CN107020093A - 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 PDF

Info

Publication number
CN107020093A
CN107020093A CN201710276403.2A CN201710276403A CN107020093A CN 107020093 A CN107020093 A CN 107020093A CN 201710276403 A CN201710276403 A CN 201710276403A CN 107020093 A CN107020093 A CN 107020093A
Authority
CN
China
Prior art keywords
component
weight
potassium
iii
solid catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201710276403.2A
Other languages
English (en)
Inventor
朱明�
苏智
岳馥莲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Normal University
Original Assignee
Sichuan Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Normal University filed Critical Sichuan Normal University
Priority to CN201710276403.2A priority Critical patent/CN107020093A/zh
Publication of CN107020093A publication Critical patent/CN107020093A/zh
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—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
    • 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
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

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、白云石、方解石、粉煤灰和煤矸石作载体，载体经次氯酸锂和双(乙酰丙酮)铍扩孔后，加入十四烷基三丁基氯化铵在超声波作用下进行活化处理，然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(2,2,6,6‑四甲基‑3,5‑庚二酮酸)钆、水合三醋酸铽、三(6,6,7,7,8,8,8‑七氟‑2,2‑二甲基‑3,5‑ 辛烯二酮)镝(III)，催化活性中心组分前驱物二茂钛环取代水杨酸配合物、乳酸锌、二硫氰酸根合银（I）酸钾、四氯金钾，在乳化剂十八烷基二甲基羟乙基高氯酸铵作用下进行水热反应，烘干除去水分后，在马弗炉内灼烧得到臭氧非均相氧化固体催化剂。

Description

臭氧非均相氧化固体催化剂的制备方法
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吸附性，使用稀土有机金属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，使用稀土有机金属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、白云石、方解石、粉煤灰、煤矸石组成，按重量计，麦饭石:硅灰石:白云石:方解石:粉煤灰:煤矸石的重量之比=（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组分是十四烷基三丁基氯化铵，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(2,2,6,6-四甲基-3,5-庚二酮酸)钆、水合三醋酸铽、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)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、乳酸锌和贵金属化合物二硫氰酸根合银（I）酸钾、四氯金钾，乳化剂十八烷基二甲基羟乙基高氯酸铵组成，按重量计，硼砂:硫酸钾:异丙氧化钪(III):三(2,2,6,6-四甲基-3,5-庚二酮酸)钆:水合三醋酸铽:三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III):二茂钛环取代水杨酸配合物:乳酸锌:二硫氰酸根合银（I）酸钾:四氯金钾:十八烷基二甲基羟乙基高氯酸铵的重量之比=（4～8）:（6～10）:（3～6）:（4～7）:（5～8）:（6～9）:（10～15）:（12～18）:（4～7）:（6～9）:（6～20）。B组分的麦饭石、硅灰石、白云石、方解石、粉煤灰、煤矸石分别进行粉碎，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、白云石、方解石、粉煤灰和煤矸石多孔材料载体，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，再加入十四烷基三丁基氯化铵C14H29N+(C4H9)3Cl-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，十四烷基三丁基氯化铵C14H29N+(C4H9)3Cl-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，催化活性助剂异丙氧化钪(III)C9H21O3Sc、三(2,2,6,6-四甲基-3,5-庚二酮酸)钆C33H57GdO6、水合三醋酸铽C6H11O7Tb、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III) C30H30DyF21O6稀土金属化合物，催化活性中心组分过渡金属二茂钛环取代水杨酸配合物(C10H10)Ti(C7H4O3)、乳酸锌C6H10O6Zn、二硫氰酸根合银（I）酸钾K[Ag(SCN)2]化合物和四氯金钾KAuCl4贵金属化合物，在乳化剂十八烷基二甲基羟乙基高氯酸铵[(C18H37)N(CH3)2CH2 CH2OH]+ClO4 -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、普通过渡有机金属化合物、贵金属化合物均匀掺杂，乳化剂十八烷基二甲基羟乙基高氯酸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、白云石、方解石、粉煤灰、煤矸石多孔材料作载体，由于次氯酸锂LiClO和双(乙酰丙酮)铍C10H14BeO4的扩孔效应，十四烷基三丁基氯化铵C14H29N+(C4H9)3Cl-、十八烷基二甲基羟乙基高氯酸铵[(C18H37)N(CH3)2CH2 CH2OH]+ClO4 -对孔道的相互连通和表面活化作用；通过水热反应使稀土有机金属化合物、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、特别是掺杂贵金属具有的稳定性和高活性，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白云石、5.75g方解石、6.75g粉煤灰、7.75g煤矸石，次氯酸锂和双(乙酰丙酮)铍的重量（3g）:多材料的重量（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十四烷基三丁基氯化铵溶于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，十四烷基三丁基氯化铵（3.25g）:扩孔改性载体（31g ）=1:9.5；控制超声功率密度为0.4W/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(2,2,6,6-四甲基-3,5-庚二酮酸)钆、2.6g水合三醋酸铽、3.05g三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、5.05g二茂钛环取代水杨酸配合物、6.1g乳酸锌、2.05g二硫氰酸根合银（I）酸钾、3.1g四氯金钾、3.05g十八烷基二甲基羟乙基高氯酸铵和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白云石、2.05g方解石、2.25g粉煤灰、2.45g煤矸石，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十四烷基三丁基氯化铵溶于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，十四烷基三丁基氯化铵（2.2g）:扩孔改性载体（11.5g ）=1:5.2；控制超声功率密度为0.7W/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(2,2,6,6-四甲基-3,5-庚二酮酸)钆、0.78g水合三醋酸铽、0.87g三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III)、1.48g二茂钛环取代水杨酸配合物、1.77g乳酸锌、0.68g二硫氰酸根合银（I）酸钾、0.87g四氯金钾、1.98g十八烷基二甲基羟乙基高氯酸铵和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。
比较例1: 制备过程不加次氯酸锂、双(乙酰丙酮)铍、十四烷基三丁基氯化铵、十八烷基二甲基羟乙基高氯酸铵、硼砂和硫酸钾外，整个制备过程、制备条件和实施例1完全相同。
实施例1、实施例2和比较例1制备的臭氧非均相氧化固体催化剂的参数列入表1。
应用实施例1:实施例1、实施例2和比较例1制备的臭氧非均相氧化固体催化剂分别在相同条件下用于乙二胺、直接红棕R和活性金黄K-2RA配制的废水进行臭氧非均相氧化处理。处理条件是：有机物废水与催化剂的投料比=1000L:1g，有机废水CODCr值765.8mg/L，臭氧投加量80mg/L，处理时间1hr，臭氧尾气用KI溶液吸收检测臭氧利用率。试验数据列入表2。
表1实施例和比较例制备臭氧非均相氧化固体催化剂参数
表2臭氧非均相氧化固体催化剂应用实施例

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、白云石、方解石、粉煤灰、煤矸石组成，按重量计，麦饭石:硅灰石:白云石:方解石:粉煤灰:煤矸石的重量之比=（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组分是十四烷基三丁基氯化铵，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(2,2,6,6-四甲基-3,5-庚二酮酸)钆、水合三醋酸铽、三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III) 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、乳酸锌和贵金属化合物二硫氰酸根合银（I）酸钾、四氯金钾，乳化剂十八烷基二甲基羟乙基高氯酸铵组成，按重量计，硼砂:硫酸钾:异丙氧化钪(III):三(2,2,6,6-四甲基-3,5-庚二酮酸)钆: 水合三醋酸铽:三(6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5- 辛烯二酮)镝(III) :二茂钛环取代水杨酸配合物:乳酸锌: 二硫氰酸根合银（I）酸钾:四氯金钾: 十八烷基二甲基羟乙基高氯酸铵的重量之比=（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、白云石、方解石、粉煤灰、煤矸石组成，麦饭石、硅灰石、白云石、方解石、粉煤灰、煤矸石分别进行粉碎，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。
CN201710276403.2A 2017-04-25 2017-04-25 臭氧非均相氧化固体催化剂的制备方法 Withdrawn CN107020093A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710276403.2A CN107020093A (zh) 2017-04-25 2017-04-25 臭氧非均相氧化固体催化剂的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710276403.2A CN107020093A (zh) 2017-04-25 2017-04-25 臭氧非均相氧化固体催化剂的制备方法

Publications (1)

Publication Number Publication Date
CN107020093A true CN107020093A (zh) 2017-08-08

Family

ID=59527078

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710276403.2A Withdrawn CN107020093A (zh) 2017-04-25 2017-04-25 臭氧非均相氧化固体催化剂的制备方法

Country Status (1)

Country Link
CN (1) CN107020093A (zh)

Similar Documents

Publication Publication Date Title
CN107159198A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008306A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107051529A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107159199A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107020093A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008409A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008305A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008304A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107020092A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008307A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008318A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008303A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107051450A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008308A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008280A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008441A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107159201A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008475A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107051524A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107051437A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008265A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008285A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008422A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107008440A (zh) 臭氧非均相氧化固体催化剂的制备方法
CN107051523A (zh) 臭氧非均相氧化固体催化剂的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170808