CN104418759A - Method for preparing glycine through alcohol phase synthesis, chromatographic separation, MVR evaporative crystallization - Google Patents

Method for preparing glycine through alcohol phase synthesis, chromatographic separation, MVR evaporative crystallization Download PDF

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Publication number
CN104418759A
CN104418759A CN201310413487.1A CN201310413487A CN104418759A CN 104418759 A CN104418759 A CN 104418759A CN 201310413487 A CN201310413487 A CN 201310413487A CN 104418759 A CN104418759 A CN 104418759A
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China
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glycine
ammonium chloride
solution
chromatographic separation
evaporative crystallization
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CN201310413487.1A
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Chinese (zh)
Inventor
李海研
薛照先
张善学
林光东
吴良荣
何昆明
侯华民
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Hainan Zhengye Zhongnong Hi Tech Co Ltd
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Hainan Zhengye Zhongnong Hi Tech Co Ltd
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Priority to CN201310413487.1A priority Critical patent/CN104418759A/en
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Abstract

The invention provides a method for preparing glycine through alcohol phase synthesis, chromatographic separation, MVR evaporative crystallization. The method comprises the following steps: dissolving chloroacetic acid and urotropin in methanol, introducing ammonia gas to prepare glycine and ammonium chloride, performing centrifugal separation on a mixture (crude product) of glycine and ammonium chloride crystals after the reaction is finished, feeding back the mother liquor to a reaction system, adding chloroacetic acid, introducing ammonia gas to react again, dissolving the crude product with water, separating the aqueous solution of the crude product by using a chromatography tank so as to obtain two solutions of glycine and ammonium chloride, further respectively performing MVR evaporation crystallization on the two solutions so as to obtain glycine and ammonium chloride crystals, performing centrifugal separation on the crystals, and feeding back the mother liquor to the system.

Description

A kind of method that alcohol is combined to, chromatographic separation, MVR evaporative crystallization prepare glycine
Technical field
The invention belongs to field of fine chemical, especially relate to a kind of method preparing glycine, concrete, relate to a kind of method that alcohol is combined to, chromatographic separation, MVR evaporative crystallization prepare glycine.
Background technology
Current amino acetic acid in China produces the method generally adopting synthesis in water alcohol to be separated, and being separated of glycine and ammonia chloride crystal mixture is difficult point in producing, employing be that the product of reaction carries out alcohol by alcohol-water mixture and analyses separation of glycine.Separation of glycine analysed by alcohol will use methyl alcohol, and the utilization again of methyl alcohol needs rectifying, the glycine such as, applied in CN1152853C and ammonium chloride preparation method and separation method.Methyl alcohol is easily caused danger in rectifying, and rectifying tower is subject to the seriously corroded of chlorion under the condition of heating, and service life of equipment is short.Separating out alcohol method glycine is separated not exclusively, and the yield of glycine is low, in alcohol solution, still there is glycine, and containing glycine impurity in the ammonium chloride obtained after rectifying, the purity of ammonium chloride is lower.This process catalyst single use, consumes high, and a large amount of sewage disposals is all white elephant to enterprise and environment.
Some technology application alcohol solution carries out electrodialysis, and result consumes a large amount of alcoholic solutions, and aftertreatment technology is more loaded down with trivial details.Method such as described in CN1176062C.
The method also had is that the glycine that utilizes moisture solvent to prepare and ammonium chloride carry out electrodialysis, moisture solvent after completion of the reaction, need to carry out subcooling to reaction solution, otherwise the amount of the glycine be dissolved in the water and ammonium chloride can be many, affect the productive rate of glycine and ammonium chloride, meanwhile, if the mother liquor isolated after glycine and ammonium chloride wants recycled, then must make-up catalyst urotropine.
Being separated at present for glycine and ammonium chloride, carry out that chromatographic separation carries out in addition, such as patent application 201210203584.3, although this application applies chromatographic separation two kinds of compositions, a complete set of technique but it is not worked good in two kinds of composition different sources situations and under different purification condition is fitted together to, and causes the chromatographic separation of only monocycle joint cannot realize its excellent effect under integrated artistic flow process.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of method that alcohol is combined to, chromatographic separation, MVR evaporative crystallization prepare glycine, the method comprises the steps:
1. synthesize: to be dissolved with Mono Chloro Acetic Acid, urotropine methanol solution synthesis reaction vessel in pass into ammonia and prepare glycine and ammonium chloride, centrifugation after completion of the reaction, obtain crude mixture and the mother liquor of glycine and ammonium chloride, mother liquor returns system time and uses, methyl alcohol after time use, through rectification under vacuum, reclaim methyl alcohol and catalyzer, add Mono Chloro Acetic Acid and pass into ammonia and carry out secondary response again; 2. chromatographic separation: crude mixture reclaims methyl alcohol through fluidised bed drying, obtain dry crude mixture, then by the dry crude mixture of the water dissolution after reverse-osmosis treated, obtain crude product solution, this solution is separated by chromatography tank, obtains glycine solution and aqueous ammonium chloride solution respectively; 3. MVR evaporative crystallization: respectively evaporative crystallization is carried out to glycine solution and aqueous ammonium chloride solution and obtain the solution containing Glycine crystals and ammonia chloride crystal, obtain glycine and ammonium chloride crystals and parting liquid respectively through centrifugation, two kinds of parting liquids return in crude product solution.
In aforesaid method, synthesis reaction vessel, except carrying water-cooling jacket, is configured with methanol vapor condenser system in addition.
In aforesaid method, synthesis reaction vessel is configured with methanol vapor condenser system, and methanol condensed liquid returns reactor.Arranging of this system one is to take away reaction heat by methyl alcohol evaporation, makes synthesis reaction temperature can maintain boiling temperature about 64.5 DEG C under methyl alcohol normal pressure, actual in 60 DEG C ~ 68 DEG C.Two are to provide whizzer rinsing methyl alcohol, otherwise mother liquor can incremental system overbalance.
In aforesaid method, after in methanol solution, glycine and ammonium chloride are prepared in reaction, because glycine and ammonium chloride are all slightly soluble in methyl alcohol, what so reaction solution is lowered the temperature, post crystallization went out is glycine and ammonium chloride crystals mixture, and after mother liquid recycle, its mol ratio is 1:1.
Chromatographic separation is adopted and is utilized multiple chromatography tank to carry out continuous chromatography separation.
As required, chromatographic separation is carried out in 4-20 chromatography tank parallel connection.
The crude product solution entering chromatographic separation can be refined, and to reduce total iron content≤50mg/L, free S≤5mg/L, preferably, to reduce total iron content≤3mg/L.Can also saltiness be controlled in addition, that is the specific conductivity≤150ms of feed liquid.
MVR evaporative crystallization is the secondary steam utilizing high energy efficiency vapour compressor Compression Evaporation to produce, improve the pressure and temperature of secondary steam, the secondary steam being enhanced heat energy is squeezed into evaporator room and is heated stoste again, reach and utilize the existing heat energy of secondary steam, do not need outside to add live steam, realized the object of evaporation concentration by vaporizer self-circulation.
Beneficial effect of the present invention:
In methanol solution, prepare glycine and ammonium chloride, gained crystal separation is complete, not containing other impurity.Synthesis mother liquid time use, reduces catalyst consumption.Two step aqueous phase separation, mother liquor reuse, improves quality product and yield.Breach water react or alcohol water react is prepared in glycine and ammonia chloride craft, glycine purity is low, and yield is low, and catalyst consumption is high, and ammonium chloride loses large problem.Alcohol of the present invention prepares glycine and ammonium chloride mutually, and then carry out chromatographic separation and MVR evaporative crystallization separation of glycine and ammonium chloride, three steps are connected closely, in preparation process, methanol loss is little, and be separated link at the aqueous solution and carry out, do not use methyl alcohol or ethanol, avoid to environmental emission organic solvent in whole preparation process.Glycine and the ammonium chloride product of acquisition are pure white, and purity is high, and yield is high.
Specific embodiment
One, synthesize
Synthesis procedure seven 5000L enamel stills are respectively used to preparation, reaction, decolouring.
Preparation still charging capacity is: methyl alcohol 3000 ~ 3500L, Mono Chloro Acetic Acid 800 ~ 1000Kg, urotropine 250 ~ 325Kg.
Reactor leads to the ammonia time and is about 40min ~ 2hr, and temperature of reaction maintains 60 DEG C ~ 70 DEG C.When reacting liquid pH value reaches 7.8, stop logical ammonia, be incubated 10 ~ 30 minutes, be then cooled to 40 DEG C of centrifugations.Obtain the mono-still meter of crude product about 1 ~ 1.3t(), crude yield is about 96 ~ 99%.Mother liquor turns back to preparation still and applies mechanically, and now only adds Mono Chloro Acetic Acid to preparation still.Mother liquor can apply mechanically about 15 ~ 26 times.
Two, chromatographic separation
By solid content 30% ~ 52%, the water of temperature after the glycine of 35 ~ 65 DEG C and ammonium chloride crude product solution reverse-osmosis treated is mixed with the aqueous solution of glycine content in crude product 1%-80%, regulate pH3.5-8.5, under 0-100 DEG C of condition, with the speed of≤2BV after insulation chromatogram pillar, using deionized water as eluent, collect eluant and debris respectively, obtain glycine and ammonium chloride solution.
Three, MVR evaporative crystallization
The glycine that chromatographic separation obtains and ammonium chloride solution through MVR evaporative crystallization, Glycine Levels 99.6%, Cl-≤0.3%, in ammonium chloride product, ammonium chloride content >99%, iron ion≤0.002%.
Glycine total recovery >=94%.
Method of the present invention is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change processing condition of the present invention and realize other objects corresponding, its relevant change can not depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included within scope of the present invention.

Claims (7)

1. the method that alcohol is combined to chromatographic separation, MVR evaporative crystallization prepares glycine, the method comprises the steps:
1. synthesize: to be dissolved with Mono Chloro Acetic Acid, urotropine methanol solution synthesis reaction vessel in pass into ammonia and prepare glycine and ammonium chloride, centrifugation after completion of the reaction, obtain crude mixture and the mother liquor of glycine and ammonium chloride, mother liquor returns system time and uses, methyl alcohol after time use, through rectification under vacuum, reclaim methyl alcohol and catalyzer, add Mono Chloro Acetic Acid and pass into ammonia and carry out secondary response again;
2. chromatographic separation: crude mixture drying reclaims methyl alcohol, obtain dry crude mixture, then by the dry crude mixture of the water dissolution after reverse-osmosis treated, obtain crude product solution, this solution is carried out chromatographic separation, obtains glycine solution and aqueous ammonium chloride solution respectively;
3. MVR evaporative crystallization: respectively evaporative crystallization is carried out to glycine solution and aqueous ammonium chloride solution and obtain the solution containing Glycine crystals and ammonia chloride crystal, obtain glycine and ammonium chloride crystals and parting liquid respectively through centrifugation, two kinds of parting liquids return in crude product solution.
2. method according to claim 1, wherein synthesis reaction vessel is except carrying water-cooling jacket, is configured with methanol vapor condenser system in addition, to obtain methanol condensed liquid.
3. method according to claim 2, methanol condensed liquid returns reactor.
4. method according to claim 1, wherein chromatographic separation is adopted and is utilized multiple chromatography tank to carry out continuous chromatography separation.
5. method according to claim 4, wherein the quantity of chromatography tank is 4-20.
6. method according to claim 1, the crude product solution wherein entering chromatographic separation is refined, to reduce total iron content≤50mg/L, free S≤5mg/L.
7. method according to claim 6, to reduce total iron content≤3mg/L.
CN201310413487.1A 2013-09-11 2013-09-11 Method for preparing glycine through alcohol phase synthesis, chromatographic separation, MVR evaporative crystallization Withdrawn CN104418759A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105294466A (en) * 2015-11-12 2016-02-03 冀州市格润德生物科技有限公司 Technology for producing high-purity aminoacetic acid based on urotropine cyclic utilization technology
CN107216262A (en) * 2017-04-18 2017-09-29 中国科学院过程工程研究所 A kind of method that homogeneous system intermediate ion liquid catalyst synthesizes glycine
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105294466A (en) * 2015-11-12 2016-02-03 冀州市格润德生物科技有限公司 Technology for producing high-purity aminoacetic acid based on urotropine cyclic utilization technology
CN105294466B (en) * 2015-11-12 2019-03-19 冀州市格润德生物科技有限公司 The production technology of high-purity amion acetic acid is produced based on methenamine recycle utilization
CN107216262A (en) * 2017-04-18 2017-09-29 中国科学院过程工程研究所 A kind of method that homogeneous system intermediate ion liquid catalyst synthesizes glycine
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

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Application publication date: 20150318