Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation

doi:10.11949/j.issn.0438-1157.20190570

Abstract

Abstract:

In this work, the effect of support materials on the kinetic behaviors of indium-based catalysts in carbon dioxide hydrogenation was studied. A series of supported indium-based catalysts were prepared and tested. Only group ⅣB metal (Ti, Zr and Hf) oxide supported indium-based catalysts had substantial catalytic activity. Particularly, In₁/HfO₂ and In₁/ZrO₂ catalysts showed high methanol selectivity, while In₁/TiO₂ mainly catalyzed the reverse water-gas shift reaction. Steady-state kinetics, in-situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed experiments indicate that the key surface reaction intermediate over In₁/HfO₂ and In₁/ZrO₂are formate and methoxy species, and methanol is produced via stepwise hydrogenation of the surface formate. In₁/HfO₂ possesses the strongest hydrogen splitting and hydrogenation ability, thus favoring methanol synthesis. Over In₁/TiO₂, no significant surface carbonaceous species was detected under reaction conditions. The improved CO production might be related to interfacial oxygen defects facilitating the redox cycle and decomposition of formate intermediate.

Key words: carbon dioxide, catalysts, kinetics, methanol synthesis, in-situ DRIFTS, temperature-programed experiments

摘要：

探讨了载体对铟基催化剂上CO₂加氢动力学的影响。通过浸渍法制备了不同载体的负载型In基催化剂，仅ⅣB族元素（Ti,Zr,Hf）氧化物负载的In基催化剂表现出明显的CO₂加氢活性，其中In₁/HfO₂和In₁/ZrO₂催化剂具有较高的甲醇选择性，而In₁/TiO₂催化剂主要起催化逆水气变换反应的作用。通过稳态动力学、高压原位漫反射红外和程序升温实验等动力学手段，证明反应条件下In₁/ZrO₂和In₁/HfO₂上的关键表面反应中间体是甲酸盐与甲氧基，甲醇主要通过表面甲酸盐的逐步加氢生成。In₁/HfO₂具有最强的氢解离与加氢能力，因此最有利于甲醇合成。In₁/TiO₂在CO₂加氢中表面无明显含碳中间物种，高CO选择性可能与界面氧空缺位点促进redox循环以及甲酸盐中间体分解相关。

关键词: 二氧化碳, 催化剂, 动力学, 甲醇合成, 原位红外, 程序升温实验

CLC Number:

TQ 018

Chenxi CAO, Tianyuan CHEN, Xiaoxu DING, Hai HUANG, Jing XU, Yifan HAN. Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation[J]. CIESC Journal, 2019, 70(10): 3985-3993.

曹晨熙, 陈天元, 丁晓旭, 黄海, 徐晶, 韩一帆. 负载型铟基催化剂二氧化碳加氢动力学研究[J]. 化工学报, 2019, 70(10): 3985-3993.

Figures/Tables 7

Table 1 Performance of supported indium-based catalysts with different supports

Catalysts	Conversion/ %	Selectivity/%
Catalysts	Conversion/ %	MeOH	CO
In₁/TiO₂	10.3	5.4	94.6
In₁/ZrO₂	3.0	57.3	42.7
In₁/HfO₂	2.0	72.0	27.0
In₁/Y₂O₃	0.17	40.2	59.7
In₁/Al₂O₃	0.90	33.0	67.0
In₁/Nb₂O₅	0.13	31.5	68.5
In₁/CeO₂	NA	NA	NA
In₁/MgO	NA	NA	NA
In₁/ZnO	NA	NA	NA
In₁/SiO₂	NA	NA	NA

Fig.1 Methanol (MeOH) and CO STY of In1/MO2 at different temperatures

Fig.2 Arrhenius plots for methanol (MeOH) and CO formation over In1/MO2 catalysts

Fig.3 Dependence of methanol (MeOH) and CO formation rates on H2 and CO2 partial pressures over In1/MO2 (M=Ti, Zr, Hf)

Fig.4 High pressure in-situ DRIFT spectra of In1/TiO2 and In1/ZrO2

Fig.5 High pressure in-situ DRIFT spectra of In0.1/HfO2 and In0.1/HfO2 catalysts

Fig.6 CO2 + H2 TPSR-MS and formic acid TPD-MS profiles of In1/MO2 catalysts and MO2 supports

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