CN107868014A - A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride - Google Patents

A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride Download PDF

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Publication number
CN107868014A
CN107868014A CN201610852413.1A CN201610852413A CN107868014A CN 107868014 A CN107868014 A CN 107868014A CN 201610852413 A CN201610852413 A CN 201610852413A CN 107868014 A CN107868014 A CN 107868014A
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triethylamine
glycine
reaction
methanol
ammonium chloride
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CN201610852413.1A
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Chinese (zh)
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李辉
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Qingdao Jiuzhou Thousand Machinery Co Ltd
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Qingdao Jiuzhou Thousand Machinery Co Ltd
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Priority to CN201610852413.1A priority Critical patent/CN107868014A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/16—Halides of ammonium
    • C01C1/164—Ammonium chloride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation 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
    • C07C227/08—Formation 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

, can be with combined producting ammonium chloride product while producing glycine the invention provides a kind of process for cleanly preparing of glycine；, can also coproduction triethylamine hydrochloride product while producing glycine.After adding solvent methanol and catalyst in the reactor of glycine ammonolysis reaction, solid ammonium chloroacetate is added, 65 DEG C is warming up to and starts to add triethylamine, triethylamine is added in one and a half hours and is finished, insulation reaction two and one-half- hours to pH value are 7.5.Cooling, freezing separation go out glycine and triethylamine hydrochloride respectively.The triethylamine inside triethylamine hydrochloride, while combined producting ammonium chloride product are reclaimed using the method for logical ammonia.

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, can be produced while producing glycine 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, and it is sweet can also to be refined into food-grade Propylhomoserin uses.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 is passed through liquefied ammonia, Ammonolysis reaction is carried out under conditions of pH value 7 or so, 80 DEG C or so of reaction temperature.Reaction obtained after terminating containing glycine and The isolated glycine product of method that the ammonolysis reaction liquid of ammonium chloride is analysed with methanol alcohol.One ton of glycine of production will produce The mother liquor containing methanol of 12--13 cubic meters or so, containing 5% or so ammonium chloride, 1% or so Wu Luotuo in methanol mother liquor Product, 0.8% or so glycine.One ton of glycine of production needs the steam of 5 tons or so of consumption to be used to reclaim methanol, produces simultaneously One ton of glycine needs the methenamine of 150 kilograms or so of consumption to recycle.One ton of glycine of production will also consume 60- 100 kilograms of methanol.Methanol mother liquor obtains dealcoholizing waste water after methanol is reclaimed in rectifying.Dealcoholizing waste water is after evaporation and concentration Byproduct ammonium chloride is obtained to be used to produce fertilizer application.And after reclaiming byproduct ammonium chloride it is remaining containing a large amount of methenamines, The black waste water of the organic matters such as glycine is very difficult, not only pollutes environment, also wastes the resource of preciousness.
Patent US5155264 and CN1080632 is using monoxone, ammonia as raw material, can be with the presence of catalyst and organic amine Isolate glycine, but catalyst inside mother liquor and organic amine are without the effective scheme of recycling.Patent CN101270061 Using monoxone, ammonia as raw material, glycine can be separated in the presence of methenamine and organic amine, but needs to consume largely Sodium alkoxide or potassium alcoholate, cost is high, without industrial value.Patent CN102030669 is being catalyzed using monoxone and ammonia as raw material Under agent effect, using organic amine as acid binding agent, the separation of glycine and ammonium chloride can be realized.But the technics comparing is complicated, reaction Terminal also more difficult control.Still there is the generation of the mixed crystal of a small amount of glycine and ammonium chloride in production process simultaneously, it is also necessary to enter The separation of one step.
The content of the invention
The invention provides a kind of process for cleanly preparing of glycine, can be produced while producing glycine with combined producting ammonium chloride Product., can also coproduction triethylamine hydrochloride product while producing glycine.
The present invention is realized by the following method：
First, it is waste glycine using ammonium chloroacetate：
In the reactor of production glycine (condenser is housed above reactor, has solvent condensation reflux unit and solvent to return Receiving apparatus) inner add solvent methanol (solvent can be that the alcohol water mixing of pure methanol solution or content more than 90% is molten Liquid) and catalyst (methenamine or paraformaldehyde) after, adding solid ammonium chloroacetate, (ammonium chloroacetate can be by production of chloroacetic acid work Chlorination reaction liquid in skill directly produces with ammonia reaction, can also by monoxone solid and ammonia in solvent (methanol or water) instead It should produce).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 finishes.Reaction, insulation amount to two and one-half- hours, are 7.5 to pH value.The mol ratio of ammonium chloroacetate and triethylamine is 1- 1.1∶1.The amount of solvent methanol is 2-8 times of ammonium chloroacetate weight.The amount that catalyst methenamine adds is ammonium chloroacetate weight 1/1st to three/8th between.
After insulation reaction terminates, reaction solution filters out Glycine crystals and filtered fluid under 30 DEG C of -60 DEG C of temperature conditionss.It is sweet Propylhomoserin crystal washs by methanol, filters, dry after obtain glycine product.After filtered fluid cooling freezing (it is cooled to -30 DEG C -- 0 DEG C), triethylamine hydrochloride solid is filtrated to get, while the reaction solution containing methenamine filtered out, adding a small amount of crow (amount that methenamine is added is 1st/10th to ten/6th of original addition methenamine amount) recycles life after the tropine of Lip river Produce glycine.
2nd, it is waste glycine using monoxone：
In the reactor of production glycine (condenser is housed above reactor, has solvent condensation reflux unit and solvent to return Receiving apparatus) inner add solvent methanol (solvent can be that the alcohol water mixing of pure methanol solution or content more than 90% is molten Liquid) and catalyst (methenamine or paraformaldehyde) after, at 10 DEG C -- under conditions of 30 DEG C, monoxone methanol solution is added dropwise Meanwhile logical ammonia reaction, the amount of logical ammonia is controlled, after the monoxone in solution is fully converted into ammonium chloroacetate, stops logical ammonia.Heating Start to add triethylamine to 60 DEG C, maintenance reaction temperature is added triethylamine between 60 DEG C -70 DEG C, in one and a half hours and finished. Reaction, insulation amount to two and one-half- hours, are 7.5 to pH value.The mol ratio of ammonium chloroacetate and triethylamine is 1-1.1: 1.Solvent first The amount of alcohol is 2-8 times of monoxone weight.The amount that catalyst methenamine adds is 1 to three/8th point of monoxone weight One of between.
After insulation reaction terminates, reaction solution filters out Glycine crystals and filtered fluid under 30 DEG C of -60 DEG C of temperature conditionss.It is sweet Propylhomoserin crystal washs by methanol, filters, dry after obtain glycine product.After filtered fluid cooling freezing (it is cooled to -30 DEG C -- 0 DEG C), triethylamine hydrochloride solid is filtrated to get, while the reaction solution containing methenamine filtered out, adding a small amount of crow (amount that methenamine is added is 1st/10th to ten/6th of original addition methenamine amount) recycles life after the tropine of Lip river Produce glycine.
3rd, triethylamine hydrochloride solid recycles 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 -- Between 50 DEG C, reaction 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 remaining containing chlorination after triethylamine The solution of ammonium, continue to lead to ammonia reaction after dissolving triethylamine hydrochloride solid, continue to generate product ammonium chloride and triethylamine, work as solution In ammonium chloride reach saturated solution after, just have ammonium chloride crystals solid generation.After reaction terminates, triethylamine is first isolated, Remaining reaction solution containing ammonia chloride crystal filters to isolate ammonium chloride product by cooling, freezing (- 30 DEG C -- 10 DEG C). Filtered fluid recycles, and continues to dissolve triethylamine hydrochloride.The mol ratio of ammonia and triethylamine hydrochloride is 1-1.2: 1.
4th, triethylamine hydrochloride solid can also handle to obtain refined triethylamine hydrochloride product in accordance with the following methods：Three Ethylamine hydrochloride solid dissolving obtains refined triethylamine hydrochloride product in water after recrystallization.
5th, the circulating mother liquor containing methanol, methenamine and triethylamine hydrochloride, the certain number 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, lead to ammonia into circulating mother liquor, the triethylamine hydrochloride in mother liquor is changed into triethylamine, contained Catalyst, ammonium chloride, the methanol solution of triethylamine and accessory substance.This methanol solution can be handled in the following ways：Evaporation Concentrate solution, obtains the mixed solution of methanol and triethylamine after condensation, this methanol solution containing triethylamine can be used as anti- Liquid is answered to recycle；Evaporating remaining impurity can be used for being processed into the chemical fertilizer raw material product using ammonium chloride as main component.
A certain amount of water, rectifying recovery methanol are added in mode 2, circulating mother liquor.Mother liquor after rectifying recovery methanol, normal temperature In the case of lead to ammonia, triethylamine and ammonium chloride are generated in mother liquor.Separate triethylamine and participate in glycine ammonolysis as acid binding agent Reaction cycle uses.The remaining mother liquor containing ammonium chloride and methenamine, after evaporation and concentration, is processed into byproduct chlorination Ammonium, used as chemical fertilizer raw material.Mother liquor containing methanol, methenamine and triethylamine hydrochloride, following side can also be used Method processing：Using activated carbon decolorizing, the filtered fluid after decolouring recycles.
Embodiment
Embodiment one：
By ammonium chloroacetate 58.3g, methanol 250ml, methenamine 15g is 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 half Hour addition finishes, and insulation reaction two and one-half- hours to pH value are 7.0-7.5, are cooled to 45 DEG C, filter to obtain Glycine crystals.It is sweet Propylhomoserin crystal obtains the Glycine crystals of content 98.01% after methanol washs (washing of 100ml methanol), filtration drying 37.81g, glycine yield are calculated as 94.2% with ammonium chloroacetate.The reaction solution cooling for filtering out glycine is refrigerated to -20 DEG C, Triethylamine hydrochloride solid 25.90g is filtered out, the Recycling Mother Solution filtered out uses, for next secondary response.
Embodiment two：
The mother liquor reclaimed in embodiment one is continuing with, ammonium chloroacetate 58.45g is dissolved, adds 2g methenamines, be warming up to 65 DEG C start that triethylamine 50.53g is added dropwise, and temperature 60 C -- 65 DEG C, addition in one and a half hours finishes, insulation reaction two and half for maintenance Hour is 7.0-7.5 to pH value, is cooled to 45 DEG C, filters to obtain Glycine crystals.Glycine crystals are washed by methanol, are filtered dry excessively After dry, the Glycine crystals 38.51g of content 97.8% is obtained, glycine yield is calculated as 95.6% with ammonium chloroacetate.Filter out The reaction solution cooling of glycine is refrigerated to -20 DEG C, filters out triethylamine hydrochloride solid 59.21g, the Recycling Mother Solution filtered out Use, for next secondary response.
Embodiment three：
The mother liquor reclaimed in embodiment two is continuing with, ammonium chloroacetate 58.51g is dissolved, adds 2g methenamines, be warming up to 65 DEG C start that triethylamine 50.52g is added dropwise, and temperature 60 C -- 65 DEG C, addition in one and a half hours finishes, insulation reaction two and half for maintenance Hour is 7.0-7.5 to pH value, is cooled to 45 DEG C, filters to obtain Glycine crystals.Glycine crystals are washed by methanol, are filtered dry excessively After dry, the Glycine crystals 38.56g of content 97.36% is obtained, glycine yield is calculated as 95.29% with ammonium chloroacetate.Filtering The reaction solution cooling for going out glycine is refrigerated to -20 DEG C, filters out triethylamine hydrochloride solid 67.58g, the mother liquor filtered out follows Ring uses, for next secondary response.

Claims (3)

  1. , can be with combined producting ammonium chloride product while producing glycine 1. a kind of process for cleanly preparing of glycine.Produce glycine While, can also coproduction triethylamine hydrochloride product.It is characterized in that this method includes following steps：
    Step 1：Solvent methanol (or methanol aqueous solution) and catalyst (methenamine are added in the reactor of production glycine Or paraformaldehyde) after, add solid ammonium chloroacetate (can also first lead to ammonia life directly using solid monoxone in reaction system Continuation and triethylamine react after into ammonium chloroacetate).It is warming up to 60 DEG C to start to add triethylamine, maintenance reaction temperature is at 60 DEG C -70 Triethylamine is added between DEG C, 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 filtering under 30 DEG C of -60 DEG C of temperature conditionss Liquid.Glycine crystals wash by methanol, filter, dry after obtain glycine product.
    Step 3：After filtered fluid cooling freezing (it is cooled to -30 DEG C -- 0 DEG C), it is filtrated to get triethylamine hydrochloride solid, while mistake The reaction solution containing methenamine come is filtered out, is used adding a small amount of methenamine Posterior circle.
    Step 4：Lead to ammonia reaction by triethylamine hydrochloride solid dissolving in water, in the case of normal temperature, reaction temperature is controlled 25 DEG C -- between 50 DEG C, reaction product is ammonium chloride and triethylamine.It is anti-as acid binding agent participation glycine ammonolysis to isolate triethylamine It should recycle.The remaining solution containing ammonium chloride after triethylamine is separated, is continued after dissolving triethylamine hydrochloride solid Logical ammonia reaction, continues to generate product ammonium chloride and triethylamine, after the ammonium chloride in solution reaches saturated solution, just has chlorination Crystalline ammonium solid produces.After reaction terminates, triethylamine is first isolated, the remaining reaction solution containing ammonia chloride crystal is by drop Warm, freezing (- 30 DEG C -- 10 DEG C), filter to isolate ammonium chloride product.Filtered fluid recycles, and continues to dissolve triethylamine hydrochloric acid Salt.
    Step 5：Circulating mother liquor containing methanol, methenamine and triethylamine hydrochloride, participating in the certain number of circular response Afterwards, can be reclaimed by the way of following：Lead to ammonia into circulating mother liquor, the triethylamine hydrochloride in mother liquor is changed into three second Amine, obtain the methanol solution containing catalyst, ammonium chloride, triethylamine and accessory substance.This methanol solution can be used with lower section Formula processing：Solution is concentrated by evaporation, the mixed solution of methanol and triethylamine, this methanol solution containing triethylamine are obtained after condensation Reaction solution can be used as to recycle.Remaining impurity can be used for being processed into using ammonium chloride as main component after evaporation and concentration Chemical fertilizer raw material product.
    Step 6：Circulating mother liquor containing methanol, methenamine and triethylamine hydrochloride, it can also be returned by the way of following Receive：A certain amount of water is added in circulating mother liquor, methanol in solution is reclaimed in rectifying.Mother liquor after rectifying recovery methanol, the feelings of normal temperature Lead to ammonia under condition, generate triethylamine and ammonium chloride in mother liquor, separate triethylamine.It is remaining containing ammonium chloride and methenamine Mother liquor, after evaporation and concentration, byproduct ammonium chloride is processed into, is used as chemical fertilizer raw material.
    Step 7：Triethylamine hydrochloride solid can also handle to obtain refined triethylamine hydrochloride product in accordance with the following methods：Three Ethylamine hydrochloride solid dissolving obtains refined triethylamine hydrochloride product in water after recrystallization.
  2. 2. the method as described in claim 1, it is characterised in that the mol ratio of ammonium chloroacetate and triethylamine is 1-1.1: 1, solvent The amount that the amount of methanol is 2-8 times of ammonium chloroacetate weight, catalyst adds be ammonium chloroacetate weight 1 to three/10th/ Between one.
  3. 3. the method as described in claim 1, it is characterised in that be that triethylamine is slowly added into instead all the time during reaction Answer the reaction for as acid binding agent produce glycine in system.
CN201610852413.1A 2016-09-26 2016-09-26 A kind of process for cleanly preparing of glycine in coproduction with ammonium chloride Pending CN107868014A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185420A (en) * 2021-04-30 2021-07-30 河北东华冀衡化工有限公司 Preparation method of glycine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185420A (en) * 2021-04-30 2021-07-30 河北东华冀衡化工有限公司 Preparation method of glycine

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Application publication date: 20180403