CN100460408C - Glyphosate catalytic oxidation preparation method for resource reutilization - Google Patents
Glyphosate catalytic oxidation preparation method for resource reutilization Download PDFInfo
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- CN100460408C CN100460408C CNB200710066935XA CN200710066935A CN100460408C CN 100460408 C CN100460408 C CN 100460408C CN B200710066935X A CNB200710066935X A CN B200710066935XA CN 200710066935 A CN200710066935 A CN 200710066935A CN 100460408 C CN100460408 C CN 100460408C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for preparing glyphosate through catalysis and oxidation. It comprises following steps: adding 2-8 by weight proportion of catalyst into glyphosate of 100 by weight proportion; ventilating oxygen-containing gas into water phase for catalytic and oxidation reaction, the reaction temperature is 70- 120 Deg. C, and reaction pressure is 0.7- 1.2 Mpa; separating catalyst in 1- 30 minutes by using solid- liquid separating device after reaction is finished, cooling, filtering reaction liquid and getting solid glyphosate; separating filtered monther liquid with osmotic evaporation membrane and getting side- product formaldehyde; the monther liquid of glyphosate can be recycly used; separated dilute formaldehyde solution can be separated and condensated with osmotic evaporation membrane, all or part of strong formaldehyde can be recycly used. The invention is characterized by environmental- friendly process and raw material, sound quality of product, high productivity, reduced cost for catalyst, high- technique of membrane separation for side product formaldehyde from glyphosate, and use of side product at maximun limit.
Description
Technical field
The present invention relates to a kind of production method of glyphosate, relate in particular to a kind of glyphosate catalytic oxidation preparation method of resource reutilization.
Background technology
The glyphosate chemical name is the N-(phosphonomethyl) glycine.Be a kind of high-efficiency broad spectrum steriland herbicide, now become the most salable in the world weedicide.Now industrialized glyphosate production technology mainly contains two, article one, be to be the dialkyl phosphite route of starting raw material with the glycine, another is to be the IDA route of starting raw material with diethanolamine or iminodiacetonitrile, and the method for its synthesizing glyphosate acid is: pmida98 in the presence of oxide catalyst (sodium wolframate) in aqueous phase with oxygenant (H
2O
2, NaClO etc.) oxidation, in the presence of reductive agent ferrous sulfate (or vanadylic sulfate), be reduced into glyphosate solution then, after crystallization, solid-liquid separation, obtain solid glyphosate, still contain formaldehyde, formic acid, unreacted pmida98, ferrous ion, iron ion etc. and cause quality problems completely in the product, and yield is not high.
Application number be 200410014897.X patent disclosure pmida98 solution in the presence of the Pd/carbon catalyst that contains Mn, Fe, Co, Cu or Ni, generate glyphosate with oxygen reaction, and with the methyl alcohol of the formaldehyde in the mother liquor, ethanol or urea reaction removal, the offal treatment difficulty that produces, environmental protection pressure is bigger, and by products such as formaldehyde do not effectively utilize.
According to US4147719, the salt of glyphosate can be by oxygen-containing gas at precious metal oxidation catalyst, and Pt (Pd) existence that promptly is carried on the gac directly prepares from the salt of pmida98 down.But Preparation of catalysts is comparatively complicated, and cost is very high, and will stop the loss of catalyzer and precious metal relatively more difficult in process of production.
Publication number be CN 1191539A patent disclosure a kind ofly replace the method for oxygen-containing gas synthesizing glyphosate with hydrogen peroxide, this method has been used the hazardous chemical hydrogen peroxide, simultaneously with oxidation of formaldehyde formic acid and carbonic acid gas.
Can see from the front, these methods or the quality product of production is bad, resource utilization is low, or used hazardous chemical, or can produce reluctant waste, produce the logistics that obtains containing toxicity metal, precious metal or strong acid, the environment protection treating difficulty is bigger.And some method must be carried out under the condition of very dilution, needs the lot of energy concentrated solution, so that reclaim the glyphosate product with the productive rate that economic worth is arranged.
Summary of the invention
The objective of the invention is to eliminate the defective of prior art, a kind of glyphosate catalytic oxidation preparation method of resource reutilization is provided.
The glyphosate catalytic oxidation preparation method of resource reutilization: 100 mass parts pmida98s add 2～8 mass parts of catalyst, feed oxygen-containing gas and carry out catalytic oxidation in aqueous phase, and temperature of reaction is 70～120 ℃, and reaction pressure is 0.7～1.2MPa; Reaction was isolated catalyzer through equipment for separating liquid from solid after finishing in 1～30 minute, reaction solution is through cooling off, filter to isolate solid glyphosate; Filtrated stock is isolated by product formaldehyde through the infiltration evaporation membrane separation unit, and glyphosate mother solution recycles, and isolated rare formalin separates concentrated again through the infiltration evaporation membrane separation unit, and concentrated formaldehyde is all or part of to be recycled.
Described catalyzer is Pt or Pd catalyzer, metal complex or the variable valency metal oxide compound of gac, gac or mordenite load.Catalyzer is preferably gac.Equipment for separating liquid from solid is board-like airtight filter, bag type filtering machine, horizontal blade filter or movable flow device.Equipment for separating liquid from solid is preferably board-like airtight filter or bag type filtering machine.The oxygen quality mark of oxygen-containing gas is 80%～100%.Temperature of reaction is 70～100 ℃, and reaction pressure is 0.7～1.0MPa.The infiltration evaporation membrane separation unit is made up of preheater, infiltration evaporation membrane separation apparatus, condenser, vacuum pump.The infiltration evaporation mould material that the infiltration evaporation membrane separation unit adopts is cellulose acetate, chitosan, organosilicon, ion-exchange composite membranes, composite membrane of polyvinyl alcohol.The infiltration vaporization membrane module form has plate and frame, spiral wound, tubular fibre or tubular type.
Building-up process of the present invention, raw material green, good product quality, yield height, reduced the cost of catalyzer significantly, adopt high-new membrane technique to separate glyphosate and by product formaldehyde, maximally utilised by product formaldehyde resource, having advantages such as green, energy-conservation, efficient, environmental protection, is typical green chemical industry and recycling economy new technology.
Description of drawings
Accompanying drawing is the simplified flow chart of the glyphosate catalytic oxidation preparation method of resource reutilization
Embodiment
Chemical equation of the present invention is as follows:
Embodiment 1
In pressurized vessel, drop into 2000ml water, 4g activated-carbon catalyst and 200g pmida98, the aerating oxygen massfraction is that 80% oxygen-containing gas carries out catalyzed oxidation, temperature of reaction is controlled at 70 ℃, reaction pressure is controlled at 0.7MPa, till pmida98 all transforms fully, stops logical oxygen, gas-phase product discharges termination reaction, is prepared into the glyphosate mixed solution; Isolated catalyzer through board-like airtight filter in 1 minute, reaction solution is through cooling off, filter to isolate solid glyphosate; Filtrated stock is isolated by product formaldehyde through the infiltration evaporation membrane separation unit of being made up of major equipments such as " preheater, infiltration evaporation membrane separation apparatus, condenser, vacuum pumps ", glyphosate mother solution recycles, isolated rare formalin separates concentrated again through the infiltration evaporation membrane separation unit, all or part of pmida98 synthetic system of returning of concentrated formaldehyde recycles.
Embodiment 2
In pressurized vessel, drop into 1800ml water, 16g activated-carbon catalyst and 200g pmida98 earlier, the aerating oxygen massfraction is that 100% oxygen-containing gas carries out catalyzed oxidation, temperature of reaction is controlled at 120 ℃, reaction pressure is controlled at 1.2Mpa, till pmida98 all transforms fully, stops logical oxygen, gas-phase product discharges termination reaction, is prepared into the glyphosate mixed solution; Isolated catalyzer rapidly through the horizontal blade filter in 30 minutes, reaction solution filters to isolate solid glyphosate through overcooling; Filtrated stock adopts infiltration vaporization membrane tripping device to isolate by product formaldehyde, and glyphosate mother solution returns in the glyphosate synthetic system and recycles; Isolated rare formalin separates concentrated again through the infiltration vaporization separation film device, concentrated formaldehyde is as the raw material of pmida98 or urea-formaldehyde resin.
Embodiment 3
In pressurized vessel, drop into 1800ml water, 10g activated-carbon catalyst and 200g pmida98 earlier, the aerating oxygen massfraction is that 90% oxygen-containing gas carries out catalyzed oxidation, temperature of reaction is controlled at 100 ℃, reaction pressure is controlled at 1.0Mpa, till pmida98 all transforms fully, stops logical oxygen, gas-phase product discharges termination reaction, is prepared into the glyphosate mixed solution; Isolated catalyzer rapidly through bag type filtering machine in 20 minutes, its reaction solution filters to isolate solid glyphosate through overcooling; Filtrated stock adopts the infiltration evaporation membrane separation unit to isolate glyphosate mother solution behind the formaldehyde and returns in the glyphosate synthetic system and recycle; Isolated rare formalin separates concentrated again through the infiltration evaporation film device, all or part of pmida98 synthetic system of returning of concentrated formaldehyde recycles.The activated-carbon catalyst incinerator burning disposal that lost efficacy.
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 being done on basis of the present invention is different from embodiment.
Claims (10)
1. a glyphosate catalytic oxidation preparation method is characterized in that, 100 mass parts pmida98s add 2～8 mass parts of catalyst, feeds oxygen-containing gas and carries out catalytic oxidation in aqueous phase, and temperature of reaction is 70～120 ℃, and reaction pressure is 0.7～1.2MPa; Reaction was isolated catalyzer through equipment for separating liquid from solid after finishing in 1～30 minute, reaction solution is through cooling off, filter to isolate solid glyphosate; Filtrated stock is through infiltration evaporation membrane separation unit separating by-products formaldehyde, and glyphosate mother solution recycles, and isolated rare formalin separates concentrated again through the infiltration evaporation membrane separation unit, and concentrated formaldehyde is all or part of to be recycled.
2. a kind of glyphosate catalytic oxidation preparation method according to claim 1 is characterized in that described catalyzer is Pt or Pd catalyzer, metal complex or the variable valency metal oxide compound of gac, gac or mordenite load.
3. a kind of glyphosate catalytic oxidation preparation method according to claim 1 and 2 is characterized in that described catalyzer is a gac.
4. a kind of glyphosate catalytic oxidation preparation method according to claim 1 is characterized in that described equipment for separating liquid from solid is board-like airtight filter, bag type filtering machine, horizontal blade filter or movable flow device.
5. according to claim 1 or 4 described a kind of glyphosate catalytic oxidation preparation methods, it is characterized in that described equipment for separating liquid from solid is board-like airtight filter or bag type filtering machine.
6. a kind of glyphosate catalytic oxidation preparation method according to claim 1, the oxygen quality mark that it is characterized in that described oxygen-containing gas is 80%～100%.
7. the glyphosate catalytic oxidation preparation method of a kind of resource reutilization according to claim 1 is characterized in that described temperature of reaction is 70～100 ℃, and reaction pressure is 0.7～1.0MPa.
8. a kind of glyphosate catalytic oxidation preparation method according to claim 1 is characterized in that described infiltration evaporation membrane separation unit is made up of preheater, infiltration evaporation membrane separation apparatus, condenser, vacuum pump.
9. a kind of glyphosate catalytic oxidation preparation method according to claim 1 is characterized in that the infiltration evaporation mould material that described infiltration evaporation membrane separation unit adopts is cellulose acetate, chitosan, organosilicon, ion-exchange composite membranes or composite membrane of polyvinyl alcohol.
10. a kind of glyphosate catalytic oxidation preparation method according to claim 9 is characterized in that described infiltration vaporization membrane module form has plate and frame, spiral wound, tubular fibre or tubular type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710066935XA CN100460408C (en) | 2007-01-26 | 2007-01-26 | Glyphosate catalytic oxidation preparation method for resource reutilization |
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| CNB200710066935XA CN100460408C (en) | 2007-01-26 | 2007-01-26 | Glyphosate catalytic oxidation preparation method for resource reutilization |
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| CN101007822A CN101007822A (en) | 2007-08-01 |
| CN100460408C true CN100460408C (en) | 2009-02-11 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7771494B2 (en) * | 2007-01-31 | 2010-08-10 | Monsanto Technology Llc | Process for selective removal of water and impurities from N-(phosphonomethyl)glycine |
| WO2009079862A1 (en) * | 2007-12-25 | 2009-07-02 | Beijing Unis Insight Chemical Technology Co., Ltd. | New preparation method of glyphosate by oxidation pmida with air |
| CN101519230B (en) * | 2008-07-23 | 2011-11-09 | 杭州天创净水设备有限公司 | Highly enriched formaldehyde solution preparation system and preparation method |
| CN101508701B (en) * | 2008-12-10 | 2012-09-05 | 上海泰禾(集团)有限公司 | Method for preparing glyphosate by oxidizing N-(Phosphonomethyl)iminodiacetic acid with active carbon as catalyst oxygen |
| CN101880293B (en) * | 2009-05-04 | 2012-09-26 | 浙江新安化工集团股份有限公司 | Improved production method of N-phosphonomethyl glycine |
| CN101690868B (en) * | 2009-09-28 | 2012-03-14 | 安徽国星生物化学有限公司 | Method for processing glyphosate esterification mother liquor |
| CN102001924A (en) * | 2010-10-09 | 2011-04-06 | 南京大学 | Technology for reclaiming low-concentration formaldehyde from pesticide wastewater through ionic liquid supported liquid membrane pervaporation-distillation coupling technology |
| CN110642888A (en) * | 2019-10-31 | 2020-01-03 | 杜伟 | Preparation method of glyphosate |
| CN110790788A (en) * | 2019-11-19 | 2020-02-14 | 杜伟 | Method for preparing glyphosate from N- (phosphonomethyl) iminodiacetic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| EP0652201A1 (en) * | 1993-10-30 | 1995-05-10 | BASF Aktiengesellschaft | Process for the production of concentrated aqueous formaldehyde solutions by pervaporation |
-
2007
- 2007-01-26 CN CNB200710066935XA patent/CN100460408C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| EP0652201A1 (en) * | 1993-10-30 | 1995-05-10 | BASF Aktiengesellschaft | Process for the production of concentrated aqueous formaldehyde solutions by pervaporation |
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| CN101007822A (en) | 2007-08-01 |
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Denomination of invention: Preparation of glyphosate by catalytic oxidation of resource reuse Effective date of registration: 20210716 Granted publication date: 20090211 Pledgee: Agricultural Bank of China Limited Longyou County sub branch Pledgor: JINGMA CHEMICALS Co.,Ltd. Registration number: Y2021330000920 |