CN104944398B - Glyphosate mother solution recoverying and utilizing method - Google Patents
Glyphosate mother solution recoverying and utilizing method Download PDFInfo
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- CN104944398B CN104944398B CN201510365757.5A CN201510365757A CN104944398B CN 104944398 B CN104944398 B CN 104944398B CN 201510365757 A CN201510365757 A CN 201510365757A CN 104944398 B CN104944398 B CN 104944398B
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Abstract
Glyphosate mother solution recoverying and utilizing method, belongs to chemical technology field.It comprises the following steps：Glyphosate and glyphosate mother solution are obtained with glycine method, the production of iminodiacetic acid (salt) acid system；Glyphosate mother solution is concentrated；Glyphosate mother solution concentrate is subjected to oxidation processes；Glyphosate mother solution oxidation solution is subjected to decrease temperature crystalline, the glyphosate mother solution oxidation solution after crystallization is taken out and is concentrated；Permeate is concentrated to obtain sodium chloride product, and distillate carries out reuse；Concentrate pH value is adjusted to 3~4, then carries out photocatalysis oxidation reaction；PH value is adjusted, disodium hydrogen phosphate product or tertiary sodium phosphate product is obtained.The present invention carries out the content of chlorion in concentration, reduction glyphosate mother solution before glyphosate mother solution oxidation, improves the concentration of reactant, improves the efficiency of subsequent oxidation reaction；Concentrate carries out hydrogen peroxide photochemical catalytic oxidation, and reaction is thorough, and oxygen-enriched wet oxidation more preferably, can be difficult to the material aoxidized, be aoxidized, reaction condition is gentle by oxidisability.
Description
Technical field
The invention belongs to chemical technology field, and in particular to glyphosate mother solution recoverying and utilizing method.
Background technology
Glyphosate because of its low toxicity, efficiently, low-residual, broad spectrum activity be that global sales is maximum and growth rate most fast agriculture
Medicine kind, and succeeding in developing and promote the use of and energy shortage causes bio-fuel along with the genetically modified crops of glyphosate
The sowing and popularization of crop, new opportunity is provided for the production of glyphosate.
Glyphosate production mainly has two kinds of synthesis modes, and one is iminodiacetic acid (salt) acid system, i.e., with diethanol amine or hydrogen cyanide
For initiation material, Meng Shan Dou Deng offshore companies of the U.S. generally use the method；Another is alkyl esterification method, and most domestic enterprise adopts
Use this method.Alkyl esterification method glyphosate production primary raw material is paraformaldehyde（Formaldehyde）, amion acetic acid, dimethylphosphite, three second
The depolymerization of amine, methanol, hydrochloric acid, wherein paraformaldehyde is using triethylamine as catalyst, by depolymerization, addition, condensation, hydrolysis instead
Should, then after desolvation methanol and excessive hydrochloric acid, glyphosate crystal is separated out.
Obtaining the glyphosate mother solution after glyphosate crystal adds alkali to carry out the recovery of catalyst of triethylamine, obtains glyphosate alkaline
Mother liquor, its main component be sodium chloride, glyphosate and its reaction intermediate and accessory substance, its sodium chloride content 12-16%,
COD30,000-70,000mg/L, Tp15,000-30,000mg/L.Processing method such as patent CN 103012474A electrocatalytic oxidations
Chemical industry skill is more complicated；CN101402652A simply reduces sodium chloride content in mother liquor, does not carry out effective resource reclaim；
CN103864040A carries out air oxidation, and efficiency is low, the problem of secondary oxidation efficiency is low, and heat utilization ratio is poor, due to reaction heat
Amount is more than the activation energy needed for reaction, produces energy accumulation phenomenon, and need noble metal catalyst.
The content of the invention
The problem of existing for prior art, it is an object of the invention to design to provide glyphosate mother solution recoverying and utilizing method
Technical scheme.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that comprise the following steps that：
1）Glyphosate and glyphosate mother solution are obtained with glycine method, the production of iminodiacetic acid (salt) acid system；
2）Glyphosate mother solution is concentrated, glyphosate mother solution concentrate is obtained；
3）Glyphosate mother solution concentrate is subjected to oxidation processes, glyphosate mother solution oxidation solution is obtained；
4）Glyphosate mother solution oxidation solution progress decrease temperature crystalline is obtained into phosphate product, the glyphosate mother solution after crystallization is taken out
Oxidation solution is concentrated, and obtains concentrate and permeate；
5）Permeate is concentrated to obtain sodium chloride product, and distillate carries out reuse；
6）Concentrate pH value is adjusted to 3~4, hydrogen peroxide and catalyst is added anti-in ultraviolet lower progress photochemical catalytic oxidation
Should；
7）Reaction terminates to add sodium hydroxide adjustment pH value to 9 ± 0.5 or 12 ± 0.5, when PH is 9, returns catalytic wet
Crystallisation by cooling or independent crystallisation by cooling obtain disodium hydrogen phosphate product to oxidation solution in the lump, and when PH is 12, Ultraviolet Oxidation liquid is independent
Crystallisation by cooling obtains tertiary sodium phosphate product.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 2）Glyphosate mother solution is concentrated into
COD is more than 50,000mg/L, and preferably COD is more than 60,000mg/L, Tp and is more than 30,000mg/L, preferably greater than 40,
000mg/L。
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 3）It is middle by glyphosate mother solution, sky
Gas and oxygen mix, at 220~260 DEG C of temperature, react 30~60min, obtain glyphosate mother solution oxidation solution.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 4）Glyphosate mother liquor oxidation solution
0~10 DEG C is cooled to be crystallized.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 4）Middle use NF membrane carries out dense
Contracting.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 5）Middle use mechanical vapour is pressed again
Contracting technology or multiple-effect evaporation technology are concentrated.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 6）Middle hydrogen peroxide presses 1L hydrogen peroxide
100~150mg/L of concentrate COD amounts per ton are consumed to be added.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 6）Middle catalyst be ferrous salt or
Mantoquita, it is 50~200mg/L that concentrate ferrous ions and copper ion concentration are controlled during addition.
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described step 6）Middle 5~48h of reaction time,
Preferably 20~40h；20~70 DEG C of reaction temperature, preferably 30~60 DEG C；180~260nm of ultraviolet light, preferably 200~
240nm。
Described glyphosate mother solution recoverying and utilizing method, it is characterised in that described glyphosate mother solution and the mass ratio of air
For 80：12~16, and be 21~50% by adding liquid oxygen to adjust content of oxygen in air.
Above-mentioned glyphosate mother solution recoverying and utilizing method, it is reasonable in design, concentration, drop are carried out before glyphosate mother solution oxidation
The content of chlorion in low glyphosate mother solution, improves the concentration of reactant, improves the efficiency of subsequent oxidation reaction；Concentrate is carried out
Hydrogen peroxide photochemical catalytic oxidation, reaction is thorough, and oxygen-enriched wet oxidation more preferably, can be difficult to the material aoxidized by oxidisability, carry out oxygen
Change, reaction condition is gentle.
Embodiment
Further illustrate the present invention with reference to embodiments.
Embodiment 1
1）Glyphosate and glyphosate mother solution are obtained with glycine method production；
2）Glyphosate mother solution is concentrated into COD 60,000mg/L, Tp 40,000mg/L, glyphosate mother solution concentration is obtained
Liquid；
3）By the glyphosate mother solution after concentration and compressed air in mass ratio 80:14 mixing, and adjusted by adding liquid oxygen
Oxygen content is 40% in compressed air, at 240 DEG C of temperature, reacts 30min, obtains glyphosate mother solution oxidation solution；
4）Glyphosate mother solution oxidation solution is cooled into 5 DEG C crystallize obtaining phosphate product, takes out careless sweet after crystallization
Phosphine mother liquor oxidation solution is concentrated using NF membrane, obtains concentrate and permeate；
5）Permeate carries out being concentrated to give sodium chloride product using mechanical vapor recompression technology or multiple-effect evaporation technology, steams
Distillate carries out reuse；
6）Concentrate pH value is adjusted to 3.5, hydrogen peroxide and catalyst is then added under temperature 50 C, 200nm ultraviolet lights
Photocatalysis oxidation reaction 20h is carried out, wherein hydrogen peroxide is added by 1L dioxygen water consumptions concentrate 120mg/L COD amounts per ton
Plus；Catalyst is ferrous salt or mantoquita, and it is 100mg/L to control concentrate ferrous ions and copper ion concentration；
7）Reaction terminates to add sodium hydroxide adjustment pH value to 9 ± 0.5 or 12 ± 0.5, when PH is 9, returns catalytic wet
Crystallisation by cooling or independent crystallisation by cooling obtain disodium hydrogen phosphate product to oxidation solution in the lump, and when PH is 12, Ultraviolet Oxidation liquid is independent
Crystallisation by cooling obtains tertiary sodium phosphate product.
Embodiment 2
1）Glyphosate and glyphosate mother solution are obtained with glycine method production；
2）Glyphosate mother solution is concentrated into COD 50,000mg/L, Tp 30,000mg/L, glyphosate mother solution concentration is obtained
Liquid；
3）By the glyphosate mother solution after concentration and compressed air in mass ratio 80:12 mixing, and adjusted by adding liquid oxygen
Oxygen content is 30% in compressed air, at 220 DEG C of temperature, reacts 50min, obtains glyphosate mother solution oxidation solution；
4）Glyphosate mother solution oxidation solution is cooled into 0 DEG C crystallize obtaining phosphate product, takes out careless sweet after crystallization
Phosphine mother liquor oxidation solution is concentrated using NF membrane, obtains concentrate and permeate；
5）Permeate carries out being concentrated to give sodium chloride product using mechanical vapor recompression technology or multiple-effect evaporation technology, steams
Distillate carries out reuse；
6）Concentrate pH value is adjusted to 3, then hydrogen peroxide is added and catalyst enters under temperature 70 C, 180nm ultraviolet lights
Row photocatalysis oxidation reaction 5h, wherein hydrogen peroxide are added by 1L dioxygen water consumptions concentrate 100mg/L COD amounts per ton；
Catalyst is ferrous salt or mantoquita, and it is 200mg/L to control concentrate ferrous ions and copper ion concentration；
7）Reaction terminates to add sodium hydroxide adjustment pH value to 9 ± 0.5 or 12 ± 0.5, when PH is 9, returns catalytic wet
Crystallisation by cooling or independent crystallisation by cooling obtain disodium hydrogen phosphate product to oxidation solution in the lump, and when PH is 12, Ultraviolet Oxidation liquid is independent
Crystallisation by cooling obtains tertiary sodium phosphate product.
Embodiment 3
1）Glyphosate and glyphosate mother solution are obtained with the production of iminodiacetic acid (salt) acid system；
2）Glyphosate mother solution is concentrated into COD 60,000mg/L, Tp 50,000mg/L, glyphosate mother solution concentration is obtained
Liquid；
3）By the glyphosate mother solution after concentration and compressed air in mass ratio 80:16 mixing, and adjusted by adding liquid oxygen
Oxygen content is 50% in compressed air, at 260 DEG C of temperature, reacts 30min, obtains glyphosate mother solution oxidation solution；
4）Glyphosate mother solution oxidation solution is cooled into 10 DEG C crystallize obtaining phosphate product, takes out careless sweet after crystallization
Phosphine mother liquor oxidation solution is concentrated using NF membrane, obtains concentrate and permeate；
5）Permeate carries out being concentrated to give sodium chloride product using mechanical vapor recompression technology or multiple-effect evaporation technology, steams
Distillate carries out reuse；
6）Concentrate pH value is adjusted to 4, then hydrogen peroxide is added and catalyst enters under 20 DEG C of temperature, 260nm ultraviolet lights
Row photocatalysis oxidation reaction 48h, wherein hydrogen peroxide are added by 1L dioxygen water consumptions concentrate 100mg/L COD amounts per ton；
Catalyst is ferrous salt or mantoquita, and it is 50mg/L to control concentrate ferrous ions and copper ion concentration；
7）Reaction terminates to add sodium hydroxide adjustment pH value to 9 ± 0.5 or 12 ± 0.5, when PH is 9, returns catalytic wet
Crystallisation by cooling or independent crystallisation by cooling obtain disodium hydrogen phosphate product to oxidation solution in the lump, and when PH is 12, Ultraviolet Oxidation liquid is independent
Crystallisation by cooling obtains tertiary sodium phosphate product.
Claims (5)
1. glyphosate mother solution recoverying and utilizing method, it is characterised in that comprise the following steps that：
1）Glyphosate and glyphosate mother solution are obtained with glycine method, the production of iminodiacetic acid (salt) acid system；
2）Glyphosate mother solution is concentrated into COD more than 50,000mg/L, Tp more than 30,000mg/L, glyphosate mother solution concentration is obtained
Liquid；
3）By glyphosate mother solution concentrate, air and oxygen mix, the glyphosate mother solution concentrate glyphosate mother solution and air
Mass ratio be 80：12~16, and be 21~50% by adding liquid oxygen to adjust content of oxygen in air, in temperature 220~260
At DEG C, 30~60min is reacted, glyphosate mother solution oxidation solution is obtained；
4）Glyphosate mother solution oxidation solution progress decrease temperature crystalline is obtained into phosphate product, the glyphosate mother solution oxidation after crystallization is taken out
Liquid is concentrated, and obtains concentrate and permeate；
5）Permeate is concentrated to obtain sodium chloride product, and distillate carries out reuse；
6）Concentrate pH value is adjusted to 3~4, hydrogen peroxide and catalyst is added in ultraviolet lower carry out photocatalysis oxidation reaction, it is double
Oxygen water is added by 1L dioxygen water consumptions 100~150mg/L of concentrate COD amounts per ton, catalyst be ferrous salt or mantoquita,
It is 50~200mg/L that concentrate ferrous ions and copper ion concentration are controlled during addition, and the reaction time is 20~40h, reaction temperature
Spend for 30~60 DEG C, ultraviolet light is 200~240nm；
7）Reaction terminates to add sodium hydroxide adjustment pH value to 9 ± 0.5 or 12 ± 0.5, when pH is 9, returns catalytic wet oxidation
Crystallisation by cooling or independent crystallisation by cooling obtain disodium hydrogen phosphate product to liquid in the lump, and when pH is 12, Ultraviolet Oxidation liquid is individually cooled down
Crystallization obtains tertiary sodium phosphate product.
2. glyphosate mother solution recoverying and utilizing method as claimed in claim 1, it is characterised in that described step 2）By glyphosate
Mother liquor concentrations are more than 60,000mg/L, Tp to COD and are more than 40,000mg/L.
3. glyphosate mother solution recoverying and utilizing method as claimed in claim 1, it is characterised in that described step 4）Glyphosate
Mother liquor oxidation solution is cooled to 0~10 DEG C and crystallized.
4. glyphosate mother solution recoverying and utilizing method as claimed in claim 1, it is characterised in that described step 4）Middle use is received
Filter membrane is concentrated.
5. glyphosate mother solution recoverying and utilizing method as claimed in claim 1, it is characterised in that described step 5）Middle use machine
Tool steam recompression technology or multiple-effect evaporation technology are concentrated.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105330688B (en) * | 2015-11-26 | 2017-08-22 | 浙江工业大学 | Utilize the method for visible light catalytic oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid |
| CN105692960A (en) * | 2016-03-04 | 2016-06-22 | 安徽国星生物化学有限公司 | Treatment method for glyphosate mother liquor |
| CN106044731B (en) * | 2016-08-13 | 2018-10-23 | 安徽东至广信农化有限公司 | A method of based on glyphosate mother solution preparing phosphoric acid disodium hydrogen |
| CN107162278A (en) * | 2017-07-13 | 2017-09-15 | 成都美富特膜科技有限公司 | A kind of recycling PMIDA produces the handling process of waste water |
| CN108689392B (en) * | 2018-07-09 | 2019-10-25 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
| CN114933289B (en) * | 2022-06-22 | 2024-03-15 | 四川福思达生物技术开发有限责任公司 | Co-production process for glyphosate and ferric phosphate |
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| CN103864040A (en) * | 2013-05-08 | 2014-06-18 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from glyphosate mother liquor |
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| CN101058586B (en) * | 2007-04-06 | 2013-04-24 | 杭州天创环境科技股份有限公司 | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique |
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| CN102795734A (en) * | 2012-08-17 | 2012-11-28 | 四川省乐山市福华通达农药科技有限公司 | Process of treating glyphosate mother solution by catalytic air oxidation method |
| CN103864040A (en) * | 2013-05-08 | 2014-06-18 | 浙江悦瑞环保工程有限公司 | Process for preparing disodium hydrogen phosphate from glyphosate mother liquor |
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Inventor after: Pan Liyong Inventor after: Zhong Wei Inventor after: Wang Fuling Inventor after: Sun Ke Inventor after: Pu Jianguo Inventor after: Liu Shaonong Inventor after: Huang Weiguo Inventor after: Lu Zongsheng Inventor after: Huang Jianmin Inventor after: Sun Zhaoyu Inventor after: He Mingjin Inventor after: Long Xingxiang Inventor before: Pan Liyong Inventor before: Wang Fuling Inventor before: Sun Ke Inventor before: Liu Shaonong Inventor before: Huang Weiguo Inventor before: Lu Zongsheng Inventor before: Huang Jianmin Inventor before: Sun Zhaoyu Inventor before: He Mingjin Inventor before: Long Xingxiang Inventor before: Zhong Wei |
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Effective date of registration: 20160217 Address after: 333332 Jiangxi city of Jingdezhen province Leping City Tashan Industrial Park Applicant after: JIANGXI JINLONG CHEMICAL CO., LTD. Applicant after: Zhejiang Jinfanda Biochemical Co., Ltd. Address before: 333332 Jiangxi city of Jingdezhen province Leping City Tashan Industrial Park Applicant before: JIANGXI JINLONG CHEMICAL CO., LTD. |
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