CN111573818A - Ozone catalytic membrane reactor assembly and application method thereof in water treatment engineering - Google Patents
Ozone catalytic membrane reactor assembly and application method thereof in water treatment engineering Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910016526 CuMn2O4 Inorganic materials 0.000 claims abstract description 35
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 20
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims abstract description 13
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000003651 drinking water Substances 0.000 claims abstract description 5
- 235000020188 drinking water Nutrition 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000001954 sterilising effect Effects 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000005949 ozonolysis reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
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- 239000007789 gas Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 231100000614 poison Toxicity 0.000 claims 1
- 230000007096 poisonous effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 15
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NEGBOTVLELAPNE-UHFFFAOYSA-N [Ti].[Ce] Chemical compound [Ti].[Ce] NEGBOTVLELAPNE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- SYBFKRWZBUQDGU-UHFFFAOYSA-N copper manganese(2+) oxygen(2-) Chemical class [O--].[O--].[Mn++].[Cu++] SYBFKRWZBUQDGU-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention relates to the technical field of environmental protection and water supply and drainage engineering, and discloses an ozone catalytic membrane reactor assembly and an application method thereof in water treatment engineering. In the catalytic membrane, the catalytic active layer is graphene and CuMn2O4A composite material. Graphene and CuMn by adopting vacuum negative pressure method2O4CompoundingThe material is loaded on the surface of the ceramic membrane to form a catalytic active layer, so that the catalytic ceramic membrane is coupled with the ozone oxidation in situ. Wherein the catalyst layer component CuMn is utilized2O4The rGO catalyzes ozone to generate hydroxyl free radicals and superoxide free radicals with higher oxidation capacity, so that organic pollutants are efficiently degraded; in the process of degrading high-risk trace organic matters, the online self-cleaning effect of the separation membrane is synchronously improved, and the generation of a toxic byproduct bromate of ozone is effectively inhibited. The ozone catalytic membrane reactor of the invention enables the removal rate of refractory organic matters to reach more than 90 percent, realizes the reinforced removal of the refractory organic matters in drinking water, municipal sewage and industrial wastewater, and achieves the purpose of efficiently purifying water quality.
Description
Technical Field
The invention relates to an ozone catalytic membrane reactor assembly and an application method thereof in water treatment engineering, belonging to the technical fields of environmental protection and water supply and drainage engineering.
Background
Catalytic ozonation is a new advanced oxidation technology developed in recent years, and means that ozone molecules are promoted to decompose by using metal ions, metal oxides or metal oxides loaded on a carrier in a solution, so as to generate active radicals with strong oxidizing property to enhance ozonation performance.
Ceramic film as a representative inorganic film is made of an inorganic material, ZrO2、Al2O3And TiO2And the pore diameter is different from dozens of nanometers to hundreds of nanometers. The good performance of the inorganic material enables the ceramic membrane to have higher chemical stability, can be filtered and cleaned under extreme conditions of acid and alkali and the like, and is suitable for being used with an oxidant; the mechanical strength is high, and the abrasion of inorganic particles can be resisted; meanwhile, the method has the advantages of high separation efficiency, strong antimicrobial capability and the like. At present, great progress is made in actual water treatment projects such as microfiltration, ultrafiltration and the like, especially in the fields of drinking water and metallurgical wastewater treatment. However, the current ceramic membrane separation technology still has the problems of reduced separation efficiency caused by concentration polarization phenomenon, secondary treatment of concentrated solution and membrane pollution.
A great number of reports prove that Graphene (Graphene) shows excellent catalytic efficiency in the catalytic ozonation water treatment technology. Graphene, a material consisting of carbon atoms in sp2The two-dimensional carbon nanomaterial which is hexagonal honeycomb lattice and formed by the hybrid tracks has the advantages of large specific surface area, high mechanical strength, good thermal conductivity and the like. However, when the graphene is applied to the catalytic ozonation water treatment technology, bottleneck problems of uneven dispersion, easy oxidation and damage of the structure caused by water non-wettability, short catalytic life and the like generally exist, and further development and wide application of the graphene catalytic ozonation technology are greatly restricted.
To compensate for these deficiencies, researchers have complexed graphene with other catalytically active components to synergistically catalyze ozone oxidation. Patent CN103991943A provides a method for catalyzing ozone treatment of refractory organics and simultaneously inhibiting the generation of bromate. The inventor compounds the graphene and the activated carbon for catalyzing ozone oxidation, and the composite catalyst remarkably improves the degradation efficiency of the ozone on the oxalic acid and effectively inhibits the generation of bromate. Patent CN107376921A discloses a method for catalyzing ozone oxidation after graphene is compounded with nickel oxide. The specific surface area of the composite catalyst is 200m2(iv)/g, dispersibility in water is also good. Due to the strong adsorbability of graphene on organic pollutants and the high catalytic activity of nickel oxide, the composite catalyst shows excellent catalytic performance in the process of treating methylene blue wastewater, and has a good decolorizing effect, the decolorizing rate reaches 90% in 5min after the reaction begins, the final decolorizing rate can reach 99%, and the removal rate of COD can reach 96%. The inventor of the invention previously issued patent CN105195168A provides a preparation method of hollow hexahedron copper manganese acid spinel and an application method of a catalytic ozone oxidation pollution removal technology thereof, and can effectively improve the enhanced removal effect of ozone on medicines and personal care products such as 2-hydroxy-4-methoxybenzophenone in water. CuMn2O4As a typical spinel material, the catalyst has high catalytic performance, is stable in structure and is not easy to generate secondary pollution. However, CuMn alone2O4The composite material has small specific surface area and limited catalytic efficiency and bromate generation inhibiting capacity, and can meet the requirement of organic pollutants in drinking water and be more efficient after being compounded with grapheneThe method treats the organic pollutants difficult to degrade and simultaneously more effectively inhibits the generation of bromate. The composite material has high catalytic efficiency, is green and environment-friendly, and has low cost, so the composite material has great potential advantages in the field of catalyzing ozone to treat organic matters.
The invention combines graphene and CuMn2O4Compounding, and making up the defects of the graphene in the catalytic ozonation technology. In order to overcome the defects that the powder catalyst is difficult to separate, is inactivated and is easy to run off in a water phase and the like, the powder catalyst is loaded on a separation membrane and is coupled with ozone. However, since ozone has strong oxidizing property and thus the organic membrane in the separation membrane has poor oxidation resistance and poor mechanical strength, the solution diffuses into the polymer membrane matrix due to long-term operation, so that the membrane undergoes swelling deformation, and ozone oxidation also accelerates the swelling rate. The organic membrane has short service life, high replacement frequency and high use cost in water treatment engineering.
Therefore, researchers load the catalyst on the ceramic membrane to be coupled with the ozone, so that the physical and chemical properties of the ceramic membrane are effectively improved, and the degradation capability of the ceramic membrane on organic matters in water is effectively improved. Patent CN102908908A provides a method for modifying ceramic microfiltration by graphene oxide modification. The modification obviously improves the separation efficiency and the acid resistance of the ceramic membrane, and is beneficial to prolonging the service life of the ceramic membrane. Patent CN104803512A provides a water treatment method and device with ozone catalytic oxidation self-cleaning ceramic membrane. Most suspended substances and oil molecules in the water are basically removed through ceramic membrane filtration; under the action of water flow, part of impurities can be attached to the surface of the ceramic filter tube, and the wall of the ceramic tube is coated with an ozone catalyst (preferably titanium manganese or titanium cerium) which can be catalytically oxidized with ozone in water to decompose part of impurities attached to the ceramic tube and slow down membrane pollution. The earlier granted patent of the inventor of the invention CN105800767A provides a construction method of a nano copper manganese acid spinel catalytic membrane reactor and an application method thereof in water treatment. The inventor combines heterogeneous catalytic ozonation with ceramic membrane filtration technology, and utilizes active components (CuMn) on the ceramic membrane catalytic layer2O4) CatalysisOzone generates OH with high oxidizing power, and the removal rate of the 2-hydroxy-4-methoxybenzophenone in water is 71.2% -76.5%.
The graphene and the ceramic membrane surface are negatively charged and mutually repel each other. Therefore, the phenomenon that the graphene surface is loaded loosely is easy to occur in the ceramic membrane modified by the graphene, so that the catalyst is lost, the degradation efficiency of organic pollutants is reduced, even blockage is formed, and the water production flux is reduced. In addition, the long-term use of the graphene modified ceramic membrane also causes membrane pollution, and causes the problems of membrane pore blockage and water flux reduction. The catalytic ozone separation membrane technology can directly attack organic pollutants through ozone or catalyze ozone to generate OH or superoxide radicals to attack the organic pollutants, and alleviate membrane pollution. The invention needs to prepare a novel catalytic ceramic membrane with strong stability, strong oxidation resistance and higher ozone catalytic capability, which can be effectively combined with ozone, improve the sewage treatment capability and provide higher quality water quality.
Disclosure of Invention
The invention aims to mix graphene and CuMn2O4Compounding, namely obtaining graphene and CuMn by using a two-step calcination method2O4Graphene and CuMn2O4Solves the bottleneck problems that when the graphene is applied to the catalytic ozonation water treatment technology, the dispersion is not uniform, the structure caused by water non-wettability is easy to be oxidized and damaged, the catalytic service life is short and the like, and simultaneously solves the problem of single CuMn2O4Small specific surface area, limited catalytic efficiency and bromate formation inhibiting ability, etc.
The invention also aims to load the obtained composite material on a ceramic membrane by using a vacuum negative pressure method and apply the composite material to water treatment engineering. The assembly of the membrane reactor overcomes the defects that the conventional powdery catalyst is not beneficial to separation and inactivation of a water phase and the like, and provides a new method for cleaning and recycling the catalyst for many times. In addition, the ceramic membrane has higher chemical stability, can be filtered and cleaned under extreme conditions such as acid and alkali resistance and the like, and is suitable for being used with an oxidant. Using CuMn2O4Coupling of/rGO catalytic membrane with ozone, surface catalytic layer inducing odorOxygen decomposition to produce hydroxyl radicals and superoxide radicals; the interception effect of the ceramic membrane can also assist in realizing the enhancement of the oxidation of the organic matters which are difficult to degrade by ozone, improve the oxidation capability of the ozone, realize the enhancement of the removal of the organic pollutants which are difficult to degrade in water, synchronously control the generation amount of bromate which is a toxic byproduct, and control the membrane pollution by self-cleaning the surface. The self property of the ceramic membrane can ensure that the membrane reactor can be repeatedly recycled under extreme conditions, thereby reducing the use cost in engineering application.
The invention adopts the technical scheme that an ozone catalytic membrane reactor assembly and an application method thereof in water treatment engineering comprise the following steps:
(1) CuMn prepared by coprecipitation method2O4And Graphene Oxide (GO) according to the mass ratio of 0.5-10: 1, mixing and uniformly grinding;
(2) transferring the obtained powder into a quartz crucible, calcining at the temperature of 300-400 ℃, wherein the heating rate is 3-7 ℃/min, the time is 0.8-1.2h, and the obtained sample is CuMn2O4a/rGO composite nanoparticle.
(3) 0.1-0.3g of CuMn2O4dispersing/rGO composite nano particles in 0.9-1.0L of deionized water, and carrying out ultrasonic treatment for 10min to form a suspension;
(4) sealing one side of the ceramic membrane, and introducing nitrogen into the CuMn2O4the/rGO composite nano-particle suspension is added until the suspension in the container is completely pressed (the pressure is 0.1 Mpa);
(5) drying the film in a vacuum drying box at 45 ℃ for 12-15h, calcining the film in a muffle furnace at 300-500 ℃ for 0.5h at the heating rate of 7-10 ℃/min to obtain CuMn2O4a/rGO catalytic membrane.
The invention has the beneficial effects that: the invention relates to CuMn2O4rGO catalytic membrane without CuMn being excluded from catalyst components2O4Besides, other copper-manganese oxides and the preparation method is simple. The composite material can effectively overcome the defects of uneven liquid phase dispersion, unstable catalytic activity and short service life of graphene in an ozone oxidation technology, can prolong the service life of a catalyst, and has stronger catalytic capability; its CuMn2O4the/rGO catalytic membrane induces ozonolysis to generate hydroxyl radicals and superoxide radicals, so that the organic pollutants difficult to degrade in water are intensively removed, the generation amount of a toxic byproduct bromate is synchronously controlled, and the membrane pollution is controlled through surface self-cleaning, so that the method has a wide application prospect.
Drawings
FIG. 1 shows graphene and CuMn according to the present invention2O4The X-ray diffraction spectrum of the composite material.
FIG. 2 is a CuMn composition of the present invention2O4Water flux diagram for/rGO catalytic membranes.
FIG. 3 shows the catalytic ozone CuMn of the present invention2O4Efficacy chart of/rGO membrane degradation 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP-4).
FIG. 4 is ozone-catalyzed CuMn of the present invention2O4Graph of bromate formation inhibition efficacy of/rGO membrane.
Detailed Description
Example 1 CuMn2O4/rGO catalytic membrane assembly
CuMn prepared by coprecipitation method2O4And Graphene Oxide (GO) according to the mass ratio of 0.5-10: 1, mixing and uniformly grinding; transferring the obtained powder into a quartz crucible, calcining at the temperature of 300-400 ℃, wherein the heating rate is 3-7 ℃/min, the time is 0.8-1.2h, and the obtained sample is CuMn2O4a/rGO composite nanoparticle. 0.1-0.3g of CuMn2O4dispersing/rGO composite nano particles in 0.9-1.0L of deionized water, and carrying out ultrasonic treatment for 10min to form a suspension; sealing one side of the ceramic membrane, and introducing nitrogen into the CuMn2O4the/rGO composite nano-particle suspension is added until the suspension in the container is completely pressed (the pressure is 0.1 Mpa); drying the film in a vacuum drying box at 45 ℃ for 12-15h, calcining the film in a muffle furnace at 300-500 ℃ for 0.5h at the heating rate of 7-10 ℃/min to obtain CuMn2O4a/rGO catalytic membrane.
Example 2 CuMn2O4Application of/rGO catalytic membrane in water production by filtration
CuMn prepared in example 12O4the/rGO catalytic membrane is used for pure water flux test. The volume of the test deionized water was 1200mL, the transmembrane pressure difference was 0.2bar, the transmembrane flow rate was 1600mL/min, and the filtration was performed at room temperature for 30 min.
In this embodiment, CuMn2O4Pure water flux of/rGO catalytic membrane (282.72LMH) is 1.1 times higher than that of unmodified ceramic membrane (265.12LMH), CuMn2O4The water flux of the ceramic membrane is remarkably improved by adding/rGO, and more water molecules can permeate into the graphene active layer.
Example 3 ozone-catalyzed CuMn2O4The 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (BP-4) in the water degraded by the rGO membrane synchronously inhibits the generation of bromate. The test solution volume of 1200mL, BP-4 initial concentration of 0.084mmol/L, bromide initial concentration of 100 u g/L, with 1mol/L sodium hydroxide to adjust the solution initial pH to 6.4, at room temperature fully stirred for 15min reaction.
Ozone-catalyzed CuMn in this embodiment2O4the/rGO membrane can efficiently degrade BP-4, and the removal rate of BP-4 after reaction for 30min can reach 100%. The molar concentration of the bromate generated after the reaction is carried out for 2 hours is lower than 10 percent of the initial bromine ion concentration, and the generation of the bromate is effectively inhibited.
Example 4 ozone-catalyzed CuMn2O4the/rGO membranes are used in water treatment.
The process flow of drinking water treatment is coagulation → precipitation → filtration → ozone catalysis CuMn2O4Filtering with rGO membrane → sterilizing → discharging water from clean water tank. The process is realized by the following steps: (1) o required for the process3The concentration is 20 mg/L; (2) CuMn required by the process2O4The adding amount of the/rGO catalyst is 0.2-0.8 g/L; (3) the contact time is 20-30 min.
The process flow of the reclaimed water treatment comprises the steps of secondary effluent → a biological filter → ozone catalysis CuMn2O4Filtering with/rGO membrane → sterilizing → discharging water. The process is realized by the following steps: (1) o required for the process3The concentration is 20 mg/L; (2) CuMn required by the process2O4The adding amount of the/rGO catalyst is 0.2-0.8 g/L; (3) contact time was 20-30min。
Claims (3)
1. An ozone catalytic membrane reactor assembly and its application method in water treatment engineering are characterized by using CuMn2O4the/rGO catalytic membrane induces ozonolysis to generate hydroxyl radicals and superoxide radicals, realizes the reinforced removal of organic pollutants difficult to degrade in water, synchronously controls the generation amount of poisonous by-product bromate, controls the membrane pollution by surface self-cleaning, and is assembled through the following processes:
(1) CuMn prepared by coprecipitation method2O4(CMO) and Graphene Oxide (GO) according to the mass ratio of 0.5-10: 1, mixing and uniformly grinding;
(2) transferring the obtained powder into a quartz crucible, calcining at the temperature of 300-400 ℃, wherein the heating rate is 3-7 ℃/min, the time is 0.8-1.2h, and the obtained sample is CuMn2O4a/rGO composite nanoparticle.
(3) 0.1-0.3g of CuMn2O4dispersing/rGO composite nano particles in 0.9-1.1L of deionized water, and carrying out ultrasonic treatment for 10min to form a suspension;
(4) sealing one side of the ceramic membrane, and introducing nitrogen into the CuMn2O4the/rGO composite nano-particle suspension is added until the suspension in the container is completely pressed (the pressure is 0.1 Mpa);
(5) drying the film in a vacuum drying box at 45 ℃ for 12-15h, calcining the film in a muffle furnace at 300-500 ℃ for 0.5h at the heating rate of 7-10 ℃/min to obtain CuMn2O4a/rGO catalytic membrane.
2. CuMn made by the process of claim 12O4the/rGO catalytic membrane is characterized in that the addition of the rGO obviously improves the CuMn2O4Specific surface area of from 2.058m2Lifting/g to 279.022m2(ii)/g; changes CuMn2O4The pore structure is characterized in that the pore size distribution interval is narrowed from 2.1-10.7nm to 3.4-4.2nm, and the pore size distribution is uniform; the water flux is 1.1 times that of the unmodified ceramic membrane.
3. The ozone-catalyzed membrane reactor assembly of claim 1 and the method of its application in water treatment projects, wherein the application in water treatment projects is accomplished by the steps of:
(1) can be used as drinking water advanced treatment technology, and the process flow is as follows: coagulation → precipitation → filtration → ozone catalysis of CuMn2O4Filtering with rGO membrane → sterilizing → discharging water from clean water pool;
(2) can be used as a reclaimed water treatment technology, and the process flow is as follows: second-stage effluent → biofilter → ozone catalysis CuMn2O4Filtering with/rGO membrane → sterilizing → discharging water;
(3)CuMn2O4CuMn required by/rGO catalytic membrane2O4the/rGO loading is 0.1-0.3 g;
(4) the concentration of ozone in reaction liquid required by the process is 5-30 mg/L;
(5) the flow rate of the ozone gas required by the process is 350-450 mL/min;
(6) the operating pressure is 0.1-0.3bar, and the operating temperature is 20-25 ℃;
(7) the concentration of refractory organics in the water body to be treated is 0.084mmol/L, the concentration of bromide ions is 100 mug/L, and the pH value is between 5 and 7.
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|---|---|---|---|---|
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745675A (en) * | 2012-06-27 | 2012-10-24 | 合肥工业大学 | Preparation method of spinel-type magnetic MFe2O4/graphene composite material |
| US20180201740A1 (en) * | 2016-06-30 | 2018-07-19 | Albemarle Corporation | Electrode Slurries Containing Halogenated Graphene Nanoplatelets, and Production and Uses Thereof |
| 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 |
| CN110420568A (en) * | 2019-09-03 | 2019-11-08 | 北京林业大学 | A method of promoting ceramic membrane permeant flux improves strainability |
| CN110436607A (en) * | 2019-09-02 | 2019-11-12 | 北京林业大学 | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process |
| US20200024162A1 (en) * | 2019-03-28 | 2020-01-23 | Central South University | Method and device for sewage treatment |
| US20200061591A1 (en) * | 2017-06-01 | 2020-02-27 | University Of Connecticut | Manganese-Cobalt Spinel Oxide Nanowire Arrays |
| CN111129494A (en) * | 2019-12-28 | 2020-05-08 | 常州大学 | Preparation method of sulfo-spinel/graphene electrode material and electrode material thereof |
-
2020
- 2020-05-27 CN CN202010460407.8A patent/CN111573818A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745675A (en) * | 2012-06-27 | 2012-10-24 | 合肥工业大学 | Preparation method of spinel-type magnetic MFe2O4/graphene composite material |
| US20180201740A1 (en) * | 2016-06-30 | 2018-07-19 | Albemarle Corporation | Electrode Slurries Containing Halogenated Graphene Nanoplatelets, and Production and Uses Thereof |
| US20200061591A1 (en) * | 2017-06-01 | 2020-02-27 | University Of Connecticut | Manganese-Cobalt Spinel Oxide Nanowire Arrays |
| 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 |
| US20200024162A1 (en) * | 2019-03-28 | 2020-01-23 | Central South University | Method and device for sewage treatment |
| CN110436607A (en) * | 2019-09-02 | 2019-11-12 | 北京林业大学 | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process |
| CN110420568A (en) * | 2019-09-03 | 2019-11-08 | 北京林业大学 | A method of promoting ceramic membrane permeant flux improves strainability |
| CN111129494A (en) * | 2019-12-28 | 2020-05-08 | 常州大学 | Preparation method of sulfo-spinel/graphene electrode material and electrode material thereof |
Non-Patent Citations (5)
| Title |
|---|
| ABEL, M. JOHN ET AL: "Flake-likeCuMn2O4 nanoparticles synthesized via co-precipitation method for photocatalytic activity", 《PHYSICA B-CONDENSED MATTER》 * |
| LILI ET AL: "CuMn2O4/grapheme nanosheets as excellent anode for lithium-ion battery", 《MATERIALS RESEARCH BULLETIN》 * |
| YIN XU ET AL: "Mechanism and kinetics of catalytic ozonation for elimination of organic compounds with spinel-type CuAl2O4 and its precursor", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
| 阮国洪: "《水的科学与健康》", 30 June 2012, 上海：复旦大学出版社 * |
| 陈瑀: "石墨烯/锰铁尖晶石催化臭氧去除水中DBP的研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑 环境科学与资源利用》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811571A (en) * | 2021-01-15 | 2021-05-18 | 贵州省材料产业技术研究院 | Ozone catalytic membrane water treatment system and method |
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