WO2015043449A1 - 一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法 - Google Patents

一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法 Download PDF

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WO2015043449A1
WO2015043449A1 PCT/CN2014/087172 CN2014087172W WO2015043449A1 WO 2015043449 A1 WO2015043449 A1 WO 2015043449A1 CN 2014087172 W CN2014087172 W CN 2014087172W WO 2015043449 A1 WO2015043449 A1 WO 2015043449A1
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anode
cathode
wastewater
chamber
storage tank
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French (fr)
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李爱民
江野立
王长明
周庆
朱兆连
王柏俊
徐子潇
王梦乔
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南京大学
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Priority to US15/023,906 priority Critical patent/US9944545B2/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4618—Supplying or removing reactants or electrolyte

Definitions

  • the invention belongs to the field of nitrotoluene production wastewater treatment, in particular to a pretreatment method for electrochemically carrying high-concentration mixed acid nitrification wastewater, and more particularly to a sludge-reduced nitrotoluene production wastewater electrocatalysis Reduction oxidation pretreatment method.
  • nitrotoluene mainly uses mixed acid nitration process, using nitric acid as nitrating agent, sulfuric acid and the like as a catalyst to react with aromatic hydrocarbons to form nitroaromatic hydrocarbons. It is a very important chemical process, and its main products are nitrobenzene and nitrate. Toluene, trinitrotoluene, nitrochlorobenzene, and the like. In the process of mixed acid nitration, wastewater with high chroma and poor biodegradability will be produced. The main components are nitrotoluene, toluidine, benzenesulfonic acid and polynitrophenol.
  • the research on the treatment process of mixed acid nitrification wastewater is a research hotspot in the field of environmental engineering at home and abroad.
  • Developed countries generally adopt the pretreatment method of stripping + thermal decomposition + ammonia distillation, which has high cost and is difficult to effectively popularize.
  • the development of chemical treatment methods developed abroad is a wet oxidation method. Since nitrobenzene and nitrophenol are relatively stable, they are not easily decomposed under normal conditions, so wet oxidation is generally operated at higher temperatures and pressures.
  • the temperature is generally 325 to 375 ° C
  • the pressure is 2.20 ⁇ 10 7 to 3.45 ⁇ 10 7 Pa
  • the reaction time is 5 min, and the organic substance is oxidized to a simple small molecule compound such as CO 2 and H 2 O.
  • the nitrobenzene or nitrochlorobenzene wastewater is heated to 100-300 ° C, at a pressure of 2 ⁇ 10 5 to 1 ⁇ 10 7 Pa, by means of a catalyst such as CuO, Al 2 O 3 or magnesium silicate or Cu, Cr, Zn oxidizes and decomposes organic matter under the action of Al 2 O 3 oxide, and nitrobenzene and nitrochlorobenzene degrade more than 90%.
  • a catalyst such as CuO, Al 2 O 3 or magnesium silicate or Cu, Cr, Zn oxidizes and decomposes organic matter under the action of Al 2 O 3 oxide, and nitrobenzene and nitrochlorobenzene degrade more than 90%.
  • the problem of the wet oxidation method is that the investment is large and the technical requirements are high, such as the tightness of the reactor and the heat resistance of the material, and an additional catalyst is required to cause secondary pollution.
  • the domestic patent application (application number: 200810121721) is pretreated by acidification + iron carbon reduction + polycondensation + flocculation sedimentation.
  • the process requires the addition of a large amount of iron powder, carbon powder, polymerization inhibitor (formaldehyde), flocculant (polymerization).
  • Acrylamide, polyaluminum chloride, ferric chloride, polyferric chloride and polyferric sulfate) produce a large amount of iron-containing sludge, which is difficult to handle.
  • a chemical plant in China adopts iron carbon reduction + Fenton oxidation + coagulation sedimentation method (related patent number: 200910031041) to treat mixed acid nitrate Waste water, adding calcium hydroxide in the coagulation section, thereby producing a large amount of iron-containing sludge and calcium-containing sludge, which makes the sludge a new pollutant, which needs to be disposed according to the standard of dangerous solid waste, and the cost is high, and There are security risks.
  • Electrochemical water, waste gas and soil pollution treatment technologies have developed rapidly since the 1980s. Electrochemical methods have good compatibility with other methods, and are easy to use together to achieve the best treatment effect.
  • the application of electrochemical method in the treatment of pollutants such as sewage, exhaust gas and heavy metal ions can be divided into electrochemical oxidation, electrochemical reduction, photoelectrochemical oxidation, electrosorption and electroflotation/electrocoagulation. Electrochemical reduction generally occurs at the cathode, and electrochemical oxidation can occur at both the anode and the cathode, and the oxidation mechanism of the cathode is O 2 reduced to H 2 O 2 , which in turn generates ⁇ OH oxidized organic matter.
  • the anode and cathode regions are generally separated by a membrane.
  • the main forms of the membrane are a salt bridge, an ion exchange membrane system, and a glass filter plate.
  • the ion exchange membrane is further divided into an anion exchange membrane and a cation exchange membrane.
  • the invention relates to a method of electrochemically treating a nitroaromatic compound comprising the steps of introducing an aqueous composition comprising at least one nitroaromatic compound into an anode compartment of an electrolysis cell, and at 0.1- Electrolysis is carried out at an anode current density of 10 kA/m2 and an electrolysis cell potential of 4-15 V, and the electrolytic cell has at least one anode comprising at least one anode segment comprising platinum or an anode segment composed of a support material and a coating, wherein
  • the support material comprises at least one metal selected from the group consisting of niobium (Nb), tantalum (Ta), titanium (Ti), and hafnium (Hf), and the coating layer is composed of boron-doped diamond.
  • the invention provides a sewage reduction process for the existing nitrotoluene production wastewater treatment process, which has high foreign introduction cost, is difficult to be popularized, has a poor conventional process effect, and has high operation requirements and a large amount of waste residue.
  • the invention relates to an electrocatalytic reduction oxidation pretreatment method for a toluene production wastewater, which can reduce the biological toxicity of the mixed acid nitrification wastewater and improve the biodegradability thereof, and transform and degrade the nitrobenzene and nitrophenol by an electrochemical reduction-electrochemical oxidation coupling process. Organic matter, providing favorable conditions for subsequent biochemistry.
  • a method for pre-treatment of electrocatalytic reduction oxidation of nitrotoluene production wastewater by sludge reduction the steps of which are:
  • the electrochemical reactor used includes Anode chamber, cathode chamber, anode, a cathode, a catholyte storage tank, a cation exchange membrane, an anolyte storage tank, and a flow meter; the anode chamber and the cathode chamber are separated by a cation exchange membrane; the anode and cathode are respectively located in the anode chamber and the cathode chamber
  • the cathode chamber includes a cathode water inlet and a cathode water outlet; the anode chamber includes an anode water outlet and an anode water inlet; the cathode water outlet is connected to the catholyte storage tank through a pipeline, and the catholyte storage tank is passed through The pipeline is connected
  • the wastewater upper layer liquid generated in the step (a) is subjected to a reduction reaction in the cathode chamber, and the wastewater treated in the cathode chamber sequentially enters the anode chamber through the cathode water outlet, the catholyte storage tank and the anode water inlet, and the wastewater An oxidation reaction occurs in the anode chamber;
  • the anode and cathode have a current density of 5-50 mA/cm 2 , and the residence time of the wastewater in the cathode chamber and the anode chamber is 1-6 h;
  • the anode and cathode have a pitch of 1.5 -3cm; reduction reaction occurs at the cathode, and nitrobenzene in the wastewater is partially reduced to oxidized substances such as aniline; electrocatalytic oxidation occurs at the anode, and aniline and nitrobenzene reduction products are opened and formed small. Molecular organic matter.
  • step (c) Discharging the wastewater after the treatment in step (b), and passing through the anolyte storage tank to enter the biochemical system.
  • the acid used in the step (a) for adjusting the pH is sulfuric acid or industrial waste acid, and the standing precipitation time is 0.5-2 h.
  • the catholyte storage tank volume in the step (a) is 5-10 times the volume of the cathode chamber.
  • the anolyte tank volume in step (a) is 5-10 times the volume of the anode chamber.
  • the present invention creatively proposes an electrochemical method which is considered to be costly and difficult to handle by a person skilled in the art to treat nitrotoluene production wastewater, and surprisingly finds the structure of the electrochemical reactor introduced by the present invention at a pH of 1.5-2.0.
  • the parameters of the electrode material, current density, electrode spacing and processing time can quickly achieve the purpose of decomposing nitrotoluene, dinitrophenol and other substances. These parameters cooperate with each other, which is low cost and easy to operate.
  • the inventors have verified through a large number of experiments, and solved the problems that those skilled in the art have been distressed.
  • the coupled electroreduction and electrocatalytic oxidation process of the present invention can not only greatly reduce the generation of pretreatment waste residue, but also has the following effects: nitrobenzene substances and aniline in high concentration wastewater (COD>7000 mg/L).
  • the sludge produced in the process is mainly produced in the acidification process. Compared with other processes, the sludge reduction can reach more than 80%, and the effluent can enter the biochemical system;
  • the acidification and sedimentation of the present invention is an indispensable pretreatment process for the electrochemical reduction-oxidation process, and the acidification process is creatively proposed, and the beneficial effects thereof are not only reflected in the conversion of sodium phenolate in water into phenol precipitation, and the electrochemical process is reduced.
  • the organic load also has a beneficial effect on the subsequent electrochemical reduction and oxidation.
  • the present invention regulates the wastewater to a strong acidic condition, electrochemically reducing the main product of the tail aniline, and the aniline under alkaline and neutral conditions.
  • the yield of the substance is very low, which affects the treatment effect of the reduction-oxidation module.
  • the invention replaces the pharmaceutical agent with electric energy, is more easy to operate and control, and does not generate waste residue, and has great academic significance and practical value for realizing efficient, stable and low-cost pretreatment of mixed acid nitrification wastewater.
  • FIG. 1 is a schematic illustration of the apparatus employed in the present invention.
  • a method for pre-treatment of electrocatalytic reduction oxidation of nitrotoluene production wastewater by sludge reduction the steps of which are:
  • the cathode chamber 4 includes a cathode water inlet 8 and a cathode water outlet 2; the anode chamber 3 includes an anode water outlet 1 and an anode water inlet 7; the cathode water outlet 2 is connected to the catholyte storage tank 9 through a pipe, and the catholyte storage tank 9 is passed again.
  • the pipe is connected to the anode water inlet 7; the anode water outlet 1 is connected to the anolyte storage tank 11 through a pipe; the flow meter 12 has two pipes respectively located between the cathode water outlet 2 and the catholyte storage tank 9 and the anode water outlet 1 on the pipe between the anolyte storage tank 11; the cathode 6 is made of graphite plate; the anode 5 It is a titanium-based stable electrode, and the coating is cerium oxide; the flow direction of the wastewater is parallel to the electrode plate; and the acid for adjusting the pH is sulfuric acid.
  • the volume of the catholyte storage tank 9 is eight times the volume of the cathode chamber 4.
  • the volume of the anolyte storage tank 11 is 9 of the volume of the anode chamber 3 Times.
  • the wastewater upper layer liquid generated in the step (a) is subjected to a reduction reaction in the cathode chamber 4, and the wastewater treated in the cathode chamber 4 is sequentially passed through the cathode water outlet 2, the catholyte storage tank 9 and the anode water inlet 7 Entering the anode chamber 3, the wastewater undergoes an oxidation reaction in the anode chamber 3;
  • the current density of the anode 5 and the cathode 6 is 10 mA/cm 2
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 is 2 h; the anode 5 and the cathode 6 The spacing is 2cm.
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.07-0.09 0.1%-0.5% Electrochemical reduction 3800-3900 0.09-0.12 1%-2% Electrochemical oxidation 3600-3700 0.35-0.4 1%-2%
  • Example 2 Same as in Example 1, except that the pH of the nitrotoluene production wastewater is 12.1, the pH is adjusted to 1.5, the acid for adjusting the pH is industrial waste acid, the standing precipitation time is 60 min, and the anode 5 and the cathode 6 are
  • the current density was 20 mA/cm 2
  • the cathode 6 was a titanium plate
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 was 2 h
  • the volume of the catholyte storage tank 9 was 5 times the volume of the cathode chamber 4.
  • the volume of the anolyte storage tank 11 is five times the volume of the anode chamber 3.
  • the distance between anode 5 and cathode 6 is 3 cm; the water output parameters of each section are shown in the following table:
  • Example 2 Same as in Example 1, except that the pH of the nitrotoluene production wastewater is 12.2, the pH is adjusted to 2.0, the standing precipitation time is 100 min, the current density of the anode 5 and the cathode 6 is 30 mA/cm 2 , and the anode 5
  • the coating was cerium oxide
  • the cathode 6 was a titanium plate loaded with cerium oxide
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 was 2 h.
  • the volume of the catholyte storage tank 9 is 10 times the volume of the cathode chamber 4.
  • the volume of the anolyte storage tank 11 is 10 times the volume of the anode chamber 3.
  • the distance between anode 5 and cathode 6 is 1.5 cm; the water output parameters of each section are shown in the following table:
  • the current density was 10 mA/cm 2
  • the residence time of the cathode 6 using the cerium oxide-loaded titanium plate wastewater in the cathode chamber 4 and the anode chamber 3 was 6 h.
  • the volume of the catholyte storage tank 9 is seven times the volume of the cathode chamber 4.
  • the volume of the anolyte storage tank 11 is seven times the volume of the anode chamber 3.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4800-5000 0.06-0.08 0.1%-0.5% Electrochemical reduction 4300-4500 0.11-0.12 2% Electrochemical oxidation 3800-4000 0.41-0.43 2%-4%
  • the current density of the anode 5 and the cathode 6 was 20 mA/cm 2 , and the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 was 3 h.
  • the distance between anode 5 and cathode 6 is 2.5 cm; the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4800-5000 0.06-0.08 0.1%-0.5% Electrochemical reduction 4200-4300 0.12-0.14 2%-4% Electrochemical oxidation 3900-4000 0.46-0.48 4%-5%
  • the current density was 50 mA/cm 2
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 was 3 h.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4800-5000 0.06-0.08 0.1%-0.5%
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 is 1 h.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.08-0.1 0.1%-0.5% Electrochemical reduction 4200-4400 0.1-0.12 1%-2% Electrochemical oxidation 3900-4000 0.25-0.30 1%-2%
  • the residence time of the wastewater in the cathode chamber 4 and the anode chamber 3 is 1 h.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.08-0.1 0.1%-0.5% Electrochemical reduction 4000-4200 0.1-0.12 1%-2% Electrochemical oxidation 3800-3900 0.28-0.32 2%
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.08-0.1 0.1%-0.5% Electrochemical reduction 3900-4000 0.11-0.12 1%-2% Electrochemical oxidation 3700-3800 0.3-0.35 2%-3%
  • the mud is discharged, the upper layer liquid enters the electrochemical reactor, and a reduction reaction occurs in the cathode chamber, the current density is 20 mA/cm 2 , and the reaction residence time is 2 h.
  • the reducing solution was refluxed to the anode chamber for catalytic oxidation, the current density was unchanged, and the residence time was 1 h.
  • the water output parameters of each section are shown in the following table:
  • the reduction reaction occurred in the cathode chamber, the current density was 20 mA/cm 2 , and the reaction residence time was 2 h.
  • the reducing solution was refluxed to the anode chamber for catalytic oxidation, the current density was unchanged, and the residence time was 1 h.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.08-0.1 0.1%-0.5% Electrochemical reduction 3900-4000 0.1-0.12 0.5%-1% Electrochemical oxidation 3700-3800 0.35-0.4 1%-2%
  • the reduction reaction occurred in the cathode chamber, the current density was 20 mA/cm 2 , and the reaction residence time was 2 h.
  • the reducing solution was refluxed to the anode chamber for catalytic oxidation, the current density was unchanged, and the residence time was 1 h.
  • the water output parameters of each section are shown in the following table:
  • Section ⁇ indicator COD B/C Semi-lethal concentration (large scale) acidification 4500-4600 0.08-0.1 0.1%-0.5% Electrochemical reduction 4000-4100 0.1-0.12 0.5%-1% Electrochemical oxidation 3800-3900 0.3-0.35 1%-2%

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Abstract

本发明公开了一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，属于硝基甲苯生产废水处理领域。其步骤为：(a)将硝基甲苯生产废水的pH调至1.5-2.0，静置沉淀，排去底部废渣，取上层液通过阴极进水口进入电化学反应器的阴极室；(b)开始电化学处理，步骤(a)中产生的废水上层液在阴极室发生还原反应，阴极室处理后的废水进入阳极室，废水在阳极室中发生氧化反应；(c)将步骤(b)处理后废水排出，经阳极液储罐调节后进入生化系统。本发明能降低混酸硝化废水的生物毒性，提高其可生化性，通过电化学还原-电化学氧化耦合工艺，转化降解硝基苯类、硝基酚类有机物，为后续生化提供有利条件。

Description

一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法 技术领域
本发明属于硝基甲苯生产废水处理领域，具体地说，采用电化学进行高浓度混酸硝化废水的预处理方法，更具体地说，涉及一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法。
背景技术
在工业领域，硝基甲苯的生产主要采用混酸硝化工艺，利用硝酸作硝化剂，硫酸等作催化剂与芳香烃反应生成硝基芳烃，是非常重要的化工工艺，其主要产品有硝基苯、硝基甲苯、三硝基甲苯、硝基氯苯等。混酸硝化过程中会产生色度高、可生化性差的废水，其主要成分为硝基甲苯类、甲苯胺类、苯磺酸类和多硝基酚类。
混酸硝化废水的处理工艺研究是国内外环境工程领域的研究热点。发达国家一般采用气提+热分解+氨蒸馏的预处理方法，成本较高，难以有效推广普及。国外开发出的化学处理法中具有发展前景的是湿式氧化法，由于硝基苯和硝基酚较为稳定，在一般条件下不易分解，因此湿式氧化一般在较高温度下和压力下操作，反应温度一般在325～375℃，压力为2.20×107～3.45×107Pa，反应时间为5min，将有机物氧化为CO2和H2O等简单的小分子化合物。如德国一个专利(USP 5,356,539)介绍，将硝基苯或硝基氯苯废水加热到100～300℃，在2×105～1×107Pa的压力下，借助催化剂，如CuO、Al2O3或硅酸镁或Cu、Cr、Zn在Al2O3氧化物的作用下氧化分解有机物，硝基苯和硝基氯苯降解90％以上。然而湿式氧化法存在的问题是投资大，对技术要求很高，比如反应器的密闭性和材料的耐热性，并且需要额外投加催化剂，从而导致二次污染。
国内对硝化废水的处理工艺以吸附法和化学药剂法为主。国内有部分厂家采用吸附方法，吸附剂主要为活性炭和树脂。以活性炭为吸附剂的吸附法存在难以对吸附剂进行再生利用的弊端，并且会产生大量废渣，这些废渣由于包含大量硝基苯类物质，属于危险固废，处理成本很高。近年来国内外对树脂吸附处理硝基苯和硝基氯苯废水有大量的文献报道，如超高交联树脂等。以树脂为吸附剂的吸附法对成分相对简单，有资源化价值的废水是一个好方法，但对成分复杂的废水存在处理成本高，且存在脱附液需进一步处置的问题。
国内专利申请(申请号：200810121721)采用酸化+铁碳还原+缩聚+絮凝沉降的方法进行预处理，其工艺中需要投加大量铁粉、碳粉、促聚剂(甲醛)、絮凝剂(聚丙烯酰胺、聚合氯化铝、三氯化铁、聚合氯化铁和聚合硫酸铁)，工艺产生大量含铁污泥，较难处置。国内某化工厂采用铁碳还原+Fenton氧化+混凝沉降的方法(相关专利号：200910031041)处理混酸硝 化废水，在混凝工段投加氢氧化钙，从而产生大量含铁污泥和含钙污泥，这使得污泥成为了新的污染物，需要按照危险固废的标准处置，成本高，并且存在安全隐患。
电化学水、废气、土壤污染处理技术自80年代以来发展迅速，电化学方法与其他方法兼容性较好，易配合使用以达到最佳处理效果。电化学法在污水、废气和重金属离子等污染物处理中的应用，从原理和方法上可以分为电化学氧化、电化学还原、光电化学氧化、电吸附和电浮选/电凝聚等，其中电化学还原一般发生在阴极，电化学氧化在阳极、阴极都可以发生，而阴极的氧化机理为O2还原成H2O2，进而生成·OH氧化有机物。阳极区和阴极区一般通过隔膜分开，隔膜的主要形式有盐桥、离子交换膜系统和玻璃滤板等，离子交换膜又分为阴离子交换膜和阳离子交换膜。但是电化学处理硝基甲苯生产废水还停留在设想阶段。德国的巴斯夫欧洲公司首先进行了尝试，其于2011年05月17日申请了名称为从废水中除去硝基芳族化合物的方法及装置的专利文件，专利申请号：201180025180.3，公开日2013年02月20日，该发明涉及一种电化学处理硝基芳族化合物的方法，其包括如下步骤：将包含至少一种硝基芳族化合物的含水组合物引入电解槽阳极室中，并且在0.1-10kA/m2的阳极电流密度和4-15V的电解槽电位下进行电解，且其电解槽具有至少一个阳极，其包含至少一个包含铂的阳极段或由载体材料和涂层构成的阳极段，其中载体材料包含至少一种选自铌(Nb)、钽(Ta)、钛(Ti)和铪(Hf)的金属，并且涂层由硼-掺杂金刚石构成。这是一个大胆的尝试，但是存在成本过高，而且处理效果差的缺点。这也让本领域的技术人员形成了电化学处理硝基甲苯生产废水存在成本高、操作困难的观念，也因此逐渐抛弃了对于电化学在处理硝基甲苯生产废水方面的研究。
发明内容
1.要解决的问题
针对现有硝基甲苯生产废水处理工艺存在国外引进成本高、难以推广，常规工艺效果较差，且运行操作要求高、有大量废渣产生的问题，本发明提供一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，本发明能降低混酸硝化废水的生物毒性，提高其可生化性，通过电化学还原-电化学氧化耦合工艺，转化降解硝基苯类、硝基酚类有机物，为后续生化提供有利条件。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其步骤为：
(a)将硝基甲苯生产废水的pH调至1.5-2.0，静置沉淀，排去底部废渣，取上层液通过阴极进水口进入电化学反应器的阴极室；所采用的电化学反应器包括阳极室、阴极室、阳极、 阴极、阴极液储罐、阳离子交换膜、阳极液储罐和流量计；所述的阳极室和阴极室之间通过阳离子交换膜隔开；所述的阳极和阴极分别位于阳极室和阴极室中；所述的阴极室包括阴极进水口和阴极出水口；所述的阳极室包括阳极出水口和阳极进水口；所述的阴极出水口通过管道与阴极液储罐连接，阴极液储罐再通过管道与阳极进水口连接；所述的阳极出水口通过管道与阳极液储罐连接；所述的流量计有两个，分别位于阴极出水口与阴极液储罐之间的管道上和阳极出水口与阳极液储罐之间的管道上；所述的阴极采用石墨板、钛板、负载钌氧化物或铱氧化物的钛板；所述的阳极为钛基形稳电极，涂层为钌氧化物或铱氧化物；废水流动方向与电极板平行；
(b)开始电化学处理，步骤(a)中产生的废水上层液在阴极室发生还原反应，阴极室处理后的废水依次通过阴极出水口、阴极液储罐和阳极进水口进入阳极室，废水在阳极室中发生氧化反应；所述的阳极和阴极的电流密度为5-50mA/cm2，废水在阴极室和阳极室的停留时间为1-6h；所述的阳极和阴极的间距为1.5-3cm；在阴极处发生还原反应，废水中的硝基苯类物质部分还原转化为苯胺类等更易被氧化的物质；阳极处发生电催化氧化反应，苯胺及硝基苯还原产物开环生成小分子有机物。经过电化学还原-氧化过程，混酸硝化废水的可生化性有明显的改善，生物毒性有明显降低；
(c)将步骤(b)处理后废水排出，经阳极液储罐调节后进入生化系统。
进一步地，所述的步骤(a)中用于调节pH的酸为硫酸或工业废酸，静置沉淀时间为0.5-2h。
优选地，所述的步骤(a)中的阴极液储罐容积是阴极室容积的5-10倍。
优选地，所述的步骤(a)中的阳极液储罐容积是阳极室容积的5-10倍。
本发明创造性地提出本领域人员认为成本高、不易操作的电化学方法处理硝基甲苯生产废水，并且惊喜的发现在pH为1.5-2.0时，再通过本发明所介绍的电化学反应器的结构、电极的材料、电流密度、电极的间距以及处理时间等参数，能快速达到分解硝基甲苯、二硝基酚等物质的目的，这些参数互相配合，不但成本低，而且操作简便。本发明人通过大量的实验进行了验证，解决了本领域技术人员一直苦恼的问题，相对于国内外技术，不但处理效果好，而且成本低，同时改变了本领域人员认为电化学方法处理硝基甲苯生产废水仅仅是个设想、成本高，而且效果不好的观念。
3.有益效果
相比于现有技术，本发明的有益效果为：
(1)本发明耦合电还原和电催化氧化工艺，不仅可以极大减少预处理废渣的产生，还具有以下效果：对高浓度废水(COD＞7000mg/L)中的硝基苯类物质和苯胺类物质的去除率达 到85％以上，COD去除率在30％以上，可生化性(以下简称为B/C)可以从原先的0.08-0.1提高至0.43-0.46，生物毒性可以降低为原水的1/20-1/10，过程中产生的污泥主要在酸化工艺中产生，相比其他工艺，其污泥减少量可以达到80％以上，出水可以进入生化系统；
(2)本发明酸化、沉降是电化学还原一氧化工艺所不可缺少的前处理工艺，创造性的提出酸化工艺，其有益效果不仅仅体现在将水中的酚钠转化成酚沉淀，减少电化学工艺的有机负荷，还对后续的电化学还原、氧化产生了有益的影响，本发明调节废水到强酸性条件下，电化学还原的主要产物尾苯胺类物质，而在碱性、中性条件下苯胺类物质产率很低，从而影响还原-氧化模块的处理效果，数据表明，在pH＝7、9、12时，还原一氧化的处理效果(芳香性、B/C和急性生物毒性)有不同程度的下降，最高可达50％(后有实施例说明)；
(3)本发明用电能取代药剂投加，更加易于操作和控制，且不会产生废渣，对于实现混酸硝化废水高效、稳定、低成本预处理有较大的学术意义和实践价值。
附图说明
图1为本发明所采用装置的示意图。
图中：1、阳极出水口；2、阴极出水口；3、阳极室；4、阴极室；5、阳极；6、阴极；7、阳极进水口；8、阴极进水口；9、阴极液储罐；10、阳离子交换膜；11、阳极液储罐；12、流量计。
具体实施方式
下面结合实施例对本发明进行详细描述。
实施例1
一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其步骤为：
(a)将硝基甲苯生产废水(COD～9000mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.3)的pH调至1.8，静置沉淀时间为30min，排去底部废渣，取上层液通过阴极进水口8进入电化学反应器的阴极室4；所采用的电化学反应器如图1所示，其包括阳极室3、阴极室4、阳极5、阴极6、阴极液储罐9、阳离子交换膜10、阳极液储罐11和流量计12；阳极室3和阴极室4之间通过阳离子交换膜10隔开；阳极5和阴极6分别位于阳极室3和阴极室4中；阴极室4包括阴极进水口8和阴极出水口2；阳极室3包括阳极出水口1和阳极进水口7；阴极出水口2通过管道与阴极液储罐9连接，阴极液储罐9再通过管道与阳极进水口7连接；阳极出水口1通过管道与阳极液储罐11连接；流量计12有两个，分别位于阴极出水口2与阴极液储罐9之间的管道上和阳极出水口1与阳极液储罐11之间的管道上；阴极6采用石墨板；阳极5为钛基形稳电极，涂层为钌氧化物；废水流动方向与电极板平行；用于调节pH的酸为硫酸。阴极液储罐9容积是阴极室4容积的8倍。阳极液储罐11容积是阳极室3容积的9 倍。
(b)开始电化学处理，步骤(a)中产生的废水上层液在阴极室4发生还原反应，阴极室4处理后的废水依次通过阴极出水口2、阴极液储罐9和阳极进水口7进入阳极室3，废水在阳极室3中发生氧化反应；阳极5和阴极6的电流密度为10mA/cm2，废水在阴极室4和阳极室3的停留时间为2h；阳极5和阴极6的间距为2cm。
(c)将步骤(b)处理后废水排出，经阳极液储罐11调节后进入生化系统。
各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.07-0.09 0.1％-0.5％
电化学还原 3800-3900 0.09-0.12 1％-2％
电化学氧化 3600-3700 0.35-0.4 1％-2％
实施例2
同实施例1，所不同的是，硝基甲苯生产废水的pH＝12.1，将pH调至1.5，用于调节pH的酸为工业废酸，静置沉淀时间为60min，阳极5和阴极6的电流密度为20mA/cm2，阴极6采用钛板；废水在阴极室4和阳极室3的停留时间为2h，阴极液储罐9容积是阴极室4容积的5倍。阳极液储罐11容积是阳极室3容积的5倍。阳极5和阴极6的间距为3cm；各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4400-4500 0.07-0.11 0.1％-0.5％
电化学还原 3600-3800 0.12-0.14 2％-3％
电化学氧化 3100-3200 0.43-0.46 3％-4％
实施例3
同实施例1，所不同的是，硝基甲苯生产废水的pH＝12.2，将pH调至2.0，静置沉淀时间为100min，阳极5和阴极6的电流密度为30mA/cm2，阳极5的涂层为铱氧化物，阴极6采用负载钌氧化物的钛板；废水在阴极室4和阳极室3的停留时间为2h。阴极液储罐9容积是阴极室4容积的10倍。阳极液储罐11容积是阳极室3容积的10倍。阳极5和阴极6的间距为1.5cm；各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4400-4500 0.07-0.11 0.1％-0.5％
电化学还原 3600-3700 0.14-0.16 2％-4％
电化学氧化 3000-3100 0.45-0.47 3.5％-4.5％
实施例4
同实施例1，所不同的是，硝基甲苯生产废水的COD～9500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至2.0，阳极5和阴极6的电流密度为10mA/cm2，阴极6采用负载铱氧化物的钛板废水在阴极室4和阳极室3的停留时间为6h。阴极液储罐9容积是阴极室4容积的7倍。阳极液储罐11容积是阳极室3容积的7倍。各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4800-5000 0.06-0.08 0.1％-0.5％
电化学还原 4300-4500 0.11-0.12 2％
电化学氧化 3800-4000 0.41-0.43 2％-4％
实施例5
同实施例1，所不同的是，硝基甲苯生产废水的COD～9500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至1.5，静置沉淀时间为120min，阳极5和阴极6的电流密度为20mA/cm2，废水在阴极室4和阳极室3的停留时间为3h。阳极5和阴极6的间距为2.5cm；各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4800-5000 0.06-0.08 0.1％-0.5％
电化学还原 4200-4300 0.12-0.14 2％-4％
电化学氧化 3900-4000 0.46-0.48 4％-5％
实施例6
同实施例1，所不同的是，硝基甲苯生产废水的COD～9500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至1.7，阳极5和阴极6的电流密度为50mA/cm2，废水在阴极室4和阳极室3的停留时间为3h。各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4800-5000 0.06-0.08 0.1％-0.5％
电化学还原 4000-4200 0.14-0.15 3％
电化学氧化 3700-3900 0.48-0.49 4％-5％
实施例7
同实施例1，所不同的是，硝基甲苯生产废水的COD～8500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，阳极5和阴极6的电流密度为10mA/cm2，废水在阴极室4和阳极室3的停留时间为1h。各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.08-0.1 0.1％-0.5％
电化学还原 4200-4400 0.1-0.12 1％-2％
电化学氧化 3900-4000 0.25-0.30 1％-2％
实施例8
同实施例1，所不同的是，硝基甲苯生产废水的COD～8500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，阳极5和阴极6的电流密度为20mA/cm2，废水在阴极室4和阳极室3的停留时间为1h。各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.08-0.1 0.1％-0.5％
电化学还原 4000-4200 0.1-0.12 1％-2％
电化学氧化 3800-3900 0.28-0.32 2％
实施例9
同实施例1，所不同的是，硝基甲苯生产废水的COD～8500mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至1.5，沉降60min，阳极5和阴极6的电流密度为30mA/cm2，废水在阴极室4和阳极室3的停留时间为1h。各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.08-0.1 0.1％-0.5％
电化学还原 3900-4000 0.11-0.12 1％-2％
电化学氧化 3700-3800 0.3-0.35 2％-3％
实施例10
同实施例1，所不同的是，硝基甲苯生产废水的COD～9000mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至3.8，沉降30min，将底部污泥排出，上层液进入电化学反应器，在阴极室发生还原反应，电流密度为20mA/cm2，反应停留时间2h。还原液回流至阳极室进行催化氧化，电流密度不变，停留时间1h，各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 6500-6600 0.05-0.07 0.05％-0.1％
电化学还原 5900-6000 0.08-0.09 0.5％-1％
电化学氧化 5700-5800 0.15-0.2 0.5％-1％
实施例11
同实施例1，所不同的是，硝基甲苯生产废水的COD～9000mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至1.8，沉降30min，将底部污泥排出，上层液将pH调至7.0后进入电化学反应器，在阴极室发生还原反应，电流密度为20mA/cm2，反应停留时间2h。还原液回流至阳极室进行催化氧化，电流密度不变，停留时间1h，各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.08-0.1 0.1％-0.5％
电化学还原 3900-4000 0.1-0.12 0.5％-1％
电化学氧化 3700-3800 0.35-0.4 1％-2％
实施例12
同实施例1，所不同的是，硝基甲苯生产废水的COD～9000mg/L，含硝基甲苯、二硝基酚等物质，pH＝12.4，将pH调至1.8，沉降30min，将底部污泥排出，上层液将pH调至12.0后进入电化学反应器，在阴极室发生还原反应，电流密度为20mA/cm2，反应停留时间2h。还原液回流至阳极室进行催化氧化，电流密度不变，停留时间1h，各工段出水参数如下表所示：
工段\指标 COD B/C 半致死浓度(大型蚤)
酸化 4500-4600 0.08-0.1 0.1％-0.5％
电化学还原 4000-4100 0.1-0.12 0.5％-1％
电化学氧化 3800-3900 0.3-0.35 1％-2％
从以上各个实施例的效果对比就可以看出，当采用本发明控制的条件时，电化学氧化后 的出水的毒性显著降低，而且B/C＞0.4，表明污水生化性能较好，适合下一步采用活性污泥法处理等常规方法进行处理，而对于不采用本发明的方法，尤其是pH为中性或者碱性条件的，即使采用了本发明所采用的反应装置，得到的结果中处理效果都不理想，尤其是B/C＜0.4，说明生化性能不好，后续处理困难。

Claims (4)

  1. 一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其步骤为：
    (a)将硝基甲苯生产废水的pH调至1.5-2.0，静置沉淀，排去底部废渣，取上层液通过阴极进水口(8)进入电化学反应器的阴极室(4)；所采用的电化学反应器包括阳极室(3)、阴极室(4)、阳极(5)、阴极(6)、阴极液储罐(9)、阳离子交换膜(10)、阳极液储罐(11)和流量计(12)；所述的阳极室(3)和阴极室(4)之间通过阳离子交换膜(10)隔开；所述的阳极(5)和阴极(6)分别位于阳极室(3)和阴极室(4)中；所述的阴极室(4)包括阴极进水口(8)和阴极出水口(2)；所述的阳极室(3)包括阳极出水口(1)和阳极进水口(7)；所述的阴极出水口(2)通过管道与阴极液储罐(9)连接，阴极液储罐(9)再通过管道与阳极进水口(7)连接；所述的阳极出水口(1)通过管道与阳极液储罐(11)连接；所述的流量计(12)有两个，分别位于阴极出水口(2)与阴极液储罐(9)之间的管道上和阳极出水口(1)与阳极液储罐(11)之间的管道上；所述的阴极(6)采用石墨板、钛板、负载钌氧化物或铱氧化物的钛板；所述的阳极(5)为钛基形稳电极，涂层为钌氧化物或铱氧化物；
    (b)开始电化学处理，步骤(a)中产生的废水上层液在阴极室(4)发生还原反应，阴极室(4)处理后的废水依次通过阴极出水口(2)、阴极液储罐(9)和阳极进水口(7)进入阳极室(3)，废水在阳极室(3)中发生氧化反应；所述的阳极(5)和阴极(6)的电流密度为5-50mA/cm2，废水在阴极室(4)和阳极室(3)的停留时间为1-6h；所述的阳极(5)和阴极(6)的间距为1.5-3cm；
    (c)将步骤(b)处理后废水排出，经阳极液储罐(11)调节后进入生化系统。
  2. 根据权利要求1所述的一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其特征在于：所述的步骤(a)中用于调节pH的酸为硫酸或工业废酸，静置沉淀时间为0.5-2h。
  3. 根据权利要求1所述的一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其特征在于：所述的步骤(a)中的阴极液储罐(9)容积是阴极室(4)容积的5-10倍。
  4. 根据权利要求1-3中任意一项所述的一种污泥减量化的硝基甲苯生产废水电催化还原氧化预处理方法，其特征在于：所述的步骤(a)中的阳极液储罐(11)容积是阳极室(3)容积的5-10倍。
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