活性炭改性对催化剂脱砷性能的影响

doi:10.16085/j.issn.1000-6613.2020-1311

摘要/Abstract

摘要：

以K₂CO₃对活性炭进行化学改性，考察K₂CO₃加入量对活性炭比表面积、孔容及孔径等物化性质的影响。随K₂CO₃与活性炭质量比（碱炭比）的增大，活性炭的比表面积呈现先增加后减小的趋势。当碱炭比为6∶1时，活性炭比表面积由初始的653.3m²/g上升至1333.6m²/g。以小分子砷化物三乙胂和大分子砷化物三苯基胂为模型化合物，配制高砷催化裂化汽油，测定催化剂的砷容和脱砷效率。实验结果表明，改性后的催化剂具有丰富的中孔-大孔多级孔结构，表现出更加优异的脱砷性能：微孔保证催化剂具有大的比表面积，使得活性组分能够高效分散；中孔-大孔有利于液态石油烃介质的扩散，从而增大砷化物与活性相的作用，提高催化剂脱砷效率。

关键词: 活性炭, 碳酸钾改性, 吸附, 载体, 催化剂

Abstract:

The activated carbon (AC) was chemically modified by K₂CO₃, and the specific surface area, pore volume and pore size of the AC after modification were investigated. As the mass ratio of K₂CO₃ to AC (alkali-carbon ratio) increased, the specific surface area of the modified AC showed a trend of increasing first and then decreasing. When the ratio of alkali to carbon was 6, the specific surface area of the modified AC increased from the initial 653.3m²/g to 1333.6m²/g. The modified AC was then used as the support to prepare an adsorption catalyst for arsenic removal, which exhibited excellent arsenic adsorption owing to the multi-level pore channels composed of micropore-mesopores. The micropore ensured the catalyst with a large specific surface area, so the active components can be efficiently dispersed on it, while the mesopore allowed the macromolecular arsenide to fully contact and react with the active metal components, and thus improved arsenic removal efficiency.

Key words: activated carbon, modification by potassium carbonate (K₂CO₃), adsorption, support, catalyst

中图分类号:

TE624

冯琪, 姜增琨, 李阳, 鞠雅娜, 赵秦峰, 李天舒, 钟海军, 葛少辉. 活性炭改性对催化剂脱砷性能的影响[J]. 化工进展, 2021, 40(6): 3215-3223.

FENG Qi, JIANG Zengkun, LI Yang, JU Ya’na, ZHAO Qinfeng, LI Tianshu, ZHONG Haijun, GE Shaohui. Effect of activated carbon modification on the catalyst for adsorption removal of arsenic[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3215-3223.

图/表 12

表1 石油烃中的典型砷化物及其沸点

砷化物	分子式	沸点/℃
砷化氢（胂）	AsH₃	-55
甲胂	CH₃AsH₂	2
二甲胂	（CH₃）₂AsH	35.6（100^①）
乙胂	C₂H₅AsH₂	36
三甲胂	（CH₃）₃As	52（98^②）
三乙胂	（C₂H₅）₃As	140（98^③）
二苯基甲胂	（C₆H₅）₂AsH	161（3^④）
三苯基胂	（C₆H₅）₃As	360

图1 碱炭比对活化产品收率的影响

图2 纯活性炭及活化后产品在77K下的氮气吸附-脱附等温线

图3 碱炭比对活化产品比表面积的影响

图4 碱炭比对活化产品孔径分布的影响

图5 碱炭比对活化产品大孔孔容的影响

图6 未活化及活化后产品的XRD谱图

图7 未活化及活化后产品的SEM表征

图8 AC/CuO、KAC2/CuO、KAC6/CuO和KAC8/CuO的XRD谱图

表2 吸附脱砷催化剂物化性质

催化剂	比表面积/m²·g^-1	中孔容积/mL·g^-1	孔径（BET测试方法）/nm	孔径（压汞测试方法）/nm
AC/CuO	506.8	0.358	4.105	389.0
KAC2/CuO	633.5	0.425	5.729	366.1
KAC6/CuO	928.2	0.533	7.570	624.7
KAC8/CuO	1266.7	0.730	10.422	1100.4

图9 反应时间对三乙胂与三苯基胂脱砷性能的影响

图10 KAC8/CuO与AC/CuO吸附脱砷效率对比

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