CN106748839A - A kind of glycine and the clean preparation method of iminodiacetic acid coproduction - Google Patents
A kind of glycine and the clean preparation method of iminodiacetic acid coproduction Download PDFInfo
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- CN106748839A CN106748839A CN201611022337.8A CN201611022337A CN106748839A CN 106748839 A CN106748839 A CN 106748839A CN 201611022337 A CN201611022337 A CN 201611022337A CN 106748839 A CN106748839 A CN 106748839A
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- glycine
- iminodiacetic acid
- hydroxyacetonitrile
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- 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
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- 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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The present invention is hydroxyacetonitrile and ammonia under conditions of high temperature, carry out aminating reaction and obtain ammonification liquid, mix with alkali, pyrohydrolysis, bipolar membrane electrodialysis are carried out after deamination and desolventing technology again, obtain the sodium water solution of glycine iminodiacetic acid one, the sodium of glycine iminodiacetic acid one that will be obtained enters desalting processing, respectively obtain glycine solution and the sodium water solution of iminodiacetic acid one, glycine solution is again by concentration, crystallization, it is dried to obtain glycine, the sodium water solution of iminodiacetic acid one is acidified again, crystallization, it is dried to obtain iminodiacetic acid.The coproduction of the achievable glycine of the present invention and iminodiacetic acid, raw material availability is high, the conversion efficiency of hydroxyacetonitrile is up to more than 93%, produced without other organic by-products, product yield high, low production cost, accessory substance is few, impurity is few, and can reclaim NaOH recycled, substantially increases the yield and purity of glycine and iminodiacetic acid.
Description
Technical field
The invention belongs to chemical field, and in particular to the clean manufacturing side of a kind of glycine and iminodiacetic acid coproduction
Method.
Background technology
Glycine is a kind of important fine chemical product, is widely used in the fields such as medicine, food, chemical industry, agricultural chemicals.It is sweet
The preparation technology of propylhomoserin has various, and Chinese patent CN1962611B discloses a kind of technique of preparing glycine by hydroxy acetonitrile method,
Comprise the following steps：1) hydroxyacetonitrile, ammoniacal liquor are mixed, the mol ratio of reaction material liquid is hydroxyacetonitrile: ammonia=1: 2~10, control
Between 20~60 DEG C, the reaction time is 0.5~8 hour to reaction temperature processed, obtains the ammonia spirit of aminoacetonitriles；2) to step
1) inorganic base is directly added into the ammonification liquid for obtaining, the mol ratio of reaction mass is aminoacetonitriles: inorganic base=1: 0.7~3.0,
Reaction temperature control is no more than 100 DEG C, reacts 1~8 hour, obtains the alkali solution liquid containing glycinate；3) by step 2) obtain
Neutralized with inorganic acid after alkali solution liquid deamination, the consumption of inorganic acid is the consumption for neutralizing inorganic base, the mol ratio used during reaction for
Glycinate: inorganic acid=1: 0.7~3.0, obtain neutralizer；4) by step 3) neutralizer that obtains adds activated carbon decolorizing,
Destainer is by concentration fractional crystallization and is recrystallized to give glycine and inorganic salts.Above-mentioned preparation technology reaction condition is gentle, holds
It is easy to control, and post processing is simple, but its there are the following problems：Raw material is easily decomposed and causes aminoacetonitriles to be pyrolyzed polymerization and accessory substance life
Into the generation of, foreign pigment it is more cause big decolouring difficulty, decolorising agent large usage quantity, energy consumption is big, product yield is low, high energy consumption, raw
Produce high cost.
In order to overcome above mentioned problem, we have carried out bold technological improvement by the R＆D personnel.In patent
In CN102432478B, aminating reaction time and the temperature (80 DEG C or so) which raises aminating reaction, sweet ammonia are substantially reduced
The yield of acid has and is significantly lifted.But problem is there is also, is mainly had：1. the inorganic salts sulphur of the substantial amounts of low value of by-product
Sour sodium；2. substantial amounts of saliferous, the waste water containing organic matter are produced；3. decolourized using substantial amounts of activated carbon；4. glycine, imido
Base oxalic acid, sodium sulphate are isolated and purified not thoroughly, cause glycine to obtain rate low, largely remain in mother liquor, cause mother liquor
Cannot circulate；5. too high (glycine is about the cost of recycling iminodiacetic acid with the mass ratio of iminodiacetic acid
10: 1), and cannot get qualified iminodiacetic acid；6. the utilization rate of hydroxyacetonitrile is not high, and only 85% or so；7. deamination
Energy consumption is higher.
From production technology, the common raw material of glycine and iminodiacetic acid is hydroxyacetonitrile and ammonia, with hydroxyl
When acetonitrile is Material synthesis glycine, (hydroxyacetonitrile is 1 with the mol ratio of ammonia: 4.0-6.0), greatly in the presence of substantial amounts of ammonia
The hydroxyacetonitrile that there are about nearly 10% or so is converted into iminodiacetic acid, and 75% or so hydroxyacetonitrile is converted into glycine, and
Nearly 25% hydroxyacetonitrile is converted into foreign pigment, and these foreign pigments cause follow-up decolouring to need to use substantial amounts of activated carbon,
Bring substantial amounts of solid waste to produce, be economically not to one's profit；When the mol ratio of hydroxyacetonitrile and ammonia is extended to 1: 1.1 or so
When, the aminate for mainly obtaining is iminodiacetonitrile, but in having nearly 10% hydroxyacetonitrile to remain in ammonification liquid, this will
Cause the waste of ammonification liquid color burn and hydroxyacetonitrile.From in terms of existing market situation, the market price of iminodiacetic acid is remote
Higher than the glycine of technical grade, industrial grade glycine is in the market price of September in 2016 about at 7500 yuan/ton.Therefore, with hydroxyl
When acetonitrile is Material synthesis glycine, the production rate for improving accessory substance iminodiacetic acid is necessary how to make completely
Rational regulation and control are very crucial, can not only obtain the glycine such as food-grade glycine of high-quality, but also can be with
Higher yields obtain iminodiacetic acid, while reducing the sodium sulphate of by-product low value as far as possible, this will be hydroxyacetonitrile method
The problem that synthesis glycine and iminodiacetic acid must all be faced.
The content of the invention
Based on above-mentioned technical problem, it is an object of the invention to provide the clear of a kind of glycine and iminodiacetic acid coproduction
Clean production method.
The purpose of the present invention is realized by following technical measures：
A kind of glycine and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that it comprises the following steps：
1. hydroxyacetonitrile and ammonia under conditions of high temperature, are quickly carried out aminating reaction and obtained by certain suitable rate of charge
To the ammonification liquid containing ammonia；
2. the ammonification liquid containing ammonia that above-mentioned steps 1 are obtained quickly is mixed with alkali, pyrohydrolysis obtains hydrolyzate；
3. the hydrolyzate for above-mentioned steps 2 being obtained carries out deamination and desolventing technology, and the hydrolyzate for obtaining carries out Bipolar Membrane electricity
Dialysis carries out removing sodium treatment, and it is 4.5~6.5 to control the terminal pH that removing sodium is processed, and respectively obtains glycine-iminodiacetic acid one
Sodium (IDA-Na) aqueous solution and sodium hydrate aqueous solution；
4. glycine-iminodiacetic acid one sodium (IDA-Na) aqueous solution for above-mentioned steps 3 being obtained enters desalting processing,
Glycine solution and iminodiacetic acid one sodium (IDA-Na) aqueous solution are respectively obtained, glycine solution is concentrated, tied
It is brilliant, be dried to obtain food-grade glycine product, iminodiacetic acid one sodium (IDA-Na) aqueous solution adds sulfuric acid acidifying, crystallization,
It is dried to obtain iminodiacetic acid (salt) acid product.
Further, the temperature of hydroxyacetonitrile is 10 DEG C -80 DEG C in the step 1, and the hydroxyacetonitrile rubs with feeding intake for ammonia
, than being 1.0: 1.05-6.0, described aminating reaction temperature is 60 DEG C -200 DEG C for you, and the described aminating reaction time is 0.5-
8min。
Further, the mass percent of the hydroxyacetonitrile is 40%~100%, and the ammonia is ammoniacal liquor, liquefied ammonia or gas
One kind in ammonia, the temperature of described hydroxyacetonitrile is preferably 20 DEG C -70 DEG C, and the hydroxyacetonitrile is excellent with the molar ratio of ammonia
Elect 1.0 as: 1.5-3.0；The aminating reaction temperature is preferably 80 DEG C -170 DEG C, and the described aminating reaction time is preferred 1.0-
6.0min。
Further, the mass percent of the hydroxyacetonitrile is preferably 50%~100%, and the ammonia is preferably gas ammonia, institute
Particularly preferred 50 DEG C -70 DEG C of the temperature of the hydroxyacetonitrile stated, the hydroxyacetonitrile is particularly preferably 1.0 with the molar ratio of ammonia
: 2.0-3.0, described aminating reaction temperature is particularly preferably 110 DEG C -170 DEG C, and the described aminating reaction time is particularly preferably
2.0-4.0min。
Further, the equipment described in the step 1 is made up of static mixer and tubular reactor, or mixed by static state
Clutch, tubular reactor and stripper composition, or these equipment any combination.
Further, the alkali in the step 2 is NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, carbon
One or more in sour potassium, described hydrolysising reacting temperature is 80 DEG C -200 DEG C, and hydrolysis time is 10-60min.
Further, the particularly preferred NaOH of described alkali, NaOH inventory is calculated as 1.0-1.5 and works as with hydroxyacetonitrile
Amount, hydrolysising reacting temperature is preferably 100 DEG C -180 DEG C, and hydrolysis time is preferred 10-40min.
Further, the NaOH inventory is calculated as 1.05-1.25 equivalents with hydroxyacetonitrile, and hydrolysising reacting temperature is special
Preferably 120 DEG C -160 DEG C, hydrolysis time is particularly preferably 15-30min.
Further, hydrolysis reactor is made up of static mixer, tubular reactor and its stripper in the step 2.
Further, described in step 3 bipolar membrane electrodialysis system side and other side is respectively equipped with built-in negative electrode
Cathode chamber (I) and the anode chamber (II) of built-in anode is provided with, film pair is provided between cathode chamber and anode chamber, a film is to by mutual
Every a Bipolar Membrane (BP) and a cation-exchange membrane (C) composition, the film is to Bipolar Membrane and the relative position of cation-exchange membrane
It is that the anode of Bipolar Membrane is located at cathode direction to put, and the negative electrode of Bipolar Membrane is located at anode direction, one is provided between two Bipolar Membranes
Cation-exchange membrane, described film constitutes alkali room (III), anode membrane and Bipolar Membrane anode side to the cathode direction and anode membrane of Bipolar Membrane
To composition salt room (IV).
Further, the bipolar membrane electrodialysis treatment of the step 3 is that Sodium Glycinate-iminodiacetic acid is passed through in salt room
The hydrolyzate of disodium, is passed through water or dilute aqueous slkali in alkali room, negative electrode and anode are passed through direct current, and the salt room pH is 4.5-
6.0, the alkali in the feed liquid and alkali room in salt room is produced respectively, it is diluted with water the alkaline concentration in alkali room.
Further, when the pH in the salt room is preferably 5.0-6.0, respectively in the feed liquid and alkali room in extraction salt room
Alkali, is diluted with water the alkaline concentration in alkali room.
Further, the desalination mode in the step 4 is continuous chromatography or electrodialysis, the preferred homogeneous membrane of described electrodialysis
The mode that electrodialysis is combined with out-phase EDBM, described continuous chromatography filler is sodium form resin, potassium type resin, ammonium type tree
One or more in fat and calcium type resin, the chromatographic isolation temperature is 20 DEG C -80 DEG C, preferably 30 DEG C -70 DEG C, especially excellent
Select 50 DEG C -70 DEG C.
Raw material and device therefor are well known to those skilled in the art needed for above-mentioned, and in the market is commercially available.
The beneficial effects of the present invention are：
The coproduction of the achievable glycine of the present invention and iminodiacetic acid, raw material availability is high, and the effective of hydroxyacetonitrile turns
Rate is produced up to more than 93% without other organic by-products, and product yield high, low production cost, accessory substance is few, and impurity is few,
And NaOH recycled can be reclaimed；In the absence of glycine and iminodiacetic acid separation problem, glycine is not only
Food-grade is obtained, but also qualified iminodiacetic acid (salt) acid product can be obtained, the method environmental protection is environment-friendly, produced
Efficiency high, it is simple to operate, substantially increase the yield and purity of glycine and iminodiacetic acid so that glycine high purity
More than 99%, impurity is less than 005%, and high income is up to more than 91.5%, iminodiacetic acid high purity more than 99.1%, impurity
Less than 0.05%, high income is up to more than 90.6%.
Brief description of the drawings
Fig. 1：Glycine of the present invention and the clean preparation method reacting flow chart of iminodiacetic acid coproduction；
Fig. 2：Bipolar membrane electrodialysis of the present invention remove sodium system schematic diagram；
Fig. 3：Homogeneous EDBM schematic diagram of the invention.
Specific embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
Device of the invention is illustrated as shown in Figure 1.Glycine and iminodiacetic acid combined production device include static mixer,
Tubular reactor, tank reactor, stripper, bipolar membrane electrodialysis, the industrial equipment such as continuous chromatography or homogeneous EDBM
And its these equipment carry out rational independent assortment.Wherein, the discharging opening of static mixer I connects with the import of static mixer II
It is logical, the charging aperture connection of the spoken tubular reactor I of discharging of static mixer II, discharging opening and the stripper I of tubular reactor I
Charging aperture connection, the discharging opening of stripper I connects with the charging aperture of static mixer III, the discharging opening of static mixer III
Charging aperture with tubular reactor II is connected, and the discharging opening of tubular reactor II is connected with the charging aperture of tank reactor, autoclave
The discharging opening of reactor is connected with the charging aperture of stripper II, is Sodium Glycinate and imino-diacetic from stripper II feed liquids out
The aqueous solution of acetic acid disodium salt, the aqueous solution by after decolouring, system being isolated and purified into bipolar membrane electrodialysis, by Bipolar Membrane
The feed liquid for the treatment of is glycine and the sodium salt mixed solution of iminodiacetic acid one, and desalting processing is then carried out again, and described is de-
Salt mode is industrial continuous chromatography or homogeneous membrane electrodialysis plant, respectively obtains glycine solution and iminodiacetic acid one
Sodium is concentrated and is acidified respectively, obtains glycine product and iminodiacetic acid (salt) acid product.
Flow chart of the invention is as shown in Figure 1.(1) aminating reaction：Hydroxyacetonitrile is preheated to 60 DEG C, then while and ammonia
Gas mixing is added in static mixer I, and hydroxyacetonitrile is 1: 2.0-3.0 with the molar ratio of ammonia, static mixer I with it is static
Blender II is connected, and steam is passed through in static mixer II, its feed temperature is risen to 130 DEG C, and material enters pipe reaction
In device I, exported from static mixer I to tubular reactor I, reaction time is 4 minutes, reaction temperature is 130 DEG C -150
DEG C, pressure is 1.0-1.5MPa.Tubular reactor I outlets are connected with stripper I, are directly entered by the ammonification liquid after stripping quiet
Mix with sodium hydrate aqueous solution in state blender III, subsequently into tubular reactor II, hydrolysising reacting temperature is 120 DEG C-
160 DEG C, the residence time is 15-30min in tubular reactor II；Enter still reaction from tubular reactor II feed liquids out
In device, reaction temperature is 100 DEG C or so, and carrying out stripping into stripper II from tank reactor feed liquid out reclaims ammonia, obtains
To hydrolyzate.The condition of specific embodiment and its results are shown in Table 1.
The preparation condition and its result of the glycine of table 1 and iminodiacetic acid coproduction hydrolyzate
Note：Described hydroxyacetonitrile conversion efficiency refers to that hydroxyacetonitrile is only converted into glycine and iminodiacetic acid；
The ※ of comparative example 20 is not preheated for hydroxyacetonitrile；
Comparative example 21* is the ammoniacal liquor of concentration 28%；
Comparative example 22# does not carry out stripper treatment deamination, direct hydrolysis for ammonification liquid；,
Hydrolyzate obtained above is carried out into activated carbon decolorizing, the hydrolyzate after filter activity charcoal enters bipolar membrane electrodialysis
Except sodium system (shown in Fig. 2).Bipolar membrane electrodialysis system side and other side be respectively equipped with built-in negative electrode cathode chamber (I) and
The anode chamber (II) of built-in anode is provided with, film pair is provided between cathode chamber and anode chamber, a film is to bipolar by spaced one
Film (BP) and a cation-exchange membrane (C) are constituted, and the film is Bipolar Membrane to the relative position of Bipolar Membrane and cation-exchange membrane
Anode be located at cathode direction, the negative electrode of Bipolar Membrane is located at anode direction, a cation exchange is provided between two Bipolar Membranes
Film, described film constitutes alkali room (III) to the cathode direction and anode membrane of Bipolar Membrane, and anode membrane and Bipolar Membrane anode direction constitute salt room
(IV).Material passes through accurate filter after decolourizing, into bipolar membrane electrodialysis system, Sodium Glycinate and imino group in salt room
By after bipolar membrane electrodialysis, its pH value is gradually reduced by original 14, when salt room, pH value is reduced to the diethyl acid disodium aqueous solution
5.0-5.5, that is, be considered as terminal, is glycine and the mixed liquor of the sodium of iminodiacetic acid one in salt room；NaOH in alkali room
Concentration be 8.0%.
It is sodium form chromatography resin with filler by the mixed liquor containing glycine and the sodium of iminodiacetic acid one obtained above
Chromatogram post separation, be eluant, eluent with water, 25 DEG C of chromatographic column temperature, respectively obtains glycine clear liquid and the sodium of iminodiacetic acid one is clear
Liquid, the rate of recovery of glycine reaches 98%, and salt rejection rate reaches more than 98%.Glycine solution is carried out into concentration and evaporation crystallization,
Glycine wet product is obtained, by drying, glycine product is obtained, its indices is analyzed, food-grade requirement is reached；By chromatogram point
Concentrated from the sodium water solution of iminodiacetic acid one for obtaining, be subsequently adding sulfuric acid and be acidified to pH=1 or so, isolated imido
Base diethyl acid product.
Or, by the mixed liquor containing glycine and the sodium of iminodiacetic acid one obtained above by accurate filter,
Desalting processing (shown in Fig. 3) is carried out into homogeneous EDBM under the conditions of maintaining the temperature at 25 DEG C, homogeneous EDBM has three
Room, is respectively pole liquid room, feed liquid room (light room) and receiving chamber (dense room), and in desalination processes, the sodium salt of iminodiacetic acid one is moved
Move to dense room.When the sodium salt of iminodiacetic acid one in feed liquid room is reduced to 5%, the material in feed liquid room is transferred to heterogeneous membrane electricity
Dialysis processing system carries out deep desalting, and by electrodialysis desalination twice, the sodium salt content of iminodiacetic acid one in feed liquid is low
In 0.01%；By after electrodialysis desalination twice, the rejection of glycine reaches 98.8%, and desalination rate reaches 99.5%.Will be sweet
The propylhomoserin aqueous solution carries out concentration and evaporation crystallization, obtains glycine wet product, by drying, obtains glycine product, analyzes it every
Index, reaches food-grade requirement；The sodium water solution of iminodiacetic acid one that chromatographic isolation is obtained is concentrated, and is subsequently adding sulphur
Acid is acidified to pH=1 or so, isolates iminodiacetic acid (salt) acid product.Experimental result is shown in Table 2：
The glycine of table 2 and iminodiacetic acid coproduction experimental result
Preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although being preferable to carry out by above-mentioned
Example is described in detail to the present invention, it is to be understood by those skilled in the art that can be in the form and details
Various changes are made to it, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of glycine and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that it comprises the following steps：
A. by hydroxyacetonitrile and ammonia under conditions of high temperature, carry out aminating reaction and obtain the ammonification liquid containing ammonia；
B. the ammonification liquid containing ammonia that will be obtained in above-mentioned steps A mixes with alkali, and pyrohydrolysis obtains hydrolyzate；
C. the hydrolyzate that will be obtained in above-mentioned steps B carries out deamination and desolventing technology, and the hydrolyzate for obtaining carries out Bipolar Membrane electric osmose
Analysis carries out removing sodium treatment, and it is 4.5~6.5 to control the terminal pH that removing sodium is processed, and respectively obtains the sodium of glycine-iminodiacetic acid one
(IDA-Na) aqueous solution and sodium hydrate aqueous solution；
D. glycine-iminodiacetic acid one sodium (IDA-Na) aqueous solution for above-mentioned steps C being obtained enters desalting processing, respectively
Glycine solution and iminodiacetic acid one sodium (IDA-Na) aqueous solution are obtained, glycine solution is concentrated, crystallized, done
Dry to obtain food-grade glycine product, iminodiacetic acid one sodium (IDA-Na) aqueous solution adds sulfuric acid acidifying, crystallizes, dry
To iminodiacetic acid (salt) acid product.
2. a kind of glycine as claimed in claim 1 and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that
The temperature of hydroxyacetonitrile is 10 DEG C -80 DEG C in the step A, and the hydroxyacetonitrile is 1.0: 1.05- with the molar ratio of ammonia
6.0, described aminating reaction temperature is 60 DEG C -200 DEG C, and the described aminating reaction time is 0.5-8min.
3. a kind of glycine as claimed in claim 1 or 2 and the clean preparation method of iminodiacetic acid coproduction, its feature exist
In the mass percent of hydroxyacetonitrile is 40%~100% in the step A, and the ammonia is in ammoniacal liquor, liquefied ammonia or gas ammonia
One kind, the temperature of described hydroxyacetonitrile is preferably 20 DEG C -70 DEG C, and the hydroxyacetonitrile is preferably with the molar ratio of ammonia
1.0∶1.5-3.0；The aminating reaction temperature is preferably 80 DEG C -170 DEG C, and the described aminating reaction time is preferred 1.0-
6.0min。
4. a kind of glycine and the clean preparation method of iminodiacetic acid coproduction as described in claim 1,2 or 3, its feature
It is that the mass percent of hydroxyacetonitrile is preferably 50%~100% in the step A, and the ammonia is preferably gas ammonia, described
Particularly preferred 50 DEG C -70 DEG C of the temperature of hydroxyacetonitrile, the molar ratio of the hydroxyacetonitrile and ammonia is particularly preferably 1.0:
2.0-3.0, described aminating reaction temperature is particularly preferably 110 DEG C -170 DEG C, and the described aminating reaction time is particularly preferably
2.0-4.0min。
5. a kind of glycine and the clean preparation method of iminodiacetic acid coproduction as described in any one of Claims 1 to 4, its
It is characterised by, the alkali in the step B is in NaOH, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate
One or more, described hydrolysising reacting temperature is 80 DEG C -200 DEG C, and hydrolysis time is 10-60min.
6. a kind of glycine as claimed in claim 5 and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that
Alkali in the step B is preferably NaOH, and NaOH inventory is calculated as 1.0-1.5 equivalents with hydroxyacetonitrile, and hydrolysis is anti-
It is preferably 100 DEG C -180 DEG C to answer temperature, and hydrolysis time is preferred 10-40min.
7. a kind of glycine as claimed in claim 6 and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that
The NaOH inventory is calculated as 1.05-1.25 equivalents with hydroxyacetonitrile, and hydrolysising reacting temperature is particularly preferably 120 DEG C -160
DEG C, hydrolysis time is particularly preferably 15-30min.
8. a kind of glycine and the clean preparation method of iminodiacetic acid coproduction as described in any one of claim 1~7, its
It is characterised by, the bipolar membrane electrodialysis treatment of the step C is that Sodium Glycinate-Iminodiacetic acid sodium salt is passed through in salt room
Hydrolyzate, is passed through water or dilute aqueous slkali in alkali room, negative electrode and anode are passed through direct current, and the salt room pH is 4.5-6.0, respectively
The alkali in feed liquid and alkali room in extraction salt room, is diluted with water the alkaline concentration in alkali room.
9. a kind of glycine as claimed in claim 8 and the clean preparation method of iminodiacetic acid coproduction, it is characterised in that
When pH in the salt room is preferably 5.0-6.0, the alkali in the feed liquid and alkali room in salt room is produced respectively, be diluted with water in alkali room
Alkaline concentration.
10. a kind of glycine and the clean preparation method of iminodiacetic acid coproduction as described in any one of claim 1~9,
Characterized in that, the desalination mode in the step D is continuous chromatography or electrodialysis, the preferred homogeneous membrane electric osmose of described electrodialysis
The mode that is combined with out-phase EDBM of analysis, described continuous chromatography filler be sodium form resin, potassium type resin, monium resin and
One or more in calcium type resin, the chromatographic isolation temperature is 20 DEG C -80 DEG C, preferably 30 DEG C -70 DEG C, particularly preferred 50
℃-70℃。
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| CN109721571A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Epoxy chloropropane production method and epoxychloropropane production system |
| CN116462599A (en) * | 2023-04-14 | 2023-07-21 | 天宝动物营养科技股份有限公司 | Co-production method of glycine and iminodiacetic acid |
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| CN107325015A (en) * | 2017-08-15 | 2017-11-07 | 阳泉煤业（集团）有限责任公司 | A kind of method that hydroxyacetonitrile serialization prepares glycine |
| CN107325015B (en) * | 2017-08-15 | 2020-03-17 | 阳泉煤业（集团）有限责任公司 | Method for continuously preparing glycine from hydroxyacetonitrile |
| CN109721571A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Epoxy chloropropane production method and epoxychloropropane production system |
| CN116462599A (en) * | 2023-04-14 | 2023-07-21 | 天宝动物营养科技股份有限公司 | Co-production method of glycine and iminodiacetic acid |
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