CN101381614B - Technique for preparing biodiesel by catalyzing oil using recovery of non-immobilized lipase - Google Patents
Technique for preparing biodiesel by catalyzing oil using recovery of non-immobilized lipase Download PDFInfo
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- CN101381614B CN101381614B CN2008102243159A CN200810224315A CN101381614B CN 101381614 B CN101381614 B CN 101381614B CN 2008102243159 A CN2008102243159 A CN 2008102243159A CN 200810224315 A CN200810224315 A CN 200810224315A CN 101381614 B CN101381614 B CN 101381614B
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- 239000004367 Lipase Substances 0.000 title claims abstract description 30
- 102000004882 Lipase Human genes 0.000 title claims abstract description 30
- 108090001060 Lipase Proteins 0.000 title claims abstract description 30
- 235000019421 lipase Nutrition 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003225 biodiesel Substances 0.000 title claims description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 102000004190 Enzymes Human genes 0.000 claims abstract description 47
- 108090000790 Enzymes Proteins 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000605 extraction Methods 0.000 claims abstract description 35
- 239000004519 grease Substances 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003921 oil Substances 0.000 claims description 77
- 235000019198 oils Nutrition 0.000 claims description 77
- 239000012071 phase Substances 0.000 claims description 27
- 239000008346 aqueous phase Substances 0.000 claims description 16
- 239000002551 biofuel Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 125000005456 glyceride group Chemical group 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 240000006439 Aspergillus oryzae Species 0.000 claims description 5
- 235000002247 Aspergillus oryzae Nutrition 0.000 claims description 5
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 5
- 102000004895 Lipoproteins Human genes 0.000 claims description 4
- 108090001030 Lipoproteins Proteins 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 4
- 239000010775 animal oil Substances 0.000 claims description 4
- 239000012075 bio-oil Substances 0.000 claims description 4
- 238000006911 enzymatic reaction Methods 0.000 claims description 4
- 230000000813 microbial effect Effects 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003925 fat Substances 0.000 claims description 3
- 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 claims description 2
- 241000894006 Bacteria Species 0.000 claims description 2
- 241001048891 Jatropha curcas Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 241000235403 Rhizomucor miehei Species 0.000 claims description 2
- 241000269319 Squalius cephalus Species 0.000 claims description 2
- 241000223258 Thermomyces lanuginosus Species 0.000 claims description 2
- 244000248162 Xanthoceras sorbifolium Species 0.000 claims description 2
- 235000009240 Xanthoceras sorbifolium Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000008157 edible vegetable oil Substances 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 210000000582 semen Anatomy 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 235000019197 fats Nutrition 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002283 diesel fuel Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 81
- 238000012856 packing Methods 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- 240000005384 Rhizopus oryzae Species 0.000 description 2
- 235000013752 Rhizopus oryzae Nutrition 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 108010091086 Recombinases Proteins 0.000 description 1
- 102000018120 Recombinases Human genes 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 108091008146 restriction endonucleases Proteins 0.000 description 1
- 210000005253 yeast cell Anatomy 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention provides a process for preparing biological diesel oil by recovering non-immobilization lipase catalyzed grease, which belongs to the field of biological fuel synthesis. The process is as follows: 4 to 9mol of short-chain alcohol based on the grease, 1 to 20 percent of water based on the weight of the grease, and 20 to 200 non-immobilization lipases of the enzyme live unit based on the mass of the unit grease are added in a biochemical reactor to react at a temperature of between 30 and 65 DEG C for 5 and 15 hours, and the yield of grease raw materials converted into the biological diesel oil reaches more than 95 percent; after the reaction, the mixture is subjected to centrifugation to remove the middle emulsion layer, and pheron in the lower-layer water phase is extracted out by utilizing the upper-layer oil phase or grease of reaction raw materials; during the extraction, a new emulsion layer is formed, and the new emulsion layer is recovered until the recovery rate of the pheron reaches more than 95 percent; and the emulsion layers are combined, and the recovered emulsion layer can be directly used for the next catalysis. The process has the advantages of effectively reducing the enzyme loss and achieving the aim of the repeated use of the lipase.
Description
Technical field
The invention belongs to the synthetic field of biofuel; Be particularly related to a kind of recovery non-immobilized lipase technique for preparing biodiesel by catalyzing oil using; Utilize non-immobilized lipase catalysis of renewable glyceride stock to prepare in the biofuel process, reclaiming the technology that non-immobilized lipase is used for biodiesel manufacture.
Background technology
Biofuel is the long chain fatty acid ester class material that is generated through transesterification reaction by the bio-oil raw material, and as a kind of recyclable organism fuel of cleaning, the research of biofuel and application have been subjected to widely to be paid close attention to.
Biofuel mainly is to use chemical method production at present, promptly uses animal-plant oil and some low-carbon alcohol (methyl alcohol or ethanol) under alkali or an acidic catalyst effect, to carry out transesterification reaction, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method prepares biofuel and has the following inevitable shortcoming: 1. free fatty acids in the glyceride stock and water have a strong impact on the carrying out of reaction; 2. methyl alcohol solvability in grease is bad, thereby is prone to cause the formation of emulsion to make subsequent processes complicated; 3. the processing requirement methanol usage substantially exceeds the reaction mol ratio, the evaporation backflow increase process energy consumption of excessive methanol.
Because free fatty acids and the less water of utilizing the biological enzyme biodiesel synthesis to have in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as enzymatic reaction, meet the developing direction of Green Chemistry, thereby receive people's attention day by day.But compare with chemical method, the cost of enzyme is too high, and this has become the main bottleneck of restriction enzyme process industrialization production biofuel.
Immobilized lipase can be reused, and this can reduce the use cost of enzyme to a certain extent.But the preparation cost of immobilized enzyme is very high, and wherein most costs ascribe the downstream process running cost of enzyme, the i.e. separation of enzyme, purifying and immobilization to.So directly utilize non-immobilized lipase (like liquid aliphatic enzyme and resolvase powder) as catalyzer, then can effectively save the separation of enzyme, purifying and immobilization supervisor can reduce the preparation cost of enzyme significantly.Yet; Utilizing non-immobilized lipase to prepare in the process of biofuel as catalyzer conversion renewable oils fat raw material; Can the repeatedly reuse that realize these non-immobilized lipases be the keys that reduce the enzyme cost, also are the main restricting factors that can non-immobilized lipase finally be applied to diesel preparation field.
The present invention proposes utilizing non-immobilized lipase (comprising liquid aliphatic enzyme and on-fixed enzyme powder) to prepare in the process of biofuel as catalyzer conversion renewable oils fat raw material; Utilize abstraction technique that above-mentioned non-immobilized lipase is reclaimed, the lypase after the recovery can continue on for the catalyzed reaction of next batch.This invention can effectively solve the reuse of non-immobilized lipase, reduces the use cost of non-immobilized lipase greatly.This technology has very important application prospect in diesel preparation field.
Summary of the invention
The object of the present invention is to provide a kind of recovery non-immobilized lipase technique for preparing biodiesel by catalyzing oil using; Utilizing non-immobilized lipase (comprising liquid aliphatic enzyme and lypase powder) conversion renewable oils fat raw material to prepare in the process of biofuel; After a collection of secondary response in front finishes, utilize abstraction technique that non-immobilized lipase is reclaimed.Oil phase (being mainly biofuel) and reaction raw materials (animal-plant oil) that extraction phase in the extraction process generates for the reaction back.This invention efficiently solves the reuse problem of non-immobilized lipase in catalysis preparing biological diesel oil by animal plant lipid process, can reduce the production cost of process for preparing biodiesel by enzyme significantly, has important prospects for commercial application.
The present invention is as the reaction acyl acceptor with the short chain alcohol roh; Utilize non-immobilized lipase to carry out the transesterification reaction biodiesel synthesis as catalyst glyceride stock and above-mentioned short chain alcohol, after reaction finishes, centrifugal; Acceleration comprises that the same oil phase of the water of lypase (is mainly biofuel; Also have a little intermediate product and unreacted grease completely) separation, emulsion layer (zymoprotein 70% or more concentrates on emulsion layer) in the middle of taking away, the zymoprotein of 25-30% is distributed in lower floor's water in addition; And then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase; Form new emulsion layer in the extraction process, wherein most of enzyme is distributed in new emulsion layer again, can repeatedly repeat this extraction step as required and reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lypase, has reached the purpose that repeats reuse lypase.
Technology of the present invention is: the short chain alcohol that adds based on grease 4-9 mole (can be taked the mode that repeatedly add intermittence in batches or even flow adds; Guarantee that the single add-on is no more than 3 moles and get final product), adding is based on the water of oil quality 1%-20%; And based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme; The lypase of different sources can make up use, packs into to be suitable in any biochemical reactor of enzyme reaction, and temperature is controlled at 30 ℃～65 ℃; React after 5-15 hours, glyceride stock transforms the yield that generates biofuel and surpasses 95%.After reaction finishes, centrifugal, emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away; Also have the zymoprotein of 25-30% to be distributed in lower floor's water, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase, oil phase is with the 0.1-4 that is in a ratio of of water; Form new emulsion layer in the extraction process; Then this emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lypase, has reached the purpose that repeats reuse lypase.
Lypase according to the invention is non-immobilized lipase, comprises deriving from yeast cell fungal cell, the liquid aliphatic enzyme of bacterium or other mikrobe or the free-fat enzyme of other form such as enzyme powder.
Grease according to the invention is that bio-oil comprises Vegetable oil lipoprotein, animal oil and fat, waste edible oil, the concise tankage of grease and microbial oil.
Vegetable oil lipoprotein according to the invention is Viscotrol C, rapeseed oil, VT 18, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, curcas oil, shinyleaf yellowhorn oil, Jatropha curcas oil.
Animal oil and fat according to the invention is fish oil, lard.
Microbial oil according to the invention is the yeast grease, the microalgae grease.
R is the alkyl with 1-5 carbon atom in the short chain alcohol roh according to the invention.
Short chain alcohol according to the invention is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
Of the present inventionly be a little, effectively reduced the loss of enzyme, reached the purpose that repeats reuse lypase.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1
With mol ratio is methyl alcohol and the rapeseed oil (rapeseed oil 9.65g) of 4:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 1%, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after; Adding is based on the liquid aliphatic enzyme that derives from Aspergillus oryzae of 40 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 600rpm, and methyl alcohol at the uniform velocity added in 6 hours, and bio-diesel yield was 85% in 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase; Oil phase is in a ratio of 0.5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required, reach more than 95% until the recovery of zymoprotein.Merge each emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 2
With mol ratio is methyl alcohol and the lard (lard 9.65g) of 9:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 10%, and place can be temperature automatically controlled reciprocal shaking table be heated to 70 ℃ after; Adding is based on the lypase powder that derives from Aspergillus oryzae of 70 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 500rpm, and methyl alcohol at the uniform velocity added in 8 hours, and bio-diesel yield was 98% in 10 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase; Oil phase is in a ratio of 1 with water, forms new emulsion layer in the extraction process, this emulsion layer is reclaimed again; Can repeatedly repeat this extraction step as required, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 3
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 6:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 15%, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after; The liquid aliphatic enzyme that derives from Aspergillus oryzae that adds 100 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 800rpm, and methyl alcohol is non-in 8 hours at the uniform velocity to add, and (addition manner was in preceding 3 hours: added 2 mole, of methanol in 0 hour, and reacted and add 1 mole again after 1 hour; Adding 2 moles after 2 hours again, add 1 mole again after 4 hours) bio-diesel yield was 95% 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase; Oil phase is in a ratio of 2 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 4
With mol ratio is methyl alcohol and the curcas oil (curcas oil 9.65g) of 4:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 2%, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after; The lypase powder that derives from Candida antarctica that adds 40 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 1000rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 85% in 6 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with upper oil phase; Oil phase is in a ratio of 5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 5
With mol ratio is ethanol and the algae grease (algae grease 9.65g) of 9:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 8%, and place can be temperature automatically controlled reciprocal shaking table be heated to 30 ℃ after; The liquid aliphatic enzyme that derives from Candida antarctica that adds 20 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 400rpm, and methyl alcohol is non-in 10 hours at the uniform velocity to add, and bio-diesel yield was 93% in 15 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 0.1 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 6
With mol ratio is ethanol and the hogwash fat (hogwash fat 9.65g) of 6:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 10%, and place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after; The liquid aliphatic enzyme that derives from Candida antarctica that adds 100 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 300rpm, and methyl alcohol at the uniform velocity added in 8 hours, and bio-diesel yield was 95% in 10 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 1 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 7
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 8:1; Adding is based on the water of oil quality 16%; Pack into and mix in the tool plug triangular flask; And place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, add 300 enzymes of unit oil quality live liquid aliphatic enzyme that derives from Rhizopus oryzae of units of the liquid aliphatic enzyme that derives from Rhizomucor miehei and 40 enzymes of unit of living, the reaction rotating speed is controlled at 500rpm; Methyl alcohol at the uniform velocity added in 10 hours, and bio-diesel yield was 95% in 12 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 2 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 8
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 9:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 20%, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after; The liquid aliphatic enzyme that derives from Thermomyces lanuginosus that adds 200 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 1000rpm, and methyl alcohol at the uniform velocity added in 12 hours, and bio-diesel yield was 95% in 14 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 3 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 9
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 10%, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after; The liquid aliphatic enzyme that derives from Rhizopus oryzae that adds 200 enzymes of unit oil quality unit alive; The reaction rotating speed is controlled at 1500rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 95% in 5 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 5 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 10
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1; Adding is based on the water of oil quality 15%; Pack into and mix in the tool plug triangular flask; And place can be temperature automatically controlled reciprocal shaking table be heated to 50 ℃ after, add 30 enzymes of unit oil quality live enzyme powder that derives from Candida antarctica of units of the liquid aliphatic enzyme that derives from Aspergillus oryzae and 20 enzymes of unit of living, the reaction rotating speed is controlled at 800rpm; Methyl alcohol is non-in 8 hours at the uniform velocity to add, and (addition manner was in preceding 3 hours: 0 hour adding 2 mole, of methanol; Reacting and add 1 mole again after 1 hour, add 2 moles again after 2 hours, add 1 mole again after 4 hours) bio-diesel yield was 95% 8 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 4 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
Embodiment 11
With mol ratio is methyl alcohol and the hogwash fat (hogwash fat 9.65g) of 7:1; Adding mixes in the tool plug triangular flask of packing into based on the water of oil quality 10%, and place can be temperature automatically controlled reciprocal shaking table be heated to 60 ℃ after; Add the lypase that reclaims among the embodiment 9; The reaction rotating speed is controlled at 1500rpm, and methyl alcohol at the uniform velocity added in 3 hours, and bio-diesel yield was 94% in 5 hours.After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then remove to extract the zymoprotein of lower floor's aqueous phase with the reaction raw materials grease; Oil phase is in a ratio of 3 with water, forms new emulsion layer in the extraction process, and this emulsion layer is reclaimed; Can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.
According to the foregoing description, this technology be with the short chain alcohol roh as the reaction acyl acceptor, utilize non-immobilized lipase to carry out the transesterification reaction biodiesel synthesis as catalyst glyceride stock and above-mentioned short chain alcohol; After reaction finishes, centrifugal, quicken to comprise that the same oil phase of water of lypase (is mainly biofuel; Also have a little intermediate product and unreacted grease completely) separation; Emulsion layer (zymoprotein 70% or more concentrates on emulsion layer) in the middle of taking away, in addition the zymoprotein of 25-30% is distributed in lower floor's water, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase; Form new emulsion layer in the extraction process; This emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lypase, has reached the purpose that repeats reuse lypase.It is characterized in that: the short chain alcohol that adds based on grease 4-9 mole (can be taked the mode that repeatedly add intermittence in batches or even flow adds; Guarantee that the single add-on is no more than 3 moles and get final product), adding is based on the water of oil quality 1%-20%; And based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme; The lypase of different sources can make up use, packs into to be suitable in any biochemical reactor of enzyme reaction, and temperature is controlled at 30 ℃～65 ℃; React after 5-15 hours, glyceride stock transforms the yield that generates biofuel and surpasses 95%.After reaction finishes, centrifugal, emulsion layer (zymoprotein more than 70% concentrates on emulsion layer) in the middle of taking away; Also have the zymoprotein of 25-30% to be distributed in lower floor's water, and then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase, oil phase is with the 0.5-4 that is in a ratio of of water; Form new emulsion layer in the extraction process; This emulsion layer is reclaimed, can repeatedly repeat this extraction step as required again, reach more than 95% until the recovery of zymoprotein.Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch then.This process can be carried out the efficient recovery of lypase, has reached the purpose that repeats reuse lypase.
Claims (9)
1. one kind is reclaimed the non-immobilized lipase technique for preparing biodiesel by catalyzing oil using; It is characterized in that: technology is: adding based on the grease mole number is 4-9 short chain alcohol roh doubly; Adding is based on the water of oil quality 1%-20%, and based on the live non-immobilized lipase of unit of the oil quality 20-200 of unit enzyme, the lypase of different sources is used alone or in combination; Pack into and be suitable in any biochemical reactor of enzyme reaction; Temperature is controlled at 30 ℃～65 ℃, reacts after 5-15 hour, and glyceride stock transforms the yield that generates biofuel and surpasses 95%; After reaction finishes, centrifugal, emulsion layer in the middle of taking away; And then with upper oil phase or utilize the reaction raw materials grease to remove to extract the zymoprotein of lower floor's aqueous phase; Oil phase is 0.1-4 with the ratio of water, forms new emulsion layer in the extraction process, this emulsion layer is reclaimed again; Repeatedly repeat this extraction step as required, reach more than 95% until the recovery of zymoprotein; Merge the emulsion layer in the aforesaid operations then, directly utilize the emulsion layer that is recovered to carry out the catalysis of next batch.
2. technology according to claim 1 is characterized in that, said lypase is non-immobilized lipase, and non-immobilized lipase comprises liquid aliphatic enzyme or lypase enzyme powder.
3. technology according to claim 1 is characterized in that, said lypase is for deriving from yeast, mould, the lypase of bacterium or other mikrobe.
4. according to claim 1 or 3 described technologies, it is characterized in that said lypase is for deriving from Candida antarctica, Rhizomucor miehei, the lypase of Thermomyces lanuginosus or Aspergillus oryzae.
5. technology according to claim 1 is characterized in that, the addition manner of short chain alcohol is taked the mode that repeatedly add intermittence in batches or even flow adds.
6. technology according to claim 1 is characterized in that, said glyceride stock is a bio-oil, and bio-oil comprises Vegetable oil lipoprotein, animal oil and fat, waste edible oil, oil and fat refining tankage or microbial oil.
7. technology according to claim 6 is characterized in that, said Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, VT 18, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, curcas oil, shinyleaf yellowhorn oil or Jatropha curcas oil; Said animal oil and fat is fish oil or lard.
8. technology according to claim 6 is characterized in that, said microbial oil is yeast grease or microalgae grease.
9. technology according to claim 1 is characterized in that, R is the alkyl with 1-5 carbon atom in the said short chain alcohol roh.
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| CN1111285A (en) * | 1993-09-17 | 1995-11-08 | 日清制油株式会社 | Transesterification method with powdery lipase |
| CN1518600A (en) * | 2001-06-21 | 2004-08-04 | T+T�ͻ�ѧ�����ɷ�����˾ | Method and device for obtaining fatty acid esters form native oils and fats by means of enzymatic separation thereof |
| CN101250424A (en) * | 2008-03-31 | 2008-08-27 | 清华大学 | Enzyme method technique for improving bio-diesel yield by adding short-chain alcohol in organic medium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1111285A (en) * | 1993-09-17 | 1995-11-08 | 日清制油株式会社 | Transesterification method with powdery lipase |
| CN1518600A (en) * | 2001-06-21 | 2004-08-04 | T+T�ͻ�ѧ�����ɷ�����˾ | Method and device for obtaining fatty acid esters form native oils and fats by means of enzymatic separation thereof |
| CN101250424A (en) * | 2008-03-31 | 2008-08-27 | 清华大学 | Enzyme method technique for improving bio-diesel yield by adding short-chain alcohol in organic medium |
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