CN101823973B - Method for separating iminodiacetic acid - Google Patents
Method for separating iminodiacetic acid Download PDFInfo
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- CN101823973B CN101823973B CN 200910096258 CN200910096258A CN101823973B CN 101823973 B CN101823973 B CN 101823973B CN 200910096258 CN200910096258 CN 200910096258 CN 200910096258 A CN200910096258 A CN 200910096258A CN 101823973 B CN101823973 B CN 101823973B
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- 0 **(CNCC(O)=O)=O Chemical compound **(CNCC(O)=O)=O 0.000 description 1
- ADUOYBVIIYZUPP-UHFFFAOYSA-N CC(CNCC(O)=O)=O Chemical compound CC(CNCC(O)=O)=O ADUOYBVIIYZUPP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a method for separating iminodiacetic acid. The method comprises the following steps of: 1) performing acidification reaction of 1 mole of iminodiacetic acid disodium salt source and 1.1 mole of hydrochloric acid or chlorine hydride gas, and controlling the pH of feed liquid to be between 6 and 8 and the reaction temperature to be between 60 and 100 DEG C to obtain solution of iminodiacetic acid monosodium salt; 2) condensing the solution of iminodiacetic acid monosodium salt obtained by the step 1, wherein dehydrating amount accounts for 10 to 50 percent of the feed liquid; cooling and crystallizing the solution to the temperature of between 0 and 30 DEG C, filtering the cooled and crystallized solution to obtain a NaCl crystal and filtrate for later use; 3) adding 1 mole of 36 percent hydrochloric acid or chlorine hydride gas into 1 mole of condensed filtrate to perform secondary acidification reaction, controlling the pH of the feed liquid to be between 1.5and 3.0 and the reaction temperature to be between 30 and 100 DEG C and stirring the mixture at a constant speed to obtain the iminodiacetic acid; and 4) cooling and crystallizing the reacted iminodiacetic acid feed liquid, filtering the cooled and crystallized feed liquid at the temperature of between 0 and 30 DEG C to obtain an IDA solid and IDA primary mother liquor, washing the IDA solid withwater and drying the washed IDA solid. The method has the characteristics of simple preparation process, capability of lowering production cost and improving production efficiency and the like.
Description
Technical field
The present invention relates to a kind of novel method of improved separation iminodiethanoic acid.
Background technology
Glyphosate (glyphosate, N-((phosphonomethyl))-glycine) is a kind of non-selective high-efficiency broad spectrum weedicide, has the characteristics of broad weed-killing spectrum, low toxicity and noresidue.1974, glyphosate was by the at first commercialization of U.S. Monsanto Company.Over more than 30 year, glyphosate is fastest-rising pesticide species in the world always, and has become the pesticide species of global consumption maximum.
The method of producing at present glyphosate is a lot, realizes the two lines that mainly contain of suitability for industrialized production, i.e. two kinds of methods, the one, glycine route, the 2nd, IDA route.The IDA method is divided into diethanolamine method (DEA process) and iminodiacetonitrile method (IDAN method), and reaction obtains identical intermediate Iminodiacetic acid sodium salt salt (DSIDA) to two kinds of methods with alkaline hydrolysis through dehydrogenation.By DSIDA prepare the pmida98 usual method be obtain DSIDA by alkaline hydrolysis after, mineral acid and phosphorous acid source, formaldehyde are added direct reaction in the alkali solution liquid in batches, obtain the pmida98 product after filtration.This method must just can obtain the pmida98 of high density with a large amount of washings, therefore can produce a large amount of waste water.
Chinese patent CN101284847A is souring agent with the vitriol oil, and through two step acidifyings, crystallisation by cooling obtains the IDA solid, and the IDA mother liquor adds in the alkali and the back concentrates, and crystallisation by cooling obtains sodium sulfate salt.There is operational hazards coefficient height in this method, and directly cooling filtration after acidifying, and IDA crystal eduction rate is not high, and yield is low; The IDA mother liquor need add the liquid caustic soda neutralization simultaneously, and reconcentration consumes a large amount of energy consumptions, has improved product cost.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, and provide a kind of technology simple, reduce production costs the new separation iminodiethanoic acid method of enhancing productivity.
The objective of the invention is to finish by following technical solution, this method comprises the steps:
1) Iminodiacetic acid sodium salt Yanyuan and hydrochloric acid or hydrogen chloride gas carry out acidification reaction, and the control material liquid pH is 6～8, obtains iminodiethanoic acid one sodium salt (MSIDA) solution;
2) gained iminodiethanoic acid one sodium salt (MSIDA) solution in the step 1 is concentrated, dehydrating amount accounts for 10%～50% of feed liquid ratio; Crystallisation by cooling is 0～30 ℃, filters, and obtains the NaCl crystal, filtrate for later use;
3) add hydrochloric acid (36%) or hydrogen chloride gas again in concentrated filtrate and carry out the after-souring reaction, the control material liquid pH is between 1.5～3.0, and 30～100 ℃ of temperature of reaction at the uniform velocity stir, and obtain iminodiethanoic acid (IDA);
When 4) completely reacted iminodiethanoic acid (IDA) feed liquid crystallisation by cooling, temperature to 0～30 ℃, filter, obtain IDA solid and IDA original nut liquid, the IDA solid is through water washing, oven dry;
The principal reaction equation is:
1) acidifying
2) after-souring
The Iminodiacetic acid sodium salt salt that iminodiethanoic acid disodium Yanyuan makes for the diethanolamine dehydrogenation in the described step 1) perhaps is the Iminodiacetic acid sodium salt salt that raw material makes with the iminodiacetonitrile.The hydrochloric acid (folding hundred) that an acidifying is used and the molar ratio of Iminodiacetic acid sodium salt salt (folding hundred) are 0.9-1.2: 1; The used hydrochloric acid of acidifying in the after-souring (folding hundred) is 0.9-1.2 with the molar ratio of iminodiethanoic acid one sodium salt (folding hundred): 1.
The original nut liquid of IDA described in the step 4) is formed the IDA mother liquor with washing water, adds alkali, and regulating pH is 6～8, obtain being rich in the feed liquid of iminodiethanoic acid one sodium salt (MSIDA), 2 steps of recycled to the concentrate, in order to take out the NaCl crystal more, reduce wastewater flow rate, saved the steam energy consumption;
After the step acidifying obtains MSIDA, concentrating among the present invention, can not only take full advantage of the heat energy of acidification reaction, saving energy consumption greatly, and the removal sodium chloride salt of energy maximum efficiency; Simultaneously, according to the difference of MSIDA and NaCl salt solubility, by concentration process, when removing NaCl salt, improved the concentration (be concentrated into saturation solubility near MSIDA) of MSIDA in feed liquid; The raising of concentration is conducive to the raising of after-souring reaction efficiency, has further improved yield and the content value of IDA.
In addition, the present invention adopts hydrochloric acid as souring agent, efficiently solves sulfuric acid as the dangerous problem of souring agent in reaction, has reduced production cost; In addition, when using sulfuric acid as souring agent, produce in the IDA product that obtains and contain sodium sulfate salt, it is bigger to influence yield in follow-up synthetic pmida98 process, uses sodium chloride salt then to influence less.
Feed liquid is after after-souring is adjusted to iso-electric point behind the desalination in addition, and IDA carries out crystallization at normal temperatures, and 10～20 ℃ can be finished to filter, easy to operate, and IDA yield, content are higher.The present invention has improved the unit productive rate of IDA solid, and has reduced the generation of wastewater flow rate, has saved the steam energy consumption, therefore, is a kind of method of feasible suitability for industrialized production iminodiethanoic acid.Technology is simple, reduces production costs, and enhances productivity.
Embodiment
Be elaborated below in conjunction with the invention of embodiment, in order to understand content of the present invention better.
Method of the present invention comprises the steps: 1) Iminodiacetic acid sodium salt Yanyuan and hydrochloric acid or hydrogen chloride gas carry out acidification reaction, and the control material liquid pH is 6～8, and 60～100 ℃ of temperature of reaction obtain iminodiethanoic acid one sodium salt solution; 2) gained iminodiethanoic acid one sodium salt solution in the step 1 is concentrated, dehydrating amount accounts for 10%～50% of feed liquid ratio; In 0～30 ℃ of following crystallisation by cooling, filtration, obtain the NaCl crystal, filtrate for later use; 3) in concentrated filtrate, add 36% hydrochloric acid or hydrogen chloride gas again and carry out the after-souring reaction, control material liquid pH between 1.5～3.0,30～100 ℃ of temperature of reaction, preferred 60-90 ℃, at the uniform velocity stir, obtain iminodiethanoic acid; When 4) completely reacted iminodiethanoic acid feed liquid crystallisation by cooling, temperature to 0～30 ℃, filter, obtain IDA solid and IDA original nut liquid, the IDA solid is through water washing, oven dry;
An acidifying principal reaction equation in the described step 1) is:
After-souring principal reaction equation in the described step 3) is:
The Iminodiacetic acid sodium salt salt that iminodiethanoic acid disodium Yanyuan makes for the diethanolamine dehydrogenation in the step 1) of the present invention perhaps is the Iminodiacetic acid sodium salt salt that raw material makes with the iminodiacetonitrile.
IDA original nut liquid described in the described step 4) is formed the IDA mother liquor with washing water, adds alkali, and regulating pH is 6～8, obtain being rich in the feed liquid of iminodiethanoic acid one sodium salt (MSIDA), and recycled is to step 2) in concentrate.
Embodiment 1 iminodiacetonitrile and water, sodium hydroxide reaction base solution obtain the DSIDA feed liquid 300g of 44% left and right sides mass concentration, at the uniform velocity stir, and 70～90 ℃ of temperature at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g, and the control material liquid pH is 6～8, makes fully to obtain MSIDA; Carry out concentrating under reduced pressure, distill out waste water 90.2g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 2 7.7g (content 〉=99.0%), filtrate 271.5g; Filtrate is put to flask, drip 36% concentrated hydrochloric acid 72.0g, the control material liquid pH is reacted 1.5～3.0; Drip and finish 40～80 ℃ of insulations in back 0.5h, make fully to obtain IDA; Finish to be cooled to 10～20 ℃, filter, add 80.0g water and wash, oven dry obtains IDA dry product 88.6g (content 98.3%), dry product yield 87.8%; Collect IDA mother liquor 313.2g, add solid caustic soda 2.5g (〉=98.0%), neutralization, adjusting material liquid pH to 6～8 fully obtain MSIDA feed liquid 315.7g, and are standby.
Embodiment 2
1) at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g in 44% DSIDA feed liquid 300g (70～90 ℃ of temperature), the control material liquid pH is 6～8, makes fully to obtain MSIDA;
2) carry out concentrating under reduced pressure, add MSIDA feed liquid 315.7g in the example 1; Distill out waste water 240.0g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 86.4g (content 〉=99.0%), filtrate 365.5g;
3) filtrate is put to flask, drip 36% concentrated hydrochloric acid 80.5g, the control material liquid pH is reacted 1.5～3.0; After dripping end, 40～80 ℃ of insulation 0.5h make fully to obtain IDA;
4) finish to be cooled to 10～20 ℃, filter, add 85.0g water and wash, oven dry obtains IDA dry product 100.2g (content 98.3%), dry product yield 88.5%;
5) collect IDA mother liquor 359.7g, add solid caustic soda 2.9g (〉=98.0%), neutralization, adjusting material liquid pH to 6～8 fully obtain MSIDA feed liquid 362.6g, and are standby.
Embodiment 3
1) at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g in 44% DSIDA feed liquid 300g (70～90 ℃ of temperature), the control material liquid pH is 6～8, makes fully to obtain MSIDA;
2) carry out concentrating under reduced pressure, add MSIDA feed liquid 362.6g in the example 2, distill out waste water 295.6g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 102.4g (content 〉=98.5%), filtrate 370.6g;
3) filtrate is put to flask, drip 36% concentrated hydrochloric acid 82.2g, the control material liquid pH is reacted 1.5～3.0; After dripping end, 40～80 ℃ of insulation 0.5h make fully to obtain IDA;
4) finish to be cooled to 10～20 ℃, filter, add 88.0g water and wash, oven dry obtains IDA dry product 100.9g (content 98.1%), dry product yield 88.4%;
5) collect IDA mother liquor 366.2g, add solid caustic soda 3.0g (〉=98.0%), neutralization, adjusting material liquid pH to 6～8 fully obtain MSIDA feed liquid 369.2g, and are standby.
Embodiment 4
1) at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g in 44% DSIDA feed liquid 300g (70～90 ℃ of temperature), the control material liquid pH is 6～8, makes fully to obtain MSIDA;
2) carry out concentrating under reduced pressure, add MSIDA feed liquid 369.2g in the example 3, concentrate out waste water 303.3g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 100.3g (content 〉=98.0%), filtrate 365.6g;
3) filtrate is put to flask, drip 36% concentrated hydrochloric acid 81.0g, the control material liquid pH is reacted 1.5～3.0; After dripping end, 40～80 ℃ of insulation 0.5h make fully to obtain IDA;
4) finish to be cooled to 10～20 ℃, filter, add 85.0g water and wash, oven dry obtains IDA dry product 104.1g (content 98.0%), dry product yield 91.0%;
5) collect IDA mother liquor 370.6g, add solid caustic soda 3.1g (〉=98.0%), neutralization, adjusting material liquid pH to 6～8 fully obtain MSIDA feed liquid 373.7g, and are standby.
Embodiment 5
1) at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g in 44% DSIDA feed liquid 300g (70～90 ℃ of temperature), the control material liquid pH is 6～8, makes fully to obtain MSIDA;
2) carry out concentrating under reduced pressure, add MSIDA feed liquid 373.7g in the example 4; Distill out waste water 313.5g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 92.0g (content 〉=98.0%), filtrate 367.0g;
3) filtrate is put to flask, drip 36% concentrated hydrochloric acid 81.5g, the control material liquid pH is reacted 1.5～3.0; After dripping end, 40～80 ℃ of insulation 0.5h make fully to obtain IDA;
4) finish to be cooled to 10～20 ℃, filter, add 85.0g water and wash, oven dry obtains IDA dry product 104.8g (content 97.9%), dry product yield 93.8%;
5) collect IDA mother liquor 382.6g, add solid caustic soda 3.3g (〉=98.0%), neutralization, adjusting material liquid pH to 6～7 fully obtain MSIDA feed liquid 385.9g, and are standby.
Embodiment 6
1) at the uniform velocity drip 36% concentrated hydrochloric acid 80.0g in 44% DSIDA feed liquid 300g (70～90 ℃ of temperature), the control material liquid pH is 6～8, makes fully to obtain MSIDA;
2) carry out concentrating under reduced pressure, add MSIDA feed liquid 385.9g in the example 5; Distill out waste water 333.9g; Feed liquid crystallisation by cooling to 20 ℃, filtration washing obtains NaCl crystal 101.2g (content 97.9%), filtrate 345.5g;
3) filtrate is put to flask, intensification limit, limit drips 36% concentrated hydrochloric acid 80.0g, and the control material liquid pH is reacted 1.5～3.0; After dripping end, 40～80 ℃ of insulation 0.5h make fully to obtain IDA;
4) finish to be cooled to 10～20 ℃, filter, add 85.0g water and wash, oven dry obtains IDA dry product 100.8g (content 97.8%), dry product yield 93.0%;
5) collect IDA mother liquor 351.2g, add solid caustic soda 2.8g (〉=98.0%), neutralization, adjusting material liquid pH to 6～7 fully obtain MSIDA feed liquid 354.0g, in order to applying mechanically to following batch of test.
Although above the specific embodiment of the present invention has been given to describe in detail and explanation; but what should indicate is; we can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; when its function that produces does not exceed spiritual that specification sheets and accompanying drawing contain yet, all should be within protection scope of the present invention.
Claims (2)
1. one kind is separated the iminodiethanoic acid method, this method comprises the steps: 1) 1 mole of Iminodiacetic acid sodium salt Yanyuan and 0.9-1.2 mole hydrochloride or hydrogen chloride gas carry out acidification reaction, the control material liquid pH is 6-8, obtain iminodiethanoic acid one sodium salt solution, the Iminodiacetic acid sodium salt salt that the Iminodiacetic acid sodium salt Yanyuan makes for the diethanolamine dehydrogenation;
2) gained iminodiethanoic acid one sodium salt solution in the step 1) is concentrated, dehydrating amount accounts for the 10%-50% of feed liquid ratio; In 0-30 ℃ of following crystallisation by cooling, filtration, obtain the NaCl crystal, filtrate for later use;
3) add 0.9-1.2 mole 36% hydrochloric acid or hydrogen chloride gas again in 1 mole of concentrated filtrate and carry out the after-souring reaction, the control material liquid pH is between 1.5-3.0, and average rate stirs, and obtains iminodiethanoic acid;
4) completely reacted iminodiethanoic acid feed liquid crystallisation by cooling, temperature filter to 0-30 ℃, obtain IDA solid and IDA original nut liquid, and the IDA solid is through water washing, oven dry;
An acidifying principal reaction equation in the described step 1) is:
After-souring principal reaction equation in the described step 3) is:
2. separation iminodiethanoic acid method according to claim 1, it is characterized in that IDA original nut liquid described in the described step 4) and washing water composition IDA mother liquor, add alkali, regulating pH is 6-8, obtain being rich in the feed liquid of iminodiethanoic acid one sodium salt, and recycled is to step 2) in concentrate.
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| CN 200910096258 CN101823973B (en) | 2009-03-02 | 2009-03-02 | Method for separating iminodiacetic acid |
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| CN 200910096258 CN101823973B (en) | 2009-03-02 | 2009-03-02 | Method for separating iminodiacetic acid |
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| CN101823973B true CN101823973B (en) | 2013-09-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613615B (en) * | 2013-12-12 | 2016-08-17 | 重庆紫光化工股份有限公司 | A kind of preparation method of PMIDA |
| CN103613617B (en) * | 2013-12-12 | 2016-06-29 | 重庆紫光化工股份有限公司 | A kind of preparation method of PMIDA |
| CN103709055A (en) * | 2013-12-24 | 2014-04-09 | 重庆紫光化工股份有限公司 | Separation method of iminodiacetic acid |
| CN107501109A (en) * | 2017-07-17 | 2017-12-22 | 南通光荣化工有限公司 | A kind of iminodiacetic acid (salt) acid treating Preparation Method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
| CN101284847A (en) * | 2008-05-20 | 2008-10-15 | 捷马化工股份有限公司 | Production method of N-phosphono methyliminodiacetic acid |
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2009
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
| CN101284847A (en) * | 2008-05-20 | 2008-10-15 | 捷马化工股份有限公司 | Production method of N-phosphono methyliminodiacetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 陈中峻等.亚氨基二乙酸合成工艺.《化工时刊》.2005,第19卷(第2期),第57-58页. * |
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