CN101284999A - Process for preparing biodiesel by enzyme method - Google Patents
Process for preparing biodiesel by enzyme method Download PDFInfo
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- CN101284999A CN101284999A CNA2008100477848A CN200810047784A CN101284999A CN 101284999 A CN101284999 A CN 101284999A CN A2008100477848 A CNA2008100477848 A CN A2008100477848A CN 200810047784 A CN200810047784 A CN 200810047784A CN 101284999 A CN101284999 A CN 101284999A
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- biodiesel
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- 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
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- 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
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Abstract
The invention provides a method for making biodiesel through enzymatic method, comprising the following concrete steps of utilizing woody plant oil and oil processing waste as raw oil, adding the raw oil and low-carbon alcohol into a reaction vessel, adding in immobilized G63 lipase as catalyst carry out transesterification, separating oil phase out from the reaction vessel, reducing pressure, distilling and recovering the low-carbon alcohol, and then biodiesel can be obtained. Compared with the prior art, the method improves the unsaturated fatty acid content in biodiesel, so as to improve the yield of dimeric ester, prolong biodiesel industry chain as well as product attributes and reduce the production cost of biodiesel greatly.
Description
Technical field
The invention belongs to preparation of biofuel enzyme process and high-valued technical field thereof.Be specifically related to utilize the waste grease of generations such as woody oleiferous plants and animal-plant oil tankage, rotten animal-plant oil and catering trade, food-processing industry to prepare biofuel for material, enzyme method, and by unsaturated fatty acid ester polycondensation dimer synthon in the biofuel, synthetic then MES, polymeric amide and urethane make the value-added method of biofuel industry.
Background technology
Animal-plant oil and short chain alcohol are under the effect of catalyzer, and the alkyl esters compound that generates by esterification and transesterification reaction is called biofuel.Biofuel is sulfur-bearing and aromatic hydrocarbons not, the cetane value height, and lubricity is good, is a kind of high-quality clean diesel.The existing patent documentation of retrieval, Patent Office of China national Department of Intellectual Property discloses a large amount of relevant with it patents of invention, drape over one's shoulders and shown that the technical scheme of utilizing producing biologic diesel oil through obsolete animal and vegetable oils in high acid value, catalyst system therefor are an acidic catalyst (as the vitriol oil, Phenylsulfonic acid) or caustic soda strong alkali catalyst.As applying date 2005.8.19; the patent document of patent No. ZL200510036639.6 " biocatalyzing ester exchange reaction of high acid value lipid production method of bio-diesel oil " has been announced with short-chain aliphatic ester as acyl acceptor; the employing alkaline matter is an additive, utilizes the technical scheme of lipase-catalyzed producing biodiesel from high acid number grease.The non-patent literature report that with the waste grease is the feedstock production biofuel is a lot, has inquired into high acid value grease esterification technology as neat Yutang, proposes high acid value oil and can adopt H respectively
2SO
4, NaOH does the esterification of catalyzer substep, emulsion serious (neat Yutang, the research of high acid value oil esterification technology, grain and oil processing and food machinery, 2004 (10): 44-45) are found in experiment.People such as Liu Zhanpeng have then proposed the first step ferric sulfate, second step was made catalyzer with sodium hydroxide, and two-step approach catalysis hogwash fat prepares method of bio-diesel oil (Liu Zhanpeng, the research that two-step approach catalysis hogwash fat prepares biofuel, Chinese oil, 2006 (5): 59-61).People such as Ma Chuanguo have studied sulphuric acid catalysis Oleum Gossypii semen soap stock and have prepared method of bio-diesel oil, having proposed optimum process condition is 60 ℃ of temperature of reaction, reaction times 60min, the ratio of methyl alcohol and lipid acid is 1: 1 (V/W) (Ma Chuanguo, Preparation of biodiesel with soapstock, Chinese oil, 2006 (4): 59-61).People such as Chen Zhifeng have inquired into immobilized lipase Novozym 435 catalysis catering trade peracid waste oil and methyl acetate transesterify production biofuel in the solvent-free system, point out to add organic bases Tutofusin tris or triethylamine and can make the operational stability of enzyme and the catalytic activity (Chen Zhifeng etc. that increase, fixed lipase catalyzed peracid waste oil transesterify production biofuel, the catalysis journal, 2006 (2): 146-150).
With inedible oil fat such as woody oleiferous plants is that the feedstock production biofuel is one of effective way of biofuel industry development, and partial monopoly and non-patent literature carried out similar report.Patent documents such as patent No. ZL200410034487.1, application number 200710017934.6, application number 200510082921.8 disclose and have utilized barbadosnut seed oil, acer truncatum seed oil and tallowseed oil to wait to prepare the biofuel patent, and the described catalyzer of above-mentioned patent is acid or alkalization chemical catalyst.Yang Ying has studied barbadosnut seed oil acid system catalysis for preparing biodiesel oil technology (Yang Ying, the research of Cortex jatrophae oil preparation biodiesel oil solid acid catalyst, Sichuan University's master thesis, 2007).Chen Shuanhu etc. have inquired into acid estersization-alkali alcoholysis two-step approach catalysis Fructus Zanthoxyli oil and have prepared biodiesel processes, drawn optimal processing parameter (Chen Shuanhu etc., by the optimum process condition research that Fructus Zanthoxyli oil prepares biofuel, grain and oil processing, 2008,1:61-63).Chen Wenwei has studied tallowseed oil and has prepared biofuel, primary study employing nano-magnetic solid catalyst and immobile surfactant-coated enzymatic two kinds of preparation method (Chen Wenwei, the research of Biodiesel Production from Chinese Tallow Kernel Oil, University Of Nanchang's doctorate paper, 2006-5).
In addition, comprehensive utilization biological diesel oil byproduct glycerin and prepare Chemicals in the middle of the dimer ester etc. according to the characteristic that biofuel contains unsaturated fatty acid ester, making the biofuel increment, reduce the production of biodiesel cost, also is another effective way of development biofuel industry.As the patent No. is preparation and the dimeric method of unsaturated fatty acids methyl esters polycondensation thereof that the patent document of ZL200410014887.6 discloses the tung oil biofuel, and the biodiesel manufacture catalyzer is the NaOH basic catalyst in the described patent.The patent document of patent No. ZL200410100479.2 discloses fatty process for preparing biodiesel by enzyme and microbial fermentation produces 1, the coupling technology of ammediol.
In a word, from existing biofuel patent and non-patent literature, we are not difficult to find that present biofuel still exists many technical barriers, be mainly reflected in: 1, use base catalysis method production biofuel, owing to there is soap stock to generate in the reaction, form flocks, make the biofuel product not easily separated; The soap stock that generates in the reaction process, glycerine easily and emulsifications such as biofuel, methyl alcohol cause the biofuel yield low; Easy waste discharge forms " secondary pollution " in the reaction; 2, use the vitriol oil to make catalyzer, although have advantages such as catalytic efficiency is higher, the reaction times is short, but same the existence easily discharged sulfuric acid wastewater containing in the reaction, form " secondary pollution ", esterification products is difficult to separate, catalyzer can not be repeated to utilize, thereby causes the more high technical barrier of production cost; 3, use biological enzyme to make catalyzer, though have the reaction conditions gentleness, enzyme catalyst can reuse, do not produce advantages such as waste water, but exist catalytic efficiency in the reaction not as soda acid two class catalyzer, and cause " the glycerine poisoning " of enzyme in the reaction easily, influence the catalytic activity of enzyme, enzyme is short work-ing life, does not have the technological deficiencies such as lipase special-purpose catalyst of independent intellectual property right in addition; 4, the soda acid chemical catalysis prepares in the biofuel process, and the unsaturated fatty acids destructiveness is big in the acid base pair biofuel, and the unsaturated fatty acid ester yield is low, and dimer ester output is not high when causing the unsaturated fatty acid ester polymerization.
Summary of the invention
Purpose of the present invention is providing a kind of method of process for preparing biodiesel by enzyme, improves the content of unsaturated fatty acids in the biofuel, has prolonged biofuel industrial chain and product attribute, and has reduced the production of biodiesel cost greatly.
A kind of method of process for preparing biodiesel by enzyme utilizes xylophyta oil plant and grease processing waste to be stock oil, and preparation process is as follows:
(1) stock oil and low-carbon alcohol are added in the reactor, add immobilization G63 lipase again and carry out transesterification reaction as catalyzer;
(2) isolate oil phase in reactor, low-carbon alcohol is reclaimed in underpressure distillation, promptly gets biofuel.
The transesterification reaction temperature of described step (1) is 30～70 ℃, and the reaction times is 10～40h, and catalyst levels is 3～20% of a stock oil quality, and oil/pure mol ratio is 1: 3～1: 14.Described immobilization G63 lipase obtains after G63 lipase is handled through immobilization, adopts the carrier of polystyrene macroporous resin as immobilized lipase in the solidification process.
As a further improvement on the present invention, after making biofuel, its unsaturated fatty acid ester that contains is carried out polycondensation, generate the fatty acid ester dimer.
Catalyzer in the described polycondensation is an organic catalyst, and temperature of reaction is 220～360 ℃, and the reaction times is 2～12h, and catalyst consumption is 4～15% of a unsaturated fatty acid ester quality.Described organic catalyst is pure aluminium silicate or carclazyte or Na
2SO
3Or aluminium hydroxide or silicon powder.
Compared with prior art, positively effect of the present invention is embodied in:
1, the G63 immobilized lipase of the present invention's employing, its enzymatic property is referring to relevant bibliographical information (Guo Daoyi, G63 lipase enzymatic property and homology efficiently express, Central China University of Science and Technology's master thesis, 2006).G63 lipase is that screening obtains from greasy dirt has higher catalytic activity (the methyl esters rate of rotation reaches more than 95%), high temperature suitability (the highest adaptive temperature reaches 70 ℃) and short chain alcohol tolerance (anti-50% methyl alcohol and 50% ethanol) more widely.
2, the present invention directly emits esterification products in still, realizes serialization production and immobilized enzyme is retained still; Simultaneously, enzyme immobilization technology adopts poly-third fixing of the ethene macroporous resin carrier, (up to 200 batches) more than the enzyme immobilization rate height (reaching 95%), excellent catalytic effect (methyl ester conversion rate reaches 98%), recycling batch.The esterification products underpressure distillation is gone out low-carbon alcohol, and capable of circulation the entering in the still of low-carbon alcohol utilized, and reduced production cost.
3, the unsaturated fatty acid ester degree of being damaged is low in the esterification products of the present invention preparation, thereby has improved dimer productive rate and output, has prolonged biofuel industrial chain and product attribute.
Embodiment
Embodiment 1:
Raw material: get Chinese tallow tree Chinese catalpa oil 100g
At first, stock oil is put into reactor, add 4g immobilized lipase and 20mL methyl alcohol successively, open water bath with thermostatic control trip switch and internal recycle trip switch, when temperature rises to 40 ℃, transesterification reaction is carried out in timing, and stopped reaction behind the reaction 20h is emitted esterification products 98g from the reactor leakage fluid dram, standing demix, collect light phase liquid, reclaim methyl alcohol simultaneously, methyl alcohol can enter again and treat next batch reaction use in the reactor after reclaiming.Then, esterification products is pumped in the polymerization reaction kettle, add the 5g pure aluminium silicate and carry out polycondensation, 240 ℃ of temperature of reaction controls, the reaction times is 4h, gets dimer ester 42g.At last dimer ester and diethylenetriamine are carried out the polyamides reaction, get flaxen polyamide resin 28g.
Embodiment 2:
Raw material: soybean oil tankage 100g, the acid value of measuring stock oil is a 85mgKOH/g oil.
At first, stock oil is put into reactor, add 6g immobilized lipase and 24mL methyl alcohol successively, open water bath with thermostatic control trip switch and internal recycle trip switch, when temperature rises to 60 ℃, transesterification reaction is carried out in timing, and stopped reaction behind the reaction 18h is emitted esterification products 97g from the reactor leakage fluid dram, standing demix, collect light phase liquid, reclaim methyl alcohol simultaneously, methyl alcohol can enter again and treat next batch reaction use in the reactor after reclaiming.Then, esterification products is pumped in the polymerization reaction kettle, add the 5g carclazyte and carry out polycondensation, 260 ℃ of temperature of reaction controls, the reaction times is 3h, gets dimer ester 40g.At last dimer ester and ethylene glycol are carried out aminating reaction, get flaxen poly-ammonia polyimide resin 22g.
Embodiment 3:
Raw material: tailing of rape oil 100g, the acid value of measuring stock oil is a 68mgKOH/g oil.
At first, stock oil is put into reactor, add 10g immobilized lipase and 26mL methyl alcohol successively, open water bath with thermostatic control trip switch and internal recycle trip switch, when temperature rises to 70 ℃, transesterification reaction is carried out in timing, and stopped reaction behind the reaction 20h is emitted esterification products 98g from the reactor leakage fluid dram, standing demix, collect light phase liquid, reclaim methyl alcohol simultaneously, methyl alcohol can enter again and treat next batch reaction use in the reactor after reclaiming.Then, esterification products is pumped in the polymerization reaction kettle, add the 5g carclazyte and carry out polycondensation, 360 ℃ of temperature of reaction controls, the reaction times is 10h, gets dimer ester 38g.At last dimer ester and ethylene glycol are carried out aminating reaction, get flaxen poly-ammonia polyimide resin 20g.
Claims (8)
1, a kind of method of process for preparing biodiesel by enzyme utilizes xylophyta oil plant and grease processing waste to be stock oil, and preparation process is as follows:
(1) stock oil and low-carbon alcohol are added in the reactor, add immobilization G63 lipase again and carry out transesterification reaction as catalyzer;
(2) isolate oil phase in reactor, low-carbon alcohol is reclaimed in underpressure distillation, promptly gets biofuel.
2, the method for process for preparing biodiesel by enzyme according to claim 1, it is characterized in that the transesterification reaction temperature of described step (1) is 30～70 ℃, the reaction times is 10～40h, catalyst levels is 3～20% of a stock oil quality, and oil/pure mol ratio is 1: 3～1: 14.
3, the method for process for preparing biodiesel by enzyme according to claim 2 is characterized in that, the catalyst levels of described step (1) is 4～18% of a stock oil quality, and oil/pure mol ratio is 1: 4～1: 12.
4, the method for process for preparing biodiesel by enzyme according to claim 1 and 2, it is characterized in that, described immobilization G63 lipase obtains after G63 lipase is handled through immobilization, adopts the carrier of polystyrene macroporous resin as immobilized lipase in the solidification process.
5, the method for process for preparing biodiesel by enzyme according to claim 1 and 2 is characterized in that, the unsaturated fatty acid ester in the biofuel that makes is carried out polycondensation, generates the fatty acid ester dimer.
6, the method for process for preparing biodiesel by enzyme according to claim 5, it is characterized in that the catalyzer in the described polycondensation is an organic catalyst, temperature of reaction is 220～360 ℃, reaction times is 2～12h, and catalyst levels is 4～15% of a unsaturated fatty acid ester quality.
7, the method for process for preparing biodiesel by enzyme according to claim 6 is characterized in that, the temperature of reaction in the described polycondensation is 230～350 ℃, and the reaction times is 4～10h, and catalyst consumption is 6～12% of a unsaturated fatty acid ester quality.
8, the method for process for preparing biodiesel by enzyme according to claim 6 is characterized in that, described organic catalyst is pure aluminium silicate or carclazyte or Na
2SO
3Or aluminium hydroxide or silicon powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100477848A CN101284999A (en) | 2008-05-21 | 2008-05-21 | Process for preparing biodiesel by enzyme method |
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| CNA2008100477848A CN101284999A (en) | 2008-05-21 | 2008-05-21 | Process for preparing biodiesel by enzyme method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272317A (en) * | 2008-10-31 | 2011-12-07 | 诺维信公司 | Enzymatic production of fatty acid ethyl esters |
| 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 |
| CN103781911A (en) * | 2011-08-31 | 2014-05-07 | 转换生物柴油有限公司 | Enzymatic transesterification with lipases immobilized on hydrophobic resins in water solutions |
| US10000731B2 (en) | 2010-03-01 | 2018-06-19 | Trans Bio-Diesel Ltd. | Enzymatic transesterification/esterification processes employing lipases immobilized on hydrophobic resins in the presence of water solutions |
| CN111349665A (en) * | 2020-03-11 | 2020-06-30 | 陕西科技大学 | Method for preparing biodiesel by catalyzing high-acid-value grease through enzyme method |
-
2008
- 2008-05-21 CN CNA2008100477848A patent/CN101284999A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272317A (en) * | 2008-10-31 | 2011-12-07 | 诺维信公司 | Enzymatic production of fatty acid ethyl esters |
| US10000731B2 (en) | 2010-03-01 | 2018-06-19 | Trans Bio-Diesel Ltd. | Enzymatic transesterification/esterification processes employing lipases immobilized on hydrophobic resins in the presence of water solutions |
| US10689607B2 (en) | 2010-03-01 | 2020-06-23 | Trans Bio-Diesel Ltd. | Enzymatic transesterification/esterification processes employing lipases immobilized on hydrophobic resins in the presence of water solutions |
| CN103781911A (en) * | 2011-08-31 | 2014-05-07 | 转换生物柴油有限公司 | Enzymatic transesterification with lipases immobilized on hydrophobic resins in water solutions |
| 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 |
| CN111349665A (en) * | 2020-03-11 | 2020-06-30 | 陕西科技大学 | Method for preparing biodiesel by catalyzing high-acid-value grease through enzyme method |
| CN111349665B (en) * | 2020-03-11 | 2022-05-24 | 陕西科技大学 | Method for preparing biodiesel by catalyzing high-acid-value grease through enzyme method |
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Application publication date: 20081015 |