CN109867608A - A kind of process for cleanly preparing of glycine co-producing potassium chloride - Google Patents

Abstract

A kind of process for cleanly preparing of glycine co-producing potassium chloride, in methanol (or ethyl alcohol) solvent, using methenamine as catalyst, with monoxone and ammonia (or ammonium chloroacetate) for raw material, with organic amine (ethylenediamine or triethylamine) for acid binding agent, the reacted mixed solution obtained containing glycine solid and organic amine salt hydrochlorate, crude product glycine obtain glycine product after filtration, washing and drying.It is recycled using the organic amine inside potassium hydroxide recycling circular response organic solvent, while obtaining byproduct potassium chloride.

Description

A kind of process for cleanly preparing of glycine co-producing potassium chloride

Technical field

The present invention relates to a kind of process for cleanly preparing of glycine, co-producing potassium chloride byproduct while producing glycine, Belong to chemical production technical field.

Background technique

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 monoxone amino solution glycine production technology is as follows: adding in the reaction kettle for be connected with cooling water Enter the aqueous solution of catalyst methenamine content 25% or so, while the chloroethene aqueous acid of 80% or so contents is added dropwise and leads to Enter liquefied ammonia, carries out ammonolysis reaction under conditions of pH value 7 or so, 70-80 DEG C of reaction temperature or so.What is obtained after reaction contains The isolated glycine product of method for thering is the ammonolysis reaction liquid methanol alcohol of glycine and ammonium chloride to analyse.Produce one ton of sweet ammonia Acid will produce 12--13 cubic metres or so of the mother liquor containing methanol, and 5% or so ammonium chloride, 1% left side are contained in methanol mother liquor Right methenamine, 0.8% or so glycine.It produces one ton of glycine and needs to consume 5 tons or so of steam for recycling first Alcohol, while producing one ton of glycine and need to consume 150 kilograms or so of methenamine and cannot recycle.Produce one ton of sweet ammonia Acid will also consume 60-100 kilograms of methanol.Methanol mother liquor obtains dealcoholizing waste water after methanol is recycled in rectifying.Dealcoholizing waste water Byproduct ammonium chloride is obtained after being concentrated by evaporation for producing fertilizer application.And after recycling byproduct ammonium chloride it is remaining containing The black waste water of the organic matters such as a large amount of methenamine, glycine is very difficult, not only polluted environment, also wastes preciousness Resource.

Patent US5155264 and CN1080632 is using monoxone, ammonia as raw material, can be in the presence of catalyst and organic amine Glycine is synthesized and isolates, but the effective scheme that catalyst inside mother liquor and organic amine do not reuse.Patent CN101270061A can be separated in the presence of catalyst (methenamine etc.) and organic amine using monoxone, ammonia as raw material Glycine.Need to consume a large amount of sodium alkoxide or potassium alcoholate when recycling organic amine, cost is high, not the economy of industrialized production Value.And after addition sodium alkoxide in recycle alcohol mother liquor or potassium alcoholate (concentration 50% of sodium alkoxide and potassium alcoholate), the body of recycle alcohol mother liquor Product can be continuously increased, and the catalyst concn in recycle alcohol mother liquor constantly reduces, in order to maintain being normally carried out for reaction, it is necessary to Continuous addition catalyst, maintains percentage of the catalyst concn in mother liquor constant.According to its experimental data, circular response is female After liquid is recycled 5 times, the volume of solvent alcohol can increase 2.5 times or more in mother liquor, and normal circular response mother liquor will use ten It more than secondary, reacts in the above manner, finally has no idea to carry out industrialized production at all.Patent CN102030669 is with chloroethene Acid and ammonia are that raw material using organic amine as acid binding agent, can be realized the separation of glycine and ammonium chloride under the action of catalyst.But The technics comparing is complicated, and reaction end is also more difficult to control.When using logical recovery ammonia triethylamine hydrochloride, it cannot return completely Triethylamine is received, because the alkalinity of triethylamine is better than ammonia.Still there are a certain amount of glycine and ammonium chloride in production process simultaneously Mixed crystal generates, it is also necessary to further separation.

A kind of process for cleanly preparing of glycine co-product calcium chloride of applicant patent CN103450039(): in first In alcoholic solvent, using methenamine as catalyst, using monoxone and ammonia as raw material, ammonium chloroacetate is generated, then three second of acid binding agent is added dropwise Amine, heat filtering goes out glycine after reaction.The circulating mother liquor for filtering out glycine is filtered out by the method for cooling down, freezing Triethylamine hydrochloride.Triethylamine hydrochloride is dissolved in water, and calcium hydroxide (or calcium oxide) is added and recycles triethylamine.Recycle three The solution of ethamine is processed into calcium chloride product.This method is during being recycled circular response mother liquor, obtained by-product Product chemical fertilizer raw material reduces the content of nitrogen in chemical fertilizer raw material since there is calcium chloride in the inside, reduces the market price of product Value.

Summary of the invention

The present invention provides a kind of process for cleanly preparing of glycine, co-producing potassium chloride product while producing glycine. With monoxone and ammonia (or ammonium chloroacetate) for raw material, using organic amine as acid binding agent, it is reacted obtained containing glycine solid and The mixed solution of organic amine salt hydrochlorate, crude product glycine obtain glycine product after filtration, washing and drying.Use hydroxide Potassium recycles the organic amine inside circular response organic solvent and is recycled, while obtaining byproduct potassium chloride.It is used in the present invention Organic amine include following two: ethylenediamine and triethylamine.

The present invention through the following steps that and method realize:

Step (1), monoxone synthesize glycine inside methanol (or ethyl alcohol) solvent: (anti-in the reactor of production glycine Answer equipped with condenser above device, condenser is connected to solvent condensation reflux unit and solvent condensate recycling device) inner addition methanol (or Ethyl alcohol), after catalyst methenamine (amount that methenamine is added is the 5% -7% of methanol (or ethyl alcohol) weight) is added, it is added Organic amine (weight ratio of organic amine and methanol (or ethyl alcohol) is 1:2-8), then monoxone is added in batches, control reaction temperature Between 40 DEG C -60 DEG C (molar ratio of monoxone and organic amine be 1:1-1.1), then lead to ammonia, reaction temperature control 60 DEG C - (molar ratio of monoxone and ammonia is 1:1-1.5) stops logical ammonia, heat preservation when the PH of solvent reaches 7-7.5 between 75 DEG C 1 hour is reacted, is cooled between 30 DEG C -50 DEG C, crude product glycine is filtered out, wash, filter by methanol (or ethyl alcohol), Glycine product is obtained after drying.

Step (2), ammonium chloroacetate synthesize glycine inside methanol (or ethyl alcohol) solvent: in the reaction of production glycine Methanol (or ethyl alcohol) is added in device, after catalyst methenamine is added, organic amine is added, is heated to 60 DEG C, then add in batches (ammonium chloroacetate is led to after ammonia to pH value 6 after monoxone is dissolved in water to ammonium chloroacetate, is obtained after cooling, crystallization, centrifugation Solid), reaction temperature (molar ratio of ammonium chloroacetate and organic amine is 1:1-1.1) between 60 DEG C -75 DEG C is controlled, when solvent When PH reaches 7-7.5,1 hour of insulation reaction, it is cooled between 30 DEG C -50 DEG C, centrifugal filtration comes out crude product glycine, Glycine product is obtained after methanol (or ethyl alcohol) washing, filtering, drying.

Step (3) recycles organic amine inside circular response solvent and obtains potassium chloride: mistake in step (1) or step (2) The circular response solvent separated is filtered, the inside is added solid potassium hydroxide, the circular response containing organic amine is obtained after reaction Solvent and solid potassium chloride obtain Potassium Chloride Product after filtering.The circular response solvent for filtering out potassium chloride, continuously adds chloroethene Acid or ammonium chloroacetate carry out the reaction of synthesis glycine.

Step (4), can also in the following ways, obtained inside circular response solvent organic amine HCl, solid and into One step recycles to obtain triethylamine and Potassium Chloride Product: the circular response solvent that centrifuge separation comes out in step (1), step (2), warp It crosses freezing to be cooled between -10 DEG C -20 DEG C, crystallizes, organic amine HCl, solid is obtained by filtration.Organic amine HCl, solid is pressed It is recycled according to following scheme: organic amine HCl, solid is dissolved in water, potassium hydroxide reaction is added in the case of room temperature, Reaction product is potassium chloride and organic amine.Since organic amine is slightly soluble in water, it may appear that liquid layered phenomenon, that separates has Machine amine is participated in glycine synthetic reaction as acid binding agent and is recycled after except water process (rectifying or drying).

The solution containing potassium chloride filtered out obtains Potassium Chloride Product after being concentrated, filtering.Potassium chloride is recycled to produce The filtered fluid containing potassium chloride after product is recycled, for dissolving organic amine hydrochlorate solid.

Step (5), containing methanol, methenamine, organic amine salt hydrochlorate circular response solvent, participate in circular response one After fixed number (10 times or so), due to generating water in potassium hydroxide in solvent and organic amine salt hydrochlorate reaction process, with dampening The increase of the impurity such as the increase of amount and by-product after the certain number of circular response, can be recycled using mode below: to A small amount of water is added in circular response mother liquor, adds potassium hydroxide, after completion of the reaction, recycles first by way of distillation (or rectifying) Pure and mild organic amine mixed solution is recycled.

Organic amine and methanol (or ethyl alcohol) remaining waste water have been recycled, it can be by being dried to obtain the change containing potassium and nitrogen Fertile raw material.Organic amine and methanol (or ethyl alcohol) remaining waste water have been recycled, catalysis oxidation can also be first passed through, has reduced the viscous of waste water After degree, drying obtains the chemical fertilizer raw material containing potassium and nitrogen.

Organic amine and methanol (or ethyl alcohol) remaining waste water have been recycled, can also handle in the following way: salt is first added Acid adjusts the pH value of waste water to 2-4, and urea is then added, after reacting a period of time, then logical ammonia, adjust the pH value 6-8 of waste water Between, then it is dried to obtain the chemical fertilizer raw material product containing potassium and nitrogen.

Specific embodiment: essentiality content of the invention is further illustrated with the embodiment of the present invention, but not with this To limit the present invention.

Embodiment one: equipped with stirring, condensation reflux unit, thermometer 500mL four-hole boiling flask in addition 300mL first Alcohol, 15g methenamine, 102g triethylamine add 96.5g monoxone (content 98%) in 30 minutes, and control reaction temperature is always At 60 DEG C or less.Then start logical ammonia, temperature controls between 60 DEG C~70 DEG C, carries out synthesis glycine reactant, leads to the ammonia time 1 A hour leads to ammonia 26g, pH value to 7.2, insulation reaction

30 minutes, 35 DEG C are cooled to, filters out crude product glycine, is washed using 30mL methanol, drying obtains the sweet of content 98.1% Propylhomoserin product 72.1g.

The circular response solvent of crude product glycine is filtered out, solid potassium hydroxide 56g is added, is sufficiently stirred, stands, mistake Crude product potassium chloride is filtered out, after methanol washing, dry, obtains Potassium Chloride Product 71.3g.Filter out following containing triethylamine Ring reaction dissolvent continues the reaction for synthesizing glycine.

Embodiment two: in the reactor of synthesis glycine, the circulation containing triethylamine is filtered out in Example one Reaction dissolvent adds 96.5g monoxone (content 98%) in 30 minutes, controls reaction temperature always at 60 DEG C or less.Then it opens Begin logical ammonia, and temperature controls between 60 DEG C~70 DEG C, carries out synthesis glycine reactant, leads to 1 hour of ammonia time, leads to ammonia 27g, until PH value is to 7.4.Insulation reaction 30 minutes, 40 DEG C are cooled to, filters out crude product glycine, is washed, is dried using 30mL methanol To the glycine product 72.6g of content 98.2%.

The circular response solvent of crude product glycine is filtered out, solid potassium hydroxide 56g is added, is sufficiently stirred, stands, mistake Crude product potassium chloride is filtered out, after methanol washing, dry, obtains Potassium Chloride Product 72.1g.Filter out following containing triethylamine Ring reaction dissolvent continues the reaction for synthesizing glycine.

Embodiment three: equipped with stirring, condensation reflux unit, thermometer 500mL four-hole boiling flask in addition 300mL first Alcohol, 15g methenamine, 102g triethylamine are heated up to 60 DEG C, in 1.5 hours, add ammonium chloroacetate 117g, temperature in batches Control insulation reaction 30 minutes, is cooled to 35 DEG C, filters out crude product glycine, use 30mL methanol between 60 DEG C~70 DEG C Washing, drying obtain the glycine product 72.8g of content 98.3%.

The circular response solvent of crude product glycine is filtered out, solid potassium hydroxide 56g is added, is sufficiently stirred, stands, filter out Crude product potassium chloride obtains Potassium Chloride Product 71.2g after methanol washing, dry.It is anti-to filter out the circulation containing triethylamine Solvent is answered, the reaction for synthesizing glycine is continued.

Example IV: equipped with stirring, condensation reflux unit, thermometer 500mL four-hole boiling flask in addition 250mL first Alcohol, 13g methenamine, 102g triethylamine add 96.5g monoxone (content 98%) in 30 minutes, and control reaction temperature is always At 60 DEG C or less.Then start logical ammonia, temperature controls between 60 DEG C~70 DEG C, carries out synthesis glycine reactant, leads to the ammonia time 1 A hour leads to ammonia 27g, until pH value is to 7.3.Insulation reaction

30 minutes, 45 DEG C are cooled to, filters out crude product glycine, is washed using 30mL methanol, drying obtains the sweet of content 98.1% Propylhomoserin product 72.7g.

The circular response solvent for filtering out glycine, is cooled to 10 DEG C, filters out triethylamine hydrochloride solid 35g.It follows Ring reaction dissolvent continues to synthesize the reaction of glycine.

Embodiment five: in the reactor of synthesis glycine, the circular response solvent filtered out in Example four,

Be added 102g triethylamine, added in 30 minutes 96.5g monoxone (content 98%), control reaction temperature always 60 DEG C with Under.Then starting logical ammonia, temperature controls between 60 DEG C~70 DEG C, carries out synthesis glycine reactant, lead to 1 hour of ammonia time, Logical ammonia 28g, until pH value is to 7.5.Insulation reaction 30 minutes, 45 DEG C are cooled to, filters out crude product glycine, is washed using 30mL methanol It washs, drying obtains the glycine product 71.4g of content 98.2%.

The circular response solvent for filtering out glycine, is cooled to 10 DEG C, filters out triethylamine hydrochloride solid 135.6g. Circular response solvent continues to synthesize the reaction of glycine.

Embodiment six: the triethylamine hydrochloride solid 135.6g that Example five obtains is dissolved in 200mL aqueous solution, 56g potassium hydroxide solid is added in batches.Reaction after standing a hour, is distilled to recover triethylamine, obtains three containing moisture Synthesis glycine is recycled as acid binding agent after past water process (rectifying or drying) in ethamine.It is surplus to be distilled to recover triethylamine Under potassium chloride solution, vacuum distillation, decrease temperature crystalline, filtering, it is dry after obtain Potassium Chloride Product 38.8g.

Claims (5)

1. a kind of process for cleanly preparing of glycine, with monoxone and ammonia (or ammonium chloroacetate) for raw material, with organic amine (ethylenediamine Or triethylamine) be acid binding agent, the reacted mixed solution obtained containing glycine solid and organic amine salt hydrochlorate, through filtering, Glycine product is obtained after washing, drying, is made using the organic amine circulation inside potassium hydroxide recycling circular response organic solvent With, while obtaining byproduct potassium chloride, it is characterised in that method includes the following steps:

(1) after methanol (or ethyl alcohol), catalyst methenamine being added in the reactor of synthesis glycine, organic amine (second is added Diamines or triethylamine), then monoxone is added in batches, reaction temperature is controlled between 40 DEG C -60 DEG C, then leads to ammonia, reaction temperature Degree control is between 60 DEG C -75 DEG C, when the PH of solvent reaches 7-7.5, stops logical ammonia, 1 hour of insulation reaction, cooling To between 30 DEG C -50 DEG C, crude product glycine is filtered out, obtains glycine after methanol (or ethyl alcohol) washing, filtering, drying Product；

(2) after methanol (or ethyl alcohol), catalyst methenamine being added in the reactor of synthesis glycine, organic amine is added, adds Heat is to 60 DEG C, then adds ammonium chloroacetate in batches, controls reaction temperature between 60 DEG C -75 DEG C, when the PH of solvent reaches 7-7.5 When, 1 hour of insulation reaction, be cooled between 30 DEG C -50 DEG C, centrifugal filtration comes out crude product glycine, by methanol (or Ethyl alcohol) it washs, filter, obtain glycine product after drying；

(3) solid potassium hydroxide, reaction is added in the circular response solvent for being separated by filtration out in step (1) or step (2), the inside Circular response solvent and solid potassium chloride containing organic amine are obtained afterwards, obtain Potassium Chloride Product after filtering；

(4) the circular response solvent for filtering out potassium chloride, continuously adds monoxone or ammonium chloroacetate carries out the anti-of synthesis glycine It answers；

(5) the circular response solvent that centrifuge separation comes out in step (1), step (2), can also be by frozen cooling to -10 Between DEG C -20 DEG C, crystallizes, organic amine HCl, solid is obtained by filtration；

(6) organic amine HCl, solid is dissolved in water, potassium hydroxide reaction is added in the case of room temperature, reaction product is chlorination Potassium and organic amine, separate organic amine, after except water process (rectifying or drying), participate in glycine synthesis as acid binding agent Reaction cycle uses；

(7) aqueous solution containing potassium chloride filtered out obtains Potassium Chloride Product after concentration, filtering, drying, recycles chlorine The filtered fluid containing potassium chloride after changing potassium product is recycled, for dissolving organic amine hydrochlorate solid；

(8) the remaining waste water of circular response solvent is recycled, the pH value of hydrochloric acid adjusting waste water is first added to 2-4, urea is then added Reaction, then logical ammonia are adjusted between the pH value 6-8 of waste water, are dried to obtain chemical fertilizer raw material product.

2. the method as described in claim 1, it is characterised in that: organic amine acid binding agent described in step (1) includes ethylenediamine, three Ethamine.

3. the method as described in claim 1, it is characterised in that: method described in step (3) is that had using potassium hydroxide recycling Machine amine acid binding agent, and obtain Potassium Chloride Product.

4. the method as described in claim 1, it is characterised in that: side described in step (6) be recycled using potassium hydroxide it is water-soluble Organic amine acid binding agent in liquid, and obtain Potassium Chloride Product.

5. the method as described in claim 1, it is characterised in that: method described in step (8) is that urea is added in waste water, so Re-dry obtains chemical fertilizer raw material product afterwards.