活性炭基Cu⁃Cr吸附剂的制备及脱COS性能的研究

doi:10.3969/j.issn.1006-396X.2022.01.009

摘要/Abstract

摘要：

采用等体积浸渍法制备了Cu?Cr改性活性炭吸附剂，以模拟焦炉气为原料，考察了不同过渡金属活性组分及其负载量、不同助剂及其负载量、焙烧温度对吸附剂脱除COS性能的影响，并采用XRD、BET、SEM等手段对Cu?Cr改性的吸附剂进行表征。结果表明，Cu和Cr共同改性的活性炭对焦炉煤气中COS的吸附性能最好。Cu?Cr改性活性炭吸附剂较佳制备条件为：Cu负载量为5.0%，Cr负载量为1.5%，焙烧温度为400 ℃。反应温度10 ℃的条件下，改性活性炭吸附剂的穿透硫容为1.47%，且该Cu?Cr改性活性炭吸附剂具有良好的再生利用性能。表征结果显示，CuO和 Cr₂O₃金属氧化物均匀负载于活性炭上，且失活后的吸附剂比表面积和孔容均减小。

关键词: 焦炉煤气, 吸附, 双金属, 改性活性炭, COS

Abstract:

Cu?Cr modified activated carbon adsorbent was prepared by equal volume impregnation method.Using simulated coke oven gas as testing material,the effects of different transition metal active components and their loadings,different additives and loadings,calcination temperature on the removal activity of COS were investigated.The Cu?Cr modified adsorbent was characterized by X?Ray Diffraction (XRD), specific surface area (BET) and scanning electron microscope (SEM). The results show that the activated carbon modified simultaneously by Cu and Cr has the best adsorption performance of COS for coke oven gas, and the optimized preparation conditions of Cu?Cr modified activated carbon adsorbent are as follows: Cu and Cr loading is 5.0%, and 1.5% respectively, calcination temperature is 400 ℃. When the reaction temperature is 10 ℃, the breakthrough sulfur capacity of the modified activated carbon adsorbent is 1.47%, and the Cu?Cr modified activated carbon adsorbent shows good recycling performance. The characterization results indicate that CuO and Cr₂O₃ metal oxides are uniformly loaded on the activated carbon, and the specific area and pore volume of the adsorbent decrease after deactivation.

Key words: Coke oven gas, Adsorption, Bimetallic, Modified activated carbon, COS

中图分类号:

TE624

周广林, 张钊, 刘世成, 李芹, 毕凤云, 郭修程, 张悦. 活性炭基Cu⁃Cr吸附剂的制备及脱COS性能的研究[J]. 石油化工高等学校学报, 2022, 35(1): 56-62.

Guanglin Zhou, Zhao Zhang, Shicheng Liu, Qin Li, Fengyun Bi, Xiucheng Guo, Yue Zhang. Preparation and Application of Activated Carbon Based Cu⁃Cr Adsorbent in Removing COS[J]. Journal of Petrochemical Universities, 2022, 35(1): 56-62.

图/表 12

表1 模拟焦炉煤气的组分与体积分数

Table 1 Composition and volume fraction of simulated coke oven gas

组分	体积分数/%
H₂	48
CH₄	26
CO	11
CO₂	8
N₂	4
C₂H₄	3

图1 单金属氧化物改性活性炭的穿透硫容

Fig.1 Breakthrough sulfur capacity of activated carbon modified by single metal oxide

图2 不同Cu负载量的Cu/Ac吸附剂的穿透硫容

Fig.2 Breakthrough sulfur capacity of Cu / Ac adsorbents with different Cu loading

图3 添加不同助剂的Cu/Ac吸附剂的穿透硫容

Fig.3 Breakthrough sulfur capacity of Cu / Ac adsorbents with different additives

图4 不同Cr负载量的Cu/Ac吸附剂的穿透硫容

Fig.4 Breakthrough sulfur capacity of Cu / Ac adsorbents with different Cr loading

图5 不同焙烧温度改性活性炭的COS吸附穿透曲线

Fig.5 COS adsorption breakthrough curve of modified activated carbon at different calcination temperatures

图6 吸附温度对COS的吸附影响

Fig.6 Effect of adsorption temperature on COS adsorption

图7 再生次数对改性活性炭的穿透硫容的影响

Fig.7 Effect of regeneration times on sulfur breakthrough capacity of modified activated carbon

图8 Ac、Cu?Cr/Ac穿透前后的SEM照片（a） Ac （b） Cu?Cr穿透前（c） Cu?Cr/Ac穿透后

Fig.8 SEM photos of Ac,Cu?Cr/Ac before and after sufer breakthrough

图9 Ac、Cu?Cr/Ac穿透前后的XRD谱图

Fig.9 XRD of Ac,Cu?Cr/Ac before and after sufer breakthrough

图10 Cu?Cr/Ac穿透前后高温吸附、脱附等温线

Fig.10 Isotherms of high temperature adsorption and desorption before and after penetration of Cu?Cr/Ac

表2 Cu?Cr/Ac 穿透前后的孔结构性质

Table 2 Pore structure properties of Cu?Cr/Ac before and after sufer breakthrough

吸附剂

比表面积/（m²

⋅

g^-1）

孔容/

（cm³ $⋅$ g^-1）