CN113289614B - 一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法 - Google Patents
一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法 Download PDFInfo
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- CN113289614B CN113289614B CN202110621142.XA CN202110621142A CN113289614B CN 113289614 B CN113289614 B CN 113289614B CN 202110621142 A CN202110621142 A CN 202110621142A CN 113289614 B CN113289614 B CN 113289614B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 12
- 239000002351 wastewater Substances 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 229910052878 cordierite Inorganic materials 0.000 claims description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000008188 pellet Substances 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J23/66—Silver or gold
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
本发明涉及环境保护技术领域，更具体地说，是涉及一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法。制备步骤为，用高分子有机化合物与水制备溶胶溶液；向溶胶溶液中加入铝盐，得到含有铝盐的胶体溶液；将研磨后的含铝粉末、造孔剂加入上述的溶胶溶液中，搅拌均匀，得到分散均匀的含有铝盐、铝粉和造孔剂的胶体溶液；将上述胶体溶液负载到催化剂载体上，先在惰性气氛下，利用微波辐射碳化造孔剂和高分子有机物，再切换至空气气氛，将涂层中碳化后的造孔剂和高分子有机物燃烧掉，形成一种三维氧化铝涂层；在上述涂覆有三维氧化铝涂层的催化剂载体上负载活性组分，即可得到最终的催化剂。
Description
技术领域：
本发明涉及环境保护技术领域，更具体地说，是涉及一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法。
背景技术：
工业上的负载型催化剂通常由三部分组成：催化剂载体、涂层及活性组分。其中常用的催化剂载体主要有氧化铝、活性炭和堇青石，催化剂载体是催化剂的骨架，决定催化剂的机械强度，气、液、固三相流体力学性质，材料的热胀冷缩、传热性能等；最常见的涂层是活性氧化铝涂层，它具有巨大的比表面积，能为活性组分提供更多的负载点位，使活性组分分散更均匀，进而提高与污染组分的接触机率，大大加速催化剂对污染物的降解速率。经过铈、锆、镧等金属改性后的氧化铝涂层，活性组分的耐高温团聚、抗中毒性能和抗脱落性得到有效改善，如专利CN109499607A、CN108607552A和CN108435163A等。活性氧化铝涂层在负载型催化剂上得到广泛应用。
制备氧化铝涂层通常需先将含铝化合物制备成铝溶胶，再将其负载在载体上。如专利CN107899570A与CN108325536A，利用分散拟薄铝石来制备铝溶胶，即将拟薄铝石分散到水溶液里，搅拌均匀，再不断加入酸液直至液体由悬浊液变成溶胶溶液，并将其负载到催化剂载体上，形成氧化铝涂层；专利CN103408330A利用有机盐异丙醇铝制备铝溶胶。如在50℃-100℃的水溶液中，加入异丙醇铝，再以硝酸做为胶溶剂，做成铝溶胶，再进行铝溶胶的负载形成活性氧化铝涂层；专利CN102432300A利用氨水，钠、钾和铵的碱或盐溶液来沉淀硫酸铝、氯化铝或者硝酸铝，陈化后过滤洗涤得到固体沉淀物，再将固体物质分散于水中，加入硫酸、盐酸、硝酸进行胶解，得到铝溶胶。
由以上可以看出，活性氧化铝涂层可以由拟薄铝石、有机铝盐和无机铝盐制备，但是，制备过程通常需要加入强酸进行胶溶，然后再调节溶液pH，控制反应温度，有些甚至需要冷凝回流，先沉淀再胶解，制备方法复杂，生产成本高昂，不利于工业化应用。
发明内容：
本发明正是针对上述问题，提供了一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法。
为了实现上述目的，本发明才采用如下技术方案，利用天然或人工合成高分子材料制备具有一定粘结性的溶胶溶液，以细小粉末状的颗粒氧化铝为涂层骨架，以溶解性含铝化合物为桥架，以活性炭粉末为造孔剂，搅拌均匀后将其负载到催化剂载体上。在惰性气氛下，利用微波辐射同时加热催化剂内部和外部，使含碳化合物碳化，可分解化合物转化为氧化物，形成具有稳定结构的涂层；再切换到空气气氛，碳被氧气氧化成二氧化碳，从而制得大比表面积、孔隙发达，具有三维结构的氧化铝涂层。将其应用在抗生素废水的臭氧催化氧化，可提高催化剂的活性。
制备步骤为，
1、用高分子有机化合物与水制备溶胶溶液；
2、向溶胶溶液中加入铝盐，得到含有铝盐的胶体溶液；
3、将研磨后的含铝粉末、造孔剂加入上述的溶胶溶液中，搅拌均匀，得到分散均匀的含有铝盐、铝粉和造孔剂的胶体溶液；
4、将上述胶体溶液负载到催化剂载体上，先在惰性气氛下，利用微波辐射碳化造孔剂和高分子有机物，再切换至空气气氛，将涂层中碳化后的造孔剂和高分子有机物燃烧掉，形成一种三维氧化铝涂层；
5、在上述涂覆有三维氧化铝涂层的催化剂载体上负载活性组分，即可得到最终的催化剂。
所述的高分子有机化合物为纤维素、壳聚糖类、丙烯酸树脂中的一种以上。
所述的铝盐为异丙醇铝、硝酸铝中的一种以上。
步骤2所制备的溶胶溶液中，按照重量比，高分子有机物：铝盐：水＝0.5～5：5～20：100。
步骤2所制备的溶胶溶液还可添加硝酸银、乙酸银或乙酸镧进行改性，添加量占铝盐的0.1％-2％。
步骤3所述含铝粉末为活性氧化铝、拟薄铝石中的一种以上，造孔剂为活性炭粉，造孔剂与铝粉重量比为1～10：100，粉末颗粒混合后，研磨过100～400目筛网；
步骤2制备的溶胶溶液与步骤3制备的混合粉末的质量比为0.2～5：1。
步骤4所述催化剂载体为氧化铝或堇青石，微波辐射温度400℃～600℃，辐射时间2h～6h，使造孔剂完全碳化，氧化铝骨架形成；空气气氛下辐射温度300℃～800℃，辐射时间6h～8h，使骨架中的碳转化成二氧化碳气体。
步骤5所述活性组分为Mn、Fe、Ni、Zn、Ag中的一种以上。
本发明的有益效果：
本发明的制备方法简单，制备过程无需添加强酸和沉淀剂，形成的氧化铝具有三维结构，孔隙发达，比表面积大，将其用于抗生素废水的臭氧催化氧化，性能优良。
具体实施方式
实施例1
1)取2kg的羧甲基纤维素钠均匀分散至100kg的水中，搅拌后形成透明溶胶溶液；
2)取20kg的异丙醇铝溶解于步骤1制备的溶胶溶液中；
3)取100kg活性氧化铝和10kg活性炭混合均匀，研磨后，过300目筛网；
4)取30kg步骤2中过筛后的混合粉末，加入到70kg步骤1中制备的溶胶溶液中，搅拌1h，混合粉末均匀分散在溶胶溶液中；
5)将上述混合溶液负载到3-5mm粒径的氧化铝小球上，先在120℃烘箱烘干，再在惰性气氛下450℃微波辐射碳化4h，切换至空气气氛，600℃辐射6h，把涂层上的碳类物质转化成二氧化碳，形成丰富的空隙和大的比表面积的三位氧化铝涂层；
6)配置20％wt的硝酸锰溶液，将上述负载完氧化铝涂层的活性氧化铝颗粒浸泡在硝酸锰溶液中，取出后在100℃烘干2h，在550℃焙烧3h，即可得到本发明的一种含有三维氧化铝结构，以氧化锰为活性组分的臭氧催化剂。
实施例2
1)取4kg羧甲基纤维素钠均匀分散至100kg水中，搅拌后形成透明溶胶溶液；
2)取10kg的硝酸铝和0.2kg硝酸银添加至步骤1)制备的溶胶溶液，形成银改性的，含有铝盐的溶胶溶液；
3)取96kg拟薄铝石和4kg活性炭混合均匀，研磨后，过300目筛网；
4)取50kg步骤3中过筛后的混合粉末，加入到50kg步骤2中制备的溶胶溶液中，搅拌1h，混合粉末均匀分散在溶胶溶液中；
5)将上述混合溶液负载到2-3mm粒径的氧化铝小球上，先在100℃烘箱烘干，再在惰性气氛下400℃微波辐射碳化5h，切换至空气气氛，600℃辐射6h，把涂层上的碳类物质转化成二氧化碳，形成一种三维氧化铝涂层的氧化铝球；
6)配置含有5％硫酸亚铁和10％高锰酸钾的混合溶液，将上述制备得到的含有三维氧化铝涂层的活性氧化铝球浸渍在混合溶液中，取出后在120℃烘干4h，在500℃焙烧2h，即可得到本发明的一种含有三维氧化铝结构，以氧化铁和氧化锰为活性组分的臭氧催化剂。
实施例3
1)取1.5kg的丙烯酸树脂均匀分散至100kg的水中，搅拌后形成透明溶胶溶液；
2)取10kg异丙醇铝加入上述的溶胶溶液中，搅拌均匀；再加入0.1kg的乙酸镧进行改性，得到含有镧、铝盐的溶胶溶液；
3)99kg活性氧化铝和1kg活性炭混合均匀，研磨后，过300目筛网；
4)取40kg步骤3)中过筛后的混合粉末，加入到60kg步骤2)中制备的溶胶溶液中，搅拌2h，混合粉末均匀分散在溶胶溶液中；
5)将上述混合溶液负载到100×100×100mm的蜂窝堇青石上，先在120℃烘箱烘干，再在惰性气氛下450℃微波辐射碳化6h，切换至空气气氛，670℃辐射8h，把涂层上的碳类物质转化成二氧化碳，形成含有银改性的三维氧化铝涂层；
6)配置30％wt的氯化锌溶液，并负载在上述涂敷有三位氧化铝涂层的蜂窝堇青石上，取出后在120℃烘干1h，在500℃焙烧2h，即可得到本发明的一种含有三维氧化铝结构，以氧化锌为活性组分的臭氧催化剂。
Claims (5)
1.一种用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法，其特征在于，制备步骤为，
(1)用高分子有机化合物与水制备溶胶溶液；
(2)向溶胶溶液中加入铝盐，得到含有铝盐的胶体溶液；
(3)将研磨后的含铝粉末、造孔剂加入上述的溶胶溶液中，搅拌均匀，得到分散均匀的含有铝盐、铝粉和造孔剂的胶体溶液；
(4)将上述胶体溶液负载到催化剂载体上，先在惰性气氛下，利用微波辐射碳化造孔剂和高分子有机物，再切换至空气气氛，将涂层中碳化后的造孔剂和高分子有机物燃烧掉，形成一种三维氧化铝涂层；
(5)在上述涂覆有三维氧化铝涂层的催化剂载体上负载活性组分，即可得到最终的催化剂；
所述的高分子有机化合物为纤维素、壳聚糖、丙烯酸树脂中的一种以上；
步骤4)所述催化剂载体为氧化铝或堇青石，惰性气氛下微波辐射温度400℃～600℃，辐射时间2h～6h，使造孔剂完全碳化，氧化铝骨架形成；空气气氛下辐射温度300℃～800℃，辐射时间6h～8h，使骨架中的碳转化成二氧化碳气体；
步骤5)所述活性组分为Mn、Fe、Ni、Zn、Ag中的一种以上。
2.根据权利要求1所述的用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法，其特征在于，所述的铝盐为异丙醇铝、硝酸铝中的一种以上。
3.根据权利要求1所述的用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法，其特征在于，步骤2)所制备的溶胶溶液中，按照重量比，高分子有机物：铝盐：水＝0.5～5：5～20：100。
4.根据权利要求1所述的用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法，其特征在于，步骤2)所制备的溶胶溶液还可添加硝酸银、乙酸银或乙酸镧进行改性，添加量占铝盐的0.1％-2％。
5.根据权利要求1所述的用于抗生素废水的三维氧化铝涂层臭氧催化剂的制备方法，其特征在于，步骤3)所述含铝粉末为活性氧化铝、拟薄铝石中的一种以上，造孔剂为活性炭粉，造孔剂与铝粉末重量比为1～10：100，粉末颗粒混合后，研磨过100～400目筛网。
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