CN110436607B - Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment - Google Patents
Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment Download PDFInfo
- Publication number
- CN110436607B CN110436607B CN201910823880.5A CN201910823880A CN110436607B CN 110436607 B CN110436607 B CN 110436607B CN 201910823880 A CN201910823880 A CN 201910823880A CN 110436607 B CN110436607 B CN 110436607B
- Authority
- CN
- China
- Prior art keywords
- membrane
- catalytic
- rgo
- separation membrane
- catalytic separation
- 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.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 205
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000926 separation method Methods 0.000 title claims abstract description 69
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 10
- 230000001276 controlling effect Effects 0.000 title claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 77
- 230000008569 process Effects 0.000 claims abstract description 48
- 230000004907 flux Effects 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000005374 membrane filtration Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000002957 persistent organic pollutant Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003651 drinking water Substances 0.000 claims description 14
- 235000020188 drinking water Nutrition 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 231100000086 high toxicity Toxicity 0.000 claims description 6
- 239000010842 industrial wastewater Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000011112 process operation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 238000005949 ozonolysis reaction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000012827 research and development Methods 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 8
- 239000012964 benzotriazole Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
-
- 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
- C02F1/72—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
According to the invention, nitrogen-doped graphene (N-rGO) is loaded on the surface of a ceramic membrane, and the water production flux, catalysis and membrane pollution resistance of the catalytic membrane are controlled by adjusting the thickness of an active layer of the N-rGO. The N-rGO catalytic separation membrane can change the hydrophilicity of the membrane surface to improve the water production flux of the ceramic membrane, and the excellent catalytic performance of the N-rGO catalytic separation membrane can help the catalytic ozonolysis of the membrane surface to generate hydroxyl radicals to degrade pollutants polluted in membrane pores, so that the water production flux of the membrane is maintained at a high level in the filtering process. In addition, for organic micro-pollutants which are high in toxicity and difficult to degrade and cannot be removed by common ceramic membrane filtration, the N-rGO catalytic separation membrane can efficiently complete enhanced removal of the organic micro-pollutants. Therefore, the catalytic separation membrane capable of regulating and controlling the interface catalytic performance has wide application prospects in the aspects of research and development of functional membranes and purification of pollutants in water.
Description
Technical Field
The invention relates to an assembly method of a novel catalytic separation membrane and an application method thereof in water treatment engineering, belonging to the field of membrane material science and engineering and environmental engineering.
Background
The application of the ultrafiltration membrane filtration process in the sewage regeneration treatment is increasingly wide. The combination of the chemical oxidation process and the ultrafiltration process can improve the quality of the effluent and relieve the membrane pollution. However, strong oxidants such as ozone are likely to cause aging damage of the organic polymer film, shorten the service life, and cause secondary pollution. The ceramic membrane has the advantages of good mechanical and thermal stability, acid resistance, alkali resistance, organic solvent resistance, strong biological pollution resistance, wide application range, easy cleaning, high separation efficiency and the like. Therefore, it is very promising to construct an ozone-ceramic membrane coupled water treatment technology. The patent CN 108101266A and the patent CN 103951028A couple the ozone oxidation technology and the ceramic membrane filtration technology, effectively treat the pollutants which are difficult to degrade in the sewage, simultaneously reduce the membrane pollution on the surface of the ceramic membrane and reduce the process reaction time. However, the oxidation capacity of ozone oxidation to organic pollutants is limited, and a large amount of organic matters in water can consume a large amount of ozone, so that the utilization efficiency of ozone is low, and the removal rate of small-molecule trace organic pollutants is low. The ineffective consumption of ozone results in effective control of ceramic membrane contamination. The ceramic membrane only has a filtering function and cannot intercept micromolecular trace organic pollutants. Therefore, the ozone-ceramic membrane coupled water treatment technology with wide application prospect has very limited capability of removing trace organic pollutants.
The heterogeneous catalytic ozonation technology is easy to operate and convenient to apply to the deep treatment engineering of drinking water and sewage because no new chemical agent is introduced. The introduction of the catalyst can catalyze ozone to generate more OH with strong oxidizing property, and organic pollutants in water and organic membrane pollution components blocked in membrane pores are removed in an enhanced manner. However, most of the heterogeneous catalytic ozone catalysts reported in a large number of patents and documents are powder, and cannot be efficiently separated in water, so that the engineering application of the heterogeneous catalytic ozone oxidation technology is greatly limited.
In view of this, there are patents and documents reporting that the assembly of a catalytic membrane is realized by using a ceramic membrane as a catalyst carrier and supporting a high-efficiency catalyst on the surface of the ceramic membrane to form a catalytic layer on the surface of the ceramic membrane.The catalytic membrane can strengthen the ozone decomposition to form OH with high oxidation capacity, and the high-efficiency removal of the nondegradable trace organic pollutants in water is realized. On the basis, the degradation of organic membrane polluted components and biological membrane polluted components can be realized by the catalytic action of the interface, the membrane pollution is relieved, the water production flux of the membrane is improved, the high-flux operation is maintained, the process operation period is delayed, and the operation economic cost is greatly reduced. Patent CN 106391034A uses layer-by-layer deposition heat treatment method to treat Fe 2 O 3 -NiO-CeO 2 The ozone catalyst is loaded on the surface of the ceramic membrane to form a catalytic separation membrane, and the catalytic separation membrane is coupled with ozone to form the ozone catalytic membrane water treatment process. The process is used for treating the steelmaking wastewater with high COD concentration and high organic matter content which is difficult to solve by the prior art, and the effluent can reach the national discharge standard; the patent CN 105800735A loads manganese cobalt composite oxide with high catalytic ozone activity on the surface of a ceramic membrane, so that the formation of membrane pollution is effectively controlled, the degradation-resistant micropollutants in a water body are intensively removed, the separation of a catalyst and water is realized, and a new method is provided for the cleaning and the repeated recycling of the catalyst; the patent CN 104841292A supports manganese oxide on the surface of a ceramic membrane through a dipping method, and the ceramic membrane supported by the manganese oxide has good capability of adsorbing and catalyzing ozone. Can effectively relieve membrane pollution while improving the ozone catalyzing capacity. The integration of multiple functions such as pollutant adsorption, catalytic ozone oxidation, membrane separation and the like is realized. In addition, in patent CN 106745673a, dysprosium nitrate, platinum nitrate and manganese nitrate solutions are doped into a ceramic membrane preparation precursor solution, and the catalytic ozone separation membrane containing dysprosium, platinum and manganese is prepared through the processes of paste mixing, mud refining, extrusion molding, drying, vacuum sintering and the like, so that the filtering performance of the ceramic membrane is improved, and the formation of membrane pollution is effectively alleviated.
However, the catalytic ozonated ceramic membrane reported in the above patent selects metals and their metal oxides as catalytic active centers. These active centers or catalysts present a potential risk of releasing metal ions during the catalytic ozonation process and are not easily applied to the advanced treatment of drinking water and the production of high-standard reclaimed water.
Therefore, the nitrogen-doped graphene (N-rGO) selected by the patent is a non-metallic carbon material, does not produce secondary pollution and has good structural and chemical stability. A large number of oxygen-containing functional groups and doped nitrogen atoms on the surface of the N-rGO can provide a large number of active sites for catalyzing ozone, strengthen the generation of more OH & ltozone, and realize the efficient degradation of small molecular trace organic pollutants in water and the synchronous degradation of organic membrane pollution components and biological membrane pollution components in water. According to the catalytic membrane, the N-rGO is loaded on the surface of the ceramic membrane to form the catalytic membrane, and in order to cope with different water inlet loads, a catalytic separation membrane capable of regulating and controlling the catalytic performance of an interface is innovatively designed, so that high-toxicity and difficult-to-degrade organic micro-pollutants which cannot be intercepted by the ceramic membrane can be removed, organic membrane pollutants and biological membrane pollutants in water can be synchronously degraded, the water production flux of an ozone-ceramic membrane system is improved, and the operation period of the ozone-ceramic membrane system is delayed. Therefore, the invention has wide application prospect in membrane water treatment.
Disclosure of Invention
The invention provides an assembly of a catalytic separation membrane with adjustable interface catalytic performance and an application method thereof in water treatment. The method is explained for the assembly method of the adjustable N-rGO modified ceramic membrane and the application method in water treatment, and the filtration, micro-pollution removal and membrane pollution resistance of the membrane are evaluated by adopting a polluted water body containing macromolecular sodium alginate and micromolecular hardly degradable Benzotriazole (BZA) organic pollutants as a treatment target. The invention utilizes the advantages of good mechanical and physical and chemical properties of N-rGO, no secondary pollution, unique layered structure and the like to modify the surface of the ceramic membrane, organically combines catalysis and membrane filtration, and further improves the capabilities of filtering, decontaminating and resisting membrane pollution of the ceramic membrane.
The invention provides an assembly of a catalytic separation membrane with adjustable interface catalytic performance and an application method thereof in water treatment, which is characterized in that the assembly of an adjustable N-rGO modified ceramic membrane can be prepared through the following processes: (1) preparing an N-rGO turbid liquid: weighing 100-300 mg of N-rGO, wherein the ratio (C/N) of the content of carbon elements to the content of nitrogen elements is 43.0-45.0, ultrasonically dispersing the N-rGO into 1.0L of ultra-pure water for 2.0h to obtain 100-300 mg/L N-rGO turbid liquid; (2) assembling N-rGO in the ceramic membrane hole: the prepared N-rGO turbid liquid is filled into a sealed stainless steel liquid storage tank (shown in figure 1 in the specification) with interfaces left at the upper part and the lower part, an opening at the upper end is connected with a nitrogen cylinder, and an opening at the lower end is connected with a membrane component. Opening nitrogen to adjust the pressure to be 0.0-4.0 bar, extruding the N-rGO turbid liquid into a membrane assembly from a stainless steel liquid storage tank in a 'dead-end filtration' mode through the pressure provided by the nitrogen, so that the N-rGO is uniformly loaded in a ceramic membrane hole, and assembling the catalytic separation membrane taking the N-rGO as a core; (3) and (3) curing: drying the prepared ceramic membrane in a vacuum drying oven at 25-60 ℃ for 12-48 h; (4) and (3) calcining: and (3) placing the dried ceramic membrane in a tubular furnace protected by high-purity nitrogen atmosphere (the gas flow rate is 100mL/min) for calcination, wherein the calcination temperature is 300-700 ℃, the heating rate is 2.5-10 ℃/min, and the calcination time is 60-90 min, so as to obtain the catalytic separation membrane.
The method is characterized in that: the N-rGO is black solid powder and is easy to disperse ultrasonically, the content ratio (C/N) of carbon element to nitrogen element is 43.0-45.0, and the specific surface area is 130.0-140.0 m 2 Per g, total pore volume of 0.2-0.3 cm 3 /g。
The method is characterized by comprising the following steps: the ceramic film adopts alpha-Al 2 O 3 As a support layer, ZrO 2 A tubular ceramic membrane as a filter layer, the size of the membrane hole is 20-50 nm, and the membrane area is 0.01-0.02 m 2 。
Characterized in that: the thickness of the catalytic active layer of the surface N-rGO can be regulated and controlled through different loading times of the N-rGO, and the catalytic performance and the water production flux of the catalytic separation membrane can be quantitatively regulated and controlled; when the N-rGO catalytic layer is thin (the catalytic active layer is less than 5.0-6.0 mu m), the water production flux of the catalytic separation membrane can be remarkably improved, and the flux is 71.73L/m compared with that of an unmodified ceramic membrane 2 H) compared with the obtained product, the flux of the modified ceramic membrane of N-rGO can be improved by 25.7% to the maximum extent; in addition, the method has an obvious improvement effect on the alleviation of membrane pollution, and the membrane pollution resistance of the ceramic membrane modified by the N-rGO can be improved by 37.3% to the maximum extent. After the modified N-rGO ceramic membrane is filtered and coupled with ozone, the membrane pollution resistance can be improved by 38.7 percent to the maximum extent; when the N-rGO catalytic layer is thick (the catalytic active layer is large)5.0-6.0 mu m), is beneficial to the degradation of organic pollutants by the catalytic separation membrane, and can improve the removal performance of the slightly polluted organic Benzotriazole (BZA) by 6.43 times.
The method is characterized by comprising the following steps: the surface roughness of the catalytic separation membrane is 200-350 nm.
Characterized in that (VI): the catalytic separation membrane and the ozone are operated in the same pool (as shown in the attached figure 2 of the specification), and the process operation parameters are as follows: (1) ozone concentration: 0-40 mg/L; (2) gas flow rate: 300-500 mL/min; (3) transmembrane pressure difference (TMP): 0.10 to 0.20 bar; (4) reflux ratio: 40% -80%; (5) the flow rate of the membrane surface is as follows: 900-1600 mL/min; (6) volume of reaction solution: 500-1000 mL; (7) raw water [ TOC ]: 0-30 mg/L; (8) concentration of organic matter of micropollutants: 0 to 20 mg/L.
Characterized in that (VII): the process can be applied to a conventional drinking water treatment process, and the filtering process in the conventional drinking water treatment is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtering process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized.
Characterized in that (eight): the process can be applied to the advanced treatment process of drinking water, and the ozone-biological activated carbon process in the advanced treatment of the drinking water is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtration process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized.
Characterized in that (nine): the process can be applied to urban reclaimed water treatment, and an N-rGO catalytic separation membrane coupled ozone structure is added after a secondary sedimentation tank process, so that the reinforced removal of small-molecular and high-toxicity refractory organic pollutants is realized, and the treatment requirement of safe regeneration is met.
Characterized in that (ten): the process can be applied to the advanced treatment of industrial wastewater, and an N-rGO catalytic separation membrane coupled ozone structure is added after the secondary sedimentation tank process, so that the high-efficiency enhanced removal of chemical oxygen demand is realized, and the emission and recycling standards of industrial wastewater are met.
The invention has the beneficial effects that: the assembly of the catalytic separation membrane with adjustable interface catalytic performance and the application method thereof in water treatment provided by the invention can adjust and control the catalytic-filtration-membrane pollution resistance of the modified ceramic membrane by adjusting and controlling the load thickness. For the condition that the load of organic membrane pollution components in water is heavy, a catalytic separation membrane with the thickness of an N-rGO catalytic layer being less than 5.0-6.0 mu m can be selected as a countermeasure, and the advantages of high filtration efficiency and good membrane pollution resistance are utilized; for the condition that the load of the small-molecular organic micro-pollutants in water is heavy, a catalytic separation membrane with the thickness of an N-rGO catalytic layer larger than 5.0-6.0 mu m can be selected as a countermeasure. The invention not only can solve the problem of high-toxicity micro-pollutants which cannot be removed by membrane filtration, but also can improve the filtration efficiency of the ceramic membrane, prolong the operation period of the membrane and save the operation cost of water treatment.
Brief description of the drawings
FIG. 1 is a diagram of an apparatus for preparing an N-rGO modified ceramic membrane by a gas pressure method according to a first embodiment. FIG. 2 is a diagram of a catalytic separation membrane coupled ozone and tank operation device obtained in the first embodiment. FIG. 3 is an evaluation of pure water flux performance of N-rGO modified ceramic membranes with different thicknesses obtained in the first embodiment, wherein ■ represents the water flux situation of unmodified ceramic membranes, ● represents the water flux situation after N-rGO (thickness: 1.52 +/-0.97 mu m) is loaded on the surfaces of the ceramic membranes, and a-solidup represents the water flux situation after N-rGO (thickness: 4.05 +/-1.59 mu m) is loaded on the surfaces of the ceramic membranes; xxx represents the water flux produced after loading N-rGO (thickness: 8.85 ± 2.89 μm) on the surface of the ceramic membrane. As can be seen from the figure, the water production flux of the ceramic membrane loaded with N-rGO (the thickness is 1.52 +/-0.97 mu m and 4.05 +/-1.59 mu m) is obviously improved compared with that of the unmodified ceramic membrane, and is respectively improved by 1.29 times and 1.14 times. And the water production flux of the ceramic membrane loaded with N-rGO (the thickness: 8.85 +/-2.89 mu m) is obviously reduced. FIG. 4 is an evaluation of the membrane fouling resistance of N-rGO modified ceramic membranes of different thicknesses obtained in the first embodiment during the filtration process. FIG. 5 is an evaluation of the membrane fouling resistance of the N-rGO modified ceramic membranes with different thicknesses obtained in the first embodiment in the process of filtering and coupling ozone. Through the change of the specific flux, the following results are found: the membrane pollution resistance of the ceramic membrane loaded with the N-rGO is obviously improved compared with that of an unmodified ceramic membrane, and the membrane pollution resistance is reduced along with the increase of the loading thickness. After ozone is introduced, the membrane pollution resistance of the ceramic membrane is obviously improved compared with that of an unmodified ceramic membrane, and the flux of the ceramic membrane can be basically recovered to 95-97% of the initial flux. FIG. 6 is a graph showing the evaluation of the catalytic performance of N-rGO modified ceramic membranes with different thicknesses obtained in the first embodiment. The N-rGO modified ceramic membrane has a very obvious improvement effect on the degradation effect of the micropollutant BZA compared with the unmodified ceramic membrane, and the degradation effect is obviously enhanced along with the increase of the loading thickness.
Detailed Description
The assembly of the catalytic separation membrane with controllable interface catalytic performance and the application method thereof in water treatment are explained, and the technical scheme of the invention is not limited to the following embodiments and also comprises any combination of the embodiments.
The first specific implementation way is as follows: the assembly of the adjustable N-rGO modified ceramic membrane can be completed by the following processes: (1) preparing an N-rGO suspension: weighing 100mg of N-rGO, ultrasonically dispersing the N-rGO into 1.0L of ultrapure water for 2.0h to obtain 100mg/L N-rGO suspension; (2) assembling N-rGO in the ceramic membrane pores: the prepared N-rGO turbid liquid is filled into a sealed stainless steel liquid storage tank (shown in figure 1 in the specification) with interfaces left at the upper part and the lower part, an opening at the upper end is connected with a nitrogen cylinder, and an opening at the lower end is connected with a membrane component. Opening nitrogen to adjust the pressure to 2.0bar, extruding the N-rGO turbid liquid into a membrane component from a stainless steel liquid storage tank in a 'dead-end filtration' mode through the pressure provided by the nitrogen, so that the N-rGO is uniformly loaded in the pores of the ceramic membrane, and the assembly of the catalytic separation membrane taking the N-rGO as the core is completed; (3) and (3) curing: drying the prepared ceramic membrane in a vacuum drying oven at 60 ℃ for 24 hours; (4) and (3) calcining: and (3) placing the dried ceramic membrane in a tubular furnace protected by high-purity nitrogen atmosphere (the gas flow rate is 100mL/min) for calcination, wherein the calcination temperature is 350 ℃, the heating rate is 5.0 ℃/min, and the calcination time is 60min, so as to obtain the catalytic separation membrane. The regulation of the thickness of the catalytic layer is realized by regulating the loading times.
The N-rGO selected by the process is black solid powder which is easy to disperse ultrasonically, the content ratio (C/N) of carbon element to nitrogen element is 43.5, and the specific surface area is 136.2m 2 Per g, total pore volume of 0.26cm 3 (iv) g. The ceramic membrane selected by the process adopts alpha-Al 2 O 3 As a support layer, ZrO 2 The tubular ceramic membrane is a filter layer, the pore size of the membrane is 50nm, and the membrane area is 0.0133m 2 。
The process can realize the regulation and control of the thickness of the catalytic active layer of the surface N-rGO through different loading times of the N-rGO, and quantitatively regulate and control the catalytic performance and the water production flux of the catalytic separation membrane; when the N-rGO catalytic layer is thin (the catalytic active layer is less than 5.0-6.0 mu m), the water production flux of the catalytic separation membrane can be remarkably improved, and the flux is 71.73L/m compared with that of an unmodified ceramic membrane 2 H) compared with the obtained product, the flux of the modified ceramic membrane of N-rGO can be improved by 25.7% to the maximum extent; in addition, the method has an obvious improvement effect on the alleviation of membrane pollution, and the membrane pollution resistance of the ceramic membrane modified by the N-rGO can be improved by 37.3% to the maximum extent. After the modified N-rGO ceramic membrane is filtered and coupled with ozone, the membrane pollution resistance can be improved by 38.7 percent to the maximum extent; when the N-rGO catalytic layer is thick (the catalytic activity layer is larger than 5.0-6.0 mu m), the degradation of organic pollutants by the catalytic separation membrane is facilitated, and the removal performance of the micro-polluted organic Benzotriazole (BZA) can be improved by 6.43 times. The surface roughness of the catalytic separation membrane prepared by the process is respectively as follows: 308 + -6.5 nm (thickness: 1.52 + -0.97 μm), 248 + -7.7 nm (thickness: 4.05 + -1.59 μm) and 215 + -16 nm (thickness: 8.85 + -2.89 μm).
The second embodiment is as follows: the process is realized by the following steps: (1) ozone concentration: 20 mg/L; (2) gas flow rate: 400 mL/min; (3) transmembrane pressure difference (TMP): 0.18-0.19 bar; (4) reflux ratio: 70 percent; (5) water temperature: 28.1 ℃; (6) the flow rate of the membrane surface is as follows: 1200 mL/min; (7) volume of reaction solution: 800 mL; (8) sodium alginate concentration: 30 mg/L; (9) benzotriazole concentration: 10 mg/L.
The third concrete implementation mode: the process can be applied to a conventional drinking water treatment process, and the filtering process in the conventional drinking water treatment is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtering process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized. The specific process flow is water inlet → coagulation → N-rGO catalytic separation membrane coupling ozone membrane filtration → disinfection → water outlet.
The fourth concrete implementation mode is as follows: the process can be applied to advanced treatment of drinking water, and an ozone-biological activated carbon process in the advanced treatment of the drinking water is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtration process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized. The process flow is water inlet → coagulation → precipitation → filtration → disinfection → N-rGO catalytic separation membrane coupling ozone membrane filtration advanced treatment → water outlet.
The fifth concrete implementation mode: the process can be applied to urban recycled water treatment, and an N-rGO catalytic separation membrane coupling ozone structure is added after a secondary sedimentation tank process, so that the reinforced removal of micromolecular and high-toxicity refractory organic pollutants is realized, and the treatment requirement of safe regeneration is met. The specific process flow is water inlet → coarse grids → an aeration grit chamber → a primary sedimentation tank → an anaerobic tank → an anoxic tank → an aerobic tank → a secondary sedimentation tank → coagulation → sedimentation → N-rGO catalytic separation membrane coupled with ozone membrane filtration → UV disinfection → water outlet.
The sixth specific implementation mode: the process can be applied to the advanced treatment of industrial wastewater, and an N-rGO catalytic separation membrane coupled ozone structure is added after a biochemical process, so that the high-efficiency enhanced removal of chemical oxygen demand is realized, and the emission and recycling standards of industrial wastewater are reached. The specific process flow is water inlet → coarse grid → regulating tank → primary sedimentation tank → biological treatment → secondary sedimentation tank → coagulation → sedimentation of N-rGO catalytic separation membrane coupling ozone membrane filtration → disinfection → water outlet.
Claims (9)
1. The assembling method of the catalytic separation membrane capable of regulating and controlling the interface catalytic performance is characterized in that nitrogen-doped graphene N-rGO is used as a core, a catalytic active layer is constructed on the surface of a ceramic membrane, the catalytic separation membrane is assembled, the catalytic separation membrane can catalyze the decomposition of ozone to generate hydroxyl free radicals with strong oxidizing property, organic pollutants in membrane pores are oxidized and degraded, small-molecule and high-toxicity refractory organic pollutants are removed in an enhanced mode, membrane pollution is relieved remarkably, the application period and the service life of the membrane are prolonged, the catalytic separation membrane realizes the regulation and control of the thickness of the catalytic active layer of the surface N-rGO through different loading times of the N-rGO, the catalytic performance and the water production flux of the catalytic separation membrane are regulated and controlled quantitatively, and the assembling method is assembled through the following steps:
(1) preparing an N-rGO turbid liquid: weighing 100-300 mg of N-rGO, wherein the ratio (C/N) of the content of carbon elements to the content of nitrogen elements is 43.0-45.0, ultrasonically dispersing the N-rGO into 1.0L of ultrapure water for 2.0h to obtain 100-300 mg/L N-rGO suspension;
(2) assembling N-rGO in the ceramic membrane hole: loading the prepared N-rGO turbid liquid into a sealed stainless steel liquid storage tank with an upper connector and a lower connector, connecting an opening at the upper end with a nitrogen bottle, connecting an opening at the lower end with a membrane module, opening nitrogen to adjust the pressure to be 0.0-4.0 bar, extruding the N-rGO turbid liquid into the membrane module from the stainless steel liquid storage tank in a dead-end filtering mode through the pressure provided by the nitrogen, and thus uniformly loading the N-rGO in the pores of the ceramic membrane to complete the assembly of the catalytic separation membrane taking the N-rGO as the core;
(3) and (3) curing: drying the prepared ceramic membrane in a vacuum drying box at the temperature of 25-60 ℃ for 12-48 h;
(4) and (3) calcining: and placing the dried ceramic membrane in a tubular furnace protected by high-purity nitrogen for calcination, wherein the gas flow rate of the high-purity nitrogen is 100mL/min, the calcination temperature is 300-700 ℃, the heating rate is 2.5-10 ℃/min, and the calcination time is 60-90 min, so as to obtain the catalytic separation membrane.
2. The method for assembling a catalytic separation membrane with controllable interfacial catalytic performance according to claim 1, wherein the N-rGO is black solid powder, is easy to disperse ultrasonically, has a carbon-to-nitrogen content ratio (C/N) of 43.0 to 45.0, and has a specific surface area of 130.0 to 140.0m 2 (ii) a total pore volume of 0.2 to 0.3cm 3 /g。
3. The method for assembling a catalytic separation membrane with controllable interfacial catalytic performance as claimed in claim 1, wherein the ceramic membrane is made of a ceramic materialα-Al 2 O 3 As a support layer, ZrO 2 The tubular ceramic membrane is a filter layer, the size of the membrane pores is 20-50 nm, and the membrane area is 0.01-0.02 m 2 。
4. The method for assembling a catalytic separation membrane with controllable interfacial catalytic performance according to claim 1, wherein the surface roughness of the catalytic separation membrane is 200 to 350 nm.
5. The method for assembling the catalytic separation membrane with adjustable interface catalytic performance in water treatment according to claim 1, wherein the catalytic separation membrane and ozone are operated in the same tank, and the process operation parameters are as follows:
(1) ozone concentration: 0-40 mg/L, excluding 0 mg/L;
(2) gas flow rate: 300-500 mL/min;
(3) transmembrane pressure difference TMP: 0.10 to 0.20 bar;
(4) reflux ratio: 40% -80%;
(5) the flow rate of the film surface is as follows: 900-1600 mL/min;
(6) volume of reaction solution: 500-1000 mL;
(7) raw water TOC concentration: 0-30 mg/L, excluding 0 mg/L;
(8) concentration of organic matter of micropollutants: 0 to 20mg/L, excluding 0 mg/L.
6. An application method of the assembly method of the catalytic separation membrane with the adjustable interface catalytic performance in water treatment according to claim 5, which is characterized in that when the assembly method is applied to a conventional drinking water treatment process, a filtration process in the conventional drinking water treatment is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtration process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized.
7. The method for assembling the catalytic separation membrane with the adjustable interface catalytic performance in water treatment according to claim 5 is applied to drinking water deep treatment, and an ozone-biological activated carbon process in the drinking water deep treatment is replaced by an N-rGO catalytic separation membrane coupled ozone membrane filtration process, so that the enhanced removal of trace organic pollutants is realized, and the water supply safety is realized.
8. The method for assembling the catalytic separation membrane with the adjustable interface catalytic performance in water treatment according to claim 5 is characterized in that the method is applied to urban reclaimed water treatment, and after a secondary sedimentation tank process, an N-rGO catalytic separation membrane is added to be coupled with an ozone structure, so that the enhanced removal of small-molecule and high-toxicity refractory organic pollutants is realized, and the treatment requirement of safe regeneration is met.
9. The method for applying the assembling method of the catalytic separation membrane with the adjustable interface catalytic performance in water treatment according to claim 5 is characterized in that the method is applied to advanced treatment of industrial wastewater, and an N-rGO catalytic separation membrane is added to be coupled with an ozone structure after a secondary sedimentation tank process, so that the high-efficiency enhanced removal of chemical oxygen demand is realized, and the emission and reuse standards of the industrial wastewater are met.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910823880.5A CN110436607B (en) | 2019-09-02 | 2019-09-02 | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910823880.5A CN110436607B (en) | 2019-09-02 | 2019-09-02 | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110436607A CN110436607A (en) | 2019-11-12 |
| CN110436607B true CN110436607B (en) | 2022-09-16 |
Family
ID=68438755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910823880.5A Active CN110436607B (en) | 2019-09-02 | 2019-09-02 | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110436607B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111420564B (en) * | 2020-03-05 | 2021-01-19 | 浙江美易膜科技有限公司 | Inorganic composite separation membrane containing graphene oxide, and preparation method and application thereof |
| CN111573818A (en) * | 2020-05-27 | 2020-08-25 | 北京林业大学 | Ozone catalytic membrane reactor assembly and application method thereof in water treatment engineering |
| CN114653391B (en) * | 2022-03-11 | 2023-10-03 | 大连工业大学 | Preparation method of carbon-based catalytic film with high selectivity and pollution resistance |
| CN115608403B (en) * | 2022-11-22 | 2023-05-16 | 中国科学院宁波材料技术与工程研究所 | Carbon-based composite ceramic catalytic membrane doped with metal by nitrogen, and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11285625A (en) * | 1998-02-09 | 1999-10-19 | Toray Ind Inc | Catalytic separation membrane, catalytic reaction method ahd production of compound |
| CN103739120A (en) * | 2014-01-10 | 2014-04-23 | 天津市环境保护科学研究院 | Coupling type membrane ozone catalytic reaction system and device for treating organic wastewater |
| CN103752354A (en) * | 2014-01-10 | 2014-04-30 | 天津市环境保护科学研究院 | Regeneration method and device used for deactivation catalyst layer of membrane ozone catalytic reactor |
| CN103951028A (en) * | 2014-04-10 | 2014-07-30 | 北京林业大学 | Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN106565008A (en) * | 2016-10-18 | 2017-04-19 | 哈尔滨工业大学 | Method for degrading antibiotic in wastewater |
| CN106582331A (en) * | 2016-12-30 | 2017-04-26 | 河海大学 | Preparation method of photocatalytic ultrafilter membrane material with visible light activity |
| CN109621974A (en) * | 2019-01-16 | 2019-04-16 | 北京林业大学 | A kind of CuMn2O4/ rGO composite material catalytic ozonation depollution method for treating water |
| CN109701585A (en) * | 2019-02-28 | 2019-05-03 | 哈尔滨工业大学 | A kind of preparation method and application of inorganic catalytic membrane |
| CN110152494A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院生态环境研究中心 | Control membrane fouling method based on graphene oxide directional separation film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10376845B2 (en) * | 2016-04-14 | 2019-08-13 | Lockheed Martin Corporation | Membranes with tunable selectivity |
| KR101934568B1 (en) * | 2016-11-25 | 2019-01-02 | 한국과학기술연구원 | Method of manufacturing nanoporous graphene membrane |
-
2019
- 2019-09-02 CN CN201910823880.5A patent/CN110436607B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11285625A (en) * | 1998-02-09 | 1999-10-19 | Toray Ind Inc | Catalytic separation membrane, catalytic reaction method ahd production of compound |
| CN103739120A (en) * | 2014-01-10 | 2014-04-23 | 天津市环境保护科学研究院 | Coupling type membrane ozone catalytic reaction system and device for treating organic wastewater |
| CN103752354A (en) * | 2014-01-10 | 2014-04-30 | 天津市环境保护科学研究院 | Regeneration method and device used for deactivation catalyst layer of membrane ozone catalytic reactor |
| CN103951028A (en) * | 2014-04-10 | 2014-07-30 | 北京林业大学 | Water treatment method for catalytic ozonation of refractory organics in water by ceramic membrane |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN106565008A (en) * | 2016-10-18 | 2017-04-19 | 哈尔滨工业大学 | Method for degrading antibiotic in wastewater |
| CN106582331A (en) * | 2016-12-30 | 2017-04-26 | 河海大学 | Preparation method of photocatalytic ultrafilter membrane material with visible light activity |
| CN110152494A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院生态环境研究中心 | Control membrane fouling method based on graphene oxide directional separation film |
| CN109621974A (en) * | 2019-01-16 | 2019-04-16 | 北京林业大学 | A kind of CuMn2O4/ rGO composite material catalytic ozonation depollution method for treating water |
| CN109701585A (en) * | 2019-02-28 | 2019-05-03 | 哈尔滨工业大学 | A kind of preparation method and application of inorganic catalytic membrane |
Non-Patent Citations (2)
| Title |
|---|
| （"N/S-doped graphene derivatives and TiO2 for catalytic ozonation and photocatalysis of water pollutants";Marta Pedrosa等;《Chemical Engineering Journal》;20180502;第348卷;第888-897页 * |
| Synthesis of N-doped and non-doped partially oxidised graphene membranes supported over ceramic materials;A. Gime´nez-Pe´rez等;《Journal of materials Science》;20160613;第51卷(第18期);第8346-8360页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110436607A (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110436607B (en) | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment | |
| Li et al. | Catalytic membrane-based oxidation-filtration systems for organic wastewater purification: A review | |
| CN102936081B (en) | Photocatalytic internal-circulation anaerobic fluidized membrane bioreactor and working method thereof | |
| CN102874960A (en) | Device and method for treating high-salinity and degradation-resistant organic industrial waste water by performing photoelectrical synchro coupling and catalytic oxidation on three-dimensional particles | |
| CN108101299B (en) | High-vanadium SCR denitration catalyst regeneration wastewater treatment method | |
| CN107698037B (en) | Method for deeply treating reverse osmosis concentrated water of landfill leachate by three-dimensional electrochemical coupling three-dimensional electrobiology | |
| CN103073150B (en) | Photocatalytic postposed internal-circulation anaerobic fluidized membrane bioreactor and working method thereof | |
| CN104828926A (en) | Wastewater advanced treatment equipment and method for catalytic ozonation membrane reactor | |
| CN102167435B (en) | Solid catalytic Fenton water treatment technique | |
| CN109621974B (en) | CuMn2O4Method for treating polluted water by ozone catalytic oxidation and removal of pollutants through rGO composite material | |
| KR102597770B1 (en) | Catalytic composite for catalytic ozone oxidation process and preparation method thereof | |
| CN108002660A (en) | Depth waste water treatment system and sewage water treatment method | |
| CN110589950A (en) | Cu/Fe-HT-CM hydrotalcite catalytic membrane, preparation method and application | |
| CN210438469U (en) | Catalytic oxidation reaction system for advanced wastewater treatment | |
| CN107986519A (en) | A kind of electro-catalysis and photocatalysis sewage processing method | |
| CN113135631B (en) | Low-sludge-yield wastewater treatment method based on multidimensional catalytic oxidation process | |
| CN113318608B (en) | Dynamically catalyzed water treatment ceramic membrane and application thereof | |
| CN202849221U (en) | Photocatalytic and internal circulation anaerobic fluidized membrane bioreactor | |
| CN115093082A (en) | Waste water treatment process and device for landfill leachate and DTRO concentrated solution | |
| CN1927745A (en) | Process for treating waste water of refined terephthalic acid | |
| CN108751573B (en) | BAME treatment and recycling method for printing and dyeing wastewater | |
| CN203007092U (en) | Photocatalysis-postpositioned internal-circulation anaerobic fluidized membrane bioreactor | |
| CN111573818A (en) | Ozone catalytic membrane reactor assembly and application method thereof in water treatment engineering | |
| CN105174565B (en) | Acrylic fiber wastewater deep treatment method | |
| Sivaprakash et al. | Applications of submerged and staged membrane systems for pollutant removal from effluents and mechanism studies–a review |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |