CN105732408B - A kind of technique of the continuity method production sodium of glutamic acid diacetic acid four - Google Patents
A kind of technique of the continuity method production sodium of glutamic acid diacetic acid four Download PDFInfo
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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
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
Abstract
A kind of technique of the continuity method production sodium of glutamic acid diacetic acid four, is produced using flow reactor, is comprised the following steps：A, using sodium glutamate salting liquid, sodium cyanide solution, formalin as raw material, above-mentioned raw materials is added in the first reactor by heat-exchange system by flow velocity stream and reacted, while ammonia caused by collection；B, reacted feed liquid in the first reactor is released to enter directly into the second reactor from bottom and continues to react, while collect caused ammonia in the second reactor；C, reacted feed liquid in the second reactor is released from bottom and entered in storage tank, decolourized, filtered, degree of thickening, obtain the sodium solution of glutamic acid diacetic acid four.This method can the sodium of continuous production glutamic acid diacetic acid four, obtained superior product quality, production stability is good, easily controllable, and can avoid still reaction generate accessory substance.
Description
Technical field
The invention belongs to the technical field of the sodium of glutamic acid diacetic acid four, it is related to the production technology of the sodium of glutamic acid diacetic acid four,
Particularly a kind of technique of the continuity method production sodium of glutamic acid diacetic acid four.This method can the sodium of continuous production glutamic acid diacetic acid four,
Obtained superior product quality, production stability is good, easily controllable, and the accessory substance that still reaction can be avoided to generate.
Background technology
The sodium of glutamic acid diacetic acid four is a kind of important chelating agent, there is very prominent effect in terms of cleaning and washing,
Also, in today that Environmental Protection Situation is increasingly serious, NTA carcinogenicity, result in that it uses is limited, EDTA not readily degradables pair
The problems such as environment is not friendly enough occurs again and again, and the sodium of glutamic acid diacetic acid four is exactly a kind of material of easily biological-degradable.
Research for the sodium of glutamic acid diacetic acid four is a lot.For example, patent DE4211713 is mentioned using glutamic acid and hydrogen cyanogen
Acid, formaldehyde reaction, alkaline hydrolysis obtain final products.Describe and amino is prepared based on acid and alkaline Strecker reaction
The method of dicarboxylic acids-N, N- oxalic acid.Now, a-amino acid and at least 2 moles of formaldehyde and at least 2 moles of hydrogen cyanide or alkali gold are made
Belong to cyanide reaction.This method results in the unwanted accessory substance for being difficult to remove based on the relatively low-yield that glutamic acid is 89%
Such as NTA, NTA trisodium salt, NTA, NTA trisodium salt are more few better, but NTA, NTA trisodium salt for preparing low content are difficult,
It is just very big often to reduce the influence of 0.01% pair of product for NTA, NTA trisodium salt in product, but the reduction of its content is difficult to realize
's.WO9622351 mentions glutamic acid diacetic acid and its salt is respectively provided with degradability.
US2500019 proposes that Cymag can be used, the sodium of Formaldehyde Production glutamic acid diacetic acid four, described by making α-ammonia
Base acid reacts with formaldehyde and Cymag preferably in strong alkaline aqueous solution at a temperature of 30-100 DEG C to be prepared this oxalic acid and spreads out
Biology, when glutamic acid is as a-amino acid, obtain the mixing of glutamic acid-N, N- oxalic acid and butyrine-N, N- oxalic acid
Thing, because terminal carboxyl group part decarboxylize under strongly alkaline conditions, this technique is batch production mode, low production efficiency.
Above-mentioned several preparation methods are the preparation methods of batch (-type) or semi continuous, on complete continuous production glutamic acid
The method of the sodium of oxalic acid four is fresh to be referred to less, and the method for the sodium of glutamic acid diacetic acid four is continuously synthesized on the method using Cymag
More without any research.Thus the research to the method for the continuous synthesis sodium of glutamic acid diacetic acid four is significant.
The content of the invention
The present invention is especially the failure to realize use to solve to fail the sodium of continuous production glutamic acid diacetic acid four in the prior art
The method that sodium cyanide solution, monosodium glutamate solution, formalin carry out the sodium of continuous production glutamic acid diacetic acid four, there is provided one kind makes
It is real with the method that sodium cyanide solution, monosodium glutamate solution, formalin are raw material, the continuous synthesis sodium of glutamic acid diacetic acid four
The existing mode of production that raw material continuously enters, product continuously goes out.
The present invention is to realize that the technical scheme that its purpose uses is：
A kind of technique of the continuity method production sodium of glutamic acid diacetic acid four, is produced using flow reactor, including following
Step：
A, using sodium glutamate salting liquid, sodium cyanide solution, formalin as raw material, above-mentioned raw materials are changed by heat-exchange system
After heat treatment, it is added in the first reactor and is reacted by flow velocity stream, while ammonia caused by collection；
B, reacted feed liquid in the first reactor is released to enter directly into the second reactor from bottom and continues to react,
Caused ammonia in the second reactor is collected simultaneously；
C, reacted feed liquid in the second reactor is released from bottom and entered in storage tank, decolourized, filtered, thickened
Degree, obtains the sodium solution of glutamic acid diacetic acid four.
The flow acceleration of sodium glutamate salting liquid is 422kg/h, and the flow acceleration of sodium cyanide solution is 327-360kg/h,
The flow acceleration of formalin is 162-178kg/h.
The concentration of monosodium glutamate solution is 30%-40%, and the concentration of sodium cyanide solution is 28%-32%, formalin
Concentration is 35%-37%.
The reaction temperature of first reactor is 60-120 DEG C, and the residence time is controlled in 0-100min.
The reaction temperature of second reactor is 80-180 DEG C, and the residence time is controlled in 0-100min.The preparation work of the present invention
Skill controls the temperature of the second reactor to be higher than the first reactor, is advantageous to sufficiently be reacted.
Described heat-exchange system is heat exchanger, and after heat-exchange system heat exchange processing, sodium glutamate salting liquid, Cymag are molten
Liquid, the feeding temperature of formalin are 60-120 DEG C.
The beneficial effects of the invention are as follows：The present invention continuously produces glutamic acid diacetic acid using sodium cyanide method, uses cyaniding
Sodium is raw material, is not limited by the use of hydrogen cyanide.The inventive method realizes the sodium of continuous production glutamic acid diacetic acid four first,
Fill up and utilized sodium cyanide solution, monosodium glutamate solution, the system that formalin is the sodium of raw material continuous production glutamic acid diacetic acid four
Standby blank, also, utilize the sodium high income of glutamic acid diacetic acid four of this method production, purity height, quality better, no coupling product, production
Product stability is good, and technological operation is simple, easy to control, continuous and automatic, has liberated labour productive forces significantly.
Generally, easily occurs the phenomenon of back-mixing using flow reactor, but the present invention is by raw material flow rate
Control and the strict control of residence time, realize the effect that flow reactor continuous production is also not in back-mixing.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
This document inventor makes Cymag, formaldehyde using flow reactor, and sodium glutamate carries out reaction and prepares glutamic acid
The sodium solution of oxalic acid four, the superior product quality that such a method obtains, production stability is good, and quality is easily controllable, and can avoid
The accessory substance of still reaction generation.With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The temperature control of the first reactor is adjusted first at 100 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 327kg/h flow velocity, and 37% formalin is with 162kg/h flow velocity and 40%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
15min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 110 DEG C, feed liquid
8min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor,
And be collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, the decolouring of next step is carried out, filtered, adjustment is dense
The processing of degree, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 94%, product are faint yellow.Utilize
HPLC is determined, and the ratio of NTA trisodium salts is 0.005 weight % in the solution.
Embodiment 2
The temperature control of the first reactor is adjusted first at 100 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 350kg/h flow velocity, and 37% formalin is with 175kg/h flow velocity and 40%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged whole system at the top of the first reactor, and is collected, and feed liquid is in the first reaction
Kettle stops 20min, and after the completion of the first order reaction, feed liquid enters the second reactor, the temperature of the second reactor of control at 110 DEG C,
Feed liquid stops 10min in the second reactor, meanwhile, further the ammonia of reaction generation is further arranged at the top of the second reactor
Go out, so as to complete whole reaction, feed liquid after reaction, into storage tank, carry out the decolouring of next step, filter, adjust the place of concentration
Reason, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 95%, product are faint yellow.Determined using HPLC,
The ratio of NTA trisodium salts is 0.005 weight % in the solution.
Embodiment 3
The temperature control of the first reactor is adjusted first at 90 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 327kg/h flow velocity, and 37% formalin is with 162kg/h flow velocity and 40%
Sodium glutamate salting liquid entered with 422kg/h flow velocity in the first reactor, under strong agitation effect, rapid effect, together
When, the ammonia for hydrolyzing generation is discharged whole system at the top of the first reactor, and feed liquid stops 30min in the first reactor, the
After the completion of first order reaction, feed liquid enters the second reactor, and the second temperature of reaction kettle of control is at 110 DEG C, and feed liquid is in the second reactor
5min is stopped, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor, whole so as to complete
Reaction, feed liquid after reaction, into storage tank, carries out the decolouring of next step, filters, adjusts the processing of concentration, finally obtaining concentration is
The sodium solution of 40% glutamic acid diacetic acid four.Yield 94.8%, product are faint yellow.Determined using HPLC, NTA trisodiums in the solution
The ratio of salt is 0.005 weight %.
Embodiment 4
The temperature control of the first reactor is adjusted first at 70 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 327kg/h flow velocity, and 37% formalin is with 162kg/h flow velocity and 40%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged whole system at the top of the first reactor, and feed liquid stops in the first reactor
30min, after the completion of the first order reaction, feed liquid enters the second reactor, and at 120 DEG C, feed liquid exists the second temperature of reaction kettle of control
Second reactor stops 13min, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor, from
And whole reaction is completed, feed liquid after reaction into storage tank, carries out the decolouring of next step, filtering, adjusts the processing of concentration, most
After to obtain concentration be the sodium solution of 40% glutamic acid diacetic acid four.Yield 94.2%, product are yellow.Determined using HPLC, this is molten
The ratio of NTA trisodium salts is 0.005 weight % in liquid.
Embodiment 5
The temperature control of the first reactor is adjusted first at 80 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
28% sodium cyanide solution after processing is with 330kg/h flow velocity, and 35% formalin is with 165kg/h flow velocity and 30%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
28min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 130 DEG C, feed liquid
15min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor,
And be collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, the decolouring of next step is carried out, filtered, adjustment is dense
The processing of degree, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 95%, product are faint yellow.Utilize
HPLC is determined, and the ratio of NTA trisodium salts is 0.005 weight % in the solution.
Embodiment 6
The temperature control of the first reactor is adjusted first at 110 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
29% sodium cyanide solution after processing is with 340kg/h flow velocity, and 36% formalin is with 168kg/h flow velocity and 35%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
18min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 140 DEG C, feed liquid
7min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor, and
It is collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, carries out the decolouring of next step, filter, adjusts concentration
Processing, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 94.6%, product are faint yellow.Utilize
HPLC is determined, and the ratio of NTA trisodium salts is 0.005 weight % in the solution.
Embodiment 7
The temperature control of the first reactor is adjusted first at 120 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
31% sodium cyanide solution after processing with 360kg/h flow velocity, 36% formalin with 1170kg/h flow velocity and
32% sodium glutamate salting liquid with 422kg/h flow velocity, add in the first reactor by stream, fast under strong agitation effect
Speed effect, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
22min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 150 DEG C, feed liquid
7min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor, and
It is collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, carries out the decolouring of next step, filter, adjusts concentration
Processing, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 94.2%, product are faint yellow.Utilize
The ratio that HPLC determines NTA trisodium salts in the solution is 0.005 weight %.
Embodiment 8
The temperature control of the first reactor is adjusted first at 100 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
32% sodium cyanide solution after processing is with 335kg/h flow velocity, and 37% formalin is with 172kg/h flow velocity and 37%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
40min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 115 DEG C, feed liquid
11min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor,
And be collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, the decolouring of next step is carried out, filtered, adjustment is dense
The processing of degree, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 95.3%, product are faint yellow.Utilize
The ratio that HPLC determines NTA trisodium salts in the solution is 0.005 weight %.
Embodiment 9
The temperature control of the first reactor is adjusted first at 100 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 345kg/h flow velocity, and 37% formalin is with 164kg/h flow velocity and 40%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
60min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 125 DEG C, feed liquid
18min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor,
And be collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, the decolouring of next step is carried out, filtered, adjustment is dense
The processing of degree, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 95.1%, product are faint yellow.Utilize
The ratio that HPLC determines NTA trisodium salts in the solution is 0.005 weight %.
Embodiment 10
The temperature control of the first reactor is adjusted first at 100 DEG C, in the presence of pump, will be passed through heat-exchange system and be exchanged heat
30% sodium cyanide solution after processing is with 355kg/h flow velocity, and 37% formalin is with 163kg/h flow velocity and 40%
Sodium glutamate salting liquid with 422kg/h flow velocity, stream is added in the first reactor, rapid to make under strong agitation effect
With, meanwhile, the ammonia for hydrolyzing generation is discharged and is collected at the top of the first reactor, and feed liquid stops in the first reactor
80min, after the completion of the first order reaction, feed liquid enters in the second reactor, controls the temperature of the second reactor at 135 DEG C, feed liquid
20min is stopped in the second reactor, meanwhile, further the ammonia of reaction generation is further discharged at the top of the second reactor,
And be collected, so as to complete whole reaction, feed liquid after reaction, into storage tank, the decolouring of next step is carried out, filtered, adjustment is dense
The processing of degree, it is the sodium solution of 40% glutamic acid diacetic acid four to finally obtain concentration.Yield 97.2%, product are faint yellow.Utilize
The ratio that HPLC determines NTA trisodium salts in the solution is 0.005 weight %.
Comparative example 1
Prepare Pidolidone-N, N- oxalic acid tetrasodium salt
It is fitted into the sodium salt monohydrate of 187g (1.0 moles) Pidolidone one in reaction vessel first in 280.5g water
About 40 weight % solution.Adding 100.0g thereto in 30 seconds in the case where stirring and not cooling down first at room temperature, (1.0 rub
You) 30 weight % formalin, 27.0g (1.0 moles) hydrogen cyanide was then added in 40 seconds.Addition terminate and then
Stir the mixture 5 minutes.Afterwards, further heat release is not detected, temperature is 45 DEG C.Then gained mixture is being stirred
And do not cool down down mixed in 70 seconds with 27.0g (1.0 moles) hydrogen cyanide first, then in 160 seconds with 100.0g (1.0
Mole) mixing of 30 weight % formalin, temperature rises to 60 DEG C in this process.It is mixed that addition terminates and then stirred this
Compound about 5 minutes.Then by the metered 489.6g of gained about 720g pale yellow solutions, (3.06 rub in 1 hour at 25 DEG C
You) in 25 weight % sodium hydroxide solutions.After addition terminates, temperature is 60 DEG C.The mixture is then heated to 100-110
DEG C being no longer tested with ammonia after about 4 hours forms.1100g yellow solutions are obtained, are analyzed according to HPLC, the solution includes
330g Pidolidones-N, N- oxalic acid tetrasodium salt, therefore form the about 30 weight % reaction mixture.Based on glutamic acid used
Salt, yield 94%.Determined using HPLC, the ratio of NTA trisodium salts is more than 0.05 weight % in the solution.
Comparative example 2
Preparing Pidolidone-N, N- oxalic acid tetrasodium salt, (operation is similar with DE 4211713 Examples 1 and 2, except making
Aspartic acid is replaced with glutaminate sodium salt)
It is fitted into the sodium salt monohydrate of 187g (1.0 moles) Pidolidone one in reaction vessel first in 300.0g water
Solution.Adding the weight % formalins of 200g (2.0 moles) 30 and 54.0g thereto in 1 hour under agitation, (2.0 rub
You) hydrogen cyanide, in this process temperature by cooling be maintained at 20-25 DEG C.After addition terminates, by the mixture at 1 hour
Inside it is heated to 70 DEG C.Then 408.0g (3.06 moles) 30 was added dropwise in gained reactant mixture at 40 DEG C in 1 hour
In weight % sodium hydroxide solutions.After addition terminates, the mixture is heated to 100 DEG C until no longer being examined after about 4 hours
Ammonia has been measured to be formed.1041g solution is obtained, is analyzed according to HPLC, the solution includes 312.4g Pidolidones-N, N- oxalic acid
Tetrasodium salt, therefore form the about 30 weight % reaction mixture.Based on glutamate used, yield 89%.Surveyed using HPLC
Fixed, the ratio of NTA trisodium salts is more than 0.35 weight % in the solution.
Compared with prior art, the present invention uses the inventive method using the continous way mode of production, comparative example 1
Be the semi continuous mode of production, comparative example 2 is known using batch production mode, those skilled in the art, institute
Meaning continous way production refers to that material is continuously added to, and product continuously exports；The production of semi continuous refers to a kind of material one
Secondary property is added, and another material or unclassified stores are continuously added to；Batch production mode refers to that material disposably adds, product
Disposable output；It will be appreciated that the mode of production of the invention and prior art are entirely different, and the paddy that the mode of the present invention produces
The concentration ratio prior art of the sodium solution of propylhomoserin oxalic acid four is higher by 10% or so, and yield is also apparently higher than prior art, in quality
Also it is more preferable.
The present invention uses the sodium of sodium cyanide method continuous production glutamic acid diacetic acid four, and for single step reaction, product is made in one step, bright
It is aobvious to shorten reaction process, make a big difference and improve compared to existing multistep reaction tool, it is existing using hydrogen cyanide
So-called continuity method is also by multistep reaction in fact, and it is by following methods that it, which uses continous way,：Diamino dicarboxylic acid and first
Aldehyde is parallel to add the first reaction zone, and hydrogen cyanide adds second reaction zone reaction；Reaction product, hydrogen cyanide, formaldehyde are parallel to be added to
Reacted in one reaction zone, in reactant mixture metered another reaction zone parallel with sodium hydroxide solution.The existing process
Principle be：
C5H9NO4(glutamic acid)+2CH2O+2HCN → product+4NaOH → GLDA-Na4+2NH3+2H2O
It reacts with formaldehyde and hydrogen cyanide first, is then reacted again with sodium hydroxide.
The present invention reaction principle be：
C5H9NO4(glutamic acid)+2NaCN+2CH2O→GLDA-4Na4+2NH3+2H2O
It will be apparent that the present invention has absolute progressive meaning, continuity method production paddy ammonia is not only truly realized
The sour sodium of oxalic acid four, and the continuous production of single step reaction is realized, this has to the field for producing the sodium of glutamic acid diacetic acid four
Far-reaching teaching meaning.
Claims (3)
1. a kind of technique of the continuity method production sodium of glutamic acid diacetic acid four, is produced, its feature using continuous tank reactor
It is, comprises the following steps：
A, using sodium glutamate salting liquid, sodium cyanide solution, formalin as raw material, by above-mentioned raw materials by heat-exchange system heat exchange at
After reason, it is added in the first reactor and is reacted by flow velocity stream, while ammonia caused by collection；The stream of sodium glutamate salting liquid adds
Speed is 422kg/h, and the flow acceleration of sodium cyanide solution is 327-360kg/h, and the flow acceleration of formalin is 162-
178kg/h；The reaction temperature of first reactor is 60-120 DEG C, and the residence time is controlled in 0-100min；
B, reacted feed liquid in the first reactor is released to enter directly into the second reactor from bottom and continues to react, simultaneously
Collect caused ammonia in the second reactor；The reaction temperature of second reactor is 80-180 DEG C, and the residence time is controlled in 0-
100min；
C, reacted feed liquid in the second reactor is released from bottom and entered in storage tank, decolourized, filtered, degree of thickening,
Obtain the sodium solution of glutamic acid diacetic acid four.
A kind of 2. technique of continuity method production sodium of glutamic acid diacetic acid four according to claim 1, it is characterised in that：Paddy ammonia
The concentration of acid sodium solution is 30%-40%, and the concentration of sodium cyanide solution is 28%-32%, and the concentration of formalin is 35%-
37%.
A kind of 3. technique of continuity method production sodium of glutamic acid diacetic acid four according to claim 1, it is characterised in that：It is described
Heat-exchange system be heat exchanger, after heat-exchange system heat exchange processing, sodium glutamate salting liquid, sodium cyanide solution, formalin
Feeding temperature is 60-120 DEG C.
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| US2500019A (en) * | 1946-10-08 | 1950-03-07 | Frederick C Bersworth | Method of producing polycarboxylic amino acids |
| DE4211713A1 (en) * | 1992-04-08 | 1993-10-14 | Basf Ag | New amino di:carboxylic-N,N-di:acetic acid deriv., useful as complexing agents - is prepd. from amino di:carboxylic acids, formaldehyde and hydrocyanic acid, or alkali metal cyanide, with amino di:carboxylic acid-N,N-di:acetonitrile as intermediate |
| MXPA02011253A (en) * | 2000-05-15 | 2003-03-10 | Monsanto Technology Llc | Preparation of iminodiacetic acid compounds from monoethanolamine substrates. |
| CN101959847B (en) * | 2008-03-03 | 2014-12-31 | 巴斯夫欧洲公司 | Method for the production of aminodicarboxylic acid-N,N-diacetic acids |
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