CN105688917B - 一种多孔陶粒芬顿催化剂及其制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000000919 ceramic Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010802 sludge Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010792 warming Methods 0.000 claims abstract description 12
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
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- 238000005660 chlorination reaction Methods 0.000 claims 1
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- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
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- 239000004088 foaming agent Substances 0.000 description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- 239000004328 sodium tetraborate Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- B01J23/76—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
- B01J23/78—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 alkali- or alkaline earth metals
-
- B01J35/615—
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
本发明公开了一种多孔陶粒芬顿催化剂及其制备方法,包括以下步骤:(1)按重量份,以市政污泥20‑60份、粘土10‑20份、高岭土10‑20份、粉煤灰10‑20份、硅源2‑5份、含铜化合物2‑5份,含铁化合物2‑5份为原料;将原料中的各组分混匀,再经挤压得陶粒坯料;硅源为水玻璃、气相二氧化硅和硅粉中的一种或几种;(2)将陶粒坯料干燥后烧结,冷却,得到多孔陶粒载体;所述烧结是将干燥后的陶粒坯料先升温至300‑600℃下保温10‑40min,再升温至950‑1150℃,保温10‑40min。本发明利用污泥制备多孔陶粒芬顿催化剂,原料简单,价格便宜,污泥也实现了资源化,具有经济优势。多孔陶粒芬顿催化剂表面粗糙、有大量贯通性孔隙,颗粒孔隙率高,比表面积高;化学性质稳定,可适应酸性环境的废水处理。
Description
技术领域
本发明涉及一种多孔陶粒芬顿催化剂及其制备方法。
背景技术
多孔陶粒是含有大量开口贯通气孔的陶粒体,孔隙率高,比表面积大,具有良好的吸附能力和活性。当其作为催化剂载体时,对催化剂起分散和承载作用,从而提高催化剂的有效表面积,提高转化效率和反应速率。多孔陶粒作为催化剂的制备主要是采用添加致孔剂的工艺,致孔剂有无机和有机两种。无机致孔剂有碳酸铵、碳酸钙、氯化铵等高温可分解盐类以及各类碳粉;有机致孔剂主要有天然纤维、高分子聚合物和有机酸等,如锯末、淀粉、甲基丙烯酸甲酯等。市政污泥有机物含量高,在高温下挥发、燃烧产生气体,将其作为致孔剂用于多孔陶粒的制备已成为一个研究热点。例如建材使用中的轻质陶粒、污水处理的生物填料等,这些材料要求多孔、轻质、抗压强度高。但作为催化剂负载体,还要求含有大量开口贯通气孔,同时对孔径及其分布情况要求较高。
目前,因包含非均相芬顿催化剂在内的多孔材料负载技术具备高效快速、操作方便、无二次污染等优点,已成为研究热点,载体就包括了凹凸棒、沸石、分子筛、氧化铝球等。中国专利CN201310000494.9公布了“一种载铁凹凸棒土非均相芬顿催化剂的制备方法”,将凹凸棒土粉磨-酸活化-粉磨-负载铁离子的方式,制得催化剂对废水中苯酚的去除率达到95%以上,但催化剂颗粒为40-200目,使用不是很方便。中国专利CN 103111321 A公布了“一种载铁分子筛类芬顿催化剂的制备方法及其应用”,将在400℃活化后的3A型分子筛放置在Na2CO3与FeSO4溶液中搅拌反应5-6h,再经过滤-洗涤-烘干制得芬顿催化剂,用于硝基苯废水处理,硝基苯降解率为85%以上,CODCr去除率在78.6%以上。3A分子筛孔径在0.1nm,为微孔结构,不适合含大分子有机物的废水处理。
发明内容
本发明解决的技术问题是,对污水处理后产生的污泥进行处理,将其用于制成多孔陶粒材料,作为芬顿处理时的催化剂。
本发明的技术方案是,提供一种多孔陶粒芬顿催化剂的制备方法,包括以下步骤:
(1)按重量份,以市政污泥20-60份、粘土10-20份、高岭土10-20份、粉煤灰10-20份、硅源2-5份、含铜化合物2-5份、含铁化合物2-5份为原料;将原料中的各组分混匀,再经挤压得陶粒坯料;所述硅源为水玻璃、气相二氧化硅和硅粉中的一种或几种;
(2)将所述陶粒坯料干燥后烧结,冷却,得到多孔陶粒载体;所述烧结是将干燥后的陶粒坯料先升温至300-600℃(优选350-500℃)下保温10-40min,再升温至950-1150℃,保温10-40min。
进一步地,所述高岭土中含SiO2 40-60wt%、含Al2O3 20-40wt%。
进一步地,所述粉煤灰中含SiO2 40-60wt%、含Al2O3 20-50wt%。
进一步地,所述粘土、高岭土和粉煤灰的粒径在500目以下。
进一步地,将所述陶粒坯料在55-65℃下干燥3-5h。
进一步地,所述市政污泥的含水率为70-85wt%,市政污泥的固形物中有机物成分40-60wt%。
进一步地,升温速率不超过5℃/min,优选2℃/min。
进一步地,所述含铜化合物为硝酸铜、硫酸铜、氯化铜、氧化铜、硫化铜中的一种或多种
进一步地,所述含铁化合物为硝酸铁、硫酸亚铁、硫酸亚铁、氯化铁、氧化铁、硫化铁中的一种或多种。
本发明进一步提供一种由上述制备方法制得的多孔陶粒载体。
市政污泥在高温烧结时有机物挥发,在陶粒内部形成细微通孔;而污泥中无机物质以Al2O3、Fe2O3、SiO2、CaO为主,是陶粒烧制的主要成分;另外污泥中有机物质燃烧发热可以提供部分热量;同时,污泥中重金属经过高温焙烧被熔融物质包裹在陶粒晶格内,不存在重金属的二次污染。综上所述,利用污泥作为致孔剂制备催化剂提升了污泥的市场价值,实现了废弃物的减量化、稳定化、无害化、资源化。
本发明的催化剂以高岭土、硅藻土、粘土等为主要原料,他们以SiO2和Al2O3成分为主,是硅铝酸盐陶瓷的主体成分,是形成强度和结构的主要结构基础。陶粒催化剂中Al2O3占10-25%,SiO2占40-79%,本发明中适当添加硅源(水玻璃、气相二氧化硅和硅粉),以增加SiO2的含量,调整Al2O3与SiO2的比例;本发明的硅源还可以作为粘结剂,为陶粒胚料的形成提供结构强度,使胚料的强度提高,易于成型。
传统多孔陶粒的成孔剂为碳酸盐类、有机物等可在高温下挥发成气体的物质。添加市政污泥制备陶粒利用其中有机物作为致孔剂,无机物作为陶粒成分(以SiO2、Al2O3、CaO、Fe2O3为主,是硅铝酸盐陶瓷烧制的原材料)。在催化剂烧制过程中,有机物在300-600℃(预烧)时氧化分解,挥发产生气体,溢出形成孔隙,在陶粒内部形成细微通孔;当温度上升到一定程度后,原料中SiO2、Al2O3、CaO、Fe2O3开始相互熔融(冷却后会形成矿物),控制烧制温度在950-1150℃,烧制温度为10-40min。CaO、Fe2O3等可以作为SiO2、Al2O3高温液化的助熔剂(不需要单独添加其他的助溶剂,如硼砂),降低形成玻璃体的温度。当烧结温度到达1200℃后或者烧结时间延长时,在颗粒表面形成一定厚度的玻璃相熔融体,冷却后成为闭孔陶粒,比表面积小,催化效率降低。升温速度过快使得颗粒表面与内部受热不均,表面容易熔融,易形成闭孔;降温速度快将使得颗粒的物理性质发生变化,容易形成裂缝。不能在颗粒表面形成玻璃体造成闭孔,同时又要求内部各组分充分熔融,有足够的物理强度,对烧结温度、温度曲线及烧结时间的控制要求精确。
将过渡金属如Fe、Cu等掺入负载于硅铝酸盐多孔陶粒载体上,通过增加活性金属的分散度或金属与载体材料的相互作用而提高催化剂的芬顿催化活性。其催化机制主要是通过催化剂表面的氧化还原反应驱动界面电子迁移,研究表明Cu离子可以降低有机物的反应自由能,而Fe离子可以诱发H2O2分解形成羟基自由基(·OH)、超氧自由基(O2 ·-)等多种活性氧物种,反应机制可以简单地表示如下:
≡Mn++H2O2—≡M(n+1)++OH-+·OH
H2O2+·OH—HO2 ·+H2O
HO2 ·+≡M(n+1)—≡Mn++H++O2
本发明制备的催化剂有以下特征:表面粗糙、大量贯通性孔隙,颗粒孔隙率高达45-55%,比表面积达200-400m2/g;化学性质稳定,1+1盐酸溶出率<1%;重金属浸出量远在危废及安全填埋的标准以下,无浸出毒性造成的二次污染;机械强度高,抗压强度达到20-30MPa,可适应酸性环境的废水处理。本发明利用污泥制备多孔陶粒芬顿催化剂,原料简单,价格便宜,污泥也实现了资源化,具有经济优势。
具体实施方式
实施例1
取污泥2.4kg、粘土0.6kg、高岭土0.4kg、粉煤灰0.4kg、气相二氧化硅0.2kg,氧化铜0.1kg,氧化铁0.1kg,充分混合均匀,造成的陶粒短柱状坯料,在高温炉中以10℃温度升温至500℃,恒温预烧20min,再以5℃/min速率升温至1100℃,烧结20min,以10℃/min速率冷却至300℃以下,取出自然冷却,得多孔陶粒载体外观为浅砖红色短柱状固体颗粒。
实施例2
取污泥2.0kg、粘土0.6kg、高岭土0.6kg、粉煤灰0.6kg、水玻璃0.2kg,氯化铜0.15kg,硫酸亚铁0.2kg充分混合均匀,造成的陶粒短柱状坯料,在高温炉中以10℃温度升温至500℃,恒温预烧20min,再以5℃/min速率升温至1100℃,烧结20min,以10℃/min速率冷却至300℃以下,取出自然冷却,得多孔陶粒载体外观为浅砖红色短柱状固体颗粒。
实施例3
取污泥2.4kg、粘土0.6kg、高岭土0.6kg、粉煤灰0.6kg、气相二氧化硅0.2kg,硫化铜0.1kg,硫酸亚铁0.2kg充分混合均匀,造成的陶粒短坯料,在高温炉中以10℃温度升温至500℃,恒温预烧20min,再以5℃/min速率升温至1150℃,烧结15min,以10℃/min速率冷却至300℃以下,取出自然冷却,得多孔陶粒载体外观为浅砖红色短柱状固体颗粒。
实施例4
取实施例1、2、3催化剂,放入填充柱;另取1L石化废水,调节pH为5-6,加入H2O24ml,循环经过催化剂填充柱,其他条件相同,反应4h后停止,检测进出水COD(均指CODCr)值。以氧化铝球制得催化剂作为比较,污泥陶粒催化剂效果更优,结果见下表。
Claims (8)
1.一种多孔陶粒芬顿催化剂的制备方法,其特征在于,包括以下步骤:
(1) 按重量份,以市政污泥20-60份、粘土10-20份、高岭土10-20份、粉煤灰10-20份、硅源2-5份、含铜化合物2-5份、含铁化合物2-5份为原料;将原料中的各组分混匀,再经挤压得陶粒坯料;所述硅源为水玻璃、气相二氧化硅和硅粉中的一种或几种;所述市政污泥的含水率为65-80wt%,市政污泥的固形物中有机物成分40-60wt%;
(2) 将所述陶粒坯料干燥后烧结,冷却,得到多孔陶粒载体;所述烧结是将干燥后的陶粒坯料先升温至300-600℃下保温10-40min,再升温至950-1150℃,保温10-40min;所述烧结过程中,升温速率不超过5℃/min。
2. 如权利要求1所述的制备方法,其特征在于,所述高岭土中含SiO2 40-60wt%、含Al2O3
20-40wt%。
3. 如权利要求1所述的制备方法,其特征在于,所述粉煤灰中含SiO2 40-60wt%、含Al2O3 20-50wt%。
4.如权利要求1所述的制备方法,其特征在于,所述粘土、高岭土和粉煤灰的粒径在500目以下。
5.如权利要求1所述的制备方法,其特征在于,将所述陶粒坯料在55-65℃下干燥3-5h。
6.如权利要求1所述的制备方法,其特征在于,所述含铜化合物为硝酸铜、硫酸铜、氯化铜、氧化铜、硫化铜中的一种或多种。
7.如权利要求1所述的制备方法,其特征在于,所述含铁化合物为硝酸铁、硫酸亚铁、硫酸亚铁、氯化铁、氧化铁、硫化铁中的一种或多种。
8.一种多孔陶粒芬顿催化剂,其特征在于,由权利要求1-7之一所述的制备方法制得。
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