NHD/MDEA/H2O复合脱硫液催化水解羰基硫

doi:10.11949/0438-1157.20200336

化工学报 ›› 2020, Vol. 71 ›› Issue (11): 5286-5293.DOI: 10.11949/0438-1157.20200336

NHD/MDEA/H₂O复合脱硫液催化水解羰基硫

刘雪珂¹(),张丽¹,刘芬¹,高帅涛¹,余江¹(),商剑锋²,欧天雄²,周政³,陈平文³

^1.北京化工大学化学工程学院，能源环境催化北京市重点实验室环境催化与分离过程研究组，北京 100029
^2.中国石油化工股份有限公司中原油田普光分公司，四川达州 635000
^3.中国石油化工股份有限公司中原油田分公司天然气处理厂，河南濮阳 457000

收稿日期:2020-03-30 修回日期:2020-06-30 出版日期:2020-11-05 发布日期:2020-11-05
通讯作者: 余江
作者简介:刘雪珂（1994—），女，硕士研究生，buct_lxk@163.com
基金资助:
国家科技部“十三五”重大专项(2016ZX05017-004)

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

Xueke LIU¹(),Li ZHANG¹,Fen LIU¹,Shuaitao GAO¹,Jiang YU¹(),Jianfeng SHANG²,Tianxiong OU²,Zheng ZHOU³,Pingwen CHEN³

^1.Research Group of Environmental Catalysis & Separation Process, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
^2.Zhongyuan Oilfield Puguang Branch of Sinopec, Dazhou 635000, Sichuan, China
^3.Natural Gas Treatment Plant of Zhongyuan Oilfield Branch of Sinopec, Puyang 457000, Henan, China

Received:2020-03-30 Revised:2020-06-30 Online:2020-11-05 Published:2020-11-05
Contact: Jiang YU

摘要/Abstract

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

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

中图分类号:

X 701. 3

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.

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.

图/表 12

图1 实验装置1—羰基硫；2—气体流量计；3—鼓泡反应器；4—玻璃砂芯；5—超级恒温水槽；6—尾气吸收瓶

Fig.1 Experimental set-up

图2 不同体系下脱硫效率-时间关系

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

图3 不同含水量的H2O/NHD体系脱硫效率-时间关系

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

图4 不同MDEA含量下脱硫效率-时间关系

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

图5 不同含水量下脱硫效率-时间关系

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

图6 不同温度下脱硫效率-时间关系

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

图7 不同COS浓度下脱硫效率-时间关系

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

图8 不同气体流量下脱硫效率-时间关系

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

图9 净化气中各组分浓度随时间的变化

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)

图10 脱硫过程示意图

Fig.10 Schematic diagram of desulfurization process

表1 不同温度下脱硫过程的表观反应速率常数及反应级数

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

图11 lnkobs与1/T的线性拟合曲线

Fig.11 lnkobs as function of 1/T

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NHD/MDEA/H₂O复合脱硫液催化水解羰基硫

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

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