CN103951101A - Treatment method and treatment system for nitrochlorobenzene production waste water - Google Patents
Treatment method and treatment system for nitrochlorobenzene production waste water Download PDFInfo
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Abstract
A treatment method and a treatment system for nitrochlorobenzene production waste water. The method comprises the following steps: pumping nitrochlorobenzene production waste water into an adjustment pool, adjusting the pH value to allow the waste water to be acidic, then allowing the waste water to enter an oxidation pool, adding oxidizing agents of sodium hypochlorite, calcium hypochlorite or hypochloric acid for chemical oxidation treatment, discharging the effluent from the oxidation pool into a neutralization pool, adjusting the pH value to allow the effluent to be neutral, discharging the effluent from the neutralization pool into a coagulation pool, adding coagulants of one or more than one of polyaluminium chloride, polyferric chloride, and polyacrylamide for a coagulation reaction, discharging the effluent from the coagulation pool into a sedimentation pool, allowing a supernatant obtained by sedimentation and separation in the sedimentation pool to overflow into a clean water pool, discharging the clean water that reaches the standard, concentrating and filtering sedimentated sludge at the bottom of the sedimentation pool for safety treatment, and discharging waste liquid generated during the concentration and filtration process into the adjustment pool for re-treatment. According to the invention, the removal rate of nitrochlorobenzene and other nitrobenzene compounds in effluent of the nitrochlorobenzene production waste water treated by the method of the invention is up to 99%, and the method of the invention has the advantages of high treatment efficiency, low operation cost, no secondary pollution, and the like.
Description
Technical field
The present invention relates to technical field of sewage, be specifically related to a kind for the treatment of process and treatment system of chloronitrobenzene producing wastewater.
Background technology
Nitro-chlorobenzene (Nitrochlorobenzenes) is that a class is chloride containing nitryl aromatic hydrocarbon compound, be widely used as the intermediate of medicine, dyestuff and pesticide producing, and China is one of country of neighbour, p-Nitrophenyl chloride output maximum in the world.2002, the output of world's Nitryl chlorobenzene compounds was 430,000 t/a, and Chinese output is 330,000 t/a, accounts for 76.7% of Gross World Product.2003, China's nitro-chlorobenzene output reached 370,000 tons, year growth by 12%.
Nitro-chlorobenzene can, by number of ways entered environment, become pollutent.Some researchs show, o-Nitrochlorobenzene is gene toxin, have " three cause " effect.European Union just announces that in nineteen eighty-two nitro-chlorobenzene is a kind of harmful especially compound, and in environment hard degradation, can cause Mammals and people's methemoglobinemia (Methemoglobinemia), and there is carcinogenesis.Therefore, this pollutant is carried out in time and effectively remove ensureing social safety, preserving the ecological environment has great importance.
Nitro-chlorobenzene, because its nitro and chlorine substituent are electron-withdrawing group, causes on phenyl ring that cloud density declines, oxidasic electrophilic is attacked and is obstructed, thereby causes such organic pollutant to be difficult to by aerobic biodegradation.For strengthening chloride conversion and degraded containing nitro aromatic compound, Chinese scholars has been carried out the aspects such as the senior chemical oxidation such as Fenton oxidation, photochemical catalytic oxidation, ozone oxidation and anaerobic biological treatment.Domestic mainly starting with from aspects such as microbiological deterioration, catalytic ozonation, electrochemical process and charcoal absorptions carried out nitro-chlorobenzene removal research.
Patent 201110320747, adopts oil of mirbane engineering bacteria, inorganic oxidizer and catalyzer to be re-dubbed the processing mode of compound, and it exists the deficiencies such as aeration power consumption is large, technical process is long.Patent CN102603050A, utilizes Iron sulfuret pre-treatment nitrobenzene-containing waste water, and in 1 ~ 3 hour treatment time, length consuming time and byproduct of reaction sulfide need subsequent technique further to process.Patent CN103214057A, adopts ultraviolet/visible light lanthanum catalysis hydrogen peroxide oxidation art breading nitro-chlorobenzene waste water, and its perovskite typed superfine powder is made complex manufacturing.Patent CN103073139A, adopts stripping and Fenton combination process to process nitro-chlorobenzene waste water, and wherein stripping processing and ultraviolet medium pressure mercury lamp all consume energy larger.In addition, Xu Heng hides and within 2010, adopts iron-carbon reduction/biological degradation/ozone combination treatment nitro-chlorobenzene class waste water, Li Jinyu carries out the research of electrochemical method processing o-Nitrochlorobenzene for 2010, discipline peak has carried out the characterization of adsorption research of Powdered Activated Carbon p-Nitrophenyl chloride pollutant for 2010, and Liu Lei etc. have carried out for 2007
comamonas sp. the experimental study of strain CNB-1 degradating chloro oil of mirbane, Du Xi has carried out the catalyzing oxidizing degrading research of Ag/TiO2 to o-Nitrochlorobenzene waste water.
Above patent and research show, for complicated component, difficult degradation nitro-chlorobenzene waste water that concentration is higher, apply the treatment process such as single biological degradation, chemistry (catalysis) oxidation, electrochemical oxidation and charcoal absorption toxicity suppress because existing, high, the secondary pollution of working cost and the problem such as mineralization of organic material is not thorough, be difficult in actual applications stablize, operation efficiently.
Summary of the invention
Object of the present invention is just to provide a kind of method and treatment system that adopts chemical oxidation and coagulating sedimentation combination process p-Nitrophenyl chloride factory effluent to process, to overcome the above-mentioned problems in the prior art.
For realizing the object of the invention, technical scheme of the present invention is: a kind for the treatment of process of chloronitrobenzene producing wastewater, and step is as follows:
(1), under stirring action, the pH value of chloronitrobenzene producing wastewater is adjusted to acidity;
(2), under stirring action, in the waste water of step (1), add oxygenant to carry out chemical oxidation treatment;
Oxygenant described in this step is clorox, Losantin or hypochlorous acid;
(3), under stirring action, the pH value of the waste water after chemical oxidation treatment is adjusted to neutrality;
(4), under stirring action, in the waste water of step (3), add coagulating agent to carry out coagulating;
(5), the throw out producing after coagulating is separated to removal.
In step (1), adopt sodium hydroxide and hydrochloric acid that the pH value of chloronitrobenzene producing wastewater is adjusted to 1 ~ 3.
In step (2), described oxygenant adopts the solution that mass concentration is 5 ~ 10%, and its dosage is 20 ~ 50L/m
3, reaction 10 ~ 30min.
In step (3), adopt sodium hydroxide that the pH value of the waste water after chemical oxidation treatment is adjusted to neutrality.
In step (4), described coagulating agent is one or more in polymerize aluminum chloride, poly-ferric chloride and polyacrylamide, and it is 5 ~ 15% solution that selected coagulating agent all adopts mass concentration, and its total dosage is 1 ~ 2L/m
3, reaction 20 ~ 30min.
In step (2), step (3) and step (4), stirring velocity is respectively 50 ~ 60r/min, 55 ~ 65r/min and 75 ~ 85r/min.
The present invention realizes the treatment system that the treatment process of above-mentioned chloronitrobenzene producing wastewater adopts, and comprises the equalizing tank, oxidation pond, neutralization tank, coagulation basin and the settling tank that connect successively, and equalizing tank is for being adjusted to acidity by the pH value of chloronitrobenzene producing wastewater; Oxidation pond is used for accepting the waste water from equalizing tank, and adds clorox, Losantin or hypochlorous acid and carry out chemical oxidation treatment; Neutralization tank is used for accepting the treatment solution from oxidation pond, and the pH value for the treatment of solution is adjusted to neutrality; Coagulation basin is used for accepting the treatment solution from neutralization tank, and carries out coagulating; Settling tank is used for accepting the treatment solution from coagulation basin, and carries out precipitate and separate; Supernatant liquor in settling tank after precipitate and separate discharges after delivering to clean water basin, mud in settling tank after precipitate and separate is sent into sludge thickener by sludge pump and is concentrated, the supernatant liquor of sludge thickener is delivered to equalizing tank, the thickened sludge of sludge thickener carries out press filtration by sludge pumping to plate-and-frame filter press, the filtrate of plate-and-frame filter press is delivered to equalizing tank, and filter cake packs Hazardous wastes safe disposal device into; Wherein oxidation pond, neutralization tank and coagulation basin are provided with stirrer.
Described equalizing tank and oxidation pond adopt Corrosion Protection of Fiber Reinforced Plastics, and saturated epoxy coating, adopts five layers of resin triplex glass cloth to construct.
Beneficial effect: the inventive method is effectively utilized Nitryl chlorobenzene compounds and clorox, Losantin or hypochlorous response characteristic, nitro-chlorobenzene and the little organism of the oxidized generation solubleness of other nitrobenzene compounds in waste water are separated out, and under the coagulation of coagulating agent precipitate and separate, make water outlet nitro-chlorobenzene and other nitrobenzene compounds clearance in chloronitrobenzene producing wastewater after treatment reach 99%, reach first discharge standard.The inventive method with respect to prior art have that processing efficiency is high, working cost is low, the advantage such as non-secondary pollution, flow process are short, processing ease, be applicable to industrial treatment.
Brief description of the drawings
Fig. 1 is the schema for the treatment of process of the present invention.
Embodiment
Describe the treatment process of chloronitrobenzene producing wastewater of the present invention in detail in conjunction with Waste Water Treatment of the present invention.
Chloronitrobenzene producing wastewater pumps into after equalizing tank, in equalizing tank, adds sodium hydroxide and hydrochloric acid soln, regulates pH value to 1 ~ 3 of waste water, makes waste water in sour environment; Equalizing tank water outlet enters into oxidation pond, in sour environment, under stirring action, in oxidation pond, add oxygenant clorox, Losantin or hypochlorous acid, nitro-chlorobenzene in oxygenant and waste water, nitrobenzene compounds generation oxidizing reaction, its primary product is the atomic water-soluble compound such as P-Chlorophenol, the chloro-2-nitrophenol of 5-, and these products are muddy shape and separate out in waste water.Oxidation pond water outlet enters neutralization tank, under stirring action, in neutralization tank, adds sodium hydroxide, and the pH value of waste water after oxidation is adjusted to neutrality.Neutralization tank water outlet enters coagulation basin, and under stirring action, to dosing coagulant in coagulation basin, under coagulating agent effect, oxidation products coagulation is gathered into macrobead.Coagulation basin water outlet enters tube settler, the macrobead thing precipitate and separate that coagulation is gathered under action of gravity.Supernatant liquor overflow in settling tank after precipitate and separate is to clean water basin, standard discharge.In settling tank, at the bottom of pond, precipitating sludge is squeezed into sludge thickener by sludge pump.Supernatant liquor after concentrated in sludge thickener enters equalizing tank, and the interior underground thickened sludge of sludge thickener is regularly squeezed into plate-and-frame filter press by sludge pump and carried out press filtration.The filtrate of plate-and-frame filter press is back to equalizing tank, and filter cake packs Hazardous wastes accumulating cylinder into, carries out safe disposal.In this process, in oxidation pond, neutralization tank and coagulation basin, being respectively arranged with stirrer stirs, mixing speed is respectively 50 ~ 60r/min, 55 ~ 65r/min and 75 ~ 85r/min, wherein equalizing tank, oxidation pond, neutralization tank, coagulation basin and settling tank, retention time of sewage is respectively: 5 ~ 10min, 10 ~ 30min, 5 ~ 10min, 20 ~ 30min, 30 ~ 50min.
Embodiment 1
Get 200ml chloronitrobenzene producing wastewater, then add sodium hydroxide and salt acid for adjusting pH to 1 ~ 3, reaction 5 ~ 10min.In mixing speed 55r/min situation, in this acid waste water, add clorox, reaction 10 ~ 30min.After reacting completely, add sodium hydroxide and regulate pH to neutral, then add polymeric aluminum chlorides solution, mixing speed is to react 20 ~ 30min in 80r/min situation, then leaves standstill 30 ~ 50min.Supernatant liquor is water outlet, and this supernatant liquor colourity, COD and nitrobenzene compounds adopt HJ 592-2010 " the mensuration vapor-phase chromatography of nitrobenzene compounds " to detect, and meet the primary standard in GB8979-1996 " integrated wastewater discharge standard ".
Embodiment 2
Adopt Waste Water Treatment of the present invention, 50m
3the nitro-chlorobenzene waste water of/d is processed for 8 hours, operation continuously, and throughput per hour is 6.25m
3.Treatment process process is shown in above-mentioned, and processing parameter is specially: in equalizing tank, the sodium hydroxide solution that employing mass concentration is 1mol/L and the hydrochloric acid soln of 1mol/L regulate pH to 2, and waste water stops 10min; The stirrer stirring velocity of oxidation pond maintains 55r/min, and oxygenant chlorine bleach liquor's mass concentration is 8%, and chlorine bleach liquor's dosage is 30L/m
3, waste water stops 20min; In neutralization tank, stirrer speed maintains 60r/min, adopts the sodium hydroxide solution that mass concentration is 1mol/L to regulate the pH of the rear waste water of oxidation for neutral, and waste water stops 8min; In coagulation basin, add mass concentration and be 10% polymeric aluminum chlorides solution, the dosage of polymeric aluminum chlorides solution is 1L/m
3, stirring velocity is 80r/min, waste water stops 25min; In settling tank, waste water stops 40min, and water outlet gets final product qualified discharge, and in clean water basin, after testing, nitro-chlorobenzene and other nitrobenzene compounds clearance reach 99% to water quality, reach first discharge standard.Concrete detected result is in table 1.
Embodiment 3
Adopt Waste Water Treatment of the present invention, 50m
3the nitro-chlorobenzene waste water of/d is processed for 8 hours, operation continuously, and throughput per hour is 6.25m
3.Treatment process process is shown in above-mentioned, and processing parameter is specially: in equalizing tank, the sodium hydroxide solution that employing mass concentration is 1mol/L and the hydrochloric acid soln of 1mol/L regulate pH to 1, and waste water stops 5min; The stirrer stirring velocity of oxidation pond maintains 50r/min, and the mass concentration of oxygenant calcium hypochlorite solution is 10%, and the dosage of calcium hypochlorite solution is 20L/m
3, waste water stops 10min; In neutralization tank, stirrer speed maintains 65r/min, adopts the sodium hydroxide solution that mass concentration is 1mol/L to regulate the pH of the rear waste water of oxidation for neutral, and waste water stops 5min; In coagulation basin, add mass concentration and be 15% poly-ferric chloride solution, the dosage of poly-ferric chloride solution is 2L/m
3, stirring velocity is 85r/min, waste water stops 20min; In settling tank, waste water stops 30min, and water outlet gets final product qualified discharge, and in clean water basin, after testing, nitro-chlorobenzene and other nitrobenzene compounds clearance reach 99% to water quality, reach first discharge standard.
Embodiment 4
Adopt Waste Water Treatment of the present invention, 50m
3the nitro-chlorobenzene waste water of/d is processed for 8 hours, operation continuously, and throughput per hour is 6.25m
3.Treatment process process is shown in above-mentioned, and processing parameter is specially: in equalizing tank, the sodium hydroxide solution that employing mass concentration is 1mol/L and the hydrochloric acid soln of 1mol/L regulate pH to 3, and waste water stops 8min; The stirrer stirring velocity of oxidation pond maintains 60r/min, and the mass concentration of oxygenant hypochlorous acid solution is 5%, and the dosage of hypochlorous acid solution is 50L/m
3, waste water stops 30min; In neutralization tank, stirrer speed maintains 55r/min, adopts the sodium hydroxide solution that mass concentration is 1mol/L to regulate the pH of the rear waste water of oxidation for neutral, and waste water stops 10min; In coagulation basin, add mass concentration and be 5% polyacrylamide solution, the dosage of polyacrylamide solution is 1L/m
3, stirring velocity is 75r/min, waste water stops 30min; In settling tank, waste water stops 50min, and water outlet gets final product qualified discharge, and in clean water basin, after testing, nitro-chlorobenzene and other nitrobenzene compounds clearance reach 99% to water quality, reach first discharge standard.
Table 1 nitrobenzene matters detected result (unit: mg/L)
Note: 1, nitro benzene series quality testing is surveyed with reference to HJ 592-2010 " the mensuration vapor-phase chromatography of nitrobenzene compounds ".
2, nitro benzene homologues emission standard is with reference to the primary standard in GB8979-1996 " integrated wastewater discharge standard ".
Claims (7)
1. a treatment process for chloronitrobenzene producing wastewater, is characterized in that: step is as follows:
(1), the pH value of chloronitrobenzene producing wastewater is adjusted to acidity;
(2), under stirring action, in the waste water of step (1), add oxygenant to carry out chemical oxidation treatment;
Oxygenant described in this step is clorox, Losantin or hypochlorous acid;
(3), under stirring action, the pH value of the waste water after chemical oxidation treatment is adjusted to neutrality;
(4), under stirring action, in the waste water of step (3), add coagulating agent to carry out coagulating;
(5), the throw out producing after coagulating is separated to removal.
2. the treatment process of a kind of chloronitrobenzene producing wastewater as claimed in claim 1, is characterized in that: in step (1), adopt sodium hydroxide and hydrochloric acid that the pH value of chloronitrobenzene producing wastewater is adjusted to 1 ~ 3.
3. the treatment process of a kind of chloronitrobenzene producing wastewater as claimed in claim 1, is characterized in that: in step (2), described oxygenant adopts the solution that mass concentration is 5 ~ 10%, and its dosage is 20 ~ 50L/m
3, reaction 10 ~ 30min.
4. the treatment process of a kind of chloronitrobenzene producing wastewater as claimed in claim 1, is characterized in that: in step (3), adopt sodium hydroxide that the pH value of the waste water after chemical oxidation treatment is adjusted to neutrality.
5. the treatment process of a kind of chloronitrobenzene producing wastewater as claimed in claim 1, it is characterized in that: in step (4), described coagulating agent is one or more in polymerize aluminum chloride, poly-ferric chloride and polyacrylamide, it is 5 ~ 15% solution that selected coagulating agent all adopts mass concentration, and its total dosage is 1 ~ 2L/m
3, reaction 20 ~ 30min.
6. the treatment process of a kind of chloronitrobenzene producing wastewater as claimed in claim 1, is characterized in that: in step (2), step (3) and step (4), stirring velocity is respectively 50 ~ 60r/min, 55 ~ 65r/min and 75 ~ 85r/min.
7. the treatment system that the treatment process of chloronitrobenzene producing wastewater claimed in claim 1 is used, it is characterized in that: comprise the equalizing tank, oxidation pond, neutralization tank, coagulation basin and the settling tank that connect successively, equalizing tank is for being adjusted to acidity by the pH value of chloronitrobenzene producing wastewater; Oxidation pond is used for accepting the waste water from equalizing tank, and adds clorox, Losantin or hypochlorous acid and carry out chemical oxidation treatment; Neutralization tank is used for accepting the treatment solution from oxidation pond, and the pH value for the treatment of solution is adjusted to neutrality; Coagulation basin is used for accepting the treatment solution from neutralization tank, and carries out coagulating; Settling tank is used for accepting the treatment solution from coagulation basin, and carries out precipitate and separate; Supernatant liquor in settling tank after precipitate and separate discharges after delivering to clean water basin, mud in settling tank after precipitate and separate is sent into sludge thickener by sludge pump and is concentrated, the supernatant liquor of sludge thickener is delivered to equalizing tank, the thickened sludge of sludge thickener carries out press filtration by sludge pumping to plate-and-frame filter press, the filtrate of plate-and-frame filter press is delivered to equalizing tank, and filter cake packs Hazardous wastes safe disposal device into; Wherein oxidation pond, neutralization tank and coagulation basin are provided with stirrer.
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| CN106830279A (en) * | 2016-12-21 | 2017-06-13 | 中国石油天然气集团公司 | A kind of processing method and processing device of nitrobenzene waste water |
| CN107512810A (en) * | 2017-07-13 | 2017-12-26 | 安徽东至广信农化有限公司 | Method of wastewater treatment after a kind of nitro-chlorobenzene production |
| CN108706785A (en) * | 2018-08-10 | 2018-10-26 | 大冶有色金属有限责任公司 | A kind of mining smelting wastewater exception water quality emergency treatment device and method |
| CN109336301A (en) * | 2018-11-09 | 2019-02-15 | 宁夏华御化工有限公司 | Waste water treatment system in nitro-chlorobenzene production |
| CN110615572A (en) * | 2019-09-29 | 2019-12-27 | 田雨春 | Organic wastewater treatment method |
| CN112023624A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Treatment method of waste acid |
| CN112794561A (en) * | 2020-12-25 | 2021-05-14 | 苏州市环境保护有限公司 | Dangerous waste liquid upgrading advanced treatment method |
| 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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| CN106830279A (en) * | 2016-12-21 | 2017-06-13 | 中国石油天然气集团公司 | A kind of processing method and processing device of nitrobenzene waste water |
| CN107512810A (en) * | 2017-07-13 | 2017-12-26 | 安徽东至广信农化有限公司 | Method of wastewater treatment after a kind of nitro-chlorobenzene production |
| CN108706785A (en) * | 2018-08-10 | 2018-10-26 | 大冶有色金属有限责任公司 | A kind of mining smelting wastewater exception water quality emergency treatment device and method |
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| CN110615572A (en) * | 2019-09-29 | 2019-12-27 | 田雨春 | Organic wastewater treatment method |
| 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 |
| CN113735300B (en) * | 2020-05-27 | 2023-03-28 | 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 |
| CN112794561A (en) * | 2020-12-25 | 2021-05-14 | 苏州市环境保护有限公司 | Dangerous waste liquid upgrading advanced treatment method |
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