280℃、压力-0.06MPa、长链烃的质量空速0.5h -1。
本实施例中，棉籽油经过系列选择性反应脱氧制备的液体燃料主要是主要成分为C 6-C 20的烃类燃料，产率达到82.3wt％，液体燃料中的氧含量为0.021wt％。另外，还可 以根据沸程将本实施例所制得的液体燃料切分得到汽油、柴油和航煤组分，或者进一步加氢精炼提高燃油品质。
对比例1
本对比例提供了一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括以下具体步骤：
油脂甲酯化转化为脂肪酸甲酯：
使酸值为30mgKOH/g的橡胶籽油与甲醇在300℃、20MPa条件下进行反应，并控制醇油摩尔比为16:1、质量空速为5h -1，以将橡胶籽油甲酯化。反应后的混合物分离回收甲醇和甘油(产率近8wt％)后，脂肪酸甲酯的含量为95wt％。
脂肪酸甲酯催化加氢转化为脂肪醇：
脂肪酸甲酯经过装填了20目的铜镍铝催化剂(Cu:Ni:Al摩尔比为1:0.3:4，共沉淀法制备)的管式反应器进行催化加氢反应，工艺条件为：温度200℃、压力6MPa、氢气与脂肪酸甲酯的体积比8000:1、质量空速2h -1。脂肪酸甲酯选择性催化加氢反应结束后，对所得产品进行闪蒸后得到的脂肪醇含量达到94wt％。
液体燃料的制备：
使脂肪醇直接经过装填了SAPO-31和SAPO-11(质量比为1:1)催化剂的管式反应器，于氮气氛下所述脂肪醇在催化剂作用下脱水异构化制得异构化的液体燃料，脱水异构化的工艺条件为：温度320℃、压力2MPa、脂肪醇的质量空速3h -1。
对比实施例2和对比例1可知，实施例2中，脂肪醇分子内脱水转化为长链烃，具体为：在装填了γ-Al 2O 3催化剂的塔式反应器中，脂肪醇分子内脱水转化为长链烃，反应工艺条件为：温度380℃、压力-0.08MPa、脂肪醇的质量空速1h -1。反应结束后，反应产物经过分离，得到长链烃含量大于97wt％，长链烃中氧含量小于0.03wt％。其中所得到的长链烃主要是端位烯烃，其含量大于95wt％。随后使这类高纯度的长链端位烯烃在装填了SAPO-31和SAPO-11(质量比为1:1)催化剂的管式反应器中，并于氮气氛下进行长链端位烯烃异构化反应得到异构化的液体燃料，具体的反应工艺条件为：温度320℃、压力2MPa、长链端位烯烃的质量空速3h -1。实施例2中先使脂肪醇分子内脱水转化为长链烃再使长链烃异构化制备得到液体燃料的方式可以抑制裂解反应产物的生成，其中，C 12-C 18组分的选择性大于80％，而且液体燃料中氧含量几乎为零；相较而言，对比例1中使脂肪酸甲酯催化加氢转化得到的脂肪醇直接脱水异构化制备异构化的液体燃料，该种制备液体燃料的方式无法抑制裂解反应产物的生成，相应地，对比例1中，C 12-C 18组分的选择性下降至62％，而且液体燃料中氧含量约为2.8wt％。
综上，本发明实施例所提供的油脂选择性催化脱氧制备液体燃料的方法先使脂肪醇分子内脱水转化为长链烃，再使长链烃异构化制备得到液体燃料，可以避免因脂肪醇催化脱氧产生的水导致的异构产物氧含量增加，即可减少副产水的不利影响，还可以延长催化剂的使用寿命；同时，该方法使脂肪醇分子内脱水转化为长链烃，再使长链烃异构化制备得到液体燃料还可以显著减少氢气消耗。
以上所述，仅为本发明的具体实施例，不能以其限定发明实施的范围，所以其等同组件的置换，或依本发明专利保护范围所作的等同变化与修饰，都应仍属于本专利涵盖的范畴。另外，本发明中的技术特征与技术特征之间、技术特征与技术发明之间、技术发明与技术发明之间均可以自由组合使用。

Claims (23)

  1. 一种油脂选择性催化脱氧制备液体燃料的方法，其中，所述方法包括：
    S1：先使油脂甲酯化转化为脂肪酸甲酯；
    S2：然后使脂肪酸甲酯催化加氢转化为脂肪醇；
    S3：再使脂肪醇分子内脱水转化为长链烃；
    S4：最后使长链烃异构化制备得到液体燃料。
  2. 根据权利要求1所述的方法，其中，所述油脂为动物油脂和/或植物油脂，所述油脂中碳链长度为C 12-C 24的脂肪酸含量大于80wt％，脂肪酸甘油酯和游离脂肪酸的总含量大于90wt％。
  3. 根据权利要求1或2所述的方法，其中，S1中，所述的油脂甲酯化为使油脂与甲醇反应转化为脂肪酸甲酯。
  4. 根据权利要求3所述的方法，其中，S1中，使油脂与甲醇在临界甲醇条件下反应、酶催化条件下反应、均相或非均相酸催化条件下反应或者均相或非均相碱催化条件下反应转化为脂肪酸甲酯。
  5. 根据权利要求1或4所述的方法，其中，S1中，油脂甲酯化并精炼后，所得产物中脂肪酸甲酯含量不小于80wt％。
  6. 根据权利要求5所述的方法，其中，S1中，油脂甲酯化并精炼后，所得产物中脂肪酸甲酯含量为95-100wt％。
  7. 根据权利要求1所述的方法，其中，S2中，脂肪酸甲酯催化加氢转化为脂肪醇所用的催化剂为负载型催化剂，所述负载型催化剂使用的加氢活性金属包括铂、钯、金、银、钴、钼、铜、镍、锌、铁、铬、钡及锰中的一种或多种，载体为活性炭、Al 2O 3或者SiO 2；
    优选地，所述加氢活性金属包括铜、钴、钼、镍、铁、锌及锰中的一种或多种。
  8. 根据权利要求1或7所述的方法，其中，S2中，脂肪酸甲酯催化加氢转化为脂肪醇的工艺条件包括：温度160-300℃、压力2-20MPa、质量空速0.3-3h -1、氢油体积比500:1-15000:1。
  9. 根据权利要求1或7所述的方法，其中，S2中，脂肪酸甲酯催化加氢转化并精炼后，所得产物中脂肪醇含量大于86wt％。
  10. 根据权利要求9所述的方法，其中，S2中，脂肪酸甲酯催化加氢转化并精炼后，所得产物中脂肪醇含量为92-100wt％。
  11. 根据权利要求1所述的方法，其中，S3中，脂肪醇分子内脱水转化为长链烃所 用的催化剂为NH 3吸附后的脱附温度为150-600℃的酸催化剂。
  12. 根据权利要求11所述的方法，其中，S3中，所述酸催化剂包括γ-Al 2O 3、ZrO 2、ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、Y分子筛和β分子筛中的一种或多种。
  13. 根据权利要求12所述的方法，其中，S3中，当将γ-Al 2O 3和/或ZrO 2与ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、Y分子筛和β分子筛中的一种或几种的组合作为酸催化剂使用时，γ-Al 2O 3的含量大于20wt％，ZrO 2的含量大于20wt％。
  14. 根据权利要求1所述的方法，其中，S3中，脂肪醇分子内脱水转化过程所涉及的反应包括脱水、裂解、异构、环化反应中的一种或多种。
  15. 根据权利要求1，11-14任一项所述的方法，其中，S3中，脂肪醇分子内脱水转化为长链烃的工艺条件包括：温度250-400℃、压力-0.1MPa至0.5MPa、质量空速为0.2-4h -1。
  16. 根据权利要求1，11-14任一项所述的方法，其中，S3中，脂肪醇分子内脱水转化并精炼后，所得长链烃中氧含量小于0.1wt％。
  17. 根据权利要求16所述的方法，其中，S3中，脂肪醇分子内脱水转化并精炼后，所得长链烃中氧含量小于0.05wt％。
  18. 根据权利要求1所述的方法，其中，S4中，长链烃异构化制备液体燃料所用的催化剂为NH 3吸附后的脱附温度为150-600℃的酸催化剂。
  19. 根据权利要求18所述的方法，其中，S4中，所述酸催化剂包括ZSM-22、ZSM-23、ZSM-48、ZSM-35、SAPO-31、SAPO-11、ZSM-5、EU-1、Y分子筛和β分子筛中的一种或多种。
  20. 根据权利要求1所述的方法，其中，S4中，长链烃异构化过程所涉及的反应包括裂解、异构、环化、叠合中的一种或多种。
  21. 根据权利要求1，18-20任一项所述的方法，其中，S4中，长链烃异构化制备液体燃料的工艺条件包括：温度200-420℃、压力-0.1MPa至4MPa、质量空速0.2-3h -1。
  22. 一种液体燃料，其中，所述液体燃料是由权利要求1-21任一项所述的油脂选择性催化脱氧制备液体燃料的方法制得。
  23. 根据权利要求22所述的液体燃料，其中，所述液体燃料的氧含量小于0.05wt％。
PCT/CN2022/126731 2021-12-23 2022-10-21 一种油脂选择性催化脱氧制备液体燃料的方法及液体燃料 Ceased WO2023116168A1 (zh)

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