CN116333823B - A method for preparing liquid fuel by selective catalytic deoxygenation of oil and fat - Google Patents
A method for preparing liquid fuel by selective catalytic deoxygenation of oil and fat Download PDFInfo
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- CN116333823B CN116333823B CN202111589504.8A CN202111589504A CN116333823B CN 116333823 B CN116333823 B CN 116333823B CN 202111589504 A CN202111589504 A CN 202111589504A CN 116333823 B CN116333823 B CN 116333823B
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- fatty acid
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- liquid fuel
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- 238000000034 method Methods 0.000 title claims abstract description 106
- 239000000446 fuel Substances 0.000 title claims abstract description 85
- 239000007788 liquid Substances 0.000 title claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 238000006392 deoxygenation reaction Methods 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 72
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 72
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 65
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 24
- 230000018044 dehydration Effects 0.000 claims abstract description 23
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 23
- 230000032050 esterification Effects 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000004519 grease Substances 0.000 claims description 38
- 235000019197 fats Nutrition 0.000 claims description 20
- 238000006317 isomerization reaction Methods 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 238000007670 refining Methods 0.000 claims description 14
- 239000003377 acid catalyst Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- 235000019737 Animal fat Nutrition 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 235000021588 free fatty acids Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000019871 vegetable fat Nutrition 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 28
- 239000001257 hydrogen Substances 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 10
- 235000014593 oils and fats Nutrition 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 239000003925 fat Substances 0.000 description 12
- 239000002283 diesel fuel Substances 0.000 description 11
- 235000011187 glycerol Nutrition 0.000 description 11
- 239000003502 gasoline Substances 0.000 description 8
- 239000003350 kerosene Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- -1 fatty acid esters Chemical class 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 6
- 229920000263 Rubber seed oil Polymers 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 235000015278 beef Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical group 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 235000012343 cottonseed oil Nutrition 0.000 description 4
- 239000002385 cottonseed oil Substances 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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, 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Catalysts (AREA)
Abstract
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。本发明所提供的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。The present invention provides a method for preparing liquid fuel by selective catalytic deoxygenation of oils and fats, wherein the method comprises: S1: first converting oils and fats into fatty acid methyl esters by methyl esterification; S2: then converting fatty acid methyl esters into fatty alcohols by catalytic hydrogenation; S3: then converting fatty alcohols into long-chain hydrocarbons by intramolecular dehydration; S4: finally isomerizing long-chain hydrocarbons to prepare liquid fuels. The method for preparing liquid fuel by selective catalytic deoxygenation of oils and fats provided by the present invention has the advantages of strong raw material adaptability, simple process flow, cheap and easy-to-obtain catalysts, significantly reduced hydrogen consumption, good selectivity of the obtained fuel products, and increased production of glycerol.
Description
Technical Field
The invention relates to a method for preparing liquid fuel by grease selective catalytic deoxidation, belonging to the technical field of biomass energy.
Background
Liquid fuels, such as gasoline, diesel oil, aviation fuel oil, etc., are very important power fuels, and are important material bases for economic and social development. The long-term use of fossil resources for the production of liquid fuels in large quantities has had a negative impact on the environment, such as greenhouse effect. And reserves of these non-renewable resources decrease year by year as they continue to consume. The deoxidized liquid fuel prepared from the renewable animal and vegetable oil has the excellent characteristics of high heat value, good combustion performance, similar composition with petrochemical fuel, good compatibility and the like, and is widely valued. Therefore, research on the technology of preparing deoxidized liquid fuel from grease is increasingly paid attention to in countries around the world.
The grease is subjected to hydrodeoxygenation under the action of a sulfurized NiMo/gamma-Al 2O3 or CoMo/gamma-Al 2O3 catalyst to be converted into long-chain alkane, and the long-chain alkane is subjected to catalytic isomerization by an acidic molecular sieve catalyst (such as Pt/ZSM-22) loaded with noble metals such as Pt and Pd to prepare the liquid fuel. The catalyst and isomerization conditions are changed, and the gasoline, diesel oil or aviation kerosene fuel can be selectively and mainly produced. For example, the technology for preparing diesel Oil with high cetane number by hydrogenating grease developed by Canmet energy technology center in Canada, the technology for preparing diesel Oil by catalytic hydrodeoxygenation of grease established by Neste Oil company Porvoo in Finland, and the technology for preparing aviation kerosene by biomass developed by UOP.
Sulfided hydrogenation catalysts can reduce catalytic activity due to sulfur loss and thus produce sulfur pollution. The hydrogenation metal catalysts such as nickel, palladium, platinum, ruthenium and the like are selected, so that the related problems of sulfur can be avoided. Recently, chinese patent CN 102876350a discloses a technology for preparing an alkane fuel by catalyzing grease or fatty acid hydrodeoxygenation with a Ru-based catalyst. Alternatively, hydrodeoxygenation and cleavage/isomerisation coupling can be accomplished directly in a single stage with a bifunctional catalyst, for example, herskowitz et al (Earth and Environmental Science (2017) 012003) using Pt/SAPO-11 to catalyze the one-step reaction of fats and oils at 300-450 ℃, 1-6MPa, 0.5-5.0h -1 to obtain a diesel fuel component with lower congealing and cold filtration points.
The grease is directly hydrodeoxygenated, and the oxygen is completely removed in the form of water, which not only consumes a great amount of hydrogen, but also can lose glycerin (hydrogenation to produce propane), for example, the theoretical hydrogen consumption of complete deoxygenation per mole of fatty acid glyceride is not less than 12 moles.
The grease is hydrolyzed (or methyl esterified) firstly to release glycerin, and then the fatty acid (or fatty acid methyl ester) is catalyzed to be selectively decarboxylated/carbonyl, so that oxygen elements are removed in the form of CO 2/CO, and the hydrogen consumption can be obviously reduced. Murzin et Al (Top Catal (2011) 54:460-466) reported that the Pt, pd noble metal supported Al 2O3 or SiO 2 catalysts were capable of highly selective catalytic fatty acid decarboxylation. At 250-350 ℃ and 0.1-2MPa, the conversion rate of stearic acid is more than 80%, and the selectivity of n-heptadecane is about 93%. Compared with hydrodeoxygenation reaction, the hydrogen consumption is reduced by 70-90%. Catalysts for the selective decarboxylation/carbonyl of fatty acid esters have also been reported, for example, pt/Al 2O3 to catalyze the non-hydrodeoxygenation of methyl stearate (CATAL LETT (2009) 130:9-18). These non-hydrodeoxygenation reactions by decarboxylation/carbonyl typically have a pressure below 2MPa and consume little or no hydrogen. These advantages have led to great interest in researchers.
The grease is hydrodeoxygenated to obtain alkane, or the alkane is obtained through the selective decarboxylation/decarbonylation of fatty acid or methyl ester thereof, and the alkane is hydrocracked/isomerized again, so that noble metals such as Pt, pd and the like are needed, and the cost of the catalyst can be obviously increased.
In order to reduce or even avoid the use of noble metal isomerization catalysts, reduce catalyst cost and simplify isomerization process, chinese patent CN107987868a discloses a method for preparing liquid fuel by step-wise deoxygenation of fats and oils, wherein the fats and oils are subjected to synchronous catalytic deoxygenation/isomerization of fatty alcohols to prepare fuel. However, the water produced by catalytic deoxygenation of fatty alcohols generally results in increased oxygen content of the isomerised products and reduced catalyst life. In order to reduce the adverse effect of byproduct water, chinese patent CN110066679a discloses a method for preparing liquid fuel from fatty alcohol, which continuously separates water produced by deoxidizing fatty alcohol and pyrolysis gas together, and hydrofining the reaction product to obtain fuel.
In order to further reduce the hydrogen consumption of grease deoxidation, avoid using a vulcanization catalyst and a noble metal catalyst and increase the yield of glycerol, so as to realize consumption reduction and synergy for preparing the deoxidized liquid fuel by the grease, the novel method for preparing the liquid fuel by the grease selective catalytic deoxidation is provided, which becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the defects and shortcomings, the invention aims to provide a method for preparing liquid fuel by selectively catalyzing and deoxidizing grease.
In order to achieve the above object, the present invention provides a method for preparing a liquid fuel by selective catalytic deoxidation of fats and oils, wherein the method comprises:
s1, firstly, esterifying and converting grease into fatty acid methyl ester;
S2, catalytically hydrogenating fatty acid methyl ester to convert the fatty acid methyl ester into fatty alcohol;
s3, intramolecular dehydration of fatty alcohol is carried out to convert into long-chain hydrocarbon;
And S4, finally isomerizing the long-chain hydrocarbon to prepare the liquid fuel.
As a specific embodiment of the method, the grease is animal grease and/or vegetable grease, the fatty acid content of the grease with the carbon chain length of C 12-C24 is more than 80wt%, and the total content of the fatty glyceride and the free fatty acid is more than 90wt%.
As a specific embodiment of the above method of the present invention, the fat comprises animal or vegetable fat such as beef tallow, lard, chicken fat, rapeseed oil, soybean oil, cotton seed oil, palm oil, corn oil, rubber seed oil, waste oil of restaurant industry, swill-cooked oil, acidified oil, rancid oil, etc., or inferior fat such as frying oil, fat lubricating oil, etc. which is used for other purposes but has no change in the main structure of fatty acid.
In order to improve the quality of liquid fuel, simplify the subsequent refining process and prolong the service life of the catalyst, the content of sulfur, phosphorus, nitrogen, chlorine, metal and other impurities in the grease raw material should be properly reduced. In some embodiments of the present invention, the oil feedstock is refined to have less than 100ppm, 200ppm, 300ppm, 400ppm, and 1000ppm of impurities such as sulfur, phosphorus, nitrogen, chlorine, and metals.
In a specific embodiment of the above method of the present invention, in S1, the fatty acid methyl ester is formed by reacting a fatty acid methyl ester with methanol.
As a specific embodiment of the above method of the present invention, in S1, the fat and oil is reacted with methanol under critical methanol conditions, enzyme catalyzed conditions, homogeneous or heterogeneous acid catalyzed conditions or homogeneous or heterogeneous base catalyzed conditions to convert to fatty acid methyl ester.
The reactor, the process conditions, the catalyst and the like used for methyl esterification of the oil in S1 are not particularly required, and a person skilled in the art can reasonably select the reactor, the process conditions, the catalyst and the like according to actual operation needs, so long as the purpose of the invention can be realized.
In some embodiments of the invention, different catalysts are needed to catalyze the methyl esterification of the grease aiming at grease raw materials with different qualities, and the technological conditions of the methyl esterification of the grease aiming at the grease raw materials with different qualities and the different catalysts comprise the temperature of 60-300 ℃, the pressure of 0.1-20MPa, the mass airspeed of 0.3-5h -1 and the alcohol-oil mole ratio of 3:1-16:1;
the reactor can be a continuous reactor such as a tower reactor or a tubular reactor, etc. so as to improve the reaction efficiency.
In the method, the mixture after the methyl esterification of the grease can be further refined and separated or distilled under reduced pressure.
As a specific embodiment of the above method of the present invention, wherein, in S1, after methyl esterification of the fat and refining, the fatty acid methyl ester content in the obtained product is not less than 80wt%.
As a specific embodiment of the above method of the present invention, wherein, in S1, after methyl esterification of the fat and refining, the fatty acid methyl ester content in the obtained product is not less than 85wt%.
As a specific embodiment of the above method of the present invention, wherein, in S1, after methyl esterification and refining of the fat, the fatty acid methyl ester content in the obtained product is 95-100wt%.
In the step S2, the catalyst used for the catalytic hydrogenation of fatty acid methyl ester to fatty alcohol is a supported catalyst, and the hydrogenation active metal used by the supported catalyst comprises one or more of platinum, palladium, gold, silver, cobalt, molybdenum, copper, nickel, zinc, iron, chromium, barium, manganese and the like, and the carrier is a high specific surface area carrier such as activated carbon, al 2O3 or SiO 2.
In view of the catalyst cost, activity and selectivity, a supported catalyst having one or more of non-noble metals such as copper, cobalt, molybdenum, nickel, iron, zinc and manganese as an active site is preferred.
As a specific embodiment of the method, in S2, the process conditions for converting fatty acid methyl ester into fatty alcohol by catalytic hydrogenation comprise 160-300 ℃ of temperature, 2-20MPa of pressure, 0.3-3h -1 of mass airspeed and 500:1-15000:1 of hydrogen-oil volume ratio. The byproduct methanol can be recycled.
As a specific embodiment of the above-described method of the present invention, wherein in S2, the reactor for catalytic hydrogenation of fatty acid methyl ester to fatty alcohol may be a reaction vessel, a column reactor, a fixed bed reactor or the like, preferably a column reactor or a fixed bed tubular reactor.
As a specific embodiment of the above method of the present invention, in S2, after catalytic hydroconversion and refining of fatty acid methyl esters, the fatty alcohol content of the obtained product is greater than 86wt%.
As a specific embodiment of the above method of the present invention, wherein, in S2, after catalytic hydroconversion and refining of fatty acid methyl esters, the fatty alcohol content of the obtained product is 92-100wt%. To improve the subsequent reaction, the high boiling point component may be separated by adsorption, distillation, or the like.
As a specific embodiment of the above method of the present invention, in S3, the catalyst used for intramolecular dehydration conversion of fatty alcohol into long-chain hydrocarbon is an acid catalyst having a desorption temperature of 150-600 ℃ after adsorption of NH 3. Wherein the acid catalyst can selectively catalyze the intramolecular dehydration and conversion of long-chain fatty alcohol into long-chain hydrocarbon under the non-hydrogen atmosphere condition. As a specific embodiment of the above method of the present invention, wherein in S3, the acid catalyst comprises one or more of gamma-Al 2O3、ZrO2, ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y molecular sieve, beta molecular sieve, etc.
In some preferred embodiments of the invention, in S3, the acid catalyst comprises gamma-Al 2O3 and/or ZrO 2, and gamma-Al 2O3 and/or ZrO 2 in combination with one or more of ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y molecular sieve, beta molecular sieve, etc.
As a specific embodiment of the above-described method of the present invention, wherein in S3, when gamma-Al 2O3 and/or ZrO 2 are used as the acid catalyst in combination with one or more of ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y molecular sieve, beta molecular sieve, etc., the content of gamma-Al 2O3 with weak acidity is more than 20wt%, and the content of ZrO 2 with weak acidity is more than 20wt%.
As a specific embodiment of the above method of the present invention, in S3, the reaction involved in the intramolecular dehydration conversion of fatty alcohol includes one or more of dehydration, cleavage, isomerization, cyclization, and the like.
As a specific embodiment of the method, in S3, the process condition for intramolecular dehydration and conversion of fatty alcohol into long-chain hydrocarbon comprises the temperature of 250-400 ℃, the pressure of-0.1 MPa to 0.5MPa and the mass space velocity of 0.2-4h -1.
As a specific embodiment of the above-described method of the present invention, wherein, in S3, the oxygen content of the obtained long-chain hydrocarbon after intramolecular dehydration conversion and refining of the fatty alcohol is less than 0.1% by weight.
As a specific embodiment of the above-described method of the present invention, wherein, in S3, the oxygen content of the obtained long-chain hydrocarbon after intramolecular dehydration conversion and refining of the fatty alcohol is less than 0.05% by weight. To improve the subsequent reaction, the high boiling point component may be separated by adsorption, distillation, or the like.
As a specific embodiment of the above-described method of the present invention, wherein in S3, the reactor used for intramolecular dehydration conversion of fatty alcohol may be a reaction vessel, a column reactor, a fixed bed reactor or the like, preferably a column reactor or a fixed bed reactor.
As a specific embodiment of the above method of the present invention, in S4, the catalyst used for preparing the liquid fuel by isomerizing the long-chain hydrocarbon is an acid catalyst having a desorption temperature of 150-600 ℃ after adsorption of NH 3. The acid catalyst can selectively catalyze isomerization of long-chain hydrocarbon under the condition of non-hydrogen atmosphere to obtain liquid fuel.
As a specific embodiment of the above method of the present invention, wherein in S4, the acid catalyst comprises one or more of ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, EU-1, Y molecular sieve, beta molecular sieve, etc.
As a specific embodiment of the above method of the present invention, wherein the reaction involved in the isomerization process of long chain hydrocarbons in S4 comprises one or more of cracking, isomerization, cyclization, folding, and the like.
As a specific embodiment of the method, in S4, the process conditions for preparing the liquid fuel by isomerizing the long-chain hydrocarbon comprise the temperature of 200-420 ℃, the pressure of-0.1 MPa to 4MPa and the mass airspeed of 0.2-3h -1.
As a specific embodiment of the above-described method of the present invention, wherein in S4, the reactor for producing the liquid fuel by isomerizing the long-chain hydrocarbon may be a reaction vessel, a column reactor, a fixed bed reactor or the like, and a column reactor or a fixed bed reactor is preferable.
According to the difference of the composition, the catalyst and the process conditions of the grease raw materials, the main component of the engine liquid fuel obtained by the method for preparing the liquid fuel by the selective catalytic deoxidation of the grease provided by the invention is hydrocarbon with the concentration of C 6-C20, and the composition of the liquid fuel can be adjusted by changing the fatty acid composition, the catalyst, the process conditions and the like of the grease raw materials.
In order to obtain a quality product suitable for gasoline, diesel oil or aviation kerosene, the liquid fuel may be further hydrofined or separated by rectification to obtain the target product of the appropriate fraction.
The method for preparing the liquid fuel by the grease selective catalytic deoxidation has obvious beneficial effects, and comprises the following steps:
1. The method has strong adaptability to raw materials, can directly process the poor-quality grease raw materials, and can obviously reduce the raw material cost;
2. the method can also avoid the related problems of the vulcanized catalyst and can remarkably simplify the process flow;
3. the method can also avoid the use of noble metal catalysts, and the used catalysts are cheap and easy to obtain, so that the cost of the catalysts is reduced;
4. The method can also remarkably reduce hydrogen consumption and material consumption;
5. the method can also increase glycerol with higher added value and increase yield;
6. the reaction process of the method is highly controllable, and the selectivity of target products is good;
7. In addition, the product composition can be flexibly adjusted by changing the raw materials, the catalyst and the process conditions in the method, so that the market adaptability is improved.
Detailed Description
It should be noted that, in the description of the present invention and in the claims, the term "comprising" and any variations thereof, is intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements that are expressly listed or inherent to such process, method, article, or apparatus.
The "range" disclosed herein is given in the form of a lower limit and an upper limit. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges defined in this way are combinable, i.e. 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 specific parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum ranges are listed as 1 and 2 and the maximum ranges are listed as 3,4 and 5, then the ranges below are all contemplated as 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
In the present invention, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout this disclosure, and "0-5" is only a shorthand representation of a combination of these values.
In the present invention, all the embodiments and preferred embodiments mentioned in the present invention may be combined with each other to form new technical solutions, unless otherwise specified.
In the present invention, all technical features mentioned in the present invention and preferred features may be combined with each other to form a new technical solution unless specifically stated otherwise.
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The following described embodiments are some, but not all, examples of the present invention and are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The experimental methods used are all conventional methods unless specified.
Example 1
The embodiment provides a method for preparing liquid fuel by grease selective catalytic deoxidation, which comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
The refined soybean oil is catalyzed to react with methanol at 80 ℃ and normal pressure by sodium methoxide (the dosage is 0.5 percent of the mass of the refined soybean oil), the molar ratio of the alcohol to the oil is controlled to be 7:1, and the mass airspeed is controlled to be 0.7h -1, so that the refined soybean oil is methyl esterified. After separation of methanol and glycerol (yield approximately 10 wt%), the fatty acid methyl ester content of the obtained product was 97wt%.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction in a tubular reactor filled with a 10-mesh copper-zinc-aluminum catalyst (the molar ratio of Cu to Zn to Al is 1:0.8:4, and the co-precipitation method is adopted), wherein the process conditions are that the temperature is 240 ℃, the pressure is 20MPa, the volume ratio of hydrogen to fatty acid methyl ester is 15000:1, and the mass space velocity is 0.5h -1. After the catalytic hydrogenation reaction of fatty acid methyl ester, the content of fatty alcohol obtained after flash evaporation reaches 98wt%.
Intramolecular dehydration of fatty alcohols to longer chain hydrocarbons:
In a tubular reactor filled with ZSM-22 and gamma-Al 2O3 (mass ratio of 1:1) catalysts, the aliphatic alcohol is dehydrated and converted into long-chain hydrocarbon in a molecule, the reaction process conditions are that the temperature is 380 ℃, the pressure is 0.1MPa, the mass airspeed of the aliphatic alcohol is 3h -1, the obtained reaction product is distilled and separated, the content of the long-chain hydrocarbon is more than 98wt%, and the oxygen content in the long-chain hydrocarbon is less than 0.04wt%.
Isomerization of long-chain hydrocarbon to obtain liquid fuel:
In a tubular reactor filled with ZSM-48 and ZSM-22 (mass ratio of 1:1) catalysts, isomerized liquid fuel is prepared by isomerizing long-chain hydrocarbon, wherein the process conditions of the reaction are that the temperature is 300 ℃, the pressure is 0.1MPa, and the mass space velocity of the long-chain hydrocarbon is 1h -1.
In this example, the liquid fuel prepared by deoxidizing refined soybean oil through a series of selective reactions was mainly hydrocarbon fuel with a main component of C 6-C20, and the yield was 83.4wt%. In addition, the liquid fuel obtained in the embodiment can be cut according to the boiling range to obtain gasoline, diesel oil and aviation kerosene components, and the quality of the product can be further improved by hydrofining.
Example 2
The embodiment provides a method for preparing liquid fuel by grease selective catalytic deoxidation, which comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
Rubber seed oil with an acid value of 30mgKOH/g and methanol are reacted under the conditions of 300 ℃ and 20MPa, the molar ratio of the alcohol to the oil is 16:1, and the mass airspeed is 5h -1, so that the rubber seed oil is subjected to methyl esterification. After methanol and glycerin (yield: approximately 8 wt%) were recovered by separation of the reacted mixture, the content of fatty acid methyl ester was 95wt%.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction in a tubular reactor filled with a 20-mesh copper-nickel-aluminum catalyst (Cu: ni: al molar ratio is 1:0.3:4 and prepared by a coprecipitation method), wherein the technological conditions are that the temperature is 200 ℃, the pressure is 6MPa, the volume ratio of hydrogen to the fatty acid methyl ester is 8000:1, and the mass space velocity is 2h -1. After the selective catalytic hydrogenation reaction of the fatty acid methyl ester is finished, the content of the fatty alcohol obtained after flash evaporation of the obtained product reaches 94wt%.
Intramolecular dehydration of fatty alcohols to longer chain hydrocarbons:
In a tower reactor filled with a gamma-Al 2O3 catalyst, the fatty alcohol is dehydrated and converted into long-chain hydrocarbon in a molecule, and the reaction process conditions are that the temperature is 380 ℃, the pressure is-0.08 MPa, and the mass space velocity of the fatty alcohol is 1h -1. After the reaction is finished, the reaction product is separated to obtain the long-chain hydrocarbon with the content of more than 97 weight percent and the oxygen content of less than 0.03 weight percent.
Isomerization of long-chain hydrocarbon to obtain liquid fuel:
In a tubular reactor filled with SAPO-31 and SAPO-11 (mass ratio of 1:1) catalysts, isomerized liquid fuel is prepared by isomerizing long-chain hydrocarbon under nitrogen atmosphere, and the reaction process conditions are that the temperature is 320 ℃, the pressure is 2MPa, and the mass space velocity of the long-chain hydrocarbon is 3h -1.
In this example, the liquid fuel prepared by deoxidizing the rubber seed oil by a series of selective reactions is mainly hydrocarbon fuel with a main component of C 6-C20, and the yield reaches 81.3wt%. In addition, the liquid fuel obtained in the embodiment can be cut according to the boiling range to obtain gasoline, diesel oil and aviation kerosene components, or further hydrofining can be carried out to improve the fuel quality.
Example 3
The embodiment provides a method for preparing liquid fuel by grease selective catalytic deoxidation, which comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
The waste oil of the restaurant industry, which is subjected to rancidity catalysis by the ZSM-5 acidic molecular sieve, is reacted with methanol at 160 ℃ and 1MPa, the molar ratio of the alcohol to the oil is controlled to be 7:1, and the mass airspeed is controlled to be 0.5h -1, so that the waste oil of the restaurant industry is methyl esterified. After the reaction, methanol and glycerin (yield about 5 wt%) were separated, and then refined fatty acid methyl ester was obtained by vacuum distillation, the content of which was 99wt%.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction in a tubular reactor filled with a 20-mesh copper-nickel-iron-aluminum catalyst (Cu: ni: fe: al molar ratio is 1:0.3:0.3:4, and prepared by a coprecipitation method), wherein the process conditions are that the temperature is 180 ℃, the pressure is 10MPa, the volume ratio of hydrogen to fatty acid methyl ester is 600:1, and the mass space velocity is 0.3h -1. After the catalytic hydrogenation reaction of fatty acid methyl ester is finished, the content of fatty alcohol obtained after flash evaporation of the product obtained by the reaction reaches 97wt%.
Intramolecular dehydration of fatty alcohols to longer chain hydrocarbons:
In a tubular reactor filled with ZSM-35 and gamma-Al 2O3 (mass ratio of 1:1) molecular sieve catalysts, the aliphatic alcohol is dehydrated and converted into long-chain hydrocarbon in the molecule, and the reaction process conditions are that the temperature is 300 ℃, the pressure is 0.2MPa and the mass airspeed of the aliphatic alcohol is 1h -1. The reaction product is distilled and separated to obtain the long-chain hydrocarbon with the content of more than 98 weight percent and the oxygen content of less than 0.035 weight percent.
Isomerization of long-chain hydrocarbon to obtain liquid fuel:
In a tubular reactor filled with ZSM-5 and Y molecular sieve (mass ratio of 1:1) catalysts, isomerizing long-chain hydrocarbon to prepare isomerized liquid fuel, wherein the reaction process conditions are that the temperature is 240 ℃, the pressure is-0.05 MPa, and the mass space velocity of the long-chain hydrocarbon is 0.3h -1.
In this example, the liquid fuel prepared by deoxidizing waste oil of the restaurant industry through a series of selective reactions is mainly hydrocarbon fuel with a main component of C 6-C20, and the yield reaches 81.3wt%. In addition, the liquid fuel prepared in the embodiment can be cut according to the boiling range to obtain gasoline, diesel oil and aviation kerosene components, or further hydrofining can be carried out to improve the fuel quality.
Example 4
The embodiment provides a method for preparing liquid fuel by grease selective catalytic deoxidation, which comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
Allowing beef tallow and methanol to react at 260 ℃ and 6MPa, controlling the mol ratio of the beef tallow to be 10:1 and the mass airspeed to be 0.5h -1, and esterifying the beef tallow. After the completion of the reaction, methanol and glycerin (glycerin yield: about 8% by weight) were recovered by separation, and the content of fatty acid methyl ester was 97% by weight.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
the fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a commercial copper-zinc-aluminum catalyst, and the process conditions are that the temperature is 230 ℃, the pressure is 16MPa, the volume ratio of hydrogen to the fatty acid methyl ester is 6000:1, and the mass space velocity is 1.2h -1. The fatty alcohol content in the product obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 96wt%.
Intramolecular dehydration of fatty alcohols to longer chain hydrocarbons:
in a tower reactor filled with ZSM-23 and gamma-Al 2O3 (mass ratio of 1:1) catalysts, the aliphatic alcohol is dehydrated and converted into long-chain hydrocarbon in a molecule, and the reaction process conditions are that the temperature is 280 ℃, the pressure is-0.09 MPa, and the mass airspeed of the aliphatic alcohol is 0.5h -1. The reaction product is separated to obtain the long-chain hydrocarbon with the content of more than 97 weight percent and the oxygen content in the long-chain hydrocarbon with less than 0.04 weight percent.
Isomerization of long-chain hydrocarbon to obtain liquid fuel:
In a tubular reactor filled with ZSM-48 and SAPO-11 (mass ratio of 1:1) catalysts, isomerized liquid fuel is prepared by isomerizing long-chain hydrocarbon, and the reaction process conditions are that the temperature is 300 ℃, the pressure is 0.1MPa, and the mass space velocity of the long-chain hydrocarbon is 1h -1.
In the embodiment of the invention, the liquid fuel prepared by deoxidizing the beef tallow through a series of selective reactions is mainly hydrocarbon fuel with the main component of C 6-C20, and the yield reaches 82.5 weight percent. In addition, the liquid fuel prepared in the embodiment can be cut according to the boiling range to obtain gasoline, diesel oil and aviation kerosene components, or further hydrofining can be carried out to improve the fuel quality.
Example 5
The embodiment provides a method for preparing liquid fuel by grease selective catalytic deoxidation, which comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
The cottonseed oil is reacted with methanol at 210 ℃ and under 6MPa, the mol ratio of the alcohol to the oil is controlled to be 9:1, and the mass airspeed is controlled to be 0.5h -1, so that the cottonseed oil is subjected to methyl esterification. After the completion of the reaction, methanol and glycerin (yield: about 9 wt%) were recovered by separation, and the content of fatty acid methyl ester was 96wt%.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
the fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a commercial copper-zinc-aluminum catalyst, and the process conditions are that the temperature is 250 ℃, the pressure is 10MPa, the volume ratio of hydrogen to fatty acid methyl ester is 2000:1, and the mass space velocity is 0.5h -1. The fatty alcohol content in the product obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 97wt%.
Intramolecular dehydration of fatty alcohols to longer chain hydrocarbons:
in a tubular reactor filled with ZrO 2 and ZSM-22 (mixed according to the mass ratio of 1:1) molecular sieve catalyst, the fatty alcohol is dehydrated and converted into long-chain hydrocarbon in the molecule, and the reaction process conditions are that the temperature is 250 ℃, the pressure is 0.1MPa and the mass airspeed of the fatty alcohol is 0.2h -1. The reaction product is separated to obtain the long-chain hydrocarbon with the content of more than 96 weight percent and the oxygen content in the long-chain hydrocarbon is less than 0.04 weight percent.
Isomerization of long-chain hydrocarbon to obtain liquid fuel:
In a tubular reactor filled with ZSM-48 and ZSM-23 (mass ratio of 1:1) catalysts, isomerized liquid fuel is prepared by isomerizing long-chain hydrocarbon, and the reaction process conditions are that the temperature is 280 ℃, the pressure is-0.06 MPa, and the mass space velocity of the long-chain hydrocarbon is 0.5h -1.
In this example, the liquid fuel prepared by deoxidizing cottonseed oil through a series of selective reactions was mainly hydrocarbon fuel with a main component of C 6-C20, and the productivity was 82.3wt%. In addition, the liquid fuel prepared in the embodiment can be cut according to the boiling range to obtain gasoline, diesel oil and aviation kerosene components, or further hydrofining can be carried out to improve the fuel quality.
Comparative example 1
The comparative example provides a method for preparing liquid fuel by grease selective catalytic deoxidation, wherein the method comprises the following specific steps:
methyl esterification of oils and fats to fatty acid methyl esters:
Rubber seed oil with an acid value of 30mgKOH/g and methanol are reacted under the conditions of 300 ℃ and 20MPa, and the molar ratio of the alcohol to the oil is controlled to be 16:1, and the mass airspeed is controlled to be 5h -1, so that the rubber seed oil is subjected to methyl esterification. After methanol and glycerin (yield: approximately 8 wt%) were recovered by separation of the reacted mixture, the content of fatty acid methyl ester was 95wt%.
Catalytic hydrogenation conversion of fatty acid methyl esters to fatty alcohols:
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction in a tubular reactor filled with a 20-mesh copper-nickel-aluminum catalyst (Cu: ni: al molar ratio is 1:0.3:4 and prepared by a coprecipitation method), wherein the technological conditions are that the temperature is 200 ℃, the pressure is 6MPa, the volume ratio of hydrogen to the fatty acid methyl ester is 8000:1, and the mass space velocity is 2h -1. After the selective catalytic hydrogenation reaction of the fatty acid methyl ester is finished, the content of the fatty alcohol obtained after flash evaporation of the obtained product reaches 94wt%.
Preparation of liquid fuel:
Directly passing fatty alcohol through a tubular reactor filled with SAPO-31 and SAPO-11 (mass ratio is 1:1) catalysts, and dehydrating and isomerizing the fatty alcohol under the action of the catalysts in nitrogen atmosphere to obtain the isomerized liquid fuel, wherein the dehydration and isomerization process conditions are that the temperature is 320 ℃, the pressure is 2MPa, and the mass space velocity of the fatty alcohol is 3h -1.
As is clear from comparative example 2 and comparative example 1, in example 2, the intramolecular dehydration of fatty alcohol was converted into long-chain hydrocarbon, specifically, in a column reactor filled with gamma-Al 2O3 catalyst, the intramolecular dehydration of fatty alcohol was converted into long-chain hydrocarbon, and the reaction process conditions were that the temperature was 380 ℃ and the pressure was-0.08 MPa, and the mass space velocity of fatty alcohol was 1h -1. After the reaction is finished, the reaction product is separated to obtain the long-chain hydrocarbon with the content of more than 97 weight percent and the oxygen content of less than 0.03 weight percent. Wherein the resulting long chain hydrocarbons are predominantly terminal olefins, in an amount greater than 95wt%. And then, the high-purity long-chain terminal olefin is subjected to long-chain terminal olefin isomerization reaction in a tubular reactor filled with SAPO-31 and SAPO-11 (the mass ratio is 1:1) catalysts under the nitrogen atmosphere to obtain the isomerized liquid fuel, wherein the specific reaction process conditions are that the temperature is 320 ℃, the pressure is 2MPa, and the mass space velocity of the long-chain terminal olefin is 3h -1. In example 2, the liquid fuel was prepared by first dehydrating and converting fatty alcohol into long-chain hydrocarbon in the molecule and isomerizing the long-chain hydrocarbon, in which the selectivity of the C 12-C18 component was more than 80% and the oxygen content in the liquid fuel was almost zero, whereas the liquid fuel was prepared by directly dehydrating and isomerizing fatty alcohol obtained by catalytic hydroconversion of fatty acid methyl ester in comparative example 1, in which the liquid fuel was not prepared by directly dehydrating and isomerizing the fatty alcohol, and accordingly, the selectivity of the C 12-C18 component was reduced to 62% in comparative example 1 and the oxygen content in the liquid fuel was about 2.8wt%.
In summary, the method for preparing the liquid fuel by the selective catalytic deoxygenation of the grease provided by the embodiment of the invention firstly dehydrates and converts the fatty alcohol into the long-chain hydrocarbon in the molecule, and then isomerizes the long-chain hydrocarbon to prepare the liquid fuel, so that the increase of the oxygen content of an isomerised product caused by water generated by catalytic deoxygenation of the fatty alcohol can be avoided, the adverse effect of byproduct water can be reduced, the service life of a catalyst can be prolonged, and meanwhile, the method dehydrates and converts the fatty alcohol into the long-chain hydrocarbon in the molecule, and then isomerizes the long-chain hydrocarbon to prepare the liquid fuel, so that the hydrogen consumption can be obviously reduced.
The foregoing description of the embodiments of the invention is not intended to limit the scope of the invention, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the invention shall fall within the scope of the patent. In addition, the technical features and the technical features, the technical features and the technical invention can be freely combined for use.
Claims (20)
1. A method of preparing a liquid fuel by selective catalytic deoxygenation of a lipid, wherein the method comprises:
s1, firstly, esterifying and converting grease into fatty acid methyl ester;
S2, catalytically hydrogenating fatty acid methyl ester to convert the fatty acid methyl ester into fatty alcohol;
S3, dehydrating and converting the fatty alcohol into long-chain hydrocarbon in a molecule, wherein in S3, the technological conditions of dehydrating and converting the fatty alcohol into the long-chain hydrocarbon in a molecule comprise the temperature of 250-400 ℃ and the pressure of-0.1 MPa to 0.5MPa, and the mass airspeed of 0.2-4h -1;
And S4, finally isomerizing the long-chain hydrocarbon to prepare the liquid fuel, wherein the process conditions for preparing the liquid fuel by isomerizing the long-chain hydrocarbon in S4 comprise the temperature of 200-420 ℃, the pressure of-0.1 MPa to 4MPa and the mass airspeed of 0.2-3h -1.
2. The method according to claim 1, wherein the fat is an animal fat and/or a vegetable fat, the fat having a fatty acid content of carbon chain length C 12-C24 of more than 80wt%, and the total content of fatty acid glycerides and free fatty acids of more than 90wt%.
3. The method of claim 1 or 2, wherein in S1, the fat is methyl esterified to convert the fat to fatty acid methyl ester by reacting the fat with methanol.
4. A process according to claim 3, wherein in S1 the fat is converted to fatty acid methyl esters by reacting with methanol under critical methanol conditions, by reacting under enzyme-catalyzed conditions, by reacting under homogeneous or heterogeneous acid-catalyzed conditions or by reacting under homogeneous or heterogeneous base-catalyzed conditions.
5. The process according to claim 1 or 4, wherein in S1, after methyl esterification of the fat and refining, the fatty acid methyl ester content in the obtained product is not less than 80wt%.
6. The process according to claim 5, wherein in S1, after methyl esterification and refining of the fat, the fatty acid methyl ester content of the resultant product is 95 to 100wt%.
7. The method of claim 1, wherein in S2, the catalyst used for catalytic hydrogenation of fatty acid methyl ester to fatty alcohol is a supported catalyst, and the hydrogenation active metal used by the supported catalyst comprises one or more of platinum, palladium, gold, silver, cobalt, molybdenum, copper, nickel, zinc, iron, chromium, barium and manganese, and the carrier is activated carbon, al 2O3 or SiO 2.
8. The method of claim 7, wherein the hydrogenation-active metal comprises one or more of copper, cobalt, molybdenum, nickel, iron, zinc, and manganese.
9. The process according to any one of claims 1,7-8, wherein the process conditions for the catalytic hydrogenation of fatty acid methyl esters to fatty alcohols in S2 comprise a temperature of 160-300 ℃, a pressure of 2-20MPa, a mass space velocity of 0.3-3h -1, a hydrogen-oil volume ratio of 500:1-15000:1.
10. The process according to any one of claims 1,7-8, wherein in S2, after catalytic hydroconversion and refining of the fatty acid methyl esters, the fatty alcohol content of the product obtained is greater than 86% by weight.
11. The process according to claim 10, wherein in S2, after catalytic hydroconversion and refining of the fatty acid methyl esters, the fatty alcohol content of the product obtained is 92-100% by weight.
12. The process according to claim 1, wherein in S3 the catalyst used for intramolecular dehydration of fatty alcohols to longer chain hydrocarbons is an acid catalyst having a desorption temperature of 150-600 ℃ after adsorption of NH 3.
13. The method of claim 12, wherein in S3 the acid catalyst comprises one or more of gamma-Al 2O3、ZrO2, ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y-molecular sieves, and beta-molecular sieves.
14. The method of claim 13, wherein in S3, when γ -Al 2O3 and/or ZrO 2 are used as the acid catalyst with one or a combination of ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, Y-molecular sieve and β -molecular sieve, the γ -Al 2O3 content is more than 20wt% and the ZrO 2 content is more than 20wt%.
15. The method of claim 1, wherein in S3, the reaction involved in the intramolecular dehydration conversion of the fatty alcohol comprises one or more of dehydration, cleavage, isomerization, and cyclization reactions.
16. The process according to any one of claims 1,12 to 15, wherein in S3, the oxygen content of the resulting long-chain hydrocarbon is less than 0.1 wt.% after intramolecular dehydration conversion of the fatty alcohol and refining.
17. The method according to claim 16, wherein in S3, after intramolecular dehydration conversion of the fatty alcohol and refining, the oxygen content of the obtained long-chain hydrocarbon is less than 0.05wt%.
18. The method according to claim 1, wherein in S4, the catalyst used for preparing the liquid fuel by isomerizing the long-chain hydrocarbon is an acid catalyst having a desorption temperature of 150-600 ℃ after adsorption of NH 3.
19. The method of claim 18, wherein in S4 the acid catalyst comprises one or more of ZSM-22, ZSM-23, ZSM-48, ZSM-35, SAPO-31, SAPO-11, ZSM-5, EU-1, Y molecular sieves, and beta molecular sieves.
20. The process of claim 1, wherein in S4 the reaction involved in the isomerization of long chain hydrocarbons comprises one or more of cracking, isomerisation, cyclisation, folding.
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| CN110066679A (en) * | 2018-01-24 | 2019-07-30 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel from fatty alcohol |
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| CN105400540B (en) * | 2015-10-22 | 2017-04-05 | 北京化工大学 | A kind of method of fatty alcohol production aviation fuel |
| CA3056537C (en) * | 2018-09-27 | 2023-02-14 | Luis Felipe Ramirez Verduzco | Hydrodeoxygenation process of vegetable oils for obtaining green diesel |
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| CN110066679A (en) * | 2018-01-24 | 2019-07-30 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel from fatty alcohol |
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