CN115106117B - 一种处理no的催化剂的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 71
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002905 metal composite material Substances 0.000 claims abstract description 16
- 238000007865 diluting Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 208000012839 conversion disease Diseases 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910005438 FeTi Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明提供一种处理NO的催化剂的制备方法,催化剂包括活性贵金属组份和载体,载体为分子筛或金属复合氧化物,包括以下步骤:a、将载体焙烧1~2h,冷却;b、取步骤a中载体质量0.1%~1%的贵金属前驱体溶液,并将溶液稀释;c、向载体粉末中滴加贵金属前驱体溶液,滴加完毕,得到混合液;d、将混合液在40‑80℃下微波0.5‑1h,之后在100‑150℃下微波烘干10min~30min,得到固体粉末;e、将固体粉末放于焙烧炉中,升温至450‑650℃并通入5%‑10%水蒸气并持续1‑3h,停止通入水蒸气,焙烧0.5h‑1h,冷却至室温,得到催化剂。本发明的处理NO的催化剂的制备方法,能在50℃下开始催化NO与H2反应,在200℃实现NO完全反应转化,且产物NH3的选择性达到100%。
Description
技术领域
本发明涉及催化剂制备技术领域,具体涉及一种处理NO的催化剂的制备方法。
背景技术
氮氧化物(NOx)是形成酸雨的主要物质之一,也是形成光化学烟雾的元凶,对环境及人类生活造成一定的危害。土壤和海洋等环境中的有机物分解的氮氧化物能够通过自然界的氮循环过程完全自消耗,而人类活动如化石燃料的燃烧,亦或来自氮肥、硅酸盐、有机中间体等的生产过程产生大量的氮氧化物,超过自然界的自循环能力,需要人为干预处理。
化石燃料燃烧产生的氮氧化物主要以NO的形式存在,约占整个氮氧化物的95%。目前处理氮氧化物的主流技术是使用还原剂(氨气、尿素、烷烃等)在催化剂作用下进行的选择性催化还原法(SCR);该技术的核心是催化剂,因应用工况的不同(如温度),相关法规的发展修正,催化剂的体系也在不断地变化。SCR技术相关的专利如 CN201310208338.1/CN106938200B 等公开了的中温V2O5-TiO2体系催化剂,CN104226361B/CN201710839712.6等公开的高温铁分子筛体系催化剂,CN102946996B/CN104624228B等公开的低温Cu分子筛体系催化剂等;上述催化剂在相对应的应用环境中都展现出优异的NO转化性能,然而在工况环境温度低于200℃,即使是Cu分子筛体系催化剂的表现也难尽人意。
另外,Iwamoto等发现Cu-ZSM-5分子筛具有分解NO活性,后期有很多围绕NO催化分解催化剂的研究报道,如文献Mater .Sci .-Poland,2016,34,177-184等;专利CN201610192429.4也公开了相关催化剂的制备方法,但其即使在350℃时达到的最高转化率也只有45.5%,与工业应用目标相差甚远。
发明内容
针对现有技术中存在的不足,本发明提供一种处理NO的催化剂的制备方法,本催化剂包括活性组分和载体,将贵金属负载于分子筛或金属复合氧化物上,先经微波及蒸汽处理,再经气氛氛围高温焙烧,即获得成品催化剂,该催化剂能在50℃下开始催化NO与H2反应,在200℃实现NO完全反应转化,且产物NH3的选择性达到100%。
本发明采用的技术方案是:
一种处理NO的催化剂的制备方法,其中:所述催化剂包括活性贵金属组份和载体,所述载体为分子筛或金属复合氧化物,所述制备方法包括以下步骤:
a、将载体焙烧1~2h,然后将载体冷却至室温;
b、取步骤a中载体质量0.1%~1%的贵金属前驱体溶液,并将溶液稀释;
c、向低速搅拌的载体粉末中逐滴滴加稀释后的贵金属前驱体溶液,直至滴加完毕,得到混合液;
d、将混合液在40-80℃下微波0.5-1h,之后在100-150℃下微波烘干10min~30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,升温至450-650℃通入5%-10%水蒸气并持续1-3h,停止通入水蒸气,焙烧0.5h-1h,冷却至室温,得到催化剂。
优选的是,所述的处理NO的催化剂的制备方法,其中:当载体为分子筛时,所述步骤a的载体焙烧温度为200℃~220℃;当载体为金属复合氧化物时,所述步骤a的载体焙烧温度为500℃~550℃。
优选的是,所述的处理NO的催化剂的制备方法,其中:当载体为分子筛时,所述步骤b的贵金属前驱体溶液稀释至溶液质量与分子筛质量比为0.8~1.1;当载体为金属复合氧化物时,所述步骤b的贵金属前驱体溶液稀释至溶液质量与复合氧化物质量比为0.5~0.8。
优选的是,所述的处理NO的催化剂的制备方法,其中:当载体为分子筛时,所述步骤c滴加完毕后静置2~3h,得到混合液;当载体为金属复合氧化物时,所述步骤c滴加完毕后搅拌1~2h,得到混合液。
优选的是,所述的处理NO的催化剂的制备方法,其中:当载体为分子筛时,所述步骤e固体粉末在氮气气氛中焙烧;当载体为金属复合氧化物时,所述步骤e固体粉末在空气气氛中焙烧。
优选的是,所述的处理NO的催化剂的制备方法,其中:所述贵金属前驱体溶液的贵金属为Pd、Pt、Rh、Ir、Ru、Au、Ag中的一种或几种。
优选的是,所述的处理NO的催化剂的制备方法,其中:所述分子筛为氢型分子筛,所述氢型分子筛为小孔、介孔或大孔分子筛中的一种或几种,且分子筛的硅铝摩尔比为5~+∞。
优选的是,所述的处理NO的催化剂的制备方法,其中:所述小孔分子筛为主孔道为8元环、10元环或12元环的硅基、硅铝基或磷铝基分子筛;所述中孔分子筛为孔径2-50nm的有序或无序中孔分子筛;所述大孔分子筛为孔径在50nm以上的多孔分子筛。
优选的是,所述的处理NO的催化剂的制备方法,其中:当载体为金属氧化物时,所述金属复合氧化物为MyFexTiO(2+x/2+y/2),其中M为V、W、Zr、Co、Ni、Ce、Mg或La的一种,所述三种金属氧化物质量比为M:Fe:Ti=(0~10%):(5%~40%):(50%~95%)。
本发明的优点:
本发明的处理NO的催化剂的制备方法,将贵金属负载于分子筛或金属复合氧化物上,先经微波及蒸汽处理,再经气氛氛围高温焙烧,即获得成品催化剂,该催化剂能在50℃下开始催化NO与H2反应,在200℃实现NO完全反应转化,且产物NH3的选择性达到100%。
附图说明
图1为本发明实施例1-2的Pt-氢型分子筛催化剂反应的NO转化效率趋势图。
图2为本发明实施例3-4的Pt-金属分子筛催化剂反应的NO转化效率趋势图。
图3为本发明实施例5-6的Pd-FeTi体系催化剂反应的NO转化效率趋势图。
具体实施方式
下面结合具体附图和实施例对本发明作进一步说明。
实施例1
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将全硅的Silicate-1分子筛(10元环)在200℃下焙烧1h,然后将其放于干燥器中冷却至室温并称重;
b、取步骤a中分子筛质量1%的Pt的前驱体溶液,并将溶液稀释至溶液质量与分子筛质量比为0.8;
c、向低速搅拌的分子筛粉末中逐滴滴加Pt金属溶液,直至滴加完毕,并静置2h,得到混合液;
d、将混合液在40℃下微波1h,再在150℃下微波烘干10min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在650℃下通入10%水蒸气并持续1h,停止水蒸气,在氮气气氛中焙烧0.5h,冷却至室温,即得催化剂样品1。
实施例2
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将硅铝比为30的H-Beta分子筛(12元环)在200℃下焙烧1h,然后将其放于干燥器中冷却至室温并称重;
b、取步骤a中分子筛质量0.5%的Pt的前驱体溶液,并将溶液稀释至溶液质量与分子筛质量比为1.1;
c、向低速搅拌的分子筛粉末中逐滴滴加Pt金属溶液,直至滴加完毕,并静置2h,得到混合液;
d、将混合液在80℃下微波0.5h,再在100℃下微波烘干30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在450℃下通入10%水蒸气并持续3h,停止水蒸气,在氮气气氛中焙烧1h,冷却至室温,即得催化剂样品2。
实施例3
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将商用硅铝比为30的Fe-Beta分子筛在200℃下焙烧1h,然后将其放于干燥器中冷却至室温并称重;
b、取步骤a中分子筛质量0.5%的Pt的前驱体溶液,并将溶液稀释至溶液质量与分子筛质量比为0.8;
c、向低速搅拌的分子筛粉末中逐滴滴加Pt金属溶液,直至滴加完毕,并静置2h,得到混合液;
d、将混合液在80℃下微波0.5h,再在100℃下微波烘干30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在450℃下通入10%水蒸气并持续3h,停止水蒸气,在氮气气氛中焙烧1h,冷却至室温,即得催化剂样品3。
实施例4:
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将商用硅铝比为5的Cu-ZZS-13分子筛(8元环)在200℃下焙烧1h,然后将其放于干燥器中冷却至室温并称重;
b、取步骤a中分子筛质量0.5%的Pt的前驱体溶液,并将溶液稀释至溶液质量与分子筛质量比为0.8;
c、向低速搅拌的分子筛粉末中逐滴滴加Pt金属溶液,直至滴加完毕,并静置2h,得到混合液;
d、将混合液在80℃下微波0.5h,再在100℃下微波烘干30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在450℃下通入10%水蒸气并持续3h,停止水蒸气,在氮气气氛中焙烧1h,冷却至室温,即得催化剂样品4。
实施例5
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将铁钛氧化物质量比为1:9的复合氧化物在500℃下焙烧1h,冷却至200℃将其放于干燥器中冷却至室温并称重;
b、取步骤a中复合氧化物质量0.5%的Pd的前驱体溶液,并将溶液稀释至溶液质量与铁钛复合氧化物质量比为0.8;
c、向低速搅拌的复合氧化物粉末中逐滴滴加Pd金属溶液,直至滴加完毕,并搅拌1h,得到混合液;
d、将混合液在40℃下微波1h,再在150℃下微波烘干10min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在650℃下通入10%水蒸气并持续1h,停止水蒸气,在空气气氛中焙烧0.5hh,冷却至室温,即得催化剂样品5。
实施例6
一种处理NO的催化剂的制备方法,包括以下步骤:
a、将钨铁钛氧化物质量比为5:10:85的复合氧化物在500℃下焙烧1h,冷却至200℃将其放于干燥器中冷却至室温并称重;
b、取步骤a中复合氧化物质量0.5%的贵金属的前驱体溶液,并将溶液稀释至溶液质量与钨铁钛氧化物质量比为0.5;
c、向低速搅拌的复合氧化物粉末中逐滴滴加贵金属溶液,直至滴加完毕,并搅拌1h,得到混合液;
d、将混合液在80℃下微波0.5h,再在100℃下微波烘干30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,在450℃下通入10%水蒸气并持续3h,停止水蒸气,在空气气氛中焙烧1h,冷却至室温,即得催化剂样品6。
实施例1-6催化剂处理转化NO性能评价:实验采用固定床微型反应器装样测试、尾气组份用MKS2030傅里叶变换红外分析仪检测,实验条件为:空速100000 h-1,NO 600ppm、1.2%H2,5% H2O、N2作为平衡气体。
图1是Pt-氢型分子筛催化剂反应的NO转化趋势图,从图中可以看出,样品1开始反应温度约50℃,最高转化率达到~83%。从曲线看样品2的开始反应温度~110℃,~200℃其能实现NO完全反应产生NH3,而过程中NH3浓度超过600ppm,是因为分子筛本身具有吸附作用,低温产生的NH3吸附于分子筛中,随着温度升高逐步释放出来;(样品1为全硅分子筛,不具有此能力)。
图2是Pt-金属分子筛催化剂反应的NO转化趋势图,从图中可以看出,两个样品能够催化NO完全转化为NH3;样品3开始反应温度高于样品4,而在250-370℃范围内生成的NH3浓度略高于样品4,同样的两个样品因分子筛吸附作用,低温产生的NH3吸附于分子筛中,随着温度升高逐步释放出来。
图3是Pd-FeTi体系催化剂反应的NO转化趋势图,从图中可以看出,两个样品能够催化NO完全转化为NH3;样品5开始反应温度低于样品6,在150-220℃范围内生成的NH3浓度略高于样品6,其他温度下的处理转化性能几乎无差异。
最后所应说明的是,以上具体实施方式仅用以说明本发明的技术方案而非限制,尽管参照实例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一种处理NO生成NH3的催化剂的制备方法,所述的催化剂催化NO与H2反应,在200℃实现NO完全反应转化,且产物NH3的选择性达到100%,其特征在于:所述催化剂包括活性贵金属组份和载体,所述载体为分子筛或金属复合氧化物,所述制备方法包括以下步骤:
a、将载体焙烧1~2h,然后将载体冷却至室温;
b、取步骤a中载体质量0.1%~1%的贵金属前驱体溶液,并将溶液稀释;
c、向低速搅拌的载体粉末中逐滴滴加稀释后的贵金属前驱体溶液,直至滴加完毕,得到混合液;
d、将混合液在40-80℃下微波0.5-1h,之后在100-150℃下微波烘干10min~30min,得到固体粉末;
e、将固体粉末放于焙烧炉中,升温至450-650℃通入5%-10%水蒸气并持续1-3h,停止通入水蒸气,焙烧0.5h-1h,冷却至室温,得到催化剂;
所述贵金属前驱体溶液的贵金属为Pd、Pt、Rh、Ir、Ru、Au、Ag中的一种或几种;当载体为金属复合氧化物时,所述金属复合氧化物为MyFexTiO(2+x/2+y/2),其中M为V、W、Zr、Co、Ni、Ce、Mg或La的一种,所述三种金属氧化物质量比为M:Fe:Ti=(0~10%):(5%~40%):(50%~95%);
当载体为分子筛时,所述步骤b的贵金属前驱体溶液稀释至溶液质量与分子筛质量比为0.8~1.1;当载体为金属复合氧化物时,所述步骤b的贵金属前驱体溶液稀释至溶液质量与复合氧化物质量比为0.5~0.8;
当载体为分子筛时,所述步骤e固体粉末在氮气气氛中焙烧;当载体为金属复合氧化物时,所述步骤e固体粉末在空气气氛中焙烧。
2.根据权利要求1所述的处理NO生成NH3的催化剂的制备方法,其特征在于:当载体为分子筛时,所述步骤a的载体焙烧温度为200℃~220℃;当载体为金属复合氧化物时,所述步骤a的载体焙烧温度为500℃~550℃。
3.根据权利要求1所述的处理NO生成NH3的催化剂的制备方法,其特征在于:当载体为分子筛时,所述步骤c滴加完毕后静置2~3h,得到混合液;当载体为金属复合氧化物时,所述步骤c滴加完毕后搅拌1~2h,得到混合液。
4.根据权利要求1所述的处理NO生成NH3的催化剂的制备方法,其特征在于:所述分子筛为氢型分子筛、Fe-Beta分子筛、Cu-ZZS-13分子筛中的一种,所述氢型分子筛为小孔、介孔或大孔分子筛中的一种或几种,且分子筛的硅铝摩尔比为5~+∞。
5.根据权利要求4所述的处理NO生成NH3的催化剂的制备方法,其特征在于:所述小孔分子筛为主孔道为8元环、10元环或12元环的硅基、硅铝基或磷铝基分子筛;所述中孔分子筛为孔径2-50nm的有序或无序中孔分子筛;所述大孔分子筛为孔径在50nm以上的多孔分子筛。
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