CN114805924A - Method for recovering cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor - Google Patents

Method for recovering cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor Download PDF

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CN114805924A
CN114805924A CN202210507942.3A CN202210507942A CN114805924A CN 114805924 A CN114805924 A CN 114805924A CN 202210507942 A CN202210507942 A CN 202210507942A CN 114805924 A CN114805924 A CN 114805924A
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linking agent
dmf
cross
waste
wastewater
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辛路
徐强
王美
宋荻
方正
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Nanjing University Environmental Planning And Design Institute Group Co ltd
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Nanjing University Environmental Planning And Design Institute Group Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/10Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • 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
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/008Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • C02F1/20Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2001/007Processes including a sedimentation step
    • 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
    • C02F2103/38Polymers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/05Conductivity or salinity
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention provides a method for recovering a cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor. The method comprises the following specific steps: s1, introducing the DMF wastewater into a pH adjusting tank, and adding waste alkali liquor into the tank to stabilize the pH value of the wastewater to be above 10; s2, introducing the wastewater after the pH adjustment treatment into a heating blow-off container, controlling the temperature and carrying out blow-off to destroy the stable state of the cross-linking agent and separate out the water-insoluble cross-linking agent from the water; s3, introducing the wastewater suspension subjected to the heating air stripping treatment into a solid-liquid separation device for solid-liquid separation to separate out generated solid precipitates; s4, washing the solid precipitate obtained in the S3 with pure water for 2-3 times; s5, putting the washed solid precipitate into an oven, and drying at 60 ℃.

Description

Method for recovering cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor
Technical Field
The invention relates to the technical field of resources and environment, in particular to a method for recovering a cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor.
Background
The cross-linking agent is a widely used organic polymer material, and has the function of generating chemical bonds among linear molecules to connect the linear molecules together to form a net structure, so that the strength and elasticity of the rubber can be improved. Cross-linking agents are customarily referred to in the rubber industry as "vulcanizing agents"; known in the plastics industry as "curing agents", "hardeners"; it is called as "curing agent", "hardener", etc. in the adhesive or coating industry. In industrial production, a cross-linking agent is usually prepared by taking DMF as a solvent, the main process is to obtain the cross-linking agent by an extraction method after polymerization reaction is carried out in a DMF solution, washing water of an extracted product is DMF waste water, and the waste water takes DMF, the cross-linking agent and salt as main pollutants. In addition, the manufacturers of crosslinking agents generally adopt lye washing as the treatment process of the waste gas generated in the production of olefins, methanol, ethanol, HCl, VOCs and the like, so that a large amount of waste gas is generated to absorb the waste lye, and the waste lye is also required to be treated.
DMF is a chemical raw material with wide application, is an excellent solvent with wide application range, can be mixed with water and most organic solvents except halogenated hydrocarbon at will, and has good dissolving capacity for various organic compounds and inorganic compounds. Because DMF can be mutually soluble with water and can also dissolve the cross-linking agent, and the cross-linking agent is insoluble in water, DMF wastewater forms a colloid in an oil-in-water form, and great economic benefit can be generated if the cross-linking agent in the wastewater can be recycled. Because the cross-linking agent is similar to colloid in the DMF solution, and has extremely strong stability, a large amount of cross-linking agent cannot be adsorbed by adopting simple adsorption (ion exchange, activated carbon adsorption and the like), and the purity of the cross-linking agent analyzed by the adsorbent is not high, so that the cross-linking agent cannot reach a crude grade, therefore, the recovery process of adopting adsorption or ion exchange as the cross-linking agent in the DMF wastewater is unrealistic in the actual engineering.
Therefore, there is an urgent need for an efficient process suitable for the recovery of the cross-linking agent from DMF wastewater.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for recovering a cross-linking agent from DMF (dimethyl formamide) wastewater by using a waste alkali solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for recovering cross-linking agent from DMF sewage by use of waste alkali solution includes such steps as adding waste alkali solution to DMF sewage generated in the process of preparing cross-linking agent, reaction while heating for stripping, solid-liquid separation, washing solid deposit with pure water and baking
In order to optimize the technical scheme, the specific measures adopted further comprise:
a method for recovering a cross-linking agent from DMF wastewater by using a waste alkali solution comprises the following steps:
s1, introducing the DMF wastewater into a pH adjusting tank, and adding waste alkali liquor into the tank to stabilize the pH value of the wastewater to be above 10;
s2, introducing the wastewater after the pH adjustment treatment into a heating blow-off container, controlling the temperature and carrying out blow-off to destroy the stable state of the cross-linking agent and separate out the water-insoluble cross-linking agent from the water;
s3, introducing the wastewater suspension subjected to the heating air stripping treatment into a solid-liquid separation device for solid-liquid separation to separate out solid precipitates, wherein the solid-liquid separation device does not need to stir so as to avoid destroying flocs;
s4, washing the solid precipitate obtained in the S3 for 2-3 times by pure water after being filtered by a water purifier;
s5, putting the washed solid precipitate into an oven, and drying at 60 ℃.
Further, in step S1, the DMF wastewater includes a cross-linking agent, DMF, and a salt, and the pH of the DMF wastewater is 4-5.
Furthermore, the concentration of the cross-linking agent is 700-2000 mg/L, the concentration of DMF is 300-800 mg/L, and the mass fraction of salt is 3% -3.5%.
Further, in step S1, the waste lye is generated by the crosslinker manufacturer after washing the waste gas with lye.
Further, the waste alkali liquor comprises NaOH and salt, and the pH value of the waste alkali liquor is 13.7-14.02.
Further, the mass fraction of NaOH is 2% -4%, and the mass fraction of salt is 2% -2.5%.
Further, in step S2, the temperature-raising stripping container is heated by a water bath to control the temperature.
Further, in step S2, the blow-off temperature was 50 ℃.
Further, in step S5, the oven is flushed with nitrogen to prevent the crude-grade crosslinking agent from being oxidized and affecting the recovery rate and recovery purity.
The method utilizes the waste alkali liquor to recover the cross-linking agent from the DMF wastewater, and simultaneously solves the treatment requirement of the waste alkali liquor generated by absorbing a large amount of waste gas. Under the condition that the aqueous solution is alkaline, DMF is easily decomposed to generate dimethylamine and formate, the colloid state of the wastewater can be damaged by the degradation of DMF, so that the water-insoluble cross-linking agent is separated from the water, and the DMF is continuously decomposed by heating and stripping, so that more colloid is broken, and more cross-linking agent is separated. The process achieves good effect through laboratory experiments. The recovery process can recover more than 75% of the cross-linking agent in the DMF wastewater, the purity of the recovered cross-linking agent can reach more than 85%, a cross-linking agent crude product is formed, and the cross-linking agent with high purity can be obtained after purification.
The invention has the beneficial effects that: the method adopts the waste alkali liquor generated by absorbing the waste gas alkali of a crosslinking agent production enterprise as a treatment agent, treats waste with waste, controls the pH value of the DMF wastewater to be more than 10, degrades DMF and destroys a colloid system of the wastewater, simultaneously promotes DMF to be continuously decomposed by heating and stripping, further separates out a large amount of crosslinking agent, not only saves the addition of liquid alkali, but also reduces the treatment cost of the waste alkali liquor and greatly reduces the treatment cost; the method can recover a large amount of cross-linking agents by simply adding the drugs, does not need to perform analytic concentration, and is more efficient than an adsorption or ion exchange type recovery method; the cross-linking agent separated by the method can reach the grade of a crude product, has no other impurities, and has higher recovery rate and higher purity; the method does not need to add any coagulant, has high solid-liquid separation rate, simple recovery device and low recovery cost; in addition, the process of recycling the cross-linking agent by using the method is easy to realize automatic control.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
Example 1
The DMF wastewater used in the embodiment is wastewater produced by a cross-linking agent production process using DMF as a solvent by a cross-linking agent manufacturer, and comprises three solutes of a cross-linking agent, DMF and salt, wherein the pH value of the wastewater is 4, the concentration of the cross-linking agent is 1600mg/L, the concentration of the DMF is 450mg/L, and the mass fraction of the salt is 3.5%; the pH value of the waste alkali liquor generated by the absorption of the waste gas alkali is 14, the mass fraction of NaOH is 2.5%, and the mass fraction of salt is 2%.
As shown in FIG. 1, the crosslinker was recovered as follows:
s1, pH adjustment treatment: introducing the DMF wastewater into a pH adjusting tank, and adding waste alkali liquor into the tank to stabilize the pH value of the wastewater to 10;
s2, heating and stripping: introducing the wastewater subjected to pH adjustment treatment into a heating blow-off container, heating in a water bath, controlling the temperature at 50 ℃, and carrying out blow-off to destroy the stable state of the crosslinking agent so as to separate out the crosslinking agent insoluble in water from the water;
s3, solid-liquid separation: introducing the waste water suspension subjected to temperature rise air stripping treatment into a solid-liquid separation device for solid-liquid separation to separate out generated solid precipitates;
s4, washing: washing the solid precipitate obtained in step S3 with pure water for 2 times;
s5, drying: and (4) putting the washed solid precipitate into an oven filled with nitrogen, and drying at 60 ℃.
After the DMF wastewater is treated according to the method, the concentration of DMF in the supernatant in the solid-liquid separation device is 15mg/L, and the concentration of the cross-linking agent is 219 mg/L; the recovery rate of the cross-linking agent reaches 86.3 percent, and the purity of the recovered crude cross-linking agent reaches 87 percent.
Example 2
The DMF wastewater used in this example is the same as in example 1, and is generated by a crosslinker production process using DMF as a solvent by a crosslinker manufacturer, and includes three solutes of a crosslinker, DMF, and salt, the pH of the wastewater is 4, the concentration of the crosslinker is 1600mg/L, the concentration of DMF is 450mg/L, and the mass fraction of the salt is 3.5%; the pH value of the waste alkali liquor generated by the absorption of the waste gas alkali is 14, the mass fraction of NaOH is 2.5%, and the mass fraction of salt is 2%.
As shown in FIG. 1, the crosslinker was recovered as follows:
s1, pH adjustment treatment: introducing the DMF wastewater into a pH adjusting tank, and adding waste alkali liquor into the tank to stabilize the pH value of the wastewater to 11;
s2, heating and stripping: introducing the wastewater subjected to pH adjustment treatment into a heating blow-off container, heating in a water bath, controlling the temperature at 50 ℃, and carrying out blow-off to destroy the stable state of the crosslinking agent so as to separate out the crosslinking agent insoluble in water from the water;
s3, solid-liquid separation: introducing the waste water suspension subjected to temperature rise air stripping treatment into a solid-liquid separation device for solid-liquid separation to separate out generated solid precipitates;
s4, washing: washing the solid precipitate obtained in step S3 with pure water for 2 times;
s5, drying: and (4) putting the washed solid precipitate into an oven filled with nitrogen, and drying at 60 ℃.
After the DMF wastewater is treated according to the method, the concentration of DMF in the supernatant in the solid-liquid separation device is 12mg/L, and the concentration of the cross-linking agent is 206 mg/L; the recovery rate of the cross-linking agent reaches 87.1 percent, and the purity of the recovered crude cross-linking agent reaches 87 percent.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.

Claims (10)

1. A method for recovering a cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor is characterized in that the waste alkali liquor is added into the DMF wastewater generated in the production process of the cross-linking agent, heating and air stripping are carried out while reaction is carried out, then solid-liquid separation is carried out, and solid precipitates are dried after being washed by pure water, so that the recovery of the cross-linking agent is completed.
2. The method for recovering the cross-linking agent from the DMF waste water by using the waste alkali solution as claimed in claim 1, which is characterized by comprising the following steps:
s1, introducing the DMF wastewater into a pH adjusting tank, and adding waste alkali liquor into the tank to stabilize the pH value of the wastewater to be above 10;
s2, introducing the wastewater after the pH adjustment treatment into a heating blow-off container, controlling the temperature and carrying out blow-off to destroy the stable state of the cross-linking agent and separate out the water-insoluble cross-linking agent from the water;
s3, introducing the wastewater suspension subjected to the heating air stripping treatment into a solid-liquid separation device for solid-liquid separation to separate out generated solid precipitates;
s4, washing the solid precipitate obtained in the S3 with pure water for 2-3 times;
s5, putting the washed solid precipitate into an oven, and drying at 60 ℃.
3. The method of claim 2, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
in step S1, the DMF wastewater comprises a cross-linking agent, DMF and salt, and the pH value of the DMF wastewater is 4-5.
4. The method of claim 3, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
the concentration of the cross-linking agent is 700-2000 mg/L, the concentration of DMF is 300-800 mg/L, and the mass fraction of salt is 3% -3.5%.
5. The method of claim 2, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
in step S1, the waste lye is generated by a crosslinker manufacturer by washing the waste gas with lye.
6. The method of claim 5, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
the waste alkali liquor comprises NaOH and salt, and the pH value of the waste alkali liquor is 13.7-14.02.
7. The method of claim 6, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
the mass fraction of NaOH is 2-4%, and the mass fraction of salt is 2-2.5%.
8. The method of claim 2, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
in step S2, the temperature-raising air stripping container is heated in a water bath to control the temperature.
9. The method of claim 2, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
in step S2, the stripping temperature was 50 ℃.
10. The method of claim 2, wherein the cross-linking agent is recovered from the DMF waste water by using waste lye,
in step S5, the oven is flushed with nitrogen gas.
CN202210507942.3A 2022-05-11 2022-05-11 Method for recovering cross-linking agent from DMF (dimethyl formamide) wastewater by using waste alkali liquor Pending CN114805924A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2653192A1 (en) * 2006-05-23 2008-02-07 V.B. Medicare Pvt. Ltd. Recovery of dimethylformamide and other solvents from process streams of manufacture of trichlorogalactosucrose
CN105198174A (en) * 2015-10-29 2015-12-30 南京大学盐城环保技术与工程研究院 Method for treating chemical industry wastewater containing organic nitrogen DMF (N,N-dimethylformamide)
CN105502855A (en) * 2016-01-29 2016-04-20 安徽汇泽通环境技术有限公司 Method for performing combined treatment on TAIC industrial wastewater through alkaline demulsification and hydrolysis-contact oxidation system
WO2016187878A1 (en) * 2015-05-28 2016-12-01 鹤山市新科达企业有限公司 Treatment technology for synthetic leather production wastewater
CN107673571A (en) * 2017-12-04 2018-02-09 湖南大辰环保科技有限公司 DMF comprehensive treatment method for wastewater and system in a kind of film production
CN111573916A (en) * 2020-05-21 2020-08-25 南京大学盐城环保技术与工程研究院 Method and system for recycling dimethyl formamide wastewater

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2653192A1 (en) * 2006-05-23 2008-02-07 V.B. Medicare Pvt. Ltd. Recovery of dimethylformamide and other solvents from process streams of manufacture of trichlorogalactosucrose
WO2016187878A1 (en) * 2015-05-28 2016-12-01 鹤山市新科达企业有限公司 Treatment technology for synthetic leather production wastewater
CN105198174A (en) * 2015-10-29 2015-12-30 南京大学盐城环保技术与工程研究院 Method for treating chemical industry wastewater containing organic nitrogen DMF (N,N-dimethylformamide)
CN105502855A (en) * 2016-01-29 2016-04-20 安徽汇泽通环境技术有限公司 Method for performing combined treatment on TAIC industrial wastewater through alkaline demulsification and hydrolysis-contact oxidation system
CN107673571A (en) * 2017-12-04 2018-02-09 湖南大辰环保科技有限公司 DMF comprehensive treatment method for wastewater and system in a kind of film production
CN111573916A (en) * 2020-05-21 2020-08-25 南京大学盐城环保技术与工程研究院 Method and system for recycling dimethyl formamide wastewater

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Application publication date: 20220729