CN1888020A - Process of producing biological diesel oil through catalysis of fatty acid and acid-containing grease with microbe cell - Google Patents

Process of producing biological diesel oil through catalysis of fatty acid and acid-containing grease with microbe cell Download PDF

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CN1888020A
CN1888020A CNA2006100897671A CN200610089767A CN1888020A CN 1888020 A CN1888020 A CN 1888020A CN A2006100897671 A CNA2006100897671 A CN A2006100897671A CN 200610089767 A CN200610089767 A CN 200610089767A CN 1888020 A CN1888020 A CN 1888020A
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oil
acid
grease
cell
reaction
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CN100347271C (en
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杜伟
刘德华
里伟
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Tsinghua University
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    • YGENERAL 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
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The microbe cell catalyzed process of converting fatty acid and acid-containing grease into biological diesel oil belongs to the field of biological grease synthesizing technology. The reaction is performed inside in a no-solvent system or an organic solvent system, and 3A type molecular sieve in the amount of 5-10 times water produced in the reaction is added into the reaction system to absorb water selectively for the balance to be shifted toward the product direction so as to raise the catalysis efficiency and to raise the yield of biological diesel oil.

Description

Microorganism cells catalysis lipid acid and acid-containing oil production method of bio-diesel oil
Technical field
The invention belongs to the synthetic field of bio-oil, particularly proposed a kind of microorganism cells catalysis lipid acid and contained acid (lipid acid) grease production method of bio-diesel oil.When utilizing the whole-cell catalytic preparing biodiesel from lipid, in reaction system, add certain water-retaining agent, the novel process that bio-diesel yield significantly improves.
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.Thereby the research of biofuel and use to be subjected to widely and pay close attention to.
The production method of biofuel mainly contains chemical method, biological enzyme and supercutical fluid method at present, wherein because free fatty acids and less water that the biological enzyme biodiesel synthesis has in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as enzymatic reaction, the developing direction that meets Green Chemistry, thereby be subject to people's attention day by day.
The obstruction biological enzyme prepares the cost of the principal element catalyzer enzyme of biofuel industrialization and compares higher with employed acid of chemical method or alkali.Adopt the microbe whole-cell that produces intracellular lipase to replace traditional fixed lipase catalyzed grease transesterification reaction to prepare biofuel, save the steps such as separation, purifying and immobilization in the immobilized lipase production process, be expected to reduce significantly the production cost of process for preparing biodiesel by enzyme.
Another principal element of decision production of biodiesel cost is the glyceride stock cost.Discussion is that the feedstock production biofuel more and more is subjected to people's attention with cheap grease.Often contain some lipid acid in the cheap glyceride stock.Lipid acid and short chain alcohol (using methyl alcohol) reaction can prepare biofuel equally, but the water byproduct that generates in the reaction process can influence the yield of biofuel, causes final grease transformation efficiency lower, and bio-diesel yield is low.So how to remove the water that generates in the reaction process timely and effectively and be the key that improves bio-diesel yield when being raw material with the acid-containing oil.
There is the scholar to propose in reaction system, to add silica gel, still because the micropore of silica gel is far longer than the molecular diameter of reactant methanol, so in suction, inevitably adsorb a certain amount of methyl alcohol to remove the water that dereaction produces.If the increase methanol usage not only increases cost, aggravated toxicity again to lipase.The present invention proposes utilizing full cell to transform as catalyzer in the process of lipid acid or preparing biodiesel by acid-containing greasy, and the adding micropore is littler than methyl alcohol diameter
Figure A20061008976700041
Molecular sieve is as water-retaining agent, and optionally the water in the absorption system does not adsorb methyl alcohol, has improved the yield of catalytic efficiency and biofuel greatly.
Summary of the invention
The object of the present invention is to provide a kind of microorganism cells catalysis lipid acid and contain acid (lipid acid) grease production method of bio-diesel oil, improved the yield of catalytic efficiency and biofuel.
The present invention carries out in the preparation process of biofuel utilizing full cell to transform lipid acid or acid-containing oil and short chain alcohol (methyl alcohol, ethanol etc.) as catalyzer, this reaction can be carried out in solvent-free system, also can in organic solvent system, carry out, be reflected at 35-50 ℃ and carry out, in reaction system, add 5-10 doubly
Figure A20061008976700042
Molecular sieve water-retaining agent (based on the water yield that produces), optionally the water in the absorption system does not adsorb methyl alcohol.
Described microbe whole-cell comprises bacterium, yeast and the fungal cell that produces intracellular lipase, and what these cells can be for free form also can be the immobilization form.Comprise R.oryzae IFO4697 free cell and be immobilized in immobilized cell on the polyurethane foam carrier, and through the crosslinked immobilized cell of linking agent (as glutaraldehyde etc.).
Described grease is a bio-oil, comprises free fatty acids, and the various Vegetable oil lipoprotein, animal grease, microbial oil, waste edible oil, the oil refining pin material that contain free fatty acids.
Described Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, tung oil, Chinese vegetable tallow.
Described animal grease is fish oil, lard.
Described microbial oil comprises yeast grease, bacterium grease, algae grease.
The carbonatoms of described free fatty acids is 12-22.
Described short chain alcohol is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol.
Described water-retaining agent is
Figure A20061008976700043
Molecular sieve.
Reaction system can be solvent-free system; Also can be organic solvent system, particularly including the t-butanol solvent system.
The invention has the advantages that: with do not add
Figure A20061008976700044
Molecular sieve is compared, and in the process of microbe whole-cell catalysis free fatty acids and acid-containing oil production biofuel, bio-diesel yield improves more than 10% in the identical time, has improved production efficiency greatly.
Embodiment
Embodiment 1
With mol ratio is 1.5: 1 methyl alcohol and oleic acid (oleic acid 5g), 3.2g
Figure A20061008976700051
Molecular sieve, 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, be about 88% through 24 hours artifact diesel oil yield, compare with contrast (do not add molecular sieve, other condition is identical), yield improves 12%.
Embodiment 2
With mol ratio be 1.5: 1 ethanol and oleic acid (oleic acid 5g), based on the trimethyl carbinol and the 6.4g of grease volume 100%
Figure A20061008976700052
Molecular sieve, 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, the adding dry weight is that the immobilization R.oryzae IFO4697 cell of oil quality 6% begins reaction, be about 90% through 24 hours artifact diesel oil yield, compare with contrast (do not add molecular sieve, other condition is identical), yield improves 14%.
Embodiment 3
With mol ratio be 4: 1 methyl alcohol and the waste oil (5g) that contains 20% (m/m) free fatty acids, based on the trimethyl carbinol and the 3.2g of grease volume 150%
Figure A20061008976700053
Molecular sieve, 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 of oil quality 5% begins reaction, through 24 hours artifact diesel oil yield was 87%, compare with contrast (do not add molecular sieve, other condition is identical), yield improves 10%.According to the foregoing description, when the microbe whole-cell catalysis free fatty acids of utilization product intracellular lipase or acid-containing oil raw material and short chain alcohol are carried out the transesterification reaction biodiesel synthesis, add an amount of
Figure A20061008976700054
Molecular sieve is removed the water that produces in the reaction process, can significantly improve bio-diesel yield.

Claims (6)

1. microorganism cells catalysis lipid acid and acid-containing oil production method of bio-diesel oil, it is characterized in that: carry out in the preparation process of biofuel utilizing full cell to transform lipid acid or acid-containing oil and short chain alcohol as catalyzer, this be reflected at carry out in the solvent-free system or organic solvent system in carry out, in reaction system, add based on the water yield 5-10 that produces in the reaction process times of 3A molecular sieve water-retaining agent, the water that generates in the absorption system optionally, balance is moved to the product direction, improved the yield of catalytic efficiency and biofuel.
2, in accordance with the method for claim 1, it is characterized in that: described microbe whole-cell comprises bacterium, yeast and the fungal cell that produces intracellular lipase, and these cells are free form or immobilization form; Comprise R.oryzae IFO 4697 free cells or be immobilized in immobilized cell on the polyurethane foam carrier, through linking agent glutaraldehyde cross-linking immobilized cell.
3, in accordance with the method for claim 1, it is characterized in that: described solvent-free system comprises the system of not adding any other reaction medium; Organic solvent system comprises the t-butanol solvent system.
4, in accordance with the method for claim 1, it is characterized in that: described acid-containing oil is a bio-oil, comprises free fatty acids, contains Vegetable oil lipoprotein, animal grease, microbial oil, the waste edible oil of free fatty acids or the pin material of refining oil; Described Vegetable oil lipoprotein is Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis, Rice pollard oil, tung oil or Chinese vegetable tallow; Described animal grease is fish oil or lard; Described microbial oil comprises yeast grease, bacterium grease or algae grease.
5, in accordance with the method for claim 4, it is characterized in that: the carbonatoms of described free fatty acids is 12-22.
6: described short chain alcohol is methyl alcohol, ethanol, propyl alcohol, butanols or amylalcohol
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012059065A1 (en) * 2010-11-04 2012-05-10 清华大学 Process for preparing biodiesel from renewable grease with lipase as catalyst and online dehydration
CN103695484A (en) * 2013-12-23 2014-04-02 山西华顿实业有限公司 Method of synthesizing biodiesel by applying lipase catalysis
CN103789364A (en) * 2013-11-19 2014-05-14 南宁市新科健生物技术有限责任公司 Method for preparing biodiesel from pichia pastoris whole-cell lipase catalysis
CN105985867A (en) * 2015-02-05 2016-10-05 昆明红火科技有限公司 Method for preparing biological fuel oil from microbial catalytic oil and fat
CN103789364B (en) * 2013-11-19 2016-11-30 南宁市新科健生物技术有限责任公司 The method of Pichia sp. Whole-cell lipase catalysis for preparing biodiesel oil
CN108384729A (en) * 2018-01-15 2018-08-10 浙江工业大学 A kind of microbial cell crystalline substance glue and its preparation method and application
CN110129400A (en) * 2019-05-25 2019-08-16 华南理工大学 A method of improving microbial oil odd numbered carbon chain fat acids content

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CN105694992A (en) * 2014-11-24 2016-06-22 曹小恭 Bionic light crude oil, and preparation method thereof

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
CN1453332A (en) * 2003-04-24 2003-11-05 华南理工大学 Biologically catalystic process of converting fat into ester to produce biological diesel oil
CN1276962C (en) * 2004-12-23 2006-09-27 大连理工大学 Process for coupling producing bioloigical diesel oil and 1,3-propylene glycol

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012059065A1 (en) * 2010-11-04 2012-05-10 清华大学 Process for preparing biodiesel from renewable grease with lipase as catalyst and online dehydration
US9249437B2 (en) 2010-11-04 2016-02-02 Tsinghua University Process for preparing biodiesel from renewable oil and fat catalyzed by lipase with online dehydration
CN103789364A (en) * 2013-11-19 2014-05-14 南宁市新科健生物技术有限责任公司 Method for preparing biodiesel from pichia pastoris whole-cell lipase catalysis
CN103789364B (en) * 2013-11-19 2016-11-30 南宁市新科健生物技术有限责任公司 The method of Pichia sp. Whole-cell lipase catalysis for preparing biodiesel oil
CN103695484A (en) * 2013-12-23 2014-04-02 山西华顿实业有限公司 Method of synthesizing biodiesel by applying lipase catalysis
CN105985867A (en) * 2015-02-05 2016-10-05 昆明红火科技有限公司 Method for preparing biological fuel oil from microbial catalytic oil and fat
CN108384729A (en) * 2018-01-15 2018-08-10 浙江工业大学 A kind of microbial cell crystalline substance glue and its preparation method and application
CN110129400A (en) * 2019-05-25 2019-08-16 华南理工大学 A method of improving microbial oil odd numbered carbon chain fat acids content
CN110129400B (en) * 2019-05-25 2023-09-01 华南理工大学 Method for improving odd-carbon chain fatty acid content of microbial oil

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