CN105925628B - The coupling technique of Production by Enzymes biodiesel and the enrichment of polybasic unsaturated fatty acid ester - Google Patents
The coupling technique of Production by Enzymes biodiesel and the enrichment of polybasic unsaturated fatty acid ester Download PDFInfo
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- CN105925628B CN105925628B CN201610529540.8A CN201610529540A CN105925628B CN 105925628 B CN105925628 B CN 105925628B CN 201610529540 A CN201610529540 A CN 201610529540A CN 105925628 B CN105925628 B CN 105925628B
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- fatty acid
- oil
- grease
- lipase
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- 102000004190 Enzymes Human genes 0.000 title claims abstract description 85
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 85
- 239000003225 biodiesel Substances 0.000 title claims abstract description 29
- 235000021122 unsaturated fatty acids Nutrition 0.000 title claims abstract description 26
- -1 unsaturated fatty acid ester Chemical class 0.000 title claims abstract description 23
- 238000010168 coupling process Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000004519 grease Substances 0.000 claims abstract description 67
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 65
- 229930195729 fatty acid Natural products 0.000 claims abstract description 65
- 239000000194 fatty acid Substances 0.000 claims abstract description 65
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000004367 Lipase Substances 0.000 claims abstract description 41
- 102000004882 Lipase Human genes 0.000 claims abstract description 41
- 108090001060 Lipase Proteins 0.000 claims abstract description 41
- 235000019421 lipase Nutrition 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000007062 hydrolysis Effects 0.000 claims abstract description 36
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 21
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 21
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000005456 glyceride group Chemical group 0.000 claims abstract description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000000413 hydrolysate Substances 0.000 claims abstract description 4
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 97
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 230000000694 effects Effects 0.000 claims description 28
- 235000019441 ethanol Nutrition 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000019197 fats Nutrition 0.000 claims description 9
- 230000002255 enzymatic effect Effects 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 5
- 239000012075 bio-oil Substances 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
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent 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
- 241000894006 Bacteria Species 0.000 claims description 3
- 230000008859 change Effects 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
- 150000002632 lipids Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 230000000813 microbial effect Effects 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 235000019871 vegetable fat Nutrition 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 235000019737 Animal fat Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 73
- 150000002148 esters Chemical class 0.000 description 41
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound 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 28
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 241001661345 Moesziomyces antarcticus Species 0.000 description 13
- 229940090949 docosahexaenoic acid Drugs 0.000 description 13
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 10
- 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 10
- 241000235403 Rhizomucor miehei Species 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 7
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 7
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 7
- 239000003925 fat Substances 0.000 description 7
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 6
- 240000006439 Aspergillus oryzae Species 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 235000002247 Aspergillus oryzae Nutrition 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 240000009108 Chlorella vulgaris Species 0.000 description 4
- 235000021342 arachidonic acid Nutrition 0.000 description 4
- 229940114079 arachidonic acid Drugs 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 230000008569 process Effects 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
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 241001536324 Botryococcus Species 0.000 description 2
- 241000957276 Thalassiosira weissflogii Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000010696 ester oil Substances 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 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
- 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
- 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
- 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
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 241000235402 Rhizomucor Species 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 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
- 241001491687 Thalassiosira pseudonana Species 0.000 description 1
- 244000248162 Xanthoceras sorbifolium Species 0.000 description 1
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000014121 butter Nutrition 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
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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 1
- 125000005908 glyceryl ester group Chemical group 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
- 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
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 239000000312 peanut oil Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
Abstract
The present invention provide Production by Enzymes biodiesel and polybasic unsaturated fatty acid ester enrichment coupling technique, comprising: S1, by grease hydrolysis at fatty acid；S2, hydrolysate carry out water-oil phase separation；S3, alcoholysis reaction mutually occurs with lipase-catalyzed oil, online dehydration is carried out by control short-chain alcohol streams adduction in reaction process, influence of the by-product water to lipase and efficiency of pcr product is eliminated, realizes the conversion from fatty acid to biodiesel；S4, reaction solution obtained by S3 is flowed into next stage enzyme reactor, the complete glyceride of unreacted and fatty acid in reaction solution is set enzymatically to react with dimethyl carbonate or diethyl carbonate, generate polybasic unsaturated fatty acid ester, online dehydration is carried out in reaction process to remove the by-product water generated in reaction process, and then is realized from grease to biodiesel and the conversion of polybasic unsaturated fatty acid ester.This technique has the advantages that glyceride stock strong applicability, production process environment-protecting clean, product quality and high yield.
Description
Technical field
The invention belongs to biological chemical fields, specifically, being related to Production by Enzymes biodiesel and polynary unsaturated fat
The coupling technique of acid esters enrichment.
Background technique
Biodiesel is the long chain fatty acids Ester generated by bio-oil by transesterification or esterification.Biology
Diesel oil is superior to petrifaction diesel in terms of flash-point, combustion efficiency, sulfur content, oxygen content, arene content, burning oxygen demand, and its
Its index is suitable with petrifaction diesel.Suspended particulate, carbon monoxide, sulfide and hydrocarbon be all significantly in combustion tail gas
It reduces, has environment friendly, be widely used in American-European countries.
Also contain polybasic unsaturated fatty acid (PUFAs) in some bio-oils.According to PUFA position of double bond again by its point
For ω -3 and ω -6 series, the carbon atom at the methyl end farthest apart from carboxyl is counted from fatty acid molecule, and first double bond goes out
Between present third and fourth carbon atom be known as ω -3PUFA, first double bond appear in the 6th and the 7th carbon atom it
Between be known as ω -6PUFA.The study found that many ω -3PUFAs are the function factors with a variety of physiological activity, therefore wide
It is general to be applied to every field.However, most of ω -3PUFA derive from deep sea fish oil, but comparision contents are low, at present ω -3PUFAs
Separation method be concentrated mainly on urea adduct method, molecular distillation, anion complexometry, supercritical extract, high performance liquid chromatography
The several methods such as method, biological enzyme.Wherein urea adduct method is more common, and urea can be with linear saturation rouge in organic solvent
Fat acid forms urea clathrate compound and crystallizes precipitation at low temperature, but the method need to use a large amount of organic solvent, participate in subsequent mention
Pure step；Molecular distillation can vaporize material to be separated at low temperature, and strict temperature control obtains the fraction of different temperatures, can be obtained compared with
High ω -3PUFAs, but energy consumption is high for process；Silver nitrate anion can be complexed with ω -3PUFAs in anion complexometry, product parent
It is aqueous strong, therefore ω -3PUFAs can enter water phase in the form of anion complex, to realize separation, but silver nitrate valence
Lattice are expensive, therefore are only limitted to laboratory and prepare in a small amount；Utilize supercritical CO2Extraction has many advantages, such as that ω -3PUFA is not aoxidized,
But the high requirements on the equipment.In short, using the above method enrichment ω -3PUFA physically or chemically, there are poor selectivity, process energy
The problems such as high is consumed, there is an urgent need to develop with high selectivity and environment amenable biological enzyme technique progress ω -3PUFAs
Enrichment.But the technique at present about enzyme method technique enrichment polybasic unsaturated fatty acid is cumbersome, at high cost, poor selectivity, industry
It is uncertain to change application prospect.
In addition, content of the polybasic unsaturated fatty acid in bio-oil is limited, remaining major part is other normal fats
Sour (such as palmitinic acid, stearic acid and oleic acid), while being enriched with polybasic unsaturated fatty acid, simultaneously by other aliphatic esters
It is converted to fatty acid short-chain ester (biodiesel), entire grease profitable transformation can be obviously improved.However, to realize life
The coupling technique of object diesel oil and the enrichment of polybasic unsaturated fatty acid ester, need to research and develop that product yield is higher, and biodiesel quality is high
Advanced preparation process.
Summary of the invention
The object of the present invention is to provide the coupling techniques that Production by Enzymes biodiesel and polybasic unsaturated fatty acid ester are enriched with.
In order to achieve the object of the present invention, Production by Enzymes biodiesel provided by the invention and polybasic unsaturated fatty acid ester are rich
The coupling technique of collection, comprising the following steps:
S1, by grease hydrolysis at fatty acid (fatty acid yield is 95% or more in hydrolysate)；
S2, hydrolysate carry out water-oil phase separation, and the oily phase being collected into is (in addition to fatty acid, also containing a little in oily phase
Monoglyceride, two glyceride and glyceryl ester etc.) for reacting in next step；
S3, alcoholysis reaction mutually occurs with lipase-catalyzed oil, during enzymatic alcoholysis reaction, by controlling short-chain alcohol streams
Adduction carries out online dehydration, eliminates influence of the by-product water to lipase and efficiency of pcr product, realizes from fatty acid to biodiesel
Conversion (conversion ratio is 96% or more)；
S4, reaction solution obtained by S3 is flowed into next stage enzyme reactor, makes the complete glyceride of unreacted in reaction solution
It enzymatically reacts with dimethyl carbonate or diethyl carbonate with fatty acid, generates polybasic unsaturated fatty acid ester, instead
Mild online dehydration should be carried out in the process to remove the by-product water generated in reaction process, and then realized from grease to biology
The conversion of diesel oil and polybasic unsaturated fatty acid ester.
Hydrolysis is directed to interval in one or more levels reactor or is continuously added to grease and is based on oil quality in S1
The water of 50-1000% carries out the hydrolysis of grease, and reaction carries out under the conditions of 100-300 DEG C, 1.0-3.0Mpa；Preferably, it hydrolyzes
Reaction is directed to interval in one or more levels reactor or is continuously added to grease and the water progress based on oil quality 50-500%
The hydrolysis of grease, reaction carry out under the conditions of 160-230 DEG C, 1.5-3Mpa.
Technique above-mentioned, hydrolysis refers in the presence of inorganic acid, short chain organic acid and surfactant in S1, Xiang Yi
Interval or grease is continuously added to and water based on oil quality 50-1000% carries out the hydrolysis of grease in grade or multistage reactor,
Reaction carries out under the conditions of 100-120 DEG C.
The inorganic acid includes sulfuric acid, hydrochloric acid or phosphoric acid etc., and the short chain organic acid includes formic acid or acetic acid etc., by grease
Quality 1-5% addition, the surfactant includes but is not limited to dodecyl sodium sulfate, is added by oil quality 0.2-2%.
Technique above-mentioned, hydrolysis is directed to interval in one or more levels reactor or is continuously added to grease and base in S1
Water in oil quality 50-1000% and the lipase based on 500-1000 standard enzyme activity of unit oil quality carry out water
Solution, reaction carry out under the conditions of 35-50 DEG C.
Technique above-mentioned, S3 are mutually packed into oily with the lipase based on 200-1000 enzyme-activity unit of unit oil quality
In one or more levels circulation flow reactor, esterification, temperature of reactor control are occurred by lipase-catalyzed fatty acid and short chain alcohol
For system at 20-50 DEG C, the short chain alcohol includes methanol, ethyl alcohol, propyl alcohol or butanol etc..
Technique above-mentioned during S3 enzymatic alcoholysis reaction, carries out non-uniform flow and adds short chain alcohol and mild online dehydration.
Technique above-mentioned, S4 are under lipase-catalyzed, by the complete glyceride of unreacted and rouge in reaction solution obtained by S3
Fat acid further reacts with dimethyl carbonate or diethyl carbonate, and mild online dehydration is used in reaction process.
Heretofore described mild online dehydration, which refers to, utilizes film, molecular sieve or short chain alcohol air lift.Used in online dehydration
Film be organic film, inoranic membrane or ceramic membrane etc.；Dehydration molecular sieve used is onlineOrMolecular sieve etc.；The short chain
Alcohol air lift is that reactor side is directly connected with the tank body equipped with anhydrous short chain alcohol, and the temperature of anhydrous short chain alcohol is 20-40 DEG C,
The other side of reactor is controlled to a vacuum pump, and then vacuum pump is connect with condenser；By vacuum control in reactor in 10-
100Mpa, condenser temperature are 5-15 DEG C；The short chain alcohol includes methanol, ethyl alcohol etc..
Production by Enzymes biodiesel of the present invention and the coupling technique flow chart of polybasic unsaturated fatty acid ester enrichment are shown in Fig. 1.
Heretofore described lipase includes the lipase from yeast, mould, bacterium or other microorganisms；Lipase
For the combination of single lipase or a variety of lipase.For example, the lipase of aspergillus oryzae (Aspergillus oryzae) is derived from,
From the lipase of antarctic candida (Candida antarctica), rhizomucor miehei (Rhizomucor is derived from
Miehei lipase etc.).
Heretofore described grease is the bio-oil containing polybasic unsaturated fatty acid, including vegetable fat, animal oil
The concise leftover bits and pieces of rouge, waste edible oil, acidification oil, grease and microbial oil etc..Wherein, the vegetable fat is castor oil, palm fibre
Palmitic acid oil, rapeseed oil, soybean oil, peanut oil, corn oil, cotton seed oil, rice bran oil, curcas oil, shinyleaf yellowhorn oil or Jatropha curcas oil etc.；
The animal fat is fish oil, butter, lard or sheep oil etc.；The microbial oil is yeast grease or microalgae quasi-grease etc..
The waste edible oil is hogwash fat or gutter oil etc.；The oil and fat refining leftover bits and pieces is acidification oil etc..
Polybasic unsaturated fatty acid involved in the present invention refers to the long chain fatty acids for having more than one double bond in molecule, packet
Include but be not limited to alpha-linolenic acid (C18:3), docosahexaenoic acid (C22:6), eicosapentaenoic acid (C20:5), arachidonic
Sour (C20:4) etc..
Present invention firstly provides high-quality biological diesel oil to prepare the coupling technique with the enrichment of polybasic unsaturated fatty acid ester, the
One stage, first the grease containing polybasic unsaturated fatty acid was hydrolyzed, and high-purity hydrolysis product fatty acid is then demultiplex out,
Various Complex ingredient can be evaded in the especially low-quality grease of grease completely in this way to the negative of subsequent lipase-catalyzed characteristic
It influences.It is prepared in biodiesel process in subsequent enzymatic fatty acid alcoholysis reaction, by mild online dehydration technique, so that
Fatty acid can be using Efficient Conversion as fatty acid short-chain ester.It, will be aforementioned for the conversion for further promoting remaining glyceride and fatty acid
Reaction solution by next stage enzyme reactor so that in reaction solution the complete glyceride of unreacted and fatty acid enzymatically with
Dimethyl carbonate or diethyl carbonate react, and remove dereaction mistake in time by mild online dehydration technique in reaction process
The by-product water generated in journey, thus realize the abundant conversion of grease to biodiesel and polybasic unsaturated fatty acid ester, it is real
The efficient coupling of the existing preparation of high-quality biological diesel oil and the enrichment of polybasic unsaturated fatty acid ester.
This technique significantly reduces influence of the complicated ingredient to enzyme activity in grease；In enzymatic grease alcoholysis reaction, participate in
The substance of reaction is high purity fatty acid, and byproduct of reaction is mainly moisture, can make to give birth to using mild online dehydration technique
At moisture on-line removal, so that reaction be made constantly to carry out towards positive reaction direction, enzymatic transformation efficiency increased substantially.Meanwhile
For the abundant conversion for further promoting remaining glyceride and fatty acid, and then under lipase-catalyzed, so that in previous reaction
Glyceride and the complete fatty acid of unreacted further react with dimethyl carbonate or diethyl carbonate, due to last
Traditional acyl acceptor first (second) alcohol is replaced using carbonic acid diformazan (second) ester in step, so that glycerol is no longer generated in reaction process,
Negative effect of the glycerol to enzymatic activity and stability is fundamentally relieved, to realize high yield and high-quality biological bavin
Oil preparation and the enrichment of polybasic unsaturated fatty acid ester.
This technique is suitable for various greases, and isolating and purifying for subsequent product is convenient and easy, has industry well
Change application prospect.
Detailed description of the invention
Fig. 1 is Production by Enzymes biodiesel of the present invention and the coupling technique flow chart that polybasic unsaturated fatty acid ester is enriched with.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment
Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.
Embodiment 1
By 10g from Chlorella vulgaris microalgae grease (containing docosahexaenoic acid), based on oil quality
50% water is placed in the hydrolysis suitable for carrying out grease in one or more levels reactor based on the formic acid of oil quality 0.5%.Control
120 DEG C, 2.0Mpa of temperature, after reaction 4 hours, the conversion ratio of effective grease to fatty acid is 95%, and water-oil phase separates after hydrolysis,
Oil be mutually further arranged in enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality derive from aspergillus oryzae
The lipase of Aspergillus oryzae), enzyme reactor side connects anhydrous methanol tank, and the other side connects vacuum pump and condensation
Device, the vacuum in control system are 10MPa, and condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, and methanol tank temperature is 25
DEG C, it reacts 5 hours, the yield of fatty acid short-chain ester is 97.4% in system.Oil containing fatty acid short-chain ester mutually further leads to
Cross second stage enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality from antarctic candida
The lipase of Candida antarctica and dimethyl carbonate based on oily weight 0.5%), the connection of enzyme reactor side is anhydrous
Dimethyl carbonate tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, condenser temperature 10
DEG C, temperature of reactor is 20 DEG C, is reacted 5 hours, and the yield of fatty acid short-chain ester is 99% in system, and acid value is 0.3mg KOH/
g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated, 20
Two carbon acid short-chain esters are then enriched in tower reactor.
Embodiment 2
Microalgae grease (containing eicosapentaenoic acid and docosahexaenoic acid) by 10g from Botryococcus sp.
Based on the water of oil quality 1000%, it is placed in the hydrolysis suitable for carrying out grease in one or more levels reactor.220 DEG C of temperature control,
3.0Mpa, after reaction 3 hours, the conversion ratio of effective grease to fatty acid is 95.5%, and water-oil phase separates after hydrolysis, oil phase into
One step be placed in enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality from aspergillus oryzae Aspergillus
The lipase of oryzae), enzyme reactor side connects anhydrous methanol tank, and the other side connects vacuum pump and condenser, control system
In vacuum be 10MPa, condenser temperature be 10 DEG C, temperature of reactor be 50 DEG C, methanol tank temperature be 25 DEG C, react 5 hours,
The yield of fatty acid short-chain ester is 98% in system.Oil containing fatty acid short-chain ester mutually further passes through second stage enzyme reaction
Device (equipped with based on 500 standard enzyme activities of unit oil quality from antarctic candida Candida antarctica's
Lipase and dimethyl carbonate based on oily weight 0.2%), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, the other side
Vacuum pump and condenser are connected, the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, and enzyme reactor temperature is 50
DEG C, it reacts 5 hours, the yield of fatty acid short-chain ester is 98.8% in system, and acid value is 0.4mg KOH/g.Further in 140-
160 DEG C, under vacuum degree 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated, the short chain of docosahexaenoic acid
Ester is then enriched in tower reactor.
Embodiment 3
Microalgae grease (containing eicosapentaenoic acid) by 10g from C.vulgaris, based on oil quality 200%
Water, the sulfuric acid based on oil quality 5% and the dodecyl sodium sulfate based on oily weight 0.2% are placed in anti-suitable for one or more levels
Answer the hydrolysis that grease is carried out in device.After 100 DEG C of temperature control, reaction 4 hours, the conversion ratio of effective grease to fatty acid is 95%.Water
Water-oil phase separates after solution, oil be mutually further arranged in enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality come
Derived from the lipase of antarctic candida Candida antarctica), enzyme reactor side connects anhydrous methanol tank, the other side
Vacuum pump and condenser are connected, the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, and temperature of reactor is 30 DEG C,
Reaction 5 hours, the yield of fatty acid short-chain ester is 97.4% in system.Oil containing fatty acid short-chain ester is mutually further by the
Two-stage enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality derive from antarctic candida Candida
The lipase of antarctica and dimethyl carbonate based on oily weight 0.5%), enzyme reactor side connects Carbon Dioxide diformazan
Ester tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, reactor
Temperature is 30 DEG C, and methanol tank temperature is 25 DEG C, is reacted 5 hours, and the yield of fatty acid short-chain ester is 99% in system, and acid value is
0.3mg KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, by the biodiesel of carbon chain length (C10-C18) point
It separates out and, docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 4
Microalgae grease (containing arachidonic acid, C20:4) by 10g from C.minutissima is based on oil quality
400% water, the hydrochloric acid based on oil quality 1.0% and the dodecyl sodium sulfate based on oily weight 0.2%, are placed in suitable for level-one
Or the hydrolysis of grease is carried out in multistage reactor.It 110 DEG C of temperature control, reacts 4 hours, the conversion ratio of effective grease to fatty acid is
94.8%, water-oil phase separates after hydrolysis, and oil is mutually further arranged in enzyme reactor (equipped with based on unit oil quality 500 marks
The lipase from rhizomucor miehei Rhizomucor miehei of quasi- enzyme activity), enzyme reactor side connects anhydrous methanol
Tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, reactor temperature
Degree is 20 DEG C, is reacted 5 hours, and the yield of fatty acid short-chain ester is 98.4% in system.Containing fatty acid short-chain ester oil mutually into
One step by second stage enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality derive from South Pole vacation silk ferment
The lipase of female Candida antarctica and dimethyl carbonate based on oily weight 0.3%), enzyme reactor side connects nothing
Aqueous carbonate dimethyl ester tank, the other side connect 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, is reacted 5 hours, and the yield of fatty acid short-chain ester is 99% in system, acid value 0.2mg
KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated,
Docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 5
Microalgae grease (containing arachidonic acid and eicosapentaenoic acid) by 10g from T.fluviatilis, based on oil
The water of lipid amount 400%, the sulfuric acid based on oil quality 1% and the dodecyl sodium sulfate based on oily weight 0.2%, are placed in and are suitable for
The hydrolysis of grease is carried out in one or more levels reactor.It 100 DEG C of temperature control, reacts 3 hours, the conversion ratio of effective grease to fatty acid
It is 95.5%, water-oil phase separates after hydrolysis, and oil is mutually further arranged in enzyme reactor (equipped with based on unit oil quality 500
The lipase from rhizomucor miehei Rhizomucor miehei of standard enzyme activity), enzyme reactor side connects anhydrous methanol
Tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, reactor temperature
Degree is 20 DEG C, is reacted 5 hours, and the yield of fatty acid short-chain ester is 98.6% in system.Containing fatty acid short-chain ester oil mutually into
One step by second stage enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality derive from South Pole vacation silk ferment
The lipase of female Candida antarctica and dimethyl carbonate based on oily weight 0.8%), enzyme reactor side connects nothing
Water methanol tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, and condenser temperature is 10 DEG C, instead
Answering device temperature is 20 DEG C, is reacted 2 hours, and the yield of fatty acid short-chain ester is 99% in system, and acid value is 0.2mg KOH/g.Into
One step is separated the biodiesel of carbon chain length (C10-C18), 22 carbon under 140-160 DEG C, vacuum degree 6-10mmHg
Acid short-chain ester is then enriched in tower reactor.
Embodiment 6
By 10g from T.pseudonana microalgae grease (containing docosahexaenoic acid (DHA, eicosapentaenoic acid and
Arachidonic acid), the water based on oil quality 1000%, based on 800 standard enzyme activities of unit oil quality from extremely false
The lipase of silk yeast Candidaantarctica, is placed in the hydrolysis suitable for carrying out grease in one or more levels reactor.Temperature control
After 40 DEG C, reaction 8 hours, the conversion ratio of effective grease to fatty acid is 94%, and water-oil phase separates after hydrolysis, and oil is mutually further
Be placed in enzyme reactor (equipped with based on 500 standard enzyme activities of unit oil quality from rhizomucor miehei Rhizomucor
The lipase of miehei), enzyme reactor side connects anhydrous methanol tank, and the other side connects vacuum pump and condenser, control system
In vacuum be 10MPa, condenser temperature be 10 DEG C, temperature of reactor be 20 DEG C, react 5 hours, the short chain of fatty acid in system
The yield of ester is 97.4%.Oil containing fatty acid short-chain ester is mutually further by second stage enzyme reactor (equipped with based on single
Position 800 standard enzyme activities of oil quality from antarctic candida Candida antarctica lipase and be based on
The diethyl carbonate of oily weight 1%), enzyme reactor side connects anhydrous methanol tank, and the other side connects vacuum pump and condenser, control
Vacuum in system is 10MPa, and condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, is reacted 5 hours, fatty acid in system
The yield of short-chain ester is 99%, and acid value is 0.2mg KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, by carbon
The biodiesel of chain length (C10-C18) is separated, and docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 7
Microalgae grease (containing arachidonic acid and eicosapentaenoic acid) by 10g from T.fluviatilis, based on oil
The water of lipid amount 50% is placed in the hydrolysis suitable for carrying out grease in one or more levels reactor.280 DEG C of temperature control, 3.0Mpa, reaction
After 8 hours, the conversion ratio of effective grease to fatty acid is 98.5%, and water-oil phase separates after hydrolysis, and oil is mutually further arranged in enzyme
Reactor (equipped with based on 500 standard enzyme activities of unit oil quality from rhizomucor miehei Rhizomucor miehei's
Lipase), enzyme reactor side connects anhydrous methanol tank, and the other side connects vacuum pump and condenser, the vacuum in control system
For 10MPa, condenser temperature is 10 DEG C, and temperature of reactor is 20 DEG C, is reacted 5 hours, the yield of fatty acid short-chain ester in system
It is 98.4%.Oil containing fatty acid short-chain ester is mutually further by second stage enzyme reactor (equipped with based on unit grease matter
Measure weighing from the lipase of antarctic candida Candida antarctica and based on oil for 800 standard enzyme activities
0.2% dimethyl carbonate), enzyme reactor side connects Carbon Dioxide dimethyl ester tank, and the other 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, is reacted 5 hours, rouge in system
The yield of fat acid short-chain ester is 99%, and acid value is 0.2mg KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg,
The biodiesel of carbon chain length (C10-C18) is separated, docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 8
By 10g from Chlorella vulgaris microalgae grease (containing DHA, docosahexaenoic acid), based on grease
The water of quality 100%, sulfuric acid based on oil quality 5% and 2% dodecyl sodium sulfate, be placed in anti-suitable for one or more levels
Answer the hydrolysis that grease is carried out in device.After 100 DEG C of temperature control, reaction 5 hours, the conversion ratio of effective grease to fatty acid is 97.3%,
Water-oil phase separates after hydrolysis, and oil is mutually further arranged in enzyme reactor (equipped with based on 1000 standard enzyme activities of unit oil quality
The lipase from rhizomucor miehei Rhizomucor miehei), enzyme reactor side connect anhydrous methanol tank, it is 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 40
DEG C, it reacts 3 hours, the yield of fatty acid short-chain ester is 98.4% in system.Oil containing fatty acid short-chain ester mutually further leads to
Cross second stage enzyme reactor (equipped with based on 1000 standard enzyme activities of unit oil quality from antarctic candida
The lipase of Candida antarctica and dimethyl carbonate based on oily weight 0.3%), the connection of enzyme reactor side is anhydrous
Dimethyl carbonate tank, the other side connect vacuum pump and condenser, and the vacuum in control system is 10MPa, condenser temperature 10
DEG C, temperature of reactor is 40 DEG C, is reacted 2 hours, and the yield of fatty acid short-chain ester is 99% in system, and acid value is 0.2mg KOH/
g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated, 20
Two carbon acid short-chain esters are then enriched in tower reactor.
Embodiment 9
Microalgae grease by 10g from Botryococcus sp. (contains eicosapentaenoic acid and two dodecahexaenes
Acid), the water based on oil quality 100%, based on 1000 standard enzyme activities of unit oil quality derive from pole Candida
The lipase of Candida antarctica, be placed in suitable in one or more levels reactor carry out grease hydrolysis, 40 DEG C of temperature control,
After reaction 8 hours, the conversion ratio of effective grease to fatty acid is 96.5%, and water-oil phase separates after hydrolysis, and oil is mutually further set
In enzyme reactor (equipped with based on 1000 standard enzyme activities of unit oil quality derive from rhizomucor miehei Rhizomucor
The lipase of miehei), enzyme reactor temperature is 25 DEG C, and methanol and fatty acid molar ratio are 5:1, and methanol is small in reaction 0 respectively
When, each 1 mole of addition in 1 hour, 2 hours, 3 hours and 4 hours, reaction process online dehydration (film or molecule as shown in Figure 1
Sieve), it reacts 3 hours, the conversion ratio of fatty acid to fatty acid short-chain ester is 98.5% in system.Oil containing fatty acid short-chain ester
Mutually further by second stage enzyme reactor (equipped with false from the South Pole based on 1000 standard enzyme activities of unit oil quality
The lipase of silk yeast Candida antarctica and dimethyl carbonate based on oily weight 0.3%), reaction process is used as schemed
It is dehydrated (film or molecular sieve) online shown in 1, is reacted 2 hours, the yield of fatty acid short-chain ester is 99% in system, and acid value is
0.2mg KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, by the biodiesel of carbon chain length (C10-C18) point
It separates out and, docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Embodiment 10
By 10g from Chlorella vulgaris microalgae grease (containing DHA, docosahexaenoic acid), based on grease
The water of quality 1000% is placed in the hydrolysis suitable for carrying out grease in one or more levels reactor.300 DEG C of temperature control, 3Mpa, reaction 4
After hour, the conversion ratio of effective grease to fatty acid is 97.6%, and water-oil phase separates after hydrolysis, and it is anti-that oil is mutually further arranged in enzyme
Answer device (equipped with based on 1000 standard enzyme activities of unit oil quality from rhizomucor miehei Rhizomucor miehei's
Lipase), enzyme reactor side connects dehydrated alcohol tank, and the other side connects vacuum pump and condenser, the vacuum in control system
For 15MPa, condenser temperature is 12 DEG C, and enzyme reactor temperature is 30 DEG C, and Ethanol tank temperature is 25 DEG C, is reacted 6 hours, in system
The yield of fatty acid short-chain ester is 98.4%.Oil containing fatty acid short-chain ester mutually further passes through second stage enzyme reactor
(equipped with the rouge from antarctic candida Candida antarctica based on 1000 standard enzyme activities of unit oil quality
Fat enzyme and diethyl carbonate based on oily weight 0.3%), enzyme reactor side connects dehydrated alcohol tank, and the other side connects vacuum
Pump and condenser, the vacuum in control system are 15MPa, and condenser temperature is 12 DEG C, and enzyme reactor temperature is 30 DEG C, Ethanol tank
Temperature is 25 DEG C, is reacted 6 hours, is reacted 3 hours, and the yield of fatty acid short-chain ester is 99% in system, acid value 0.2mg
KOH/g.Further under 140-160 DEG C, vacuum degree 6-10mmHg, the biodiesel of carbon chain length (C10-C18) is separated,
Docosahexaenoic acid short-chain ester is then enriched in tower reactor.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (11)
1. the coupling technique of Production by Enzymes biodiesel and the enrichment of polybasic unsaturated fatty acid ester, which is characterized in that including following
Step:
S1, by grease hydrolysis at fatty acid；
S2, hydrolysate carry out water-oil phase separation, and the oil being collected into mutually for reacting in next step；
S3, alcoholysis reaction mutually occurs with lipase-catalyzed oil, during enzymatic alcoholysis reaction, passes through control short-chain alcohol streams adduction
Online dehydration is carried out, influence of the by-product water to lipase and efficiency of pcr product is eliminated, realizes and turns from fatty acid to biodiesel
Change；
S4, reaction solution obtained by S3 is flowed into next stage enzyme reactor, makes the complete glyceride of unreacted and rouge in reaction solution
Fat acid enzymatically reacts with dimethyl carbonate or diethyl carbonate, generates polybasic unsaturated fatty acid ester, reacted
Online dehydration is carried out in journey to remove the by-product water generated in reaction process, and then is realized from grease to biodiesel and more
The conversion of first unsaturated fatty acid ester.
2. technique according to claim 1, which is characterized in that hydrolysis is directed in one or more levels reactor in S1
Grease is intermittently or serially added and the water based on oil quality 50-1000% carries out the hydrolysis of grease, reacts at 100-300 DEG C,
It is carried out under the conditions of 1.0-3.0Mpa.
3. technique according to claim 2, which is characterized in that hydrolysis is directed in one or more levels reactor in S1
Grease is intermittently or serially added and the water based on oil quality 50-500% carries out the hydrolysis of grease, reacts at 160-230 DEG C,
It is carried out under the conditions of 1.5-3Mpa.
4. technique according to claim 1, which is characterized in that hydrolysis refers in inorganic acid, short chain organic acid in S1
In the presence of surfactant, interval or grease is continuously added to and based on oil quality 50- into one or more levels reactor
1000% water carries out the hydrolysis of grease, and reaction carries out under the conditions of 100-120 DEG C；
The inorganic acid includes sulfuric acid, hydrochloric acid or phosphoric acid, and the short chain organic acid includes formic acid or acetic acid, by oil quality 1-
5% addition, the surfactant includes dodecyl sodium sulfate, is added by oil quality 0.2-2%.
5. technique according to claim 1, which is characterized in that hydrolysis is directed in one or more levels reactor in S1
Grease and water based on oil quality 50-1000% is intermittently or serially added and is marked based on unit oil quality 500-1000
The lipase of quasi- enzyme activity is hydrolyzed, and reaction carries out under the conditions of 35-50 DEG C.
6. technique according to claim 1, which is characterized in that S3 is by oily mutually and based on unit oil quality 200-1000
The lipase of a enzyme-activity unit is fitted into one or more levels circulation flow reactor, is occurred by lipase-catalyzed fatty acid and short chain alcohol
Esterification, temperature of reactor are controlled at 20-50 DEG C, and the short chain alcohol includes methanol, ethyl alcohol, propyl alcohol or butanol.
7. technique according to claim 1, which is characterized in that during S3 enzymatic alcoholysis reaction, implementation non-uniform flow adds short
The pure and mild online dehydration of chain；The online dehydration, which refers to, utilizes film, molecular sieve or short chain alcohol air lift.
8. technique according to claim 1, which is characterized in that S4 be under lipase-catalyzed, will be in reaction solution obtained by S3
The complete glyceride of unreacted and fatty acid further react with dimethyl carbonate or diethyl carbonate, make in reaction process
With online dehydration；The online dehydration, which refers to, utilizes film, molecular sieve or short chain alcohol air lift.
9. technique according to claim 7, which is characterized in that online dehydration film used is organic film, inoranic membrane or pottery
Porcelain film；Dehydration molecular sieve used is onlineOrMolecular sieve；The short chain alcohol air lift be by reactor side directly with
Tank body equipped with anhydrous short chain alcohol is connected, and the temperature of anhydrous short chain alcohol is 20-40 DEG C, and the other side of reactor and vacuum pump connect
It connects, then vacuum pump is connect with condenser；By vacuum control in reactor in 10-100Mpa, condenser temperature is 5-15 DEG C；Institute
Stating short chain alcohol includes methanol, ethyl alcohol.
10. -9 described in any item techniques according to claim 1, which is characterized in that the lipase includes from yeast, mould
The lipase of bacterium, bacterium or other microorganisms；Lipase is the combination of single lipase or a variety of lipase.
11. -9 described in any item techniques according to claim 1, which is characterized in that the grease is to contain polynary unsaturated lipid
The bio-oil of fat acid, including the concise leftover bits and pieces of vegetable fat, animal fat, waste edible oil, acidification oil, grease and microbial oil
Rouge.
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