Mercury adsorption characteristics of petroleum coke activated by SO2

doi:10.11949/j.issn.0438-1157.20170621

Abstract

Abstract:

Petroleum coke as a kind of by-product in petrochemical industry was chosen to prepare the mercury removal adsorbent with high sulfur and activity by SO₂ activation. The effects of adsorption temperature, inlet Hg⁰ concentration, flue gas composition and thermal regeneration on mercury removal characteristic were investigated in a fixed bed reactor system. Meanwhile, the removal mercury mechanism was put forward by applying characterization methods, including surface area and porosity analyzer, elemental analyzer and X-ray photoelectron spectroscopy (XPS). The experimental results showed that the physical and chemical properties of SAPC were significantly improved. And carbonyl, ester and non-oxidized sulfur were the main active sites of Hg⁰ capture. Furthermore, the mercury removal capacity decreased with increasing adsorption temperature. The mercury adsorption rate was faster, while the initial mercury removal efficiency became lower at elevated initial Hg⁰ concentration. SO₂ had unconspicuous effect on mercury removal. Hg⁰ on or close to surfaces was oxidized by the adsorbed oxygen, and mercuric ions were more readily bound to sulfur via the Hg-S bond, while some will bind to oxygen. The absorption capacity of regenerated petroleum coke was weakened because of the loss of active sites in the regeneration process.

Key words: petroleum coke, mercury adsorption, sulfur dioxide, sulfur forms

摘要：

利用SO₂气体对石化工业副产物石油焦进行活化改性以制成富硫高活性脱汞吸附剂（SAPC）。在固定床实验装置上进行SAPC吸附脱除汞的实验研究，考察吸附温度、入口Hg⁰浓度、烟气成分以及热再生等因素对脱汞特性的影响规律，同时结合比表面积及孔隙度分析、元素分析和X射线光电子能谱（XPS）等表征手段深入分析SAPC的汞吸附机理。结果表明，SO₂活化改性石油焦的物理和化学特性得到极大改善，羰基、酯基以及非氧化态硫是Hg⁰的主要活性吸附位。吸附温度的升高会抑制对Hg⁰的吸附脱除，烟气中较高的Hg⁰浓度会降低汞脱除效率，但对其汞吸附速率有促进作用。SO₂对SAPC的脱汞性能影响较小，O₂易将Hg⁰氧化成为更容易与含氧、含硫官能团结合的氧化态汞，从而促进对Hg⁰的脱除。热再生时吸附态汞化合物受热分解的过程伴随着吸附剂表面化学活性位的损失，导致再生后汞吸附性能大幅下降。

关键词: 石油焦, 汞吸附, 二氧化硫, 硫形态

CLC Number:

TQ534.9

WANG Chenping, DUAN Yufeng, SHE Min, ZHU Chun, YANG Zhizhong. Mercury adsorption characteristics of petroleum coke activated by SO₂[J]. CIESC Journal, 2017, 68(12): 4764-4773.

王晨平, 段钰锋, 佘敏, 朱纯, 杨志忠. SO₂活化改性石油焦吸附剂的汞吸附特性[J]. 化工学报, 2017, 68(12): 4764-4773.

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Mercury adsorption characteristics of petroleum coke activated by SO₂

SO₂活化改性石油焦吸附剂的汞吸附特性

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