CN103086900B - Method of production of glycine by circulation environmental-friendly method in alcohol phase - Google Patents
Method of production of glycine by circulation environmental-friendly method in alcohol phase Download PDFInfo
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- CN103086900B CN103086900B CN201110346586.3A CN201110346586A CN103086900B CN 103086900 B CN103086900 B CN 103086900B CN 201110346586 A CN201110346586 A CN 201110346586A CN 103086900 B CN103086900 B CN 103086900B
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Abstract
The present invention relates to a method of production of glycine by a circulation environmental-friendly method in an alcohol phase, which is characterized in that: ammonia is fed into a mixture of methanol, chloroacetic acid and urotropin, the reaction system is a closed system and is provided with a condensing device, methanol liquid condensed by the condensing device is directly transported to the reaction system, and the solid and the liquid are separated by centrifugation when the temperature drops to 40-45 DEG C after the reaction. The method of the present invention achieves improvement of the overall yield and improvement of the utilization of the catalyst and the solvent, and helps to prevent precipitation of urotropin resulted from methanol reduction, so that the product does not contain urotropin and the product quality is high.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to the preparation method of glycine, particularly relate to a kind of alcohol mutually in carry out environment-friendly cycle method and produce the method for glycine.
Background technology
The alcohol of glycine is combined to method and has many reports.People are finding always and are improving glycine synthesis yield and quality, and reduce urotropine consumption, the method reduced costs.
Disclose in publication number CN1410417A a kind of alcohol mutually in prepare the method for glycine, it comprises the steps: (1) passes into ammonia in the mixture of Mono Chloro Acetic Acid and alcohol, obtains product ammonium chloroacetate; (2) in the mixture of ammonium chloroacetate, alcohol and urotropine, pass into ammonia, obtain glycine.Method in this patent of invention is carried out in two steps, and two steps adopt specific condition respectively, attempt the recycle number of times improving urotropine, but two-step approach makes reaction process complex operation, in fact still extends the time of reaction.
In current process for preparing glycine, that reaction process is dangerous on the one hand, especially the reaction disclosed in publication number CN1340498A, although disclose mother liquor can recycle, but do not solve the problem that methyl alcohol overcomes as solution circulated reaction needed, such as reaction is pipe reaction, when violent or when passing into ammonia, reaction is easily blasted, further, the middle product that alcohol phase reaction obtains will be separated, preparation process complicated operation, long in time limit, and be not easy to industrial process operation.
The present invention is directed to the defect that in prior art, process for preparing glycine exists, preparation technology is improved, overcome the defect of prior art, solve the problem that insoluble suitability for industrialized production is dangerous, preparation process is loaded down with trivial details for a long time, achieve the production method of the full-range energy-conserving and environment-protective of one.The object of the invention is to overcome above-mentioned defect, provide a kind of constant product quality, yield is high, and cost is low, is applicable to the process for preparing glycine of industrialization scale operation.This technique, by continuous circulation synthesis and multicomponent solvent multi-cycle separation two closed systems, obtains glycine, and can obtain the byproduct ammonium chloride of industrial first grade.
Summary of the invention
For solving the problem, the invention provides a kind of alcohol mutually in carry out environment-friendly cycle method and produce the method for glycine, the method comprises: first set reaction is to methyl alcohol, Mono Chloro Acetic Acid, ammonia is passed in the mixture of urotropine, react under cooling conditions, after reaction terminates, reaction soln is centrifugal, obtain glycine and ammonia chloride crystal mixture solid and mother liquor, solid is used for therefrom separation of glycine and ammonium chloride, mother liquor is used as the raw material next time reacted, in mother liquor, add Mono Chloro Acetic Acid and pass into ammonia carry out second time reaction prepare glycine and ammonium chloride, circulation like this, the mother liquor that front primary first-order equation obtains prepares glycine and ammonium chloride as the raw material of rear primary first-order equation, it is characterized in that: reaction system is closed system, and be provided with condensing works, the methanol liquid directly defeated time reaction system of condensing works institute condensation, continue to cool to 40-45 DEG C after reaction terminates and carry out centrifugation solid and liquid.
In aforesaid method, urotropine is reused in reaction process, and need not add urotropine in multiple working cycle, alcohol is reused in reaction process, need not add liquid alcohol in multiple working cycle.
Production method of the present invention is only only applicable to Methanol for glycine, is not suitable for aqueous phase or alcohol aqueous phase prepares glycine.
In method of the present invention, described methyl alcohol water content lower than 0.15wt%, preferably, lower than 0.10wt%.In whole reaction system, anhydrous implication is except the negligible methyl alcohol existed in methyl alcohol, the negligible water that may contain in Mono Chloro Acetic Acid, and Mono Chloro Acetic Acid employing is industrial Mono Chloro Acetic Acid, water content is wherein lower than 0.1%, preferably, the Mono Chloro Acetic Acid lower than 0.05% is adopted.
The above-mentioned method preparing glycine of the present invention, on the one hand, ensure that the amount of methyl alcohol in reaction system does not reduce by condensing equipment, can ensure that urotropine is not separated out like this, because quantity of methyl alcohol reduces, urotropine can be separated out due to supersaturation, is mixed in the crystallization of glycine and ammonium chloride, cause containing urotropine impurity in product, in follow-up process, be difficult to removing.The recovery of methyl alcohol, after also ensureing to isolate product, in mother liquor, the amount of methyl alcohol still can maintain the needs of following cycle reaction.Generally, 20-30 DEG C to be cooled to reaction system after having reacted, few with the product making more glycine and ammonium chloride be dissolved at low temperatures in methyl alcohol, and the present invention is used for recycling due to mother liquor, so need not stick to single to obtain more product, the product be dissolved in methyl alcohol can not lost by circulating reaction, so reaction solution is cooled to 40-45 DEG C, ensure the time shorten of cooling, save the energy required for cooling.These 2 is the present invention is realize the more efficient and more feasible effective measure taked of circulation.
Prepare in the reaction of glycine at use urotropine, generally need water that reaction rapid reaction can be made complete, if do not have water to participate in reaction, then reaction needed raised temperature improves speed of response, otherwise the reaction times is long, so the by product of reaction will be made to increase once improve temperature, such as by product NH (CH
2cOOH)
2or by product N (CH
2cOOH)
3so other approach can only be taked to solve this problem, the two-step approach such as, used in publication number CN1410417A is prepared glycine, the preparation of this two-step approach makes the process of reacting become loaded down with trivial details, complicated operation in a large amount of industrial production, extend the production time on the contrary, although shorten the reaction times, on integrated artistic, the time does not shorten.
And method of the present invention, be lower the temperature in reaction process, do not heat up, cool in reaction process to reactor cooling jacket, low-temp reaction avoids the generation of by product.
Reaction of the present invention is owing to being circulating reaction, productive rate is high or impurity is few to realize not to be positioned through certain particular step, but come the lifting of realization response productive rate and the reduction of impurity by the circulation of total system, ensure the utilising efficiency of system, namely the reaction times does not extend simultaneously.
Because in method of the present invention, reaction system does not cool to low temperature, the time shorten of such cooling, cool to 40 DEG C-45 DEG C periods, although also have saturated ammonia, glycine and ammonium chloride in mother liquor, but because it still will enter next reaction process, so it still in systems in which, does not in fact cause the loss of raw material.
In aforesaid method, there is in reactor agitator reaction soln is stirred, ensure that reaction evenly.
The temperature that method of the present invention breaks through reaction system on the one hand must cool to the problem that low temperature just carries out separate solid and mother liquor, but the mode that have employed methanol phase circulating reaction is produced, while realizing the lifting of overall productivity, and improve the utilization ratio of catalysts and solvents.On the other hand, ensure that quantity of methyl alcohol in reaction system by the recovery of methyl alcohol, avoid the minimizing of methyl alcohol to cause the precipitation of catalyzer urotropine, make not containing urotropine in product, the quality of product is higher.
Embodiment
In order to understand the present invention, further illustrate the present invention with embodiment below, but do not limit the present invention.
Embodiment 1
Which step mentioned in embodiment is actually the division carried out in order to clear elaboration reaction process, and real reaction process is not that whole reaction process is actually continuous print so step by step.
The first step: by the urotropine mixture of the methyl alcohol of the Mono Chloro Acetic Acid of 1000kg, 4000L, 260Kg in 5 cubic metres of reactors, reactor is provided with condenser, in the liquid exit access reactor of condenser, pass into ammonia and start reaction, with cooling jacket, reactor is cooled in reaction process, the pH of reaction system reach 7.8 and keep 5 minutes constant after, no longer pass into ammonia
Second step: reacted rear cooling jacket and continued cooling reactor, when the temperature of reaction soln reaches 40 DEG C time, passed into by solution in whizzer, the mixed crystal solid of centrifugation glycine and ammonium chloride and mother liquor, mother liquor enters reaction process next time.
3rd step: mother liquor is joined in another reactor, reactor is provided with condenser, in the liquid exit access reactor of condenser, adds the Mono Chloro Acetic Acid of 1000kg in mother liquor, then pass into ammonia to react, with cooling jacket, reactor is cooled in reaction process; The pH of reaction system reach 7.8 and keep 5 minutes constant after, no longer pass into ammonia.
Then second step, three-step reaction is repeated.So recycle mother liquor and carry out circulating reaction, again carry out 18 reaction cycle, carry out 20 circulations altogether.
Carry out Measurement and analysis after each circulation produces glycine and ammonia chloride crystal mixture solid, measure the gross weight of glycine and ammonium chloride, after separation of glycine and ammonium chloride, weigh the weight of glycine and ammonium chloride respectively.Calculate the productive rate of each circulation and the accumulative overall yield that altogether circulates.Test the amount of the impurity that each circulation produces simultaneously.
The data results of the several circulations in the result of 20 that measure circulations is described below:
Wherein impurity 1 represents NH (CH
2cOOH)
2, impurity 2 represents N (CH
2cOOH)
3, impurity 3 represents urotropine
Can find out from above, by circulating reaction of the present invention, not only the overall yield of glycine is high, can reach 96%, and the time of a circulating reaction is short, does not have the three wastes to produce in reaction process, and catalysts and solvents methyl alcohol can efficiency utilization.
In time cooling to 30 temperature, by the relation of the productive rate of simultaneous test confirmatory reaction time and reaction.
When greenhouse cooling is to 30 DEG C time, although overall yield slightly promotes, time lengthening, close to the time of one day, for suitability for industrialized production, reduces production capacity about 30%, significantly reduces production efficiency.So the present invention has found out from industrial practice ensure that the situation of productive rate effectively improves the method for productive rate, namely when cyclic production, ensure that overall production rate, and carried out centrifugal under high temperature, neither affected overall production rate and effectively can improve production capacity again.
Claims (3)
1. one kind alcohol mutually in carry out environment-friendly cycle method and produce the method for glycine, the method comprises: first set reaction is to methyl alcohol, Mono Chloro Acetic Acid, ammonia is passed in the mixture of urotropine, react under cooling conditions, after reaction terminates, reaction soln is centrifugal, obtain glycine and ammonia chloride crystal mixture solid and mother liquor, solid is used for therefrom separation of glycine and ammonium chloride, mother liquor is used as the raw material next time reacted, in mother liquor, add Mono Chloro Acetic Acid and pass into ammonia carry out second time reaction prepare glycine and ammonium chloride, circulation like this, the mother liquor that front primary first-order equation obtains prepares glycine and ammonium chloride as the raw material of rear primary first-order equation, it is characterized in that: reaction system is closed system, and be provided with condensing works, the methanol liquid directly defeated time reaction system of condensing works institute condensation, continue to cool to 40-45 DEG C after reaction terminates and carry out centrifugation solid and liquid.
2. method according to claim 1, wherein methyl alcohol water content is lower than 0.15wt%.
3. method according to claim 2, wherein methyl alcohol water content is lower than 0.10wt%.
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|---|---|---|---|
| CN201110346586.3A CN103086900B (en) | 2011-11-04 | 2011-11-04 | Method of production of glycine by circulation environmental-friendly method in alcohol phase |
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| CN201110346586.3A CN103086900B (en) | 2011-11-04 | 2011-11-04 | Method of production of glycine by circulation environmental-friendly method in alcohol phase |
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| CN103086900B true CN103086900B (en) | 2015-02-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
| CN107216262B (en) * | 2017-04-18 | 2020-06-05 | 中国科学院过程工程研究所 | Method for synthesizing glycine under catalysis of ionic liquid in homogeneous system |
| CN111087319A (en) * | 2019-12-28 | 2020-05-01 | 中国天辰工程有限公司 | Method for continuously preparing glycine in alcohol phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1410417A (en) * | 2001-09-24 | 2003-04-16 | 北京清华紫光英力化工技术有限责任公司 | Preparation method of glycine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3510515A (en) * | 1970-03-09 | 1970-05-05 | Chatten Drug & Chem Co | Method of making glycine |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1410417A (en) * | 2001-09-24 | 2003-04-16 | 北京清华紫光英力化工技术有限责任公司 | Preparation method of glycine |
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