CN102633835B - Method for synthetizing N-( phosphonomethyl) iminodiacetic acid - Google Patents
Method for synthetizing N-( phosphonomethyl) iminodiacetic acid Download PDFInfo
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- CN102633835B CN102633835B CN201210095353.5A CN201210095353A CN102633835B CN 102633835 B CN102633835 B CN 102633835B CN 201210095353 A CN201210095353 A CN 201210095353A CN 102633835 B CN102633835 B CN 102633835B
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- acid
- ida
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- phosphonomethyl
- pmida
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Abstract
The invention discloses a method for synthetizing N-( phosphonomethyl) iminodiacetic acid, which includes: subjecting iminodiacetic acid disodium salt and phosphorous acid to react to form a salt-mixed water solution, adding the obtained salt-mixed water solution to a bi-pole film system, generating phosphorous acid liquor containing IDA (imino diethyl acetic acid) to be PMIDA (N-phosphonomethyl iminodiaceticacid) generation sources, subjecting the obtained PMIDA generation sources to react with formaldehyde on the acidic condition, and preparing N-(phosphonic acid methyl) iminodiacetic acid. The method for synthetizing N-( phosphonomethyl) iminodiacetic acid overcomes the defects in the prior art, is simple, convenient and easy to operate and is a typical cleaning production process.
Description
Technical field
The present invention relates to a kind of synthetic N-((phosphonomethyl)) method of iminodiethanoic acid.
Background technology
N-((phosphonomethyl) in existing technology) production technique of imino-acetic acid (pmida98 is called for short PMIDA); main method is as its acquisition methods of starting raw material, to have two kind one to be to be to obtain with the dehydrogenation of diethanolamine alkali with iminodiacetonitrile alkaline hydrolysis deamination two with iminodiacetic acid disodium salt (IDA-2Na); though it all uses the acid of a great deal of and has a large amount of sodium-chlor association ZL200410014898.4 can solve the difficult point in many production technique in producing, also there is the low deficiency that waits of resource utilization.
Existing PMIDA production process reactions steps content:
Step 1, iminodiacetic acid disodium salt NH (CH
2cOONa)
2(be called for short: IDA-2Na) produce process, main two kinds of its method
(1) iminodiacetonitrile (be called for short: IDAN) alkaline hydrolysis main reaction formula:
NH(CH
2CN)
2 + 2NaOH + 2H
2O --- NH(CH
2COONa)
2 + 2NH
3
(2) diethanolamine (be called for short: DEA) catalytic dehydrogenation method main reaction formula:
NH(CH
2CH
2OH)
2 + 2NaOH + 2H
2O --- NH(CH2COONa)
2 + 4H
2
Step 2, utilize IDA-2Na produce iminodiethanoic acid (be called for short: IDA) reaction formula:
NH (CH
2cOONa)
2+ 2HCl---NH (CH
2cOOH)
2+ 2NaCl solid IDA processed also further reclaims IDA or its concentrated solution by-product NaCl by saliferous mother liquor
The IDA that step 3, use are produced reacts and makes N-((phosphonomethyl) with phosphorous acid, formaldehyde under acidic conditions) iminodiethanoic acid (be called for short: PMIDA) reaction formula:
NH(CH
2COOH)
2 + H
3PO
3 + CH
2O --- (HO)
2POCH
2N(CH
2COOH)
2 + H
2O
The defect of existing production method process system:
1, in production process, consume a large amount of alkali (generally using 32% liquid NaOH);
2, in production process, use and consume a large amount of large acid (generally using 30% hydrochloric acid);
3, the NaCl of a large amount of low values of by-product can causing causes with IDA or PMIDA mutually carrying secretly in various degree that quality product is low or it runs off, and the 2nd, desalination evaporative desalination difficulty and produce that the high-salt wastewater amount forming is large and biochemical treatment expense is high.
Summary of the invention
The object of the present invention is to provide the synthetic N-((phosphonomethyl) that a kind of method is easy, easy to operate, clean) method of iminodiethanoic acid.
Technical solution of the present invention is:
Synthetic N-((phosphonomethyl)) method for iminodiethanoic acid, is characterized in that: comprise the following steps:
(1) iminodiacetic acid disodium salt reacts with phosphorous acid and forms mixed-salt aqueous solution,
Reaction formula: IDA-2Na+H
3pO
3---IDA-Na+NaH
2pO
3;
(2) mixed-salt aqueous solution obtaining is entered to Bipolar Membrane system, sour district reclaim contain IDA phosphorous acid liquid as PMIDA production source,
Reaction formula: IDA-Na+NaH
2pO
3+ 2H
2o---IDAH
3pO
3+ 2NaOH;
(3) PMIDA production source step (2) being obtained under acid washing conditions with formaldehyde reaction, make product N-((phosphonomethyl)) iminodiethanoic acid,
Reaction formula: IDA+H
3pO
3+ CH
2o---PMIDA+H
2o; The acid of described acidic conditions is hydrochloric acid or sulfuric acid.
The temperature of reaction of step (3) is 105-140 ℃, reaction pressure <0.3MPa, and reaction mass mole proportioning is IDA: H
3pO
3: CH
2o:HCl=1:1.05-1.2:1.1-1.3:0.3-1.5.
By liquid-solid after synthetic PMIDA reaction in step (3), through solid-liquid separation, obtain PMIDA product, mother liquor or washings are directly got back under this reactive system in secondary response, reclaim product wherein and the raw material of complete reaction not; Also can after reaction finishes or in reaction process, steam acid and formalin and be back to lower secondary response.
Reactant molar ratio IDA-2Na:H in step (1)
3pO
3=1:1-1.2, temperature of reaction 20-95 ℃.Step (2) Zhong Jian district recovery NaOH is back to and produces IDA-2Na reaction process.
The present invention has overcome the defect of prior art, and method is easy, easy to operate, is typical process for cleanly preparing.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Synthetic N-((phosphonomethyl)) method for iminodiethanoic acid, comprises the following steps:
(1) iminodiacetic acid disodium salt reacts with phosphorous acid and forms mixed-salt aqueous solution,
Reaction formula: IDA-2Na+H
3pO
3---IDA-Na+NaH
2pO
3; Reactant molar ratio IDA-2Na:H
3pO
3=1:1-1.2, temperature of reaction 20-95 ℃.
Iminodiacetic acid disodium salt NH (CH2COONa) wherein
2(be called for short: IDA-2Na) produce process, its method can adopt one of following two kinds of ordinary methods:
(1) iminodiacetonitrile (be called for short: IDAN) alkaline hydrolysis main reaction formula:
NH(CH
2CN)
2 + 2NaOH + 2H
2O --- NH(CH2COONa)
2 + 2NH
3
(2) diethanolamine (be called for short: DEA) catalytic dehydrogenation method main reaction formula:
NH(CH
2CH
2OH)
2 + 2NaOH + 2H
2O --- NH(CH
2COONa)
2+ 4H
2
The IDA-2Na that makes of reaction through being mixed with (as need to add abandon ionized water method according to the former IDA-2Na concentration making) the 3-15%IDA aqueous solution (in IDA) is by filtration, decolouring is used after except mechanical impurity and basic metal throw out.
The above-mentioned mixed-salt aqueous solution making (in IDA 3-15%) enters lower step after processing and uses through essence filter, the further removal of impurities of ultrafiltration again;
(2) mixed-salt aqueous solution obtaining is entered to Bipolar Membrane system, the 3-15% NaOH that alkali district reclaims is back to and produces IDA-2Na reaction process (being preferably used further to reaction by evaporation concentration to 10-30%), the phosphorous acid liquid that the recovery of acid district contains IDA, as PMIDA production source, more can be usingd IDA 30-50%IDA high concentration liquid (keeping 45-100 ℃ of formation of certain temperature can carry feed liquid) as PMIDA production source through being concentrated into;
Reaction formula: IDA-Na+NaH
2pO
3+ 2H
2o---IDAH
3pO
3+ 2NaOH;
(3) PMIDA production source step (2) being obtained under acidic conditions with formaldehyde reaction, make product N-((phosphonomethyl)) iminodiethanoic acid,
Reaction formula: IDA+H
3pO
3+ CH
2o---PMIDA+H
2o; The acid of described acidic conditions is hydrochloric acid or sulfuric acid.
The temperature of reaction of step (3) is 105-140 ℃, reaction pressure <0.3MPa, and reaction mass mole proportioning is IDA: H
3pO
3: CH
2o:HCl=1:1.05-1.2:1.1-1.3:0.3-1.5.
By liquid-solid after synthetic PMIDA reaction in step (3), through solid-liquid separation, obtain PMIDA product, mother liquor or washings are directly got back under this reactive system in secondary response, reclaim product wherein and the raw material of complete reaction not; Also can after reaction finishes or in reaction process, steam acid and formalin and be back to lower secondary response.
Claims (5)
1. synthetic N-((phosphonomethyl)) method for iminodiethanoic acid, is characterized in that: comprise the following steps:
(1) iminodiacetic acid disodium salt reacts with phosphorous acid and forms mixed-salt aqueous solution,
Reaction formula: IDA-2Na+H
3pO
3---IDA-Na+NaH
2pO
3;
(2) mixed-salt aqueous solution obtaining is entered to Bipolar Membrane system, sour district obtains the phosphorous acid solution of IDA as PMIDA production source,
Reaction formula: IDA-Na+NaH
2pO
3+ 2H
2o---IDAH
3pO
3+ 2NaOH;
(3) PMIDA production source step (2) being obtained under acidic conditions with formaldehyde reaction, make product N-((phosphonomethyl)) iminodiethanoic acid,
Reaction formula: IDA+H
3pO
3+ CH
2o---PMIDA+H
2o; The acid of described acidic conditions is hydrochloric acid or sulfuric acid.
2. synthetic N-((phosphonomethyl) according to claim 1) method of iminodiethanoic acid, is characterized in that: the temperature of reaction of step (3) is 105-140 ℃, reaction pressure <0.3MPa, and reaction mass mole proportioning is IDA:H
3pO
3: CH
2o:HCl=1:1.05-1.2:1.1-1.3:0.3-1.5.
3. the synthetic N-((phosphonomethyl) according to claim 1) method of iminodiethanoic acid, it is characterized in that: by liquid-solid after synthetic PMIDA reaction in step (3), through solid-liquid separation, obtain PMIDA product, mother liquor or washings are directly got back under this reactive system in secondary response, reclaim product wherein and excessive raw material; Also can after reaction finishes or in reaction process, steam acid and formalin and be back to lower secondary response.
4. according to the synthetic N-((phosphonomethyl) described in claim 1,2 or 3) method of iminodiethanoic acid, it is characterized in that: reactant molar ratio IDA-2Na:H in step (1)
3pO
3=1:1-1.2, temperature of reaction 20-95 ℃.
5. according to the synthetic N-((phosphonomethyl) described in claim 1,2 or 3) method of iminodiethanoic acid, it is characterized in that: step (2) Zhong Jian district reclaims NaOH and is back to and produces IDA-2Na reaction process.
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|---|---|---|---|
| CN201210095353.5A CN102633835B (en) | 2012-03-31 | 2012-03-31 | Method for synthetizing N-( phosphonomethyl) iminodiacetic acid |
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|---|---|---|---|
| CN201210095353.5A CN102633835B (en) | 2012-03-31 | 2012-03-31 | Method for synthetizing N-( phosphonomethyl) iminodiacetic acid |
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|---|---|
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| CN102633835B true CN102633835B (en) | 2014-10-29 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609112A (en) * | 2004-05-12 | 2005-04-27 | 江苏好收成韦恩农药化工有限公司 | Production process of N-phosphono methyl imido diacetic acid |
-
2012
- 2012-03-31 CN CN201210095353.5A patent/CN102633835B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609112A (en) * | 2004-05-12 | 2005-04-27 | 江苏好收成韦恩农药化工有限公司 | Production process of N-phosphono methyl imido diacetic acid |
Non-Patent Citations (2)
| Title |
|---|
| IDA路线草甘膦的清洁生产方法和绿色化学合成技术;徐国明 等;《农药》;20071031;第46卷(第10期);656-658 * |
| 徐国明 等.IDA路线草甘膦的清洁生产方法和绿色化学合成技术.《农药》.2007,第46卷(第10期),656-658. |
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