Acta Petrolei Sinica ›› 2026, Vol. 47 ›› Issue (10): 2045-2056.DOI: 10.7623/syxb202610009

• OIL FIELD DEVELOPMENT • Previous Articles    

Effects of H2O,H2S,and CS2 in natural gas on the synergistic removal performance of COS and elemental mercury in materials with venation-like fractal structure

Liu Ting1,2, Hao Kaiyu1,2, Li Jie1,2, Liu Sicheng1,2, Li Zishun3, Zhang Huawei1,2   

  1. 1. School of Environmental and Municipal Engineering, Qingdao University of Technology, Shandong Qingdao 266520, China;
    2. Shandong Provincial Key Laboratory of High-Value Utilization of Multi-Source Solid Waste and Pollution Prevention,Shandong Qingdao 266520, China;
    3. Zibo Jiahua Advanced Material Resources Co., Ltd., Shandong Zibo 255438, China
  • Received:2025-11-18 Revised:2026-07-03 Published:2026-11-05

天然气中H2O、H2S和CS2对羰基硫和单质汞在分形叶脉结构材料中协同脱除性能的影响

刘亭1,2, 郝凯宇1,2, 李洁1,2, 刘思诚1,2, 李子顺3, 张华伟1,2   

  1. 1. 青岛理工大学环境与市政工程学院 山东青岛 266520;
    2. 山东省多源固废高值利用及污染防治重点实验室 山东青岛 266520;
    3. 淄博加华新材料有限公司 山东淄博 255438
  • 通讯作者: 张华伟,男,1980年8月生,2013年获山东科技大学博士学位,现为青岛理工大学环境与市政工程学院教授、博士生导师,主要从事气态污染物控制、有机固废资源化和新能源材料研究。Email:sdkdzhw@163.com
  • 作者简介:刘亭,女,1988年12月生,2017年获华中科技大学博士学位,现为青岛理工大学环境与市政工程学院副教授、硕士生导师,主要从事固废资源化利用和气态污染物控制研究。Email:07liuting@163.com
  • 基金资助:
    国家自然科学基金区域创新发展联合基金重点支持项目(No.U24A2070)、国家自然科学基金项目(No.52402363,No.22078168)和山东省自然科学基金项目(ZR2022QB084)资助。

Abstract: To address the challenge of low-temperature synergistic removal of carbonyl sulfide (COS) and elemental mercury (Hg0) from natural gas in the presence of H2O, H2S, and CS2 impurities, a nitrogen-doped copper-loaded carbon aerogel (PPD-Cu/CA) with a venation-like fractal structure was prepared using sodium alginate as a template. The effects of these impurity gases on the synergistic removal of COS and Hg0 were systematically investigated at 40 ℃, and the underlying mechanisms and product evolution patterns were elucidated using SEM, CO2-TPD, XPS, and Hg-TPD. The results show that an appropriate concentration of water vapor (1%) promotes COS hydrolysis and the oxidation of Hg0 to HgO by providing reactive oxygen species, achieving 100% synergistic removal of both COS and Hg0. In contrast, high concentrations of H2S [(0-150)×10-6] and CS2 [(0-100)×10-6]markedly inhibit COS conversion but have no appreciable effect on Hg0 removal. H2S alters the surface chemistry of the catalyst by occupying basic sites and increasing the proportion of sulfate species, thereby poisoning Cu2+ active sites and consuming surface-adsorbed oxygen. This disrupts the Cu2+/Cu+ redox cycle required for COS hydrolysis and promotes the formation of CuS. Meanwhile, H2S reacts with Hg0 to generate HgS, which accounts for 71.59% of the mercury-containing products. CS2 competes with COS for the same basic sites, while the active sulfur species released during its decomposition shift the Hg0 transformation pathway from HgO formation to one dominated by HgS. The proportion of Cu2+ increases from 34.0% to 67.3%, whereas low-valent copper primarily forms Cu2S, accompanied by an anomalous enrichment of surface-adsorbed oxygen. The venation-like fractal structure of the carbon aerogel promotes the dispersion of metal and nitrogen-doped active sites and enhances mass transfer, while the nitrogen-doped carbon support exhibits excellent stability and outstanding resistance to impurity interference.

Key words: carbonyl sulfide, elemental mercury, carbon aerogel, impurity gases, synergistic removal, nitrogen doping, copper loading

摘要: 针对天然气中羰基硫(COS)和单质汞(Hg0)低温协同脱除及存在H2O、H2S和CS2杂质气体干扰的难题,以海藻酸钠为模板制备了具有分形叶脉结构的氮掺杂铜负载碳气凝胶(PPD-Cu/CA),在低温(40℃)条件下系统考察杂质气体对COS与Hg0协同脱除性能的影响,结合扫描电镜、CO2程序升温脱附、X射线光电子能谱和汞程序升温脱附等表征手段揭示了可能的作用机制与产物演化规律。结果表明:适量水蒸气(1%)可以提供活性氧物种促进COS水解并氧化Hg0生成HgO,实现两者100%协同脱除;H2S[(0~150)×10-6]和CS2[(0~100)×10-6]高浓度下显著抑制COS转化,但对Hg0脱除无明显影响;H2S通过占据碱性位点、促进硫酸盐类比例增加等方式改变催化剂表面化学环境,毒化Cu2+位点并消耗表面吸附氧,打断COS水解依赖的Cu2+/Cu+循环并生成CuS,同时可与Hg0生成HgS(占比为71.59%);CS2与COS消耗相同碱性位点,分解释放的活性硫也使Hg0转化路径由HgO生成逆转为HgS主导,Cu2+占比由34.0%升至67.3%,低价铜主要生成Cu2S并伴随表面吸附氧反常富集;碳气凝胶材料的分形叶脉结构强化了金属和氮掺杂活性位点分散与传质,氮掺杂载体稳定性优异,抗杂质干扰性能突出。

关键词: 羰基硫, 单质汞, 碳气凝胶, 杂质气体, 协同脱除, 氮掺杂, 铜负载

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