CN109529924B - 一种doc分子筛催化剂及其制备和催化氧化柴油车尾气的用途 - Google Patents
一种doc分子筛催化剂及其制备和催化氧化柴油车尾气的用途 Download PDFInfo
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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 title claims abstract description 71
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
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- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- 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 description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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Abstract
本发明涉及一种DOC分子筛催化剂及其制备和催化氧化柴油车尾气的用途,将分子筛载体经过脱Si或脱Al处理后,将贵金属引入到载体上,利用分子筛载体的离子交换位点和缺陷位将贵金属固定在载体结构上,有效抑制了贵金属在高温下的烧结,并且分子筛本身具有较强的骨架结构稳定性,能够显著提高催化剂的热稳定性。将该催化剂应用于柴油车尾气催化氧化反应DOC中,不仅能够提高催化剂的抗水热老化能力,还能利用分子筛载体比表面积大、酸性强、孔径小的特点,提升催化剂的反应活性、抗化学物质中毒能力和硫中毒后的再生能力。
Description
技术领域
本发明属于柴油车尾气处理技术领域,特别涉及一种DOC分子筛催化剂及其制备方法和催化氧化柴油车尾气的用途。
背景技术
柴油车凭借其在动力、安全和运行成本上的绝对优势,承担起了公路汽运的重任。然而,柴油车尾气排放带来的环境污染问题也日益严重,柴油车尾气污染物也已经成为大气污染的主要来源,给生态环境以及人类身体健康带来的危害不容小觑。治理柴油车尾气污染物已经成为全球各国共同关注的问题。
柴油车尾气催化氧化技术(Diesel Oxidation Catalysts,DOC)是柴油车后处理技术中的关键技术环节。DOC通过其较强的催化氧化能力,能够消除柴油发动机尾气中大部分的CO、HCs(碳氢化合物)和SOF(可溶性有机物),有效的降低了污染物排放。此外,DOC还能够将发动机尾气中部分的NO氧化为NO2,不仅能够降低下游颗粒捕集器(Diesel ParticleFilter,DPF)中碳烟的燃烧温度,还能促进选择性催化反应器(Selective CatalyticReduction,SCR)中快速SCR反应的发生。
高性能DOC催化剂的研究一直是DOC技术的关键。随着柴油车排放标准的进一步提高,日益复杂的柴油车后处理***对DOC催化剂的性能也提出了更加严苛的要求。DPF燃烧碳烟的温度较高,要求上游的DOC装置产生大量的热,因此给DOC催化剂带来的水热老化影响不容忽视。传统的DOC催化剂主要是将Pt和Pd等贵金属负载在Al2O3、CeO2、ZrO2和TiO2等氧化物载体上,在高温老化条件下很容易发生贵金属的烧结,还会导致载体结构的坍塌和贵金属的包埋等一系列问题,从而导致催化剂的失活。除此之外,柴油车尾气中还会含有K、Ca、Na、Mg、Zn、P等化学物质,这些物质主要来源于柴油添加剂和润滑油中,会随着尾气吸附在催化剂的表面,长时间的积累将会堵塞催化剂的孔道甚至破坏其骨架结构。以氧化物作为DOC催化剂的载体,其比表面积较小并且酸性较弱,容易受到化学物质沉积所带来的影响,从而导致催化剂的性能的大幅度降低。柴油中的硫成分经过一系列的氧化后将生成SO3,而SO3与H2O反应生成的H2SO4进一步反应生成的硫酸盐将覆盖在催化剂表面和孔道结构中,造成催化剂的硫中毒,大幅减小了催化剂的使用寿命。随着新的排放法规加强了对排放***耐久性的要求,DOC催化剂也必须具有优良的稳定性和更长的使用寿命。
发明内容
为了克服上述现有技术传统氧化物型DOC催化剂高温易失活和抗化学物质中毒能力差等缺点,本发明的目的在于提供一种DOC分子筛催化剂及其制备和催化氧化柴油车尾气的用途,选用分子筛作为载体,利用脱Si或者脱Al处理后,将贵金属负载到分子筛上,利用分子筛上的离子交换位点,使金属离子能进入分子筛框架结构,并通过将金属颗粒牢牢固定在分子筛的骨架上,有效防止金属离子在反应过程中的聚集烧结或流失,提高催化剂的热稳定性。水热老化结果表明,优选催化剂在水蒸气含量为5%的条件下,750℃水热老化16h后,CO和C3H6的起燃温度仅分别提高15℃和20℃。利用分子筛载体较大的比表面积和较强的酸性来提高催化剂的抗化学物质中毒能力。化学物质中毒实验结果表明,优选催化剂在K金属中毒后,催化剂的转化性能基本没有发生变化。利用分子筛对HC较强的吸附能力,通过在低温下对HC进行吸附,到达起燃温度时再释放HC,并将其消除,从而有效减少柴油车低温冷启动时HC的排放问题,降低了HC的起燃温度。将优选催化剂与商用Pt/Pd-Al2O3催化剂相比,CO和C3H6的起燃温度分别下降了35℃和55℃。
为了实现上述目的,本发明采用的技术方案是:
一种DOC分子筛催化剂,以脱Si或脱Al后的分子筛作为载体,负载贵金属。
所述贵金属为Pt、Pd、Au、Ag、Rh和Ru中的一种或几种,所述分子筛为MOR、Beta、ZSM-5、SSZ-13、SAPO-34、SAPO-18和SSZ-39中的一种或几种。
所述贵金属的质量分数为0.5~3wt.%。
所述DOC分子筛催化剂的制备方法之一,采用等体积浸渍法,步骤如下:
步骤一:对分子筛进行脱Si或脱Al处理;
步骤二:将贵金属盐溶于去离子水中配制成溶液,并按贵金属占载体质量分数的比例,用移液枪将其滴加在分子筛粉体上,使分子筛充分润湿,之后放置得到样品;
步骤三:将所得样品在真空干燥箱内完全烘干,再于马弗炉内焙烧得到DOC分子筛催化剂。
所述步骤二中,在25~80℃的条件下放置1~6h;所述步骤三中,在真空干燥箱内80~120℃干燥6~12h,在马弗炉内500~600℃焙烧3~6h。
所述DOC分子筛催化剂的制备方法之二,采用离子交换法,步骤如下:
步骤一:对分子筛进行脱Si或脱Al处理;
步骤二:将贵金属盐溶于去离子水中配制成溶液,并按贵金属占载体质量分数的比例,加入分子筛粉体,搅拌得到样品;
步骤三:将所得样品在真空干燥箱内完全烘干,再于马弗炉内焙烧得到DOC分子筛催化剂。
所述步骤二中,在25~120℃的条件下搅拌1~6h;所述步骤三中,在真空干燥箱内80~120℃干燥6~12h,在马弗炉内500~600℃焙烧3~6h。
本发明中,脱Si处理的步骤如下:
将无机碱溶于去离子水中配制成浓度为0.05~2.0mol/L的碱液;无机碱包括但不限于氢氧化钠、氢氧化钾等。按照(0.1~10)g:100mL的比例将分子筛与所得碱液混合,在25~70℃下搅拌0.5~6h,过滤洗涤后得到脱Si处理后的分子筛载体;
脱Al处理的步骤如下:
将分子筛放置于固定床反应器中,在水蒸气体积含量为2%的条件下,500~800℃水热老化6~18h,烘干后得到脱Al处理后的分子筛载体。
本发明所得DOC分子筛催化剂可用于催化氧化柴油车尾气。将所述催化剂涂敷在堇青石载体上,并置于柴油车尾气下游的DOC反应器中。柴油车尾气通过DOC反应器的过程中,催化剂可将尾气中大部分的CO、HCs催化氧化为对环境无害的CO2和H2O,有效减小环境的污染。
本发明提供的用于柴油车尾气催化氧化DOC分子筛催化剂的性能评价在固定床中进行,反应条件为:CO=2000ppm、C3H6=500ppm、NO=500ppm、O2=10%,H2O=5%、N2作为载气,总流量为1000mL/min,反应温度区间为100~350℃。DOC分子筛催化剂的老化在固定床中进行,老化条件为:H2O=5%、空速为1000mL/min、老化温度为750℃,老化时间为16h。DOC分子筛催化剂的K金属化学中毒条件为:将1.0mmol/gcatal的K通过浸渍法负载在催化剂上。DOC分子筛催化剂的硫化在固定床中进行,硫化条件为:SO2=100ppm、硫化温度为200℃、硫化时间为12h。DOC分子筛催化剂硫化后样品的再生在固定床中进行,再生条件为:再生温度为500℃、再生时间为0.5h。
与现有技术相比,本发明的有益效果是:
采用两种方法制备的贵金属负载分子筛型催化剂,都表现出了优异的CO和C3H6转化效率,与商用Pt/Pd-Al2O3催化剂相比,具有更低的CO和C3H6起燃温度,明显拓宽了催化剂的温度窗口。经过脱Al改性后的贵金属负载分子筛催化剂,在750℃的高温处理16h后,CO和C3H6起燃温度的上升程度明显低于商用Pt/Pd-Al2O3催化剂,说明贵金属负载分子筛催化剂具有更好的热稳定性,能够有效抑制活性组分贵金属的烧结和催化剂结构的坍塌。此外,对硫化后的贵金属负载分子筛催化剂在500℃下再生0.5h后,就能基本恢复到新鲜催化剂的催化性能,说明该催化剂有着更好的抗硫中毒性能和优异的再生能力,能够适应柴油车***中含硫的尾气环境。
附图说明
图1为实施例1合成贵金属负载分子筛催化剂和商用Pt/Pd-Al2O3催化剂的CO转化率测试结果。
图2为实施例1合成贵金属负载分子筛催化剂和商用Pt/Pd-Al2O3催化剂的C3H6转化率测试结果。
图3为实施例2合成贵金属负载分子筛催化剂和商用Pt/Pd-Al2O3催化剂的CO转化率测试结果。
图4为实施例2合成贵金属负载分子筛催化剂和商用Pt/Pd-Al2O3催化剂的C3H6转化率测试结果。
图5为实施例2合成贵金属负载分子筛催化剂水热老化前后的CO转化率测试结果。
图6为实施例2合成贵金属负载分子筛催化剂水热老化前后的C3H6转化率测试结果。
图7为实施例2合成贵金属负载分子筛催化剂K化学中毒前后的CO转化率测试结果。
图8为实施例2合成贵金属负载分子筛催化剂K化学中毒前后的C3H6转化率测试结果。
图9为实施例2合成贵金属负载分子筛催化剂硫中毒再生后的CO转化率测试结果。
图10为实施例2合成贵金属负载分子筛催化剂硫中毒再生后的C3H6转化率测试结果。
具体实施方式
下面结合附图和实施例详细说明本发明的实施方式。
实施例1
将5g的SSZ-13分子筛(Si/Al=10)放入200mL的1.0mol/L的NaOH溶液中,并在40℃下搅拌4h,在100℃下烘干12h后得到脱Si处理后的分子筛载体。然后,将一定量的Pt(NO3)2、Pd(NO3)2与去离子水混合均匀,用移液枪滴加在分子筛载体上,并在80℃下静置3h,再放入100℃真空干燥箱中干燥12h,经过550℃煅烧4h后得到Pt质量分数为1.0wt.%,Pd质量分数为0.5wt.%的贵金属负载分子筛催化剂,本实施例催化剂命名为Pt/Pd-SSZ-13-Si。
如图1和图2所示,本实施例催化剂表现出优异的催化活性,CO和C3H6的起燃温度分别为170℃和190℃,相比商业Pt/Pd-Al2O3催化剂的起燃温度分别下降了30℃和45℃,在220℃左右,CO和C3H6的转化率超过90%。
实施例2
将5g的SSZ-13分子筛(Si/Al=10)在H2O=2%、空速为400mL/min,温度为550℃条件下处理6h,得到脱Al处理后的分子筛载体。然后,将一定量的Pt(NO3)2、Pd(NO3)2与去离子水混合均匀,用移液枪滴加在分子筛载体上,并在80℃下静置3h,再放入100℃真空干燥箱中干燥12h,经过550℃煅烧4h后,得到Pt质量分数为1.0wt.%,Pd质量分数为0.5wt.%的贵金属负载分子筛催化剂,本实施例催化剂命名为Pt/Pd-SSZ-13-Al。
如图3和图4所示,本实施例催化剂表现出优异的催化活性,CO和C3H6的起燃温度分别为175℃和180℃,相比商业Pt/Pd-Al2O3催化剂的起燃温度分别下降了35℃和55℃,在220℃左右,CO和C3H6的转化率超过90%。经过750℃老化16h后,如图5和图6所示,本实施例催化剂依然能够保持较好的反应性能,CO和C3H6的起燃温度略微上升至190℃和200℃,说明该催化剂具有优秀的稳定性,这是因为脱Al处理后的分子筛载体能够有效限制金属颗粒在高温下的烧结以及分子筛载体本身较强的骨架结构可以承受高温水热老化处理。在1.0mmol/gcatal的K化学中毒后,如图7和图8所示,本实施例催化剂的CO和C3H6的转化率基本没有变化,说明该催化剂有着较强的抗化学物质中毒能力,这是因为分子筛载体具有较大的比表面积和较强的酸性。对硫中毒后的本实施例催化剂,如图9和图10所示,在500℃下再生0.5h后,催化活性能够恢复至新鲜催化剂的性能,表现出较强的再生能力,这是因为分子筛载体的孔径较小,能够有效抑制硫酸盐物种在孔道内沉积,显著降低了催化剂的再生温度和时间。
在本发明更多的实施例中,贵金属还可以为Au、Ag、Rh或者Ru,也可采用多种贵金属混合,混合组份包括Pt、Pd、Au、Ag、Rh和Ru。
在本发明更多的实施例中,分子筛还可以为MOR、Beta、ZSM-5、SAPO-34、SAPO-18和SSZ-39,也可采用多种分子筛混合,混合组份包括MOR、Beta、ZSM-5、SSZ-13、SAPO-34、SAPO-18和SSZ-39。
本发明中,贵金属在催化剂中的含量以0.5~3wt.%为宜。
Claims (4)
1.一种DOC分子筛催化剂用于催化氧化柴油车尾气的用途,所述DOC分子筛催化剂以脱Si或脱Al后的分子筛作为载体,负载贵金属,所述分子筛为SSZ-13,其中:
脱Si处理的步骤如下:
将无机碱溶于去离子水中配制成浓度为0.05~2.0mol/L的碱液,按照(0.1~10)g:100mL的比例将分子筛与所得碱液混合,在25~70℃下搅拌0.5~6h,过滤洗涤后得到脱Si处理后的分子筛载体;
脱Al处理的步骤如下:
将分子筛放置于固定床反应器中,在水蒸气体积含量为2%的条件下,500~800℃水热老化6~18h,烘干后得到脱Al处理后的分子筛载体。
2.根据权利要求1所述的用途,其特征在于,所述贵金属为Pt、Pd、Au、Ag、Rh和Ru中的一种或几种。
3.根据权利要求1或2所述的用途,其特征在于,所述贵金属的质量分数为0.5~3wt.%。
4.根据权利要求1所述的用途,其特征在于,将所述催化剂涂敷在堇青石载体上,并置于柴油车尾气下游的DOC反应器中,消除柴油车尾气中CO、HCs和SOFs对环境的污染。
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