铁基离子液体/NHD吸收氧化H2S的反应动力学

doi:10.7503/cjcu20190474

摘要/Abstract

摘要：

以铁基离子液体(Fe-IL) /聚乙二醇二甲醚(NHD)为脱硫体系, 通过静态吸收反应装置研究了共溶体系吸收氧化H₂S的动力学过程. 结果表明, 纯Fe-IL脱硫体系的动力学方程可表示为r=54.62exp(-11720/RT)· $c H 2 S$ ·c_Fe(Ⅲ), Fe-IL/NHD吸收氧化H₂S属于快速拟一级反应, 复配NHD后, 对Fe(Ⅲ)的反应级数随NHD复配比的增大而增大, 提高温度和NHD的复配比可强化传质过程, 提高脱硫过程的反应速率.

关键词: 铁基离子液体, 聚乙二醇二甲醚, 硫化氢, 脱硫, 动力学

Abstract:

The addition of organic solvents in iron-based ionic liquids(Fe-IL) enhances the gas-liquid mass transfer of hydrogen sulfide(H₂S) during desulfurization, which can significantly improve the desulfurization efficiency. Definitely, the addition of organic solvents must has a certain influence on the dynamic properties of the desulfurization system. The dynamic properties of H₂S absorption in the co-solution desulfurization system of Fe-IL/NHD(polyethylene glycol dimethyl ether) in a static absorption reactor was studied. The results show that the dynamic equation of pure Fe-IL desulfurization system is $r = 54.62 exp (- 11720 / RT) · c H 2 S · c Fe (Ⅲ),$ and the absorption and oxidation of H₂S by Fe-IL/NHD is a fast pseudo-first order reaction. After mixing with NHD, the reaction order of Fe(Ⅲ) increases with the increase of the ratio of NHD to Fe-IL. Thus increasing reaction temperature and the ratio of NHD to Fe-IL can enhance the mass transfer process and the reaction rate during the desulfurization process.

Key words: Iron-based ionic liquid, Polyethylene glycol dimethyl ether, H₂S, Desulfurization, Dynamic

中图分类号:

O641
TQ028.8

TrendMD:

张丽,钱明超,刘雪珂,高帅涛,余江,谢海深,王宏斌,孙风江,苏向红. 铁基离子液体/NHD吸收氧化H₂S的反应动力学. 高等学校化学学报, 2020, 41(2): 317.

ZHANG Li,QIAN Mingchao,LIU Xueke,Gao Shuaitao,YU Jiang,XIE Haishen,WANG Hongbin,SUN Fengjiang,SU Xianghong. Dynamic Study of Oxidative Desulfurization by Iron-based Ionic Liquids/NHD ^†. Chem. J. Chinese Universities, 2020, 41(2): 317.

图/表 13

Fig.1 Static absorption reactor 1. H2S gas tank; 2. gas reducing valve; 3. pressure flange; 4. precision pressure gauge; 5. thermostat water bath; 6. high pressure absorption reactor; 7. magneto; 8. thermometer; 9. speed controller; 10. inlet valve; 11. outlet valve; 12. tail gas treatment unit.

Table 1 Determination method of dynamic region*

Variable	Dynamic region
Variable	A	B	C	D	E	F	G	H
Concentration of Fe(Ⅲ)	+	-	+	+	?	?	+	+
Volume fraction of H₂S	+	+	+	+	?	?	+	+
Phase interfacial area	+	+	+	+	+	+	+	-
Volume of desulfurization liquid	-	-	-	-	+	+	+	+
Coefficient of mass transfer in liquid phase	+	-	-	-	?	+	+	-
Coefficient of mass transfer in gas phase	+	-	+	+	?	?	+	-
Second-order reaction rate constant	-	-	+	+	?	?	-	+

Table 2 Effect of liquid-phase volume on H2S absorption rate(mol·m-2·min-1)*

No.	Liquid-phase volume/mL
No.	60	80	100
1	1.51	1.49	1.48
2	1.54	1.47	1.49
3	1.52	1.49	1.48

Table 3 Effect of kL on H2S absorption rate(mol·m-2·min-1)*

No.	K_L/(r·min^-1)
No.	100	150
1	1.48	1.50
2	1.49	1.52
3	1.48	1.52

Table 4 Effect of different mass ratios of Fe-IL/NHD on H2S absorption rate(mol·m-2·min-1)*

No.	Mass ratio of Fe-IL/NHD
No.	8:1	6:1	4:1	1:0
1	1.35	1.41	1.48	1.29
2	1.33	1.42	1.49	1.28
3	1.32	1.42	1.48	1.29

Fig.2 Model of double membrane theory about H2S absorption in Fe-IL/NHD

Fig.3 Fitting relation of interfacial concentration of H2S with absorption rate at different mass ratios of Fe-IL/NHD

Fig.4 Relationship between kov and temperature at different mass ratios of Fe-IL/NHD

Fig.5 Relationship between cFe(Ⅲ) and time at different mass ratios of Fe-IL/NHD

Fig.6 Fitting relation of lnr with lncFe(Ⅲ) at different mass ratios of Fe-IL/NHD

Table 5 Ftting relation of lnr with lncFe(Ⅲ)

Mass ratio of Fe-IL/NHD	b	R²
1:0	1.07	0.9779
8:1	1.15	0.9771
6:1	1.39	0.9813
4:1	1.56	0.9999

Fig.7 Relationship between Fe(Ⅲ) content and time at different temperatures

Fig.8 Fitting relation of lnr with 1/T

参考文献 28

[1]	Zhang Q., Hou Y. C., Ren S. H., Zhang K., Wu W. Z., Chem. Eng., 2019,7(12), 10931— 10936
[2]	Debski B., Hanel A., Aranowski R., Stolte S., Markiewicz M., Veltzke T., Cichowska-Kopczynska I ., J. Mol. Lid., 2019,291, 110477
[3]	Zheng W. T., Wu D. S., Feng X., Hu J. L., Zhang F., Wu Y. T., Hu X. B., J. Mol. Lid., 2018,263, 209— 217
[4]	Paramanik M., Singh R., Mukhopadhyay S., Ghosh S. K., J. Fluorine Chem., 2015,178, 47— 55 doi: 10.1016/j.jfluchem.2015.06.022 URL
[5]	Ruan C. X., Sun Z. L., Lu S. S., Li L. F., Lou J., Sun W., Russ. J. Electrochem., 2014,50(2), 129— 135 doi: 10.1134/S1023193513020158 URL
[6]	Ma Y. Q., Liu X. P., Wang R., J. Hazard. Mater., 2017,331, 109— 116 doi: 10.1016/j.jhazmat.2017.02.036 URL
[7]	Liu X. P., Qang R., Fuel Process. Technol., 2017,160, 78— 85 doi: 10.1016/j.fuproc.2017.02.024 URL
[8]	Lv B. H., Jing G. H., Qian Y. H., Zhou Z. M., Chem. Eng. J., 2016,289, 212— 218 doi: 10.1016/j.cej.2015.12.096 URL
[9]	Kazmi B., Haider J., Qyyum M. A., Saeed S., Kazmi M. R., Int. J. Greenhouse Gas Control, 2019,87, 88— 99
[10]	Dai F., Chen X. J., He B., Liu R. X., Zhang S. J., Cat. Sci. Technol., 2018,8(17), 4515— 4525 doi: 10.1039/C8CY01023D URL
[11]	Ding W. J., Zhu W. S., Xiong J., Yang L., Wei A. M., Zhang M., Li H. M., Chem. Eng. J., 2015,266, 213— 221 doi: 10.1016/j.cej.2014.12.040 URL
[12]	Xie M. Y., Li P. P., Guo H. F., Gao L. X., Yu J., Chinese J. Chem. Eng., 2012,1, 140— 145
[13]	Lee S. H., Hu S. H., You C. Y., Koo Y. M., Korean J. Chem. Eng., 2007,24, 436— 437 doi: 10.1007/s11814-007-0075-x URL
[14]	He Y., Yu J., Chen L. B., CIESC J., 2010,61(4), 963— 968
	( 何义, 余江, 陈灵波 . 化工学报, 2010,61(4), 963— 968)
[15]	Wang J. H., Chen J. Q., Yan H. Z., Chem. Res., 2012,23(1), 9— 13
	( 王建宏, 陈家庆, 阎红昭 . 化学研究, 2012,23(1), 9— 13)
[16]	Wang J. H., Zhang W. D., Energy Fuels, 2014,28(9), 5930— 5935 doi: 10.1021/ef500527w URL
[17]	Guo Z. H., Zhang T. T., Sun L. L., He Y., Yu J., Fresenius Environ. Bulletin, 2015,24(8A), 2587— 2592
[18]	Guo Z. H., Zhang T. T., Liu T. T., Du J., Jia B., Gao S. J., Yu J., Environ. Sci. Technol., 2015,49(9), 5697— 5703 doi: 10.1021/es505728f URL
[19]	Hu J. C., Gao L. X., Liu W. H., Zhao Y. L., Gao S., Pan X. P., Guo Z. H., Yu J., CIESC J., 2016,67(S1), 347— 352
	( 胡锦超, 高丽霞, 刘伟海, 赵永禄, 高尚, 潘兴朋, 郭智慧, 余江 . 化工学报, 2016,67(S1), 347— 352)
[20]	Liu K., Liu H. J., Guo Q., Chem. Enterprise Management, 2019, ( 11), 185— 186
	( 刘凯, 刘海菊, 郭琦 . 化工管理, 2019, ( 11), 185— 186)
[21]	Rayer A. V., Henni A., Tontiwachwuthikul P., Can. J. Chem. Eng., 2012,90(3), 576— 583 doi: 10.1002/cjce.20615 URL
[22]	Schmidt K. A. G., Mather A. E., Can. J. Chem. Eng., 2001,79(6), 946— 960 doi: 10.1002/cjce.v79:6 URL
[23]	Lin M. H., Guo S. C., Chem. Eng., 2000, ( 3), 58— 61
	( 林民鸿, 郭淑翠 . 化学工程, 2000, ( 3), 58— 61)
[24]	Xu B ., Chem. Enterprise Management, 2016, ( 18), 87
	( 徐斌 . 化工管理, 2016, ( 18), 87)
[25]	Feng S., Anhui Chem. Industry, 2018,44(1), 49— 52
	( 冯升 . 安徽化工, 2018,44(1), 49— 52)
[26]	Karamanev D. G., Nikolov L. N., Mamatarkova V., Minerals Eng., 2002,15(5), 341— 345 doi: 10.1016/S0892-6875(02)00026-2 URL
[27]	Chen J., Luo W. L., Li H., CIESC J., 2014,65(1), 12— 21
	( 陈健, 罗伟亮, 李晗 . 化工学报, 2014,65(1), 12— 21)
[28]	Shen Y. T., Zhang H. T., Fang D. Y., Li T., J. East China University Sci. Technol.(Nat. Sci. Ed.), 2016,42(4), 446— 453
	( 沈叶婷, 张海涛, 房鼎业, 李涛 . 华东理工大学学报(自然科学版), 2016,42(4), 446— 453)

铁基离子液体/NHD吸收氧化H₂S的反应动力学

Dynamic Study of Oxidative Desulfurization by Iron-based Ionic Liquids/NHD ^†

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