Moderate temperature COS hydrolysis activity of γ-Al2O3 based catalyst modified by TiO2

doi:10.16085/j.issn.1000-6613.2017-2296

Abstract

Abstract: Catalytic hydrolysis of COS at moderate temperature is one of the keys to achieve fine desulfurization and purification of gas. Although the addition of TiO₂ can obviously improve the sulfate resistance of the γ-Al₂O₃ based catalyst at low temperature, the influence of physical and chemical properties of TiO₂ on the catalytic activity of COS is crucial for the preparation of COS hydrolysis catalysts at moderate temperature. Therefore, two kinds of COS hydrolysis catalysts at moderate temperature were modified by commercial TiO₂ or nanometer TiO₂ which was prepared by chemical precipitation. In a fixed bed, the effects of temperature, space velocity, COS inlet concentration, and the changes in O₂ atmosphere on the COS hydrolysis conversion were investigated. Using XRD, BET and CO₂-TPD and other characterization means, we characterized the physical and chemical properties of the prepared catalysts, and analyzed the relationship between the properties and the catalytic activity of catalysts. The results show that the COS hydrolysis reactions with the two kinds of catalysts at moderate temperature (150-350℃) are both first order, and the COS conversion is as high as 97% when temperature is 300℃ and space velocity is 9000h^-1; The γ-Al₂O₃ based catalyst modified by nanometre TiO₂ has a good pore structure that is advantageous to decrease the internal diffusion resistance, and is beneficial to the mass transfer and desorption of H₂SThe γ-Al₂O₃ based catalyst modified by nanometer. TiO₂ has good stability in the O₂ atmosphere and therefore it has resistance to oxygen poisoning. The anatase-TiO₂ can obviously enhance the anti-oxygen poisoning ability of the catalysts at moderate temperature.

Key words: moderate temperature, COS hydrolysis, catalyst, TiO₂ modification, reactivity

摘要： 中温催化水解羰基硫（COS）是实现气体精细脱硫净化的关键之一。虽然TiO₂的加入可以明显提升γ-Al₂O₃基低温COS水解催化剂的抗硫酸盐中毒性能，但探讨TiO₂物化性质对COS催化水解活性的影响将对制备中温COS水解催化剂至关重要。因此，分别添加商用TiO₂或通过化学沉淀法获得的纳米TiO₂制备出两类TiO₂改性γ-Al₂O₃基中温COS水解催化剂。在固定床装置上，考察了两类催化剂的COS水解转化率随空速、温度、COS进口浓度等因素的变化规律及随O₂存在的气氛效应，并且通过XRD、BET和CO₂-TPD等手段表征了催化剂的物化性质，分析了催化剂物化性质与催化水解活性之间的关系。研究结果表明：两类催化剂的中温（150~350℃）水解COS反应呈一级，在300℃、9000h^-1时，COS水解转化率高达97%以上；TiO₂改性γ-Al₂O₃基催化剂具有良好的孔隙结构，降低了内扩散阻力，有利于COS水解产物H₂S的传质，即H₂S的脱附；化学沉淀法获得的纳米TiO₂改性γ-Al₂O₃基催化剂在含O₂气氛中水解转化率稳定性较好，具有一定的抗氧中毒能力，这表明锐钛矿型TiO₂能更明显提升催化剂的抗氧中毒能力。

关键词: 中温, 羰基硫水解, 催化剂, TiO₂改性, 活性

CLC Number:

TQ09

LIU Yanxia, SHANGGUAN Ju, WANG Zexin, XU Yikun, LIN Long. Moderate temperature COS hydrolysis activity of γ-Al₂O₃ based catalyst modified by TiO₂[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3885-3894.

刘艳霞, 上官炬, 王泽鑫, 徐壹堃, 蔺隆. TiO₂改性γ-Al₂O₃基催化剂的中温水解羰基硫活性[J]. 化工进展, 2018, 37(10): 3885-3894.

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Moderate temperature COS hydrolysis activity of γ-Al₂O₃ based catalyst modified by TiO₂

TiO₂改性γ-Al₂O₃基催化剂的中温水解羰基硫活性

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