CN102786415A - Method for synthesizing long-chain dibasic acid diester - Google Patents
Method for synthesizing long-chain dibasic acid diester Download PDFInfo
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- CN102786415A CN102786415A CN2011101273426A CN201110127342A CN102786415A CN 102786415 A CN102786415 A CN 102786415A CN 2011101273426 A CN2011101273426 A CN 2011101273426A CN 201110127342 A CN201110127342 A CN 201110127342A CN 102786415 A CN102786415 A CN 102786415A
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Abstract
The invention relates to a preparation method of a long-chain dibasic acid diester, and especially relates to a method for preparing a long-chain dibasic acid diester through using a long-chain binary acid produced by a fermentation process. According to the method, the long-chain dibasic acid diester is prepared through adopting a novel nanometer catalyst and a one-step solvent extraction reaction, so the product yield is improved, the technological process is simplified, energy consumption and material consumption are small, the process is environmentally-friendly, the application amount and the loss amount of a low-carbon alcohol are small, the purity of the long-chain dibasic acid diester can reach above 99w%, and organic solvents used each time can be repeatedly used without rectification.
Description
Technical field: the present invention relates to a kind of long-chain biatomic acid with biological fermentation is raw material, the compound method of synthetic corresponding long chain diacid dibasic ester.
Background technology: long-chain biatomic acid is meant that charcoal chain number at ten and above diprotic acid, refers generally to the straight chain diprotic acid.It generally prepares and production through the method for microbial fermentation.With it is raw material, and synthetic long-chain biatomic acid dibasic acid esters is a kind of chemical intermediate, can be widely used in industries such as spices, senior lubricant, macromolecular material, liquid crystal, has important economic value.The production of traditional production long chain diacid dibasic ester uses the vitriol oil to have etching apparatus as catalyzer, contaminate environment, shortcomings such as the many and aftertreatment technology complicacy of side reaction.Therefore developing a kind of synthetic route based on the novel green catalyzer becomes a urgent problem.In addition, in building-up process, often will add excessive alcohol, so that reaction is carried out fully, this must make the technical process of reaction complicated, thereby cost is increased
Chinese patent CNI056882C has introduced a kind of method for preparing the long-chain biatomic acid ester, and what this method adopted is the high pressure esterification process.Because facility investment is big, turnout is little, yield is low, this method seldom is used for industrialized production.Chinese patent CN1351004A has introduced a kind of method for preparing the long-chain biatomic acid ester, and what this method adopted is lipid acid extraction method method.This method mixes thick diprotic acid or carry disease germs thick diprotic acid and gac; Pack into and put into extractor behind the cylinder shape filter cloth bag; Heated solvent makes its vaporization, and condensed fresh hot solvent contacts with diprotic acid, the extracting while decolouring; Extract returns the solvent still after a certain amount of, in the solvent still, carry out esterification.Though this method equipment is few, simple to operate, need thick diprotic acid or carry disease germs thick diprotic acid and gac be mixed, put into extractor behind the cylinder shape filter cloth bag of packing into, this equipment is difficult to carry out large-scale industrial production.Japanese Patent JP57-105.193 has introduced the thick product prepn binary of a kind of long-chain biatomic acid dibasic acid esters method.The thick product of long-chain biatomic acid that this invention adopts traditional method to obtain; Use the low-boiling point alcohol and the catalyzer of 10 times of diprotic acid weight; Heat and make the diprotic acid esterification more than 270 0C; Carry out underpressure distillation on the top of same reactor drum then, fractionate out excessive alcohol, water and highly purified binary acid diester.Because excessive alcohol, water is separated earlier in the vacuum distillation process; And catalyzer and binary acid diester are in the pyritous reaction kettle; Therefore binary acid diester is prone to produce hydrolysis, oxidative cracking reaction and reduces yield; The color of binary acid diester is darker: esterification reaction temperature is high, and the consumption of alcohol is big with loss, and energy consumption and material consumption are bigger.U.S. Pat 6087527 has proposed employing multistep esterification process, when the first step esterification arrives certain transformation efficiency, sloughs the process of water generation reaction.Filter out catalyzer earlier, steam unreacted alcohol, water again, obtain thick long-chain biatomic acid dibasic acid esters, diprotic acid mixture, in this mixture, add catalyzer, alcohol again and carry out esterification again.Such esterification can repeat repeatedly.Though this method transformation efficiency has improved, process step is many, complex operation, and the time is long, and the consumption and the loss amount of alcohol are big.
Summary of the invention: the objective of the invention is for a kind of compound method of novel synthetic long chain diacid dibasic ester is provided; In the present invention, adopted novel nano-material, the long-chain biatomic acid dibasic acid esters that adopts SX to generate simultaneously as catalyzer; Thereby the raising product yield is simplified technical process.This building-up process has the high characteristics of green, environmental protection and product purity.
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Figure is the building-up process schema.
In order to realize the foregoing invention purpose, the present invention provides following technical scheme:
As shown in the figure, at first long-chain biatomic acid is added in the back flow reaction still, add low-carbon alcohol, catalyzer, and extraction solvent, the consumption of low-carbon alcohol is 0.5-20 a times of long-chain biatomic acid weight, is preferably 1-8 doubly.The add-on of catalyzer is the 0.05%-20% of long-chain biatomic acid weight, is preferably 0.5%-10%.Reflux temperature be 60 spend to 150 the degree, reflux time is 1-15 hour, is preferably 2-4 hour.Extraction solvent and the long-chain biatomic acid that adds, alcohol is all immiscible and mix with the long-chain biatomic acid dibasic acid esters, consumption be long-chain biatomic acid weight 0.5-15 doubly, be preferably 2-8 times.Question response finishes, and isolates the upper materials that contains long-chain biatomic acid dibasic acid esters and solvent and contains lower floor's material of unreacted long-chain biatomic acid and low-carbon alcohol.At last lower floor's material is carried out secondary back esterification and SX again, this process can be carried out repeatedly, preferably carries out twice: upper materials is distilled, steam solvent, promptly get the long-chain biatomic acid dibasic acid esters.
The described long-chain biatomic acid of aforesaid method can be the fermented liquid that contains long-chain biatomic acid that obtains by biological fermentation process through minute oil, filtration sterilization, acidizing crystal, refilter remove filtrating, drying obtains the low-purity diprotic acid; Or (handle fermented liquid according to the disclosed pretreatment process of Chinese patent CN 1070394A without the diprotic acid that the filtering thalline directly obtains carrier; Gained diprotic acid content is about 87w%, and thalline content is about 10%w).The said long-chain biatomic acid of the present invention is the straight chain aliphatic alpha of C10--C16, and the ω dicarboxylicacid has general general molecular formula HOOC (CH
2)
nCOOH (n=9-16).Both can be the dicarboxylicacid of the single component of single alkane production, also can be two or more any component of two or more mixed alkanes production, the mixed dicarboxylic acid of arbitrary proportion.
If said process is selected the nano-solid catalyzer for use, can before the backflow esterification, decolour, the gac add-on is the heavy 0.5w%-20w% of diprotic acid, is preferably 1w%-10w%.Bleaching temperature 40-100 degree decoloured 0.1-2 hour, was preferably 0.3-1 hour.Decolouring filters out gac and low-carbon alcohol insolubles, in order to avoid the pollution solid catalyzer makes it repeatedly to use after finishing.
Described nanocatalyst is the heteropolyacid and the tosic acid of carbon nano material load, the tin protochloride catalyzer.Described carbon nano material comprises Graphene, carbon nanotube etc.Described heteropolyacid includes, but are not limited to the 12-phospho-molybdic acid, 12-silicomolybdic acid, 12-phospho-wolframic acid, 12-silicotungstic acid, 12-molybdovanaphosphoric acid, 12-silicon molybdenum vanadic acid, 12-tungstovanadophosphoric acid, 12-silicon tungsten vanadic acid etc.
The content of carbon nano material is 0.01w%-20w% in the described catalyzer, is preferably 0.5-10w%.Described extraction solvent is a non-polar solvent, includes but not limited to: hexanaphthene, benzene, toluene, saturated hydrocarbons, chloroform, ether etc.
Compared with prior art, the inventive method has the following advantages:
(1) product yield is high, and the two enzymes of the long-chain biatomic acid of preparation need not reduce pressure and steam shop purity and reach more than the 99w%.
(2) present method can be handled the low-purity diprotic acid, also can handle the diprotic acid that carries disease germs, and method is simple and practical:
(3) esterification reaction temperature is low, and low-carbon alcohol, solvent loss are little, and solvent need not be handled again, and energy consumption is low, has simplified technological process, thereby production cost is greatly reduced.
(4) adopt the novel nano catalyzer, speed of response is accelerated greatly, productive rate promotes greatly.
(5) in reaction process, add extraction solvent, but not reaction is carried out extracting and separating after finishing, and has simplified technical process greatly.Adopt non-polar solvent to extract, the pigment that long-chain biatomic acid brings, thalline, impurity etc. stay polar water, alcohol mutually in, can not adopt decolorization, long-chain biatomic acid dibasic acid esters purity can reach more than the 99w%.
(5) esterification reaction temperature is low, does not have catalyzer, the long-chain biatomic acid dibasic acid esters phase that coexists, and has avoided the hydrolysis of long-chain biatomic acid dibasic acid esters, oxidation, has improved the enzyme yield;
Embodiment:
Embodiment 1
Preparation dodecanedioic acid dioctyl ester.
A. the positive structure dodecanedioic acid of 10kg that obtains with biological fermentation in the back flow reaction of packing into the still, adds octanol 40kg, and hexanaphthene 30kg, the rare nanocatalyst 0.5kg of phospho-wolframic acid/graphite, reflux temperature are 65 degree, back flow reaction 2 hours.
C. separate the levels material that is obtained
D. the lower floor's material that step C is obtained carries out once backflow esterification and the extractive reaction process like step a again.
E. the upper materials that step C is obtained is squeezed in the still kettle, is heated to 82 degree, steams cyclohexane solvent, and solvent can be reused once more.Obtain the dodecanedioic acid dioctyl ester, its purity is 99.6w%, product recovery rate 97.3w%.Aqueous phase steams octanol, continues to use.
Embodiment 2
Preparation undecane dicarboxylic acid diethyl ester
A. the positive structure undecane dicarboxylic acid of 10kg that obtains with biological fermentation in the back flow reaction of packing into the still, adds ethanol 50kg, and benzene 10kg, the rare nanocatalyst 1kg of phospho-molybdic acid/graphite, reflux temperature are 70 degree, back flow reaction 5 hours.
C. separate the levels material that is obtained
D. the lower floor's material that step C is obtained carries out once backflow esterification and the extractive reaction process like step a again.
E. the upper materials that step C is obtained is squeezed in the still kettle, is heated to 82 degree, steams benzene solvent, and solvent can be reused once more.Obtain the undecane dicarboxylic acid diethyl ester, its purity is 99.6w%, product recovery rate 97.3w%.Aqueous phase steams octanol, continues to use.
Claims (9)
1. the preparation method of a long-chain biatomic acid dibasic acid esters comprises: at first long-chain biatomic acid is added in the back flow reaction still, adds low-carbon alcohol, catalyzer, and extraction solvent, the consumption of low-carbon alcohol be long-chain biatomic acid weight 0.5-20 doubly, be preferably 1-8 doubly.The add-on of catalyzer is the 0.05%-20% of long-chain biatomic acid weight, is preferably 0.5%-10%.Reflux temperature be 60 spend to 150 the degree, reflux time is 1-15 hour, is preferably 2-4 hour.Extraction solvent and the long-chain biatomic acid that adds, alcohol is all immiscible and mix with the long-chain biatomic acid dibasic acid esters, consumption be long-chain biatomic acid weight 0.5-15 doubly, be preferably 2-8 times.Question response finishes, and isolates the upper materials that contains long-chain biatomic acid dibasic acid esters and solvent and contains lower floor's material of unreacted long-chain biatomic acid and low-carbon alcohol.At last lower floor's material is carried out secondary back esterification and SX again, this process can be carried out repeatedly, preferably carries out twice: upper materials is distilled, steam solvent, promptly get the long-chain biatomic acid dibasic acid esters.
2. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1, it is characterized in that described long-chain biatomic acid is the straight chain aliphatic alpha of C10-C16, the ω dicarboxylicacid.
3. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1; It is characterized in that described long-chain biatomic acid be the fermented liquid that contains the long-chain triprotic acid that obtains by biological fermentation process through minute oil, filtration sterilization, acidizing crystal, refilter remove filtrating, drying obtains long-chain biatomic acid, or directly obtains the long-chain biatomic acid of carrier without the filtering thalline.
4. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1, it is characterized in that described low-carbon alcohol is to be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the isopropylcarbinol one or more.
5. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1 or 4, the consumption that it is characterized in that described low-carbon alcohol be long-chain biatomic acid weight 0.5-20 doubly, be preferably 1-8 doubly.
6. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1, it is characterized in that described nanocatalyst is the heteropolyacid and the tosic acid of carbon nano material load, the tin protochloride catalyzer.Described carbon nano material comprises Graphene, carbon nanotube etc.Described heteropolyacid includes, but are not limited to the 12-phospho-molybdic acid, 12-silicomolybdic acid, 12-phospho-wolframic acid, 12-silicotungstic acid, 12-molybdovanaphosphoric acid, 12-silicon molybdenum vanadic acid, 12-tungstovanadophosphoric acid, 12-silicon tungsten vanadic acid etc.
7. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1 or 6, the add-on that it is characterized in that described catalyzer is the 0.05w%-20w% of long-chain biatomic acid weight.
8. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1, it is characterized in that described extraction solvent is selected from hexanaphthene, benzene, toluene, tetracol phenixin, normal paraffin, ether, one or more in the chloroform.
9. according to the preparation method of the long-chain biatomic acid dibasic acid esters of claim 1 or 8, it is characterized in that 0.5-15 that described extraction solvent consumption is a long-chain biatomic acid weight doubly, is preferably 2-8 doubly.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| CN104860822A (en) * | 2014-05-23 | 2015-08-26 | 山东瀚霖生物技术有限公司 | Asymmetric diester and preparation method |
| CN107345169A (en) * | 2016-05-06 | 2017-11-14 | 中国科学院过程工程研究所 | A kind of fully synthetic lubricating oil in esters base oil and its synthetic method |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
-
2011
- 2011-05-17 CN CN2011101273426A patent/CN102786415A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860822A (en) * | 2014-05-23 | 2015-08-26 | 山东瀚霖生物技术有限公司 | Asymmetric diester and preparation method |
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| CN107345169A (en) * | 2016-05-06 | 2017-11-14 | 中国科学院过程工程研究所 | A kind of fully synthetic lubricating oil in esters base oil and its synthetic method |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114369024B (en) * | 2021-12-31 | 2024-01-30 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
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Application publication date: 20121121 |