Methanol Synthesis Technology

ChemTech Innovators R&D Center’s Methanol Synthesis Process Prototype (An Internal View)

Our research group had been the only academic participant of the technology pool of DOE/EPRI for the development of the liquid phase methanol synthesis process (LPMeOH™). Research funding for this project was received from 1982 through 1993 from the Electric Power Research Institute (EPRI). We developed major patents involving catalyst regeneration, post-treatment, and subsequent conversion to gasoline-range hydrocarbons and olefins. Other achievements include phase equilibrium study, confirmation of CO2 hydrogenation reaction mechanism, elucidation of catalyst deactivation mechanism, analysis of pore diffusion limitation in the liquid phase synthesis, reactor thermal stability analysis, and external mass transfer limitation, studies on various reactor configurations, investigation of reaction kinetics, and acquisition of scale-up data, etc. This research has served as a precursor for the single-stage dimethyl ether (ssDME) synthesis, selective synthesis of propylene from syngas, and the synthesis of targeted hydrocarbons via DME route. More recent research efforts in this area involves methanol and derivatives from biological feedstocks as well as smaller-scale methanol synthesis with high energy efficiency.

Dr. Lee has authored a book that covers all the theoretical as well as practical aspects of methanol synthesis in great detail:

  • S. Lee, author, “Methanol Synthesis Technology”, CRC Press, Boca Raton, FL, ISBN-0-8493-4610-X, 1990.
  • S. Lee, “Methanol Synthesis from Syngas”, in Handbook of Alternative Fuel Technologies, 2nd Edition, Eds. S. Lee, J.G. Speight, S, K. Loyalka, Chapter 10, CRC Press, Boca Raton, 2014.

A large number of journal articles, proceedings papers, and published monographs and reports generated from research in this technology are available. Dr. Lee’s comprehensive research monographs published by the EPRI on the subject area are:

  • S. Lee [PI], “Research to support Liquid Phase Methanol Process Development”, EPRI AP-4429, pp. 1-312, Palo Alto, CA, February 1986.
  • S. Lee [PI], “Mass Transfer Characteristics of the Liquid Phase Methanol Synthesis Process”, EPRI AP-5758, pp. 1-214, Palo Alto, CA, April 1988.
  • S. Lee [PI] and V. Parameswaran, “Reaction Mechanism in Liquid-Phase Methanol Synthesis”, EPRI ER/GS-6715, pp. 1-206, Palo Alto, CA, February 1990.
  • S. Lee [PI] and M. R. Gogate, “Dimethyl Ether Synthesis Process”, EPRI TR-100246 (Licensable Material), pp. 1-179, EPRI, Palo Alto, CA, February, 1992.
  • S. Lee, V. Parameswaran, C. J. Kulik, and I. Wender, “The Roles of Carbon Dioxide in Methanol Synthesis”, Fuel Sci. & Tech. Int’l., 7(8), pp. 1021-1057, 1989.
  • V. Parameswaran, S. Lee*, and I. Wender, “The Role of Water in Methanol Synthesis”, Fuel Sci. & Tech. Int’l., 7(7), pp. 899-918, 1989.
  • S. Lee, M.R. Gogate, and C.J. Kulik, “A Novel Single-step Dimethyl Ether (DME) Synthesis in a Ihree-phase Slurry Reactor from CO-rich Syngas”, Chemical engineering science 47 (13-14), pp. 3769-3776, 1992.

Even though more scientists agree with the CO2 hydrogenation as the principal mechanistic reaction step for the synthesis of methanol from syngas over the conventional Cu/ZnO/Al2O3 catalyst system, most technologists fail to mention that the conventional methanol synthesis does not achieve a net positive conversion of CO2 that is a component of syngas. This is due to the presence of very active water gas shift reaction that is also catalyzed by the same catalyst. The scientific observations of no net overall conversion (consumption) of CO2 are true, regardless of type of syngas, i.e., H2-rich vs. CO-rich, or balanced gas vs. unbalanced gas. Needless to say, more conversion of CO2 by methanol synthesis reaction is highly desirable.

More recent interests and efforts in this field of R&D involve: (1) development of a novel catalytic synthesis process for methanol using CO2-rich syngas, (2) direct conversion of CO2 and H2O into transportation fuels via methanol synthesis, (3) use of syngas derived from alternate sources for methanol and dimethyl ether synthesis, (4) design and development of a small-scale energy-efficient methanol synthesis process, (5) novel catalyst for lower temperature synthesis, (6) flexible and switchable synthesis between DME and methanol, (7) robust catalyst for dirty syngas, (9) catalyst modification based on zinc carbonate (ZnCO3) formulation, and (9) process integration opportunities for the hypothetical methanol economy.