CN101691383A - Method for processing PMIDA synthesis mother liquor - Google Patents
Method for processing PMIDA synthesis mother liquor Download PDFInfo
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- CN101691383A CN101691383A CN200910035810A CN200910035810A CN101691383A CN 101691383 A CN101691383 A CN 101691383A CN 200910035810 A CN200910035810 A CN 200910035810A CN 200910035810 A CN200910035810 A CN 200910035810A CN 101691383 A CN101691383 A CN 101691383A
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- mother liquor
- pmida
- pmida98
- reverse osmosis
- concentrated solution
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Abstract
The invention discloses a method for processing PMIDA synthesis mother liquor by adopting a combination membrane technique. The method aims at acidic mother liquor generated in the technique for preparing PMIDA by taking iminodiacetonitrile as the raw material and adopting IDA route, alkali is used for adjusting the pH value of the mother liquor to be 6-11, a reverse osmosis membrane is used for concentrating to obtain a concentrated liquor, and the concentrated liquor is subject to pervaporation and recovery to obtain formaldehyde. Concentrated liquor of PMIDA with mass percentage concentration being over 9% can be obtained by adopting the inventive method, the concentrated liquor of PMIDA can be directly prepared into aqueous solution agent to be sold or taken as raw material for producing pesticide glyphosate, and at the same time, the invention has lower energy consumption and no pollution to the environment in the operation process.
Description
Technical field
The present invention relates to the separating technology of film combination, be specifically related to a kind of treatment process of PMIDA synthesis mother liquor, after promptly utilizing iminodiacetonitrile to produce pmida98, the pmida98 in the pmida98 mother liquor, formaldehyde are carried out Separation and Recovery by its character and purposes, belong to liquid liquid separation technology field.
Background technology
Glyphosate is a kind of inner sucting conduction type wide spectrum steriland herbicide, the main interior enol acetonyl shikimin phosphate synthase of object that suppresses, thereby suppress the conversion of shikimin to phenylalanine, cruel propylhomoserin and tryptophane, make proteinic synthetic being interfered cause plant death, seed and soil microorganisms hiding in the soil are had no adverse effects.And pmida98 is the important intermediate in the IDA method production glyphosate process.Mother liquor involved in the present invention is for the iminodiacetonitrile being IDA route production waste water that pmida98 produced of raw material, building-up process is: iminodiacetonitrile is produced Iminodiacetic acid sodium salt salt through the sodium hydroxide alkaline hydrolysis, add hydrochloric acid then and return acid back and phosphorous acid, formaldehyde reacts under acidic conditions produces pmida98, pmida98 is separated out in repeated hydrogenation sodium oxide pH=0.5～1.5 that neutralize, obtain the solid pmida98 after separating mother liquor, mother liquor is as wastewater treatment, often need wash owing to synthesize, processes such as separation, therefore often contain pmida98 in the mother liquor that produces, formaldehyde, raw material or products such as acid, the complicated component of mother liquor, biochemical treatment is difficult to qualified discharge, so the recovery of pmida98 and formaldehyde then becomes the problem that numerous producers are concerned about in the pmida98 mother liquor.
Patent CN 1762835A adopts steam heating normal pressure or vacuum distillation method concentrated mother liquor, is isolating formaldehyde in rectifying still.This technology all than higher, has increased the cost of waste water dis posal to the requirement of heat energy and pressure when reaching the purpose that useful matter reclaims.
Compositions such as the glyphosate in the patent CN 101348299A employing nanofiltration membrane recovery mother liquor, pmida98 are used multiple reverse osmosis technology concentrated mother liquor waste water again, reclaim the materials such as formaldehyde in a large amount of low concentration wastewaters.Patent CN 101007822A is divided into glyphosate concentrated mother liquor and low concentration formaldehyde solution with infiltration evaporation with mother liquor, reduces the water yield with infiltrating and vaporizing membrane again, reaches the purpose that concentrates formaldehyde.More than though two patents adopt all is more advanced membrane process, the membrane process in two steps all need be handled a large amount of waste water, the total amount of waste water dis posal is very big, and the waste water load degree of film has been proposed very high requirement.
Summary of the invention
The objective of the invention is provides a kind of method of handling PMIDA synthesis mother liquor for fear of above-mentioned weak point.
The objective of the invention is to implement in the following manner:
A kind of method of handling PMIDA synthesis mother liquor, this method is to be that the pmida98 mother liquor that obtains behind the raw material production pmida98 is regulated the pH value 6～11 through alkali with adopting iminodiacetonitrile, adopt reverse osmosis method to concentrate the pmida98 mother liquor and obtain concentrated solution, concentrated solution reclaims formaldehyde through infiltration evaporation again, the remaining spissated pmida98 concentrated solution of end product that is.
Described employing reverse osmosis concentration pmida98 mother liquor is when reverse osmosis concentration, the temperature of mother liquor is controlled at 20 ℃～60 ℃, the reverse osmosis working pressure is 3.0MPa～8.0MPa, reverse osmosis can be removed and be accounted for mother liquor and weigh 65%～80% moisture, obtaining excess is the concentrated solution that contains formaldehyde and pmida98, and the formaldehyde content of measuring in the concentrated solution is 2%～10%.Reverse osmosis membrane preferably adopts polyamide composite film.
With the infiltration evaporation device concentrated solution that contains formaldehyde and pmida98 of gained is carried out infiltration evaporation again and separate, obtain the formaldehyde concentrated solution and the pmida98 concentrated solution of end product, recording concentration of formaldehyde in the formaldehyde concentrated solution is 15～40%.
The temperature that infiltration evaporation adopts is 70 ℃～90 ℃, and osmotic lateral pressure is 7 * 103Pa～10 * 103Pa, and infiltrating and vaporizing membrane is a polyamide composite film, is preferably high silica ZSM-5 zeolite filled silicon rubber film, is beneficial to the separation of formaldehydes volatile matter in the mother liquor.
The water of reverse osmosis per-meate side can be used as the water of productive use reuse in the inventive method, after the retentate side organic liquor enters heat-exchanger rig and is heated to bubble point, enter the infiltration evaporation device, through infiltration vaporization membrane module, membrane module upstream product (being mainly glyphosate class material) enters storage tank, is recovered in the reactor of top reaction; Vacuumize in the membrane module downstream, the formaldehyde of per-meate side and water are vaporized under vacuum condition, see through film and separated, and to obtain concentration in per-meate side be 15～40% formaldehyde concentrated solution.
Material of the present invention is commercially available getting.
For the recovery method of pmida98 mother liquor, the method that adopts underpressure distillation, crystallization to separate out is also arranged, through the pmida98 mother liquor of the recovery of this method, pmida98 concentration is for usually being lower than 5%; And present method is controlled when proper when two step membrane technique conditions, can obtain concentration at the pmida98 concentrated solution more than 9%, this pmida98 concentrated solution can directly be processed into aqua to be sold, or as the raw material of producing the agricultural chemicals glyphosate, simultaneously, the energy consuming ratio of present method is lower, and environment friendly and pollution-free in the operating process.Percentage composition of the present invention is the quality percentage composition.
Beneficial effect of the present invention compared with the prior art:
The present invention has adopted reverse osmosis process earlier pending liquid to be concentrated, reduced the mother liquor amount of subsequent film treatment process, because reverse osmosis process per-meate side water quality will be higher than technologies such as nanofiltration, infiltration evaporation, therefore, this process can obtain the good industrial circulating water of a large amount of water quality simultaneously; Second go on foot infiltration evaporation technology simultaneously, what adopt is comparatively advanced at present oleophylic infiltrating and vaporizing membrane, can make the formaldehyde in the concentrated solution be able to effective separation by the vaporization film, guarantee the high density of the formaldehyde solution of gained behind the vaporization membrane sepn, maximum concentration can be up to 40%.Membrane process is all lower to the requirement of temperature and pressure, has reduced the cost of waste water dis posal.The recovery respectively of pmida98 and formaldehyde has improved resource utilization, has fundamentally solved pollution problem, and the inventive method technical process is simple, is easy to promote.
Embodiment
Embodiment 1
Utilize iminodiacetonitrile (to contain formaldehyde 0.7% 1t for the pmida98 mother liquor that raw material adopts the IDA route to produce, pmida98 1.0%, formic acid 1.2%) regulate and enter reverse osmosis membrane apparatus equipment after pH is 6 (reverse osmosis membrane is a polyamide composite film through adding alkali (add mass percent concentration be the NaOH solution of 0.1mol/l), manufacturer is the HPA-FR-4040 of a Hydranautics company series membranes element), at working pressure is 6.0MPa, temperature is to carry out reverse-osmosis treated under 20 ℃ the condition to obtain the fresh water of 0.7t and the concentrated solution of 0.3t, concentrated solution enters infiltration evaporation film device (infiltrating and vaporizing membrane is a high silica ZSM-5 zeolite filled silicon rubber film), in temperature is 70 ℃, and osmotic lateral pressure is 8 * 10
3Under the condition of Pa, reclaim through infiltration evaporation that to obtain mass percentage concentration be that 36.7% formaldehyde concentrated solution and mass percentage concentration are 9.1% pmida98 concentrated solution.
Embodiment 2
Utilize iminodiacetonitrile (to contain formaldehyde 0.7% 1t for the pmida98 mother liquor that raw material adopts the IDA route to produce, pmida98 1.0%, formic acid 1.2%) (reverse osmosis membrane is a polyamide composite film to enter reverse osmosis membrane apparatus equipment after feeding ammoniacal liquor transfers pH to be 10, be the HPA-FR-4040 of Hydranautics company series membranes element), at working pressure position 7.0MP, temperature is to handle under 30 ℃ the condition to obtain the fresh water of 0.72t and the concentrated solution of 0.28t, concentrated solution enters infiltration evaporation film device (infiltrating and vaporizing membrane is a high silica ZSM-5 zeolite filled silicon rubber film), in temperature is 80 ℃, and osmotic lateral pressure is 7 * 10
3Under the condition of Pa, reclaim through infiltration evaporation that to obtain mass percentage concentration be that 37.8% formaldehyde concentrated solution and mass percentage concentration are 9.2% pmida98 concentrated solution.
The present invention adopts reverse osmosis technology to handle the pmida98 mother liquor waste water, carrying out infiltration evaporation on the basis that has greatly concentrated the mother liquor waste water amount again separates, reduced isolating scale effectively, and then the scale and the cost recovery of aftertreatment device have been reduced, the formaldehyde concentrated solution of gained can be used as raw material and is back in the reaction of synthetic pmida98, the pmida98 aqueous solution that obtains both can be used as agricultural chemicals and had sold, also can be used for producing in the technology of glyphosate, the fresh water water quality of reverse osmosis operation discharging is good, can be used for industrial circulating water.
Claims (5)
1. the treatment process of a PMIDA synthesis mother liquor, it is characterized in that, the pmida98 mother liquor that obtains after utilizing iminodiacetonitrile for the raw material production pmida98 is regulated the pH value 6～11 through alkali, adopt reverse osmosis concentration to obtain concentrated solution, concentrated solution reclaims formaldehyde through infiltration evaporation again, the remaining end product pmida98 concentrated solution that is.
2. the treatment process of PMIDA synthesis mother liquor according to claim 1 is characterized in that when reverse osmosis concentration, and the temperature of mother liquor is controlled at 20 ℃～60 ℃, and the reverse osmosis working pressure is 3.0～8.0MPa.
3. the treatment process of PMIDA synthesis mother liquor according to claim 1 is characterized in that the temperature that described infiltration evaporation adopts is 70 ℃～90 ℃, and osmotic lateral pressure is 7 * 10
3Pa～10 * 10
3Pa.
4. the treatment process of PMIDA synthesis mother liquor according to claim 1 is characterized in that the reverse osmosis membrane that adopts is a polyamide composite film.
5. the treatment process of PMIDA synthesis mother liquor according to claim 1 is characterized in that the infiltrating and vaporizing membrane that adopts is a high silica ZSM-5 zeolite filled silicon rubber film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200910035810XA CN101691383B (en) | 2009-09-28 | 2009-09-28 | Method for processing PMIDA synthesis mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910035810XA CN101691383B (en) | 2009-09-28 | 2009-09-28 | Method for processing PMIDA synthesis mother liquor |
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| Publication Number | Publication Date |
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| CN101691383A true CN101691383A (en) | 2010-04-07 |
| CN101691383B CN101691383B (en) | 2012-03-21 |
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| CN200910035810XA Active CN101691383B (en) | 2009-09-28 | 2009-09-28 | Method for processing PMIDA synthesis mother liquor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115281A (en) * | 2011-01-18 | 2011-07-06 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
| CN102198989A (en) * | 2011-04-22 | 2011-09-28 | 安徽国星生物化学有限公司 | Method for treating PMIDA wastewater |
| CN102702254A (en) * | 2010-10-18 | 2012-10-03 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| US8669396B2 (en) | 2009-05-18 | 2014-03-11 | Monsanto Technology Llc | Recovery of phosphorus values and salt impurities from aqueous waste streams |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100554192C (en) * | 2007-03-06 | 2009-10-28 | 杭州天创净水设备有限公司 | Waste water treatment process in a kind of pmida98 preparation process |
| CN101284847B (en) * | 2008-05-20 | 2012-11-14 | 捷马化工股份有限公司 | Production method of N-phosphono methyliminodiacetic acid |
| CN101348266B (en) * | 2008-09-05 | 2010-06-02 | 江苏扬农化工股份有限公司 | Comprehensive processing method of N-phosphonomethyliminodiacelic acid mother liquor |
-
2009
- 2009-09-28 CN CN200910035810XA patent/CN101691383B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8669396B2 (en) | 2009-05-18 | 2014-03-11 | Monsanto Technology Llc | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| US9394173B2 (en) | 2009-05-18 | 2016-07-19 | Monsanto Technology Llc | Recovery of phosphorus values and salt impurities from aqueous waste streams |
| CN102702254A (en) * | 2010-10-18 | 2012-10-03 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| CN102702254B (en) * | 2010-10-18 | 2015-04-15 | 浙江拜克开普化工有限公司 | Method for recycling N-(Phosphonomethyl) iminodiacetic acid from production process wastewater of N-(Phosphonomethyl) iminodiacetic acid to prepare glyphosate aqueous solution |
| CN102115281A (en) * | 2011-01-18 | 2011-07-06 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
| CN102115281B (en) * | 2011-01-18 | 2012-07-04 | 中国中化股份有限公司 | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) |
| CN102198989A (en) * | 2011-04-22 | 2011-09-28 | 安徽国星生物化学有限公司 | Method for treating PMIDA wastewater |
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| Publication number | Publication date |
|---|---|
| CN101691383B (en) | 2012-03-21 |
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Owner name: ANHUI GUOXING BIOCHEMICAL CO., LTD. Free format text: FORMER OWNER: NANJING FIRST PESTICIDE GROUP CO., LTD. Effective date: 20110922 |
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Effective date of registration: 20110922 Address after: 243100 Dangtu Economic Development Zone in Anhui Applicant after: Anhui Guoxing Biochemistry Co., Ltd. Address before: 211300 Pagoda Road 269, Gaochun County, Jiangsu, Nanjing Applicant before: Nanjing First Pesticide Group Co., Ltd. |
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