CN111252884A - Integrated catalytic membrane ozone gas distributor, preparation method and application - Google Patents
Integrated catalytic membrane ozone gas distributor, preparation method and application Download PDFInfo
- Publication number
- CN111252884A CN111252884A CN202010186877.XA CN202010186877A CN111252884A CN 111252884 A CN111252884 A CN 111252884A CN 202010186877 A CN202010186877 A CN 202010186877A CN 111252884 A CN111252884 A CN 111252884A
- Authority
- CN
- China
- Prior art keywords
- ozone
- membrane
- gas distributor
- ozone gas
- wastewater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- 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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of wastewater treatment, and discloses an integrated catalytic membrane ozone gas distributor, a preparation method and application. The integrated catalytic membrane ozone gas distributor takes a ceramic membrane with micron-sized pore passages as a main body, and an ozone active catalytic material layer is loaded on the outer surface of the ceramic membrane. The main component of the catalytic material layer comprises gamma-Al2O3. The integrated catalytic membrane ozone gas distributor can be effectively used for deep treatment of refractory fine chemical wastewater in industries such as medicine, pharmacy, dye, petrifaction, intermediates and the likeAnd (4) the wastewater treatment efficiency.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an integrated catalytic membrane ozone gas distributor, a preparation method and application.
Background
The treatment of the difficult-to-degrade fine chemical wastewater in the industries such as medicine, pharmacy, dye, petrifaction, intermediates and the like belongs to a typical representative for the difficult-to-treat industrial wastewater, and the difficult problem to be solved by enterprises is urgently needed due to the problems of large total COD (chemical oxygen demand), high content of toxic substances, poor biodegradability and the like.
Advanced oxidation technologies (AOPs) utilize generated hydroxyl radicals to rapidly mineralize organic pollutants or improve the biochemical performance of wastewater, and have the advantages of high reaction speed, wide application range, strong oxidation capacity and the like. Ozone has strong oxidizing power and can directly mineralize organic matters into substances with smaller molecular weight.
Catalytic ozonation is a typical advanced oxidation technology. Compared with other technologies, the catalytic ozonation technology utilizes ozone gas, is high in organic matter degradation speed, mild in condition, free of secondary pollution and good in application prospect. Catalytic ozonation can be divided into two forms of homogeneous and heterogeneous catalytic ozone. In a homogeneous catalysis system, the used catalyst is transition metal ions, the catalysis process is simple and easy to implement, but the metal ion catalyst is difficult to recover, and is easy to lose and causes secondary pollution of the metal ions. In order to improve the phenomenon, the solid granular catalyst is added into the ozone oxidation system, so that the catalyst can decompose ozone into OH with strong catalytic capability, thereby catalytically oxidizing organic pollutants in water and achieving the aim of mineralizing organic matters. Heterogeneous ozone catalyst is generally applied to ozone catalyst because of the advantages of being convenient for separating from liquid phase, not causing pollution of extra input active metal ions and the like, and compared with homogeneous ozone catalytic oxidation, heterogeneous ozone oxidation technology is widely applied in the actual production process, especially the deep treatment of actual industrial wastewater.
However, there are still some drawbacks in the heterogeneously catalyzed ozone process, for example the contact pattern of ozone and waste water, which is to be improved, i.e. the gas distribution pattern of the ozone gas in the ozone oxidation plant. Ozone has low solubility in water and poor stability, and a proper gas-liquid contact technology is required to realize rapid mixing of ozone gas and wastewater, so that the ineffective loss and release of ozone in a mass transfer process are reduced. The ozone gas distribution method in the traditional catalytic ozone oxidation technology is roughly divided into: the device comprises a bubbling type titanium disc type aeration mode, a titanium disc type aeration mode and a jet flow aeration mode, wherein the titanium disc type aeration mode has relatively wide application range because the disc type structure has relatively small pore passages and relatively small generated bubbles. However, the bubbling type, titanium disk type and jet aeration modes still have the problems that the mass transfer rate of ozone is not high enough due to the open pore mode of the pore diameter of the gas distribution equipment, and the problems of flooding, emulsion, foam, aerosol entrainment and the like still easily occur in an ozone oxidation reaction device. Therefore, an economical and rapid gas distribution mode is urgently needed to be researched.
Through retrieval, related applications are disclosed in the prior art, for example, the prior art with the publication number of CN203683278U discloses a coupled membrane ozone catalytic reaction device for treating organic wastewater, which comprises a primary pretreatment reactor, a secondary pretreatment reactor, a membrane catalytic main reactor, a membrane catalytic reactor monitoring and intelligent control system and a membrane cleaning system; it is characterized in that the primary pretreatment reactor comprises: a stepless speed change stirrer, a water inlet and outlet flow meter, a thermometer and a pH probe; the secondary pretreatment reactor comprises: a multi-medium filter containing filter material quartz sand; the membrane catalytic main reactor comprises: the activated carbon treatment area and the catalytic membrane module area are additionally provided with a vacuum pump, a water inlet system and an air inlet/exhaust system; the membrane cleaning system includes: a backwashing pump, a metering pump, 1 clean water tank and 2 medicine tanks. The ozone catalytic reaction and the membrane separation function are coupled, the catalytic oxidation reaction and the membrane separation process are integrated in one unit device by loading a catalyst on the surface of an inorganic membrane, nondegradable organic pollutants with structures such as high-molecular polymeric compounds, chlorinated aromatics, polycyclic aromatic hydrocarbons, heterocyclic compounds and the like in wastewater are selectively enriched and treated, the treated purified water is quickly removed out of a system by separation and filtration of the membrane, and high-molecular organic matters which are not completely decomposed are enriched on the stock solution side of the membrane, so that the limitation of concentration balance is broken, the reaction efficiency is improved, and a higher treatment effect is obtained under a milder condition. In this application, the filtration separation of the membrane and the catalytic action of the membrane surface are mainly utilized.
The prior art with the publication number of CN105800735B discloses a water treatment method based on a manganese-cobalt composite oxide nanoparticle modified ceramic membrane, and provides an assembly method of a novel manganese-cobalt composite oxide nanoparticle catalyst loaded ceramic membrane, aiming at the defect that a conventional powdery catalyst is not beneficial to realizing separation and inactivation in a water phase. It aims to combine the multiphase ozone oxidation with the ceramic membrane filtration technology and utilize the ceramic membrane structure and the active component (MnO) on the catalytic layer2And Co3O4) The ozone is catalyzed to generate OH with high oxidation capability, and organic matters can directly react with molecular ozone or react with OH generated by ozone decomposition to realize the enhanced removal of medicines and personal care products (PPCPs) such as 2-hydroxy-4-methoxybenzophenone in water. The manganese cobalt composite oxide nano particles are loaded on the surface of the ceramic membrane, so that the separation of the catalyst and water is realized, and a new method is provided for the cleaning and the repeated recycling of the catalyst. In the patent, cobalt-manganese inorganic salt is used for dipping, calcining and molding on the surface of a ceramic membrane, and then the ceramic membrane is used in a reaction device, and wastewater is directly discharged after membrane treatment.
The prior art with the publication number of CN105800767B discloses a construction method of a nano copper manganese oxide spinel catalytic membrane reactor and an application method thereof in water treatment, and provides a construction method of a novel nano copper manganese oxide spinel catalytic membrane reactor aiming at the defects that a conventional powdery catalyst is not beneficial to separation in a water phase and is easy to inactivate and the like. The method combines heterogeneous catalytic ozonation with a ceramic membrane filtration technology, utilizes active components (CuMnO) on a ceramic membrane catalysis layer to catalyze ozone to generate OH with high oxidation capacity, and organic matters can directly react with molecular ozone or react with OH generated by ozone decomposition, and meanwhile, the interception effect of the ceramic membrane can also assist in removing 2-hydroxy 4-methoxybenzophenone in water in an enhanced manner. In addition, ozone can react with humic acid and Natural Organic Substances (NOMs) in the water body, and membrane pollution is effectively prevented from being formed.
Although the above two applications improve the wastewater treatment efficiency to some extent, they have the following disadvantages: 1) the ceramic membrane is used as a water phase separator, the suspended matters in the wastewater are effectively separated from the wastewater only by physical filtration, the ceramic membrane only plays a role in physical filtration and separation, the effect of improving the quality of the wastewater is not great, and meanwhile, the ozone gas is in a conventional disc type or bubbling type aeration mode which is utilized and is not different from the conventional ozone aeration mode. 2) In the process of flushing the catalytic membrane by ozone gas, the material on the outer surface of the membrane is easily blown off and dissolved in water phase, the problem of secondary metal ion pollution is caused, and the ozone catalytic capability disappears after the catalytic component is lost over time.
Based on the defects of the prior art, a new method capable of improving the utilization efficiency of ozone needs to be invented.
Disclosure of Invention
1. Problems to be solved
Aiming at the defects of low ozone utilization rate, low solubility, poor stability and easy secondary pollution caused by catalyst in the prior art, which are caused by gas-liquid contact in bubbling, titanium disc and jet aeration modes during ozone catalysis, the invention uses the ceramic membrane for the ozone distributor capable of carrying out ozone aeration, and simultaneously loads the ozone catalyst layer on the surface of the ceramic membrane to realize ozone aeration through micron-level pore channels, thereby providing a novel gas-liquid contact mode to improve the mass transfer efficiency of ozone, and the ozone can be uniformly and rapidly distributed in a wastewater system through a large number of membrane pore channels The contact area of the ozone and the organic matters in the wastewater effectively improves the wastewater treatment efficiency.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides an integrated catalytic membrane ozone gas distributor, which takes a ceramic membrane with micron-sized pore passages as a main body, wherein the outer surface of the main body of the ceramic membrane is loaded with an ozone active catalytic material layer, and the main component of the catalytic material layer comprises gamma-Al2O3。
As a further improvement of the invention, the average pore diameter of the micron-sized pore passage is 1-20 μm, and the porosity is 30-60%.
As a further improvement of the invention, the preparation method comprises the following steps:
step 1), mixing Al (OH)3Roasting the powder to convert the powder into gamma-Al2O3；
Step 2), treating the gamma-Al treated in the step 1)2O3Grinding into uniform powder particles with 5000-10000 meshes for later use;
step 3), washing the powder particles obtained in the step 2) with dilute acid and dilute alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying;
step 4), dispersing the powder particles obtained in the step 3) in a solution containing a binder, uniformly shaking to form a coating liquid, coating the coating liquid on the outer surface of the ceramic membrane main body to form a coating, and drying;
and 5) carrying out high-temperature secondary roasting on the ceramic membrane treated in the step 4) to remove the binder.
As a further improvement of the invention, in the step 1), Al (OH)3The powder is roasted for 4 to 6 hours at the temperature of 450-650 ℃ to ensure that the powder is completely converted into gamma-Al2O3。
As a further improvement of the present invention, the binder used in step 4) includes one or more of polyvinyl alcohol, carboxymethyl cellulose, or polyvinyl butyral, and the coating manner of the coating solution includes any one of spraying, dip-coating, or spin-coating.
As a further improvement of the invention, the temperature for drying in the step 3) and the step 4) is 100 ℃.
As a further improvement of the invention, the high-temperature secondary roasting temperature in the step 5) is 450-650 ℃, and the roasting time is 4-6 h.
As a further improvement of the invention, the ozone gas distributor is applied to the catalytic ozonation treatment of chemical wastewater.
As a further improvement of the invention, the ozone gas distributor is applied to the advanced treatment of refractory fine chemical wastewater in the industries of medicine, pharmacy, dye, petrifaction and intermediates.
As a further improvement of the invention, the application method comprises the following steps:
1) introducing wastewater to be treated into an ozone oxidation reaction device, and diffusing ozone into the wastewater through the integrated catalytic membrane ozone gas distributor through a pipeline to uniformly release ozone bubbles;
2) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to an integrated catalytic membrane ozone gas distributor, wherein a ceramic membrane is used for an ozone distributor capable of carrying out ozone aeration, and a catalytic material layer is loaded on the surface of a main body of the ceramic membrane, so that the pore channel distribution of the ceramic membrane can be efficiently utilized to integrate the gas-liquid mass transfer function and the ozone catalytic oxidation function of ozone, the volume of an ozone oxidation device can be obviously reduced, the problems of difficult recovery of a homogeneous ozone catalyst and low ozone mass transfer efficiency in the ozone oxidation process can be effectively solved, a water distribution system is matched in the wastewater treatment process, the invention provides a novel gas-liquid contact mode to improve the mass transfer efficiency of ozone, ozone can be uniformly and rapidly distributed in the wastewater system through a large number of membrane pores, and in the process, the catalyst active components on the surface of the membrane can effectively catalyze the ozone gas to form enough active free radicals, organic pollutants in the wastewater are oxidized and destroyed, the mobility of water and the diffusivity of gas are effectively utilized in the whole treatment process, the contact area of a catalyst, ozone and organic matters in the wastewater is greatly increased, and the wastewater treatment efficiency is remarkably improved.
(2) The integrated catalytic membrane ozone gas distributor provided by the invention takes the ceramic membrane as the ozone gas distributor, can effectively overcome the defects of low solubility and poor stability of ozone in water in the ozone gas distribution mode in the prior art, can effectively utilize the micro-nano-grade pore channels passing through the surface of the ceramic membrane by taking the ceramic membrane as the distributor, not only provides rich specific surface area, but also can realize stable and uniform contact of ozone gas with wastewater, has the functions of improving mass transfer and oxidation rate of ozone gas, and can effectively reduce ineffective loss and release of ozone in the mass transfer process.
(3) When the catalyst layer of the integrated catalytic membrane ozone gas distributor is prepared, Al (OH) is firstly added3Calcination conversion to gamma-Al2O3Grinding the ceramic membrane into powder, dispersing the powder into a solution containing a binder to prepare a coating solution, coating the coating solution on the outer surface of the ceramic membrane main body to form a coating, and roasting at high temperature to remove the binder2O3The catalyst is loaded on the surface of the same kind of substance (alumina) in a coating mode, so that on one hand, the whole components are simple, the secondary pollution is reduced, on the other hand, the catalyst layer can be firmly attached to the surface of the ceramic membrane by utilizing the characteristics of stability and high mechanical strength of the ceramic membrane, and no matter gamma-Al is loaded in the long-term wastewater treatment process2O3The catalyst layer is a ceramic membrane, can resist the impact of water scouring force and strong oxidizing force generated by ozone on the material, has stable performance, can economically and efficiently realize advanced treatment of wastewater, and has simple steps and easy control.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
The preparation method of the catalytic membrane ozone gas distributor of the embodiment is as follows:
step 1: mixing Al (OH)3Roasting the powder, and calcining the powder at 450 ℃ for 6 hours to ensure that the powder is completely converted into gamma-Al2O3；
Step 2: pre-burning the gamma-Al2O3Grinding the powder into uniform powder particles of 5000-6000 meshes for later use;
and step 3: washing the powder particles obtained in the step 2 with dilute sulfuric acid and dilute liquid alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying at 100 ℃;
and 4, step 4: dispersing the granular material obtained in the step (3) in a solution containing a binder polyvinyl alcohol, uniformly shaking to form a coating solution, coating the coating solution on the outer surface of the ceramic membrane main body in a spraying mode to form a coating, and drying at 100 ℃;
and 5: and (3) carrying out high-temperature secondary roasting on the catalytic ceramic membrane coated with the catalytic material in the step (4), calcining for 6 hours at 450 ℃ to remove the binder and sinter and form a membrane by the active catalytic material, and using the ceramic membrane material obtained in the step (5) as an ozone distributor for wastewater treatment. The treatment process is as follows: a) introducing wastewater to be treated into an ozone oxidation reaction device, wherein ozone is diffused into the wastewater through an ozone gas distributor through a pipeline to uniformly release ozone bubbles, the ozone generation amount is 1g/h, and the gas flow is 0.5L/min; b) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized.
Simultaneously, setting a comparison experiment: the contrast group is a traditional sand core aeration head gas distributor, and gamma-Al with the mass concentration of 5 percent is added in the treatment process2O3The ozone catalyst solid material has consistent other test conditions, the test wastewater is taken from biochemical tail water of a centralized sewage treatment plant in a certain chemical industrial park, and the test results are shown in table 1:
table 1 results of treatment of example 1
Example 2
The preparation method of the catalytic membrane ozone gas distributor of the embodiment is as follows:
step 1: mixing Al (OH)3Roasting the powder at 550 deg.c for 5 hr to convert the powder into gamma-Al2O3；
Step 2: pre-burning the gamma-Al2O3Grinding the powder into uniform powder particles of 7000-plus 8000 meshes for later use;
and step 3: washing the powder particles obtained in the step 2 with dilute sulfuric acid and dilute liquid alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying at 100 ℃;
and 4, step 4: dispersing the granular material obtained in the step (3) in a solution containing binder carboxymethyl cellulose, uniformly shaking to form a coating solution, coating the coating solution on the outer surface of the ceramic membrane main body in a dipping and pulling mode to form a coating, and drying at 100 ℃;
and 5: and (4) roasting the catalytic ceramic membrane coated with the catalytic material in the step (4) at a high temperature for 5 hours at 550 ℃ to remove the binder and sinter the active catalytic material to form a membrane. And (5) taking the ceramic membrane material obtained in the step (5) as an ozone distributor for wastewater treatment. The treatment process is as follows: a) introducing wastewater to be treated into an ozone oxidation reaction device, and diffusing ozone into the wastewater through an ozone gas distributor through a pipeline to uniformly release ozone bubbles; the ozone generation amount is 1g/h, and the gas flow is 0.5L/min; b) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized.
Simultaneously, setting a comparison experiment: the comparison group is a traditional sand core aeration head gas distributor, and gamma-Al with the mass concentration of 5 percent is added in the treatment process2O3The ozone catalyst solid material has consistent other test conditions, the test wastewater is taken from biochemical tail water of a centralized sewage treatment plant in a certain chemical industrial park, and the test results are shown in table 2:
table 2 results of the treatment of example 2
Example 3
The ceramic membrane with the ozone catalytic active material of the present example was prepared by the following steps:
step 1: mixing Al (OH)3Roasting the powder at 650 deg.C for 4 hr to convert it into gamma-Al2O3；
Step 2: pre-burning the gamma-Al2O3Grinding the powder into 9000-10000-mesh uniform powder particles for later use;
and step 3: washing the powder particles obtained in the step 2 with dilute sulfuric acid and dilute liquid alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying at 100 ℃;
and 4, step 4: dispersing the granular material obtained in the step 3 in a solution containing a binder and polyvinyl butyral, uniformly shaking to form a coating solution, coating the coating solution on the outer surface of the ceramic membrane main body in a rotary coating mode to form a coating, and drying at 100 ℃;
and 5: and (4) roasting the catalytic ceramic membrane coated with the catalytic material in the step (4) at a high temperature for 4 hours at 650 ℃ to remove the binder and sinter the active catalytic material to form a membrane. And (5) taking the ceramic membrane material obtained in the step (5) as an ozone distributor for wastewater treatment. The treatment process is as follows: a) introducing wastewater to be treated into an ozone oxidation reaction device, and diffusing ozone into the wastewater through an ozone gas distributor through a pipeline to uniformly release ozone bubbles; the ozone generation amount is 1g/h, and the gas flow is 0.5L/min; b) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized.
Simultaneously, setting a comparison experiment: the comparison group is a traditional sand core aeration head gas distributor, and gamma-Al with the mass concentration of 5 percent is added in the treatment process2O3The ozone catalyst solid material has consistent other test conditions, the test wastewater is taken from biochemical tail water of a centralized sewage treatment plant in a certain chemical industrial park, and the test results are shown in table 3:
table 3 results of treatment of example 3
The results of the examples 1 to 3 show that compared with the traditional sand core aeration head gas distributor, the ceramic membrane ozone gas distributor provided by the invention has the advantages that under the condition of equivalent catalyst input amount, the dispersion and mass transfer efficiency of ozone in a water body is greatly improved, the ozone utilization rate is improved, the wastewater treatment efficiency is finally improved, and on the other hand, the addition of gamma-Al is added2O3Compared with ozone catalyst, the integrated ozone gas distributor of the invention has the main body coated with gamma-Al on the outer surface2O3A material layer of the gamma-Al in a wastewater treatment process2O3The material layer can effectively catalyze the ozone gas to form enough active free radicals, oxidize and destroy organic pollutants in the wastewater, effectively utilize the fluidity of water and the diffusivity of gas in the whole treatment process, greatly improve the contact area of the catalyst, the ozone and the organic matters in the wastewater, and synergistically and efficiently improve the wastewater treatment efficiency. The method of the invention avoids the problems of secondary pollution and overhigh cost caused by repeatedly adding the catalyst, and the ceramic membrane ozone gas distributor of the invention can be repeatedly applied to wastewater treatment.
Comparative example 1
The ceramic membrane with the ozone catalytic active material in the comparative example is prepared by the following steps:
step 1: mixing Al (OH)3Roasting the powder at 650 deg.C for 4 hr to convert it into gamma-Al2O3；
Step 2: pre-burning the gamma-Al2O3Grinding the powder into 9000-10000-mesh uniform powder for later use;
and step 3: washing the powder obtained in the step 2 with dilute sulfuric acid and dilute liquid alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying at 100 ℃;
and 4, step 4: dispersing the granular material obtained in the step 3 in a solution containing a binder and polyvinyl butyral, uniformly shaking to form a coating solution, coating the coating solution on the outer surface of the ceramic membrane main body in a rotary coating mode to form a coating, and drying at 100 ℃;
and 5: and (4) roasting the catalytic ceramic membrane coated with the catalytic material in the step (4) at a high temperature for 4 hours at 650 ℃ to remove the binder and sinter the active catalytic material to form a membrane. And (5) taking the ceramic membrane material obtained in the step (5) as an ozone distributor for wastewater treatment. The treatment process is as follows: a) introducing wastewater to be treated into an ozone oxidation reaction device, wherein ozone is diffused into the wastewater through an ozone gas distributor through a pipeline to uniformly release ozone bubbles, the ozone generation amount is 1g/h, and the gas flow is 0.5L/min; b) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized. c) A ceramic membrane filter (filter for filtration, aeration with no ozone gas) was added to the treatment system, and the ceramic membrane prepared in step 5 was also used as the filter.
Simultaneously, setting a comparison experiment: the contrast group adopts a traditional sand core aeration head gas distributor to introduce ozone into the wastewater, and gamma-Al with the mass concentration of 5 percent is added in the treatment process2O3Ozone catalyst solid material was added to the control group along with a ceramic membrane filter (filter for filtration, aeration with no ozone gas), which was also used with the ceramic membrane prepared in step 5. Other test conditions were consistent.
The test wastewater is obtained from biochemical tail water of a centralized sewage treatment plant in a certain chemical industry park, and the experimental results are shown in Table 4:
table 4 treatment results of comparative example 1
The results show that the ceramic membrane coated with the catalytic layer on the surface is used as a filter, so that the ceramic membrane can play the roles of interception and catalysis at the same time and can also assist in realizing the effect of strengthening the ozone oxidation of refractory organic matters, but the catalytic effect of the ozone can be obviously improved only by adding a large amount of catalyst, so that the catalytic effect of the catalytic layer loaded on the surface of the ceramic membrane is not favorably played by using the ceramic membrane as the filter, the catalytic effect of the catalytic layer loaded on the surface of the ceramic membrane can be more favorably played by using the ceramic membrane as an ozone gas distributor and by using the mass transfer contact of the ozone, the ozone can be uniformly and rapidly distributed in a wastewater system through a large amount of membrane pore channels, and meanwhile, the catalyst active component on the surface of the membrane can effectively catalyze the ozone gas to form enough active free radicals to, the whole treatment process effectively utilizes the fluidity of water and the diffusivity of gas, greatly improves the contact area of the catalyst, ozone and organic matters in the wastewater, obviously improves the wastewater treatment efficiency, and can reach excellent COD removal rate without additionally adding the catalyst.
It should be noted that, the manufacturing steps described in the above specific embodiments are only for illustrating the implementation examples of the present invention, and are not limited to the present invention, and the variations and modifications of the above implementation examples are within the scope of the claims of the present invention as long as they are within the spirit and scope of the present invention.
Claims (10)
1. An integrated catalytic membrane ozone gas distributor, characterized in that: the integrated catalytic membrane ozone gas distributor takes a ceramic membrane with micron-sized pore passages as a main body, and an ozone active catalytic material layer is loaded on the outer surface of the main body of the ceramic membrane.
2. The integrated catalytic membrane ozone gas distributor of claim 1, wherein: the main component of the ozone active catalytic material layer comprises gamma-Al2O3。
3. The integrated catalytic membrane ozone gas distributor of claim 1 or 2, wherein: the average pore diameter of the micron-sized pore channel is 1-20 mu m, and the porosity of the ceramic membrane is 30-60%.
4. The method of any one of claims 1-3, wherein the method comprises: the preparation method comprises the following steps:
step 1), mixing Al (OH)3Roasting the powder to convert the powder into gamma-Al2O3；
Step 2), treating the gamma-Al treated in the step 1)2O3Grinding into uniform powder particles for later use;
step 3), washing the powder particles obtained in the step 2) with dilute acid and dilute alkali respectively, finally washing with deionized water until the pH of effluent is neutral, and drying;
step 4), dispersing the powder particles obtained in the step 3) in a solution containing a binder, uniformly shaking to form a coating liquid, coating the coating liquid on the outer surface of the ceramic membrane main body to form a coating, and drying;
and 5) carrying out high-temperature secondary roasting on the ceramic membrane treated in the step 4) to remove the binder.
5. The method of claim 4, wherein the method comprises the steps of: in the step 1), Al (OH)3The powder is roasted for 4 to 6 hours at the temperature of 450-650 ℃ to ensure that the powder is completely converted into gamma-Al2O3。
6. The method of claim 5, wherein the method comprises the steps of: the binder used in the step 4) comprises one or more of polyvinyl alcohol, carboxymethyl cellulose or polyvinyl butyral, and the coating mode of the coating liquid comprises any one of spraying, dip-coating and spin-coating.
7. The method of claim 6, wherein the method comprises the steps of: the high-temperature secondary roasting temperature in the step 5) is 450-650 ℃, and the roasting time is 4-6 h.
8. The method of claim 7, wherein the method comprises the steps of: the powder particles ground in the step 2) are between 5000-10000 meshes.
9. Use of the integrated catalytic membrane ozone gas distributor of claims 1-3, characterized in that: the ozone gas distributor is applied to the catalytic ozonation treatment of chemical wastewater.
10. Use of the integrated catalytic membrane ozone gas distributor according to claim 9, characterized in that: the application method comprises the following steps:
1) introducing the wastewater to be treated into an ozone oxidation reaction device, wherein ozone is diffused into the wastewater through a pipeline by the ozone gas distributor to uniformly release ozone bubbles;
2) in the wastewater treatment process, ozone gas contacts with the ozone active catalytic material layer to generate an ozone catalytic oxidation reaction, and pollutants in the wastewater are oxidized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010186877.XA CN111252884A (en) | 2020-03-17 | 2020-03-17 | Integrated catalytic membrane ozone gas distributor, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010186877.XA CN111252884A (en) | 2020-03-17 | 2020-03-17 | Integrated catalytic membrane ozone gas distributor, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111252884A true CN111252884A (en) | 2020-06-09 |
Family
ID=70943196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010186877.XA Pending CN111252884A (en) | 2020-03-17 | 2020-03-17 | Integrated catalytic membrane ozone gas distributor, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111252884A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
| CN114180706A (en) * | 2021-12-31 | 2022-03-15 | 福建龙净环保股份有限公司 | Ozone catalytic oxidation wastewater treatment equipment and wastewater treatment method |
| CN114887480A (en) * | 2022-06-15 | 2022-08-12 | 江苏省环境工程技术有限公司 | Device and method for treating VOCs (volatile organic compounds) by using membrane catalysis to strengthen ozone microbubbles |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518624A (en) * | 1994-05-06 | 1996-05-21 | Illinois Water Treatment, Inc. | Ultra pure water filtration |
| EP2409954A1 (en) * | 2010-07-20 | 2012-01-25 | National Center for Scientific Research Demokritos | Photocatalytic purification device |
| CN103240111A (en) * | 2013-05-03 | 2013-08-14 | 东南大学 | Structured catalyst for treating printing and dyeing wastewater and preparation method thereof |
| CN104671392A (en) * | 2015-02-13 | 2015-06-03 | 常州大学 | Photocatalytic device for treating organic wastewater |
| CN204454721U (en) * | 2015-04-30 | 2015-07-08 | 上海自来水投资建设有限公司 | A kind of ozone catalytic dissolved air release |
| CN107337326A (en) * | 2017-09-06 | 2017-11-10 | 江西博鑫精陶环保科技有限公司 | A kind of ceramic membrane aeration and pressure-fired ozone film reused water processing method and processing unit |
-
2020
- 2020-03-17 CN CN202010186877.XA patent/CN111252884A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518624A (en) * | 1994-05-06 | 1996-05-21 | Illinois Water Treatment, Inc. | Ultra pure water filtration |
| EP2409954A1 (en) * | 2010-07-20 | 2012-01-25 | National Center for Scientific Research Demokritos | Photocatalytic purification device |
| CN103240111A (en) * | 2013-05-03 | 2013-08-14 | 东南大学 | Structured catalyst for treating printing and dyeing wastewater and preparation method thereof |
| CN104671392A (en) * | 2015-02-13 | 2015-06-03 | 常州大学 | Photocatalytic device for treating organic wastewater |
| CN204454721U (en) * | 2015-04-30 | 2015-07-08 | 上海自来水投资建设有限公司 | A kind of ozone catalytic dissolved air release |
| CN107337326A (en) * | 2017-09-06 | 2017-11-10 | 江西博鑫精陶环保科技有限公司 | A kind of ceramic membrane aeration and pressure-fired ozone film reused water processing method and processing unit |
Non-Patent Citations (2)
| Title |
|---|
| 厉衡隆等: "《铝冶炼生产技术手册 上》", 31 July 2011, 冶金工业出版社 * |
| 莫立焕等: ""γ-Al2O3催化臭氧深度处理蔗渣制浆废水"", 《华南理工大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772843A (en) * | 2021-09-15 | 2021-12-10 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by using special ceramic membrane separation integration technology |
| CN113772843B (en) * | 2021-09-15 | 2023-09-08 | 南京钛净膜材料科技有限公司 | Method for treating alizarin red wastewater by utilizing special ceramic membrane separation integration technology |
| CN114180706A (en) * | 2021-12-31 | 2022-03-15 | 福建龙净环保股份有限公司 | Ozone catalytic oxidation wastewater treatment equipment and wastewater treatment method |
| CN114180706B (en) * | 2021-12-31 | 2024-04-09 | 福建龙净环保股份有限公司 | Ozone catalytic oxidation wastewater treatment equipment and wastewater treatment method |
| CN114887480A (en) * | 2022-06-15 | 2022-08-12 | 江苏省环境工程技术有限公司 | Device and method for treating VOCs (volatile organic compounds) by using membrane catalysis to strengthen ozone microbubbles |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Catalytic membrane-based oxidation-filtration systems for organic wastewater purification: A review | |
| Li et al. | Bi-metal oxide-modified flat-sheet ceramic membranes for catalytic ozonation of organic pollutants in wastewater treatment | |
| CN111252884A (en) | Integrated catalytic membrane ozone gas distributor, preparation method and application | |
| CN102219323B (en) | Method for simultaneously removing organic pollutants and ammonia in waste water and reactor | |
| CN104828926A (en) | Wastewater advanced treatment equipment and method for catalytic ozonation membrane reactor | |
| CN107010709B (en) | Method for purifying high-concentration phenol-containing wastewater in production process of o/hydroquinone | |
| CN111530506B (en) | Ceramic membrane catalyst for ozone catalytic oxidation, preparation method thereof, ceramic membrane catalytic reactor and wastewater treatment process | |
| CN112321026A (en) | Wastewater treatment device and method by coupling ozone micro-nano bubble catalytic oxidation technology with ceramic membrane | |
| CN101386439B (en) | Technique for processing organic wastewater by atmospheric catalytic oxidation at low-temperature | |
| CN110436607A (en) | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process | |
| CN115215492B (en) | Electric flocculation-ozone catalytic oxidation-ceramic membrane coupling water treatment technology for removing residual medicines in pharmaceutical wastewater | |
| CN108126739A (en) | Catalyst of COD and preparation method thereof in a kind of ozone heterocatalysis oxidized waste water | |
| CN109775893A (en) | A kind of persulfate step oxidation coupling membrane filtration purifier and its operation method | |
| CN110563118A (en) | Efficient and stable ozone catalytic oxidation reaction device and sewage treatment method thereof | |
| CN215756632U (en) | Integrated device for coupling ceramic flat membrane with ozone catalytic oxidation | |
| CN208038252U (en) | A kind of waste water removes the device of COD | |
| CN114452977A (en) | Dual-functional material capable of being circularly integrated and simultaneously adsorbing, catalyzing and removing VOCs (volatile organic compounds) under low temperature condition as well as preparation method and application thereof | |
| CN106630109B (en) | Ceramic membrane and preparation method thereof, ceramic membrane module and wastewater treatment system | |
| Li et al. | Advanced treatment of biologically pretreated coal chemical industry wastewater using the catalytic ozonation process combined with a gas-liquid-solid internal circulating fluidized bed reactor | |
| CN210438469U (en) | Catalytic oxidation reaction system for advanced wastewater treatment | |
| CN107585852B (en) | Method and device for carrying out heterogeneous catalytic oxidation on COD (chemical oxygen demand) in wastewater by using ozone | |
| CN102372378A (en) | Treatment method of waste water produced by adopting castor oil to prepare decanedioic acid | |
| CN215233314U (en) | Device for treating VOCs (volatile organic compounds) by micro-nano bubble catalytic oxidation and adsorption coupling | |
| CN215161949U (en) | Reverse osmosis concentrated water recovery device | |
| CN113244945B (en) | Preparation method of heterogeneous Fenton catalyst for wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200609 |