CN101284847B - Production method of N-phosphono methyliminodiacetic acid - Google Patents
Production method of N-phosphono methyliminodiacetic acid Download PDFInfo
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- CN101284847B CN101284847B CN2008100616361A CN200810061636A CN101284847B CN 101284847 B CN101284847 B CN 101284847B CN 2008100616361 A CN2008100616361 A CN 2008100616361A CN 200810061636 A CN200810061636 A CN 200810061636A CN 101284847 B CN101284847 B CN 101284847B
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Abstract
The invention discloses a method for manufacturing N-phosphonomethyliminodiacetic acid (PMIDA). The method comprises the following steps: (1) IDA disodium salt source is reacted with sulphuric acid to obtain IDA monosodium salt solution; (2) the IDA monosodium salt solution is then reacted with sulphuric acid to separate out iminodiacetic acid (IDA), and reaction mother liquor is treated by liquid alkali to obtain Na2SO4 after evaporated dehydration; moreover, the mother liquor is treated as the raw material of the step (2); (3) the IDA is mixed with phosphorous acid and formaldehyde to generate PMIDA through reaction under the condition of sulphuric acid, wherein the PMIDA is obtained through cooling crystallization and filtration after formaldehyde-containing waste water is separated through evaporation; the mother liquor is treated as the raw material of PMIDA; the formaldehyde-containing waste water separates concentrated and reclaimed concentrated formaldehyde through a pervaporation membrane separating device, and the separated concentrated formaldehyde is treated as formaldehyde raw material; and discharged water is used for reclaimed water recovery after resin treatment. The invention reclaims the byproduct of Na2SO4 and makes effective use of resources such as PMIDA, IDA, formaldehyde, sulphuric acid and water in the production waste water of PMIDA.
Description
Technical field
The present invention relates to a kind of working method of N-phosphonomethyliminoacidetic acidetic, more particular is with the pmida98 in the waste water that produces in N-phosphonomethyliminoacidetic acidetic (pmida98) production process, sulfuric acid, formaldehyde, water, the iminodiethanoic acid of complete reaction (IDA) and by-product sodium sulfate are not recycled.
Background technology
Pmida98 is a precursor of producing the broad-spectrum herbicide Glyphosate 62 IPA Salt.Present working method mainly contains three kinds: a kind of be as in the CN1132838C patent with dripping phosphorus trichloride in the Iminodiacetic acid sodium salt salt, generate pmida98 with formolite reaction again.Second kind be as in the CN1221557C patent with Iminodiacetic acid sodium salt salt and inorganic acid reaction direct midbody Iminodiacetic acid sodium salt salt inorganic acid salt, generate pmida98 with phosphorous acid source, formolite reaction again.The third is to make iminodiethanoic acid like iminodiethanoic acid disodium salt and hydrochloric acid reaction in the CN1283646C patent, and iminodiethanoic acid, phosphorous acid, formaldehyde hybrid reaction are generated pmida98.Above several method finishes to add alkali (preferred NaOH) in reaction and neutralizes or dewater and separate out pmida98, again through separate, washing obtains finished product, exists that quantity of alkali consumption is big, pollutent is many, wastewater flow rate is big and shortcoming such as biodegradability difference; And the reaction mother liquor complicated component, not Separation and Recovery utilizations of useful component such as a large amount of mineral acids that contain, salt, formaldehyde, residual pmida98, IDA, it is few even can't apply mechanically that Recycling Mother Solution is applied mechanically number of times.These deficiencies make the production of pmida98 face more and more serious environmental issue.
Summary of the invention
The objective of the invention is provides a kind of working method of N-phosphonomethyliminoacidetic acidetic in order to solve the problem of above existence.
The working method of N-phosphonomethyliminoacidetic acidetic comprises the steps:
1) with 1mol Iminodiacetic acid sodium salt Yanyuan and 0.4～0.7mol sulfuric acid reaction, control pH value is 5～8, separates obtaining iminodiethanoic acid one sodium salt solution;
2) 1mol iminodiethanoic acid one sodium salt is separated out iminodiethanoic acid with 0.4～0.7mol sulfuric acid reaction to iso-electric point again; Controlled temperature obtains the solid iminodiethanoic acid 32～50 ℃ of separation; Reaction mother liquor neutralizes with liquid caustic soda; Control pH value is 5～8, dehydration by evaporation, and controlled temperature obtains Na 0～30 ℃ of separation
2SO
410H
2O and the mother liquor that is rich in iminodiethanoic acid, the mother liquor that is rich in iminodiethanoic acid recycles as above-mentioned iminodiethanoic acid one sodium salt solution raw material;
3) 1mol solid iminodiethanoic acid mixes with 1～1.5mol phosphorous acid, 1～1.5mol formaldehyde, 2～5mol material water gaging; Reaction generates the N-phosphonomethyliminoacidetic acidetic in the presence of 0.5～1.0mol sulfuric acid; Evaporative condenser reclaims formaldehyde-containing wastewater; Crystallisation by cooling, separation obtain the N-phosphonomethyliminoacidetic acidetic and are rich in N-phosphonomethyliminoacidetic acidetic mother liquor; The mother liquor that is rich in the N-phosphonomethyliminoacidetic acidetic recycles as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic; The formaldehyde-containing wastewater that evaporative condenser reclaims separates the concentrated formaldehyde that concentrates recovery through the infiltration evaporation membrane separation unit and recycles as above-mentioned formaldehyde raw material, and the waste water of discharge control formaldehyde mass percent concentration after the primary amine resin exchange is not more than 50ppm, water reuse in carrying out.
Iminodiethanoic acid disodium Yanyuan makes Iminodiacetic acid sodium salt salt for the diethylolamine dehydrogenation in the said step 1), or is the Iminodiacetic acid sodium salt salt that raw material makes with the NSC 263496.Step 1) and step 2) in used sulfuric acid mass percent concentration be 30%～98%.Step 2) controlled temperature that separation obtains the solid iminodiethanoic acid in is at 36～42 ℃; Step 2) separates in and obtain Na
2SO
410H
2The controlled temperature of O and the mother liquor that is rich in iminodiethanoic acid is at 5～10 ℃.Step 2) liquid caustic soda is that mass percent concentration is 32% sodium hydroxide solution in.Step 2) mother liquor that is rich in iminodiethanoic acid in recycles 2～30 times as above-mentioned iminodiethanoic acid one sodium salt solution raw material.The mother liquor that is rich in the N-phosphonomethyliminoacidetic acidetic in the step 3) recycles 2～30 times as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic.It is 18%～37% that the formaldehyde-containing wastewater that evaporative condenser reclaims in the step 3) separates the concentrated formaldehyde mass percent concentration that concentrates recovery through the infiltration evaporation membrane separation unit.The formaldehyde-containing wastewater that evaporative condenser reclaims in the step 3) separates the waste water of discharging through the infiltration evaporation membrane separation unit and controls the formaldehyde mass percent concentration less than 0.1%.
The present invention utilizes Na
2SO
4More than 32 ℃ in water solubleness bigger, and less with temperature rising changes in solubility; And below 32 ℃ the time, Na
2SO
4Solubility with temperature descends and sharply to diminish in water, after the supersaturation with Na
2SO
410H
2The characteristic that the O form is separated out, effectively separate solid IDA and by product Na
2SO
410H
2O, thus realized recycling of IDA mother liquor, reduce three waste discharge, improve the IDA yield, cut down the consumption of energy.
The present invention is blended in sulfuric acid with solid IDA and phosphorous acid, formaldehyde, water again and has down that reaction generates pmida98, and evaporative condenser reclaims formaldehyde-containing wastewater, crystallisation by cooling separate pmida98, reaction mother liquor recycles as the raw material of above-mentioned pmida98.The formaldehyde-containing wastewater of above-mentioned evaporative condenser recovery separates concentrated through the infiltration evaporation membrane separation unit, the concentrated formaldehyde of recovered overhead recycles as the formaldehyde raw material, and the waste water that the tower still is discharged carries out middle water reuse after the primary amine resin exchange.It is complicated that foregoing invention has overcome pmida98 mother liquor component, and useful component is difficult to the shortcoming that Separation and Recovery is utilized, and has realized the resource utilization maximization, realizes the zero release of waste liquid basically.
Embodiment
The working method of N-phosphonomethyliminoacidetic acidetic comprises the steps:
1) with 1mol Iminodiacetic acid sodium salt Yanyuan and 0.4～0.7mol sulfuric acid reaction, control pH value is 5～8, separates obtaining iminodiethanoic acid one sodium salt solution;
2) 1mol iminodiethanoic acid one sodium salt is separated out iminodiethanoic acid with 0.4～0.7mol sulfuric acid reaction to iso-electric point again; Controlled temperature obtains the solid iminodiethanoic acid 32～50 ℃ of separation; Reaction mother liquor neutralizes with liquid caustic soda; Control pH value is 5～8, dehydration by evaporation, and controlled temperature obtains Na 0～30 ℃ of separation
2SO
410H
2O and the mother liquor that is rich in iminodiethanoic acid, the mother liquor that is rich in iminodiethanoic acid recycles as above-mentioned iminodiethanoic acid one sodium salt solution raw material;
3) 1mol solid iminodiethanoic acid mixes with 1～1.5mol phosphorous acid, 1～1.5mol formaldehyde, 2～5mol material water gaging; Reaction generates the N-phosphonomethyliminoacidetic acidetic in the presence of 0.5～1.0mol sulfuric acid; Evaporative condenser reclaims formaldehyde-containing wastewater; Crystallisation by cooling, separation obtain the N-phosphonomethyliminoacidetic acidetic and are rich in N-phosphonomethyliminoacidetic acidetic mother liquor; The mother liquor that is rich in the N-phosphonomethyliminoacidetic acidetic recycles as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic; The formaldehyde-containing wastewater that evaporative condenser reclaims separates the concentrated formaldehyde that concentrates recovery through the infiltration evaporation membrane separation unit and recycles as above-mentioned formaldehyde raw material, and the waste water of discharge control formaldehyde mass percent concentration after the primary amine resin exchange is not more than 50ppm, water reuse in carrying out.
Iminodiethanoic acid disodium Yanyuan makes Iminodiacetic acid sodium salt salt for the diethylolamine dehydrogenation in the said step 1), or is the Iminodiacetic acid sodium salt salt that raw material makes with the NSC 263496.Step 1) and step 2) in used sulfuric acid mass percent concentration be 30%～98%.Step 2) controlled temperature that separation obtains the solid iminodiethanoic acid in is at 36～42 ℃; Step 2) separates in and obtain Na
2SO
410H
2The controlled temperature of O and the mother liquor that is rich in iminodiethanoic acid is at 5～10 ℃.Step 2) liquid caustic soda is that mass percent concentration is 32% sodium hydroxide solution in.Step 2) mother liquor that is rich in iminodiethanoic acid in recycles 2～30 times as above-mentioned iminodiethanoic acid one sodium salt solution raw material.The mother liquor that is rich in the N-phosphonomethyliminoacidetic acidetic in the step 3) recycles 2～30 times as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic.It is 18%～37% that the formaldehyde-containing wastewater that evaporative condenser reclaims in the step 3) separates the concentrated formaldehyde mass percent concentration that concentrates recovery through the infiltration evaporation membrane separation unit.The formaldehyde-containing wastewater that evaporative condenser reclaims in the step 3) separates the waste water of discharging through the infiltration evaporation membrane separation unit and controls the formaldehyde mass percent concentration less than 0.1%.
Method described in the invention can be carried out multiple combination, does not do the limit explanation in the present invention, also should be included within the present invention even the processing scheme of on basis of the present invention, being done is different from embodiment.
Below in conjunction with embodiment the present invention is done further elaboration.
Embodiment 1 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 802g, and the IDA mass percent concentration is 25.54%.
Be furnished with at 1L and add IDA one sodium salt solution for preparing in the 802g above-mentioned steps in the flask of reflux and stirring; The dropping mass percent concentration is 50% sulfuric acid 165g in 1 hour, is incubated 2 hours, 34 ℃ of controlled temperature; Filtering separation, dry 186g solid IDA (the IDA mass percent concentration is 95.20%; Is 86.45% from IDA one sodium salt solution to solid IDA yield) and 750g mother liquor, it is that 32% liquid caustic soda 65g neutralizes that mother liquor adds mass percent concentration, concentrates water 170g; The cooling crystallisation by cooling obtains 520g Na in 2 ℃ of filtering separation
2SO
410H
2O and 121g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 140g solid IDA (1mol) that makes in the above-mentioned steps and 100g water, 85g mass percent concentration in the flask of reflux and stirring be that 50% phosphorous acid, mass percent concentration are 98% sulfuric acid 100g; Be warmed up to backflow; In 1 hour, drip mass percent concentration and be 37% formaldehyde 122g, continue reaction 1 hour.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 160g.Cooling crystallisation by cooling, filtration, oven dry obtain the 230g pmida98, and (the pmida98 mass percent concentration is 95.12%; Is 96.21% from solid IDA to solid pmida98 yield); Pmida98 mother liquor 130g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 160g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 7.81%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 35.80% formaldehyde solution 35g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.08% waste water 124g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 38ppm, water reuse in can carrying out.
Embodiment 2 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 799g, and the IDA mass percent concentration is 25.63%.
Is furnished with the 121gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 799g above-mentioned steps in the flask of reflux and stirring and embodiment 1 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 36 ℃ of controlled temperature; Filter, dry 205g solid IDA (the IDA mass percent concentration is 96.58%; Is 96.68% from IDA one sodium salt solution to solid IDA yield) and 875g mother liquor, it is that 32% liquid caustic soda 80g neutralizes that mother liquor adds mass percent concentration, concentrates water 220g; The cooling crystallisation by cooling obtains 572g Na in 4 ℃ of filtering separation
2SO
410H
2O and 150g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 138g solid IDA (1mol), 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 130g embodiment 1; Be warmed up to backflow; In 1 hour, drip mass percent concentration and be the 35g formaldehyde that 37% 89g formaldehyde and embodiment 1 reclaim, continue reaction 1 hour.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 156g.The cooling crystallisation by cooling; Filtration, oven dry obtain the 233g pmida98, and (the pmida98 mass percent concentration is 95.42%; Is 97.77% from solid IDA to solid pmida98 yield), pmida98 mother liquor 132g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 156g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 8.03%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 32.12% formaldehyde solution 38g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.06% waste water 116g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 18ppm, water reuse in can carrying out.
Embodiment 3 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 800g, and the IDA mass percent concentration is 25.58%.
Is furnished with the 150gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 800g above-mentioned steps in the flask of reflux and stirring and embodiment 2 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 38 ℃ of controlled temperature; Filter, dry 208g solid IDA (the IDA mass percent concentration is 95.08%; Is 96.64% from IDA one sodium salt solution to solid IDA yield) and 921g mother liquor, it is that 32% liquid caustic soda neutralizes that mother liquor adds the 80g mass percent concentration, concentrates water 270g; The cooling crystallisation by cooling obtains 568g Na in 6 ℃ of filtering separation
2SO
410H
2O and 148g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 140g solid IDA (1mol), 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 132g embodiment 2; Be warmed up to backflow; In 2 hours, drip mass percent concentration and be the 38g formaldehyde that 37% 89g formaldehyde and embodiment 2 reclaim, continue reaction 2 hours.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 162g.The cooling crystallisation by cooling; Filtration, oven dry obtain the 229g pmida98, and (the pmida98 mass percent concentration is 97.15%; Is 97.96% from solid IDA to solid pmida98 yield), pmida98 mother liquor 135g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 162g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 8.33%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 28.62% formaldehyde solution 47g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.08% waste water 113g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 32ppm, water reuse in can carrying out.
Embodiment 4 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 796g, and the IDA mass percent concentration is 25.73%.
Is furnished with the 148gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 796g above-mentioned steps in the flask of reflux and stirring and embodiment 3 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 40 ℃ of controlled temperature; Filter, dry 206g solid IDA (the IDA mass percent concentration is 95.78%; Is 96.33% from IDA one sodium salt solution to solid IDA yield) and 902g mother liquor, it is that 32% liquid caustic soda neutralizes that mother liquor adds the 80g mass percent concentration, concentrates water 262g; The cooling crystallisation by cooling obtains 560g Na in 8 ℃ of filtering separation
2SO
410H
2O and 151g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 139g solid IDA (1mol), 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 135g embodiment 3; Be warmed up to backflow; In 3 hours, drip mass percent concentration and be mass percent concentration that 37% 89g formaldehyde and embodiment 3 reclaim and be 28.62% formaldehyde solution 47g, continue reaction 2 hours.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 166g.The cooling crystallisation by cooling; Filtration, oven dry obtain 230g pmida98 solid, and (the pmida98 mass percent concentration is 97.42%; Is 98.64% from solid IDA to solid pmida98 yield), pmida98 mother liquor 135g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 166g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 8.20%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 24.21% formaldehyde solution 56g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.09% waste water 110g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 22ppm, water reuse in can carrying out.
Embodiment 5 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 801g, and the IDA mass percent concentration is 25.64%.
Is furnished with the 151gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 801g above-mentioned steps in the flask of reflux and stirring and embodiment 4 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 42 ℃ of controlled temperature; Filter, dry 204g solid IDA (the IDA mass percent concentration is 96.37%; Is 95.72% from IDA one sodium salt solution to solid IDA yield) and 909g mother liquor, it is that 32% liquid caustic soda neutralizes that mother liquor adds the 80g mass percent concentration, concentrates water 271g; The cooling crystallisation by cooling obtains 555g Na in 10 ℃ of filtering separation
2SO
410H
2O and 148g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 138g solid IDA (1mol), 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 135g embodiment 4; Be warmed up to backflow; In 3 hours, drip mass percent concentration and be mass percent concentration that 37% 89g formaldehyde and embodiment 4 reclaim and be 24.21% formaldehyde solution 56g, continue reaction 2 hours.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 170g.The cooling crystallisation by cooling; Filtration, oven dry obtain 229g pmida98 solid, and (the pmida98 mass percent concentration is 97.66%; Is 98.56% from solid IDA to solid pmida98 yield), pmida98 mother liquor 134g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 170g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 8.00%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 20.60% formaldehyde solution 66g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.09% waste water 102g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 32ppm, water reuse in can carrying out.
Embodiment 6 is furnished with at a 1L and adds the 640hIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 798g, and the IDA mass percent concentration is 25.60%.
Is furnished with the 148gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 798g above-mentioned steps in the flask of reflux and stirring and embodiment 5 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 44 ℃ of controlled temperature; Filter, dry 202g solid IDA (the IDA mass percent concentration is 96.18%; Is 95.10% from IDA one sodium salt solution to solid IDA yield) and 914g mother liquor, it is that 32% liquid caustic soda neutralizes that mother liquor adds the 80g mass percent concentration, concentrates water 266g; The cooling crystallisation by cooling obtains 550g Na in 12 ℃ of filtering separation
2SO
410H
2O and 149g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 138g solid IDA, 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 134g embodiment 5; Be warmed up to backflow; In 3 hours, drip mass percent concentration and be mass percent concentration that 37% 89g formaldehyde and embodiment 5 reclaim and be 20.60% formaldehyde solution 66g, continue reaction 2 hours.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 186g.The cooling crystallisation by cooling; Filtration, oven dry obtain 230g pmida98 solid, and (the pmida98 mass percent concentration is 96.82%; Is 98.33% from solid IDA to solid pmida98 yield), pmida98 mother liquor 136g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 186g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 7.73%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 18.41% formaldehyde solution 77g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.09% waste water 108g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 28ppm, water reuse in can carrying out.
Embodiment 7 is furnished with at a 1L and adds the 640gIDA disodium salt in the flask of stirring, drips mass percent concentration and be 50% sulfuric acid 166g, crosses and filters IDA one sodium salt solution 800g, and the IDA mass percent concentration is 25.66%.
Is furnished with the 149gIDA concentrated mother liquor that IDA one sodium salt solution that adds the preparation of 800g above-mentioned steps in the flask of reflux and stirring and embodiment 6 make at a 1L; 1 hour dropping mass percent concentration is 50% sulfuric acid 190g, insulation crystallization 2 hours, 46 ℃ of controlled temperature; Filter, dry 200g solid IDA (the IDA mass percent concentration is 96.76%; Is 94.27% from IDA one sodium salt solution to solid IDA yield) and 912g mother liquor, it is that 32% liquid caustic soda neutralizes that mother liquor adds the 80g mass percent concentration, concentrates water 286g; The cooling crystallisation by cooling obtains 542g Na in 14 ℃ of filtering separation
2SO
410H
2O and 151g concentrated mother liquor, this mother liquor is used among the next embodiment as above-mentioned IDA one sodium salt solution raw material cover.
Be furnished with at a 1L that to add the 138g solid IDA, 60g water, the 85g mass percent concentration that make in the above-mentioned steps in the flask of reflux and stirring be that 50% phosphorous acid, 10g mass percent concentration are 98% sulfuric acid and the pmida98 mother liquor of 136g embodiment 6; Be warmed up to backflow; In 3 hours, drip mass percent concentration and be mass percent concentration that 37% 89g formaldehyde and embodiment 6 reclaim and be 18.41% formaldehyde solution 77g, continue reaction 2 hours.Carry out concentrating under reduced pressure then, deviate from formaldehyde-containing wastewater 201g.The cooling crystallisation by cooling; Filtration, oven dry obtain 230g pmida98 solid, and (the pmida98 mass percent concentration is 97.12%; Is 98.04% from solid IDA to solid pmida98 yield), pmida98 mother liquor 132g, this mother liquor is used among the next embodiment as the raw material cover of above-mentioned pmida98.Get the formaldehyde-containing wastewater 201g that above-mentioned steps reclaims; The formaldehyde mass percent concentration is 7.15%; Separate to concentrate through the infiltration evaporation membrane separation unit, make the formaldehyde mass percent concentration and be 18.06% formaldehyde solution 78g, go out the formaldehyde mass percent concentration at the bottom of the tower and be 0.09% waste water 120g.This waste water uses primary amine resin to handle in ion exchange column, and the mass percent concentration of processed waste water formaldehyde is 25ppm, water reuse in can carrying out.
Claims (10)
1. the working method of a N-phosphonomethyliminoacidetic acidetic is characterized in that comprising the steps:
1) with 1mol Iminodiacetic acid sodium salt Yanyuan and 0.4～0.7mol sulfuric acid reaction, control pH value is 5～8, separates obtaining iminodiethanoic acid one sodium salt solution;
2) 1mol iminodiethanoic acid one sodium salt is separated out iminodiethanoic acid with 0.4～0.7mol sulfuric acid reaction to iso-electric point again; Controlled temperature obtains the solid iminodiethanoic acid 32～50 ℃ of separation; Reaction mother liquor neutralizes with liquid caustic soda; Control pH value is 5～8, dehydration by evaporation, and controlled temperature obtains Na 0～30 ℃ of separation
2SO
410H
2O and the mother liquor that is rich in iminodiethanoic acid, the mother liquor that is rich in iminodiethanoic acid recycles as above-mentioned iminodiethanoic acid one sodium salt solution raw material;
3) 1mol solid iminodiethanoic acid mixes with 1～1.5mol phosphorous acid, 1～1.5mol formaldehyde, 2～5mol water; Reaction generates the N-phosphonomethyliminoacidetic acidetic in the presence of 0.5～1.0mol sulfuric acid; Evaporative condenser reclaims formaldehyde-containing wastewater; Crystallisation by cooling, separation obtain the N-phosphonomethyliminoacidetic acidetic and are rich in N-phosphonomethyliminoacidetic acidetic mother liquor; The mother liquor that is rich in the N-phosphonomethyliminoacidetic acidetic recycles as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic; The formaldehyde-containing wastewater that evaporative condenser reclaims separates the concentrated formaldehyde that concentrates recovery through the infiltration evaporation membrane separation unit and recycles as above-mentioned formaldehyde raw material, and the waste water of discharge control formaldehyde mass percent concentration after the primary amine resin exchange is not more than 50ppm, water reuse in carrying out.
2. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1; It is characterized in that iminodiethanoic acid disodium Yanyuan makes Iminodiacetic acid sodium salt salt for the diethylolamine dehydrogenation in the said step 1), or be the Iminodiacetic acid sodium salt salt that raw material makes with the NSC 263496.
3. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that said step 1) and step 2) in used sulfuric acid mass percent concentration be 30%～98%.
4. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that said step 2) in separate obtain the solid iminodiethanoic acid controlled temperature at 36～42 ℃.
5. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that said step 2) obtain Na middle the separation
2SO
410H
2The controlled temperature of O and the mother liquor that is rich in iminodiethanoic acid is at 5～10 ℃.
6. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that said step 2) in liquid caustic soda be that mass percent concentration is 32% sodium hydroxide solution.
7. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that said step 2) in the mother liquor that is rich in iminodiethanoic acid recycle 2～30 times as above-mentioned iminodiethanoic acid one sodium salt solution raw material.
8. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1, the mother liquor that it is characterized in that being rich in the said step 3) N-phosphonomethyliminoacidetic acidetic recycles 2～30 times as the raw material of above-mentioned N-phosphonomethyliminoacidetic acidetic.
9. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that the formaldehyde-containing wastewater that evaporative condenser reclaims in the said step 3) is 18%～37% through the concentrated formaldehyde mass percent concentration that the infiltration evaporation membrane separation unit separates concentrated recovery.
10. the working method of a kind of N-phosphonomethyliminoacidetic acidetic according to claim 1 is characterized in that the formaldehyde-containing wastewater of evaporative condenser recovery in the said step 3) is controlled the formaldehyde mass percent concentration less than 0.1% through the waste water that the infiltration evaporation membrane separation unit separates discharge.
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| CN101823973B (en) * | 2009-03-02 | 2013-09-25 | 浙江新安化工集团股份有限公司 | Method for separating iminodiacetic acid |
| AU2010251897A1 (en) | 2009-05-28 | 2011-11-24 | Straitmark Holding Ag | Method for the manufacture of phosphonoalkyl iminodiacetic acids |
| CN101691383B (en) * | 2009-09-28 | 2012-03-21 | 安徽国星生物化学有限公司 | Method for processing PMIDA synthesis mother liquor |
| CN102040303B (en) * | 2009-10-23 | 2012-07-18 | 中国石油化工股份有限公司 | Method for recovering organic matters in wastewater generated in process for preparing olefin from methanol |
| ES2522065T3 (en) | 2009-10-27 | 2014-11-13 | Straitmark Holding Ag | Manufacturing procedure of phosphonoalkyl iminodiacetic acids |
| CN101891765B (en) * | 2010-07-23 | 2013-08-14 | 重庆紫光化工股份有限公司 | Method for producing N-(phosphonomethyl) iminodiacetic acid (PMIDA) |
| CN104098602B (en) * | 2014-07-08 | 2016-08-24 | 重庆紫光化工股份有限公司 | A kind of energy-saving clean production method of PMIDA |
| 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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| WO1994015939A1 (en) * | 1993-01-14 | 1994-07-21 | Zeneca Limited | Process for the manufacture of n-phosphonomethyliminodiacetic acid |
| 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 |
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| WO1994015939A1 (en) * | 1993-01-14 | 1994-07-21 | Zeneca Limited | Process for the manufacture of n-phosphonomethyliminodiacetic acid |
| 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 |
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