激光拉曼光谱法天然气原料气中CO<sub>2</sub>和H<sub>2</sub>S在线分析研究及应用

doi:10.3964/j.issn.1000-0593(2023)11-3551-08

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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H₂S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CO₂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。

关键词：拉曼光谱；天然气；在线分析；硫化氢；二氧化碳

Abstract：To address the lack of online analysis for CO₂ and H₂S 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 H₂S 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 CO₂ 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.

Key words：Raman spectroscopy; Natural gas; Online analysis; Hydrogen sulfide; Carbon dioxide

收稿日期: 2023-02-13 修订日期: 2023-08-10

中图分类号:

TE132.1

基金资助: 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

作者简介: 朱华东, 1983年生, 中国石油西南油气田分公司天然气研究院高级工程师 e-mail: zhu_hd@petrochina.com.cn

引用本文:

朱华东，张思琦，唐纯洁. 激光拉曼光谱法天然气原料气中CO₂和H₂S在线分析研究及应用[J]. 光谱学与光谱分析, 2023, 43(11): 3551-3558.
ZHU Hua-dong, ZHANG Si-qi, TANG Chun-jie. Research and Application of On-Line Analysis of CO₂ and H₂S in Natural Gas Feed Gas by Laser Raman Spectroscopy. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(11): 3551-3558.

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