CN103073139A - Method and device used for processing nitrochlorobenzene production wastewater - Google Patents
Method and device used for processing nitrochlorobenzene production wastewater Download PDFInfo
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Abstract
The invention provides a method and a device used for processing nitrochlorobenzene production wastewater. The method comprises the steps that: (1) nitrochlorobenzene production wastewater is subjected to a stripping treatment; and tower-top steam of a stripping tower is directly used in a production process; (2) the pH value of water delivered from a stripping tower kettle is regulated until the water is acidic; (3) an oxidant (hydrogen peroxide) and a reducing agent (ferrous ion) are used for carrying out a photo-assisted Fenton catalytic oxidation process upon the water delivered from the stripping tower kettle under the irradiation of an ultraviolet medium-pressure mercury lamp; (4) the pH value of the water obtained from the catalytic oxidation process is regulated to approximately neutral; and reactions such as dissolved iron precipitation and decomposition of residual hydrogen peroxide in water are carried out; and (5) water obtained in the reactions is subjected to slag-water separation; the separated slag can be used as a flocculating agent; and the water reaches a standard and can be discharged. With the method provided by the invention, nitrochlorobenzene production wastewater chromaticity, COD, TOC, and nitrochlorobenzene content can be effectively reduced, and waste water can reach a discharging standard.
Description
Technical field
The present invention relates to the treatment process of organic chemical waste water, especially relate to the treatment process of difficult for biological degradation organic chemical waste water, specifically a kind of method and apparatus of processing chloronitrobenzene producing wastewater.
Background technology
Nitro-chlorobenzene is the intermediate of many fine chemical products such as medicine, agricultural chemicals, dyestuff.The production of nitro-chlorobenzene is take chlorobenzene as former section, and it is nitrated to adopt nitration mixture to be that nitrating agent carries out, and the nitrated crude product that obtains need to pass through alkali cleaning and washing, then carries out separating-purifying with rectifying tower, obtains p-Nitrophenyl chloride and o-Nitrochlorobenzene.Adopt above-mentioned production technique, produce nitro-chlorobenzene product per ton and will produce about 1.2-1.8 tons of waste water, this waste water mainly contains the pollutents such as nitro-chlorobenzene, nitrochlorophenol, has colourity height, strong, the characteristics such as salinity is high, toxicity is large, difficult for biological degradation of alkalescence.
Chinese patent CN1055902C discloses the method for wastewater treatment of a kind of oil of mirbane and nitro-chlorobenzene production, the method is to add tetracol phenixin or benzene in waste water, static layering after fully vibrating, tetracol phenixin or benzene with equal volume behind minute water-yielding stratum extract, after the continuous extraction repeatedly, i.e. not nitrobenzene-containing or nitro-chlorobenzene in the waste water.According to this patent, use the tetracol phenixin identical with wastewater volume that waste water is carried out the single extraction operation and can be reduced to 60ppm to the content of nitro-chlorobenzene in the waste water by 700ppm.Although the method that this patent proposes has a significant effect really to the nitro-chlorobenzene that separates in the waste water, but still there is the problem of following aspect in the method: at first, through after the extracting operation, the content of nitro-chlorobenzene also is difficult to reach the requirement of emission standard in the waste water; Secondly, the method has only been paid close attention to the variation of nitro-chlorobenzene content in the waste water, other indexs relevant with discharged wastewater met the national standard (such as colourity, COD etc.) is not considered; Moreover how the tetracol phenixin that contains nitro-chlorobenzene is processed remains a difficult problem.In brief, rely on merely the method also to be difficult to effectively solve the qualified discharge problem of chloronitrobenzene producing wastewater.
The resin absorption that Chinese patent CN1233570C discloses nitro-chlorobenzene in a kind of chloronitrobenzene producing wastewater reclaims technique, it be with chloronitrobenzene producing wastewater after mechanical impurity is removed in pre-treatment, with the flow below the 10BV/h by being filled with the adsorption column of vinylbenzene-divinylbenzene polymeric adsorbent, make the nitro-chlorobenzene selective adsorption on resin, the nitropheneol material is not adsorbed, nitro-chlorobenzene content in the absorption effluent is below 2mg/L, the polymeric adsorbent that has adsorbed nitro-chlorobenzene uses water vapor as the desorbing agent desorption and regeneration, resulting vapour, liquid mixture cools off, the Separation and Recovery nitro-chlorobenzene.Although this patent can be from chloronitrobenzene producing wastewater the effective separation nitro-chlorobenzene, the nitropheneol material in the waste water still needs to process, and the reproduction ratio of polymeric adsorbent difficulty.
Based on defects, the invention provides a kind of method and apparatus of processing chloronitrobenzene producing wastewater, can effectively reduce colourity, COD, TOC and the feature pollutant load of waste water, realize discharged wastewater met the national standard.
Summary of the invention
The purpose of this invention is to provide a kind of method and apparatus of processing chloronitrobenzene producing wastewater.
The water quality of indication chloronitrobenzene producing wastewater of the present invention is as follows: pH〉8; Salts contg is 0.5 ~ 5%; Nitro-chlorobenzene content is 200 ~ 1200mg/L; Colourity is 500 ~ 5000 times.
For reaching above purpose, method of the present invention may further comprise the steps:
1) stripping is processed: chloronitrobenzene producing wastewater is carried out stripping at stripping tower process; Stripping tower tower reactor temperature is controlled to be 102 ~ 120 ℃, and stripping tower tower top pressure (gauge pressure) is controlled to be 0 ~ 0.08MPa;
Under the aforesaid operations condition, the content that stripping is processed nitro-chlorobenzene in the water outlet can be reduced in the 100mg/L.Adopt steam stripped method that above-mentioned chloronitrobenzene producing wastewater is processed, can reclaim most nitro-chlorobenzene in the waste water, not only improved the yield of nitro-chlorobenzene product, and can effectively reduce the pressure of subsequent wastewater treatment.
In the step 1), the number of theoretical plate that stripping is processed the stripping tower that adopts is controlled to be 10 ~ 30, and stripping tower overhead streams output is controlled to be into 8 ~ 25% of the tower water yield.
In the step 1), described chloronitrobenzene producing wastewater enters before the stripping tower, heat up with slag-water separator water outlet, the water outlet of stripping tower tower reactor and stripping tower overhead vapours indirect heat exchange successively, utilize tower reactor water outlet and overhead vapours p-Nitrophenyl chloride factory effluent to carry out effective utilization that the indirect heat exchange intensification can realize heat energy.
In the step 1), the stripping tower overhead vapours that is rich in nitro-chlorobenzene through the indirect heat exchange cooling after direct reuse in production technique
After step 1), step 2) before, also comprise step 2 ') with the pH regulator to 2.0 of stripping tower tower reactor water outlet～4.0;
The purpose of this step is to guarantee the needed pH condition of follow-up catalytic oxidation, and the water outlet of wherein said stripping tower tower reactor is that to have utilized chloronitrobenzene producing wastewater to carry out indirect heat exchange cooled.
2) Treatment by Photocatalysis Oxidation is carried out in the stripping tower tower reactor water outlet that the upper step was obtained in oxidation reactor;
Oxygenant adopts hydrogen peroxide, and the consumption of hydrogen peroxide adds by every L waste water 0.55 ~ 1.375g active principle; Preferred 27.5% hydrogen peroxide, the hydrogen peroxide take 27.5% is example, the consumption of hydrogen peroxide adds by every L waste water 2 ~ 5g;
Catalyzer adopts ferrous sulfate, and the consumption of ferrous salt is by every L waste water 20 ~ 200mg Fe
2+Add;
Light source adopts the ultraviolet medium pressure mercury lamp, is positioned in the middle of the oxidation reactor prolonged exposure in reaction process;
The pressure of reaction system is normal pressure; Temperature is 40 ~ 60 ℃; Reaction times or mean residence time are 10 ~ 60 min;
3) be adjusted in the precipitation reactor water outlet pH to 6.0 ~ 9.0 after the oxide treatment with sodium hydroxide;
This step is the decomposition reaction for residual hydrogen peroxide in the precipitin reaction of carrying out soluble iron and the water, and the purpose of this step mainly contains three: the one, guarantee that wastewater pH satisfies the qualified discharge requirement; The 2nd, allow the iron precipitation fully (it is following that the solubilised state total iron content reaches 1mg/L) of solubilised state in the waste water, the recovery that realizes iron precipitate to be conducive to next step; The 3rd, allow in the waste water residual decomposing hydrogen dioxide solution complete.The quality of this step operating effect can produce material impact to the water quality of final processing water outlet.
Decompose as far as possible fully in order to ensure residual hydrogen peroxide, should allow the waste water that regulates pH in reactor, mix 5 ~ 30min; The temperature of reactor should be controlled at 40 ~ 60 ℃; Reaction pressure is normal pressure.
4) utilize slag-water separator to carry out the pulp water lock out operation step 3) reaction effluent;
Isolated slag can adopt ordinary method to dispose or fully utilize or recycle, and isolated water qualified discharge after process and chloronitrobenzene producing wastewater indirect heat exchange are lowered the temperature.
With aforesaid method to cooperating, the present invention also provides the device of realizing aforesaid method, described device comprises:
Steam stripping unit: be used for that chloronitrobenzene producing wastewater is carried out stripping and process, its entrance is introduced respectively chloronitrobenzene producing wastewater and steam, its outlet is respectively nitro-chlorobenzene vapour outlet and treatment of wastewater from stripping outlet, the nitro-chlorobenzene vapour outlet is communicated with nitro-chlorobenzene raw materials for production opening for feed, and the treatment of wastewater from stripping outlet is communicated with the treatment of wastewater from stripping entrance of photochemical catalytic oxidation unit;
Photochemical catalytic oxidation unit: be used for photochemical catalytic oxidation is carried out in the treatment of wastewater from stripping outlet, its entrance comprises oxidant inlet and treatment of wastewater from stripping entrance, described treatment of wastewater from stripping entrance is communicated with the treatment of wastewater from stripping outlet of steam stripping unit, its outlet is communicated with the photochemical catalytic oxidation entrance of precipitin reaction unit for the photochemical catalytic oxidation wastewater outlet;
Precipitin reaction unit: be used for photochemical catalytic oxidation waste water is carried out precipitin reaction, its entrance comprises precipitation agent entrance and photochemical catalytic oxidation waterwater entrance, its photochemical catalytic oxidation waterwater entrance is communicated with the photochemical catalytic oxidation wastewater outlet, its outlet is communicated with the entrance of pulp water separating unit for the outlet of precipitin reaction thing;
The pulp water separating unit: be used for that pulp water is carried out in precipitin reaction and separate, its entrance is precipitin reaction thing entrance, is communicated with the outlet of precipitin reaction unit, and its outlet comprises waste residue outlet and wastewater outlet, and wastewater outlet is communicated with discharge water.
In addition, between steam stripping unit and photochemical catalytic oxidation unit, described device also comprises the pH regulator unit: the pH value that is used for regulating treatment of wastewater from stripping, its entrance comprises pH value conditioning agent entrance and treatment of wastewater from stripping entrance, described treatment of wastewater from stripping entrance is communicated with the treatment of wastewater from stripping outlet of steam stripping unit, its outlet is communicated with the treatment of wastewater from stripping entrance of photochemical catalytic oxidation unit for regulating the outlet of pH value treatment of wastewater from stripping;
Described device also comprises heat exchange unit, is used for described chloronitrobenzene producing wastewater is entered before the steam stripping unit, and water outlet, steam stripping unit water outlet and the steam stripping unit nitro-chlorobenzene steam indirect heat exchange with the pulp water separating unit heats up successively.Utilize tower reactor water outlet and overhead vapours p-Nitrophenyl chloride factory effluent to carry out effective utilization that the indirect heat exchange intensification can realize heat energy.
Specifically, the technical scheme taked of the present invention is:
1) enter stripping tower after chloronitrobenzene producing wastewater heats up with slag-water separator water outlet, the water outlet of stripping tower tower reactor and stripping tower overhead vapours indirect heat exchange successively and carry out stripping and process, the stripping tower overhead vapours that is rich in nitro-chlorobenzene through the indirect heat exchange cooling after direct reuse in production technique;
Stripping tower tower reactor temperature is controlled to be 102 ~ 120 ℃, and stripping tower tower top pressure (gauge pressure) is controlled to be 0 ~ 0.08MPa, and the stripping tower number of theoretical plate is controlled to be 10 ~ 30, and stripping tower overhead streams output is controlled to be into 8 ~ 25% of the tower water yield.
Under the aforesaid operations condition, the content of nitro-chlorobenzene can be reduced in the 100mg/L in the water outlet of stripping tower tower reactor.Adopt steam stripped method that above-mentioned chloronitrobenzene producing wastewater is processed, can reclaim most nitro-chlorobenzene in the waste water, not only improved the yield of nitro-chlorobenzene product, and can effectively reduce the pressure of subsequent wastewater treatment.In addition, utilize tower reactor water outlet and overhead vapours p-Nitrophenyl chloride factory effluent to carry out effective utilization that the indirect heat exchange intensification can realize heat energy.
2) utilizing chloronitrobenzene producing wastewater to carry out the pH regulator to 2.0 of the stripping tower tower reactor water outlet of indirect heat exchange cooling～4.0;
The purpose of this step is to guarantee the needed pH condition of follow-up catalytic oxidation.
3) in oxidation reactor, Treatment by Photocatalysis Oxidation is carried out in the stripping tower tower reactor water outlet of having regulated pH.Oxygenant adopts 27.5% hydrogen peroxide, and the consumption of hydrogen peroxide adds by every L waste water 2 ~ 5g; Catalyzer adopts ferrous sulfate, and the consumption of ferrous salt adds by every L waste water 20 ~ 200mg Fe2+; Light source adopts the ultraviolet medium pressure mercury lamp, is positioned in the middle of the oxidation reactor prolonged exposure in reaction process; The pressure of reaction system is normal pressure; Temperature is 40 ~ 60 ℃; Reaction times or mean residence time are 10 ~ 60 min.
4) in precipitation reactor, regulate water outlet pH to 6.0 ~ 9.0 after the oxide treatment with sodium hydroxide, with the decomposition reaction of residual hydrogen peroxide in the precipitin reaction of carrying out soluble iron and the water.Decompose as far as possible fully in order to ensure residual hydrogen peroxide, should allow the waste water that regulates pH in reactor, mix 5 ~ 30min; The temperature of reactor should be controlled at 40 ~ 60 ℃.Reaction pressure is normal pressure.The purpose of this step mainly contains three: the one, guarantee that wastewater pH satisfies the qualified discharge requirement; The 2nd, allow the iron precipitation fully (it is following that the solubilised state total iron content reaches 1mg/L) of solubilised state in the waste water, the recovery that realizes iron precipitate to be conducive to next step; The 3rd, allow in the waste water residual decomposing hydrogen dioxide solution complete.The quality of this step operating effect can produce material impact to the water quality of final processing water outlet.
5) utilize slag-water separator to carry out the pulp water lock out operation step 4) reaction effluent, isolated slag can adopt ordinary method to dispose or fully utilize or recycle, and isolated water qualified discharge after process and chloronitrobenzene producing wastewater indirect heat exchange are lowered the temperature.
The novelty of the technical program:
1) realized that stripping is processed and the combination of catalytic oxidation treatment, adopt steam stripped method p-Nitrophenyl chloride factory effluent to process, not only can reclaim the nitro-chlorobenzene of the overwhelming majority in the waste water, and the nitro-chlorobenzene that reclaims can all directly turn back to production technique.So not only improve the yield of nitro-chlorobenzene product, effectively reduced the pressure of subsequent wastewater treatment, and do not had extraction agent in the prior art, adsorbent reactivation hard problem.Certainly, only rely on stripping to process effectively to solve the qualified discharge problem of chloronitrobenzene producing wastewater, and catalyzed oxidation just in time can solve behind the stripping processing difficult problem of residue nitro-chlorobenzene in the waste water and nitrochlorophenol.
2) inventor herein finds, use the Fenton system (namely with hydrogen peroxide as oxygenant, when the catalytic oxidation system take ferrous ion as catalyzer) processing the water outlet of stripping tower tower reactor, the final processing degree of depth that can reach depends primarily on the Pollutant levels in the water outlet of stripping tower tower reactor, especially the concentration of nitro-chlorobenzene, if the concentration of nitro-chlorobenzene is higher in the water outlet of stripping tower tower reactor, even adopt the rising temperature of reaction, significantly increase the oxygenant consumption, adjust catalyst levels, prolong the reaction times, the means such as change reaction system pH all are difficult to make the final outflow water qualified discharge.This is explanation just, adopts the fully organism in the water outlet of mineralising stripping tower tower reactor of Fenton system, and it is inadequate to cause processing the degree of depth.Inventor herein's creative research is found, in the identical situation of other conditions, by UV-light being introduced in the Fenton's reaction system, can make mineralization of organic material more abundant, thereby greatly improve the ability of Fenton reagent catalyzed oxidation chloronitrobenzene producing wastewater, thereby significantly improve the degree of depth of final processing, obviously reduce COD and the TOC of final outflow water, reach qualified discharge.
After chloronitrobenzene producing wastewater adopts disposal methods of the present invention, can realize the qualified discharge of waste water.By the product water after the disposal methods of the present invention, its water-quality guideline is: pH6 ~ 9, colourity are no more than 10 times, COD and are no more than that 60mg/L, TOC are no more than 30mg/L, nitro-chlorobenzene content is no more than 0.5 mg/L.The present invention have operational condition gentleness, flexible operation mode, treatment effect stable, take up an area little, reduced investment, be easy to the advantage such as industry amplification.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.Specialize such as nothing, the raw material that adopts among the embodiment is commercial.
Embodiment 1
The pH value of certain company's chloronitrobenzene producing wastewater is 12.0, and salts contg is 2.7%, and the content of nitro-chlorobenzene is 1100mg/L, and colourity is 5000 times.
Be that 115 ℃, stripping tower tower top pressure (gauge pressure) are controlled to be 0.05MPa, the stripping tower number of theoretical plate is 25 in the stripping tower working temperature, when stripping tower overhead streams output is under the condition of the tower water yield 20%, the nitro-chlorobenzene content in the water outlet of stripping tower tower reactor can drop to below the 30mg/L.
Next, be under 40 ℃ the condition, waste water to be carried out light help the Fenton catalytic oxidation treatment at wastewater temperature.To regulate wastewater pH with 98% sulfuric acid be 2.5, adopt 27.5% hydrogen peroxide is that the consumption of oxygenant, hydrogen peroxide adds by every L waste water 4g, and the employing ferrous sulfate is that the consumption of catalyzer, ferrous salt is by every L waste water 80mgFe
2+Add, light source adopts the ultraviolet medium pressure mercury lamp, be positioned in the middle of the oxidation reactor, and prolonged exposure in reaction process, the W-response time is 30 min.
Next, be 40 ℃ at wastewater temperature, to regulate wastewater pH with 10% sodium hydroxide solution be 8.5, then reaction 25min carries out pulp water and separates, adopting prior art mensuration water pH8.5,3 times of colourities, COD is that 40mg/L, TOC are 9.6mg/L, and nitro-chlorobenzene content is less than 0.5mg/L.
Embodiment 2:
The pH value of certain company's chloronitrobenzene producing wastewater is 13, and salts contg is 2.3%, and the content of nitro-chlorobenzene is 780 mg/L, and colourity is 4200 times.
Be that 105 ℃, normal pressure, stripping tower number of theoretical plate are that stripping tower overhead streams output is under the condition of the tower water yield 10% under 10 the condition in the stripping tower working temperature, the nitro-chlorobenzene content in the water outlet of stripping tower tower reactor can drop to below the 50mg/L.
Next, at wastewater temperature be under 50 ℃ of conditions, waste water is carried out light help the Fenton catalytic oxidation treatment.To regulate wastewater pH with 98% sulfuric acid be 3.0, adopt 27.5% hydrogen peroxide is that to add, adopt ferrous sulfate by every L waste water 3g be that the consumption of catalyzer, ferrous salt is by every L waste water 100mg Fe for the consumption of oxygenant, hydrogen peroxide
2+Add, light source adopts the ultraviolet medium pressure mercury lamp, be positioned in the middle of the oxidation reactor, and prolonged exposure in reaction process, the reaction times is 40 min.
Next, be 50 ℃ at wastewater temperature, to regulate wastewater pH with 10% sodium hydroxide solution be 6.8, reacts 10 min, then carry out pulp water and separate, mensuration water pH6.8,5 times of colourities, COD are that 55mg/L, TOC are 24mg/L, and nitro-chlorobenzene content is less than 0.5mg/L.
Claims (12)
1. a method of processing chloronitrobenzene producing wastewater is characterized in that, may further comprise the steps:
1) stripping is processed: chloronitrobenzene producing wastewater is carried out stripping at stripping tower process; Stripping tower tower reactor temperature is controlled to be 102 ~ 120 ℃, and the stripping tower tower top pressure is controlled to be 0 ~ 0.08MPa, obtains stripping tower overhead vapours and the water outlet of stripping tower tower reactor;
2) Treatment by Photocatalysis Oxidation is carried out in the stripping tower tower reactor water outlet that the upper step was obtained in oxidation reactor;
Oxygenant adopts hydrogen peroxide, and the consumption of hydrogen peroxide is by every L waste water 0.55 ~ 1.375g active principle H
2O
2Add;
Catalyzer adopts ferrous sulfate, and the consumption of ferrous salt is by every L waste water 20 ~ 200mg Fe
2+Add;
Light source adopts the ultraviolet medium pressure mercury lamp, is positioned in the oxidation reactor prolonged exposure in reaction process;
The pressure of reaction system is normal pressure; Temperature is 40 ~ 60 ℃; Reaction times or mean residence time are 10 ~ 60 min;
3) in precipitation reactor with the pH to 6.0 of water outlet after the oxide treatment ~ 9.0;
4) utilize slag-water separator to carry out the pulp water lock out operation step 3) reaction effluent.
2. method according to claim 1 is characterized in that, in the step 1), the number of theoretical plate that described stripping is processed the stripping tower that adopts is controlled to be 10 ~ 30, and stripping tower overhead streams output is controlled to be into 8 ~ 25% of the tower water yield.
3. method according to claim 1 and 2 is characterized in that, in the step 1), described chloronitrobenzene producing wastewater enters before the stripping tower, heats up with slag-water separator water outlet, the water outlet of stripping tower tower reactor and stripping tower overhead vapours indirect heat exchange successively.
4. according to claim 1 or 3 described methods, it is characterized in that in the step 1), described stripping tower overhead vapours direct reuse is in production.
5. method according to claim 1 is characterized in that, after step 1), step 2) before, described method also comprises step 2 ') with the pH regulator to 2.0 of stripping tower tower reactor water outlet～4.0.
6. method according to claim 1 is characterized in that step 2) in, described hydrogen peroxide is 27.5% hydrogen peroxide; Waste water mixes 5 ~ 30min in oxidation reactor; The temperature of oxidation reactor should be controlled at 40 ~ 60 ℃; The reaction pressure of photochemical catalytic oxidation is normal pressure.
7. method according to claim 1 is characterized in that, in the step 3), regulates described pH value with sodium hydroxide.
8. the application of arbitrary described method is characterized in that according to claim 1-7, and for the treatment of chloronitrobenzene producing wastewater, the water quality of described chloronitrobenzene producing wastewater is as follows: pH〉8; Salts contg is 0.5 ~ 5%; Nitro-chlorobenzene content is 200 ~ 1200mg/L; Colourity is 500 ~ 5000 times.
9. the device of arbitrary described method is characterized in that according to claim 1 ~ 7, and described device comprises:
Steam stripping unit: be used for that chloronitrobenzene producing wastewater is carried out stripping and process, its entrance is introduced respectively chloronitrobenzene producing wastewater and steam, its outlet is respectively nitro-chlorobenzene vapour outlet and treatment of wastewater from stripping outlet, the nitro-chlorobenzene vapour outlet is communicated with nitro-chlorobenzene raw materials for production opening for feed, and the treatment of wastewater from stripping outlet is communicated with the treatment of wastewater from stripping entrance of photochemical catalytic oxidation unit;
Photochemical catalytic oxidation unit: be used for photochemical catalytic oxidation is carried out in the treatment of wastewater from stripping outlet, its entrance comprises oxidant inlet and treatment of wastewater from stripping entrance, described treatment of wastewater from stripping entrance is communicated with the treatment of wastewater from stripping outlet of steam stripping unit, its outlet is communicated with the photochemical catalytic oxidation entrance of precipitin reaction unit for the photochemical catalytic oxidation wastewater outlet;
Precipitin reaction unit: be used for photochemical catalytic oxidation waste water is carried out precipitin reaction, its entrance comprises precipitation agent entrance and photochemical catalytic oxidation waterwater entrance, its photochemical catalytic oxidation waterwater entrance is communicated with the photochemical catalytic oxidation wastewater outlet, its outlet is communicated with the entrance of pulp water separating unit for the outlet of precipitin reaction thing;
The pulp water separating unit: be used for that pulp water is carried out in precipitin reaction and separate, its entrance is precipitin reaction thing entrance, is communicated with the outlet of precipitin reaction unit, and its outlet comprises waste residue outlet and wastewater outlet, and wastewater outlet is communicated with discharge water.
10. device according to claim 9, it is characterized in that, between steam stripping unit and photochemical catalytic oxidation unit, described device also comprises the pH regulator unit: the pH value that is used for regulating treatment of wastewater from stripping, its entrance comprises pH value conditioning agent entrance and treatment of wastewater from stripping entrance, described treatment of wastewater from stripping entrance is communicated with the treatment of wastewater from stripping outlet of steam stripping unit, and its outlet is communicated with the treatment of wastewater from stripping entrance of photochemical catalytic oxidation unit for regulating the outlet of pH value treatment of wastewater from stripping.
11. according to claim 9 or 10 described devices, it is characterized in that, described device also comprises heat exchange unit, be used for described chloronitrobenzene producing wastewater is entered before the steam stripping unit, water outlet, steam stripping unit water outlet and the steam stripping unit nitro-chlorobenzene steam indirect heat exchange with the pulp water separating unit heats up successively.
12. arbitrary described method is characterized in that according to claim 1-7, may further comprise the steps:
1) enter stripping tower after chloronitrobenzene producing wastewater heats up with slag-water separator water outlet, the water outlet of stripping tower tower reactor and stripping tower overhead vapours indirect heat exchange successively and carry out stripping and process, the stripping tower overhead vapours that is rich in nitro-chlorobenzene through the indirect heat exchange cooling after direct reuse in production technique;
Stripping tower tower reactor temperature is controlled to be 102 ~ 120 ℃, and stripping tower tower top pressure (gauge pressure) is controlled to be 0 ~ 0.08MPa, and the stripping tower number of theoretical plate is controlled to be 10 ~ 30, and stripping tower overhead streams output is controlled to be into 8 ~ 25% of the tower water yield;
2) utilizing chloronitrobenzene producing wastewater to carry out the pH regulator to 2.0 of the stripping tower tower reactor water outlet of indirect heat exchange cooling～4.0;
3) in oxidation reactor, Treatment by Photocatalysis Oxidation is carried out in the stripping tower tower reactor water outlet of having regulated pH; Oxygenant adopts 27.5% hydrogen peroxide, and the consumption of hydrogen peroxide adds by every L waste water 2 ~ 5g; Catalyzer adopts ferrous sulfate, and the consumption of ferrous salt adds by every L waste water 20 ~ 200mg Fe2+; Light source adopts the ultraviolet medium pressure mercury lamp, is positioned in the oxidation reactor prolonged exposure in reaction process; The pressure of reaction system is normal pressure; Temperature is 40 ~ 60 ℃; Reaction times or mean residence time are 10 ~ 60 min;
4) in precipitation reactor, with water outlet pH to 6.0 ~ 9.0 after the sodium hydroxide adjusting oxide treatment, waste water mixes 5 ~ 30min in reactor; The temperature of reactor should be controlled at 40 ~ 60 ℃; Reaction pressure is normal pressure;
5) utilize slag-water separator to carry out the pulp water lock out operation step 4) reaction effluent, isolated slag can adopt ordinary method to dispose or fully utilize or recycle, and isolated water qualified discharge after process and chloronitrobenzene producing wastewater indirect heat exchange are lowered the temperature.
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| CN108178400A (en) * | 2018-01-09 | 2018-06-19 | 东莞道汇环保科技股份有限公司 | A kind of processing method of COD titration waste liquid |
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| CN113735300A (en) * | 2020-05-27 | 2021-12-03 | 中石化南京化工研究院有限公司 | Method for treating high-concentration high-salinity wastewater in nitrochlorobenzene meta-position oil separation |
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