CN100488938C - Process for producing lactic ester - Google Patents
Process for producing lactic ester Download PDFInfo
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- CN100488938C CN100488938C CNB2005800081671A CN200580008167A CN100488938C CN 100488938 C CN100488938 C CN 100488938C CN B2005800081671 A CNB2005800081671 A CN B2005800081671A CN 200580008167 A CN200580008167 A CN 200580008167A CN 100488938 C CN100488938 C CN 100488938C
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- lactic acid
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- 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
Abstract
A process for producing a lactic ester having a low rate of amide generation and high optical activity. The process for producing a lactic ester, i.e., a product of the esterification of an alcohol and lactic acid and/or a lactic acid salt, comprises a step in which a liquid reaction mixture comprising an alcohol and lactic acid and/or a lactic acid salt is esterified until the degree of esterification reaches 60 to 90%, a step in which the lactic ester and the alcohol which are contained in the resultant liquid reaction mixture are distilled off, and a step in which an alcohol is added to the resultant distillation residue to conduct esterification again. By the process, a lactic ester having high optical activity can be produced in high yield in a short time.
Description
Technical field
The present invention relates to the manufacture method of the lactate of yield excellence, particularly use and contain the method that lactic acid or Lactated lactic acid fermentation liquid are made lactate efficiently.
Background technology
Lactic acid is to be used in the manufacturing of pure mellow wine, refreshment drink, salted vegetables, soy sauce, bread or beer etc. as foodstuff additive, in addition, and as the industrial useful compound that is used in the manufacturings such as leather, fiber, plastics, medicine or agricultural chemicals.Recently, as safe solvent or washing composition, its purposes broadens as ester classes such as the ethyl lactate of the derivative of lactic acid or synthetic intermediate or n-Butyl lactates.Particularly, when being utilized as the raw material of medicine, agricultural chemicals, high-pure lactic acid or its ester body with high optical activity necessitate, and just produce by lactic fermentation.
As the manufacture method of this lactate, the use lactic acid fermentation liquid is disclosed, be accompanied by the carrying out of lactobacillus-fermented, the pH that utilizes neutralization such as ammonia to reduce, ferment simultaneously, the gained lactic acid salt changes into lactic acid with sulfuric acid, the method for utilizing the Virahol equal solvent to extract.The lactic acid that extracts uses methanol esterification (the Japanese Patent spy opens clear 58-56690 communique).
In addition, the gaseous mixture that will contain carboxylate in addition in esterification lactic acid partly condenses, then by vacuum distilling concentrated lactic acid ester, and to spissated rough lactate enforcement distillatory method (the Japanese Patent spy the opens clear 58-189138 communique) second time.If this method is to make carboxylate in view of the use lactic acid aqueous solution, then carboxylate decomposes on this point in the presence of water easily, carboxylate is carried out once more the method for esterification.
In addition, the pH of the substratum when utilizing ammonia to adjust lactic fermentation in addition, add the alcohol of carbonatoms 4 or 5 in containing by the lactic acid fermentation liquid of this fermentation gained DL-Lactic acid ammonium salt, esterification is carried out in heating, makes the method (Japanese patent laid-open 6-311886 communique) of corresponding lactate.In Japanese patent laid-open 6-311886 communique, in the solution that obtains by esterification, add mineral acid as esterification promotor, under acidity, heat and dewater, promote and finish this lactic acid and this pure esterification.In addition, use the reason of the alcohol of carbonatoms 4 or 5 to be, when should alcohol using, also play a role as azeotropy dehydrant as esterification feed.Gained esterification liquid is moisture hardly, microorganism, other impurity such as inorganic acid salt, milk-acid bacteria of containing remaining alcohol, this pure lactate, ammonia, because ammonium salt, high molecular impurity or milk-acid bacteria etc. exist as slurries, therefore carry out the distillation process of intermittent type or continous way, separating lactic acid ester and alcohol.
Summary of the invention
Lactate use as himself or hydrolysis after use as lactic acid.Purposes also relates to a plurality of branches such as foodstuff additive, industrial, medicine, agricultural chemicals, and as the poly(lactic acid) of polymkeric substance still as the biodegradability polymkeric substance and the compound of being expected.Therefore, the yield of lactate and the raising of making efficient are important problem very.In addition, because lactic acid is optically active compound, the therefore also strong manufacture method of wishing to develop the high lactate of optical activity.
In this case, the invention provides the more efficient manufacture method of lactate.
The inventor etc. study in great detail the manufacture method of lactate, found that the reaction solution to containing lactic acid or lactic acid salt and alcohol carries out esterification, at esterification yield is temporarily to interrupt in 60～90% o'clock, contained lactate is separated with alcohol, when interpolation alcohol carries out esterification once more in raffinate, the lactate that obtains by the esterification first time and esterification for the second time amounts to esterification yield above 90%, the situation that obtains lactate with single is compared, amount of by-products such as yield height and amidate extremely reduce, purity improves, and then finished the present invention.The present invention can also can carry out with intermittent type with continous way, can also shorten esterification time, improves optical purity.
And then, also find during enzymatic synthesis condition in research, with in the ammonia and lactic acid fermentation liquid during,, then can make optical purity height, lactate that yield is high easily if heat according to lactic amide production rate 0～6.0% as lactic raw material.
Promptly, the invention provides a kind of manufacture method of lactate, this method is an alcohol and the manufacture method of lactic acid and/or Lactated carboxylate, comprising: carry out esterification and reach the operation of contained lactate in 60～90% operation, this reaction solution of fractionation and add the operation that alcohol carries out esterification once more in distillation residue until esterification yield containing alcohol and lactic acid and/or Lactated reaction solution.
In addition, the present invention is the manufacture method of the lactate of a kind of optical purity 95～100%ee, it is characterized in that, in the lactic amide production rate is 0～6.0% scope, makes in the ammonia and carries out esterification with lactic acid fermentation liquid and alcohol.
Can make the high lactate of yield with easy method by the present invention.And, because the enzymatic synthesis condition gentleness, so the energy efficiency excellence.In addition, by the present invention,, therefore can access the high lactate of optical purity owing to be under the enzymatic synthesis condition of gentleness, to react.
The present invention is owing to can when therefore making carboxylate after obtaining lactic acid by lactic fermentation, especially can operate effectively with lactic acid fermentation liquid as raw material.
Description of drawings
[Fig. 1] Fig. 1 is the figure of expression with the device of continous way manufacturing lactate of the present invention.
[Fig. 2] Fig. 2 is the figure of expression with the device of intermittent type manufacturing lactate of the present invention.
Embodiment
First invention of the present invention is a kind of manufacture method of lactate, this method is an alcohol and the manufacture method of lactic acid and/or Lactated carboxylate, comprising: carry out esterification and reach the operation of contained lactate in 60～90% operation, this reaction solution of fractionation and add the operation that alcohol carries out esterification once more in distillation residue until esterification yield containing alcohol and lactic acid and/or Lactated reaction solution.
The lactic acid of Shi Yonging can be the lactic acid that makes by any method in the present invention, can use the lactic acid of material that the rac-Lactide of two molecule lactic acid be combined intos makes through hydrolysis, chemosynthesis or lactic acid that the lactic acid made by the biology manufacture method of utilizing lactic acid fermenting bacteria etc. obtains by any means.If use the lactic acid that utilizes lactic acid fermenting bacteria to make, then can access the lactate of optical activity excellence, therefore preferred especially.
As lactic acid salt, do not break away from and carry out the just passable of esterification from lactic acid so long as when esterification, do not hinder salt, can use any lactic acid salt.Can enumerate salt with calcium ion, ammonium ion and amine as this lactic acid salt.Contained lactic acid salt and be owing to considered the processing by the lactic acid manufacturing process of neutralization etc., end article becomes Lactated situation.
Among the present invention, lactic acid or lactic acid salt (the following lactic acid (salt) that only is called) can be supplied with the aqueous solution.When using this lactic acid (salt) aqueous solution, convert with lactic acid and preferably to contain 30～85 quality %, the more preferably lactic acid (salt) of 45～75 quality %, preferred especially 50～70 quality %.In addition, lactic acid content is in above-mentioned scope the time, can also concentrated lactic acid or lactic acid salt or the solution that will dilute according to above-mentioned concentration as lactic acid (salt) aqueous solution.Among the present invention, can use lactic acid fermentation liquid as this lactic acid (salt) aqueous solution.And this lactic acid fermentation liquid is the fermented liquid that contains lactic acid when utilizing lactic acid fermenting bacteria biology ground to make lactic acid.Owing to pH along with lactic acid fermented carrying out reduces, therefore neutralize by adding alkaline matter usually, ferment simultaneously, preferably use ammonia to use as this alkaline matter.Among the present invention, this lactic acid fermentation liquid is called " in the ammonia and lactic acid fermentation liquid ".Carry out in the ammonia and the time, can also in esterification, fractionation reclaim free ammonia.As in this ammonia and lactic acid fermentation liquid, for example can open the method modulation of clear 58-56690 communique, the record of Japanese patent laid-open 6-311886 communique by the Japanese Patent spy.
As the alcohol that uses in the esterification, especially preferably use the alcohol of carbonatoms 4～6.Can use for example propyl carbinol, isopropylcarbinol, the trimethyl carbinol, Pentyl alcohol (n-amylalcohol), sec.-amyl alcohol, tertiary amyl alcohol, primary isoamyl alcohol, secondary primary isoamyl alcohol, active amyl alcohol, diethyl carbinol, tertiary butyl methyl alcohol, Pentyl alcohol (n-pentyl alcohol) etc., more preferably propyl carbinol as this alcohol.Because propyl carbinol and water azeotropic, therefore after this Azeotrope compositions is suitably cooled off collection, propyl carbinol and water are carried out 2 be separated, just propyl carbinol can be used for the esterification system once more, very saving.In addition, carbonatoms surpass 6 pure the time, the free of ammonia that esterification produces is possible, but because the lactate boiling point height that is generated, and passes through the refining difficulty that often becomes that the lactate distillation is carried out after therefore.The alcohol of carbonatoms 1～3 particularly because insufficient with being separated of water, therefore often not energy efficiency work well.
Among the present invention, consider reaction efficiency etc., lactic acid (salt) aqueous solution and this pure ratio of mixture are preferably 0.3～100 mole times, more preferably 1～10 mole times, preferred especially 3～6 moles times with respect to lactic acid (salt).Be lower than 0.3 mole doubly, then have lactic acid dimer to become situation many, that reaction is not carried out.On the contrary, if surpass 100 moles doubly, then the temperature of reaction solution being risen to esterification temperature needs for a long time, and temperature control thereafter also becomes difficulty.Below, as an example of embodiment of the present invention, to using continous way lactate manufacturing installation shown in Figure 1, using in the ammonia and situation that lactic acid fermentation liquid and propyl carbinol are made lactate describes.
In the device 101 shown in Figure 1, first reactor 103, film distillator 104, second reactor 105 and film distillator 106 are connected with 110 with pipe arrangement 108,109 respectively.
At first, in this first reactor 103, add the ammonia and lactic acid fermentation liquid, add propyl carbinols from pipe arrangement 116 and make reaction solution, heat under the stirring of the stirring rake in being installed in this first reactor 103, carry out esterification from pipe arrangement 107.Distillation tower 114 on the top that is equipped on first reactor 103, more be connected with water cooler 117 with pipe arrangement 118 in top at it, propyl carbinol or, and Azeotrope compositions, the lactate of propyl carbinol in water cooler 117, be collected, be separated into water and butanols in the two liquid phase separation jars 119 below this water cooler 117 mutually.The propyl carbinol of last phase composition (containing lactate and less water) is back to distillation tower 114 tops by pipe arrangement 122, and the water of following phase composition (containing a small amount of propyl carbinol and ammonia) is drawn out of, is recovered in the water accumulator tank by pipe arrangement 121 at any time.In addition, the most of ammonia that has passed through distillation tower 114 all is collected in water cooler 117, and remaining ammonia is collected by the ammonia absorber of ice-cold ability of swimming via pipe arrangement 120.
Enzymatic synthesis condition changes according to kind of used alcohol etc., and distillation tower top of tower pressure is that normal pressure gets final product.Temperature of reaction is also according to used alcohol and difference, usually 100～170 ℃, preferably under 120～130 ℃ scope, carry out.This temperature is during less than 100 ℃, and existence can't be met the situation of industrial speed of response.When this temperature surpassed 170 ℃, lactic acid partial racemizationization, the corresponding phenomenons such as ether of 2 molecules alcohol formation can appear.
In addition, in the esterification of DL-Lactic acid ammonium salt and propyl carbinol, temperature is 100～170 ℃, more preferably 110～150 ℃, is preferably 120～130 ℃ especially.In this scope, the reactivity height of DL-Lactic acid ammonium salt and the yield of lactate are also high.At this moment, preferably only heat in the ammonia and lactic acid fermentation liquid, when wherein adding alcohol, make its reaction.If add alcohol in the back like this, then can shorten the reaction times.For example, the situation of propyl carbinol that doubly drops into 117.7 ℃ of boiling points with 3 moles of DL-Lactic acid ammonium salt is as example, the azeotropic point that reaches propyl carbinol and water more than 92.3 ℃ after, be accompanied by the carrying out of dehydrationization and esterification, temperature rises, therefore for esterification reach equilibrium state, esterification temperature reaches constant needs the long period.If but only heat in the ammonia and lactic acid fermentation liquid, then because the effect of salt, be accompanied by the boiling point that concentrates and surpass water and reach about 107 ℃, therefore can improve fluid temperature at short notice.Therefore, if add alcohol, then can when control to the goal response temperature rapidly, shorten reaction time of esterification and make lactate thereafter.
Among the present invention, above-mentioned esterification reaches 60～90%, preferred 65～90%, preferred especially 70～90% according to the esterification yield of lactic acid in the reactor 103 modulates, and transfers to next operation.If esterification yield surpasses 90%, then the time of the condition of high temperature long, therefore often optical activity reduction.On the other hand, if esterification yield less than 60%, then production rate reduces, and is unfavorable.
Esterification yield is that 60～90% reaction solution is supplied in the film distillator 104 by pipe arrangement 108, herein, lactate and alcohol is distilled away from cat head.The separating lactic acid ester is in order to prevent optically active reduction and to improve esterification speed from reaction solution before carrying out the esterification second time.
Distillation tower top of tower pressure can suitably be selected by the lactate kind of rectifying, is preferably 0.67～13.33kPa usually, is preferably 1.33～2.67kPa especially.If be higher than 13kPa, then the distillation of lactate, alcohol and water is insufficient.On the other hand, even less than 0.67kPa, also very little to the influence of distilling effect.Under the situation of n-Butyl lactate, tower top pressure is that 0.67～13kPa, tower top temperature are 61～125 ℃.The n-Butyl lactate that distilled this moment is called first lactate (A).
Distillation residue are imported in second reactor 105 by pipe arrangement 109, carry out esterification once more.When avoidance is heat-treated the lactate that is generated, in distillation residue, add alcohol again and react, can decompose lactic amide effectively thus, improve the yield of lactate, guarantee whole optical purity.
Contain sugar from lactic acid fermentation liquid, starch, tarry matters, lact-acid oligomer, saccharolactic acid ester, lactic amide, rac-Lactide, lactic acid polymer, lactic acid (salt), water, alcohol, lactate etc. in this nubbin.By pipe arrangement 116 ' to wherein supplying with propyl carbinol.The alcohol amount of adding in above-mentioned distillation residue is that benchmark converts according to contained lactic acid production in the above-mentioned distillation residue.Lactic acid or lactic acid salt generate lactate by the reaction with alcohol, but lactic amide, rac-Lactide and lact-acid oligomer, lactic acid polymer etc. also resolve into lactic acid, become lactate.Among the application, in the conversion of the alcohol amount in adding distillation residue to, the compound that can change lactic acid into also is converted into a unit with contained lactic acid and calculates.For example, the lact-acid oligomer that forms of 1 molar lactic acid and 3 molecule lactic acid polymerizes is as 4 molar lactic acid.Preferably with respect to contained lactic acid in the distillation residue add 0.3～100 mole doubly, 0.5～80 mole of alcohol doubly more preferably.If less than 0.3 mole times, then esterification is slack-off; On the other hand, if surpass 100 moles doubly, then often esterification efficient reduces.
Reaction conditions in second reactor 105 according to the changes such as kind of used alcohol, is 100～150 ℃, more preferably 120～150 ℃.
Follow the carrying out of esterification, produce water byproduct, be accompanied by the distillation of this water byproduct, alcohol also component distillation is gone out, but after preferably this alcohol and water being separated with this alcohol reflux in second reactor.Thus, can utilize this alcohol effectively again, also excellent economically.
In addition, among the present invention, can also be when esterification, in reaction solution, add mineral acid and under acidity, heat, promote this lactic acid and this pure esterification.In the esterification, often self condensation of a part of lactic acid becomes the reason that the lactate production rate reduces.Therefore, 0.005～0.8 mole of the lactic acid that add to generate doubly, be preferably 0.01～0.2 mole of mineral acid doubly as acid catalyst.By adding acid catalyst, rac-Lactide, lact-acid oligomer, lactic acid polymer hydrolysis become lactic acid, improve the yield of lactate.At this moment,, then temperature can be reduced, side reactions such as ether can be suppressed to generate if under reduced pressure carry out thermal dehydration.In addition, be not particularly limited as the upper limit of the addition of the mineral acid of acid catalyst, normally the following mineral acid of 0.2 of the lactic acid of Sheng Chenging times of equivalent is just enough.In addition, the mineral acid that uses as acid catalyst has sulfuric acid.The interpolation of this mineral acid can be added in any one in first reactor and second reactor, but in the present invention, preferably in second reactor and interpolation later on thereof.Its reason is, because esterification yield is controlled at 60～90%, so the interpolation meaning of mineral acid is little in first reactor.In addition, when in second reaction vessel, adding mineral acid, for example can add by pipe arrangement 125.If continue heating under the stirring of the stirring rake in being installed in this second reactor 105 under 120～130 ℃ of scopes, then esterification is promoted.In addition, by the water and the Azeotrope compositions of propyl carbinol that this reacting by heating produces, the distillation tower 123 that passes through the top of this second reactor 105 is collected in by the water cooler 126 above these distillation tower 123 cats head, be separated into water and butanols in the two liquid phase separation jars 128 below this water cooler 126 mutually.Last phase composition propyl carbinol (containing less water) is back to distillation tower 123 tops by pipe arrangement 131, and following phase composition water (containing a small amount of propyl carbinol) is drawn out of, is recovered in the water accumulator tank by pipe arrangement 132 at any time.In addition, the ammonia of denier leads to treatment unit and processed by aiutage 130.
The esterification yield of second reactor is not particularly limited, and is preferably 40～95% of the lactic acid that is directed to second reactor, and more preferably 50～80%.
At last, by pipe arrangement 110 reaction solution in above-mentioned second reactor 105 is delivered to thin film distillation device 106.In this device 106 under 100～150 ℃, 1.33～6.66kPa, this reaction solution remained under the equilibrium state be separated into liquid and gas, other resistatess such as the acid ammonium sulfate of liquid composition are recovered in the residue accumulator tank by pipe arrangement 134, and the n-Butyl lactate of gas phase composition and propyl carbinol are collected in the n-Butyl lactate recovery tower by pipe arrangement 133.The n-Butyl lactate that obtained this moment is called second lactate (B).
According to the manufacture method of lactate of the present invention, merge the lactate that above-mentioned first lactate (A) and second lactate (B) obtain, the production rate of by products such as its amidate for example is low to moderate 0～6.0%, and yield height and optical activity are also high.
In addition, Fig. 1 is to use the mode of continuous apparatus, but also can carry out each operation with intermittent type.In addition, in method shown in Figure 1, the device that need from the reaction solution that contains lactate, divide the extracting lactic acid ester, but also can above-mentioned reaction solution esterification is reached 60～90% operation to esterification yield after, use the operation of contained lactate in same this reaction solution of reactor fractionation.
In addition, can also carry out operation that above-mentioned reaction solution esterification to esterification yield is reached 60～90% operation and contained lactate in this reaction solution and alcohol are distilled simultaneously.By this method, can use same raw material, make lactate with easier device.With reference to Fig. 2 this method is described.
At first, in reactor 203, add in the ammonia and lactic acid solution (lactic acid content 30～85 quality %) and the propyl carbinol of 3～7 times of moles are made reaction solution, heat under the stirring of the stirring rake in being installed in this reactor 203 and react.Temperature of reaction is 100～170 ℃, more preferably 120～130 ℃ when carrying out esterification, and pressure is 40.00～101.30kPa, 93.33～101.30kPa more preferably.The alcohol of using with water azeotropic propyl carbinol, esterification, the lactate water cooler 206 above distillation tower 204 cats head that are arranged in above the reactor 203 is collected, be separated into water and butanols in the two phase separator 207 below water cooler 206 mutually, last phase composition butanols (containing lactate and less water) is back to the cat head of distillation tower 204 by pipe arrangement 210, following phase composition water (containing a small amount of propyl carbinol) is drawn out of by pipe arrangement 211 at any time, is recovered in the water accumulator tank.The ammonia that is not collected can be emitted from pipe arrangement 209, utilizes ammonia recovery unit to reclaim., finally reach for 60～90% stage at the esterification yield of reaction solution thereafter, according to reacting liquid temperature reach 100～170 ℃, more preferably 130～150 ℃ reaction unit is decompressed to 1.33～13.33kPa.Thus, the lactate and the alcohol fractionation from reaction solution that are contained in the reaction solution can be come out.When temperature rises, close the valve of being located on the pipe arrangement 210 210 ', stop the backflow of the last phase of two phase separator 207, lactate and alcohol arrive water cooler 206 from distillation tower 204, are directed to after the cooling in the two phase separator 207.Lactate can reclaim via pipe arrangement 211.In addition, esterification is also underway during this fractionation operation.
Then, add 1～10 mole doubly, 2～5 moles of alcohol of contained lactic acid in the residual distillation residue in reactor 203 doubly more preferably, carry out esterification once more.In addition, the alcohol amount of being added is same as described above, and the compound that can be transformed into lactic acid also is converted into a unit with contained lactic acid and obtains.100～170 ℃ of temperature of reaction, more preferably 120～150 ℃, pressure 40.00～101.3kPa, 93.33～101.30kPa reaction down more preferably.Esterification for the second time can be carried out equally with the esterification first time.But esterification yield is not limited to 60～90%.For the second time in the esterification, same with first invention, can reclaim lactates from pipe arrangement 211, can not separate lactate yet and be included in the reaction solution.Solids removed by filtration composition from reaction solution and contain lactate and alcohol in the filtrate that obtains.The lactate that obtains in the lactate that obtains in first esterification and the esterification is for the second time merged, distill, just can the fine purification of lactic acid ester.According to the manufacture method of lactate of the present invention, also can under the state that optical activity is maintained high value, reduce the acid amides production rate even reaction time of esterification is identical.In addition, can also shorten esterification time, reduction acid amides production rate and raising optical activity and yield.
Second invention of the present invention is the manufacture method of lactate of a kind of optical purity 95～100%ee, it is characterized in that, makes in the ammonia and lactic acid fermentation liquid and alcohol carry out esterification in the lactic amide production rate is 0～6.0% scope.If will carry out esterification with lactic acid fermentation liquid as lactic raw material in the ammonia, then because lactic acid carries out esterification after as the existence of lactic acid ammonium salt, therefore need breaking away from ammonia from the lactic acid ammonium salt.If this deamination rate is low, then esterification yield can not rise.In addition, lactic acid and ammonia react produce amidates such as lactic amide.Find among the present invention, be proportionate between deamination rate and the esterification yield, and be retrocorrelation relation between acid amides production rate and the deamination rate, if when esterification, the acid amides production rate is limited in the specialized range, then can make deamination rate and esterification yield excellence, optical purity is the lactate of 95～100%ee.
Among the present invention, in ammonia and in the esterification of lactic acid solution and alcohol, the acid amides production rate is preferably 0～6.0%, more preferably 0～5.0%.If surpass 6.0%, then yield reduces, optical activity descends in addition.
Carry out esterification method as this lactic amide production rate being controlled in 0～6.0% the scope, the method for making above-mentioned first lactate is for example arranged.At this moment, though esterification yield is unqualified, but it is identical with the above-mentioned first lactate manufacture method, temporarily interrupt if reach at 60～90% o'clock at esterification yield, separate after the lactate that is generated, in unreacted lactic acid, add alcohol and carry out esterification method once more, just can shorten the heat-up time that is used for esterification, and can access purity lactic acid esters with high, therefore preferred.
In addition, in above-mentioned first and second methods, react, can decompose lactic amide, reduce final acid amides production rate by in distillation residue, adding alcohol once more.
According to second invention, can suppress racemization, can make optical activity 95～100%ee, the lactate of 98～100%ee more preferably.
The 3rd invention of the present invention is a kind of manufacture method of lactic acid, it is characterized in that, the lactate by above-mentioned any one method manufacturing is hydrolyzed.The method that the manufacture method of lactic acid of the present invention is to use common acid catalyst to be hydrolyzed and to finish by the lactate that above-mentioned lactate manufacture method makes.By this method, the alcohol that constitutes lactate can be removed, can access by highly refined lactic acid.Can make spent ion exchange resin, mineral acid etc. as above-mentioned acid catalyst.In addition, as mentioned above, according to the manufacture method of lactate of the present invention, because the optical activity height, therefore the lactic acid that its hydrolysis is obtained also can be kept very high optical activity.
Embodiment
Below, enumerate embodiment and specify the present invention, but these embodiment do not limit the present invention.In addition, quantitatively all being undertaken of the lactic acid in the fermented liquid in following examples by high performance liquid chromatography (ultraviolet absorption detector).Equally, the analysis of the n-Butyl lactate in the reaction solution is carried out with vapor-phase chromatography, and the analysis of ammonia is undertaken by titration.
(comparative example 1)
In ester reactor 203 shown in Figure 2, add in the ammonia of 500g lactic acid 70 quality % and the concentrated solution of lactic acid fermentation liquid and 1440g propyl carbinol (5 times of moles of lactic acid) as reaction solution, heating makes it its reaction under the stirring of the stirring rake in being installed in this reactor 203.The Heating temperature (oil bath temperature of oil bath 202) of this moment is 140～170 ℃ of scopes.By heating, be collected with the water cooler 206 of water azeotropic propyl carbinol above distillation tower 204 cats head that are arranged in above the reactor 203, be separated into water and butanols in the two phase separator 207 below water cooler 206 mutually, last phase composition butanols (containing less water) is back to the cat head of distillation tower 204 by pipe arrangement 210, following phase composition water (containing a small amount of propyl carbinol) is drawn out of by pipe arrangement 211 at any time, is recycled in the water accumulator tank.In addition, the ammonia majority of evaporation is dissolved in the concentrated solution that produces in water cooler 206, and remaining use ammonia absorber (cold water of sulfuric acid) is collected.
Temperature of reaction in the reactor 203 is 123～128 ℃ of following almost fixed.When keeping this state continuance and carrying out 18 hours esterification, the esterification yield of the lactic acid in the reaction solution reaches 85%.Below, provided reaction conditions, esterification yield, deamination rate, acid amides production rate, the optical purity of each embodiment and comparative example in the table 1.
(embodiment 1)
Except esterification time is 8 hours, to operate equally with comparative example 1, the esterification yield that obtains lactic acid is 69% reaction solution.Then, with contained lactate in this reaction solution and alcohol fractionation under 130～150 ℃ of temperature, pressure 1.33～101.30kPa, reach 150 ℃, pressure until the liquid temperature and reach 1.33kPa.Distillation residue in the reactor are 156g.
In these distillation residue, add 156g alcohol, under 125～135 ℃ of temperature, normal atmosphere, carry out 10 hours esterification.The final esterification yield of the lactate that obtains in embodiment 1 is 94%.In addition, adding alcohol amount in the distillation residue this moment to is that 1.8 moles of contained lactic acid doubly in the distillation residue.
(embodiment 2)
Except esterification time is 12 hours, to operate equally with comparative example 1, the esterification yield that obtains lactic acid is 80% reaction solution.Then, contained lactate in this reaction solution and alcohol under 130～150 ℃ of temperature, pressure 1.33～101.30kPa, are reached the condition distillation that 150 ℃, pressure reach 1.33kPa with the liquid temperature.Distillation residue in the reactor are 114g.
In these distillation residue, add 114g alcohol, under 125～135 ℃ of temperature, normal atmosphere, carry out 6 hours esterification.The final esterification yield of the lactate that obtains in embodiment 2 is 92%.In addition, adding alcohol amount in the distillation residue this moment to is that 2.0 moles of contained lactic acid doubly in the distillation residue.
(comparative example 2)
Except esterification time is 32 hours, to operate equally with comparative example 1, the esterification yield that obtains lactic acid is 93% reaction solution.
(embodiment 3)
Except esterification time is 24 hours, to operate equally with comparative example 1, the esterification yield that obtains lactic acid is 90% reaction solution.Then, contained lactate in this reaction solution and alcohol under 130～150 ℃ of temperature, pressure 1.33～101.30kPa, are reached the condition distillation that 150 ℃, pressure reach 1.33kPa with the liquid temperature.Distillation residue in the reactor are 76g.
In these distillation residue, add 76g alcohol, under 125～135 ℃ of temperature, normal atmosphere, carry out 8 hours esterification.The final esterification yield of the lactate that obtains in embodiment 3 is 95%.In addition, adding alcohol amount in the distillation residue this moment to is that 1.6 moles of contained lactic acid doubly in the distillation residue.
Table 1
| First esterification time (hr) | First esterification yield (%) | Second esterification time (hr) | Deamination rate (%) | Final esterification yield (%) | Acid amides production rate (%) | Optical purity (%ee) | |
| Comparative example 1 | 18 | 85 | 0 | 88 | 85 | 8.9 | 99.9 |
| |
8 | 69 | 10 | 96 | 94 | 3.0 | 99.9 |
| Embodiment 2 | 12 | 80 | 6 | 94 | 92 | 5.0 | 99.7 |
| Comparative example 2 | 32 | 93 | 0 | 94 | 93 | 4.8 | 96.5 |
| Embodiment 3 | 24 | 90 | 8 | 96 | 95 | 3.0 | 98.8 |
(result)
(1) total esterification time that first esterification time and second esterification time amount among embodiment 1 and the embodiment 2 is all 18 hours mutually with comparative example 1, but the comparative example 1 of not implementing second esterification compares with embodiment 1,2, and acid amides production rate height and deamination rate are low.Think its reason be since embodiment 1,2 when carrying out esterification, the deamination operation is carried out rapidly and the ammonia that produces is split into outside the system, and the decomposition of acid amides is carried out more efficiently than comparative example 1.In addition, compare with comparative example 1, the esterification yield of embodiment 1,2 improves, and yield improves.In addition, optical activity also improves than comparative example 1.
(2) total esterification time that first esterification time and second esterification time amount among the embodiment 3 is all 32 hours mutually with comparative example 2, but the comparative example 2 of not implementing second esterification compares with embodiment 3, and acid amides production rate height and deamination rate are low.In addition, comparative example 2 and embodiment 2 are compared, deamination rate, esterification yield, acid amides production rate are the numerical value of equal extent, but optical purity obviously descends.
(3) though embodiment 3 and comparative example 2 esterification times were all 32 hours, and embodiment 3 reaches the example of implementing second esterification on 90% the basis again carrying out esterification to esterification yield, deamination rate and esterification yield are higher than comparative example 2.But these numerical value of embodiment 3 and embodiment 1 are equal extent.This shows, is temporarily to stop in 60～90% o'clock, carry out second esterification method behind the separating lactic acid ester at esterification yield, and carries out carrying out second esterification again after esterification to esterification yield reaches 90% and compares, and especially can suppress racemization efficiently.
Industrial applicability
According to the present invention, can make at short notice the high lactate of yield with easy device, gained lactate optical purity is also high, and is industrially useful.
Claims (20)
1. the manufacture method of a lactate, this method is an alcohol and the manufacture method of lactic acid and/or Lactated carboxylate, comprising: to contain alcohol and lactic acid and/or Lactated reaction solution carry out esterification until esterification yield reach 60～90% operation, with this reaction solution in the operation that distills of contained lactate and described alcohol and in the gained distillation residue, add the operation that alcohol carries out esterification once more.
2. the manufacture method of lactate according to claim 1 is characterized in that, described reaction solution contains alcohol and the lactic acid aqueous solution and/or the lactic acid salt aqueous solution.
3. the manufacture method of lactate according to claim 2 is characterized in that, the described lactic acid aqueous solution and/or the lactic acid salt aqueous solution are in the ammonia and lactic acid fermentation liquid.
4. according to the manufacture method of each described lactate in the claim 1～3, it is characterized in that described alcohol is the alcohol of carbonatoms 4～6.
5. according to the manufacture method of each described lactate in the claim 1～3, it is characterized in that, add alcohol amount in the described distillation residue to and be 0.3～100 mole of contained lactic acid in the described distillation residue doubly.
6. the manufacture method of lactate according to claim 3 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
7. the manufacture method of lactate according to claim 4 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
8. the manufacture method of lactate according to claim 5 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
9. the manufacture method of lactate according to claim 3 is characterized in that, the lactic amide production rate is in 0～6.0% scope.
10. the manufacture method of lactate according to claim 9 is characterized in that, described alcohol is the alcohol of carbonatoms 4～6.
11. the manufacture method of lactic acid, it is characterized in that, this method be by to contain alcohol and lactic acid and/or Lactated reaction solution carry out esterification until esterification yield reach 60～90% operation, with this reaction solution in the operation that distills of contained lactate and described alcohol and in the gained distillation residue, add the operation that alcohol carries out esterification once more and prepare lactate, then with resulting lactate hydrolysis.
12. the manufacture method of lactic acid according to claim 11 is characterized in that, described reaction solution contains alcohol and the lactic acid aqueous solution and/or the lactic acid salt aqueous solution.
13. the manufacture method of lactic acid according to claim 12 is characterized in that, the described lactic acid aqueous solution and/or the lactic acid salt aqueous solution are in the ammonia and lactic acid fermentation liquid.
14. the manufacture method according to each described lactic acid in the claim 11～13 is characterized in that, described alcohol is the alcohol of carbonatoms 4～6.
15. the manufacture method according to each described lactic acid in the claim 11～13 is characterized in that, adds alcohol amount in the described distillation residue to and be 0.3～100 mole of contained lactic acid in the described distillation residue doubly.
16. the manufacture method of lactic acid according to claim 13 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
17. the manufacture method of lactic acid according to claim 14 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
18. the manufacture method of lactic acid according to claim 15 is characterized in that, ammonia contained in the described reaction solution is reclaimed with the lactate that is generated.
19. the manufacture method of lactic acid according to claim 13 is characterized in that, the lactic amide production rate is in 0～6.0% scope.
20. the manufacture method of lactic acid according to claim 19 is characterized in that, described alcohol is the alcohol of carbonatoms 4～6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP076463/2004 | 2004-03-17 | ||
| JP2004076463 | 2004-03-17 |
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| JP (1) | JP4685766B2 (en) |
| CN (1) | CN100488938C (en) |
| WO (1) | WO2005087702A1 (en) |
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| EP2470494B1 (en) * | 2009-09-07 | 2013-12-11 | Council of Scientific & Industrial Research | Process for preparation of pure alkyl esters from alkali metal salt of carboxylic acid |
| BE1019555A3 (en) * | 2010-10-28 | 2012-08-07 | Galactic Sa | PROCESS FOR PRODUCING A LACTIC ESTER FROM A FERMENTATION JUICE CONTAINING AMMONIUM LACTATE |
| JP6183263B2 (en) * | 2014-03-28 | 2017-08-23 | 王子ホールディングス株式会社 | Process for producing D-lactic acid with improved process for purification of D-lactic acid |
| KR101981391B1 (en) * | 2017-03-15 | 2019-05-23 | 씨제이제일제당 (주) | Method for preparation of alkyl lactate |
| CN114539052A (en) * | 2022-01-30 | 2022-05-27 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lactate by taking lactic acid fermentation liquor as raw material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104254A (en) * | 1993-03-02 | 1995-06-28 | 株式会社武藏野化学研究所 | Method for production of lactic acid and lactic esters |
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| JP2000300898A (en) * | 1999-04-16 | 2000-10-31 | Matsushita Electric Ind Co Ltd | Steam iron |
| JP2003073330A (en) * | 2001-06-18 | 2003-03-12 | Ikuko Wakejima | Method for producing lactic acid ester |
| JP4158396B2 (en) * | 2002-03-28 | 2008-10-01 | トヨタ自動車株式会社 | Method and apparatus for producing lactate ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104254A (en) * | 1993-03-02 | 1995-06-28 | 株式会社武藏野化学研究所 | Method for production of lactic acid and lactic esters |
Non-Patent Citations (4)
| Title |
|---|
| 乳酸酯及其衍生物的合成研究进展. 陈丹云.化工进展，第21卷第4期. 2002 |
| 乳酸酯及其衍生物的合成研究进展. 陈丹云.化工进展，第21卷第4期. 2002 * |
| 催化合成乳酸酯的研究. 李善吉.化学工程师，第105卷第6期. 2004 |
| 催化合成乳酸酯的研究. 李善吉.化学工程师，第105卷第6期. 2004 * |
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| Publication number | Publication date |
|---|---|
| CN1930110A (en) | 2007-03-14 |
| JP4685766B2 (en) | 2011-05-18 |
| JPWO2005087702A1 (en) | 2008-01-24 |
| WO2005087702A1 (en) | 2005-09-22 |
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