CN110184313B - Method for preparing biodiesel by promoting enzyme catalysis of ionic liquid - Google Patents
Method for preparing biodiesel by promoting enzyme catalysis of ionic liquid Download PDFInfo
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- CN110184313B CN110184313B CN201910493359.XA CN201910493359A CN110184313B CN 110184313 B CN110184313 B CN 110184313B CN 201910493359 A CN201910493359 A CN 201910493359A CN 110184313 B CN110184313 B CN 110184313B
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
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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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Abstract
The invention discloses a method for preparing biodiesel by catalyzing enzyme with ionic liquid, which is prepared by mixing grease and ionic liquid [ CH ]][H 2 PO 4 ]Placing lipase Novozym 435 and methanol in a reaction container, reacting at 25-100 ℃ for 3-24h, cooling to room temperature after the reaction is finished, automatically layering the system, and preparing ionic liquid [ CH][H 2 PO 4 ]In the lower layer, lipase Novozym 435 in the middle layer, biodiesel in the upper layer, and ionic liquid [ CH][H 2 PO 4 ]And the lipase Novozym 435 can be recycled after recovery. Ionic liquid [ CH ] used in the invention][H 2 PO 4 ]The method has the advantages of low toxicity, easy preparation, low cost, strong biocompatibility, easy degradation and the like, the catalytic effect of the ionic liquid and the enzyme is not obviously reduced after the ionic liquid and the enzyme are recycled for six times, the reaction system is simple, and the grease from different sources can be efficiently converted into the biodiesel.
Description
Technical Field
The invention belongs to the technical field of preparation of biodiesel, and particularly relates to a method for preparing biodiesel by catalyzing enzyme with ionic liquid.
Background
The shortage of fossil resources and the increasing demand for energy and environment for human beings makes it urgent to develop alternative energy sources with reproducibility, sustainability and minimization of greenhouse gas emissions, as compared with petroleum diesel. Biodiesel is a mixture of alkyl esters of long chain Fatty Acids (FAME), usually made from edible or non-edible oils and animal fats, which has been recognized as a green alternative to petroleum diesel.
The problem of food shortage is aggravated by using edible oil as a raw material to prepare biodiesel, and in order to solve the problem, a raw material for continuously preparing biodiesel is sought, and castor oil attracts people's extensive attention. The castor oil is obtained by squeezing castor oil fruits, has strong adaptability to the castor oil, strong drought resistance and alkali resistance, and is suitable for planting in barren mountains and barren slopes, so that the castor oil becomes one of ten oil plants and four inedible oil plants in the world.
Compared with the time-consuming and labor-consuming chemical production of acid or base catalyzed biodiesel, the enzyme catalysis method has the advantages of mild reaction conditions, low alcohol-oil ratio, no need of pretreatment of various raw materials, simple and convenient operation and more attention.
Due to the unique physical and chemical properties of the ionic liquid, the ionic liquid is considered to be a green medium for replacing an organic volatile solvent, and the ionic liquid is used in the field of preparing biodiesel through enzyme catalysis in recent years. At present, most of ionic liquids used for preparing biodiesel are hydrophobic ionic liquids, are not biodegradable and have high toxicity to water environment. Therefore, the development of a biodegradable and low-toxicity method for preparing biodiesel by promoting enzyme catalysis by a medium is of great significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing biodiesel by promoting enzyme catalysis of ionic liquid with simple catalytic system and mild reaction conditions, wherein the ionic liquid [ CH ] used in the method][H 2 PO 4 ]The method has the advantages of low toxicity, easy preparation, low cost, strong biocompatibility, easy degradation and the like, the catalytic effect of the ionic liquid and the enzyme is not obviously reduced after the ionic liquid and the enzyme are recycled for six times, the reaction system is simple, and the grease from different sources can be efficiently converted into the biodiesel.
The invention adopts the following technical scheme for solving the technical problems, and the method for preparing the biodiesel by catalyzing the enzyme with the ionic liquid is characterized by comprising the following specific processes: mixing oil and fat, and ionic liquid [ CH ]][H 2 PO 4 ]Placing the lipase Novozym 435 and methanol in a reaction container, reacting at 25-100 ℃ for 3-24h, cooling to room temperature after the reaction is finished, automatically layering the system, and preparing the ionic liquid [ CH][H 2 PO 4 ]In the lower layer, lipase Novozym 435 in the middle layer, biodiesel in the upper layer, and ionic liquid [ CH][H 2 PO 4 ]And lipase Novozym 435, wherein the oil is triolein, inedible castor oil or sunflowerOne or more of oils.
Preferably, the ionic liquid [ CH][H 2 PO 4 ]The mass ratio of the lipase to the oil is 0.1-1, the molar ratio of methanol to the oil is 4-14.
Preferably, the ionic liquid [ CH][H 2 PO 4 ]And lipase Novozym 435 can be repeatedly recycled for 6 times, the catalytic effect is not obviously reduced, and the ionic liquid [ CH][H 2 PO 4 ]And lipase Novozym 435 has good reusability.
Preferably, the method for preparing the biodiesel by promoting enzyme catalysis of the ionic liquid is characterized by comprising the following specific steps of: mixing oil and fat with glycerol trioleate and ionic liquid [ CH][H 2 PO 4 ]The lipase Novozym 435 and methanol were placed in a reaction vessel in which an ionic liquid [ CH][H 2 PO 4 ]The mass ratio of the mixture to the oil is 0.5, the molar ratio of methanol to the oil is 10][H 2 PO 4 ]In the lower layer, the lipase Novozym 435 is in the middle layer, the biodiesel is in the upper layer, and the yield of the biodiesel reaches 99 percent.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the ionic liquid is simple to prepare, low in toxicity, low in cost and good in biocompatibility, the ionic liquid and the enzyme can be repeatedly recycled, and the catalytic effect is not obviously reduced;
2. the preparation process has mild reaction conditions, can efficiently convert the grease from different sources into the biodiesel, and has simple reaction system and higher yield of the biodiesel.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Into a round-bottomed flask were added glycerol trioleate (0.5mmol, 442.5mg) and an ionic liquid [ CH ] in this order][H 2 PO 4 ](221.25mg, 50wt%), methanol (5.0mmol, 160mg) and lipase Novozym 435 (22.125mg, 5wt%), mixing uniformly, placing in an oil bath at 60 ℃ for reacting for 12h, stopping the reaction, and cooling to room temperature to obtain the biodiesel. Adding decyl caproate into the reaction liquid, extracting and shaking by ethyl acetate, centrifuging, and finally measuring that the yield of the biodiesel reaches 99%.
Example 2
Sunflower oil (0.5 mmol,442.5 mg) and ionic liquid (CH) are added into a round-bottom flask in sequence][H 2 PO 4 ](221.25mg, 50wt%), methanol (5.0 mmol, 160mg) and lipase Novozym 435 (22.125mg, 5wt%), mixing uniformly, placing in oil bath at 60 ℃ for reaction for 12h, stopping reaction, cooling to room temperature to obtain the biodiesel. Adding decyl caproate into the reaction liquid, extracting and shaking by ethyl acetate, and centrifuging to finally determine that the yield of the biodiesel reaches 96%.
Example 3
Adding non-edible oil castor oil (0.5mmol, 442.5mg) and ionic liquid (CH) into a round-bottom flask in turn][H 2 PO 4 ](221.25mg, 50wt%), methanol (5.0mmol, 160mg) and lipase Novozym 435 (22.125mg, 5wt%), mixing uniformly, placing in an oil bath at 60 ℃ for reacting for 12h, stopping the reaction, and cooling to room temperature to obtain the biodiesel. Adding decyl caproate into the reaction liquid, extracting and oscillating by ethyl acetate, centrifuging, and finally measuring that the yield of the biodiesel reaches 96%.
Example 4
Sequentially adding inedible castor oil (2mmol, 2g) and ionic liquid [ CH ] into a round-bottom flask][H 2 PO 4 ](1g, 50wt%), methanol (22.6mmol, 723mg) and lipase Novozym 435 (0.1g, 5wt%), mixing uniformly, placing in an oil bath at 60 ℃ for reacting for 12h, stopping the reaction, and cooling to room temperature to obtain the biodiesel. Adding hexyl decanoate into the reaction solution, extracting and oscillating by ethyl acetate, centrifuging,finally, the yield of the biodiesel is 92 percent.
Example 5
Into a round-bottomed flask were added glycerol trioleate (0.5mmol, 442.5mg) and an ionic liquid [ CH ] in this order][H 2 PO 4 ](221.25mg, 50wt%), methanol (5.0mmol, 160mg) and lipase Novozym 435 (22.125mg, 5wt%), mixing uniformly, placing in an oil bath at 60 ℃ for reacting for 12h, stopping the reaction, and cooling to room temperature to obtain the biodiesel. Adding decyl caproate into the reaction liquid, extracting and shaking by ethyl acetate, centrifuging, and finally measuring that the yield of the biodiesel reaches 99 percent. Wherein the lipase Novozym 435 is washed by ethyl acetate, dried at room temperature and directly used for the next circulation; ionic liquid [ CH][H 2 PO 4 ]Washed with ethyl acetate, spin-dried, dried in an oven at 50 ℃ and used directly for the next reaction. After the ionic liquid and the enzyme are circularly used for five times, the catalytic activity of the ionic liquid and the enzyme is not obviously reduced, and in the sixth circular use, the reaction time is prolonged to 17 hours, the yield of the biodiesel can reach 99 percent, and the effect is the same as the initial effect.
While the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (2)
1. A method for preparing biodiesel by catalyzing enzyme with ionic liquid is characterized by comprising the following specific processes: mixing oil and fat with glycerol trioleate and ionic liquid [ CH][H 2 PO 4 ]Lipase Novozym 435 and methanol were placed in a reaction vessel with an ionic liquid [ CH][H 2 PO 4 ]The mass ratio of the fatty acid to the fatty acid triolein is 0.5Layer, ionic liquid [ CH][H 2 PO 4 ]In the lower layer, the lipase Novozym 435 is in the middle layer, the biodiesel is in the upper layer, and the yield of the biodiesel reaches 99 percent.
2. The method for preparing biodiesel by enzymatic catalysis of ionic liquid according to claim 1, wherein: the ionic liquid [ CH][H 2 PO 4 ]And lipase Novozym 435 can be repeatedly recycled for 6 times, the catalytic effect is not obviously reduced, and the ionic liquid [ CH][H 2 PO 4 ]And lipase Novozym 435 has good reusability.
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| CN201910493359.XA CN110184313B (en) | 2019-06-07 | 2019-06-07 | Method for preparing biodiesel by promoting enzyme catalysis of ionic liquid |
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| CN110184313B true CN110184313B (en) | 2022-10-11 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055661A1 (en) * | 2005-11-14 | 2007-05-18 | Agency For Science, Technology And Research | Enzymatic production of biodiesels |
| CN102533907A (en) * | 2012-01-10 | 2012-07-04 | 华南理工大学 | Method for increasing enzymolysis efficiency of rice straws through choline and amino acid ionic liquid pretreatment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2189535A1 (en) * | 2008-11-21 | 2010-05-26 | Centre National de la Recherche Scientifique | Use of ionic liquids for implementing a process for the preparation of biodiesel |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055661A1 (en) * | 2005-11-14 | 2007-05-18 | Agency For Science, Technology And Research | Enzymatic production of biodiesels |
| CN102533907A (en) * | 2012-01-10 | 2012-07-04 | 华南理工大学 | Method for increasing enzymolysis efficiency of rice straws through choline and amino acid ionic liquid pretreatment |
Non-Patent Citations (5)
| Title |
|---|
| Cleaner enzymatic production of biodiesel with easy separation procedures triggered by a biocompatible hydrophilic ionic liquid;Anlian Zhu等;《The Royal Society of Chemistry》;20200215;全文 * |
| 功能化季铵盐离子液体在制备生物柴油中的应用;孙亚飞等;《华侨大学学报(自然科学版)》;20111120(第06期);全文 * |
| 碱性离子液体的研究进展;白漫等;《化学工程与装备》;20160715(第07期);全文 * |
| 离子液体在生物柴油合成中的应用研究进展;杨建军等;《化工进展》;20130805(第08期);全文 * |
| 胆碱类离子液体在催化制备生物柴油中的应用研究;胡彩玲等;《粮食与油脂》;20151010(第10期);全文 * |
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