CN1022320C - Process for purification of glycine - Google Patents
Process for purification of glycine Download PDFInfo
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- CN1022320C CN1022320C CN 89109134 CN89109134A CN1022320C CN 1022320 C CN1022320 C CN 1022320C CN 89109134 CN89109134 CN 89109134 CN 89109134 A CN89109134 A CN 89109134A CN 1022320 C CN1022320 C CN 1022320C
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- glycine
- solution
- ammonia
- water solution
- purification
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Abstract
The present invention provides a method for purifying and refining glycine water solution prepared from the reaction and synthesis of chloroacetic acid and liquid ammonia or commercial product glycine prepared from the water solution. The method comprises the following steps that under the conditions that temperature is low than 60 DEG C and glycine water solution is in the acidic state, strong basic anion-exchange resin with positive-valence ammonia active groups is used for carrying out absorption and exchange processing for the glycine water solution to absorb organic and inorganic impurities in the glycine water solution and to simultaneously convert ammonium chloride into ammonium hydroxide. The processed solution is heated to eliminate ammonia, and consequently refined glycine which is in accordance with the plant use of pharmaceuticals can be obtained.
Description
The present invention relates to a kind of glycine, particularly by the method for purification of Mono Chloro Acetic Acid and liquefied ammonia synthetic glycine.
Glycine is a kind of amino acid that essential industry is worth that has, is widely used in agricultural, livestock industry, food, medicine and the organic synthesis industry, and be a kind of important basic chemical raw materials, it also is synthetic other amino acid whose raw materials.The method that present industrial system extraction glycine generally adopts is to be reacted in the presence of urotropine by Mono Chloro Acetic Acid and liquefied ammonia to produce glycine solution, produces by crystallization then and obtains the industrial goods glycine.The advantage of this synthetic method is that Mono Chloro Acetic Acid obtains easily, and liquefied ammonia can use fertilizer plant to pay the liquefied ammonia of product, and synthesis technique, condition are easily grasped and controlled, and helps industrially normally carrying out, and the glycine yield is higher, and product cost is lower.But, contain a large amount of ammonium chloride and other mineral compound impurity in the glycine solution of producing by this method and by paying the coloured of large, medium and small molecule that reaction produces and meeting the organic impurities of thermo-color, therefore by ammonium chloride in the industrial goods glycine of separating out in the solution and other mineral compound impurity and coloured and chance thermo-color organic compound foreign matter content height, limited the use of glycine greatly.
The content of the industrial goods glycine product glycine of being produced by this synthetic method is about 90-95%, foreign matter content is 4-10%, thereby generally have a darker color, because purity is low, the foreign matter content height does not meet the service requirements that pharmaceuticals are produced, and therefore can not be directly used in the production of pharmaceuticals, the industrial goods glycine must be carried out purification, its purity, foreign matter content be reached produce the specification of quality of pharmaceuticals with glycine.The method of industrial refining purification glycine is to carry out recrystallization after utilizing the activated carbon adsorption decolouring at present.It is the industrial goods glycine to be dissolved in water make the aqueous solution, carries out adsorption bleaching with activated carbon then.Solution after decolouring is handled heats concentrated, liquor capacity is concentrated into to stop two of stoste volume/a period of time heating and cool off make solution temperature reduce to normal temperature, will in the liquor capacity 3-4 ethanol adding concentrated solution doubly glycine crystallization be separated out again.In order to meet the requirements of glycine content, wherein foreign matter content is reduced to require in the limits, decolouring, crystallization operation carries out 2-3 time repeatedly.Because activated carbon is to inorganic salt and small molecules is coloured and chance thermo-color organism adsorptive power is poor, thereby the impure slightly color of glycine crystallization color after refining the purification.This process for purification long flow path, step part activator species many, when solution contacts with activated carbon in addition in the activated carbon (are generally muriate such as ZnCl
2Deng, also have plenty of mineral acid or salt such as phosphoric acid, potassium sulphide) enter in the solution, increased the kind of inorganic impurity in the solution and content to make glycine in the further recovery mother liquor difficulty more that becomes, so mother liquor can not be repeatedly used.So the treatment losses of this process for purification is big, the glycine yield is low, generally has only 60-70%, simultaneously, consume a large amount of activated carbon and ethanol, causes system elaboration glycine cost to raise significantly.
Shortcoming for eliminate activity carbon method, reduce the refining cost of glycine, someone has proposed employing weak base anion-exchange resin replacement activated carbon is the thick glycine solution of neutral condition refinement treatment at glycine solution, thereby obtain the glycine process for purification of purified glycine, but, according to the present inventor by adopting polystyrene weak base anion-exchange resin D390(trade(brand)name) be that the test-results of handling 1000 gram industrial goods glycine under the neutral condition are seen at glycine solution, the yield of refining glycine is about 90%, but the muriate in the highly finished product glycine, vitriol and level of residue have all surpassed the specified requirement of pharmaceuticals with the foreign matter content of glycine.Therefore, utilize the refining purification of this method by Mono Chloro Acetic Acid and liquefied ammonia synthetic industrial goods glycine, its effect is still unsafty.The clear 54-1686 of Japanese Patent " glycine process for purification " provides a kind of employing active group to be-NH2, two NH, the weak base anion-exchange resin of three N or neutral anionite-exchange resin are at the thick glycine solution of the following refinement treatment of glycine solution pH7 and then produce the method for highly finished product glycine, but, the thick glycine solution that utilizes this method refinement treatment must be the thick glycine solution that passes through desalting treatment in advance, thereby utilizes this method directly to handle by Mono Chloro Acetic Acid and liquefied ammonia and react the synthetic glycine solution or be difficult by the industrial glycine that this solution is produced.
The purpose of this invention is to provide and a kind ofly adopt strongly basic anion exchange resin refining purification under acidic conditions it to be met make the glycine process for refining and purifying that pharmaceuticals are used the glycine specification of quality by Mono Chloro Acetic Acid and liquefied ammonia reaction synthetic glycine solution or by the ammonium chloride industrial goods glycine that contains that this aqueous solution is produced.
Make the glycine that pharmaceuticals use, require its glycine content more than 99.0%, chloride content≤0.007%, sulphate content≤0.006%, amounts of ammonium salt≤0.02%, residue≤0.01%.Glycine is a kind of neutral amino acids, and its iso-electric point is 5.97, and it is neutral that the aqueous solution is.When glycine solution was acidity, glycine was with NH
+ 3CH
2The form of COO-H exists in solution, and is alkalescence and work as glycine solution, and glycine is with NH
2CH
2COO
-Form exist in solution.This specific character according to glycine, the present inventor finds when adopting the strongly basic anion exchange resin that has nominal price nitrogen active group to handle to be contained by Mono Chloro Acetic Acid and liquefied ammonia reaction synthetic the coloured of a large amount of ammonium chlorides and other mineral compound impurity and large, medium and small molecule ammonium chloride can be converted to unsettled ammonium hydroxide with the glycine solution of chance thermo-color organic compound impurity or during the industrial goods glycine of producing in by this solution, and thereby organic and inorganic impurity absorption can be removed the purpose that reaches the purification glycine, and and then finished the present invention.
The strongly basic anion exchange resin purification that utilization has a nominal price nitrogen active group is to have as-N by Mono Chloro Acetic Acid and liquefied ammonia reaction synthetic glycine solution or by the employed strongly basic anion exchange resin of producing in this aqueous solution of industrial goods glycine
+(CH
3)
3,
One class has the strongly basic anion exchange resin of the active group of nominal price nitrogen, and selects for use coloured and to meet the big wide aperture OH type strongly basic anion exchange resin of thermo-color organism loading capacity be favourable to the purification of glycine to large, medium and small molecule.Can use wide aperture polystyrene strongly basic anion exchange resin 204 * 4,201 * 7, D296, D261(trade(brand)name in actual use) and other similar with it OH type strong basicity resistance ion exchange resin.
The pH value of solution value of the industrial goods glycine that adopts strongly basic anion exchange resin to purify to produce by Mono Chloro Acetic Acid and liquefied ammonia synthetic glycine solution or by this solution is 4-5, and glycine is with NH at this moment
3CH
2COOH exists in solution, and is exchanged by resin absorption hardly, and only adsorbs large, medium and small molecule organism coloured and the chance thermo-color, and the chlorion in the solution is then by resins exchange OH
-Enter solution.Glycine solution after the processing is a water white transparency, the pH value of solution value about 8, the NH in the solution
4Ion is that the form of ammonium hydroxide exists, and heating promptly becomes NH
3From solution, overflow.
How many resin demands can according to the deciding of organic and inorganic impurity in the glycine content size in the glycine solution, the solution when absorption exchange was handled, and glycine concentration is big, the foreign matter content height, and resin demand is big, on the contrary resin demand is little.
The concentration of glycine solution got final product below the glycine saturation concentration when treatment temp when the absorption exchange was handled, generally be preferably 20-25%, can directly handle carried out purification by Mono Chloro Acetic Acid and liquefied ammonia synthetic glycine solution like this, solution needn't concentrate or dilute.
The absorption switching process time is 10-60 minute, is generally 15-30 minute.Solution temperature is no more than 60 ℃ and gets final product during processing, is generally normal temperature.
Absorption exchange is handled operation and can be adopted anionite-exchange resin added in the glycine solution and mix, after handling, the absorption exchange filters the batch operation that resin is told, also anionite-exchange resin can be filled in the resin column, make glycine solution glycine solution be adsorbed exchange and handle by resin column.The solution space velocity is generally 2-5(liter/liters per hour during processing).
Resin absorption exchanges when reaching capacity or the glycine solution after handling exchanges the processing operation above stopping absorption when requiring, employing 4-5%(W/D) hydrochloric acid is handled with the identical solution space velocity feeding resin column of exchange processing, and then makes resin be reduced into OH type strongly basic anion exchange resin with same space velocity by resin column with the aqueous sodium hydroxide solution of same concentrations.Can feed glycine solution after the regeneration once more and adsorb the exchange processing.
The glycine solution of handling by strongly basic anion exchange resin decolouring heat temperature raising under condition of stirring steams ammonia to 70-100 ℃, about 2-3 of time hour ammonia can all steam only, solution vapor does not have ammonia flavor and gets final product in the actually operating, steam except that the later aqueous solution of ammonia and throw away the thunderbolt colourless transparent solution, can stop heating when using alcohols material that glycine crystallization is separated out.Adding liquor capacity 3-5 alcohols material (being generally ethanol) doubly then separates out the glycine knot, during without alcohols material, ammonia steams except that heating under the temperature of 70-100 ℃ of back continuation maintenance is concentrated into and stops when glycine content reaches 40-50% in the solution heating and cooling off under condition of stirring glycine crystallization is separated out.The glycine crystallization of separating out separates with mother liquor by filtering, and is the highly finished product glycine behind the crystallizing and drying.The mother liquor of telling after the crystallization is that colourless transparent solution can be recycled.Glycine content is more than 99.5% in the highly finished product glycine, and yield is 92-95%.Because mother liquor is reusable.The treatment losses of its glycine seldom.
Glycine method of purification provided by the invention can be directly to being synthesized the saliferous glycine solution that obtains or carrying out purification by the industrial goods glycine of producing in this solution and handle by Mono Chloro Acetic Acid and liquefied ammonia reaction, technology is simple, the yield height, glycine content is more than 99.5% in the highly finished product glycine, little by 0.02% on the amounts of ammonium salt, other organic and inorganic impurity are lower than the specified requirement of pharmaceuticals production with the foreign matter content of glycine, reduced the refining cost of glycine significantly, thereby be suitable for adopting on the industrial production.
Be embodiments of the invention below, further specify the present invention in conjunction with the embodiments.
Embodiment 1
Get 1000 grams by producing the industrial goods glycine that obtains in Mono Chloro Acetic Acid and the liquefied ammonia reaction synthetic glycine solution, wherein glycine content 96.0%, chloride content 1.20%, sulphate content 0.04%, amounts of ammonium salt 2.5%, it is complete to restrain dissolved in distilled water with 4000, is made into 25% glycine solution.This moment, solution was yellow, little muddiness, pH6.5, add hydrochloric acid conditioning solution pH value to 4-5 by 1: 1 amount, by D290 wide aperture strong basicity quaternary ammonium type anion exchange resin post is housed, the solution space velocity is 2.5, handles at normal temperatures then, glycine solution after the processing is a water white transparency liquid, pH8.1.With the glycine solution heat temperature raising to 100 after handling ℃, steam major part that discharge this moment be ammonia, and the ammonia flavor disappears and stops to heat after half an hour, and the thin layer crystallisate appears in the close liquid level place of heating container.Stop to heat back pH value of solution 6.8, colourless, strength of solution is about 35-40%.Solution stirs cooling, and glycine crystallization is separated out, and solution is reduced to filter behind the normal temperature and told crystallization.Filtrate the reheating that obtains is warming up to 90 ℃ and concentrates, and stops heating when strength of solution reaches 35-40%, and cooling by aforesaid operations separates out glycine crystallization, repeatable operation three times, and the gained crystallisate combines, and is the highly finished product glycine.Glycine highly finished product yield is 95%, and wherein glycine content is 99.6%, and foreign matter content is less than pharmacopeia set quota standard (carrying out analyzing and testing by the pharmacopeia analytical procedure).It is colourless that mother liquor behind the Crystallization Separation end of operation is thrown away thunderbolt.
Embodiment 2
Concentrating the ethanol that adds 90% left and right sides concentration of 4 times of solution amount after ammonia still process is finished immediately by the ion exchange resin of the working method of embodiment 1, use and the resulting glycine treatment solution of material consumption stirs cooling glycine crystallization is separated out.Solution stops to stir to filter telling glycine crystallization after reducing to normal temperature, and the crystallization that obtains is through 50 ℃.Drying was the highly finished product glycine in one hour, utilized the method for testing and analyzing and the index project of pharmacopeia regulation to carry out analyzing and testing, and glycine content is 99.5% in the highly finished product glycine, and yield is 94.3%, and other indexs are all within the scope of regulation.
Embodiment 3
Directly get Mono Chloro Acetic Acid and liquefied ammonia and react 1000 milliliters of the synthetic liquid of resulting glycine, glycine content is 20% in the synthetic liquid, muriate is 5%, sulphate content is 2%, amounts of ammonium salt is 6%, residue content is 2.5%, solution is deep yellow, pH6.8, added hydrochloric acid conditioning solution pH value to 4-5, then at normal temperatures by the interior wide aperture polystyrene strongly basic anion exchange resin 201 * 4(trade(brand)name of filling out by 1: 1 of solution amount) resin column, processing the time solution space velocity be that 4(is equivalent to 25 minutes treatment times).Through the synthetic liquid water white transparency of plastic resin treatment, pH8.4, treatment solution is colourless by the strong solution that the method for embodiment 1 heats after ammonia excretion, ammonia excretion finish.Method by example 1 or embodiment 2 is produced the highly finished product glycine crystallization, and the glycine yield is 94.2%, and glycine content is 99.5%, and all within the scope of regulation, the mother liquor of telling after the crystallization is thrown away the thunderbolt water white transparency to other indexs.
Embodiment 4
Adopt the inventive method to select for use different strongly basic anion exchange resin purifications as shown in table 1 by the experimental result that Mono Chloro Acetic Acid and liquefied ammonia react the industrial goods glycine of producing in the glycine solution that obtains.(table 1 is seen the literary composition back)
Embodiment 5
It is as shown in table 2 that the highly finished product glycine that the refining purification of industrial goods glycine of adopting the activated carbon recrystallization method of the inventive method and present industrial use to carry out being produced by Mono Chloro Acetic Acid and liquefied ammonia reaction obtains carries out results measured by the standard of the 1982 editions glycine in Chinese Pharmacopoeia tianjin local standards.(table 2 is seen the literary composition back)
Table 1
Resin sample size sample glycine highly finished product must be measured the sweet ammonia of highly finished product
Other indexs of yield %
(gram) content (gram) (gram) acid content %
* 201 * 4 1,000 96 905 94.2 99.5 is qualified
（7117）
* 201 * 7 1,000 96 908 94.5 99.7 is qualified
（714）
* D296 1,000 96 908 94.5 99.6 is qualified
* D261 1,000 96 911 94.9 99.6 is qualified
* D201 * 7 1,000 96 908 94.5 99.66 are qualified
* trade(brand)name, wide aperture season ammonia ammonium alkali type strongly basic anion exchange resin
Table 2
Bent standard (82 editions) the inventive method activated carbon of index project medicine recrystallization method
Appearance white crystalline powder pure white crystalline powder near-white crystalline powder
Content 99% 99.6% 99.1%
It is colourless little turbid that the solution color and luster should be clarified achromaticity and clarification
And clarity
Acidity pH5.5-7.0 6.5 6.2
Muriate≤0.007% 0.007% are near 0.007%
Vitriol≤0.006% 0.006% are near 0.006%
Ammonium salt≤0.02% 0.002% are near 0.02%
Heavy metal≤20ppm 20ppm≤20ppm
Arsenic salt≤2ppm 2ppm 2ppm
Fe salt≤0.005% 0.005% 0.005%
Dry vector≤0.3% 0.16% 0.25%
Calcining residue≤0.1% 0.025% 0.15%
Yield is more than 94% 64.3%
Claims (2)
1, a kind of method of purification of the industrial goods glycine of making by the synthetic glycine that obtains of Mono Chloro Acetic Acid and liquefied ammonia reaction or by this aqueous solution, it is characterized in that adopting OH type wide aperture quaternary ammonium hydroxide type strongly basic anion exchange resin, handle synthetic glycine solution that contains ammonium chloride that obtains or the industrial goods glycine of being produced by this aqueous solution in the pH value for directly adsorbing exchange under the condition of 4-5, the glycine solution after the adsorption treatment is got rid of ammonia by heating.
2, press the method for purification of the described glycine of claim 1, it is characterized in that temperature be below 60 ℃ directly the absorption exchange handle by Mono Chloro Acetic Acid and liquefied ammonia reaction and synthesize glycine solution that obtains or the industrial goods glycine of producing by this aqueous solution, the glycine solution after the adsorption treatment is heated to 70-100 ℃ ammonia is got rid of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109134 CN1022320C (en) | 1989-12-16 | 1989-12-16 | Process for purification of glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109134 CN1022320C (en) | 1989-12-16 | 1989-12-16 | Process for purification of glycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052479A CN1052479A (en) | 1991-06-26 |
| CN1022320C true CN1022320C (en) | 1993-10-06 |
Family
ID=4857881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109134 Expired - Fee Related CN1022320C (en) | 1989-12-16 | 1989-12-16 | Process for purification of glycine |
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| Country | Link |
|---|---|
| CN (1) | CN1022320C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984735A (en) * | 2015-05-26 | 2015-10-21 | 安徽皖东树脂科技有限公司 | Adsorption resin |
-
1989
- 1989-12-16 CN CN 89109134 patent/CN1022320C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1052479A (en) | 1991-06-26 |
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