天然气净化厂尾气达标排放对策
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摘要
近年来,有关部门相继出台了严格的硫磺回收装置尾气排放控制指标,天然气净化厂硫磺回收装置尾气排放达标面临着巨大的压力和严峻的挑战。为此,对比了加拿大和美国天然气净化厂尾气SO_2排放标准,分析了我国天然气净化厂尾气SO_2排放执行标准的制订现状,以中国石油西南油气田公司(以下简称西南油气田)为例,对其现有的天然气净化厂尾气处理装置进行了技术经济性对比分析,并基于对技术先进性和经济合理性的综合考虑推荐了改造工艺。研究结果表明:①天然气净化厂硫磺回收率指标,我国明显高于欧美国家;②针对西南油气田各天然气净化厂特点,提出了升级溶剂并优化运行参数、有机胺法SO_2吸收技术改造、络合铁液相氧化还原技术改造和关停等4种改造方案,预计改造投资为5.59亿元;③对于硫磺回收规模较大(超过200 t/d)的天然气净化厂,建议选用还原吸收类工艺;④对于硫磺回收规模中等(5～200 t/d)的天然气净化厂,建议选用有机胺法和SO_2吸收工艺;⑤对于原料气中低潜硫量(不足10 t/d)的天然气处理装置,建议采用液相氧化还原工艺。结论认为,按推荐工艺改造完成后,西南油气田所有的硫磺回收装置尾气SO_2排放均能满足国家标准的规定,并且能达到国际先进水平。
In recent years, relevant authorities have successively issued strict control indicators on the tail gas emission of sulfur recovery facilities, so standard tail gas emission from the sulfur recovery facilities in natural gas purification plants is faced with enormous pressure and severe challenges. In this paper, the SO_2 emission standards of natural gas purification plants in Canada and America were compared, and the formulation status of domestic SO_2 emission standards was analyzed. Then, the existing tail gas processing units in natural gas purification plants were analyzed and compared technologically and economically with the PetroChina Southwest Oil & Gasfield Company as an example. Finally, the transformation process was recommended in consideration of technological advancement and economical rationality comprehensively. And the following research results were obtained. First, the domestic indicator of sulfur recovery ratio of natural gas purification plants is much higher than that in Europe and America. Second, considering the characteristics of all natural gas purification plants in this company, 4 transformation schemes are proposed, including solvent upgrading & operation parameter optimization, transformation of SO2 absorption technology based on organic amine method, transformation of liquid-phase complex iron oxidation/reduction technology, and shut down. And the transformation investment is expected to be CNY 559 million. Third, as for the natural gas purification plants with higher sulfur recovery rates(>200 t/d), it is recommended to select the technologies of reduction absorption. Fourth, as for the natural gas purification plants with moderate sulfur recovery rates(5–200 t/d), it is recommended to select the SO_2 absorption technology based on organic amine method. Fifth, as for the natural gas processing facilities whose potential sulfur rates of feed gas are low(<10 t/d), it is recommended to adopt the liquid-phase oxidation/reduction technology. In conclusion, tail gas emission from all sulfur recovery facilities of this company can satisfy the national SO_2 emission standard and reach the international advanced level after they are transformed by means of the recommended technologies.
In recent years, relevant authorities have successively issued strict control indicators on the tail gas emission of sulfur recovery facilities, so standard tail gas emission from the sulfur recovery facilities in natural gas purification plants is faced with enormous pressure and severe challenges. In this paper, the SO_2 emission standards of natural gas purification plants in Canada and America were compared, and the formulation status of domestic SO_2 emission standards was analyzed. Then, the existing tail gas processing units in natural gas purification plants were analyzed and compared technologically and economically with the PetroChina Southwest Oil & Gasfield Company as an example. Finally, the transformation process was recommended in consideration of technological advancement and economical rationality comprehensively. And the following research results were obtained. First, the domestic indicator of sulfur recovery ratio of natural gas purification plants is much higher than that in Europe and America. Second, considering the characteristics of all natural gas purification plants in this company, 4 transformation schemes are proposed, including solvent upgrading & operation parameter optimization, transformation of SO2 absorption technology based on organic amine method, transformation of liquid-phase complex iron oxidation/reduction technology, and shut down. And the transformation investment is expected to be CNY 559 million. Third, as for the natural gas purification plants with higher sulfur recovery rates(>200 t/d), it is recommended to select the technologies of reduction absorption. Fourth, as for the natural gas purification plants with moderate sulfur recovery rates(5–200 t/d), it is recommended to select the SO_2 absorption technology based on organic amine method. Fifth, as for the natural gas processing facilities whose potential sulfur rates of feed gas are low(<10 t/d), it is recommended to adopt the liquid-phase oxidation/reduction technology. In conclusion, tail gas emission from all sulfur recovery facilities of this company can satisfy the national SO_2 emission standard and reach the international advanced level after they are transformed by means of the recommended technologies.
引文
[1]温崇荣,段勇,朱荣海,胡天友,李小云.我国硫磺回收装置排放烟气中SO2达标方案探讨[J].石油与天然气化工,2017,46(1):1-7.Wen Chongrong,Duan Yong,Zhu Ronghai,Hu Tianyou&Li Xiaoyun.Discussion on the SO2 emission reach standard of tail gas from sulfur recovery unit in China[J].Chemical Engineering of Oil&Gas,2017,46(1):1-7.
[2]陈赓良,李劲.对降低尾气处理装置SO2排放的认识与建议[J].石油与天然气化工,2014,43(3):217-222.Chen Gengliang&Li Jin.Review and suggestions on reducing SO2 emission concentration of Claus tail gas treatment unit[J].Chemical Engineering of Oil&Gas,2014,43(3):217-222.
[3]周理,陈赓良,郭开华.对天然气推荐性国家标准GB/T 31253的讨论[J].天然气工业,2017,37(12):87-91.Zhou Li,Chen Gengliang&Guo Kaihua.A discussion on the Chinese National Standard GB/T 31253:From Recommendatory(GB/T)to Guidance(GB/Z)[J].Natural Gas Industry,2017,37(12):87-91.
[4]张金河.一种新型脱硫技术在硫磺回收装置尾气达标排放中的应用[J].石油与天然气化工,2017,46(5):25-29.Zhang Jinhe.Application of a new desulfurization technology in tail gas up-to-standard emission of sulfur recovery device[J].Chemical Engineering of Oil&Gas,2017,46(5):25-29.
[5]熊钢,杨子海,何金龙,李富元,蒋吉强,胡天友,等.位阻胺选择性配方溶剂尾气处理装置工业应用[J].天然气工业,2018,38(10):114-119.Xiong Gang,Yang Zihai,He Jinlong,Li Fuyuan,Jiang Jiqiang,Hu Tianyou,et al.A selective formulated solvent based on steric hindered amine applied to tail gas treatment[J].Natural Gas Industry,2018,38(10):114-119.
[6]王建宏,于鑫萍,詹敏述,许波,朱玲,王亚飞.[bmim]OH和[A336][FeCl4]混合离子液体氧化吸收硫化氢[J].天然气工业,2018,38(7):100-107.Wang Jianhong,Yu Xinping,Zhan Minshu,Xu Bo,Zhu Ling&Wang Yafei.Oxidation absorption of H2S by[bmim]OH and[A336][FeCl4]mixed ionic liquid[J].Natural Gas Industry,2018,38(7):100-107.
[7]中国国务院办公厅.能源发展战略行动计划(2014-2020年)[EB/OL].[2014-11-19].http://www.gov.cn/zhengce/content/2014-11/19/content_9222.htm.The State Council.Strategic Action Plan for Energy Development(2014-2020)[EB/OL].[2014-11-19].http://www.gov.cn/zhengce/content/2014-11/19/content_9222.htm.
[8]宋彬,李金金,龙晓达.天然气净化厂尾气SO2排放治理工艺探讨[J].天然气工业,2017,37(1):137-144.Song Bin,Li Jinjin&Long Xiaoda.Treatment of tail gas SO2emitted from natural gas purification plants[J].Natural Gas Industry,2017,37(1):137-144.
[9]国家环境保护局.大气污染物综合排放标准:GB 16297-1996[S].北京:中国标准出版社,1996.State Environmental Protection Administration.Integrated emission standard of air pollutants:GB 16297-1996[S].Beijing:Standard Press of China,1996.
[10]环境保护部,国家质量监督检验检疫总局.石油炼制工业污染物排放标准:GB 31570-2015[S].北京:中国环境科学出版社,2015.Ministry of Environmental Protection&General Administration of Quality Supervision,Inspection and Quarantine of the PRC.Emission standard of pollutants for petroleum refining industry:GB 31570-2015[S].Beijing:China Environmental Science Press,2015.
[11]中国环境科学研究院.陆上石油天然气开采工业污染物排放标准(征求意见稿)[R].北京:中国环境科学研究院,2014.Chinese Research Academy of Environmental Sciences.Emission standards of pollutants for onshore petroleum exploitation and production industry(Edition for Discussion)[R].Beijing:Chinese Research Academy of Environmental Sciences,2014.
[12]国家环境保护局.恶臭污染排放标准:GB/T 14554-1993[S].北京:中国标准出版社,1994.State Environmental Protection Administration.Emission standard for order pollutants:GB/T 14554-1993[S].Beijing:Standard Press of China,1994.
[13]中华人民共和国卫生部.工作场所有害因素职业接触限值第1部分化学有害因素:GBZ 2.1-2007[S].北京:人民卫生出版社,2007.Ministry of Health of the PRC.Occupational exposure limits for hazardous agents in the workplace Part 1 Chemical hazardous agents:GBZ 2.1-2007[S].Beijing:People's Medical Publishing House,2007.
[14]杨威,常宏岗,何金龙,吴明鸥,刘卓旻,陈超,等.西南地区天然气净化厂尾气减排方案探讨[J].石油与天然气化工,2015,44(1):17-20.Yang Wei,Chang Honggang,He Jinlong,Wu Ming'ou,Liu Zhuomin,Chen Chao,et al.Discussion on emission reduction of tail gas from natural gas purification in Southwest China[J].Chemical Engineering of Oil&Gas,2015,44(1):17-20.
[15]赵雅晶.循环流化床在烟气脱硫中的应用分析[J].化工设计通讯,2016,42(7):11.Zhao Yajing.Application of circulating fluidized bed in flue gas desulfurization[J].Chemical Engineering Design Communications,2016,42(7):11.
[16]常宏岗,朱荣海,刘宗社,何金龙,温崇荣,张素娟,等.克劳斯尾气低温加氢水解催化剂研究与工业应用[J].天然气工业,2015,35(4):88-93.Chang Honggang,Zhu Ronghai,Liu Zongshe,He Jinlong,Wen Chongrong,Zhang Sujuan,et al.Development and industrial application of the catalyzers for low-temperature hydrogenation hydrolysis of Claus tail gas[J].Natural Gas Industry,2015,35(4):88-93.
[17]张伍,何金龙,常宏岗,涂彦,李必忠.络合铁法液相氧化还原脱硫技术应用现状与前景分析[J].石油与天然气化工,2008,37(增刊1):130-133.Zhang Wu,He Jinlong,Chang Honggang,Tu Yan&Li Bizhong.The applications status and prospect analysis of iron-redox desulfurization technology[J].Chemical Engineering of Oil&Gas,2008,37(S1):130-133.
[18]杨威,常宏岗,何金龙,杨亚宇,吴明鸥,刘卓旻,等.具有高选择性和可再生性的SO2脱除溶剂研发[J].石油与天然气化工,2016,45(1):8-13.Yang Wei,Chang Honggang,He Jinlong,Yang Yayu,Wu Ming′ou,Liu Zhuomin,et al.Research and development of SO2removal solvent with high selectivity and regeneration performance[J].Chemical Engineering of Oil&Gas,2016,45(1):8-13.
[19]周明宇,赵华莱,刘健,程林,陈运强.自主开发的含硫尾气处理技术及其应用[J].天然气与石油,2018,36(4):36-41.Zhou Mingyu,Zhao Hualai,Liu Jian,Cheng Lin&Chen Yunqiang.Self-developed sulfur-containing tail gas treatment technology and its application[J].Natural Gas and Oil,2018,36(4):36-41.
[20]何登华,黄黎明,何金龙,陈昌介,温崇荣,常宏岗,等.一种克劳斯尾气SO2吸附剂及其制备和应用:中国,201310219881.1[P].2013-06-05.He Denghua,Huang Liming,He Jinlong,Chen Changjie,Wen Chongrong,Chang Honggang,et al.A SO2 adsorbent for Claus tail gas and its preparation and application:China,201310219881.1[P].2013-06-05.
[2]陈赓良,李劲.对降低尾气处理装置SO2排放的认识与建议[J].石油与天然气化工,2014,43(3):217-222.Chen Gengliang&Li Jin.Review and suggestions on reducing SO2 emission concentration of Claus tail gas treatment unit[J].Chemical Engineering of Oil&Gas,2014,43(3):217-222.
[3]周理,陈赓良,郭开华.对天然气推荐性国家标准GB/T 31253的讨论[J].天然气工业,2017,37(12):87-91.Zhou Li,Chen Gengliang&Guo Kaihua.A discussion on the Chinese National Standard GB/T 31253:From Recommendatory(GB/T)to Guidance(GB/Z)[J].Natural Gas Industry,2017,37(12):87-91.
[4]张金河.一种新型脱硫技术在硫磺回收装置尾气达标排放中的应用[J].石油与天然气化工,2017,46(5):25-29.Zhang Jinhe.Application of a new desulfurization technology in tail gas up-to-standard emission of sulfur recovery device[J].Chemical Engineering of Oil&Gas,2017,46(5):25-29.
[5]熊钢,杨子海,何金龙,李富元,蒋吉强,胡天友,等.位阻胺选择性配方溶剂尾气处理装置工业应用[J].天然气工业,2018,38(10):114-119.Xiong Gang,Yang Zihai,He Jinlong,Li Fuyuan,Jiang Jiqiang,Hu Tianyou,et al.A selective formulated solvent based on steric hindered amine applied to tail gas treatment[J].Natural Gas Industry,2018,38(10):114-119.
[6]王建宏,于鑫萍,詹敏述,许波,朱玲,王亚飞.[bmim]OH和[A336][FeCl4]混合离子液体氧化吸收硫化氢[J].天然气工业,2018,38(7):100-107.Wang Jianhong,Yu Xinping,Zhan Minshu,Xu Bo,Zhu Ling&Wang Yafei.Oxidation absorption of H2S by[bmim]OH and[A336][FeCl4]mixed ionic liquid[J].Natural Gas Industry,2018,38(7):100-107.
[7]中国国务院办公厅.能源发展战略行动计划(2014-2020年)[EB/OL].[2014-11-19].http://www.gov.cn/zhengce/content/2014-11/19/content_9222.htm.The State Council.Strategic Action Plan for Energy Development(2014-2020)[EB/OL].[2014-11-19].http://www.gov.cn/zhengce/content/2014-11/19/content_9222.htm.
[8]宋彬,李金金,龙晓达.天然气净化厂尾气SO2排放治理工艺探讨[J].天然气工业,2017,37(1):137-144.Song Bin,Li Jinjin&Long Xiaoda.Treatment of tail gas SO2emitted from natural gas purification plants[J].Natural Gas Industry,2017,37(1):137-144.
[9]国家环境保护局.大气污染物综合排放标准:GB 16297-1996[S].北京:中国标准出版社,1996.State Environmental Protection Administration.Integrated emission standard of air pollutants:GB 16297-1996[S].Beijing:Standard Press of China,1996.
[10]环境保护部,国家质量监督检验检疫总局.石油炼制工业污染物排放标准:GB 31570-2015[S].北京:中国环境科学出版社,2015.Ministry of Environmental Protection&General Administration of Quality Supervision,Inspection and Quarantine of the PRC.Emission standard of pollutants for petroleum refining industry:GB 31570-2015[S].Beijing:China Environmental Science Press,2015.
[11]中国环境科学研究院.陆上石油天然气开采工业污染物排放标准(征求意见稿)[R].北京:中国环境科学研究院,2014.Chinese Research Academy of Environmental Sciences.Emission standards of pollutants for onshore petroleum exploitation and production industry(Edition for Discussion)[R].Beijing:Chinese Research Academy of Environmental Sciences,2014.
[12]国家环境保护局.恶臭污染排放标准:GB/T 14554-1993[S].北京:中国标准出版社,1994.State Environmental Protection Administration.Emission standard for order pollutants:GB/T 14554-1993[S].Beijing:Standard Press of China,1994.
[13]中华人民共和国卫生部.工作场所有害因素职业接触限值第1部分化学有害因素:GBZ 2.1-2007[S].北京:人民卫生出版社,2007.Ministry of Health of the PRC.Occupational exposure limits for hazardous agents in the workplace Part 1 Chemical hazardous agents:GBZ 2.1-2007[S].Beijing:People's Medical Publishing House,2007.
[14]杨威,常宏岗,何金龙,吴明鸥,刘卓旻,陈超,等.西南地区天然气净化厂尾气减排方案探讨[J].石油与天然气化工,2015,44(1):17-20.Yang Wei,Chang Honggang,He Jinlong,Wu Ming'ou,Liu Zhuomin,Chen Chao,et al.Discussion on emission reduction of tail gas from natural gas purification in Southwest China[J].Chemical Engineering of Oil&Gas,2015,44(1):17-20.
[15]赵雅晶.循环流化床在烟气脱硫中的应用分析[J].化工设计通讯,2016,42(7):11.Zhao Yajing.Application of circulating fluidized bed in flue gas desulfurization[J].Chemical Engineering Design Communications,2016,42(7):11.
[16]常宏岗,朱荣海,刘宗社,何金龙,温崇荣,张素娟,等.克劳斯尾气低温加氢水解催化剂研究与工业应用[J].天然气工业,2015,35(4):88-93.Chang Honggang,Zhu Ronghai,Liu Zongshe,He Jinlong,Wen Chongrong,Zhang Sujuan,et al.Development and industrial application of the catalyzers for low-temperature hydrogenation hydrolysis of Claus tail gas[J].Natural Gas Industry,2015,35(4):88-93.
[17]张伍,何金龙,常宏岗,涂彦,李必忠.络合铁法液相氧化还原脱硫技术应用现状与前景分析[J].石油与天然气化工,2008,37(增刊1):130-133.Zhang Wu,He Jinlong,Chang Honggang,Tu Yan&Li Bizhong.The applications status and prospect analysis of iron-redox desulfurization technology[J].Chemical Engineering of Oil&Gas,2008,37(S1):130-133.
[18]杨威,常宏岗,何金龙,杨亚宇,吴明鸥,刘卓旻,等.具有高选择性和可再生性的SO2脱除溶剂研发[J].石油与天然气化工,2016,45(1):8-13.Yang Wei,Chang Honggang,He Jinlong,Yang Yayu,Wu Ming′ou,Liu Zhuomin,et al.Research and development of SO2removal solvent with high selectivity and regeneration performance[J].Chemical Engineering of Oil&Gas,2016,45(1):8-13.
[19]周明宇,赵华莱,刘健,程林,陈运强.自主开发的含硫尾气处理技术及其应用[J].天然气与石油,2018,36(4):36-41.Zhou Mingyu,Zhao Hualai,Liu Jian,Cheng Lin&Chen Yunqiang.Self-developed sulfur-containing tail gas treatment technology and its application[J].Natural Gas and Oil,2018,36(4):36-41.
[20]何登华,黄黎明,何金龙,陈昌介,温崇荣,常宏岗,等.一种克劳斯尾气SO2吸附剂及其制备和应用:中国,201310219881.1[P].2013-06-05.He Denghua,Huang Liming,He Jinlong,Chen Changjie,Wen Chongrong,Chang Honggang,et al.A SO2 adsorbent for Claus tail gas and its preparation and application:China,201310219881.1[P].2013-06-05.
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