CN102634548A - Method for producing biodiesel by using low-temperature active lipase catalytic oil - Google Patents
Method for producing biodiesel by using low-temperature active lipase catalytic oil Download PDFInfo
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- CN102634548A CN102634548A CN2012101236794A CN201210123679A CN102634548A CN 102634548 A CN102634548 A CN 102634548A CN 2012101236794 A CN2012101236794 A CN 2012101236794A CN 201210123679 A CN201210123679 A CN 201210123679A CN 102634548 A CN102634548 A CN 102634548A
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Abstract
The invention relates to a method for producing biodiesel by using low-temperature active lipase catalytic oil. The method comprises the steps of conducting transesterification reaction between the lipase catalytic raw material oil with low-temperature transesterification activity and short-chain alcohol to prepare biodiesel, wherein the mole ratio of the short-chain alcohol to the raw material oil is 2:1-5:1, and the reaction temperature is 20-40 DEG C; and reacting in a solvent-free system or a n-hexane system, adding 60-130U enzyme in per g of grease, and fast transforming and synthesizing the raw material oil into the biodiesel. With the adoption of the method, the higher esterification rate can be achieved at low temperature in the reaction process of the raw material oil and the methanol, regenerable grease raw materials can be effectively transformed at lower temperature so as to obtain high-yield biodiesel. The process not only can reduce energy consumption in production, but also overcomes the defect of the poor stability of the lipase.
Description
Technical field
The invention belongs to the lipase-catalyzed grease production method of bio-diesel oil of bio-oil synthesis technical field, particularly low temperature active.
Background technology
Utilizing low-temperature lipase as catalyzer, bio-oil raw material and short chain alcohol are passed through transesterification reaction, generate long chain fatty acid ester class material, is a kind of novel pollution-free renewable energy source, is called biofuel.Its combustionproperty can be compared with traditional petrifaction diesel, and research of biofuel at present and application have been subjected to widely to be paid close attention to, and the Production by Enzymes biofuel receives increasing concern especially.
At present the production technique of biofuel mainly comprises three kinds of chemical method, physics method and biological enzymes.But what be applied to suitability for industrialized production mainly is to use chemical method, and promptly animal-plant oil and low-carbon alcohol are carried out transesterification under alkali or an acidic catalyst effect, generate corresponding fatty acid methyl ester or ethyl ester.Chemical method prepares biofuel and has some problems that are difficult to avoid, and as free lipid acid and water-content in the raw material are had higher requirements, react the after product complex disposal process, and the discharging of spent acid (alkali) liquid causes secondary pollution etc. to environment easily.Utilize biological enzyme to prepare free fatty acids and a spot of water that biofuel then has in reaction conditions gentleness, non-pollution discharge, the glyceride stock and do not influence advantages such as enzymatic reaction; Utilize biological lypase can also further synthesize the product of some other high value in addition; Comprise biodegradable lubricant and be used for additive of fuel and lubricant etc.; These advantages make lypase become a kind of suitable biological catalyst in the production of biodiesel; Its production technique meets the environmental protection developing direction, thereby receives people's attention day by day.But also there are some problem demanding prompt solutions in the technology of biological enzyme biodiesel synthesis at present; As: lypase is lower to the transformation efficiency of short chain alcohol; Not as effective to the esterification or the transesterificationization of long-chain alcohol, and short chain alcohol has certain toxicity to enzyme, and shortened the work-ing life of enzyme; Costing an arm and a leg of lypase, production cost is higher, has limited its application in the industrial-scale production biofuel.So the biological enzyme technology that exploitation is cheap is sought new biological enzyme agent and technology, the yield that reduces enzyme use cost and raising biological enzyme biodiesel synthesis is to realize the key of biological enzyme industrialization production biofuel.
Yet the present biological enzyme raw oil material of reporting carries out in the synthesis technique of biofuel, and the enzymatic transesterification reaction optimum temperuture of most lypase is all at 30-50 ℃, and still, the inactivation of enzyme is quickened in the high meeting of temperature, influences the yield of biofuel.
Summary of the invention
The purpose of this invention is to provide the method that a kind of lypase with low temperature active produces thing diesel oil next life; Utilize the low temperature esterification characteristic of this enzyme; Be used for the fcc raw material grease with the methyl alcohol biodiesel synthesis that reacts, thereby on the basis that obtains higher bio-diesel yield, cut down the consumption of energy; Overcome on the basis of weakness of enzyme heat stability difference, effectively reduce the production of biodiesel cost.
The lypase that the present invention will have the low temperature esterification activity is used for catalyzed transesterification, utilizes the cold property of this lypase, and raw oil material is effectively transformed the generation biofuel.
Concrete grammar is following:
To have the active lypase of high transesterificationization at low temperatures and be used for fcc raw material grease and short chain alcohol reaction; The reaction mol ratio of short chain alcohol and raw oil material is 2:1-5:1; The lypase addition adds by every gram grease 60～130U; Be reflected in the biochemical reactor that is suitable for enzymic catalytic reaction and carry out, temperature of reaction is 20 ℃-40 ℃; Reaction system is solvent-free system and normal hexane solvent system.
This method can almost completely transform the generation biofuel with raw oil material fast under the situation of lower temperature conditions and less enzyme amount.
Lypase according to the invention is L-10000 low temperature acid lipase enzyme preparation, available from Kunming, Yunnan Province Ai Kete Bioisystech Co., Ltd.
Grease according to the invention is a bio-oil, comprises Vegetable oil lipoprotein and sewer oil.
Vegetable oil lipoprotein according to the invention is rapeseed oil, Jatropha curcas oil, VT 18, Semen Maydis oil, sunflower seed oil.
Short chain alcohol according to the invention is a methyl alcohol.
It is active to the invention has the advantages that lipase-catalyzed dose of being used for this technology has a low temperature transesterification; This technology can reach high methyl ester conversion rate at lesser temps with in the short period; Can effectively transform the renewable oils fat raw material at a lower temperature, obtain the biofuel of high yield.This method has not only reduced the energy consumption of producing, and has also overcome the weakness of the thermally-stabilised difference of lypase.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is done further detailed explanation:
The highest yield of methyl esters was 95.1% when Fig. 1 prepared 20 ℃ of the temperature curves of biofuel for rapeseed oil.
Fig. 2 is the temperature curve of Study on Preparation of Biodiesel from Soybean oil, and the highest yield of methyl esters is 95% in the time of 20 ℃.
Fig. 3 prepares the temperature curve of biofuel for sewer oil, and the highest yield of methyl esters is 94.97% in the time of 20 ℃.
Fig. 4 prepares the temperature curve of biofuel for Jatropha curcas oil, and the highest yield of methyl esters is 94.13% in the time of 25 ℃.
Fig. 5 prepares the temperature curve of biofuel for Semen Maydis oil, and the highest yield of methyl esters is 97.33% in the time of 25 ℃.
Fig. 6 is the temperature curve of prepared from sunflower oil biofuel, and the highest yield of methyl esters is 95.94% in the time of 20 ℃.
Embodiment
The preparation of lipase solution: L-10000 low temperature acid lipase enzyme preparation is dissolved in a certain amount of zero(ppm) water, places 20 ℃, shake up 60min in the shaking table of 180r/min, take out solution, centrifugal 10 minutes of 5000g/min gets supernatant, is lipase solution.
Transesterification reaction system: in the reactor drum that is fit to enzymic catalytic reaction, add a certain amount of raw oil and methyl alcohol; Place the preheating of water bath with thermostatic control shaking table after 5 minutes, add the lipase solution for preparing and begin reaction, after reaction finishes; With sample centrifugal 10 minutes with 10000g/min; Get 100ul upper strata ester phase, be dissolved in the 900ul normal hexane, with the fatty acid methyl ester in the gas chromatography mass spectrometry assay products.
Further specify the present invention through embodiment below, but the present invention is not limited only to following instance:
Embodiment 1
With molar ratio of methanol to oil is methyl alcohol and the rapeseed oil of 5:1, adds in the reactor drum, and reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃; After shaking up 5min in the constant temperature shaking table of 150r/min, add enzyme liquid respectively, enzyme adds unit and adds by every gram grease 105U; It is heavy by 20% that the water addition is calculated as oil according to enzyme liquid, takes a sample behind the reaction 12h, with sample with 10000g/min centrifugal 10 minutes; Get 100ul upper strata ester phase, be dissolved in the 900ul normal hexane, with the fatty acid methyl ester in the GC-MS assay products; The yield that can obtain biofuel is the highest, is about 97.58%, and is as shown in Figure 1.
With molar ratio of methanol to oil is methyl alcohol and the VT 18 of 3:1, joins in the reactor drum, and reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, shake up 5min in the constant temperature shaking table of 150r/min after; Add enzyme liquid, the enzyme addition adds by every gram grease 91U, the water addition according to enzyme liquid be calculated as oil heavy 10%; Take a sample behind the reaction 24h, utilize GC-MS to analyze and to know, when temperature of reaction is 20 ℃; The yield of biofuel is the highest, is about 95%, and is as shown in Figure 2.
Embodiment 3
With molar ratio of methanol to oil is methyl alcohol and the sewer oil of 2:1, and accounts for oily 10% the normal hexane that weighs, and joins in the reactor drum; Reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, shake up 5min in the constant temperature shaking table of 150r/min after, add enzyme liquid; The enzyme addition adds by every gram grease 62U, the water addition according to enzyme liquid be calculated as oil heavy 10%, take a sample behind the reaction 24h; Utilizing GC-MS to analyze can know when temperature of reaction is 20 ℃; The yield of biofuel is the highest, is about 94.97%, and is as shown in Figure 3.
Embodiment 4
With molar ratio of methanol to oil is methyl alcohol and the Jatropha curcas oil of 3:1, and accounts for oily 10% the normal hexane that weighs, and joins in the reactor drum; Reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, shake up 5min in the constant temperature shaking table of 150r/min after, add enzyme liquid; The enzyme addition adds by every gram grease 130U, the water addition according to enzyme liquid be calculated as oil heavy 10%, take a sample behind the reaction 24h; Utilize GC-MS to analyze and to know that when temperature of reaction was 25 ℃, the yield of biofuel was the highest; Be about 94.13%, as shown in Figure 4.
Embodiment 5
With molar ratio of methanol to oil is methyl alcohol and the Semen Maydis oil of 3:1, joins in the reactor drum, and reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, shake up 5min in the constant temperature shaking table of 150r/min after; Add enzyme liquid, the enzyme addition adds by every gram grease 91U, the water addition according to enzyme liquid be calculated as oil heavy 10%; Take a sample behind the reaction 24h, utilize GC-MS to analyze and to know, when temperature of reaction is 25 ℃; The yield of biofuel is the highest, is about 97.33%, and is as shown in Figure 5.
Embodiment 6
With molar ratio of methanol to oil is methyl alcohol and the Trisun Oil R 80 of 4:1, joins in the reactor drum, and reactor drum is placed 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, shake up 5min in the constant temperature shaking table of 150r/min after; Add enzyme liquid, the enzyme addition adds by every gram grease 91U, the water addition according to enzyme liquid be calculated as oil heavy 10%; Take a sample behind the reaction 24h, utilize GC-MS to analyze and to know, when temperature of reaction is 20 ℃; The yield of biofuel is the highest, is about 95.94%, and is as shown in Figure 6.
Claims (3)
1. one kind with the lipase-catalyzed grease production method of bio-diesel oil of low temperature active; It is characterized in that: prepare biofuel with having active lipase-catalyzed raw oil of low temperature transesterification and short chain alcohol generation transesterification reaction; Short chain alcohol and raw oil reaction mol ratio are 2:1-5:1, and temperature of reaction is 15 ℃-40 ℃; Be reflected at solvent-free system or normal hexane system, the enzyme addition adds 60～130U by every gram grease, at low temperatures, fast raw oil material is transformed biodiesel synthesis.
2. according to claim 1 with the lipase-catalyzed grease production method of bio-diesel oil of low temperature active, it is characterized in that: the related raw oil material of stating is Vegetable oil lipoprotein rapeseed oil, Jatropha curcas oil, VT 18, Semen Maydis oil, sunflower seed oil, and sewer oil.
3. according to claim 1 with the lipase-catalyzed grease production method of bio-diesel oil of low temperature active, it is characterized in that: said short chain alcohol is a methyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710158A (en) * | 2014-01-02 | 2014-04-09 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640991A (en) * | 2004-12-06 | 2005-07-20 | 华中科技大学 | Method for producing biological diesel using lipase |
Non-Patent Citations (1)
| Title |
|---|
| HERNANDEZ-MARTIN, E., OTERO, C.: "Different enzyme requirements for the synthesis of biodiesel: Novozym 435 and Lipozyme TL IM", 《BIORESOURCE TECHNOLOGY》, no. 99, 23 February 2007 (2007-02-23) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710158A (en) * | 2014-01-02 | 2014-04-09 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
| CN103710158B (en) * | 2014-01-02 | 2015-01-21 | 华南农业大学 | Method for producing biodiesel by using kitchen wastes |
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Application publication date: 20120815 |