引用本文:王南伟,王雪凝,刘东,戴攀,薛靖文,陈鸿元,等. 基于铜基配位的新型氧化还原脱硫溶剂开发[J]. 石油与天然气化工, 2025, 54(2): 9-15.
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基于铜基配位的新型氧化还原脱硫溶剂开发
王南伟,王雪凝,刘东,戴攀,薛靖文,陈鸿元,陈焰洪,邱奎
1.重庆相国寺储气库有限公司;2.重庆科技大学化学化工学院;3.中国石油西南油气田公司川中油气矿;4.中国石油西南油气田公司天然气研究院
摘要:
目的 针对适用于中、小规模含硫井口气脱硫的Lo-cat液相氧化还原脱硫工艺,改善传统液相氧化还原脱硫剂存在的稳定性差、硫容量低、产物易堵塞设备等问题,进一步研发出更加绿色高效的湿法氧化还原脱硫剂体系。方法 以N,N?二甲基甲酰胺(N,N-Dimethylformamide,DMF)和水的混合物作为溶剂,加入氯化铜和螯合剂制备出绿色高效的铜基湿法氧化还原脱硫剂,对该脱硫剂的结构和热稳定性进行测定,开展脱硫实验,以考查不同种类的螯合剂、铜离子与螯合剂比例、温度、水含量及H2S气体流量对脱硫性能的影响,同时考查了吸收、再生过程中氧化还原电位和pH的变化规律及脱硫剂的重复脱硫性能。结果 所研发的脱硫剂在60 ℃以下可稳定工作,最佳脱硫温度为40 ℃,在30 mL DMF+10 mL水所构成的脱硫溶液中,加入2 g CuCl2和2 g胺类螯合剂组成的脱硫剂具有相对较高的脱硫效果,硫容高达14.83 g/L。结论 所研发的脱硫剂可在高效吸收H2S的同时得到较高的硫容量,可为天然气脱硫工艺提供参考。
关键词:  天然气  脱硫  DMF  氯化铜  螯合剂  液相氧化还原  铜基配位
DOI:10.3969/j.issn.1007-3426.2025.02.002
分类号:
基金项目:国家科技重大专项“高含硫气藏安全高效开发技术”(2016ZX05017);中石化集团公司2020年科技项目“有机硫催化水解技术提升元坝气田商品气质量研究”(120049-1)
Development of a new oxidation-reduction desulfurization solvent based on copper-based coordination
Nanwei WANG1, Xuening WANG2, Dong LIU3, Pan DAI2, Jingwen XUE4, Hongyuan CHEN2, Yanhong CHEN2, Kui QIU2
1.Chongqing Xiangguosi Underground Gas Storage Co., Ltd., Chongqing, China;2.School of Chemistry and Chemical Engineering, Chongqing University of Science and Technology, Chongqing, China;3.Central Sichuan Oil and Gas District, PetroChina Southwest Oil & Gasfield Company, Suining, Sichuan, China;4.Research Institute of Natural Gas Technology, PetroChina Southwest Oil & Gasfield Company, Chengdu, Sichuan, China
Abstract:
Objective The aim is to improve the situation of poor stability, low sulfur capacity and easy blockage of equipment in the traditional liquid phase oxidative-reduction desulfurizer for the Lo-cat liquid phase oxidative-redution desulfurization process suitable for medium and small-scale sulfur-containing wellhead gas desulfurization, and to further develop a greener and more efficient wet oxidation desulfurizer system. Method A green and efficient copper-based wet oxidative-reduction desulfurization agent was prepared by adding copper chloride and chelating agent with a mixture of N, N-Dimethylformamide (DMF) and water as solvent. The structure and thermal stability of the desulfurization agent were determined, and desulfurization experiments were carried out in order to test the effects of different kinds of chelating agents, the ratio of copper ions and chelating agent, temperature, water content, and gas flow rate of H2S on the desulfurization performance. At the same time, the change rule of redox potential and pH during the absorption and regeneration process and the repeated desulfurization performance of desulfurization agents were investigated. Result The developed desulfurizer could work stably below 60 ℃, and the optimal desulfurization temperature was 40 ℃. In the desulfurization solution composed of 30 mL DMF+10 mL water, the desulfurizer composed of 2 g CuCl2 and 2 g amine chelating agent had a relatively high desulfurization effect, and the sulfur capacity was up to 14.83 g/L. Conclusion The developed desulfurizer has a high sulfur capacity while efficiently absorbing H2S, which can provide a reference for the natural gas desulfurization process.
Key words:  natural gas  desulfurization  DMF  copper chloride  chelating agent  liquid phase oxidative-reduction  copper-based coordination