CN107051541A - 臭氧非均相氧化固体催化剂的制备方法 - Google Patents
臭氧非均相氧化固体催化剂的制备方法 Download PDFInfo
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- 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 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 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 13
- 239000004575 stone Substances 0.000 claims abstract description 13
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 239000010456 wollastonite Substances 0.000 claims abstract description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 8
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940094989 trimethylsilane Drugs 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 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 7
- DYYFBWLZDJSPGO-UHFFFAOYSA-H holmium(3+);oxalate Chemical class [Ho+3].[Ho+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DYYFBWLZDJSPGO-UHFFFAOYSA-H 0.000 claims abstract description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 7
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- BOLCLFSSFZOGPX-UHFFFAOYSA-N N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C Chemical class N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C BOLCLFSSFZOGPX-UHFFFAOYSA-N 0.000 claims abstract description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 235000005340 Asparagus officinalis Nutrition 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- BENADMAVJUZZBP-UHFFFAOYSA-N [O-2].C(C)(C)[Sc+2] Chemical compound [O-2].C(C)(C)[Sc+2] BENADMAVJUZZBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 5
- KZXFBCUXEQXICP-UHFFFAOYSA-N [W].C=1(O)C(O)=CC=CC1.C(CN)N Chemical compound [W].C=1(O)C(O)=CC=CC1.C(CN)N KZXFBCUXEQXICP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 235000016768 molybdenum Nutrition 0.000 claims abstract 3
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- -1 erbium Rare-earth Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 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 description 9
- 229910052934 alunite Inorganic materials 0.000 claims description 8
- 239000010424 alunite Substances 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 125000005594 diketone group Chemical group 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 241000234427 Asparagus Species 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- ZQSSRUAWBFTSKE-UHFFFAOYSA-N benzene-1,2-diol;tungsten Chemical compound [W].OC1=CC=CC=C1O ZQSSRUAWBFTSKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 2
- 229910001791 alunite group Inorganic materials 0.000 claims 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 abstract description 8
- 238000001994 activation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 abstract description 4
- 244000003416 Asparagus officinalis Species 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 229940037003 alum Drugs 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 4
- 230000008901 benefit 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
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- ONRPGGOGHKMHDT-UHFFFAOYSA-N benzene-1,2-diol;ethane-1,2-diamine Chemical class NCCN.OC1=CC=CC=C1O ONRPGGOGHKMHDT-UHFFFAOYSA-N 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
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 150000003870 salicylic acids Chemical class 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 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
- 235000009582 asparagine Nutrition 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
- 230000008859 change 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
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 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
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 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
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种臭氧非均相氧化固体催化剂的制备方法，属环保和化工催化剂技术领域。用麦饭石、硅灰石、蒙脱土、钾石盐、水滑石和明矾石作载体，载体经次氯酸锂和双(乙酰丙酮)铍扩孔后，加入氯化十八烷基三甲基铵经超声波作用活化处理后，活化载体在水热反应釜中与复合矿化剂硼砂和硫酸钾，催化活性助剂前驱物异丙氧化钪(III)、三(6,6,7,7,8,8,8‑七氟‑2,2‑二甲基‑3,5‑ 辛烯二酮)镝(III)、十水草酸钬、三[N,N‑双(三甲基硅烷)胺]铒，催化活性中心组分前驱物二茂钛环取代水杨酸配合物、L‑天门冬氨基酸钼、邻苯二酚乙二胺钨配合物和二硫氰酸根合银（I）酸钾，在双十四烷基二甲基氯化铵作用下进行水热反应，烘干除去水分，在马弗炉内灼烧得到臭氧非均相氧化固体催化剂。
Description
技术领域
本发明涉及一种臭氧非均相氧化固体催化剂的制备方法，属环保和化工催化剂技术领域。
背景技术
臭氧氧化技术利用臭氧氧化能力强的特点，能将许多有机污染物氧化分解，广泛用于废水处理。臭氧催化氧化技术分为臭氧均相催化氧化和臭氧非均相催化氧化，臭氧均相催化氧化存在催化剂较难分离回收重复使用、臭氧利用率低导致水处理运行成本较高，同时有机污染物去除率较低和易造成水体二次污染使其应用受到局限；臭氧非均相催化氧化技术具有催化剂易于分离回收并可重复使用、臭氧利用率高、有机污染物去除率较高，降低了水处理运行成本和不会造成二次污染等优点使其应用受到广泛关注。臭氧非均相催化氧化有机物分解是经过催化剂表面吸附有机物达到局部有机物富集，同时臭氧分子吸附在催化剂表面在催化剂作用下产生高活性的羟基自由基使有机物分解。臭氧非均相催化氧化处理废水技术中，核心技术是臭氧非均相氧化固体催化剂的制备。
臭氧非均相氧化固体催化剂通常由载体、活性中心和助剂组成。由于废水中污染物种类繁多、化学成分复杂的特征，会对催化剂的使用性能如吸附、抗毒性产生不良影响。目前制备臭氧非均相氧化固体催化剂使用的载体结构较单一，吸附性较低；活性中心普遍采用普通过渡金属盐，抗毒性较差；制备方法主要有浸渍法、沉淀法、混合法及溶胶凝胶等方法附着活性中心和助剂组分于载体表面，活性中心和助剂组分容易熔析出，导致催化剂容易失去催化活性。针对目前臭氧非均相氧化固体催化剂制备方法中存在催化剂吸附性较低、抗毒性较差和容易失去催化活性问题，开发采用多组分多孔载体经扩孔、表面活化增强催化剂的吸附性，使用稀土金属有机化合物作催化活性助剂前驱物、普通过渡金属有机化合物和贵金属化合物作催化活性中心前驱物与多组分多孔载体经水热反应、高温灼烧制备含多元金属的臭氧非均相氧化固体催化剂以提高催化剂抗毒性和催化活性的制备方法，具有较大的环境效益和较高的实用价值。
发明内容
针对目前臭氧非均相氧化固体催化剂制备方法中存在催化剂吸附性较低、抗毒性较差和容易失去催化活性问题，开发采用多组分多孔载体经扩孔、表面活化增强催化剂的吸附性，使用稀土金属有机化合物作催化活性助剂前驱物、普通过渡金属有机化合物和贵金属化合物作催化活性中心前驱物与多组分多孔载体经水热反应、高温灼烧制备含多元金属的臭氧非均相氧化固体催化剂以提高催化剂抗毒性和催化活性的制备方法，其特征是在可密闭反应器中加入A组分和去离子水搅拌制备水溶液，控制A组分的重量浓度为2%～6%，溶液制备完成后，在搅拌下加入B组分，升温至35℃～50℃，继续搅拌反应3h～6h，过滤，反应产物在102℃～106℃干燥恒重后得到扩孔改性载体；扩孔改性载体投入超声波反应器，加入由C组分和去离子水配制的水溶液，C组分的重量浓度为3%～8%，搅拌混合均匀，控制超声功率密度为0.3～0.8W/m3、频率20kHz～30kHz、40℃～55℃，超声振荡2h～5h，得到超声表面活化载体混合液；超声表面活化载体混合液转移至水热反应釜中，再加入D组分和去离子水配制的水溶液，D组分的重量浓度为40%～55%，按重量计，D组分去离子水溶液:超声表面活化载体混合液的重量比=1:（1.5～2），控制温度120℃～180℃，水热反应时间为8h～16h，然后烘干得细颗粒物；细颗粒物在马弗炉内，600℃～950℃，灼烧3h～8h，得到臭氧非均相氧化固体催化剂。所述A组分由次氯酸锂、双(乙酰丙酮)铍组成，按重量计，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:（1～1.6），B组分由麦饭石、硅灰石、蒙脱土、钾石盐、水滑石、明矾石组成，按重量计，麦饭石:硅灰石:蒙脱土:钾石盐:水滑石:明矾石的重量之比=（5～15）:（7～17）:（9～19）:（11～21）:（13～23）:（15～25），按重量计，A组分:B组分的重量之比=1:（10～20），C组分是氯化十八烷基三甲基铵，按重量计，C组分:扩孔改性载体的重量之比=1:（5～10），D组分由复合矿化剂硼砂、硫酸钾，催化活性助剂前驱物异丙氧化钪(III)、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、十水草酸钬、三[N,N-双(三甲基硅烷)胺]铒稀土金属有机化合物，催化活性中心前驱物普通过渡金属有机化合物二茂钛环取代水杨酸配合物、L-天门冬氨基酸钼、邻苯二酚乙二胺钨配合物和贵金属化合物二硫氰酸根合银（I）酸钾，乳化剂双十四烷基二甲基氯化铵组成，按重量计，硼砂:硫酸钾:异丙氧化钪(III):三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III):十水草酸钬:三[N,N-双(三甲基硅烷)胺]铒:二茂钛环取代水杨酸配合物:L-天门冬氨基酸钼:邻苯二酚乙二胺钨配合物:二硫氰酸根合银（I）酸钾:双十四烷基二甲基氯化铵的重量之比=（4～8）:（6～10）:（3～6）:（4～7）:（5～8）:（6～9）:（10～15）:（12～18）:（4～7）:（6～9）:（6～20）。所述B组分的麦饭石、硅灰石、蒙脱土、钾石盐、水滑石、明矾石分别进行粉碎，去离子水洗涤干燥除去水分后，经标准筛进行-200目、+400目筛分，控制粒径为0.0370mm～0.0750 mm。
本发明的技术方法是这样实现的：在可密闭反应器中加入次氯酸锂LiClO、双(乙酰丙酮)铍C10H14BeO4和去离子水搅拌制备水溶液，加入筛分后粒径为0.0370mm～0.0750mm的麦饭石、硅灰石、蒙脱土、钾石盐、水滑石和明矾石多孔材料载体，在一定温度和搅拌条件下，水溶液中离子半径小的Be2+（0.31Å）、Li+（0.60Å）置换出多孔材料中部分离子半径大的Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）等离子，多孔材料载体的孔径变大、表面粗糙度增加，过滤，干燥恒重后的扩孔改性载体投入超声波反应器，再加入氯化十八烷基三甲基铵[C18H37N(CH3)3]+Cl- 水溶液，控制超声功率密度、超声波频率、温度和超声振荡时间，在超声波空化作用下，氯化十八烷基三甲基铵[C18H37N(CH3)3]+Cl- 易于从水溶液逸出进入扩孔改性载体孔道或附着在扩孔改性载体表面，有益于载体孔道的相互连通和载体表面活化，增强了吸附性；超声活化完成后，超声表面活化载体混合液转移至水热反应釜中，与硼砂Na2B4O7·10H2O、硫酸钾K2SO4复合矿化剂，催化活性助剂前驱物异丙氧化钪(III)C9H21O3Sc、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)C30H30DyF21O6、十水草酸钬C6Ho2O12、三[N,N-双(三甲基硅烷)胺]铒C18H54ErN3Si6稀土金属有机化合物，催化活性中心组分前驱物普通过渡金属有机化合物二茂钛环取代水杨酸配合物(C10H10)Ti(C7H4O3)、L-天门冬氨基酸钼Mo[OOCCH2CH(NH2)COO]3(H2O)3、邻苯二酚乙二胺钨配合物(NH2CH2CH2NH3)2[W(VI)O2 (OC6H4O)2]和二硫氰酸根合银（I）酸钾K[Ag(SCN)2]贵金属化合物，在乳化剂双十四烷基二甲基氯化铵[(C14H29)2N(CH3)2]+Cl- 作用下进行水热反应，矿化剂加速扩散作用、使反应物晶格活化，促进了固相反应的进行，超声表面活化载体与稀土金属有机化合物、普通过渡金属有机化合物、贵金属化合物均匀掺杂，乳化剂双十四烷基二甲基氯化铵使反应液形成准稳态的乳液防止了固液分离、沉降，同时对多孔载体进一步表面活化，通过在一定温度、时间的水热反应，烘干得到均匀掺杂的细粉粒物；均匀掺杂的细粉粒物在马弗炉内，经高温灼烧，其中的有机物完全碳化进一步强化了多孔载体的微孔结构，得到多孔载体负载稀土金属氧化物、过渡金属氧化物和贵金属形成的催化活性中心的臭氧非均相氧化固体催化剂，提高了催化剂的抗毒性和催化活性。
相对于现有技术方法，本发明突出特点是制备技术中使用麦饭石、硅灰石、蒙脱土、钾石盐、水滑石、明矾石多孔材料作载体，由于次氯酸锂LiClO和双(乙酰丙酮)铍C10H14BeO4的扩孔效应，氯化十八烷基三甲基铵[C18H37N(CH3)3]+Cl-、双十四烷基二甲基氯化铵[(C14H29)2N(CH3)2]+Cl- 对孔道的相互连通和表面活化作用；通过水热反应使稀土金属有机化合物、普通过渡金属有机化合物和贵金属化合物达到均匀掺杂并附着于载体表面和孔道内，高温灼烧使有机物完全碳化强化和形成了多层次的微孔结构，多孔载体负载稀土金属氧化物、过渡金属氧化物和贵金属形成的多元金属催化活性中心与多孔载体结合更加牢固，制备的臭氧非均相氧化固体催化剂具有更强的吸附性，多元金属的协同效应、特别是掺杂的贵金属具有稳定性和高活性，可以抑制金属催化活性组分的熔析出，提高了催化剂的抗毒性和催化活性，具有良好的环境效益和经济效益。
具体实施方式
实施例1:1.35g次氯酸锂，1.65g双(乙酰丙酮)铍，140ml去离子水，加入到容积为500ml的可密闭反应器中搅拌混合均匀，该水溶液的重量浓度为2.1%，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:1.2；加入去离子水洗涤至中性、103℃干燥除去水分后过筛-200目～+400目标准筛的2.75g麦饭石、3.75g硅灰石、4.75g蒙脱土、5.75g钾石盐、6.75g水滑石、7.75g明矾石，次氯酸锂和双(乙酰丙酮)铍的重量（3g）:多孔材料的重量（31.5g）=1:10.5，升温至36℃，继续搅拌反应3.2h，过滤，103℃干燥恒重后得到扩孔改性载体31g；在500ml超声波反应器中，投入扩孔改性载体31g，再加入3.25g氯化十八烷基三甲基铵溶于100ml去离子水的水溶液，该水溶液的重量浓度为3.1%，搅拌混合均匀，氯化十八烷基三甲基铵（3.25g）:扩孔改性载体（31g ）=1:9.5；控制超声功率密度为0.4 W/m3、超声波频率21kHz、温度41℃，超声振荡2.2h；超声活化完成后，把超声波反应器中的超声表面活化载体混合液转移至500ml水热反应釜中，再加入由2.1g硼砂、3.05g硫酸钾、1.6g异丙氧化钪(III)、2.05g三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、2.6g十水草酸钬、3.05g三[N,N-双(三甲基硅烷)胺]铒 、5.05g二茂钛环取代水杨酸配合物、6.1gL-天门冬氨基酸钼、2.05g 邻苯二酚乙二胺钨配合物、3.1g二硫氰酸根合银（I）酸钾、3.05g双十四烷基二甲基氯化铵 和50ml去离子水配制的水溶液，该水溶液的重量浓度为40.3%，该水溶液的重量:超声表面活化载体混合液的重量=83.8g:134.25g =1:1.6，控制温度125℃，水热反应时间为8.3h，然后105℃烘干得细粉粒物；细粉粒物在马弗炉内，620℃，灼烧3.2h，降温冷却后，可得到细粉颗粒状的臭氧非均相氧化固体催化剂。
实施例2: 0.24g次氯酸锂，0.36g双(乙酰丙酮)铍，10ml去离子水，加入到容积为100ml的可密闭反应器中搅拌混合均匀，该水溶液的重量浓度为5.7%，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:1.5；加入去离子水洗涤至中性、103℃干燥除去水分后过筛-200目～+400目标准筛的1.45g麦饭石、1.65g硅灰石、1.85g蒙脱土、2.05g钾石盐、2.25g水滑石、2.45g明矾石，次氯酸锂和双(乙酰丙酮)铍的重量（0.6g）:多孔材料的重量（11.7g）=1:19.5，升温至48℃，继续搅拌反应5.8h，过滤，105℃干燥恒重后得到扩孔改性载体11.5g；在100ml超声波反应器中，投入扩孔改性载体11.5g，再加入2.2g氯化十八烷基三甲基铵溶于26ml去离子水的水溶液，该水溶液的重量浓度为7.8%，搅拌混合均匀，氯化十八烷基三甲基铵（2.2g）:扩孔改性载体（11.5g ）=1:5.2；控制超声功率密度为0.7 W/m3、超声波频率29kHz、温度54℃，超声振荡4.7h；超声活化完成后，把超声波反应器中的超声表面活化载体混合液转移至100ml水热反应釜中，再加入由0.78g硼砂、0.97g硫酸钾、0.58g异丙氧化钪(III)、0.67g三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、0.78g十水草酸钬、0.87g三[N,N-双(三甲基硅烷)胺]铒 、1.48g二茂钛环取代水杨酸配合物、1.77gL-天门冬氨基酸钼、0.68g 邻苯二酚乙二胺钨配合物、0.87g二硫氰酸根合银（I）酸钾、1.98g双十四烷基二甲基氯化铵和10ml去离子水配制的水溶液，该水溶液的重量浓度为53.3%，该水溶液的重量:超声表面活化载体混合液的重量=21.43g:39.7g =1:1.9，控制温度175℃，水热反应时间为15.5h，然后105℃烘干得细粉粒物；细粉粒物在马弗炉内，930℃，灼烧7.5h，降温冷却后，可得到细粉颗粒状的臭氧非均相氧化固体催化剂。
Claims (2)
1.一种臭氧非均相氧化固体催化剂的制备方法，其特征是在可密闭反应器中加入A组分和去离子水搅拌制备水溶液，控制A组分的重量浓度为2%～6%，溶液制备完成后，在搅拌下加入B组分，升温至35℃～50℃，继续搅拌反应3h～6h，过滤，反应产物在102℃～106℃干燥恒重后得到扩孔改性载体，扩孔改性载体投入超声波反应器，加入由C组分和去离子水配制的水溶液，C组分的重量浓度为3%～8%，搅拌混合均匀，控制超声功率密度为0.3～0.8W/m3、频率20kHz～30kHz、40℃～55℃，超声振荡2h～5h，得到超声表面活化载体混合液，转移至水热反应釜中，再加入D组分和去离子水配制的水溶液，D组分的重量浓度为40%～55%，按重量计，D组分去离子水溶液:超声表面活化载体混合液的重量比=1:（1.5～2），控制温度120℃～180℃，水热反应时间为8h～16h，然后烘干得细粉粒物，细粉粒物在马弗炉内，600℃～950℃，灼烧3h～8h，得到臭氧非均相氧化固体催化剂；所述A组分由扩孔剂次氯酸锂、双(乙酰丙酮)铍组成，按重量计，次氯酸锂:双(乙酰丙酮)铍的重量之比=1:（1～1.6），B组分由麦饭石、硅灰石、蒙脱土、钾石盐、水滑石、明矾石组成，按重量计，麦饭石:硅灰石:蒙脱土:钾石盐:水滑石:明矾石的重量之比=（5～15）:（7～17）:（9～19）:（11～21）:（13～23）:（15～25），按重量计，A组分:B组分的重量之比=1:（10～20），C组分是氯化十八烷基三甲基铵，按重量计，C组分:扩孔改性载体的重量之比=1:（5～10），D组分由复合矿化剂硼砂、硫酸钾，催化活性助剂前驱物异丙氧化钪(III)、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、十水草酸钬、三[N,N-双(三甲基硅烷)胺]铒稀土金属有机化合物，催化活性中心前驱物普通过渡金属有机化合物二茂钛环取代水杨酸配合物、L-天门冬氨基酸钼、邻苯二酚乙二胺钨配合物和贵金属化合物二硫氰酸根合银（I）酸钾，乳化剂双十四烷基二甲基氯化铵组成，按重量计，硼砂:硫酸钾:异丙氧化钪(III):三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III):十水草酸钬:三[N,N-双(三甲基硅烷)胺]铒:二茂钛环取代水杨酸配合物:L-天门冬氨基酸钼:邻苯二酚乙二胺钨配合物:二硫氰酸根合银（I）酸钾:双十四烷基二甲基氯化铵 的重量之比=（4～8）:（6～10）:（3～6）:（4～7）:（5～8）:（6～9）:（10～15）:（12～18）:（4～7）:（6～9）:（6～20）。
2.根据权利要求1所述B组分由麦饭石、硅灰石、蒙脱土、钾石盐、氢氧化铝、明矾石组成，麦饭石、硅灰石、蒙脱土、钾石盐、氢氧化铝、明矾石分别进行粉碎，去离子水洗涤干燥除去水分后，经标准筛进行筛分，控制粒径为0.0370mm～0.0750mm。
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