WO2005087702A1 - Procede de fabrication d'ester lactique - Google Patents

Procede de fabrication d'ester lactique Download PDF

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Publication number
WO2005087702A1
WO2005087702A1 PCT/JP2005/004128 JP2005004128W WO2005087702A1 WO 2005087702 A1 WO2005087702 A1 WO 2005087702A1 JP 2005004128 W JP2005004128 W JP 2005004128W WO 2005087702 A1 WO2005087702 A1 WO 2005087702A1
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Prior art keywords
lactic acid
alcohol
lactate
esterification
producing
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PCT/JP2005/004128
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English (en)
Japanese (ja)
Inventor
Takashi Watanabe
Hiroyuki Ueda
Yasunori Sakai
Shigenobu Miura
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Musashino Chemical Laboratory, Ltd.
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Priority to JP2006510969A priority Critical patent/JP4685766B2/ja
Publication of WO2005087702A1 publication Critical patent/WO2005087702A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

  • the present invention relates to a method for producing a lactic acid ester having an excellent yield, and more particularly to a method for efficiently producing a lactic acid ester using a lactic acid fermentation solution containing lactic acid or lactate.
  • Lactic acid is used as a food additive in the manufacture of sake, soft drinks, pickles, soy sauce, bread and beer, and for industrial use in the manufacture of leather, fiber, plastics, pharmaceuticals, and agricultural chemicals. It is a useful compound.
  • esters of lactic acid derivatives or synthetic intermediates such as ethyl lactate and butyl lactate have been widely used as highly safe solvents and detergents.
  • high-purity lactic acid and its ester having high optical activity are required, and production by lactic acid fermentation is performed.
  • a lactic acid fermentation liquor is used, and the fermentation is carried out while neutralizing a decrease in pH with ammonia or the like as the fermentation of lactic acid bacteria progresses.
  • an acid salt is converted into lactic acid by acidification with sulfuric acid, followed by extraction with a solvent such as isopropyl alcohol.
  • the extracted lactic acid is esterified using methanol (Japanese Patent Publication No. 5869056).
  • the pH of the medium during the lactic acid fermentation is adjusted with ammonia, and an alcohol having 4 or 5 carbon atoms is added to a lactic acid fermentation liquor containing an ammonium lactate obtained by the fermentation, and the mixture is heated to give ester ester
  • an alcohol having 4 or 5 carbon atoms is added to a lactic acid fermentation liquor containing an ammonium lactate obtained by the fermentation, and the mixture is heated to give ester ester
  • JP-A-6-311886 discloses a solution obtained by an esterification reaction. A mineral acid is added to the liquid as an esterification accelerator, and heating and dehydration are performed under acidic conditions to promote and complete the esterification of the lactic acid and the alcohol.
  • the reason why the alcohol having 4 or 5 carbon atoms is used is that the alcohol is used as an esterification raw material and at the same time acts as an azeotropic dehydrating agent.
  • the obtained esteri-dani reaction liquid contains almost no water, contains excess alcohol, lactic acid esters of the alcohol, mineral salts of ammonia, microorganisms such as lactic acid bacteria, and other impurities. Since it is present as a slurry of impurities or lactic acid bacteria, a batch or continuous distillation step is performed to separate the lactic acid ester and alcohol.
  • Lactic acid esters are used as such or as hydrolyzed as lactic acid.
  • the applications are diverse, such as food additives, industrial use, pharmaceuticals, and agricultural chemicals, and polylactic acid, a polymer, is also expected to be a biodegradable polymer. For this reason, improving the yield and production efficiency of lactic acid esters is a very important issue.
  • lactic acid is an optically active compound, development of a method for producing a lactic acid ester having high optical activity has been strongly demanded.
  • the present invention provides a more efficient method for producing a lactic acid ester.
  • the present inventors have studied in detail the method for producing a lactic acid ester.
  • the reaction solution containing lactic acid or lactate and an alcohol is esterified to obtain an esterification rate of 60 to 90%.
  • the lactate ester and the alcohol contained were separated, the alcohol was added to the remaining liquid, and the esteri-dani was performed again.
  • the total amount of the obtained lactate ester is higher than the case where the lactate ester is obtained in a single step with the esterification ratio exceeding 90%.
  • the present invention was found to be improved, and the present invention was completed.
  • the present invention can be carried out by either a continuous method or a notch method, which is intended to shorten the esterification time and improve the optical purity.
  • the present invention relates to a method for producing an esterified product of an alcohol and lactic acid and Z or a lactate, wherein a reaction solution containing an alcohol and lactic acid and Z or a lactate has an esterification ratio of 60-.
  • a process for producing a lactate ester comprising the steps of esterifying to 90%, fractionating the lactic acid ester contained in the reaction solution, and adding alcohol to the distillation residue and re-esterifying. Is provided.
  • the present invention is characterized in that the ammonia-neutralized lactic acid fermentation liquor and the alcohol are esterified with a lactate amide generation rate in the range of 0 to 6.0%, wherein the optical purity is 95 to 100% ee.
  • This is a method for producing a lactate ester.
  • a lactate ester can be produced at a high yield by a simple method.
  • the strength is also excellent in energy efficiency because the esteri-dani conditions are mild.
  • the reaction is performed under mild esterification conditions, a lactic acid ester having high optical purity can be obtained.
  • the lactic acid fermentation liquid can be used as a raw material, the operation can be performed particularly efficiently when the lactic acid is obtained by lactic acid fermentation and then the esterified product is produced.
  • FIG. 1 is a view showing an apparatus for continuously producing a lactic acid ester of the present invention.
  • FIG. 2 is a view showing an apparatus for producing the lactate ester of the present invention in a batch system.
  • the first aspect of the present invention relates to a method for producing an esterified product of an alcohol and lactic acid and Z or a lactate, wherein the reaction solution containing the alcohol and lactic acid and Z or a lactate is subjected to an esterification process. Is reduced to 60-90%, a step of fractionating lactic acid ester contained in the reaction solution, and a step of adding alcohol to the distillation residue and performing esterification again. This is a method for producing an ester.
  • the lactic acid used in the present invention may be produced by any method, may be produced by hydrolyzing lactide bound to two lactic acid molecules, may be produced by chemical synthesis, or may be produced by lactic acid fermentation. Those obtained by any method such as those prepared by a biological production method using bacteria can be used. The use of a lactic acid fermentation bacterium is particularly preferred, since a lactic acid ester having excellent optical activity can be obtained.
  • the lactate may be any lactate as long as the salt is removed from the lactic acid during the esterification and does not hinder the esterification. Examples of such a lactate include salts with calcium ions, ammonium ions, and amines. The lactate was included in consideration of cases where the final product was converted into lactate by the lactate production process such as neutralization.
  • lactic acid and lactate (hereinafter, also simply referred to as lactic acid (salt)) can be supplied in an aqueous solution.
  • aqueous solution of lactic acid (salt) contains 30 to 85% by mass, more preferably 45 to 75% by mass, particularly preferably 50 to 70% by mass of lactic acid (salt) in terms of lactic acid. Is preferred.
  • lactic acid or lactate may be concentrated or diluted to the above concentration and used as an aqueous lactic acid (salt) solution.
  • a lactic acid fermentation liquor can be used as such a lactic acid (salt) aqueous solution.
  • the lactic acid fermentation liquid is a fermentation liquid containing lactic acid when biologically producing lactic acid by a lactic acid fermenting bacterium. Since the pH is lowered by the progress of lactic acid fermentation, it is general that the fermentation proceeds while being neutralized with an alkali substance-added saccharine. However, the use of ammonia as such an alkaline substance is preferred. In the present invention! / Such a lactic acid fermentation liquor is referred to as "ammonia neutralized lactic acid fermentation liquor". In the case of ammonia neutralization, ammonia liberated simultaneously with esterification can be recovered by fractional distillation. Such an ammonia-neutralized lactic acid fermentation solution can be prepared, for example, by the methods described in JP-A-58-56690 and JP-A-6-311886.
  • an alcohol having 416 carbon atoms is particularly preferably used.
  • Such alcohols eg, n-butyl alcohol, isobutanol chill alcohol, t-butyl alcohol, n over ⁇ mill alcohols, s ec - ⁇ Mill alcohol
  • T-amyl alcohol iso-amyl alcohol, sec-iso-amyl alcohol, activated amyl alcohol, getyl carbinol, t-butyl carbinol, n -pentyl alcohol, etc., and more preferably n-butyl alcohol .
  • n-butyl alcohol azeotropes with water, if this azeotropic composition is appropriately cooled and collected, and then n-butyl alcohol and water are separated into two phases, it is possible to reuse n-butyl alcohol in the esterification reaction system. It is possible and economical. In the case of alcohols having more than 6 carbon atoms, liberation of ammonia by esterification is possible.
  • the mixing ratio of the aqueous solution of lactic acid (salt) and the alcohol is preferably 0.3 to 100 times the molar amount of lactic acid (salt) in consideration of reaction efficiency and the like.
  • the molar ratio is preferably 1 to 10 times, particularly preferably 3 to 6 times. If it is less than 0.3 mole times, the amount of lactic acid dimer increases and the reaction may not proceed. On the other hand, if it exceeds 100 mole times, it takes a long time to raise the reaction solution to the esterification temperature, and it may be difficult to control the temperature thereafter.
  • a continuous lactate ester production apparatus shown in FIG. 1 is used to produce a lactic acid ester using an ammonia-neutralized lactic acid fermentation solution and n-butanol will be described. .
  • a first reactor 103 a thin-film still 104, a second reactor 105, and a thin-film still 106 are connected by pipes 108, 109 and 110, respectively.
  • an ammonia-neutralized lactic acid fermentation liquid was added to the first reactor 103 from a pipe 107, and n-butanol was added to the pipe 116 from a pipe 116 to form a reaction liquid, which was provided in the first reactor 103.
  • the mixture is heated under stirring by a stirring blade to carry out the esterification reaction.
  • a condenser 117 is further connected to the distillation tower 114 disposed above the first reactor 103 by a pipe 118, and n-butanol, an azeotropic composition with n-butanol, and lactate ester are cooled by a condenser.
  • n-butanol containing lactate ester and a small amount of water
  • the lower phase component water containing a small amount of n-butanol and ammonia
  • Most of the ammonia gas that has passed through the distillation column 114 is collected by the cooler 117, and the remaining ammonia is collected by the ice-cooled water type ammonia absorber via the pipe 120.
  • the pressure at the top of the distillation column which varies depending on the type of alcohol used, may be any normal pressure.
  • the reaction temperature varies depending on the alcohol used. The reaction is usually carried out at a temperature of preferably from 100 to 170 ° C, more preferably from 120 to 130 ° C. If the temperature is lower than 100 ° C, an industrially satisfactory reaction rate cannot be obtained. Sometimes. When the temperature exceeds 170 ° C, lactic acid may partially racemize, or a corresponding ether consisting of two alcohol molecules may be produced.
  • the temperature is 100 to 170 ° C., more preferably 110 to 150 ° C., and particularly preferably 120 to 130 ° C. Within this range, the reaction rate of ammonium lactate is high and the yield of lactate ester is high. At this time, it is preferable to heat only the ammonia-neutralized lactate fermented liquor and react it while adding alcohol thereto. In this way, the post-addition of alcohol can shorten the reaction time.
  • the esterification is adjusted so that the esterification ratio of lactic acid in the reactor 103 is 60 to 90%, preferably 65 to 90%, particularly preferably 70 to 90%. Move to the process. When the esterification ratio exceeds 90%, the high-temperature state becomes long-lasting, and the optical activity may decrease. On the other hand, if the esterification ratio is less than 60%, productivity is low and disadvantageous.
  • the reaction solution having an esterification ratio of 60 to 90% is supplied to a thin-film evaporator 104 through a pipe 108, where the lactate ester and alcohol are distilled off at the top of the column.
  • the reason why the lactate ester is separated from the reaction liquid prior to the second esteri-dani is to prevent a decrease in optical activity and to improve the esteri-dani reaction rate.
  • the pressure at the top of the distillation column may be appropriately selected depending on the type of lactic acid ester to be rectified. Generally, the pressure is preferably 0.67 to 13.33 kPa, particularly preferably 1.33 to 2.67 kPa. It is. If the pressure exceeds 13 kPa, the distillation of lactate, alcohol and water is sufficient Not. On the other hand, even if it is less than 0.67 kPa, the effect on the distillation effect is small. In the case of butyl lactate, the top pressure is 0.67 to 13 kPa and the top temperature is 61 to 125 ° C. The butyl lactate distilled here is referred to as primary lactate ester (A).
  • A primary lactate ester
  • the distillation residue is introduced into the second reactor 105 via the pipe 109, and esterification is performed again.
  • the residue contains sugar, starch, tar-like substances, oligolactic acid, sugar lactate ester, lactamide, lactide, lactic acid polymer, lactic acid (salt), water, alcohol, lactate ester, etc., derived from the lactic acid fermentation broth.
  • This is supplied with n-butanol via line 116 '.
  • the amount of alcohol added to the distillation residue is converted based on the amount of lactic acid contained in the distillation residue. Lactic acid and lactate generate lactic acid ester by reaction with alcohol. Lactic acid amide, lactide-oligolactic acid, lactic acid polymer, etc. are also decomposed into lactic acid to form lactic acid ester.
  • the compounds that can be converted to lactic acid are also calculated by converting the lactic acid contained into one unit.
  • the amount is 4 mol of lactic acid.
  • the alcohol is added in an amount of 0.3 to 100 times, more preferably 0.5 to 80 times the lactic acid contained in the distillation residue. If it is less than 0.3 mole times, the esterification reaction becomes slow, while if it exceeds 100 mole times, the esterification efficiency may decrease.
  • reaction conditions in the second reactor 105 vary depending on the type of alcohol used and the like, but are 100 to 150 ° C, more preferably 120 to 150 ° C.
  • By-product water is generated as the esterification process proceeds, and alcohol is azeotropically distilled off as the by-product water is distilled.
  • the alcohol and water are separated to separate the alcohol. It is desirable to reflux to the two reactors. As a result, the alcohol can be effectively reused, and it is economically excellent.
  • a mineral acid may be added to the reaction solution and heated under acidity to promote the esterification of the lactic acid and the alcohol.
  • a part of lactic acid may be self-condensed, which causes a decrease in the production rate of lactic acid ester. . Therefore, a mineral acid of 0.005 to 0.8 mole times, preferably 0.01 to 0.2 mole times of lactic acid to be produced is added to make an acid catalyst. Addition of an acid catalyst hydrolyzes latatide, oligolactic acid, and lactic acid polymer into lactic acid, thereby improving the yield of lactic acid ester.
  • the upper limit of the amount of the mineral acid added as the acid catalyst is not particularly limited, but generally, a mineral acid of 0.2 equivalent or less of the generated lactic acid is sufficient.
  • the mineral acid used as the acid catalyst is sulfuric acid.
  • Such a mineral acid-added kashi can be added to either the first reactor or the second reactor, but in the present invention, it is preferable to add it to the second reactor or later. In the first reactor, since the esterification ratio is limited to 60-90%, the significance of adding the mineral acid is small.
  • a mineral acid is added to the second reactor, it may be added through, for example, a pipe 125.
  • the heating is continued in the range of 120 to 130 ° C. under stirring by the stirring blade provided in the second reactor 105, esterification is promoted.
  • the azeotropic composition of water and n-butanol produced by the heating reaction passes through the distillation column 123 above the second reactor 105 and is collected by the cooler 126 above the top of the distillation column 123.
  • the water phase and the butanol phase are separated in a two-liquid phase separator 128 below the cooler 126.
  • the upper-phase component n-butanol (containing a small amount of water) is refluxed to the top of the distillation column 123 through the pipe 131, and the lower-phase component water (containing a small amount of n-butanol) is withdrawn through the pipe 132 as needed. Collected in the collection tank. In addition, a very small amount of ammonia gas goes to a processing device from the exhaust stack 130 and is processed.
  • the ester reaction rate of the second reactor is not particularly limited, and is preferably 40 to 95% of lactic acid introduced into the second reactor, more preferably 50 to 80%.
  • reaction solution in the second reactor 105 is sent to a thin-film distillation apparatus 106 through a pipe 110. 100-150 inside the device 106.
  • the reaction solution was kept in an equilibrium state and separated into a liquid phase and a gas phase.Other residues such as acid ammonium sulfate as a liquid phase component were collected in a residue collection tank through a pipe 134.
  • Gas phase components of butyl lactate and n-butanol are collected in a butyl lactate recovery tower through a pipe 133.
  • the butyl lactate obtained here is referred to as a second lactic acid ester (B).
  • the first lactic acid ester (A) The lactate ester obtained by combining the lactate ester (B) has a low yield of by-products such as amidates, for example, 0 to 6.0%, and has a high yield and high optical activity. .
  • FIG. 1 shows an embodiment using a continuous apparatus
  • each step may be performed in a batch system.
  • the step of esterifying the reaction solution until the esterification ratio becomes 60-90% is required in the next step, which requires an apparatus for separating the lactate ester from the reaction solution containing the lactate ester.
  • a step of fractionating lactate contained in the reaction solution using the same reactor may be performed.
  • the step of esterifying the reaction solution until the esterification ratio becomes 60 to 90% and the step of distilling off the lactic acid ester and alcohol contained in the reaction solution may be performed simultaneously. According to this method, a lactate ester can be produced with a simpler apparatus using the same raw materials. Such a method will be described with reference to FIG.
  • an ammonia-neutralized lactic acid solution (lactic acid content 30-85% by mass) and n-butanol 3-7 times mol were added to the reactor 203 to form a reaction solution, which was provided in the reactor 203.
  • the reaction is carried out under stirring with stirring blades.
  • the reaction temperature is 100-170 for the esterification reaction.
  • C more preferably 120-130.
  • C pressure 40.00-101.30 kPa, more preferably 93.33-101.30 kPa.
  • N-Butanol azeotropic with water, alcohol for esterification reaction, and lactate ester are collected by the condenser 206 above the top of the distillation column 204 located above the reactor 203 and collected below the condenser 206.
  • the aqueous phase and the butanol phase are separated by the two-phase separator 207, and the upper phase component butanol (containing lactate ester and a small amount of water) is refluxed to the top of the distillation column 204 through the pipe 210, and the lower phase component water ( A small amount of n-butanol (including a small amount of n-butanol) is withdrawn as needed through the pipe 211 and collected in the water recovery tank.
  • the ammonia gas that has not been collected is released from the pipe 209 and can be recovered using an ammonia recovery device.
  • the reaction apparatus is set to 1.33 so that the reaction solution temperature becomes 100 to 170 ° C, more preferably 130 to 150 ° C. — 13. Reduce the pressure to 33 kPa.
  • the lactate ester and alcohol contained in the reaction solution can be fractionated with the reaction solution power.
  • the cock 210 ′ provided in the pipe 210 is closed, and the reflux of the upper phase of the two-phase separator 207 is stopped. It is introduced into the phase separator 207.
  • the lactate ester can be recovered via line 211. The esterification reaction proceeds during this fractionation operation.
  • alcohol is added in an amount of 110 to 10 times, more preferably 2 to 5 times the molar amount of lactic acid contained in the distillation residue remaining in the reactor 203, and esterification is performed again.
  • the amount of alcohol to be added is calculated by converting the lactic acid contained in the compound that can be converted into lactic acid into one unit as described above.
  • the reaction is carried out at a reaction temperature of 100 to 170 ° C, more preferably 120 to 150 ° C, and a pressure of 40.00 to 101.3 kPa, more preferably 93.3 to 101.3 kPa.
  • the second esteri-dani can be performed in the same manner as the first esteri-dani.
  • the ratio of beauty salon is not limited to 60-90%.
  • the lactate ester may be recovered from the pipe 211 and the lactate ester may be kept in the reaction solution without being separated.
  • the filtrate obtained by removing solids from the reaction solution by filtration contains lactate and alcohol. If the lactate ester obtained in the first esteri-dani and the lactate ester obtained in the second esteri-dani are combined and distilled, the lactate ester can be purified.
  • the amide production rate can be reduced while maintaining a high optical activity even when the esterification reaction time is the same. Further, it is also possible to shorten the esterification time, reduce the amide production rate, and improve the optical activity and the yield.
  • the second aspect of the present invention is characterized in that the ammonia-neutralized lactic acid fermentation liquor and the alcohol are esterified at a lactate amide formation rate of SO-6.0%, and the optical purity is 95-100%.
  • This is a method for producing ee lactic acid ester.
  • the ammonia-neutralized lactic acid fermentation liquor is used as a lactic acid raw material, since lactic acid exists as an ammonium lactate salt, the ammonium lactate salt must also release ammonia and then be esterified. If the deammonia rate is low, the esterification ratio does not improve.
  • lactic acid and ammonia react with each other to generate amide amides such as lactic acid amide.
  • the amide generation rate is preferably 0 to 6.0%, more preferably 0 to 5.0%. . If it exceeds 6.0%, the yield may decrease or the optical activity may decrease.
  • the esterification rate is not limited, but the esterification rate is 60 to 90% and the reaction is interrupted as in the first method for producing a lactic acid ester.
  • a method in which alcohol is added to lactic acid and then esterification is performed again is advantageous in that the heating time for esterification can be shortened, and a high-purity lactic acid ester can be obtained. is there.
  • lactamide is decomposed by further adding alcohol to the distillation residue and reacting to reduce the final amide production rate.
  • a lactic acid ester having optical activity of 95-100% ee, more preferably 98-100% ee can be produced by suppressing racemization.
  • a third aspect of the present invention is a method for producing lactic acid, comprising hydrolyzing the lactic acid ester produced by any of the methods described above.
  • the method for producing lactic acid of the present invention is carried out by hydrolyzing the lactic acid ester obtained by the above-mentioned method for producing lactic acid ester, usually using an acid catalyst. Thereby, the alcohol constituting the lactic acid ester can be removed, and highly purified lactic acid can be obtained.
  • the acid catalyst for example, ion exchange resin, mineral acid, and the like can be used. According to the method for producing a lactic acid ester of the present invention as described above, since the optical activity is high, lactic acid obtained by hydrolyzing the lactic acid ester can also maintain a high optical activity.
  • an ester reactor 203 shown in Fig. 2 500 g of a concentrated solution of 70% by mass of lactic acid and an ammonia-neutralized lactic acid fermentation solution and 1440 g of n-butanol (5.0 times the mol of lactic acid) were added to form a reaction solution.
  • the mixture was heated and reacted under stirring by a stirring blade provided in the reactor 203.
  • the heating temperature (oil bath temperature of oil bath 202) at this time was in the range of 140 to 170 ° C.
  • the n-butanol which azeotropes with water due to the heating is collected in the cooler 206 above the distillation column 204 located above the reactor 203, and is collected in the two-phase separator 207 below the cooler 206.
  • the upper phase component, butanol (containing a small amount of water), is separated into an aqueous phase and a butanol phase.
  • the upper phase component, butanol (containing a small amount of water), is returned to the top of the distillation column 204 through the pipe 210, and the lower phase component water (containing a small amount of n-butanol) is removed. At any time, it was withdrawn through the pipe 211 and collected in the water recovery tank. Most of the evaporated ammonia gas was dissolved in the condensate generated in the cooler 206, and the remainder was collected using an ammonia absorber (cold sulfuric acid water).
  • the temperature of the reaction solution in the reactor 203 was generally constant at 123 to 128 ° C. When this state was maintained and the esterification was continued for 18 hours, the esterification rate of lactic acid in the reaction solution became 85%.
  • Table 1 shows the reaction conditions, esterification rate, deammonification rate, amide generation rate, and optical purity of each Example and Comparative Example.
  • the distillation residue was added with 156 g of alcohol, and esterification was performed at 125 to 135 ° C under atmospheric pressure for 10 hours.
  • the final esterification ratio of the lactic acid ester obtained in Example 1 was 94%.
  • the amount of alcohol added to the distillation residue was 1.8 mol times the amount of milk acid contained in the distillation residue.
  • Example 1 and Example 2 were the same as Comparative Example 1 in that the total esterification time obtained by adding the times of the first esterification and the second esterification was 18 hours.
  • the amide generation rate was higher and the deammonification rate was higher than in Examples 1 and 2. Low. This is because in Examples 1 and 2, the deammonification step proceeded quickly during esterification, the generated ammonia was separated out of the system, and the decomposition of the amide proceeded more efficiently than in Comparative Example 1. it is conceivable that.
  • the esterification ratio was improved, and the yield was improved. Further, the optical activity is also improved as compared with Comparative Example 1.
  • Example 3 As in Comparative Example 2, the total esterification time obtained by adding the times of the first esterification and the second esterification was 32 hours. In Example 2, the amide formation rate was higher and the deammonification rate was lower than in Example 3. When Comparative Example 2 and Example 2 are compared, the deammonia rate, esterification rate, and amide generation rate are almost the same, but the optical purity is clearly reduced.
  • Example 3 and Comparative Example 2 have the same force in 32 hours of esteri-dani time.
  • Example 3 carried out the second esteri-dani after proceeding with esteri-dani up to 90% esteri-dani ratio.
  • the rate of deammonification and the rate of esterification were higher than those of Comparative Example 2.
  • these values in the third embodiment are similar to those in the first embodiment. This means that, rather than performing the second esterification after the esterification to 90%, the esterification is stopped at a rate of 60-90% and the second esterification after the lactate ester is separated. In particular, it shows that racemization can be suppressed efficiently.
  • a lactate ester can be produced in a high yield in a short time with a simple apparatus, and the obtained lactate ester is industrially useful because of its high optical purity.

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Abstract

Un procédé de fabrication d'un ester lactique ayant un faible taux de sécrétion d'amide et une activité optique élevée. Le procédé de fabrication d'un ester lactique, c'est-à-dire d'un produit d'estérification d'un alcool et d'acide lactique et/ou d'un sel d'acide lactique, comprend une étape dans laquelle un mélange réactionnel liquide comprenant un alcool et de l'acide lactique et/ou un sel d'acide lactique est estérifié jusqu'à ce que le degré d'estérification atteigne 60 à 90%, une étape dans laquelle l'ester lactique et l'alcool contenus dans le mélange réactionnel liquide résultant sont distillés, et une étape dans laquelle un alcool est ajouté au résidu de distillation résultant pour procéder de nouveau à une estérification. Par ce procédé, un ester lactique ayant une activité optique peut être produit avec un rendement élevé en peu de temps.
PCT/JP2005/004128 2004-03-17 2005-03-09 Procede de fabrication d'ester lactique WO2005087702A1 (fr)

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JP2015188371A (ja) * 2014-03-28 2015-11-02 王子ホールディングス株式会社 Ｄ−乳酸の精製のための工程が改良されたｄ−乳酸の製造方法
JP2020514336A (ja) * 2017-03-15 2020-05-21 シージェイ チェイルジェダン コーポレーション アルキル乳酸の製造方法

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BE1019555A3 (fr) * 2010-10-28 2012-08-07 Galactic Sa Procede de production d'un ester lactique a partir d'un jus de fermentation contenant du lactate d'ammonium.
CN114539052A (zh) * 2022-01-30 2022-05-27 安徽丰原发酵技术工程研究有限公司 一种以乳酸发酵液为原料制备乳酸酯的方法

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