CN106007167B - The processing method of the pickling waste waters containing incretion interferent - Google Patents

Abstract

The invention provides a treatment method for pickling wastewater containing endocrine disruptors. The components of the pickling wastewater from China National Offshore Oil Corporation are mainly acids, metal ions and organic matter, and the endocrine disruptors are nonylphenol polyoxyethylene ethers, which are a type of surface active substances. , is a common organic substance used in the coating process of offshore oil fields, which will cause certain harm to the ecology. Through foam separation, Fenton oxidation reaction, flocculation precipitation, A ² /O biochemical treatment, CMF reaction and activated carbon filtration on the above wastewater, the harmful substances in the wastewater are removed, and the treated effluent reaches the pollution level of urban sewage treatment plants. Class I Class B standard of the Waste Emission Standard, which is again used for pipeline spray cooling. The degree of automation is high, the reaction process can be adjusted flexibly, and it can adapt to different water quality requirements of influent and effluent. This process not only enables COD discharge to meet the standard, but also reduces the treatment cost of waste water, realizing the high efficiency and economy of waste water treatment.

Description

Treatment method of pickling wastewater containing endocrine disruptors

The application of the present invention is a divisional application of the parent application "a treatment device and process method for pickling wastewater containing endocrine disruptors". The application number of the parent application is 2015101401704, and the application date of the parent application is March 27, 2015 day.

technical field

The invention belongs to the technical field of environmental protection of acid treatment waste liquid, more specifically, for marine engineering associated pickling liquid, the endocrine disruptor contained in it is used as a treatment device and process method of persistent organic matter.

Background technique

The main methods currently available for pickling wastewater treatment are classified as follows:

Sulfuric acid pickling wastewater treatment processes mainly include neutralization method, ferric sulfate method, organic solution extraction method, dialysis method, ion exchange method and other methods. The latter three methods are still in the stage of experimental research. In addition, there are iron oxide red sulfur ammonium method, wetland method and biological method. In recent years, "zero discharge" of wastewater has been mentioned more and more frequently in the industrial field, and it has also become an important indicator in the planning review of various industries. With the progress of research, foreign countries have begun to use diffusion dialysis-diaphragm electrolysis, biosorption technology, micellar enhanced ultrafiltration and other processes to treat pickling wastewater containing endocrine disruptors.

Main process introduction

(1) Foam separation process: According to the principle of surface adsorption, foam separation uses the air bubbles formed in the liquid phase as carriers to separate the solute or particles in the liquid phase, so it is also called foam adsorption separation.

Foam separation technology is one of the new separation technologies developed in the past ten years. Foam separation is based on the principle of adsorption, to aerate the liquid containing surface active substances, so that the surface active substances in the liquid gather on the air-liquid interface (the surface of the bubbles), and form a foam layer above the liquid body, and separate the foam layer and The separation of the liquid phase main body can achieve the purpose of concentrating the surface active substance (in the foam layer) and purifying the liquid phase main body.

Foam separation consists of two basic processes: (1) the solute to be separated is adsorbed on the gas-liquid interface; (2) the substance adsorbed by the foam to the gas-liquid interface is collected and destroyed by chemical, thermal or mechanical methods. foam to extract the solute. Therefore, its main equipment is foam tower and foam breaker.

Foam separation technology has the following advantages:

(1) The foam separation structure is relatively simple and easy to scale up;

(2) Simple operation and low energy consumption;

(3) It can be operated continuously or intermittently;

(4) It is used in the initial stage of biological downstream processing to deal with bulky diluents;

(5) As long as the operating conditions are designed reasonably, high separation efficiency can be obtained.

After analyzing the characteristics of acidic wastewater containing endocrine disruptors and the feasibility of the foam separation process, the experiments were carried out. After the pickling wastewater was treated by foam separation, the COD concentration and the total P concentration were greatly reduced.

(2) Fenton oxidation process: Fenton reaction is a waste water treatment method in which ferrous ion (Fe ²⁺ ) is used as a catalyst to chemically oxidize hydrogen peroxide (H ₂ O ₂ ). The system composed of ferrous ions and hydrogen peroxide, also known as Fenton's reagent, can generate strong oxidative hydroxyl radicals, which can form organic free radicals with refractory organic substances in aqueous solution to destroy their structures, and finally oxidize and decompose.

The Fenton reaction is a series of free radical reactions catalyzed by ferrous ions. The main reactions are roughly as follows:

Fe ²⁺ +H ₂ O ₂ ＝＝Fe ³⁺ +OH-+HO·

Fe ³⁺ +H ₂ O ₂ +OH-==Fe ²⁺ +H ₂ O+HO·

Fe ³⁺ +H ₂ O ₂ == Fe ²⁺ +H ⁺ +HO ₂

HO ₂ +H ₂ O ₂ ＝＝H ₂ O+O ₂ ↑+HO·

Through the above reaction, Fenton reagent continuously produces HO (hydroxyl radical, electrode potential 2.80EV, second only to F2), which makes the whole system have strong oxidative properties, and can oxidize chlorobenzene, benzyl chloride, grease, etc. Oxidants (chlorine, sodium hypochlorite, chlorine dioxide, ozone, the electrode potential of ozone is only 2.23EV) oxidize substances. Under the action of hydroxyl radicals, some refractory organic matter in sewage is degraded into degradable organic matter, which improves the biodegradability of sewage.

(3) A ² /O process: A ² /O process is mainly composed of hydrolytic acidification pool, anaerobic pool and aerobic nitrification pool. As shown in Figure 1. Functions of each reactor unit:

1. Anaerobic reactor, the raw sewage and the phosphorus-containing return sludge discharged from the sedimentation tank enter simultaneously. The main function of this reactor is to release phosphorus and oxidize some organic matter at the same time;

2. Anoxic reactor, the primary function is denitrification, nitrate nitrogen is sent from the aerobic reactor through internal circulation, and the amount of mixed liquid in the circulation is relatively large, generally 2Q (Q is the flow rate of raw sewage);

3. Aerobic reactor - aeration tank, this reaction unit is multi-functional, BOD removal, nitrification and phosphorus absorption are all carried out here. Flow is the mixed solution of 2Q backflow to anoxic reactor from here;

4. Sedimentation tank, the function is to separate mud and water, part of the sludge is returned to the anaerobic reactor, and the supernatant is discharged as treated water.

Process features:

1. This process can be called the simplest simultaneous denitrification and phosphorus removal process on the system, and the total hydraulic retention time is less than other types of processes; the process efficiency can generally reach: BOD5 and SS are 90%-95%, total nitrogen more than 70%, phosphorus is about 90%;

2. Under anaerobic (anoxic) and aerobic alternating operating conditions, filamentous bacteria cannot proliferate in large quantities, and sludge filamentous expansion is not easy to occur, and the SVI value is generally less than 100;

3. The sludge contains high phosphorus and has high fertilizer efficiency;

4. No dosing is required during operation, and the two A sections only need to be gently stirred, so as not to increase dissolved oxygen, and the operating cost is low;

5. Anaerobic, anoxic, and aerobic three different environmental conditions and the organic combination of different types of microbial flora, and at the same time have the functions of removing organic matter, nitrogen and phosphorus.

(4) CMF process: continuous membrane filtration (Continuous Membrane Filtration, CMF for short) technology is a new type of membrane separation process, through modular structure design, cross-flow filtration and intermittent automatic cleaning (gas, water washing process ) system, combined into a complete set of closed continuous membrane filtration system.

CMF system technical features:

1. High-strength polypropylene hollow fiber microfiltration membrane or ultrafiltration membrane is used, which is resistant to oxidation, easy to clean and has a long service life;

2. Due to the unique elasticity of the PP hollow fiber membrane, the micropores can be expanded, and the compressed air backwashing technology is used to make this membrane have a good membrane flux recovery rate;

3. Low requirements on raw water quality, clear and transparent produced water, stable SDI ≤ 3, which is better than the water inlet requirements of RO system;

4. The system control has a high degree of automation, simple operation, and effectively reduces labor intensity;

5. The equipment is compact in structure and occupies a small area, and the modular combination design is suitable for water treatment of various scales;

6. The equipment investment and operation costs are low, and the cost performance is the highest among the same type of equipment at home and abroad.

Contents of the invention

The present invention discovers and proposes for the first time the impact of endocrine disruptors used in marine engineering construction (drilling, oil production, subsea pipeline anticorrosion pretreatment, crude oil demulsifier, drilling equipment cleaning, oil production additives, etc.) on ecology. For the impact on ecology, on the basis of studying the monitoring of the Internet of Things, an efficient and economical solution process is proposed, and efforts are made to overcome the shortcomings of traditional treatment processes such as difficult biodegradation, high treatment costs, difficulty, and low efficiency, and to achieve the removal of endocrine disrupting substances Enrichment, recycling and reuse, reducing emissions, has a unique advantage of circular economy. From a long-term perspective, the adoption of this process can not only make its COD discharge meet the standard, but also reduce the cost of wastewater treatment, and realize the efficiency and economy of wastewater treatment.

The purpose of the present invention is achieved through the following technical solutions.

A treatment device for pickling wastewater containing endocrine disruptors, comprising a first regulating tank, a foam separation device, a Fenton oxidation device, a reaction sedimentation tank, a ^second regulating tank, an A2/O biochemical treatment device, a sedimentation tank, and an intermediate water tank , CMF device, activated carbon filter tank and produced water tank, of which:

The first regulating tank is connected to the foam separation device, the first regulating tank is connected to the waste water outlet, and the first regulating tank is connected to the CMF device and the activated carbon filter device;

The foam separation device is connected with the foam breaker, and the foam separation device is connected with the Fenton oxidation device;

The ferrous sulfate dosing tank is connected with the Fenton oxidation device, the hydrogen peroxide dosing tank is connected with the Fenton oxidation device, and the Fenton oxidation device is connected with the reaction precipitation tank;

The calcium chloride dosing tank is connected to the reaction sedimentation tank, the PAC dosing tank is connected to the reaction sedimentation tank, the PAM dosing tank is connected to the reaction sedimentation tank, and the reaction sedimentation tank is connected to the mud storage tank. The reaction sedimentation tank is connected to the second adjustment tank, and a first online pH detection device is set in the reaction sedimentation tank to detect the acidic pH value environment in the reaction sedimentation tank;

The A ² /O biochemical treatment device includes anaerobic reactor, anoxic reactor and aerobic reactor; the anaerobic reactor is connected with the anoxic reactor, and the anoxic reactor is connected with the good An oxygen reactor is connected, and the aerobic reactor is connected with the sedimentation tank;

The second adjustment tank is connected with the nutrient dosing tank, the second adjustment tank is connected with the anaerobic reactor in the A2/O biochemical treatment device, and a ^second online pH detecting device, to detect the acidic pH value environment in the second regulating tank;

The sedimentation tank is connected to the anaerobic reactor in the A ² /O biochemical treatment device, the sedimentation tank is connected to the mud storage tank, the mud storage tank is connected to the plate and frame filter press, and the sedimentation tank connected with the intermediate water tank;

The intermediate water tank is connected to the CMF device, the CMF device is connected to the activated carbon filter device, the activated carbon filter device is connected to the water production tank, and the water production tank is connected to the chlorine tablet dosing tank;

The pickling waste water is directly passed into the first regulating tank through the waste water pipe, and the water inlet pump is arranged on the waste water pipe;

The bottom of the first regulating tank is connected to the top of the foam separation device through a first water outlet pipe, and a first lift pump is arranged on the first water outlet pipe;

The bottom of the second regulating tank is connected to the top of the anaerobic reactor in the A2/O biochemical treatment device through a fifth outlet pipe, and a ^second lift pump is arranged on the fifth outlet pipe;

The bottom of the sedimentation tank is connected to the top of the anaerobic reactor in the A2/O biochemical treatment device through a return sludge pipe, and a sludge pump is arranged ^on the return sludge pipe;

The bottom of the sludge storage tank is connected to the plate and frame filter press through a sludge outlet pipe, and a screw pump is arranged on the sludge outlet pipe;

The bottom of the intermediate water tank is connected to the bottom of the CMF device through the eighth water outlet pipe, a booster pump and a self-cleaning filter are arranged on the eighth water outlet pipe, and the booster pump is connected to the self-cleaning filter;

The activated carbon filter device is connected to the water production tank through the tenth water outlet pipe, and a backwash water pump is arranged on the tenth water outlet pipe;

Select pipe runs as connecting elements for the individual components.

A stirring device is installed in the mud storage tank, and the stirring device is a QJB submersible mixer, so as to realize the technological requirements of homogeneity and flow of solid-liquid two-phase flow and solid-liquid-gas three-phase flow.

The aerobic reaction tank in the A ² /O biochemical treatment device is connected with a blower, and the blower is a Roots blower to realize functions such as BOD removal, nitrification and phosphorus absorption.

The number of the first lift pump, the second lift pump, the sludge pump, the screw pump, the booster pump and the backwash water pump is two.

When using the above-mentioned treatment device of the present invention to carry out pickling wastewater treatment, the whole treatment device (that is, a whole treatment device containing endocrine disruptor pickling wastewater) is selected to be fixed in a movable device, such as in a mobile container, to Realize mobile work and meet the requirements of mobile treatment of pickling wastewater.

A treatment process for pickling waste water containing endocrine disruptors, carried out according to the following steps:

Step 1, adjusting the water inlet pump to control the flow rate of pickling wastewater to 2-5m ³ /h, preferably 3m ³ /h;

Step 2, settling aside, the adjustment tank adjusts the water quality and quantity of the wastewater, so that the wastewater reaches a stable state, the pH value is 0.5-1.5 (free acid 0.5-2%), it is strongly acidic, and the wastewater is in the adjustment tank The residence time is 44-50h, preferably 48h;

Step 3, the residence time of the waste water in the foam separation device is 10-40min, preferably 20-30min, 60%-70% of endocrine disruptors are removed by the foam breaker, and the effluent treated by the foam breaker , further concentrated treatment is required, and the high concentration of the effluent from the foam breaker indicates that the active substance can be used as a low-end cleaning agent;

Step 4, the residence time of the wastewater in the Fenton oxidation device is 4-10h, preferably 6-8h, and the medicines added in the Fenton oxidation device include ferrous sulfate (FeSO ₄ 7H ₂ O) and hydrogen peroxide (H ₂ O ₂ ), wherein the ratio of Fe ²⁺ and hydrogen peroxide is 1-4:1, preferably 3:1, and the mass percentage of FeSO ₄ ·7H ₂ O is 2wt%-20wt%, preferably 5wt%-15wt%, over The mass percentage of hydrogen peroxide is 20-40wt%, preferably 30-35wt%, and the amount of hydrogen peroxide generally added is twice the COD to be removed;

Step 5, the residence time of the wastewater in the reaction precipitation tank is 1-9h, preferably 3-7h, and the medicines added in the reaction precipitation tank include polyacrylamide (PAM), polyaluminum chloride (PAC) and Calcium chloride (CaCl ₂ ), the addition of the flocculant can remove 10%-17% of the precipitate formed by the small molecule organic matter oxidized by Fenton, and the first online pH detection device is connected with the reaction precipitation tank to Ensure that the water quality in the reaction sedimentation tank reaches a pH of about 9-10;

Step 6, the residence time of the wastewater in the second regulating tank is 20-26h, preferably 24h, and nutrients are added to further adjust the water sample, the water environment suitable for microbial growth, through the second online pH The detection device is connected to the second adjustment pool to ensure that the water quality in the second adjustment pool reaches a pH of about 6-8;

Step 7, when performing biochemical treatment of pickling wastewater, adjust the second lift pump to control the flow rate to 1-5m ³ /h, preferably 2-3m ³ /h;

Step 8, the total residence time of the wastewater in the A ² /O biochemical treatment device is 20-24h, preferably 23h, and the residence time in the anoxic reactor is 2-6h, preferably 4-5h. The residence time in the anaerobic reactor is 3-9h, preferably 6-8h, the residence time in the aerobic reactor is 9-15h, preferably 10-13h, aeration in the aerobic reactor , choose to adjust the aeration air flow through the Roots blower to be 0.5-1.8m ³ /min, preferably 1.0-1.3m ³ /min;

Step 9, the residence time of the wastewater in the settling tank is 1-8h, preferably 2-6h, the function is to separate mud and water, a part of the sludge is returned to the anaerobic reactor, and the supernatant is used as treated water to flow into the settling tank through the outlet pipe. The intermediate water tank, the remaining sludge in the settling tank is discharged into the sludge storage tank through the sludge pipe;

Step 10, adjust the booster pump, adjust the flow rate not to exceed 2.4m ³ /h, preferably 1.5-2.2m ³ /h, after being treated by the activated carbon filter device, in a word, the effluent after CMF treatment can reach the "urban sewage treatment The Class I B standard in the Factory Pollutant Discharge Standard (GB18918-2002) is again used for spray cooling of pipelines.

In the technical solution of the present invention, a variety of waste water treatment methods are effectively combined, and the rational use of the foam separation device can remove 60%-70% of endocrine disruptors. The combination of the Fenton oxidation device and the reaction precipitation device can Remove 10%-17% of endocrine disruptors, and through the aeration device, further adjust the pH value of the wastewater, create a more favorable environment for the growth of microorganisms, create conditions for the biochemical reaction to proceed, and save the dosage Regulate the pH of the medicine, saving the cost of processing. Calculated by purchasing chemicals, fuel and power costs based on the consumption provided by relevant professionals and the information provided by the owner: the cost of chemicals per ton of wastewater is 30.04 yuan, and the comprehensive electricity price is 0.80 yuan/kW·h, which is higher than that of the same type of pickling wastewater. has declined. The invention has a high degree of automation, can flexibly adjust the reaction process, and can adapt to different water quality requirements of inflow and outflow, and is an efficient treatment device for pickling wastewater of endocrine disruptors.

Description of drawings

Fig. 1 is a schematic diagram of the connection structure of the device of the present invention.

In the figure: 1 is the water inlet pump, 2 is the first regulating tank, 3 is the first lifting pump, 4 is the bubble film separation tank, 5 is the destroyer, 6 is the Fenton oxidation device, 7 is the ferrous sulfate storage tank, 8 1 is the hydrogen peroxide storage tank, 9 is the reaction precipitation tank, 10 is the PAM storage tank, 11 is the PAC storage tank, 12 is the calcium oxide storage tank, 13 is the second adjustment tank, 14 is the nutrient substance dosing tank, 15 is the second lifting Pump, 16 is the A ² /O biochemical treatment device, 17 is the sludge pump, 18 is the sedimentation tank, 19 is the mud storage tank, 20 is the screw pump, 21 is the plate and frame filter press, 22 is the intermediate water tank, 23 is the tank Pressure pump, 24 is a CMF device, 25 is an activated carbon filter device, 26 is a backwash pump, 27 is a water production tank, and 28 is a chlorine flake storage tank; A is the waste water inlet pipe, B is the first water outlet pipe, and C is the foam outlet pipe , _C0 is the water outlet pipe of the foam breaker, D is the second water outlet pipe, E is the ferrous sulfate dosing pipe, F is the hydrogen peroxide dosing pipe, G is the third water outlet pipe, H is the calcium chloride dosing pipe, I is the PAC dosing pipe, J is the PAM dosing pipe, K is the fourth outlet pipe, L is the nutrient dosing pipe, M is the fifth water outlet pipe, N is the sixth water outlet pipe, O is the return sludge pipe, P is the remaining sludge outlet, Q is the sedimentation outlet, R is the sludge outlet, R ₀ is the mud cake outlet, S is the seventh outlet pipe, T is the eighth outlet pipe, U is the ninth outlet pipe, and V is the ninth outlet pipe. Ten water outlet pipes, W is the chlorine tablet dosing pipe, X is the first backflow water pipe, Y is the second backflow water pipe, Z is the eleventh water outlet pipe, and _Z0 is the third backflow water pipe.

Detailed ways

The technical solutions of the present invention will be further described below through specific examples.

The pickling wastewater containing endocrine disruptors used in this example is from the pickling wastewater of China National Offshore Oil Corporation, and the secretion disruptors in the pickling wastewater of this company are mainly nonylphenol polyoxyethylene ether.

As shown in Figure 1, 1 is the water inlet pump, 2 is the first regulating tank, 3 is the first lift pump, 4 is the bubble film separation tank, 5 is the destroyer, 6 is the Fenton oxidation device, and 7 is the sulfurous acid Iron storage tank, 8 is a hydrogen peroxide storage tank, 9 is a reaction precipitation tank, 10 is a PAM storage tank, 11 is a PAC storage tank, 12 is a calcium oxide storage tank, 13 is a second adjustment tank, 14 is a nutrient dosing tank, 15 is the ^second lift pump, 16 is the A2/O biochemical treatment device, 17 is the sludge pump, 18 is the sedimentation tank, 19 is the mud storage tank, 20 is the screw pump, 21 is the plate and frame filter press, 22 is the middle Water tank, 23 is a pressurized pump, 24 is a CMF device, 25 is an activated carbon filter device, 26 is a backwash water pump, 27 is a water production tank, 28 is a chlorine sheet storage tank; A is an inlet and waste water pipe, B is the first water outlet pipe, C is the foam outlet pipe, _C0 is the outlet pipe of the foam breaker, D is the second outlet pipe, E is the ferrous sulfate dosing pipe, F is the hydrogen peroxide dosing pipe, G is the third water outlet pipe, and H is calcium chloride Dosing pipe, I is the PAC dosing pipe, J is the PAM dosing pipe, K is the fourth outlet pipe, L is the nutrient dosing pipe, M is the fifth water outlet pipe, N is the sixth water outlet pipe, O is the return flow Sludge pipe, P is the remaining sludge outlet pipe, Q is the sediment outlet pipe, R is the sludge outlet pipe, R ₀ is the mud cake outlet pipe, S is the seventh outlet pipe, T is the eighth water outlet pipe, U is the ninth Water outlet pipe, V is the tenth water outlet pipe, W is the chlorine tablet dosing pipe, X is the first backflow water pipe, Y is the second backflow water pipe, Z is the eleventh water outlet pipe, and _Z0 is the third backflow water pipe.

The water inlet pipe A is connected to the first regulating tank 2 through the first pump 1, the first water outlet pipe B is connected to the foam separator 4 through the second pump 3, and the foam outlet pipe C is connected to the foam breaker 5 through the foam separator 4. Foam separation of pickling wastewater can effectively reduce the concentration of COD and P in the influent.

The second outlet pipe D is connected to the Fenton oxidation device 6 by the foam separation device 4, and what is stored in the ferrous sulfate storage dosing tank 7 is the aqueous solution of the first catalyst ferrous sulfate (FeSO ₄ 7H ₂ O), and passes through the sulfuric acid The ferrous ferrous dosing pipe E is connected to the Fenton oxidation device 6, and the first oxidant hydrogen peroxide (H ₂ O ₂ ) solution is stored in the hydrogen peroxide storage tank 8, and is connected to the Fenton oxidation device 6 through the hydrogen peroxide dosing pipe F . The system composed of ferrous ions and hydrogen peroxide can generate strong oxidative hydroxyl radicals (HO·), which can form organic free radicals with refractory organic matter in aqueous solution to destroy their structure and eventually oxidize and decompose.

The third outlet pipe G is connected to the reaction precipitation tank 9 through the Fenton oxidation device 6, and the PAM storage and dosing tank 10 stores a polymer water treatment flocculant polyacrylamide ((C ₃ H ₅ NO) _n ), And be connected with reaction precipitation tank 9 through PAM dosing pipe J; What store in PAC storage dosing tank 11 is a kind of inorganic polymer coagulant polyaluminum chloride (Al ₂ (OH) _n Cl ₆ -nm), and Be connected to reaction precipitation tank 9 by PAC dosing pipe I; Calcium chloride is stored in dosing tank 12 and store is calcium chloride (CaCl ₂ ), and is connected to reaction precipitation tank 9 by calcium chloride dosing pipe H; An online pH detection device is connected with the reaction precipitation tank 9 to ensure that the water quality in the reaction precipitation tank 9 reaches a predetermined pH value.

The fourth outlet pipe K is connected to the second regulating tank 13 through the reaction sedimentation tank 9, and the nutrients suitable for the growth of microorganisms are stored in the nutrient substance dosing tank 14, and is connected to the second regulating pond 13 through the nutrient substance dosing pipe L , the second on-line pH detection device is connected to the second regulating tank 13 to ensure that the water quality in the second regulating tank 13 reaches a predetermined pH value.

The fifth water outlet pipe M provided with the third pump 15 is connected to the anaerobic reactor in the A2/O biochemical treatment device 16 through the ^second regulating tank 13, and the sixth water outlet pipe N is passed through the A2/O biochemical treatment device ¹⁶ . The oxygen reactor is connected to the sedimentation tank 18 , and the return sludge pipe O provided with the sludge pump 17 is connected to the anaerobic reactor in the A ² /O biochemical treatment device 16 through the sedimentation tank 18 .

The remaining sludge outlet pipe P is connected to the mud storage tank 19 through the sedimentation tank 18, the sedimentation outlet pipe Q is connected to the mud storage tank 19 through the reaction sedimentation tank 9, and the sludge outlet pipe R provided with the screw pump 20 is connected to the sludge storage tank 19 through the sludge storage tank 19 The plate and frame filter presses 21 are connected, and a mud cake outlet pipe _R0 is connected to the plate and frame filter presses 21.

The seventh outlet pipe S is connected to the intermediate water tank 22 through the sedimentation tank 18, the eighth outlet pipe T equipped with a booster pump 23 is connected to the CMF device 24 through the intermediate water tank 22, and the ninth outlet pipe U is connected to the activated carbon filter device through the CMF device 24 25, and the tenth outlet pipe V provided with a backwash water pump 26 is connected to the produced water tank 27 through an activated carbon filter device 25.

What stored in the chlorine tablet storage dosing tank 28 is novel and efficient disinfection, bleaching agent chlorine tablet, and links to each other with the water production tank 27 through the chlorine tablet dosing pipe W, and the first return water pipe X is respectively connected to the CMF device 24 and the CMF device 24 through the water production tank 27 The activated carbon filter device 25 is connected to each other, and the second backflow pipe Y is connected to the CMF device 24 and the activated carbon filter device 25 respectively through the first regulating tank 2 .

The third return water pipe _Z0 is connected to the second regulating tank 13 through the water production tank 27. When the production stagnates and the production wastewater is no longer continuously supplied, the third return water pipe _Z0 is opened for operation.

When using the above-mentioned treatment device of the present invention to carry out pickling wastewater treatment, the whole treatment device (that is, a whole treatment device containing endocrine disruptor pickling wastewater) is selected to be fixed in a movable device, such as in a mobile container, to Realize mobile work and meet the requirements of mobile treatment of pickling wastewater.

In the foam separation device, the air bubbles formed in the liquid phase are used as carriers to separate the solute or particles in the liquid phase. The experimental results prove the correctness of the selected process of the present invention. After the pickling wastewater was treated by foam separation, the COD dropped from the original 9871mg/L to about 3000mg/L, and the total P dropped from the original 8000mg/L to 33mg/L. In the Fenton oxidation device, Fenton's reagent ferrous sulfate and hydrogen peroxide are used to react to produce hydroxyl radicals with strong oxidative properties. Under the action of hydroxyl radicals, some refractory organic substances in sewage are degraded into degradable organic substances, improving biodegradability of sewage. The ratio of Fe ²⁺ to hydrogen peroxide is 3:1, and the amount of hydrogen peroxide is generally twice the amount of COD to be removed. After being oxidized by Fenton's reagent, the polymer water treatment flocculant polyacrylamide, inorganic polymer coagulant polyaluminum chloride and calcium chloride can remove short-chain organic pollutants, so that the pH after reaction precipitation =10, greatly improving the biochemical performance. After A ² /O treatment, the COD removal rate was about 93.1%, and the effluent COD dropped from 1617mg/L to 112mg/L; the ammonia nitrogen removal rate was about 81.3%, and the effluent ammonia nitrogen dropped from 30.5mg/L to 5.7mg/L. In the above ^- mentioned treatment device for pickling wastewater containing endocrine disruptors, the aerobic reaction tank in the A2/O biochemical treatment device is connected to a blower, and the blower is a Roots blower to realize BOD removal, nitrification and absorption Phosphorus etc. Use the set first online pH detection device and the second online pH detection device to strictly check the water environment in the reaction tank, and use the stirring device QJB submersible mixer set in the mud storage tank for stirring to realize solid-liquid two-phase flow and solid-liquid two-phase flow. Process requirements for homogeneity and flow of liquid-gas three-phase flow.

Aeration experiment: Through aeration treatment, the COD content in the water sample is initially reduced, and the total nitrogen content in the water sample is also removed.

Experimental steps:

(1) Take 800ml of water sample, air flotation for 1h, 761ml of water remains after the reaction, and the volume difference between before and after the water sample is 4.88%.

(2) Take 800ml of water sample and add H ₂ O ₂ (add 8.0mL) with 1% of the volume of the water sample. After the reaction, 758ml of water remains, and the volume difference between the front and back water samples is 5.25%. During the air flotation process, the foam produced is obviously less than that of the water sample without H ₂ O ₂ , and there is white flocculent precipitate after air flotation.

(3) Take 800ml of water sample and add H ₂ O ₂ (add 4.0mL) with 0.5% of the volume of the water sample. After the reaction, 760ml of water remains, and the volume difference between the front and back water samples is 5%.

(4) Take 800ml of water sample and add H ₂ O ₂ (add 16.0mL) with 2% of the volume of the water sample. After the reaction, 764ml of water remains, and the volume difference between the front and back water samples is 4.5%.

Coagulation experiment: Through coagulation treatment, the COD content in the water sample is reduced, and the total phosphorus content in the water sample is also removed.

Experimental steps:

(1) Take 100ml of the remaining No. 2 water sample and add 2.95ml Ca(OH) ₂ , the pH is 10.20, let it stand for 30 minutes and filter it, and use it as No. 6 water sample.

(2) Take 100ml of the remaining No. 3 water sample and add 3.6ml of Ca(OH) ₂ , the pH is 10.18, let it stand for 30 minutes and filter it, and use it as No. 7 water sample.

Analysis of results:

(1) The COD of raw water is relatively large, and part of COD can be removed after air flotation, with removal rates of 17.79% and 24.09%; the removal rates of COD after coagulation and sedimentation are 22.29% and 31.15%, indicating that part of COD can be removed by precipitation, which is It may be that part of the organic matter is attached to the sediment and removed by filtration, or it may be that some reducing inorganic substances in the water sample that interfere with COD are removed by precipitation.

(2) The remaining H ₂ O ₂ in the water sample can have a great interference effect on COD. Since potassium dichromate is more oxidizing than H ₂ O ₂ , when there is potassium dichromate, H ₂ O ₂ acts as a reducing agent. The agent consumes potassium dichromate, resulting in high COD results. Therefore, if the water sample with excessive H ₂ O ₂ is added, the remaining H ₂ O ₂ should be decomposed before the COD is measured. According to experience, a small amount of manganese sulfate can be added and left overnight.

Aerate the water samples No. 4 and No. 5 after coagulation for 6 hours, and then analyze parameters such as pH, BOD, COD, TN, and TP. The purpose of the experiment is to verify the effect of aeration and coagulation experiments on the treatment of pickling wastewater containing endocrine disruptors, including COD removal effect, biochemical improvement effect, total nitrogen and total phosphorus removal effect, and to analyze the effect of continuous aeration on the pH of water samples. worthy of influence.

(1) BOD, COD, TN, TP according to "Water and Wastewater Monitoring and Analysis Methods" (Fourth Edition):

BOD is determined by activated sludge aeration degradation method; CODcr is determined by potassium dichromate method;

TN is oxidized by potassium persulfate and measured by ultraviolet spectrophotometry;

TP was digested by potassium persulfate method, and molybdenum-antimony anti-spectrophotometric method was used for determination.

(2) pH and conductivity were measured with a Sartorius pH meter.

Verification experiment result analysis

(1) After the initial aeration treatment, using the characteristics of the surfactant that is easy to foam, hang it out first, which can initially reduce the COD in the water body and reduce the load for the later biochemical treatment.

(2) Aeration has a certain effect on adjusting the pH value, and can reduce the dosage of drugs for adjusting the pH value.

(3) The biodegradability of the raw water sample is low. Adding a certain amount of hydrogen peroxide can just form Fenton’s reagent with the ferrous ion in the water sample, degrade the organic matter, and increase the biodegradability for the next step of biochemical treatment.

(4) After the first step and the second step of treatment, the concentration of TN and TP can be effectively reduced. The effluent TN of the water sample without hydrogen peroxide decreased from 321.5 mg/L to 38.2 mg/L, and the removal rate was about 88.1%; TP dropped from 1183.6 mg/L to 19.0 mg/L, and the removal rate was about 98.4%. The effluent TN of the water sample added with 1% hydrogen peroxide decreased from 321.5 mg/L to 37.3 mg/L, and the removal rate was about 88.4%; TP dropped from 1183.6 mg/L to 4.6 mg/L, and the removal rate was about 99.6%.

Implementation of experimental equipment

(1) A ² /O reactor: anaerobic reactor, anoxic reactor, aerobic reactor, and sedimentation tank are all covered cylinders made of plexiglass. The specifications are 90cm high, 20cm outer diameter, and 19cm inner diameter. Water inlet, sampling port, water outlet and mud discharge port are set at different heights on both sides of the reactor. The top of the anaerobic pool is vacuum sealed, the anoxic pool is half open, and the aerobic pool is pressurized by the aeration pump.

(2) Aeration device: use a marine electromagnetic air compressor, connect the latex tube, and add a rod-shaped microporous aeration head at the end to supply air to the aerobic reactor, and control the dissolution of the aerobic reactor by controlling the air volume through the screw clamp oxygen.

(3) Heating device: Jiabao 2010 heating rod is used to heat the aerobic reactor and automatically control its temperature.

(4) Thermometer: Use a mercury thermometer (range 0-100° C.) to measure the temperature of the water in the reactor.

After the system was running stably, the COD of the effluent treated with A ² /O dropped from 1617mg/L to 112mg/L, with a removal rate of about 93.1%; ammonia nitrogen dropped from 30.5mg/L to 5.7mg/L, with a removal rate of about was 81.3%.

After a series of treatments such as A ² /O (anoxic, anaerobic, and eutrophic) and sedimentation, most of the COD, ammonia nitrogen, and total P in the water are removed. At this time, the effluent can meet the relevant discharge standards stipulated by Tianjin. Subsequent advanced treatment with CMF technology further improves water quality. The effluent treated by CMF can be mixed with the effluent treated by A ² /O in a certain proportion, and it can also meet the first-class B standard in the "Pollutant Discharge Standard for Urban Sewage Treatment Plants" (GB18918-2002). Reduce operating costs.

In summary, after pre-aeration, coagulation treatment, A ² /O process and CMF process, the effluent COD and ammonia nitrogen have reached the relevant emission standards. It is proved that this experimental method can ensure the effect of reaching the standard of effluent water quality, and has the potential of practical application.

The present invention has been described as an example above, and it should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be made by those skilled in the art without creative labor all fall within the scope of this invention. protection scope of the invention.

Claims (10)

1. the processing method that contains endocrine disruptor pickling wastewater, is characterized in that: utilize the device that contains endocrine disruptor pickling wastewater to process pickling wastewater according to the following steps: Step 1, adjust the water inlet pump, and control the pickling wastewater flow rate to 2-5m ³ /h; Step 2, set aside to settle, and adjust the water quality and quantity of the wastewater in the regulating tank, so that the wastewater reaches a stable state, with a pH value of 0.5-1.5, showing strong acidity, and the wastewater stays in the regulating tank for 44-50 hours; Step 3: The waste water stays in the foam separation device for 10-40 minutes, and 60%-70% of endocrine disruptors are removed through the foam breaker. The effluent treated by the foam breaker needs further centralized treatment. Contains a high concentration of surfactants as a low-end cleaning agent; Step 4, the residence time of wastewater in the Fenton oxidation device is 4-10h, and the medicines added in the Fenton oxidation device include FeSO ₄ 7H ₂ O and hydrogen peroxide (H ₂ O ₂ ), wherein the ratio of Fe ²⁺ to hydrogen peroxide is 1-4:1, the mass percent of FeSO ₄ 7H ₂ O is 2wt%-20wt%, the mass percent of hydrogen peroxide is 20-40wt%, and the amount of hydrogen peroxide added is twice the COD to be removed; Step 5, the residence time of the wastewater in the reaction sedimentation tank is 1-9h, the medicines added in the reaction sedimentation tank include polyacrylamide, polyaluminum chloride and calcium chloride, and the addition of flocculant can remove 10%-17% The precipitation formed by the small molecular organic matter oxidized by Fenton is connected to the reaction precipitation tank through the first online pH detection device to ensure that the water quality in the reaction precipitation tank reaches a pH of 9-10; Step 6, the residence time of the wastewater in the second adjustment pool is 20-26h, and nutrients are added to further adjust the water sample, the water environment suitable for microbial growth, through the second online pH detection device and the second adjustment pool Connected to ensure that the water quality in the second adjustment pool reaches a pH of 6-8; Step 7, when performing biochemical treatment of pickling wastewater, adjust the second lift pump to control the flow rate to 1-5m ³ /h; Step ⁸ , the total residence time of the wastewater in the A2/O biochemical treatment device is 20-24h, the residence time in the anoxic reactor is 2-6h, and the residence time in the anaerobic reactor is 3-9h, The residence time in the aerobic reactor is 9-15h. When aerating in the aerobic reactor, the air flow of the aeration is adjusted by the blower to 0.5-1.8m ³ /min; Step 9, the residence time of wastewater in the sedimentation tank is 1-8h, the function is to separate mud and water, a part of the sludge is returned to the anaerobic reactor, the supernatant is used as treated water and flows into the intermediate water tank through the outlet pipe, and the remaining sludge in the sedimentation tank is Discharge into the sludge storage tank through the sludge pipe; Step 10, adjust the booster pump, adjust the flow rate not to exceed 2.4m ³ /h, and pass through the activated carbon filter device; The device for pickling wastewater containing endocrine disruptors includes a first regulating tank, a foam separation device, a Fenton oxidation device, a reaction sedimentation tank, a ^second regulating tank, an A2/O biochemical treatment device, a sedimentation tank, an intermediate water tank, a CMF device, Activated carbon filter tank and product water tank, of which: The first regulating tank is connected to the foam separation device, the first regulating tank is connected to the waste water outlet, and the first regulating tank is connected to the CMF device and the activated carbon filter device; The foam separation device is connected with the foam breaker, and the foam separation device is connected with the Fenton oxidation device; The ferrous sulfate dosing tank is connected with the Fenton oxidation device, the hydrogen peroxide dosing tank is connected with the Fenton oxidation device, and the Fenton oxidation device is connected with the reaction precipitation tank; The calcium chloride dosing tank is connected to the reaction sedimentation tank, the PAC dosing tank is connected to the reaction sedimentation tank, the PAM dosing tank is connected to the reaction sedimentation tank, and the reaction sedimentation tank is connected to the mud storage tank. The reaction sedimentation tank is connected to the second regulating tank, and the first online pH detection device is set in the reaction sedimentation tank; The A ² /O biochemical treatment device includes anaerobic reactor, anoxic reactor and aerobic reactor; the anaerobic reactor is connected with the anoxic reactor, and the anoxic reactor is connected with the good An oxygen reactor is connected, and the aerobic reactor is connected with the sedimentation tank; The second adjustment tank is connected with the nutrient dosing tank, the second adjustment tank is connected with the anaerobic reactor in the A2/O biochemical treatment device, and a ^second online pH detection device; The sedimentation tank is connected to the anaerobic reactor in the A ² /O biochemical treatment device, the sedimentation tank is connected to the mud storage tank, the mud storage tank is connected to the plate and frame filter press, and the sedimentation tank connected with the intermediate water tank; The intermediate water tank is connected to the CMF device, the CMF device is connected to the activated carbon filter device, the activated carbon filter device is connected to the water production tank, and the water production tank is connected to the chlorine tablet dosing tank; The pickling waste water is directly passed into the first regulating tank through the waste water pipe, and the water inlet pump is arranged on the waste water pipe; The bottom of the first regulating tank is connected to the top of the foam separation device through a first water outlet pipe, and a first lift pump is arranged on the first water outlet pipe; The bottom of the second regulating tank is connected to the top of the anaerobic reactor in the A2/O biochemical treatment device through a fifth outlet pipe, and a ^second lift pump is arranged on the fifth outlet pipe; The bottom of the sedimentation tank is connected to the top of the anaerobic reactor in the A2/O biochemical treatment device through a return sludge pipe, and a sludge pump is arranged ^on the return sludge pipe; The bottom of the sludge storage tank is connected to the plate and frame filter press through a sludge outlet pipe, and a screw pump is arranged on the sludge outlet pipe; The bottom of the intermediate water tank is connected to the bottom of the CMF device through the eighth water outlet pipe, a booster pump and a self-cleaning filter are arranged on the eighth water outlet pipe, and the booster pump is connected to the self-cleaning filter; The activated carbon filter device is connected to the water production tank through the tenth water outlet pipe, and a backwash water pump is arranged on the tenth water outlet pipe; Select pipe runs as connecting elements for the individual components. 2. The method for treating pickling wastewater containing endocrine disruptors according to claim 1, wherein a stirring device is arranged in the mud storage tank, and the stirring device is a QJB submersible mixer. 3. The treatment method of pickling wastewater containing endocrine disruptors according to claim ¹ , characterized in that: the aerobic reaction tank in the A2/O biochemical treatment device is connected to a blower, and the blower is a Roots blower. 4. the treatment method containing endocrine disruptor pickling waste water according to claim 1, is characterized in that: described first lift pump, described second lift pump, described sludge pump, described screw pump, all The number of the booster pump and the backwash water pump is two. 5. The method for treating pickling wastewater containing endocrine disruptors according to claim 1, characterized in that: the treatment device is fixed in a movable device. 6. The method for treating pickling wastewater containing endocrine disruptors according to claim 5, characterized in that: the movable device is a mobile container. 7. The method for treating pickling wastewater containing endocrine disruptors according to claim 1, characterized in that: the flow rate of the inlet pump is 3m ³ /h, and the flow rate of the second lift pump is 2-3m ³ /h h, the air flow rate of the blower for aeration is 1.0-1.3m ³ /min, and the flow rate of the booster pump is 1.5-2.2m ³ /h. 8. the treatment method containing endocrine disruptor pickling waste water according to claim 1, is characterized in that: the time that stays in described adjusting tank is 48h, the time that stays in described foam separation device is 20-30min, The residence time of wastewater in the Fenton oxidation unit is 6-8h, the residence time of wastewater in the reaction sedimentation tank is 3-7h, and the residence time of wastewater in the second regulating tank is 24h. The residence time of the wastewater in the sedimentation tank is 2-6h. 9. the treatment method containing endocrine disruptor pickling waste water according to claim 1, is characterized in that: in described step 6, Fe ²⁺ and hydrogen peroxide ratio are 3:1, the quality of FeSO ₄ 7H ₂ O The percentage is 5wt%-15wt%, and the mass percent of hydrogen peroxide is 30-35wt%. 10. The method for treating pickling wastewater containing endocrine disruptors according to claim 1, characterized in that: in the step ⁸ , the total residence time of the wastewater in the A2/O biochemical treatment device is 23h, The residence time in the anoxic reactor is 4-5h, the residence time in the anaerobic reactor is 6-8h, and the residence time in the aerobic reactor is 10-13h.