CN110204031B - Optical Fenton-forward osmosis integrated device for combined treatment of biologically refractory organic wastewater and its use method - Google Patents
Optical Fenton-forward osmosis integrated device for combined treatment of biologically refractory organic wastewater and its use method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明涉及一种光芬顿‑正渗透联合处理生物难降解有机废水的一体化装置及其使用方法，该装置包括光芬顿单元和浸没式正渗透单元。使用该装置进行水处理的方法包括光芬顿过程和正渗透过程，利用光芬顿处理单元有效降解或转化有机污染物的同时，利用正渗透膜选择透过性截留光芬顿过程降解或转化不完全的有机污染物，浸没式正渗透单元采用浸没式正渗透结构，无需进水端循环泵及进水罐体，整体结构紧凑、能耗低、易与其他工艺或装置联合。光芬顿单元产生的活性物质在污染物降解转化及在向正渗透单元迁移过程中耗尽，其强氧化性不会影响膜的稳定性，废水处理率高、效果好，适用于推广使用。
The invention relates to an integrated device for combined optical Fenton-forward osmosis treatment of biologically refractory organic wastewater and a method for using the same. The device comprises an optical Fenton unit and a submerged forward osmosis unit. The method of using the device for water treatment includes a photo-Fenton process and a forward osmosis process. While the photo-Fenton treatment unit is used to effectively degrade or convert organic pollutants, the selective permeability of the forward osmosis membrane is used to intercept the photo-Fenton process. Complete organic pollutants, the submerged forward osmosis unit adopts a submerged forward osmosis structure, without the need for a circulating pump at the inlet end and a water inlet tank, the overall structure is compact, the energy consumption is low, and it is easy to combine with other processes or devices. The active substances produced by the photo-Fenton unit are depleted in the process of pollutant degradation and transformation and migration to the forward osmosis unit. Its strong oxidizing property will not affect the stability of the membrane, and the wastewater treatment rate is high and the effect is good, which is suitable for popularization and use.
Description
Technical Field
The invention belongs to the field of wastewater treatment, relates to a wastewater biodegradation advanced treatment technology, and particularly relates to an integrated device for treating biologically-refractory organic wastewater by combining photo-Fenton and forward osmosis and a use method thereof.
Background
With the rapid development of modern industry and related industries, the types of pollutants in industrial wastewater increase year by year, so that the industrial wastewater has the characteristics of complex components, high pollution load, high toxicity risk and the like. The current industrial wastewater treatment process usually adopts an aerobic-anaerobic combined microbial method to remove organic pollutants so as to achieve the purpose of reducing COD, however, the potential toxicity and the biological degradation difficulty (BOD) of some organic pollutants difficult to degrade5/COD<0.4), the degradation and conversion of organic pollutants can not be effectively realized by a microbiological method (including a membrane bioreactor MBR), and finally, the organic pollutants are accumulated in the wastewater, and the effluent can not meet the emission standard and threatens the ecological environment. The traditional pressure membrane technologies such as nanofiltration, reverse osmosis and the like are associated with a large amount of high-concentration organic wastewater during the production of purified water, further treatment is needed, and the problem of membrane pollution is also that the membrane passing is restrictedTechnical pain points and difficulties of process popularization and application; the adsorption method has problems of treatment and disposal such as regeneration and recovery of the adsorbent.
Compared with the physical and biological treatment process, the Fenton reagent (H) is used as an important branch in the chemical water treatment process, namely an advanced oxidation technology represented by a Fenton (Fenton) process2O2And Fe2+) The generated strong oxidation active substances are not selectively degraded or even completely mineralized to organic pollutants, thereby effectively improving the biodegradability of the wastewater and improving the effluent quality and the wastewater reuse rate. However, the traditional Fenton process has strict requirements on the pH of inlet water, and H is generated in the treatment process2O2The usage amount is large, and iron mud is easy to generate. The derivative light-Fenton technology overcomes the defects of the traditional Fenton, and has mild reaction conditions and H2O2Low use amount, no secondary pollution and the like, and shows potential industrial application prospect in the field of high-concentration hardly biodegradable organic wastewater.
The invention discloses a device for deeply treating coal chemical wastewater through photo-Fenton catalytic oxidation and a use method thereof (CN105236510A), wherein the coal chemical wastewater contains a large amount of phenols, polycyclic aromatic compounds, cyanogen, oil, ammonia nitrogen and other toxic and harmful substances, so that the environment is easily polluted. The device has the advantages that the removal rate of COD and ammonia nitrogen in the coal chemical industry wastewater reaches more than 95 percent, but the removal efficiency of soluble salt in the wastewater, such as CN-plasma, is not mentioned; the process adopts Prussian blue immobilized active carbon as a catalyst, and the heterogeneous Fenton catalyst relates to the post-treatment problems of recycling and the like; the service life of the used ultraviolet lamp source is short, the permeability in the waste water is poor, and the operation efficiency and the stability of the system are influenced; the ultraviolet lamp source generates heat seriously, and the added temperature control system increases the complexity and the energy consumption of the device.
The invention relates to a photo-Fenton reactor for treating refractory organic wastewater (CN207210048U), which adopts an ultraviolet light-emitting diode as a light source to overcome the defects of the traditional ultraviolet lamp in the photo-Fenton process, but FeSO is used as the reactor4Is a homogeneous photo-Fenton catalyst, Fe in the wastewater treatment process2+Is easy to be oxidized and enters the water outlet chamber above the reactor through the middle flow guide pipe, and homogeneous phase is caused if the subsequent treatment unit is not addedThe catalyst runs off and finally influences the quality of the effluent.
The invention discloses a method for treating sewage through ultraviolet light-assisted heterogeneous Fenton oxidation, wherein a photo-Fenton catalyst is an immobilized catalyst membrane with mesoporous pore channels, the configuration solves the problem of heterogeneous Fenton catalyst recovery, the decolorization rate of a model to low-concentration dye wastewater exceeds 90%, but the effective catalytic area and the treated water amount of the membrane catalyst are limited, the installation and the maintenance are difficult, and the water flow impact resistance is weak. The device adopts the traditional ultraviolet light source, which is easy to cause the problem in the invention patent CN 105236510A.
The forward osmosis process is a membrane process which is driven by osmotic pressure difference and spontaneously performed, no additional driving force is needed, the energy consumption required by water production is low, the structure of a pollutant layer on the outer side of the membrane is loose, the problem of compactness of a pollutant layer on the surface of the membrane caused by high-pressure driving in the traditional pressure membrane process is solved, and the forward osmosis process is combined with other processes to be used for treating waste (polluted) water. However, in the process of single forward osmosis, due to the selective interception of the membrane, the concentration of pollutants outside the membrane is continuously increased, so that the phenomenon of external concentration polarization is easily caused, the water production efficiency is influenced, and the high-concentration organic pollutant wastewater at the water inlet end needs to be further treated and disposed after the forward osmosis process.
Disclosure of Invention
The invention aims to overcome the defects of single photo-Fenton and forward osmosis membrane processes and devices for treating biologically-nondegradable organic wastewater in the prior art, and considers the great difficulty in treating the biologically-nondegradable organic wastewater and the potential harm to the ecological environment, and provides an integrated device for biologically-nondegradable organic wastewater and a using method thereof.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
an integrated device for treating biologically-refractory organic wastewater by using photo-Fenton-forward osmosis combination comprises photo-phenolThe optical Fenton unit is connected with the immersed forward osmosis unit and comprises a lift pump and an H2O2/H2SO4The submerged forward osmosis unit comprises a forward osmosis unit water inlet pool, a liquid suction tank and a suction pump, and H2O2/H2SO4The feeding tank and the lift pump are respectively connected with an inlet of the stainless steel columns in series connection through pipelines, a quartz tube is arranged in each stainless steel column in series connection, ultraviolet light or visible light emitting diodes are arranged in the quartz tubes, glass beads loaded with photo-Fenton catalysts are filled outside each quartz tube, a plate-frame type forward osmosis membrane assembly is arranged in the forward osmosis unit water inlet tank, a drawing liquid input tube is connected to the lower end of the plate-frame type forward osmosis membrane assembly, the other end of the drawing liquid input tube is connected to a drawing liquid tank through a drawing pump, a drawing liquid output tube is connected above the drawing liquid tank, and the other end of the drawing liquid output tube is connected to the upper end of the plate-frame type forward osmosis membrane assembly.
And the inlet and outlet ends of each series stainless steel column are provided with filter screens, and the diameter of each filter screen of the series stainless steel columns is smaller than the outer diameter of each glass bead.
And the plate-frame forward osmosis membrane component is immersed in the forward osmosis unit water inlet pool, a forward osmosis membrane active layer of the forward osmosis membrane component is contacted with the effluent of the photo-Fenton unit, and a forward osmosis membrane mechanical supporting layer is contacted with the drawing liquid.
And, said H2O2/H2SO4The material of the feeding tank and the stainless steel columns connected in series is titanium steel.
A method for using an integrated device for treating biologically-refractory organic wastewater by combining photo-Fenton and forward osmosis comprises the following steps:
(1) the light-Fenton process is carried out in a light-Fenton unit, wastewater containing the pollutants difficult to degrade biologically flows through the light-Fenton unit, an ultraviolet light or visible light emitting diode provides ultraviolet light or visible light, and glass beads loaded with a light-Fenton catalyst are irradiated by the ultraviolet light or the visible light and then react with H2O2Active substances such as hydroxyl radical OH & are generated, and the organic pollutants which are difficult to degrade and are biologically in the wastewater are degraded or converted in a short time and high efficiency;
(2) the forward osmosis process is carried out in an immersed forward osmosis unit, wastewater after passing through a photo-Fenton unit flows into a forward osmosis unit water inlet tank, a plate-frame forward osmosis membrane assembly is immersed in the forward osmosis unit water inlet tank, high-concentration draw solution flows from bottom to top in the plate-frame membrane assembly, osmotic pressure difference is formed on two sides of the forward osmosis membrane due to the fact that the draw solution osmotic pressure is higher than the wastewater osmotic pressure, under the driving of the osmotic pressure difference, purified water in the forward osmosis unit water inlet tank penetrates through the forward osmosis membrane to diffuse towards the draw solution side, and organic pollutants which are not completely degraded or converted in the photo-Fenton process are effectively retained in a forward osmosis unit water inlet tank outside the membrane;
(3) the wastewater treated in the steps (1) and (2) can be further used with a biological method or other physical and chemical method water treatment processes, so that the wastewater treatment rate and the reuse rate are improved.
And (3) after the wastewater treated in the step (1) is discharged from the photo-Fenton unit, the wastewater can be returned to the photo-Fenton unit for advanced treatment again according to the water quality.
Moreover, the photo-Fenton process is operated at a pH of less than or equal to 7.
Moreover, the glass beads supporting the photo-Fenton catalyst include glass beads of an ultraviolet photo-Fenton catalyst and glass beads of a visible light photo-Fenton catalyst.
Moreover, the preparation method of the ultraviolet light Fenton catalyst glass bead is as follows: dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at the temperature of more than 100 ℃, repeatedly rinsing and drying the product by using ethanol and water to obtain cobalt/iron layered double metal hydroxide (3D-LDHs) with a 3D structure, dispersing the 3D-LDHs in 0g-10g/L ferric chloride, immersing the glass beads in 0g-10g/L tannic acid solution for 20-60 minutes, immersing the glass beads coated with tannic acid in the ferric chloride dispersed with the 3D-LDHs again, and repeatedly rinsing and drying by using ultrapure water to obtain the glass beads loaded with the Fenton catalyst.
Moreover, the preparation method of the visible light Fenton catalyst glass beads comprises the following steps: heating melamine to 550 ℃ at a heating rate of 2.3 ℃ per minute, heating to 500 ℃ at a heating rate of 5 ℃ per minute to prepare graphite-phase carbon nitride (g-C3N4), dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, adding g-C3N4, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at a temperature of more than 100 ℃ for a certain time, repeatedly rinsing and drying the product with ethanol and water to prepare graphite-phase carbon nitride loaded cobalt/iron layered double metal hydroxide (g-C3N4/3D-LDHs) with a 3D structure, dispersing the g-C3N4/3D-LDHs in 0g-10g/L ferric chloride, immersing glass beads in 0g-10g/L tannic acid solution for 20-60min, and immersing the glass beads coated with the tannic acid into ferric chloride dispersed with g-C3N4/3D-LDHs for a certain time, and repeatedly rinsing and drying by ultrapure water to obtain the visible light photo-Fenton catalyst glass beads.
The invention has the advantages and positive effects that:
1. the device has the advantages that the photo-Fenton treatment unit can reduce the concentration of pollutants difficult to degrade biologically, relieve the phenomenon of concentration polarization outside the forward osmosis process, further reduce the organic pollution load and organic pollution risk of the forward osmosis membrane, and simultaneously solve the problem of treatment of high COD (chemical oxygen demand) concentrated water at the water inlet end after the traditional membrane process is operated; the ultraviolet light can effectively get rid of the microorganism in the waste water among the light fenton processing unit, saves complicated waste water preliminary treatment bacteria removing device and process, has eliminated forward osmosis membrane microbial contamination risk.
2. This device light fenton unit adopts filled type configuration, the glass pearl of light fenton catalyst load is filled around the light source, light energy utilization is high, it is easier to retrieve and recycle to compare the granular light fenton catalyst of receiving a little level, and the glass pearl of light fenton catalyst load has reduced the pollution risk and the solid-supported light fenton coating catalyst of receiving a little heterogeneous light fenton catalyst to low reaches forward osmosis membrane and has compared, the filled type structure is closely porous, light fenton catalyst half-packing mode does not influence water and pollutant mass transfer, water impact resistance can the reinforce.
3. The device adopts the ultraviolet light emitting diode as the light Fenton light source, overcomes the problems of large heat productivity and low energy density of the traditional ultraviolet lamp, and does not need to install an additional cooling system.
4. This device is when utilizing the effective degradation of light fenton processing unit or conversion organic pollutant, utilize positive osmotic membrane selective permeability to hold back light fenton process degradation or the incomplete organic pollutant of conversion, the positive osmotic unit of submergence formula adopts the positive osmotic structure of submergence, need not into water end circulating pump and the jar body of intaking, overall structure is compact, the energy consumption is low, easily unite with other technology or device, the active material that light fenton unit produced is degrading the conversion and being exhausted to positive osmotic unit migration in-process, its strong oxidizing property can not influence the stability of membrane, the waste water treatment rate is high, and is good in effect, and is suitable for being generalized to use.
Drawings
Fig. 1 is a schematic structural diagram of the present invention, wherein:
1-Lift Pump, 2-H2O2/H2SO4The device comprises a feeding tank, 3-stainless steel columns connected in series, 4-quartz tubes, 5-ultraviolet light or visible light emitting diodes, 6-glass beads loaded with a photo-Fenton catalyst, 7-filter screens, 8-plate frame type forward osmosis membrane components, 9-a drawing liquid input tube, 10-a drawing pump, 11-a drawing liquid tank, 12-a drawing liquid output tube and 13-a forward osmosis unit water inlet tank.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
The utility model provides an integrated device of biological difficult degradation organic waste water is jointly handled to light fenton-just infiltration, as shown in figure 1, including light fenton unit and submergence formula just infiltration unit, the positive infiltration unit of submergence formula is connected to light fenton unit, light fenton list including elevator pump 1, H2O2/H2SO4A feeding tank 2 and a stainless steel column 3 connected in series, wherein the immersed forward osmosis unit comprises a forward osmosis unit water inlet tank 13, a liquid drawing tank 11 and a drawing pump 10, H2O2/H2SO4The feed tank and the lift pump are respectively connected with the string through pipelinesThe stainless steel column is connected with the inlet, a quartz tube 4 is arranged in each series stainless steel column, an ultraviolet light or visible light emitting diode 5 is arranged in each quartz tube, quartz materials are selected for the quartz tubes to ensure effective transmission of ultraviolet light/visible light, glass beads 6 loaded with photo-Fenton catalysts are filled outside each quartz tube, a filter screen 7 is arranged at the inlet and outlet end of each series stainless steel column, and the filter screens can effectively prevent the glass beads loaded with the photo-Fenton catalysts from flowing and being washed away due to waste water and losing from the stainless steel columns.
Blending H2O2/H2SO4The wastewater flows in from the inlet on the left side of the stainless steel column in series in sequence, reaches the bottom of the stainless steel column through the glass beads loaded with the photo-Fenton catalyst under the action of gravity, and then flows to the right side of the stainless steel column in series in sequence, and the gaps among the photo-Fenton catalysts ensure that the wastewater is in full contact with the glass beads loaded with the photo-Fenton catalyst and the mass transfer of the wastewater and pollutants is not influenced.
The forward osmosis unit intake pond in be provided with plate and frame forward osmosis membrane subassembly 8, this plate and frame forward osmosis membrane subassembly submergence is in the forward osmosis unit intake pond, is connected with the liquid input tube 9 of drawing at plate and frame forward osmosis membrane subassembly lower extreme, the liquid input tube other end of drawing is connected to the fluid reservoir of drawing through the pump of drawing. A drawing liquid output pipe 12 is connected above the drawing liquid tank, and the other end of the drawing liquid output pipe is connected to the upper end of the plate-frame type forward osmosis membrane component.
And the outlet water of the photo-Fenton unit flows into a water inlet pool of the forward osmosis unit until the plate-frame forward osmosis membrane component is immersed. And the draw solution is stored in a draw solution tank, is conveyed by a draw pump, enters from the lower part of the plate-frame type forward osmosis membrane component through a draw solution input pipe, and circularly flows from bottom to top in the plate-frame type forward osmosis membrane component. Because of drawing liquid osmotic pressure and being higher than waste water osmotic pressure, form osmotic pressure difference in positive osmotic membrane both sides, under osmotic pressure difference's drive, the pure water permeates the positive osmotic membrane and draws liquid side diffusion in the positive osmotic unit intake pool, and the organic pollutant that light fenton process degradation or conversion are incomplete is effectively detained in the positive osmotic unit intake pool outside the positive osmotic membrane. And the drawing liquid in the plate-frame forward osmosis membrane component is diluted due to the entering of purified water, and the diluted drawing liquid flows out from a drawing liquid output pipe at the upper end of the plate-frame forward osmosis membrane component and then enters a drawing liquid tank for recycling.
A method for using an integrated device for treating biologically-refractory organic wastewater by combining photo-Fenton and forward osmosis comprises the following steps:
(1) the light-Fenton process is carried out in a light-Fenton unit, wastewater containing the pollutants difficult to degrade biologically flows through the light-Fenton unit, an ultraviolet light or visible light emitting diode provides ultraviolet light or visible light, and glass beads loaded with a light-Fenton catalyst are irradiated by the ultraviolet light or the visible light and then react with H2O2And (2) generating active substances such as hydroxyl radicals OH & and the like, efficiently degrading or converting biologically-nondegradable organic pollutants in the wastewater in a short time, operating the photo-Fenton process under the condition that the pH value is less than or equal to 7, and returning the wastewater treated in the step (1) to the photo-Fenton unit for advanced treatment again according to the water quality after the wastewater is discharged from the photo-Fenton unit.
(2) The forward osmosis process is carried out in the immersed forward osmosis unit, wastewater after passing through the photo-Fenton unit flows into a forward osmosis unit water inlet pool, the plate-frame forward osmosis membrane assembly is immersed in the forward osmosis unit water inlet pool, high-concentration draw liquid flows from bottom to top inside the plate-frame membrane assembly, the draw liquid osmotic pressure is higher than the wastewater osmotic pressure, osmotic pressure difference is formed on two sides of the forward osmosis membrane, under the driving of the osmotic pressure difference, purified water in the forward osmosis unit water inlet pool penetrates through the forward osmosis membrane to diffuse towards the draw liquid side, and organic pollutants which are not completely degraded or converted in the photo-Fenton process are effectively retained in the forward osmosis unit water inlet pool outside the membrane.
(3) The wastewater treated in the steps (1) and (2) can be further used with a biological method or other physical and chemical method water treatment processes, so that the wastewater treatment rate and the reuse rate are improved.
The glass beads supporting the photo-Fenton catalyst include ultraviolet light photo-Fenton catalyst glass beads and visible light photo-Fenton catalyst glass beads. The preparation method of the ultraviolet light Fenton catalyst glass bead comprises the following steps: dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at the temperature of more than 100 ℃, repeatedly rinsing and drying the product by using ethanol and water to obtain cobalt/iron layered double metal hydroxide (3D-LDHs) with a 3D structure, dispersing the 3D-LDHs in 0g-10g/L ferric chloride, immersing the glass beads in 0g-10g/L tannic acid solution for 20-60 minutes, immersing the glass beads coated with tannic acid in the ferric chloride dispersed with the 3D-LDHs again, and repeatedly rinsing and drying by using ultrapure water to obtain the glass beads loaded with the Fenton catalyst. The preparation method of the visible light photo-Fenton catalyst glass bead comprises the following steps: heating melamine to 550 ℃ at a heating rate of 2.3 ℃ per minute, heating to 500 ℃ at a heating rate of 5 ℃ per minute to prepare graphite-phase carbon nitride (g-C3N4), dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, adding g-C3N4, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at a temperature of more than 100 ℃ for a certain time, repeatedly rinsing and drying the product with ethanol and water to prepare graphite-phase carbon nitride loaded cobalt/iron layered double metal hydroxide (g-C3N4/3D-LDHs) with a 3D structure, dispersing the g-C3N4/3D-LDHs in 0g-10g/L ferric chloride, immersing glass beads in 0g-10g/L tannic acid solution for 20-60min, and immersing the glass beads coated with the tannic acid into ferric chloride dispersed with g-C3N4/3D-LDHs for a certain time, and repeatedly rinsing and drying by ultrapure water to obtain the visible light photo-Fenton catalyst glass beads.
H of the device2O2/H2SO4The material of the feeding tank is titanium steel, the serial stainless steel column is cylindrical, and the material is also titanium steel. The light Fenton light source is an ultraviolet light or visible light emitting diode, and an additional cooling system is not required to be installed. The light-Fenton light source in the light-Fenton unit can be started simultaneously or intermittently. The light-Fenton unit adopts a filling type configuration, glass beads loaded by the light-Fenton catalyst are filled around the light source, and the filling height is slightly higher than that of the light source. The photo-Fenton catalyst in the glass beads loaded with the photo-Fenton catalyst is an iron-based catalyst thin film layer which is synthesized by a chemical method and has an ultraviolet or visible light Fenton catalytic effect. The glass beads loaded with the photo-Fenton catalyst can be recycled and then modified so as to ensure the photo-Fenton catalytic activity and the recycling rate of the glass beads.
The diameter of the filter screen of the series stainless steel column is smaller than the outer diameter of the glass beads, so that the glass beads loaded with the photo-Fenton catalyst in the series stainless steel column are prevented from being lost due to flowing scouring of wastewater. The drawing liquid adopts high-concentration salt solution with the osmotic pressure higher than that of the wastewater. Each group of plate-frame forward osmosis membrane assemblies consists of two forward osmosis membranes, wherein the active layers of the forward osmosis membranes are outwards contacted with the effluent of the photo-Fenton unit, and the mechanical supporting layers of the forward osmosis membranes are inwards contacted with the drawing liquid. The absorption liquid can be recycled by the absorption liquid recovery device.
The plate-frame forward osmosis membrane component is immersed in the forward osmosis unit water inlet pool, a forward osmosis membrane active layer of the forward osmosis membrane component is in contact with the outlet water of the photo-Fenton unit, and a forward osmosis membrane mechanical supporting layer is in contact with the drawing liquid. The plate-frame forward osmosis membrane component membrane can be CTA-ES (American HTI), CTA-W, CTA-NW (cellulose triacetate) forward osmosis membrane, TFC-ES polyamide thin-layer composite membrane, and Aquaporin-TFC Aquaporin-polyamide thin-layer composite membrane;
through many times of experiments, the water treatment effect is good, and the specific test data is as follows:
the pH is adjusted to be acidic, the ultraviolet light/visible light emitting diode is started for 30min-180min, the removal rate of the photo-Fenton unit to the COD of the hardly biodegradable organic wastewater reaches more than 80%, and the removal rate of the TOC reaches more than 60%; when the active layer of the plate-frame forward osmosis membrane assembly membrane goes out of water towards the photo-Fenton unit, the removal rate of COD is over 80 percent.
The invention can treat not only the organic wastewater which is difficult to be degraded biologically, but also the wastewater containing soluble salt, heavy metal ions and microorganisms, and can also be combined with other physical, chemical and biological water treatment processes and devices to treat the wastewater. From the above description, those skilled in the art can make various changes and modifications within the scope of the technical idea of the present invention without departing from the scope of the present invention. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (7)
1. Integration of biological difficult degradation organic waste water is handled in combination of light fenton-forward osmosisThe device is characterized in that: including positive infiltration unit of light fenton unit and submergence formula, positive infiltration unit of submergence formula is connected to light fenton unit, light fenton list include elevator pump, H2O2/H2SO4The submerged forward osmosis unit comprises a forward osmosis unit water inlet pool, a liquid suction tank and a suction pump, and H2O2/H2SO4The feeding tank and the lift pump are respectively connected with inlets of serial stainless steel columns through pipelines, a quartz tube is arranged in each serial stainless steel column, an ultraviolet light or visible light emitting diode is arranged in each quartz tube, glass beads loaded with a photo-Fenton catalyst are filled outside each quartz tube, a plate-frame type forward osmosis membrane assembly is arranged in the forward osmosis unit water inlet tank, the lower end of the plate-frame type forward osmosis membrane assembly is connected with a drawing liquid input tube, the other end of the drawing liquid input tube is connected to a drawing liquid tank through a drawing pump, a drawing liquid output tube is connected above the drawing liquid tank, the other end of the drawing liquid output tube is connected to the upper end of the plate-frame type forward osmosis membrane assembly, and the glass beads loaded with the photo-Fenton catalyst comprise ultraviolet light Fenton catalyst glass beads and visible light Fenton catalyst glass beads;
the preparation method of the ultraviolet light Fenton catalyst glass bead comprises the following steps: dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at the temperature of more than 100 ℃, repeatedly rinsing and drying the product by using ethanol and water to obtain cobalt/iron layered double metal hydroxide (3D-LDHs) with a 3D structure, dispersing the 3D-LDHs in 0g-10g/L ferric chloride, immersing glass beads in 0g-10g/L tannic acid solution for 20-60 minutes, immersing the glass beads coated with tannic acid on the surface in the ferric chloride dispersed with the 3D-LDHs again, and repeatedly rinsing and drying by using ultrapure water to obtain the glass beads loaded with the Fenton catalyst;
the preparation method of the visible light Fenton catalyst glass bead comprises the following steps: heating melamine to 550 ℃ at a heating rate of 2.3 ℃ per minute, heating to 500 ℃ at a heating rate of 5 ℃ per minute to prepare graphite-phase carbon nitride (g-C3N4), dissolving 0-10mmol of cobalt nitrate, ferrous sulfate, ammonium fluoride and urea in deionized water, fully stirring and mixing, adding g-C3N4, transferring the mixed solution to a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at a temperature of more than 100 ℃ for a certain time, repeatedly rinsing and drying the product with ethanol and water to prepare graphite-phase carbon nitride loaded cobalt/iron layered double metal hydroxide (g-C3N4/3D-LDHs) with a 3D structure, dispersing the g-C3N4/3D-LDHs in 0g-10g/L ferric chloride, immersing glass beads in 0g-10g/L tannic acid solution for 20-60min, and immersing the glass beads coated with the tannic acid into ferric chloride dispersed with g-C3N4/3D-LDHs for a certain time, and repeatedly rinsing and drying by ultrapure water to obtain the visible light photo-Fenton catalyst glass beads.
2. The integrated device for treating hardly biodegradable organic wastewater by using the combination of photo-Fenton and forward osmosis according to claim 1, wherein: and the inlet and outlet ends of each series stainless steel column are respectively provided with a filter screen, and the diameter of the filter screen of each series stainless steel column is smaller than the outer diameter of the glass beads.
3. The integrated device for treating hardly biodegradable organic wastewater by using the combination of photo-Fenton and forward osmosis according to claim 1, wherein: the plate-frame forward osmosis membrane component is immersed in the forward osmosis unit water inlet pool, a forward osmosis membrane active layer of the forward osmosis membrane component is in contact with the outlet water of the photo-Fenton unit, and a forward osmosis membrane mechanical supporting layer is in contact with the drawing liquid.
4. The integrated device for treating hardly biodegradable organic wastewater by using the combination of photo-Fenton and forward osmosis according to claim 1, wherein: said H2O2/H2SO4The material of the feeding tank and the stainless steel columns connected in series is titanium steel.
5. A method for using the integrated device for treating the hardly biodegradable organic wastewater by the combined photo-Fenton-forward osmosis according to any one of claims 1 to 4, wherein the integrated device comprises: the method comprises a photo-Fenton process and a forward osmosis process, and comprises the following specific steps:
(1) the light-Fenton process is carried out in a light-Fenton unit, wastewater containing the pollutants difficult to degrade biologically flows through the light-Fenton unit, an ultraviolet light or visible light emitting diode provides ultraviolet light or visible light, and glass beads loaded with a light-Fenton catalyst are irradiated by the ultraviolet light or the visible light and then react with H2O2Active substances such as hydroxyl radical OH & are generated, and the organic pollutants which are difficult to degrade and are biologically in the wastewater are degraded or converted in a short time and high efficiency;
(2) the forward osmosis process is carried out in an immersed forward osmosis unit, wastewater after passing through a photo-Fenton unit flows into a forward osmosis unit water inlet tank, a plate-frame forward osmosis membrane assembly is immersed in the forward osmosis unit water inlet tank, high-concentration draw solution flows from bottom to top in the plate-frame membrane assembly, osmotic pressure difference is formed on two sides of the forward osmosis membrane due to the fact that the draw solution osmotic pressure is higher than the wastewater osmotic pressure, under the driving of the osmotic pressure difference, purified water in the forward osmosis unit water inlet tank penetrates through the forward osmosis membrane to diffuse towards the draw solution side, and organic pollutants which are not completely degraded or converted in the photo-Fenton process are effectively retained in a forward osmosis unit water inlet tank outside the membrane;
(3) the wastewater treated in the steps (1) and (2) is used together with a biological method or other physical and chemical method water treatment processes, so that the wastewater treatment rate and the reuse rate are improved.
6. The use method of the integrated device for treating the biologically-nondegradable organic wastewater by combining the photo-Fenton and forward osmosis according to claim 5 is characterized in that: and (3) returning the wastewater treated in the step (1) from the photo-Fenton unit to the photo-Fenton unit for advanced treatment again after the wastewater is discharged from the photo-Fenton unit.
7. The use method of the integrated device for treating the biologically-nondegradable organic wastewater by combining the photo-Fenton and forward osmosis according to claim 5 is characterized in that: the photo-Fenton process is operated under the condition that the pH value is less than or equal to 7.
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| AU2020100939A AU2020100939A4 (en) | 2019-06-05 | 2020-06-04 | Integrated apparatus for combined photo-fenton and forward osmosis treatment of non-biodegradable organic wastewater and use method thereof |
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