CN100404643C - Process for transferring grease for producing biodiesel oil using microorganism cell conversion in organic medium reaction system - Google Patents
Process for transferring grease for producing biodiesel oil using microorganism cell conversion in organic medium reaction system Download PDFInfo
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- CN100404643C CN100404643C CNB2006100896448A CN200610089644A CN100404643C CN 100404643 C CN100404643 C CN 100404643C CN B2006100896448 A CNB2006100896448 A CN B2006100896448A CN 200610089644 A CN200610089644 A CN 200610089644A CN 100404643 C CN100404643 C CN 100404643C
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 45
- 239000004519 grease Substances 0.000 title claims abstract description 44
- 244000005700 microbiome Species 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000003225 biodiesel Substances 0.000 title claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 235000021588 free fatty acids Nutrition 0.000 claims abstract description 20
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011187 glycerol Nutrition 0.000 claims abstract description 13
- 239000004367 Lipase Substances 0.000 claims abstract description 10
- 102000004882 Lipase Human genes 0.000 claims abstract description 10
- 108090001060 Lipase Proteins 0.000 claims abstract description 10
- 235000019421 lipase Nutrition 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000002551 biofuel Substances 0.000 claims description 22
- 239000003921 oil Substances 0.000 claims description 22
- 235000019198 oils Nutrition 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 240000005384 Rhizopus oryzae Species 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000012075 bio-oil Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000008157 edible vegetable oil Substances 0.000 claims description 4
- 230000003834 intracellular effect Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 31
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 210000000582 semen Anatomy 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 102000004895 Lipoproteins Human genes 0.000 description 2
- 108090001030 Lipoproteins Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 210000001822 immobilized cell Anatomy 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- 241000269319 Squalius cephalus Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 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
- 235000021323 fish oil Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002383 tung oil Substances 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
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to a process for converting grease for producing biologic diesel oil by using microorganism cell conversion in an organic medium reaction system, which belongs to the synthesizing field of biologic grease. The process uses short chain alcohol ROH as a reacting acyl receptor and uses a kind of tert-butyl alcohol of a relatively hydrophilic organic solvent, which does not have a negative effect on the reactivity of a microorganism whole cell, the microorganism whole cell of lipase in a producing cell is used to catalyze the grease raw material to carry out transesterification reaction, and thus, the biologic diesel oil is synthesized. The short chain alcohol, the grease and the microorganism whole cell of the lipase in the producing cell are placed in a bioreactor and are uniformly mixed, the grease or a raw material of free fatty acid are converted to generate the biologic diesel oil and by-product glycerin by heating to 20DEG. C to 60DEG. C after reacting for 5 to 48 hours, and the yield of the biologic diesel oil can reach 80 percent. The present invention has the advantages that the accumulating situation of the glycerol in the microorganism cell can be effectively improved; the reactivity can be obviously raised; the reaction time is shortened; the service life of the microorganism cell is prolonged.
Description
Technical field
The invention belongs to the synthetic field of bio-oil, the technology of transferring grease for producing biodiesel oil using microorganism cell conversion in a kind of organic medium reaction system particularly is provided.Utilize organic solvent to transform grease (or free fatty acids) production biofuel as microbe whole-cell in a kind of organic medium reaction system of catalyzer as reaction medium, microorganism cells.
Background technology
One of prospect of oil prodution industry-biofuel is by the long chain fatty acid ester class material of bio-oil raw material by the transesterification reaction generation, is a kind of novel non-pollution of renewable energy.The combustionproperty of biofuel can be that diesel oil matches in excellence or beauty with traditional oil.Simultaneously, it is that diesel oil compares that to have a raw material renewable with traditional oil, environmental friendliness, flash-point height, cetane value advantages of higher.Research of biofuel at present 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) to carry out transesterification reaction under alkali or an acidic catalyst effect, 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 easily causes the formation of emulsion to make the subsequent processes complexity; 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 are subject to people's attention day by day.
The cost that main weak point of biological enzyme is the catalyzer enzyme is compared higher with employed acid of chemical method or alkali.This also is to hinder biological enzyme to prepare the principal element of biofuel industrialization.Adopt the microbe whole-cell that produces intracellular lipase to replace traditional fixed lipase catalyzed grease transesterification reaction of commercialization to prepare biofuel, the steps such as separation, purifying and immobilization in traditional immobilized lipase production process have been saved, and the cost of these steps accounts for more than 70% of immobilized lipase total production cost usually, therefore adopts the microbe whole-cell that produces intracellular lipase to be considered to be expected to reduce significantly a developing direction of biological enzyme cost.At [Kazuhiro Ban et al.Repeated use of whole-cell biocatalysts immobilized within biomass supportparticles for biodiesel fuel production, Journal of Molecular Catalysis B:Enzymatic, 2002,17:157-165] to report in the document: the solvability of methyl alcohol in glyceride stock is relatively poor, is unfavorable for the carrying out that reacts; The existence of excessive methanol can cause the serious inactivation of full cell, so in the technological process of utilizing full cell as the Catalyst Production biofuel, adopt to add the mode of short chain alcohol to alleviate the toxic action of its pair cell in batches.This mode complex operation, the reaction times is longer; In addition, we find under study for action, with the acyl acceptor of short chain alcohol as reaction, have by-product glycerin to produce in the reaction process, and the glycerine of generation in full cell interior accumulation, has a strong impact on the diffusion of substrate in born of the same parents, thereby influences the reactive behavior of cell easily.For improving above situation, we adopt organic solvent reaction system biodiesel synthesis.
Summary of the invention
The object of the present invention is to provide the technology of transferring grease for producing biodiesel oil using microorganism cell conversion in a kind of organic medium reaction system.These organic medium reaction systems can promote the dissolvings of short chain alcohol in grease such as methyl alcohol, and can promote the diffusion of by-product glycerin, effectively improve the accumulation situation of glycerine in microorganism cells, thereby can significantly improve reactive behavior, shorten the reaction times and prolong work-ing life of microorganism cells, bio-diesel yield is reached more than 80%.
The present invention is as the reaction acyl acceptor with the short chain alcohol roh; as reaction medium, utilize microbe whole-cell catalysis grease (or free fatty acids) raw material that produces intracellular lipase to carry out the transesterification reaction biodiesel synthesis with the hydrophilic relatively phosphoric acid buffer that the microbe whole-cell reactive behavior is not had negative impact and the organic solvent trimethyl carbinol.Its technology is:
With short chain alcohol and grease mol ratio be 3: 1～6: 1 short chain alcohol and grease (or short chain alcohol and free fatty acids rub mol ratio be 1: 1～2: 1 short chain alcohol and free fatty acids), based on the organic solvent of grease (or free fatty acids) volume 20-300% with account for the microorganism cells of grease (or free fatty acids) quality 2～30%, pack into and mix in the reactor, be heated to 20 ℃～60 ℃, react after 5-48 hour, grease (or free fatty acids) raw material can transform and generate biofuel and by-product glycerin (with the free fatty acids for raw material time do not have glycerine generate).
Microbe whole-cell of the present invention is to can be used for the whole-cell catalyst that the catalyzed oil lipidol is separated the prepared in reaction biofuel, can be free cell, also can be immobilized cell.Comprise R.oryzae IFO4697 free cell or immobilized cell.
Grease of the present invention is that bio-oil comprises Vegetable oil lipoprotein, animal grease, microbial oil, waste edible oil, oil refining pin material and free fatty acids.
Vegetable oil lipoprotein of the present invention is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, tung oil, Chinese vegetable tallow.
Animal grease of the present invention is fish oil, lard.
Microbial oil of the present invention comprises yeast grease, bacterium grease, algae grease.
R is the alkyl with 11-21 carbon atom among the free fatty acids RCOOH of the present invention.
R is the alkyl with 1-5 carbon atom in the short chain alcohol roh of the present invention.
Short chain alcohol of the present invention is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
The invention has the beneficial effects as follows the reactive behavior that has improved the yielding lipase microorganism cells, the work-ing life that has prolonged microorganism cells, shortened the reaction times.Can promote the dissolvings of short chain alcohol in grease such as methyl alcohol with the trimethyl carbinol as novel organic medium reaction system, effectively reduce the negative impact of short chain alcohol the microorganism cells reactive behavior; Secondly, in this organic medium reaction system, can disposable adding react required low-carbon alcohol, thereby can significantly shorten the reaction times; In addition, hydrophilic relatively organic solvent can be partly dissolved glycerine, can effectively reduce reactant low-carbon alcohol and by-product glycerin to the negative impact of microorganism cells reactive behavior, significantly improve the microorganism cells reactive behavior, effectively improve the accumulation situation of glycerine in microorganism cells, improve the reactive behavior of microorganism cells and prolong its work-ing life.
Embodiment
Embodiment 1
With mol ratio is 4: 1 methyl alcohol and soybean oil (soybean oil 5g), 0.15g phosphoric acid buffer and based on the trimethyl carbinol of grease volume 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 35 ℃ after, the adding dry weight is that the immobilization R.oryzae IFO4697 cell of oil quality 6% begins reaction, produced biofuel 4.15g after 24 hours, bio-diesel yield is about 83%.
Embodiment 2
With mol ratio is 3: 1 methyl alcohol and rapeseed oil (rapeseed oil 5g), 0.25g phosphoric acid buffer and based on the trimethyl carbinol of grease volume 100%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 30 ℃ after, the adding dry weight is that the free R.oryzae IFO4697 cell of oil quality 5% begins reaction, produced biofuel 4.0g after 24 hours, bio-diesel yield is 80%.
Embodiment 3
With mol ratio is 5: 1 ethanol and Oleum Gossypii semen (Oleum Gossypii semen 5g), 0.50g phosphoric acid buffer and based on the trimethyl carbinol of grease volume 200%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 45 ℃ after, the adding dry weight is that the immobilization R.oryzae IFO4697 cell of oil quality 8% begins reaction, produced biofuel 4.3g after 12 hours, bio-diesel yield is 86%.
Embodiment 4
With mol ratio be 3: 1 butanols and waste edible oil (waste edible oil 5g), based on the trimethyl carbinol of grease volume 80%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, the adding dry weight is that the free R.oryzae IFO4697 cell of oil quality 15% begins reaction, produced biofuel 4.05g after 8 hours, bio-diesel yield is 81%.
Embodiment 5
With mol ratio is 4: 1 methyl alcohol and lard (lard 5g), 0.05g phosphoric acid buffer and based on the trimethyl carbinol of grease volume 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, what add dry weight and be oil quality 15% begins reaction through the immobilization R.oryzae of glutaraldehyde cross-linking IFO4697 cell, produced biofuel 4.1g after 8 hours, bio-diesel yield is 82%.
Embodiment 6
With mol ratio be 1.5: 1 methyl alcohol and oleic acid (oleic acid 5g), based on the trimethyl carbinol of grease volume 120%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, the adding dry weight is that the immobilization R.oryzae IFO4697 cell of oil quality 8% begins reaction, produced biofuel 4.3g after 12 hours, bio-diesel yield is 86%.
Embodiment 7
With mol ratio is 4: 1 amylalcohol and rapeseed oil (rapeseed oil 5g), 1.0g phosphoric acid buffer and based on the trimethyl carbinol of grease volume 200%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 35 ℃ after, the adding dry weight is that the free R.oryzae IFO4697 cell through glutaraldehyde cross-linking of oil quality 20% begins reaction, produced biofuel 4.5g after 12 hours, bio-diesel yield is 90%.
Embodiment 8
With mol ratio be 1: 1 ethanol and oleic acid (oleic acid 5g), based on the trimethyl carbinol of grease volume 150%, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, the adding dry weight is that the immobilization R.oryzae IFO4697 cell of oil quality 5% begins reaction, produced biofuel 4.3g after 24 hours, bio-diesel yield is 86%.
Embodiment 9:
Reacted microorganism cells among the embodiment 1 directly leached be used for next batch reaction, other reaction conditionss are with embodiment 1, so with microorganism continuous reuse 10 times.In the 10th reaction batch, react and can produce biofuel 8.1g in 24 hours, bio-diesel yield is still up to 82%.
According to the foregoing description; with the trimethyl carbinol as organic medium reaction system; during short chain alcohol roh (R is the alkyl with 1-5 carbonatoms) conduct reaction acyl acceptor; the R.oryzae IFO4697 free cell that adds oil quality 2%～30% under suitable temperature range, different bio-oil raw materials are generated biofuel by efficient the conversion.The reaction mol ratio of short chain alcohol and grease optimum is that (the reaction mol ratio of short chain alcohol and free fatty acids optimum was 1: 1～2: 1 in 3: 1～5: 1, optimum organic solvent addition is the 100%-200% based on the grease volume, and optimum temperature of reaction is 30 ℃～50 ℃.
Claims (4)
1. the microbe whole-cell that produces intracellular lipase in the organic medium reaction system transforms the grease production biodiesel processes, with the short chain alcohol roh as the reaction acyl acceptor, as reaction medium, utilize R.oryzae IFO4697 free cell catalysis grease or free-fat acid starting material to carry out the transesterification reaction biodiesel synthesis with the hydrophilic relatively phosphoric acid buffer that the microbe whole-cell reactive behavior is not had negative impact and the organic solvent trimethyl carbinol; Its technology is: with short chain alcohol and grease mol ratio is that 3: 1～6: 1 reaction substrate or short chain alcohol and free fatty acids mol ratio are 1: 1～2: 1 reaction substrate, organic solvent and the microorganism cells that accounts for grease or free fatty acids quality 2～30% based on grease or lipid acid volume 20-300%, pack into and mix in the biochemical reactor, be heated to 20 ℃～60 ℃, react after 5-48 hour, grease or free fatty acids feedstock conversion generate biofuel and by-product glycerin; Do not generate when there is glycerine during for raw material with the free fatty acids.
2. technology according to claim 1 is characterized in that: be heated to 30 ℃～50 ℃ in the biochemical reactor; Short chain alcohol and grease mol ratio are 3: 1～5: 1; The reaction mol ratio of short chain alcohol and free fatty acids is 1: 1～2: 1.
3. technology according to claim 1 and 2 is characterized in that: described short chain alcohol is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
4. technology according to claim 1 and 2 is characterized in that: described grease is a bio-oil, comprises rapeseed oil, soybean oil, oleum gossypii seminis, lard, waste edible oil, oil refining pin material or contains the free fatty acids of 12-22 carbon atom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100896448A CN100404643C (en) | 2006-07-07 | 2006-07-07 | Process for transferring grease for producing biodiesel oil using microorganism cell conversion in organic medium reaction system |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100896448A CN100404643C (en) | 2006-07-07 | 2006-07-07 | Process for transferring grease for producing biodiesel oil using microorganism cell conversion in organic medium reaction system |
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| CN1884440A CN1884440A (en) | 2006-12-27 |
| CN100404643C true CN100404643C (en) | 2008-07-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074389A (en) * | 2013-02-04 | 2013-05-01 | 东莞市合能微生物能源有限公司 | Method for preparing biodiesel by using biological enzyme |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102864164B (en) * | 2011-07-04 | 2014-04-09 | 深圳市绿微康生物工程有限公司 | Expansion of application of penicillium lipase in biodiesel preparation |
| EP2751237A4 (en) * | 2011-09-30 | 2016-08-17 | Univ Singapore | Method of converting grease containing high content of free fatty acids to fatty acid esters and catalysts for use in said method |
| CN105462692A (en) * | 2014-08-20 | 2016-04-06 | 丰益(上海)生物技术研发中心有限公司 | Biodiesel preparation method |
Citations (2)
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|---|---|---|---|---|
| CN1557913A (en) * | 2004-01-16 | 2004-12-29 | �廪��ѧ | Novel process for preparing biological diesel oil from grease catalyzed by lipase in the reaction system with organic substrate as medium |
| CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557913A (en) * | 2004-01-16 | 2004-12-29 | �廪��ѧ | Novel process for preparing biological diesel oil from grease catalyzed by lipase in the reaction system with organic substrate as medium |
| CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074389A (en) * | 2013-02-04 | 2013-05-01 | 东莞市合能微生物能源有限公司 | Method for preparing biodiesel by using biological enzyme |
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| CN1884440A (en) | 2006-12-27 |
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