CN102030669B - Production method for glycine - Google Patents
Production method for glycine Download PDFInfo
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- CN102030669B CN102030669B CN200910019123.9A CN200910019123A CN102030669B CN 102030669 B CN102030669 B CN 102030669B CN 200910019123 A CN200910019123 A CN 200910019123A CN 102030669 B CN102030669 B CN 102030669B
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- glycine
- ammonia
- organic amine
- acetic acid
- mono chloro
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Abstract
The invention discloses a clean production method for glycine. In the presence of a catalyst, chloroacetic acid and ammonia serving as raw materials and organic amine serving as an acid binding agent are reacted to obtain a mixture containing the glycine and organic amine hydrochloride. In mother liquor from which the glycine is separated, the ammonia and the organic amine hydrochloride are reacted to obtain a reactant containing ammonium chloride and free organic amine, the ammonium chloride in the mother liquor is separated and the mother liquor is returned to the first step. In the method, the reaction process is simple, a plurality of refining processes in glycine production are reduced, and the solvent loss is low and the utilization rate of the raw materials is high. The glycine and the ammonium chloride are easy to separate and the product purity is high. Industrial waste water is not generated and industrial production is facilitated.
Description
Invention field: the preparation method who the present invention relates to glycine.
Background technology: glycine is the important source material of the industries such as chemical industry, medicine, agricultural chemicals, and output is large, purposes is wide.The method of producing at present glycine mostly adopts α-Mono Chloro Acetic Acid or Strecker legal system for glycine.
α-chloroactic acid method is prepared glycine and is had the advantages such as technical maturity, safety simple to operate, facility investment be low, but mostly has problem: catalyzer can not reclaim, consume high, ammonium chloride and Formation of glycine compound that reaction produces, separation difficulty, system alkalescence is strong, and facile hydrolysis produces oxyacetic acid, easily produces iminodiethanoic acid [NH (CH the in the situation that of comparatively high temps ammonia deficiency
2cOOH)
2] and nitrilotriacetic acid [N (CH
2cOOH)
3] etc. by product, in order to address the above problem, although the technique that patent CN1410417A has taked alcohol phase two-step approach to prepare glycine has alleviated the problems referred to above, it is larger that by product reduces amplitude, can be controlled in below 0.5%, and what produce is the mixture of ammonium chloride and glycine, patent US5155264 and CN1080632 are with Mono Chloro Acetic Acid, ammonia is raw material, at paraformaldehyde, organic amine can be isolated the glycine that content is higher under existing, but the catalyzer in mother liquor and organic amine are without the effective scheme of recycling, patent CN101270061 is with Mono Chloro Acetic Acid, ammonia is raw material, under urotropine and organic amine existence, also can isolate the glycine that content is higher, but for the effective constituent of recycling in mother liquor need to consume a large amount of sodium alkoxide or potassium alcoholate, this is uneconomic on producing, excessive alcohol need to reclaim and will cause the rising of energy consumption and the increase of investment simultaneously, and produce the little salt slurry of utility value, in addition, may also can more or less there is following problem in above three kinds of schemes: 1. must use excess of ammonia in order to improve yield, and excess of ammonia very easily causes separating out of ammonium chloride, thereby cause in glycine ammonium chloride content higher, this contradiction is difficult on producing control, 2. the reaction of carrying out in the situation of comparatively high temps ammonia deficiency, adding of organic amine increased chloroacetic chlorine activity, also increased the amino activity of glycine, adopts the mode of the logical ammonia of high temperature, will certainly increase the formation of by product, 3. the logical ammonia of high temperature is found in test, and the in the situation that of ammonia deficiency, product appearance is easily turned to be yellow, and after heating up, logical ammonia react is fast, easily plugging road, and this produces tissue is disadvantageous, 4. the logical ammonia of high temperature is unfavorable for the absorption of ammonia, easily causes the loss of ammonia.
Summary of the invention: for solving the problem and blemish of aforesaid method existence, the object of this invention is to provide the novel method of the friendly type production of the environmental protection glycine that a kind of production cost is low, product purity is high, operation steps is few, more energy-conservation.
The present invention realizes by the following technical solutions:
(1). in continuous or reactor intermittently, in solvent, be raw material by Mono Chloro Acetic Acid and ammonia, under catalyzer exists, be that Fu's acid agent is through reaction with organic amine, produce the reaction mixture that contains glycine and organic amine salt hydrochlorate, utilize glycine indissoluble and easily molten characteristic of organic amine salt hydrochlorate, adopt continuously or intermittent mode separates and obtained at least containing the solid of a kind of composition of glycine and the mother liquor (A) that contains organic amine salt hydrochlorate;
(2). by the mother liquor that contains organic amine salt hydrochlorate (A) and ammonia react, there is displacement and obtained the reaction-ure mixture that contains ammonium chloride and organic amine in organic amine salt hydrochlorate and ammonia wherein, adopt continuously or intermittent mode is isolated after the solid that at least contains a kind of composition of ammonium chloride, obtain at least containing the solution (B) of organic amine
(3). solution (B) carries out next production cycle for (1).
According to this programme, wherein the organic amine salt hydrochlorate mother liquor (A) that contains of isolating after glycine described in (1) can be but be not limited to obtain via following method arbitrary or combination: (a). in solution (B) or the solution that contains catalyzer and organic amine in new preparation, under low temperature, reacted forming section or whole ammonium chloroacetates (or directly adding part or all of ammonium chloroacetate) with ammonia by Mono Chloro Acetic Acid, continue at again high temperature and in the situation that adding or do not add ammonia, react generation glycine, isolate at least containing the mother liquor obtaining after the solid of a kind of composition of glycine, (b). in solution (B) or the solution containing catalyzer and organic amine in new preparation, (or directly add the mixture of Mono Chloro Acetic Acid and ammonium chloroacetate by excessive Mono Chloro Acetic Acid and ammonia, this mixture can be to add and obtain after Mono Chloro Acetic Acid mixes after adding with ammonium chloroacetate or mixes) reaction, the mother liquor obtaining after separation of glycine, maybe this mother liquor is continued to react with excess ammonia, and isolate the mother liquor obtaining after the mixture of glycine and ammonium chloride.
According to such scheme, described catalyzer is a kind of or its mixture in urotropine, formaldehyde, polyoxymethylene, formaldehyde acetal.
According to such scheme, solution (B) can be to pass into excess of ammonia in mother liquor (A), and excess of ammonia naturally participates in next circulation of producing after isolating ammonium chloride.
According to such scheme, the addition sequence of the solution containing catalyzer and organic amine of new preparation or solution (B) and Mono Chloro Acetic Acid, ammonia in no particular order.
According to such scheme, (b) in step, separate the glycine that obtains and the mixture of ammonium chloride and can be brought in (a) or reacting (b).
According to such scheme, ammonium chloroacetate can be the wet product of dry product or coordinative solvent.
According to such scheme, ammonia can be to add with liquid state, gaseous state or solution form, also can use volatile salt or bicarbonate of ammonia, by-product ammonia or its carbonate that can also use additive method to obtain.
According to such scheme, wherein under the low temperature described in (a) method, reaction can be that Mono Chloro Acetic Acid and ammonia form ammonium chloroacetate at≤40 DEG C, pyroreaction can be the boiling point of solvent under relevant pressure or below boiling point, more than 40 DEG C reaction form glycine and organic amine salt hydrochlorate, low-temp reaction and pyroreaction can be the temperature controlled processes of an interruption or the continuous temperature control processs that raises gradually.
According to such scheme, (b) excessive the referring to of the Mono Chloro Acetic Acid described in method can be by being controlled at the mol ratio >1:1 of Mono Chloro Acetic Acid and ammonia, or by monitoring Mono Chloro Acetic Acid the arbitrary step of reaction in must not disappearance situation, and be not limited to the disposable glycine of isolating, for example: can in the time that Mono Chloro Acetic Acid transformation efficiency reaches about 30%, 60%, 90%, isolate respectively glycine; Excessive the referring to of described ammonia can be by controlling the mol ratio <1:1 of Mono Chloro Acetic Acid and ammonia.
According to such scheme, can, by HLPC or PH detection reaction progress, can improve reaction control accuracy by automatic regulator device equipment.
According to such scheme, for the balance that ensures that Recycling Mother Solution is applied mechanically, the washing alcohol after separation of glycine or ammonium chloride can part and mother liquor mixing capsule use, part for reclaim.
According to such scheme, described alcohol is C
1～C5 is not limited to a kind of and nonessential anhydrous alcohol.
According to such scheme, described organic amine is selected from trialkylamine, preferably triethylamine.
By method as above, Recycling Mother Solution can be utilized by reclaiming the effective constituents such as corresponding alcohol, organic amine after certain batch, and solvent, ammonia and amine dry or reaction process volatilization can be recycled.
By method as above, can reject mechanical impurity by filtration, can be to the processing of decolouring of reaction solution and mother liquor, discoloring agent can be selected but be not limited to use gac.
Technique effect: adopt this explained hereafter glycine tool to have the following advantages:
1. this programme adopts the control method of low temperature salify, high temperature transposition, has reduced oxyacetic acid in production glycine process, iminodiethanoic acid [NH (CH
2cOOH)
2] and nitrilotriacetic acid [N (CH
2cOOH)
3] etc. the formation volume of by product;
2. efficiently solve puzzlement chloroactic acid method and produce glycine and the separation problem that is difficult to of ammonium chloride that glycine exists, and there is the problem of high flow rate in new technology, can obtain glycine and the ammonium chloride of high-content;
3. the mother liquor after separation of glycine, with ammonia react and in separating and obtaining ammonium chloride, wherein excess of ammonia has participated in the circulation of next production naturally, and raw material availability is high; And can alleviate plugging road and material jaundice.
4. no waste discharge, production process environment-protecting clean, the environmental issue of having avoided using the high flow rate of sodium alkoxide, potassium alcoholate generation and having produced salt slurry.
Embodiment: the present invention can do nonrestrictive further illustrating to this programme with following instance.
Embodiment 1
Agitator is being housed, thermometer, in the 500ml there-necked flask of reflux, add 150ml dehydrated alcohol, 15g paraformaldehyde, 70g triethylamine, be controlled at 0～30 DEG C and add the solution that drips 51.5g (99%) Mono Chloro Acetic Acid and 50ml dehydrated alcohol, drip the chloroacetic logical ammonia that simultaneously starts, time-consuming about 30min drips Mono Chloro Acetic Acid and finishes and start to promote temperature, time-consuming 1.5 hours logical ammonia 18g also evenly rise to 60 ± 5 DEG C by temperature, 60 ± 5 DEG C of insulations 1 hour, cool to 45 DEG C, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain glycine content 98.4%, yield 95.9%, filtrate continuation passes into ammonia 15g at 10～20 DEG C, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain ammonium chloride 28.1g, content 98.7%.
Embodiment 2
Agitator is being housed, thermometer, in the 500ml there-necked flask of reflux, add 51.5g (99%) Mono Chloro Acetic Acid, be controlled at 10～30 DEG C of mother liquors (wherein containing the about 5g of ammonia) that add embodiment 1, stir 0.5 hour, start logical ammonia and heat up, time-consuming 30min is by temperature increase to 60 ± 5 DEG C, controlling logical ammonia speed also just disappears with HLPC chlorine detection acetic acid, stop logical ammonia, remain on 60 ± 5 DEG C 1 hour, cool to 45 DEG C, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain glycine content 98.2%, yield 100.2%, filtrate continues to pass into ammonia and detect at 10～20 DEG C when Triethylammonium chloride 90% is converted into free organic amine, to stop logical ammonia, continuing to stir 1 disappears, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain ammonium chloride 27.2g, content 98.5%.
Embodiment 3
In the there-necked flask that agitator, thermometer, reflux are housed, add 100ml dehydrated alcohol, 70g Mono Chloro Acetic Acid, be controlled at 20～30 DEG C of logical ammonias to PH6.5～7.5 after stirring and dissolving, filtering separation obtains ammonium chloroacetate, and mother liquor is capable of circulation for the production of ammonium chloroacetate.
Agitator is being housed, thermometer, in the 500ml there-necked flask of reflux, add, the ammonium chloroacetate 56g (0.502mol) that the method for adding obtains, be controlled at 10～30 DEG C of mother liquors that drip embodiment 2, stir 0.5 hour, time-consuming 60min is by temperature increase to 60 ± 5 DEG C, remain on 60 ± 5 DEG C 1 hour, cool to 45 DEG C, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain glycine content 98.7%, yield 99.4%, filtrate continues to pass into ammonia and detect at 10～20 DEG C when Triethylammonium chloride 90% is converted into free organic amine, to stop logical ammonia, continue to stir 1 hour, filter, wash at twice with 20ml dehydrated alcohol, be dried to obtain ammonium chloride 28.5g, content 98.7%.
Embodiment 4
In the 500ml there-necked flask that agitator, thermometer, reflux are housed, add 200ml dehydrated alcohol, 8g urotropine, 70g triethylamine, stir and be controlled at 0～30 DEG C and add 51.5g (99%) Mono Chloro Acetic Acid, rise to gradually and remain on 60 ± 5 DEG C at 0～30 DEG C of logical ammonia and by temperature, while reaching 90% with HLPC chlorine detection acetic acid transformation efficiency, stop logical ammonia, be incubated 1.5 hours, cool to 45 DEG C, filter, use 20ml absolute ethanol washing, be dried to obtain glycine content 99.4%, yield 91.2%; Mother liquor continues to pass into ammonia and detects relatively all Mono Chloro Acetic Acids excessive 10% of ammonia at 40～45 DEG C, insulation 60min, be cooled to 15～20 DEG C, separation, 10ml absolute ethanol washing, dry, obtain the mixed crystal 6.1g (containing glycine 57%, ammonium chloride 42%) of glycine and ammonium chloride, and filtrate continuation passes into ammonia 14g at 15～20 DEG C, filter, use 10ml absolute ethanol washing, be dried to obtain ammonium chloride 24.9g, content 98.9%.
Embodiment 5
In the 500ml there-necked flask that agitator, thermometer, reflux are housed, add the mother liquor with embodiment 4, the mixture 6.1g of the glycine that embodiment 1 separates and ammonium chloride, be controlled at 0～30 DEG C and add Mono Chloro Acetic Acid 51.5g, control temperature and rise to gradually and remain on 60 ± 5 DEG C of insulation 30min, logical ammonia stops logical ammonia in the time that HLPC chlorine detection acetic acid transformation efficiency reaches 90%, be incubated 1.5 hours, cool to 40 DEG C, filter, use 20ml absolute ethanol washing, be dried to obtain glycine 40.2g, content 99.1%; Mother liquor continues to pass into ammonia and detects relatively all Mono Chloro Acetic Acids excessive 10% of ammonia at 40～45 DEG C, insulation 60min, be cooled to 15～20 DEG C, separation, 10ml absolute ethanol washing, dry, obtain the mixed crystal 6.9g (containing glycine 45%, ammonium chloride 55%) of glycine and ammonium chloride, and filtrate continuation passes into ammonia 14g at 15～20 DEG C, filter, use 10ml absolute ethanol washing, be dried to obtain ammonium chloride 26.2g, content 98.4%.
Claims (7)
1. a production method for glycine, is characterized in that: preparation method is as follows:
(1) in continuous or reactor intermittently, in solvent, be raw material by Mono Chloro Acetic Acid and ammonia, under catalyzer exists, be that acid binding agent is through reaction with organic amine, produce the reaction mixture that contains glycine and organic amine salt hydrochlorate, utilize glycine indissoluble and easily molten characteristic of organic amine salt hydrochlorate, adopt continuously or intermittent mode separates and obtained at least containing the solid of a kind of composition of glycine and the mother liquor (A) that contains organic amine salt hydrochlorate;
(2) by the mother liquor that contains organic amine salt hydrochlorate (A) and ammonia react, there is displacement and obtained the reaction-ure mixture that contains ammonium chloride and organic amine in organic amine salt hydrochlorate and ammonia wherein, adopt continuously or intermittent mode is isolated after the solid that at least contains a kind of composition of ammonium chloride, obtained at least solution (B) containing organic amine;
(3) solution (B) carries out next production cycle for (1);
Described organic amine is selected triethylamine.
2. method according to claim 1, is characterized in that: the described mother liquor (A) of isolating after glycine is but is not limited to obtain via following method arbitrary or combination:
A. solution (B) or in the solution that at least contains catalyzer and organic amine of new configuration, under low temperature, reacted forming section or whole ammonium chloroacetates with ammonia by Mono Chloro Acetic Acid, or directly add part or all of ammonium chloroacetate, continue at again high temperature and in the situation that adding or do not add ammonia, react generation glycine, isolate at least containing the mother liquor obtaining after the solid of a kind of composition of glycine;
B. solution (B) or in the solution that at least contains catalyzer and organic amine of new configuration, by excessive Mono Chloro Acetic Acid and ammonia react, or directly add the mixture of Mono Chloro Acetic Acid and ammonium chloroacetate, this mixture is to add and obtain after Mono Chloro Acetic Acid mixes after adding with ammonium chloroacetate or mixes, the mother liquor obtaining after separation of glycine, maybe this mother liquor is continued to react with excess ammonia, and isolate the mother liquor obtaining after the mixture of glycine and ammonium chloride.
3. method according to claim 2, it is characterized in that under the low temperature described in a reaction be Mono Chloro Acetic Acid with ammonia at≤40 DEG C of formation ammonium chloroacetates, pyroreaction be the boiling point of solvent under relevant pressure or below boiling point, more than 40 DEG C reaction form glycine and organic amine salt hydrochlorate, low-temp reaction and pyroreaction are the temperature controlled processes of an interruption or the continuous temperature control processs that raises gradually.
4. method according to claim 2, it is characterized in that the excessive mol ratio > 1:1 referring to by being controlled at Mono Chloro Acetic Acid and ammonia of Mono Chloro Acetic Acid described in b, or by the arbitrary step of reaction in not disappearance situation of monitoring Mono Chloro Acetic Acid, and be not limited to the disposable glycine of isolating; The excessive mol ratio < 1:1 referring to by controlling Mono Chloro Acetic Acid and ammonia of described ammonia.
5. according to the method described in any one in claim 1,2,3 or 4, it is that urotropine, formaldehyde, polyoxymethylene, formaldehyde acetal, structure are NH that described catalyzer is selected
x(CH
2oR)
yin be not limited to one, wherein x=0,1 or 2, y=1,2 or 3, R be C
1~ C
5alkane or hydrogen.
6. method according to claim 1 and 2, is characterized in that the addition sequence of the new solution containing catalyzer and organic amine configuring or solution (B) and Mono Chloro Acetic Acid, ammonia in no particular order.
7. according to the method described in any one in aforementioned claim 1,2,3 or 4, it is characterized in that: described solvent is selected C
1~ C
5be not limited to a kind of and nonessential anhydrous alcohol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910019123.9A CN102030669B (en) | 2009-09-25 | 2009-09-25 | Production method for glycine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910019123.9A CN102030669B (en) | 2009-09-25 | 2009-09-25 | Production method for glycine |
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|---|---|
| CN102030669A CN102030669A (en) | 2011-04-27 |
| CN102030669B true CN102030669B (en) | 2014-07-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016135397A1 (en) * | 2015-02-27 | 2016-09-01 | Afyren | Process for producing amino acids from precursors obtained by anaerobic fermentation from fermentable biomass |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570568A (en) * | 2012-08-06 | 2014-02-12 | 刘长飞 | Clean production process of glycine in coproduction with ammonium chloride |
| CN103351314A (en) * | 2013-07-29 | 2013-10-16 | 刘长飞 | Cleaner production process for combined glycine and calcium sulfate |
| CN103524352A (en) * | 2013-10-28 | 2014-01-22 | 刘长飞 | Method for recovering glycine acid-binding agent triethylamine employing triethylamine method |
| FR3033168B1 (en) | 2015-02-27 | 2017-03-10 | Afyren | PROCESS FOR THE PRODUCTION OF POLYHYDROXYALKANOATES FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS |
| CN113563214B (en) * | 2021-07-06 | 2024-02-02 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Synthesis method of glycine |
| CN115925567A (en) * | 2022-12-21 | 2023-04-07 | 河南格莱信商贸有限公司 | Process for recycling mother liquor in glycine production process by chloroacetic acid ammonolysis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215736A (en) * | 1964-03-20 | 1965-11-02 | Prod Chim Ind S P C I Soc D | Preparation of amino acids |
| US3510515A (en) * | 1970-03-09 | 1970-05-05 | Chatten Drug & Chem Co | Method of making glycine |
| CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
-
2009
- 2009-09-25 CN CN200910019123.9A patent/CN102030669B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215736A (en) * | 1964-03-20 | 1965-11-02 | Prod Chim Ind S P C I Soc D | Preparation of amino acids |
| US3510515A (en) * | 1970-03-09 | 1970-05-05 | Chatten Drug & Chem Co | Method of making glycine |
| CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016135397A1 (en) * | 2015-02-27 | 2016-09-01 | Afyren | Process for producing amino acids from precursors obtained by anaerobic fermentation from fermentable biomass |
| FR3033166A1 (en) * | 2015-02-27 | 2016-09-02 | Afyren | PROCESS FOR THE PRODUCTION OF AMINO ACIDS FROM PRECURSORS OBTAINED BY ANAEROBIC FERMENTATION FROM FERMENTABLE BIOMASS |
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| CN102030669A (en) | 2011-04-27 |
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