CN1183238C - Method of manufacturing vegetable oil methyl aliphate using biological enzyme method - Google Patents
Method of manufacturing vegetable oil methyl aliphate using biological enzyme method Download PDFInfo
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- CN1183238C CN1183238C CNB031214940A CN03121494A CN1183238C CN 1183238 C CN1183238 C CN 1183238C CN B031214940 A CNB031214940 A CN B031214940A CN 03121494 A CN03121494 A CN 03121494A CN 1183238 C CN1183238 C CN 1183238C
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Abstract
The present invention relates to a method for manufacturing fatty acid methyl ester of vegetable oil with a biological enzyme method. Natural vegetable oil and methanol are used as raw materials by the method. Cosolvent is added for reaction under the action of an immobilized lipase catalyst so as to prepare the fatty acid methyl ester of vegetable oil. A conversion rate reaches above 95%. The method for manufacturing fatty acid methyl ester of vegetable oil of the present invention has the advantages of mild reaction conditions, little alcohol consumption, simple technology, capacity of directly obtaining the fatty acid methyl ester of vegetable oil and byproduct glycerol, no need of refining processing, energy saving, no pollutant emission, high conversion rate, high product quality, etc.
Description
Technical field
The present invention relates to a kind ofly prepare the novel method of fatty acid methyl ester, particularly relate to a kind of novel method of making the vegetable fatty acids methyl esters with biological enzyme with biological enzyme.
Background technology
Vegetables oil or natural fats and oils fatty acid methyl esters are the important intermediate during oiling is learned, and very wide application field is arranged.It is a basic raw material of producing kinds of surface promoting agents such as non-ionic type, anionic, senior perfumed soap.The vegetable fatty acids methyl esters still is a kind of comparatively ideal leather fat simultaneously, particularly prepares one of important intermediate raw material of combined fat liquor.High carbon number fatty acid methyl ester also can be used as senior lubricant and cuts the oil that disappears, cooling fluid, rolls the additive that grinds oil and change hole wet goods mechanical workout oil product.In order to protect the limited petroleum resources of environment and saving that the exploitation of alternate energy source is seemed more and more important, the vegetable fatty acids methyl esters has also caused attention widely as the research that substitutes of diesel oil in recent years.The vegetable fatty acids methyl esters also has the cetane value higher than diesel oil, good lubricity and environmental-protecting performance except that having the performance similar to diesel oil, Given this, the whole world is just growing to the demand of vegetable fatty acids methyl esters.It is a lot of that the production of relevant vegetable fatty acids methyl esters prepares patent, described in the United States Patent (USP) 2271619 natural fats and oils and low mass molecule alcohol such as methyl alcohol and ℃ reaction of basic catalyst Hybrid Heating to 80, deglycerizin from reaction mixture, steam behind the excessive alcohol the method for fatty acid methyl ester.United States Patent (USP) 465206, Japan special permission communique (B) is clear and 60-25478 and Chinese patent application numbers 89107686.7, has all reported in the CN1073474 prospectus and has adopted an acidic catalyst to carry out adopting basic catalyst to carry out the method that alcoholysis prepares the vegetable fatty acids methyl esters after the pre-esterification.
The method of above-mentioned use chemical catalyst exists complex process, alcohol must be excessive, and subsequent technique must have corresponding pure retrieving arrangement, energy consumption height; Because adopt homogeneous catalyst last handling process complexity, homogeneous catalyst and reacted glycerine are removed and can not reuse, need neutralization, washing, can bring a large amount of trade effluents, cause environmental pollution; Moreover the more economic factors of alcoholysis technology is the purification of by-product glycerin, and when a large amount of inorganic materials must be removed, this purification was more difficult.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, be engaged in the development research and the suitability for industrialized production practice of vegetable fatty acids methyl esters for many years through the contriver, it is simple that exploitation proposes a kind of technology, the reaction conditions gentleness, need not refinement treatment, non-pollution discharge, high conversion, high-quality biological enzyme are made the novel method of vegetable fatty acids methyl esters.
The method that biological enzyme provided by the invention is made the vegetable fatty acids methyl esters comprises:
---vegetables oil, methyl alcohol, solubility promoter vegetable fatty acids methyl esters are dropped into closure and be equipped with in the container of stirring, after stirring, add the biological enzyme agent again, screw container cover, and the container that reaction mass will be housed is put into vibrator and is vibrated, the concussion frequency is 100-200rpm, under 30-60 ℃ of temperature, reacted 20-48 hour, wherein in 100 weight part vegetables oil, solubility promoter vegetable fatty acids methyl esters is the 50-100 weight part, biological enzyme agent 4-8 weight part, the mol ratio of methyl alcohol and vegetables oil is 1: 1.
---by filtering the biological enzyme agent is shifted out from reaction product.
---reactant placed leaves standstill more than 12 hours, treat deglycerizin layer after the layering, product vegetable fatty acids formicester.
Make according to biological enzyme provided by the invention in the novel method of vegetable fatty acids methyl esters, described vegetables oil comprises rapeseed oil, Oleum Gossypii semen, soya-bean oil, peanut oil, plam oil, Oleum Cocois.Siritch, Oleum Helianthi, sesame oil, Semen Maydis oil, broccoli oil or castor-oil plant wet goods are preferably rapeseed oil, Oleum Gossypii semen, soya-bean oil, peanut oil, broccoli oil, plam oil or Oleum Cocois.Main component is a tri-glyceride in described vegetables oil, wherein fatty acid part comprises components such as unsaturated fatty acids and saturated fatty acid, unsaturated fatty acids and saturated fatty acid content and degree of unsaturation and to some extent difference different along with vegetable oil kind, do not have essential difference but the present invention is made the vegetable fatty acids methyl esters with biological enzyme, can both realize purpose of the present invention.Vegetable fatty acids methyl esters of the present invention is exactly the general designation of the vegetable fatty acids methyl esters that made by above-mentioned vegetables oil, and rapeseed oil fatty acid methyl esters, cottonseed oil fatty acid methyl esters, methyl soyate, palm oil fatty acid methyl esters, peanut oil fatty acid methyl esters, coconut oil fatty acid methyl ester or broccoli fatty acid oil methyl esters etc. are arranged respectively.
Described solubility promoter vegetable fatty acids methyl esters is identical with above-mentioned vegetable fatty acids methyl esters, comprises rapeseed oil fatty acid methyl esters, cottonseed oil fatty acid methyl esters, methyl soyate, palm oil fatty acid methyl esters, peanut oil fatty acid methyl esters, coconut oil fatty acid methyl ester or broccoli fatty acid oil methyl esters etc.Make in the vegetable fatty acids methyl esters method at biological enzyme, the vegetables oil of preferred used solubility promoter vegetable fatty acids methyl esters and material plant oil phase are together, the various vegetable fatty acids methyl esters that are beneficial to make need not separate the direct pure vegetable fatty acids methyl esters that gets, otherwise get the mixed vegetable oil fatty acid methyl ester.The mutual solubility of these solubility promoter vegetable fatty acids methyl esters and methyl alcohol is good, simultaneously might as well with the vegetables oil mutual solubility, putting into the vegetable fatty acids methyl esters in reaction mixture just can make vegetables oil and methanol mixed even, accelerate response speed, also avoided methyl alcohol separately the toxic action of lipase to be caused the lipase inactivation simultaneously.The consumption of solubility promoter vegetable fatty acids methyl esters is counted the 50-100 weight part with 100 weight part vegetables oil.
Described methyl alcohol must be purity greater than more than 99.5%, for example industrial grade benzenemethanol or chemical reagent-grade methyl alcohol, analytical pure methyl alcohol etc., purity is all more than 99.5%, all applicable in the inventive method, methanol purity is high more favourable more to the biological enzyme agent.Methanol usage is and plant wet goods mole that both vegetables oil methyl alcohol mol ratio was 1: 1.
Described biological enzyme is meant lipase, NOVOZYM435 immobilized lipase (CANDIDA ANTARCTICA for example, NOVO NORDISK company sell goods), LIPOZYME RM IM immobilized lipase (RHIZOMUCOR MIEHEI, NOVONORDISK company sell goods), LIPASE-RH immobilized lipase (RHIZOPUSDELEMAR, TANABE SEIYAKU company limited sell goods), be preferably the NOVOZYM435 immobilized lipase, its consumption is the 4-8 weight part with respect to 100 weight part vegetables oil.
The novel method characteristics that biological enzyme provided by the invention is made the vegetable fatty acids methyl esters adopt biological enzyme one immobilized lipase to do to make vegetable fatty acids by the reaction of crude vegetal and methyl alcohol under the condition of catalyzer and importing solubility promoter vegetable fatty acids methyl esters.This method has the reaction conditions gentleness, pure consumption is little, and technology is simple, can directly obtain fatty acid methyl ester and by-product glycerin, need not refinement treatment, and save energy, advantages such as non-pollutant discharge, reaction conversion ratio height, the product quality height of conversion.
Embodiment
The present invention further specifies the present invention with the following examples, but protection scope of the present invention is not limited to embodiment.
Embodiment 1
After in the Erlenmeyer flask of 50ml, adding Oleum Gossypii semen 11.5 grams, methyl alcohol 0.4 gram, the abundant stirring of cottonseed oil fatty acid methyl esters 6.0 grams, add NOVOZYM435 immobilized lipase 0.5 gram, with tapered bottleneck sealing, and put it in the vibrator, open vibrator, shake under the frequency of 150RPM, be warming up to 30 ℃, reaction was carried out about 24 hours.After reaction finishes, the NOVOZYM435 immobilized lipase is shifted out from reaction product, reaction product is placed left standstill 13 hours then, treat deglycerizin layer after the layering by filtering, product cottonseed oil fatty acid methyl esters, the transformation efficiency of reaction is 97.8%.
Embodiment 2
After in the Erlenmeyer flask of 50ml, adding rapeseed oil 10.0 grams, methyl alcohol 0.4 gram, the abundant stirring of rapeseed oil fatty acid methyl esters 5.2 grams, add NOVOZYM435 immobilized lipase acid enzyme 0.4 gram, with tapered bottleneck sealing, and put it in the vibrator, open vibrator, shake under the frequency of 150RPM, be warming up to 30 ℃, reaction was carried out about 24 hours.After reaction finishes, the NOVOZYM435 immobilized lipase is shifted out from reaction product, reactant is placed left standstill 12 hours then, treat deglycerizin layer after the layering by filtering, product rapeseed oil fatty acid methyl esters, the transformation efficiency of reaction reaches 95.6%.
Embodiment 3
After in the Erlenmeyer flask of 50ml, adding soya-bean oil 11.0 grams, methyl alcohol 0.45 gram, the abundant stirring of methyl soyate 5.8 grams, add NOVOZYM435 immobilized lipase acid enzyme 0.45 gram, with tapered bottleneck sealing, and put it in the vibrator, open vibrator, shake under the frequency of 150RPM, be warming up to 30 ℃, reaction was carried out about 24 hours.After reaction finishes, the NOVOZYM435 immobilized lipase is shifted out from reaction product, reaction product is placed left standstill 15 hours then, treat deglycerizin layer after the layering by filtering, the product methyl soyate, the transformation efficiency of reaction reaches 96.2%.
Embodiment 4
Preparation method's step of embodiment 4 is same as embodiment 1, and not being both lipase is LIPOZYMERM ZI immobilized lipase, and the transformation efficiency of its reaction reaches 59%.
Claims (6)
1, a kind of biological enzyme is made the method for vegetable fatty acids methyl esters, it is characterized in that this method comprises:
---with vegetables oil, methyl alcohol and solubility promoter vegetable fatty acids methyl esters, drop into closure and be equipped with in the container of stirring, after stirring, add lipase-catalyzed dose again, screw container cover, and the container that reactant will be housed is put into vibrator and is vibrated, oscillation frequency is 100RPM-200RPM, under 30 ℃ of-60 ℃ of temperature, reacted about 20-48 hour, wherein in 100 weight part vegetables oil, solubility promoter vegetable fatty acids methyl esters is the 50-100 weight part, lipase-catalyzed dose is the 4-8 weight part, and the mol ratio of vegetables oil and methyl alcohol is 1: 1;
---by filtering lipase-catalyzed dose is shifted out from reaction product;
---reaction product placed leaves standstill more than 12 hours, treat deglycerizin layer after the layering, product vegetable fatty acids methyl esters.
2, biological enzyme according to claim 1 prepares the method for vegetable fatty acids methyl esters, it is characterized in that described vegetables oil is Oleum Gossypii semen, rapeseed oil, soya-bean oil, peanut oil, plam oil, Oleum Cocois, siritch, Oleum Helianthi, sesame oil, Semen Maydis oil, broccoli oil or Viscotrol C.
3, biological enzyme according to claim 1 prepares the method for vegetable fatty acids methyl esters, it is characterized in that described vegetables oil is rapeseed oil, Oleum Gossypii semen, soya-bean oil, peanut oil, plam oil or Oleum Cocois.
4, biological enzyme according to claim 1 is made the method for vegetable fatty acids methyl esters, it is characterized in that described methanol purity is greater than 99.5%.
5, biological enzyme according to claim 1 is made the method for vegetable fatty acids methyl esters, it is characterized in that described solubility promoter vegetable fatty acids methyl esters is vegetable seed grease fat methyl esters, cottonseed oil fatty acid methyl esters, methyl soyate or palm oil fatty acid methyl esters, peanut oil fatty acid methyl esters, coconut oil fatty acid methyl ester or broccoli fatty acid oil methyl esters.
6, biological enzyme according to claim 1 is made the method for vegetable fatty acids methyl esters, it is characterized in that described lipase is NOVOZYM435 immobilized lipase, LIPOZYME RM IM immobilized lipase or LIPASE-RH immobilized lipase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB031214940A CN1183238C (en) | 2003-03-28 | 2003-03-28 | Method of manufacturing vegetable oil methyl aliphate using biological enzyme method |
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| CNB031214940A CN1183238C (en) | 2003-03-28 | 2003-03-28 | Method of manufacturing vegetable oil methyl aliphate using biological enzyme method |
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| CN1183238C true CN1183238C (en) | 2005-01-05 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7473539B2 (en) | 2004-09-20 | 2009-01-06 | Sunho Biodiesel Corporation | Methods for producing alkyl esters |
| BRPI0611892A2 (en) | 2005-06-13 | 2011-01-04 | Novozymes As | method for producing reduced phosphorus alkyl fatty acid esters |
| CN101831280B (en) * | 2010-05-19 | 2013-12-18 | 濮阳市诚信钻采助剂有限公司 | Carrier of active ingredient of defoaming agent and preparation method thereof |
| WO2011159998A2 (en) * | 2010-06-18 | 2011-12-22 | Butamax(Tm) Advanced Biofuels Llc | Production of alcohol esters and in situ product removal during alcohol fermentation |
| CN103119172B (en) * | 2010-06-18 | 2016-05-11 | 布特马斯先进生物燃料有限责任公司 | Extract in fermentation, remove for alcohol derive from oily extraction solvent |
| CN103695184A (en) * | 2013-12-31 | 2014-04-02 | 张锦碧 | Novel process for preparing biodiesel from illegal cooking oil |
| CN109852483A (en) * | 2018-12-29 | 2019-06-07 | 中南林业科技大学 | A method of fatty acid methyl ester is prepared with Rice bran crude oil |
| CN111378700A (en) * | 2020-02-24 | 2020-07-07 | 广东聚石化学股份有限公司 | Preparation method of camellia oil fatty acid ester |
| CN111437220B (en) * | 2020-04-29 | 2022-09-06 | 广东聚石化学股份有限公司 | Camellia oil fatty acid ester composition and preparation method and application thereof |
| CN115197784B (en) * | 2022-07-08 | 2024-01-09 | 华南理工大学 | Lard oil substituted grease and preparation method and application thereof |
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