CN106082515B - A kind of incineration treatment technology of glyphosate mother solution - Google Patents

A kind of incineration treatment technology of glyphosate mother solution Download PDF

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CN106082515B
CN106082515B CN201610476393.2A CN201610476393A CN106082515B CN 106082515 B CN106082515 B CN 106082515B CN 201610476393 A CN201610476393 A CN 201610476393A CN 106082515 B CN106082515 B CN 106082515B
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sent
incineration
crystallization
burning
separation
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CN106082515A (en
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张华�
杨国华
唐建军
杨吉
景凡
李�权
石好
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Sichuan Fusida Biotechnology Development Co Ltd
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Sichuan Fusida Biotechnology Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • 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
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00Halides of sodium, potassium or alkali metals in general
    • C01D3/04Chlorides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/38Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3808Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813N-Phosphonomethylglycine; Salts or complexes thereof
    • 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
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity
    • 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
    • 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
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/74Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention discloses a kind of incineration treatment technologies of glyphosate mother solution, including glyphosate mother solution is sent into membrane treatment appts, obtain concentrated mother liquor and permeate, concentrated mother liquor mentions powder for glyphosate, it is separated with through once oxidation, primary crystallization, after the separation of film separation system, secondary crystallization, be sent into incineration system, obtain sodium pyrophosphate, burn generation flue gas separation dust after carry out second-time burning again after discharge.The present invention for the first time combines the film process concentration technique of glyphosate mother solution with burning process, for thoroughly solving the problems, such as the processing of glyphosate mother solution, the salt obtained after burning can be with recycling and reusing, the flue gas generated is burned through separation dust and second-time burning, the generation that dioxin in flue gas can significantly be reduced, meets environmental requirement.

Description

A kind of incineration treatment technology of glyphosate mother solution
Technical field
The present invention is a kind of incineration treatment technology of glyphosate mother solution, and in particular to has recycled the glyphosate of mixed phosphate sodium Mother liquor incineration treatment technology, belongs to pesticide production technology field.
Background technique
The prevailing technology of China's glyphosate production is completed using glycine method (also known as alkyl vinegar method), synthetic reaction Being separated by solid-liquid separation when extracting glyphosate afterwards can generate a large amount of acid mother liquids (pH < 1. 0), and the three of about 24% are contained in the acid mother liquid Ethylamine hydrochloride, the glyphosate of 1-3% and glyphosine, methyl glyphosate, AminomethylphosphoniAcid Acid, phosphonous acid diformazan vinegar, Phos Hydrochlorate etc..Since mother liquor contains largely organic equal pollutants, serious environmental problem will be brought by being directly discharged into environment.2010 Before year, domestic enterprise substantially uses and handles the method that glyphosate mother solution is configured to 10% gyphosate solution.But by All impurity in mother liquor are all introduced into formulation products, are all caused to soil environment and food safety long-term potential Negative effect.Therefore, 2 months 2009, the Ministry of Agriculture made an announcement, and 10% gyphosate solution is prohibited to produce.In this way, glyphosate The processing of mother liquor is bound to seek new method.
The processing method of existing glyphosate mother solution is usually: (1) after mother liquor acid adding becomes secondary acid mother liquor, by UF membrane skill Art recovery section glyphosate;(2) mother liquor after recovery section glyphosate, using high-temperature oxydation, supercritical oxidation, Fenton oxidation etc. Then plus the alkaline matters such as calcium oxide technology will be decomposed wherein phosphorus-containing matter, be formed calcium phosphate precipitation not soluble in water and got off. By the precipitating then passed through plus precipitating reagent (calcium salt, molysite) carries out, the phosphate product added value of formation is low, due to being added newly Substance causes the phosphate component generated more complicated, and deep processing difficulty increases.
A kind of existing processing method of glyphosate mother solution of patent document CN102874786A(, 2013.1.16) propose one Kind will be concentrated through triethylamine glyphosate mother solution after the recovery through multiple-effect evaporation, and after being cooled to room temperature, filtering takes filter cake, washing removes Go organic matter to get inorganic salts;It takes filtrate to burn the process to get pyrophosphate at 600-900 DEG C through incinerator, there is work Skill is simple, environment friendly and pollution-free feature.
Summary of the invention
The purpose of the present invention is to provide a kind of incineration treatment technologies of glyphosate mother solution, using UF membrane, an oxygen Change,;Twice Crystallization Separation, incineration system burn and etc. efficient combination, can effectively solve recycling mixed phosphate sodium after grass Sweet phosphine mother liquor is again introduced into the low problem of wet oxidation system oxidation conversion ratio, thoroughly solves the problems, such as the processing of glyphosate mother solution, Should be widely promoted use.
The present invention is achieved through the following technical solutions: a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 10~ 20% mentions powder for glyphosate, and 80~90% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate enters second-time burning after burning the flue gas separation dust of generation.
Glyphosate mother solution of the present invention is from the glyphosate alkali mother liquor after triethylamine recyclable device, TP concentration 20000mg/l。
The permeate that the permeate and film separation system that the membrane treatment appts obtain obtain is sent to concentration refined unit, Refined brine is prepared or solid recycling Nacl, the waste water that concentration purification generates are sent into sewage treatment plant.
The heat source that the concentration refined unit uses is the steam that coal-burning boiler provides, for producing refined brine or solid Recycle Nacl.
In the present invention, membrane treatment appts and film separation system can effectively be intercepted organic matter, and membrane treatment appts obtain Sodium chloride Nacl can be obtained after being concentrated by evaporation in the permeate obtained, and (TOC≤200ppm) meets modified diaphragm burning after refining Alkali production, can make full use of glyphosate production byproduct sodium chloride;Film separation system purifies Phos in permeate, improves Disodium yield.
The mixed phosphate sodium that the primary crystallization separation, secondary crystallization separation obtain is for producing sodium tripolyphosphate or six partially Sodium phosphate.The mixed phosphate sodium includes 12 water disodium hydrogen phosphate of by-product etc..
In the step B, once oxidation includes: that concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 180~260 DEG C of temperature are controlled, 2.5~8MPa of pressure blasts air and aoxidized, and the gas for aoxidizing generation is washed After tower processing, it is sent into incineration system.The gas that above-mentioned oxidation generates is mainly the organic amines such as inorganic ammonia and ethanol amine, is usually adopted After being extracted out gas with negative pressure exhausting, carrying out washing treatment is washed with three-level, then by pipeline air inducing to incineration system centralized burning.
The crystallization temperature that the primary crystallization separation is separated with secondary crystallization is 5~18 DEG C.
Crystallization kettle of the present invention is low temperature crystallization kettle, and the rate of recovery of primary crystallization separation can reach 70%, secondary crystallization For the isolated rate of recovery up to 85%, the cold source of Crystallization Separation uses five degree of water and minus five degree of water.Refrigeration unit is set, and refrigerant is R22, refrigerant are ethylene glycol.
In the step C, incineration system uses scale plate incinerator, and centrifugal filtrate is atomized in penetrating incinerator and is burnt Fuel burning contact, the burning fuel is using one of coal gas, coke-stove gas, natural gas, hydrogen or diesel oil or a variety of groups At mixture.
The Con trolling index of the incineration system meets:
Incineration temperature: 800~1000 DEG C;
The high-temperature flue gas residence time: > 2S.
Incineration system of the present invention can realize efficiency of combustion 99.9%, destroy removal rate 99.99%, the hot igloss of residue by fire The technological effect of rate≤5% has operating cost low, and organic matter burns complete feature, meets environmental requirement.
After the flue gas separation dust for burning and generating, second-time burning, the temperature of second-time burning are carried out in incineration system Degree control is at 1100 DEG C, gas residence time > 2S.
Compared with prior art, the present invention have the following advantages that and the utility model has the advantages that
(1) present invention is the work of the thoroughization recovery processing carried out to the glyphosate alkali mother liquor after triethylamine recyclable device Skill, be related to UF membrane, concentration purification, high-temperature oxydation, Crystallization Separation, high temperature incineration and etc. use, can effectively solve to recycle Glyphosate mother solution after mixed phosphate sodium is again introduced into the low problem of wet oxidation system oxidation conversion ratio, thoroughly solves glyphosate The processing problem of mother liquor, reduces the environmental protection pressure of process for synthesizing glyphosate.
(2) present invention is combined using membrane treatment appts with refined unit is concentrated, for the concentration and separation of glyphosate mother solution, Concentrate after film process mentions powder and high-temperature oxydation for glyphosate, and the permeate after film process is sent into concentration refined unit, warp The sodium chloride Nacl obtained after evaporation and concentration, (TOC≤200ppm) meets modified diaphragm production of caustic soda after refining, can be abundant Using glyphosate production byproduct sodium chloride, three-protection design is reduced, reduces caustic soda cost, realizes circular economy and sustainable development.
(3) present invention is concentrated glyphosate mother solution by membrane treatment appts, and operating cost is lower, and is concentrated by evaporation Compared to a large amount of steam can be saved, energy consumption is reduced, cost control is conducive to.
(4) once oxidation process of the present invention is concentrated mother liquor after film process in high-temperature oxidation device, in ruthenium Under catalyst action, 180~260 DEG C of temperature, under 2.5~8MPa of pressure, blast the oxidation process of air progress, should during it is single The organic phosphine conversion ratio of secondary oxidation is greater than 90%, and non-exhaust emission aoxidizes inorganization gas (inorganic ammonia and ethanol amine etc. of generation Organic amine), after scrubbing tower processing, by pipeline air inducing to incineration system centralized burning.
(5) in the method for the present invention, a centrifugal filtrate after primary crystallization separation enters film separation system, is cut by nanofiltration Phosphorus (Phos, organic phosphine) is stayed, 95% is greater than to the rejection of phosphorus, the total phosphorus concentration of the concentrate after UF membrane is about Wherein Phos is greater than 15000mg/l to 50000mg/l(), then secondary crystallization separation is carried out, it is saturating after film separation system separates Crossing in liquid total phosphorus concentration is 600~800mg/l, and permeate enters concentration purification, should during, film separation system can to once from Phos is purified in heart filtrate, further increases disodium yield.
(6) biochemical treatment of waste water in each step can be achieved in the present invention, the permeate including obtaining membrane treatment appts and The permeate that membrane separation device obtains is concentrated by evaporation the dirty cold water generated, washing water is sent into sewage treatment plant's biochemical treatment;It will The concentrate that the permeate that the permeate and membrane separation device that membrane treatment appts obtain obtain is produced through evaporation is for producing purified salt Water or solid recycle Nacl;The water outlet of normal temperature oxidation device enters Wastewater Pretreatment, and total phosphorus concentration is lower than 10mg/ after processing After l, sewage treatment plant's biochemical treatment etc. is sent.
(7) the method for the present invention can realize the extraction of P elements in glyphosate mother solution, pass through primary crystallization separation, secondary crystallization The mixed phosphates sodium such as the 12 water disodium hydrogen phosphate of by-product obtained are separated for producing sodium tripolyphosphate and calgon, and burning The sodium pyrophosphate of system production realizes recycling for P elements, has not only reduced the influence to environment but also had for producing phosphate fertilizer There is certain economic benefit, is suitable for being widely used to promote.
(8) present invention for the first time combines the film process concentration technique of glyphosate mother solution with burning process, obtains after burning Salt can be with recycling and reusing, treating capacity is big, treatment process to salt content no requirement (NR), burn the flue gas of generation through separation dust and Second-time burning can significantly reduce the generation of dioxin in flue gas, meet environmental requirement.
(9) present invention burns film process concentrate using incineration system, and coal gas, coke-stove gas, day can be used Right gas, hydrogen, diesel oil etc. are fuel, and the byproduct steam of incinerator may be incorporated into System steam pipe network and realize energy regenerating, reduce life Produce cost, energy conservation and environmental protection.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present invention is described in further detail below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 10% is used Powder is mentioned in glyphosate, 90% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
Embodiment 2:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 20% is used Powder is mentioned in glyphosate, 80% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
The permeate that permeate and film separation system that in the above process, membrane treatment appts are obtained obtain is sent to concentration Refined unit, is prepared refined brine or solid recycling Nacl, the waste water that concentration purification generates are sent into sewage treatment plant, this In embodiment, the heat source that concentration refined unit uses is the steam that coal-burning boiler provides, and is returned for producing refined brine or solid Receive Nacl.
Embodiment 3:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 15% is used Powder is mentioned in glyphosate, 85% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
In the above process, the mixed phosphate sodium that primary crystallization separation, secondary crystallization separation obtain is for producing tripolyphosphate Sodium or calgon.
Embodiment 4:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 12% is used Powder is mentioned in glyphosate, 88% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
In above-mentioned steps B, once oxidation includes: that concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 180 DEG C of temperature are controlled, pressure 2.5MPa blasts air and aoxidized, and aoxidizes the washed tower processing of gas of generation Afterwards, it is sent into incineration system.
Embodiment 5:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 18% is used Powder is mentioned in glyphosate, 82% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
In the above process, the crystallization temperature of primary crystallization separation is 5 DEG C, and the crystallization temperature of secondary crystallization separation is 5 DEG C.
Embodiment 6:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, comprising the following steps:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 10% is used Powder is mentioned in glyphosate, 90% for completing the operation of step B;
B, the concentrated mother liquor successively through once oxidation, primary crystallization separation after, be made a centrifugal filtrate, will once from Heart filtrate is sent into film separation system, obtains concentrate and permeate;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, is obtained Sodium pyrophosphate carries out second-time burning after burning the flue gas separation dust of generation.
In above-mentioned steps C, incineration system uses scale plate incinerator, and centrifugal filtrate is atomized in penetrating incinerator and burning Fuel contact, the burning fuel use coal gas.
Embodiment 7:
The present embodiment is defined the Con trolling index of incineration system on the basis of embodiment 6, the incineration system Con trolling index meets:
Incineration temperature: 800 DEG C;
The high-temperature flue gas residence time: 5S.
Embodiment 8:
The present embodiment and the difference of embodiment 7 are: in the present embodiment, burning the flue gas of generation after separating dust, In Second-time burning is carried out in incineration system, the temperature of second-time burning is controlled at 1100 DEG C, and gas residence time 4S prevents dioxin It generates again.
Embodiment 9:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 20% mentions powder for glyphosate, and 80% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 80% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 260 DEG C of temperature, pressure 8MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into knot Brilliant reaction kettle;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: the crystallization temperature for controlling crystallization reactor is 18 DEG C, completes primary crystallization separation, is obtained primary Centrifugal filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 18 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as coke-stove gas), and control incineration temperature is 1000 DEG C, high temperature After gas residence time is 3S, sodium pyrophosphate is obtained;The flue gas that burning generates carries out in incinerator secondary after separating dust The temperature of burning, second-time burning is controlled at 1100 DEG C, and gas residence time 2.5S obtains incineration flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 10:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 16% mentions powder for glyphosate, and 84% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 84% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 200 DEG C of temperature, pressure 5.5MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into Crystallization reactor;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: control crystallization reactor crystallization temperature be 8 DEG C, complete primary crystallization separation, obtain once from Heart filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 10 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: natural gas), and control incineration temperature is 900 DEG C, high temperature cigarette After the gas residence time is 5S, sodium pyrophosphate is obtained;It burns the flue gas generated and carries out secondary combustion in incinerator after separating dust It burns, the temperature of second-time burning is controlled at 1100 DEG C, and gas residence time 3S obtains incineration flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 11:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 14% mentions powder for glyphosate, and 86% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 86% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 220 DEG C of temperature, pressure 6.5MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into Crystallization reactor;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: control crystallization reactor crystallization temperature be 6 DEG C, complete primary crystallization separation, obtain once from Heart filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 8 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: the mixture of coal gas and natural gas composition), and control is burnt Burning temperature is 1000 DEG C, after the high-temperature flue gas residence time is 3S, obtains sodium pyrophosphate;The flue gas generated is burned after separating dust Second-time burning is carried out in incinerator, the temperature of second-time burning is controlled at 1100 DEG C, gas residence time 4S, obtains burning cigarette Gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 12:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 13% mentions powder for glyphosate, and 87% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 87% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 250 DEG C of temperature, pressure 4MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into knot Brilliant reaction kettle;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: the crystallization temperature for controlling crystallization reactor is 16 DEG C, completes primary crystallization separation, is obtained primary Centrifugal filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 12 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: the mixture of coke-stove gas, natural gas and hydrogen composition), Controlling incineration temperature is 880 DEG C, after the high-temperature flue gas residence time is 3S, obtains sodium pyrophosphate;The flue gas generated is burned through separating Second-time burning is carried out after dust in incinerator, the temperature of second-time burning is controlled at 1100 DEG C, and gas residence time 3S is obtained Incineration flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 13:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 10% mentions powder for glyphosate, and 90% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 90% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 245 DEG C of temperature, pressure 6MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into knot Brilliant reaction kettle;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: control crystallization reactor crystallization temperature be 6 DEG C, complete primary crystallization separation, obtain once from Heart filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 8 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: diesel oil), and control incineration temperature is 800 DEG C, high-temperature flue gas After residence time is 5S, sodium pyrophosphate is obtained;It burns the flue gas generated and carries out second-time burning in incinerator after separating dust, The temperature of second-time burning is controlled at 1100 DEG C, and gas residence time 3S obtains incineration flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 14:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 20% mentions powder for glyphosate, and 80% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 80% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 260 DEG C of temperature, pressure 5MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into knot Brilliant reaction kettle;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: control crystallization reactor crystallization temperature be 8 DEG C, complete primary crystallization separation, obtain once from Heart filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 5 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: coke-stove gas), and control incineration temperature is 950 DEG C, high temperature After gas residence time is 4S, sodium pyrophosphate is obtained;The flue gas that burning generates carries out in incinerator secondary after separating dust The temperature of burning, second-time burning is controlled at 1100 DEG C, and gas residence time 3.5S obtains incineration flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
Embodiment 15:
The present embodiment proposes a kind of incineration treatment technology of glyphosate mother solution, as shown in Figure 1, comprising the following steps:
(1) film process: glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, the concentrated mother liquor In, 15% mentions powder for glyphosate, and 85% for completing the operation of step B;Above-mentioned permeate is then sent to concentration refined unit, preparation Obtain refined brine or solid recycling Nacl.
(2) high-temperature oxydation: in step (1) 85% concentrated mother liquor is sent into high-temperature oxidation device, existing for ruthenium catalyst In the case of, 235 DEG C of temperature, pressure 3.6MPa are controlled, air is blasted and carries out once oxidation.Concentrate after once oxidation is sent into Crystallization reactor;After the gas generated after once oxidation is sent into scrubbing tower processing, then send to incineration system.
(3) Crystallization Separation: control crystallization reactor crystallization temperature be 7 DEG C, complete primary crystallization separation, obtain once from Heart filtrate and mixed phosphate sodium, the mixed phosphate sodium is for producing sodium tripolyphosphate or calgon.
(4) UF membrane: a centrifugal filtrate is sent into film separation system, concentrate is obtained and permeate, the permeate is sent To concentration refined unit, refined brine or solid recycling Nacl is prepared.
(5) concentrate that film separation system obtains in step (4) Crystallization Separation: is sent into crystallization reactor, control crystallization Temperature is 5 DEG C, completes secondary crystallization separation, and the isolated centrifugal filtrate of secondary crystallization is sent into incineration system, secondary crystallization point From obtained mixed phosphate sodium for producing sodium tripolyphosphate or calgon.
(6) burning process: incineration system uses scale plate incinerator, in step (5) by secondary crystallization it is isolated from Heart filtrate sprays into incinerator through atomization and contacts with burning fuel (such as: the mixture of coal gas and coke-stove gas composition), controls Incineration temperature is 850 DEG C, after the high-temperature flue gas residence time is 4.5S, obtains sodium pyrophosphate;The flue gas generated is burned through separating powder Second-time burning is carried out after dirt in incinerator, the temperature of second-time burning is controlled at 1100 DEG C, and gas residence time 6S is burnt Burn flue gas.
In the present embodiment, in step (1), step (4), the waste water that concentration purification generates is sent into sewage treatment plant, concentration essence The heat source that unit processed uses is the steam that provides of coal-burning boiler, for producing refined brine or solid recycling Nacl, complete every Film production of caustic soda or soda manufacture.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is all according to According to technical spirit any simple modification to the above embodiments of the invention, equivalent variations, protection of the invention is each fallen within Within the scope of.

Claims (4)

1. a kind of incineration treatment technology of glyphosate mother solution, it is characterised in that: the following steps are included:
A, glyphosate mother solution is sent into membrane treatment appts, obtains concentrated mother liquor and permeate, in the concentrated mother liquor, 10~20% are used Powder is mentioned in glyphosate, 80~90% for completing the operation of step B;
B, the concentrated mother liquor is made a centrifugal filtrate, will once be centrifuged filter successively after once oxidation, primary crystallization separation Liquid is sent into film separation system, obtains concentrate and permeate, once oxidation include: that concentrated mother liquor is sent into high-temperature oxidation device, In the presence of ruthenium catalyst, 180~260 DEG C of temperature are controlled, 2.5~8MPa of pressure blasts air and aoxidized, oxidation After the washed tower processing of the gas of generation, it is sent into incineration system;
C, the concentrate for obtaining film separation system carries out secondary crystallization separation, and centrifugal filtrate is sent into incineration system, obtains burnt phosphorus Sour sodium carries out second-time burning after burning the flue gas separation dust of generation,
The permeate that the permeate and film separation system that the membrane treatment appts obtain obtain is sent to concentration refined unit, preparation It obtains refined brine or solid recycling Nacl, the waste water that concentration purification generates is sent into sewage treatment plant, the primary crystallization point The mixed phosphate sodium obtained from the separation of, secondary crystallization for producing sodium tripolyphosphate or calgon,
The Con trolling index of the incineration system meets: incineration temperature: 800~1000 DEG C;The high-temperature flue gas residence time: > 2S, it will After the flue gas separation dust for burning generation, second-time burning is carried out in incineration system, the temperature control of second-time burning exists 1100 DEG C, gas residence time > 2S.
2. a kind of incineration treatment technology of glyphosate mother solution according to claim 1, it is characterised in that: the concentration purification The heat source that unit uses is the steam that coal-burning boiler provides, for producing refined brine or solid recycling Nacl.
3. a kind of incineration treatment technology of glyphosate mother solution according to claim 1, it is characterised in that: the primary crystallization Separating the crystallization temperature separated with secondary crystallization is 5~18 DEG C.
4. a kind of incineration treatment technology of glyphosate mother solution according to claim 1, it is characterised in that: in the step C In, incineration system uses scale plate incinerator, and centrifugal filtrate is sprayed into incinerator through atomization and contacted with burning fuel, described to burn Fuel burning is using one of coal gas, coke-stove gas, natural gas, hydrogen or diesel oil or the mixture of a variety of compositions.
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CN106746347B (en) * 2017-01-11 2019-02-26 江苏南大华兴环保科技股份公司 A kind of imidazole aldehyde waste water treatment process and its operation method
CN107556002A (en) * 2017-09-04 2018-01-09 肇庆市欧陶新型材料有限公司 The preparation method and its application method of construction sanitary ceramic mud degumming agent
CN109704367A (en) * 2018-12-27 2019-05-03 镇江江南化工有限公司 A kind of glyphosate by-product Nacl process for refining and purifying
CN110812877B (en) * 2019-10-12 2021-03-23 西安交通大学 Glyphosate mother liquor treatment method and device

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