CN1472280A - Method for synthetizing biological diesel oil by oil and fat materials - Google Patents
Method for synthetizing biological diesel oil by oil and fat materials Download PDFInfo
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- CN1472280A CN1472280A CNA031502318A CN03150231A CN1472280A CN 1472280 A CN1472280 A CN 1472280A CN A031502318 A CNA031502318 A CN A031502318A CN 03150231 A CN03150231 A CN 03150231A CN 1472280 A CN1472280 A CN 1472280A
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- 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
Abstract
A process for synthesizing biologic diesel oil from raw oil material features that the short-chain ester of fatty acid (methyl acetate or ethyl acetate) is used as acyl receptor and the biologic enzyme is used to catalyze the transesterifying reaction of oil, and includes such steps as transesterifying reaction between said ester of fatty acid and oil to obtain biologic diesel oil and glyceride triacetate, and reaction between said glyceride triacetate and methanol to obtain short-chain ester for fatty acid for cyclic use.
Description
Technical field
The invention belongs to the synthetic field of bio-oil materials, a kind of method of utilizing the glyceride stock biodiesel synthesis particularly is provided.As acyl acceptor, utilize the biological enzyme bio-oil to carry out transesterification reaction production biofuel with short-chain aliphatic ester; The by product vanay further can obtain above-mentioned short-chain aliphatic ester again with methyl alcohol reaction, and the short-chain aliphatic ester of generation is capable of circulation to be used for the synthetic of biofuel.
Background technology
By the long chain fatty acid ester class material that transesterification reaction generates, is a kind of novel pollution-free renewable energy source by the bio-oil raw material, is called as biofuel.Its combustionproperty can be that diesel oil matches in excellence or beauty with traditional oil, because objectionable impurities has reduced by 50% than traditional petrifaction diesel in the tail gas that biofuel burning rear engine gives off.Research of biofuel at present and application have been subjected to widely to be paid close attention to.
Biofuel mainly is to use chemical method production at present, promptly uses animal-plant oil and some low-carbon alcohol (methyl alcohol or ethanol) to carry out transesterification reaction under alkali or an acidic catalyst effect, generates corresponding fatty acid methyl ester or ethyl ester.Chemical method prepares biofuel and has the following inevitable shortcoming: 1. free fatty acids in the glyceride stock and water have a strong impact on the carrying out of reaction; 2. methyl alcohol solvability in grease is bad, thereby easily causes the formation of emulsion to make the subsequent processes complexity; 3. the processing requirement methanol usage substantially exceeds the reaction mol ratio, the evaporation backflow increase process energy consumption of excessive methanol.
Because free fatty acids and the less water of utilizing the biological process biodiesel synthesis to have in reaction conditions gentleness, non-pollutant discharge, the glyceride stock do not influence advantages such as enzymatic reaction, meet the developing direction of Green Chemistry, thereby are subject to people's attention day by day.Preparing in the production technique of biofuel at the present biological enzyme of reporting that utilizes, mainly is to utilize the acyl acceptor as reaction such as some short chain alcohol such as methyl alcohol, ethanol.These acyl acceptors have a strong impact on activity of enzyme reaction, reduce the work-ing life of enzyme, and byproduct of reaction glycerine influence mass transfer very easily attached to the enzyme molecular surface; Simultaneously, enzyme is before reuse, need carry out some special processing (as utilizing organic solvent flushing by-product glycerin etc.) to enzyme just can make enzyme partly recover active, the use of a large amount of organic solvents has not only increased the cost of whole production technology, and also the operation control for scale operation brings certain difficulty.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the glyceride stock biodiesel synthesis, related to short-chain aliphatic ester (methyl acetate, ethyl acetate etc.) and be acyl acceptor, reproducible bio-oil feedstock conversion generated the technology of biofuel.In this novel process, the by product vanay after the separation further can obtain above-mentioned short-chain aliphatic ester again with methyl alcohol reaction, and the short-chain aliphatic ester of generation is capable of circulation to be used for the synthetic of biofuel.
Formation of the present invention: as acyl acceptor, utilize the biological enzyme glyceride stock to carry out the transesterification reaction biodiesel synthesis with short-chain aliphatic ester.These short-chain aliphatic esters and grease dissolve each other and activity of enzyme reaction are not had negative impact.Short-chain aliphatic ester: greasy mol ratio is 3: 1～20: 1, after reaction in 4～20 hours, promptly produces biofuel.By product vanay after the separation further can obtain above-mentioned short-chain aliphatic ester again with the methyl alcohol reaction, methyl alcohol and vanay dissolve each other, this step is reflected under the chemical catalyst effect carries out easily, and the short-chain aliphatic ester of generation is capable of circulation to be used for synthetic (as shown in Figure 1) of biofuel.
Its Production Flow Chart is:
1, short-chain aliphatic ester and oil are referred to be to mix in the tool plug triangular flask of packing in 3: 1～20: 1 in molar ratio;
2, place can be temperature automatically controlled reciprocal shaking table be heated to 20 ℃～60 ℃;
3, the lipase of adding oil quality 5～30% begins reaction, can produce biofuel and by product vanay after 4～20 hours;
4. the by product vanay after separating further reacts with methyl alcohol, can obtain glycerine and short-chain aliphatic ester;
5. the short-chain aliphatic ester of Sheng Chenging can be used for the synthetic of biofuel again.
Described short-chain aliphatic ester is methyl acetate, ethyl acetate.
Described lipase is Novozym 435 or other lipase.
Described grease is a bio-oil, as Viscotrol C, rapeseed oil, soybean oil, peanut oil, Semen Maydis oil, oleum gossypii seminis and other Vegetable oil lipoprotein, fish oil, lard and other animal grease and algae grease etc.
The invention has the beneficial effects as follows the reaction conditions gentleness, have environment friendly, reaction process is simple and easy to control; Direct cyclically utilizing after after the reaction lipase being leached, reply utilize in lipase still can keep high catalytic activity; By product vanay after the separation further can obtain short-chain aliphatic ester again with methyl alcohol reaction, and the short-chain aliphatic ester of generation is capable of circulation to be used for the synthetic of biofuel.The raw material of whole technology is grease and low-carbon alcohol, and product is low-carbon ester of fatty acid (biofuel) and glycerine, and is identical with traditional technology.
Description of drawings:
Fig. 1 is the technical process that the present invention utilizes bio-oil raw material biodiesel synthesis, with short-chain aliphatic ester as the acyl acceptor biodiesel synthesis.
Embodiment
Example 1: with methyl acetate 9.6g and soybean oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.2g after 5～7 hours.
Example 2: with ethyl acetate 10g and soybean oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.2g after 10～14 hours.
Example 3: with methyl acetate 9.6g and rapeseed oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.2g after 5～7 hours.
Example 4: with ethyl acetate 10g and rapeseed oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.5g after 10～14 hours.
Example 5: with methyl acetate 9.6g and Viscotrol C 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.2g after 5～7 hours.
Example 6: with ethyl acetate 10g and Viscotrol C 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.5g after 10～14 hours.
Example 7: with methyl acetate 9.6g and fish oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.1g after 7～9 hours.
Example 8: with ethyl acetate 10g and fish oil 9.65g, 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, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.5g after 10～14 hours.
Example 9: with methyl acetate 9.6g and lard 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.1g after 7～9 hours.
Example 10: with ethyl acetate 10g with and lard 9.65g, 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, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.5g after 10～14 hours.
Example 11: with methyl acetate 9.6g and algae grease 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 9.1g after 7～9 hours.
Example 12: with ethyl acetate 10g and algae grease 9.65g, 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, adding begins reaction based on the immobilized lipase Novozym 435 of oil quality 30%, produces biofuel 8.6g after 10～14 hours.
Example 13: with methyl acetate 9.6g and soybean oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Lipozyme RM IM of oil quality 30%, produces biofuel 8.9g after 5～7 hours.
Example 14: with ethyl acetate 10g and soybean oil 9.65g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the immobilized lipase Lipozyme RM IM of oil quality 30%, produces biofuel 8.5g after 5～7 hours.
Example 15: by product vanay 52g, methyl alcohol 5.3g, pack into and mix in the tool plug triangular flask, and place can be temperature automatically controlled reciprocal shaking table be heated to 40 ℃ after, adding begins reaction based on the NaOH of nitrilotriacetic glyceride quality 0.6%, after reaction in 2～4 hours, 99% methanol conversion becomes methyl acetate, and the methyl acetate of generation can directly circulate after simple distillation and be used for the synthetic of biofuel.
According to the foregoing description; respectively with short-chain aliphatic ester methyl acetate or ethyl acetate as acyl acceptor; the immobilized lipase Novozym 435 (deriving from Candida antarctic) or the Lipozyme RM IM (deriving from Rhizomucor miehei) that under suitable temperature range, add oil quality 5%～30%; different bio-oil raw material (Viscotrol C; rapeseed oil; soybean oil, fish oil, lard, algae grease etc.) can both effectively be transformed the generation biofuel.The reaction mol ratio of short-chain aliphatic ester and grease optimum is 4: 1～14: 1, place can be temperature automatically controlled reciprocal shaking table to be heated to optimum temperature of reaction be 30 ℃～60 ℃.The by product vanay further can obtain above-mentioned short-chain aliphatic ester again with methyl alcohol reaction, and the short-chain aliphatic ester of generation is capable of circulation to be used for the synthetic of biofuel.
Claims (5)
1, a kind of method of utilizing the glyceride stock biodiesel synthesis, it is characterized in that: with short-chain aliphatic ester as acyl acceptor, utilize the biological enzyme bio-oil to carry out transesterification reaction, short-chain aliphatic ester: greasy mol ratio is 3: 1～20: 1, after reaction in 4～20 hours, produce biofuel; The by product vanay further can obtain above-mentioned short-chain aliphatic ester again with methyl alcohol reaction, and the short-chain aliphatic ester of generation is capable of circulation to be used for the synthetic of biofuel; Its Production Flow Chart is:
A, be to mix in the tool plug triangular flask of packing in 3: 1～20: 1 in molar ratio with short-chain aliphatic ester and grease;
B, place can be temperature automatically controlled reciprocal shaking table be heated to 20 ℃～60 ℃;
C, the lipase that adds based on oil quality 5%～30% begin reaction, after reaction in 4～20 hours, can produce biofuel;
D, by product vanay further carry out transesterification reaction with methyl alcohol, obtain short-chain aliphatic ester.
2, the method for utilizing the glyceride stock biodiesel synthesis according to claim 1, it is characterized in that: the preferential range of choice of short-chain aliphatic ester and grease reaction mol ratio is 4: 1～14: 1, and the preferential range of choice that places reciprocal shaking table reacting by heating temperature that can be temperature automatically controlled is 30 ℃～60 ℃.
3, the method for utilizing the glyceride stock biodiesel synthesis according to claim 1 and 2, it is characterized in that: described short-chain aliphatic ester is: methyl acetate or ethyl acetate.
4, the method for utilizing the glyceride stock biodiesel synthesis according to claim 1 and 2 is characterized in that: described lipase is Novozym 435 and lipase Lipozyme RM IM.
5, the method for utilizing the glyceride stock biodiesel synthesis according to claim 1 and 2 is characterized in that: described grease is a bio-oil: Viscotrol C, rapeseed oil, soybean oil, fish oil, lard, algae grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB031502318A CN1190471C (en) | 2003-07-22 | 2003-07-22 | Method for synthetizing biological diesel oil by oil and fat materials |
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| CNB031502318A CN1190471C (en) | 2003-07-22 | 2003-07-22 | Method for synthetizing biological diesel oil by oil and fat materials |
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| CN1472280A true CN1472280A (en) | 2004-02-04 |
| CN1190471C CN1190471C (en) | 2005-02-23 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374529C (en) * | 2006-04-26 | 2008-03-12 | 储浩 | Method for preparing biological diesel oil from saurauia tristyla var oldhamii oil |
| CN100460482C (en) * | 2005-08-31 | 2009-02-11 | 中国石油化工股份有限公司 | Method of preparing organism diesel oil from mixing plant oil |
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| WO2010148652A1 (en) | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Diesel composition and process for improving oxidation stability of biodiesel |
| CN102021207A (en) * | 2010-11-04 | 2011-04-20 | 清华大学 | On-line dehydration process for preparing biodiesel from renewable grease through catalysis of lipase |
| CN101429469B (en) * | 2007-11-08 | 2012-01-25 | 中国石油化工股份有限公司 | Chemical processing method for lipid |
| US8288573B2 (en) | 2006-12-15 | 2012-10-16 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
| CN103074389A (en) * | 2013-02-04 | 2013-05-01 | 东莞市合能微生物能源有限公司 | Method for preparing biodiesel by using biological enzyme |
| WO2013081446A1 (en) * | 2011-12-02 | 2013-06-06 | Universiti Malaya | A process for producing biodiesel from natural oil and a system thereof |
| US8500828B2 (en) | 2006-12-15 | 2013-08-06 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
-
2003
- 2003-07-22 CN CNB031502318A patent/CN1190471C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460482C (en) * | 2005-08-31 | 2009-02-11 | 中国石油化工股份有限公司 | Method of preparing organism diesel oil from mixing plant oil |
| CN100374529C (en) * | 2006-04-26 | 2008-03-12 | 储浩 | Method for preparing biological diesel oil from saurauia tristyla var oldhamii oil |
| US8288573B2 (en) | 2006-12-15 | 2012-10-16 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
| US8500828B2 (en) | 2006-12-15 | 2013-08-06 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
| CN101429469B (en) * | 2007-11-08 | 2012-01-25 | 中国石油化工股份有限公司 | Chemical processing method for lipid |
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| WO2010148652A1 (en) | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Diesel composition and process for improving oxidation stability of biodiesel |
| CN102021207A (en) * | 2010-11-04 | 2011-04-20 | 清华大学 | On-line dehydration process for preparing biodiesel from renewable grease through catalysis of lipase |
| WO2013081446A1 (en) * | 2011-12-02 | 2013-06-06 | Universiti Malaya | A process for producing biodiesel from natural oil and a system thereof |
| CN103074389A (en) * | 2013-02-04 | 2013-05-01 | 东莞市合能微生物能源有限公司 | Method for preparing biodiesel by using biological enzyme |
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| CN1190471C (en) | 2005-02-23 |
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Granted publication date: 20050223 |