CN1098835C - Method for catalytically synthesizing ethyl lactate from ammonium lactate - Google Patents
Method for catalytically synthesizing ethyl lactate from ammonium lactate Download PDFInfo
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- CN1098835C CN1098835C CN00130093A CN00130093A CN1098835C CN 1098835 C CN1098835 C CN 1098835C CN 00130093 A CN00130093 A CN 00130093A CN 00130093 A CN00130093 A CN 00130093A CN 1098835 C CN1098835 C CN 1098835C
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- lactic acid
- ammonium salt
- ethyl lactate
- acid ammonium
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Abstract
The present invention discloses a method for synthesizing ethyl lactate by catalyzing ammonium lactate. Ammonium lactate generated by regulating the pH value of fermentation liquor by ammonia water in the procedure of producing lactic acid by using a fermentation method is taken as raw material, or directly, the ammonium lactate is taken as the raw material, and a metal halide is taken as a catalyst, and then alcohol is added to react with the raw material to generate ethyl lactate. The present invention is characterized in that the used metal halide is a catalyst and the used benzen is a dewatering agent. The catalyst used by the present invention has the advantages of low price, easy acquirement, low production cost and no environment pollution. The yield of the ethyl lactate can reach 12.7% to 20.1% and is higher than the yield reported by the American patent, wherein the yield reported by the American patent reaches 9.17% to 11.7%.
Description
Technical field
The present invention relates to a kind of DL-Lactic acid ammonium salt catalysis Synthesis of ethyl lactate method, is to belong to the ethyl lactate technology of preparing.
Background technology
Ethyl lactate is the colourless transparent liquid with aroma fragrance, claims the 2 hydroxy propanoic acid ethyl ester again.Be used in foodstuff additive, medicine intermediate in traditional consumer field more.Boiling point is low, nontoxic, solvability is good because it has, and has a wide range of applications as green solvent.
The production of domestic ethyl lactate is divided into two portions: the one, and by the fermentation method obtain lactic acid, the 2nd, lactic acid and ethanol synthesis obtain lactic acid ethyl ester.In above-mentioned obtain lactic acid process owing to generate byproduct calcium sulfate, not only caused environmental pollution, increased manufacturing cost again, and lactic acid put forward also more complicated of dense process; Adopt the vitriol oil to make catalyzer in the process of the second step obtain lactic acid ethyl ester, etching apparatus is serious, the production cost height.
United States Patent (USP) (5723,639,1998,3,3) has been reported the method by DL-Lactic acid ammonium salt and ethanol synthesis Synthesis of ethyl lactate.This method adopts DMAP (4-Dimethylamino pyridine) to make catalyzer.Do not generate the calcium sulfate by product, and adopt membrane separation technique the product deamination that dewaters.The catalyzer that this patented method adopted costs an arm and a leg, and domestic being difficult to of the membrane technique that membrane sepn adopts realizes that the yield of ethyl lactate is 9.17～11.7%.
Summary of the invention
Purpose of the present invention is to provide a kind of method by DL-Lactic acid ammonium salt catalysis Synthesis of ethyl lactate.No coupling product in the middle of this method production process, free from environmental pollution, equipment there is not corrosion, ethyl lactate yield height.
For achieving the above object, the present invention is realized by following technical proposals.With in fermentative Production lactic acid process, generating DL-Lactic acid ammonium salt by the pH value that adopts ammoniacal liquor to regulate fermented liquid is raw material, or directly be raw material with the DL-Lactic acid ammonium salt, add catalyzer and produce ethyl lactate with ethanol synthesis, product is through rectified purified acquisition ethyl lactate product, it is characterized in that: a. catalyzer adopts metal halide, and its consumption is 1～2% of a DL-Lactic acid ammonium salt; B. DL-Lactic acid ammonium salt and alcoholic acid molar ratio are 1: 1.5～1: 3.5, and the reaction times is 24～96h; C. carry out adding benzene to reactor in the catalyzed reaction in DL-Lactic acid ammonium salt and ethanol, realize alcohol, water, benzene three-phase azeotropic dehydration.
Above-mentioned metal halide is FeBr
3, FeCl
3, CuCl
2, TiCl
3, ZnCl
2, PtCl
2, AlCl
3
Below the present invention is described in detail.
Adopting DL-Lactic acid ammonium salt and dehydrated alcohol is raw material, and its proportioning is an ethanol: DL-Lactic acid ammonium salt (mol ratio)=1.5: 1～3.5: 1, and the adding metal halide is a catalyzer, and its consumption is 1%～2% of a DL-Lactic acid ammonium salt weight, and other adds benzene (analytical pure) is dewatering agent.
To drop into by the raw material of said ratio preparation in the reactor, carry out under the temperature for making to be reflected at stably, part ethanol adopts constant pressure funnel to drip, temperature of reaction kettle is controlled at below 80 ℃, the heating condensation, the very fast layering of phegma in water trap, lower floor is a water-rich phase, the upper strata is rich organic phase, when the water surface during near return line, beginning slowly discharges water, and the rate-controlling that discharges water is in that to keep the water surface motionless substantially, when treating that the water surface no longer rises, stop heating, the reaction times is 24～96h, reaction solution is transferred to carried out atmospheric distillation (tower height 1000mm in the still kettle earlier, internal diameter 35mm, filler is a stainless steel θ ring filler), the control tower top temperature is below 100 ℃, and reflux ratio is 1: 1, at this moment overhead fraction mainly is benzene and alcoholic acid mixture, and then still liquid carried out underpressure distillation, and residual voltage is controlled at 6.0～6.7KPa, and reflux ratio is 2: 1, collect 60～90 ℃ cut, this cut is the product ethyl lactate.
Above product is through gas chromatographic analysis, and the yield of ethyl lactate is 12.7～20.1%.
Embodiment
The invention will be further described with embodiment more below:
Example one:
Raw material is formed: DL-Lactic acid ammonium salt (70～80%), ethanol (anhydrous)
Ethanol: DL-Lactic acid ammonium salt=2.5: 1 (mol ratio), catalyzer are AlCl
3, consumption is 2% of a DL-Lactic acid ammonium salt weight.Other adds benzene (analytical pure) and makes dewatering agent and a little zeolite.
Raw material is dropped in the 500ml reactor heating of electricity consumption heating jacket by above proportioning.Adopt constant pressure funnel to drip ethanol, tower top temperature is controlled at 64～65 ℃, temperature of reaction kettle is controlled at below 80 ℃, the phegma layering after the condensation in water trap, and lower floor is a water-rich phase, the upper strata is rich organic phase, as long as the water surface does not touch the return line mouth of pipe, just do not discharge water always, when rising to the mouth of pipe, the water surface begins slowly to discharge water, it is motionless substantially that the speed that discharges water maintains the control water surface, reacts to stop after 96 hours.When temperature of reaction kettle drops to below 40 ℃, product is moved on in the still kettle, adopt atmospheric distillation earlier, reflux ratio is 1: 1, and tower top temperature is controlled at below 100 ℃, and at this moment steaming cut mainly is benzene and alcoholic acid mixture, and this mixture can be recycled.Carry out underpressure distillation again, residual voltage is controlled at 6.0～6.7Kpa, reflux ratio 2: 1, and reclaim 60～90 ℃ cut this moment, is considered as the product ethyl lactate, and products obtained therefrom adopts gas chromatographic analysis, and the ethyl lactate yield is 20.1%.
Example two:
Ethanol: DL-Lactic acid ammonium salt=1.5: 1 (mol ratio), catalyzer are FeCl
3, consumption is 1.5% of a DL-Lactic acid ammonium salt weight, and the reaction times is 96h, and the ethyl lactate yield is 17.4%, and all the other are with example one
Example three:
Ethanol: DL-Lactic acid ammonium salt=3.5: 1 (mol ratio), catalyzer are ZnCl
2, consumption is 1% of a DL-Lactic acid ammonium salt weight, and the reaction times is 96h, and the ethyl lactate yield is 12.7%, and all the other are with example one.
The present invention compares with existing ethyl lactate preparation method, and its advantage is: the catalyzer of employing is cheap and easy to get, has reduced production cost, and production process does not cause environmental pollution, and the entrainer evaporation is adopted in dehydration, and technology maturation is easy to grasp; The ethyl lactate yield can reach 12.7～20.1%, 9.17～11.7% the ethyl lactate yield that is higher than that United States Patent (USP) reports.
Claims (2)
1, a kind of method by DL-Lactic acid ammonium salt catalysis Synthesis of ethyl lactate, it is with in fermentative Production lactic acid process, the DL-Lactic acid ammonium salt that generates by the pH value that adopts ammoniacal liquor to regulate fermented liquid is a raw material, it perhaps directly is raw material with the DL-Lactic acid ammonium salt, add catalyzer and produce ethyl lactate with ethanol synthesis, product is characterized in that through rectified purified acquisition ethyl lactate product: a. catalyzer adopts metal halide, and its consumption is 1～2% of a DL-Lactic acid ammonium salt; B. DL-Lactic acid ammonium salt and alcoholic acid molar ratio are 1: 1.5～1: 3.5, and the reaction times is 24～96h; C. carry out adding benzene to reactor in the catalyzed reaction in DL-Lactic acid ammonium salt and ethanol, realize alcohol, water, benzene three-phase azeotropic dehydration.
2, according to the said method by DL-Lactic acid ammonium salt catalysis Synthesis of ethyl lactate of claim 1, it is characterized in that: the metal halide catalyst that is adopted is FeBr
3, FeCl
3, CuCl
2, TiCl
3, ZnCl
2, PtCl
2, AlCl
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130093A CN1098835C (en) | 2000-10-27 | 2000-10-27 | Method for catalytically synthesizing ethyl lactate from ammonium lactate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130093A CN1098835C (en) | 2000-10-27 | 2000-10-27 | Method for catalytically synthesizing ethyl lactate from ammonium lactate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1290686A CN1290686A (en) | 2001-04-11 |
| CN1098835C true CN1098835C (en) | 2003-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00130093A Expired - Fee Related CN1098835C (en) | 2000-10-27 | 2000-10-27 | Method for catalytically synthesizing ethyl lactate from ammonium lactate |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2842932A4 (en) | 2012-04-27 | 2015-12-23 | Xiaogan Esun New Material Co Ltd | Method for continuously producing high-content high-optical-purity lactate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723639A (en) * | 1995-10-16 | 1998-03-03 | University Of Chicago | Esterification of fermentation-derived acids via pervaporation |
-
2000
- 2000-10-27 CN CN00130093A patent/CN1098835C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723639A (en) * | 1995-10-16 | 1998-03-03 | University Of Chicago | Esterification of fermentation-derived acids via pervaporation |
Non-Patent Citations (3)
| Title |
|---|
| 哈尔滨工业大学学报，31卷，1期 1999-02-01 郝素娥等，乳酸乙酯合成的研究47-50 * |
| 广西化工，28卷，3期 1999-09-01 李汝珍，苏涛，乳酸酯化催化剂比较35-37 * |
| 广西化工，28卷，3期 1999-09-01 李汝珍，苏涛，乳酸酯化催化剂比较35-37;哈尔滨工业大学学报，31卷，1期 1999-02-01 郝素娥等，乳酸乙酯合成的研究47-50 * |
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| CN1290686A (en) | 2001-04-11 |
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