CN102627666A - Method for synthesis of N-(phosphonomethyl) iminodiacetic acid - Google Patents

Method for synthesis of N-(phosphonomethyl) iminodiacetic acid Download PDF

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Publication number
CN102627666A
CN102627666A CN2012100815056A CN201210081505A CN102627666A CN 102627666 A CN102627666 A CN 102627666A CN 2012100815056 A CN2012100815056 A CN 2012100815056A CN 201210081505 A CN201210081505 A CN 201210081505A CN 102627666 A CN102627666 A CN 102627666A
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Prior art keywords
ida
pmida
acid
production source
phosphonomethyl
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刘卫伟
江连
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JIANGSU GOOD HARVEST-WEIEN AGROCHEMICAL Co Ltd
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JIANGSU GOOD HARVEST-WEIEN AGROCHEMICAL Co Ltd
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Abstract

The invention discloses a method for synthesis of N-(phosphonomethyl) iminodiacetic acid. The method comprises steps of: introducing IDA-2Na through a bipolar membrane system to acquire iminodiacetic acid- sodium salt; reacting the obtained IDA-Na with acid for an acidizing reaction to obtain IDA solid as a PMIDA production source a, and separating IDA solid from reactants to obtain a mother liquor; entering the mother liquid into a secondary bipolar membrane system for secondary recovery of 3-15%NaOH, and in an acid region generating IDA-containing acidic solution as a PMIDA production source b or as a replacement of acid used in the acidizing reaction; mixing the PMIDA production source a and the production source b to form a production source C, and blending the production source C into suitable reaction molar ratio (IDA:H3PO3:HCl = 1:1.05-1.2:0.3-1.5) for a PMIDA synthesis reaction; and reacting the production source C with formaldehyde to prepare PMIDA. The invention overcomes the defects of the prior art, is simple, easy to operate, and is a typical clean production technique.

Description

The method of synthetic N-((phosphonomethyl)) iminodiethanoic acid
Technical field
The present invention relates to the method for a kind of synthetic N-((phosphonomethyl)) iminodiethanoic acid.
Background technology
The production technique of N-in the existing technology ((phosphonomethyl)) imino-acetic acid (pmida98 is called for short PMIDA); Main method is to have two kind one to be to be to obtain with the dehydrogenation of diethylolamine alkali with NSC 263496 alkaline hydrolysis deamination two with Iminodiacetic acid sodium salt salt (IDA-2Na) as its acquisition methods of starting raw material; Though all use the acid of a great deal of during it is produced and have a large amount of sodium-chlor association ZL200410014898.4 can solve the difficult point in many production technique, also have the low deficiency that waits of resource utilization.
Existing PMIDA production process reactions step content:
Step 1, Iminodiacetic acid sodium salt salt NH (CH2COONa) 2 (are called for short: IDA-2Na) produce process, main two kinds of its method
(1) NSC 263496 (be called for short: IDAN) alkaline hydrolysis method main reaction formula:
NH(CH 2CN) 2+2NaOH+2H 2O---NH(CH 2COONa) 2+NH 3
(2) diethylolamine (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
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 makes solid IDA and the saliferous mother liquor is further reclaimed IDA or its liquid concentrator and by-product NaCl
The IDA that step 3, usefulness are produced and phosphorous acid, formaldehyde react under acidic conditions and make the PMIDA reaction formula:
NH(CH 2COOH) 2+H 3PO 3+CH 2O---(HO) 2POCH 2N(CH 2COOH) 2+H 2O
The defective of existing working method process system:
1, consumes a large amount of alkali (generally using 32% liquid NaOH) in the production process;
2, use and consume a large amount of big acid (generally using 30% hydrochloric acid) in the production process;
3, the NaCl of a large amount of low values of by-product and can cause with IDA or PMIDA carrying secretly each other in various degree and cause quality product low or it runs off, the 2nd, desalination evaporative desalination difficulty and to produce the high-salt wastewater amount that forms big and the biochemical treatment expense is high.
Summary of the invention
The object of the present invention is to provide that a kind of method is easy, easy to operate, the method for synthetic N-((phosphonomethyl)) iminodiethanoic acid of cleaning.
Technical solution of the present invention is:
The method of a kind of synthetic N-((phosphonomethyl)) iminodiethanoic acid is characterized in that: comprise the following steps:
(1) IDA-2Na obtains iminodiethanoic acid one sodium salt after through a bipolar membrane electrodialysis system, i.e. IDA-Na;
Reaction formula: IDA-2Na+H 2O---IDA-Na+NaOH;
Produce 3-15% NaOH in the alkali district, the acid district produces IDA-Na;
(2) carry out acidification reaction with IDA-Na that obtains and acid and make the IDA solid as PMIDA production source a, reactant obtains mother liquor after telling the IDA solid;
(3) above-mentioned steps (2) mother liquid obtained entering secondary bipolar EDBM system is carried out secondary recovery 3-15%NaOH, and the acid solution that generation contains IDA in the acid district is as PMIDA production source b;
(4) PMIDA production source a is mixed formation production source C with production source b, be used for the PMIDA building-up reactions;
(5) (mol ratio IDA: HCl=1: 0.5-1.5) reaction makes PMIDA at acidic conditions for production source C and formaldehyde.
The 3-15%NaOH that step (1) and step (3) obtain is used to make the IDA-2Na reaction process.
The PMIDA mother liquor recovery set that step (5) makes behind the PMIDA is used for step (5).
In the step (1) IDA-2Na is handled through filtration, decolouring and nanofiltration removal of impurities; IDA-2Na concentration is counted 3-12% with IDA, and control operation pH is minimum to be not less than 3 and to guarantee that the Bipolar Membrane system moves homogeneous phase under 10-45 ℃ of condition.
Acid in the step (2) is HCl, H 2SO 4Or H 3PO 3, or H 3PO 3With HCl, H 2SO 4One of nitration mixture or step (3) in the H that contains IDA that produces 3PO 3Liquid; Use when reactant is told the IDA solid the reaction solution refrigerative method solid IDA that separates out as much as possible, do not have solid phase when making mother liquor get into the Bipolar Membrane system.
H 3PO 3Concentration is that 30-70%, HCl concentration are 5-36%HCl, H 2SO 4Concentration is 20-98%.
Add the used IDA mother liquor pH value of sour ratio method control through adjusting in the step (3) and be 0.5-3, keep not containing the IDA solid and separate out.
Before the synthetic PMIDA of step (4) to PMIDA production source b adopt concentrate earlier after again with production source a Hybrid Heating to keeping forming soluble liquid more than at least 45 ℃.
It is liquid-solid through solid-liquid separation to react the back in the step (5), and PMIDA mother liquor or washings are directly got back to this reactive system; Finishing to steam in back or the reaction process hydrochloric acid in reaction is back in the secondary response with formalin.
Part is used for obtaining PMIDA in the excessive acid of step (5) reaction post neutralization among the 3-15%NaOH that step (1) and step (3) obtain.
The present invention has overcome the defective of prior art, and method is easy, easy to operate, is typical process for cleanly preparing.
Below in conjunction with embodiment the present invention is described further.
Embodiment
The method of a kind of synthetic N-((phosphonomethyl)) iminodiethanoic acid comprises the following steps:
(1) IDA-2Na obtains iminodiethanoic acid one sodium salt after through a bipolar membrane electrodialysis system, i.e. IDA-Na;
Reaction formula: IDA-2Na+H 2O---IDA-Na+NaOH;
Produce 3-15% NaOH in the alkali district, the acid district produces IDA-Na;
(2) carry out acidification reaction with IDA-Na that obtains and acid and make the IDA solid as PMIDA production source a, reactant obtains mother liquor after telling the IDA solid;
Reaction formula: IDA-Na+H 3PO 3---IDA+NaH 2PO 3
(3) the mother liquid obtained entering secondary bipolar of above-mentioned steps (2) film system is carried out secondary recovery 3-15%NaOH, and produce the H that contains IDA in the positive column 3PO 3Liquid is as PMIDA production source b;
Reaction formula: NaH 2PO 3+ H 2O---H 3PO 3+ NaOH;
(4) PMIDA production source a is mixed formation production source C with production source b, be used for the PMIDA building-up reactions;
(5) production source C and formolite reaction make PMIDA;
Reaction formula: IDA+H 3PO 3+ CH 2O---PMIDA+H 2O.
The 3-15%NaOH that step (1) and step (3) obtain is used to make the IDA-2Na reaction process.
The PMIDA mother liquor recovery set that step (5) makes behind the PMIDA is used for step (5).
In the step (1) IDA-2Na is handled through filtration, decolouring and nanofiltration removal of impurities, remove mechanical impurity and basic metal throw out; IDA-2Na concentration is counted 3-12% with IDA, and control operation pH is 3-8, guarantees that the Bipolar Membrane system moves homogeneous phase under 10-45 ℃ of condition.
H in the step (2) 3PO 3Can replace to HCl or H 2SO 4Or H 3PO 3With HCl, H 2SO 4One of nitration mixture or step (3) in the acid solution that contains IDA that produces; Use when reactant is told the IDA solid the reaction solution refrigerative method solid IDA that separates out as much as possible, do not have solid phase when making mother liquor get into the Bipolar Membrane system.
H 3PO 3Concentration is that 30-70%, HCl concentration are 5-36%HCl, H 2SO 4Concentration is 20-98%.
Add the used IDA mother liquor pH value of sour ratio method control through adjusting in the step (3) and be 0.5-3, keep not containing the IDA solid and separate out.
Before the synthetic PMIDA of step (4) to PMIDA production source b adopt concentrate earlier after again with production source a Hybrid Heating to 45 ℃-100 ℃, keep forming soluble liquid.
It is liquid-solid through solid-liquid separation to react the back in the step (5), and PMIDA mother liquor or washings are directly got back to this reactive system; Finishing to steam in back or the reaction process hydrochloric acid in reaction is back in the secondary response with formalin.
Part is used for obtaining PMIDA in the excessive acid of step (5) reaction post neutralization among the 3-15%NaOH that step (1) and step (3) obtain, and small amounts of salts does not influence the mother liquor situation of applying mechanically, and can reduce to apply mechanically time.
The consumption mol ratio of each reactant in the step (2): IDA-Na: H 3PO 3=1: 0.8-1.2, the reaction times is: 10-90 minute; The consumption mol ratio of each reactant in the step 4: IDA: H 3PO 3: CH 2O: HCl=1: 1.05-1.2: 1.1-1.3: 0.3-1.5, the reaction times is insulation 2-5 hour;
Adopting first dehydration by evaporation to concentrate to PMIDA production source b before the synthetic PMIDA in the step (4) makes wherein with H 3PO 3Meter concentration reaches 70%.

Claims (10)

1. the method for a synthetic N-((phosphonomethyl)) iminodiethanoic acid is characterized in that: comprise the following steps:
(1) IDA-2Na obtains iminodiethanoic acid one sodium salt after through a bipolar membrane electrodialysis system, i.e. IDA-Na;
Reaction formula: IDA-2Na+H 2O---IDA-Na+NaOH;
Produce 3-16% NaOH in the alkali district, the acid district produces IDA-Na;
(2) carry out acidification reaction with IDA-Na that obtains and acid and make the IDA solid as PMIDA production source a, reactant obtains mother liquor after telling the IDA solid;
(3) above-mentioned steps (2) mother liquid obtained entering secondary bipolar EDBM system is carried out secondary recovery 3-15% NaOH, and the acid solution that generation contains IDA in the acid district is as PMIDA production source b;
(4) PMIDA production source a is mixed formation production source C with production source b, be used for the PMIDA building-up reactions;
(5) production source C and formaldehyde react under sour condition and make PMIDA.
2. the method for synthetic N-according to claim 1 ((phosphonomethyl)) iminodiethanoic acid is characterized in that: the 3-15% NaOH that step (1) and step (3) obtain is used to make the IDA-2Na reaction process.
3. the method for synthetic N-according to claim 1 ((phosphonomethyl)) iminodiethanoic acid is characterized in that: the PMIDA mother liquor recovery set that step (5) makes behind the PMIDA is used for step (5).
4. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: in the step (1) IDA-2Na is handled through filtration, decolouring or nanofiltration removal of impurities; IDA-2Na concentration is counted 3-12% with IDA, and the minimum pH of control operation is not less than 3 and guarantees that the Bipolar Membrane system moves homogeneous phase under 10-45 ℃ of condition.
5. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: the acid in the step (2) is HCl, H 2SO 4Or H 3PO 3, or H 3PO 3With HCl, H 2SO 4One of nitration mixture or step (3) in the acid solution that contains IDA that produces; Use when reactant is told the IDA solid the reaction solution refrigerative method solid IDA that separates out as much as possible, do not have solid phase when making mother liquor get into the Bipolar Membrane system.
6. the method for synthetic N-according to claim 5 ((phosphonomethyl)) iminodiethanoic acid is characterized in that: H 3PO 3Concentration is that 30-70%, HCl concentration are 5-36%HCl, H 2SO 4Concentration is 20-98%
7. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: add the used IDA mother liquor pH value of sour ratio method control through adjusting in the step (3) and be 0.5-3, keep not containing the IDA solid and separate out.
8. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: before the synthetic PMIDA of step (4) to PMIDA production source b adopt concentrate earlier after again with production source a Hybrid Heating to keeping forming soluble liquid more than at least 45 ℃.
9. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: liquid-solid through solid-liquid separation after will reacting in the step (5), PMIDA mother liquor or washings are directly got back to this reactive system; Finishing to steam in back or the reaction process hydrochloric acid in reaction is back in the secondary response with formalin.
10. according to the method for claim 1,2 or 3 described synthetic N-((phosphonomethyl)) iminodiethanoic acids, it is characterized in that: part is used for obtaining PMIDA in the excessive acid of step (5) reaction post neutralization among the 3-15%NaOH that step (1) and step (3) obtain.
CN2012100815056A 2012-03-23 2012-03-23 Method for synthesis of N-(phosphonomethyl) iminodiacetic acid Pending CN102627666A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098602A (en) * 2014-07-08 2014-10-15 重庆紫光化工股份有限公司 Energy-saving and clean production method of PMIDA
CN104119243A (en) * 2014-07-08 2014-10-29 重庆紫光化工股份有限公司 Iminodiacetic acid energy saving cleaning production method
CN104710319A (en) * 2015-01-22 2015-06-17 重庆紫光化工股份有限公司 Green environmentally-friendly method for combined production of amino acid and analog thereof by using membrane integration technology

Citations (1)

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CN101709064A (en) * 2009-11-13 2010-05-19 安徽广信农化股份有限公司 Process for synthesizing glyphosate

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101709064A (en) * 2009-11-13 2010-05-19 安徽广信农化股份有限公司 Process for synthesizing glyphosate

Non-Patent Citations (1)

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Title
曾小君: "双极性膜电渗析技术在亚氨基二乙酸制备中的应用", 《精细化工》, vol. 19, no. 4, 30 April 2002 (2002-04-30), pages 204 - 207 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098602A (en) * 2014-07-08 2014-10-15 重庆紫光化工股份有限公司 Energy-saving and clean production method of PMIDA
CN104119243A (en) * 2014-07-08 2014-10-29 重庆紫光化工股份有限公司 Iminodiacetic acid energy saving cleaning production method
CN104119243B (en) * 2014-07-08 2016-04-27 重庆紫光化工股份有限公司 A kind of energy-saving clean production method of iminodiethanoic acid
CN104710319A (en) * 2015-01-22 2015-06-17 重庆紫光化工股份有限公司 Green environmentally-friendly method for combined production of amino acid and analog thereof by using membrane integration technology

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Application publication date: 20120808