CN106955728A - A kind of preparation method of high efficiency load type ozone oxidation catalyst and application - Google Patents
A kind of preparation method of high efficiency load type ozone oxidation catalyst and application Download PDFInfo
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- CN106955728A CN106955728A CN201710188142.9A CN201710188142A CN106955728A CN 106955728 A CN106955728 A CN 106955728A CN 201710188142 A CN201710188142 A CN 201710188142A CN 106955728 A CN106955728 A CN 106955728A
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- titanium
- molecular sieve
- oxidation catalyst
- ozone oxidation
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 230000003647 oxidation Effects 0.000 title claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 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 43
- 239000010936 titanium Substances 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 239000002351 wastewater Substances 0.000 claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000003115 biocidal effect Effects 0.000 claims abstract description 13
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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 6
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 5
- 230000008569 process Effects 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 4
- 229930182555 Penicillin Natural products 0.000 claims abstract description 3
- 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 3
- 108010059993 Vancomycin Proteins 0.000 claims abstract description 3
- 229940097572 chloromycetin Drugs 0.000 claims abstract description 3
- 229960003276 erythromycin Drugs 0.000 claims abstract description 3
- 229940049954 penicillin Drugs 0.000 claims abstract description 3
- 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 claims abstract description 3
- 229960001732 pipemidic acid Drugs 0.000 claims abstract description 3
- 229960003165 vancomycin Drugs 0.000 claims abstract description 3
- 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 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 18
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 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
- 238000005406 washing Methods 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 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 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 229960005322 streptomycin Drugs 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
- 238000005516 engineering process Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- -1 metal oxide modified molecular sieve Chemical class 0.000 description 3
- 239000000126 substance Substances 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
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003814 drug Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 206010059866 Drug resistance Diseases 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 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
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to catalyst technical field, more particularly to a kind of preparation method of ozone oxidation catalyst.A kind of preparation method for high efficiency load type ozone oxidation catalyst that the present invention is provided, includes preparation, the preparation of template sol solution, the preparation of mesoporous TiO 2 molecular sieve precursor, the demoulding of mesoporous TiO 2 molecular sieve precursor and the MnO of titanium sol solution2Five processes of load of active component, the present invention is carrier by using self-control meso-porous titanium dioxide titanium molecular sieve, Mn metal oxide catalyst is loaded in titanium molecular sieve internal gutter structure, molecular sieve is also the composition of active component, active component content is high in catalysis material, pollutants removal rate is high, catalytic activity is high, loss of active component is few, catalytic ozonation processing is carried out to antibiotic waste waters such as chloromycetin wastewater, penicillin wastewater, erythromycin wastewater, streptomycin wastewater, vancomycin waste water and pipemidic acid waste water, with obvious catalytic effect.
Description
Technical field
The invention belongs to catalyst technical field, more particularly to a kind of preparation method of ozone oxidation catalyst.
Background technology
Antibiotic pollution is most important one kind in medicine and personal care product (PPCPs) pollution, because antibiotic has
Pollute wide, difficult degradation, toxicity is big, the features such as easily deposit, and traditional water treatment technology is to antibiotic poor removal effect, it is micro
Antibiotic is that possible cause the drug resistance of microorganism, and human health and the ecosystem are caused a significant threat.Antibiotic waste water is normal
Treatment technology includes burning method, micro-electrolysis method, Fenton reagent method and other high-level oxidation technologies etc..Wherein micro-electrolysis method
It is to form small galvanic cell, release nascent state Fe using iron carbon2+[H] reacts with the component in solution, and then reaches
The purpose of depollution thing, however exist it is relatively low to antibiotic agents clearance the problem of；Fenton reagent method is a kind of tradition
Water technology, deep oxidation is carried out to useless Organic substance in water by producing the extremely strong OH free radicals of oxidability, but
Fenton methods usually require to add a large amount of added regents, produce a large amount of iron cements, while the problem of existence and stability is poor.
Ozonation technology is widely applied in water treatment field, such as the sterilizing of city water, industrial wastewater
Advanced treating etc..The current technology is in terms of organic wastewater particularly difficult for biological degradation treatment of Organic Wastewater by more and more
Attention.But due to its oxidation selectivity, ozone utilization rate is low, operating cost is high the problems such as, the popularization of ozonation technology should
With severely limited.As background, ozone oxidation efficiency, enhancing ozone oxidation ability, reduction are improved using catalyst
The technology of operating cost receives much concern.
CN104646020A Chinese patent applications disclose a kind of preparation method of catalyst, its preparation process：(1)
Using activated carbon as carrier, sequentially pass through after alkali cleaning, pickling, deionized water rinsing, dry for standby；(2) under the conditions of 50~80 DEG C
3~5h is impregnated in ferric nitrate, manganese nitrate solution, 2~3h is dried at 100~120 DEG C；(3) 2 are calcined at 300~500 DEG C
~3h, is made ozone oxidation catalyst.
CN104289250A Chinese patent applications disclose a kind of preparation method of catalyst, by transition metal nitrate
Solution is dissolved in cetyl trimethylammonium bromide solution, adds ammoniacal liquor formation sol solution, molecular sieve is mixed in colloidal sol
Stir, metal oxide modified molecular sieve, modified molecular screen and adsorbent, additive are obtained through filtration washing drying and roasting
Uniform mixing soluble in water, cellular activated carbon is impregnated in the solution 20~60 minutes, is dried, in 500~600 DEG C of nitrogen
Roasting obtains support type ozone oxidation catalyst in 2~6 hours.
The preparation of above-mentioned ozone oxidation catalyst is that, in supported on carriers active component, catalyst has certain catalysis
Activity, but using inert substance as carrier material, active component content is less, and catalytic activity is relatively low；And active component can only be born
Carrier surface is loaded in, active component is easy to run off during long-time use, causes catalyst to inactivate.
The content of the invention
It is an object of the invention to for above-mentioned the deficiencies in the prior art there is provided a kind of active constituent content is high,
Pollutants removal rate is high, and catalytic activity is high, the system of the high efficiency load type ozone oxidation catalyst for the advantages of loss of active component is few
Preparation Method.
In order to achieve the above object, the preparation method for a kind of high efficiency load type ozone oxidation catalyst that the present invention is provided,
It is preparation including titanium sol solution, the preparation of template sol solution, the preparation of mesoporous TiO 2 molecular sieve precursor, mesoporous
The demoulding of titania molecule sieve presoma and MnO2Five processes of load of active component, are comprised the following steps that：
The preparation of first step titanium sol solution：Using the one or more in titanium sulfate, titanium chloride and Titanium Nitrate as titanium source,
It is dissolved in ultra-pure water, prepares the titanium sol solution that titanium salt concentration is 0.1~5mol/L, abbreviation A liquid；
The preparation of second step template sol solution：With cetyl trimethylammonium bromide (abbreviation CTAB) for structure directing
Agent, using ultra-pure water as solvent, with Ti4+：CTAB mol ratios are 20:1~1:20, prepare the titanium sol solution body prepared with the first step
Product identical CTAB solution, as template sol solution, abbreviation B liquid；
The preparation of 3rd step mesoporous TiO 2 molecular sieve precursor：B liquid is added slowly with stirring in A liquid,
At 40~90 DEG C, 4~24h of reaction obtains mesoporous TiO 2 molecular sieve precursor mixed liquor, is situated between after centrifuging washing
Porous titanium dioxide molecular sieve precursor, is placed on dry for standby in baking oven；
The demoulding of 4th step mesoporous TiO 2 molecular sieve precursor：The mesoporous TiO 2 that 3rd step is prepared point
Son sieve presoma is placed in Muffle furnace, is warming up to 150~1000 DEG C with constant heating rate, the calcining at constant temperature time is for 1-8h
Drying for standby in baking oven is placed in after obtaining meso-porous titanium dioxide titanium molecular sieve, ground screen cloth excessively；
5th step MnO2The load of active component：It is mesoporous with the drying that 1~50g/L dosage prepares the 4th step
Titania molecule sieve is impregnated in the Mn (NO that concentration is 0.1~2mol/L3)21~10h of concussion absorption in solution；It is placed in after filtering
Dried in baking oven, after be placed in Muffle furnace 200~800 DEG C, 40~240min of calcining at constant temperature be warming up to constant heating rate
Mn (NO afterwards3)2Reaction generation MnO2, high efficiency load type ozone oxidation catalyst powder is produced, it is adhesion-molded rear i.e. usable.
Preferably, the temperature of ultra-pure water described in the first step is 30~50 DEG C, the pH of the ultra-pure water is 0.1~9.5.
Preferably, the temperature of ultra-pure water described in second step is 30~50 DEG C.
As further preferred, ultrapure coolant-temperature gage described in second step is consistent with ultrapure coolant-temperature gage described in the first step.
Preferably, the mixing speed described in the 3rd step is 60~400rad/min.
Preferably, the Muffle furnace heating rate described in the 4th step is 2~10 DEG C/min.
Preferably, crossing 100 eye mesh screens after being ground described in the 4th step.
Preferably, the oven temperature described in third and fourth step is 105 DEG C.
Preferably, the drying temperature described in the 5th step is 60~80 DEG C, drying time is 4~6h.
Preferably, the Muffle furnace heating rate described in the 5th step is 5~20 DEG C/min.
It is a further object to provide a kind of high efficiency load type ozone oxidation catalyst answering in waste water treatment
With the ozone oxidation catalyst prepared using the inventive method is given up to chloromycetin wastewater, penicillin wastewater, erythromycin
The antibiotic waste waters such as water, streptomycin wastewater, vancomycin waste water and pipemidic acid waste water carry out catalytic ozonation processing.
The present invention is carrier by using self-control meso-porous titanium dioxide titanium molecular sieve, and Mn metal oxide catalyst is loaded
Into self-control meso-porous titanium dioxide titanium molecular sieve internal gutter structure, the mesoporous dioxy of carrier material in the efficient ozone oxidation catalyst
Change active component content in the composition that titanium molecular sieve is also active component, catalysis material high, then catalytic activity height；Simultaneously Ti and
It can be acted synergistically between Mn bimetallic oxides, the extremely strong hydroxyl radical free radical (OH) of catalysis ozone molecule formation oxidisability,
Solve that micro-electrolysis method clearance is relatively low, Fenton methods added amount of chemical has greatly secondary pollution, the independent low problem of ozone efficiency,
It is good to the degradation effect of antibiotic waste water, repeatable to utilize.Specifically, the present invention possesses following beneficial relative to prior art
Effect：
1st, the present invention with homemade meso-porous titanium dioxide titanium molecular sieve as carrier, in supported on carriers MnO2For catalytic activity
Component, the catalysis material of preparation is porous, and specific surface area is big, absorption property is strong, good without other inert components and catalytic performance, obtains
To a kind of new ozone oxidation catalyst, ozone molecule is adsorbed on catalyst surface duct, with active component and pollutant
Fully contact, considerably increases the utilization ratio of ozone molecule, improves ozone reaction speed, can efficiently degrade antibioticses
Waste water.
2nd, the ozone oxidation catalyst that the inventive method is obtained utilizes TiO2And MnO2Concerted catalysis ozone molecule, which is produced, to be had
The OH of strong oxidizing property, solves low traditional micro-electrolysis method clearance, the additional a large amount of chemical agents of Fenton methods needs and is difficult
Control, the problems such as operating cost is high.
3rd, the ozone oxidation catalyst that the inventive method is obtained is by the MnO with catalysis2It is carried on equally to have and urges
Change the TiO of function2In skeleton, catalysis material is all active component composition, substantially increases the face body ratio of active component, is using
During, the loss of a small amount of catalysis material does not interfere with the catalytic activity of catalyst, catalyst long service life, long-play
Under the conditions of only need to supplement a small amount of catalysis material, processing cost is substantially reduced.
The ozone oxidation catalyst that the inventive method is obtained is placed in ozone reactor, ozone can be carried out simultaneously direct
Oxidation and intermediate product indirect oxidation, being that a kind of synthesis is a variety of acts on integral high-level oxidation technology.With traditional ozone skill
Art, Fenton technologies are compared, and it has contaminant removal efficiency high, and ozone utilization rate is high, the advantages of without outer adding medicine.With biography
The ozone oxidation catalyst of system is compared, high with catalytic activity, and catalyst life is long, the low feature of operating cost.
Embodiment
Technical scheme and beneficial effect are described further with reference to specific embodiment.Embodiment 1-3
Described catalyst material loading is 20-30g/L.
Embodiment 1：
(1) preparation of titanium sol solution：Using Titanium Nitrate as titanium source, it is dissolved in pH=1,50 DEG C of ultra-pure water, prepares titanium
Salinity is 2mol/L titanium sol solution, abbreviation A liquid；
(2) preparation of template sol solution：Using CTAB as structure directing agent, using 50 DEG C of ultra-pure water as solvent, Ti4+：
CTAB mol ratios are 10:1, prepare and titanium sol solution volume identical CTAB solution, as template sol solution, abbreviation B
Liquid；
(3) preparation of mesoporous TiO 2 molecular sieve precursor：B liquid is slowly added under 100rad/min mixing speeds
Into A liquid, at a temperature of 80 DEG C, reaction 20h obtains mesoporous TiO 2 molecular sieve precursor mixed liquor, centrifuges after washing
Mesoporous TiO 2 molecular sieve precursor is obtained, dry for standby in 105 DEG C of baking ovens is placed on；
(4) demoulding of mesoporous TiO 2 molecular sieve precursor：The meso-porous titanium dioxide titanium molecule that 3rd step is prepared
Sieve presoma is placed in Muffle furnace, is warming up to 500 DEG C with 5 DEG C/min heating rates, calcining at constant temperature 4h produces mesoporous TiO 2
Drying for standby in 105 DEG C of baking ovens is placed in after molecular sieve, the ground eye mesh screen of mistake 100；
(5)MnO2The load of active component：With 15g/L dosage, the mesoporous dioxy of drying that the 4th step is prepared
Change the Mn (NO that titanium molecular sieve is impregnated in 2mol/L3)2In solution, concussion absorption 6h is placed in baking oven after filtering at a temperature of 80 DEG C
Dry 6h, after be placed in Muffle furnace Mn (NO after 650 DEG C, calcining at constant temperature 150min be warming up to 5 DEG C/min heating rates3)2Reaction
Generate MnO2, high efficiency load type ozone oxidation catalyst powder is produced, it is adhesion-molded rear i.e. usable.
Embodiment 2：
(1) preparation of titanium sol solution：Using titanium chloride as titanium source, it is dissolved in pH=3,50 DEG C of ultra-pure water, prepares titanium
Salinity is 1mol/L titanium sol solution, abbreviation A liquid；
(2) preparation of template sol solution：Using CTAB as structure directing agent, using 50 DEG C of ultra-pure water as solvent, Ti4+：
CTAB mol ratios are 15:1, prepare and titanium sol solution volume identical CTAB solution, as template sol solution, abbreviation B
Liquid；
(3) preparation of mesoporous TiO 2 molecular sieve precursor：B liquid is slowly added under 150rad/min mixing speeds
Into A liquid, at a temperature of 80 DEG C, reaction 15h obtains mesoporous TiO 2 molecular sieve precursor mixed liquor, centrifuges after washing
Mesoporous TiO 2 molecular sieve precursor is obtained, dry for standby in 105 DEG C of baking ovens is placed on；
(4) demoulding of mesoporous TiO 2 molecular sieve precursor：The meso-porous titanium dioxide titanium molecule that 3rd step is prepared
Sieve presoma is placed in Muffle furnace, is warming up to 600 DEG C with 5 DEG C/min heating rates, calcining at constant temperature 4h produces mesoporous TiO 2
Drying for standby in 105 DEG C of baking ovens is placed in after molecular sieve, the ground eye mesh screen of mistake 100；
(5)MnO2The load of active component：With 10g/L dosage, dried mesoporous dioxy prepared by the 4th step
Change the Mn (NO that titanium molecular sieve is impregnated in 1mol/L3)2In solution, concussion absorption 8h is placed in baking oven after filtering at a temperature of 80 DEG C
Dry 6h, after be placed in Muffle furnace Mn (NO after 750 DEG C, calcining at constant temperature 200min be warming up to 5 DEG C/min heating rates3)2Reaction
Generate MnO2, high efficiency load type ozone oxidation catalyst powder is produced, it is adhesion-molded rear i.e. usable.
Embodiment 3：
(1) preparation of titanium sol solution：Using titanium sulfate as titanium source, it is dissolved in pH=4,40 DEG C of ultra-pure water, prepares titanium
Salinity is 0.5mol/L titanium sol solution, abbreviation A liquid；
(2) preparation of template sol solution：Using CTAB as structure directing agent, using 40 DEG C of ultra-pure water as solvent, Ti4+：
CTAB mol ratios are 5:1, prepare and titanium sol solution volume identical CTAB solution, as template sol solution, abbreviation B
Liquid；
(3) preparation of mesoporous TiO 2 molecular sieve precursor：B liquid is slowly added under 130rad/min mixing speeds
Into A liquid, at a temperature of 80 DEG C, reaction 18h obtains mesoporous TiO 2 molecular sieve precursor mixed liquor, centrifuges after washing
Mesoporous TiO 2 molecular sieve precursor is obtained, dry for standby in 105 DEG C of baking ovens is placed on；
(4) demoulding of mesoporous TiO 2 molecular sieve precursor：The meso-porous titanium dioxide titanium molecule that 3rd step is prepared
Sieve presoma is placed in Muffle furnace, is warming up to 500 DEG C with 5 DEG C/min heating rates, calcining at constant temperature 4h produces mesoporous TiO 2
Drying for standby in 105 DEG C of baking ovens is placed in after molecular sieve, the ground eye mesh screen of mistake 100；
(5)MnO2The load of active component：With 10g/L dosage, the mesoporous dioxy of drying that the 4th step is prepared
Change the Mn (NO that titanium molecular sieve is impregnated in 0.7mol/L3)2In solution, concussion absorption 8h is placed in baking oven after filtering in 80 DEG C of temperature
Lower dry 6h, after be placed in Muffle furnace Mn (NO after 350 DEG C, calcining at constant temperature 120min be warming up to 5 DEG C/min heating rates3)2Instead
MnO should be generated2, high efficiency load type ozone oxidation catalyst powder is produced, it is adhesion-molded rear i.e. usable.
Test example 1
Common oxygen of the equivalent with particle diameter is filled respectively in the cylindrical reactor that three specifications are identical, effective volume is 10L
Change aluminium ball, carrier ozone catalyst (using aluminum oxide as carrier, manganese dioxide and titanium dioxide are catalytic active component) and this hair
High efficiency load type ozone oxidation catalyst prepared by bright embodiment 1, to chloramphenicol simulated wastewater under the conditions of same operational factor
(COD：150mg/L~200mg/L) carry out advanced treating, process conditions：Wastewater pH is 7~8, ozone dosage 20mg/L, HRT
For 30min, catalyst dosing rate 80%.
Different ozone oxidation catalyst catalytic effect contrasts are shown in Table 1.
Table 1
| Wire feeding | Influent COD (mg/L) | Water outlet COD (mg/L) | COD clearances (%) |
| Common alumina balls | 178 | 123 | 30.9 |
| Carrier ozone catalyst | 185 | 98 | 47.0 |
| Make ozone catalyst by oneself | 187 | 68 | 63.6 |
By table 1 it can be found that under identical service condition, catalyst effect prepared by the present invention is far above common oxygen
Change aluminium ball, compared to general carrier ozone catalyst, COD clearances lifting about 15% illustrates high efficiency load type prepared by the present invention
Ozone oxidation catalyst catalytic performance is splendid.
Test example 2
The present invention of the equivalent with particle diameter is filled respectively in the cylindrical reactor that four specifications are identical, effective volume is 10L
High efficiency load type ozone oxidation catalyst prepared by embodiment 1, to several different antibiotic moulds under the conditions of same operational factor
Intend waste water and carry out advanced treating, process conditions：Ozone dosage 20mg/L, HRT are 30min, catalyst dosing rate 80%；
Different industries wastewater biochemical pond goes out water treatment efficiency and is shown in Table 2；
Table 2
As shown in Table 2, under certain operating conditions, the ozone oxidation catalyst that prepared by the present invention is to different antibiotic waste waters
COD clearances have 60~75%, be that the lifting of 25~40%, COD clearances is near compared to direct ozone oxidation COD clearances
35%, and high efficiency load type ozone oxidation catalyst prepared by the present invention degrades catalytic performance to antibiotic ozone oxidation with wide
Spectrality.
Claims (10)
1. a kind of preparation method of high efficiency load type ozone oxidation catalyst, it is characterised in that：Preparation including titanium sol solution,
The preparation of template sol solution, the preparation of mesoporous TiO 2 molecular sieve precursor, mesoporous TiO 2 molecular sieve precursor
The demoulding and MnO2Five processes of load of active component, are comprised the following steps that：
The preparation of first step titanium sol solution：Using the one or more in titanium sulfate, titanium chloride and Titanium Nitrate as titanium source, it is dissolved in
In ultra-pure water, the titanium sol solution that titanium salt concentration is 0.1~5mol/L, abbreviation A liquid are prepared；
The preparation of second step template sol solution：With cetyl trimethylammonium bromide (abbreviation CTAB) for structure directing agent,
Using ultra-pure water as solvent, with Ti4+：CTAB mol ratios are 20:1~1:20, prepare the titanium sol solution volume prepared with the first step
Identical CTAB solution, as template sol solution, abbreviation B liquid；
The preparation of 3rd step mesoporous TiO 2 molecular sieve precursor：B liquid is added slowly with stirring in A liquid, 40~
At 90 DEG C, 4~24h of reaction obtains mesoporous TiO 2 molecular sieve precursor mixed liquor, and mesoporous two are obtained after centrifuging washing
Titanium oxide molecular sieve precursor, is placed on dry for standby in baking oven；
The demoulding of 4th step mesoporous TiO 2 molecular sieve precursor：The meso-porous titanium dioxide titanium molecular sieve that 3rd step is prepared
Presoma is placed in Muffle furnace, is warming up to 150~1000 DEG C with constant heating rate, the calcining at constant temperature time produces Jie for 1-8h
Drying for standby in baking oven is placed in after porous titanium dioxide molecular sieve, ground screen cloth excessively；
5th step MnO2The load of active component：The mesoporous dioxy of drying for being prepared the 4th step with 1~50g/L dosage
Change titanium molecular sieve and be impregnated in the Mn (NO that concentration is 0.1~2mol/L3)21~10h of concussion absorption in solution；Baking oven is placed in after filtering
Middle drying, after be placed in Muffle furnace Mn after 200~800 DEG C, 40~240min of calcining at constant temperature be warming up to constant heating rate
(NO3)2Reaction generation MnO2, high efficiency load type ozone oxidation catalyst powder is produced, it is adhesion-molded rear i.e. usable.
2. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
The temperature of ultra-pure water described in one step is 30~50 DEG C, and the pH of the ultra-pure water is 0.1~9.5.
3. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
The temperature of ultra-pure water described in two steps is 30~50 DEG C.
4. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 3, it is characterised in that：The
Ultrapure coolant-temperature gage described in two steps is consistent with ultrapure coolant-temperature gage described in the first step.
5. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
Mixing speed described in three steps is 60~400rad/min, and the oven temperature described in third and fourth step is 105 DEG C.
6. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
Muffle furnace heating rate described in four steps is 2~10 DEG C/min.
7. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
100 eye mesh screens are crossed after being ground described in four steps.
8. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
Drying temperature described in five steps is 60~80 DEG C, and drying time is 4~6h.
9. a kind of preparation method of high efficiency load type ozone oxidation catalyst according to claim 1, it is characterised in that：The
Muffle furnace heating rate described in five steps is 5~20 DEG C/min.
10. a kind of application of high efficiency load type ozone oxidation catalyst in waste water treatment, it is characterised in that：Usage right requirement
The ozone oxidation catalyst that any one is prepared in 1-9 is to chloromycetin wastewater, penicillin wastewater, erythromycin wastewater, strepto-
The antibiotic waste waters such as plain waste water, vancomycin waste water and pipemidic acid waste water carry out catalytic ozonation processing.
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| CN113318608A (en) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | Dynamically catalyzed water treatment ceramic membrane and application thereof |
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| CN107597090A (en) * | 2017-08-22 | 2018-01-19 | 西安建筑科技大学 | A kind of preparation of ozone-enhanced catalysis material and application process |
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| 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 |
| CN110818059A (en) * | 2019-11-29 | 2020-02-21 | 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 |
| CN110803745A (en) * | 2019-12-16 | 2020-02-18 | 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 |
| 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 |
| CN113318608A (en) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | Dynamically catalyzed water treatment ceramic membrane and application thereof |
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