CN104402924A - Novel process for producing sodium-free pmida - Google Patents
Novel process for producing sodium-free pmida Download PDFInfo
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- CN104402924A CN104402924A CN201410691920.2A CN201410691920A CN104402924A CN 104402924 A CN104402924 A CN 104402924A CN 201410691920 A CN201410691920 A CN 201410691920A CN 104402924 A CN104402924 A CN 104402924A
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- pmida98
- mother liquor
- membrane concentration
- acid
- membrane
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Abstract
The invention provides a novel process for producing sodium-free pmida. The novel process for producing the sodium-free pmida comprises the following steps: (1) adding hydrochloric acid into iminodiacetonitrile for acidolysis to generate iminodiacetic acid and ammonium chloride; (2) neutralizing iminodiacetonitrile after being subjected to acidolysis through liquid ammonia until the pH value of the iminodiacetonitrile is suitable for crystallizing; (3) adding a neutralization solution into a crystallizer for crystallizing, separating a crystal from a mother solution, transferring the separated iminodiacetic acid into a process of synthesizing pmida, concentrating a first mother solution, in which the crystal is separated, by a membrane, carrying out environmental degradation on permeate liquid, and transferring a concentration solution into a process of synthesizing pmida; (4) mixing the iminodiacetic acid crystal prepared by the step (3) and the membrane concentration solution, diluting, carrying out condensation reaction on phosphorous acid and formaldehyde and crystallizing to obtain the finished product pmida; (5) separating a second mother solution, in which the crystal is separated, by the membrane to obtain the permeate liquid, carrying out chemical oxidation degradation dephosphorization on the permeate liquid, then carrying out biochemical treatment, and then discharging the permeate liquid; reusing the membrane concentration solution in the step (4) for diluting iminodiacetic acid. The purpose of recycling pmida and phosphorous acid is achieved.
Description
Technical field
The invention belongs to agrochemical industry pmida98 production technical field.
Background technology
The synthesis technique of domestic glyphosate mainly contains glycine method and iminodiacetic acid (salt) acid system (IDA); This wherein IDA method be developed in the later stage nineties 20th century, the method produces simple, environmental friendliness, easy to operate, with low costly at home and abroad develop rapidly, the synthesis technique wherein preparing the intermediate pmida98 of glyphosate have also been obtained research and practice widely.The pmida98 synthesis technique flow process of current main flow is as Fig. 1.Its chemical equation is as follows:
NH(CH
2CN)
2+2NaOH+2H
2O→NH(CH
2COONa)
2+2NH
3
NH(CH
2COONa)
2+2HCl→NH(CH
2COOH)
2+2NaCl
NH(CH
2COOH)
2+H
3PO
3+CH
2O→(HO)
2P(O)CH
2N(CH
2COOH)
2+H
2O
This flow process is longer, and intermediate product relates to ammonia and discharges and need do vent gas treatment; The generation of a large amount of sodium-chlor, the sodium-chlor subsequent treatment cost of generation is high, and commercial value is low, and iminodiacetic acid (salt) acid mother liquor, pmida98 mother liquor not easily resource utilization reuse cause the wasting of resources.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of pmida98 without sodium new process of production.For this reason, the present invention is by the following technical solutions:
Its technological reaction process is as follows:
NH(CH
2CN)
2+2HCl+4H
2O→NH(CH
2COOH)
2+2NH
4Cl
NH(CH
2COOH)
2+H
3PO
3+CH
2O→(HO)
2P(O)CH
2N(CH
2COOH)
2+H
2O
Its process program step is as follows:
(1), iminodiacetonitrile adds hydrochloric acidolysis, generation iminodiethanoic acid and ammonium chloride;
(2), neutralize with liquefied ammonia the pH value being suitable for crystallization after acidolysis;
(3), neutralizer puts into crystallizer intercrystalline, and after xln is separated with mother liquor, isolated iminodiethanoic acid proceeds to synthesis pmida98 operation and uses; The first mother liquor after fractional crystallization body crosses membrane concentration, and permeate carries out environment-friendly degradable process, and concentrated solution proceeds to pmida98 operation and uses;
(4), the iminodiethanoic acid xln of step (3) gained and cross that membrane concentration liquid merges, dilution, carry out the condensation reaction of phosphorous acid, formaldehyde, crystallization, obtain pmida98 finished product;
(5) the second mother liquor, after isolation of crystalline, crosses membrane sepn, obtains permeate, and permeate is discharged carry out biochemical treatment after chemical oxidation degraded dephosphorization treatment after; The reuse of membrane concentration liquid to step (4), for diluting iminodiethanoic acid; Reach the object reclaiming pmida98 and phosphorous acid.
Further, in step (1), acidolysis temperature 30-90 DEG C.
Further, in step (2), pH value is 1-5.
Further, in step (3), Tc 10-25 DEG C; With 1-5 DEG C of water cooling.
Further, in step (4), after iminodiethanoic acid xln and the excessively merging of membrane concentration liquid, be dissolved in water the mass percent concentration 20%-50% of iminodiethanoic acid, heat temperature raising, adds phosphorous acid and hydrochloric acid simultaneously, during to appearance backflow, slowly add formalin, carry out polycondensation.
The advantage that the present invention has is as follows:
1, the present invention compared with prior art, and reaction process shortens, technique simple optimizing.
2, the present invention compared with prior art, occurs to reduce after-treatment device without ammonia.
3, the present invention compared with prior art, alkali-free solution preocess, and non-sodium chloride produces, after the reaction of iminodiacetonitrile direct acidolysis, enter condensation reaction and generate pmida98, the salt of intermediate formation is ammonium chloride, the commodity value of ammonium chloride, much larger than sodium-chlor, reduces production cost simultaneously.
4, the present invention compared with prior art, and iminodiacetic acid (salt) acid mother liquor realizes resource utilization reuse by membrane treatment appts, and wherein residual iminodiethanoic acid reclamation rate reaches more than 90%, reduces follow-up waste liquid oxidation load.
5, the present invention compared with prior art, due to film processing system Embedded Application, achieves the resource utilization reuse of iminodiacetic acid (salt) acid mother liquor, and effectively solve the pressure of follow-up liquid waste disposal; Due to film processing system Embedded Application, achieve pmida98 mother liquor and realize resource utilization reuse by membrane treatment appts, contribute to the environmental protection treatment difficult problem solving mother liquor in pmida98 production process comparatively like a cork, wherein pmida98 reclamation rate reaches 90% phosphorous acid reclamation rate and reaches more than 60%; Due to film processing system Embedded Application, achieve the separation of ammonium chloride in pmida98 mother liquor, the commercial grade ammonium chloride product that quality is higher can be obtained, chemical fertilizer raw material reuse can be done, reduce load and the difficulty of follow-up waste liquid environmental protection treatment.
Considerably reduce unit consumption and the cost of pmida98 production, the organic quantity discharged of waste liquid is compared old technique and is reduced 90%., a mother liquor environmental protection treatment difficult problem for long-standing problem pmida98 industry obtains solving comparatively like a cork.
Accompanying drawing explanation
Fig. 1 is the process flow sheet preparing pmida98 in background technology.
Fig. 2 is the process flow sheet preparing pmida98 of the present invention.
Embodiment
Below in conjunction with embodiment, essentiality content of the present invention is described in further detail.
Embodiment 1
1, iminodiacetonitrile adds hydrochloric acidolysis, generate iminodiethanoic acid and ammonium chloride, acidolysis temperature 60 DEG C, neutralizes PH2 with liquefied ammonia after acidolysis, neutralizer puts into crystallizer intercrystalline, operable crystallizer: stirring tank, fine motion stirred crystallization groove, Tc 15 DEG C, with 5 DEG C of water coolings, crystal solution centrifugation, isolated iminodiethanoic acid does not wash, moist, directly proceeds to synthesis pmida98 operation and uses.The first mother liquor after fractional crystallization body crosses membrane concentration, and permeate carries out environment-friendly degradable process.Concentrated solution proceeds to pmida98 operation and uses.The iminodiethanoic acid solid of above-mentioned 3 gained and the iminodiethanoic acid membrane concentration liquid of 4 gained merge, be dissolved in water finite concentration 20%-50%, heat temperature raising, adds phosphorous acid and hydrochloric acid simultaneously, during to appearance backflow, slowly add the formalin of 37%, after adding, insulation 30min has crystal to separate out, after vacuum depickling to PH=0.5, proceed to crystallization kettle, be cooled to 10-25 DEG C.Centrifugation, soft water washs, and obtains pmida98 finished product.The second mother liquor after fractional crystallization body, crosses membrane sepn;
Obtain permeate, permeate is discharged carry out biochemical treatment after chemical oxidation degraded dephosphorization treatment after.Membrane concentration reuse to condensation reaction, for diluting iminodiethanoic acid.
Embodiment 2
The embodiment of the present embodiment is substantially the same manner as Example 1, on this basis:
The first described mother liquor is crossed membrane concentration and is referred to the first mother liquor after pre-treatment removal macrobead thing, through first step membrane concentration, second stage membrane concentration.Concentrated dope reuse is in condensation reaction, and directly generate pmida98, permeate enters environment-friendly degradable process.
Embodiment 3
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
In described first step membrane concentration process, in the membrane concentration process of the second stage, the first step, the second stage concentrate the multiplying power of 3 times by concentrated de-light liquid process control.
Embodiment 4
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described first step membrane concentration mother liquor control pH is 2.5.
Described second stage membrane concentration mother liquor control pH is 3.
Embodiment 5
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
First mother liquor pre-treatment refers to sand filtration, carbon filter, ultrafiltration.
Embodiment 6
The embodiment of the present embodiment is substantially the same manner as Example 1, on this basis:
In described second mother liquor membrane concentration sepn process, concentrating and separating liquid returns condensation reaction and reclaims pmida98 and phosphorous acid, and permeate enters oxidative degradation process.
Embodiment 7
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis:
The second described mother liquor film is crossed in membrane separating process, is divided into first step membrane concentration, second stage membrane concentration, third stage electrodialysis separation.
The concentration ratio of described first step film is 2 times, and the concentration ratio of second stage film is 2 times.
It is 2.0 that described first step membrane concentration mother liquor pH controls.
It is 2.5 that described second stage membrane concentration mother liquor pH controls.
Ammonium chloride content 0.5%, pH=3.0 in described electrodialysis concentrating and separating product.
Embodiment 8
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis:
In described third stage electrodialytic membranes treating processes, by adding NH in water management parting liquid
4cl concentration is 9% (dense side recovery NH
4cl).
The concentration ratio of described first step film is 3 times, and the concentration ratio of second stage film is 3 times.
It is 3.0 that described first step membrane concentration mother liquor pH controls.
It is 3.5 that described second stage membrane concentration mother liquor pH controls.
It is 10%, pH=2 that third stage electrodialytic membranes is separated NH4Cl content in mother liquor.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 1NTU.
Embodiment 9
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis: in described third stage electrodialytic membranes treating processes, is 6% (NH4Cl is reclaimed in dense side) by adding NH4Cl concentration in water management parting liquid.
The concentration ratio of described first step film is 4 times, and the concentration ratio of second stage film is 2 times.
It is 4.0 that described first step membrane concentration mother liquor pH controls.
It is 4.5 that described second stage membrane concentration mother liquor pH controls.
NH in the separation mother liquor of described third stage electrodialytic membranes
4cl content is 8%, pH=3.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 2NTU.
The pmida98 content of described first step membrane concentration mother liquor is 1%, and the pmida98 content of second stage membrane concentration mother liquor is 4%, and after third stage electrodialysis, the pmida98 content of mother liquor is 8%.NH after third stage electrodialytic membranes is separated
4cl concentration is less than 1%.
Embodiment 10
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis: in described third stage electrodialytic membranes treating processes, by adding NH in water management parting liquid
4cl concentration is 4% (dense side recovery NH
4cl).
The concentration ratio of described first step film is 2 times, and the concentration ratio of secondary membrane is 2 times.
It is 4.0 that described first step membrane concentration mother liquor pH controls.
It is 4.5 that described second stage membrane concentration mother liquor pH controls.
Described third stage electrodialytic membranes is separated NH in mother liquor
4cl content is 8%, pH=3.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 5NTU.
The pmida98 content of described first step membrane concentration mother liquor is 2%, and the pmida98 content of second stage membrane concentration mother liquor is 4%, and the pmida98 content of third stage electrodialytic membranes concentrated mother liquor is 8%.NH after third stage electrodialytic membranes is separated
4cl is less than 1%.
Embodiment 11
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis: in described third stage electrodialytic membranes treating processes, by adding NH in water management parting liquid
4cl concentration is 12% (NH4Cl is reclaimed in dense side).
The concentration ratio of described first step film is 1.5 times, and the concentration ratio of second stage film is 1.5 times.
It is 2.0 that described first step membrane concentration mother liquor pH controls.
It is 2.5 that described second stage membrane concentration mother liquor pH controls.
Described third stage electrodialytic membranes is separated NH in mother liquor
4cl content is 10%, pH=3.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 5NTU.
The pmida98 content of described first step membrane concentration mother liquor is 4%, and the pmida98 content of second stage membrane concentration mother liquor is 6%, and the pmida98 content of third stage electrodialytic membranes concentrated mother liquor is 9%.NH after third stage electrodialytic membranes is separated
4cl is less than 1%.
Use reducing solution cleaning third stage electrodialytic membranes.
Embodiment 12
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis: in described third stage electrodialytic membranes treating processes, by adding NH in water management parting liquid
4cl concentration is 12% (dense side recovery NH
4cl).
The concentration ratio of described first step film is 1.5 times, and the concentration ratio of second stage film is 1.5 times.
It is 2.0 that described first step membrane concentration mother liquor pH controls.
It is 2.5 that described second stage membrane concentration mother liquor pH controls.
Described third stage electrodialytic membranes is separated NH in mother liquor
4cl content is 10%, pH=3.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 5NTU.
The pmida98 content of described first step membrane concentration mother liquor is 4%, and the pmida98 content of second stage membrane concentration mother liquor is 6%, and the pmida98 content that third stage electrodialytic membranes is separated mother liquor is 9%.NH after third stage electrodialytic membranes is separated
4cl is less than 1%.
Use reducing solution cleaning third stage electrodialytic membranes.
The second described mother liquor is for returning in the condensation reaction of front end and phosphorous acid, formaldehyde.
Embodiment 13
The embodiment of the present embodiment is substantially the same manner as Example 6, on this basis: in described third stage electrodialytic membranes treating processes, by adding NH in water management parting liquid
4cl concentration is 12% (dense side recovery NH
4cl).
The concentration ratio of described first step film is 1.5 times, and the concentration ratio of second stage film is 1.5 times.
It is 2.0 that described first step membrane concentration mother liquor pH controls.
It is 2.5 that described second stage membrane concentration mother liquor pH controls.
Described third stage electrodialytic membranes is separated NH in mother liquor
4cl content is 10%, pH=3.
Described pmida98 original nut liquid, be also the second mother liquor, after pre-treatment, turbidity is 5NTU.
The pmida98 content of described first step membrane concentration mother liquor is 4%, and the pmida98 content of second stage membrane concentration mother liquor is 6%, and the pmida98 content of third stage membrane concentration mother liquor is 9%.NH after third stage electrodialytic membranes is separated
4cl is less than 1%.
Use reducing solution cleaning third stage electrodialytic membranes.
The second described mother liquor is for returning in the condensation reaction of front end and phosphorous acid, formaldehyde.
Claims (7)
1. pmida98 is without a sodium new process of production, it is characterized in that,
Its technological reaction process is as follows:
NH(CH
2CN)
2+2HCl+4H
2O→NH(CH
2COOH)
2+2NH
4Cl
NH(CH
2COOH)
2+H
3PO
3+CH
2O→(HO)
2P(O)CH
2N(CH
2COOH)
2+H
2O
Its process program step is as follows:
(1), iminodiacetonitrile adds hydrochloric acidolysis, generation iminodiethanoic acid and ammonium chloride;
(2), neutralize with liquefied ammonia the pH value being suitable for crystallization after acidolysis;
(3), neutralizer puts into crystallizer intercrystalline, and after xln is separated with mother liquor, isolated iminodiethanoic acid proceeds to synthesis pmida98 operation and uses; The first mother liquor after fractional crystallization body crosses membrane concentration, and permeate carries out environment-friendly degradable process, and concentrated solution proceeds to pmida98 operation and uses;
(4), the iminodiethanoic acid xln of step (3) gained and cross that membrane concentration liquid merges, dilution, carry out the condensation reaction of phosphorous acid, formaldehyde, crystallization, obtain pmida98 finished product;
(5) the second mother liquor, after isolation of crystalline crosses membrane sepn, obtains permeate, and permeate is discharged carry out biochemical treatment after chemical oxidation degraded dephosphorization treatment after; The reuse of membrane concentration liquid is step (4) extremely, for diluting iminodiethanoic acid; Reach the object reclaiming pmida98 and phosphorous acid.
2. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (1), and acidolysis temperature 30-90 DEG C.
3. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (2), pH value is 1-5.
4. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (3), and Tc 10-25 DEG C; With 1-5 DEG C of water cooling.
5. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (4), after iminodiethanoic acid xln and the excessively merging of membrane concentration liquid, the mass percent concentration 20%-50% of the iminodiethanoic acid that is dissolved in water, heat temperature raising, add phosphorous acid and hydrochloric acid simultaneously, during to appearance backflow, slowly add formalin, carry out polycondensation.
6. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (3), the first mother liquor is crossed membrane concentration and referred to: the first mother liquor is removed after macrobead thing, through first step membrane concentration, second stage membrane concentration through pre-treatment.
7. a kind of pmida98 as claimed in claim 1 is without sodium new process of production, it is characterized in that, in step (5), the second mother liquor is removed after macrobead thing through pre-treatment, crosses membrane sepn and is divided into first step membrane concentration, second stage membrane concentration, third stage electrodialysis separation.
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| CN201410691920.2A CN104402924A (en) | 2014-11-26 | 2014-11-26 | Novel process for producing sodium-free pmida |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410691920.2A CN104402924A (en) | 2014-11-26 | 2014-11-26 | Novel process for producing sodium-free pmida |
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Family
ID=52640603
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175444A (en) * | 2015-09-11 | 2015-12-23 | 重庆华歌生物化学有限公司 | Novel method of preparing N-phosphonomethyl iminodiacetic acid |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
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| CN105175444A (en) * | 2015-09-11 | 2015-12-23 | 重庆华歌生物化学有限公司 | Novel method of preparing N-phosphonomethyl iminodiacetic acid |
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| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
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