CN102503810B - Method for recovering and recycling L-tartaric acid - Google Patents
Method for recovering and recycling L-tartaric acid Download PDFInfo
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- CN102503810B CN102503810B CN201110342199.2A CN201110342199A CN102503810B CN 102503810 B CN102503810 B CN 102503810B CN 201110342199 A CN201110342199 A CN 201110342199A CN 102503810 B CN102503810 B CN 102503810B
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Abstract
The invention provides a method for recovering and recycling L-tartaric acid. The method comprises the following steps of: performing acidification and precipitation specific to waste water containing tartaric acid diammonium generated in a process for splitting racemic 4-methylsulfonylphenyl serine ethyl ester to form and separate a tartaric acid hydrogen ammonium salt; and acidizing and desalting to obtain a methanol solution of the L-tartaric acid. The method can be directly applied to the splitting process of racemic 4-methylsulfonylphenyl serine ethyl ester, and the recovery and recycling of the L-tartaric acid are realized. The method provided by the invention has mild reaction conditions and simple process operation, and the production cost of the splitting process can be greatly lowered.
Description
Technical field
The present invention relates to a kind of method that reclaims and recycle L-TARTARIC ACID.
Background technology
Levotartaric acid (L-TARTARIC ACID), molecular formula: C4H606, molecular weight: 150.09, No. CAS: 87-69-4.This product be colourless translucent crystal or white carefully to coarse crystallization powder, have tart flavour.
L-TARTARIC ACID (levotartaric acid) is widely used as the acidic flavoring agent of beverage and other food, for grape wine, soft drink, candy, bread, some gluey sweet food.Utilize its optical activity, as chemical resolving agent, for the manufacture of the fractionation of anti-tuberculosis drugs intermediate DL-amino butanol; Can also serve as chiral raw material synthesizing for tartaric acid derivatives; Utilize its acidity, as the catalyzer of polyester piece good resination, the PH conditioning agent that thiaminogen is produced; Utilize its complexing, as the reserving agent of the complexing agent in plating, desulfurization, pickling and chemical analysis, pharmaceutical test, sequestering agent, sequestrant, printing and dyeing; Utilize its reductibility, as the reductive agent of chemistry mirror processed.The photographic developer of taking a picture.Can also with many kinds of metal ions complexing, can make clean-out system and the rumbling compound of metallic surface.
D-pmethylsulfonyl phenyleneserine ethyl ester is the key intermediate of synthetic thiamphenicol and florfenicol.D-pmethylsulfonyl phenyleneserine ethyl ester is by racemic pmethylsulfonyl phenyleneserine ethyl ester is split and obtained.Industrial generally take methyl alcohol as solvent, take L-TARTARIC ACID as resolving agent, racemic pmethylsulfonyl phenyleneserine ethyl ester is added and carries out resolution reaction, after fractionation, obtain the D-pmethylsulfonyl phenyleneserine ethyl ester of chirality, obtain the waste water that contains tartrate diamines simultaneously.
L-TARTARIC ACID is the chiral resolving agent that a class is comparatively expensive, if the above-mentioned waste water that contains tartrate diamines is not carried out to tartaric recycling, will cause huge waste so, and has greatly increased the production cost of product.Therefore be necessary this waste water that contains tartrate diamines to carry out recovery and the recycle of L-TARTARIC ACID.At present, tartaric recoverying and utilizing method generally comprises following two classes:
1. add calcium chloride to react industrial can containing in the waste water of tartrate diamines, produce Calcium Tartrate, thereby tartrate is separated from waste water.Take water as solvent, add calcium tartrate again, then add sulfuric acid to carry out stirring reaction, the calcium sulfate of production can filtering from water, then the aqueous tartaric acid solution obtaining is carried out to evaporating, concentrating and crystallizing, is recycled tartrate.The method has been used a large amount of calcium chloride, and has generated a large amount of calcium sulfate byproducts, and because the paratartaric acid aqueous solution has carried out evaporating, concentrating and crystallizing, energy consumption is very large, and cost is higher.
2.CN00817998 reported a kind of by form and fractional crystallization bitartrate from resolution of racemic 2-amino-2, in the moisture organic liquid waste stream that 3-nitrile dimethyl process produces, recovery is essentially the tartaric method of D-of enantiomer-pure.To, containing carrying out acidifying in disodium tartrate, di-potassium tartrate, ammonium tartrate or mixture, by forming D-sodium hydrotartrate or D-tartarus precipitation, thereby realize tartaric separation.And then in methyl alcohol or alcohol solvent, process with sulfuric acid, after stirring reaction, remove inorganic salt, thus the tartaric methanol solution of the D-being recycled, further can recycle.In the method, need to use D-sodium hydrotartrate or D-tartarus precipitation that sylvite or sodium salt just can obtain needs, cost is higher.And the method mainly for be D-tartrate.
To sum up, all there are various defects in existing various tartaric recoverying and utilizing methods, or generated a large amount of calcium sulfate byproducts, and because the paratartaric acid aqueous solution has carried out evaporating, concentrating and crystallizing, energy consumption is very large, and cost is higher; Or need to form D-sodium hydrotartrate or D-tartarus precipitation, thereby realize tartaric separation, the more high defect of cost.
Summary of the invention
The present invention is directed to problems of the prior art, a kind of simple to operate, a kind of method that reclaims and recycle L-TARTARIC ACID that cost is low is provided.
The present invention, for achieving the above object, is to realize by such technical scheme:
The present invention is a kind of method that reclaims and recycle L-TARTARIC ACID, the waste water containing tartrate two ammoniums producing for the pmethylsulfonyl phenyleneserine ethyl ester process of resolution of racemic, pass through acid precipitation, form and separate hydrogen tartrate ammonium salt, and then acidifying desalination, obtain the methanol solution of L-TARTARIC ACID, can be directly used in the split process of racemic pmethylsulfonyl phenyleneserine ethyl ester, thereby realize the recovery of L-TARTARIC ACID and recycle, chemical equation is as follows:
Contain in the waste water of tartrate two ammoniums described, be acidified with acid rear formation ammonium hydrogen tartrate precipitation, filter, after gained ammonium hydrogen tartrate precipitation drying and dehydrating, adopt the methanol solvate identical with resolution reaction, further acidifying, filtering inorganic salt, obtain the methanol solution of L-TARTARIC ACID, thereby can be directly used in next step resolution reaction, concrete preparation process is as follows:
(1) acid precipitation: what produce in the pmethylsulfonyl phenyleneserine ethyl ester process of resolution of racemic contains in the waste water of tartrate two ammoniums, be acidified with acid rear formation ammonium hydrogen tartrate precipitation, temperature of reaction is 0～50 ℃, reaction times 0.5～4h, after acidifying, pH is 2.5～4.5, and gained precipitation is carried out drying and dehydrating and obtained ammonium hydrogen tartrate;
(2) acidifying desalination: by the product ammonium hydrogen tartrate of gained in step (1), adopt the methyl alcohol identical with splitting step as reaction solvent, further be acidified with acid, stirring reaction time 2～10h, temperature of reaction is 0～45 ℃, reacting liquid filtering, and filtrate is the methanol solution of L-TARTARIC ACID, can be directly used in next step resolution reaction, thereby realized the recovery of L-TARTARIC ACID and recycled.
Improve as one, in step of the present invention (1) acid precipitation, institute's acid adding is hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid, is preferably hydrochloric acid.
Improve as one, in step of the present invention (2) acidifying desalination, institute's acid adding is sulfuric acid, acetic acid or anhydrous hydrogen chloride, is preferably sulfuric acid.
Improve as one, in step of the present invention (2) acidifying desalination, the molar equivalent of institute's acid adding is 0.95～1.0: 1.0 with the ratio of the molar equivalent of ammonium hydrogen tartrate.
Beneficial effect of the present invention is as follows:
Synthetic method of the present invention, a large amount of waste water containing tartrate two ammoniums that produce in split process for racemic pmethylsulfonyl phenyleneserine ethyl ester, obtain ammonium hydrogen tartrate precipitation by being acidified with acid, and realize tartaric separating-purifying.And then by after gained ammonium hydrogen tartrate precipitation drying and dehydrating, adopt the methanol solvate identical with resolution reaction, and further acidifying, filtering inorganic salt, obtain the methanol solution of L-TARTARIC ACID, thereby can directly carry out next step resolution reaction.Compare traditional technique, not only can reduce in a large number the generation of calcium sulfate waste, and can reduce energy consumption, significantly reduce costs.The tartaric recovery circulation technology of D-of comparing patent report, does not use sylvite or sodium salt, greatly reduces cost.Use recoverying and utilizing method of the present invention, reaction conditions gentleness, technological operation is simple, can greatly reduce the production cost of split process.
Embodiment
The face technical scheme of the present invention of in conjunction with the embodiments opposing is described in further detail, but scope of the present invention is not limited to embodiment.HPLC represents high performance liquid chromatography.As illustrated without other, all umbers are parts by weight.
Embodiment 1
(1) acid precipitation: get the waste water 1000g (7wt%L-tartrate) containing tartrate two ammoniums that racemic pmethylsulfonyl phenyleneserine ethyl ester split process produces, be 45-50 ℃ in temperature of reaction, be acidified to pH as 3 take concentrated hydrochloric acid, the reaction times is 0.5h.Reaction solution forms ammonium hydrogen tartrate precipitation, filters.Gained precipitation is carried out drying and dehydrating and is obtained ammonium hydrogen tartrate 66.5g (rate of recovery 85.3%).L-TARTARIC ACID hydrogen ammonium is off-white color solid, measures according to HPLC, and purity is greater than 99%, and optical purity is 100%.
(2) acidifying desalination: get the product ammonium hydrogen tartrate 33.4g of gained in step (1), add 135g methyl alcohol, add the 10g vitriol oil, carry out acidification reaction.Temperature of reaction is 42-45 ℃, and the reaction times is 2h.After having reacted, remove by filter inorganic salt, the filtrate obtaining is the methanol solution of L-TARTARIC ACID.With reference to comparative example 1, this solution is directly used in the resolution reaction of racemic pmethylsulfonyl phenyleneserine ethyl ester, obtains D-pmethylsulfonyl phenyleneserine ethyl ester 23.6g (yield: 85.8%, HPLC:99.1%).
Embodiment 2
(1) acid precipitation: get the waste water 1000g (8wt%L-tartrate) containing tartrate two ammoniums that racemic pmethylsulfonyl phenyleneserine ethyl ester split process produces, it is 0 ℃ in temperature of reaction, be acidified to pH as 2.5 take the vitriol oil, the reaction times is 2h.Reaction solution forms ammonium hydrogen tartrate precipitation, filters.Gained precipitation is carried out drying and dehydrating and is obtained ammonium hydrogen tartrate 81.9g (rate of recovery 92.0%).L-TARTARIC ACID hydrogen ammonium is off-white color solid, measures according to HPLC, and purity is greater than 99%, and optical purity is 100%.
(2) acidifying desalination: get the product ammonium hydrogen tartrate 33.4g of gained in step (1), add 135g methyl alcohol, add 23.1g methanol hydrochloride solution (30%), carry out acidification reaction.Temperature of reaction is 20-25 ℃, and the reaction times is 6h.After having reacted, remove by filter inorganic salt, the filtrate obtaining is the methanol solution of L-TARTARIC ACID.With reference to comparative example 1, this solution is directly used in the resolution reaction of racemic pmethylsulfonyl phenyleneserine ethyl ester, obtains D-pmethylsulfonyl phenyleneserine ethyl ester 22.8g (yield: 82.9%, HPLC:98.8%).
Embodiment 3
(1) acid precipitation: get the waste water 1000g (10wt%L-tartrate) containing tartrate two ammoniums that racemic pmethylsulfonyl phenyleneserine ethyl ester split process produces, be 25-30 ℃ in temperature of reaction, be acidified to pH as 4.0-4.5 take phosphoric acid, the reaction times is 4h.Reaction solution forms ammonium hydrogen tartrate precipitation, filters.Gained precipitation is carried out drying and dehydrating and is obtained ammonium hydrogen tartrate 92.4g (rate of recovery 83.0%).L-TARTARIC ACID hydrogen ammonium is off-white color solid, measures according to HPLC, and purity is greater than 99%, and optical purity is 100%.
(2) acidifying desalination: get the product ammonium hydrogen tartrate 33.4g of gained in step (1), add 135g methyl alcohol, add 12g acetic acid, carry out acidification reaction.Temperature of reaction is 0 ℃, and the reaction times is 10h.After having reacted, remove by filter inorganic salt, the filtrate obtaining is the methanol solution of L-TARTARIC ACID.With reference to comparative example 1, this solution is directly used in the resolution reaction of racemic pmethylsulfonyl phenyleneserine ethyl ester, obtains D-pmethylsulfonyl phenyleneserine ethyl ester 23.0g (yield: 83.6%, HPLC:99.0%).
Embodiment 4
(1) acid precipitation: get the waste water 1000g (7.5wt%L-tartrate) containing tartrate two ammoniums that racemic pmethylsulfonyl phenyleneserine ethyl ester split process produces, be 30-35 ℃ in temperature of reaction, be acidified to pH as 3 take acetic acid, the reaction times is 3h.Reaction solution forms ammonium hydrogen tartrate precipitation, filters.Gained precipitation is carried out drying and dehydrating and is obtained ammonium hydrogen tartrate 72.7g (rate of recovery 87%).L-TARTARIC ACID hydrogen ammonium is off-white color solid, measures according to HPLC, and purity is greater than 99%, and optical purity is 100%.
(2) acidifying desalination: get the product ammonium hydrogen tartrate 33.4g of gained in step (1), add 135g methyl alcohol, add the 9.8g vitriol oil, carry out acidification reaction.Temperature of reaction is 25-30 ℃, and the reaction times is 6h.After having reacted, remove by filter inorganic salt, the filtrate obtaining is the methanol solution of L-TARTARIC ACID.With reference to comparative example 1, this solution is directly used in the resolution reaction of racemic pmethylsulfonyl phenyleneserine ethyl ester, obtains D-pmethylsulfonyl phenyleneserine ethyl ester 23.5g (yield: 85.4%, HPLC:99.1%).
Comparative example 1
Get 30g and newly purchase L-TARTARIC ACID (purity is greater than 99%, and optical purity is 100%), add 135g methyl alcohol, be stirred to entirely molten.Under stirring, slowly drop into racemic pmethylsulfonyl phenyleneserine ethyl ester 55g, be warming up to backflow, reaction 2h, cooled and filtered.Filter cake adds 200g water dissolution, under room temperature, adjusts PH to 8.0 with ammoniacal liquor, filters, is dried, and obtains D-pmethylsulfonyl phenyleneserine ethyl ester 23.8g (yield: 86.5%, HPLC:99.2%).
What more than enumerate is only part specific embodiment of the present invention; obviously, the invention is not restricted to above embodiment, can also have many distortion; all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (1)
1. one kind is reclaimed and recycles the method for L-TARTARIC ACID, it is characterized in that, the waste water containing tartrate two ammoniums producing for the pmethylsulfonyl phenyleneserine ethyl ester process of resolution of racemic, by acid precipitation, form and separate hydrogen tartrate ammonium salt, and then acidifying desalination, obtain the methanol solution of L-TARTARIC ACID, can be directly used in the split process of racemic pmethylsulfonyl phenyleneserine ethyl ester, thereby realize the recovery of L-TARTARIC ACID and recycle, chemical equation is as follows:
Contain in the waste water of tartrate two ammoniums described, be acidified with acid rear formation ammonium hydrogen tartrate precipitation, filter, after gained ammonium hydrogen tartrate precipitation drying and dehydrating, adopt the methanol solvate identical with resolution reaction, further acidifying, filtering inorganic salt, obtain the methanol solution of L-TARTARIC ACID, thereby can be directly used in next step resolution reaction, concrete preparation process is as follows:
(1) acid precipitation: what produce in the pmethylsulfonyl phenyleneserine ethyl ester process of resolution of racemic contains in the waste water of tartrate two ammoniums, be acidified with acid rear formation ammonium hydrogen tartrate precipitation, temperature of reaction is 0 ~ 50 ℃, reaction times 0.5 ~ 4h, after acidifying, pH is 2.5 ~ 4.5, gained precipitation is carried out drying and dehydrating and is obtained ammonium hydrogen tartrate, and added acid is hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid;
(2) acidifying desalination: by the product ammonium hydrogen tartrate of gained in step (1), adopt the methyl alcohol identical with splitting step as reaction solvent, further be acidified with acid, stirring reaction time 2 ~ 10h, temperature of reaction is 0 ~ 45 ℃, reacting liquid filtering, filtrate is the methanol solution of L-TARTARIC ACID, can be directly used in next step resolution reaction, thereby realize the recovery of L-TARTARIC ACID and recycled, institute's acid adding is sulfuric acid or acetic acid, and the molar equivalent of institute's acid adding is 0.95 ~ 1.0:1.0 with the ratio of the molar equivalent of ammonium hydrogen tartrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105152911A (en) * | 2015-08-17 | 2015-12-16 | 浙江邦成化工有限公司 | Recovery method of tartaric acid |
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| CN104326901B (en) * | 2014-10-16 | 2016-09-07 | 安徽扬子化工有限公司 | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production |
| CN104355990B (en) * | 2014-10-16 | 2016-09-07 | 安徽扬子化工有限公司 | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production |
| CN107417585B (en) * | 2017-06-22 | 2019-05-03 | 浙江海翔川南药业有限公司 | A kind of synthetic method of pharmaceutical intermediate |
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| US6534678B1 (en) * | 1998-05-04 | 2003-03-18 | Metallgesellschaft Aktiengesellschaft | Process for producing tartaric acid from a raw material containing potassium hydrogentartrate |
| CN1414939A (en) * | 1999-12-28 | 2003-04-30 | 巴斯福股份公司 | Process for recovery and recycle of D-tartaric acid |
| CN102093208A (en) * | 2010-12-27 | 2011-06-15 | 常茂生物化学工程股份有限公司 | Method for producing L (+) tartaric acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534678B1 (en) * | 1998-05-04 | 2003-03-18 | Metallgesellschaft Aktiengesellschaft | Process for producing tartaric acid from a raw material containing potassium hydrogentartrate |
| CN1414939A (en) * | 1999-12-28 | 2003-04-30 | 巴斯福股份公司 | Process for recovery and recycle of D-tartaric acid |
| CN102093208A (en) * | 2010-12-27 | 2011-06-15 | 常茂生物化学工程股份有限公司 | Method for producing L (+) tartaric acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152911A (en) * | 2015-08-17 | 2015-12-16 | 浙江邦成化工有限公司 | Recovery method of tartaric acid |
| CN105152911B (en) * | 2015-08-17 | 2017-05-31 | 浙江邦成化工有限公司 | A kind of recovery method of tartaric acid |
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