Skip to main content
SpringerLink
Log in

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

  • Research Article
  • Published:
Frontiers of Chemical Science and Engineering Aims and scope Submit manuscript

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 (2C2H5OH ⇔ C2H5OC2H5 + H2O), (2) dehydrogenation of ethanol to acetaldehyde (C2H5OH ⇔ CH3CHO + H2), (3) esterification of acetic acid with ethanol (C2H5OH + CH3COOH ⇔ CH3COOC2H5 + H2O), (4) dehydrogenation of ethanol to ethyl acetate (2C2H5OH ⇔ CH3COOC2H5 + 2H2), and (5) oxidative dehydrogenation of ethanol to ethyl acetate (2C2H5OH + O2 ⇔ CH3COOC2H5 + 2H2O). 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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ni M, Leung D Y C, Leung M K H. A review on reforming bioethanol for hydrogen production. International Journal of Hydrogen Energy, 2007, 32(15): 3238–3247

    Article  CAS  Google Scholar 

  2. Al-Hasan M. Effect of ethanol-unleaded gasoline blends on engine performance and exhaust emission. Energy Conversion and Management, 2003, 44(9): 1547–1561

    Article  CAS  Google Scholar 

  3. Hansen A C, Zhang Q, Lyne P W L. Ethanol-diesel fuel blends—a review. Bioresource Technology, 2005, 96(3): 277–285

    Article  CAS  Google Scholar 

  4. Dien B S, Cotta M A, Jeffries T W. Bacteria engineered for fuel ethanol production: Current status. Applied Microbiology and Biotechnology, 2003, 63(3): 258–266

    Article  CAS  Google Scholar 

  5. Gnansounou E, Dauriat A. Techno-economic analysis of lignocellulosic ethanol: A review. Bioresource Technology, 2010, 101(13): 4980–4991

    Article  CAS  Google Scholar 

  6. Haider M A, Gogate M R, Davis R J. Fe-promotion of supported Rh catalysts for direct conversion of syngas to ethanol. Journal of Catalysis, 2009, 261(1): 9–16

    Article  CAS  Google Scholar 

  7. Pan X, Fan Z, Chen W, Ding Y, Luo H, Bao X. Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles. Nature Materials, 2007, 6(7): 507–511

    Article  CAS  Google Scholar 

  8. Kitson M, Williams P. Catalyzed hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters. US Patent, 4985572, 1991-01-15

  9. Xingang L, Xiaoguang S, Yi Z, Takashi I, Ming M, Yisheng T, Noritatsu T. Direct synthesis of ethanol from dimethyl ether and syngas over combined H-Mordenite and Cu/ZnO catalysts. ChemSusChem, 2010, 3(10): 1192–1199

    Article  Google Scholar 

  10. Llano-Restrepo M, Muñoz-Muñoz Y M. 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

    Article  CAS  Google Scholar 

  11. Ding Y. 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

    Google Scholar 

  12. Castellanos-Beltran I J, Assima G P, Lavoie J M. 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

    Article  CAS  Google Scholar 

  13. Cai D, Cui Y, Jia Z, Wang Y, Wei F. 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

    Article  CAS  Google Scholar 

  14. Gilliland E R, Gunness R C, Bowles V O. Free energy of ethylene hydration. Industrial & Engineering Chemistry, 1936, 28(3): 370–372

    Article  CAS  Google Scholar 

  15. Ushikubo T. Recent topics of research and development of catalysis by niobium and tantalum oxides. Catalysis Today, 2000, 57(3): 331–338

    Article  CAS  Google Scholar 

  16. Katada N, Iseki Y, Shichi A, Fujita N, Ishino I, Osaki K, Torikai T, Niwa M. 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

    Article  CAS  Google Scholar 

  17. Towler G, Lynn S. Novel applications of reaction coupling: Use of carbon dioxide to shift the equilibrium of dehydrogenation reactions. Chemical Engineering Science, 1994, 49(16): 2585–2591

    Article  CAS  Google Scholar 

  18. Sun A, Qin Z, Wang J. Reaction coupling of ethylbenzene dehydrogenation with water-gas shift. Applied Catalysis A, General, 2002, 234(1): 179–189

    Article  CAS  Google Scholar 

  19. Qin Z, Liu J, Sun A, Wang J. Reaction coupling in the newprocesses for producing styrene from ethylbenzene. Industrial & Engineering Chemistry Research, 2003, 42(7): 1329–1333

    Article  CAS  Google Scholar 

  20. Sun A, Qin Z, Wang J. Reaction coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation. Catalysis Letters, 2002, 79(1): 33–37

    Article  CAS  Google Scholar 

  21. Abashar M E E. Coupling of ethylbenzene dehydrogenation and benzene hydrogenation reactions in fixed bed catalytic reactors. Chemical Engineering and Processing: Process Intensification, 2004, 43(10): 1195–1202

    Article  CAS  Google Scholar 

  22. Perry R H. Perry’s Chemical Engineers’ Handbook. 7th ed. New York: McGraw-Hill, 1999, 230–650

    Google Scholar 

  23. Sanders F J, Dodge B F. Catalytic vapor-phase hydration of ethylene. Industrial & Engineering Chemistry, 1934, 26(2): 208–214

    Article  CAS  Google Scholar 

  24. Cope C S. Equilibria in the hydration of ethylene and of propylene. AIChE Journal. American Institute of Chemical Engineers, 1964, 10 (2): 277–281

    Article  CAS  Google Scholar 

  25. Garbarino G, Riani P, Villa Garcia M, Finocchio E, Sánchez Escribano V, Busca G. A study of ethanol conversion over zinc aluminate catalyst. Reaction Kinetics, Mechanisms and Catalysis, 2018, 124(2): 503–522

    Article  CAS  Google Scholar 

  26. Guan Y, Hensen E J M. 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

    Article  CAS  Google Scholar 

  27. Rodriguez-Gomez A, Holgado J P, Caballero A. Cobalt carbide identified as catalytic site for the dehydrogenation of ethanol to acetaldehyde. ACS Catalysis, 2017, 7(8): 5243–5247

    Article  CAS  Google Scholar 

  28. Liu P, Li T, Chen H, Hensen E J M. Optimization of Au0-Cu+ synergy in Au/MgCuCr2O4 catalysts for aerobic oxidation of ethanol to acetaldehyde. Journal of Catalysis, 2017, 347: 45–56

    Article  CAS  Google Scholar 

  29. He R, Zou Y, Dong Y, Muhammad Y, Subhan S, Tong Z. Kinetic study and process simulation of esterification of acetic acid and ethanol catalyzed by. Chemical Engineering Research & Design, 2018, 137: 235–245

    Article  CAS  Google Scholar 

  30. Nielsen M, Junge H, Kammer A, Beller M. 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

    Article  CAS  Google Scholar 

  31. McCullough L R, Cheng E S, Gosavi A A, Kilos B A, Barton D G, Weitz E, Kung H H, Notestein J M. Gas phase acceptorless dehydrogenative coupling of ethanol over bulk MoS2 and spectroscopic measurement of structural disorder. Journal of Catalysis, 2018, 366: 159–166

    Article  CAS  Google Scholar 

  32. Lin T B, Chung D L, Chang J R. 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

    Article  CAS  Google Scholar 

  33. Jørgensen B, Egholm Christiansen S, Dahl Thomsen M L, Christensen C H. 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

    Article  Google Scholar 

  34. Weinstein R D, Ferens A R, Orange R J, Lemaire P. Oxidative dehydrogenation of ethanol to acetaldehyde and ethyl acetate by graphite nanofibers. Carbon, 2011, 49(2): 701–707

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work is supported by the National Key Research and Development Program of China (Grant No. 2018YFB0604802), the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDA21020500), the National Natural Science Foundation of China (Grant Nos. U1862101 and 21773281), the CAS/SAFEA International Partnership Program for Creative Research Teams (No. 2015YC901) and Natural Science Foundation of Shanxi Province of China (No. 201601D202014).

Author information

Authors and Affiliations

  1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, China

    Jie Gao, Zhikai Li, Mei Dong, Weibin Fan & Jianguo Wang

  2. University of the Chinese Academy of Sciences, Beijing, 100049, China

    Jie Gao & Jianguo Wang

Authors
  1. Jie Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhikai Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mei Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Weibin Fan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jianguo Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jianguo Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, J., Li, Z., Dong, M. et al. Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction. Front. Chem. Sci. Eng. 14, 847–856 (2020). https://doi.org/10.1007/s11705-019-1848-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11705-019-1848-6

Keywords

Search

Navigation