CN100548964C - A kind of esterification process of lipid acid - Google Patents
A kind of esterification process of lipid acid Download PDFInfo
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- CN100548964C CN100548964C CNB2006100761898A CN200610076189A CN100548964C CN 100548964 C CN100548964 C CN 100548964C CN B2006100761898 A CNB2006100761898 A CN B2006100761898A CN 200610076189 A CN200610076189 A CN 200610076189A CN 100548964 C CN100548964 C CN 100548964C
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Abstract
A kind of esterification process of lipid acid comprises: lipid acid is reacted under the condition of pressure 4～12MPa 200～400 ℃ of temperature with pure, collect fatty acid ester.The carbon number of said lipid acid is 10～30.Said alcohol is that carbon number is 1～6 straight chain or the Fatty Alcohol(C12-C14 and C12-C18) that has side chain.The inventive method is compared with traditional esterification technique, not only has higher fatty acid ester yield, and does not need catalyzer, and technical process is greatly simplified; No spent acid discharging, environmentally safe; Alcohol/sour mol ratio is low, has effectively improved usage ratio of equipment, has reduced the yield of methyl alcohol, and energy consumption is significantly descended.
Description
Technical field
The present invention relates to the preparation method of fatty acid ester.
Background technology
Lipid acid and alcohol carry out esterification and generate fatty acid ester, the reaction that generates fatty acid ester is reversible balanced reaction, and long chain fatty acid is under general operational condition, even stirring, vacuumizing reaction down, in time remove the water that reaction generates, speed of response is also very slow.The boiling point of long chain fatty acid is all higher, and for improving the transformation efficiency of long chain fatty acid, reaction generally needs bigger alcohol/lipid acid mol ratio and long reaction times, alcohol/lipid acid mol ratio even up to 44.5: 1.Under the condition of less alcohol/lipid acid mol ratio, use sulfuric acid to do catalyzer induce reaction the easily charing of thing and the generation of side reaction, but can use the comparatively gentle tosic acid of character etc.Adopt the shortcoming of high alcohol/lipid acid mol ratio to be: 1. when having improved conversion rate of fatty acid, to reduce pure transformation efficiency, reduced usage ratio of equipment widely; 2. strengthen pure yield, caused energy consumption significantly to rise.
JP04001156A2 has introduced and has a kind ofly contained IV family metal and SO
4 2-Solid acid have down reaction conditions: 230 ℃, be decompressed to 5mmHg, oleic acid and pure esterification prepare ester, and yield can reach 95%.But the catalyzer life cycle is short, needs frequently to change.
JP11263750 adopts KWI56 lipase as catalyzer, at 35 ℃ oleic acid and methyl alcohol is carried out the 50h esterification and prepares Witconol 2301, and the ester yield can reach 87.2%, but enzyme catalyst needs frequent replacing.
By above-mentioned prior art as can be seen: lipid acid and pure esterification, generally need an acidic catalyst, as sulfuric acid, it can produce a large amount of spent acid and waste water, environment is produced pollute.As use solid acid, catalyst deactivation is fast.In addition, for longer chain fatty acid, required alcohol/lipid acid mol ratio height.Adopt lipase as catalyzer, the subject matter of this method is that catalyzer is expensive, and is easy to inactivation in methyl alcohol.And production concentration is very low in the reactor, puies forward dense expense costliness, as is used for commercial production and need be permitted great reactor, and facility investment is big.
Summary of the invention
The invention provides a kind of esterification process of longer chain fatty acid, this method need not catalyzer, and fatty acid ester yield height.
Method provided by the invention comprises: lipid acid is reacted under the condition of pressure 4～12MPa 200～400 ℃ of temperature with pure, collect fatty acid ester.
Specifically, lipid acid and alcohol are transported in the reactor, 200～400 ℃ of temperature of reactor, under the condition of pressure 4～12MPa, a kind of material or whole system in lipid acid or the alcohol are under the super critical condition, carry out esterification, lipid acid is 1.5～20: 1 with the mol ratio of alcohol, preferred 3～12: 1.
The preferred tubular reactor of said reactor.
Temperature raises, and helps improving reaction conversion ratio, but temperature is when too high, and reaction product is black, has burnt matter to produce.Therefore, temperature remains on 200～400 ℃ and is advisable, and preferred 280～370 ℃, more preferably 320～370 ℃.
Pressurization is to reacting favourable, but pressure is too high, and it is more that the investment of device and process cost are improved, so pressure should be at 4～12MPa, preferred 6～11MPa is advisable.
The reaction that generates fatty acid ester is reversible balanced reaction, and for improving the transformation efficiency of lipid acid, bigger alcohol/sour mol ratio can make balance move to the product direction, but excessive mol ratio shortens material residence time in reactor, and transformation efficiency descends.Plant energy consumption and process cost are increased, usage ratio of equipment is descended.So alcohol/sour mol ratio remains on 1.5～20: 1, preferred 3～12: 1, material residence time in reactor is preferably 0.2～3 hour.
Said lipid acid can be carbon number greater than 10 longer chain fatty acid, also can be carbon number less than 10 short chain fatty acid.Wherein the carbon number of longer chain fatty acid can be 10～30, preferred 14～24.Aliphatic group can be straight chain or have side chain, can contain or not contain unsaturated link(age) in the aliphatic group, preferably contain unsaturated link(age).The general normal temperature of unsaturated fatty acids for liquid, is convenient to charging down.For example, said lipid acid can be docosahexenoic acid, docosapentanoic acid, eicosapentaenic acid, arachidonic acid, therapic acid, lauric acid, ten tetra-carbonics, palmitinic acid (hexadecanoic acid), Zoomeric acid (suitable-palmitoleic acid) stearic acid (octadecanoic acid), oleic acid (suitable-the 9-octadecenoic acid), linolic acid (suitable-9, suitable-the 12-octadecadienoic acid), linolenic acid (suitable-9, suitable-12, suitable-the 15-punicic acid), eicosanoic acid (arachic acid), eicosenoic acid (suitable-the 5-eicosenoic acid) docosoic (docosoic acid), erucic acid (suitable-the 13-Decosahedaenoic acid) or the like.
Said alcohol is that carbon number is 1～6 straight chain or the Fatty Alcohol(C12-C14 and C12-C18) that has side chain, particular methanol, ethanol, propyl alcohol or butanols.
The inventive method is compared with traditional esterification technique, conversion rate of fatty acid height not only, and do not need catalyzer, technical process is greatly simplified; No spent acid discharging, environmentally safe; Alcohol/sour mol ratio is low, has effectively improved usage ratio of equipment, has reduced the yield of methyl alcohol, and energy consumption is significantly descended.
Embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
Embodiment 1
Respectively oleic acid and methyl alcohol are provided in the tubular reactor with 1: 4.4 (mol ratio), 320 ℃ of temperature, react under the condition of pressure 6.4MPa, oleic acid transformation efficiency 95mol% almost all changes into fatty acid methyl ester.
Embodiment 2
Respectively oleic acid and methyl alcohol are provided in the tubular reactor with 1: 5 (mol ratio), are reflected at 320 ℃ of temperature, react under the condition of pressure 7.2MPa, oleic acid transformation efficiency 96.5mol% almost all changes into fatty acid methyl ester.
Embodiment 3
Respectively oleic acid and methyl alcohol are provided in the tubular reactor with 1: 10 (mol ratio), 350 ℃ of temperature, react under the condition of pressure 9MPa, oleic acid transformation efficiency 95.5mol% almost all changes into fatty acid methyl ester.
Embodiment 4
Respectively oleic acid and methyl alcohol are provided in the tubular reactor with 1: 3.5 (mol ratio), 270 ℃ of temperature, react under the condition of pressure 8MPa, oleic acid transformation efficiency 90.7mol% almost all changes into fatty acid methyl ester.
Embodiment 5
Respectively oleic acid and butanols are provided in the tubular reactor with 1: 6 (mol ratio),, react under the condition of pressure 8MPa, oleic acid transformation efficiency 81.5mol% 260 ℃ of temperature.
Claims (12)
1. the esterification process of a lipid acid is that lipid acid is reacted in reactor under the condition of pressure 4～9MPa 280～370 ℃ of temperature with pure, collects fatty acid ester.
2. in accordance with the method for claim 1, it is characterized in that reaction pressure is 6～8MPa.
3. in accordance with the method for claim 1, it is characterized in that alcohol/sour mol ratio is 1.5～20: 1.
4. in accordance with the method for claim 3, it is characterized in that alcohol/sour mol ratio is 3～12: 1.
5. in accordance with the method for claim 1, it is characterized in that the residence time of material in reactor is 0.2～3 hour.
6. in accordance with the method for claim 1, it is characterized in that the carbon number of said lipid acid is 10～30.
7. in accordance with the method for claim 1, it is characterized in that the carbon number of said lipid acid is 14～24.
8. in accordance with the method for claim 1, it is characterized in that said lipid acid is one or more in docosahexenoic acid, docosapentanoic acid, eicosapentaenic acid, arachidonic acid, lauric acid, ten tetra-carbonics, therapic acid, palmitinic acid, Zoomeric acid, stearic acid, oleic acid, linolic acid, linolenic acid, eicosanoic acid, eicosenoic acid, docosoic or the erucic acid.
9. in accordance with the method for claim 1, it is characterized in that said alcohol is straight chain or the Fatty Alcohol(C12-C14 and C12-C18) that has side chain.
10. in accordance with the method for claim 1, it is characterized in that said alcohol is that carbon number is 1～6 Fatty Alcohol(C12-C14 and C12-C18).
11. in accordance with the method for claim 1, it is characterized in that said alcohol is methyl alcohol, ethanol, propyl alcohol or butanols.
12. in accordance with the method for claim 1, it is characterized in that said reactor is a tubular reactor.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100761898A CN100548964C (en) | 2006-04-28 | 2006-04-28 | A kind of esterification process of lipid acid |
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| CNB2006100761898A CN100548964C (en) | 2006-04-28 | 2006-04-28 | A kind of esterification process of lipid acid |
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| CN101062894A CN101062894A (en) | 2007-10-31 |
| CN100548964C true CN100548964C (en) | 2009-10-14 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544559B (en) * | 2009-02-18 | 2014-03-05 | 江西省宜春远大化工有限公司 | Method for separating and extracting isostearic acid from monomer acid |
| JP6497496B2 (en) * | 2014-06-04 | 2019-04-10 | 日産化学株式会社 | Method for producing multi-branched aliphatic ester |
| CN106748759A (en) * | 2015-11-24 | 2017-05-31 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of bio-based pentaerythritol fatty ester |
| CN108048224A (en) * | 2018-01-25 | 2018-05-18 | 南通金利油脂工业有限公司 | Aliphatic acid produces the device and method of aliphatic ester |
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Non-Patent Citations (4)
| Title |
|---|
| 单甘酯的制备与分离. 湛日景等.中国油脂，第2期. 1993 |
| 单甘酯的制备与分离. 湛日景等.中国油脂，第2期. 1993 * |
| 甘油单月硅酸酯的制备及医药应用. 宋国胜等.应用化工，第30卷第5期. 2001 |
| 甘油单月硅酸酯的制备及医药应用. 宋国胜等.应用化工，第30卷第5期. 2001 * |
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