CN110563093A - Membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device and process - Google Patents
Membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device and process Download PDFInfo
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- 238000004043 dyeing Methods 0.000 description 3
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Classifications
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device which comprises a wastewater storage tank (1), a multi-chamber electrolytic tank (6), a membrane integrated aeration device (18), an acid liquor high-level storage tank (28), an alkali liquor high-level storage tank (29) and a DCS computer control system, wherein a catalyst and a particle electrode are combined into a whole, a cathode is a modified porous carbon felt (7), and an anode is a ruthenium iridium titanium electrode (8). Compared with a conventional reactor, the novel membrane integrated heterogeneous three-dimensional electro-Fenton system water treatment device has the advantages of high mass transfer efficiency, good aeration effect, large wastewater treatment capacity, good treatment effect and low cost, and is particularly suitable for treating refractory organic high-salt wastewater such as dye, chemical industry, medicine, pesticide and the like.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device and process for efficiently treating organic high-salt wastewater difficult to biodegrade.
Background
With the continuous development of the chemical industry, a large amount of waste water of petrifaction, medicines, pesticides and dyes is discharged into the environment, which causes irreversible harm to water, especially a series of waste water which has various organic pollutants, complex structure, toxicity, harm and the like and can not be degraded by a biological method, which is always a key point and a difficult point in the field of waste water treatment.
The advanced oxidation technology generates hydroxyl free radicals (. OH) with extremely strong activity and oxidation capacity through different physical and chemical ways such as electricity, sound, light and the like, and the oxidation potential of the hydroxyl free radicals is 2.8V, which is second to fluorine in nature. The hydroxyl free radicals have almost no selectivity on the organic pollutants which are difficult to degrade in the wastewater, can be quickly oxidized and degraded into small molecular substances, and can even be directly mineralized into carbon dioxide and water, so that the complete degradation of the organic matters is achieved. The Fenton process is one of the advanced oxidation techniques, which passes Fe2+And H2O2The reaction takes place to produce OH with strong oxidizing property. Hydrogen peroxide presents a great risk in transportation, storage and handling; and a large amount of Fe is generated in the reaction process due to the need of adding a large amount of ferrous salt3+A large amount of iron sludge is formed, and the non-sustainable development property exists.
Heterogeneous electro-Fenton is based on the basic action mechanism of the traditional Fenton method and the Fenton-like method, and the two major components of the Fenton reagent are completely generated by electrochemical reaction without adding ferrous salt and H2O2Hydrogen peroxide is generated by reduction of dissolved oxygen in water at a cathode, and ferrous ions are replaced by a heterogeneous catalyst, so that the addition of iron salt is greatly reduced, and secondary pollution is greatly reduced. It has many advantages, its operation pH range is wide, and the catalyst is easy to separate and recover.
The three-dimensional electro-Fenton reactor overcomes a plurality of defects of a two-dimensional system by uniformly arranging porous substances or solid particles with catalytic action between electrodes on the basis of a two-dimensional electro-Fenton reactor, plays a role in enlarging the contact reaction area and improving the mass transfer rate, simultaneously combines a catalyst and a particle electrode into a whole, greatly improves the efficiency and reduces the cost.
The ceramic membrane has the characteristics of small aperture, large porosity, corrosion resistance and the like, and can ensure that oxygen molecules are better distributed and dissolved in water in a short time, thereby greatly improving the efficiency in the actual aeration process, realizing the purpose of replacing pure oxygen with low-flow air and achieving the same effect, reducing the treatment cost and avoiding the unsafe problem of the pure oxygen in transportation and storage.
Chinese patent (application No. 201420244519.X) discloses a three-dimensional electro-Fenton water treatment device which consists of a reactor, a porous electrode plate, an activated carbon-loaded zero-valent metal Fenton catalyst, a water outlet, a water inlet, a positive electrode and a negative electrode, and can remarkably improve the chroma and COD (chemical oxygen demand) in printing and dyeing wastewaterCrThe removal efficiency of the method ensures that the effluent reaches the national industrial wastewater reuse standard. Chinese patent (application number 201010168426.X) discloses a three-dimensional electrode/electro-Fenton reactor, which is provided with a mesh-shaped annular anode and a hollow columnar cathode, adopts a circular design, enables the mixing in the reactor to be uniform, has no dead angle, has high electrolysis efficiency, and can realize the purpose of treating organic wastewater difficult to degrade. Chinese patent application No. 201520413867.X discloses a simple structure, convenient installation and maintenance, which can improve the wastewater treatment effect by combining electrolysis technology with fluidized bed technology. The cleaning of the polar plate can be kept by utilizing the sweeping effect of the catalytic carrier which circulates at high speed in the operation process, so that the reaction is continuously and stably operated. Chinese patent (application No. 201611105495.X) discloses a method and apparatus for treating organic wastewater by electro-Fenton method, which uses composite catalyst to contact with organic wastewater and adsorb organic pollutants while generating Fe2+The method can be further combined with microwave, photochemical and other means to enhance the treatment effect. Chinese patent (application No. 201610971528.2) discloses a method for treating printing and dyeing wastewater by using three-dimensional electrode-electro-Fenton coupling, which adopts a flat iron plate as an anode, porous carbon as a cathode, and activated carbon columns and nano-iron binary mixed particles as a third stage, and aerates the system through an aeration device, and the stirring device stirs and applies direct current voltage stabilization at the same time.
The three-dimensional electro-Fenton organic wastewater treatment method disclosed above adopts a three-dimensional homogeneous electro-Fenton system, and the catalyst is Fe2+Or other metal ions, while improving treatment efficacy, introduce new contamination, add pressure and cost to subsequent removal, while operating in the pH rangeThe fenton reaction is not extensive, and the best effect can be achieved only under the acidic condition. The organic wastewater treatment devices disclosed above are all single electrolytic tanks, and have limited volume and treatment capacity.
Disclosure of Invention
The invention aims to provide a high-efficiency, economic and stable membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device aiming at the defects of the existing electro-Fenton technology; another object of the present invention is to provide a process for treating wastewater using the above apparatus.
The technical scheme of the invention is as follows: a membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device is characterized by comprising a wastewater storage tank, a multi-chamber electrolytic tank, a membrane integrated aeration device, an acid liquor high-level storage tank, an alkali liquor high-level storage tank and a DCS computer control system; wherein the multi-chamber electrolytic bath is internally provided with modified porous carbon felt cathodes and ruthenium iridium titanium anode plates which are alternately arranged in sequence at equal intervals, the upper end of each insulating plate for fixing the cathode is provided with an overflow port, and the lower end of each anode plate is provided with a drainage port; particle electrodes are filled between each pair of positive and negative electrodes; the water inlet pipeline, the liquid inlet pipeline and the wastewater circulating pipeline are vertically inserted into the bottom from one side of the multi-chamber electrolytic tank side by side, wherein the other end of the water inlet pipeline is connected with the wastewater storage tank through a water inlet valve, and the other end of the liquid inlet pipeline is connected with the acid liquid high-level storage tank, the alkali liquid inlet valve and the alkali liquid high-level storage tank through an acid liquid outlet valve and an acid liquid/alkali liquid inlet valve respectively; the bottom of the other side of the multi-chamber electrolytic tank is connected with an inlet of a bottom membrane component of the membrane integrated aeration device through a waste water circulating valve and a rotor flow meter by a water outlet pipeline, one side of the membrane integrated aeration device is connected with a main air inlet by an air inlet valve, and the air inlet valves are air inlet valves of the single membrane component respectively; the outlet of the membrane component at the upper end of the membrane integrated aeration device is connected with a wastewater circulating pipeline; the water outlet pipeline is connected with the water outlet through a waste water outlet valve; a DO online detector, a COD online detector and a pH online detector are sequentially arranged on the outlet pipeline; the DCS computer control system contains real-time control of all the valves and dc power supplies of the device, with all the meter readings displayed on it.
The membrane integrated aeration device is formed by connecting 1 or 2-5 membrane components in series, and the membraneThe assembly is vertically provided with 9-42 ceramic membrane tubes in a concentric circle manner; the ceramic membrane tubes are all single channels, the aperture is 50nm-3000nm, the thickness is 2-5mm, and the length is 15-50 cm. The slope theta of the hollow round tables at the upper end and the lower end of each membrane component is 60-75 degrees, and the height is 15-30 cm; the height difference h between the height of the upper end socket of the membrane integrated aeration device and the liquid level of the electrolytic bath is 0-50 cm; the main component of the ceramic membrane tube is Al2O3or ZrO2。
The particle electrode (5) is active carbon particles loaded with transition metal elements or noble metal oxides, the particle size of the active carbon particles is 1-5mm, the load elements are one or more of Pt, Pd, Rh, Mn, Fe, Cu or Ni, the load mass is 1-10%, and the filling height is flush with the overflow outlet of the cathode. The loading method is a conventional impregnation and calcination method in an air atmosphere, and the activated carbon particles are impregnated in nitrate aqueous solution of one or more elements of Pt, Pd, Rh, Mn, Fe, Cu or Ni, dried and then placed in a muffle furnace, the calcination temperature is set to be 400-600 ℃, the heating rate is 5-10 ℃/min, and the calcination time is 3-6h, so that the catalyst is obtained.
The cathode is a modified porous carbon felt cathode which is a carbon felt loaded with rare earth metal element oxides, the loaded elements are one or more of Ce, Pr, La and Nd, and the loading mass is 1-5%. The method comprises the steps of putting a carbon felt into a hydrothermal kettle by adopting a conventional hydrothermal synthesis method, adding a nitrate aqueous solution of one or more elements of Ce, Pr, La and Nd into the hydrothermal kettle, enabling the nitrate aqueous solution to submerge the carbon felt, and putting a sealing opening into an oven at 80-200 ℃ for 12-36 hours to obtain the carbon felt.
The overflow port and the drainage port are both provided with interception nets made of high-strength corrosion-resistant polytetrafluoroethylene materials, and the mesh size of the interception nets is smaller than the diameter of the particle electrode.
The DO online detector, the COD online detector and the pH online detector online monitoring equipment are all connected to the DCS computer control system; the wastewater inlet valve, the acid/alkali liquor inlet valve, the acid liquor outlet valve, the alkali liquor inlet valve, the wastewater outlet valve, the wastewater circulating valve, the inlet valves (comprising a first gas inlet valve, a second gas inlet valve, a third gas inlet valve, a fourth gas inlet valve and a fifth gas inlet valve) of the single membrane module and the direct-current power switch are connected to the DCS computer control system.
The multi-chamber electrolytic tank adopts glass fiber reinforced plastics (except electrodes) with high strength, corrosion resistance and insulating materials.
The invention also provides a process for treating wastewater by using the membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device, which comprises the following specific steps: the waste water in the waste water storage tank enters from one side of the multi-chamber electrolytic tank through a water inlet valve and a water inlet pipeline, when the water level exceeds an overflow port, the waste water overflows to the next small electrolytic tank and then flows into the next small electrolytic tank through a drainage port at the bottom, and the waste water sequentially enters the rest small electrolytic tanks according to the mode; after the wastewater is full, the wastewater flows out from the bottom of the other side of the multi-chamber electrolytic tank, then flows through a DO online detector, a COD online detector and a pH online detector through a water outlet pipeline in sequence, displays the DO value, the COD value and the pH value of the wastewater in real time and transmits the wastewater to a DCS; waste water enters the membrane integrated aeration device through the circulating valve and the rotor flow meter in sequence, when the height difference h between the liquid level of the electrolytic bath and the upper end socket of the membrane integrated aeration device is within the range of 0-50cm, the water inlet valve is closed and the pressure pump is opened at the same time, gas is blown into the membrane integrated aeration device through the total gas inlet to be aerated, and oxygen-enriched waste water flows into the waste water inlet side of the multi-chamber electrolytic bath again through the waste water circulating pipeline to form circulation; adjusting the opening degrees of an acid liquor outlet valve, an alkali liquor inlet valve and an acid/alkali liquor inlet valve by a DCS computer control system to adjust the pH to 1-9, and closing the acid liquor outlet valve, the alkali liquor inlet valve and the acid/alkali liquor inlet valve when the required pH value is reached; and adjusting the opening degree of a gas inlet valve of a single membrane module by the DCS computer control system to adjust a DO value, turning on a direct-current power switch by the DCS computer control system to electrify after the DO value is saturated, adjusting the voltage or the current to adjust the COD value of the effluent of the wastewater, closing a circulating valve and opening a wastewater outlet valve to discharge the treated wastewater after the COD value is in the range of 100-15000mg/L, then opening a water inlet valve to add the wastewater, and repeating the steps in the above way.
The wastewater treated by the process is organic high-salt wastewater, COD is 1000-50000mg/L, salt content is 0.5-200g/L, and water temperature is 25-85 ℃; the COD of the effluent is 100-15000mg/L, and the removal rate of the COD is 70-90%.
The aeration gas adopts air, oxygen or ozone. The wastewater passes through the ceramic membrane tube, high-pressure gas is filled in the shell of the membrane component and permeates through the ceramic membrane tube from outside to inside for aeration, and the aeration strength is 5-25m3/m2·h。
The retention time of the wastewater in the multi-chamber electrolytic tank is 20-200min, the pH of the wastewater in the multi-chamber electrolytic tank is adjusted to 1-9 by adopting dilute sulfuric acid with the concentration of 5-10 wt.% and NaOH solution with the concentration of 5-10 wt.%, the number of positive and negative electrode pairs is 1-20 pairs, and the current density is 5-100mA/cm2The operating voltage is 5-50V, and the control system is connected to a DCS computer control system and is adjusted in real time.
The device adopts heterogeneous electro-Fenton system to transition metal element oxide is the catalyst, when improving the treatment effect, can not produce secondary pollution, and the while operation pH scope obtains enlarging, all can reach best effect under acid and alkaline condition. The device is also provided with a plurality of electrolytic tanks, thereby greatly improving the treatment capacity and the treatment efficiency. In the dynamic circulation process, the membrane integrated aeration device strengthens the aeration efficiency, and simultaneously gives the wastewater circulating power without the assembly of a pump, so that the cost is reduced.
The invention can obtain the following effects:
(1) The traditional aeration method has low utilization rate of oxygen, the aeration device disclosed by the invention can better dissolve the oxygen in the air into the wastewater through the ceramic membrane with the nano-scale aperture, and simultaneously, the kinetic energy given by the airflow and the static pressure given by the electrolytic bath are utilized to drive the wastewater to circularly flow, so that the use of a pump is avoided, the electric power is saved, the energy consumption is reduced, and the cost is saved.
(2) The cathode used in the device is a modified carbon felt material, the modified material greatly improves the electrochemical performance of the original material, greatly improves the generation efficiency of hydrogen peroxide, and does not need H compared with the traditional Fenton oxidation technology2O2And (4) adding the medicament.
(3) The particle electrode and the catalyst are combined into one, and the catalyst has the advantages of low cost, high stability, good effect and the like, so that the addition of Fe is not required2+The reaction rate is improved while the salt is added, and the problem of secondary pollution such as iron mud does not need to be treated in the later treatment period.
Drawings
FIG. 1 is a system diagram of the membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device; wherein 1-a wastewater storage tank; 2-a water inlet valve; 3-an overflow port; 4-a drainage port; 5-a particle electrode; 6-a multi-chamber electrolytic cell; 7-porous modified cathode carbon felt electrode; an 8-ruthenium iridium titanium anode plate; 9-DO online detector; 10-COD on-line detector; 11-pH on-line detector; 12-a waste water outlet valve; 13-a waste water circulation valve; 14-a water outlet; 15-a rotameter; 16-a membrane module; 18-membrane integrated aeration device; 19-a first gas inlet valve; 20-a second gas inlet valve; 21-a third gas inlet valve; 22-a fourth gas inlet valve; 23-a fifth gas inlet valve; 24-total air intake; 25-acid/lye inlet valves; 26-an acid liquor outlet valve; 27-lye inlet valves; 28-acid liquor storage tank; 29-an alkali liquor storage tank; a-a water inlet pipeline; b-a liquid inlet pipeline; c-a waste water circulation pipeline; d-a water outlet pipeline; h-height difference between an upper end socket of the aeration device and the liquid level of the electrolytic bath;
FIG. 2 is a schematic illustration of a pair of electrodes (positive and negative); wherein 3-an overflow port at the upper end of the cathode; 4-a drainage port at the lower end of the anode plate; 7-carbon felt cathode; an 8-ruthenium iridium titanium anode plate; 30-a retention net; 31-an insulating plate to which the cathode is fixed;
FIG. 3 is a schematic view of a single membrane module; wherein theta is the gradient of the hollow truncated cones at the upper end and the lower end of the membrane integrated aeration device;
FIG. 4 is an axial cross-sectional view of a single membrane module; 17-ceramic membrane tubes.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited thereto.
Example 1
The system diagram of the membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device of the embodiment is shown in figure 1 and comprises a wastewater storage tank 1, a multi-chamber electrolytic tank 6, a membrane integrated aeration device 18, an acid liquor high-level storage tank 28, an alkali liquor high-level storage tank 29 and a DCS computer control system; wherein the multi-chamber electrolytic bath 6 is internally provided with modified porous carbon felt cathodes 7 and ruthenium iridium titanium anode plates 8 which are arranged alternately in sequence at equal intervals, the electrolytic bath is cut into a plurality of small electrolytic baths, the upper end of each insulating plate 31 for fixing the cathodes is provided with an overflow port 3, the lower end of each anode plate is provided with a drainage port 4, and the overflow port 3 and the drainage port 4 are both provided with an interception net 30 (shown in figure 2) made of high-strength corrosion-resistant polytetrafluoroethylene materials; a particle electrode 5 is filled between each pair of the positive and negative electrodes; one side of the multi-chamber electrolytic tank 6 is provided with a wastewater storage tank 1, a water inlet valve 2 and a water inlet pipeline a thereof, an acid/alkali liquid inlet valve 25 for adjusting pH and a liquid inlet pipeline b thereof, wherein the upper end of the acid/alkali liquid inlet valve 25 is connected with an acid liquid high-level storage tank 28 and an acid liquid outlet valve 26, and an alkali liquid high-level storage tank 29 and an alkali liquid inlet valve 27; the outlet of the wastewater circulating pipeline c, a water inlet pipeline a connected with the wastewater storage tank 1 through a water inlet valve 2 and a liquid inlet pipeline connected with the acid/alkali liquid high-level storage tank through an acid/alkali liquid inlet valve 25 are arranged in parallel and vertical to the bottom of the multi-chamber electrolytic tank 6 and are inserted into the bottom; the DO online detector 9, the COD online detector 10 and the pH online detector 11 are sequentially positioned on an outlet pipeline d at the bottom of the other side of the multi-chamber electrolytic tank 6, a wastewater outlet valve 12 and a wastewater outlet 14 are positioned on the left side of the outlet pipeline d, a wastewater circulating valve 13 and a rotor flow meter 15 are positioned on the right side of the outlet pipeline d, an inlet at the bottom of the membrane integrated aeration device 18 is connected with an outlet of the rotor flow meter 15, a total air inlet 24 is positioned on one side of the membrane integrated aeration device 18, and an inlet of a wastewater circulating pipeline c is connected with an outlet of a membrane component at the; online monitoring equipment of a DO online detector 9, a COD online detector 10 and a pH online detector 11 are all connected to a DCS computer control system; a wastewater inlet valve 2, an acid/alkali liquor inlet valve 25, an acid liquor outlet valve 26, an alkali liquor inlet valve 27, a wastewater outlet valve 12, a wastewater circulating valve 13, a first gas inlet valve 19, a second gas inlet valve 20, a third gas inlet valve 21, a fourth gas inlet valve 22, a fifth gas inlet valve 23 and a direct-current power switch of a single membrane module are connected to a DCS computer control system.
Opening the water inlet valve 2 to enable the wastewater in the wastewater storage tank 1 to enter from one side of the multi-chamber electrolytic tank 6 through the water inlet pipeline a; after the wastewater is full, the wastewater flows out from the bottom of the other side of the multi-chamber electrolytic tank 6 and then flows into the membrane integrated aeration device 18, when the height difference h between the liquid level of the electrolytic tank and the head at the upper end of the membrane integrated aeration device 18 is in the range of 0-50cm, the water inlet valve 2 is closed and the pressure pump is opened at the same time, the gas is blown into the membrane integrated aeration device 18 through the main gas inlet 24 for aeration, and the oxygen-enriched wastewater flows into the wastewater inlet side of the multi-chamber electrolytic tank 6 again through the wastewater circulating pipeline c to form circulation; reading out a DO value, a COD value and a pH value by a DCS computer control system, then adjusting the opening degrees of an acid liquor outlet valve 26, an alkali liquor inlet valve 27 and an acid/alkali liquor inlet valve 25 to adjust the pH value to 1-9, and closing the acid liquor outlet valve 26, the alkali liquor inlet valve 27 and the acid/alkali liquor inlet valve 25 when the required pH value is reached; adjusting the opening degrees of a first gas inlet valve 19, a second gas inlet valve 20, a third gas inlet valve 21, a fourth gas inlet valve 22 and a fifth gas inlet valve 23 of a single membrane module to adjust a DO value, turning on a direct current power switch to conduct electrification after the DO value reaches saturation, adjusting the voltage or current to adjust the COD value of the effluent water of the wastewater, closing a circulating valve 13 and opening a wastewater outlet valve 12 to discharge the treated wastewater after the COD value is in the range of 100-15000mg/L, then opening a water inlet valve 2 to add the wastewater, and performing reciprocating circulation in such a way.
Example 2
The device and the operation process of the embodiment are the same as those of embodiment 1, wherein the treated wastewater is organic high-salinity wastewater of a chemical industry enterprise, COD is 1000mg/L, salt content is 0.5g/L, and water temperature is 30 ℃. The membrane integrated aeration device adopts 1 membrane component, the ceramic membrane tube adopts a ceramic membrane with a single channel, an aperture of 500nm, a length of 50cm and a thickness of 2mm, and the main component is Al2O326 ceramic membranes are arranged, the slope of the hollow circular truncated cone at the upper end and the lower end of the device is 75 degrees, the height of the hollow circular truncated cone is 15cm, the height of an end socket at the upper end of the device is 25cm lower than the liquid level of the electrolytic tank, air is used for aeration, and the aeration intensity is 5m3/m2H; the particle size of the active carbon particle electrode is 3mm, the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, the calcining time is 3h, the load elements are metal oxides of Cu and Ni, and the load capacity is 5 wt.%; the porous carbon felt electrode adopts a hydrothermal method to load Pr oxide, the load is 3 wt.%, the hydrothermal temperature is 120 ℃, and the hydrothermal time is 24 h; the retention time of the wastewater is 30min, and the current density is 40mA/cm2The operating voltage is 10V, the number of the positive and negative electrodes is 10 pairs, and the pairs areThe pH of the wastewater is adjusted to 3 by using dilute sulfuric acid with the concentration of 5 wt.% and NaOH solution with the concentration of 5 wt.%, the COD of the effluent is 100mg/L, and the removal rate reaches 90%.
Example 3
The device and the operation process of the embodiment are the same as those of embodiment 1, wherein the treated wastewater is organic high-salinity wastewater of a certain MTO enterprise, COD is 10000mg/L, salt content is 50g/L, and water temperature is 85 ℃. The membrane integrated aeration device adopts 5 membrane components, the ceramic membrane tube adopts a single channel, the aperture is 50nm, the length is 15cm, and the thickness is 4mm, the number of the ceramic membranes is 9, and the main component of the ceramic membranes is Al2O3(ii) a The slope of the hollow truncated cone at the upper end and the lower end of the device is 60 degrees, the height is 20cm (as shown in figure 3), the height of the end socket at the upper end of the device is equal to the liquid level of the electrolytic bath, ozone is used for aeration, and the aeration intensity is 15m3/m2H; the particle size of the active carbon particle electrode is 5mm, the calcining temperature is 400 ℃, the heating rate is 8 ℃/min, the calcining time is 6h, the load elements are metal oxides of Mn and Fe, and the load capacity is 10 wt.%; the porous carbon felt electrode adopts a hydrothermal method to load Ce and La oxides, the load is 5 wt.%, the hydrothermal temperature is 80 ℃, the hydrothermal time is 36h, the retention time of wastewater is 120min, and the current density is 5mA/cm2The operating voltage is 5V, the number of positive and negative electrodes is 15 pairs, the pH value of the waste water is adjusted to 1 by using dilute sulfuric acid with the concentration of 10 wt% and 10 wt.% of NaOH solution, the COD of the effluent is 2000mg/L, and the removal rate reaches 80%.
Example 4
The device and the operation process of the embodiment are the same as those of the embodiment 1, wherein the treated wastewater is organic high-salinity wastewater of certain printing and dyeing enterprises, the COD is 50000mg/L, the salt content is 200g/L, and the water temperature is 25 ℃. The membrane integrated aeration device adopts 3 membrane components, the ceramic tube adopts a single channel ceramic membrane with the aperture of 1000nm, the length of 25cm and the thickness of 5mm, the number of the ceramic membranes is 42 (as shown in figure 4), and the main component of the ceramic membrane is ZrO2(ii) a The slope of the hollow truncated cone at the upper end and the lower end of the device is 70 degrees, the height of the hollow truncated cone is 30cm, the height of the end socket at the upper end of the device and the liquid level difference of the electrolytic bath are 50cm, the aeration is carried out by using ozone, and the aeration intensity is 25m3/m2H; of electrodes of activated carbon particlesThe particle size is 1mm, the calcination temperature is 700 ℃, the temperature rate is 10 ℃/min, the calcination time is 4h, the load elements are metal oxides of Pt and Rh, and the load amount is 1 wt.%; the porous carbon felt electrode adopts a hydrothermal method to load Ce and Pr oxides, the load is 1 wt.%, the hydrothermal temperature is 200 ℃, the hydrothermal time is 12h, the wastewater retention time is 200min, and the current density is 100mA/cm2The operating voltage is 50V, the number of positive and negative electrodes is 20 pairs, the pH of the wastewater is adjusted to 9 by using dilute sulfuric acid with the concentration of 8 wt.% and NaOH solution with the concentration of 8 wt.%, the COD of the effluent is 15000mg/L, and the removal rate reaches 70%.
Example 5
The device and the operation process of the embodiment are the same as those of the embodiment 1, wherein the treated wastewater is organic high-salinity wastewater of a pesticide enterprise, the COD is 30000mg/L, the salt content is 50g/L, and the water temperature is 40 ℃. The membrane integrated aeration device adopts 4 membrane components, the ceramic tube adopts a single channel ceramic membrane with the aperture of 3000nm, the length of 40cm and the thickness of 4mm, the number of the ceramic membranes is 26, and the main component of the ceramic membrane is Al2O3(ii) a The slope of the hollow truncated cone at the upper end and the lower end of the device is 65 degrees, the height of the hollow truncated cone is 25cm, the height of the end socket at the upper end of the device and the liquid level difference of the electrolytic bath are 10cm, oxygen is used for aeration, and the aeration intensity is 20m3/m2H; the particle size of the active carbon particle electrode is 3mm, the calcining temperature is 600 ℃, the temperature rate is 7 ℃/min, the calcining time is 5h, the load element is Pd metal oxide, and the load capacity is 3 wt.%; the porous carbon felt electrode adopts a hydrothermal method to load La and Pr oxides, the load is 4 wt.%, the hydrothermal temperature is 180 ℃, the hydrothermal time is 24h, the retention time of wastewater is 20min, and the current density is 50mA/cm2The operating voltage is 25V, the number of positive and negative electrodes is 5 pairs, the pH of the waste water is adjusted to 5 by using dilute sulfuric acid with the concentration of 7.5 wt.% and NaOH solution with the concentration of 7.5 wt.%, the COD of the effluent is 7500mg/L, and the removal rate reaches 75%.
Example 6
The device and the operation process of the embodiment are the same as those of embodiment 1, wherein the treated wastewater is organic high-salinity wastewater of a chemical industry enterprise, COD is 25000mg/L, salt content is 150g/L, and water temperature is 45 ℃. The membrane integrated aeration device adopts 2 membrane components, and the ceramic membrane tube is selected from a single membraneChannels, an inner membrane with the aperture of 200nm, the thickness of 3mm and the length of 45cm, 42 ceramic membranes, and the main component of the ceramic membranes is ZrO2(ii) a The slope of the hollow round tables at the upper end and the lower end of the device is 65 degrees, the height of the hollow round tables is 20cm, the height of the seal head at the upper end of the device is lower than the liquid level of the electrolytic tank by 35cm, air is used for aeration, and the aeration intensity is 20m3/m2H; the particle size of the active carbon particle electrode is 2mm, the calcining temperature is 600 ℃, the temperature rate is 8 ℃/min, the calcining time is 5h, the load element is Mn metal oxide, and the load capacity is 7.5 wt.%; the porous carbon felt electrode adopts a hydrothermal method to load Ce oxide, the load is 5 wt.%, the hydrothermal temperature is 150 ℃, the hydrothermal time is 36h, the retention time of wastewater is 180min, and the current density is 75mA/cm2The operating voltage is 35V, the number of positive and negative electrodes is 15 pairs, the pH value of the waste water is adjusted to 4 by using dilute sulfuric acid with the concentration of 10 wt.% and NaOH solution with the concentration of 10 wt.%, the COD of the effluent is 3750mg/L, and the removal rate reaches 85%.
Claims (10)
1. A membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device is characterized by consisting of a wastewater storage tank (1), a multi-chamber electrolytic tank (6), a membrane integrated aeration device (18), an acid liquor high-level storage tank (28), an alkali liquor high-level storage tank (29) and a DCS computer control system; wherein the multi-chamber electrolytic bath (6) is internally provided with modified porous carbon felt cathodes (7) and ruthenium iridium titanium anode plates (8) which are alternately arranged in sequence at equal intervals, the upper end of each insulating plate (31) for fixing the cathodes is provided with an overflow port (3), and the lower end of each anode plate is provided with a drainage port (4); particle electrodes (5) are filled between each pair of positive and negative electrodes; a water inlet pipeline (a), a liquid inlet pipeline (b) and a wastewater circulating pipeline (c) are vertically inserted into the bottom of the multi-chamber electrolytic tank (6) side by side, wherein the other end of the water inlet pipeline (a) is connected with a wastewater storage tank (1) through a water inlet valve (2), and the other end of the liquid inlet pipeline (b) is respectively connected with an acid/alkali liquor inlet valve (25) through an acid/alkali liquor outlet valve (26) and an acid liquor high-level storage tank (28), an alkali liquor inlet valve (27) and an alkali liquor high-level storage tank (29); the bottom of the other side of the multi-chamber electrolytic tank (6) is connected with an inlet of a bottom membrane component (16) of the membrane integrated aeration device (18) through a waste water circulating valve (13) and a rotor flow meter (15) by a water outlet pipeline (d), and one side of the membrane integrated aeration device (18) is connected with a total air inlet (24) by a gas inlet valve; the outlet of the membrane component (16) at the upper end of the membrane integrated aeration device (18) is connected with a wastewater circulating pipeline (c); the water outlet pipeline (d) is connected with the water outlet (14) through a waste water outlet valve (12); a DO online detector (9), a COD online detector (10) and a pH online detector (11) are sequentially arranged on the outlet pipeline (d); the DCS computer control system contains real-time control of all the valves and dc power supplies of the device, with all the meter readings displayed on it.
2. The membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device according to claim 1, wherein the membrane integrated aeration device (18) is composed of 1 or 2-5 membrane modules (16) connected in series, and the membrane modules (16) are vertically arranged with 9-42 ceramic membrane tubes (17) in a concentric circle manner; the ceramic membrane tubes (17) are all single channels, the aperture is 50-3000nm, the thickness is 2-5mm, and the length is 15-50 cm; the slope theta of the hollow round tables at the upper end and the lower end of each membrane component (16) is 60-75 degrees, and the height is 15-30 cm; the height difference h between the upper end socket of the membrane integrated aeration device (18) and the liquid level of the electrolytic bath is 0-50 cm.
3. The membrane integrated heterogeneous three-dimensional electro-fenton chemical wastewater treatment device according to claim 1, wherein the particle electrode (5) is activated carbon particles loaded with transition metal elements or noble metal oxides, the particle size of the activated carbon particles is 1-5mm, the loading elements are one or more of Pt, Pd, Rh, Mn, Fe, Cu or Ni, and the loading mass is 1-10%; the filling height is flush with the cathode overflow outlet.
4. the membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device according to claim 1, wherein the cathode is a modified porous carbon felt cathode (7) which is a carbon felt loaded with rare earth metal oxides, the loaded elements are one or more of Ce, Pr, La and Nd, and the loading mass is 1-5%.
5. The membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device according to claim 1, wherein the overflow port (3) and the drainage port (4) are both provided with an interception net (30) made of high-strength corrosion-resistant polytetrafluoroethylene materials, and the mesh number of the interception net is smaller than the diameter of the particle electrode (5).
6. The membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device according to claim 1, wherein online monitoring equipment of a DO online detector (9), an COD online detector (10) and a pH online detector (11) are connected to a DCS computer control system; a wastewater inlet valve (2), an acid/alkali liquor inlet valve (25), an acid liquor outlet valve (26), an alkali liquor inlet valve (27), a wastewater outlet valve (12), a wastewater circulating valve (13), an inlet valve of a single membrane component and a direct-current power switch are connected to a DCS computer control system.
7. A process for treating wastewater by using the membrane integrated heterogeneous three-dimensional electro-Fenton chemical wastewater treatment device of claim 1, comprising the following specific steps: wastewater in the wastewater storage tank (1) enters from one side of the multi-chamber electrolytic tank (6) through a water inlet pipe (a) by a water inlet valve (2), overflows to the next small electrolytic tank when the water level exceeds an overflow port (3), then flows into the next small electrolytic tank through a drainage port (4) at the bottom, and sequentially enters the rest small electrolytic tanks according to the mode; after the wastewater is full, the wastewater flows out from the bottom of the other side of the multi-chamber electrolytic tank (6), then sequentially flows through a DO online detector (9), a COD online detector (10) and a pH online detector (11) through a water outlet pipeline (d), displays the DO value, the COD value and the pH value of the wastewater in real time and transmits the wastewater to a DCS; waste water enters the membrane integrated aeration device (18) through the circulating valve (13) and the rotor flow meter (15) in sequence, when the height difference h between the liquid level of the electrolytic bath and the upper end socket of the membrane integrated aeration device (18) is in the range of 0-50cm, the water inlet valve (2) is closed and the booster pump is opened at the same time, gas is blown into the membrane integrated aeration device (18) through the main gas inlet (24) for aeration, and oxygen-enriched waste water flows into the waste water inlet side of the multi-chamber electrolytic bath (6) again through the waste water circulating pipeline (c) to form circulation; adjusting the opening degrees of an acid liquor outlet valve (26), an alkali liquor inlet valve (27) and an acid/alkali liquor inlet valve (25) by a DCS computer control system to adjust the pH to 1-9, and closing the acid liquor outlet valve (26), the alkali liquor inlet valve (27) and the acid/alkali liquor inlet valve (25) when the required pH value is reached; the DCS computer control system adjusts the opening degree of the single membrane module gas inlet valves (19) - (23) to adjust the DO value, when the DO value is saturated, the DCS computer control system opens the direct current power switch to conduct power on, and adjusts the voltage or the current to adjust the COD value of the wastewater effluent, when the COD value is in the range of 100-15000mg/L, the circulating valve (13) is closed, the wastewater outlet valve (12) is opened to discharge the treated wastewater, then the water inlet valve (2) is opened to add the wastewater, and the steps are repeated and circulated.
8. The process according to claim 7, characterized in that the treated wastewater is organic high-salt wastewater, COD is 1000-50000mg/L, salt content is 0.5-200g/L, water temperature is 25-85 ℃; the COD of the effluent is 100-15000mg/L, and the removal rate of the COD is 70-90%.
9. The process according to claim 7, wherein the aeration gas is air, oxygen or ozone; the wastewater passes through the ceramic membrane tube (17), high-pressure gas is filled in the shell of the membrane component (16), and the wastewater permeates through the ceramic membrane tube from outside to inside for aeration, wherein the aeration strength is 5-25m3/m2·h。
10. The process as claimed in claim 7, characterized in that the retention time of the wastewater in the multi-chamber electrolytic cell is 20-200min, and the pH of the wastewater in the multi-chamber electrolytic cell (6) is adjusted to 1-9 by using dilute sulfuric acid with a mass concentration of 5-10% and NaOH solution with a mass concentration of 5-10%; the number of the positive and negative electrode pairs is 1-20 pairs, and the current density is 5-100mA/cm2The operating voltage is 5-50V.
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