CN105778976B - Method for preparing biodiesel by catalytic deoxidation of grease - Google Patents
Method for preparing biodiesel by catalytic deoxidation of grease Download PDFInfo
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- CN105778976B CN105778976B CN201410820643.0A CN201410820643A CN105778976B CN 105778976 B CN105778976 B CN 105778976B CN 201410820643 A CN201410820643 A CN 201410820643A CN 105778976 B CN105778976 B CN 105778976B
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- Prior art keywords
- grease
- zinc
- catalyst
- biodiesel
- catalytic deoxidation
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- 239000004519 grease Substances 0.000 title claims abstract description 57
- 239000003225 biodiesel Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003752 zinc compounds Chemical class 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 4
- 229940007718 zinc hydroxide Drugs 0.000 claims description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 239000012495 reaction gas Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 235000014692 zinc oxide Nutrition 0.000 description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 4
- 229940073769 methyl oleate Drugs 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects 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
- 239000007789 gas Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
- Catalysts (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for preparing biodiesel by grease catalytic deoxidation, which comprises the step of catalyzing grease to perform deoxidation reaction by using a zinc-containing catalyst in an organic solvent and in a reaction atmosphere to generate C-containing10～C18The hydrocarbon biodiesel according to (2), wherein the zinc-containing catalyst is a zinc oxide-containing catalyst, and the mass fraction of the zinc oxide in the zinc-containing catalyst is 20-100%. The invention has the advantages of cheap and easily obtained catalyst, simple process flow, low reaction pressure, no or little consumption of hydrogen and the like.
Description
Technical field
The present invention relates to a kind of method of grease catalytic deoxidation, belong to biomass energy technology field, more specifically relate to
And grease deoxidation in the case where being acted on containing zinc catalyst prepares alkanes biodiesel.
Background technology
Diesel oil is a kind of important power fuel, and its consumption rises year by year with economic development.Long-term a large amount of useizations
Stone class A fuel A, adverse effect is also generated to environment.And the non-renewable of these resources determines that they are reduced year by year.For
Realize sustainable development, the research of the reproducible green diesel of countries in the world pay attention to day by day.
Hydro carbons biodiesel fuel prepared by animal and plant fat deoxidation, there is calorific value height, Cetane number height, combustibility
Good, the excellent characteristics such as get well similar, compatible to petrifaction diesel composition are in widespread attention.Traditional vulcanization NiMo/ γ-Al2O3With
CoMo/γ-Al2O3Catalyst has been used to oil hydrogenation deoxidation industrial production hydro carbons biodiesel, for example, Canadian Canmet
The oil hydrogenation of energy technology center exploitation prepares the technology of high cetane number diesel oil, and Neste Oil companies of Finland exist
The grease catalytic hydrodeoxygenation that Porvoo is established prepares diesel oil.Sulphur losing issue be present in traditional vulcanization hydrogenation catalyst, and because
This reduces catalytic activity and produces sulphur pollution to product.In order to avoid the relevant issues of sulphur, can select nickel, copper, palladium, platinum,
The metallic catalysts such as ruthenium.Recently, the A of CN 102876350 disclose Ru series catalysts catalysis grease or aliphatic acid hydrogenation deoxidation system
The technology of standby alkane class A fuel A.
Oil hydrogenation deoxidation, oxygen element are removed in the form of water, and this needs to consume substantial amounts of hydrogen, for example, every mole of fat
Fatty acid glyceride is hydrogenated with complete deoxidation theory hydrogen-consuming volume and is more than 12 moles.And hydrogenation deoxidation reaction pressure is generally higher, about
4-9MPa.For example, a kind of Zn contents disclosed in the A of CN 103721741 account for catalyst gross mass 0.1-5% hydrogenation deoxidation catalysis
Agent, it is supported on using Ni etc. as hydrogenation active component on the carriers such as SAPO-11 or ZSM-5, the hydrogen pressure of castor oil hydrogenation deoxidation
Power is 1.0-5.0MPa, hydrogen and castor oil volume ratio 600-3000.
Grease selectivity decarboxylation/carbonyl is catalyzed, oxygen element is with CO2/ CO form removing, can reduce reaction pressure, significantly subtract
Few hydrogen consumption.Murzin seminars of Finland delivered series of articles (Ind.Eng.Chem.Res.2006,
Appl.Catal.A-Gen.2009, and ACS 2011 etc.) report load Pd metallic catalyst energy high selectivity catalysis aliphatic acid
Decarboxylation.The catalyst of fatty acid ester selectivity decarboxylation/carbonyl is also reported that for example, the non-hydrogenation of PtSnK/SiO2 catalyzing glycerol esters
Deoxidation (Fuel 2011), Pt/Al2O3It is catalyzed the non-hydrogenation deoxidation of methyl stearate (Catal.Lett.2009).These pass through de-
The non-hydrogenation deoxidation reaction pressure of carboxylic/carbonyl is usually less than 2MPa, hardly consumes hydrogen, or seldom consume hydrogen.These advantages
The great interest of researcher is caused, Jeremy Glen Immer, Fu Jie thesis for the doctorate (2010) all have extensively studied
Pd, Pt precious metal catalyst decarboxylation of fatty acids/carbonyl reaction.But noble metal catalyst is expensive, and inactivation is very easy to, this
Limit their applications industrially.
Dehydrogenation catalyst disclosed in some patents is only used for the oxygen in removing process, rather than the oxygen member in molecular structure
Element.For example, it is 5%-20% dehydrogenation catalysts that the A of CN 101204660, which disclose a kind of ZnO content,.It is reduction with hydrogen or CO
Agent, the dehydrogenation catalyst can remove the O in chlorohydrination production expoxy propane tail gas2, i.e., the oxygen member in oxygen, rather than molecular structure
Element.Grease catalytic deoxidation prepares HC fuel, it is necessary to removes the oxygen element in molecular structure.
In summary, grease catalytic deoxidation prepares hydrocarbon fuel and still needs to try to reduce operation pressure, reduces hydrogen consumption,
And reduce catalyst price.
The content of the invention
It is an object of the invention to provide a kind of method that grease catalytic deoxidation prepares biodiesel, to overcome in the prior art
The defects of hydrogen consumption is greatly and noble metal catalyst is expensive.
The present invention is achieved by the following technical solutions：Under organic solvent and reaction atmosphere, urged with containing zinc catalyst
Carburetion fat carries out deoxygenation, and generation contains C10~C18Hydro carbons biodiesel, wherein, it is described containing zinc catalyst be containing
The catalyst of zinc oxide, mass fraction of the zinc oxide in containing zinc catalyst are 20%~100%.
Wherein, the zinc oxide is calcined 1 by using organic or inorganic zinc compound in 300~500 DEG C of air atmosphere
After~4h cooling obtain, wherein, the organic or inorganic zinc compound include metallic zinc, zinc oxide, zinc hydroxide, zinc carbonate,
At least one of basic zinc carbonate, zinc nitrate, zinc acetate or zinc stearate.
Wherein, described containing zinc catalyst is zinc oxide and one in copper, nickel, cobalt, molybdenum, platinum or palladium hydrogenation metal catalyst
Kind or a variety of mixtures.
Wherein, mass fraction of the zinc oxide in containing zinc catalyst is 30%~80%.
Wherein, the organic solvent is the organic solvent between carbon number is 6-30, including hexamethylene, petroleum ether, stone
At least one of cerebrol, petrifaction diesel and grease deoxidation products.
Wherein, the grease is at least one of fatty glyceride, fatty acid methyl ester, fatty-acid ethyl ester and aliphatic acid,
The fat content of the grease is more than 90%.
Wherein, the content of sulphur in the grease, phosphorus, chlorine and metal impurities be respectively smaller than 400ppm, 500ppm, 500ppm and
1000ppm。
Wherein, mass fraction of the grease in the mixed liquor of grease and organic solvent is 5%~90%.
Wherein, the reaction atmosphere is at least one of hydrogen or water.
Wherein, the water consumption is the 0%~20% of oil quality, and the mol ratio of the hydrogen and grease is 0:1~3:
1。
Wherein, the reaction temperature of the deoxygenation is 210~420 DEG C, and reaction pressure is more than or equal to 0MPa and is less than
1MPa, the volume space velocity of grease is 0.02h-1~3h-1。
The beneficial effects of the invention are as follows：1st, catalyst is cheap and easy to get, can partially or completely replace noble metal；2nd, technological process
Simply, reaction pressure is low, does not consume or seldom consumes hydrogen；3rd, product cleans, and positive structure and isoparaffin kind compound content is high,
Hardly sulfur-bearing and aromatic compound.
Embodiment
The present invention provides one kind and prepares hydro carbons biodiesel using catalysis grease deoxidation under certain atmosphere containing zinc catalyst
The method of fuel.Obtaining Main Ingredients and Appearance with catalysis grease deoxygenation under organic solvent and reaction atmosphere containing zinc catalyst is
C10-C18Hydro carbons biodiesel, with reduce operation pressure and reduce hydrogen consumption.
In the above method, described containing zinc catalyst is the catalyst containing zinc oxide in catalyst.Use organic or inorganic
Zinc compound, including but not limited to following compound：Metallic zinc, zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate, nitric acid
At least one of zinc, zinc acetate, zinc stearate etc., 1h-4h is calcined in 300 DEG C -500 DEG C of air atmosphere, is obtained after cooling
Zinc oxide.In order to adjust the composition of grease deoxidation products, zinc oxide can be with the hydrogenation gold such as nickel, copper, cobalt, molybdenum, palladium and platinum
Metal catalyst is used in mixed way.In the catalyst, the mass fraction of zinc oxide is 20%-100%.Preferably：30%-80%.
In the above method, the grease can be fatty glyceride, fatty acid methyl ester, fatty-acid ethyl ester and aliphatic acid in extremely
Few one kind.Grease (including fatty acid ester and aliphatic acid) content should be greater than 90%, be preferably：Fat content is more than 98%.
In order that HC fuel product meets specific requirement, and extend the life-span of catalyst, it should suitably reduce grease
Middle sulphur, phosphorus, the content of chlorine and metal impurities.By refinement treatment, make the content difference of sulphur, phosphorus, chlorine and metal impurities small
In 400ppm, 500ppm, 500ppm and 1000ppm.
In the above method, the solvent is the organic solvent between carbon number is 6-30, including but not limited to hexamethylene,
Petroleum ether, naphtha, petrifaction diesel and grease deoxidation products.In the solution that solvent dissolving grease is formed, the content of grease is
5%-90%, preferably 30%-80%.
In the above method, the reaction atmosphere can be at least one of water, hydrogen.Water consumption is the 0%- of oil quality
20%, be preferably：0.5%-11%.The mol ratio of hydrogen and grease is 0:1-3:1 (volume ratio is less than 67, de- much smaller than hydrogenation
The theoretical hydrogen consumption mol ratio 12 of oxygen：1), preferably 0.3:1-1.5:1.
In the above method, the temperature of the reaction can be 210 DEG C -420 DEG C, preferably 260-380 DEG C；The reaction it is exhausted
It can be 0MPa-2MPa to pressure, preferably greater than equal to 0MPa and be less than 1MPa；The volume space velocity of grease is 0.02h-1-3h-1,
Preferably 0.07h-1-1.5h-1。
In the above method, hydro carbons biodiesel that the grease deoxygenation obtains may be used as the blending of petrifaction diesel
It component, also can be used alone, or used as solvent., can also be according to needed for boiling point cutting in order to improve properties
Specific components.
In above-mentioned method, catalysis grease deoxygenation can select reactor or tubular reactor, can select interval
Technique or continuous processing.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1
Zinc carbonate is in the obtained zinc oxides of 400 DEG C of roasting 3h and the Cu/SiO for having loaded 10% bronze medal2By 30:70 quality
Than being mixed to prepare containing zinc catalyst.
Soybean oil is dissolved in petroleum ether, forms the solution that fat content is 30%, reaction is sent into the lump with water and hydrogen
Device, water are the 6% of oil quality, and hydrogen is 1.5 with soybean molar equivalent:1.Grease containing zinc catalyst in the case where acting in tubular type device
Middle reaction, reaction pressure 0.9MPa, reaction temperature are 370 DEG C, and the volume space velocity of grease is 1.5h-1.Deoxygenation product passes through
Air-distillation, 125 DEG C -365 DEG C of cutting flow, hydro carbons biodiesel yield are 62%.
Embodiment 2
Zinc stearate is in the obtained zinc oxides of 500 DEG C of roasting 4h and has loaded the Pd/C of 5% palladium by 80:20 mass ratio
It is mixed to prepare containing zinc catalyst.
Stearic acid mixes with stearic acid deoxidation products, forms the solution that content of fatty acid is 40%, is sent into the lump with hydrogen
Reactor, hydrogen are 0.3 with stearic mol ratio:1.Stearic acid is anti-in tubular type device under catalytic action containing zinc catalyst
Should, reaction pressure 0.2MPa, reaction temperature is 300 DEG C, and the volume space velocity of grease is 0.07h-1.Hydro carbons biodiesel production rate energy
Reach 73%.Deoxygenation product section returns and is used as solvent, partly can be as the addO-on therapy of diesel oil.
Embodiment 3
Zinc hydroxide is in the obtained zinc oxides of 300 DEG C of roasting 1h and skeleton nickel by 60:40 mass ratio carries out mixing system
Zinc catalyst must be contained.
Methyl oleate mixes with petrifaction diesel, forms the solution that methyl oleate content is 80%, is sent into the lump with hydrogen anti-
Answer device, the mol ratio of hydrogen and methyl oleate is 1.2:1.Methyl oleate is reacting under being acted on containing zinc catalyst in tubular type device,
Reaction pressure is 0.5MPa, and reaction temperature is 320 DEG C, and the volume space velocity of grease is 1h-1.Hydro carbons biodiesel production rate can reach
69%.
Embodiment 4
Zinc nitrate is in the obtained zinc oxides of 400 DEG C of roasting 4h and the Cu/ γ-Al for having loaded 10%Cu2O3It is made and is urged containing zinc
Agent.
Lard fatty acid methyl ester mixes with its deoxidation products, formed fatty acid methyl ester be 60% solution, with water and
Hydrogen is sent into reactor in the lump, and water is the 4% of oil quality, and hydrogen is 0.6 with fatty acid methyl ester mol ratio:1.Grease is containing zinc
Reacted under catalyst action in autoclave device, reaction absolute pressure is 0.03MPa, and reaction temperature is 260 DEG C, fatty acid methyl ester
Volume space velocity is 0.7h-1.Successive reaction simultaneously distills out product, and hydro carbons biodiesel yield is 71%.
Embodiment 5
Zinc oxide is after 300 DEG C of roasting 4h with having loaded the Ni/SiO2 of 10% nickel by 60:40 mass ratio carries out mixing system
Zinc catalyst must be contained.
Ethyl stearte mixes with petrifaction diesel, forms the solution that ethyl stearte content is 50%, is sent into the lump with water
Reactor, water are the 4% of ethyl stearte quality, and hydrogen is 0.6 with ethyl stearte mol ratio:1.The catalysis containing zinc catalyst is hard
Resin acid ethyl ester reacts in tubular type device, reaction pressure 0.2MPa, and reaction temperature is 380 DEG C, and the volume space velocity of grease is 0.6h-1.Hydro carbons biodiesel production rate can reach 70%.
The beneficial effects of the invention are as follows：1st, catalyst is cheap and easy to get, can partially or completely replace noble metal；2nd, technological process
Simply, reaction pressure is low, does not consume or seldom consumes hydrogen；3rd, product cleans, and positive structure and isoparaffin kind compound content is high,
Hardly sulfur-bearing and aromatic compound.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of method that grease catalytic deoxidation prepares biodiesel, it is characterised in that under organic solvent and reaction atmosphere, use
The catalysis grease containing zinc catalyst carries out deoxygenation, and generation contains C10~C18Hydro carbons biodiesel, wherein, it is described to contain zinc
Catalyst is the catalyst containing zinc oxide, mass fraction of the zinc oxide in containing zinc catalyst be 20%~
100%.
2. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the zinc oxidation
Thing is calcined after 1~4h to cool down in 300~500 DEG C of air atmosphere and obtained by using organic or inorganic zinc compound, wherein, institute
Stating organic or inorganic zinc compound includes metallic zinc, zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate, zinc nitrate, acetic acid
At least one of zinc or zinc stearate.
3. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that described to be urged containing zinc
Agent is zinc oxide and one or more mixtures in copper, nickel, cobalt, molybdenum, platinum or palladium hydrogenation metal catalyst.
4. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the deoxidation is anti-
The reaction temperature answered is 210~420 DEG C, and reaction pressure is more than or equal to 0MPa and is less than 1MPa, and the volume space velocity of grease is
0.02h-1~3h-1。
5. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the zinc oxidation
Mass fraction of the thing in containing zinc catalyst is 30%~80%.
6. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the grease is
At least one of fatty glyceride, fatty acid methyl ester, fatty-acid ethyl ester and aliphatic acid, the fat content of the grease are more than
90%.
7. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that described organic molten
Agent is the organic solvent between carbon number is 6-30, including hexamethylene, petroleum ether, naphtha, petrifaction diesel and grease deoxidation
At least one of product.
8. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the grease exists
Mass fraction in the mixed liquor of grease and organic solvent is 5%~90%.
9. the method that grease catalytic deoxidation according to claim 1 prepares biodiesel, it is characterised in that the reaction gas
Atmosphere is at least one of hydrogen or water.
10. the method that grease catalytic deoxidation according to claim 9 prepares biodiesel, it is characterised in that the water is used
Measure as the 0%~20% of oil quality, the mol ratio of the hydrogen and grease is 0:1~3:1.
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| AU2011343489A1 (en) * | 2010-12-16 | 2013-08-01 | Energia Technologies, Inc. | Catalysts, methods of preparation of catalyst, methods of deoxygenation, and systems for fuel production |
| CN103721741B (en) * | 2014-01-13 | 2016-06-29 | 南开大学 | Oleum Ricini Hydrogenation is for the Catalysts and its preparation method of biodiesel |
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| 脂肪酸（酯）非临氢催化脱羧反应研究;杨翠月;《中国优秀硕士学位论文全文数据库（电子期刊）》;20140615;第8-9页 * |
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