CN1232036A - Production of sucrose ester by homogeneous solventless process - Google Patents
Production of sucrose ester by homogeneous solventless process Download PDFInfo
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- CN1232036A CN1232036A CN 99113469 CN99113469A CN1232036A CN 1232036 A CN1232036 A CN 1232036A CN 99113469 CN99113469 CN 99113469 CN 99113469 A CN99113469 A CN 99113469A CN 1232036 A CN1232036 A CN 1232036A
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Abstract
A non-solvent homogeneous process for preparing sucrose ester includes such steps as mixing sucrose and fatty acid ester with soap body of fatty acid, adding biosurfactant and homogenous synthesis. Said biosurfactant is rhamnolipid or modified rhamnolipid, or sophorolipid or modified sophorolipid, or the mixture of rhamnolipid or modified rhamnolipid with sophorolipid or modified sophorolipid. The reaction is effected at 110-145 deg.C and 10-30 mmHg for 1-4 hr. The yield of reaction is 55-60%. Its advantages are uniform low-temp reaction, no toxicity, low cost and high conversion.
Description
Sucrose ester, i.e. sucrose fatty ester is prominent a kind of tensio-active agent at present, its good surface properties and widely the scope of application be subjected to people's welcome.Japan, the U.S., European Economic Community various countries, the FAO of Food and Argriculture OrganizationFAO and the WHO of the World Health Organization etc. all approved sucrose ester are a kind of foodstuff additive.
The surface tension that sucrose ester can reduce water reaches 32.5mN/m, and interfacial tension reaches 14mN/m between reduction water and n-Hexadecane.The sucrose ester nontoxicity, do not have smell, colourless, tasteless, human body skin is had no stimulation, have good emulsifying, dispersion, solubilising, numerous characteristics such as wetting, fresh-keeping.Can be widely used in fields such as food, medicine, makeup, sugaring, preserving fruit and vegetable utilizing, chemical fertilizer, feed and explosive.Become sucrose and edible fat acid after the sucrose ester hydrolysis, have nutritive value.Different with general synthetic tensio-active agent, sucrose ester can both biological degradation under aerobic and anaerobic condition, and this handles for three wastes of environment and has brought convenience.
Synthesis of sucrose ester generally adopts transesterification reaction theoretically: promptly in " Surfactants in Consumer Products " .Edited by J.Falbe, the sucrose of mentioning among the springer-Verlag.Berlin.Heidelberg.New York.P.101.1987 and the permutoid reaction of glycerol fatty acid ester; And " Sugar EstersPreparation and Applications " .London, the mentioned sucrose and the transesterification reaction of fatty acid ester among the Noyes DataCorporation.1974.At present, in the world synthesis of sucrose ester adopt three kinds of feasible synthetic methods are arranged: one. be that sucrose and lipid acid acyl chlorides react in the presence of pyridine; Two. be the reaction of sucrose and fatty acid anhydride, as U.S.Pat, disclosed sucrose and isobutyl acid anhydride react in acetic aid medium and prepare oxalic acid six isobutyl ester sucrose ester SAIB in 3096324; Three. be that sucrose and fatty acid ester carry out transesterification reaction.And first method causes the productive rate of this method not high because the lipid acid acyl chlorides is easy to deliquescence in air; Second method is owing to complicated operation, and product cost is also high; These two kinds of methods have limited the application of sucrose ester; The third method is owing to be that reactant is in the presence of catalyzer, high temperature decompression or high-temperature pressure react, this method on the cost of preparation sucrose ester tensio-active agent than the excellent benefit of the first two kind method, the research that people carry out this is also a lot, and the difference of sucrose and fatty acid ester physico-chemical property has determined can only take place inhomogeneous reaction in same solvent, directly has influence on the transformation efficiency of reactant.The technological process of differential responses condition for this reason, is suggested in succession.Hasssnell etc. have selected amphoteric solvent N in US.Pat2970962, dinethylformamide DMF is a reaction medium, with salt of wormwood is catalyzer, and sucrose and fatty acid methyl ester are reacted under 90 ℃, and reduces pressure except that the by product of dereaction in reaction process.Though DMF can improve the contact between the reactant, it is a toxicant, and the unavoidable residual DMF that has of final product is restricted the use range of product.Osipow etc. are at U.S.pat, replace DMF with propylene glycol in 3480616, will react under reduced pressure with the butter methyl compound after the sucrose dissolved; People such as Nebnaska adopt emulsifying agent again, and reactant is prepared into the microemulsion state, and emulsion reaction is carried out in decompression.Though this two kinds of methods have been avoided toxicant residual in the product, factors such as solvent make the production cost of sucrose ester higher.Japanese Patent JP311092 in 1989 introduces and adopts solventless method to prepare the tensio-active agent sucrose ester, and entire reaction is carried out in water solution system, does not use any noxious solvent, and obviously the productive rate of this method is not high.Feuge etc. are at Brit, Pat., GB1332190 has proposed a solvent-free method for preparing sucrose ester, sucrose is molten state and fatty acid methyl ester reacts in this method, temperature of reaction is up to 170-190 ℃, but sucrose is very unstable under the high temperature, the coking of very easily luming, and reaction generally just had to stop in 2-20 minute.Though done improvement by modest, the gloomy positive youth down in the wood south of Japan etc. afterwards, and reached 50% yield, need decompression in synthetic, fatty acid methyl ester needs again to prepare separately, and product cost is still very high.People such as Parker were at Brit in 1973, Pat., all proposed directly to obtain the method for sucrose ester in GB1339053 and the U.S. Pat 4298730 with the sucrose reaction by fatty acid glyceryl ester, the particulate state sucrose of equimolar amount directly and glycerin fatty acid ester in the presence of the catalyzer carbonic acid potassium of 5-12% in 110-140 ℃ temperature, react under the normal pressure, need not any solvent, the content of sucrose ester can reach 40% in the reactant, Parker points out in the text, and tensio-active agent has and helps the carrying out that react.But this method is at high temperature, the viscosity degradation of glyceryl ester, and it is difficult to make that granular sucrose suspends, and exists although have to stir, and caking and coking take place in sucrose, and along with the time increases, the coking intensification.1980, Harry etc. proposed a kind of method with the fatty acid soaps accelerated reaction.In experimenting, we find out that, when reactant and soap body be blended in necessarily than the time, promptly become a homogeneous mixture, and do not change with the variation in temperature and reaction times.The synthetic method of sucrose ester and operational path are constantly improving and are developing, experienced typically the solvent synthesis method is arranged, microemulsified synthesis method, solvent-free vacuum synthesis method and solvent-free high-temperature pressure synthesis method.
Purpose of the present invention just provided a kind of with sucrose and fatty acid ester as reactant, and add the production method that bio-surfactant carries out homogeneous phase solventless method synthesis of sucrose ester again after the lipid acid soap body mixes.
The present invention is achieved by the following scheme, and promptly makes raw material with saturated food oils, by the esterification obtain fatty acid ester of saturated food oils; The fatty acid ester that will prepare, sucrose add in the lipid acid soap body that is formed through the regular hour under suitable temperature and pressure by lipid acid and inorganic salt and mix again, and add behind the bio-surfactant under certain pressure and temperature condition to react through after a while and promptly obtain sucrose ester.Wherein the esterification of saturated food oils can be esterification or ethyl esterization; Lipid acid and inorganic salt are 0.5-1 hour obtain fatty acid soap body of reaction under the pressure of 120-130 ℃ and 100-150mmHg, and inorganic salt are K
2CO
3, lipid acid is stearic acid or other long chain fatty acid; Bio-surfactant is the mixture of the sophorolipid of the rhamnolipid of the sophorolipid of rhamnolipid, sophorolipid or modification of rhamnolipid or modification and different proportioning rhamnolipid or modification and sophorolipid or modification; Reaction pressure is 10-30mmHg, and temperature of reaction is 110-145 ℃, and the reaction times is 1-4 hour, and the reaction yield is 55-60%.Key of the present invention is can be according to the different sucrose esters of producing different HLB values of bio-surfactant consumption and proportioning, to adapt to the demand in market, wherein the feed ratio of reactant fatty acid ester and sucrose is 1: 2-2: 1 (w/w), the rhamnolipid of rhamnolipid or modification, the consumption of the mixture of the rhamnolipid of the sophorolipid of sophorolipid or modification and different proportioning rhamnolipid or modification and the sophorolipid of sophorolipid or modification is the 0.5-5% of reaction raw materials total amount, and the sophorolipid proportioning of the rhamnolipid of rhamnolipid or modification and sophorolipid or modification is 1: 5～5: 1 (w/w).
Present device is simple, easy to operate, and the reaction times is shorter, saves power consumption; Its sucrose ester suitability for industrialized production yield can reach 55-60%; The present invention have reaction evenly, low, the nontoxicity of temperature, cost is low, transformation efficiency is high characteristics, can be applicable to industrial production.
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1
In 1 liter three-necked bottle, add saturated plant or animal oil 270g, methyl alcohol or ethanol 165ml, under agitation drip vitriol oil 3ml, back flow reaction 6-8 hour, after the question response thing static layering, upper strata oily product is washed with water to PH neutrality, obtains corresponding mixed methyl aliphatic ester or fatty-acid ethyl ester 277g.
In the 500ml three-necked bottle, add the 22g palmitinic acid, add Anhydrous potassium carbonate 6g after the heated and stirred to 100 ℃, at 130 ℃, 100mmHg reaction down generated lipid acid sylvite in 1 hour.The mixed methyl aliphatic ester or the fatty-acid ethyl ester that add above-mentioned preparation then, edible sucrose, add homogeneous catalyst one biological tensio-active agent again, wherein sophorolipid or modification sophorolipid: the rhamnolipid of rhamnolipid or modification (w/w) has certain proportioning, reacts the regular hour under certain temperature and pressure.Reaction obtains product after finishing: have different HLB value sucrose esters.Data such as following table:
| Numbering | Raw material (g) | Temperature of reaction (℃) | Reaction times (h) | Homogeneous catalyst | Sucrose ester (g) | Yield (%) | HL B value * | ||
| Sucrose | Fatty acid ester | Consumption (g) | Sophorolipid: rhamnolipid (w/w) | ||||||
| ?1 | ????65 | ????40 | ?125±2 | ?2.3 | ?4 | ????1∶1 | ?62.6 | ?59.6 | ?11 |
| ?2 | ????60 | ????45 | ?130±2 | ?2.3 | ?3 | ????2∶1 | ?59.5 | ?56.7 | ?9 |
| ?3 | ????70 | ????35 | ?123±2 | ?2 | ?1.5 | ????1∶2 | ?57.9 | ?55.1 | ?13 |
| ?4 | ????72 | ????33 | ?122±2 | ?2.2 | ?3.5 | ????1∶3.8 | ?61.2 | ?58.3 | ?15 |
| ?5 | ????57 | ????48 | ?132±2 | ?2.5 | ?1.8 | ????2.7∶1 | ?58.8 | ?56 | ?7 |
| ?6 | ????73 | ????32 | ?112±2 | ?4 | ?5 | ????1∶5 | ?61.9 | ?58.9 | ?15 |
| ?7 | ????55 | ????50 | ?143±2 | ?1 | ?0.6 | ????5∶1 | ?57.8 | ?55 | ?6 |
* the mensuration of HLB value system is calculated behind the single, double and polyester content by the high pressure liquid chromatographic analysis product.
Embodiment 2
In 1 liter three-necked bottle, add saturated plant or animal oil 270g, methyl alcohol or ethanol 165ml, under agitation drip vitriol oil 3ml, back flow reaction 6-8 hour, after the question response thing static layering, upper strata oily product is washed with water to PH neutrality, obtains corresponding mixed methyl aliphatic ester or fatty-acid ethyl ester 277g.
In the 500ml three-necked bottle, add the 22g stearic acid, add Anhydrous potassium carbonate 6g after the heated and stirred to 100 ℃, at 125 ℃, 130mmHg reaction down generated lipid acid sylvite in 40 minutes.The mixed methyl aliphatic ester or the fatty-acid ethyl ester that add above-mentioned preparation then, edible sucrose adds the rhamnolipid of homogeneous catalyst one rhanolipid as biosurfactant or modification again, reacts the regular hour under certain temperature and pressure.Reaction obtains product after finishing: the sucrose ester with higher HLB value.Data such as following table:
| Numbering | Raw material (g) | Temperature of reaction (℃) | Reaction times (h) | The rhamnolipid of rhamnolipid or modification (g) | Sucrose ester (g) | Yield (%) | HL B value * | |
| Sucrose | Fatty acid ester | |||||||
| ?1 | ????65 | ????40 | ?110±2 | ???4 | ????2.5 | ?58.1 | ?55.3 | ?13 |
| ?2 | ????60 | ????45 | ?143±2 | ???1 | ????0.8 | ?58.5 | ?55.7 | ?11 |
| ?3 | ????70 | ????35 | ?130±2 | ???2 | ????3.5 | ?60.4 | ?57.5 | ?15 |
| ?4 | ????72 | ????33 | ?120±2 | ???2.3 | ????4.5 | ?61.2 | ?58.3 | ?16 |
| ?5 | ????73 | ????32 | ?125±2 | ???2.5 | ????5 | ?61.7 | ?58.8 | ?16 |
* calculate behind the mensuration of HLB value system, the polyester content single, double by the high pressure liquid chromatographic analysis product.
Embodiment 3
In 1 liter three-necked bottle, add saturated plant or animal oil 270g, methyl alcohol or ethanol 165ml, under agitation drip vitriol oil 3ml, back flow reaction 6-8 hour, after the question response thing static layering, upper strata oily product is washed with water to PH neutrality, obtains corresponding mixed methyl aliphatic ester or fatty-acid ethyl ester 277g.
In the 500ml three-necked bottle, add the 22g palmitinic acid, add Anhydrous potassium carbonate 6g after the heated and stirred to 100 ℃, at 120 ℃, 150mmHg reaction down generated lipid acid sylvite in 0.5 hour.The mixed methyl aliphatic ester or the fatty-acid ethyl ester that add above-mentioned preparation then, edible sucrose adds the sophorolipid of homogeneous catalyst one biological tensio-active agent sophorolipid or modification again, reacts the regular hour under certain temperature and pressure.Reaction obtains product after finishing: have different HLB value sucrose esters.Data such as following table:
| Numbering | Raw material (g) | Temperature of reaction (℃) | Reaction times (h) | The sophorolipid of sophorolipid or modification (g) | Sucrose ester (g) | Yield (%) | HL B value * | |
| Sucrose | Fatty acid ester | |||||||
| ?1 | ????65 | ????40 | ?110±2 | ?4 | ????2.5 | ?57.9 | ?55.1 | ?7 |
| ?2 | ????60 | ????45 | ?120±2 | ?2.5 | ????0.5 | ?57.3 | ?54.6 | ?6 |
| ?3 | ????70 | ????35 | ?130±2 | ?2.2 | ????5 | ?60.4 | ?57.5 | ?9 |
| ?4 | ????55 | ????50 | ?143±2 | ?1 | ????2 | ?59.8 | ?57.0 | ?5 |
| ?5 | ????57 | ????48 | ?135±2 | ?2 | ????4 | ?60.9 | ?58.0 | ?4 |
* the mensuration of HLB value system is calculated behind the single, double and polyester content by the high pressure liquid chromatographic analysis product.
Claims (3)
1. the method for a production of sucrose ester by homogeneous solventless process, be to be reactant with fatty acid ester, sucrose and lipid acid soap body, it is characterized in that after mixing in fatty acid ester, the sucrose adding lipid acid soap body, add bio-surfactant again, under 10-30mmHg pressure and 110-145 ℃ of temperature condition, obtaining sucrose ester through reaction in 1-4 hour.
2. the method for production sucrose ester as claimed in claim 1 is characterized in that bio-surfactant is the mixture of the sophorolipid of the rhamnolipid of the sophorolipid of rhamnolipid, sophorolipid or modification of rhamnolipid or modification and different proportioning rhamnolipid or modification and sophorolipid or modification.
3. the method for production sucrose ester as claimed in claim 1 or 2, the feed ratio that it is characterized in that reactant fatty acid ester and sucrose, the different sucrose esters of producing different HLB values of bio-surfactant consumption and proportioning, wherein the weight ratio that feeds intake of reactant fatty acid ester and sucrose is 1: 2-2: 1, the rhamnolipid of rhamnolipid or modification, the consumption of the mixture of the rhamnolipid of the sophorolipid of sophorolipid or modification and different proportioning rhamnolipid or modification and the sophorolipid of sophorolipid or modification is the 0.5-5% of reaction raw materials total amount, and the weight proportion of the sophorolipid of the rhamnolipid of rhamnolipid or modification and sophorolipid or modification is 1: 5-5: 1.
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| CN99113469A CN1082512C (en) | 1999-02-10 | 1999-02-10 | Production of sucrose ester by homogeneous solventless process |
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| CN99113469A CN1082512C (en) | 1999-02-10 | 1999-02-10 | Production of sucrose ester by homogeneous solventless process |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323086C (en) * | 2005-03-30 | 2007-06-27 | 天津科技大学 | Method for synthesizing fatty ester of maltose |
| CN100374545C (en) * | 2006-01-13 | 2008-03-12 | 山东大学 | Wickerhamiella domercqiae Y2A for producing sophorose lipid and its uses |
| CN102093438A (en) * | 2010-11-22 | 2011-06-15 | 柳州爱格富食品科技股份有限公司 | Process for synthesizing sucrose polyester by using rotating film transesterification flow reactor |
| CN101514218B (en) * | 2009-03-16 | 2012-01-11 | 袁长贵 | Raw materials formula for synthetic sucrose fatty ester and synthetic method thereof |
| CN1839892B (en) * | 2006-01-13 | 2012-09-19 | 山东大学 | Preparation method of yeast W.domercqiaeY2A variation waufa glucolipid crude extract with antineoplastic activity |
| CN102850413A (en) * | 2012-05-29 | 2013-01-02 | 常州大学 | Method for preparing sucrose fatty acid ester |
| CN103130844A (en) * | 2013-03-07 | 2013-06-05 | 广西云鹏工贸有限责任公司 | Process for synthesizing defoaming agent sucrose fatty acid ester for sugar refining process |
| CN105037450A (en) * | 2015-07-20 | 2015-11-11 | 浙江科技学院 | Method for preparing sucrose esters with series HLB values |
| CN110229197A (en) * | 2019-07-06 | 2019-09-13 | 潍坊大耀新材料有限公司 | A kind of preparation method of the one's own physical property sucrose ester of small molecule without solvent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0320043B1 (en) * | 1987-12-11 | 1994-04-13 | Unilever N.V. | Process for the synthesis of polyol fatty acid esters |
-
1999
- 1999-02-10 CN CN99113469A patent/CN1082512C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323086C (en) * | 2005-03-30 | 2007-06-27 | 天津科技大学 | Method for synthesizing fatty ester of maltose |
| CN100374545C (en) * | 2006-01-13 | 2008-03-12 | 山东大学 | Wickerhamiella domercqiae Y2A for producing sophorose lipid and its uses |
| CN1839892B (en) * | 2006-01-13 | 2012-09-19 | 山东大学 | Preparation method of yeast W.domercqiaeY2A variation waufa glucolipid crude extract with antineoplastic activity |
| CN101514218B (en) * | 2009-03-16 | 2012-01-11 | 袁长贵 | Raw materials formula for synthetic sucrose fatty ester and synthetic method thereof |
| CN102093438A (en) * | 2010-11-22 | 2011-06-15 | 柳州爱格富食品科技股份有限公司 | Process for synthesizing sucrose polyester by using rotating film transesterification flow reactor |
| CN102850413A (en) * | 2012-05-29 | 2013-01-02 | 常州大学 | Method for preparing sucrose fatty acid ester |
| CN103130844A (en) * | 2013-03-07 | 2013-06-05 | 广西云鹏工贸有限责任公司 | Process for synthesizing defoaming agent sucrose fatty acid ester for sugar refining process |
| CN105037450A (en) * | 2015-07-20 | 2015-11-11 | 浙江科技学院 | Method for preparing sucrose esters with series HLB values |
| CN110229197A (en) * | 2019-07-06 | 2019-09-13 | 潍坊大耀新材料有限公司 | A kind of preparation method of the one's own physical property sucrose ester of small molecule without solvent |
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| CN1082512C (en) | 2002-04-10 |
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