位阻胺选择性配方溶剂尾气处理装置工业应用
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摘要
为了解决常规甲基二乙醇胺(MDEA)脱硫溶剂在低压下脱硫效果不理想,导致排放尾气中SO_2浓度升高的问题,利用位阻胺与H_2S反应具有良好活性、同时能较好抑制位阻胺与CO_2反应的特点,研究开发出了位阻胺选择性脱硫配方溶剂,并在处理量为1×10~4m~3/d的装置上进行中间放大试验的基础上,在中国石油西南油气田公司川中油气矿龙岗天然气净化厂硫磺回收加氢尾气脱硫装置上进行了工业应用。在工业应用期间,考察了溶剂在不同吸收塔板数、不同贫液入塔温度、不同溶液循环量等条件下的吸收性能,还考察了脱硫溶液的再生性能,确定了较适宜的工艺操作参数。应用1年后的考核结果表明:(1)该位阻胺选择性脱硫配方溶剂在进尾气脱硫吸收塔气体中H_2S含量为0.77%～3.96%、CO_2含量为23.91%～32.79%的气质条件下,可使净化尾气中H_2S含量低于30 mg/m~3;(2)与装置原用的常规MDEA相比,净化尾气中H_2S含量降低58.45%;(3)该位阻胺选择性脱硫配方溶剂的再生性能良好,再生后贫液中H_2S和CO_2含量均小于0.12 g/L。
Due to the MDEA's unsatisfactory desulfurization performance at low pressures, which leads to the increase of SO_2 concentration in tail gas release, a formulated solvent based on steric hindered amine(SHA) was thus developed, in virtue of SHA's good absorbing activity with H_2 S and lower reacting inclination with CO_2. This solvent was applied first to a pilot plant with the capacity of 10 thousand m~3/d and then formally to the Claus hydrogenation tail gas desulfurization units in the Longgang Natural Gas Purification Plant operated by the PetroChina Southwest Company. During this solvent's industrial application time, its absorbing performance was evaluated under different conditions such as numbers of contact plates of the absorbing tower, lean amine temperatures into the absorbing tower, amine cycling amounts, etc., based on which the operating parameters were optimized. In addition, the recycling of desulfurizing solutions was examined and the favorable operating parameters were determined. After one year's application, the following findings were achieved. With this solvent in treatment, the H_2 S content in the desulfurized tail gas(originally, there was 0.77–3.96% H_2 S and 23.91–32.79% CO_2), was reduced to less than 30 mg/m~3, and by 58.45% compared to the MDEA previously used in this desulfurization plant. The rich amine solution can be easily regenerated with both H_2 S and CO_2 content less than 0.12 g/L in the regenerated lean amine stream.
Due to the MDEA's unsatisfactory desulfurization performance at low pressures, which leads to the increase of SO_2 concentration in tail gas release, a formulated solvent based on steric hindered amine(SHA) was thus developed, in virtue of SHA's good absorbing activity with H_2 S and lower reacting inclination with CO_2. This solvent was applied first to a pilot plant with the capacity of 10 thousand m~3/d and then formally to the Claus hydrogenation tail gas desulfurization units in the Longgang Natural Gas Purification Plant operated by the PetroChina Southwest Company. During this solvent's industrial application time, its absorbing performance was evaluated under different conditions such as numbers of contact plates of the absorbing tower, lean amine temperatures into the absorbing tower, amine cycling amounts, etc., based on which the operating parameters were optimized. In addition, the recycling of desulfurizing solutions was examined and the favorable operating parameters were determined. After one year's application, the following findings were achieved. With this solvent in treatment, the H_2 S content in the desulfurized tail gas(originally, there was 0.77–3.96% H_2 S and 23.91–32.79% CO_2), was reduced to less than 30 mg/m~3, and by 58.45% compared to the MDEA previously used in this desulfurization plant. The rich amine solution can be easily regenerated with both H_2 S and CO_2 content less than 0.12 g/L in the regenerated lean amine stream.
引文
[1]Saha AK,Biswas AK&Bandyopadhyay SS.Absorption of CO2in a sterically hindered amine:Modeling absorption in a mechanically agitated contactor[J].Separation and Purification Technology,1999,15(2):101-112.
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[3]Idris Z&Eimer DA.Representation of CO2 absorption in sterically hindered amines[J].Energy Procedia,2014,51(7):247-252.
[4]Sartori G&Savage DW.Sterically hindered amines for carbon dioxide removal from gases[J].Industrial&Engineering Chemistry Fundamentals,1983,22(2):239-249.
[5]Say GR,Heinzelmann FJ,Iyengar JN&Sartori GS.New,hindered amine concept for simultaneous removal of CO2 and H2Sfrom gases[J].Chemical Engineering Progress,1984,80(10):72-77.
[6]Mandal BP,Biswas AK&Bandyopadhyay SS.Selective absorption of H2S from gas streams containing H2S and CO2 into aqueous solutions of N-methyldiethanolamine and 2-amino-2-methyl-1-propanol[J].Separation&Purification Technology,2004,35(3):191-202.
[7]Fedich RB,Woerrner AC,Chitnis GK.Selective H2S removal[J].Hydrocarbon Engineering,2004,9(5):89-92.
[8]王开岳.天然气净化工艺:脱硫脱碳、脱水、硫磺回收及尾气处理[M].北京:石油工业出版社,2015.Wang Kaiyue.Natural gas purification process:Desulphurization,decarbonization,dehydration,sulfur recovery and tail gas treatment[M].Beijing:Petroleum Industry Press,2015.
[9]陈赓良,常宏岗.配方型溶剂的应用与气体净化工艺的发展动向[M].北京:石油工业出版社,2009.Chen Gengliang&Chang Honggang.Application of formulated solvents and development trend of gas purification process[M].Beijing:Petroleum Industry Press,2009.
[10]李云涛,李露露,李辉,张智,徐计雷.空间位阻胺脱硫选择性及再生性能的研究[J].西南石油大学学报(自然科学版),2017,39(3):173-179.Li Yuntao,Li Lulu,Li Hui,Zhang Zhi&Xu Jilei.Desulfurization selectivity and regeneration studies of sterically hindered amines[J].Journal of Southwest Petroleum University(Science&Technology Edition),2017,39(3):173-179.
[11]杨波,诸林,杨超越,唐诗.空间位阻胺1,3-二(二乙胺基)-2-丙醇的合成及脱硫性能评价[J].现代化工,2017,37(3):146-150.Yang Bo,Zhu Lin,Yang Chaoyue&Tang Shi.Synthesis and desulfurization performance evaluation of steric hindrance amine1,3-bis(diethylamine)-2-propanol[J].Modern Chemical Industry,2017,37(3):146-150.
[12]王治红,张诗悦,高阳.含空间位阻基团的选择性脱硫剂的合成与表征[J].石油与天然气化工,2016,45(1):14-20.Wang Zhihong,Zhang Shiyue&Gao Yang.Synthesis and characterization of selective desulfurizer with steric hindrance group[J].Chemical Engineering of Oil&Gas,2016,45(1):14-20.
[13]胡天友,何金龙,彭修军.高效有机硫脱除溶剂CT8-24的研究[J].石油与天然气化工,2013,42(3):205-210.Hu Tianyou,He Jinlong&Peng Xiujun.Study on high effective organic sulfur removal solvent CT8-24[J].Chemical Engineering of Oil&Gas,2013,42(3):205-210.
[14]何金龙,杨春生,常宏岗,陈胜勇,印敬,胡天友.位阻胺选择性脱硫配方溶剂(CT8-16)脱除天然气中H2S、CO2应用试验[J].石油与天然气化工,2010,39(6):487-490.He Jinlong,Yang Chunsheng,Chang Honggang,Chen Shengyong,Yin Jing&Hu Tianyou.Field application of sterical hindrance amine formula sweetening solvent(CT8-16)on selective removal of H2S and CO2 from natural gas[J].Chemical Engineering of Oil&Gas,2010,39(6):487-490.
[15]胡天友,熊钢,何金龙,印敬,彭修军.胺法脱硫装置溶液发泡预防及控制措施[J].天然气工业,2009,29(3):101-103.Hu Tianyou,Xiong Gang,He Jinlong,Yin Jing&Peng Xiujun.Prevention and control measures for foaming in amine desulfurization unit[J].Natural Gas Industry,2009,29(3):101-103.
[2]Taheri M,Mohebbi A,Hashemipour H&Rashidi AM.Simultaneous absorption of carbon dioxide(CO2)and hydrogen sulfide(H2S)from CO2-H2S-CH4 gas mixture using amine-based nanofluids in a wetted wall column[J].Journal of Natural Gas Science and Engineering,2016,28(1):410-417.
[3]Idris Z&Eimer DA.Representation of CO2 absorption in sterically hindered amines[J].Energy Procedia,2014,51(7):247-252.
[4]Sartori G&Savage DW.Sterically hindered amines for carbon dioxide removal from gases[J].Industrial&Engineering Chemistry Fundamentals,1983,22(2):239-249.
[5]Say GR,Heinzelmann FJ,Iyengar JN&Sartori GS.New,hindered amine concept for simultaneous removal of CO2 and H2Sfrom gases[J].Chemical Engineering Progress,1984,80(10):72-77.
[6]Mandal BP,Biswas AK&Bandyopadhyay SS.Selective absorption of H2S from gas streams containing H2S and CO2 into aqueous solutions of N-methyldiethanolamine and 2-amino-2-methyl-1-propanol[J].Separation&Purification Technology,2004,35(3):191-202.
[7]Fedich RB,Woerrner AC,Chitnis GK.Selective H2S removal[J].Hydrocarbon Engineering,2004,9(5):89-92.
[8]王开岳.天然气净化工艺:脱硫脱碳、脱水、硫磺回收及尾气处理[M].北京:石油工业出版社,2015.Wang Kaiyue.Natural gas purification process:Desulphurization,decarbonization,dehydration,sulfur recovery and tail gas treatment[M].Beijing:Petroleum Industry Press,2015.
[9]陈赓良,常宏岗.配方型溶剂的应用与气体净化工艺的发展动向[M].北京:石油工业出版社,2009.Chen Gengliang&Chang Honggang.Application of formulated solvents and development trend of gas purification process[M].Beijing:Petroleum Industry Press,2009.
[10]李云涛,李露露,李辉,张智,徐计雷.空间位阻胺脱硫选择性及再生性能的研究[J].西南石油大学学报(自然科学版),2017,39(3):173-179.Li Yuntao,Li Lulu,Li Hui,Zhang Zhi&Xu Jilei.Desulfurization selectivity and regeneration studies of sterically hindered amines[J].Journal of Southwest Petroleum University(Science&Technology Edition),2017,39(3):173-179.
[11]杨波,诸林,杨超越,唐诗.空间位阻胺1,3-二(二乙胺基)-2-丙醇的合成及脱硫性能评价[J].现代化工,2017,37(3):146-150.Yang Bo,Zhu Lin,Yang Chaoyue&Tang Shi.Synthesis and desulfurization performance evaluation of steric hindrance amine1,3-bis(diethylamine)-2-propanol[J].Modern Chemical Industry,2017,37(3):146-150.
[12]王治红,张诗悦,高阳.含空间位阻基团的选择性脱硫剂的合成与表征[J].石油与天然气化工,2016,45(1):14-20.Wang Zhihong,Zhang Shiyue&Gao Yang.Synthesis and characterization of selective desulfurizer with steric hindrance group[J].Chemical Engineering of Oil&Gas,2016,45(1):14-20.
[13]胡天友,何金龙,彭修军.高效有机硫脱除溶剂CT8-24的研究[J].石油与天然气化工,2013,42(3):205-210.Hu Tianyou,He Jinlong&Peng Xiujun.Study on high effective organic sulfur removal solvent CT8-24[J].Chemical Engineering of Oil&Gas,2013,42(3):205-210.
[14]何金龙,杨春生,常宏岗,陈胜勇,印敬,胡天友.位阻胺选择性脱硫配方溶剂(CT8-16)脱除天然气中H2S、CO2应用试验[J].石油与天然气化工,2010,39(6):487-490.He Jinlong,Yang Chunsheng,Chang Honggang,Chen Shengyong,Yin Jing&Hu Tianyou.Field application of sterical hindrance amine formula sweetening solvent(CT8-16)on selective removal of H2S and CO2 from natural gas[J].Chemical Engineering of Oil&Gas,2010,39(6):487-490.
[15]胡天友,熊钢,何金龙,印敬,彭修军.胺法脱硫装置溶液发泡预防及控制措施[J].天然气工业,2009,29(3):101-103.Hu Tianyou,Xiong Gang,He Jinlong,Yin Jing&Peng Xiujun.Prevention and control measures for foaming in amine desulfurization unit[J].Natural Gas Industry,2009,29(3):101-103.