Catalytic hydrolysis of carbonyl sulfide with application of NHD/MDEA/H2O

doi:10.11949/0438-1157.20200336

Abstract

Abstract:

To solve the problems of lower removal efficiency of organic sulfide and large amount of by-products in the traditional wet desulfurization process, a novel wet catalytic hydrolysis system of carbonyl sulfide was developed. The system was constructed with application of polyethylene glycol dimethyl ether (NHD), N-methyldiethanolamine (MDEA), and water as desulfurization agent with optimal compositions of 25% MDEA/15% H₂O/60% NHD. The effect of the desulfurization operation parameters, reaction temperature, gas concentration and gas flow rate on the desulfurization of COS was investigated. Furthermore the possible mechanism and kinetic of the desulfurization process were proposed and determined in reference of the results of GC and IC. The results show that the removal efficiency of COS is above 80% under low temperature (298.15—343.15 K) and normal pressure. The absorption process conforms to pseudo-first-order reaction kinetics. The organic solvent contents in the developed desulfurization system is more than 85%, which can effectively avoid the production of by-products and consumption of alkali in the desulfurization system, and is expected to be treated as an alternative for COS removal with high desulfurization efficiency.

Key words: carbonyl sulfide, polyethylene glycol dimethyl ether, N-methyldiethanolamine, wet desulfurization

摘要：

为解决传统湿法脱硫工艺中有机硫脱除效率低、副产物多等问题，依托配方型溶剂脱硫工艺，以聚乙二醇二甲醚（NHD）、N-甲基二乙醇胺（MDEA）和水为原料构建新型湿法催化水解羰基硫（COS）脱硫体系。优化复配溶剂组成比例，确立配方溶剂组成为25% MDEA/15% H₂O/60% NHD，考察了脱硫操作参数、反应温度、气体浓度、气体流量等因素对脱硫的影响，使用气相色谱和离子色谱分析探究脱硫过程及反应动力学。结果表明，在低温（298.15~343.15 K）、常压条件下对COS的脱除效率达80%以上；复配溶液将吸收后的COS催化水解为H₂S和CO₂，吸收过程符合准一级反应动力学。该脱硫液中有机溶剂含量占85%以上，可解决脱硫副产物产生多和碱耗大的问题，是一种新型有机介质脱硫工艺。

关键词: 羰基硫, 聚乙二醇二甲醚, N-甲基二乙醇胺, 湿法脱硫

CLC Number:

X 701. 3

Xueke LIU,Li ZHANG,Fen LIU,Shuaitao GAO,Jiang YU,Jianfeng SHANG,Tianxiong OU,Zheng ZHOU,Pingwen CHEN. Catalytic hydrolysis of carbonyl sulfide with application of NHD/MDEA/H₂O[J]. CIESC Journal, 2020, 71(11): 5286-5293.

刘雪珂,张丽,刘芬,高帅涛,余江,商剑锋,欧天雄,周政,陈平文. NHD/MDEA/H₂O复合脱硫液催化水解羰基硫[J]. 化工学报, 2020, 71(11): 5286-5293.

Figures/Tables 12

Fig.1 Experimental set-up

Fig.2 Desulfurization efficiency as function of time at different system

Fig.3 Desulfurization efficiency as function of time for H2O/NHD with volume ratios

Fig.4 Desulfurization efficiency as function of time with different MDEA contents

Fig.5 Desulfurization efficiency as function of time with different volume ratios

Fig.6 Desulfurization efficiency as function of time at different temperature(P=0.1 MPa, Vg=30 ml/min, CCOS =1339 mg/m3)

Fig.7 Desulfurization efficiency as function of time with different COS concentration(P=0.1 MPa, T=298.15 K, Vg=30 ml/min)

Fig.8 Desulfurization efficiency as function of time at different gas flow(P=0.1 MPa, T=298.15 K, CCOS=1339 mg/m3)

Fig.9 Concentrations of treated tail gas as function of time(P=0.1 MPa, T=313.15 K, Vg=30 ml/min, CCOS=1339 mg/m3)

Fig.10 Schematic diagram of desulfurization process

Table 1 The apparent reaction rate constants and reaction order of desulfurization processe at different temperatures

T/K	lnk_obs	k_obs/(L/(mol·min))	n	R²
298.15	-3.9269	0.0197	1.226	0.9972
313.15	-3.8560	0.0212	1.139	0.9804
323.15	-3.8097	0.0222	1.125	0.9820
333.15	-3.7812	0.0228	1.118	0.9874
343.15	-3.7496	0.0235	1.110	0.9941

Fig.11 lnkobs as function of 1/T

References 29

1	易红宏. 羰基硫低温催化水解技术[M]. 北京: 科学出版社, 2014.
	Yi H H. Catalytic Hydrolysis of Carbonyl Sulfide at Low Temperature[M]. Beijing: Science Press, 2014.
2	Rhodes C, Riddel S A, West J. Low-temperature hydrolysis of carbonyl sulfide and carbon disulfide: a review[J]. Catalysis Today, 2000, 59(3): 443-464.
3	Svoronos P D N, Bruno T J. Carbonyl sulfide: a review of its chemistry and properties[J]. Industrial & Engineering Chemistry Research, 2002, 41(22): 5321-5336.
4	朱本启, 黄长胜, 王高峰. 焦炉气干法脱硫流程的优化[J]. 煤化工, 2010, 38(5): 55-58.
	Zhu B Q, Huang C S, Wang G F. Optimization of coke oven gas dry desulfurization process[J]. Coal Chemical Industry, 2010, 38(5): 55-58.
5	Tsakoumis N E, Ronning M, Oyvind B. Deactivation of cobalt based Fischer-Tropsch catalysts: a review[J]. Catalysis Today, 2010, 154(3): 162-182.
6	王亚军, 李春虎, 薛真. 溶剂法脱除天然气中有机硫的原理及发展趋势[J]. 天然气与石油, 2015, 33(3): 28-32.
	Wang Y J, Li C H, Xue Z. The principle and development trend of organic sulfur removal from natural gas by solvent method[J]. Natural Gas and Oil, 2015, 33(3): 28-32.
7	Pal P, Abukashabeh A, Al-Asheh S. Role of aqueous methyldiethanolamine (MDEA) as solvent in natural gas sweetening unit and process contaminants with probable reaction pathway[J]. Journal of Natural Gas Science and Engineering, 2015, 24: 124-131.
8	Amararene F, Bouallou C. Kinetics of carbonyl sulfide (COS) absorption with aqueous solutions of diethanolamine and methyldiethanolamine[J]. Industrial & Engineering Chemistry Research, 2004, 43(19): 6136-6141.
9	许辉宗. 新配方溶剂脱除液化气中有机硫的工业侧线试验研究[J]. 广东化工, 2001, (6): 38-39.
	Xu H Z. Experimental study on industrial side line of organic sulfur removal from liquefied gas by new formulation solvent[J]. Guangdong Chemical Industry, 2001, (6): 38-39.
10	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 G L. A review of mercaptan removal from natural gas[J]. Chemical Engineering of Oil and Gas, 2017, 46(5): 1-8.
11	Hwang K S, Park S W, Park D W. Absorption of carbon dioxide into diisopropanolamine solutions of polar organic solvents[J]. Journal of the Taiwan Institute of Chemical Engineer, 2010, 41(1): 16-21.
12	Ghanbarabadi H, Khoshandam B. Simulation and comparison of sulfinol solvent performance with amine solvents in removing sulfur compounds and acid gases from natural sour gas[J]. Journal of Natural Gas Science and Engineering, 2015, 22: 415-420.
13	胡天友, 何金龙, 王晓东. 环丁砜-甲基二乙醇胺溶液脱除高酸性天然气中H₂S、CO₂及有机硫实验研究[J]. 石油与天然气化工, 2009, 38(3): 207-211.
	Hu T Y, He J L, Wang X D. Experimental study on the removal of H₂S, CO₂ and organic sulfur from highly acidic natural gas by sulfoxide - methyl diethanolamine solution[J]. Chemical Engineering of Oil and Gas, 2009, 38(3): 207-211.
14	Shokouhi M, Farahani H, Vahidi M. Experimental solubility of carbonyl sulfide in sulfolane and γ-butyrolactone[J]. Journal of Chemical & Engineering Data, 2017, 62(10): 3401-3408.
15	Zhang F, Shen B, Sun H. Rational formulation design and commercial application of a new hybrid solvent for selectively removing H₂S and organosulfurs from sour natural gas[J]. Energy & Fuels, 2016, 30(1): 12-19.
16	Alhseinat E, Keewan M, Banat F. Impact of dissolved and undissolved organics on foaming of industrial amine[J]. International Journal of Greenhouse Gas Control, 2017, 60: 156-161.
17	孙姣, 孙兵, 姬春彦. 天然气脱硫过程的胺液污染问题及胺液净化技术研究进展[J]. 化工进展, 2014, 33(10): 2771-2777.
	Sun J, Sun B, Ji C Y. Ammonia liquid pollution in natural gas desulfurization process and research progress of amine liquid purification technology[J]. Chemical Industry and Engineering Progress, 2014, 33(10): 2771-2777.
18	Islam M S, Yusoff R, Ali B S. Degradation studies of amines and alkanolamines during sour gas treatment process[J]. International Journal of Physical Sciences, 2011, 6(25): 5883-5896.
19	范峥, 黄风林, 王迪. 天然气脱硫溶液失活原因分析与降解机理研究[J]. 高校化学工程学报, 2016, 30(6): 1436-1444.
	Fan Z, Huang F L, Wang D. Study of deactivation reasons and degradation mechanism of natural gas desulfurization solution[J]. Journal of Chemical Engineering of Chinese Universities, 2016, 30(6): 1436-1444.
20	Jamali S H, Ramdin M, Becker T M. Solubility of sulfur compounds in commercial physical solvents and an ionic liquid from Monte Carlo simulations[J]. Fluid Phase Equilibria, 2017, 433: 50-55.
21	Matthew B M, David R L, Robert M E. CO₂-philic oligomers as novel solvents for CO₂absorption[J]. Energy Fuels, 2010, 24(11): 6214-6219.
22	李正西, 秦旭东, 宋洪强. 浅谈聚乙二醇二甲醚与醇胺的复配[J]. 天然气与石油, 2008, 46(1): 42-45.
	Li Z X, Qin X D, Song H Q. The compounding of polyethylene glycol dimethyl ether and alcohol amine[J]. Natural Gas and Oil, 2008, 46(1): 42-45.
23	Alper E, Al-Roweih M, Bouhamra W. Reaction kinetics of COS with primary and secondary amines in alcoholic solutions[J]. The Chemical Engineering Journal and the Biochemical Engineering Journal, 1994, 55(1): 53-59.
24	Mathpati R N, Hudge P G, Kanse K S. Dielectric relaxation and hydrogen bonding interaction of polyethylene glycol dimethyl ether in water mixture[J]. Physics and Chemistry of Liquids, 2019, 10: 1-11.
25	Li X X, Liu Y X, Wei X H. Hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water[J]. Journal of Chemical Industry and Engineering, 2005, 13(2): 88-92.
26	Littel R J, Versteeg G F, van Swaaij W P M. Kinetic study of COS with tertiary alkanolamine solutions (1): Experiments in an intensely stirred batch reactor[J]. Industrial & Engineering Chemistry Research, 1992, 31(5): 1262-1269.
27	Tinoco R R, Bouallou C. Kinetic study of carbonyl sulfide (COS) absorption by methyldiethanolamine aqueous solutions from 415 mol/m³ to 4250 mol/m³ and 313 K to 353 K[J]. Industrial & Engineering Chemistry Research, 2007, 46(20): 6430-6434.
28	Barry B, Lyddon L. A comparison of physical solvents for acid gas removal[C]//GPA Annual Convention Proceeding. Bryan, Texas, USA: Bryan Research & Engineering, Inc., 2008.
29	朱林, 艾珍, 王大军. 使用N-甲酰吗啉和聚乙二醇二甲醚溶剂分离H₂S和CO₂流程模拟比较[J]. 化工学报, 2017, 68: 218-224.
	Zhu L, Ai Z, Wang D J. Simulation and comparison of H₂S and CO₂ separation processes using N-formyl morpholine and polyethylene glycol dimethyl ether solvent[J]. CIESC Journal, 2017, 68: 218-224.

[1]	Feng ZHU, Kailin CHEN, Xiaofeng HUANG, Yinzhu BAO, Wenbin LI, Jiaxin LIU, Weiqiang WU, Wangwei GAO. Performance study of KOH modified carbide slag for removal of carbonyl sulfide [J]. CIESC Journal, 2023, 74(6): 2668-2679.
[2]	Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite [J]. CIESC Journal, 2023, 74(4): 1772-1780.
[3]	Jun HUANG, Yiliang LIU, Peng WU, Kai SHEN, Yaping ZHANG. Poisoning mechanism and antioxidant performance of TiAl-based carbonyl sulfur hydrolysis catalyst [J]. CIESC Journal, 2022, 73(10): 4461-4471.
[4]	GAO Shuaitao, LIU Xueke, ZHANG Li, LIU Fen, YU Jiang, SHANG Jianfeng, OU Tianxiong, ZHOU Zheng, CHEN Pingwen. Aspen Plus simulation on selective separation of high concentration acid gas of H₂S and CO₂ [J]. CIESC Journal, 2021, 72(S1): 413-420.
[5]	Hongchen LIU, Feng ZHOU, Chaoqun YAO, Guangwen CHEN. Flow behavior and stripping enhancement of CO₂ desorption process in microreactor [J]. CIESC Journal, 2019, 70(7): 2448-2455.
[6]	ZHU Lin, AI Zhen, WANG Dajun, WANG Weidong, JIN Xin, DING Liang, XU Guangwen. Simulation and comparison of H₂S and CO₂ separation processes using N-formyl morpholine and polyethylene glycol dimethyl ether solvent [J]. CIESC Journal, 2017, 68(S1): 218-224.
[7]	ZHAO Qinghua, QUAN Xuejun, CHENG Zhiliang, YAN Yunpeng. Wet desulfurization of flue gas and mass transfer mechanism in water-sparged aerocyclone [J]. CIESC Journal, 2013, 64(11): 3993-4000.
[8]	REN Xiaoguang，LI Ziyan，WANG Xueqian，CHEN Wei，BAI Yangwei，JIANG Ming，SUN Baiyu. Treatment of COS by modified activated carbon under low-oxygen content conditions [J]. , 2011, 30(2): 425-.

Catalytic hydrolysis of carbonyl sulfide with application of NHD/MDEA/H₂O

NHD/MDEA/H₂O复合脱硫液催化水解羰基硫

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 29

Related Articles 8

Recommended Articles 0

Metrics

Comments