CN107987868B - Method for preparing liquid fuel by stepwise deoxygenation of grease - Google Patents
Method for preparing liquid fuel by stepwise deoxygenation of grease Download PDFInfo
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- CN107987868B CN107987868B CN201610946837.4A CN201610946837A CN107987868B CN 107987868 B CN107987868 B CN 107987868B CN 201610946837 A CN201610946837 A CN 201610946837A CN 107987868 B CN107987868 B CN 107987868B
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- grease
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- 239000000446 fuel Substances 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 239000004519 grease Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006392 deoxygenation reaction Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 37
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000006317 isomerization reaction Methods 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 241001465754 Metazoa Species 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000005456 glyceride group Chemical group 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000011987 methylation Effects 0.000 claims description 4
- 238000007069 methylation reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021588 free fatty acids Nutrition 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims 2
- 238000005815 base catalysis Methods 0.000 claims 2
- 235000013311 vegetables Nutrition 0.000 claims 2
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000263 Rubber seed oil Polymers 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- -1 fatty acid esters Chemical class 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 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
- 239000002028 Biomass Substances 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
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 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
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 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
- 229910052759 nickel Inorganic materials 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
- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- 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
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing liquid fuel by grease step-by-step deoxidation, which comprises the following steps: (1) methyl esterification of greaseConversion to fatty acid methyl esters; (2) fatty acid methyl ester and hydrogen are converted into fatty alcohol under the action of a copper-based catalyst; and (3) dehydrating and isomerizing the fatty alcohol under the action of a molecular sieve catalyst to prepare olefin, wherein the content of the isomerized olefin in the olefin exceeds 86 percent, the reaction temperature is 190-240 ℃, the absolute pressure of the reaction is 0.1-0.5 MPa, and the volume space velocity of the fatty alcohol is 0.2h‑1～3h‑1The molecular sieve catalyst is one or more of ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, β molecular sieve and mordenite.
Description
Technical Field
The invention relates to a method for preparing liquid fuel by grease deoxidation, belonging to the technical field of biomass energy. More particularly relates to a liquid fuel prepared by methyl esterification, hydrogenation, dehydration/isomerization step-by-step deoxidation of grease.
Background
Liquid fuels, such as gasoline, diesel oil, aviation fuel oil and the like, are very important power fuels and are important material bases for the development of economic society. The liquid fuel prepared by using a large amount of fossil resources for a long time has negative effects such as greenhouse effect on the environment. And the reserves of these non-renewable resources are reduced year by year with continued consumption. The liquid fuel prepared by deoxidizing 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 regarded. Therefore, the world countries increasingly pay attention to the research on the technology for preparing liquid fuel by deoxidizing grease.
The liquid fuel is prepared by deoxidizing the oil, and the oil can be firstly vulcanized in NiMo/gamma-Al2O3Or CoMo/gamma-Al2O3The long-chain alkane is catalyzed and isomerized by an acidic molecular sieve (such as Pt/ZSM-22) loaded with noble metals such as Pt, Pd and the like to prepare the liquid fuel. The catalyst and isomerization conditions are changed, and the gasoline, diesel oil or aviation fuel can be selectively produced. For example, the technology developed by Canmet energy technology center, Canada for the hydrogenation of fats and oils to produce high cetane number diesel, and the technology developed by UOP for the catalytic hydrodeoxygenation of fats and oils established in Porvoo by Neste Oil, Finland.
Sulfided hydrogenation catalysts can suffer from reduced catalytic activity due to sulfur loss and thus sulfur contamination. The hydrogenation metal catalyst such as nickel, palladium, platinum, ruthenium and the like is selected, so that the related problem of sulfur can be avoided. Recently, CN 102876350 a discloses a technology for preparing alkane fuel by grease or fatty acid hydrodeoxygenation catalyzed by Ru catalyst. Or directly using a bifunctional catalyst to couple hydrodeoxygenation and cracking/isomerization in a single stage, for example, Herskowitz and the like, using Pt/SAPO-11 to catalyze grease at 300-450 ℃, 1-6 MPa and 0.5-5.0 h-1The reaction in the next step obtains the diesel oil component with lower freezing point and cold filter plugging point. However, the use of noble metal catalysts such as Pt and Pd significantly increases the cost of the catalyst.
Furthermore, the fats and oils are directly hydrodeoxygenated and the oxygen is removed in the form of complete hydrogenation to water, which not only requires the consumption of a large amount of hydrogen but also the loss of glycerin (hydrogenation to produce propane), for example, the theoretical hydrogen consumption of complete deoxygenation is not less than 12 moles per mole of glycerin stearate.
For example, CN103725305A discloses a method for preparing liquid hydrocarbon fuel from fatty acid methyl ester, which comprises subjecting fatty acid methyl ester to hydrodeoxygenation and cracking/isomerization under the action of Ni/H β bifunctional catalyst to obtain liquid fuel, catalyzing selective decarboxylation/carbonylation of fatty acid (or fatty acid methyl ester) to make oxygen element in form of CO2The removal of the/CO form can obviously reduce the consumption of hydrogen. Murzin et Al report Pt, Pd noble metal-loaded Al2O3Or SiO2The catalyst can catalyze the decarboxylation of fatty acid with high selectivity. Under the conditions of 250-350 ℃ and 0.1-2 MPa, the conversion rate of stearic acid is more than 80%, and the selectivity of n-heptadecane is about 93%. The hydrogen consumption is significantly reduced compared to hydrodeoxygenation reactions. Catalysts for selective decarboxylation/carbonylation of fatty acid esters have also been reported, for example, Pt/Al2O3Catalyzing the non-hydrodeoxygenation of methyl stearate. These non-hydrodeoxygenation by decarboxylation/carbonylation reactions are generally at pressures below 2MPa and can significantly reduce hydrogen consumption. These advantages have attracted considerable interest to researchers.
The direct hydrodeoxygenation of fats and oils, either via hydrodeoxygenation of fatty acids or their methyl esters or selective decarboxylation/decarbonylation to give alkanes, requires isomerization to improve the low temperature properties (cold filter plugging point, freezing point) of the fuel. Alkane hydroisomerization not only reduces the yield of liquid fuel due to the generation of gas-phase components by cracking, but also requires the use of noble metals such as Pt, Pd and the like, which can obviously improve the cost of the catalyst. For this reason, CN101331210A provides a pre-isomerization method, in which unsaturated fatty acids or esters thereof are subjected to skeletal isomerization and then hydrodeoxygenation, to obtain liquid fuels excellent in low-temperature properties.
CN101484552A discloses a process for producing base oil, which comprises reacting fatty acid with higher alcohol to form ester, hydrogenating to alcohol, dehydrating alcohol to α -olefin under the action of alumina or alumina catalyst loaded with zirconia, oligomerizing α -olefin, and hydrogenating to obtain base oil, wherein the fatty alcohol is converted to α -olefin by alumina or alumina catalyst loaded with zirconia, α -olefin is suitable raw material for preparing lubricating oil by oligomerization, but is still straight chain hydrocarbon, and low temperature property of the base oil as fuel is to be improved.
Disclosure of Invention
The invention mainly aims to provide a method for preparing liquid fuel by grease step-by-step deoxidation, which solves the problems of high cost and harsh reaction conditions of noble metal catalysts used in the existing method for preparing liquid fuel.
The invention provides a method for preparing liquid fuel by grease step-by-step deoxidation, which comprises the following steps:
(1) converting the grease into fatty acid methyl ester through methyl esterification;
(2) fatty acid methyl ester and hydrogen are converted into fatty alcohol under the action of a copper-based catalyst; and
(3) the aliphatic alcohol is dehydrated and isomerized to prepare the olefin under the action of a molecular sieve catalyst, and the content of the isomerized olefin in the olefin exceeds 86 percent.
To improve liquid fuel properties, the isoolefins may be further separated by hydrogenation or rectification.
The method for preparing the liquid fuel by the step-by-step deoxygenation of the oil is characterized in that the oil is animal and vegetable oil, the total content of fatty glyceride and free fatty acid in the animal and vegetable oil is more than 90%, and the length of a fatty carbon chain in the fatty glyceride is C12～C24The content of (A) is more than 80%.
The method for preparing the liquid fuel by the step-by-step deoxidation of the grease, disclosed by the invention, comprises the step of respectively reducing the contents of sulfur, phosphorus, nitrogen, chlorine and metal impurities in the grease to less than 100ppm, 200ppm, 300ppm, 400ppm and 800 ppm.
The method for preparing the liquid fuel by the step-by-step deoxygenation of the grease comprises the step of carrying out methylation on the grease to obtain the grease, and reacting the grease with methanol to obtain the fatty acid methyl ester. The oil methylation is a homogeneous acid catalytic reaction, a heterogeneous acid catalytic reaction, a homogeneous base catalytic reaction, a heterogeneous base catalytic reaction or a supercritical reaction.
The invention relates to a method for preparing liquid fuel by grease step-by-step deoxidation, wherein the reaction conditions in the step (2) are as follows: adopts copper asThe hydrogenation catalyst of the metal active center, the reaction temperature is 180-280 ℃; the absolute pressure of the reaction is 2MPa to 6 MPa; the molar ratio of the hydrogen to the fatty acid methyl ester is 5: 1-20: 1; the volume space velocity of the fatty acid methyl ester is 0.4h-1～2h-1. The hydrogenation catalyst with copper as the metal active center can be added with metals such as zinc, iron, chromium, barium, manganese and the like and dispersed in Al2O3、SiO2High specific surface area carrier to raise catalyst activity.
The method for preparing the liquid fuel by the step-by-step deoxygenation of the grease comprises the following steps of (1) dehydrating and isomerizing the fatty alcohol in the step (3) at the reaction temperature of 190-240 ℃, preferably 190-200 ℃; the absolute pressure of the reaction is 0.1MPa to 0.5MPa, preferably 0.1MPa to 0.3 MPa; the volume space velocity of the fatty alcohol is 0.2h-1～3h-1。
The method for preparing the liquid fuel by the step-by-step deoxygenation of the grease comprises the step (3) of preparing one or more molecular sieves from ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, β molecular sieve and mordenite.
The invention has the beneficial effects that:
1. in the existing technology for preparing liquid fuel from grease, the improvement of a catalyst is mainly dedicated, so that the grease can be hydrogenated into alkane, and then isomerization reaction is carried out under the action of a bifunctional catalyst loaded with noble metal to obtain the liquid fuel; the method mainly adopts multi-step mild reaction, utilizes an acidic molecular sieve to catalyze alcohol to be dehydrated and converted into olefin, and synchronously isomerizes to obtain isomerized olefin, the catalyst is a commercial molecular sieve catalyst which is cheap and easy to obtain, and the method prepares highly isomerized liquid fuel;
2. compared with the mode of directly hydrodeoxygenating ester, the method provided by the invention has the advantages that hydrogen consumption is obviously reduced, material consumption is reduced, and yield and added value of the glycerol product are increased.
Detailed Description
The process of the present invention is further illustrated by the following examples, in which the experimental procedures used are conventional unless otherwise specified.
The grease can be beef tallow, lard, chicken oil, rapeseed oil, soybean oil, cottonseed oil, palm oil, corn oil, rubber seed oil, waste oil in catering industry, illegal cooking oil, acidified oil, rancid oil and the like.
In order to improve the quality of liquid fuel, simplify the subsequent refining process and prolong the service life of the catalyst, the contents of impurities such as sulfur, phosphorus, nitrogen, chlorine, metal and the like in the grease should be properly reduced, and after the grease is refined, the contents of the impurities such as sulfur, phosphorus, nitrogen, chlorine and metal should be respectively less than 100ppm, 200ppm, 300ppm, 400ppm and 800 ppm.
The reaction of fatty acid methyl ester with hydrogen uses the hydrogenation catalyst with copper as metal active center, can incorporate zinc, iron, chromium, barium, manganese and other metals, and disperses in Al2O3、SiO2High specific surface area carrier to raise catalyst activity.
The reactor for catalytic hydrogenation of fatty acid methyl ester and hydrogen can be a reaction kettle, a moving bed reactor, a fixed bed reactor and the like, and is preferably a fixed bed tubular reactor.
Heterogeneous acid catalyst, meaning a catalyst having a solubility in the reaction system of less than 0.1% and NH3The acid catalyst with desorption temperature of 150-600 deg.c after adsorption is preferably ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, β molecular sieve and mordenite.
The reactor for dehydrating and isomerizing the fatty alcohol can be a reaction kettle, a tower reactor and a fixed bed reactor, and preferably the tower reactor or the fixed bed reactor.
The liquid fuel component obtained in the step (3) of the method is mainly C6–C18The olefin can be directly added into the liquid fuel for use, or can be continuously hydrogenated to branched alkane and then added into the liquid fuel; wherein the content of isoolefins or branched paraffins exceeds 86%, the presence of isoolefins or branched paraffins may increase the octane number of the liquid fuel.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
And (3) reacting the catalytically refined soybean oil with methanol (the molar ratio of alcohol to oil is 6: 1) at 60 ℃ for 2h by using sodium methoxide (the dosage is 0.5 percent of the mass of the oil), and carrying out methyl esterification on the oil. After separation, the fatty acid methyl ester content was 97%.
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a commercial Cu-Zn-Al hydrogenation catalyst, and the process conditions are as follows: at 180 ℃, 6MPa, the molar ratio of hydrogen to fatty acid methyl ester is 20:1, and the volume space velocity is 0.4h-1. The content of fatty alcohol obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 98 percent.
In a tubular reactor filled with a ZSM-35 molecular sieve catalyst, the technological conditions of the fatty alcohol dehydration isomerization reaction are 240 ℃, 0.1MPa and the volume space velocity of the fatty alcohol is 0.3h-1. Reaction to obtain C6-C18The content of isoolefine can reach 96%.
Example 2
The rubber seed oil with the acid value of 30mgKOH/g and methanol react for 1h at 240 ℃, and the oil is subjected to methyl esterification. After separating and recovering methanol, the content of fatty acid methyl ester was 90%.
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a commercial copper-chromium catalyst, and the process conditions are as follows: 280 ℃, 2MPa, a molar ratio of hydrogen to fatty acid methyl ester of 5:1 and a volume space velocity of 2h-1. The content of fatty alcohol obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 92 percent.
In a tower reactor filled with ZSM-5 molecular sieve catalyst, the technological conditions of dehydration/isomerization reaction of the fatty alcohol are 190 ℃, 0.2MPa and the volume space velocity of the fatty alcohol is 1.6h-1. Reaction to obtain C6-C18The content of isoolefine can reach 90%.
Example 3
The waste oil in catering industry which is catalyzed by ZSM-5 acidic molecular sieve and rancid reacts with methanol at 160 ℃ for 2h to methyl-esterify the grease. After separation, the fatty acid methyl ester content was 92%.
Catalytic hydrogenation of fatty acid methyl ester by tubular reactor filled with commercial Cu-Zn-Al catalystThe reaction has the following process conditions: at 210 ℃, 4MPa, the molar ratio of hydrogen to fatty acid methyl ester of 8:1 and the volume space velocity of 1h-1. The content of fatty alcohol obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 95 percent.
In a tubular reactor filled with ZSM-22 molecular sieve catalyst, the technological conditions of fatty alcohol dehydration/isomerization reaction are 200 ℃, 0.3MPa and the volume space velocity of the fatty alcohol is 0.8h-1. Reaction to obtain C6-C18The content of isoolefine can reach 86%.
Example 4
The beef tallow reacts with methanol at 260 ℃ and 6MPa for 2h to methyl esterify the grease. After the methanol was separated and recovered, the content of fatty acid methyl ester was 96%.
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a copper-zinc-aluminum catalyst with iron content of 1 percent, and the process conditions are as follows: at 240 ℃, 4MPa, the molar ratio of hydrogen to fatty acid methyl ester of 5:1 and the volume space velocity of 1.5h-1. The content of fatty alcohol obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 94 percent.
In a tubular reactor filled with SAPO-31 molecular sieve catalyst, the technological conditions of the dehydration/isomerization reaction of the fatty alcohol are 220 ℃, 0.5MPa and the volume space velocity of the fatty alcohol is 1.6h-1. Reaction to obtain C6-C18The content of isoolefine can reach 94%.
Example 5
Reacting cottonseed oil with methanol at 210 ℃ for 1.5h to methyl-esterify the oil. After the methanol was separated and recovered, the content of fatty acid methyl ester was 94%.
The fatty acid methyl ester is subjected to catalytic hydrogenation reaction by a tubular reactor filled with a commercial Cu-Zn-Al catalyst, and the process conditions are as follows: 250 ℃, 5MPa, a molar ratio of hydrogen to fatty acid methyl ester of 7:1 and a volume space velocity of 0.6h-1. The content of fatty alcohol obtained by the catalytic hydrogenation reaction of fatty acid methyl ester reaches 97 percent.
In a tubular reactor filled with ZSM-5 and ZSM-22 (1: 1 mixed) molecular sieve catalysts, the technological conditions of the dehydration/isomerization reaction of the fatty alcohol are 200 ℃, 0.1MPa and the volume space velocity of the fatty alcoholIs 2.5h-1. Reaction to obtain C6-C18The content of isoolefine can reach 98%.
The invention has the beneficial effects that:
1. in the existing technology for preparing liquid fuel from grease, the improvement of a catalyst is mainly dedicated, so that the grease can be hydrogenated into alkane, and then isomerization reaction is carried out under the action of a bifunctional catalyst loaded with noble metal to obtain the liquid fuel; the method mainly adopts multi-step mild reaction, utilizes an acidic molecular sieve to catalyze alcohol to be dehydrated and converted into olefin, and synchronously isomerizes to obtain isomerized olefin, the catalyst is a commercial molecular sieve catalyst which is cheap and easy to obtain, and the method prepares highly isomerized liquid fuel (the reaction obtains C)6-C18Isoolefin content of greater than 86%);
2. compared with the mode of directly hydrodeoxygenating ester, the method provided by the invention has the advantages that hydrogen consumption is obviously reduced, material consumption is reduced, and yield and added value of the glycerol product are increased.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing liquid fuel by grease step-by-step deoxidation is characterized by comprising the following steps:
(1) converting the grease into fatty acid methyl ester through methyl esterification;
(2) fatty acid methyl ester and hydrogen are converted into fatty alcohol under the action of a copper-based catalyst; and
(3) dehydrating and isomerizing fatty alcohol under the action of a molecular sieve catalyst to prepare olefin, wherein the content of isoolefin in the olefin exceeds 86%;
wherein the molecular sieve catalyst is one or more of ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, β molecular sieve and mordenite.
2. The method for preparing the liquid fuel by the step-by-step deoxidation of the grease as claimed in claim 1, wherein the grease is animal and vegetable grease, the total content of fatty glyceride and free fatty acid in the animal and vegetable grease is more than 90%, and the length of a fatty carbon chain in the fatty glyceride is C12～C24The content of (A) is more than 80%.
3. The method for preparing the liquid fuel by the step-by-step deoxidation of the grease according to claim 2, wherein the contents of sulfur, phosphorus, nitrogen, chlorine and metal impurities in the grease are respectively less than 100ppm, 200ppm, 300ppm, 400ppm and 800 ppm.
4. The method for preparing the liquid fuel by the step-by-step deoxygenation of the oil and fat according to claim 1, wherein the oil and fat methylation is carried out to convert the oil and fat into fatty acid methyl ester by reacting with methanol.
5. The method for preparing the liquid fuel through the step-by-step deoxidation of the grease according to claim 4, wherein the grease methylation is a homogeneous acid catalysis reaction, a heterogeneous acid catalysis reaction, a homogeneous base catalysis reaction, a heterogeneous base catalysis reaction or a supercritical reaction.
6. The method for preparing the liquid fuel by the step-by-step deoxygenation of the grease according to claim 1, wherein the reaction conditions of the step (2) are as follows: the method adopts a hydrogenation catalyst taking copper as a metal active center, the reaction temperature is 180-280 ℃, the absolute pressure of the reaction is 2-6 MPa, the molar ratio of hydrogen to fatty acid methyl ester is 5: 1-20: 1, and the volume space velocity of the fatty acid methyl ester is 0.4h-1～2h-1。
7. The method for preparing the liquid fuel by the step-by-step deoxygenation of the oil and fat according to any one of claims 1 to 6, wherein the reaction temperature of the dehydration and isomerization of the fatty alcohol in the step (3) is 190-240 ℃, the absolute pressure of the reaction is 0.1-0.5 MPa, and the volume space velocity of the fatty alcohol is 0.2h-1～3h-1。
8. The method for preparing the liquid fuel by the step-by-step deoxygenation of the fat and oil according to claim 7, wherein the reaction temperature of the dehydration and isomerization of the fatty alcohol in the step (3) is 190-220 ℃, the absolute pressure of the reaction is 0.1-0.3 MPa, and the volume space velocity of the fatty alcohol is 0.2h-1～3h-1。
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| CN114480024A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel from grease |
| CN113004953B (en) * | 2021-03-16 | 2022-05-20 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN116333823B (en) * | 2021-12-23 | 2025-01-24 | 中国石油天然气股份有限公司 | A method for preparing liquid fuel by selective catalytic deoxygenation of oil and fat |
| CN116333782A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by grease selective hydrodeoxygenation |
| CN114574233A (en) * | 2022-03-11 | 2022-06-03 | 福州大学化肥催化剂国家工程研究中心 | Method for preparing second-generation biodiesel from acidified oil |
| CN116440946A (en) * | 2023-03-30 | 2023-07-18 | 华南理工大学 | A kind of Ni-Mo double transition metal catalyst and its preparation method and application |
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