CN1101341A - Purifying process for glycine - Google Patents
Purifying process for glycine Download PDFInfo
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- CN1101341A CN1101341A CN 94105988 CN94105988A CN1101341A CN 1101341 A CN1101341 A CN 1101341A CN 94105988 CN94105988 CN 94105988 CN 94105988 A CN94105988 A CN 94105988A CN 1101341 A CN1101341 A CN 1101341A
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- glycine
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Abstract
Based on the principle that the solubility of glycine in water varies with temp., a crystallizing process is used to purify industrial glycine for medical use. By exchanging part of crystallizing mother liquid with saturated glycine solution, the mother liquid may be cyclically used. Its advantages include simple technology, low cost and high product quality.
Description
The present invention relates to a kind of method of purification of aminocarboxylic acid, the method for purification of a kind of glycine of saying so more specifically.
Glycine (Glycine) has another name called Padil (AminoacetiAcid) or aminoacetic acid, and structural formula is H
2NCH
2COOH, it is an amino carboxyl fatty acid/amino acid of simple in structure and unique no opticity in the natural a-amino acid.Glycine is widely used in medicine (as the amino acid transfusion preparation, flush fluid for vesica urinaria during surgical operation), organic synthesis (as synthetic L-DOPA class medicine, herbicide glyphosate, synthetic surfactant intermediate iminodiethanoic acid etc.) and food, fodder additives and biochemical reagents.
According to China the Ministry of Chemical Industry standard (HG2029-91), with the Mono Chloro Acetic Acid is the synthetic glycine product of industry that raw material makes through ammonification, its glycine content 〉=97.5%(acceptable end product) reaches 〉=the 95.5%(salable product), chloride content (in Cl)≤0.70%(acceptable end product) reaches≤the 0.90%(salable product), also contain a small amount of other water-soluble inorganic and organic impurity, do not reach medicinal standard (pharmaceutical grade product requirement glycine content 〉=99.0%, Cl≤0.007%).The technical grade glycine must carry out purification, after making its purity, foreign matter content reach pharmaceutical grade to require, just can be used for medicine production.
At present, the purification glycine mainly contains two kinds of methods: (1) separating out alcohol method (French Patent Fr1237327): after the technical grade glycine is made into the aqueous solution, through activated carbon decolorizing, analyse with methyl alcohol (or ethanol) alcohol of 3-5 times of volume again.Often need repeatedly alcohol to analyse repeatedly, just can make glycine product reach the pharmaceutical grade standard.This method expends a large amount of methyl alcohol (or ethanol), has increased the burdens of a large amount of recovery alcohol in producing greatly, thereby refining cost is improved.Simultaneously, use methyl alcohol also dangerous to producing in a large number, because of methyl alcohol is inflammable, explosive product, and methyl alcohol also has injury to operator's eyes, is detrimental to health.Because gac is relatively poor to the adsorptive power of inorganic salt and some coloring matter, refining back glycine still has faint yellow in addition, and the product foreign matter content is higher.Use sweet ammonia that pure analysis method (especially the higher alcohol of working concentration carry out alcohol analyse) obtains often for Powdered, rather than the white crystals particulate state, store transportation and be easy to caking, can not satisfy the export requirement of food and pharmaceutical grade glycine.(2) ion exchange method: after this method is mixed with the aqueous solution of 15-25% with the technical grade glycine earlier, under acidic conditions, by strong anion-exchange resin (CN89109134C) or by the strong-acid cation-exchange resin acidifying, activated carbon decolorizing, reconcentration, crystallisation by cooling (EP0459803A) or add acetate and separate out.Its yield of spent ion exchange resin highly industry glycine can be reached more than 90%, and its purity and foreign matter content also can the requirements of fulfilling medicinal level.But this method weak point is to need to concentrate glycine solution, and volume is very big, wasteful calorimetric energy, and simultaneously, its yield of ion exchange resin highly industry glycine can reach more than 90%, and its purity and foreign matter content also can the requirements of fulfilling medicinal level.But this method weak point is to need to concentrate glycine solution, and volume is very big, wasteful calorimetric energy, and simultaneously, the frequent regeneration of ion exchange resin and gac will expend a large amount of acid-base solutions, and the industrial production cycle is long, and production cost is still higher.
The purpose of this invention is to provide that a kind of technology is simple, operation is simple and easy, safety, good product quality, glycine method of purification that production cost is low.
The present invention implements like this, and its technological process is as follows:
(1) prepares new mother liquor: be made into saturated solution with refining solid glycine, its chloride content (in Cl)≤0.01%;
(2) the technical grade glycine is refining: the glycine of technical grade is dissolved in the above-mentioned new mother liquor, and heating is until whole dissolvings, filtered while hot at once, treat the filtrate cool to room temperature after, refilter, obtain filter cake and crystalline mother solution.Filter cake with new mother liquor drip washing after heat drying, promptly obtain purified glycine white crystal;
(3) recycling of crystalline mother solution: from crystalline mother solution, take out a part of mother liquor, in the mother liquor of remainder, add then and the identical new mother liquor of taking-up partial volume, the mixing mother liquor that obtains can be used as the mother liquor of highly industry level glycine, and its treating process (2) is set by step carried out.Each circulation gained crystalline mother solution all can repeatedly recycle by this process.
Glycine is soluble in water, and the solubility with temperature in water raises and increases.And after certain amount of industrial level glycine is dissolved in the crystalline mother solution, this solution is cooled to room temperature under comparatively high temps, and refining glycine is promptly separated out with white crystals, and various impurity are then stayed in the crystalline mother solution.In order to make the glycine behind purification reach medicinal requirements, make simultaneously crystalline mother solution can continue circulation again and be used for the purifying industrial grade glycine, just must limit the accumulation of various impurity in mother liquor, make various foreign matter contents relatively stable in certain allowed band.For this reason, take out partial volume at every turn and replace with new mother liquor from crystalline mother solution, general displaced volume accounts for the 5-30% of crystalline mother solution volume.The volume of changing mother liquor is very little the time, and quality product may be defective; But the volume of changing mother liquor is too big, economically just may be uneconomical.In the purification process, the mother liquor consumption depends on the purity of technical grade glycine of input and the amount of input.The volume (liter) of the mother liquor that uses (new mother liquor or the mother liquor that recycles) is 3: 1～8: 1 with the ratio of the technical grade glycine weight (kilogram) of being purified.Use too much mother liquor purifying industrial grade glycine can cause crystallisation by cooling to separate out the time lengthening of glycine.But use very few mother liquor, must improve dissolving technical grade glycine solid temperature, and prolong the time of heating for dissolving, and when dissolution filter, temperature reduces slightly, and the easy crystallization of glycine is separated out, can make troubles to actually operating, also tend to make refining back product content impurity higher.
In the purification process, the temperature of dissolved solids glycine and heat-up time length obviously influence the color of mother liquor.Can dissolve technical grade glycine solid faster and more though improve temperature, but solution colour is deepened, even making solution become red-brown, the glycine crystallization that cooling is separated out from this solution often has color, rather than pure white.The present invention controls Heating temperature between 60-90 ℃, and be 0.5-2 hour heat-up time, and cooling off the refining glycine of separating out with this understanding is the pure white crystalline particle, and behind the suction filtration, its crystalline mother solution also can keep faint yellow and can continue to use.Filter cake can be guaranteed the purity of filter cake like this with new mother liquor drip washing.The volume of the new mother liquor of drip washing is 3: 100～8: 100 with the ratio of the weight of filter cake.
Technology provided by the invention is applicable to that it is the medicinal glycine solid that industrial glycine solid is made with extra care, and yield can reach 90-97%, and crystalline mother solution can recycle for a long time.For the mother liquor that should not continue to use, can add to 2-3 and doubly separate out glycine in the methyl alcohol of (mother liquor volume), the glycine solid of recovery still can be used as refining raw material to be used.
The present invention has following advantage: cancelled a large amount of methyl alcohol (or ethanol) that use of separating out alcohol method, both saved raw material cost, and saved again to steam and reclaimed a large amount of heat energy that a large amount of methyl alcohol (or ethanol) are consumed, owing to do not adopt a large amount of methyl alcohol, make production safer, environmental pollution is also little.Cancelled the use of gac simultaneously, also saved regeneration of activated carbon and produced safelyr, environmental pollution is also little.A large amount of acid-base solutions.Cancel the glycine solution enrichment process in the ion exchange method, thereby saved the energy, cancelled the use of ion exchange resin, thus a large amount of acid, the alkali reagent that use when also having saved resin regeneration.In a word, production cost of the present invention is low, the simple easy handling of technology, and good product quality, yield are also higher.
The embodiment of the invention is as follows:
Embodiment 1
The preparation of new mother liquor:
With glycine content 〉=98.5%, the refining glycine of 370 grams of Cl%≤0.01% is added in 1400 milliliters the deionized water, heat dissolved in 1 hour after, 90 ℃ of filtrations.Filtrate is cooled to 25 ℃ of filtrations, and filtrate is water white saturated glycine solution, promptly new mother liquor.
Take by weighing technical grade glycine solid 250 grams (glycine content 97.90%, Cl are 0.43%) and be added in 1500 milliliters of new mother liquors, after 90 ℃ of dissolvings in 0.5 hour of stirring heating, filtered while hot, the filtrate crystallisation by cooling, 25 ℃ of suction filtrations obtain filter cake 243.5 grams, with 10 milliliters of new mother liquor drip washing, got pure white crystal 2 27.5 grams (glycine content 99.92%, Cl%＜0.007%), glycine yield 92.88% down in dry 1 hour at 60 ℃, get 1500 milliliters of crystalline mother solutions, be faint yellow.
Embodiment 2
Take out 75 milliliters of mother liquors from 1500 milliliters of crystalline mother solutions of example 1 gained, add 75 milliliters of new mother liquors again, after mixing, 250 gram technical grade glycine (the glycine quality is with example 2) are added in this mother liquor, heating is also stirred dissolving in 0.5 hour, 85 ℃ of filtrations, filtrate are cooled to 25 ℃ of suction filtrations, filter cake with 10 milliliters of new mother liquor drip washing after in 60 ℃ of dryings 1 hour, get glycine white crystal 236.7 gram (glycine content 99.79%, Cl%＜0.007%, yield 96.51%), it is faint yellow that crystalline mother solution is.
Embodiment 3
Example 2 gained crystalline mother solutions are taken out 250 milliliters, after 250 milliliters of new mother liquors replacings, mix adding 250 gram technical grade glycine (glycine content is 96.58%, and Cl% is 0.75%), after heating dissolving in 0.5 hour, 80 ℃ of filtrations, filtrate are cooled to 20 ℃ of suction filtrations, filter cake with 10 milliliters of drip washing of new mother liquor after 50 ℃ of dryings 1.5 hours, obtain glycine crystal 2 38.4 gram (glycine content 99.91%, Cl%＜0.007%, yield 97.32%), it is faint yellow that crystalline mother solution is.
Embodiment 4
Example 3 gained crystalline mother solutions are taken out 250 milliliters, add 250 milliliters of new mother liquors again, add 250 gram technical grade glycine (the glycine quality is with example 4), by refining glycine 229.6 gram (the glycine content 99.87% that obtain of example 3 methods to this mother liquor, Cl%＜0.007%, yield 94.97%).
Embodiment 5
Example 4 gained crystalline mother solutions are taken out 300 milliliters, after mixing with 300 milliliters of new mother liquors replacings again, add 250 gram technical grade glycine (quality of glycine is with example 4), after the heated and stirred dissolving in 0.5 hour, 78 ℃ of filtrations, filtrate are cooled to 18 ℃ of filtrations, and filter cake washs with 20 milliliters of new mother liquors, in 60 ℃ of dryings 1 hour, get white crystals 225.9 grams (glycine content 99.79%, Cl%＜0.007%, yield 93.36%), get 1500 milliliters of crystalline mother solutions, be yellow.
The crystalline mother solution that each time test changes is got 1000 milliliters, under agitation be added in 3000 ml methanol (content 95%(V/V), left standstill 1 hour, the glycine precipitation is separated out, suction filtration again, filter cake with a little methanol wash after, in 40 ℃ of dryings 2 hours, get pale yellow powder shape crystallization 204.5 grams (glycine content 98.75%, Cl% are 0.027%).Refining with the inventive method again, promptly get the purified glycine.
The refining glycine crystal of preparing new mother liquor can be made by the technical grade glycine, and embodiment is as follows:
Be added in 2000 ml deionized water with technical grade glycine 1000 grams; After the heating for dissolving, 85 ℃ of filtered while hot with filtrate cooling, have the pure white glycine crystallization to separate out, 25 ℃ of suction filtrations, and a little washing with alcohol of filter cake, 60 ℃ of dryings 1 hour obtain making with extra care glycine (glycine content 〉=98.5%).Again with preparing new mother liquor by method (1) by refining glycine.
More than each time all meet British Pharmacopoeia (88 editions) specification of quality by the refining back of technical grade glycine glycine.
Claims (6)
1, a kind of method of purification of glycine is characterized in that the step of this method is as follows:
(1) preparation of new mother liquor: be made into saturated solution with refining solid glycine, its chloride content (in Cl)≤0.01%;
(2) purification of industrial glycine: in new mother liquor, add the technical grade glycine, heating and stirring, make the glycine dissolving, filtered while hot then, after treating that filtrate is cooled to room temperature, refilter, obtain filter cake and crystalline mother solution, filter cake with new mother liquor drip washing after after 40-70 ℃ of following drying, promptly obtain refining glycine crystal;
(3) recycling of crystalline mother solution: from the crystalline mother solution that (2) step obtains, take out a part of mother liquor, in the mother liquor of remainder, add then and the identical new mother liquor of taking-up partial volume, the mixing mother liquor that obtains can be used as the mother liquor of highly industry level glycine, and its treating process (2) is set by step carried out.
2, method of purification according to claim 1 is characterized in that the temperature of heating for dissolving technical grade glycine in the step (2) is 60-90 ℃, is good with 75-85 ℃.
3, method of purification according to claim 1 is characterized in that the time of dissolving technical grade glycine in the step (2) is 0.5-2 hour.
4, method of purification according to claim 1, when it is characterized in that dissolving the technical grade glycine, the mother liquor volume is 3: 1～8: 1 with the ratio of industrial glycine weight.
5, method of purification according to claim 1, when it is characterized in that crystalline mother solution recycles, the volume of a part of mother liquor that takes out from crystalline mother solution accounts for the 5-30% of crystalline mother solution volume.
6, method of purification according to claim 1, the new mother liquor volume that it is characterized in that the drip washing filter cake is 3: 100～8: 100 with the ratio of the weight of filter cake.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94105988A CN1039810C (en) | 1994-06-10 | 1994-06-10 | Purifying process for glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94105988A CN1039810C (en) | 1994-06-10 | 1994-06-10 | Purifying process for glycine |
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| Publication Number | Publication Date |
|---|---|
| CN1101341A true CN1101341A (en) | 1995-04-12 |
| CN1039810C CN1039810C (en) | 1998-09-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94105988A Expired - Fee Related CN1039810C (en) | 1994-06-10 | 1994-06-10 | Purifying process for glycine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829472A (en) * | 2015-05-15 | 2015-08-12 | 南通荣泰生物科技有限公司 | Refining process for glycine |
| CN114057610A (en) * | 2021-11-30 | 2022-02-18 | 湖北省宏源药业科技股份有限公司 | Production method of high-purity guanidine thiocyanate |
| CN115043746A (en) * | 2022-06-21 | 2022-09-13 | 山西晶硕科技有限公司 | Preparation method of food-grade glycine capable of preventing agglomeration |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254729A (en) * | 1990-05-31 | 1993-10-19 | Mitsui Toatsu Chemicals, Inc. | Method for purifying glycine |
-
1994
- 1994-06-10 CN CN94105988A patent/CN1039810C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829472A (en) * | 2015-05-15 | 2015-08-12 | 南通荣泰生物科技有限公司 | Refining process for glycine |
| CN114057610A (en) * | 2021-11-30 | 2022-02-18 | 湖北省宏源药业科技股份有限公司 | Production method of high-purity guanidine thiocyanate |
| CN115043746A (en) * | 2022-06-21 | 2022-09-13 | 山西晶硕科技有限公司 | Preparation method of food-grade glycine capable of preventing agglomeration |
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| Publication number | Publication date |
|---|---|
| CN1039810C (en) | 1998-09-16 |
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