激光拉曼光谱法天然气原料气中CO_(2)和H_(2)S在线分析研究及应用  

Research and Application of On-Line Analysis of CO_(2) and H_(2)S in Natural Gas Feed Gas by Laser Raman Spectroscopy

作　　者：朱华东[1,2,3] 张思琦 唐纯洁[1,2,3] ZHU Hua-dong;ZHANG Si-qi;TANG Chun-jie(Research Institute of Natural Gas Technology,PetroChina Southwest Oil&Gasfield Company,Chengdu 610213,China;Key Laboratory of Natural Gas Quality and Energy Measurement for State Market Regulation,Chengdu 610213,China;Key Laboratory of Natural Gas Quality and Energy Measurement,CNPC,Chengdu 610213,China)

机构地区：[1]中国石油天然气股份有限公司西南油气田分公司天然气研究院,四川成都610213 [2]国家市场监管重点实验室(天然质量控制和能量计量),四川成都610213 [3]中国石油天然气集团公司天然质量控制和能量计量重点实验室,四川成都610213

出　　处：《光谱学与光谱分析》2023年第11期3551-3558,共8页Spectroscopy and Spectral Analysis

基　　金：国家重大科学仪器设备开发专项课题(2012YQ16000707);中国石油西南油气田公司科学研究与技术开发项目(20210308-02);中国石油西南油气田公司科研项目(20220308-03)资助。

摘　　要：为了解决天然气净化厂缺乏原料气中的二氧化碳和硫化氢在线分析方法问题,针对天然气原料气含水、油污、颗粒物杂质、含硫和二氧化碳等强腐蚀性的特点,研制了激光拉曼天然气原料气在线分析仪和配套预处理装置,首次建立激光拉曼在线分析新方法,在天然气净化厂开展现场应用测试,考察了二氧化碳和硫化氢测量准确度和重复性,验证了在线分析方法可靠性,并开展了在线分析方法的校准技术研究。方法性能测试试验结果表明,硫化氢激光拉曼测定结果和标气示值的偏差小于1.0%,两种方法的检测结果相符,7次测量结果的相对标准偏差小于0.6%;二氧化碳拉曼分析结果和标气示值的相对偏差小于1.0%,7次测量结果的相对标准偏差小于0.76%。应用测试试验结果表明拉曼光谱H_(2)S在线测定和碘量法离线测定结果相对偏差范围为0.3%~7.5%(90%以上数据小于3%),拉曼光谱CO_(2)在线测定和气相色谱法离线测定结果相对偏差范围为0.6%~8.4%(80%以上数据小于3%),激光拉曼在线分析方法的校准周期为3 d。形成的激光拉曼在线分析仪现场运行平稳,可实时反馈气质变化,能够满足天然气净化厂掌握原料气中酸气成分含量的需求。To address the lack of online analysis for CO_(2) and H_(2)S in the purification of raw natural gas,a cutting-edge laser Raman analyzer and accompanying pre-treatment device have been developed.These advancements aim to tackle the highly corrosive properties of raw natural gas,including water content,oil pollution,particulate matter impurities,high sulfur content,and carbon dioxide.Additionally,a pioneering online analysis method utilizing laser Raman spectroscopy was established.The accuracy and repeatability of carbon dioxide and hydrogen sulfide measurements were thoroughly investigated,confirming the reliability of the online analysis methods.Calibration on these methods was also studied.On-site application experiments were conducted in natural gas purification plants to assess the effectiveness of the developed technology.The method performance testing experiment,demonstrated a deviation of less than 1.0%between the laser Raman test results of hydrogen sulfide and the standard gas indication value,with a relative standard deviation of less than 0.6%across seven measurement results.Similarly,the relative deviation between Raman test results of carbon dioxide and the standard gas indication value was less than 1.0%,with a relative standard deviation of less than 0.76%across seven measurement results.In the application experiments,the relative deviation between on-line Raman spectroscopy and offline iodimetry for H_(2)S test results ranged from 0.3%to 7.5%(with over 90%of the data falling below 3%).In comparison,the relative deviation between on-line Raman spectroscopy and offline gas chromatography for CO_(2) test results ranged from 0.6%to 8.4%(with over 80%of the data falling below 3%).The calibration cycle was set at 3 days.The online Raman spectrometer operated smoothly and consistently,enabling real-time monitoring of composition dynamics,thus satisfying the on-line analysis needs of natural gas purification plants.

关 键 词：拉曼光谱 天然气 在线分析 硫化氢 二氧化碳 

分 类 号：TE132.1[石油与天然气工程—油气勘探]