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

doi:10.1007/s11705-019-1848-6

Front. Chem. Sci. Eng.

2020, Vol. 14

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

RESEARCH ARTICLE

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.

Keywords ethylene ethanol thermodynamics coupling

Corresponding Author(s): Zhikai Li,Jianguo Wang

Just Accepted Date: 22 October 2019 Online First Date: 20 December 2019 Issue Date: 25 May 2020

Cite this article:

Jie Gao,Zhikai Li,Mei Dong, et al. Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction[J]. Front. Chem. Sci. Eng., 2020, 14(5): 847-856.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1848-6
https://academic.hep.com.cn/fcse/EN/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

Tab.1 Standard molar formation enthalpy, standard molar formation Gibbs energy and the parameter of heat capacity (C_P/R= A+ BT+ CT² + DT^?²) of the species involved in this work^a)

Tab.2 Critical parameters and the acentric factor of species used in this work

Fig.1 (a) Equilibrium constant of vapor phase hydration of ethylene; (b) effect of H₂O/C₂H₄ ratio on equilibrium ethylene conversions at atmospheric pressure; (c) effect of pressure on equilibrium ethylene conversions at H₂O/C₂H₄ ratio of 8.

Fig.2 (a) Effect of temperature on equilibrium constant of dehydration of ethanol to ethyl ether; (b) comparison of equilibrium ethylene conversions at H₂O/C₂H₄ ratio of 2 between the single and the coupled reaction; (c) effect of temperature on product distribution of the coupled reaction at pressure of 30 atm and H₂O/C₂H₄ ratio of 2.

Fig.3 (a) Effect of temperature on the equilibrium constant of dehydrogenation of ethanol to acetaldehyde; (b) effect of pressure on ethylene conversion of the single and coupled reactions; (c) product distribution over temperature at a pressure of 30 atm and water to ethylene ratio of 2.

Fig.4 (a) Effect of temperature on the equilibrium constant of esterification of acetic acid with ethanol to ethyl acetate; (b) effects of pressure and temperature on ethylene conversion of the single and coupled reactions; (c) effect of the content of acetic acid on ethylene conversion with water to ethylene ratio of 2 at 10 atm; (d) product distribution for the coupled reaction at 10 atm and H₂O:C₂H₄:CH₃COOH= 2:1:1.

Fig.5 (a) Effect of temperature on the equilibrium constant of dehydrogenation of ethanol to ethyl acetate; (b) effects of pressure and temperature on ethylene conversion of the single and coupled reactions; (c) product distribution for the coupled reaction at 10 atm and H₂O:C₂H₄ = 2:1.

Fig.6 Effect of temperature on reaction enthalpy (a) and equilibrium constant (b) of oxidative dehydrogenation of ethanol to ethyl acetate.

Fig.7 Coupling effects comparison between different schemes under conditions of water to ethylene ratio of 2, pressure of 10 atm and reaction temperature of 300°C.

1	M Ni, D Y C Leung, M K H Leung. A review on reforming bio-ethanol for hydrogen production. International Journal of Hydrogen Energy, 2007, 32(15): 3238–3247 https://doi.org/10.1016/j.ijhydene.2007.04.038
2	M Al-Hasan. Effect of ethanol-unleaded gasoline blends on engine performance and exhaust emission. Energy Conversion and Management, 2003, 44(9): 1547–1561 https://doi.org/10.1016/S0196-8904(02)00166-8
3	A C Hansen, Q Zhang, P W L Lyne. Ethanol–diesel fuel blends––a review. Bioresource Technology, 2005, 96(3): 277–285 https://doi.org/10.1016/j.biortech.2004.04.007
4	B S Dien, M A Cotta, T W Jeffries. Bacteria engineered for fuel ethanol production: Current status. Applied Microbiology and Biotechnology, 2003, 63(3): 258–266 https://doi.org/10.1007/s00253-003-1444-y
5	E Gnansounou, A Dauriat. Techno-economic analysis of lignocellulosic ethanol: A review. Bioresource Technology, 2010, 101(13): 4980–4991 https://doi.org/10.1016/j.biortech.2010.02.009
6	M A Haider, M R Gogate, R J Davis. Fe-promotion of supported Rh catalysts for direct conversion of syngas to ethanol. Journal of Catalysis, 2009, 261(1): 9–16 https://doi.org/10.1016/j.jcat.2008.10.013
7	X Pan, Z Fan, W Chen, Y Ding, H Luo, X Bao. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles. Nature Materials, 2007, 6(7): 507–511 https://doi.org/10.1038/nmat1916
8	M Kitson, P Williams. Catalyzed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters. US Patent, 4985572, 1991-01-15
9	L Xingang, S Xiaoguang, Z Yi, I Takashi, M Ming, T Yisheng, T Noritatsu. Direct synthesis of ethanol from dimethyl ether and syngas over combined H-Mordenite and Cu/ZnO catalysts. ChemSusChem, 2010, 3(10): 1192–1199 https://doi.org/10.1002/cssc.201000109
10	M Llano-Restrepo, Y M Muñoz-Muñoz. Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng-Robinson-Stryjek-Vera equation of state and the Wong-Sandler mixing rules. Fluid Phase Equilibria, 2011, 307(1): 45–57 https://doi.org/10.1016/j.fluid.2011.05.007
11	Y Ding. Research progress of synthesis of ethanol and mixed high carbon primary alcohols from syngas derived from coal. Coal Chemical Industry, 2018, 46(1): 1–5
12	I J Castellanos-Beltran, G P Assima, J M Lavoie. Effect of temperature in the conversion of methanol to olefins (MTO) using an extruded SAPO-34 catalyst. Frontiers of Chemical Science and Engineering, 2018, 12(2): 226–238 https://doi.org/10.1007/s11705-018-1709-8
13	D Cai, Y Cui, Z Jia, Y Wang, F Wei. High-precision diffusion measurement of ethane and propane over SAPO-34 zeolites for methanol-to-olefin process. Frontiers of Chemical Science and Engineering, 2018, 12(1): 77–82 https://doi.org/10.1007/s11705-017-1684-5
14	E R Gilliland, R C Gunness, V O Bowles. Free energy of ethylene hydration. Industrial & Engineering Chemistry, 1936, 28(3): 370–372 https://doi.org/10.1021/ie50315a023
15	T Ushikubo. Recent topics of research and development of catalysis by niobium and tantalum oxides. Catalysis Today, 2000, 57(3): 331–338 https://doi.org/10.1016/S0920-5861(99)00344-2
16	N Katada, Y Iseki, A Shichi, N Fujita, I Ishino, K Osaki, T Torikai, M Niwa. Production of ethanol by vapor phase hydration of ethene over tungsta monolayer catalyst loaded on titania. Applied Catalysis A, General, 2008, 349(1): 55–61 https://doi.org/10.1016/j.apcata.2008.07.005
17	G Towler, S Lynn. Novel applications of reaction coupling: Use of carbon dioxide to shift the equilibrium of dehydrogenation reactions. Chemical Engineering Science, 1994, 49(16): 2585–2591 https://doi.org/10.1016/0009-2509(94)E0074-Z
18	A Sun, Z Qin, J Wang. Reaction coupling of ethylbenzene dehydrogenation with water-gas shift. Applied Catalysis A, General, 2002, 234(1): 179–189 https://doi.org/10.1016/S0926-860X(02)00222-3
19	Z Qin, J Liu, A Sun, J Wang. Reaction coupling in the new processes for producing styrene from ethylbenzene. Industrial & Engineering Chemistry Research, 2003, 42(7): 1329–1333 https://doi.org/10.1021/ie020762y
20	A Sun, Z Qin, J Wang. Reaction coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation. Catalysis Letters, 2002, 79(1): 33–37 https://doi.org/10.1023/A:1015395906114
21	M E E Abashar. Coupling of ethylbenzene dehydrogenation and benzene hydrogenation reactions in fixed bed catalytic reactors. Chemical Engineering and Processing: Process Intensification, 2004, 43(10): 1195–1202 https://doi.org/10.1016/j.cep.2003.11.004
22	R H Perry. Perry’s Chemical Engineers’ Handbook. 7th ed. New York: McGraw-Hill, 1999, 230–650
23	F J Sanders, B F Dodge. Catalytic vapor-phase hydration of ethylene. Industrial & Engineering Chemistry, 1934, 26(2): 208–214 https://doi.org/10.1021/ie50290a019
24	C S Cope. Equilibria in the hydration of ethylene and of propylene. AIChE Journal. American Institute of Chemical Engineers, 1964, 10(2): 277–281 https://doi.org/10.1002/aic.690100230
25	G Garbarino, P Riani, M Villa García, E Finocchio, V Sánchez Escribano, G Busca. A study of ethanol conversion over zinc aluminate catalyst. Reaction Kinetics, Mechanisms and Catalysis, 2018, 124(2): 503–522 https://doi.org/10.1007/s11144-018-1395-z
26	Y Guan, E J M Hensen. Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen. Applied Catalysis A, General, 2009, 361(1-2): 49–56 https://doi.org/10.1016/j.apcata.2009.03.033
27	A Rodriguez-Gomez, J P Holgado, A Caballero. Cobalt carbide identified as catalytic site for the dehydrogenation of ethanol to acetaldehyde. ACS Catalysis, 2017, 7(8): 5243–5247 https://doi.org/10.1021/acscatal.7b01348
28	P Liu, T Li, H Chen, E J M Hensen. Optimization of Au0–Cu+ synergy in Au/MgCuCr2O4 catalysts for aerobic oxidation of ethanol to acetaldehyde. Journal of Catalysis, 2017, 347: 45–56 https://doi.org/10.1016/j.jcat.2016.11.040
29	R He, Y Zou, Y Dong, Y Muhammad, S Subhan, Z Tong. Kinetic study and process simulation of esterification of acetic acid and ethanol catalyzed by. Chemical Engineering Research & Design, 2018, 137: 235–245 https://doi.org/10.1016/j.cherd.2018.07.020
30	M Nielsen, H Junge, A Kammer, M Beller. Towards a green process for bulk-scale synthesis of ethyl acetate: Efficient acceptorless dehydrogenation of ethanol. Angewandte Chemie International Edition, 2012, 51(23): 5711–5713 https://doi.org/10.1002/anie.201200625
31	L R McCullough, E S Cheng, A A Gosavi, B A Kilos, D G Barton, E Weitz, H H Kung, J M Notestein. Gas phase acceptorless dehydrogenative coupling of ethanol over bulk MoS2 and spectroscopic measurement of structural disorder. Journal of Catalysis, 2018, 366: 159–166 https://doi.org/10.1016/j.jcat.2018.07.039
32	T B Lin, D L Chung, J R Chang. Ethyl acetate production from water-containing ethanol catalyzed by supported Pd catalysts: Advantages and disadvantages of hydrophobic supports. Industrial & Engineering Chemistry Research, 1999, 38(4): 1271–1276 https://doi.org/10.1021/ie9805887
33	B Jørgensen, S Egholm Christiansen, M L Dahl Thomsen, C H Christensen. Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: Efficient routes to acetic acid and ethyl acetate. Journal of Catalysis, 2007, 251(2): 332–337 https://doi.org/10.1016/j.jcat.2007.08.004
34	R D Weinstein, A R Ferens, R J Orange, P Lemaire. Oxidative dehydrogenation of ethanol to acetaldehyde and ethyl acetate by graphite nanofibers. Carbon, 2011, 49(2): 701–707 https://doi.org/10.1016/j.carbon.2010.10.027

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