CN102936079B - Method for removing aniline from industrial high salt-containing aniline wastewater - Google Patents
Method for removing aniline from industrial high salt-containing aniline wastewater Download PDFInfo
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- CN102936079B CN102936079B CN201110462376.0A CN201110462376A CN102936079B CN 102936079 B CN102936079 B CN 102936079B CN 201110462376 A CN201110462376 A CN 201110462376A CN 102936079 B CN102936079 B CN 102936079B
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Abstract
The invention provides a method for removing aniline from industrial high salt-containing aniline wastewater. The method comprises the steps of processing aniline wastewater via a solvent extraction method under the action of a salting-out effect; mixing the wastewater, sodium chloride and nitrobenzene used as an extracting solvent in an atmospheric static mixing reactor; pumping the mixture to a tubular static mixing reactor via a raw material pump to make the extracting solvent nitrobenzene mixed with the aniline wastewater thoroughly; processing the raffinate with an aerobic-anaerobic microbial oxidation combined process; passing the raffinate through the anaerobic tank to perform anaerobic degradation treatment; and passing the anaerobic treated wastewater into the aerobic tank to perform aerobic degradation treatment. With the method for removing aniline from industrial aniline wastewater, aniline can be separated out from the industrial aniline wastewater effectively; the extracted and separated aniline and the extracting agent can be reused without separation; the separating process generates no pollutions; energy consumption of the separation is low; and processing cost of the separation is low. The method can be used for the aniline wastewater generated by industries of dye, agriculture, medicine, military industry, chemical industry, etc.
Description
Technical field
The invention provides a kind for the treatment of process of industrial aniline waste water, especially a kind ofly from the high saliferous aniline waste water of industry, remove aniline, to realize the method for recycling of waste water.
Background technology
Aniline is a kind of important Organic Chemicals and Chemicals, the Chemicals that made by it and intermediate have kind more than 300, produce at MDI (diphenylmethanediisocyanate), the industries such as dyestuff, pigment, medicine, agricultural chemicals, explosive, rubber ingredients have a wide range of applications.Aniline waste water concentration high (aniline content 4% left and right), toxicity is large, color and luster is dark, saltiness high (16%), biodegradability is poor, and COD index reaches 40000mg/L, traditional physico-chemical process processing efficiency is very low, belong to extremely unmanageable dangerous organic industrial sewage, this direct discharging of waste water will cause great pollution and harm to environment and the mankind's health, and China is listed in " Chinese environmental priority pollutant Black List ".
Existing aniline waste water treatment process mainly contains absorption method, oxidation style, extraction process etc.Absorption method is not good for the higher aniline waste water treatment effect of concentration, and aniline recovery difficulty after absorption, and desorption liquid is difficult for recycling, and adsorbent reactivation difficulty, causes aniline processing cost higher; Oxidation style will consume a large amount of oxygenants, thereby processing cost is higher; Anaerobic-aerobic biological treatment is at present still in the exploratory stage, and the screening of special efficacy bacterial classification and cultivation are the directions of studying from now on effort.
Therefore seek development process cost low, facility investment is few, simple to operate, can effectively reclaim the aniline in waste water, realizes the reuse of aniline waste water, and the new processing method producing without new pollution is again very meaningful.
Summary of the invention
Technical problem to be solved by this invention is, a kind of method of removing aniline from the high saliferous aniline waste water of industry is provided, and realizes the recovery of aniline, and waste water after treatment meets reuse requirement.
The present invention is achieved in that the method for removing aniline from the high saliferous aniline waste water of industry, and the step of described method is:
A, with solvent extration under salting out, aniline waste water is processed, in normal pressure static mixing reactor, waste water, sodium-chlor and the oil of mirbane as extraction solvent are mixed, control waste water ph is 10-13, the volume ratio of waste water and oil of mirbane 3: 1～2: 1, the consumption of sodium-chlor is 1%～10% of waste water weight, squeeze into tubular type static mixing reactor through feedstock pump, at 20 ℃～30 ℃ temperature, residence time 2min～5min, extraction solvent oil of mirbane is fully mixed with aniline waste water, then enter storage tank, organic phase reuse after layering in storage tank;
B, be that raffinate carries out the processing of Aerobic-anaerobic microbiological oxidation combination process by the water after layering in storage tank, be at water inlet flow velocity that 20～200ml/min, water inlet pH value are 7.0～10, under the condition of 10～30 hours residence time, make raffinate stream carry out anaerobic degradation processing through anaerobic pond, the anerobe of selecting is human skin bacillus (Dermabacter hominis); Be that 20～200ml/min, aeration time are that 8～10 hours, sedimentation time are that 2～5 hours, water inlet pH value are 7.0～10 o'clock through the waste water of anaerobic treatment at flow velocity, enter Aerobic Pond and carry out aerobic degradation processing, the aerobic bacteria of selecting is excrement bacterioide (Bacteroides caccae).
This method of removing aniline from industrial aniline waste water, can effectively realize from industrial aniline waste water and isolate aniline, and the aniline that extracting and separating goes out does not need to separate with extraction agent, can direct reuse.After the salt tolerant Novel engineering bacterium aerobic treatment of raffinate through screening, tame, extraction agent and a small amount of residual aniline that the extraction process of can effectively degrading dissolves, light salt brine after treatment meets reuse requirement.Generation that sepn process is pollution-free, and the energy consumption separating is low, processing cost is low.This method can be used for the aniline waste water that the industries such as dyestuff, agricultural, medicine, military project, chemical industry produce.Application Areas is extensive, remarkable in economical benefits.
Embodiment
Further illustrate the present invention below.
Water in by storage tank after layering is that raffinate carries out Aerobic-anaerobic microbiological oxidation combination process while processing, anerobe, aerobic bacteria respectively by biofilm to the carrier in anaerobic pond and Aerobic Pond, thickness approximately 100 μ m.
In anaerobic pond, Aerobic Pond, the useful volume that the initial content of mud is 2～8%.Light salt brine after treatment can direct reuse.
After the present invention's method is processed, Aniline, extraction agent content can reduce to 0.001%, close to 0.
Add after these inorganic salt of sodium-chlor, by salting out, can increase the solubleness of aniline in extraction agent.
By raffinate being carried out to the processing of Aerobic-anaerobic microbiological oxidation combination process, oxidation-degradable extracts aniline residual in rear water and the micro-extraction agent of dissolving.In the time that influent COD fluctuates between 50.57-217.6mg/L, the COD of water outlet is less than 37mg/L, and COD clearance reaches 90%.
Embodiment 1
The method of removing aniline from the high saliferous aniline waste water of industry, the step of described method is:
A, with solvent extration under salting out, aniline waste water is processed, in normal pressure static mixing reactor, waste water, sodium chloride solution and the oil of mirbane as extraction solvent are mixed, controlling waste water ph is 10, the volume ratio of waste water and oil of mirbane 2: 1, the week amount of sodium-chlor is 1% of waste water weight, squeeze into tubular type static mixing reactor through feedstock pump, at 30 ℃ of temperature, residence time 2min, extraction solvent oil of mirbane is fully mixed with aniline waste water, then enter storage tank, organic phase reuse after layering in storage tank;
B, be that raffinate carries out the processing of Aerobic-anaerobic microbiological oxidation combination process by the water after layering in storage tank, be at water inlet flow velocity that 200ml/min, water inlet pH value are 7.0, under the condition of 30 hours residence time, make raffinate stream carry out anaerobic degradation processing through anaerobic pond, the anerobe of selecting is human skin bacillus (Dermabacter hominis); Be that 20ml/min, aeration time are that 10 hours, sedimentation time are that 2 hours, water inlet pH value are 10 o'clock through the waste water of anaerobic treatment at flow velocity, enter Aerobic Pond and carry out aerobic degradation processing, the aerobic bacteria of selecting is excrement bacterioide (Bacteroides caccae).
Embodiment 2
The method of removing aniline from the high saliferous aniline waste water of industry, is characterized in that, the step of described method is:
A, with solvent extration under salting out, aniline waste water is processed, in normal pressure static mixing reactor, waste water, sodium chloride solution and the oil of mirbane as extraction solvent are mixed, controlling waste water ph is 13, the volume ratio of waste water and oil of mirbane 3: 1, the consumption of sodium-chlor is 10% of waste water weight, squeeze into tubular type static mixing reactor through feedstock pump, at 20 ℃ of temperature, residence time 5min, makes extraction solvent oil of mirbane fully mix with aniline waste water, then enter storage tank, organic phase reuse after layering in storage tank;
B, be that raffinate carries out the processing of Aerobic-anaerobic microbiological oxidation combination process by the water after layering in storage tank, be at water inlet flow velocity that 20ml/min, water inlet pH value are 10, under the condition of 10 hours residence time, make raffinate stream carry out anaerobic degradation processing through anaerobic pond, the anerobe of selecting is human skin bacillus (Dermabacter hominis); Be that 200ml/min, aeration time are that 8 hours, sedimentation time are that 5 hours, water inlet pH value are 7.0 o'clock through the waste water of anaerobic treatment at flow velocity, enter Aerobic Pond and carry out aerobic degradation processing, the aerobic bacteria of selecting is excrement bacterioide (Bacteroides caccae).
Embodiment 3
The method of removing aniline from the high saliferous aniline waste water of industry, is characterized in that, the step of described method is:
A, with solvent extration under salting out, aniline waste water is processed, in normal pressure static mixing reactor, waste water, sodium chloride solution and the oil of mirbane as extraction solvent are mixed, controlling waste water ph is 12, the volume ratio of waste water and oil of mirbane 2.5: 1, the consumption of sodium-chlor is 5% of waste water weight, squeeze into tubular type static mixing reactor through feedstock pump, at 25 ℃ of temperature, residence time 4min, extraction solvent oil of mirbane is fully mixed with aniline waste water, then enter storage tank, organic phase reuse after layering in storage tank;
B, be that raffinate carries out the processing of Aerobic-anaerobic microbiological oxidation combination process by the water after layering in storage tank, be at water inlet flow velocity that 140ml/min, water inlet pH value are 8.5, under the condition of 25 hours residence time, make raffinate stream carry out anaerobic degradation processing through anaerobic pond, the anerobe of selecting is human skin bacillus (Dermabacter hominis); Be that 160ml/min, aeration time are that 9 hours, sedimentation time are that 4 hours, water inlet pH value are 8.5 o'clock through the waste water of anaerobic treatment at flow velocity, enter Aerobic Pond and carry out aerobic degradation processing, the aerobic bacteria of selecting is excrement bacterioide (Bacteroides caccae).
Claims (1)
1. the method for removing aniline from the high saliferous aniline waste water of industry, is characterized in that, the step of described method is:
A, with solvent extration under salting out, aniline waste water is processed, in normal pressure static mixing reactor, waste water, sodium-chlor and the oil of mirbane as extraction solvent are mixed, control waste water ph is 10-13, the volume ratio of waste water and oil of mirbane 3: 1～2: 1, the consumption of sodium-chlor is 1%～10% of waste water weight, squeeze into tubular type static mixing reactor through feedstock pump, at 20 ℃～30 ℃ temperature, residence time 2min～5min, extraction solvent oil of mirbane is fully mixed with aniline waste water, then enter storage tank, organic phase reuse after layering in storage tank;
B, be that raffinate carries out the processing of Aerobic-anaerobic microbiological oxidation combination process by the water after layering in storage tank, be at water inlet flow velocity that 20～200ml/min, water inlet pH value are 7.0～10, under the condition of 10～30 hours residence time, make raffinate stream carry out anaerobic degradation processing through anaerobic pond, the anerobe of selecting is human skin bacillus (Dermabacter hominis); Be that 20～200ml/min, aeration time are that 8～10 hours, sedimentation time are that 2～5 hours, water inlet pH value are 7.0～10 o'clock through the waste water of anaerobic treatment at flow velocity, enter Aerobic Pond and carry out aerobic degradation processing, the aerobic bacteria of selecting is excrement bacterioide (Bacteroides caccae).
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| CN201110462376.0A CN102936079B (en) | 2011-12-30 | 2011-12-30 | Method for removing aniline from industrial high salt-containing aniline wastewater |
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| CN201110462376.0A CN102936079B (en) | 2011-12-30 | 2011-12-30 | Method for removing aniline from industrial high salt-containing aniline wastewater |
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| CN102936079B true CN102936079B (en) | 2014-05-14 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104261590A (en) * | 2014-10-08 | 2015-01-07 | 上海博丹环境工程技术有限公司 | Treatment method and system for high concentration salt-containing wastewater for production of nigrosine |
| CN105237408A (en) * | 2015-10-30 | 2016-01-13 | 重庆长风化学工业有限公司 | Method for extracting aniline with nitrobenzene |
| CN105294451A (en) * | 2015-10-30 | 2016-02-03 | 重庆长风化学工业有限公司 | Treatment method for extracting aniline by means of nitrobenzene |
| CN108786176B (en) * | 2018-01-08 | 2020-11-03 | 华南农业大学 | Method for liquid-liquid microextraction of fungomycin in fruit juice by aid of acid-assisted dispersion liquid |
| CN108516650B (en) * | 2018-04-16 | 2021-05-28 | 扬州大学 | Comprehensive treatment method for industrial wastewater generated in polyaniline production by oxidative polymerization |
| CN110563069B (en) * | 2018-06-06 | 2020-12-22 | 中国石油化工股份有限公司 | Comprehensive utilization method of nitrobenzene tar and aniline wastewater |
| CN110857233B (en) * | 2018-08-22 | 2022-05-17 | 沈阳化工研究院设计工程有限公司 | Device and method for treating high-salinity wastewater containing phenol and aniline |
| CN110075721B (en) * | 2019-05-10 | 2021-10-19 | 万华化学（宁波）有限公司 | Preparation method of PDMS-PP composite membrane and application of PDMS-PP composite membrane in treatment of MDI waste brine |
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| CN101759244A (en) * | 2008-11-19 | 2010-06-30 | 陶伟平 | Method for treating wastewater in manufacturing process of aniline through nitrobenzene hydrogenation |
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| CN101759244A (en) * | 2008-11-19 | 2010-06-30 | 陶伟平 | Method for treating wastewater in manufacturing process of aniline through nitrobenzene hydrogenation |
| CN101830606A (en) * | 2010-05-19 | 2010-09-15 | 北京丰泽绿源环境技术有限公司 | Method for treating 2,4,6-trinitrotoluene waste water and application thereof |
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