CN101597306B - Method for nanofiltration separation and comprehensive utilization of glyphosate mother liquor - Google Patents
Method for nanofiltration separation and comprehensive utilization of glyphosate mother liquor Download PDFInfo
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- CN101597306B CN101597306B CN2009100627958A CN200910062795A CN101597306B CN 101597306 B CN101597306 B CN 101597306B CN 2009100627958 A CN2009100627958 A CN 2009100627958A CN 200910062795 A CN200910062795 A CN 200910062795A CN 101597306 B CN101597306 B CN 101597306B
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Abstract
The invention discloses a method which is suitable for the separation and the comprehensive utilization of components of glyphosate mother liquor. The method adopts three-stage nanofiltration separation glyphosate mother liquor, the concentrated water side of a nanofiltration membrane is provided with glyphosate concentrated liquor, and percolate of the nanofiltration membrane is concentrated sodium chloride solution. First stage nanofiltration concentrated liquor is diluted by water and then is led into a second stage nanofiltration; and second stage nanofiltration concentrated liquor is diluted by water and then is led into a third stage nanofiltration. The glyphosate solution concentrated by the three-stage nanofiltration is recycled to be used as water for rinsing products. The concentrated sodium chloride solution which is processed by three-stage nanofiltration permeation contains micromolecule organic matters and is processed by the photocatalysis-chemical oxidation method to obtain brine to be used as a raw material for producing sodium hudroxide. The method carries out the operation of three-stage nanofiltration separation and photocatalysis-chemical oxidation on the glyphosate mother liquor, can realize the zero release comprehensive utilization of the glyphosate mother liquor, and has outstanding economic and environmentally friendly benefits.
Description
Technical field
The present invention is specifically related to a kind of glyphosate waste water nanofiltration separation and comprehensive utilization method, belongs to field of environment engineering technology, also belongs to technical field of chemical engineering.
Background technology
Glyphosate is a kind of high-efficiency low-toxicity weedicide, is the big special phosphorus chemical product of price height, demand.Because its market outlook are good, profit is high, in several years, domestic production producer develops family more than 3000 rapidly.But processing wastewater---the glyphosate mother solution of glyphosate production flow process discharging has salts contg height, organic concentration height, characteristics that density is big.For this waste water, still there is not a kind of treatment process effectively at present, in case discharging, will be to water, make into severe contamination with local methods, ecotope is done great damage.
The main component of glyphosate waste water is inorganic salt and organism, and inorganics mainly is a sodium-chlor, and organic main component is glyphosate, methyl alcohol, methylal, triethylamine etc.In glyphosate waste water, NaCl content is up to 145g/L, and COD is up to 30g/L, and wherein glyphosate content is 10g/L～12g/L, and density is up to 1.18g/mL.Because salts contg is high and have bio-toxicity, the organism in this waste water cannot carry out biochemical degradation to be handled.At present, the main path of domestic processing glyphosate waste water is to add the glyphosate powdered preparation to become gyphosate solution to sell.Because contain a large amount of sodium-chlor in the gyphosate solution, cause the Cl-severe overweight, cause the water and soil severe contamination.Therefore, country has prohibited glyphosate production enterprise marketing lower concentration gyphosate solution product.Because a large amount of glyphosate waste waters can not get effective utilization, can not directly discharge again, and not have economic and practical treatment process, therefore, glyphosate waste water has become glyphosate production enterprise millstone around one's neck, becomes the technical barrier of serious restriction enterprise development.
This project seminar has carried out deep research to glycine method synthesizing glyphosate technology, glyphosate waste water is carried out complete water quality analysis and characteristic research, proposed the technical thought of glyphosate waste water " three grades nanofiltration separation, photochemical catalysis-chemical oxidation treatment " comprehensive utilization.Glyphosate solution after the separation, direct reuse are made the make up water of glyphosate powder washing water in the synthetic glyphosate technology, have both reclaimed glyphosate products, have also reclaimed a part of water; The isolated sodium chloride solution that contains small organic molecule adopts photochemical catalysis-chemical oxidation technology further to handle, and preparation bittern had both reclaimed salt, reclaims the water of a part in addition again.Can realize the main component high efficiente callback and the wastewater zero discharge of glyphosate waste water.
Summary of the invention
The objective of the invention is, at glyphosate waste water sodium-chlor and the high characteristics of glyphosate content, adopt the suitable technique measure to carry out separating treatment, recovery has the resource of economic use value, realize waste water reclaiming, avoid discharge of wastewater to cause serious water and soil problem of environmental pollution.
Technical thought of the present invention is, adopts three grades of nanofiltration techniques to separate glyphosate and sodium-chlor in the waste water, and the dense water side of nanofiltration membrane is the glyphosate concentrated solution, nanofiltration membrane to see through liquid be sodium chloride solution.First step nanofiltration concentrated solution, dilute with water enters second stage nanofiltration; Second stage nanofiltration concentrated solution, dilute with water enters third stage nanofiltration.Through three grades of spissated glyphosate solution of nanofiltration, the product bath water is made in reuse.Three grades of sodium chloride solutions that nanofiltration sees through contain small organic molecule, adopt processings that mineralize of photochemical catalysis-chemical oxidization method, are prepared into bittern, are used as the production of caustic soda raw material.
A kind of components of glyphosate mother liquor that is applicable to that the present invention proposes is separated and comprehensive utilization method, a kind of components of glyphosate mother liquor that is applicable to is separated and comprehensive utilization method, it is characterized in that: adopt three grades of glyphosate and sodium-chlor in the sodium filtering technologies separation glyphosate mother solution, the dense water side of sodium filter membrane is the glyphosate concentrated solution, and the liquid that sees through of sodium filter membrane is the sodium-chlor concentrated solution; Isolated glyphosate concentrated solution, the product bath water is made in reuse; Isolated sodium-chlor concentrated solution adopts photochemical catalysis-chemical oxidation treatment to be prepared into bittern.
Above-mentioned first step sodium filter concentration liquid after the de-mineralized water dilution, enters second stage sodium filter, carries out the second time and separates; Second stage sodium filter concentration liquid with the de-mineralized water dilution, enters the filter of third stage sodium, separates for the third time.
The used sodium filter membrane of the present invention is for can molecular weight cut-off being the nanofiltration membrane of 169 glyphosate.
Glyphosate waste water of the present invention is through first step nanofiltration, and the solution that sees through nanofiltration membrane is one-level nanofiltration separation sodium chloride solution; The solution that does not see through is one-level nanofiltration separation glyphosate concentrated solution, with de-mineralized water dilution one-level nanofiltration separation glyphosate concentrated solution, as the water inlet of second stage nanofiltration; Handle through second stage nanofiltration separation, the solution that sees through nanofiltration membrane is secondary nanofiltration separation sodium chloride solution; The solution that does not see through is secondary nanofiltration separation glyphosate concentrated solution, with de-mineralized water dilution secondary nanofiltration separation glyphosate concentrated solution, as the water inlet of third stage nanofiltration; Handle through third stage nanofiltration separation, the solution that sees through nanofiltration membrane is three grades of nanofiltration separation sodium chloride solutions; The solution that does not see through is three grades of nanofiltration separation glyphosate concentrated solutions, and this concentrated solution is back in the process for synthesizing glyphosate, as the bath water of glyphosate products; Collect three grades of sodium chloride solutions that nanofiltration separation goes out, adopt photochemical catalysis-chemical oxidation combination treatment method,, be prepared into bittern, be used as the production of caustic soda raw material the small organic molecule that it contained processings that mineralize.
The present invention adopts technique scheme, and the washing water that glyphosate powder in the synthetic technology is made in isolated glyphosate solution reuse had both reclaimed the high glyphosate of economic worth, had and had reclaimed the process water that specific water quality requirement is arranged.Isolating sodium chloride solution is used to prepare bittern, has both reclaimed the industrial salt that may cause the water and soil salinization, has realized the resource utilization of waste water again.
The technology that the present invention forms is expected to obtain widespread use in the pesticide chemical industry of producing glyphosate, has substantial economics and environmental benefit, and the synthesized competitiveness of carrying out, promote enterprise smoothly that ensures glyphosate production enterprise industry is had strategic importance.
Description of drawings
Accompanying drawing is glyphosate waste water nanofiltration separation of the present invention and comprehensive utilization method and process flow sheet.
Embodiment
Three grades of nanofiltration separation technical process of glyphosate waste water of the present invention as shown in Figure 1.Glyphosate waste water in the glyphosate waste water case 1, at first in heat exchanger 2, carry out heat exchange with isolated sodium chloride solution, make the higher glyphosate waste water cooling of temperature, to adapt to the temperature requirement of nanofiltration membrane water inlet, the sodium chloride aqueous solution temperature is raise, help the carrying out of redox reaction in the sodium chloride solution; Cooled glyphosate waste water is the pre-filtering dress device 3 (deep bed filter or pipe filter) of 5 μ m through the aperture, removes suspended substance and particulate matter, and the strainer water outlet enters the nanofiltration membrane system; Nanofiltration system employings at different levels can molecular weight cut-off be the nanofiltration membrane of 169 glyphosate; The strainer water outlet at first enters one-level nanofiltration membrane 4, and the glyphosate concentrated solution of one-level nanofiltration membrane 4 through the make up water dilution from sweet-water tank 8, reaches the water quality requirement of secondary nanofiltration water inlet; Concentrated solution through the water-reducible one-level nanofiltration 4 of desalination enters secondary nanofiltration membrane 5, the glyphosate concentrated solution of secondary nanofiltration membrane 5, and the make up water dilution through from sweet-water tank 8 reaches the influent quality requirement of three grades of nanofiltration membrane 6; Glyphosate concentrated solution through dilution enters the glyphosate concentrated solution of 6, three grades of nanofiltration membrane 6 of three grades of nanofiltration membrane, enters glyphosate concentrated solution water tank 7, promptly obtains the glyphosate solution of using as the washing glyphosate products.Through three grades of nanofiltration separation, the product water that sees through nanofiltration membrane at different levels is the sodium chloride aqueous solution that contains small organic molecule, through over-heat-exchanger 3, enter photochemical catalysis-chemical oxidation device 9, and oxygenant H2O2 added in photochemical catalysis-chemical oxidation devices 9 by H2O2 water tank 12, under the condition that the nano TiO 2 catalyzer exists, use UV-irradiation, the organism in the sodium chloride solution is carried out co-oxidation handle; The water outlet of photochemical catalysis-chemical oxidation device 9 enters spray upgrading tower 10, carries out stripping, evaporation, cooling, and the bittern that finally obtains enters bittern case 11.
Claims (3)
1. one kind is applicable to components of glyphosate mother liquor separation and comprehensive utilization method, it is characterized in that: adopt three grades of glyphosate and sodium-chlor in the nanofiltration techniques separation glyphosate mother solution, the dense water side of nanofiltration membrane is the glyphosate concentrated solution, and the liquid that sees through of nanofiltration membrane is the sodium-chlor concentrated solution; The glyphosate concentrated solution that first step nanofiltration produces after the de-mineralized water dilution, enters second stage nanofiltration, carries out the second time and separates; The glyphosate concentrated solution of the generation that second stage nanofiltration produces with the de-mineralized water dilution, enters third stage nanofiltration, separates for the third time; Isolated glyphosate concentrated solution, the product bath water is made in reuse; Isolated sodium-chlor concentrated solution adopts photochemical catalysis-chemical oxidation treatment to be prepared into bittern.
2. method according to claim 1 is characterized in that: used nanofiltration membrane is for can molecular weight cut-off being the nanofiltration membrane of 169 glyphosate.
3. method according to claim 1 and 2 is characterized in that: glyphosate waste water is through first step nanofiltration, and the solution that sees through nanofiltration membrane is one-level nanofiltration separation sodium chloride solution; The solution that does not see through is one-level nanofiltration separation glyphosate concentrated solution, with de-mineralized water dilution one-level nanofiltration separation glyphosate concentrated solution, as the water inlet of second stage nanofiltration; Handle through second stage nanofiltration separation, the solution that sees through nanofiltration membrane is secondary nanofiltration separation sodium chloride solution; The solution that does not see through is secondary nanofiltration separation glyphosate concentrated solution, with de-mineralized water dilution secondary nanofiltration separation glyphosate concentrated solution, as the water inlet of third stage nanofiltration; Handle through third stage nanofiltration separation, the solution that sees through nanofiltration membrane is three grades of nanofiltration separation sodium chloride solutions; The solution that does not see through is three grades of nanofiltration separation glyphosate concentrated solutions, and this concentrated solution is back in the process for synthesizing glyphosate, as the bath water of glyphosate products; Collect three grades of sodium chloride solutions that nanofiltration separation goes out, adopt photochemical catalysis-chemical oxidation combination treatment method,, be prepared into bittern, be used as the production of caustic soda raw material the small organic molecule that it contained processings that mineralize.
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| CN2009100627958A CN101597306B (en) | 2009-06-23 | 2009-06-23 | Method for nanofiltration separation and comprehensive utilization of glyphosate mother liquor |
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| CN2009100627958A CN101597306B (en) | 2009-06-23 | 2009-06-23 | Method for nanofiltration separation and comprehensive utilization of glyphosate mother liquor |
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| CN101597306B true CN101597306B (en) | 2011-08-17 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786735A (en) * | 2010-02-11 | 2010-07-28 | 浙江新安化工集团股份有限公司 | Film treatment method of glyphosate mother liquor |
| CN102161677B (en) * | 2010-02-18 | 2015-07-22 | 浙江新安化工集团股份有限公司 | Membrane process technology for extracting glyphosate from glyphosate mother liquor |
| CN104163519B (en) * | 2014-05-23 | 2016-05-04 | 杭州天创环境科技股份有限公司 | The process for purification of effluent brine in a kind of glyphosate production |
| CN107098360B (en) * | 2017-04-28 | 2018-09-28 | 湖北兴瑞化工有限公司 | The method for producing ion film caustic soda raw material using glyphosate effluent brine |
| EP3708698A1 (en) * | 2019-03-13 | 2020-09-16 | Covestro Deutschland AG | Method for reprocessing and reuse of process water containing salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827626A (en) * | 2006-04-07 | 2006-09-06 | 浙江龙游绿得农药化工有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
| CN101041527A (en) * | 2007-03-06 | 2007-09-26 | 杭州天创净水设备有限公司 | Wastewater treatment technique for PMIDA preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1827626A (en) * | 2006-04-07 | 2006-09-06 | 浙江龙游绿得农药化工有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
| CN101041527A (en) * | 2007-03-06 | 2007-09-26 | 杭州天创净水设备有限公司 | Wastewater treatment technique for PMIDA preparation process |
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