CN105833867A - 一种应用于NO+CO反应的Au-Ce/AlTiOx的制备方法及其应用 - Google Patents
一种应用于NO+CO反应的Au-Ce/AlTiOx的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000010931 gold Substances 0.000 claims abstract description 35
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052737 gold Inorganic materials 0.000 claims abstract description 20
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- 229910010052 TiAlO Inorganic materials 0.000 claims description 10
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 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 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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Abstract
本发明提供了一种应用于NO+CO反应的Au‑Ce/AlTiOx的制备方法,属于催化材料和纳米材料制备技术领域。采用三嵌段共聚物模板法制备催化剂的铝钛氧化物载体,以四氯金酸为金前驱物,用沉积沉淀法将金负载在载体上,使纳米金颗粒高度分散在载体上,利用浸渍法引入Ce,得到高效Au‑Ce/AlTiOx催化剂。本发明制备方法简单,反应条件易于控制,对设备要求低,制得的Au‑Ce/AlTiOx材料金颗粒直径为10nm,比表面积在370m2/g。反应的测试条件为:500ppm NO,500ppm CO,He作为平衡气体,烟气的总流量为300ml/min,300℃时下脱硝催化效率达到100%。
Description
技术领域
本发明提供了一种通过三嵌段共聚物软模板法和沉积沉淀法合成Au-Ce/AlTiOx的方法,属于催化材料和纳米材料制备技术领域。本发明应用于大气污染防治领域,涉及以Au-Ce/AlTiOx为催化剂将有害的NO和CO转化成N2和CO2。
背景技术
近年来大气污染日趋严重,造成污染的原因,既有自然因素也有人为因素,其中人为的破坏占据了主要部分,如煤炭燃烧、工业废气的随意排放、机动车辆行驶过程中排放的尾气等。大气污染物可根据其存在的状态分为颗粒污染物和气态污染物,主要的污染物有粉尘、二氧化硫(SO2)、氮氧化物(NOx)、一氧化碳(CO)、碳氢化合物等。
目前,关于NOx消除的技术研究得到越来越广泛地关注,。在众多的NOx处理方法中,选择性催化还原法(SCR)被认为是用于固定源的最有效和应用最广泛的脱硝技术。用于选择性催化还原的催化剂的主要类型有:单金属氧化物,复合金属氧化物、金属负载氧化物、负载金属氧化物的碳材料、分子筛催化剂。许多SCR反应的催化剂都含有过渡金属(如Fe、V、Cr、Cu、Co和Mn等)这些催化剂在低温下都具有较好的选择性催化还原活性。考虑到催化剂组分和环境温度会影响(NH4)2SO4、NH4NO3和N2O的形成,因此研究的重点是运用的载体和开发高活性、高选择性和运行温度范围广的低温SCR催化剂。
非贵金属催化剂虽然制造成本低廉,但是无论在抗中毒能力、起燃特性、还是空燃比特性等方面都很难与贵金属催化剂相提并论,因此贵金属催化剂在汽车尾气净化中仍占主导地位。金虽然也是贵金属的一种,由于它的化学惰性极高,长期以来都被认为不可作为催化剂的活性组分。但是近年来有研究发现,当金颗粒的粒径处于纳米级时,其表面具有大量的低配位原子,使其具备了高效的催化性能。尽管金属于贵金属的范畴,但是与Pt、Pd、Rh这些常用的贵金属材料相比还是具有相对的价格优势,储量也相对更加丰富,而且对金的回收技术也比较成熟。因此使用金作为催化材料可以降低贵金属催化剂的成本同时还能保持同样高效的催化性能,有很广泛的应用前景。
金的催化活性与负载的载体也有关,金需要通过负载到合适的载体的形成较小的纳米金粒子才能发挥有效的催化活性,载体的选择会直接影响其催化剂的性能,Fe2O3、γ-Al2O3、CeO2、ZnO等都可以被用作载体来制备负载型金催化剂。过渡金属和稀土金属氧化物被认为是最适合作为贵金属催化剂的载体的物质,在稀土金属中Ce不仅具有良好的储存氧和释放氧的能力,CeO2作为载体能够更好使贵金属在氧化物载体表面分散,与贵金属发挥协同作用,从而增加催化剂的活性和稳定性。有研究表明Ce可以改变CO氧化反应的活化能,还能在被还原以后在催化剂的表面提供氧空穴使得NO更易于解离,而且铈在Ce4+和Ce3+之间的转化会在很大程度上影响NO的还原。近年来的研究显示,由于电子在金与金属氧化物之间的转移,金的粒径和金与载体氧化物之间的相互作用对催化性能至关重要。本发明首次利用铝钛氧化物作为载体,氧化铝载体具有高比表面积,本发明将TiO2和氧化铝结合,既解决了二氧化钛的比表面积受限的问题,也发挥了氧化铝抗压强度高的优势。
发明内容
针对现有的催化剂在反应温度高,抗中毒能力、起燃特性、空燃比特性上的不足等问题,本发明首先采用三嵌段共聚物软模板法合成载体AlTiOx,再用沉积沉淀法将Au负载在该载体上,最后通过浸渍法引入过渡金属Ce,最终合成在低温下能够高效去除NO和CO的催化剂Au-Ce/AlTiOx。
本发明的技术方案:
一种应用于NO+CO反应的Au-Ce/AlTiOx的制备方法,步骤如下:
1)催化剂载体AlTiOx的合成:将0.1g/mL的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与0.1mmol/mL的异丙醇钛的乙醇溶液以体积比为1:1混合,搅拌4h;将1.8mmol/mL异丙醇铝的无水乙醇溶液与硝酸以体积比为25:8混合;将上述两种溶液充分混合,使体系中元素Ti与Al的摩尔比为1:9,继续搅拌5h;将所得的溶液放置于50-70℃鼓风干燥箱中48h烘干,再将固体在马弗炉中在空气气氛下于400℃煅烧4h;
2)Au/AlTiOx的制备:将0.6μg/mL的HAuCl4·3H2O的水溶液在70℃条件下,缓慢滴入1mol/mL氨水调节溶液pH至7.0,此时形成黄色的金胶体溶液;再加入步骤1)得到的催化剂载体AlTiOx,使体系中的元素金的质量分数为3%,搅拌1h,即得悬浮液;然后将所得悬浮液在室温下真空抽滤,所得的固体在50-70℃干燥箱烘干,并在马弗炉中在空气气氛下于300℃煅烧1h,即得Au/AlTiOx;
3)Au-Ce/AlTiOx的制备:将步骤2)得到的Au/AlTiOx为母体,在0.02g/mL的Au/AlTiOx的水溶液中加入硝酸铈,使Au和Ce的物质的量之比为1:0.5,搅拌1h,即得悬浮液;将悬浮液置于60℃的水浴中,在大气压下保持1h;然后降温至35℃,抽真空并继续保持此温度至蒸发溶剂;将所得到固体样品置于50-70℃的干燥箱中烘干,并置于马弗炉中在空气气氛下与300℃煅烧1h,得到Au-Ce/TiAlOx催化剂,x=5。
上述制备的Au-Ce/TiAlOx催化剂用于处理含NO和CO的烟气,反应的测试条件为:500ppm NO,500ppm CO,He作为平衡气体;烟气的总流量为300ml/min,催化剂的体积的空速为30,000ml/g-catalyst/h,活性测试温度为30-300℃。
本发明的有益效果:本发明合成的Au-Ce/TiAlOx催化剂具有良好的孔道结构,比表面积达356m2/g,孔容为对0.397mL/g,对NO+CO具有良好的低温催化活性,在300℃能达到NO转化率可达到100%,是一种操作简单、绿色高效的催化剂。
附图说明
图1是制备的Au-Ce/TiAlOx的透射电镜图。
图2是制备的Au-Ce/TiAlOx的氢气程序升温还原反应曲线图。
图3(a)是制备的Au-Ce/TiAlOx的光电子能谱图图。
图3(b)是制备的Au-Ce/TiAlOx的光电子能谱图图。
图3(c)是制备的Au-Ce/TiAlOx的光电子能谱图图。
图3(d)是制备的Au-Ce/TiAlOx的光电子能谱图图。
图4是制备的Au-Ce/TiAlOx的反应活性测试图。
具体实施方式
以下结合附图和技术方案详细叙述本发明的具体实施方式。
实施例1
溶液A:将5.0g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与与5.0mmol异丙醇钛溶于50mL无水乙醇中,搅拌4h;溶液B:将45mmol异丙醇铝溶于8ml硝酸和25mL无水乙醇的混合液中;将溶液A、B混合,继续搅拌5h;将所得的溶液放置于50℃鼓风干燥箱中48h烘干,再将固体在马弗炉中在空气气氛下于400℃煅烧4h。将0.6μg/mL的HAuCl4·3H2O的水溶液在70℃条件下,缓慢滴入1mol/mL氨水调节溶液pH至7.0,此时形成黄色的金胶体溶液;再加入催化剂载体AlTiOx使元素金的质量分数为3%,搅拌1h,即得悬浮液;然后将所得悬浮液在室温下真空抽滤,所得的Au/AlTiOx固体在50℃干燥箱烘干,并在马弗炉中在空气气氛下于300℃煅烧1h,即得Au/AlTiOx。在0.02g/mL的Au/AlTiOx的水溶液中加入硝酸铈,使元素Au和Ce的物质的量之比为1:0.5,搅拌1h,即得悬浮液;将悬浮液置于60℃的水浴中,在大气压下保持1h;然后降温至35℃,抽真空并继续保持此温度至蒸发溶剂;将所得到固体样品置于50-70℃的干燥箱中烘干,并置于马弗炉中在空气气氛下与300℃煅烧1h,得到Au-Ce/TiAlOx催化剂,x=5。
实施例2
按照实施例1本发明中将10.0g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与与10.0mmol异丙醇钛溶于100mL无水乙醇中,搅拌4h;将90mmol异丙醇铝溶于16ml硝酸和50mL无水乙醇的混合液中,其他条件不变,制得Au-Ce/TiAlOx。
实施例3
按照实施例1本发明中将20.0g的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与与20.0mmol异丙醇钛溶于200mL无水乙醇中,搅拌4h;将180mmol异丙醇铝溶于32ml硝酸和100mL无水乙醇的混合液中,其他条件不变,制得Au-Ce/TiAlOx。
实施例4
按照实施例1本发明中将溶液A、B混合后继续搅拌5h;将所得的溶液放置于60℃鼓风干燥箱中48h烘干,再将固体在马弗炉中在空气气氛下于400℃煅烧4h。
实施例6
按照实施例1本发明中将溶液A、B混合后继续搅拌5h;将所得的溶液放置于70℃鼓风干燥箱中48h烘干,再将固体在马弗炉中在空气气氛下于400℃煅烧4h。
实施例7
按照实施例1本发明中将所得的Au/AlTiOx固体在60℃干燥箱烘干,并在马弗炉中在空气气氛下于300℃煅烧1h,其他步骤不变,制得Au-Ce/TiAlOx。
实施例8
按照实施例1本发明中将所得的Au/AlTiOx固体在70℃干燥箱烘干,并在马弗炉中在空气气氛下于300℃煅烧1h,其他步骤不变,制得Au-Ce/TiAlOx。
Claims (2)
1.一种应用于NO+CO反应的Au-Ce/AlTiOx的制备方法,其特征在于,步骤如下:
1)催化剂载体AlTiOx的合成:将0.1g/mL的聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物与0.1mmol/mL的异丙醇钛的乙醇溶液以体积比为1:1混合,搅拌4h;将1.8mmol/mL异丙醇铝的无水乙醇溶液与硝酸以体积比为25:8混合;将上述两种溶液充分混合,使体系中元素Ti与Al的摩尔比为1:9,继续搅拌5h;将所得的溶液放置于50-70℃鼓风干燥箱中48h烘干,再将固体在马弗炉中在空气气氛下于400℃煅烧4h;
2)Au/AlTiOx的制备:将0.6μg/mL的HAuCl4·3H2O的水溶液在70℃条件下,缓慢滴入1mol/mL氨水调节溶液pH至7.0,此时形成黄色的金胶体溶液;再加入步骤1)得到的催化剂载体AlTiOx,使体系中的元素金的质量分数为3%,搅拌1h,即得悬浮液;然后将所得悬浮液在室温下真空抽滤,所得的固体在50-70℃干燥箱烘干,并在马弗炉中在空气气氛下于300℃煅烧1h,即得Au/AlTiOx;
3)Au-Ce/AlTiOx的制备:将步骤2)得到的Au/AlTiOx为母体,在0.02g/mL的Au/AlTiOx的水溶液中加入硝酸铈,使Au和Ce的物质的量之比为1:0.5,搅拌1h,即得悬浮液;将悬浮液置于60℃的水浴中,在大气压下保持1h;然后降温至35℃,抽真空并继续保持此温度至蒸发溶剂;将所得到固体样品置于50-70℃的干燥箱中烘干,并置于马弗炉中在空气气氛下与300℃煅烧1h,得到Au-Ce/TiAlOx催化剂,x=5。
2.权利要求1制备得到的Au-Ce/TiAlOx催化剂的应用,其特征在于,将所述的Au-Ce/TiAlOx催化剂用于处理含NO和CO的烟气,反应的测试条件为:500ppmNO,500ppm CO,He作为平衡气体;烟气的总流量为300ml/min,催化剂的体积的空速为30,000ml/g-catalyst/h,活性测试温度为30-300℃。
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