无铬中变催化剂中铈的助催化作用及YBa_2Cu_3O_(7-δ)对甲苯的催化氧化
摘要
本论文由两部分组成。
第一部分主要讨论了铈对无铬中变催化剂的影响。目前在CO变换
反应中铁铬系催化剂一直是最常用的催化剂。但由于铬氧化物有剧毒而
且价格昂贵，限制了它在工业上的应用，人们越来越注重能够替代铬的
助剂的研究。通过XRD，TPR，SEM和GC等手段的研究，结果发现：水
在含铈氧化铁样品表面的吸附符合焦姆金方程。铈的加入降低了水在样
品表面的吸附热，从而使反应活性增加。在还原过程中，铈有细化颗粒
的作用和表面富集现象，从而使初始还原温度降低而还原结束温度升
高。
第二部分研究了以YBa_2Cu_3O_(7-δ)作催化剂对甲苯的催化燃烧。
YBa_2Cu_3O_(7-δ)作为一种高温超导体，它不仅具有导电性和磁性，而且本身
对氧化反应固有的催化特性，引起科研工作者的广泛兴趣。YBa_2Cu_3O_(7-δ)
即可以用作轻度氧化催化剂，与碳氢化合物作用，产生用途广泛的工业
品；而且能充当深度氧化的催化剂，有效地消除有机废气对环境的污染。
在甲苯的氧化燃烧反应中，YBa_2Cu_3O_(7-δ)具有较高的催化活性和热稳定
性，并且与贵金属催化剂相比，成本相当低。基于以上所提原因，
YBa_2Cu_3O_(7-δ)是一种颇具发展前景的氧化催化剂。
Abstract
This dissertation consists two sections.
The first section mainly dissusses about the effects of ceria
in non梒hromia iron based CO high temperature shift catalyst.
Currently, chromia iron based catalyst is still the most common in
the water梘as shift reaction. But the poisonousness and the
prohibitive material price of the chromia hold back the path leading
to the industrial application. To solve the problems mentioned
above, the research on the Fe~O.3桟eO~ catalyst was carried out. By
XRD, TPR, SEM, XPS and GC, the experimental results show that the
adsorption of water on the surface of ceria梒ontaining Fe203
catalyst obeys Temkin Equation. When the ceria is added in, the
adsorption heat of water on the surface of catalyst decreases,
therefore, the catalytic activity is improved greatly. It has also
been found that ceria can refine Fe20.3 grains and is riched on the
surface of catalyst in the process of reduction, which lead to a
decrease of the initial reductive temperature and an increase of
the final reductive temperature.
In the second section, the catalytic activity of YBa2Cu3O-~
for toluene combustion has been investigated. YBa2Cu30-8, known as
high桾e superconductor, has recently gathered great attention, not
only due to its electric and megnetie characteristics but also due
to its intrinsic catalytic activity for oxidation. YBa,Cu3O~ can
2
work as both mild and deep oxidation catalysts,whieh is used to
produce a wide range of industrial chemicals from hydrocarbons and
is becoming important in the cleaning of emissions from combustion
of carbonaceous fuels. In the complete oxidation of toluene,
Y
YBa0Cu;30> ~ exhibits high catalytic activity and high thermal
stability. Compared with nobel metal catalysts, YBa2Cu3O-8also has
remarkable lower material cost. With the advantages mentioned above,
YBa-,Cu30.-8 could become a more promising catalyst of oxidation.
第一部分主要讨论了铈对无铬中变催化剂的影响。目前在CO变换
反应中铁铬系催化剂一直是最常用的催化剂。但由于铬氧化物有剧毒而
且价格昂贵，限制了它在工业上的应用，人们越来越注重能够替代铬的
助剂的研究。通过XRD，TPR，SEM和GC等手段的研究，结果发现：水
在含铈氧化铁样品表面的吸附符合焦姆金方程。铈的加入降低了水在样
品表面的吸附热，从而使反应活性增加。在还原过程中，铈有细化颗粒
的作用和表面富集现象，从而使初始还原温度降低而还原结束温度升
高。
第二部分研究了以YBa_2Cu_3O_(7-δ)作催化剂对甲苯的催化燃烧。
YBa_2Cu_3O_(7-δ)作为一种高温超导体，它不仅具有导电性和磁性，而且本身
对氧化反应固有的催化特性，引起科研工作者的广泛兴趣。YBa_2Cu_3O_(7-δ)
即可以用作轻度氧化催化剂，与碳氢化合物作用，产生用途广泛的工业
品；而且能充当深度氧化的催化剂，有效地消除有机废气对环境的污染。
在甲苯的氧化燃烧反应中，YBa_2Cu_3O_(7-δ)具有较高的催化活性和热稳定
性，并且与贵金属催化剂相比，成本相当低。基于以上所提原因，
YBa_2Cu_3O_(7-δ)是一种颇具发展前景的氧化催化剂。
Abstract
This dissertation consists two sections.
The first section mainly dissusses about the effects of ceria
in non梒hromia iron based CO high temperature shift catalyst.
Currently, chromia iron based catalyst is still the most common in
the water梘as shift reaction. But the poisonousness and the
prohibitive material price of the chromia hold back the path leading
to the industrial application. To solve the problems mentioned
above, the research on the Fe~O.3桟eO~ catalyst was carried out. By
XRD, TPR, SEM, XPS and GC, the experimental results show that the
adsorption of water on the surface of ceria梒ontaining Fe203
catalyst obeys Temkin Equation. When the ceria is added in, the
adsorption heat of water on the surface of catalyst decreases,
therefore, the catalytic activity is improved greatly. It has also
been found that ceria can refine Fe20.3 grains and is riched on the
surface of catalyst in the process of reduction, which lead to a
decrease of the initial reductive temperature and an increase of
the final reductive temperature.
In the second section, the catalytic activity of YBa2Cu3O-~
for toluene combustion has been investigated. YBa2Cu30-8, known as
high桾e superconductor, has recently gathered great attention, not
only due to its electric and megnetie characteristics but also due
to its intrinsic catalytic activity for oxidation. YBa,Cu3O~ can
2
work as both mild and deep oxidation catalysts,whieh is used to
produce a wide range of industrial chemicals from hydrocarbons and
is becoming important in the cleaning of emissions from combustion
of carbonaceous fuels. In the complete oxidation of toluene,
Y
YBa0Cu;30> ~ exhibits high catalytic activity and high thermal
stability. Compared with nobel metal catalysts, YBa2Cu3O-8also has
remarkable lower material cost. With the advantages mentioned above,
YBa-,Cu30.-8 could become a more promising catalyst of oxidation.
引文
[1]张洪全等，一氧化碳变换反应无铬中变催化剂研制进展，化工部第二届催化剂交流会论文，1986，苏州
[2]南京大学化学系催化教研室，南京化学工业公司催化剂厂，一氧化碳中温变换催化剂．北京，化学工业出版社，1979
[3]Chcmical Abstracts 78:P20728g;84:141185k;77:P224338;78:P89094g;78:102424u;82:606716;81:17212r;
[4]姜圣阶等，合成氨工业，第二卷，北京，石油化学工业出版社，1978
[5]霍包根，淡世韶，梁生兆，SXB低铬稀土中变催化剂的研制，化肥与催化，1989，(3)：2
[6]郑起，徐建本，魏可镁，无铬CO高温变换催化剂的研究，催化学报，1998，19(6)
[7]杨顺利等，环境科学与保护，1986，(4)：49
[8]柴之芳等，环境科学，1978，(3)：47
[9]周灵萍等，Preparation and characterization of a high temperature water-gas shift catalyst, 催化学报,1996,17,(5):394
[10]嵇世山，李增喜，谭瑞琴等，无铬CO高温变换催化剂的研究，催化学报，1999，20(1)
[11]李室文，催化剂研究方法(四)，石油化工，1980，9(6)：376
[12]黄开辉，万惠霖，催化原理，科学出版社，北京，1983：417
[13]Nicholas A. Katsanas, et al., Thermodynamics of adsorption based on gas-solid chromatography. J. chem. Soc. Faraday Trans. Ⅰ,1978,74(3):575
[14]林伟忠，脉冲色谱法研究催化剂表面可逆吸附中心的强度和数目，石油化工，1983，12(2)：74
[15]徐杰，王文祥，马福勤，氧化铁(Ⅲ)还原动力学研究，物理化学学报，1988，4(3)：332
[16]郭益群等，无铬中变催化剂的研究，郑州大学学报，1996，28(3)：81
[17]卢冠中，汪仁，氧化铈在非贵金属氧化物催化剂中的作用，中国稀土学报，1999，17(3)：213
[2]南京大学化学系催化教研室，南京化学工业公司催化剂厂，一氧化碳中温变换催化剂．北京，化学工业出版社，1979
[3]Chcmical Abstracts 78:P20728g;84:141185k;77:P224338;78:P89094g;78:102424u;82:606716;81:17212r;
[4]姜圣阶等，合成氨工业，第二卷，北京，石油化学工业出版社，1978
[5]霍包根，淡世韶，梁生兆，SXB低铬稀土中变催化剂的研制，化肥与催化，1989，(3)：2
[6]郑起，徐建本，魏可镁，无铬CO高温变换催化剂的研究，催化学报，1998，19(6)
[7]杨顺利等，环境科学与保护，1986，(4)：49
[8]柴之芳等，环境科学，1978，(3)：47
[9]周灵萍等，Preparation and characterization of a high temperature water-gas shift catalyst, 催化学报,1996,17,(5):394
[10]嵇世山，李增喜，谭瑞琴等，无铬CO高温变换催化剂的研究，催化学报，1999，20(1)
[11]李室文，催化剂研究方法(四)，石油化工，1980，9(6)：376
[12]黄开辉，万惠霖，催化原理，科学出版社，北京，1983：417
[13]Nicholas A. Katsanas, et al., Thermodynamics of adsorption based on gas-solid chromatography. J. chem. Soc. Faraday Trans. Ⅰ,1978,74(3):575
[14]林伟忠，脉冲色谱法研究催化剂表面可逆吸附中心的强度和数目，石油化工，1983，12(2)：74
[15]徐杰，王文祥，马福勤，氧化铁(Ⅲ)还原动力学研究，物理化学学报，1988，4(3)：332
[16]郭益群等，无铬中变催化剂的研究，郑州大学学报，1996，28(3)：81
[17]卢冠中，汪仁，氧化铈在非贵金属氧化物催化剂中的作用，中国稀土学报，1999，17(3)：213