CN102826694B - Method for processing industrial wastewater by membrane separation/catalytic degradation composite process - Google Patents
Method for processing industrial wastewater by membrane separation/catalytic degradation composite process Download PDFInfo
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- CN102826694B CN102826694B CN2012103396637A CN201210339663A CN102826694B CN 102826694 B CN102826694 B CN 102826694B CN 2012103396637 A CN2012103396637 A CN 2012103396637A CN 201210339663 A CN201210339663 A CN 201210339663A CN 102826694 B CN102826694 B CN 102826694B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides a method for processing industrial wastewater by a membrane separation/catalytic degradation composite process. The method comprises the following steps that 1, the industrial wastewater with the COD (chemical oxygen demand) greater than or equal to 10000mg/L is subjected to membrane separation treatment, and substances such as suspended matters, polymers and oil in sewage are removed; 2, filtrate after membrane separation is subjected to electric catalytic treatment, organic pollutants in water are degraded, and in addition, harmlessness or mineralization is realized for metal ions in the water; 3, the filtrate is further subjected to photoelectrocatalysis treatment, and pollutants in the water are degraded until the COD of the treated water is smaller than or equal to 90mg/L. The method has the advantages that the process is simple, the operation is safe, the control is easy, the membrane separation technology and the catalytic degradation technology are combined, the problems of time consumption, energy consumption and low efficiency of the simple membrane separation treatment method are solved, meanwhile, the difficult problem that useful matters in the sewage cannot be easily recovered and reutilized by the catalytic degradation treatment method is solved, and in addition, the obvious decontamination and purification efficiency is realized.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to the method that a kind of membrane sepn/catalyzed degradation recombining process is handled industrial sewage.
Background technology
At present, China's recycling rate of water used by the industries less than 50% is compared the gap great disparity with advanced international standard.Along with the quickening of process of industrialization, process water will increase substantially, and the water resources imbalance between supply and demand will be more outstanding.Therefore, development and large-scale application industrial sewage advanced purification technology and equipment to improve constantly recycling rate of water used by the industries, are embodied as the Sustainable development of economic society, just seem very necessary.
Micro-filtration or ultra-filtration membrane isolation technique are as a rising new technology, water outlet effect with its stable high-quality, save advantages such as occupation of land, with in the application of field of waste water treatment more and more widely, be widely used in the treating processes of advanced treatment, boiler de-salted water, high strength domestic sewage etc. of oily(waste)water, recirculated cooling water, tap water.Simultaneously, sintered glass, stupalith such as titanium oxide (TiO
2), silicon nitride (Si
3N
4), silicon carbide (SiC), inorganic micro filtering or the ultra-filtration membrane of the preparation of metal oxide or alloy have higher relatively wear resistance, chemically-resistant and heat-resisting degradation property also are applicable to the operating environment of harshnesses such as corrosion and high temperature.
The process of micro-filtration or ultra-filtration membrane removal pollutants in sewage is the effect that directly screens out by fenestra, and size is had fabulous stability in its removal of holding back the pollutent more than the scope.Yet, holding back the pollutent in aperture for size less than it, can't remove, therefore can't satisfy the requirement of trade effluent deep purifying.
The exploitation film makes up with membrane separation technique, with electrochemistry with photoelectrochemistry combines with membrane separation technique and membrane technique and other isolation technique are carried out combination, research and develop out novel advanced treatment of industrial waste water and plant and become present development trend.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned the deficiencies in the prior art, provide that a kind of technology is simple, operational safety, be easy to control, method that the sewage disposal cycle is short and sewage treating efficiency is high membrane sepn/catalyzed degradation recombining process is handled industrial sewage.This method combines membrane separation technique and catalyzed degradation technology, can solve not only that the single one physical filter method is consuming time, the problem of power consumption and poor efficiency, and can solve utilize separately the chemical catalysis degradation method can't recycling sewage in the difficult problem of useful matter, have scrubbing detergent power efficiently.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that this method may further comprise the steps:
Step 1, with membrane separation apparatus the pending industrial sewage of COD 〉=10000mg/L is carried out membrane sepn and handle and obtain filtrate, the aperture of filter membrane is 20nm～500nm in the described membrane separation apparatus;
Step 2, being the electrocatalysis treatment solution with filtrate described in the step 1, is negative electrode with the Graphite Electrodes, with surface-coated SnO is arranged
2The POROUS TITANIUM electrode of base coating is anode, is that 20 ℃～25 ℃ and voltage are to carry out electrocatalysis under the condition of 3V～20V to handle COD≤900mg/L to described filtrate in temperature;
Step 3, the filtrate after handling with electrocatalysis in the step 2 are the photoelectrocatalysis treatment solution, are negative electrode with the Graphite Electrodes, with surface attachment TiO are arranged
2The matrix of nanotube is the light anode, is irradiates light with sunlight or simulated solar irradiation, is that 20 ℃～25 ℃, voltage are that 0.1V～4V and light intensity are 80mW/cm in temperature
2～230mW/cm
2Condition under carry out photoelectrocatalysis and handle the COD≤90mg/L of the industrial sewage after handling.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that, the temperature that membrane sepn described in the step 1 is handled is 5 ℃～90 ℃, and the pressure that membrane sepn is handled is 0.3MPa～1.0MPa.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the material of filter membrane described in the step 1 is ZrO
2Pottery, Al
2O
3Pottery or TiO
2Pottery.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that SnO described in the step 2
2SnO in the base coating
2Granularity be 20nm～50nm, SnO
2Mass percent be 50%～70%.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that SnO described in the step 2
2The base coating is Sn-Ru-Ti oxide coating, Sn-Ir-Ti oxide coating or Sn-Ir-Sb oxide coating.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that surface-coated has SnO described in the step 2
2The POROUS TITANIUM electrode of base coating be shaped as sheet, tubulose or netted.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the material of matrix described in the step 3 is titanium or titanium alloy.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the TiO2 nanotube that is attached to matrix surface in the step 3 is anatase structured, described TiO
2The internal diameter of nanotube is 10nm～250nm, and length is 0.2 μ m～15 μ m, and specific surface area is 20m
2g
-1～75m
2g
-1, porosity is 50%～70%.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the preparation method of described smooth anode is: earlier matrix is placed NH
4Carry out anodic oxidation treatment in the F-ethylene glycol solution, obtain non-crystalline state TiO at matrix surface
2Nanotube will be attached to the non-crystalline state TiO of matrix surface then
2Nanotube is heat-treated, and carries out hydrogen treatment after the thermal treatment again; Described NH
4NH in the F-ethylene glycol solution
4The mass percent concentration of F is 0.2%～0.8%, and described anodised voltage is 10V～75V, and the anodised time is 0.1h～5h, and anodised temperature is 5 ℃～75 ℃.
Above-mentioned a kind of membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that described heat treated concrete technology is: the non-crystalline state TiO that will be attached to matrix surface
2Nanotube is to be incubated 4h～12h under 300 ℃～580 ℃ the condition in temperature; Described hydrotreated concrete technology is: with the non-crystalline state TiO after the thermal treatment
2Nanotube places hydrogen furnace, in hydrogen atmosphere, temperature is to carry out hydrogen treatment 0.5h～10h under 280 ℃～550 ℃ the condition; The flow of described hydrogen is 2 * 10
-2m
3.Min
-1～9 * 10
-2m
3.Min
-1
Among the present invention, the described SnO that is coated on the POROUS TITANIUM electrode surface
2The base coating refers to contain SnO
2Coating of metal oxides, preferred SnO
2The base coating is Sn-Ru-Ti oxide coating, Sn-Ir-Ti oxide coating or Sn-Ir-Sb oxide coating.Described Sn-Ru-Ti oxide coating, Sn-Ir-Ti oxide coating and Sn-Ir-Sb oxide coating all adopt existing ordinary method to prepare, the present invention is preferably brushing-thermal decomposition method, its preparation process is: elementary composition according to required coating, and from Ti (OC
4H
9)
4, SnCl
44H
2O, RuCl
33H
2O, SbCl
33H
2O and H
2IrCl6
InChoosing corresponding component is raw material, is dissolved in the mixing solutions that was mixed and made in 1: 1 by volume by Virahol and propyl carbinol, regulates the total concn of metal ion in the mixing solutions to 0.08mol/L～0.1mol/L, obtains the coating slip; The coating slip is coated in the POROUS TITANIUM surface of adopting after etching method is carried out surface preparation; Be dry 10min under 110 ℃ the condition in temperature then, placing temperature again is to take out naturally cooling behind 450 ℃～550 ℃ the retort furnace thermal treatment 10min; Again by described drying, thermal treatment and cooling step repetitive operation 7 times, be sintering 0.5h～1h under 450 ℃～550 ℃ the condition in temperature at last.
Among the present invention, the COD(of described industrial sewage is chemical oxygen demand (COD)) all adopt potassium dichromate process to measure, see standard GB/T11914 " the mensuration dichromate titration of hydrochemistry oxygen requirement " or international standard ISO6060 " mensuration of hydrochemistry oxygen requirement " for details.
Among the present invention, described membrane separation apparatus is conventional membrane separation plant, described ZrO
2Ceramic material, Al
2O
3Ceramic material and TiO
2The filter membrane of ceramic material is the commercially available commodity that are easy to get.
The present invention compared with prior art has the following advantages:
(1) the present invention combines physical method (being membrane separation technique) and chemical process (being electrocatalysis degradation technique and photoelectric catalysis degrading technology), industrial sewage to COD 〉=10000mg/L carries out the deep purifying processing, can solve not only that the single one physical method is consuming time, the problem of power consumption, and can solve utilize separately chemical process can't recycling sewage in the difficult problem of useful matter.
(2) simple, the operational safety of technology of the present invention, be easy to control, the sewage disposal cycle is short, scrubbing purification efficiency height; It is that the micro-filtration of 20nm～500nm or ultra-filtration membrane isolation technique are removed suspended substance, polymkeric substance, the wet goods impurity in the industrial sewage that the present invention adopts the aperture earlier, and can make the useful matter in the membrane sepn trapped substance carry out subsequent extracted and recycling; The organic pollutant in the degradation water is handled in the process electrocatalysis again, and makes the metal ion in the water realize innoxious or mineralising; Handle through photoelectrocatalysis then and carry out the degraded of further pollutent.Show that through a large amount of research experiments the COD≤90mg/L of water after the present invention handles illustrates that the present invention has significant scrubbing purification efficiency.
(3) microfiltration membrane of ceramic material used in the present invention or ultra-filtration membrane have higher wear resistance, and chemically-resistant and heat-resisting degradation property are applicable to the operating environment that corrosion and high temperature etc. are harsh.
(4) the present invention carries out adopting in the electrocatalysis treating processes surface-coated that SnO is arranged
2The POROUS TITANIUM electrode of base coating is anode, has good electrical conductivity, erosion resistance, higher porosity, is conducive to electrolytical transmission and circulation, can significantly improve electrocatalytic reaction speed; POROUS TITANIUM has flourishing specific surface area simultaneously, is conducive to SnO
2The even dispersion of base coating has increased the active points quantity that electrocatalysis is handled, and has not only effectively improved catalytic activity, and has significantly reduced the current density of electrode, has improved the solidity to corrosion of electrode, has prolonged the work-ing life of electrode greatly; The electrochemical activity of this electrode has improved more than the twice than traditional titanium anode, has improved work-ing life more than 1.5 times.
(5) the present invention adopts the photoelectrocatalysis treatment technology, serial reaction takes place under the effect of illumination and faint extra electric field, generation has the free radical of strong oxidizing property, various poisonous and hazardous organic pollutants can not only be decoloured, degraded, mineralising, finally is decomposed into CO
2And H
2O, thus it eliminated to the pollution of environment, and some precious metal ion redox can be reached the purpose that turns waste into wealth, the preferred TiO of the present invention
2The efficient of the photoelectric catalysis degrading organic pollutant of nanotube light anode and traditional TiO
2Nanotube light anode material is compared and has been improved 1.5～2.7 times.
Be described in further detail below in conjunction with the present invention of embodiment.
Embodiment
Embodiment 1
The method that the membrane sepn of present embodiment/catalyzed degradation recombining process is handled industrial sewage may further comprise the steps:
Step 1, accurately measure the Shaanxi seal paper money industrial sewage 10L of factory, it is as shown in table 1 to record its water quality analysis data, adopting pending industrial sewage that membrane separation apparatus will measure is that the microfiltration membrane of 200nm is carried out membrane sepn and handled by the aperture, makes the useful matter in the membrane sepn trapped substance carry out subsequent extracted and recycling; The temperature that described membrane sepn is handled is 40 ℃, and the pressure that membrane sepn is handled is 0.5MPa, and described microfiltration membrane is TiO
2Ceramic membrane;
Step 2, be the electrocatalysis treatment solution with the filtrate after membrane sepn is handled in the step 1, be negative electrode with the Graphite Electrodes, with the thick surface-coated of 1.2mm the flake porous titanium electrode of Sn-Ru-Ti oxide coating being arranged is anode, is that 25 ℃, voltage are to carry out electrocatalysis under the condition of 20V to handle COD≤900mg/L that 10h makes filtrate in temperature; Wherein be coated on SnO in the Sn-Ru-Ti oxide coating of POROUS TITANIUM electrode surface
2Granularity be 40nm, SnO
2Mass percent be 70%, described Sn-Ru-Ti oxide coating adopts brushing-thermal decomposition method to prepare, preparation process is: with Ti (OC
4H
9)
4, SnCl
44H
2O and RuCl
33H
2O is dissolved in the mixing solutions that was mixed and made in 1: 1 by volume by Virahol and propyl carbinol, regulates the total concn of metal ion in the mixing solutions to 0.08mol/L, obtains the coating slip; The coating slip being coated in the POROUS TITANIUM surface of adopting after etching method is carried out surface preparation, is dry 10min under 110 ℃ the condition in temperature then again, takes out naturally cooling after placing 450 ℃ retort furnace thermal treatment 10min; Then by described drying, thermal treatment and cooling step repetitive operation 7 times, be sintering 0.5h under 550 ℃ the condition in temperature at last;
Step 3, being the photoelectrocatalysis treatment solution with the filtrate after electrocatalysis is handled in the step 2, is negative electrode with the Graphite Electrodes, with surface attachment TiO is arranged
2The titanium matrix of nanotube is the light anode, is irradiates light with the sunlight, is that 25 ℃, voltage are that 4V, light intensity are 150mW/cm in temperature
2Condition under carry out photoelectrocatalysis and handle, the time that photoelectrocatalysis is handled is 1h; The described TiO that is attached to the titanium matrix surface
2Nanotube is anatase structured, and internal diameter is 100nm, and length is 8 μ m, and specific surface area is 45m
2g
-1, porosity is 60%; The described TiO that is attached to the titanium matrix surface
2Nanotube is containing 0.2wt%NH earlier by the titanium matrix
4Carry out anodic oxidation treatment in the ethylene glycol solution of F, heat-treat then, carry out at last obtaining after the hydrogen treatment; Described anodised voltage is 75V, and the anodised time is 0.1h, and anodised temperature is 75 ℃; Described heat treated temperature is 500 ℃, and heat treatment period is 8h; Described hydrotreated temperature is 350 ℃, and the hydrotreated time is 5h, and the flow of hydrogen is 5 * 10
-2m
3.Min
-1The water quality analysis data of the industrial sewage after present embodiment is handled are as shown in table 1.
Water quality analysis comparing result before and after table 1 embodiment of the invention 1 industrial sewage is handled
| ? | Before the processing | After the processing | Clearance |
| Chemical oxygen demand (COD) (COD, mg/L) | 20987 | 90 | ＞99% |
| Suspended substance (SS, mg/L) | 24500 | 18 | ＞99% |
| Solid content (%) | 3.4 | 0.1 | ＞97% |
| Printing ink (oil, mg/L) | 7.2 | 0.1 | ＞98% |
As shown in Table 1, the chemical oxygen demand (COD) (COD) of the industrial sewage after membrane sepn/catalyzed degradation recombining process of the employing embodiment of the invention 1 is handled is down to 90mg/L by 20987mg/L, suspended substance (SS) content is down to 18mg/L by 24500mg/L, solid content is down to 0.1% by 3.4%, printing ink content is down to 0.1mg/L by 7.2mg/L, illustrates that the method for membrane sepn of the present invention/catalyzed degradation recombining process processing industrial sewage has scrubbing purification efficiency efficiently.
Embodiment 2
The method that the membrane sepn of present embodiment/catalyzed degradation recombining process is handled industrial sewage may further comprise the steps:
Step 1, accurately measure Hanzhong City paper mill, Shaanxi Province industrial sewage 5L, it is as shown in table 2 to record its water quality analysis data, adopting pending industrial sewage that membrane separation apparatus will measure is that the ultra-filtration membrane of 20nm carries out membrane sepn and handles by the aperture, makes the useful matter in the membrane sepn trapped substance carry out subsequent extracted and recycling; The temperature that described membrane sepn is handled is 40 ℃, and the pressure that membrane sepn is handled is 0.3MPa, and described ultra-filtration membrane is Al
2O
3Ceramic membrane;
Step 2, be the electrocatalysis treatment solution with the filtrate after membrane sepn is handled in the step 1, be negative electrode with the Graphite Electrodes, with the thick surface-coated of 0.2mm the flake porous titanium electrode of Sn-Ir-Ti oxide coating being arranged is anode, is that 20 ℃, voltage are to carry out electrocatalysis under the condition of 3V to handle COD≤900mg/L that 6h makes filtrate in temperature; Wherein be coated on SnO in the Sn-Ir-Ti oxide coating of POROUS TITANIUM electrode surface
2Granularity be 50nm, SnO
2Mass percent be 50%, described Sn-Ir-Ti oxide coating adopts brushing-thermal decomposition method to prepare, preparation process is: with Ti (OC
4H
9)
4, SnCl
44H
2O and H
2IrCl
6Be dissolved in the mixing solutions that was mixed and made in 1: 1 by volume by Virahol and propyl carbinol, regulate the total concn of metal ion in the mixing solutions to 0.08mol/L, obtain the coating slip; The coating slip is coated in the POROUS TITANIUM surface of adopting after etching method is carried out surface preparation, is dry 10min under 110 ℃ the condition in temperature then, takes out naturally cooling after placing 550 ℃ retort furnace insulation 10min; Again by described drying, thermal treatment and cooling step repetitive operation 7 times, be sintering 1h under 450 ℃ the condition in temperature at last;
Step 3, being the photoelectrocatalysis treatment solution with the filtrate after electrocatalysis is handled in the step 2, is negative electrode with the Graphite Electrodes, with surface attachment TiO is arranged
2The titanium matrix of nanotube is the light anode, and the simulated solar irradiation that sends with solar simulator is irradiates light, is that 20 ℃, voltage are that 0.1V, light intensity are 80mW/cm in temperature
2Condition under carry out photoelectrocatalysis and handle, the time that described photoelectrocatalysis is handled is 2h; The described TiO that is attached to the titanium matrix surface
2Nanotube is anatase structured, and internal diameter is 250nm, and length is 15 μ m, and specific surface area is 75m
2g
-1, porosity is 50%; The described TiO that is attached to the titanium matrix surface
2Nanotube is containing 0.5wt%NH earlier by the titanium matrix
4Carry out anodic oxidation treatment in the ethylene glycol solution of F, heat-treat then, carry out at last obtaining after the hydrogen treatment; Described anodised voltage is 10V, and the anodised time is 5h, and anodised temperature is 5 ℃, and described heat treated temperature is 580 ℃, and heat treatment period is 12h; Described hydrotreated temperature is 280 ℃, and the hydrotreated time is 10h, and the flow of hydrogen is 2 * 10
-2m
3.Min
-1The Analysis Results of Water Quality of the industrial sewage after present embodiment is handled is as shown in table 2.
Water quality analysis comparing result before and after table 2 embodiment of the invention 2 industrial sewages are handled
| ? | Before the processing | After the processing | Clearance |
| Chemical oxygen demand (COD) (COD, mg/L) | 23700 | 75 | >99% |
| Suspended substance (SS, mg/L) | 523 | 1 | >99% |
As shown in Table 2, the chemical oxygen demand (COD) (COD) of the industrial sewage after membrane sepn/catalyzed degradation recombining process of the employing embodiment of the invention 2 is handled is down to 75mg/L by 23700mg/L, suspended substance (SS) is down to 1mg/L by 523mg/L, illustrates that the method for membrane sepn of the present invention/catalyzed degradation recombining process processing industrial sewage has decontamination purification efficiency efficiently.
Embodiment 3
The method that the membrane sepn of present embodiment/catalyzed degradation recombining process is handled industrial sewage may further comprise the steps:
Step 1, accurately measure the long celebrating in Shaanxi oil field industrial sewage 20L, it is as shown in table 3 to record its water quality analysis data, adopting pending industrial sewage that membrane separation apparatus will measure is that the microfiltration membrane of 500nm is carried out membrane sepn and handled by the aperture, makes the useful matter in the membrane sepn trapped substance carry out subsequent extracted and recycling; The temperature that described membrane sepn is handled is 90 ℃, and the pressure that membrane sepn is handled is 0.8MPa, and described microfiltration membrane is ZrO
2Ceramic membrane;
Step 2, be the electrocatalysis treatment solution with the filtrate after membrane sepn is handled in the step 1, be negative electrode with the Graphite Electrodes, with surface-coated the tubulose POROUS TITANIUM electrode of Sn-Ir-Sb oxide coating being arranged is anode, is that 25 ℃, voltage are to carry out electrocatalysis under the condition of 20V to handle COD≤900mg/L that 23h makes filtrate in temperature; Wherein be coated on SnO in the Sn-Ir-Sb oxide coating of POROUS TITANIUM electrode surface
2Granularity be 20nm, the mass percent of SnO2 is 60%, described Sn-Ir-Sb oxide coating adopts brushing-thermal decomposition method to prepare, preparation process is: with SbCl
33H
2O, SnCl
44H
2O and H
2IrCl
6Be dissolved in the mixing solutions that was mixed and made in 1: 1 by volume by Virahol and propyl carbinol, regulate the total concn of metal ion in the mixing solutions to 0.08mol/L, obtain the coating slip; The coating slip is coated in the POROUS TITANIUM surface of adopting after etching method is carried out surface preparation, is dry 10min under 110 ℃ the condition in temperature then, takes out naturally cooling after placing 450 ℃ retort furnace insulation 10min; Again by described drying, thermal treatment and cooling step repetitive operation 7 times, be sintering 0.5h under 550 ℃ the condition in temperature at last;
Step 3, being the photoelectrocatalysis treatment solution with the filtrate after electrocatalysis is handled in the step 2, is negative electrode with the Graphite Electrodes, with surface attachment TiO is arranged
2The titanium alloy substrate of nanotube is the light anode, and the simulated solar irradiation that sends with solar simulator is irradiates light, is that 25 ℃, voltage are that 4V, light intensity are 230mW/cm in temperature
2Condition under carry out photoelectrocatalysis and handle, the time that photoelectrocatalysis is handled is 1.2h; Described TiO
2Nanotube is anatase structured, and internal diameter is 10nm, and length is 0.2 μ m, and specific surface area is 20m
2g
-1, porosity is 70%; The described TiO that is attached to titanium alloy-based surface
2Nanotube is containing 0.8wt%NH earlier by the titanium matrix
4Carry out anodic oxidation treatment in the ethylene glycol solution of F, heat-treat then, carry out at last obtaining after the hydrogen treatment, described anodised voltage is 50V, and the anodised time is 2h, and anodised temperature is 55 ℃, described heat treated temperature is 300 ℃, and heat treatment period is 4h; Described hydrotreated temperature is 550 ℃, and the hydrotreated time is 0.5h, and the flow of hydrogen is 9 * 10
-2m
3.Min
-1The water quality analysis data of the industrial sewage after present embodiment is handled are as shown in table 3.
Water quality analysis comparing result before and after table 3 embodiment of the invention 3 industrial sewages are handled
| ? | Before the processing | After the processing | Clearance |
| Chemical oxygen demand (COD) (COD, mg/L) | 55123 | 69 | >99% |
| Suspended substance (SS, mg/L) | 50.62 | 5 | >90% |
As shown in Table 3, the chemical oxygen demand (COD) (COD) of the industrial sewage after membrane sepn/catalyzed degradation recombining process of the employing embodiment of the invention 3 is handled is down to 69mg/L by 55123mg/L, suspended substance (SS) is down to 5mg/L by 50.62mg/L, illustrates that the method for membrane sepn of the present invention/catalyzed degradation recombining process processing industrial sewage has decontamination purification efficiency efficiently.
Embodiment 4
The method that the membrane sepn of present embodiment/catalyzed degradation recombining process is handled industrial sewage may further comprise the steps:
Step 1, accurately measure the industrial sewage 50L of Xian City, Shanxi Province mechanical workout factory, it is as shown in table 4 to record its water quality analysis data, adopting pending industrial sewage that membrane separation apparatus will measure is that the microfiltration membrane of 180nm is carried out membrane sepn and handled by the aperture, makes the useful matter in the membrane sepn trapped substance carry out subsequent extracted and recycling; The temperature that described membrane sepn is handled is 5 ℃, and the pressure that membrane sepn is handled is 1.0MPa, and described microfiltration membrane is Al
2O
3Ceramic membrane;
Step 2, be the electrocatalysis treatment solution with the filtrate after membrane sepn is handled in the step 1, be negative electrode with the Graphite Electrodes, with surface-coated the mesh structural porous titanium electrode of Sn-Ir-Ti oxide coating being arranged is anode, is that 23 ℃, voltage are to carry out electrocatalysis under the condition of 10V to handle COD≤900mg/L that 15h makes filtrate in temperature; Wherein be coated on SnO in the Sn-Ir-Ti oxide coating of POROUS TITANIUM electrode surface
2Granularity be 20nm, SnO
2Mass percent be 50%, described Sn-Ir-Ti oxide coating adopts brushing-thermal decomposition method to prepare, preparation process is: with Ti (OC
4H
9)
4, SnCl
44H
2O and H
2IrCl
6Be dissolved in the mixing solutions that was mixed and made in 1: 1 by volume by Virahol and propyl carbinol, regulate the total concn of metal ion in the mixing solutions to 0.1mol/L, obtain the coating slip; Be coated in the POROUS TITANIUM surface of adopting after etching method is carried out surface preparation again; Be dry 10min under 110 ℃ the condition in temperature then, take out naturally cooling after placing 450 ℃ retort furnace thermal treatment 10min; Again by described drying, thermal treatment and cooling step repetitive operation 7 times; Be sintering 1h under 450 ℃ the condition in temperature at last;
Step 3, being the photoelectrocatalysis treatment solution with the filtrate after electrocatalysis is handled in the step 2, is negative electrode with the Graphite Electrodes, with surface attachment TiO is arranged
2The titanium alloy substrate of nanotube is the light anode, and the simulated solar irradiation that sends with solar simulator is irradiates light, is that 25 ℃, voltage are that 3V, light intensity are 100mW/cm in temperature
2Condition under carry out photoelectrocatalysis and handle, the time that described photoelectrocatalysis is handled is 1h; Described TiO
2Nanotube is anatase structured, and internal diameter is 100nm, and length is 7 μ m, and specific surface area is 25m
2g
-1, porosity is 56%; The described TiO that is attached to titanium alloy-based surface
2Nanotube is containing 0.8wt%NH earlier by titanium alloy substrate
4Carry out anodic oxidation treatment in the ethylene glycol solution of F, heat-treat then, carry out at last obtaining after the hydrogen treatment; Described anodised voltage is 20V, and the anodised time is 4h, and anodised temperature is 20 ℃; Described heat treated temperature is 400 ℃, and heat treatment period is 10h; Described hydrotreated temperature is 280 ℃, and the hydrotreated time is 2h, and the flow of hydrogen is 3 * 10
-2m
3.Min
-1The water quality analysis data of the industrial sewage after present embodiment is handled are as shown in table 4.
Water quality analysis comparing result before and after table 4 embodiment of the invention 4 industrial sewages are handled
| ? | Before the processing | After the processing | Clearance |
| Chemical oxygen demand (COD) (COD, mg/L) | 10390 | 48 | >99% |
| Suspended substance (SS, mg/L) | 438 | 12 | >97% |
As shown in Table 4, the chemical oxygen demand (COD) (COD) of the industrial sewage after membrane sepn/catalyzed degradation recombining process of the employing embodiment of the invention 4 is handled is down to 48mg/L by 10390mg/L, suspended substance (SS) is down to 12mg/L by 438mg/L, illustrates that the method for membrane sepn of the present invention/catalyzed degradation recombining process processing industrial sewage has decontamination purification efficiency efficiently.
The above only is preferred embodiment of the present invention, is not that the present invention is imposed any restrictions.Every any simple modification, change and equivalence of above embodiment being done according to the invention technical spirit changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (10)
1. a membrane sepn/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that this method may further comprise the steps:
Step 1, adopt membrane separation apparatus that the pending industrial sewage of COD 〉=10000mg/L is carried out membrane sepn to handle and obtain filtrate, the aperture of filter membrane is 20nm～500nm in the described membrane separation apparatus;
Step 2, being the electrocatalysis treatment solution with filtrate described in the step 1, is negative electrode with the Graphite Electrodes, with surface-coated SnO is arranged
2The POROUS TITANIUM electrode of base coating is anode, is that 20 ℃～25 ℃ and voltage are to carry out electrocatalysis under the condition of 3V～20V to handle COD≤900mg/L to described filtrate in temperature;
Step 3, the filtrate after handling with electrocatalysis in the step 2 are the photoelectrocatalysis treatment solution, are negative electrode with the Graphite Electrodes, with surface attachment TiO are arranged
2The matrix of nanotube is the light anode, is irradiates light with sunlight or simulated solar irradiation, is that 20 ℃～25 ℃, voltage are that 0.1V～4V and light intensity are 80mW/cm in temperature
2～230mW/cm
2Condition under carry out photoelectrocatalysis and handle the COD≤90mg/L of the industrial sewage after handling.
2. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that, the temperature that membrane sepn described in the step 1 is handled is 5 ℃～90 ℃, and the pressure that membrane sepn is handled is 0.3MPa～1.0MPa.
3. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the material of filter membrane described in the step 1 is ZrO
2Pottery, Al
2O
3Pottery or TiO
2Pottery.
4. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that SnO described in the step 2
2SnO in the base coating
2Granularity be 20nm～50nm, SnO
2Mass percent be 50%～70%.
5. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that SnO described in the step 2
2The base coating is Sn-Ru-Ti oxide coating, Sn-Ir-Ti oxide coating or Sn-Ir-Sb oxide coating.
6. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that surface-coated has SnO described in the step 2
2The POROUS TITANIUM electrode of base coating be shaped as sheet, tubulose or netted.
7. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the material of matrix described in the step 3 is titanium or titanium alloy.
8. a kind of membrane sepn according to claim 1/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that, is attached to the TiO of matrix surface in the step 3
2Nanotube is anatase structured, described TiO
2The internal diameter of nanotube is 10nm～250nm, and length is 0.2 μ m～15 μ m, and specific surface area is 20m
2g
-1～75m
2g
-1, porosity is 50%～70%.
9. a kind of membrane sepn according to claim 8/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that the preparation method of described smooth anode is: earlier matrix is placed NH
4Carry out anodic oxidation treatment in the F-ethylene glycol solution, obtain non-crystalline state TiO at matrix surface
2Nanotube will be attached to the non-crystalline state TiO of matrix surface then
2Nanotube is heat-treated, and carries out hydrogen treatment after the thermal treatment again; Described NH
4NH in the F-ethylene glycol solution
4The mass percent concentration of F is 0.2%～0.8%, and described anodised voltage is 10V～75V, and the anodised time is 0.1h～5h, and anodised temperature is 5 ℃～75 ℃.
10. a kind of membrane sepn according to claim 9/catalyzed degradation recombining process is handled the method for industrial sewage, it is characterized in that described heat treated concrete technology is: the non-crystalline state TiO that will be attached to matrix surface
2Nanotube is to be incubated 4h～12h under 300 ℃～580 ℃ the condition in temperature; Described hydrotreated concrete technology is: with the non-crystalline state TiO after the thermal treatment
2Nanotube places hydrogen furnace, in hydrogen atmosphere, temperature is to carry out hydrogen treatment 0.5h～10h under 280 ℃～550 ℃ the condition; The flow of described hydrogen is 2 * 10
-2m
3.Min
-1～9 * 10
-2m
3.Min
-1
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| CN105858984A (en) * | 2016-05-25 | 2016-08-17 | 哈尔滨工程大学 | Device and method for treating vessel oily sewage by ultrasonic strengthening membrane with combination of photo-electrocatalytic technology |
| CN106958033B (en) * | 2017-03-17 | 2019-03-26 | 南开大学 | Magn é li phase TinO2n-1The preparation method of nanotube electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0453706A2 (en) * | 1990-04-25 | 1991-10-30 | Dornier Gmbh | Detoxification of exhausted baths of photographic processes and washings by means of anodic oxidation |
| CN2848826Y (en) * | 2005-05-24 | 2006-12-20 | 武汉大学 | Device for deepling purification of drinking water |
| CN101555082A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院理化技术研究所 | Wastewater treatment method and device combining electrochemical degradation and photocatalysis oxidation technologies |
| CN102092878A (en) * | 2010-12-08 | 2011-06-15 | 湖州森蓝环境工程有限公司 | Treatment method of heavy metal organic industrial waste water |
| CN102603037A (en) * | 2012-04-01 | 2012-07-25 | 南京工业大学 | Organic wastewater treatment film reactor utilizing sunlight-assisted electro-catalysis |
Family Cites Families (1)
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| PT1945576E (en) * | 2005-10-28 | 2013-01-16 | Apr Nanotechnologies S A | Device comprising an electrode with nanocoating for preparing a highly stable aqueous solution and method for making this aqueous solution |
-
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- 2012-09-14 CN CN2012103396637A patent/CN102826694B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0453706A2 (en) * | 1990-04-25 | 1991-10-30 | Dornier Gmbh | Detoxification of exhausted baths of photographic processes and washings by means of anodic oxidation |
| CN2848826Y (en) * | 2005-05-24 | 2006-12-20 | 武汉大学 | Device for deepling purification of drinking water |
| CN101555082A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院理化技术研究所 | Wastewater treatment method and device combining electrochemical degradation and photocatalysis oxidation technologies |
| CN102092878A (en) * | 2010-12-08 | 2011-06-15 | 湖州森蓝环境工程有限公司 | Treatment method of heavy metal organic industrial waste water |
| CN102603037A (en) * | 2012-04-01 | 2012-07-25 | 南京工业大学 | Organic wastewater treatment film reactor utilizing sunlight-assisted electro-catalysis |
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