高含有机硫天然气的净化研究与探索

doi:10.16085/j.issn.1000-6613.2021-2646

摘要/Abstract

摘要：

在使用单一甲基二乙醇胺（MDEA）溶液脱除天然气中H₂S的过程中，随着有机硫含量不断地增加，常常造成出料气中H₂S和总硫含量均不能满足国家二类天然气质量要求。在改变关键参数后，脱硫效果仍然不能改善。因此，本文针对高含量的有机硫，开展了MDEA+DIPA、MDEA+DEA、环丁砜+MDEA、环丁砜+DIPA 4组高效脱硫剂的复配研究，通过对比H₂S及有机硫在溶液中的吸收分压，筛选出了吸收效果较优的脱硫剂组合为：环丁砜+MDEA。随后再利用BBD响应面分析法，以环丁砜、MDEA、H₂O的不同配比为变量，以H₂S和总硫脱除率最高为目标函数进行寻优，经过混料实验与复合优化，最终得出最优脱硫剂配比为：23.3%环丁砜+54.6%MDEA+22.1%H₂O。最优配比脱硫剂经现场装置使用后的效果表明，H₂S脱除率达到99.964%，总硫脱除率达到99.833%，出料气中H₂S含量为14.4mg/m³，总硫含量为78.5mg/m³，满足二类气标准。

关键词: 天然气, 硫化氢, 有机硫, 脱硫剂, 响应面分析法, 配比优化

Abstract:

In the process of removing H₂S from natural gas usng a single MDEA solution, both H₂S and total sulfur content in the output gas always cannot meet the quality requirements of national class II natural gas with the continuous increase of organic sulfur content. After changing the key parameters, the desulfurization effect still could not be improved. Therefore, for the high content of organic sulfur, this paper carried out the research on the compound of MDEA+DIPA, MDEA+DEA, sulfolane+MDEA and sulfolane+DIPA four groups of efficient desulfurizers. By comparing the absorption partial pressure of H₂S and organic sulfur in solution, the better absorption desulfurizer combination was selected as sulfolane+MDEA. Then, the BBD response surface methodology was used according to the different ratio of sulfoxane, MDEA and H₂O as variables, and the optimal ratio of H₂S and total sulfur removal rate was optimized as the objective function. After mixing experiments and composite optimization, the optimal ratio of desulfurizer was obtained as 23.3% sulfoxane+54.6% MDEA+22.1% H₂O. The results of the optimal proportion of desulfurizer after the use of the field device showed that the removal rate of H₂S reached 99.964%, the removal rate of total sulfur was 99.833%, the content of H₂S in the effluent gas was 14.4mg/m³ and the total sulfur content was 78.5mg/m³, which met the national standard of class II gas.

Key words: natural gas, hydrogen sulfide, organic sulfur, desulfurizer, response surface methodology, composition adjustment

中图分类号:

TE644

冷南江, 马国光, 张涛, 雷洋, 彭豪, 熊祚帅, 陈玉婷. 高含有机硫天然气的净化研究与探索[J]. 化工进展, 2022, 41(10): 5342-5353.

LENG Nanjiang, MA Guoguang, ZHANG Tao, LEI Yang, PENG Hao, XIONG Zuoshuai, CHEN Yuting. Research and exploration on purification of natural gas with high organic sulfur content[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5342-5353.

图/表 27

参考文献 25

1	汤晟, 孙永尧. 塔河油田某天然气处理装置优化升级改造及效果评价[J]. 石油与天然气化工, 2021, 50(4): 33-38.
	TANG Sheng, SUN Yongyao. Optimization upgrade and effect evaluation of a natural gas treatment unit in Tahe oilfield[J]. Chemical engineering of oil & gas, 2021, 50(4): 33-38.
2	陈昌介, 何金龙, 温崇荣. 高含硫天然气净化技术现状及研究方向[J]. 天然气工业, 2013, 33(1): 112-115.
	CHEN Changjie, HE Jinlong, WEN Chongrong. A state of the art of high-sulfur natural gas sweetening technology and its research direction[J]. Natural Gas Industry, 2013, 33(1): 112-115.
3	黄维和, 唐蒙, 常宏岗, 等. 天然气: [S]. 北京: 中国标准出版社, 2018.
	HUANG Weihe, TANG Meng, CHANG Honggang, et al. Natural gas: [S]. Beijing: Standards Press of China, 2018.
4	赵凌霜, 王闯. 基于HYSYS软件的MDEA溶液进料参数研究[J]. 石油化工建设, 2021, 43(S1): 112-115.
	ZHAO Lingshuang, WANG Chuang. Research on feeding parameters of MDEA solution based on HYSYS software[J]. Petroleum and Chemical Construction, 2021, 43(S1): 112-115.
5	杨超越, 刘可, 李林峰, 等. 天然气净化装置影响有机硫脱除的因素研究[J]. 石油与天然气化工, 2021, 50(2): 9-16.
	YANG Chaoyue, LIU Ke, LI Linfeng, et al. Research on the factors affecting organic sulfur removal of natural gas purification unit[J]. Chemical Engineering of Oil & Gas, 2021, 50(2): 9-16.
6	马孟平, 吕岳琴, 万书华, 等. 深度脱除高含硫天然气中有机硫的Sulfinol-X脱硫工艺[J]. 天然气工业, 2021, 41(10): 127-132.
	MA Mengping, Yueqin LYU, WAN Shuhua, et al. Sulfinol-X desulfurization process for deep removal of organic sulfur from high-sulfur natural gas[J]. Natural Gas Industry, 2021, 41(10): 127-132.
7	唐建峰, 李晶, 陈杰, 等. TEA+DETA混合胺液脱除天然气中H₂S性能优选[J]. 石油学报, 2015, 36(8): 1004-1011.
	TANG Jianfeng, LIjing, CHEN Jie, et al. Optimization on the performance of H₂S removal from natural gas by TEA+DETA mixed amine solution[J]. Acta Petrolei Sinica, 2015, 36(8): 1004-1011.
8	李晶. 天然气选择性脱硫胺液配方筛选实验研究[D]. 青岛: 中国石油大学(华东), 2016.
	LI Jing. Experimental study on screening formula of amine solution in natural gas selective desulfurization[D]. Qingdao: China University of Petroleum(East China), 2016.
9	姚丽蓉, 赵德银, 崔伟, 等. 基于响应面分析法的天然气脱氮工艺优化[J]. 天然气化工(C₁化学与化工), 2020, 45(6): 75-81.
	YAO Lirong, ZHAO Deyin, CUI Wei, et al. Optimization of nitrogen rejection process based on response surface analysis[J]. Natural Gas Chemical Industry, 2020, 45(6): 75-81.
10	石晓青, 朱炜玄, 叶昊天, 等. 碳五隔壁反应精馏预处理工艺模拟及多目标优化[J]. 化工学报, 2021: 1-14.
	SHI Xiaoqing, ZHU Weixuan, YE Haotian, et al. Pretreatment process simulation and multi-objective optimization of C₅ by reactive dividing wall column[J]. CIESC Journal, 2021: 1-14.
11	余小翠, 刘高峰. 响应面分析法在中药提取和制备工艺中的应用[J]. 中药材, 2010, 33(10): 1651-1655.
	YU Xiaocui, LIU Gaofeng. Application of response surface methodology in extraction and preparation of traditional Chinese medicine[J]. Journal of Chinese Medicinal Materials, 2010, 33(10): 1651-1655.
12	李莉, 张赛, 何强, 等. 响应面法在试验设计与优化中的应用[J]. 实验室研究与探索, 2015, 34(8): 41-45.
	LI Li, ZHANG Sai, HE Qiang, et al. Application of response surface methodology in experiment design and optimization[J]. Research and Exploration in Laboratory, 2015, 34(8): 41-45.
13	梁平, 卢海东, 张哲, 等. 长庆油田某天然气净化厂实现GB 17820—2018达标工艺方案研究[J]. 石油与天然气化工, 2020, 49(1): 1-7.
	LIANG Ping, LU Haidong, ZHANG Zhe, et al. Process scheme study on the realization of GB 17820—2018 standardization in a natural gas purification plant of Changqing Oilfield[J]. Chemical Engineering of Oil & Gas, 2020, 49(1): 1-7.
14	马国光, 曹连进, 钟荣强, 等. 塔二联轻烃站脱硫系统参数调整分析[J]. 石油与天然气化工, 2015, 44(1): 21-24.
	MA Guoguang, CAO Lianjin, ZHONG Rongqiang, et al. Parameters adjustment analysis of desulfurization system of Tahe 2^# light hydrocarbon station[J]. Chemical Engineering of Oil & Gas, 2015, 44(1): 21-24.
15	高明, 苏昊, 冯志远, 等. Aspen HYSYS酸性气流体包的应用及有机硫计算分析[J]. 石油与天然气化工, 2021, 50(4): 39-46.
	GAO Ming, SU Hao, FENG Zhiyuan, et al. Application of acid gas fluid packages in Aspen HYSYS and analysis and calculation of organic sulfur[J]. Chemical engineering of oil & gas, 2021, 50(4): 39-46.
16	韩鹏飞, 蒋洪, 韩勇. 活化MDEA半贫液工艺脱碳模拟与研究[J]. 石油化工应用, 2017, 36(1): 139-144.
	HAN Pengfei, JIANG Hong, HAN Yong. Simulation and research of the activated MDEA method Semi-lean process based on HYSYS[J]. Petrochemical Industry Application, 2017, 36(1): 139-144.
17	商剑峰, 邱敏, 姬忠礼. 高含硫天然气脱酸气装置提效降耗优化[J]. 天然气工业, 2019, 39(2): 102-110.
	SHANG Jianfeng, QIU Min, JI Zhongli. Efficiency improvement, consumption reduction and optimization of high-sulfur natural gas sweetening units[J]. Natural Gas Industry, 2019, 39(2): 102-110.
18	付东, 华雪莹, 徐怡斐, 等. 醇胺水溶液粘度的实验和理论研究[J]. 化学学报, 2011, 69(7): 772-776.
	FU Dong, HUA Xueying, XU Yifei, et al. Experimental and theoretical study on the viscosity of aqueous solution of alkanol amines[J]. Acta Chimica Sinica, 2011, 69(7): 772-776.
19	罗威. 天然气脱硫脱碳净化工艺技术研究[D]. 大庆: 东北石油大学, 2013.
	LUO wei. Study on desulphurization and decarbonization of natural gas purification technology[D]. Daqing: Northeast Petroleum University, 2013.
20	谭更彬, 王志泉, 吴钟旺. 天然气脱除硫化氢的研究[J]. 应用化工, 2020, 49(12): 3108-3110.
	TAN Gengbin, WANG Zhiquan, WU Zhongwang. Study on removal of hydrogen sulfide from natural gas[J]. Applied Chemical Industry, 2020, 49(12): 3108-3110.
21	王金玉, 王治红, 黄志宇. 高含硫天然气净化工艺技术进展[J]. 石油化工应用, 2008, 27(6): 4-8.
	WANG Jinyu, WANG Zhihong, HUANG Zhiyu. High sour natural gas purifying technology processing[J]. Petrochemical Industry Application, 2008, 27(6): 4-8.
22	毛松柏, 周志斌, 朱道平, 等. 选择性脱除克劳斯硫回收装置尾气中硫化物的研究[J]. 能源化工, 2017, 38(3): 30-34.
	MAO Songbai, ZHOU Zhibin, ZHU Daoping. Study on selective removal of sulfur compounds from Claus unit tail gas[J]. Energy Chemical Industry, 2017, 38(3): 30-34.
23	唐建峰, 张春, 郭清, 等. 海上浮式液化天然气脱酸气技术[J]. 化工进展, 2011, 30(10): 2178-2185.
	TANG Jianfeng, ZHANG Chun, GUO Qing, et al. Offshore floating LNG acid gas removal process technology[J]. Chemical Industry and Engineering Progress, 2011, 30(10): 2178-2185.
24	常军, 张利波, 彭金辉, 等. 微波强化焙烧氧化锌烟尘提铟工艺优化研究[J]. 有色金属(冶炼部分), 2018(3): 39-44.
	CHANG jun, ZHANG Libo, PENG Jinhui, et al. Optimization extraction of indium by microwave enhanced roasting process from zinc oxide dust[J]. Nonferrous Metals(Extractive Metallurgy), 2018(3): 39-44.
25	王元丰, 余弘, 谭思思, 等. 棉织物泡沫染色工艺的筛选和优化[J]. 纺织学报, 2014, 35(3): 68-74.
	WANG Yuanfeng, YU Hong, TAN Sisi, et al. Selecting and optimizing of parameters of foam dyeing process of cotton fabrics[J]. Journal of Textile Research, 2014, 35(3): 68-74.

组分	摩尔分数/%	组分	摩尔分数/%	组分	含量/mg·m^-3
CH₄	44.079	C₆₊	2.579	COS	18.16
C₂H₆	9.666	O₂	0.100	CH₃SH	576.43
C₃H₈	8.166	He	0.020	C₂H₅SH	89.68
i-C₄H₁₀	1.709	H₂	0.100	CS₂	12.69
n-C₄H₁₀	5.507	CO₂	6.157
i-C₅H₁₂	2.479	N₂	13.394
n-C₅H₁₂	3.328	H₂S	2.669

组分	摩尔分数/%	组分	摩尔分数/%	组分	含量/mg·m^-3
CH₄	44.079	C₆₊	2.579	COS	18.16
C₂H₆	9.666	O₂	0.100	CH₃SH	576.43
C₃H₈	8.166	He	0.020	C₂H₅SH	89.68
i-C₄H₁₀	1.709	H₂	0.100	CS₂	12.69
n-C₄H₁₀	5.507	CO₂	6.157
i-C₅H₁₂	2.479	N₂	13.394
n-C₅H₁₂	3.328	H₂S	2.669

项目	装置设计参数	实际运行参数
进料气量/10⁴m³·d^-1	40	22
进料气H₂S含量/mg·m^-3	20000	40000
进料气有机硫含量/mg·m^-3	100	700
出料气H₂S含量/mg·m^-3	≤20	37
出料气有机硫含量/mg·m^-3	≤100	84
脱硫负荷/t·d^-1	8.05	10.5
进料气温度/℃	53	50
进料气压力/MPa	2.5	2.5
脱硫剂配比（MDEA质量分数）/%	40	40
MDEA溶液循环量/m³·h^-1	26	22~24

项目	装置设计参数	实际运行参数
进料气量/10⁴m³·d^-1	40	22
进料气H₂S含量/mg·m^-3	20000	40000
进料气有机硫含量/mg·m^-3	100	700
出料气H₂S含量/mg·m^-3	≤20	37
出料气有机硫含量/mg·m^-3	≤100	84
脱硫负荷/t·d^-1	8.05	10.5
进料气温度/℃	53	50
进料气压力/MPa	2.5	2.5
脱硫剂配比（MDEA质量分数）/%	40	40
MDEA溶液循环量/m³·h^-1	26	22~24

单元	设备	参数	模拟数据	实测数据	误差 /%
脱硫单元	MDEA吸收塔	顶部压力/MPa	2.53	2.53	0
		顶部温度/℃	50.46	50	0.90
		底部压力/MPa	2.72	2.72	0
		底部温度/℃	52.05	52	0.96
	净化气分离器	压力/MPa	2.53	2.53	0
		温度/℃	47.46	48	1.13
		硫化氢含量/mg·m^-3	36.76	36	2.11
		总硫含量/mg·m^-3	126.46	123	3.10
再生单元	MDEA再生塔	顶部压力/kPa	80	80	0
		顶部温度/℃	92.55	92	0.60
		底部压力/kPa	120	120	0
		底部温度/℃	112.8	113	0.18
		胺液循环量/m³·h^-1	30	30	0
	塔底重沸器	压力/kPa	120	120	0
	塔底重沸器	温度/℃	112.8	113	0.18