CN102633398A - Method for recovering organic effluent brine - Google Patents

Method for recovering organic effluent brine Download PDF

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Publication number
CN102633398A
CN102633398A CN2011100369402A CN201110036940A CN102633398A CN 102633398 A CN102633398 A CN 102633398A CN 2011100369402 A CN2011100369402 A CN 2011100369402A CN 201110036940 A CN201110036940 A CN 201110036940A CN 102633398 A CN102633398 A CN 102633398A
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China
Prior art keywords
organic
brine
effluent brine
organic effluent
recovery
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CN2011100369402A
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Chinese (zh)
Inventor
傅立德
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HYFLUX FILTERING TECHNOLOGY (SHANGHAI) Co Ltd
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HYFLUX FILTERING TECHNOLOGY (SHANGHAI) Co Ltd
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Publication of CN102633398A publication Critical patent/CN102633398A/en
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Abstract

The invention discloses a method for recovering organic effluent brine. The method comprises the following steps: introducing organic effluent brine containing inorganic salts and organic matter into a prefiltration system, an evaporation crystallization system and a dry-method high temperature oxidation reaction system, after filtration, evaporation, and oxidation treatment, allowing the obtained inorganic salt product to be dissolved to become saturated brine, wherein the total organic carbon TOC is less than 10 ppm. With the method of the invention, more than 90% of water and inorganic salts can be recovered, and the zero discharge standard for waste water is basically reached; the recovery rate for the recycling of organic effluent brine is effectively increased; and great benefits are generated for environment protection and resource recovery; additionally, the obtained inorganic salt product can be used as an industrial raw material for recycling in ionic membrane electrolytic devices.

Description

A kind of method that reclaims organic effluent brine
Technical field
The present invention relates to a kind of treatment process of industrial waste salt water, relate in particular to the method for the recycling of the organic effluent brine of a kind of industry.
Background technology
In the process of heavy chemicals production and pharmacy; Contain organism and highly-saline waste water reaction normal generation that finish except producing needed product; In general this type waste water organism by total organic carbon (TOC) understand from hundreds of extremely tens thousand of between; And its inorganic salinity such as sodium-chlor, the concentration of sodium sulfate or calcium chloride can be from 10% to more than 20%.Because the supersalinity of this type waste water; General biochemical treatment can't be degraded to organism wherein voluntarily; Common treatment process reduces its organic concentration for adopting oxidation, flocculation or absorption, IX, membrane sepn etc.; But because composition is complicated, these technology are limited to organic removal efficient, and cost is very high.Even if also because its high salinity, and can not discharge through organic effluent brine of above processing.Therefore, consider that from sustainable development and recycling economy aspect best treatment process is after this type of organic effluent brine is carried out advanced treatment, to make wherein salinity such as resources such as sodium-chlor and water obtain recycling.The electrolyzer that for example effluent brine of sodium chloride-containing is back to chlor-alkali plant is to produce chlorine and sodium hydroxide; But electrolysis with ion-exchange film has strict requirement to the salt solution water quality of advancing groove; Except other metals ion can not be arranged, its organic content was less than 10ppm by total organic carbon (TOC).General water technology all can't stabilizing effective be reduced to this level with this type of organic high slat-containing wastewater, therefore to the recycling of this type of organic effluent brine, makes its organic content satisfy the requirement of ion film caustic soda production technique, is a general difficult problem.
Chinese patent CN 1745914C discloses a kind of treatment process to the Hydrazine Hydrate 80 effluent brine, but this method only reclaims its acetone and ammonia, to salt solution and be untreated; Disclosed treatment process to the Hydrazine Hydrate 80 effluent brine among the CN1792825A though adopt air stripping and oxidation, can only be reduced to 30ppm with ammonia in the effluent brine and acetone, can not conform with the standard of electrolysis with ion-exchange film, causes the effluent brine can not reuse.
Chinese patent ZL200710013817.2 discloses a kind of method of extraction polymethylene polyphenyl polyamine from salt solution continuously; This method is not owing to there is the measure of follow-up effluent brine advanced treatment; Effluent brine organism (TOC and TN value are higher) content is higher, is not suitable for the requirement relatively harsher to the organic content index in the salt solution of electrolysis with ion-exchange film technology.
Chinese patent ZL200710138065.2 discloses the method for the advanced treatment of the effluent brine that produces in a kind of MDI production process; This method is owing to adopted conventional extraction treatment of a step, and the steam that stripping tower consumes is more, and energy consumption is higher; Simultaneously; Because the organic content of effluent brine before the advanced treatment is higher, have that the oxygenant that consumes in the advanced treatment process is many, the sorbent material consumption is big, defectives such as processing cost height.
In addition, Chinese patent CN101143753 discloses the method that the effluent brine that produces in the MDI production is adopted oxidation aeration and absorption, and one Chinese patent application CN101665302A employing extracts; Aeration, methods such as absorption are handled effluent brine, and TOC can be less than 8ppm; Total nitrogen is less than 2.5ppm; But this complex process and long flow path is blown into the atmospheric influence environment with large amount of organic again in aeration process, and the regeneration cost height of extraction agent and sorbent material has also reduced the practicality of this processing method.
Because the reuse of organic effluent brine difficulty, therefore, those skilled in the art is devoted to develop a kind of simple and effective abraum salt water recovery process, to guarantee that effluent brine complete-reclaiming is not as much as possible produced simultaneously the exhaust emission environment.
Summary of the invention
Because the above-mentioned defective of prior art the purpose of this invention is to provide a kind of method that reclaims organic effluent brine.
The method of the organic effluent brine of recovery of the present invention, be with organic effluent brine through after pre-filtering, evaporative crystallization and the high temperature oxidation process, make wherein organism TOC less than 10ppm.
The method of the organic effluent brine of recovery of the present invention; Comprise and to contain inorganic salt and organic organic effluent brine introducing pre-filtration system, evaporation and crystallization system and dry method high temperature oxidation reactive system; After filtration, evaporation, oxide treatment, make the inorganic salt product that obtains change into saturated brine after total organic carbon TOC less than 10ppm.
Concrete, the method for the organic effluent brine of recovery of the present invention may further comprise the steps:
1) said organic effluent brine is introduced said pre-filtration system, separate the impurity that comprises suspended substance, colloid and high-molecular-weight organic material wherein;
2) treated said organic effluent brine is introduced said evaporation and crystallization system, makes wherein inorganic salt, obtain the inorganic salt crystallized product through evaporation concentration, and after making said inorganic salt crystallized product change into saturated brine TOC less than 300ppm;
3) said inorganic salt crystallized product is introduced said dry method high temperature oxidation reactive system in the presence of oxygenant and carry out oxidation, obtain said inorganic salt product, and make it change into TOC behind the saturated brine less than 10ppm.
In the method for the organic effluent brine of recovery of the present invention, pre-filtration system, evaporation and crystallization system and dry method high temperature oxidation system all can adopt this area system device and conventional process condition commonly used.
In preferred implementation of the present invention, said pre-filtration system comprises the ultra-filtration equipment that is applicable to brine filter.In the method for the invention; Pre-filtration system mainly is to the suspended substance in organic effluent brine; Colloid can separate through the impurity that filtering system is removed with high-molecular-weight organic material etc., with the problem that reduces follow-up evaporation and crystallization system fouling and make impurity and organism in the crystalline salt reduce to minimum.Preferably also reduce organic content as far as possible, to make organism TOC in the organic effluent brine that gets into evaporation and crystallization system less than 1000ppm through filtering.Therefore; When practical implementation of the present invention; For the effluent brine of high organic content, greater than 1000ppm, then said pre-filtration system also is included in the nf membrane that installs additional behind the said ultra-filtration equipment like the TOC of organic effluent brine; This nf membrane should be removed the organism in the effluent brine as far as possible under not holding back inorganic salt, the organism TOC in said organic effluent brine is reduced to less than 1000ppm.
When practical implementation of the present invention, pre-filtration system can be selected the various brinish strainers that are appropriate to, but its filtering accuracy requires and should improve as much as possible, and the ideal filtering accuracy is the most suitable at the ultra-filtration equipment of 0.01 to 0.03 micron of pore size.In addition, ultrafiltration or nf membrane filtration unit need adopt and be fit to the especially device of high density salt solution and temperature of salt solution.
The high density salt solution of indication is meant the waste water solution that salts contg is higher among this paper, is higher than more than the 5wt% like salts contg.
General biochemical system promptly is difficult to utilize the mikrobe organism wherein of degrading when salts contg is higher than 1%; The present invention can be used for the brine waste of various concentration; But under high salt concn the required energy consumption of its evaporation can decline to a great extent; The total amount of the salt that its recovery obtains also can improve with its value, makes its economic worth more obviously with outstanding.
In the method for the invention, evaporation and crystallization system is to utilize organic effluent brine is carried out evaporation concentration, and inorganic salt such as sodium-chlor to saturated post crystallization are separated out.When practical implementation of the present invention, said evaporation and crystallization system can adopt multi-effect evaporating device, or the vacuum flashing device.The thermal source of evaporative process can adopt high pressure or LP steam; Also can adopt the used heat in the factory; Owing to the organism in the effluent brine might enrichment be separated out the quality of polluting the inorganic salt product and cause fouling of heat exchangers to reduce heat exchanger effectiveness in concentrate; So crystallization apparatus and interchanger in the evaporation will be directed against this type of problem and design, to reduce its organic content as far as possible through the inorganic salt crystallized product of evaporative crystallization and be beneficial to follow-up dry method high temperature oxidation effect and reduce its running cost.
When practical implementation of the present invention, preferably with said organic effluent brine through evaporation concentration, after the steam condensation that obtains of evaporation as as pure water or service water reuse.
In the method for the invention; Adopt the method for dry oxidation to become carbonic acid gas through the organic matter degradation in the inorganic salt crystallized product that evaporative crystallization obtains; Its organic TOC after changing into saturated brine such as inorganic salt such as sodium-chlor is reduced to below the 10ppm, to meet the standard of ion-exchange membrane electrolyzer.
In the method for the invention, said dry method high temperature oxidation can carry out under 250 ℃ to 650 ℃ of temperature.
In described dry method high temperature oxidation system, inorganic salt crystallized product and oxygenant are mixed the back introduce high temperature service and make the organism complete oxidation, the inorganic salt product changes into behind the saturated brine its TOC and can stablize and reduce to below the 10ppm.
In the dry method high-temperature oxidation process, get into High Temperature Furnaces Heating Apparatus after employing oxygenant and inorganic salt mix again and can guarantee that oxidation reaches the needed degradation temperature of reduction fully to cut down the consumption of energy.Said oxygenant can use multiple different types of oxygenant, as is selected from least a in oxygenant and the ydrogen peroxide 50 of chloride oxygenant, sulfur-bearing.Chloride oxygenant can be hypochlorite, perchlorate or oxymuriate, and the oxygenant of sulfur-bearing can be a persulphate.In practical implementation, said oxygenant is preferably from Youxiaolin, Losantin, potassium hypochlorite, VAL-DROP, calcium chlorate, Potcrate, ydrogen peroxide 50, Sodium Persulfate, Potassium Persulphate, at least a among potassium perchlorate and the sodium perchlorate.For different organic pollutants, oxygenant can be separately or is mixed and use, and can solid form or be made into the aqueous solution after mix with the inorganic salt crystallized product.Those skilled in the art can confirm actual which kind of oxygenant that uses according to organic composition, type and concentration in the organic waste water.
In general, improve oxidizing reaction temperature, increase the oxygenant consumption, can improve organic oxidation effectiveness in the crystalline inorganic salt, impel it to degrade.Degree of oxidation is darker, and degraded more thoroughly.
The oxygenant that the present invention adopted both can be the general-purpose industrial product, also can be the recovery article of commercial run by-product.The add-on of said oxygenant can be confirmed according to employed chemical oxidizing agent and concrete processing condition by those skilled in the art.The preferred chloride oxygenant of said oxygenant also can be considered from the effusive light salt brine (being chloride light salt brine) that contains free chlorine and oxymuriate of chlor-alkali factory ion-exchange membrane electrolyzer; And add-on does not wait from 1: 1 to 10: 1 according to oxygenant and TOC part by weight, and preferred oxygenant and TOC part by weight are 3: 1 to 5: 1.
Another object of the present invention provides inorganic salt product that the method for the organic effluent brine of recovery that uses the invention described above obtains as the application of raw material in ion-membrane electrolysis device.
The TOC content that uses the inorganic salt product that the method for the organic effluent brine of recovery of the present invention obtains is less than 10ppm, meets the index of the TOC of ion-exchange membrane electrolyzer into less than 10ppm fully, can be recycled to electrolysis fully and use.
Method of the present invention is particularly useful for the trade effluent of inorganic salt content more than 5wt% applicable to the organic effluent brine of various industry, promptly high salt organic waste water.
The method of the organic effluent brine of recovery of the present invention has following beneficial effect:
1, uses method of the present invention; Total yield can reach 90%, promptly can reclaim water and inorganic salt more than 90%, reaches the standard of wastewater zero discharge basically; Improved the recovery in organic effluent brine reuse process effectively, the protection of environment and resource have been reclaimed all produce great benefit;
2, method of the present invention had not both had the exhaust emission environment, did not need regenerated sorbent material and extraction liquid again, thus there is not secondary pollution problem, and Ca in organic effluent brine 2+, Mg 2+Clearance can reach 98% respectively, more than 85%;
3, method of the present invention adopts oxygenant to make the more complete and temperature reduction of effect of high temperature oxidation, can practice thrift a large amount of energy consumptions;
4, method flow of the present invention is short, simple operation, and level of automation is high;
5, the inorganic salt product that obtains of the method for the organic effluent brine of recovery of the present invention can be used as the industrial raw material reuse to ion-membrane electrolysis device, and very big economic benefit and social benefit are arranged.
Description of drawings
Fig. 1 is the schematic flow sheet of preferred embodiments of the method for the organic effluent brine of recovery of the present invention.
Embodiment
Below will the technique effect of method of the present invention and generation be described further, to understand the object of the invention, characteristic and effect fully.
Embodiment 1
The saltiness of the organic effluent brine of processing procedure of certain insecticide factory is 15%, and its TOC is about 7000ppm, and salt is mainly sodium-chlor, adopts method of the present invention to handle to this organic effluent brine.
At first, organic effluent brine is introduced pre-filtration system, TOC reduces to 1000ppm with its effluent brine organism.The filtering accuracy of ultra-filtration equipment is about 0.03 micron at pore size, adopts external-compression type hollow fiber ultrafiltration film (KRIM-0850FR of Kaimo Filteration Tech (Shanghai) Co., Ltd.), installs nf membrane simultaneously additional, adopts the GE DK of company film.
Get into evaporation and crystallization system then, make the crystallization sodium-chlor that obtains be made into saturated brine after its TOC between 100 to 300ppm.Evaporation and crystallization system adopts the triple effect evaporation device.Adopt LP steam (105 ℃) to heat; Triple effect adopts vacuum flashing; And the sodium-chlor crystallization is separated out, and sodium chloride crystal is after centrifuge dehydration, and organic content is 250 to 350ppm in its saturated solution; Mother liquor after centrifugal is back to the pre-filtration system cyclically utilizing, and about 5% high concentration organic effluent brine effluxes to avoid organism enrichment on crystal salt after evaporation.
At last, with crystallization sodium-chlor through dry method high temperature oxidation system, after carrying out oxidation about 350 ℃, make sodium-chlor be made into saturated brine after its TOC reduce to 2 to 8ppm.Before introducing dry method high temperature oxidation system, oxygenant is sneaked into crystallization sodium-chlor, oxygenant uses VAL-DROP and sodium perchlorate's mixture, and the weight ratio of used oxygenant and TOC is 3: 1.
If crystallization sodium-chlor only adopts high temperature oxidation, and does not sneak into oxygenant, salt still is beige more than 700 ℃ even be heated to, and can know that oxidation operation wherein is incomplete, still has 40 to 60ppm and survey its saturated brine TOC.
Embodiment 2
Hydrazine Hydrate 80 effluent brine to certain chemical plant is handled, and the sodium chloride concentration of its waste water is about 12%, and organism TOC content is between 200 to 300ppm.
Behind this effluent brine process ultrafiltration membrance filter and evaporative crystallization, its TOC still had 52 to 86ppm after crystallization sodium-chlor changed into saturated brine.The water of condensation that evaporation obtains is as the pure water reuse.
Crystallization sodium-chlor and oxygenant are mixed, and oxygenant uses chloride light salt brine, wherein contains Youxiaolin and VAL-DROP, and its oxidizer containing chlorine total concn is about 1wt%, and its consumption calculates with the weight that is converted to Youxiaolin, with the weight ratio of TOC be 4.5: 1.
Behind 300 ℃ dry method high temperature oxidation, its TOC reduced to below the 1ppm after the sodium-chlor product that obtains changed into saturated brine.
With saturated brine of sodium chloride as raw material reuse to ion-membrane electrolysis device to produce chlorine and sodium hydroxide.
As this crystallization sodium-chlor is only carried out high temperature oxidation, and do not add oxygenant, its TOC can only reduce between 19 to 25ppm.Effective and the meliority that adopts method of the present invention is described.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variation.Therefore, all technician in the art all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology through the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (12)

1. method that reclaims organic effluent brine; Comprise and to contain inorganic salt and organic organic effluent brine introducing pre-filtration system, evaporation and crystallization system and dry method high temperature oxidation reactive system; After filtration, evaporation, oxide treatment, make the inorganic salt product that obtains change into saturated brine after total organic carbon TOC less than 10ppm.
2. the method for the organic effluent brine of recovery as claimed in claim 1 may further comprise the steps:
1) said organic effluent brine is introduced said pre-filtration system, separate the impurity that comprises suspended substance, colloid and high-molecular-weight organic material wherein;
2) treated said organic effluent brine is introduced said evaporation and crystallization system, makes wherein inorganic salt, obtain the inorganic salt crystallized product through evaporation concentration, and after making said inorganic salt crystallized product change into saturated brine TOC less than 300ppm;
3) said inorganic salt crystallized product is introduced said dry method high temperature oxidation reactive system in the presence of oxygenant and carry out oxidation, obtain said inorganic salt product, and make it change into TOC behind the saturated brine less than 10ppm.
3. according to claim 1 or claim 2 the method for the organic effluent brine of recovery, wherein said pre-filtration system comprises the ultra-filtration equipment that is applicable to brine filter.
4. the method for the organic effluent brine of recovery as claimed in claim 3; Wherein at the TOC of said organic effluent brine during greater than 1000ppm; Said pre-filtration system also is included in the nf membrane that said ultra-filtration equipment installs additional, and the organism TOC in said organic effluent brine is reduced to less than 1000ppm.
5. the method for the organic effluent brine of recovery as claimed in claim 3, the filtering accuracy of wherein said ultra-filtration equipment is 0.01 to 0.03 micron at pore size.
6. according to claim 1 or claim 2 the method for the organic effluent brine of recovery, wherein said evaporation and crystallization system can adopt multi-effect evaporating device, or the vacuum flashing device.
7. according to claim 1 or claim 2 the method for the organic effluent brine of recovery, wherein with said organic effluent brine through evaporation concentration, reuse after the steam condensation that evaporation obtains.
8. according to claim 1 or claim 2 the method for the organic effluent brine of recovery, wherein said oxygenant is selected from one or more in hypochlorite, perchlorate, oxymuriate, persulphate and the ydrogen peroxide 50.
9. the method for the organic effluent brine of recovery as claimed in claim 8, wherein said oxygenant is selected from Youxiaolin, Losantin, potassium hypochlorite; VAL-DROP, calcium chlorate, Potcrate, Sodium Persulfate; Potassium Persulphate, potassium perchlorate, at least a in sodium perchlorate and the ydrogen peroxide 50.
10. the method for the organic effluent brine of recovery as claimed in claim 8; After wherein said oxygenant and said inorganic salt crystallized product being mixed, introduce said dry method high temperature oxidation system, make oxidation operation wherein; After the said inorganic salt product that obtains changed into saturated brine, its TOC reduced to 10ppm.
11. the method for the organic effluent brine of recovery as claimed in claim 10, wherein said dry method high temperature oxidation carries out under 250 ℃ to 650 ℃ of temperature.
12. the inorganic salt product that the method for the organic effluent brine of the described recovery of one of claim 1-11 obtains is as the application of raw material in ion-membrane electrolysis device.
CN2011100369402A 2011-02-12 2011-02-12 Method for recovering organic effluent brine Pending CN102633398A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420533A (en) * 2013-02-21 2013-12-04 宜兴统一环保科技有限公司 Treatment method for high-concentration organic wastewater
CN103787373A (en) * 2014-01-28 2014-05-14 南京曙光硅烷化工有限公司 Method for purifying polysulfide silane coupling agent byproduct salt
CN104477942A (en) * 2014-12-24 2015-04-01 江苏恒安化工有限公司 Method for treating potassium chloride residues in organic fluorination reaction
CN104529049A (en) * 2014-11-19 2015-04-22 宜宾天原集团股份有限公司 Treatment method for using ketazine process hydrazine hydrate brine waste in ion exchange membrane electrolysis
CN105366749A (en) * 2015-12-15 2016-03-02 河南师范大学 Treatment method of high-salinity organic volatile waste water
CN105525306A (en) * 2016-01-19 2016-04-27 湖北可赛化工有限公司 System and method for removing TOC in high-concentration saline water
CN105692986A (en) * 2014-11-24 2016-06-22 中国石油化工股份有限公司 Waste salt comprehensive utilization processing method
CN106006681A (en) * 2016-05-18 2016-10-12 化工部长沙设计研究院 Method for resourceful treatment of high-salt wastewater
CN108164069A (en) * 2017-12-27 2018-06-15 惠州市宙邦化工有限公司 A kind of processing method of tetraethylammonium tetrafluoroborate production waste water
CN109896683A (en) * 2019-03-26 2019-06-18 江苏春江润田农化有限公司 The cycling and reutilization treatment process of time acid producing waste water
CN110282806A (en) * 2019-07-26 2019-09-27 西南石油大学 A kind of magnetic transition metal particle activation persulfate wastewater processing technology
WO2021035768A1 (en) * 2019-08-30 2021-03-04 万华化学集团股份有限公司 Phosgene synthesis and brine evaporation electrolysis integrated treatment process

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103420533A (en) * 2013-02-21 2013-12-04 宜兴统一环保科技有限公司 Treatment method for high-concentration organic wastewater
CN103420533B (en) * 2013-02-21 2015-12-09 宜兴统一环保科技有限公司 A kind for the treatment of process of high concentrated organic wastewater
CN103787373B (en) * 2014-01-28 2016-03-02 南京曙光硅烷化工有限公司 The method of purification polysulfide silanes coupling agent by-product salt solution
CN103787373A (en) * 2014-01-28 2014-05-14 南京曙光硅烷化工有限公司 Method for purifying polysulfide silane coupling agent byproduct salt
CN104529049A (en) * 2014-11-19 2015-04-22 宜宾天原集团股份有限公司 Treatment method for using ketazine process hydrazine hydrate brine waste in ion exchange membrane electrolysis
CN105692986B (en) * 2014-11-24 2018-12-28 中国石油化工股份有限公司 A kind of processing method of abraum salt comprehensive utilization
CN105692986A (en) * 2014-11-24 2016-06-22 中国石油化工股份有限公司 Waste salt comprehensive utilization processing method
CN104477942B (en) * 2014-12-24 2016-01-27 江苏恒安化工有限公司 The treatment process of Repone K residue in organic fluoride reaction
CN104477942A (en) * 2014-12-24 2015-04-01 江苏恒安化工有限公司 Method for treating potassium chloride residues in organic fluorination reaction
CN105366749A (en) * 2015-12-15 2016-03-02 河南师范大学 Treatment method of high-salinity organic volatile waste water
CN105525306A (en) * 2016-01-19 2016-04-27 湖北可赛化工有限公司 System and method for removing TOC in high-concentration saline water
CN106006681A (en) * 2016-05-18 2016-10-12 化工部长沙设计研究院 Method for resourceful treatment of high-salt wastewater
CN108164069A (en) * 2017-12-27 2018-06-15 惠州市宙邦化工有限公司 A kind of processing method of tetraethylammonium tetrafluoroborate production waste water
CN108164069B (en) * 2017-12-27 2021-05-14 惠州市宙邦化工有限公司 Treatment method of tetraethylammonium tetrafluoroborate production wastewater
CN109896683A (en) * 2019-03-26 2019-06-18 江苏春江润田农化有限公司 The cycling and reutilization treatment process of time acid producing waste water
CN110282806A (en) * 2019-07-26 2019-09-27 西南石油大学 A kind of magnetic transition metal particle activation persulfate wastewater processing technology
WO2021035768A1 (en) * 2019-08-30 2021-03-04 万华化学集团股份有限公司 Phosgene synthesis and brine evaporation electrolysis integrated treatment process

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Application publication date: 20120815