CN106699583A - Preparation method of glycine - Google Patents

Preparation method of glycine Download PDF

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Publication number
CN106699583A
CN106699583A CN201510789530.3A CN201510789530A CN106699583A CN 106699583 A CN106699583 A CN 106699583A CN 201510789530 A CN201510789530 A CN 201510789530A CN 106699583 A CN106699583 A CN 106699583A
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CN
China
Prior art keywords
glycine
preparation
mixed liquor
mixed solution
catalyst
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Pending
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CN201510789530.3A
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Chinese (zh)
Inventor
李春梅
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Qingdao Senmeike Chemical Technology Co Ltd
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Qingdao Senmeike Chemical Technology Co Ltd
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Priority to CN201510789530.3A priority Critical patent/CN106699583A/en
Publication of CN106699583A publication Critical patent/CN106699583A/en
Pending legal-status Critical Current

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of glycine and belongs to the field of a food additive and a preparation method thereof. The preparation method of the glycine comprises the following steps: (1) adding chloroacetic acid, a catalyst and a multi-component solvent into a reactor by adopting a halogenated acid method, introducing liquid ammonia for cyclic synthesis reaction to obtain a glycine and ammonium chloride mixed solution and recycling the catalyst; (2) enabling the mixed solution to enter an ion membrane separation device, controlling the PH value of an isoelectric point under the action of a direct-current electric field, respectively migrating out NH4<+> and Cl<->, forming an NH4Cl solution and leaving most of the glycine after NH4Cl is migrated out of and separated from the mixed solution; (3) separating out the residual mixed solution through crystallization to obtain the product glycine. The preparation method of the glycine, provided by the invention, has the advantages of being efficient, energy-saving and free from three wastes, saving raw materials, improving the product quality, and the like, thereby conforming to the green process trend vigorously promoted in the current industry.

Description

The preparation method of glycine
Technical field
The present invention relates to a kind of preparation method of glycine, belong to food additives and preparation method thereof field.
Background technology
Glycine is a kind of important amino acid, be food industry, medical industry, pesticide industry, organic synthesis and The important source material of biochemical research etc., is widely used as food additives, feed addictive, chemical additives etc. In the industries such as food, feed, daily use chemicals.More than 60,000 tons, production technology uses halogen for country's annual production at present Generation sour synthetic method, synthetic reaction generation glycine and ammonium chloride mixt, industrially separates sweet ammonia using methyl alcohol chromatography Acid and ammonium chloride, this needs to make glycine separate precipitation with substantial amounts of methyl alcohol, and mother liquor is carbinol mixture, by rectifying, Methyl alcohol is reclaimed, rectifying residue discharge, its technical process is remained in some problems:1st, large steam consumption;2nd, first Alcohol volatilization is big, and consumption is high;3rd, methyl alcohol causes production environment severe contamination, and production is also increased not using a large amount of methyl alcohol Security;4th, mixed liquor impurity is more, and ammonium chloride seriously corroded, rectifying column requirement for anticorrosion is high, and investment is big, rectifying column dimension Repair costly.5th, by-product ammonium chloride can not be reclaimed.6th, catalyst consumption is big, it is impossible to reclaim.
In recent years, all advocating energetically and studying Green Chemistry both at home and abroad, also known as cleaning chemistry, it was being managed Green Chemistry Think to be not use poisonous and harmful substance, no longer produce waste, do not reprocess waste, pollution is prevented from source. Green Chemistry requirement utilizes " clean technology " or " environmentally-friendly technique ", using " friendly process " or " few Useless non-waste technology ", both pursues economically feasible, also pursues sanitary safe, and environmental protection makes full use of resource.It is green Color production technology include saving material with the energy, using clean energy resource, without harmful poisonous raw material, in all rows Put thing and reduce its quantity and toxicity before waste leaves technique, green production at this stage is mainly:Subtract dirty, consumption reduction, Comprehensive utilization.
Therefore, studying a kind of green method production glycine has obvious economic and social benefit.
The content of the invention
The present invention is intended to provide a kind of efficient, energy-conservation, three wastes, save material, the sweet ammonia of improve product quality The environment-friendly preparation method thereof of acid.
The preparation method of glycine of the present invention, comprises the following steps:
(1) monoxone, catalyst and multicomponent solvent are added in reactor using halo acid system, are passed through liquefied ammonia and enter Row round-robin method synthetic reaction, can obtain glycine and ammonium chloride mixed liquor, catalyst circulating and recovering.
(2) mixed liquor enter ion membrane separation device in, DC electric field effect under, control isoelectric point pH value and Current density, NH4+ and Cl- are migrated away respectively, form NH4Cl solution, transport in mixed liquor After NH4Cl, most of glycine is left.
(3) residual mixed liquor is obtained final product product by crystallizing precipitation.
Preferably, the ion membrane separation device in step of the present invention (2) uses feedback cycle formula ionic membrane point From device.
(isoelectric pH in ion membrane separating process in 2 is it is further preferred that step of the present invention PH5.8-6.0。
Still more preferably, the current density in the ion membrane separating process in step of the present invention (2) is 15-35A/cm 2。
The preparation method of glycine of the present invention, has the characteristics that:
(1) avoid using poisonous and harmful substance
The a large amount of poisonous and harmful substance methyl alcohol used in old technique separating out alcohol method are avoided in ionic membrane method glycine separating technology, Methyl alcohol can cause poisoning through alimentary canal, respiratory tract and Cutaneous permeation etc. into human body, the most serious to optic nerve lesion. Methyl alcohol boiling point is 64.7 DEG C, is the mixture of volatile easy firing liquid, its steam and air, and explosion limit is 6.0 - 36.5% (volume).More than ten tons of methyl alcohol of product need per ton carry out alcohol crystallization in separating out alcohol method, and methyl alcohol volatile quantity is big, raw Produce environmental pollution serious, substantial amounts of methanol mother liquid flow easily causes work safety accident.
(2) reducing energy consumption.Use clear energy sources.
The a large amount of of steam are avoided in ionic membrane method glycine separating technology to use.Steam is consumed in separating out alcohol method to be produced up to 12t/t Product, a large amount of turnover methyl alcohol are reclaimed with rectifying.Clear energy sources have been used in ionic membrane method --- electric power, it is free from environmental pollution.From Proton exchange method technical process in normal temperature, without phase transformation under conditions of realize material separate, distillation process is a kind of phase transformation Journey.Consumed energy than phase transition process without phase transition process low, in ion exchange membrane separation process, institute's consuming electric power is mainly used Electrolyte ion in migration solution.During reaction type ion exchange membrane separation device separation of glycine, electric current effect Rate will be significantly higher than common ion exchange membrane separation device, and current efficiency is up to more than 75%.Current efficiency is higher, Consumption electric energy is lower.Energy Consumption Cost is less than the 50% of alcohol chromatography process in ionic membrane method separation of glycine technique.
(3) equipment investment is reduced, it is to avoid use corrosive equipment
Ionic membrane method glycine separating technology is avoided and uses the big rectifying column for easily being corroded by ammonium chloride.It is to subtract in separating out alcohol method The deep-etching of few ammonium chloride, often in rectifying column stripping section, then boils in the equipment such as heater using expensive titanium, if Standby maintenance cost is high, and in ion exchange film separation system, in addition to portion of external part metal, amberplex is used Macromolecular material is made, and is made of plastics or rubber more than dividing plate, transfusion system, circulating slot and other parts, this A little insulation resistances and corrosion resistance are all fine, and ion membrane separation device long service life, operation is easy to maintenance, easily Realize Automated condtrol.The investment of ionic membrane method glycine Separation process arrangements is substantially reduced than separating out alcohol method.
(4) product quality is significantly improved, and accessory substance is effectively utilized, catalyst recycling
Ionic membrane method separating technology can directly obtain crystal glycine, and product heap density can reach 0.8g/ml, and alcohol is analysed Method is 0.55g/ml or so.And new technology is without recrystallization refining process, higher sweet of quality scale is just can obtain Propylhomoserin product, added value of product is improved.
In new technology catalyst can repeatedly continuous reuse, catalyst consumption reduced to below 90kg/t.
By-product ammonium chloride mother liquor, outward appearance clarification, white crystalline ammonium chloride is can obtain by condensing crystallizing, also can be straight Connect mother liquor as raw material, produce other products.Ammonium chloride mother liquor is yellow oil, complicated, warp in separating out alcohol method Partial oxidation ammonium mixture is can extract after concentration, but outward appearance is buff, and ammonium chloride content is not high.
Ionic membrane method separating technology has not only efficiently separated major-minor product, and significantly improves major-minor product quality, by-product Product are all reclaimed, and reduce three waste discharge.
The preparation method of glycine of the present invention, possesses efficient, energy-conservation, three wastes, saves material, and improves and produces The advantages such as quality, meet the friendly process trend advocated energetically in current industry.
Specific embodiment
The present invention is further illustrated below by specific embodiment.These embodiments are not the limitations to the content of the invention, are appointed What equivalent or known change belong to the scope of the present invention.
Embodiment one:
Monoxone, catalyst and multicomponent solvent are added in reactor using new halo acid system, logical liquefied ammonia is circulated method conjunction Into reaction, glycine and ammonium chloride mixed liquor are can obtain, catalyst circulating and recovering, mixed liquor enters reaction type ion UF membrane In device, under DC electric field effect, it is that PH5.8-6.0 and electric current are close to control the isoelectric pH in ion membrane separating process 15-35A/cm 2 is spent, NH4+ and Cl- are migrated away respectively, form NH4Cl solution, migrated in mixed liquor After separating NH4Cl, most of glycine is left, residual mixed liquor is obtained final product product glycine by crystallizing precipitation.From In sub- membrane separating process in non-isoelectric point, glycine also has partial ionization and migrates, in reaction type ion membrane separation device In, the glycine migrated out after partial ionization can be reclaimed by feedback loop system, without generally electricity Isoelectric focusing control in dialysis UF membrane.The handicraft product yield is high, and product heap density can reach 0.8g/ml, is analysed higher than alcohol Method is 0.55g/ml or so.

Claims (3)

1. the preparation method of glycine, comprises the following steps:
(1) monoxone, catalyst and multicomponent solvent are added in reactor using halo acid system, are passed through liquefied ammonia and are circulated method Synthetic reaction, can obtain glycine and ammonium chloride mixed liquor, catalyst circulating and recovering;
(2) mixed liquor enters in ion membrane separation device, under DC electric field effect, controls isoelectric point pH value and current density, NH 4+ and Cl- are migrated away respectively, form the Cl solution of NH 4, in mixed liquor after the Cl of transport NH 4, stay Lower most of glycine;
(3) residual mixed liquor is obtained final product product glycine by crystallizing precipitation.
2. the preparation method of glycine as claimed in claim 1, it is characterised in that the ionic membrane point in described step (2) Feedback cycle formula ion membrane separation device is used from device.
3. the preparation method of glycine as claimed in claim 1 or 2, it is characterised in that the ion in described step (2) Isoelectric pH in membrane separating process is PH5.8-6.0.
CN201510789530.3A 2015-11-16 2015-11-16 Preparation method of glycine Pending CN106699583A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510789530.3A CN106699583A (en) 2015-11-16 2015-11-16 Preparation method of glycine

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Application Number Priority Date Filing Date Title
CN201510789530.3A CN106699583A (en) 2015-11-16 2015-11-16 Preparation method of glycine

Publications (1)

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CN106699583A true CN106699583A (en) 2017-05-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109507127A (en) * 2018-12-07 2019-03-22 上海浩港生物技术有限公司 It is a kind of for detecting the kit of LBP content in human blood

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109507127A (en) * 2018-12-07 2019-03-22 上海浩港生物技术有限公司 It is a kind of for detecting the kit of LBP content in human blood

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