提高UDS溶剂脱除塔河油田伴生天然气中有机硫效率

doi:10.16085/j.issn.1000-6613.2019-0222

摘要/Abstract

摘要：

为了解决新疆塔河油田伴生天然气中高含量有机硫的脱除难题，需开发高效脱硫溶剂。基于已在天然气净化领域工业应用的UDS-2溶剂的初始组成，采用量子化学计算并结合溶解度COSMO-RS模型预测优选提高甲硫醇(MeSH)溶解性能的溶剂组分，改进原UDS-2溶剂对MeSH的脱除性能，并分别在常压和高压吸收实验装置上对比考察不同溶剂对模拟塔河油田伴生天然气的吸收净化效果。结果表明，聚合度为5的聚乙二醇二甲醚（PEGDME-3）与MeSH分子之间的相互作用最强，对MeSH的溶解性能最好，相同条件下，MeSH在PEGDME-3中的亨利系数最小，40℃时的亨利系数为14.9 MPa·L/mol。PEGDME-3调配入原UDS-2溶剂中获得的改进UDS溶剂，对MeSH和总有机硫的脱除率较改进前原UDS-2溶剂分别提高了10.1%～11.4%和7.2%～8.5%。所得结论将有助于进一步提高UDS溶剂的有机硫脱除效率，满足塔河油田伴生天然气高含量有机硫的脱除净化需求。

关键词: 有机硫, 油田伴生气, 脱硫溶剂, 溶解度

Abstract:

Desulfurization solvent with high performance is required in order to effectively remove the high-content organosulfide compounds from the associated natural gas of Tahe Oilfield. Based on the original composition of UDS-2 solvent which had been developed and commercially applied in natural gas purification, optimum component with excellent removing efficiency for MeSH was screened via quantum calculation coupled with solubility predication using COSMO-RS model to enhance the performance of UDS-2 for MeSH removal. In addition, the purification performance of different solvents for simulated Tahe oilfield associated natural gas was evaluated under atmospheric and high pressure absorption conditions, respectively. PEGDME-3 having degree of polymerization of 5 showed the strongest intermolecular interaction with MeSH, which contributed to the highest solubility and the smallest Henry constant of 14.9 MPa·L/mol at 40℃. As compared to the parent UDS-2 solvent, the modified UDS solvent with the addition of PEGDME-3 was found to have 10.1—11.4 percentage points and 7.2—8.5 percentage points higher removal efficiencies for MeSH and total organosulfide respectively. As a result, the modified UDS solvent with largely enhanced removal efficiencies for organosulfides can be promising desulfurization solvent for the purification of Tahe associated natural gas containing high content of organosulfur compounds.

Key words: organicsulfur, oilfield associated gas, desulfurization solvent, solubility

中图分类号:

TE644

杨世伦,安阳,孙辉,沈本贤,汤晟,赵德银. 提高UDS溶剂脱除塔河油田伴生天然气中有机硫效率[J]. 化工进展, 2019, 38(10): 4534-4541.

Shilun YANG,Yang AN,Hui SUN,Benxian SHEN,Sheng TANG,Deyin ZHAO. Modification on UDS solvent for enhanced organosulfides removal from Tahe associated natural gas[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4534-4541.

图/表 11

表1 模拟塔河天然气组成

组分	含量
H₂S体积分数/% CO₂体积分数/%	4.5 7.5
有机硫化物/mg·m^-3
甲硫醇（MeSH）	500.0
乙硫醇（EtSH）	42.8
羰基硫（COS）	28.6

图1 天然气常压吸收净化实验流程 1—原料气钢瓶；2—原料气缓冲罐；3—流量计；4—吸收塔；5—溶液储罐；6—蠕动泵；7—恒温水浴；8—溶液缓冲罐；9—温度计；10—尾气收集口；11—富液储罐；12—尾气处理器；13—排液法气体流量校正系统

图2 天然气高压吸收净化实验流程 1—脱硫塔；2—闪蒸罐；3—换热器；4—再生器；5—溶液泵；6—冷却器；S1—原料气；S2—净化气；S3—富液；S4—贫液；S5—再生酸性气； S6—冷却后贫液；S7—闪蒸气

表2 复合物体系的结合能

复合物	ΔE/kJ·mol^-1
MeSH-MDEA MeSH-MOR	-10.545 -12.354
MeSH-PC	-23.545
MeSH-SUL	-18.578
MeSH-NMP	-25.658
MeSH-PEGDME-1	-43.135
MeSH-PEGDME-2	-43.244
MeSH-PEGDME-3	-43.358
MeSH-PEGDME-4	-43.127

图3 MeSH和各溶剂分子的表面电荷密度分布图

图4 MeSH和各溶剂分子的表面电荷密度分布曲线

图5 MeSH在各溶剂中的气液相平衡

表3 MeSH在各溶剂中的亨利系数

溶剂	H/MPa·L·mol^-1	溶剂	H/MPa·L·mol^-1
MDEA	40.5	PC	24.6
MOR	31.6	NMP	26.5
PEGDME-3	14.9	SUL	28.6
原UDS-2^①	21.8

图6 改进UDS溶液的密度、黏度和表面张力

图7 常压条件下不同溶剂对MeSH以及总有机硫的脱除率溶剂种类

图8 高压条件下MeSH以及总有机硫脱除率溶剂种类

参考文献 18

1	BP投资有限公司 . BP世界能源统计年鉴[EB/OL]. 北京: BP中国对外事务部. [2018-7-30]..
	Investment Co. BP , Ltd . BP Statistical Review of World Energy[EB/OL].Beijing: BP China Foreign Affairs Department.[2018-7-30]..
2	BUEWELL K , KUBEK D , SIGMUND P . Alkanolamine treating[J]. Hydrocarbon Processing, 1982, 3:108-116.
3	BAKER R , LOKHANDWALA K . Natural gas processing with membranes: an overview[J]. Industrial & Engineering Chemistry Research, 2008, 47(7): 2109-2121.
4	XIAO Y , LOW B, HOSSEINI S , et al . The strategies of molecular architecture and modification of polyimide-based membranes for CO₂ removal from natural gas:a review[J]. Progress in Polymer Science, 2009, 34(6): 561-580.
5	BEDELL S , MILLER M . Aqueous amines as reactive solvents for mercaptan removal[J]. Industrial & Engineering Chemistry Research, 2007, 46: 3729-3733.
6	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]. 2版. 北京: 石油工业出版社, 2009.
	CHEN Gengliang , CHANG Honggang . Applications of formulated solvents and perspective of gas purification processes[M]. 2nd ed.,Beijing: Petroleum Industrial Press, 2009.
7	陈赓良 . 天然气脱硫醇工艺评述[J]. 石油与天然气化工, 2017, 46(5): 1-8.
	CHEN Gengliang . A review on demercaptan process of natural gas[J]. Chemical Engineering of Oil and Gas, 2017, 46(5):1-8.
8	沈本贤, 章建华, 储政, 等 . 高酸性石油天然气的高效净化脱硫剂: CN 200910233505.1[P]. 2009-10-28.
	SHEN Benxian , ZHANG Jianhua , CHU Zheng , et al . Desulfurization solvent with high-performance for purification of high sour natural gas: ZL 200910233505.1[P]. 2009-10-28.
9	张峰, 沈本贤, 孙辉, 等 . 基于分子管理的脱有机硫复配型溶剂的开发与应用[J]. 化工进展, 2015, 34(6): 1786-1791, 1803.
	ZHANG Feng , SHEN Benxian , SUN Hui , et al . Development and application of formulated solvents based on molecular management theory for removing organic sulfur[J]. Chemical Industry and Engineering Progress, 2015, 34(6): 1786-1791, 1803.
10	ZHANG F , SHEN B , SUN H , et al . Rational formulation design and commercial application of a new hybrid solvent for selectively removing H₂S and organosulfurs from sour natural gas[J]. Energy & Fuels, 2015, 30(1): 12-19.
11	ZHANG Jianhua , SHEN Benxian , SUN Hui , et al . A study on the desulfurization performance of solvent UDS for purifying high sour natural gas[J]. Petroleum Science & Technology, 2011, 29(1): 48-58.
12	于惠波, 沈本贤, 孙辉, 等 . 改性UDS溶剂提高天然气中甲硫醇脱除效率的研究[J]. 石油炼制与化工, 2017, 48(7): 28-33.
	YU Huibo , SHEN Benxian , SUN Hui , et al . Study of improving MeSH removal efficiency by modified UDS solvent from natural gas[J]. Petroleum Processing and Petrochemicals, 2017, 48(7): 28-33.
13	霍珍珍, 沈本贤, 陈曦, 等 . UDS溶剂组分设计及其脱除黏胶纤维废气中CS₂效果[J]. 化工进展, 2018, 37(1): 292-300.
	HUO Zhenzhen , SHEN Benxian , CHEN Xi , et al . Compositional design of UDS and its application on removal of CS₂ from viscose fiber waste gas[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 292-300.
14	PARNIS J , ENG A, MACKAY D , et al . Characterizing PUF disk passive air samplers for alkyl-substituted PAHs: measured and modelled PUF-AIR partition coefficients with COSMO-RS[J]. Chemosphere, 2016, 145: 360-364.
15	LIU X , ZHOU T , ZHANG X , et al . Application of COSMO-RS and UNIFAC for ionic liquids based gas separation[J]. Chemical Engineering Science, 2018, 192: 816-828.
16	KLAMT A . The COSMO and COSMO-RS solvation models[J]. Wiley Interdisciplinary Reviews: Computational Molecular Science, 2011, 1(5): 699-709.
17	祁影霞, 王禹贺, 车闫瑾, 等 . 混合制冷剂(R600a+R152a+R134)的气液相平衡分析[J]. 化学工程, 2018, 46(7): 42-46.
	QI Yingxia , WANG Yuhe , CHE Yanjin , et al . Vapor-liquid phase equilibrium analysis of mixed refrigerant(R600a+R152a+R134)[J]. Chemical Engineering, 2018, 46(7): 42-46.
18	陈燕鑫, 童赛, 张美景, 等 . 基于COSMO-RS模型L-丙氨酸-L-谷胺酰胺结晶溶剂的筛选及其溶液热力学性质研究[J]. 化学工业与工程, 2016, 33(3): 31-38.
	CHEN Yanxin , TONG Sai , ZHANG Meijing , et al . Solvent screening via COSMO-RS model and measurement of solution thermodynamics for crystallization of N-(2)-L-alanyl-L-glutamine[J]. Chemical Industry and Engineering, 2016, 33(3): 31-38.

[1]	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.
[2]	杨超越, 易铧, 刘可, 何金龙, 倪伟, 常宏岗, 胡超, 胡天友, 陈世明, 陈文科. 高效有机硫脱除溶剂CT8-24的工业应用[J]. 化工进展, 2020, 39(8): 3371-3379.
[3]	仝玉军, 沈本贤, 刘纪昌, 黄恒文. 基于柱色谱分离的阿曼减压渣油结构表征与溶解度参数测定[J]. 化工进展, 2018, 37(07): 2547-2556.
[4]	王敏, 曹睿, 刘艳升, 徐泓. 烃-水体系互溶度预测模型的研究进展[J]. 化工进展, 2017, 36(12): 4343-4349.
[5]	李华锋, 黄尚顺, 廖青, 秦高雄, 覃佑康, 王俊, 陈钊民. 剑麻皂甙元在甲醇和乙醇中溶解度的测定及应用[J]. 化工进展, 2016, 35(S1): 31-34.
[6]	王清清, 孙勤, 杨阿三, 程榕, 郑燕萍. 缬沙坦在乙酸乙酯中的溶解度及介稳区[J]. 化工进展, 2016, 35(08): 2329-2333.
[7]	宋昌斌, 李润超. 碳酸锂在水中的溶解度和超溶解度的测定及热力学分析[J]. 化工进展, 2016, 35(08): 2350-2354.
[8]	孙飞飞, 雷乐成, 朱京科. 定量结构-性质关系在化合物溶解度预测中的研究进展[J]. 化工进展, 2015, 34(05): 1215-1219.
[9]	李颖，金君素，张泽廷. 含夹带剂超临界体系溶解度模型的改进及验证[J]. 化工进展, 2013, 32(10): 2297-2301.
[10]	王世丽1，2，翟康1，2，张瑞芹1，2，范利杰2，刘永刚1，2. 氢气在柴油中溶解度的测定与模拟计算[J]. 化工进展, 2013, 32(09): 2049-2055.
[11]	李小康，刘应书，张辉，魏广飞，李虎，张四宗. DEA复配水溶液二氧化碳溶解度的测定实验[J]. 化工进展, 2013, 32(04): 769-773.
[12]	祝勇仁，王循明. 超临界二氧化碳染色技术研究进展[J]. 化工进展, 2012, 31(09): 1891-1898.
[13]	丁靖，熊焰，虞大红. CO2在离子液体中溶解度的实验测定与模型化方法[J]. 化工进展, 2012, 31(04): 732-741.
[14]	孙学文. 炼油厂产品深度脱硫工艺的研究进展 [J]. 化工进展, 2009, 28(4): 610-.
[15]	顾丹丹，辛梅华，李明春，周景润. O-二酸单酯-N,N双长链烷基壳寡糖的制备及表征 [J]. 化工进展, 2008, 27(7): 1106-.