CN105925628A - Coupling process for producing biodiesel with enzymic method and enriching polyunsaturated fatty acid ester - Google Patents
Coupling process for producing biodiesel with enzymic method and enriching polyunsaturated fatty acid ester Download PDFInfo
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- CN105925628A CN105925628A CN201610529540.8A CN201610529540A CN105925628A CN 105925628 A CN105925628 A CN 105925628A CN 201610529540 A CN201610529540 A CN 201610529540A CN 105925628 A CN105925628 A CN 105925628A
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- fatty acid
- oil
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- lipase
- reactor
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Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003225 biodiesel Substances 0.000 title claims abstract description 31
- 238000010168 coupling process Methods 0.000 title claims abstract description 13
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 title claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 87
- 108090000790 Enzymes Proteins 0.000 claims abstract description 87
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 67
- 229930195729 fatty acid Natural products 0.000 claims abstract description 67
- 239000000194 fatty acid Substances 0.000 claims abstract description 67
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004367 Lipase Substances 0.000 claims abstract description 40
- 102000004882 Lipase Human genes 0.000 claims abstract description 40
- 108090001060 Lipase Proteins 0.000 claims abstract description 40
- 235000019421 lipase Nutrition 0.000 claims abstract description 40
- 230000007062 hydrolysis Effects 0.000 claims abstract description 36
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000018044 dehydration Effects 0.000 claims abstract description 20
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 20
- 239000004519 grease Substances 0.000 claims abstract description 17
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 8
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 113
- 235000019198 oils Nutrition 0.000 claims description 103
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 235000014593 oils and fats Nutrition 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 25
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 19
- -1 unsaturated fatty acid ester Chemical class 0.000 claims description 16
- 239000003925 fat Substances 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 230000002255 enzymatic effect Effects 0.000 claims description 8
- 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 8
- 239000000376 reactant Substances 0.000 claims description 7
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012075 bio-oil Substances 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000010775 animal oil Substances 0.000 claims description 3
- 239000008157 edible vegetable oil Substances 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 102000004895 Lipoproteins Human genes 0.000 claims description 2
- 108090001030 Lipoproteins Proteins 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 32
- MBMBGCFOFBJSGT-KUBAVDMBSA-N docosahexaenoic acid Natural products CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 15
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 12
- DVSZKTAMJJTWFG-UHFFFAOYSA-N docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCCC=CC=CC=CC=CC=CC=CC(O)=O DVSZKTAMJJTWFG-UHFFFAOYSA-N 0.000 description 12
- 235000019197 fats Nutrition 0.000 description 12
- 241001661345 Moesziomyces antarcticus Species 0.000 description 11
- 241000235403 Rhizomucor miehei Species 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 6
- 240000006439 Aspergillus oryzae Species 0.000 description 5
- 235000002247 Aspergillus oryzae Nutrition 0.000 description 5
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 5
- 229940114079 arachidonic acid Drugs 0.000 description 5
- 235000021342 arachidonic acid Nutrition 0.000 description 5
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 5
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 5
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 240000009108 Chlorella vulgaris Species 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 235000007089 Chlorella vulgaris Nutrition 0.000 description 3
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 241000589220 Acetobacter Species 0.000 description 2
- 241001536324 Botryococcus Species 0.000 description 2
- WKFDWSVVMAKCDI-UHFFFAOYSA-N C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] Chemical compound C(C=1C(C(=O)OCC)=CC=CC1)(=O)OCC.[C] WKFDWSVVMAKCDI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000957276 Thalassiosira weissflogii Species 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- GLCGEJFIZRSXBL-UHFFFAOYSA-N dodeca-1,3,5,7,9,11-hexaene Chemical compound C=CC=CC=CC=CC=CC=C GLCGEJFIZRSXBL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 201000002909 Aspergillosis Diseases 0.000 description 1
- 208000036641 Aspergillus infections Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000043665 Clenchiella minutissima Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000283898 Ovis Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000282894 Sus scrofa domesticus Species 0.000 description 1
- 241001491687 Thalassiosira pseudonana Species 0.000 description 1
- 244000248162 Xanthoceras sorbifolium Species 0.000 description 1
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 description 1
- UCVQOIPQDBZRMG-UHFFFAOYSA-N [C].COC(C=1C(C(=O)OC)=CC=CC1)=O Chemical compound [C].COC(C=1C(C(=O)OC)=CC=CC1)=O UCVQOIPQDBZRMG-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6472—Glycerides containing polyunsaturated fatty acid [PUFA] residues, i.e. having two or more double bonds in their backbone
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a coupling process for producing biodiesel with an enzymic method and enriching polyunsaturated fatty acid ester. The coupling process comprises the following steps: S1, hydrolyzing grease into fatty acid; S2, performing oil-water two-phase separation on a hydrolysis product; S3, generating alcoholysis reaction with a lipase catalyzing oil phase, wherein during reaction, the influence of byproduct water on lipase and product yield can be eliminated by controlling short chain alcohol feeding and implementing online dehydration, thus achieving conversion from fatty acid to biodiesel; and S4, enabling a reaction solution obtained in S3 to flow into an enzyme reactor of the next stage, so that glyceride and fatty acid with incomplete reaction in the reaction solution react with dimethyl carbonate or diethyl carbonate under enzyme catalysis, thus producing polyunsaturated fatty acid ester; and in reaction, online dehydration is implemented to remove byproduct water produced in reaction, and further, conversion from grease to biodiesel and polyunsaturated fatty acid ester is realized. The process has the advantages of being strong in grease material applicability, environment-friendly and clean in production process and high in product quality and yield.
Description
Technical field
The invention belongs to biological chemical field, specifically, relate to Production by Enzymes biodiesel and
The coupling technique of polybasic unsaturated fatty acid ester enrichment.
Background technology
Biodiesel, is the long-chain fatty acid generated by transesterification or esterification by bio-oil
Ester.Biodiesel flash-point, combustion efficiency, sulfur content, oxygen content, arene content,
Burning oxygen consumption aspect is superior to petrifaction diesel, and other index is suitable with petrifaction diesel.Burning
In tail gas, particle, carbon monoxide, sulfide and Hydrocarbon are all greatly lowered,
Possess environment friendly, be widely used in American-European countries.
Possibly together with polybasic unsaturated fatty acid (PUFAs) in some bio-oils.According to PUFA
Position of double bond is classified as again ω-3 and ω-6 series, and from fatty acid molecule, distance carboxyl is farthest
The carbon atom counting of methyl end, first double bond occurs between third and fourth carbon atom
Being referred to as ω-3PUFA, first double bond occurs in being referred to as between the 6th and the 7th carbon atom
ω-6PUFA.Research finds, a lot of ω-3PUFAs be the function with multiple physiologically active because of
Son, is therefore widely used in every field.But, most of ω-3PUFA derive from deep-sea
Fish oil, but comparision contents is low, and the separation method of current ω-3PUFAs is concentrated mainly on carbamide bag
Legal, molecular distillation, anion complexometry, supercritical extraction, high performance liquid chromatography, life
The several methods such as thing enzyme process.Wherein urea adduct method is the most conventional, and carbamide can in organic solvent
To form urea clathration complex crystallization at low temperatures, but this method with linear saturated fatty acids
Substantial amounts of organic solvent need to be used, participate in subsequent purification steps；Molecular distillation can vapour at low temperatures
Changing material to be separated, strict temperature control obtains the fraction of different temperatures, available higher
ω-3PUFAs, but process energy consumption is big；In anion complexometry, silver nitrate anion can be with
ω-3PUFAs complexation, product hydrophilic is strong, and therefore ω-3PUFAs can be with anion complex
Form enter aqueous phase, thus realize separating, but silver nitrate is expensive, therefore is only limitted to experiment
Room preparation in a small amount；Utilize supercritical CO2Extraction has ω-3PUFA and the advantages such as oxidation does not occur,
But it is higher to equipment requirements.In a word, above method enrichment ω-3PUFA physically or chemically is used
There is poor selectivity, the problems such as process energy consumption is high, in the urgent need to exploitation have high selectivity,
And environment amenable biological enzyme technique carries out the enrichment of ω-3PUFAs.But at present about enzyme
The technique of method technique enrichment polybasic unsaturated fatty acid is loaded down with trivial details, and cost is high, poor selectivity, industry
Change application prospect uncertain.
It addition, the content that polybasic unsaturated fatty acid is in bio-oil is limited, remaining major part
Sour (such as Palmic acid, stearic acid and oleic acid etc.) for other normal fat, polynary not in enrichment
While satisfied fatty acid, other fatty acid ester is changed into simultaneously fatty acid short-chain ester (biological
Diesel oil), whole oils and fats profitable transformation can be obviously improved.But, biology to be realized
Diesel oil and the coupling technique of polybasic unsaturated fatty acid ester enrichment, need to research and develop product yield higher,
The advanced preparation technology that biodiesel quality is high.
Summary of the invention
It is an object of the invention to provide Production by Enzymes biodiesel and polybasic unsaturated fatty acid ester
The coupling technique of enrichment.
In order to realize the object of the invention, the present invention provide Production by Enzymes biodiesel and polynary not
The coupling technique of polyunsaturated fatty acid ester enrichment, comprises the following steps:
S1, grease hydrolysis is become fatty acid (in hydrolyzate, fatty acid yield is more than 95%)；
S2, hydrolyzate carry out water-oil phase separation, the oil phase collected (except fatty acid,
Possibly together with fraction of monoglyceride, two glyceride and triglyceride etc. in oil phase) for next
Step reaction；
S3, by lipase-catalyzed oil phase generation alcoholysis reaction, during enzymatic alcoholysis reaction,
Add by controlling short-chain alcohol streams and carry out online dehydration, eliminating water byproduct to lipase and product
The impact of yield, it is achieved the conversion (conversion ratio is more than 96%) from fatty acid to biodiesel；
S4, S3 gained reactant liquor is flowed in next stage enzyme reactor, make in reactant liquor the most anti-
Should glyceride and fatty acid enzymatically send out with dimethyl carbonate or diethyl carbonate completely
Raw reaction, generates polybasic unsaturated fatty acid ester, carries out gentle online dehydration in course of reaction
To remove the water byproduct generated in course of reaction, so realize from oils and fats to biodiesel and
The conversion of polybasic unsaturated fatty acid ester.
During in S1, hydrolysis is directed to one or more levels reactor interval or be continuously added to oils and fats
With the hydrolysis that water based on oil quality 50-1000% carries out oils and fats, react at 100-300 DEG C,
Carry out under the conditions of 1.0-3.0Mpa；Preferably, hydrolysis is directed to one or more levels reactor
Middle interval or be continuously added to oils and fats and water based on oil quality 50-500% carries out the water of oils and fats
Solving, reaction, at 160-230 DEG C, is carried out under the conditions of 1.5-3Mpa.
Aforesaid technique, in S1, hydrolysis refers to live on mineral acid, short chain organic acid and surface
Property agent in the presence of, in one or more levels reactor interval or be continuously added to oils and fats and based on oils and fats
The water of quality 50-1000% carries out the hydrolysis of oils and fats, and reaction is carried out under the conditions of 100-120 DEG C.
Described mineral acid includes sulphuric acid, hydrochloric acid or phosphoric acid etc., and described short chain organic acid includes formic acid
Or acetic acid etc., adding by oil quality 1-5%, described surfactant includes but not limited to 12
Sodium alkyl sulfonate, is added by oil quality 0.2-2%.
Aforesaid technique, interval or company during in S1, hydrolysis is directed to one or more levels reactor
Continue and add oils and fats and water based on oil quality 50-1000% and based on unit oil quality
The lipase of 500-1000 standard enzyme work is hydrolyzed, and reaction is carried out under the conditions of 35-50 DEG C.
Aforesaid technique, S3 is by oil phase and to live single based on 200-1000 enzyme of unit oil quality
Position lipase load in one or more levels circulation flow reactor, by lipase-catalyzed fatty acid with
Short chain alcohol generation esterification, temperature of reactor controls at 20-50 DEG C, and described short chain alcohol includes
Methanol, ethanol, propanol or butanol etc..
Aforesaid technique, during S3 enzymatic alcoholysis reaction, carries out non-uniform flow and adds short chain alcohol and temperature
The online dehydration of sum.
Aforesaid technique, S4 is under lipase-catalyzed, by complete for unreacted in S3 gained reactant liquor
Full glyceride and fatty acid react with dimethyl carbonate or diethyl carbonate further, instead
Gentle online dehydration is used during Ying.
The online dehydration of heretofore described gentleness refers to utilize film, molecular sieve or short chain alcohol gas
Carry.Film used by online dehydration is organic membrane, inoranic membrane or ceramic membrane etc.；Online dehydration is used
Molecular sieve beOrMolecular sieve etc.；Described short chain alcohol air stripping is by direct for reactor side
Being connected with the tank body equipped with anhydrous short chain alcohol, the temperature of anhydrous short chain alcohol is 20-40 DEG C, reaction
The opposite side of device is connected with vacuum pump, and then vacuum pump is connected with condenser；By true in reactor
Sky controls at 10-100Mpa, and condenser temperature is 5-15 DEG C；Described short chain alcohol include methanol,
Ethanol etc..
Production by Enzymes biodiesel of the present invention and the coupling work of polybasic unsaturated fatty acid ester enrichment
Process flow figure is shown in Fig. 1.
Heretofore described lipase includes deriving from yeast, mycete, antibacterial or other microorganism
Lipase；Lipase is single lipase or the combination of multiple lipase.Such as, derive from
The lipase of aspergillus oryzae (Aspergillus oryzae), derives from antarctic candida (Candida
Antarctica) lipase, derives from the fat of rhizomucor miehei (Rhizomucor miehei)
Fat enzyme etc..
Heretofore described oils and fats is the bio-oil containing polybasic unsaturated fatty acid, including planting
The concise leftover bits and pieces of thing oils and fats, animal oil, waste edible oil, acidification oil, oils and fats and microbial oil
Fat etc..Wherein, described Vegetable oil lipoprotein is Oleum Ricini, Petiolus Trachycarpi oil, Oleum Brassicae campestris, soybean oil, flower
Oil generation, Semen Maydis oil, Oleum Gossypii semen, Testa oryzae oil, curcas oil, shinyleaf yellowhorn oil or Jatropha curcas oil etc.；
Described animal oil is fish oil, Adeps Bovis seu Bubali, Adeps Sus domestica or Adeps Caprae seu ovis etc.；Described microbial grease is yeast
Oils and fats or microalgae oils and fats etc..Described waste edible oil is hogwash fat or waste oil etc.；Described oils and fats
Refine leftover bits and pieces is acidification oil etc..
The polybasic unsaturated fatty acid related in the present invention refers to there is more than one double bond in molecule
Long-chain fatty acid, include but not limited to alpha-linolenic acid (C18:3), docosahexenoic acid
(C22:6), eicosapentaenoic acid (C20:5), arachidonic acid (C20:4) etc..
Present invention firstly provides the preparation of high-quality biological diesel oil and polybasic unsaturated fatty acid ester is rich
The coupling technique of collection, the oils and fats containing polybasic unsaturated fatty acid first carries out water by the first stage
Solve, be then demultiplex out high-purity water hydrolysis products fatty acid, so can evade oils and fats completely especially
It it is the Various Complex composition negative effect to follow-up lipase-catalyzed characteristic in low-quality oils and fats.?
Follow-up enzymatic fatty acid alcoholysis reaction is prepared in biodiesel process, is taken off online by gentle
Water technology so that fatty acid can be with Efficient Conversion as fatty acid short-chain ester.Remaining for promoting further
Lower glyceride and the conversion of fatty acid, by previous reaction liquid by next stage enzyme reactor, make
In reactant liquor unreacted glyceride completely and fatty acid enzymatically with dimethyl carbonate
Or diethyl carbonate reacts, course of reaction is removed in time by gentle online dehydration technique
During dereaction generate water byproduct, thus realize oils and fats to biodiesel and polynary not
The abundant conversion of polyunsaturated fatty acid ester, it is achieved the preparation of high-quality biological diesel oil and polynary unsaturated lipid
The efficient coupling of fat acid esters enrichment.
This technique significantly reduces the impact that in oils and fats, enzyme is lived by complicated ingredient；At enzymatic oils and fats alcohol
Solving in reaction, the material participating in reaction is high purity fatty acid, and byproduct of reaction is mainly moisture,
Use gentle online dehydration technique that the moisture on-line of generation just can be made to remove, so that reaction is not
Breaking and carry out towards positive reaction direction, Enzymatic transformation efficiency increases substantially.Meanwhile, for promoting further
Enter the abundant conversion of remaining glyceride and fatty acid, and then under lipase-catalyzed so that aforementioned
Glyceride in reaction and unreacted fatty acid completely further with dimethyl carbonate or carbon
Diethyl phthalate reacts, owing to using carbonic acid diformazan (second) ester to replace tradition in final step
Acyl acceptor first (second) alcohol so that course of reaction no longer produces glycerol, fundamentally solves
Except glycerol is to enzymatic activity and the negative effect of stability, it is achieved thereby that high yield and Gao Pin
The preparation of matter biodiesel and the enrichment of polybasic unsaturated fatty acid ester.
This technique is applicable to various oils and fats, subsequent product isolated and purified convenient and easy,
There is good industrial applications prospect.
Accompanying drawing explanation
Fig. 1 is Production by Enzymes biodiesel of the present invention and the coupling of polybasic unsaturated fatty acid ester enrichment
Close process chart.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.If not
Specialize, the routine that technological means used in embodiment is well known to those skilled in the art
Means, raw materials used are commercial goods.
Embodiment 1
By 10g from Chlorella vulgaris microalgae grease (containing docosahexenoic acid),
Water based on oil quality 50%, formic acid based on oil quality 0.5%, be placed in be suitable to one-level or
Multistage reactor carries out the hydrolysis of oils and fats.Temperature control 120 DEG C, 2.0Mpa, after reacting 4 hours,
Effectively oils and fats is 95% to the conversion ratio of fatty acid, and after hydrolysis, water-oil phase separates, and oil phase enters one
Step is placed in enzyme reactor and (derives from rice equipped with live based on 500 standard enzyme of unit oil quality
The lipase of aspergillosis Aspergillus oryzae), enzyme reactor side connects absolute methanol tank, separately
Side connects vacuum pump and condenser, and the vacuum in control system is 10MPa, condenser temperature
Being 10 DEG C, temperature of reactor is 20 DEG C, and methanol tank temperature is 25 DEG C, reacts 5 hours, system
The yield of middle fatty acid short-chain ester is 97.4%.Oil phase containing fatty acid short-chain ester leads to further
Cross second stage enzyme reactor (equipped with the source lived based on 500 standard enzyme of unit oil quality
In antarctic candida Candida antarctica lipase and based on oil weigh 0.5% carbon
Dimethyl phthalate), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and opposite side connects vacuum
Pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, reaction
Device temperature is 20 DEG C, reacts 5 hours, and in system, the yield of fatty acid short-chain ester is 99%, acid
Valency is 0.3mg KOH/g.Further at 140-160 DEG C, under vacuum 6-10mmHg, by carbon
The biodiesel of chain length (C10-C18) is separated, and docosahexenoic acid short-chain ester is the richest
Collection is in tower reactor.
Embodiment 2
By 10g from the microalgae grease of Botryococcus sp. (containing eicosapentaenoic acid and two
Dodecahexaene acid) water based on oil quality 1000%, it is placed in and is suitable to one or more levels reaction
Device carries out the hydrolysis of oils and fats.Temperature control 220 DEG C, 3.0Mpa, after reacting 3 hours, effective oils and fats
Conversion ratio to fatty acid is 95.5%, and after hydrolysis, water-oil phase separates, and oil phase is further arranged in
Enzyme reactor (derives from aspergillus oryzae equipped with live based on 500 standard enzyme of unit oil quality
The lipase of Aspergillus oryzae), enzyme reactor side connects absolute methanol tank, opposite side
Connecting vacuum pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10
DEG C, temperature of reactor is 50 DEG C, and methanol tank temperature is 25 DEG C, reacts 5 hours, fat in system
The yield of fat acid short-chain ester is 98%.Oil phase containing fatty acid short-chain ester is further by second
Stage enzyme reactor (derives from the South Pole equipped with live based on 500 standard enzyme of unit oil quality
The lipase of candida mycoderma Candida antarctica and weigh based on oil 0.2% carbonic acid diformazan
Ester), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and opposite side connects vacuum pump and cold
Condenser, the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, enzyme reactor temperature
Degree is 50 DEG C, reacts 5 hours, and in system, the yield of fatty acid short-chain ester is 98.8%, and acid value is
0.4mg KOH/g.Further at 140-160 DEG C, under vacuum 6-10mmHg, by carbon chain length
(C10-C18) biodiesel is separated, and docosahexenoic acid short-chain ester is then enriched in
In tower reactor.
Embodiment 3
By 10g from the microalgae grease (containing eicosapentaenoic acid) of C.vulgaris, based on oil
The water of lipid amount 200%, sulphuric acid based on oil quality 5% and based on oil weigh 0.2% dodecane
Base sodium sulfonate, is placed in the hydrolysis being suitable to carry out oils and fats in one or more levels reactor.Temperature control 100
DEG C, after reacting 4 hours, the conversion ratio of effective oils and fats to fatty acid is 95%.Profit after hydrolysis
Two-phase laminated flow, oil phase is further arranged in enzyme reactor (equipped with based on unit oil quality 500
The lipase deriving from antarctic candida Candida antarctica that standard enzyme is lived), enzyme is anti-
Answering device side to connect absolute methanol tank, opposite side connects vacuum pump and condenser, in control system
Vacuum be 10MPa, condenser temperature is 10 DEG C, and temperature of reactor is 30 DEG C, and reaction is 5 little
Time, in system, the yield of fatty acid short-chain ester is 97.4%.Oil phase containing fatty acid short-chain ester
Further by second stage enzyme reactor (equipped with based on 500 standard enzyme of unit oil quality
Live the lipase deriving from antarctic candida Candida antarctica and based on oil weight
The dimethyl carbonate of 0.5%), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, opposite side
Connecting vacuum pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10
DEG C, temperature of reactor is 30 DEG C, and methanol tank temperature is 25 DEG C, reacts 5 hours, fat in system
The yield of fat acid short-chain ester is 99%, and acid value is 0.3mg KOH/g.Further at 140-160 DEG C,
Under vacuum 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated,
Docosahexenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 4
By 10g from C.minutissima microalgae grease (containing arachidonic acid, C20:4),
Water based on oil quality 400%, hydrochloric acid based on oil quality 1.0% and based on oil weigh 0.2%
Dodecyl sodium sulfate, be placed in the hydrolysis being suitable to carry out oils and fats in one or more levels reactor.
Temperature control 110 DEG C, reacts 4 hours, and the conversion ratio of effective oils and fats to fatty acid is 94.8%, hydrolysis
Rear water-oil phase separates, and oil phase is further arranged in enzyme reactor (equipped with based on unit oil quality
The lipase deriving from rhizomucor miehei Rhizomucor miehei that 500 standard enzyme are lived), enzyme
Reactor side connects absolute methanol tank, and opposite side connects vacuum pump and condenser, controls system
In vacuum be 10MPa, condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, react 5
Hour, in system, the yield of fatty acid short-chain ester is 98.4%.Oil containing fatty acid short-chain ester
The most further by second stage enzyme reactor (equipped with based on 500 standards of unit oil quality
Enzyme live the lipase deriving from antarctic candida Candida antarctica and based on oil
Weigh the dimethyl carbonate of 0.3%), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is
10 DEG C, temperature of reactor is 20 DEG C, reacts 5 hours, the yield of fatty acid short-chain ester in system
Being 99%, acid value is 0.2mg KOH/g.Further at 140-160 DEG C, vacuum 6-10mmHg
Under, the biodiesel of carbon chain length (C10-C18) to be separated, docosahexenoic acid is short
Chain ester is then enriched in tower reactor.
Embodiment 5
By 10g from the microalgae grease of T.fluviatilis (containing arachidonic acid and 20 carbon five
Olefin(e) acid), water based on oil quality 400%, sulphuric acid based on oil quality 1% and based on oil weight
The dodecyl sodium sulfate of 0.2%, is placed in the water being suitable to carry out oils and fats in one or more levels reactor
Solve.Temperature control 100 DEG C, reacts 3 hours, and the conversion ratio of effective oils and fats to fatty acid is 95.5%,
After hydrolysis, water-oil phase separates, and oil phase is further arranged in enzyme reactor (equipped with based on unit oils and fats
The fat deriving from rhizomucor miehei Rhizomucor miehei that 500 standard enzyme of quality are lived
Enzyme), enzyme reactor side connects absolute methanol tank, and opposite side connects vacuum pump and condenser,
Vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C,
Reacting 5 hours, in system, the yield of fatty acid short-chain ester is 98.6%.Containing fatty acid short-chain ester
Oil phase further by second stage enzyme reactor (equipped with based on unit oil quality 500
The lipase deriving from antarctic candida Candida antarctica of standard enzyme work and base
The dimethyl carbonate of 0.8% is weighed in oil), enzyme reactor side connects absolute methanol tank, opposite side
Connecting vacuum pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10
DEG C, temperature of reactor is 20 DEG C, reacts 2 hours, and in system, the yield of fatty acid short-chain ester is
99%, acid value is 0.2mg KOH/g.Further at 140-160 DEG C, vacuum 6-10mmHg
Under, the biodiesel of carbon chain length (C10-C18) to be separated, docosahexenoic acid is short
Chain ester is then enriched in tower reactor.
Embodiment 6
By 10g from the microalgae grease of T.pseudonana (containing docosahexenoic acid
(DHA, eicosapentaenoic acid and arachidonic acid), water based on oil quality 1000%,
Pole candida mycoderma Candida is derived from based on what 800 standard enzyme of unit oil quality were lived
The lipase of antarctica, is placed in the hydrolysis being suitable to carry out oils and fats in one or more levels reactor.
Temperature control 40 DEG C, after reacting 8 hours, the conversion ratio of effective oils and fats to fatty acid is 94%, hydrolysis
Rear water-oil phase separates, and oil phase is further arranged in enzyme reactor (equipped with based on unit oil quality
The lipase deriving from rhizomucor miehei Rhizomucor miehei that 500 standard enzyme are lived), enzyme
Reactor side connects absolute methanol tank, and opposite side connects vacuum pump and condenser, controls system
In vacuum be 10MPa, condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, react 5
Hour, in system, the yield of fatty acid short-chain ester is 97.4%.Oil containing fatty acid short-chain ester
The most further by second stage enzyme reactor (equipped with based on 800 standards of unit oil quality
Enzyme live the lipase deriving from antarctic candida Candida antarctica and based on oil
Weigh the diethyl carbonate of 1%), enzyme reactor side connects absolute methanol tank, and opposite side connects true
Empty pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, instead
Answering device temperature is 20 DEG C, reacts 5 hours, and in system, the yield of fatty acid short-chain ester is 99%,
Acid value is 0.2mg KOH/g.Further at 140-160 DEG C, under vacuum 6-10mmHg, will
The biodiesel of carbon chain length (C10-C18) is separated, and docosahexenoic acid short-chain ester is then
It is enriched in tower reactor.
Embodiment 7
By 10g from the microalgae grease of T.fluviatilis (containing arachidonic acid and 20 carbon five
Olefin(e) acid), water based on oil quality 50%, be placed in and be suitable to one or more levels reactor is carried out
The hydrolysis of oils and fats.Temperature control 280 DEG C, 3.0Mpa, after reacting 8 hours, effective oils and fats is to fatty acid
Conversion ratio be 98.5%, after hydrolysis water-oil phase separate, oil phase is further arranged in enzyme reactor
(derive from rhizomucor miehei equipped with live based on 500 standard enzyme of unit oil quality
The lipase of Rhizomucor miehei), enzyme reactor side connects absolute methanol tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is
10 DEG C, temperature of reactor is 20 DEG C, reacts 5 hours, the yield of fatty acid short-chain ester in system
It is 98.4%.Oil phase containing fatty acid short-chain ester is further by second stage enzyme reactor (dress
Have and derive from antarctic candida Candida based on what 800 standard enzyme of unit oil quality were lived
The lipase of antarctica and weigh based on oil 0.2% dimethyl carbonate), enzyme reactor side
Connecting Carbon Dioxide dimethyl ester tank, opposite side connects vacuum pump and condenser, in control system
Vacuum is 10MPa, and condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, reacts 5 hours,
In system, the yield of fatty acid short-chain ester is 99%, and acid value is 0.2mg KOH/g.Exist further
140-160 DEG C, under vacuum 6-10mmHg, by the biodiesel of carbon chain length (C10-C18)
Separating, docosahexenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 8
By 10g from Chlorella vulgaris microalgae grease (containing DHA, two dodecahexaenes
Acid), water based on oil quality 100%, sulphuric acid based on oil quality 5% and the 12 of 2%
Sodium alkyl sulfonate, is placed in the hydrolysis being suitable to carry out oils and fats in one or more levels reactor.Temperature control 100
DEG C, after reacting 5 hours, the conversion ratio of effective oils and fats to fatty acid is 97.3%, profit after hydrolysis
Two-phase laminated flow, oil phase is further arranged in enzyme reactor (equipped with based on unit oil quality 1000
The lipase deriving from rhizomucor miehei Rhizomucor miehei that individual standard enzyme is lived), enzyme is anti-
Answering device side to connect absolute methanol tank, opposite side connects vacuum pump and condenser, in control system
Vacuum be 10MPa, condenser temperature is 10 DEG C, and temperature of reactor is 40 DEG C, and reaction is 3 little
Time, in system, the yield of fatty acid short-chain ester is 98.4%.Oil phase containing fatty acid short-chain ester
Further by second stage enzyme reactor (equipped with based on 1000 standard enzyme of unit oil quality
Live the lipase deriving from antarctic candida Candida antarctica and based on oil weight
The dimethyl carbonate of 0.3%), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, opposite side
Connecting vacuum pump and condenser, the vacuum in control system is 10MPa, and condenser temperature is 10
DEG C, temperature of reactor is 40 DEG C, reacts 2 hours, and in system, the yield of fatty acid short-chain ester is
99%, acid value is 0.2mg KOH/g.Further at 140-160 DEG C, vacuum 6-10mmHg
Under, the biodiesel of carbon chain length (C10-C18) to be separated, docosahexenoic acid is short
Chain ester is then enriched in tower reactor.
Embodiment 9
By 10g from the microalgae grease of Botryococcus sp. (containing eicosapentaenoic acid and two
Dodecahexaene acid), water based on oil quality 100%, based on unit oil quality 1000
The lipase deriving from pole candida mycoderma Candida antarctica that standard enzyme is lived, is placed in and is suitable to
One or more levels reactor carries out the hydrolysis of oils and fats, temperature control 40 DEG C, after reacting 8 hours, has
Effect oils and fats is 96.5% to the conversion ratio of fatty acid, and after hydrolysis, water-oil phase separates, and oil phase enters one
Step is placed in enzyme reactor and (derives from rice equipped with live based on 1000 standard enzyme of unit oil quality
The lipase of Rhizomocur miehei Rhizomucor miehei), enzyme reactor temperature is 25 DEG C, methanol
Be 5:1 with fatty acid mol ratio, methanol respectively reaction 0 hour, 1 hour, 2 hours, 3
Hour and within 4 hours, respectively add 1 mole, course of reaction with as shown in Figure 1 online dehydration (film or
Molecular sieve), to react 3 hours, in system, fatty acid to the conversion ratio of fatty acid short-chain ester is
98.5%.Oil phase containing fatty acid short-chain ester is further by second stage enzyme reactor (dress
Have and derive from antarctic candida Candida based on what 1000 standard enzyme of unit oil quality were lived
The lipase of antarctica and weigh based on oil 0.3% dimethyl carbonate), course of reaction is with such as
Online dehydration (film or molecular sieve) shown in Fig. 1, reacts 2 hours, fatty acid short chain in system
The yield of ester is 99%, and acid value is 0.2mg KOH/g.Further at 140-160 DEG C, vacuum
Under 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated, 22
Carbon acid short-chain ester is then enriched in tower reactor.
Embodiment 10
By 10g from Chlorella vulgaris microalgae grease (containing DHA, two dodecahexaenes
Acid), water based on oil quality 1000%, be placed in and be suitable to one or more levels reactor is carried out
The hydrolysis of oils and fats.Temperature control 300 DEG C, 3Mpa, after reacting 4 hours, effective oils and fats is to fatty acid
Conversion ratio be 97.6%, after hydrolysis water-oil phase separate, oil phase is further arranged in enzyme reactor
(derive from rhizomucor miehei equipped with live based on 1000 standard enzyme of unit oil quality
The lipase of Rhizomucor miehei), enzyme reactor side connects dehydrated alcohol tank, another
Side connects vacuum pump and condenser, and the vacuum in control system is 15MPa, and condenser temperature is
12 DEG C, enzyme reactor temperature is 30 DEG C, and Ethanol tank temperature is 25 DEG C, reacts 6 hours, system
The yield of middle fatty acid short-chain ester is 98.4%.Oil phase containing fatty acid short-chain ester leads to further
Cross second stage enzyme reactor (equipped with the source lived based on 1000 standard enzyme of unit oil quality
In antarctic candida Candida antarctica lipase and based on oil weigh 0.3% carbon
Diethyl phthalate), enzyme reactor side connects dehydrated alcohol tank, and opposite side connects vacuum pump and cold
Condenser, the vacuum in control system is 15MPa, and condenser temperature is 12 DEG C, enzyme reactor temperature
Degree is 30 DEG C, and Ethanol tank temperature is 25 DEG C, reacts 6 hours, reacts 3 hours, fat in system
The yield of acid short-chain ester is 99%, and acid value is 0.2mg KOH/g.Further at 140-160 DEG C,
Under vacuum 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated,
Docosahexenoic acid short-chain ester is then enriched in tower reactor.
Although, the most with a general description of the specific embodiments the present invention has been made in detail
Most description, but on the basis of the present invention, it can be made some modifications or improvements, this is to this
It is apparent from for skilled person.Therefore, on the basis without departing from spirit of the present invention
Upper these modifications or improvements, belong to the scope of protection of present invention.
Claims (10)
1. Production by Enzymes biodiesel and the coupling technique of polybasic unsaturated fatty acid ester enrichment,
It is characterized in that, comprise the following steps:
S1, grease hydrolysis is become fatty acid；
S2, hydrolyzate carry out water-oil phase separation, and the oil phase collected reacts for next step；
S3, by lipase-catalyzed oil phase generation alcoholysis reaction, during enzymatic alcoholysis reaction,
Add by controlling short-chain alcohol streams and carry out online dehydration, eliminating water byproduct to lipase and product
The impact of yield, it is achieved the conversion from fatty acid to biodiesel；
S4, S3 gained reactant liquor is flowed in next stage enzyme reactor, make in reactant liquor the most anti-
Should glyceride and fatty acid enzymatically send out with dimethyl carbonate or diethyl carbonate completely
Raw reaction, generates polybasic unsaturated fatty acid ester, carries out online dehydration to remove in course of reaction
In course of reaction generate water byproduct, and then realize from oils and fats to biodiesel and polynary not
The conversion of polyunsaturated fatty acid ester.
Technique the most according to claim 1, it is characterised in that in S1, hydrolysis refers to
In one or more levels reactor interval or be continuously added to oils and fats and based on oil quality
The water of 50-1000% carries out the hydrolysis of oils and fats, and reaction is at 100-300 DEG C, under the conditions of 1.0-3.0Mpa
Carry out；Preferably, during hydrolysis is directed to one or more levels reactor interval or be continuously added to
Oils and fats and water based on oil quality 50-500% carry out the hydrolysis of oils and fats, and reaction is at 160-230
DEG C, carry out under the conditions of 1.5-3Mpa.
Technique the most according to claim 1, it is characterised in that in S1, hydrolysis refers to
In the presence of mineral acid, short chain organic acid and surfactant, in one or more levels reactor
Intermittently or serially addition oils and fats and water based on oil quality 50-1000% carry out the hydrolysis of oils and fats,
Reaction is carried out under the conditions of 100-120 DEG C；
Described mineral acid include sulphuric acid, hydrochloric acid or phosphoric acid, described short chain organic acid include formic acid or
Acetic acid, is added by oil quality 1-5%, and described surfactant includes dodecyl sodium sulfate,
Add by oil quality 0.2-2%.
Technique the most according to claim 1, it is characterised in that in S1, hydrolysis refers to
In one or more levels reactor interval or be continuously added to oils and fats and based on oil quality
The water of 50-1000% and lipase based on 500-1000 the standard enzyme work of unit oil quality
Being hydrolyzed, reaction is carried out under the conditions of 35-50 DEG C.
Technique the most according to claim 1, it is characterised in that S3 be by oil phase and based on
It is anti-that the lipase of 200-1000 enzyme of unit oil quality unit alive loads one or more levels circulation
Answer in device, by lipase-catalyzed fatty acid and short chain alcohol generation esterification, temperature of reactor
Controlling at 20-50 DEG C, described short chain alcohol includes methanol, ethanol, propanol or butanol.
Technique the most according to claim 1 or 5, it is characterised in that S3 enzymatic alcoholysis is anti-
During Ying, carry out non-uniform flow and add short chain alcohol and online dehydration；Described online dehydration refers to utilize
Film, molecular sieve or short chain alcohol air stripping.
Technique the most according to claim 1, it is characterised in that S4 is lipase-catalyzed
Under, by unreacted glyceride completely and fatty acid in S3 gained reactant liquor further with carbonic acid two
Methyl ester or diethyl carbonate react, and use online dehydration in course of reaction；Described online de-
Water refers to utilize film, molecular sieve or short chain alcohol air stripping.
8. according to the technique described in claim 6 or 7, it is characterised in that online dehydration is used
Film be organic membrane, inoranic membrane or ceramic membrane；Molecular sieve used by online dehydration isOr
Molecular sieve；Described short chain alcohol air stripping is reactor side is direct and equipped with anhydrous short chain alcohol tank
Body is connected, and the temperature of anhydrous short chain alcohol is 20-40 DEG C, and the opposite side of reactor is with vacuum pump even
Connecing, then vacuum pump is connected with condenser；By vacuum control in reactor at 10-100Mpa,
Condenser temperature is 5-15 DEG C；Described short chain alcohol includes methanol, ethanol.
9. according to the technique described in any one of claim 1-8, it is characterised in that described fat
Enzyme includes the lipase deriving from yeast, mycete, antibacterial or other microorganism；Lipase is single
Plant lipase or the combination of multiple lipase.
10. according to the technique described in any one of claim 1-9, it is characterised in that described oil
Fat is the bio-oil containing polybasic unsaturated fatty acid, including Vegetable oil lipoprotein, animal oil,
The concise leftover bits and pieces of waste edible oil, acidification oil, oils and fats and microbial grease.
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| CN114657062A (en) * | 2022-04-25 | 2022-06-24 | 广州市朗坤环境科技有限公司 | Reactor and method for preparing biodiesel by lipase catalysis for deacidification |
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