CN1132838C - Process for preparing N,N-diacetate aminomethylene phosphoric acid (diglycerophosphine) - Google Patents
Process for preparing N,N-diacetate aminomethylene phosphoric acid (diglycerophosphine) Download PDFInfo
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- CN1132838C CN1132838C CN00116540A CN00116540A CN1132838C CN 1132838 C CN1132838 C CN 1132838C CN 00116540 A CN00116540 A CN 00116540A CN 00116540 A CN00116540 A CN 00116540A CN 1132838 C CN1132838 C CN 1132838C
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- iminodiacetic acid
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Abstract
The present invention relates to a process for preparing N, N-aminomethylene phosphoric acid diacetate (N-(Phosphonomethyl) iminodiacetic acid). The process comprises the steps that disodium salt of imino diacetic acid is converted into hydrochloride of imino diacetic acid under the conditions of vacuum, low temperature and reflux, and formaldehyde is added under the conditions of normal pressure and reflux so as to generate a phosphoryl methylation reaction to obtain a product. Compared with the prior art, the process of the present invention has the advantages of simplicity, convenient operation, small equipment investment and low energy consumption.
Description
The invention relates to an improved process for preparing N, N-diacetic acid aminomethylene phosphoric acid (also called N-phosphonomethyl iminodiacetic acid).
N, N-diacetic acid amino methylene phosphoric acid (N-phosphonomethyl iminodiacetic acid) is an intermediate for preparing broad-spectrum herbicide glyphosate, more than 95 percent of manufacturers for producing glyphosate in China currently adopt glycine as a raw material to produce the glyphosate, and the route has the advantages of low product quality, overlarge equipment investment and high energy consumption. In US3,288846, the iminodisodium salt is first converted to iminodiacetic acid hydrochloride and then phosphonomethylated with phosphorous acid and formaldehyde, whereas the hydrochloric acid used in US4,724103 and the phosphorous acid undergoing phosphonomethylation are both carried out with phosphorus trichloride and water at reflux temperatures of 110 to 120 ℃. However, this process is difficult to implement in mass production, and persons familiar with the process of phosphorus trichloride products know that the vaporization temperature of phosphorus trichloride is 75.5 ℃, so that most of the above-mentioned reactions are carried out in the vapor phase, and the operation is careless, and it is likely that the vapor phase reaction temperature will be sharply raised to 200 ℃, which is mainly characterized by that in the course of reaction of phosphorus trichloride with water in the vapor phase phosphorous acid and hydrochloric acid are produced, and these two reactions are exothermic reactions, and at this time the produced phosphorous acid can be decomposed into phosphoric acid and phosphine (which is extremely toxic and self-ignited at 100 ℃). Therefore, although the above process is feasible, the operation difficulty is large, so that improvement of the process in operability is an urgent requirement for realization of industrial production.
The invention aims to overcome the defects in the prior art and provide a process for preparing N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl iminodiacetic acid) with simple process and convenient operation.
The object of the invention can be achieved by: a process for preparing N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid comprises dehydrogenating diethanolamine to form the disodium salt of iminodiacetic acid, converting the disodium salt to the hydrochloride salt of iminodiacetic acid, and performing phosphonomethylation to obtain the product N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid represented by the following formula:the method is characterized by comprising the following specific process steps: firstly, adding iminodiacetic acid disodium salt into a reactor, adding phosphorus trichloride under the conditions of vacuum and low-temperature reflux, and directly reacting with moisture in the iminodiacetic acid disodium salt, wherein hydrogen chloride gas generated by the reaction is absorbed by water to be hydrochloric acid, and the hydrochloric acid and the iminodiacetic acid disodium salt are subjected to neutralization reaction and then to addition reaction to obtain hydrochloride of the iminodiacetic acid; secondly, the reactor is switched to normal pressure, formaldehyde is slowly added under the reflux condition to carry out phosphoryl methylation reaction, and stirring and heat preservation are carried out for a period of time; first, theAnd thirdly, adding sodium hydroxide into the reactor, washing with water, filtering to obtain a wet powder product, and drying to obtain a dry powder product.
The vacuum and low-temperature reflux conditions are 200-750 mm Hg, and the vapor phase temperature is lower than the liquid phase temperature.
The molar ratio of the phosphorus trichloride to the iminodiacetic acid disodium salt is 1: 1-2.
The concentration of the iminodiacetic acid disodium salt is 35-48% (by weight).
After the reactor is switched to normal pressure, the concentration of hydrochloric acid in the reactant is not lower than 5 percent (weight).
The concentration of formaldehyde added in the phosphoryl methylation reaction is 30-48% (by weight).
The stirring and heat preservation time is 60-120 minutes.
The invention reduces the steps of producing N- (phosphonomethyl) iminodiacetic acid by the traditional method, wherein phosphorus trichloride and water are reacted to generate a phosphorous acid solution and a dilute hydrochloric acid solution, and then phosphorous acid is crystallized out through concentration and circulation respectively to improve the concentration of hydrochloric acid. In addition, the invention also improves the traditional process, which comprises converting the iminodiacetic acid disodium salt into iminodiacetic acid hydrochloride under the vacuum low-temperature reflux state, and then adding formaldehyde aqueous solution under the normal-temperature reflux condition to carry out phosphoryl methylation reaction; practice proves that the improved process is simple to operate, is not easy to generate flammable, explosive and toxic gases, and is safer in industrial production.
The present invention will be described in more detail with reference to examples.
The PMIDA produced by us is prepared by dehydrogenating diethanolamine to generate iminodiacetic acid disodium salt, and the PMIDA is prepared from the disodium salt. The first step is to put phosphorus trichloride under the conditions of vacuum and low-temperature reflux and directly react with moisture in disodium salt, and the reaction equation is as follows:
hydrogen chloride gas generated by the reaction is absorbed by water to be hydrochloric acid, the generated hydrochloric acid and disodium salt are subjected to neutralization reaction firstly, and then addition reaction is carried out, and the reaction equation is as follows:
the phosphorous acid formed simultaneously here serves as starting material for the phosphonomethylation. In order to reduce the generation of side reactions and improve the yield, the mole number of the phosphorus trichloride and the mole number of the disodium salt are controlled to be 1: 1 to 1: 2. Moreover, according to our experiments, the concentration of disodium salt in the reaction is preferably between 35% and 48% by weight, since below this concentration productivity is reduced and there is no opportunity for some iminodiacetic acid to participate in the reaction; above this concentration, the concentration of the reactants will increase, which may block the feed tube, rendering the hydrolysis reaction of the first step impossible or will make the vapor phase reaction quite violent, thus causing danger. When the reaction of this step is completed, it is immediately brought to normal pressure and it is necessary to add hydrochloric acid at a concentration of 31% by weight, in order to increase the concentration of hydrochloric acid (water only) in the addition reaction product to not less than 5% by weight. If less than 5%, it will not function to mask the side reactions of iminodiacetic acid and formaldehyde, leading to the formation of N-methyliminodiacetic acid which is undesirable for us. Subsequently, 37% by weight of technical formaldehyde was added to the reaction mixture to carry out the phosphonomethylation reaction.
The process can be reflected by the following examples. The pilot experiment was carried out in a 1000ml flask with reflux and stirring, plus a vacuum generator. The industrial production is carried out in a 3000L glass lining reaction kettle, and a stirring condenser and a vacuum pump are also necessary. Wherein the concentrations are weight concentrations.
Example 1
420 g of iminodiacetic acid disodium salt is added into a reactor, and simple titration analysis shows that the concentration of the iminodiacetic acid disodium salt is 41.4%. Vacuum is pumped to 400mmHg, and then 150 g PCl is dripped at the speed of 0.745mol/min3Controlling the reflux temperature, wherein the dripping temperature is 62 ℃ when the dripping is started, and is 78 ℃ when the dripping is finished; the concentration of iminodiacetic acid was 29.12% and the amount of water evaporated was 70 g (300 g water added, 370 g evaporated); then, the mixture is shifted to normal pressure, 60 g of hydrochloric acid with the concentration of 31 percent (weight) is added, 120 g of formaldehyde with the concentration of 37 percent (weight) is uniformly and quickly dripped in 68 minutes, the temperature is controlled, the experimental measurement shows that the temperature is 120 ℃ when the formaldehyde is dripped, 118 ℃ when 40 g is dripped, 114 ℃ when 80 g is dripped, and 114 ℃ when 100 g is dripped; then stirring and keeping the temperature for 90 minutes, and adding 40 g of sodium hydroxide; washing with water and filtering to obtain 261 g of N- (phosphonomethyl) iminodiacetic acid wet powder and 770 g of mother solution; drying to obtain 98.4% dry powder203 g, calculated yield 89.7%.
Example 2
420 gof iminodiacetic acid disodium salt is added into a reactor, and simple titration analysis shows that the concentration of the iminodiacetic acid disodium salt is 37.5%. Vacuum is pumped to 400mmHg, and then 150 g PCl is dripped at the speed of 0.745mol/min3Controlling the reflux temperature, wherein the dripping temperature is 62 ℃ when the dripping is started, and is 78 ℃ when the dripping is finished; then, the concentration of the iminodiacetic acid is 26.8 percent, the iminodiacetic acid is shifted to normal pressure, 20 g of hydrochloric acid with the concentration of 31 percent (weight) is added, 120 g of formaldehyde with the concentration of 37 percent (weight) can be dripped at a uniform speed within 68 minutes, the temperature is controlled, the temperature is measured in experiments, the temperature is 120 ℃ when the formaldehyde is dripped, 118 ℃ when 40 g is dripped, and 115 ℃ when 80 g is dripped; dropping 100 g of the mixture at 114 ℃, stirring and preserving heat for 90 minutes, and adding 40 g of sodium hydroxide; washing with water and filtering to obtain 294 g of PMIDA wet powder and 820 g of mother liquor; and then dried to obtain 188 g of dry powder with the content of 98.4 percent, and the calculated yield is 90.54 percent.
Claims (5)
1. A process for the preparation of N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid comprising the dehydrogenation of diethanolamine to formThe disodium salt of iminodiacetic acid is then converted to the hydrochloride salt of iminodiacetic acid and is then subjected to phosphoryl methylation to yield the N, N-diacetic acid aminomethylene phosphoric acid (pmida) product represented by the following formula:the method is characterized by comprising the following specific process steps: adding iminodiacetic acid disodium salt into a reactor, adding phosphorus trichloride under the conditions of vacuum and low-temperature reflux, directly reacting with moisture in the iminodiacetic acid disodium salt, absorbing hydrogen chloride gas generated by the reaction into hydrochloric acid by water, performing neutralization reaction on the hydrochloric acid and the iminodiacetic acid disodium salt, and then performing addition reaction to obtain hydrochloride of the iminodiacetic acid, wherein the vacuum condition is 200-750 mm Hg, the low-temperature reflux condition is 62-78 ℃, and the vapor phase temperature is lower than the liquid phase temperature; secondly, turning the reactor to normal pressure, slowly adding formaldehyde to carry out phosphoryl methylation reaction under the reflux condition, stirring and preserving heat for a period of time, and adding 31 percent (by weight) of hydrochloric acid after the reactor is turned to normal pressure to ensure that the concentration of the hydrochloric acid in the reactant is not lower than 5 percent (by weight); and thirdly, adding sodium hydroxide into the reactor, washing with water, filtering to obtain a wet powder product, and drying to obtain a dry powder product.
2. The process for preparing N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid according to claim 1, wherein the molar ratio of phosphorus trichloride to iminodiacetic acid disodium salt is 1: 1-2.
3. The process according to claim 1, wherein the concentration of iminodiacetic acid disodium salt is 35 to 48 wt%.
4. The process for preparing N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid according to claim 1, wherein the concentration of formaldehyde added in the said phosphonomethylation reaction is 30-48% by weight.
5. The process for preparing N, N-diacetic acid aminomethylene phosphoric acid (N-phosphonomethyl) iminodiacetic acid according to claim 1, wherein the stirring and holding time is 60-120 minutes.
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| CN00116540A CN1132838C (en) | 2000-06-15 | 2000-06-15 | Process for preparing N,N-diacetate aminomethylene phosphoric acid (diglycerophosphine) |
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| CN00116540A CN1132838C (en) | 2000-06-15 | 2000-06-15 | Process for preparing N,N-diacetate aminomethylene phosphoric acid (diglycerophosphine) |
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| CN1132838C true CN1132838C (en) | 2003-12-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100436460C (en) * | 2005-10-08 | 2008-11-26 | 重庆三峡英力化工有限公司 | Synthetic method for N-phosphonyl methyl imino diacetic acid |
| CN100400543C (en) * | 2006-09-08 | 2008-07-09 | 四川贝尔实业有限责任公司 | Method for preparing Phosphonomethyl iminodiacetic acid (PMIDA) through hydrolysis of imino diacetonitrile |
| WO2012009860A1 (en) * | 2010-07-23 | 2012-01-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phosphonomethyl iminodiacetic acid |
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Assignee: Kaipu Fine Chemical Industry Co., Ltd., Shanghai Assignor: Kaipu Fine Chemical Industry Co., Ltd., Shanghai Contract fulfillment period: 2008.10.1 to 2020.6.15 contract change Contract record no.: 2008330001430 Denomination of invention: Method for preparing N-formyl morpholine Granted publication date: 20031231 License type: Exclusive license Record date: 20081028 |
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