CN107051502A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051502A CN107051502A CN201710275563.5A CN201710275563A CN107051502A CN 107051502 A CN107051502 A CN 107051502A CN 201710275563 A CN201710275563 A CN 201710275563A CN 107051502 A CN107051502 A CN 107051502A
- Authority
- CN
- China
- Prior art keywords
- weight
- component
- solid catalyst
- ozone heterogeneous
- weight ratio
- 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.)
- Withdrawn
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 carbonic acid lutetium hydrate Rare-earth Chemical class 0.000 claims abstract description 11
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 10
- 239000011029 spinel Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000010428 baryte Substances 0.000 claims abstract description 9
- 229910052601 baryte Inorganic materials 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- 239000010970 precious metal Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims abstract description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004472 Lysine Substances 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 6
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims abstract description 4
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 240000007817 Olea europaea Species 0.000 claims 1
- TZIZDKHKROKBAJ-UHFFFAOYSA-N [Rh].[Na].[Na].[Na] Chemical compound [Rh].[Na].[Na].[Na] TZIZDKHKROKBAJ-UHFFFAOYSA-N 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 claims 1
- 239000011435 rock Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 235000018977 lysine Nutrition 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YPUOTXOJCHHZIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;ytterbium(3+) Chemical compound [Yb+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YPUOTXOJCHHZIY-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-O hydron;octadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCC[NH3+] REYJJPSVUYRZGE-UHFFFAOYSA-O 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002669 lysines Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MAUMSNABMVEOGP-UHFFFAOYSA-N (methyl-$l^{2}-azanyl)methane Chemical compound C[N]C MAUMSNABMVEOGP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910020252 KAuCl4 Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- GDJKGUGXMBNRHL-UHFFFAOYSA-N O.[Lu].C(O)(O)=O Chemical compound O.[Lu].C(O)(O)=O GDJKGUGXMBNRHL-UHFFFAOYSA-N 0.000 description 1
- JTPIELSRLONMBL-UHFFFAOYSA-N [K].[Au].[Cl] Chemical compound [K].[Au].[Cl] JTPIELSRLONMBL-UHFFFAOYSA-N 0.000 description 1
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.The preparation method is to use gamma-alumina, barite, shepardite, serpentinite, magnesia spinel and peridotite porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add the double octadecyl ammoniums of surfactant chlorodimethyl and surface activation process is carried out under ul-trasonic irradiation, then ultrasonic surface activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor four (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) cerium (IV), acetylacetone,2,4-pentanedione samarium, three (trifluoromethanesulfonimide) ytterbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound lysine manganese, zirconium carbonate ammonium and the golden potassium of precious metal chemical complex tetrachloro, six nitroso rhodium trisodiums, in emulsifying agent dodecyldimethylamine base（2 hydroxyls）Ethyl ammonium chloride effect is lower to carry out hydro-thermal reaction, and reaction product drying is removed after moisture, and in Muffle furnace, calcination obtains ozone Heterogeneous oxidation solid catalyst under certain temperature.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using rare earth organo-metallic compound and closes
Thing and precious metal chemical complex are made catalytic active center predecessor and contained with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering preparation
The ozone Heterogeneous oxidation solid catalyst of multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
Larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using rare earth organo-metallic compound
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by gama-alumina, barite, shepardite, serpentinite,
Magnesia spinel, peridotite composition, by weight, gama-alumina:Barite:Shepardite:Serpentinite:Magnesia spinel:Olive
Lan Yan weight ratio=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, A
Component:Weight ratio=1 of B component:（10~20）, component C is the double octadecyl ammoniums of chlorodimethyl, by weight, component C:
Weight ratio=1 of reaming modified support:（5~10）, D components are before composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent
Drive thing four (DPM dpm,dipivalomethane acid) cerium (IV), acetylacetone,2,4-pentanedione samarium, three (trifluoromethanesulfonimide) ytterbiums,
Carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound lysine
The golden potassium of manganese, zirconium carbonate ammonium and precious metal chemical complex tetrachloro, six nitroso rhodium trisodiums, emulsifying agent dodecyldimethylamine base（2- hydroxyls）
Ethyl ammonium chloride is constituted, by weight, borax:Potassium sulfate:Four (DPM dpm,dipivalomethane acid) ceriums (IV):Second
Acyl acetone samarium:Three (trifluoromethanesulfonimide) ytterbiums:Carbonic acid lutetium hydrate:Lysine manganese:Zirconium carbonate ammonium:Tetrachloro gold potassium:Six is sub-
Nitro rhodium trisodium:Dodecyldimethylamine base（2- hydroxyls）The weight ratio of ethyl ammonium chloride=（4~8）:（6~10）:（3~
6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.In the B component
Gama-alumina, barite, shepardite, serpentinite, magnesia spinel and peridotite are crushed respectively, deionized water washing
Dry and remove after moisture, -200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Gama-alumina, barite, shepardite, serpentinite, magnesia spinel and peridotite porous material carrier, in certain temperature
Under stirring condition, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace separation in the middle part of porous material
The big Ca of sub- radius2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, it is thick that the aperture of porous material carrier becomes big, surface
Rugosity increase, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds chlorodimethyl double 18
Alkylammonium [(CH3)2N(C18H37)2]+Cl-The aqueous solution, when control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation
Between, under ultrasonic cavitation effect, double the octadecyl ammonium [(CH of chlorodimethyl3)2N(C18H37)2]+Cl-It is easy to escape from the aqueous solution
Go out to enter reaming modified support duct or be attached to reaming modified support surface, be beneficial to being interconnected and carrier for carrier duct
Surface active, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred to hydrothermal reaction kettle
In, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, (2,2,6, the 6- tetramethyls of catalytic activity auxiliary agent predecessor four
Base -3,5- heptadione acid) cerium (IV) C22H38CeO4, acetylacetone,2,4-pentanedione samarium C15H25O8Sm, three (trifluoromethanesulfonimide) ytterbiums
[(CF3SO2)2N]3Yb, carbonic acid lutetium hydrate C3H2Lu2O10Rare-earth chemicals, catalytic active center component predecessor
Normal transition metallo-organic compound lysine manganese C12H26N4O4, zirconium carbonate ammonium (NH4)2·C2H2O8Zr and precious metal chemical complex four
Chlorine gold potassium KAuCl4, six nitroso rhodium trisodium Na3Rh(NO2)6, in emulsifying agent dodecyldimethylamine base（2- hydroxyls）Ethylmercury chloride
Ammonium [C14H29N(CH3)2CH2CH2(OH)]+Cl-Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, makes reactant brilliant
Lattice are activated, and promote the progress of solid phase reaction, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metal
Organic compound, precious metal chemical complex Uniform Doped, emulsifying agent dodecyldimethylamine base（2- hydroxyls）Ethyl ammonium chloride makes reaction
Liquid forms quasi-stationary emulsion and prevents separation of solid and liquid, sedimentation, while to the further surface active of porous mineral carrier, by
Certain temperature, the hydro-thermal reaction of time, drying obtain the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace
Interior, through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains porous carrier
The ozone Heterogeneous oxidation of the catalytic active center of supported rare earth metal oxide, transition metal oxide and noble metal formation is consolidated
Body catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that gama-alumina, barite, water are used in technology of preparing
Magnesite, serpentinite, magnesia spinel, peridotite porous material make carrier, due to lithium hypochlorite LiClO and couple (acetylacetone,2,4-pentanedione)
Beryllium C10H14BeO4Reaming effect, double the octadecyl ammonium [(CH of chlorodimethyl3)2N(C18H37)2]+Cl-, dodecyldimethylamine base
（2- hydroxyls）Ethyl ammonium chloride [C14H29N(CH3)2CH2CH2(OH)]+Cl-To being interconnected and surface activation for duct, lead to
Cross hydro-thermal reaction and reach Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex and uniformly mix
Miscellaneous and be attached in carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level micropore knot
In structure, the multi-element metal catalytic activity of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
The heart is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, polynary
The cooperative effect of metal, stability and high activity that particularly doped precious metal has, can suppress metal catalytic activity component
Liquate out, the mithridatism and catalytic activity of catalyst are improved, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, being added to volume is
500ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
2.75g gama-aluminas, 3.75g barites, 4.75g shepardites, 5.75g serpentinites, the 6.75g magnesium point of 400 mesh standard sieves are brilliant
The weight of stone, 7.75g peridotites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:
10.5,36 DEG C are warming up to, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；
In 500ml ultrasound reactors, reaming modified support 31g is put into, the double octadecyl ammoniums of 3.25g chlorodimethyls is added and is dissolved in
The aqueous solution of 100ml deionized waters, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, chlorodimethyl double 18
Alkylammonium（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency
41 DEG C of 21kHz, temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 500ml hydrothermal reaction kettles, is added by 2.1g boraxs, 3.05g potassium sulfates, 1.6g tetra- (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) cerium (IV), 2.05g acetylacetone,2,4-pentanediones samarium, 2.6g tri- (trifluoromethanesulfonimide) ytterbium, 3. 05g carbon
The golden potassium of sour lutetium hydrate, 5.05g lysines manganese, 6.1g zirconium carbonate ammoniums, 2. 05g tetrachloros, the nitroso rhodium trisodiums of 3.1g six,
3.05g dodecyldimethylamine base（2- hydroxyls）The aqueous solution that ethyl ammonium chloride and 50ml deionized waters are prepared, the weight of the aqueous solution
It is 40.3%, the weight of the aqueous solution to measure concentration:Weight=83.8g of ultrasonic surface activated carrier mixed liquor:134.25g =1:
1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace
Interior, 620 DEG C, calcination 3.2h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
1.45g gama-aluminas, 1.65g barites, 1.85g shepardites, 2.05g serpentinites, the 2.25g magnesium point of 400 mesh standard sieves are brilliant
The weight of stone, 2.45g peridotites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=
1:19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, the double octadecyl ammoniums of 2.2g chlorodimethyls are added
The aqueous solution of 26ml deionized waters is dissolved in, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, chlorodimethyl double ten
Eight alkylammoniums（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic wave frequency
54 DEG C of rate 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor is activated and carried
Body mixed liquor is transferred in 100ml hydrothermal reaction kettles, add by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tetra- (2,2,6,
6- tetramethyl -3,5- heptadione acid) cerium (IV), 0.67g acetylacetone,2,4-pentanediones samarium, 0.78g tri- (trifluoromethanesulfonimide) ytterbium,
The golden potassium of 0.87g carbonic acid lutetiums hydrate, 1.48g lysines manganese, 1.77g zirconium carbonate ammoniums, 0.68g tetrachloros, the nitroso rhodiums three of 0.87g six
Sodium, 1.98g dodecyldimethylamine bases（2- hydroxyls）The aqueous solution that ethyl ammonium chloride and 10ml deionized waters are prepared, the aqueous solution
Weight concentration be 53.3%, the weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g =
1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in horse
Not in stove, 930 DEG C, calcination 7.5h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A is by lithium hypochlorite, double (acetyl
Acetone) beryllium composition, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by γ-
Aluminum oxide, barite, shepardite, serpentinite, magnesia spinel, peridotite composition, by weight, gama-alumina:Weight is brilliant
Stone:Shepardite:Serpentinite:Magnesia spinel:The weight ratio of peridotite=（5~15）:（7~17）:（9~19）:（11~
21）:（13~23）:（15~25）, by weight, component A:Weight ratio=1 of B component:（10~20）, component C is chlorination two
Methyldioctadecylammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by being combined
Mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor four (2,2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV), second
Acyl acetone samarium, three (trifluoromethanesulfonimide) ytterbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center
The golden potassium of predecessor normal transition metallo-organic compound lysine manganese, zirconium carbonate ammonium and precious metal chemical complex tetrachloro, six nitrosos
Rhodium trisodium, emulsifying agent dodecyldimethylamine base（2- hydroxyls）Ethyl ammonium chloride is constituted, by weight, borax:Potassium sulfate:Four (2,
2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV):Acetylacetone,2,4-pentanedione samarium:Three (trifluoromethanesulfonimide) ytterbiums:Carbonic acid lutetium
Hydrate:Lysine manganese:Zirconium carbonate ammonium:Tetrachloro gold potassium:Six nitroso rhodium trisodiums:Dodecyldimethylamine base（2- hydroxyls）Second
The weight ratio of ammonium chloride=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~
18）:（4~7）:（6~9）:（6~20）.
2. B component is by gama-alumina, barite, shepardite, serpentinite, magnesia spinel, olive according to claim 1
Rock is constituted, and gama-alumina, barite, shepardite, serpentinite, magnesia spinel, peridotite are crushed respectively, deionization
Water washing, which is dried, to be removed after moisture, is sieved through standard screen, and it is 0.0370mm~0.0750mm to control particle diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275563.5A CN107051502A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275563.5A CN107051502A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107051502A true CN107051502A (en) | 2017-08-18 |
Family
ID=59604595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710275563.5A Withdrawn CN107051502A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051502A (en) |
-
2017
- 2017-04-25 CN CN201710275563.5A patent/CN107051502A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107051448A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008395A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008400A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051529A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051502A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159203A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020089A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008311A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051534A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051494A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008315A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107138159A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020128A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008352A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008309A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008310A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159206A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008392A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159207A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051519A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088411A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008292A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008298A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051437A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008440A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170818 |
|
| WW01 | Invention patent application withdrawn after publication |