Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

doi:10.1007/s11705-019-1848-6

Frontiers of Chemical Science and Engineering

2020, Vol. 14

Issue (5): 847-856 https://doi.org/10.1007/s11705-019-1848-6

本期目录

Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Jie Gao^1,², Zhikai Li¹(

), Mei Dong¹, Weibin Fan¹, Jianguo Wang^1,²

¹. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
². University of the Chinese Academy of Sciences, Beijing 100049, China

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Abstract：

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature. To improve ethylene conversion, coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodynamically. Five reactions have been attempted and compared: (1) dehydration of ethanol to ethyl ether ( $2C 2 H 5 OH ⇔$ $C 2 H 5 OC 2 H 5 +H 2 O$ ), (2) dehydrogenation of ethanol to acetaldehyde ( $C 2 H 5 OH ⇔ CH 3 CHO+H 2$ ), (3) esterification of acetic acid with ethanol ( $C 2 H 5 OH+CH 3 COOH$ $⇔ CH 3 COOC 2 H 5 +H 2 O$ ), (4) dehydrogenation of ethanol to ethyl acetate ( $2C 2 H 5 OH ⇔ CH 3 COOC 2 H 5 +2H 2$ ), and (5) oxidative dehydrogenation of ethanol to ethyl acetate ( $2C 2 H 5 OH+O 2 ⇔ CH 3 COOC 2 H 5 +2H 2 O$ ). The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition, temperature and pressure upon the ethylene equilibrium conversion were examined. The results show that dehydrogenation of ethanol to acetaldehyde has little effect on ethylene conversion, whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate, ethylene conversion can be improved from 8% to 12.8% and 18.5%, respectively, under conditions of H₂O/C₂H₄ = 2, 10 atm and 300°C. The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%; in particular, ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.

Key words： ethylene ethanol thermodynamics coupling

收稿日期: 2019-02-26 出版日期: 2020-05-25

Corresponding Author(s): Zhikai Li,Jianguo Wang

引用本文:

. [J]. Frontiers of Chemical Science and Engineering, 2020, 14(5): 847-856.
Jie Gao, Zhikai Li, Mei Dong, Weibin Fan, Jianguo Wang. Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction. Front. Chem. Sci. Eng., 2020, 14(5): 847-856.

链接本文:

https://academic.hep.com.cn/fcse/CN/10.1007/s11705-019-1848-6
https://academic.hep.com.cn/fcse/CN/Y2020/V14/I5/847

Species	$Δ f H m è$ /(kJ?mol^?1)	$Δ f G m è$ /(kJ?mol^?1)	A	B×10³	C×10⁶	D×10^?5
C₂H₄ (g)	52.26	68.15	1.424	14.394	?4.392	0
H₂O (g)	?241.818	?228.572	3.470	1.450	0	0.121
C₂H₅OH (g)	?235.10	?168.49	3.518	20.001	?6.002	0
C₂H₅OC₂H₅ (g)	?252.21	?112.19	0.1013	49.5	2.0078	0
CH₃CHO (g)	?166.1	?133.0	1.693	17.978	?6.158	0
H₂ (g)	0	0	3.249	0.422	0	0.083
CH₃COOH (g)	?432.2	?374.2	0.7119	26.338	?10.417	0
C₄H₈O₂ (g)	?443.6	?327.4	2.2089	43.159	?17.265	0
O₂ (g)	0	0	3.693	0.506	0	?0.227

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