CN106955728B - Preparation method and application of efficient supported ozone oxidation catalyst - Google Patents
Preparation method and application of efficient supported ozone oxidation catalyst Download PDFInfo
- Publication number
- CN106955728B CN106955728B CN201710188142.9A CN201710188142A CN106955728B CN 106955728 B CN106955728 B CN 106955728B CN 201710188142 A CN201710188142 A CN 201710188142A CN 106955728 B CN106955728 B CN 106955728B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium dioxide
- dioxide molecular
- wastewater
- solution
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 131
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 67
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 65
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 18
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 claims abstract description 8
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 claims abstract description 8
- 229960005091 chloramphenicol Drugs 0.000 claims abstract description 5
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims abstract description 5
- 229930182555 Penicillin Natural products 0.000 claims abstract description 4
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims abstract description 4
- 229960003276 erythromycin Drugs 0.000 claims abstract description 4
- 229940049954 penicillin Drugs 0.000 claims abstract description 4
- 229960005322 streptomycin Drugs 0.000 claims abstract description 4
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 108010059993 Vancomycin Proteins 0.000 abstract description 2
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 abstract description 2
- 229960001732 pipemidic acid Drugs 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 229960003165 vancomycin Drugs 0.000 abstract description 2
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 abstract description 2
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- -1 metal oxide modified molecular sieve Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-O vancomycin(1+) Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C([O-])=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)[NH2+]C)[C@H]1C[C@](C)([NH3+])[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-O 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/60—
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of an ozone oxidation catalyst. The invention provides a preparation method of an efficient supported ozonation catalyst, which comprises the steps of preparing a titanium sol solution, preparing a template agent sol solution, preparing a mesoporous titanium dioxide molecular sieve precursor, demolding the mesoporous titanium dioxide molecular sieve precursor and MnO2The invention adopts a self-made mesoporous titanium dioxide molecular sieve as a carrier, and loads a metal oxide catalyst of Mn into an internal pore channel structure of the titanium molecular sieve, and the molecular sieve is also formed by active components, so that the catalytic material has extremely high content of the active components, high pollutant removal rate, high catalytic activity and less loss of the active components, and has obvious catalytic effect on the catalytic oxidation treatment of the ozone of antibiotic wastewater such as chloramphenicol wastewater, penicillin wastewater, erythromycin wastewater, streptomycin wastewater, vancomycin wastewater, pipemidic acid wastewater and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of an ozone oxidation catalyst.
Background
Antibiotic pollution is the most important pollution of medicines and personal care products (PPCPs), because antibiotics have the characteristics of wide pollution area, difficult degradation, high toxicity, easy deposition and the like, and the traditional water treatment process has poor antibiotic removal effect, and trace antibiotics can cause microorganismsThe drug resistance of (b) poses a significant threat to human health and ecosystem. Common treatment techniques for antibiotic wastewater include incineration, microelectrolysis, Fenton's reagent, and other advanced oxidation techniques. Wherein the micro-electrolysis method uses iron and carbon to form a micro primary battery and release nascent state Fe2+And [ H]The product reacts with components in the solution to further achieve the purpose of removing pollutants, but the problem of low removal rate of antibiotic substances exists; the Fenton reagent method is a traditional water treatment technology, organic matters in wastewater are deeply oxidized by generating OH free radicals with strong oxidizing capability, however, the Fenton method usually needs to add a large amount of additional reagents to generate a large amount of iron mud, and has the problem of poor stability.
Ozone oxidation technology has been widely used in the field of water treatment, such as sterilization of municipal water supply, advanced treatment of industrial wastewater, and the like. At present, the technology receives more and more attention in the aspect of organic wastewater treatment, particularly the treatment of organic wastewater difficult to biodegrade. However, the popularization and application of the ozone oxidation technology are severely limited due to the problems of low oxidation selectivity, low ozone utilization rate, high operation cost and the like. With this as a background, a technique of improving the ozone oxidation efficiency, enhancing the ozone oxidation ability, and reducing the running cost by using a catalyst has been attracting attention.
Chinese patent application No. CN104646020A discloses a method for preparing a catalyst, which comprises the following steps: (1) taking active carbon as a carrier, sequentially carrying out alkali washing, acid washing and deionized water washing, and drying for later use; (2) dipping in ferric nitrate and manganese nitrate solution for 3-5 h at 50-80 ℃, and drying for 2-3 h at 100-120 ℃; (3) roasting for 2-3 h at 300-500 ℃ to prepare the ozone oxidation catalyst.
The Chinese patent application No. CN104289250A discloses a preparation method of a catalyst, which comprises the steps of dissolving a transition metal nitrate solution in a hexadecyl trimethyl ammonium bromide solution, adding ammonia water to form a sol solution, mixing a molecular sieve in the sol, uniformly stirring, filtering, washing, drying and roasting to obtain a metal oxide modified molecular sieve, uniformly mixing the modified molecular sieve, an adsorbent and an additive in water, soaking honeycomb activated carbon in the solution for 20-60 minutes, drying, and roasting in nitrogen at 500-600 ℃ for 2-6 hours to obtain the supported ozone oxidation catalyst.
The preparation of the ozone oxidation catalyst is that active components are loaded on a carrier, the catalyst has certain catalytic activity, but inert substances are used as carrier materials, the content of the active components is low, and the catalytic activity is low; and the active component can only be loaded on the surface of the carrier, so that the active component is easy to lose in the long-time use process, and the catalyst is inactivated.
Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency supported ozone oxidation catalyst, which has the advantages of extremely high active component content, high pollutant removal rate, high catalytic activity, less active component loss and the like, aiming at overcoming the defects of the prior art.
In order to achieve the aim, the preparation method of the high-efficiency supported ozonation catalyst comprises the steps of preparing a titanium sol solution, preparing a template agent sol solution, preparing a mesoporous titanium dioxide molecular sieve precursor, demolding the mesoporous titanium dioxide molecular sieve precursor, and MnO2Five processes for loading active components are specifically as follows:
the first step of preparing titanium sol solution: dissolving one or more of titanium sulfate, titanium chloride and titanium nitrate serving as a titanium source in ultrapure water to prepare a titanium sol solution with the titanium salt concentration of 0.1-5 mol/L, referred to as solution A for short;
preparing a template agent sol solution: cetyl Trimethyl Ammonium Bromide (CTAB) is used as a structure guiding agent, ultrapure water is used as a solvent, and Ti is used as a solvent4+: preparing a CTAB solution with the volume same as that of the titanium sol solution prepared in the first step, namely a template agent sol solution, namely B solution, wherein the CTAB molar ratio is 20: 1-1: 20;
the third step is that the mesoporous titanium dioxide molecular sieve precursor is prepared: slowly adding the solution B into the solution A under stirring, reacting for 4-24 hours at 40-90 ℃ to obtain a mesoporous titanium dioxide molecular sieve precursor mixed solution, centrifugally separating and washing to obtain a mesoporous titanium dioxide molecular sieve precursor, and drying in an oven for later use;
and fourthly, demolding the mesoporous titanium dioxide molecular sieve precursor: placing the mesoporous titanium dioxide molecular sieve precursor prepared in the third step into a muffle furnace, heating to 150-1000 ℃ at a constant heating rate, calcining at a constant temperature for 1-8 hours to obtain a mesoporous titanium dioxide molecular sieve, grinding the mesoporous titanium dioxide molecular sieve, and then placing the mesoporous titanium dioxide molecular sieve precursor into an oven for drying for later use;
fifth step MnO2Loading of active components: the dry mesoporous titanium dioxide molecular sieve prepared in the fourth step is soaked in Mn (NO) with the concentration of 0.1-2 mol/L in the adding amount of 1-50 g/L3)2Oscillating and adsorbing in the solution for 1-10 h; filtering, drying in an oven, heating to 200-800 deg.C at constant temperature in a muffle furnace, calcining at constant temperature for 40-240 min, and adding Mn (NO)3)2Reaction to MnO2To obtain the high-efficiency supported ozone oxidation catalyst powder which can be used after being bonded and formed.
Preferably, the temperature of the ultrapure water in the first step is 30 to 50 ℃, and the pH of the ultrapure water is 0.1 to 9.5.
Preferably, the temperature of the ultrapure water in the second step is 30 to 50 ℃.
As a further preference, the temperature of the ultrapure water in the second step is kept in agreement with the temperature of the ultrapure water in the first step.
Preferably, the stirring speed in the third step is 60 to 400 rad/min.
Preferably, the temperature rise rate of the muffle furnace in the fourth step is 2-10 ℃/min.
Preferably, in the fourth step, the mixture is passed through a 100-mesh screen after grinding.
Preferably, the oven temperature in the third and fourth steps is 105 ℃.
Preferably, the drying temperature in the fifth step is 60-80 ℃, and the drying time is 4-6 h.
Preferably, the temperature rise rate of the muffle furnace in the fifth step is 5-20 ℃/min.
The invention also aims to provide the application of the high-efficiency supported ozone oxidation catalyst in wastewater treatment, namely the ozone oxidation catalyst prepared by the method is used for performing ozone catalytic oxidation treatment on antibiotic wastewater such as chloramphenicol wastewater, penicillin wastewater, erythromycin wastewater, streptomycin wastewater, vancomycin wastewater, pipemidic acid wastewater and the like.
According to the invention, the self-made mesoporous titanium dioxide molecular sieve is used as a carrier, the Mn metal oxide catalyst is loaded into the internal pore channel structure of the self-made mesoporous titanium dioxide molecular sieve, the carrier material mesoporous titanium dioxide molecular sieve in the high-efficiency ozone oxidation catalyst is also formed by active components, and the catalytic activity is high when the content of the active components in the catalytic material is extremely high; meanwhile, Ti and Mn double metal oxides can generate synergistic action to catalyze ozone molecules to form hydroxyl free radicals (OH) with strong oxidizability, so that the problems of low removal rate of a micro-electrolysis method, secondary pollution caused by large dosage of a Fenton method medicament, low efficiency of single ozone and the like are solved, the degradation effect on antibiotic wastewater is good, and the antibiotic wastewater can be recycled. Specifically, compared with the prior art, the invention has the following beneficial effects:
1. the invention uses a self-made mesoporous titanium dioxide molecular sieve as a carrier, and MnO is loaded on the carrier2The prepared catalytic material is porous, has large specific surface area, strong adsorption performance, no other inert components and good catalytic performance, and obtains a novel ozone oxidation catalyst.
2. The ozone oxidation catalyst obtained by the method utilizes TiO2And MnO2The synergistic catalysis of ozone molecules to generate strong oxidizing OH solves the problems of low removal rate of the traditional micro-electrolysis method, addition of a large amount of chemical agents, difficulty in control, high operation cost and the like in the Fenton method.
3. The ozone oxidation catalyst obtained by the method of the invention is MnO with a catalytic function2Loaded on TiO with catalytic function2In the framework, the catalytic material is composed of active components, so that the surface area ratio of the active components is greatly improved, and the catalytic material is less in useThe loss of catalytic materials does not affect the catalytic activity of the catalyst, the service life of the catalyst is long, only a small amount of catalytic materials need to be supplemented under the long-time operation condition, and the treatment cost is greatly reduced.
The ozone oxidation catalyst obtained by the method of the invention is placed in an ozone reactor, can simultaneously carry out direct oxidation of ozone and indirect oxidation of intermediate products, and is an advanced oxidation technology integrating multiple functions. Compared with the traditional ozone technology and Fenton technology, the method has the advantages of high pollutant removal efficiency, high ozone utilization rate, no need of additional medicament and the like. Compared with the traditional ozone oxidation catalyst, the catalyst has the characteristics of high catalytic activity, long service life, low operation cost and the like.
Detailed Description
The technical solution and the beneficial effects of the present invention will be further explained with reference to the specific embodiments. The loading of the catalyst material described in examples 1-3 was 20-30 g/L.
Example 1:
(1) preparing a titanium sol solution: dissolving titanium nitrate serving as a titanium source in ultrapure water with the pH value of 1 and the temperature of 50 ℃ to prepare a titanium sol solution with the titanium salt concentration of 2mol/L, referred to as solution A for short;
(2) preparing a template agent sol solution: CTAB is used as a structure guiding agent, ultrapure water at 50 ℃ is used as a solvent, and Ti4+: preparing a CTAB solution with the same volume as the titanium sol solution, namely a template agent sol solution, referred to as B solution for short, wherein the CTAB molar ratio is 10: 1;
(3) preparing a mesoporous titanium dioxide molecular sieve precursor: slowly adding the solution B into the solution A at a stirring speed of 100rad/min, reacting for 20 hours at the temperature of 80 ℃ to obtain a mesoporous titanium dioxide molecular sieve precursor mixed solution, centrifugally separating and washing to obtain a mesoporous titanium dioxide molecular sieve precursor, and drying the mesoporous titanium dioxide molecular sieve precursor in an oven at the temperature of 105 ℃ for later use;
(4) demolding of the mesoporous titanium dioxide molecular sieve precursor: placing the mesoporous titanium dioxide molecular sieve precursor prepared in the third step in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4 hours to obtain a mesoporous titanium dioxide molecular sieve, grinding the mesoporous titanium dioxide molecular sieve, passing the mesoporous titanium dioxide molecular sieve through a 100-mesh screen, and then placing the mesoporous titanium dioxide molecular sieve precursor in an oven at 105 ℃ for drying for later use;
(5)MnO2loading of active components: the dry mesoporous titanium dioxide molecular sieve prepared in the fourth step is soaked in 2mol/L Mn (NO)3)2Adsorbing in the solution by shaking for 6h, filtering, drying in an oven at 80 deg.C for 6h, heating to 650 deg.C at a heating rate of 5 deg.C/min in a muffle furnace, calcining at constant temperature for 150min, and adding Mn (NO)3)2Reaction to MnO2To obtain the high-efficiency supported ozone oxidation catalyst powder which can be used after being bonded and formed.
Example 2:
(1) preparing a titanium sol solution: dissolving titanium chloride serving as a titanium source in ultrapure water with the pH value of 3 and the temperature of 50 ℃ to prepare a titanium sol solution with the titanium salt concentration of 1mol/L, which is called solution A for short;
(2) preparing a template agent sol solution: CTAB is used as a structure guiding agent, ultrapure water at 50 ℃ is used as a solvent, and Ti4+: preparing a CTAB solution with the same volume as the titanium sol solution, namely a template agent sol solution, referred to as B solution, wherein the CTAB molar ratio is 15: 1;
(3) preparing a mesoporous titanium dioxide molecular sieve precursor: slowly adding the solution B into the solution A at a stirring speed of 150rad/min, reacting for 15 hours at the temperature of 80 ℃ to obtain a mesoporous titanium dioxide molecular sieve precursor mixed solution, centrifugally separating and washing to obtain a mesoporous titanium dioxide molecular sieve precursor, and drying the mesoporous titanium dioxide molecular sieve precursor in an oven at the temperature of 105 ℃ for later use;
(4) demolding of the mesoporous titanium dioxide molecular sieve precursor: placing the mesoporous titanium dioxide molecular sieve precursor prepared in the third step in a muffle furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4 hours to obtain a mesoporous titanium dioxide molecular sieve, grinding the mesoporous titanium dioxide molecular sieve, passing the mesoporous titanium dioxide molecular sieve through a 100-mesh screen, and then placing the mesoporous titanium dioxide molecular sieve precursor in an oven at 105 ℃ for drying for later use;
(5)MnO2loading of active components: the dried mesoporous titanium dioxide molecular sieve prepared in the fourth step is dipped into 1mol/L of Mn (NO) by the adding amount of 10g/L3)2Adsorbing in the solution by shaking for 8h, filtering, drying in an oven at 80 deg.C for 6h, and heating in a muffle furnace at a temperature rise rate of 5 deg.C/minHeating to 750 deg.C, calcining at constant temperature for 200min to obtain Mn (NO)3)2Reaction to MnO2To obtain the high-efficiency supported ozone oxidation catalyst powder which can be used after being bonded and formed.
Example 3:
(1) preparing a titanium sol solution: dissolving titanium sulfate as a titanium source in ultrapure water with the pH value of 4 and the temperature of 40 ℃ to prepare a titanium sol solution with the titanium salt concentration of 0.5mol/L, referred to as solution A for short;
(2) preparing a template agent sol solution: CTAB is used as a structure guiding agent, ultrapure water at 40 ℃ is used as a solvent, and Ti4+: preparing a CTAB solution with the same volume as the titanium sol solution, namely a template agent sol solution, referred to as B solution for short, wherein the CTAB molar ratio is 5: 1;
(3) preparing a mesoporous titanium dioxide molecular sieve precursor: slowly adding the solution B into the solution A at a stirring speed of 130rad/min, reacting for 18h at the temperature of 80 ℃ to obtain a mesoporous titanium dioxide molecular sieve precursor mixed solution, centrifugally separating and washing to obtain a mesoporous titanium dioxide molecular sieve precursor, and drying the mesoporous titanium dioxide molecular sieve precursor in an oven at the temperature of 105 ℃ for later use;
(4) demolding of the mesoporous titanium dioxide molecular sieve precursor: placing the mesoporous titanium dioxide molecular sieve precursor prepared in the third step in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4 hours to obtain a mesoporous titanium dioxide molecular sieve, grinding the mesoporous titanium dioxide molecular sieve, passing the mesoporous titanium dioxide molecular sieve through a 100-mesh screen, and then placing the mesoporous titanium dioxide molecular sieve precursor in an oven at 105 ℃ for drying for later use;
(5)MnO2loading of active components: the dry mesoporous titanium dioxide molecular sieve prepared in the fourth step is soaked in 0.7mol/L Mn (NO)3)2Oscillating and adsorbing in the solution for 8h, filtering, drying in an oven at 80 deg.C for 6h, heating to 350 deg.C in a muffle furnace at a heating rate of 5 deg.C/min, calcining at constant temperature for 120min, and calcining to obtain Mn (NO)3)2Reaction to MnO2To obtain the high-efficiency supported ozone oxidation catalyst powder which can be used after being bonded and formed.
Test example 1
The three columnar reactors with the same specification and the effective volume of 10L are respectively filled with common alumina balls with the same quantity and the same grain diameter, a carrier ozone catalyst (alumina is taken as a carrier, manganese dioxide and titanium dioxide are taken as catalytic active components) and the high-efficiency supported ozone oxidation catalyst prepared in the embodiment 1 of the invention, and chloramphenicol simulation wastewater (COD is 150 mg/L-200 mg/L) is deeply treated under the condition of the same operation parameters, and the process conditions are as follows: the pH value of the wastewater is 7-8, the adding amount of ozone is 20mg/L, the HRT is 30min, and the catalyst adding rate is 80%.
The catalytic effects of different ozone oxidation catalysts are compared in table 1.
TABLE 1
| Type of packing | Water COD (mg/L) | COD of effluent (mg/L) | COD removal Rate (%) |
| Common alumina ball | 178 | 123 | 30.9 |
| Carrier ozone catalyst | 185 | 98 | 47.0 |
| Self-made ozone catalyst | 187 | 68 | 63.6 |
From table 1, it can be found that under the same operation conditions, the catalytic effect of the catalyst prepared by the invention is much higher than that of a common alumina ball, and compared with a common carrier ozone catalyst, the COD removal rate is improved by about 15%, which indicates that the high-efficiency supported ozone oxidation catalyst prepared by the invention has excellent catalytic performance.
Test example 2
The high-efficiency supported ozone oxidation catalyst prepared in the embodiment 1 of the invention with the same amount and the same particle size is respectively filled in four columnar reactors with the same specification and the effective volume of 10L, and the advanced treatment is carried out on several different antibiotic simulated wastewater under the condition of the same operation parameters, wherein the process conditions are as follows: the adding amount of ozone is 20mg/L, the HRT is 30min, and the catalyst adding rate is 80%;
the effluent treatment effects of wastewater biochemical tanks in different industries are shown in table 2;
TABLE 2
As can be seen from Table 2, under certain operating conditions, the COD removal rate of the ozone oxidation catalyst prepared by the invention on different antibiotic wastewater is 60-75%, compared with the COD removal rate of direct ozone oxidation which is 25-40%, the COD removal rate is increased by nearly 35%, and the high-efficiency supported ozone oxidation catalyst prepared by the invention has broad-spectrum performance on the catalytic performance of the antibiotic ozone oxidation degradation.
Claims (1)
1. The utility model provides a carry out high-efficient load type ozone oxidation catalyst that catalytic oxidation of ozone handled to chloramphenicol waste water, penicillin waste water, erythromycin waste water, streptomycin waste water which characterized in that: the catalyst is prepared by the following method: comprises the preparation of titanium sol solution, the preparation of template agent sol solution, the preparation of mesoporous titanium dioxide molecular sieve precursor, the demoulding of mesoporous titanium dioxide molecular sieve precursor and MnO2Five processes for loading active components are specifically as follows:
(1) preparing a titanium sol solution: dissolving titanium nitrate serving as a titanium source in ultrapure water with the pH =1 and the temperature of 50 ℃ to prepare a titanium sol solution with the titanium salt concentration of 2mol/L, referred to as solution A for short;
(2) preparing a template agent sol solution: CTAB is used as a structure directing agent, ultrapure water at 50 ℃ is used as a solvent, and the ratio of Ti4 +: preparing a CTAB solution with the same volume as the titanium sol solution, namely a template agent sol solution, referred to as B solution for short, wherein the CTAB molar ratio is 10: 1;
(3) preparing a mesoporous titanium dioxide molecular sieve precursor: slowly adding the solution B into the solution A at a stirring speed of 100rad/min, reacting for 20 hours at the temperature of 80 ℃ to obtain a mesoporous titanium dioxide molecular sieve precursor mixed solution, centrifugally separating and washing to obtain a mesoporous titanium dioxide molecular sieve precursor, and drying the mesoporous titanium dioxide molecular sieve precursor in an oven at the temperature of 105 ℃ for later use;
(4) demolding of the mesoporous titanium dioxide molecular sieve precursor: placing the mesoporous titanium dioxide molecular sieve precursor prepared in the third step in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4 hours to obtain a mesoporous titanium dioxide molecular sieve, grinding the mesoporous titanium dioxide molecular sieve, passing the mesoporous titanium dioxide molecular sieve through a 100-mesh screen, and then placing the mesoporous titanium dioxide molecular sieve precursor in an oven at 105 ℃ for drying for later use;
(5) loading of MnO2 active component: soaking the dried mesoporous titanium dioxide molecular sieve prepared in the fourth step in 2mol/L of Mn (NO 3) 2 solution at the addition of 15g/L, vibrating and adsorbing for 6h, filtering, placing in an oven to dry for 6h at the temperature of 80 ℃, placing in a muffle furnace to heat to 650 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 150min, reacting Mn (NO 3) 2 to generate MnO2, and obtaining the high-efficiency supported ozone oxidation catalyst powder which can be used after bonding and forming;
carrying out catalytic ozonation treatment on chloramphenicol wastewater, penicillin wastewater, erythromycin wastewater and streptomycin wastewater by using the prepared ozone oxidation catalyst; the process conditions are as follows: the adding amount of ozone is 20mg/L, the HRT is 30min, and the catalyst adding rate is 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710188142.9A CN106955728B (en) | 2017-03-27 | 2017-03-27 | Preparation method and application of efficient supported ozone oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710188142.9A CN106955728B (en) | 2017-03-27 | 2017-03-27 | Preparation method and application of efficient supported ozone oxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106955728A CN106955728A (en) | 2017-07-18 |
| CN106955728B true CN106955728B (en) | 2020-05-12 |
Family
ID=59471616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710188142.9A Active CN106955728B (en) | 2017-03-27 | 2017-03-27 | Preparation method and application of efficient supported ozone oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106955728B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597090B (en) * | 2017-08-22 | 2019-12-06 | 西安建筑科技大学 | Preparation and application method of ozone-enhanced catalytic material |
| CN107876045A (en) * | 2017-11-01 | 2018-04-06 | 南京理工大学 | A kind of TiO2(A B) load MnCe oxidizing and denitrating ozone catalyst and preparation method thereof, application |
| CN110818059B (en) * | 2019-11-29 | 2022-04-01 | 北京碧水源科技股份有限公司 | Non-photoelectric response composite deammoniation material, preparation method and application thereof in sewage deammoniation |
| CN110803745B (en) * | 2019-12-16 | 2022-04-01 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN111250145A (en) * | 2019-12-16 | 2020-06-09 | 嘉兴市众盛环保科技有限公司 | TiO 22OMS ozone oxidation catalyst, preparation method and application thereof |
| CN113318608B (en) * | 2021-05-17 | 2022-07-08 | 浙江理工大学 | Dynamically catalyzed water treatment ceramic membrane and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361385A2 (en) * | 1988-09-26 | 1990-04-04 | Sakai Chemical Industry Co., Ltd., | Deodorizing method and deodorizing catalyst |
| CN102367180A (en) * | 2011-03-17 | 2012-03-07 | 中国科学院过程工程研究所 | Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source |
| CN104529048A (en) * | 2014-11-03 | 2015-04-22 | 江苏省环境科学研究院 | System and method for treating refractory organics |
-
2017
- 2017-03-27 CN CN201710188142.9A patent/CN106955728B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361385A2 (en) * | 1988-09-26 | 1990-04-04 | Sakai Chemical Industry Co., Ltd., | Deodorizing method and deodorizing catalyst |
| CN102367180A (en) * | 2011-03-17 | 2012-03-07 | 中国科学院过程工程研究所 | Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source |
| CN104529048A (en) * | 2014-11-03 | 2015-04-22 | 江苏省环境科学研究院 | System and method for treating refractory organics |
Non-Patent Citations (2)
| Title |
|---|
| Decomposition of Hydrogen Peroxide on MnO2/TiO2 Catalysts;Annamaria Russo Sorge et al.;《JOURNAL OF PROPULSION AND POWER》;20130819;第20卷(第6期);第1069-1075页 * |
| 介孔二氧化钛分子筛的合成、表征及其机理研究;邹菲;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140315(第3期);B014-99 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106955728A (en) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955728B (en) | Preparation method and application of efficient supported ozone oxidation catalyst | |
| CN108993491B (en) | Activated persulfate catalyst prepared from modified carbon nano tube, and preparation and application thereof | |
| CN108404950A (en) | A method of handling industrial wastewater for the catalyst of catalytic ozonation, preparation method and using it | |
| CN105363465A (en) | Preparation method of ozone oxidation catalyst loaded with polymetallic oxide | |
| CN104874347B (en) | A kind of TiO2Load the preparation method and applications of nitrogen-doped graphene sponge | |
| CN103979631B (en) | A kind of absorption-catalytic oxidation degradation method of phenol in wastewater | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| CN104289250A (en) | Loaded type ozone catalyst and preparation method and application thereof | |
| CN107737594B (en) | Catalyst for degrading formaldehyde wastewater and preparation method and application thereof | |
| CN106622227A (en) | Preparation method of monoatomic catalyst for indoor air purification | |
| CN106540686A (en) | For the activated carbon supported manganese dioxide titanium dioxide ozone catalyst and preparation method of advanced treating | |
| CN106925253B (en) | Preparation method and application of nano-scale ozone oxidation catalyst | |
| CN104190422A (en) | Heterogeneous light fenton catalyst and application thereof | |
| CN102500356A (en) | Preparation method for carbon nanotube-nano-bismuth vanadate composite photocatalyst | |
| CN111111685A (en) | Catalyst for removing quinoline in wastewater by catalytic ozonation and preparation method thereof | |
| CN108579755B (en) | Wastewater treatment catalyst and application thereof | |
| CN106881090A (en) | A kind of ozone catalytic oxidation catalyst method of modifying | |
| CN105013500B (en) | Heterogeneous fenton catalyst of degrading azoic dye waste water and its production and use | |
| CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
| CN106345450A (en) | Loaded ozonation catalyst and preparation method and application thereof | |
| CN114713280A (en) | Preparation method of supported catalyst for catalytic oxidation treatment of refractory wastewater by ozone | |
| CN106345486A (en) | High-efficiency solid-phase ozone oxidation catalyst, and preparation method and application thereof | |
| CN105478121A (en) | Preparation method for ferric oxide-modified titanium dioxide high-efficiency visible photocatalyst | |
| CN106512988A (en) | Molecular sieve loaded MnO2-ZnO ozone catalyst and preparation method thereof | |
| CN104307484A (en) | Novel breathing-effect composite material for enriching and carrying out catalytic degradation on organic matter |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 314500 No. 1500 rice road, Indus street, Tongxiang, Zhejiang Applicant after: Zhejiang Juneng Environmental Engineering Co Ltd Address before: 314500, No. 1500 rice road, Indus street, Tongxiang, Zhejiang, Jiaxing Applicant before: ZHEJIANG JUNENG CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |