CN1287572A - Process for preparing alkyl esters of fatty acids from fats and oils - Google Patents
Process for preparing alkyl esters of fatty acids from fats and oils Download PDFInfo
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- CN1287572A CN1287572A CN 99801744 CN99801744A CN1287572A CN 1287572 A CN1287572 A CN 1287572A CN 99801744 CN99801744 CN 99801744 CN 99801744 A CN99801744 A CN 99801744A CN 1287572 A CN1287572 A CN 1287572A
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Abstract
A process for preparing alkyl esters of fatty acids from fats and oils by reacting fats and oils with an alcohol to transesterify the triglycerides contained in the fats and oils, in which the reaction is conducted without a metallic alkali catalyst or an acid catalyst in such an atmosphere as makes the alcohol exist in a supercritical state, whereby the pretreatment step of esterifying free fatty acids can be dispensed with and the formation of fatty acid soap as by-product can be eliminated to thereby omit or simplify the step of recovery and purification of products.
Description
The present invention relates to a kind of is to make effectively to utilize effective for treatment of premature ejaculation as diesel combustion wet goods useful method.This method is by make the equivalent thing oil of rapeseed oil, sesame oil, soya-bean oil, Semen Maydis oil, sunflower oil, plam oil, palm-kernel oil, Oleum Cocois and Thistle oil with alcohol, the animal oil of butter, lard, fish oil etc., even use in the lipid of back waste edible oils etc. contained tri-glyceride to carry out transesterification reaction at these and carry out.
As everybody knows, though at present use a part that above-mentioned various grease classes and its use back oil (above-mentioned waste edible oil) to be reused as the raw material of soap etc. in that China is a large amount of, its major part does not reclaim and is transported to that the disposal site is burned with combustible garbage or with the buried processing of non-ignitibility rubbish.
On the other hand, people know, by making glyceryl monoacetate, diglyceride, tri-glyceride and alkyl alcohol carry out transesterification reaction, can obtain fatty acid alkyl ester [for example, " organic chemistry handbook " skill newspaper hall is published p1407～1409 (1988)] as grease class main component.In addition, utilize this reaction so far, for various reports also being arranged (for example as the technology of the oily alkyl ester that uses of diesel combustion by the lipid manufacturing, Te Kaiping 7-197, flat 7-310 is opened in No. 047, spy, No. 090 etc.), but can not get satisfying alkyl ester with these technology about the JIS standard of existing light oil.
As by tri-glyceride, particularly by the method for tri-glyceride contained in natural grease class at industrial manufacturing fatty acid ester, prevailing method is in there being the method that makes the glycerin fatty acid ester reaction under the base metal catalysts under near temperature lower alcohol and the boiling point under normal pressure.But in this reaction, owing to be to use in that the state that has dissolved base metal catalysts is following in reaction soln, therefore, alkaline catalysts is dissolved in the Generation Liquid, has its separation and the difficult problem of recovery.
In addition, in natural grease, contain a large amount of free fatty acidies usually,, on average all contain more than 3% though various different contents are arranged according to source or its facture difference of raw material.And when under the many situations of free fatty acid content, using base metal catalysts, generate and pay a product fatty acid soaps, it is excessive that base metal catalysts needs, and perhaps produces because the fatty acid soaps that is generated makes the problem that becomes fatty acid ester layer and separating of glycerin layer etc.For this reason, when in the presence of base metal catalysts, carrying out the transesterification reaction of glycerin fatty acid ester, need be for removing the pretreatment procedure of free fatty acids.
For fear of the problems referred to above, for example to open in the clear 61-14044 communique the spy, the method that also discloses a kind of ester that changes the free fatty acids that uses acid catalyst into is as pretreatment procedure.In the method, as the pre-treatment of in the presence of base metal catalysts, carrying out the transesterification reaction of glycerin fatty acid ester, make free fatty acids be transformed into ester, but when carrying out the transesterification reaction of glycerin fatty acid ester, when a residual acid catalyzer, then just be neutralized, therefore, have the problem of so-called this part base metal catalysts of increase.
In addition, as the manufacture method of the fatty acid ester that does not need above-mentioned pretreatment procedure, also once reported method (for example, the spy opens flat 6-313, No. 188) with solid acid catalyst.But acid catalyst is compared with base metal catalysts has fatal shortcoming, and promptly therefore active low to grease class transesterification reaction exist in the problem that needs a large amount of catalyzer in the transesterification reaction of using acid catalyst.
The present invention be directed to the problems referred to above makes, a kind of method of being made fatty acid alkyl ester by lipid that provides is provided, this method is without the pretreatment procedure of esterification free fatty acids, and do not generate the by product of fatty acid soaps and can omit or simplify the recovery refining step of resultant.
The inventive method to achieve these goals is to make grease class and alcohol reaction and make to contain tri-glyceride adding transesterification reaction manufacturing effective for treatment of premature ejaculation in the grease class, at described alcohol is in the atmosphere gas of supercritical state, and also without any method that makes its reaction in base metal catalysts or the acid catalyst.
In order to carry out aforesaid method, the limit is passed through lipid and alcohol continuously in tubular reactor, and it is ideal that the limit makes its reaction.In addition, when stating tubular reactor in the use, making is that the liquid air speed of benchmark is that to react in 2-240/ hour be ideal with the tri-glyceride in tubular reactor.And in above-mentioned method, from generating the viewpoint of high-quality lower alkyl esters, using carbon number is ideal as the lower alcohol of 1-5 as diesel engine fuel oil.
Present inventors study from the various angles that can address the above problem, it found that: when alcohol is supercritical state in the atmosphere gas, if make grease class and alcohol reaction, even without any in base metal catalysts or the acid catalyst, also can generate alkyl acid by tri-glyceride contained in the grease class efficiently, and then finish the present invention.In addition, according to the present invention,, therefore do not need the pretreatment procedure of esterification free fatty acids, and the by product of FAF soap generates the recovery refining step that can omit or simplify resultant without any in base metal catalysts or the acid catalyst.
As the grease class of using in the present invention, can enumerate natural Vegetable oil lipoprotein and animal grease.As Vegetable oil lipoprotein, can enumerate Oleum Cocois, plam oil, palm-kernel oil, soya-bean oil, vegetable seed wet goods, and can enumerate butter, lard, fish oil etc. as the animality grease.In addition, also comprise these greases are made waste edible oil after specific purpose is used.These grease classes can be used alone or as a mixture, but the angle from resource is utilized again, and utilizing the waste edible oil after using is ideal
On the other hand, as with the alcohol of lipid reaction, from generating the viewpoint of fine lower alkyl esters as diesel engine fuel oil, using carbon numbers such as methyl alcohol, ethanol, propyl alcohol, Virahol is ideal as the lower alcohol of 1-5.Wherein, methyl alcohol particularly is so because its cost is low and to reclaim easily be ideal.
In the present invention, with above-mentioned raw material, it is characterized in that it being in alcohol is the atmosphere gas of supercritical state, to make it the sour permutoid reaction of carrying out.By adopting above-mentioned method,, can consider following reason to obtaining above-mentioned effect.
For example, using methyl alcohol to do under the situation of alcohol,, can think CH if be under the condition of abundant supercritical state at this methyl alcohol
3O
-And H
+Dissociate, make the alcohol activation, and pass through by proton (H
+) effect, make tri-glyceride activation, thus, can carry out transesterification reaction effectively.And present inventors have proved by experiment, when using methyl alcohol, if 250 ℃, more than the 9MPa, then under the grease coexistence, become supercritical state, under catalyst-free, can react.
But by carry out transesterification reaction under high temperature and high pressure, the technology that improves its reaction efficiency also is well-known.As such technology, for example at " JAOCS " vol 61, No.2 has reported the condition as transesterification reaction among the p343 (1984), is used under 240 ℃, 9MPa to react with methyl alcohol.But in this technology, be to be prerequisite, and under above-mentioned condition, can not become supercritical state in order to make grease coexistence methyl alcohol under base metal catalysts, to make its reaction.For this technology, present inventors can confirm, under the condition shown in above-mentioned, almost can not carry out without the catalyzer transesterification reaction.That is to say, in the example shown in the above-mentioned document, though be condition for the situation of using methyl alcohol, for the balance that reaches supercritical state, temperature and pressure also is important.If from this viewpoint, much less above-mentioned technology can not satisfy becomes supercritical state pressure and temperature scope, and under such condition, alcohol can not chemically be activated fully, therefore needs base metal catalysts.
At the pressure and temperature that carries out when of the present invention, can be alcohol in the condition that becomes supercritical state fully, and according to the kind difference of alcohol, the condition when using lower alkyl alcohol is generally the scope of following temperature and pressure.Temperature of reaction is generally 250-300 ℃, and ideal is 250-280 ℃, and pressure is generally 3-15MPa, and ideal is 5-13MPa.In the temperature and pressure scope lower, can not keep alcohol in supercritical state fully, and under the temperature higher than this, it is big that the thermolysis of reactive material becomes, and also be disadvantageous economically under the pressure higher than this than these.And can find out that from the aim of the above even be the scope of above-mentioned temperature and pressure, keep sufficient supercritical state in order to make alcohol, the balance of temperature and pressure also is important.
The form of reaction also can be batch-wise, but the easier continous way of control in the reaction times under the high temperature and high pressure condition is an ideal.Particularly surpassing under 250 ℃ the condition, in order to suppress the thermolysis of glycerine etc., needing will be controlled in the reaction times in 30 minutes, ideal is in 5 minutes, therefore, recommends to make raw material by the tubular reactor and the form of reacting continuously.
When utilizing above-mentioned tubular reactor, making tri-glyceride in tubular reactor is that the liquid air speed of benchmark is that to react in 2-240/ hour be ideal.That is, when liquid air speed during less than 2/ hour, the productivity step-down of unit reactor volume and uneconomical then, but surpass 240/ hour when the liquid air speed, then can not get sufficient reaction yield.From this viewpoint, the scope of ideal fluid air speed is 12-120/ hour.In addition, in the present invention owing at high temperature carry out, even also can fully react at short notice, still, in reaction times during less than 0.25 minute because reaction can not reach equilibrium state, thus the reaction times be at least more than 0.25 minute better.In addition, so-called aforesaid liquid air speed is that benchmark defines with tri-glyceride feed rate (being converted into 15 ℃, 1atm lower volume feed rate).
Carrying out when of the present invention, can doubly carry out at 1.2-50 by stoichiometric requirement for the tri-glyceride and the mol ratio of alcohol.The scope of this mol ratio of ideal is 1.2-30 times.When this mol ratio less than 1.2 times, then keep the supercritical state of alcohol to finish because of difficulty, and when surpassing 50 times up to reaction, the volumetric efficiency step-down of reactor then, the yield that increases alcohol is uneconomic.
As in the reaction solution of above-mentioned gained, except that the fatty acid ester that produces as purpose, also contain glycerine and lower alcohol.And owing in reaction, there is the alcohol of supercritical state, therefore increase by the solubleness in the grease of glycerine, make how many step-downs of balanced reaction rate, but by in reaction, make temperature or pressure reduce layering and deglycerizin, and heat up once more or boost and make it to be reacted into reaction of high order, can obtain the desired response yield.
To directly import to distiller by the resulting reaction solution of flow reactor, remove alcohol after, by ordinary methods such as standing separation, centrifugations, can be separated into oil reservoir (fatty acid ester) and glycerin layer (glycerine).When in oil reservoir, containing unreacted stock oil,, can obtain the fine fatty acid ester by distillation.
Below, give more specific description by embodiment to effect of the present invention and effect, but the invention is not restricted to following embodiment, so long as carry out suitable change and implement all will be included among the technical scope of the present invention in suitable scope before and after it.
Embodiment 1
In stainless steel 300ml autoclave, add edible rapeseed oil and soya-bean oil (The Nisshin Oil Mills, Ltd's system) and add up to 75g and methyl alcohol 72g (be 9 times of mole number of stoichiometry aequum), be warmed up to 260 ℃ of maintenances 10 minutes.At this moment pressure is 8.4MPa.Then, chilling, separation of glycerin layer and oil layer.The result that the production rate of the fatty acid methyl ester of oil layer is measured according to gas chromatography is 54%.
Comparative example
Except that temperature of reaction is 240 ℃, under same condition, react.At this moment pressure is 8.1MPa.The result who analyzes similarly to Example 1, the production rate of the fatty acid methyl ester of grease layer is 3%.
Embodiment 2
In the container identical, add acid number and be 6 refining plam oil 69g and methyl alcohol 97g (for 10 times of the mole number of stoichiometry aequum), be warmed up to 280 ℃, kept 10 minutes with embodiment 1.At this moment pressure is 11MPa.With the result that embodiment 1 analyzes equally, the production rate of the fatty acid methyl ester of oil layer is 55%.
Embodiment 3
In the stainless steel steel pipe of diameter 10mm, long 100mm, feeding continuously at embodiment 1 employed lipid per minute 1.5g, methyl alcohol per minute 0.76g (for 5 times of stoichiometry mole number), is that the liquid air speed of benchmark is 13.5/ hour by tri-glyceride).Temperature of reaction is remained on 270 ℃ then, will press reaction pressure to be controlled at 12MPa by discharge control valve.
Separate oil layer from glycerin layer, the result of the production rate of the fatty acid methyl ester of the reactant oil layer of analysis gained is 60%.
By above-mentioned the present invention who constitutes, when carrying out the transesterification reaction of grease class and alcohol, this alcohol be in the atmosphere gas of supercritical state by carrying out transesterification reaction, any without base metal catalysts or acid catalyst can carry out above-mentioned reaction effectively.Under catalyst-free, do not need esterification or remove the pretreatment procedure of the free fatty acids in the grease, can extremely simplify or omit production process.Particularly, this method is useful as making the method that can be used as the lower alkyl esters of diesel engine fuel oil.
Claims (4)
1. method of making fatty acid alkyl ester by fats, be to make grease class and alcohol reaction, in transesterification reaction, add the tri-glyceride that is contained in the grease class and make effective for treatment of premature ejaculation, it is characterized in that any making it reacted in the atmosphere gas of described alcohol one-tenth supercritical state and in without base metal catalysts or acid catalyst.
2. manufacture method according to claim 1 is to make grease class and alcohol make it reaction by the limit continuously at the tubular reactor inner edge.
3. manufacture method according to claim 2 is that to make be that the liquid air speed of benchmark is to react in 2-240/ hour with the triglyceride level ester in tubular reactor.
4. according to any described manufacture method among the claim 1-3, alcohol is the lower alcohol of carbon number 1-5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP284261/1998 | 1998-10-06 | ||
| JP28461198A JP3651280B2 (en) | 1998-10-06 | 1998-10-06 | Inkjet recording head, inkjet recording method, and inkjet recording apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1287572A true CN1287572A (en) | 2001-03-14 |
| CN1111591C CN1111591C (en) | 2003-06-18 |
Family
ID=17680711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99801744A Expired - Fee Related CN1111591C (en) | 1998-10-06 | 1999-10-01 | Make the method for effective for treatment of premature ejaculation by lipid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3651280B2 (en) |
| CN (1) | CN1111591C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329175C (en) * | 2003-02-17 | 2007-08-01 | 深圳市海川实业股份有限公司 | Lubricant for processing polyvinyl chloride |
| CN100365106C (en) * | 2002-06-13 | 2008-01-30 | 京都朗福发展株式会社 | Process for producing fatty acid alkyl ester composition |
| CN101331209A (en) * | 2005-11-18 | 2008-12-24 | 卢敏正 | A method for producing biodiesel using supercritical alcohols |
| CN101550082A (en) * | 2008-04-02 | 2009-10-07 | 拜耳技术工程（上海）有限公司 | Method and device for continuously producing carboxylic ether |
| CN101200674B (en) * | 2006-12-13 | 2010-05-19 | 中国石油化工股份有限公司 | Method for reducing fatty acid value |
| US8288573B2 (en) | 2006-12-15 | 2012-10-16 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
| CN103173281A (en) * | 2011-12-21 | 2013-06-26 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN103184107A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Continuous ester exchange reaction equipment and continuous ester production method using same |
| US8500828B2 (en) | 2006-12-15 | 2013-08-06 | China Petroleum & Chemical Corporation | Process for preparing a bio-diesel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120124896A1 (en) | 2009-06-26 | 2012-05-24 | Research Institute Of Petroleum Processing, Sinopec | Diesel Composition and Method of Increasing Biodiesel Oxidation Stability |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06313188A (en) * | 1993-04-28 | 1994-11-08 | Kao Corp | Production of fatty acid ester |
| JPH07310090A (en) * | 1994-05-19 | 1995-11-28 | Tensei Seiyu Kk | Production of fatty acid methyl ester |
-
1998
- 1998-10-06 JP JP28461198A patent/JP3651280B2/en not_active Expired - Fee Related
-
1999
- 1999-10-01 CN CN99801744A patent/CN1111591C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365106C (en) * | 2002-06-13 | 2008-01-30 | 京都朗福发展株式会社 | Process for producing fatty acid alkyl ester composition |
| CN1329175C (en) * | 2003-02-17 | 2007-08-01 | 深圳市海川实业股份有限公司 | Lubricant for processing polyvinyl chloride |
| CN101331209A (en) * | 2005-11-18 | 2008-12-24 | 卢敏正 | A method for producing biodiesel using supercritical alcohols |
| CN101200674B (en) * | 2006-12-13 | 2010-05-19 | 中国石油化工股份有限公司 | Method for reducing fatty acid value |
| 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 |
| CN101550082A (en) * | 2008-04-02 | 2009-10-07 | 拜耳技术工程（上海）有限公司 | Method and device for continuously producing carboxylic ether |
| CN103173281A (en) * | 2011-12-21 | 2013-06-26 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN103173281B (en) * | 2011-12-21 | 2014-12-31 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN103184107A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Continuous ester exchange reaction equipment and continuous ester production method using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111591C (en) | 2003-06-18 |
| JP2000108379A (en) | 2000-04-18 |
| JP3651280B2 (en) | 2005-05-25 |
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