CN106630348A - Treatment method for glyphosate waste water - Google Patents

Treatment method for glyphosate waste water Download PDF

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Publication number
CN106630348A
CN106630348A CN201611173272.7A CN201611173272A CN106630348A CN 106630348 A CN106630348 A CN 106630348A CN 201611173272 A CN201611173272 A CN 201611173272A CN 106630348 A CN106630348 A CN 106630348A
Authority
CN
China
Prior art keywords
glyphosate
content
hydrochloric acid
waste water
production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611173272.7A
Other languages
Chinese (zh)
Inventor
孙亚峰
石进
董垒
王建清
蔡荣军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangshan Pesticides & Chemical Co Ltd Nantong
Original Assignee
Jiangshan Pesticides & Chemical Co Ltd Nantong
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangshan Pesticides & Chemical Co Ltd Nantong filed Critical Jiangshan Pesticides & Chemical Co Ltd Nantong
Priority to CN201611173272.7A priority Critical patent/CN106630348A/en
Publication of CN106630348A publication Critical patent/CN106630348A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/38Condensed phosphates
    • C01B25/42Pyrophosphates
    • C01B25/425Pyrophosphates of alkali metals
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/04Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH

Abstract

The invention provides a treatment method for glyphosate waste water. Acidic waste water generated in a glyphosate production process or waste acid generated in the production processes of other products is added into glyphosate mother liquor obtained with an IDA method, the glyphosate mother liquor obtained with the IDA method is neutralized to pH (potential of hydrogen) of 5-9, then, the glyphosate mother liquor enters an evaporator to be subjected to evaporation concentration, an evaporation concentration multiple can be improved to 4-6 times from original 3 times, and the incineration temperature of evaporation raffinate is lowered to be about 600DEG C. According to the treatment method, the concentrated acid multiple of evaporation concentrated solution can be improved, the incineration temperature of the raffinate is lowered, meanwhile, the acidic waste water generated in the glyphosate production process is disposed, and the treatment method is environmentally-friendly and economic.

Description

The processing method of glyphosate waste water
Technical field
The present invention relates in a kind of pesticide producing waste water treatment technology.
Background technology
Current is recovery glyphosate about the method for the recycling of waste water to glyphosate production according to document report With recovery P elements, the method for reclaiming glyphosate is exactly that glyphosate can not be used directly until its purity is relatively low, and P elements Reclaim is exactly by carrying out directly or indirectly burning realization to waste water.
Using glycine method(IDA methods)Contain glyphosate, glyphosine, methyl glyphosate, phosphorus in the mother liquor of production glyphosate Hydrochlorate, sodium chloride, sodium hydroxide and other matter, wherein sodium chloride-containing are 14 ~ 18%.
Production glyphosate(N- (phosphonomethyl) glycines)Process:Basic fluxing raction is carried out with alkali and iminodiacetonitrile, Alkaline hydrolysis finishes rear acid adding and carries out acidification reaction.Then intensification separated goes out partially acidic waste water, and imino-diacetic is obtained after filtration Acetic acid sodium salt solution, finally adds again hydrochloric acid to carry out after acidification reaction, refilters so as to obtain iminodiacetic acid solid.Then will Iminodiacetic acid carries out condensation reaction and obtains PMIDA mother liquor and condensation water, finally makes glyphosate by PMIDA mother liquor female Liquid, glyphosate mother solution evaporation obtains glyphosate finished product and filtrate(Raffinate).
The N-(phosphonomethyl) iminodiacetic acid wastewater of generation, PMIDA make the waste water produced during glyphosate after condensation reaction, due to being all acidity, Substantial amounts of alkaline matter need to be added in waste water to neutralize, then sweet phosphine mother liquor is directly sent into evaporimeter and is evaporated concentration, it is dense Filtrate after contracting delivers to incinerator burning, and incineration temperature is high, and burning obtains in product that pyrophosphate content is low, and phosphorous recovery is low. And due to containing substantial amounts of sodium chloride, organic phosphorus compound, particularly waste water in mother liquor for alkalescence(PH is 10 ~ 13), can lead Concentration raffinate after induced evaporation becomes a kind of very sticky pasty masses, it is impossible to continue to concentrate, concentration rate is extremely difficult to 3 More than times, desalination rate is low, and burning disposal amount is big, with high costs;The sodium chloride abraum salt being evaporated carries substantial amounts of concentrated mother liquor And need to process again for alkalescence, bring serious secondary pollution.Sodium ion excessively causes burnt in incineration ashes in due to evaporating liquid Phosphoric acid sodium content is low, produces pollution during recycling again.
Number of patent application is that 2005100600209 invention is related to be given up in glyphosate synthesis intermediate PMIDA preparation process The new method of water process.The method is mainly in PMIDA preparation process, filters and removes after PMIDA crystal, toward remaining filtrate Or a certain amount of ammonium hydrogen carbonate is added in filtrate after concentration, fully reaction is filtered, and obtains sodium acid carbonate and the filtrate containing ammonium chloride. Sodium acid carbonate can recycle the preparation in PMIDA, and concentrating filter liquor is obtained ammonium chloride by-product.The method needs to consume big The ammonium hydrogen carbonate of amount, ammonium chloride remains a need for Crystallization Separation, relatively costly.
The content of the invention
Goal of the invention:There is provided one kind can improve evaporation and concentration multiple, reduce raffinate incineration temperature, fully recycle it It reacts the processing method of the glyphosate waste water of spent acid.
Technical scheme:In the processing method of the glyphosate waste water of the present invention, the glyphosate mother solution obtained using IDA methods is not straight Evaporation is connect, but is first added thereto to the acid waste water produced in glyphosate production process(It is sweet that glyphosate mother solution Jing films reclaim grass The condensation point of film dope, PMIDA mother liquor or PMIDA production of the acid filtrate, glyphosate mother solution after phosphine Jing after film concentration Water etc.)Or the spent acid produced in other products production process(The waste hydrochloric acid of production trichloroacetaldehyde by-product, the esters resistance of production pyrophosphoric acid The by-product waste hydrochloric acid of combustion agent), IDA method glyphosate mother solutions are neutralized into pH for after 5 ~ 9(It is preferred that neutral)After enter back into evaporimeter and enter Row is concentrated by evaporation, and can will be concentrated by evaporation multiple and be improved to 4 ~ 6 times by original 3 times.
Wherein it is possible to from following process parameter:
Glyphosate by using glycine mother liquor(PH is 10 ~ 12, and glyphosate content is 0.8 ~ 1.2%, and sodium chloride content is 13 ~ 18%, total phosphorus For 0.8 ~ 1.5%)Directly do not evaporate, be added thereto to acid filtrate of the IDA methods glyphosate mother solution Jing after film reclaims glyphosate(pH For 0.7 ~ 1.5, glyphosate content is 3 ~ 6%, and total phosphorus is 0.8 ~ 1.5%), IDA methods glyphosate mother solution Jing film concentration after film dope (PH is 1 ~ 2, and glyphosate content is 7 ~ 10%, and total phosphorus is 1.5 ~ 3%), PMIDA mother liquor(PH is -0.3 ~ 2, and PMIDA content is 0.5 ~ 2%, total phosphorus is 0.8 ~ 1.5%), PMIDA production condensation point water(Content of hydrochloric acid is 10 ~ 20%)Deng glyphosate production process One or more in the acid waste water of middle generation, or add production trichloroacetaldehyde by-product waste hydrochloric acid(Content of hydrochloric acid be 25 ~ 31%), production NLD-02 fire retardant by-product waste hydrochloric acids(Content of hydrochloric acid is 25 ~ 31%)In one or two.
It is white granular thing to steam salt, neutral, and containing NaCl 98%, total phosphorus content is 50 ~ 400ppm.Steaming water total phosphorus is Below 40ppm, can directly discharge Jing after biochemical treatment.
Steam concentrate(Raffinate)For bright orange concentrated liquid, proportion is 1.48 ~ 1.55g/ml, and total phosphorus is 9 ~ 18%.Now evaporate Obtain raffinate(Include the materials such as neutral salt)Burn, incineration temperature can be dropped to 600 DEG C or so by 800 DEG C or so, burn and produce Thing for greyish white to white powdery solids, the sodium pyrophosphate content after burning in remaining product by 84% or so bring up to 96% with On, incineration ashes stay in grade.
Beneficial effect:
The present invention provides a kind of concentrated acid multiple that can improve evaporation concentrated solution, reduces the incineration temperature of raffinate, improves concentrated acid effect Rate, reduces energy resource consumption.
Meanwhile, can by the acid waste water produced in glyphosate production process while dispose, without the need for other alkaline cleaning, And the phosphorus in acid waste water is fully reclaimed, total phosphorous recovery is up to more than 98%.Reach with the purpose of dirty pollution treatment, comprehensive utilization.Should N-(phosphonomethyl) iminodiacetic acid wastewater and IDA methods glyphosate waste water in process route without the need for other route processing, can and glyphosate by using glycine Mother liquor mixing is directly processed.Trichloroacetaldehyde, NLD-02 flame retardant products by-product hydrochloric acid in the process route is without the need for other road Line process, can directly be processed with the mixing of glyphosate by using glycine mother liquor.Environmental protection index and economic benefit are projected.
Specific embodiment
The present invention is further elaborated below in conjunction with example, it should be appreciated that, following examples are intended merely to solution The present invention is released, its particular content is not limited.
Embodiment 1
Glyphosate by using glycine mother liquor 1000g, there is after testing chlorion 13.5%, and total phosphorus 0.95% adds trichloroacetaldehyde by-product to give up Hydrochloric acid(Content of hydrochloric acid is 28.5%), glyphosate by using glycine waste water is adjusted into pH to 7.0, negative pressure multiple-effect evaporation is to cycles of concentration For 5, filter, filter cake slightly washs removing organic matter, obtains sodium chloride 221.7g, salt clearance is 93.2% in glyphosate waste water, is steamed Total phosphorus content is 11ppm in water outlet, can be used for the preparation of the diluted alkaline of PMIDA production, concentrate(Proportion is 1.51g/ml)Jing 600 DEG C of burnings, obtain sodium pyrophosphate 41.9g, and content is 98.5%, and phosphorus conversion ratio is 98.8%.
Embodiment 2
Glyphosate by using glycine mother liquor 1000g, there is after testing chlorion 13.5%, total phosphorus 0.95%;IDA method glyphosate mother solution Jing films The acid filtrate after glyphosate is reclaimed, after testing pH is 1.6, and total phosphorus is 1.2%.It is sweet grass to be reclaimed with IDA method glyphosate mother solution Jing films Glyphosate by using glycine mother liquor is adjusted pH to 7.0 by the acid filtrate after phosphine, and negative pressure multiple-effect evaporation to cycles of concentration is 4.5, mistake Filter, filter cake slightly washs removing organic matter, obtains sodium chloride 199.3g, and salt clearance is 89.6% in glyphosate by using glycine waste water, It is 1.2ppm to steam water TP Jing after biochemical treatment, and COD is 12ppm, and formaldehyde is 0.7ppm;Concentrate(Proportion is 1.50g/ml)Jing 600 DEG C of burnings, obtain sodium pyrophosphate 73.3g, and content is 98.9%, and phosphorus conversion ratio is 98.9%.

Claims (2)

1. a kind of processing method of glyphosate waste water, the glyphosate mother solution obtained using IDA methods, it is characterised in that:Described grass Sweet phosphine mother liquor does not directly evaporate, but is first added thereto to the acid waste water of generation or production trichlorine in glyphosate production process The waste hydrochloric acid of acetaldehyde by-product or the by-product waste hydrochloric acid of production pyrophosphate based flame retardant, by IDA method glyphosate mother solutions pH is neutralized to Concentration is evaporated to enter back into evaporimeter after 5 ~ 9;Evaporate raffinate incineration temperature be 600 DEG C or so.
2. the processing method of glyphosate waste water as claimed in claim 1, it is characterised in that:PH is that 10 ~ 12, glyphosate content is 0.8 ~ 1.2% glyphosate by using glycine mother liquor does not directly evaporate, and it is 0.7 ~ 1.5 glyphosate content to be added thereto to described pH For 3 ~ 6% glyphosate mother solution Jing film reclaim glyphosate after acid filtrate, or add pH be 1 ~ 2, glyphosate content be 7 ~ Film dope of the 10% IDA methods glyphosate mother solution Jing after film concentration, or add pH to be -0.3 ~ 2, PMIDA content is 0.5 ~ 2% PMIDA mother liquor, or add content of hydrochloric acid for 10 ~ 20% condensation point water that produces of PMIDA, or add content of hydrochloric acid For 25 ~ 31% production trichloroacetaldehyde by-product waste hydrochloric acid, or add content of hydrochloric acid for 25 ~ 31% production NLD-02 fire retardant pairs Produce waste hydrochloric acid in one or two.
CN201611173272.7A 2016-12-18 2016-12-18 Treatment method for glyphosate waste water Pending CN106630348A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110550793A (en) * 2018-05-30 2019-12-10 杭州九清科技有限公司 Purification process of salt in phosphate-containing wastewater

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003531090A (en) * 2000-04-14 2003-10-21 ダウ・アグロサイエンス・エル・エル・シー Removal of chloride from phosphonomethyliminodiacetic acid process
CN103274380A (en) * 2013-05-08 2013-09-04 山东潍坊润丰化工有限公司 Glyphosate mother liquid treatment method and device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003531090A (en) * 2000-04-14 2003-10-21 ダウ・アグロサイエンス・エル・エル・シー Removal of chloride from phosphonomethyliminodiacetic acid process
CN103274380A (en) * 2013-05-08 2013-09-04 山东潍坊润丰化工有限公司 Glyphosate mother liquid treatment method and device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110550793A (en) * 2018-05-30 2019-12-10 杭州九清科技有限公司 Purification process of salt in phosphate-containing wastewater
CN110550793B (en) * 2018-05-30 2022-02-11 杭州九清科技有限公司 Purification process of salt in phosphate-containing wastewater

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Application publication date: 20170510