Cr基催化剂上VOCs催化氧化性能研究
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摘要
催化燃烧是一种能耗低、处理效率高的有机废气(VOCs)治理方法,该法因设备简单,不易形成NOx二次污染等优点在当前VOCs处理技术中备受关注。其中催化剂是VOCs催化燃烧技术的核心。含氯有机废气是较难处理的一类废气,目前报道的含氯有机废气净化催化剂需要的反应温度较高、而且使用寿命较短,因此迫切需要提高催化剂的性能。对于含氯有机废气的处理,通常采用Cr基催化剂。Cr基催化剂对含氯有机废气有较高的催化性能,但是对碳氢化合物有机废气的催化性能却不高。然而工业排放废气往往是多种VOCs同时存在,即除了含氯有机物外,还有芳烃、酯、醇等。因此,开发对含氯有机物、含氧烃和芳烃有机物均具有高催化性能的催化剂,以满足工业有机废气处理的需要,是本论文的研究目标。获得如下研究结果：
1.采用沉积沉淀法制备了不同Cr含量的CrOx/ZrO2催化剂,并考察了该催化剂对CH4氧化的催化性能。实验结果表明,催化剂中Cr物种以晶相Cr2O3形式存在,而载体ZrO2以单斜相为主。随着焙烧温度升高,催化剂中ZrO2和Cr2O3的晶粒明显增大。Cr2O3和ZrO2之间的相互作用使得双组分CrOx/ZrO2催化剂的比表面积大于相应的单组份催化剂。催化剂对CH4氧化性能随着Cr含量的提高而增强,Cr含量20%时催化剂的活性最高,CH4完全转化温度为450℃。进一步增加Cr含量催化活性下降是由于Cr2O3晶粒增大的缘故。
2.通过对CrOx/Al2O3催化剂的XRD和Raman表征,发现催化剂中大部分的Cr物种以晶相Cr2O3形式存在,少量以非晶相或高分散的高价态形式存在。催化剂对CH2Cl2的催化反应结果显示,Cr含量为20%时催化剂表现出较高的氧化活性和反应稳定性,CH2Cl2的完全转化温度为350℃。从NH3-TPD表征结果可知,Cr负载增加的同时提高了催化剂的表面酸性,而且负载20%Cr使表面酸性增加量最大。综合活性测试和表征结果,我们认为催化剂中高价态Cr物种是催化氧化CH2Cl2的活性相,且催化剂表面酸中心有利于CH2Cl2的氧化。
3.通过对照CrOx-ZrO2、Pd/ZrO2和Pd/CrOx-ZrO2催化剂对CH2Cl2、乙酸乙酯和甲苯的催化性能和表征结果,发现CrOx-ZrO2对CH2C12和乙酸乙酯的氧化性能高于对甲苯的氧化性能,而Pd/ZrO2对甲苯表现出较好的氧化性能；双组份Pd/CrOx-ZrO2催化剂对三种反应物都表现出较高的催化性能。BET测试和NH3-TPD表征结果显示,Pd和Cr的添加增大了催化剂的比表面积,提高了催化剂的表面酸性。这可能是Pd/CrOx-ZrO2表现较高催化效果的原因。此外,Pd/CrOx-ZrO2具有较好的反应稳定性。
Among technologies for elimination of volatile organic compounds (VOCs) emissions, catalytic combustion has been paid much attention because of its low energy consumption, high efficiency and simple equipment. Moreover, there is no associated pollution such as nitrogen oxides (NOX) production, as it is operated at low temperature. A catalyst with high activity is the key to catalytic combustion. Among the catalysts for chlorinated volatile organic compounds (CVOCs) catalytic combustion, most reports focus on the chromium-based catalysts. However, the Cr-based catalysts usually need high operation temperature and have short service life, so catalysts with high activity and thermal stability are therefore desirable. The chromium-based catalysts are more active for CVOCs abatement than for hydrocarbon. Since the industrial exhaust gases usually contain various kinds of VOCs, such as CVOCs, aromatic, ester, et al, a multi-functional catalyst was developed with the chromium-based catalyst supported Pd, which is effective for CVOCs, oxygenated and aromatic compounds. The detailed contents of this thesis are as follows:
1. A series of CrOx/ZrO2 catalysts were prepared by a deposition-precipitation method, and tested for CH4 catalytic oxidation. The XRD results indicated that the chromium species were in form of Cr2O3, while the support ZrO2 was monoclinic, and the crystallite sizes of Cr2O3 and ZrO2 increased with increasing calcination temperature. The cooperation of Cr2O3 and ZrO2 resulted in an increase of the surface area of CrOx/ZrO2 catalysts. It was also found that enhanced activity was obtained on the catalyst with high Cr content, but further increasing Cr content resulted in a suppressed activity. This was due to the increasing amount of active sites with increasing Cr content, but higher Cr content led to larger crystallite of Cr2O3.
2. CrOx/Al2O3 samples were characterized using XRD and Raman techniques. It was found that most of the chromium species were in form of crystalline Cr2O3, and some was in form of high oxidation state. The activities of different catalysts for catalytic combustion of dichloromethane were tested, and the results indicated that the catalyst with 20% Cr loading gave the highest reactivity and high thermal stability, with a complete dichloromethane oxidation temperature of 350℃. The NH3-TPD results showed that the increasing Cr loadings enhanced the strength of the acid sites, which reached a maximum on the catalyst with 20% Cr loading. All the results suggested the high oxidation state Cr species may be the active phase, and the acid sites were in favor of the reaction.
3. CrOx-ZrO2, Pd/ZrO2 and Pd/CrOx-ZrO2 samples were tested for catalytic combustion of dichloromethane, ethyl acetate and toluene. It was found that the CrOx-ZrO2 catalyst exhibited better activity for catalytic combustion of ethyl acetate and dichloromethane than for toluene, while the Pd/ZrO2 catalyst gave good activity in catalytic combustion of toluene. By adding Pd to the CrOx-ZrO2 catalysts, the reactivity of the catalysts was enhanced. The dual-component catalyst Pd/CrOx-ZrO2 exhibited fairly good activity for catalytic combustion of all the three reactants. The BET and NH3-TPD results indicated that the addition of Pd and Cr increased the specific surface area of the catalyst and the strength of the acid sites, which may improve the activity of the CrOx-ZrO2 catalysts. Also the Pd/CrOx-ZrO2 catalyst showed high thermal stability in the reaction.
1.采用沉积沉淀法制备了不同Cr含量的CrOx/ZrO2催化剂,并考察了该催化剂对CH4氧化的催化性能。实验结果表明,催化剂中Cr物种以晶相Cr2O3形式存在,而载体ZrO2以单斜相为主。随着焙烧温度升高,催化剂中ZrO2和Cr2O3的晶粒明显增大。Cr2O3和ZrO2之间的相互作用使得双组分CrOx/ZrO2催化剂的比表面积大于相应的单组份催化剂。催化剂对CH4氧化性能随着Cr含量的提高而增强,Cr含量20%时催化剂的活性最高,CH4完全转化温度为450℃。进一步增加Cr含量催化活性下降是由于Cr2O3晶粒增大的缘故。
2.通过对CrOx/Al2O3催化剂的XRD和Raman表征,发现催化剂中大部分的Cr物种以晶相Cr2O3形式存在,少量以非晶相或高分散的高价态形式存在。催化剂对CH2Cl2的催化反应结果显示,Cr含量为20%时催化剂表现出较高的氧化活性和反应稳定性,CH2Cl2的完全转化温度为350℃。从NH3-TPD表征结果可知,Cr负载增加的同时提高了催化剂的表面酸性,而且负载20%Cr使表面酸性增加量最大。综合活性测试和表征结果,我们认为催化剂中高价态Cr物种是催化氧化CH2Cl2的活性相,且催化剂表面酸中心有利于CH2Cl2的氧化。
3.通过对照CrOx-ZrO2、Pd/ZrO2和Pd/CrOx-ZrO2催化剂对CH2Cl2、乙酸乙酯和甲苯的催化性能和表征结果,发现CrOx-ZrO2对CH2C12和乙酸乙酯的氧化性能高于对甲苯的氧化性能,而Pd/ZrO2对甲苯表现出较好的氧化性能；双组份Pd/CrOx-ZrO2催化剂对三种反应物都表现出较高的催化性能。BET测试和NH3-TPD表征结果显示,Pd和Cr的添加增大了催化剂的比表面积,提高了催化剂的表面酸性。这可能是Pd/CrOx-ZrO2表现较高催化效果的原因。此外,Pd/CrOx-ZrO2具有较好的反应稳定性。
Among technologies for elimination of volatile organic compounds (VOCs) emissions, catalytic combustion has been paid much attention because of its low energy consumption, high efficiency and simple equipment. Moreover, there is no associated pollution such as nitrogen oxides (NOX) production, as it is operated at low temperature. A catalyst with high activity is the key to catalytic combustion. Among the catalysts for chlorinated volatile organic compounds (CVOCs) catalytic combustion, most reports focus on the chromium-based catalysts. However, the Cr-based catalysts usually need high operation temperature and have short service life, so catalysts with high activity and thermal stability are therefore desirable. The chromium-based catalysts are more active for CVOCs abatement than for hydrocarbon. Since the industrial exhaust gases usually contain various kinds of VOCs, such as CVOCs, aromatic, ester, et al, a multi-functional catalyst was developed with the chromium-based catalyst supported Pd, which is effective for CVOCs, oxygenated and aromatic compounds. The detailed contents of this thesis are as follows:
1. A series of CrOx/ZrO2 catalysts were prepared by a deposition-precipitation method, and tested for CH4 catalytic oxidation. The XRD results indicated that the chromium species were in form of Cr2O3, while the support ZrO2 was monoclinic, and the crystallite sizes of Cr2O3 and ZrO2 increased with increasing calcination temperature. The cooperation of Cr2O3 and ZrO2 resulted in an increase of the surface area of CrOx/ZrO2 catalysts. It was also found that enhanced activity was obtained on the catalyst with high Cr content, but further increasing Cr content resulted in a suppressed activity. This was due to the increasing amount of active sites with increasing Cr content, but higher Cr content led to larger crystallite of Cr2O3.
2. CrOx/Al2O3 samples were characterized using XRD and Raman techniques. It was found that most of the chromium species were in form of crystalline Cr2O3, and some was in form of high oxidation state. The activities of different catalysts for catalytic combustion of dichloromethane were tested, and the results indicated that the catalyst with 20% Cr loading gave the highest reactivity and high thermal stability, with a complete dichloromethane oxidation temperature of 350℃. The NH3-TPD results showed that the increasing Cr loadings enhanced the strength of the acid sites, which reached a maximum on the catalyst with 20% Cr loading. All the results suggested the high oxidation state Cr species may be the active phase, and the acid sites were in favor of the reaction.
3. CrOx-ZrO2, Pd/ZrO2 and Pd/CrOx-ZrO2 samples were tested for catalytic combustion of dichloromethane, ethyl acetate and toluene. It was found that the CrOx-ZrO2 catalyst exhibited better activity for catalytic combustion of ethyl acetate and dichloromethane than for toluene, while the Pd/ZrO2 catalyst gave good activity in catalytic combustion of toluene. By adding Pd to the CrOx-ZrO2 catalysts, the reactivity of the catalysts was enhanced. The dual-component catalyst Pd/CrOx-ZrO2 exhibited fairly good activity for catalytic combustion of all the three reactants. The BET and NH3-TPD results indicated that the addition of Pd and Cr increased the specific surface area of the catalyst and the strength of the acid sites, which may improve the activity of the CrOx-ZrO2 catalysts. Also the Pd/CrOx-ZrO2 catalyst showed high thermal stability in the reaction.
引文
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