CN113019360A - 一种负载型复合氧化物催化剂及其制备方法和应用 - Google Patents
一种负载型复合氧化物催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN113019360A CN113019360A CN202110289789.7A CN202110289789A CN113019360A CN 113019360 A CN113019360 A CN 113019360A CN 202110289789 A CN202110289789 A CN 202110289789A CN 113019360 A CN113019360 A CN 113019360A
- Authority
- CN
- China
- Prior art keywords
- composite oxide
- catalyst
- oxide catalyst
- chlorine
- cordierite
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 238000007084 catalytic combustion reaction Methods 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 11
- 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 abstract description 11
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 5
- 150000000703 Cerium Chemical class 0.000 claims abstract description 3
- MSEHWVYDQZCSPJ-UHFFFAOYSA-N [Mn].[Ce].[Zr] Chemical compound [Mn].[Ce].[Zr] MSEHWVYDQZCSPJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002696 manganese Chemical class 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 231100000572 poisoning Toxicity 0.000 abstract description 8
- 230000000607 poisoning effect Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000010815 organic waste Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229910009112 xH2O Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910004625 Ce—Zr Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic 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
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 degreasers Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- B01J23/16—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
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明属于催化燃烧环境保护技术领域,涉及一种负载型复合氧化物催化剂及其制备方法和应用。该催化剂以锰铈锆复合氧化物为活性组分,堇青石为载体,其中活性组分中Mn、Ce、Zr的摩尔比为(4~6):1:(0.8~1.2),活性组分的质量负载量为20~40%,以可溶性锰盐、铈盐和锆盐为原料,以弱碱为沉淀剂,经沉积‑沉淀法负载于堇青石载体。本发明的负载型复合氧化物催化剂对含氯挥发性有机物具有良好的催化活性和抗氯中毒能力,无多氯代副产物形成,且制备工艺简单、成本低,适用于含氯有机废气的净化处理。
Description
技术领域
本发明属于催化燃烧环境保护技术领域,涉及一种负载型复合氧化物催化剂及其制备方法以及在含氯挥发性有机物低温催化燃烧中的应用。
背景技术
含氯挥发性有机物(CVOCs)主要包括氯代芳香烃(如氯苯、二氯苯等)和氯代非芳香烃(如二氯甲烷、二氯乙烷、三氯乙烯等)。CVOCs具有良好的化学和热稳定性,自然环境下很难降解,可造成持久性污染。此外,CVOCs还可通过系列光化学反应生成O3、PM2.5等二次污染物造成复合型大气污染。
工业上CVOCs有着广泛的应用,一方面它们可直接用作溶剂、清洁剂、脱脂剂、化学萃取剂,也可用作油漆、油墨以及粘合剂的添加剂;另一方面它们还是药物、农药以及聚合物合成的重要前体原料。使用过程中它们可通过挥发、泄漏或直接排放等形式造成大气污染。
催化燃烧技术借助催化剂的作用能够实现较低温度范围内CVOCs的无焰燃烧,生成可排放的CO2、H2O和HCl,是一种高效、节能、环保的废气治理技术,因而高催化活性、高抗中毒且具有一定机械强度的催化剂一直是该领域科研工作者的研究焦点。工业上,催化燃烧用催化剂一般是由活性组分和载体两大部分构成,其中活性组分是催化燃烧效能的主要承担者,以贵金属和复合氧化物为主。贵金属资源稀缺,价格高昂,与氯物种间存在强烈的相互作用,极易导致催化剂活性下降,表现为氯中毒现象,因而贵金属催化剂较少应用于CVOCs的催化燃烧。相比之下复合金属氧化物要“物美价廉”的多,得益于拥有更高的活性表面积以及便于掺杂改性的特性,复合金属氧化物可以表现出更好的催化活性和抗氯中毒能力。此外,为增强催化剂机械强度,满足工业化应用需求,活性组分通常负载于载体上使用,常用的载体主要有Al2O3、TiO2、SiO2、分子筛以及堇青石。载体的使用除了起机械承载作用外,还有助于催化剂表面积、热稳定性以及活性组分分散度的提高等。
发明内容
本发明的目的是针对现有技术存在的不足而提供一种高催化活性、高抗氯中毒性能的负载型复合氧化物催化剂,本发明的另一目的是提供催化剂的制备方法,本发明还有一个目的是提供上述催化剂的应用,具体是指负载于堇青石载体的Mn-Ce-Zr三元复合氧化物催化剂及其制备方法以及在含氯挥发性有机物低温催化燃烧中的应用。
本发明的技术方案为:一种负载型复合氧化物催化剂,其特征在于以锰铈锆复合氧化物为活性组分,堇青石为载体,其中活性组分中Mn、Ce、Zr的摩尔比为(4~6):1:(0.8~1.2),活性组分的质量负载量为20~40%。
本发明还提供了一种制备上述的负载型复合氧化物催化剂的方法,其特征在于以可溶性锰盐、铈盐和锆盐为原料,以弱碱为沉淀剂,经沉积-沉淀法负载于堇青石载体,其具体步骤如下:将三种可溶性金属盐溶解于水中,同时加入堇青石,缓慢滴加弱碱溶液至溶液呈碱性,沉淀物静置老化后经过滤、洗涤、干燥,再于高温下焙烧制得负载型复合氧化物催化剂。
优选上述的可溶性锰盐、铈盐和锆盐为含金属的硝酸盐或乙酸盐。
优选所述的弱碱为氨水、碳酸氢钠或碳酸钠的水溶液,浓度为0.5~1.5mol/L。
优选所述的碱性为pH至8-10。
优选所述的焙烧的温度为500~600℃,焙烧的时间为3~6h。
本发明还提供了上述的催化燃烧用催化剂在含氯挥发性有机物低温催化燃烧中的应用。
优选上述的含氯挥发性有机物为氯苯、二氯苯、三氯乙烯、二氯乙烷、二氯甲烷或一氯甲烷。
有益效果:
本发明的负载型复合氧化物催化剂对多种含氯挥发性有机物的低温催化燃烧具有良好的催化活性和抗氯中毒能力,燃烧产物主要是二氧化碳和氯化氢,无多氯代副产物形成,同时制备工艺简单、成本低,具有净化工业废气的广阔前景。
具体实施方式
下面结合具体实施例对本发明中的负载型催化剂作进一步说明。应理解,本发明的保护范围并不仅限于以下实施例:
实施例1
将6.30g50%Mn(NO3)2水溶液、1.91gCe(NO3)3·6H2O、1.02gZrO(NO3)2·xH2O溶解于150mL去离子水中,搅拌均匀后加入10g堇青石载体,剧烈搅拌1h后缓慢滴加1mol/L氨水溶液,滴加至混悬液的pH达到9后于室温下静置老化12h,再经过滤、洗涤后于110℃下干燥6h,最后于550℃下焙烧4h制得堇青石负载型复合氧化物催化剂。该催化剂中Mn、Ce、Zr的摩尔比为4:1:1,负载量为20%。
实施例2
以实施例1相同的操作,不同之处在于:将4.72g50%Mn(NO3)2水溶液、1.91gCe(NO3)3·6H2O、1.02gZrO(NO3)2·xH2O溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为3:1:1,负载量为20%。
实施例3
以实施例1相同的操作,不同之处在于:将9.45g50%Mn(NO3)2水溶液、1.91gCe(NO3)3·6H2O、1.02gZrO(NO3)2·xH2O溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为6:1:1,负载量为20%。
实施例4
以实施例1相同的操作,不同之处在于:将6.30g50%Mn(NO3)2水溶液、1.91gCe(NO3)3·6H2O、0.51gZrO(NO3)2·xH2O溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为4:1:0.8,负载量为20%。
实施例5
以实施例1相同的操作,不同之处在于:将9.45g50%Mn(NO3)2水溶液、2.87gCe(NO3)3·6H2O、1.53gZrO(NO3)2·xH2O溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为4:1:1,负载量为30%。
实施例6
以实施例1相同的操作,不同之处在于:将12.74g50%Mn(NO3)2水溶液、3.86gCe(NO3)3·6H2O、2.06gZrO(NO3)2·xH2O溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为4:1:1,负载量为40%。
实施例7
以实施例1相同的操作,不同之处在于:将4.15gMn(CH3COO)2、1.90gCe(CH3COO)3·nH2O、1.96gZr(CH3COO)4溶解于150mL去离子水中。该催化剂中Mn、Ce、Zr的摩尔比为4:1:1,负载量为20%。
实施例8
以实施例1相同的操作,不同之处在于:对于沉淀剂,以1.5mol/L的碳酸氢钠水溶液代替1mol/L的氨水溶液。
实施例9
以实施例1相同的操作,不同之处在于:对于滴定终点,滴加1mol/L氨水溶液至混悬液的pH达到10。
实施例10
以实施例1相同的操作,不同之处在于:对于焙烧温度,于马弗炉中600℃焙烧4h。
实施例11
以实施例1相同的操作,不同之处在于:对于焙烧时间,于马弗炉中550℃焙烧6h。
1~11实例中各负载型催化剂对氯苯的催化氧化活性如表1所示:
表1各实施例中催化剂对氯苯的催化氧化活性
注:催化剂装样体积为0.3mL、粒经为40-60目,体积空速为20000h-1。
实施例12
测试实施例1和实施例5中催化剂分别对三氯乙烯、二氯乙烷和二氯甲烷的催化氧化活性,结果如表2所示:
表2实施例1和实施例5中催化剂对不同CVOCs的催化氧化活性
注:催化剂装样体积为0.3mL、催化剂粒经为40-60目,体积空速为20000h-1。
实施例13
设置反应温度为300℃,评价实施例5中催化剂连续催化氧化氯苯的催化稳定性,结果显示在30小时的连续反应内,氯苯的转化率始终保持在93%以上,未出现氯中毒失活现象。产物分析表明在实施例5催化剂的作用下,氯苯燃烧尾气中主要含有二氧化碳和氯化氢,没有检测到多氯代副产物,完全燃烧后的尾气可通过稀碱溶液吸收后外排。
上述实施例及测试结果表明,本发明的负载型复合氧化物催化剂对含氯挥发性有机物具有良好的催化活性和抗氯中毒能力,燃烧产物中未形成可导致大气二次污染的多氯代副产物,且制备工艺简单,成本低,稳定性好,具有净化工业废气的广阔前景。
Claims (8)
1.一种负载型复合氧化物催化剂,其特征在于以锰铈锆复合氧化物为活性组分,堇青石为载体,其中活性组分中Mn、Ce、Zr的摩尔比为(4~6):1:(0.8~1.2),活性组分的质量负载量为20~40%。
2.一种制备如权利要求1所述的负载型复合氧化物催化剂的方法,其特征在于以可溶性锰盐、铈盐和锆盐为原料,以弱碱为沉淀剂,经沉积-沉淀法负载于堇青石载体,其具体步骤如下:将三种可溶性金属盐溶解于水中,同时加入堇青石,滴加弱碱溶液至溶液呈碱性,沉淀物静置老化后经过滤、洗涤、干燥,再于高温下焙烧制得负载型复合氧化物催化剂。
3.根据权利要求2所述的方法,其特征在于所述的可溶性锰盐、铈盐和锆盐为硝酸盐或乙酸盐。
4.根据权利要求2所述的方法,其特征在于所述的弱碱为氨水、碳酸氢钠或碳酸钠的水溶液,浓度为0.5~1.5mol/L。
5.根据权利要求2所述的方法,其特征在于所述的碱性为pH至8-10。
6.根据权利要求2所述的方法,其特征在于焙烧的温度为500~600℃,焙烧的时间为3~6h。
7.一种如权利要求1所述的催化燃烧用催化剂在含氯挥发性有机物低温催化燃烧中的应用。
8.根据权利要求7所述的应用,其特征在于所述的含氯挥发性有机物为氯苯、二氯苯、三氯乙烯、二氯乙烷、二氯甲烷或一氯甲烷。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110289789.7A CN113019360A (zh) | 2021-03-17 | 2021-03-17 | 一种负载型复合氧化物催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110289789.7A CN113019360A (zh) | 2021-03-17 | 2021-03-17 | 一种负载型复合氧化物催化剂及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113019360A true CN113019360A (zh) | 2021-06-25 |
Family
ID=76471352
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110289789.7A Pending CN113019360A (zh) | 2021-03-17 | 2021-03-17 | 一种负载型复合氧化物催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113019360A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113713820A (zh) * | 2021-07-31 | 2021-11-30 | 中国计量大学 | 一种用于含氯发挥性有机物催化氧化的铈钴基酸改性催化剂及其制备方法 |
CN114950423A (zh) * | 2022-06-08 | 2022-08-30 | 重庆大学 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152613A1 (ko) * | 2014-03-31 | 2015-10-08 | (주)써스텍 | 혼합금속산화물 촉매 제조방법 |
CN106111122A (zh) * | 2016-06-20 | 2016-11-16 | 浙江大学 | 用于降解含氟氯VOCs三元复合氧化物型催化剂及其制备方法 |
CN106423148A (zh) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种锆掺杂铈锰氧化物催化剂及制备和应用 |
WO2017164518A1 (ko) * | 2016-03-24 | 2017-09-28 | 한국화학연구원 | 휘발성 유기화합물 제거용 다성분계 세리아-지르코니아 기반 복합 금속 산화물 촉매 및 이의 제조방법 |
CN107469812A (zh) * | 2017-10-10 | 2017-12-15 | 北京科技大学 | 低温脱除燃煤废气中NOx和VOCs的催化剂制备方法 |
-
2021
- 2021-03-17 CN CN202110289789.7A patent/CN113019360A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015152613A1 (ko) * | 2014-03-31 | 2015-10-08 | (주)써스텍 | 혼합금속산화물 촉매 제조방법 |
WO2017164518A1 (ko) * | 2016-03-24 | 2017-09-28 | 한국화학연구원 | 휘발성 유기화합물 제거용 다성분계 세리아-지르코니아 기반 복합 금속 산화물 촉매 및 이의 제조방법 |
CN106111122A (zh) * | 2016-06-20 | 2016-11-16 | 浙江大学 | 用于降解含氟氯VOCs三元复合氧化物型催化剂及其制备方法 |
CN106423148A (zh) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种锆掺杂铈锰氧化物催化剂及制备和应用 |
CN107469812A (zh) * | 2017-10-10 | 2017-12-15 | 北京科技大学 | 低温脱除燃煤废气中NOx和VOCs的催化剂制备方法 |
Non-Patent Citations (3)
Title |
---|
GAOYUAN LONG,ET AL.: "One-pot synthesis of monolithic Mn-Ce-Zr ternary mixed oxides catalyst for the catalytic combustion of chlorobenzene", 《CHEMICAL ENGINEERING JOURNAL》 * |
LEI ZHU,ET AL.: "High Catalytic Performance of Mn-Doped Ce-Zr Catalysts for Chlorobenzene Elimination", 《NANOMATERIALS》 * |
XIN LI,ET AL.: "Enhancement of SCR performance of monolithic Mn-Ce/Al2O3/cordierite catalysts by using modified deposition precipitation method", 《ASIA‐PAC J CHEM ENG.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113713820A (zh) * | 2021-07-31 | 2021-11-30 | 中国计量大学 | 一种用于含氯发挥性有机物催化氧化的铈钴基酸改性催化剂及其制备方法 |
CN114950423A (zh) * | 2022-06-08 | 2022-08-30 | 重庆大学 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
CN114950423B (zh) * | 2022-06-08 | 2023-06-09 | 重庆大学 | 室内低浓度甲醛净化催化剂产品及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105214679B (zh) | 一种抗水抗硫型烟气脱硝粉体催化剂、制备方法及其用途 | |
CN108722477B (zh) | 一种抗碱中毒高效脱硝催化剂及其制备方法和应用 | |
CN102500358B (zh) | 一种具有良好抗碱金属和碱土金属中毒性能的脱硝催化剂 | |
WO2020151577A1 (zh) | 磷酸修饰的氧化铈催化剂及其制备方法和应用 | |
CN102658172B (zh) | 一种scr脱硝催化剂及其制备方法和应用 | |
CN105289644B (zh) | 一种平板式抗硫低温scr脱硝催化剂及其制备方法 | |
CN113019360A (zh) | 一种负载型复合氧化物催化剂及其制备方法和应用 | |
CN106179326B (zh) | 一种氧化锰纳米管负载型脱硝催化剂及其制备方法 | |
CN103230813A (zh) | 一种适用于水泥窑炉的抗碱中毒的脱硝催化剂的制备方法 | |
CN105013508A (zh) | 用于氯代挥发性有机物低温催化燃烧的催化剂及制备方法 | |
CN113083280B (zh) | 一种催化氧化VOCs的高负载钒-氧化钛催化剂及其制备方法与用途 | |
CN110947394A (zh) | 一种基于ZIF-67-Mn/Co的低温NO氧化催化剂及制备方法与应用 | |
CN108479762A (zh) | 一种锰氧化物催化剂及其制备方法和应用 | |
CN106902814A (zh) | 一种催化燃烧用稀土基有序介孔整体式催化剂及其制备方法 | |
CN106944093B (zh) | 一种钙钛矿型蜂窝整体式甲烷催化燃烧催化剂及其制备方法 | |
CN106540698A (zh) | 一种氯代硝基苯选择性加氢合成氯代苯胺的负载型镍基催化剂的制备方法 | |
CN109603807B (zh) | 一种改性活性炭Ce-Nb/TiO2@AC低温高效脱硫脱硝催化剂及其制备方法 | |
CN111939907A (zh) | 一种低温氨分解制氢催化剂及其制备方法和应用 | |
CN114832829B (zh) | 一种燃气尾气高温脱硝催化剂及其制备方法 | |
CN108906044A (zh) | 一种锰铈钌复合氧化物催化剂及其制备方法和用途 | |
CN104971719B (zh) | 用于rco‑scr一体式反应的催化剂的制备方法 | |
CN113426458A (zh) | 一种用于含卤素挥发性有机物催化燃烧的催化剂及其用途 | |
CN113289605A (zh) | 一种低温no氧化催化剂及其制备方法 | |
CN115722220B (zh) | 一种催化氧化催化剂及其制备方法和应用 | |
CN111744499A (zh) | 一种低温催化氧化VOCs催化剂及其制备方法及应用 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210625 |