CeO2/TiO2吸附剂煤气脱汞产物的浸出规律

doi:10.16085/j.issn.1000-6613.2022-1631

摘要/Abstract

摘要：

基于金属氧化物脱汞吸附剂后续无害化处理要求，本文提出采用硫代硫酸钠（Na₂S₂O₃）溶液浸出金属氧化物脱汞产物的新思路。CeO₂/TiO₂吸附剂（CeTi）吸附汞后得到含汞吸附剂（Hg-CeTi），利用汞程序升温脱附实验（Hg-TPD）确定其表面吸附态汞的赋存形态。随后探究Na₂S₂O₃溶液对于Hg-CeTi表面脱汞产物的浸出能力，着重分析不同赋存形态的汞在Na₂S₂O₃溶液中的迁移规律。Hg-TPD结果表明，模拟煤气中脱汞产物以HgCl₂、HgO和HgS为主。由于硫代硫酸根（S₂O $3 2 -$ ）与Hg²⁺的配合能力，HgO易从Hg-CeTi表面脱附并向液相迁移；HgCl₂会在液相中与OH^-反应生成HgO，再被Na₂S₂O₃溶液浸出；对于两种不同晶型的HgS，提高Na₂S₂O₃溶液浓度可促进HgS(black)向液相迁移，但对于更稳定的HgS(red)收效甚微。在1.0mol/L的Na₂S₂O₃溶液中浸出1h后，汞浸出率可达97.3%，且剩余的汞以稳定的HgS形态存在。

关键词: 浸出, 汞, 吸附剂, 稳定性, 合成气, 废物处置

Abstract:

In view of the requirements of the subsequent innocuity treatment of metal oxide adsorbents for mercury removal, a brand-new idea of leaching Hg-absorption products from metal oxide using sodium thiosulfate (Na₂S₂O₃) solution was proposed in this paper. Mercury-containing adsorbents (Hg-CeTi) was obtained by CeO₂/TiO₂ sorbents (CeTi) after mercury adsorption. Mercury temperature-programmed desorption (Hg-TPD) was used to determine the occurrence form of adsorbed-Hg on the surface of Hg-CeTi. Then, the extraction capacity of Na₂S₂O₃ solution on the Hg-absorption products from the Hg-CeTi was studied, and the migration mechanism of mercury with different occurrence forms in Na₂S₂O₃ solution was emphatically analyzed. The results of Hg-TPD showed that HgCl₂, HgO and HgS were the main Hg-adsorption products in the syngas. HgO was easy to desorb from Hg-CeTi and migrate to the liquid phase due to the coordination ability of thiosulfate (S₂O $3 2 -$ ) with Hg²⁺. HgCl₂ reacted with OH^- in the liquid phase to form HgO, which was subsequently leached by Na₂S₂O₃ solution. For two different crystalline forms of HgS, the increase in the concentration of Na₂S₂O₃ solution could promote the migration of HgS (black) to the liquid phase, but it had a slight effect on the HgS (red) due to the stability of HgS (red). After leaching in 1.0mol/L Na₂S₂O₃ solution for 1h, the mercury leaching rate could reach 97.3%, and the remaining mercury existed in stable HgS form.

Key words: leaching, mercury, adsorbents, stability, syngas, waste treatment

中图分类号:

TK09

陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.

LU Yang, ZHOU Jinsong, ZHOU Qixin, WANG Tang, LIU Zhuang, LI Bohao, ZHOU Lingtao. Leaching mechanism of Hg-absorption products on CeO₂/TiO₂ sorbentsin syngas[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3875-3883.

图/表 11

图1 实验装置示意图

表1 吸附实验气氛及温度

Hg-CeTi	气体组分及体积分数	吸附温度/℃
N₂-CeTi	N₂	120
HCl-CeTi	N₂+0.001% HCl	120
H₂S-CeTi	N₂+0.04% H₂S	120
Syngas-CeTi	N₂+30% H₂+20% CO+0.1% NH₃+ 0.001% HCl+0.04% H₂S	120

图2 N2-CeTi表面脱汞产物形态以及浸出率

图3 HCl-CeTi表面脱汞产物形态以及浸出率

图4 HCl-CeTi浸出后表面吸附态汞赋存形态

图5 H2S-CeTi表面脱汞产物形态以及浸出率

图6 x-H2S-CeTi Hg-TPD拟合曲线（x=0.1、0.2、0.5、1.0和2.0）

图7 x-H2S-CeTi中不同形态汞的质量、浸出率以及分布（x=0.1、0.2、0.5、1.0和2.0）

图8 Syngas-CeTi 表面脱汞产物形态以及浸出率

图9 x-Syngas-CeTi Hg-TPD曲线对比以及1.0-Syngas-CeTi表面汞赋存形态

图10 吸附剂汞吸附效率测试

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CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律

Leaching mechanism of Hg-absorption products on CeO₂/TiO₂ sorbentsin syngas

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