用于丙烷催化燃烧的PdxPty-ZSM-5/Cordierite整体式催化剂

doi:10.11949/j.issn.0438-1157.20181110

摘要/Abstract

摘要：

以ZSM-5分子筛、铝溶胶、硝酸钯、硝酸铂和水为原料制备分子筛浆料，采用真空抽提-一次涂覆法在堇青石蜂窝陶瓷载体表面制备出Pd_xPt_y-ZSM-5/Cordierite整体式催化剂，考察了Pd负载量、ZSM-5分子筛的硅铝比和Pd/Pt质量比对整体式催化剂的丙烷催化燃烧性能的影响，并用超声波振荡、SEM、XRD、H₂-TPR和C₃H₈-TPD等手段对整体式催化剂进行了表征。当球磨时间为60 min，分子筛浆料固含量为38%时，整体式催化剂的涂层上载量可达到178 g?L^-1，涂层脱落率低于0.5%。Pd₂Pt₃-ZSM-5/Cordierite整体式催化剂（贵金属总负载量为1.2 g?L^-1）对于丙烷的催化燃烧具有较好的催化活性（T₅₀=259℃，T₉₀=323℃）和稳定性，具有良好的工业应用前景，其中较低的ZSM-5分子筛硅铝比以及Pd和Pt之间的相互作用增加了对丙烷的吸附能力和表面活性氧物种的数量，从而提高了整体式催化剂的催化活性。

关键词: 丙烷, 催化燃烧, 真空抽提-一次涂覆法, 整体式催化剂, 分子筛浆料, 贵金属

Abstract:

Pd_xPt_y-ZSM-5/Cordierite monolithic catalysts were prepared on the surface of the cordierite honeycomb supports, via vacuum extraction and one coating method, in which ZSM-5 molecular sieve, alumina sol, platinum or palladium nitrates and water were used as raw materials to prepare molecular sieve slurry. Effects of Pd loading, Si/Al ratio of ZSM-5, the mass ratio of Pd/Pt on the catalytic performance of the monolithic catalysts for the catalytic combustion of propane were investigated. The monolithic catalysts were characterized by ultrasonic oscillation, SEM, XRD, H₂-TPR and C₃H₈-TPD. When the ball milling time is 60 min and the molecular sieve slurry solid content is 38%, the coating amount of the monolith catalyst can reach 178 g?L^-1, and the coating detachment rate is less than 0.5%. Pd₂Pt₃-ZSM-5/Cordierite catalyst (total loading of noble metals of 1.2 g?L^-1 ) exhibits better catalytic activity and stability (T₅₀=259℃, T₉₀=323℃) for the catalytic combustion of propane, which has better industrial application prospect. Lower Si/Al ratio of ZSM-5 and the interaction between Pd and Pt increase the amounts of adsorbed propane and surface active oxygen species, thus increases the catalytic performance of the monolithic catalyst.

Key words: propane, catalytic combustion, vacuum extraction and one coating method, monolithic catalyst, molecular sieves slurry, noble metals

中图分类号:

TE 991.1

唐铨, 郭杨龙, 詹望成, 郭耘, 王丽, 王筠松. 用于丙烷催化燃烧的Pd_xPt_y-ZSM-5/Cordierite整体式催化剂[J]. 化工学报, 2019, 70(3): 944-950.

Quan TANG, Yanglong GUO, Wangcheng ZHAN, Yun GUO, Li WANG, Yunsong WANG. Catalytic combustion of propane over Pd_xPt_y-ZSM-5/Cordierite monolithic catalyst[J]. CIESC Journal, 2019, 70(3): 944-950.

图/表 11

表1 不同球磨时间处理的浆料的涂覆效果比较

Table 1 Effect of milling time for slurry on washcoat performance

球磨时间/min	黏度/(mPa·s)	平均粒径/μm	上载量/(g?L^-1)	脱落率/%
0	84	5.6	73	3.6
30	264	3.3	168	0.2
60	378	3.2	178	0.5
90	439	3.5	198	3.5
150	523	3.4	210	5.3

图1 浆料固含量对涂层上载量和脱落率的影响

Fig.1 Effect of solid content of slurry on loading and mass loss of washcoat

图2 Pd负载量对整体式催化剂催化活性的影响

Fig.2 Effect of Pd loading on catalytic activity of monolith catalysts

图3 ZSM-5硅铝比对整体式催化剂催化活性的影响

Fig.3 Effect of Si/Al ratio of ZSM-5 on catalytic activity of monolith catalysts

图4 Pd/Pt质量比对整体式催化剂催化活性的影响

Fig.4 Effect of mass ratio of Pd/Pt on catalytic activity of monolithic catalysts

表2 Pd/Pt质量比对整体式催化剂催化活性的影响

Table 2 Effect of mass ratio of Pd/Pt on catalytic activity of monolithic catalysts

催化剂	T₅₀/℃	T₉₀ /℃
Pd-ZSM-5/Cordierite	302	342
Pd₄Pt₁-ZSM-5/Cordierite	337	383
Pd₂Pt₃-ZSM-5/Cordierite	259	323
Pd₃Pt₂-ZSM-5/Cordierite	293	337
Pd₁Pt₄-ZSM-5/Cordierite	301	374
Pt-ZSM-5/Cordierite	319	403

图5 整体式催化剂的XRD谱图

Fig.5 XRD patterns of monolith catalysts

图6 整体式催化剂H2-TPR谱图

Fig.6 H2-TPR profiles of monolith catalysts

图7 整体式催化剂的C3H8-TPD谱图

Fig.7 C3H8-TPD profiles of monolith catalysts

图8 堇青石载体和分子筛涂层的SEM图

Fig.8 SEM images of cordierite support and ZSM-5 washcoat

图9 在400℃下整体式催化剂的稳定性

Fig.9 Stability of monolith catalyst at 400℃

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