CN103540413A - Method for preparing fatty acid monoglyceride by taking basic ionic liquid as catalyst - Google Patents
Method for preparing fatty acid monoglyceride by taking basic ionic liquid as catalyst Download PDFInfo
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- CN103540413A CN103540413A CN201310495503.6A CN201310495503A CN103540413A CN 103540413 A CN103540413 A CN 103540413A CN 201310495503 A CN201310495503 A CN 201310495503A CN 103540413 A CN103540413 A CN 103540413A
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- ionic liquid
- fatty acid
- catalyzer
- alkali ionic
- prepare
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- VYWZQURGEMHISO-WEVVVXLNSA-N CCCCC/[N+](/C)=C/C Chemical compound CCCCC/[N+](/C)=C/C VYWZQURGEMHISO-WEVVVXLNSA-N 0.000 description 1
- ZMGNKMXNBLBQCQ-QXMHVHEDSA-N CCCCCC[N+](/C=C\N(C)CC)=C Chemical compound CCCCCC[N+](/C=C\N(C)CC)=C ZMGNKMXNBLBQCQ-QXMHVHEDSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N C[n]1cncc1 Chemical compound C[n]1cncc1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a method for preparing fatty acid monoglyceride by taking basic ionic liquid as a catalyst. The method specifically comprises the following steps of (1), adding oil fat and glycerinum into a reaction kettle according to the mol ratio of 1:(3-8); (2), adding basic ionic liquid as the catalyst, wherein the weight of the basic ionic liquid is 2-12% of that of the oil fat; (3), introducing nitrogen to protect; (4), stirring at 120-200 DEG C for 0.5-3 hours; (5), adding an extraction agent after cooling, standing and layering; (6), taking the upper phase in the step (5), and carrying out reduced-pressure distillation to remove the extraction agent to obtain fatty acid monoglyceride; and (7), taking the lower phase in the step (5), and washing by using a detergent to remove redundant fatty acid monoglyceride in the lower phase, wherein the catalyst and glycerinum can be recycled after washing by the detergent. Compared with the traditional inorganic strong base catalytic method, the method disclosed by the invention has the advantages that the catalytic efficiency is relatively high; the product separation and post-treatment processes are very simple; the basic ionic liquid and the glycerinum can be recycled for next reaction after being simply processed.
Description
Technical field
The present invention relates to the preparation method of monoglyceride, particularly a kind of alkali ionic liquid that adopts is the method that catalyzer is prepared glycerine monofatty ester, belongs to chemical industry technical field.
Background technology
Monoglyceride (Monoglycerides), be called for short mono-glycerides (MG), it is a kind of polyol-based non-ionic surfactant, be widely used as emulsifying agent and the dispersion agent of the aspects such as daily chemical industry such as food, dairy products industry and makeup, toothpaste and hair conditioner, also can in fiber finishing process, be used as emulsifying agent, in polyethylene, polypropylene etc., making static inhibitor, is the fatty acid ester tensio-active agent of consumption maximum.In addition, because mono-glycerides has good bio-compatibility, in pharmaceutical industries, also have important application, as the mono-glycerides that contains polyunsaturated fatty acid (CLA, EPA, DHA) has prophylactic effect to cardiovascular disorder.
The synthetic method of mono-glycerides can be divided into chemical catalysis synthesis method and enzyme catalysis synthesis method.Industrial most widely used be chemical catalysis synthesis method, comprise two kinds of base types of direct esterification and glycerine solution.Direct esterification is the method for synthetic mono-glycerides the earliest, i.e. lipid acid and glycerine direct esterification under the effect of catalyzer generates the mixture of single, double and three acid esters of glycerine.In the disclosed preparation method of Chinese patent " a kind of glycerol fatty acid ester its preparation method " (Granted publication CN101691525B), take lipid acid and glycerine as raw material, adopting the highly basic such as sodium carbonate, potassium hydroxide, sodium hydroxide is catalyzer, in temperature of reaction, be at 200～245 ℃, to be incubated esterification 40-90min, can obtain the product that contains mono-glycerides.The temperature of reaction required due to this alkali catalyst is higher, Chinese patent " a kind of glycerol fatty acid ester its preparation method " (application publication number CN102701966A) improves catalyzer, adopting N-alkyl pyrrolidone group toluene sulfonic acide ionic liquid as catalyzer, is at 90～110 ℃, to react just can obtain mono-glycerides in 2～4 hours in temperature.
Along with the price of the lipid acid such as stearic acid goes up day by day, adopt the manufacturer of direct esterification obviously to reduce.And glycerine solution is that to take grease and glycerine be raw material, under the effect of catalyzer, carries out transesterification reaction and generate Tegin 55G.Because the price of grease is relatively low, therefore adopt glycerine solution obviously to reduce production costs.At present, the catalyzer that glycerine solution adopts is mainly the basic catalysts such as sodium hydroxide or potassium hydroxide or sodium ethylate.In the disclosed method of Chinese patent " one-step process for producting mono-fatty glyceride " (Granted publication CN86104493B), take sodium hydroxide as catalyzer, catalysis Vegetable oil lipoprotein and glycerine carry out transesterification reaction and obtain mono-glycerides.Yet the compatibility of grease and glycerine and these highly basic is poor, need the higher higher and longer reaction times of temperature of reaction.In addition, after having reacted, need to add the mineral acids such as sulfuric acid or hydrochloric acid to neutralize, basic catalyst could be separated from product, can cause like this complex manufacturing and can produce a large amount of waste water, contaminate environment.
Therefore, need a kind of catalytic efficiency higher, be easy to and product separation, eco-friendly catalyzer, to simplify production technique and to reduce production costs.
Summary of the invention
The object of the invention is to replace the method that traditional inorganic strong alkali catalyzed transesterification is prepared monoglyceride, a kind of efficient, eco-friendly catalyzer is provided, under relatively gentle reaction conditions, catalysis grease reacts the novel method of preparing monoglyceride with glyceride transesterification, for monoglyceride synthetic provides an eco-friendly operational path.
The alkali ionic liquid of take is prepared the method for mono fatty acid glycidol as catalyzer, and concrete preparation method is as follows:
1) by grease and glycerine, the ratio with mol ratio 1:3～8 joins in reactor;
2) add account for grease weight 2～12% alkali ionic liquid as catalyzer;
3) be filled with nitrogen protection;
4) under the condition of 120～200 ℃, stir 0.5～3 hour;
5) after cooling, add extraction agent, static layering;
6) the upper strata phase of learning from else's experience after step 5), underpressure distillation removes extraction agent, obtains monoglyceride;
7) lower floor's phase of learning from else's experience after step 5), with detergent washing, remove lower floor mutually in unnecessary monoglyceride, washing composition rear catalyst and glycerine can be recycled.
On the basis of such scheme, the negatively charged ion of described alkali ionic liquid is: hydroxide radical, imidazoles root, carbonate, acetate or phenol root.
On the basis of such scheme, described extraction agent is sherwood oil, hexane, chloroform, tetracol phenixin or toluene.
On the basis of such scheme, described grease is Vegetable oil lipoprotein or animal grease.
On the basis of such scheme, the temperature of reaction of described step 4) is 160 ℃.
On the basis of such scheme, the reaction times of described step 4) is 2 hours.
On the basis of such scheme, described Vegetable oil lipoprotein is: soybean oil, rapeseed oil, Oleum Gossypii semen, Trisun Oil R 80, Cortex jatrophae wet goods.
On the basis of such scheme, described animal grease is lard.
On the basis of such scheme, the washing composition in described step 7) is sherwood oil or toluene.
The present invention compares with the method for traditional inorganic strong alkali catalysis, has following advantage:
(1) catalytic efficiency of alkali ionic liquid is higher, can play the dual function of alkaline catalysts and phase-transfer catalyst, and required temperature of reaction is lower, the reaction times is shorter;
(2) alkali ionic liquid and product are not miscible, after standing, can carry out separated with product, make separation and the aftertreatment technology of product very simple, without passing through again treatment steps such as adding acid neutralization, washing, also can avoid in process of production the generation of the pollutents such as waste water, belong to eco-friendly operational path simultaneously.
(3) alkali ionic liquid and glycerine can be used for next time reaction after simple process, and the catalytic performance of ionic liquid has no reduction, can effectively reduce production costs.
Embodiment
Following examples, only for the present invention will be further described, are not for limiting the scope of the invention.
Embodiment 1
[BMIm] Im alkaline ionic liquid catalyst of 100kg rapeseed oil, 90kg glycerine and 10kg is joined in reactor; under nitrogen protection; at 160 ℃, stirring reaction is 2 hours; cooling and add petroleum ether extraction product; after stratification, separate upper strata phase; after underpressure distillation removes sherwood oil, obtain monoglyceride, yield is 61%.Catalyzer and the glycerine of lower floor's phase can be recycled after petroleum ether.
Embodiment 2
[BMIm] OH alkaline ionic liquid catalyst of 100kg Oleum Gossypii semen, 80kg glycerine and 8kg is joined in reactor; under nitrogen protection; at 150 ℃, stirring reaction is 3 hours; cooling and add ethyl acetate extraction product; after stratification, separate upper strata phase; after underpressure distillation desolvation, obtain monoglyceride, yield is 52%.Catalyzer and the glycerine of lower floor's phase can be recycled after toluene wash.
Embodiment 3:
By [BMIm] CH of 100kg lard, 80kg glycerine and 10kg
3cOO alkaline ionic liquid catalyst joins in reactor, and under nitrogen protection, at 190 ℃, stirring reaction is 2 hours; cooling and add chloroform extraction product, after stratification, separate upper strata phase, after underpressure distillation desolvation; obtain monoglyceride, yield is 58%.Catalyzer and the glycerine of lower floor's phase can be recycled after petroleum ether.
Embodiment 4:
[HMIm] Im alkaline ionic liquid catalyst of 100kg Trisun Oil R 80,80kg glycerine and 8kg is joined in reactor; under nitrogen protection; at 170 ℃, stirring reaction is 1 hour; cooling and add carbon tetrachloride extraction product; after stratification, separate upper strata phase; after underpressure distillation desolvation, obtain monoglyceride, yield is 68%.Catalyzer and the glycerine of lower floor's phase can be recycled after toluene wash.
Embodiment 5:
[HMIm] Im alkaline ionic liquid catalyst of 100kg rapeseed oil, 70kg glycerine and 4kg is joined in reactor; under nitrogen protection; at 170 ℃, stirring reaction is 1.5 hours; cooling and add toluene extraction product; after stratification, separate upper strata phase; after underpressure distillation desolvation, obtain monoglyceride, yield is 59%.Catalyzer and the glycerine of lower floor's phase can be recycled after petroleum ether.
Embodiment 6:
[BPy] Im alkaline ionic liquid catalyst of 100kg jatropha curcas oil, 90kg glycerine and 10kg is joined in reactor; under nitrogen protection; at 180 ℃, stirring reaction is 1 hour; cooling and add petroleum ether extraction product; after stratification, separate upper strata phase; after underpressure distillation desolvation, obtain monoglyceride, yield is 65%.Catalyzer and the glycerine of lower floor's phase can be recycled after petroleum ether.
Embodiment 7:
[HPy] Im alkaline ionic liquid catalyst of 100kg Oleum Gossypii semen, 70kg glycerine and 6kg is joined in reactor; under nitrogen protection; at 160 ℃, stirring reaction is 1 hour; cooling and add appropriate petroleum ether extraction product; after stratification, separate upper strata phase; after underpressure distillation desolvation, obtain monoglyceride, yield is 63%.Catalyzer and the glycerine of lower floor's phase can be recycled after petroleum ether.
Above-mentioned embodiment is intended to illustrate the present invention and can be professional and technical personnel in the field's realization or use; it will be apparent for those skilled in the art that above-mentioned embodiment is modified; therefore the present invention includes but be not limited to above-mentioned embodiment; any these claims or specification sheets of meeting described; meet and principle disclosed herein and novelty, the method for inventive features, technique, product, within all falling into protection scope of the present invention.
Embodiment alkaline ionic liquid catalyst molecular structure and chemical name
[BMIm] Im1-butyl-3-Methylimidazole imidazole salts
[BMIm] OH hydroxide 1-butyl-3-methylimidazole salt
[BMIm] CH
3cOO1-butyl-3-Methylimidazole acetate
[HMIm] Im1-is base-3-Methylimidazole imidazole salts
[BPy] Im1-butyl-pyridine imidazole salts
[HBy] Im1-is base-pyridine imidazole salts.
Claims (9)
1. the alkali ionic liquid of take is prepared the method for mono fatty acid glycidol as catalyzer, it is characterized in that concrete preparation method is as follows:
1) by grease and glycerine, the ratio with mol ratio 1:3～8 joins in reactor;
2) add account for grease weight 2～12% alkali ionic liquid as catalyzer;
3) be filled with nitrogen protection;
4) under the condition of 120～200 ℃, stir 0.5～3 hour;
5) after cooling, add extraction agent, static layering;
6) the upper strata phase of learning from else's experience after step 5), underpressure distillation removes extraction agent, obtains monoglyceride;
7) lower floor's phase of learning from else's experience after step 5), with detergent washing, remove lower floor mutually in unnecessary monoglyceride, washing composition rear catalyst and glycerine can be recycled.
2. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that the negatively charged ion of described alkali ionic liquid is: hydroxide radical, imidazoles root, carbonate, acetate or phenol root.
3. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that described extraction agent is sherwood oil, hexane, ethyl acetate, chloroform, tetracol phenixin or toluene.
4. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that described grease is Vegetable oil lipoprotein or animal grease.
5. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, the temperature of reaction that it is characterized in that described step 4) is 160 ℃.
6. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, the reaction times that it is characterized in that described step 4) is 2 hours.
7. according to claim 1ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that the washing composition in described step 7) is sherwood oil or toluene.
8. according to claim 4ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that described Vegetable oil lipoprotein is: soybean oil, rapeseed oil, Oleum Gossypii semen or jatropha curcas oil.
9. according to claim 4ly a kind ofly take alkali ionic liquid and prepare the method for mono fatty acid glycidol as catalyzer, it is characterized in that described animal grease is lard.
Priority Applications (1)
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| CN201310495503.6A CN103540413B (en) | 2013-10-21 | 2013-10-21 | Method for preparing fatty acid monoglyceride by taking basic ionic liquid as catalyst |
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| CN201310495503.6A CN103540413B (en) | 2013-10-21 | 2013-10-21 | Method for preparing fatty acid monoglyceride by taking basic ionic liquid as catalyst |
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| CN103540413A true CN103540413A (en) | 2014-01-29 |
| CN103540413B CN103540413B (en) | 2015-05-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152276A (en) * | 2014-07-14 | 2014-11-19 | 石家庄新泰特种油有限公司 | Method for catalytic synthesis of monoglyceride from ionic liquid |
| CN105647654A (en) * | 2016-01-18 | 2016-06-08 | 佳力士添加剂（海安）有限公司 | Monoglyceride preparation technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747997A (en) * | 2010-01-25 | 2010-06-23 | 南昌大学 | Method for preparing monolaurin |
| CN102876466A (en) * | 2012-10-05 | 2013-01-16 | 盐城师范学院 | Method for catalyzing ester exchange reaction with alkaline ionic liquid |
-
2013
- 2013-10-21 CN CN201310495503.6A patent/CN103540413B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747997A (en) * | 2010-01-25 | 2010-06-23 | 南昌大学 | Method for preparing monolaurin |
| CN102876466A (en) * | 2012-10-05 | 2013-01-16 | 盐城师范学院 | Method for catalyzing ester exchange reaction with alkaline ionic liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152276A (en) * | 2014-07-14 | 2014-11-19 | 石家庄新泰特种油有限公司 | Method for catalytic synthesis of monoglyceride from ionic liquid |
| CN105647654A (en) * | 2016-01-18 | 2016-06-08 | 佳力士添加剂（海安）有限公司 | Monoglyceride preparation technology |
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| CN103540413B (en) | 2015-05-20 |
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Granted publication date: 20150520 Termination date: 20201021 |