引用本文:刘宗社,熊钢,周孝胜,温崇荣,刘其松,廖铁,等. 天然气固定床羰基硫水解技术现场试验及工业应用[J]. 石油与天然气化工, 2023, 52(6): 1-8.
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天然气固定床羰基硫水解技术现场试验及工业应用
刘宗社1,2,3,4,熊钢1,2,3,4,周孝胜5,温崇荣1,2,3,4,刘其松1,2,3,4,廖铁5,赵书梅5
1.中国石油西南油气田公司天然气研究院;2.国家能源高含硫气藏开采研发中心 ;3.国家市场监管重点实验室(天然气质量控制和能量计量) ;4.中国石油天然气集团公司高含硫气藏开采先导性试验基地;5.中国石油西南油气田公司天然气净化总厂
摘要:
目的 验证实验室研究开发的固定床羰基硫(COS)水解工艺及催化剂在工厂气质条件下长周期运行的性能稳定性,为工艺包开发、工业装置设计及应用提供基础数据。方法 自主设计建设了6 000 m3/d天然气固定床COS水解技术现场试验装置,以工厂湿法脱硫吸收塔出口天然气为试验原料气,考查了试验装置连续运行时间超过16 000 h后 COS水解率的稳定性。结果 试验结果表明,当反应温度大于70 ℃和100 ℃、体积空速小于6 000 h-1时,COS水解率可以稳定大于98%和99%。工艺和催化剂研究成果应用于天然气净化厂产品气气质升级改造工程,工业装置稳定运行时间超过5 600 h,装置72 h性能考核结果表明,水解反应温度为100~120 ℃,反应器出口COS质量浓度<0.3 mg/m3,平均水解率达到99.69%。结论 实验室研究开发的天然气固定床COS水解技术工艺稳定可靠,催化剂水解率高,可为国内含硫气田以COS为主要有机硫组成且含量较高的天然气选择性脱硫提供技术方案。 
关键词:  固定床  羰基硫  催化剂  CT6-16  水解率  现场试验 
DOI:10.3969/j.issn.1007-3426.2023.06.001
分类号:
基金项目:中国石油天然气集团有限公司科学研究与技术开发项目“含硫天然气硫磺回收及氧化吸收尾气处理关键技术研究”(2021DJ2603);中国石油西南油气田公司科技计划项目“低密度高比表面积改性氧化铝制备技术研究”(20220306-01)
Field test and industrial application of natural gas fixed bed carbonyl sulfur hydrolysis technology
Liu Zongshe1,2,3,4, Xiong Gang1,2,3,4, Zhou Xiaosheng5, Wen Chongrong1,2,3,4, Liu Qisong1,2,3,4, Liao Tie5, Zhao Shumei5
1. Research Institute of Natural Gas Technology, PetroChina Southwest Oil & Gasfield Company, Chengdu, Sichuan, China;2. National Energy R&D Center of High Sulfur Gas Exploitation, Chengdu, Sichuan, China;3. Key Laboratory of Natural Gas Quality Control and Energy Measurement for State Market Regulation, Chengdu, Sichuan, China;4. High Sulfur Gas Exploitation Pilot Test Center, CNPC, Chengdu, Sichuan, China;5. Natural Gas Purification Plant General, PetroChina Southwest Oil & Gasfield Company, Chongqing, China
Abstract:
Objective The aim is to verify the stability of the fixed bed carbonyl sulfur(COS) hydrolysis process developed in the laboratory and catalyst in long-term operation under factory gas quality conditions, so as to provide basic data for process package development, industrial device design and application. Methods A 6 000 m3/d natural gas fixed-bed COS hydrolysis technology field test device was independently designed and constructed. The stability of COS hydrolysis rate of the test device for more than 16 000 h continuous operation was investigated by using the natural gas from the outlet of the wet desulfurization absorber of the factory as the test raw material. Results The experimental results showed that when the reaction temperature was greater than 70 ℃ and 100 ℃ respectively, and the volumetric space velocity was less than 6 000 h-1, the COS hydrolysis rate can be stably greater than 98% and 99%. The process and catalyst achievements were applied to the upgrading and renovation project of product gas quality in natural gas purification plants. The industrial unit operated stably for over 5 600 h, and the 72 h performance evaluation results of the unit showed that the hydrolysis reaction temperature was 100-120 ℃, the carbonyl sulfur mass concentration at the reactor outlet was less than 0.3 mg/m3, and the average hydrolysis rate reached 99.69%. Conclusion sThe natural gas fixed bed COS hydrolysis technology developed in the laboratory is stable and reliable, with high catalyst hydrolysis rate. It can provide a technical solution for selective desulfurization of natural gas with COS as the main organic sulfur component and high content in domestic sulfur-containing gas fields.
Key words:  fixed bed  carbonyl sulfur(COS)  catalyst  CT6-16  hydrolysis rate  field test