CN106699591A - Clean production process of glycine and co-produced ammonium chloride - Google Patents

Clean production process of glycine and co-produced ammonium chloride Download PDF

Info

Publication number
CN106699591A
CN106699591A CN201510789414.1A CN201510789414A CN106699591A CN 106699591 A CN106699591 A CN 106699591A CN 201510789414 A CN201510789414 A CN 201510789414A CN 106699591 A CN106699591 A CN 106699591A
Authority
CN
China
Prior art keywords
triethylamine
glycine
reaction
ammonium chloride
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510789414.1A
Other languages
Chinese (zh)
Inventor
李春梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Senmeike Chemical Technology Co Ltd
Original Assignee
Qingdao Senmeike Chemical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao Senmeike Chemical Technology Co Ltd filed Critical Qingdao Senmeike Chemical Technology Co Ltd
Priority to CN201510789414.1A priority Critical patent/CN106699591A/en
Publication of CN106699591A publication Critical patent/CN106699591A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/16Halides of ammonium
    • C01C1/164Ammonium chloride
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82Purification; Separation; Stabilisation; Use of additives
    • C07C209/84Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups

Abstract

The invention provides a clean production process of glycine. The clean production process can be used for co-producing an ammonium chloride product when being used for producing glycine. In a process of producing glycine, a triethylamine hydrochloride product can be co-produced. After a solvent, namely methanol, and a catalyst are added into a reactor of a glycine ammonolysis reaction, solid ammonium chloroacetate is added; after the temperature is raised to 65 DEG C, triethylamine is added; all triethylamine is added within one and a half hours; and the heat is kept and a reaction is carried out for two and a half hours until the pH (Potential of Hydrogen) value is 7.5. The glycine and triethylamine hydrochloride are separated through cooling and freezing respectively. The triethylamine in the triethylamine hydrochloride is recycled through an ammonia introducing method; and meanwhile, the ammonium chloride product is co-produced.

Description

A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride
Technical field
The present invention relates to a kind of process for cleanly preparing of glycine, while production glycine can with combined producting ammonium chloride product, Can also coproduction triethylamine hydrochloride product, belong to chemical production technical field.
Background technology
Glycine is the important source material of the products such as glyphosate, glycine ethyl ester hydrochloride, it is also possible to be refined into the sweet ammonia of food-grade Acid is used.Domestic traditional chloroactic acid method glycine production technology is as follows:Catalysis is added in the reactor for be connected with cooling water The aqueous solution of agent methenamine content 25% or so, while the chloroethene aqueous acid of 70% or so content is added dropwise and liquid is passed through Ammonia, ammonolysis reaction is carried out under conditions of pH value 7 or so, 80 DEG C or so of reaction temperature.What reaction was obtained after terminating contains There is the isolated glycine product of method of the ammonolysis reaction liquid methyl alcohol alcohol analysis of glycine and ammonium chloride.One ton of sweet ammonia of production Acid will produce 12--13 cubic metres or so of the mother liquor containing methyl alcohol, containing 5% or so ammonium chloride, 1% in methanol mother liquor Methenamine, 0.8% or so the glycine of left and right.One ton of glycine of production needs the steam of 5 tons or so of consumption to be used for back Methyl alcohol is received, while one ton of glycine of production needs the methenamine of 150 kilograms or so of consumption can not to recycle.Production one Ton glycine will also consume 60-100 kilograms of methyl alcohol.Methanol mother liquor obtains dealcoholizing waste water after methyl alcohol is reclaimed in rectifying. Dealcoholizing waste water is by obtaining byproduct ammonium chloride for producing fertilizer application after evaporation and concentration.And after reclaiming byproduct ammonium chloride The remaining black waste water containing organic matters such as a large amount of methenamines, glycine is very difficult, not only pollutes environment, Also waste the resource of preciousness.
Patent US5155264 and CN1080632 with monoxone, ammonia as raw material, in the presence of catalyst and organic amine, can To isolate the effective scheme that catalyst and organic amine inside glycine, but mother liquor are not reused.Patent CN101270061 can separate glycine with monoxone, ammonia as raw material in the presence of methenamine and organic amine, But need to consume substantial amounts of sodium alkoxide or potassium alcoholate, high cost does not have industrial value.Patent CN102030669 is with chlorine Acetic acid and ammonia are raw material, under catalyst action, with organic amine as acid binding agent, can realize glycine and ammonium chloride point From.But the technics comparing is complicated, reaction end also compares difficult control.Still there is a small amount of glycine in production process simultaneously Mixed crystal with ammonium chloride is produced, in addition it is also necessary to further to separate.
The content of the invention
The invention provides a kind of process for cleanly preparing of glycine, can be with combined producting ammonium chloride product while production glycine. While production glycine, it is also possible to coproduction triethylamine hydrochloride product.
The present invention is realized by the following method:
First, it is waste glycine using ammonium chloroacetate:
(condenser is housed above reactor, there is solvent condensation reflux unit and solvent recovery to fill in the reactor of production glycine Put) it is inner addition solvent methanol (solvent can be the alcohol water mixed solution of pure methanol solution, or content more than 90%) and After catalyst (methenamine or paraformaldehyde), (ammonium chloroacetate can be by preparation process for chloroacetic acid to add solid ammonium chloroacetate The reaction of chlorination reaction liquid and ammonia directly produce, can also reaction be made in solvent (methyl alcohol or water) by monoxone solid and ammonia Take).It is warming up to 60 DEG C to start to add triethylamine, maintenance reaction temperature is added between 60 DEG C -70 DEG C in one and a half hours Triethylamine is finished.Reaction, insulation amount to two and one-half- hours, are 7.5 to pH value.The mol ratio of ammonium chloroacetate and triethylamine It is 1-1.1: 1.The amount of solvent methanol is 2-8 times of ammonium chloroacetate weight.The amount that catalyst methenamine is added is monoxone Between 1st/to three/8th of ammonium weight.
After insulation reaction terminates, reaction solution filters out Glycine crystals and filtered fluid under 30 DEG C of -60 DEG C of temperature conditionss.Sweet ammonia Acid crystal after methyl alcohol washing, filtering, drying by obtaining glycine product.(- 30 DEG C are cooled to after filtered fluid cooling freezing -- 0 DEG C), triethylamine hydrochloride solid is filtrated to get, while the reaction solution containing methenamine for filtering out, few adding (amount that methenamine is added is to add 1st/10th to ten/6th of methenamine amount originally) circulation makes after amount methenamine With production glycine.
2nd, it is waste glycine using monoxone:
(condenser is housed above reactor, there is solvent condensation reflux unit and solvent recovery to fill in the reactor of production glycine Put) inner addition solvent methanol (solvent can be the alcohol water mixed solution of pure methanol solution, or content more than 90%), After catalyst (methenamine or paraformaldehyde), at 10 DEG C -- under conditions of 30 DEG C, while monoxone methanol solution is added dropwise, Logical ammonia reaction, the amount of the logical ammonia of control after the monoxone in solution is fully converted into ammonium chloroacetate, stops logical ammonia.Heat up Start to add triethylamine to 60 DEG C, it is complete that maintenance reaction temperature adds triethylamine between 60 DEG C -70 DEG C, in one and a half hours Finish.Reaction, insulation amount to two and one-half- hours, are 7.5 to pH value.Ammonium chloroacetate is 1-1.1 with the mol ratio of triethylamine: 1.The amount of solvent methanol is 2-8 times of monoxone weight.The amount that catalyst methenamine is added is eight points of monoxone weight One of between 1/3rd.
After insulation reaction terminates, reaction solution filters out Glycine crystals and filtered fluid under 30 DEG C of -60 DEG C of temperature conditionss.Sweet ammonia Acid crystal after methyl alcohol washing, filtering, drying by obtaining glycine product.(- 30 DEG C are cooled to after filtered fluid cooling freezing -- 0 DEG C), triethylamine hydrochloride solid is filtrated to get, while the reaction solution containing methenamine for filtering out, few adding (amount that methenamine is added is to add 1st/10th to ten/6th of methenamine amount originally) circulation makes after amount methenamine With production glycine.
3rd, triethylamine hydrochloride solid is recycled according to following scheme:
Lead to ammonia reaction by triethylamine hydrochloride solid dissolving in water, in the case of normal temperature, reaction temperature is controlled at 25 DEG C -- 50 DEG C Between, product is ammonium chloride and triethylamine.Because triethylamine is slightly soluble in water, it may appear that liquid layered phenomenon, point Separate out triethylamine and participate in the recycling of glycine ammonolysis reaction as acid binding agent.Separate and remaining after triethylamine contain chlorine Change the solution of ammonium, continue to lead to ammonia reaction after dissolving triethylamine hydrochloride solid, continue to generate product ammonium chloride and triethylamine, After the ammonium chloride in solution reaches saturated solution, the generation of ammonium chloride crystals solid is just had.After reaction terminates, first separate Go out triethylamine, the remaining reaction solution containing ammonia chloride crystal filters to isolate chlorine by cooling, freezing (- 30 DEG C -- 10 DEG C) Change ammonium product.Filtered fluid is recycled, and continues to dissolve triethylamine hydrochloride.Ammonia is with the mol ratio of triethylamine hydrochloride 1-1.2∶1。
4th, triethylamine hydrochloride solid can also in accordance with the following methods be processed and obtain refined triethylamine hydrochloride product:Three second Amine hydrochlorate solid dissolving in water, by obtaining refined triethylamine hydrochloride product after recrystallization.
5th, containing the circulating mother liquor of methyl alcohol, methenamine and triethylamine hydrochloride, the certain number of times of circular response is being participated in Afterwards, due to the increase of the impurity such as accessory substance, can be reclaimed by the way of following:
Mode 1, in circulating mother liquor lead to ammonia, the triethylamine hydrochloride in mother liquor is changed into triethylamine, contained The methanol solution of catalyst, ammonium chloride, triethylamine and accessory substance.This methanol solution can be processed in the following ways: Solution is concentrated by evaporation, the mixed solution of methyl alcohol and triethylamine is obtained after condensation, this methanol solution containing triethylamine can be with Recycled as reaction solution;Evaporate remaining impurity and can be used to be processed into chemical fertilizer raw material with ammonium chloride as main component Product.
A certain amount of water is added in mode 2, circulating mother liquor, methyl alcohol is reclaimed in rectifying.The mother liquor after methyl alcohol is reclaimed in rectifying, often Lead to ammonia in the case of temperature, triethylamine and ammonium chloride are generated in mother liquor.Separate triethylamine and participate in glycine as acid binding agent Ammonolysis reaction is recycled.The remaining mother liquor containing ammonium chloride and methenamine, by after evaporation and concentration, being processed into pair Product ammonium chloride, uses as chemical fertilizer raw material.Mother liquor containing methyl alcohol, methenamine and triethylamine hydrochloride, it is also possible to Processed using following method:Using activated carbon decolorizing, the filtered fluid after decolouring is recycled.
Specific embodiment
Embodiment one:
Ammonium chloroacetate 58.3g, methyl alcohol 250ml, methenamine 15g are incorporated with agitator, thermometer and reflux condenser Four-hole boiling flask in, stirring and dissolving, be warming up to 65 DEG C start be added dropwise triethylamine 50.5g, maintain temperature 60 C -- 65 DEG C, one And a half hours addition finish, insulation reaction two and one-half- hours to pH value be 7.0-7.5, be cooled to 45 DEG C, filter to obtain sweet ammonia Acid crystal.Glycine crystals obtain content 98.01% after methyl alcohol washs (washing of 100ml methyl alcohol), filtration drying Glycine crystals 37.81g, glycine yield is calculated as 94.2% with ammonium chloroacetate.Filter out the reaction solution cooling of glycine - 20 DEG C are refrigerated to, triethylamine hydrochloride solid 25.90g is filtered out, the Recycling Mother Solution for filtering out is used, for next time Reaction.
Embodiment two:
The mother liquor reclaimed in embodiment one is continuing with, ammonium chloroacetate 58.45g is dissolved, 2g methenamines are added, is warming up to 65 DEG C start that triethylamine 50.53g is added dropwise, and temperature 60 C -- 65 DEG C, addition in an and a half hours is finished, insulation reaction two for maintenance And a half hours to pH value be 7.0-7.5, be cooled to 45 DEG C, filter to obtain Glycine crystals.Glycine crystals are washed by methyl alcohol Wash, after filtration drying, obtain the Glycine crystals 38.51g of content 97.8%, glycine yield is calculated as with ammonium chloroacetate 95.6%.The reaction solution cooling for filtering out glycine is refrigerated to -20 DEG C, filters out triethylamine hydrochloride solid 59.21g, mistake Leach the Recycling Mother Solution come to use, for next secondary response.
Embodiment three:
The mother liquor reclaimed in embodiment two is continuing with, ammonium chloroacetate 58.51g is dissolved, 2g methenamines are added, is warming up to 65 DEG C start that triethylamine 50.52g is added dropwise, and temperature 60 C -- 65 DEG C, addition in an and a half hours is finished, insulation reaction two for maintenance And a half hours to pH value be 7.0-7.5, be cooled to 45 DEG C, filter to obtain Glycine crystals.Glycine crystals are washed by methyl alcohol Wash, after filtration drying, obtain the Glycine crystals 38.56g of content 97.36%, glycine yield is calculated as with ammonium chloroacetate 95.29%.The reaction solution cooling for filtering out glycine is refrigerated to -20 DEG C, filters out triethylamine hydrochloride solid 67.58g, mistake Leach the Recycling Mother Solution come to use, for next secondary response.

Claims (3)

1. a kind of process for cleanly preparing of glycine, can be with combined producting ammonium chloride product while production glycine.While production glycine, Can also coproduction triethylamine hydrochloride product.It is characterized in that the method includes following steps:
Step one:Solvent methanol (or methanol aqueous solution) and catalyst are added in the reactor of production glycine, and (methenamine is more Polyformaldehyde) after, add solid ammonium chloroacetate (can also first lead to ammonia generation chloroethene directly using solid monoxone in reaction system Continue and triethylamine react after sour ammonium).Be warming up to 60 DEG C start add triethylamine, maintenance reaction temperature between 60 DEG C -70 DEG C, Triethylamine is added in one and a half hours to finish.Reaction, insulation amount to two and one-half- hours, are 7.5 to pH value.
Step 2:After insulation reaction terminates, reaction solution filters out Glycine crystals and filtered fluid under 30 DEG C of -60 DEG C of temperature conditionss. Glycine crystals after methyl alcohol washing, filtering, drying by obtaining glycine product.
Step 3:After filtered fluid cooling freezing (it is cooled to -30 DEG C -- 0 DEG C), triethylamine hydrochloride solid is filtrated to get, while filtering The reaction solution containing methenamine out, uses a small amount of methenamine Posterior circle is added.
Step 4:Lead to ammonia reaction by triethylamine hydrochloride solid dissolving in water, in the case of normal temperature, reaction temperature is controlled at 25 DEG C -- between 50 DEG C, product is ammonium chloride and triethylamine.Triethylamine is isolated to be followed as acid binding agent participation glycine ammonolysis reaction Ring is used.The remaining solution containing ammonium chloride after triethylamine is separated, logical ammonia is anti-after continuing to dissolve triethylamine hydrochloride solid Should, continue to generate product ammonium chloride and triethylamine, after the ammonium chloride in solution reaches saturated solution, just have ammonium chloride crystals Solid is produced.After reaction terminates, triethylamine is first isolated, the remaining reaction solution containing ammonia chloride crystal is by cooling, freezing (- 30 DEG C -- 10 DEG C), filter to isolate ammonium chloride product.Filtered fluid is recycled, and continues to dissolve triethylamine hydrochloride.
Step 5:Circulating mother liquor containing methyl alcohol, methenamine and triethylamine hydrochloride, is participating in the certain number of times of circular response Afterwards, can be reclaimed by the way of following:To ammonia is led in circulating mother liquor, the triethylamine hydrochloride in mother liquor is set to change into three second Amine, obtains the methanol solution containing catalyst, ammonium chloride, triethylamine and accessory substance.This methanol solution can be used with lower section Formula treatment:Solution is concentrated by evaporation, the mixed solution of methyl alcohol and triethylamine, this methanol solution containing triethylamine are obtained after condensation Can be recycled as reaction solution.Remaining impurity can be used to be processed into the change with ammonium chloride as main component after evaporation and concentration Fertile raw produce.
Step 6:Circulating mother liquor containing methyl alcohol, methenamine and triethylamine hydrochloride, it would however also be possible to employ mode below is reclaimed: A certain amount of water is added in circulating mother liquor, methyl alcohol in solution is reclaimed in rectifying.In the case that the mother liquor after methyl alcohol, normal temperature are reclaimed in rectifying Logical ammonia, generates triethylamine and ammonium chloride in mother liquor, separate triethylamine.The remaining mother liquor containing ammonium chloride and methenamine, By after evaporation and concentration, being processed into byproduct ammonium chloride, used as chemical fertilizer raw material.
Step 7:Triethylamine hydrochloride solid can also in accordance with the following methods be processed and obtain refined triethylamine hydrochloride product:Three second Amine hydrochlorate solid dissolving in water, by obtaining refined triethylamine hydrochloride product after recrystallization.
2. the method for claim 1, it is characterised in that ammonium chloroacetate and the mol ratio of triethylamine are 1-1.1: 1, solvent methanol Amount be 2-8 times of ammonium chloroacetate weight, the amount that adds of catalyst be between 1st/1st to three/10th of ammonium chloroacetate weight.
3. the method for claim 1, it is characterised in that be all the time that triethylamine is slowly added into reaction system during reaction The middle reaction for as acid binding agent produce glycine.
CN201510789414.1A 2015-11-16 2015-11-16 Clean production process of glycine and co-produced ammonium chloride Pending CN106699591A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510789414.1A CN106699591A (en) 2015-11-16 2015-11-16 Clean production process of glycine and co-produced ammonium chloride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510789414.1A CN106699591A (en) 2015-11-16 2015-11-16 Clean production process of glycine and co-produced ammonium chloride

Publications (1)

Publication Number Publication Date
CN106699591A true CN106699591A (en) 2017-05-24

Family

ID=58932484

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510789414.1A Pending CN106699591A (en) 2015-11-16 2015-11-16 Clean production process of glycine and co-produced ammonium chloride

Country Status (1)

Country Link
CN (1) CN106699591A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108101799A (en) * 2018-01-30 2018-06-01 严世佳 A kind of high-efficient production technology of glycine
CN109836344A (en) * 2017-11-26 2019-06-04 刘长飞 A kind of method of organic solvent production glycine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836344A (en) * 2017-11-26 2019-06-04 刘长飞 A kind of method of organic solvent production glycine
CN108101799A (en) * 2018-01-30 2018-06-01 严世佳 A kind of high-efficient production technology of glycine

Similar Documents

Publication Publication Date Title
CN105693559B (en) A kind of method for preparing taurine and coproduction bicarbonate
CN103880625B (en) Method for preparing D, L-mandelic acid and derivative of D, L-mandelic acid
CN103570568A (en) Clean production process of glycine in coproduction with ammonium chloride
CN105859571A (en) Method for producing glycine by mixed solvent method
CN107033107A (en) A kind of method for preparing epoxychloropropane
CN104829495A (en) Method for preparation of high purity and high yield metformin hydrochloride by two-component solvent
CN106699570A (en) Synthesis method for (2-chloro-5-iodophenyl)(4-fluorophenyl)ketone
CN106699591A (en) Clean production process of glycine and co-produced ammonium chloride
CN103288685B (en) Preparation method of 3-guanidino propanoic acid
CN102030669B (en) Production method for glycine
CN110078097A (en) A kind of technique of instant solution process for preparing potassium nitrate by double decomposition
CN103420833A (en) Method for synthesizing p-toluenesulfonic acid-catalyzed dimethyl malonate
CN109503424A (en) N- cyanoethyl-Phenhenzamine production equipment and method
CN108203392A (en) A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride
CN103508974A (en) Method for treating methyl 2-(aminosulfonyl)benzoate crystallization mother solution
CN105271406B (en) A kind of preparation method of sodium metavanadate
CN106699582A (en) Method for producing glycine by using organic solvent
CN104496825B (en) The preparation method of 2-fluorine ethylamine hydrochloride
CN104387301B (en) The synthetic method of the fluoro-4-Methyl benzenesulfonyl of a kind of 2-methyl isonitrile
CN108203390A (en) A kind of method using organic solvent production glycine
CN106496031A (en) A kind of method for improving dimethyl malenate yield
CN107868014A (en) A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride
CN105236483B (en) A kind of preparation method of potassium metavanadate
CN104478747B (en) A kind of method utilizing organic solvent to produce glycine
CN107868010A (en) A kind of production technology of glycine coproduction triethylamine hydrochloride

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170524

WD01 Invention patent application deemed withdrawn after publication