CN107008416A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008416A CN107008416A CN201710275831.3A CN201710275831A CN107008416A CN 107008416 A CN107008416 A CN 107008416A CN 201710275831 A CN201710275831 A CN 201710275831A CN 107008416 A CN107008416 A CN 107008416A
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- weight
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- double
- solid catalyst
- deionized water
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019362 perlite Nutrition 0.000 claims abstract description 12
- 239000002367 phosphate rock Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 11
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims abstract description 11
- 229910052656 albite Inorganic materials 0.000 claims abstract description 10
- 229910052934 alunite Inorganic materials 0.000 claims abstract description 10
- 239000010424 alunite Substances 0.000 claims abstract description 10
- 239000010451 perlite Substances 0.000 claims abstract description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 hydroxypropyl dichloride ammonium Chemical compound 0.000 claims abstract description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- 235000005340 Asparagus officinalis Nutrition 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 8
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 8
- 235000016768 molybdenum Nutrition 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims abstract description 7
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940094989 trimethylsilane Drugs 0.000 claims abstract description 7
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 229940009662 edetate Drugs 0.000 claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 229910052691 Erbium Inorganic materials 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
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 5
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 241000234427 Asparagus Species 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 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 claims 1
- SYGKRYHXHZWFMX-UHFFFAOYSA-K [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F Chemical compound [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F SYGKRYHXHZWFMX-UHFFFAOYSA-K 0.000 claims 1
- 229910001791 alunite group Inorganic materials 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000001994 activation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 3
- GDJKGUGXMBNRHL-UHFFFAOYSA-N O.[Lu].C(O)(O)=O Chemical compound O.[Lu].C(O)(O)=O GDJKGUGXMBNRHL-UHFFFAOYSA-N 0.000 abstract description 3
- 244000003416 Asparagus officinalis Species 0.000 abstract 1
- 238000003889 chemical engineering Methods 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
- 229910001868 water Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 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
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 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
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 229940048820 edetates Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J23/8993—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 chromium, molybdenum or tungsten
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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 perlite, albite, inclined aluminium hydroxide, phosphorite, hydrotalcite and alunite porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant nonyl phenolic group bi-quaternary ammonium salt 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 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, three [N, double (trimethyl silane) amine of N] erbium, carbonic acid lutetium hydrate (III) Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate, citric acid nickel, L lucid asparagus amino acid molybdenums and the nitroso rhodium trisodium Pt of precious metal chemical complex six, hydro-thermal reaction is carried out under the effect of the hydroxypropyl dichloride ammonium of ten alkyl dimethyl N' trimethyls of emulsifying agent N 2, reaction product drying is removed after moisture, 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
The adsorptivity of catalyst, catalytic activity auxiliary agent predecessor, normal transition Organometallic are made using Rare-earth chemicals
Compound and precious metal chemical complex are made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering
Ozone Heterogeneous oxidation solid catalyst containing multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
There are 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 chemicals
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 is by perlite, albite, inclined aluminium hydroxide, phosphorite, water
Talcum, alunite composition, by weight, perlite:Albite:Inclined aluminium hydroxide:Phosphorite:Hydrotalcite:The weight of alunite
The ratio between=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:B component
Weight ratio=1:（10~20）, component C is nonyl phenolic group bi-quaternary ammonium salt, by weight, component C:The weight of reaming modified support
The ratio between amount=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, the trifluoro second of catalytic activity auxiliary agent predecessor 1,1,1-
Acyl acetone neodymium, three (DPM dpm,dipivalomethane acid) gadoliniums, three [double (trimethyl silane) amine of N, N-] erbiums, carbonic acid lutetium
Hydrate Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound cobalt edetate,
Citric acid nickel, L- lucid asparagus amino acid molybdenums and the nitroso rhodium trisodium of precious metal chemical complex six, the alkyl dimethyls of emulsifying agent N- ten-
N'- trimethyl -2- hydroxypropyl dichlorides ammonium is constituted, by weight, borax:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three
(DPM dpm,dipivalomethane acid) gadolinium:Three [double (trimethyl silane) amine of N, N-] erbiums:Carbonic acid lutetium hydrate:Grape
Saccharic acid cobalt:Citric acid nickel:L- lucid asparagus amino acid molybdenums:Six nitroso rhodium trisodiums:Alkyl dimethyl-N'- trimethyl -2- the hydroxyls of N- ten
The weight ratio of propyl group dichloride ammonium=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:
（12~18）:（4~7）:（6~9）:（6~20）.Perlite, albite, inclined aluminium hydroxide, phosphorite, the water of the B component
Talcum, alunite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh are carried out through standard screen
Screening, 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
Perlite, albite, inclined aluminium hydroxide, phosphorite, hydrotalcite and alunite porous material carrier, in certain temperature and stirring
Under the conditions of, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material
Big Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds nonyl phenolic group bi-quaternary ammonium salt
[(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature
Degree and sonic oscillation time, under ultrasonic cavitation effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)
CH2N(C2H5)3]2 +Br2 -It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support surface,
It is beneficial to being interconnected and carrier surface activation for carrier duct, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic surface is lived
Change carrier mixed liquor to be transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalysis
Coagent predecessor 1,1,1- trifluoroacetylacetone (TFA) neodymiums C15H12F9NdO6, three (DPM dpm,dipivalomethanes acid)
Gadolinium C33H57GdO6, three [N, N- double (trimethyl silane) amine] erbium C18H54ErN3Si6, carbonic acid lutetium hydrate C3H2Lu2O10Rare earth gold
Belong to organic compound, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co、
Citric acid nickel C12H10O14Ni3, L- lucid asparagus amino acid molybdenum Mo [OOCCH2CH(NH2)COO]3(H2O)3With six nitroso rhodium trisodiums
Na3Rh(NO2)6Precious metal chemical complex, in the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of emulsifying agent N- ten
C10H21N+(CH3)2CH2CH(OH)CH2N+(CH3)3Cl2 -Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, makes reaction
Thing lattice is activated, and promotes the progress of solid phase reaction, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition
Metallo-organic compound, precious metal chemical complex Uniform Doped, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyls two of emulsifying agent N- ten
Ammonium chloride make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while to the further surface of porous carrier live
Change, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；The fine silt of Uniform Doped
Thing is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains
Ozone to the catalytic active center of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation is non-
Homogeneous oxidizing solid catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that perlite, albite, inclined hydrogen-oxygen are used in technology of preparing
Change aluminium, phosphorite, hydrotalcite, alunite porous material and make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -、
Alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums the C of N- ten10H21N+(CH3)2CH2CH(OH)CH2N+(CH3)3Cl2 -It is right
The interconnected and surface activation in duct；There are Rare-earth chemicals, normal transition metal by hydro-thermal reaction
Machine compound and precious metal chemical complex reach Uniform Doped and are attached in carrier surface and duct that high temperature sintering makes organic matter complete
Multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide are strengthened and formd in full carbonization
More firm, the ozone Heterogeneous oxidation of preparation is combined with porous carrier with the multi-element metal catalytic active center of noble metal formation
Solid catalyst has a stronger adsorptivity, the cooperative effect of multi-element metal, the noble metal of particularly doping have stability and
High activity, can suppress liquating out for metal catalytic activity component, the mithridatism and catalytic activity of catalyst be improved, with good
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 are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
2.75g perlites, 3.75g albites, the inclined aluminium hydroxides of 4.75g, 5.75g phosphorites, 6.75g hydrotalcites, the 7.75g of standard screen
The weight of alunite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, it is warming up to
36 DEG C, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；It is anti-in 500ml ultrasonic waves
Answer in device, put into reaming modified support 31g, add 3.25g nonyl phenolic group bi-quaternary ammonium salts and be dissolved in the water-soluble of 100ml deionized waters
Liquid, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt（3.25g）:Reaming modified support
（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation
2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals anti-
Answer in kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g1,1,1- trifluoroacetylacetone (TFA) neodymium, 2.05g tri- (2,2,6,6-
Tetramethyl -3,5- heptadione acid) gadolinium, 2.6g tri- [N, N- double (trimethyl silane) amine] erbium, 3.05g carbonic acid lutetiums hydrate, 5.05g
Cobalt edetate, 6.1g citric acids nickel, 2.05g L- lucid asparagus amino acid molybdenum, the nitroso rhodium trisodiums of 3.1g six, the alkane of 3.05gN- ten
The aqueous solution that base dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums and 50ml deionized waters are prepared, the weight of the aqueous solution
Concentration is 40.3%, the weight of the aqueous solution: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 in Muffle furnace,
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~+
The 1.45g perlites of 400 mesh standard sieves, 1.65g albites, the inclined aluminium hydroxides of 1.85g, 2.05g phosphorites, 2.25g hydrotalcites,
The weight of 2.45g alunites, 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, 2.2g nonyl phenolic group bi-quaternary ammonium salts is added and is dissolved in 26ml
The aqueous solution of deionized water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt
（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency 29kHz,
54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor
It is transferred in 100ml hydrothermal reaction kettles, adds by 0.78g boraxs, 0.97g potassium sulfates, 0.58g1,1,1- trifluoroacetylacetone (TFA)
Neodymium, 0.67g tri- (DPM dpm,dipivalomethane acid) gadolinium, 0.78g tri- [double (trimethyl silane) amine of N, N-] erbium,
0.87g carbonic acid lutetiums hydrate, 1.48g cobalt edetates, 1.77g citric acids nickel, 0.68g L- lucid asparagus amino acid molybdenum, 0.87g
Six nitroso rhodium trisodiums, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of 1.98gN- ten and 10ml deionized waters are matched somebody with somebody
The aqueous solution of system, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier mixed liquor
Weight=21.43g:39.7g =1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries carefully for 105 DEG C
Powder material；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, and after cooling down, the ozone that can obtain fine particle shape is non-
Homogeneous oxidizing solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, nonyl phenolic group bi-quaternary ammonium salt, the alkane of N- ten
Outside base dimethyl-N '-trimethyl -2- hydroxypropyl dichlorides ammonium, borax and potassium sulfate, whole preparation process, preparation condition and reality
Apply example 1 identical.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
| Project | Average pore size (nm) | Pore volume (cm3/g) | BET is than surface (m2/g) |
| Embodiment 1 | 4.599 | 0.6103 | 781.11 |
| Embodiment 2 | 4.116 | 0.5629 | 672.97 |
| Comparative example 1 | 2.227 | 0.3239 | 477.57 |
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 by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Divide and be made up of perlite, albite, inclined aluminium hydroxide, phosphorite, hydrotalcite, alunite, by weight, perlite:Albite:
Inclined aluminium hydroxide:Phosphorite:Hydrotalcite:The weight ratio of alunite=（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 that nonyl phenolic group is double
Quaternary ammonium salt, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components by composite mineralizer borax,
Potassium sulfate, the trifluoroacetylacetone (TFA) neodymium of catalytic activity auxiliary agent predecessor 1,1,1-, three (2,2,6,6- tetramethyl -3,5- heptadione acid)
Gadolinium, three [double (trimethyl silane) amine of N, N-] erbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center forerunner
Thing normal transition metallo-organic compound cobalt edetate, citric acid nickel, L- lucid asparagus amino acid molybdenums and precious metal chemical complex six
Nitroso rhodium trisodium, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichlorides ammoniums of emulsifying agent N- ten composition, by weight, boron
Sand:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (DPM dpm,dipivalomethane acid) gadoliniums:Three [N, N- double (three
Methyl-monosilane) amine] erbium:Carbonic acid lutetium hydrate:Cobalt edetate:Citric acid nickel:L- lucid asparagus amino acid molybdenums:Six nitroso rhodiums three
Sodium:The weight ratio of the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of N- ten=（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 perlite, albite, inclined aluminium hydroxide, phosphorite, hydrotalcite, alunite group according to claim 1
Into perlite, albite, inclined aluminium hydroxide, phosphorite, hydrotalcite, alunite are crushed respectively, deionized water washing drying
Remove after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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