Reaction Kinetics of

Methanol Synthesis
Jill DeTroye, Brandon Hurn,
Kyle Ludwig, and Isaac Zaydens
Overview
Review the Reactions
Brief Introduction of Catalytic Kinetics
Discussion of Reaction Kinetics
Summary and Conclusions
Questions
Reactions
Our proposed process reactions include:
Methane-Steam Reforming (MSR)
Water-Gas Shift (WGS)
Methane Oxidation (MO)
Methanol Synthesis (MS)
Reactions
Reaction Name Reactions Chemical Formula
Methane Steam Reforming CH4 + H2O CO + 3H2

Water Gas Shift CO2 + H2O CO + H2

Methane Oxidation CH4 + 2O2 CO2 + 2H2O

Methanol Synthesis #1 (Syngas) CO + 2H2 CH3OH

Methanol Synthesis #2 (CO2) CO2 + 3H2 CH3OH + H2O

Catalytic Reaction Rates
Homogeneous - Reactants/Catalysts in same phase
Heterogeneous - Reactants/Catalysts in different phase
Our purposes: Solid-Phase Catalyst w/ Gas/Vapor Phase
Reactants
Adsorption Constants (generally K)
Rate Constants (generally k)
Partial Pressures (pi)
Methane Steam Reforming

Main process for the production

of syngas using nickel-alumina
catalysts
High ratio of steam to methane
Moderate temperature
Low/moderate pressure
Methane Steam Reforming
Steam Methane Reforming
Coefficients change depending
on temperature, pressure, and
steam-to-methane ratio
Rates use partial pressures,
typical of catalytic kinetics
Steam Methane Reforming
Steam Methane Reforming
Steam Methane Reforming
Activation Energies, Adsorption Enthalpies, Pre-
Exponential Factors
Water-Gas Shift

Moderately exothermic
K decreases with increasing T
Kinetically favored at high T, but Thermodynamically
favored at low T
Catalyzed by metals and metal-oxides
Hfo = -41.09 kJ/mol
Water-Gas Shift
Regenerative Mechanism Associative Mechanism
Water-Gas Shift
Water-Gas Shift
Reaction rate based on Langmuir:
Methane Oxidation

Go= -801.06 kJ/mol

Hfo= -802.64 kJ/mol
Highly exothermic - Increase in heat shifts
reaction to the left
Pressure - No change
Methane Oxidation
Figures adapted from Veldsink et al.
Methane Oxidation

Catalyst: CuO--Al2O3

k0 = 1.08 (kmol kgcat-1 Pa-1 s-1) KH2O = 1.2 x 10-2 (Pa-1)

EA = 1.25 x 105 (J mol-1) KCO2 = 5.0 x 10-3 (Pa-1)
K02 = 1.2 x 10-2 (Pa-1)
Figures adapted from Veldsink et al.

Methane Oxidation
Methane Oxidation

Optimal operating conditions:

pCH4 6 kPa
pH2O 8 kPa
pCO2 20 kPa
0.06 kPa pCO2 22 kPa
723 K T 923 K
Methanol Synthesis

Hfo = -90.55 kJ/mol at 298K

Go = -25.34 kJ/mol
Exothermic: higher methanol yields are obtained at
lower temperatures and higher pressures
Methanol Synthesis

ZnO/Cr2O3 catalyst with copper dispersed on the zinc-

based catalysts.
Methanol Synthesis
Hfo = -49.43 kJ/mol
Go = 3.30 kJ/mol
Exothermic: higher methanol yields are obtained at
lower temperatures and higher pressures
Methanol Synthesis

ZnO/Cr2O3 catalyst with copper dispersed on the zinc-

based catalysts
Sources
Hou, Kaihu, and Ronald Hughes. "The Kinetics of Methane Steam Reforming over a Ni/alpha-Al2O
Catalyst." Chemical Engineering Journal 82 (2001): 311-28. Web. 10 Feb. 2015.
Smith, Byron, RJ, Muruganandam Loganathan, and Murthy S. Shantha. "A Review of the Water Gas Shift
Reaction Kinetics." INTERNATIONAL JOURNAL OF CHEMICAL REACTOR ENGINEERING R4 8
(2010): 1-32. Web. 10 Feb. 2015.
Veldsink, J.W., G.F. Versteeg, and W.P.M. Van Swaaij. "Intrinsic Kinetics of the Oxidation of Methane
Over an Industrial Copper(II) Oxide Catalyst on a Gamma-Alumina Support." The Chemical Engineering
Journal 57 (1995): 273-83. Print.
"Industrial Methanol from Syngas: Kinetic Study and Process Simulation : International Journal of
Chemical Reactor Engineering." Industrial Methanol from Syngas: Kinetic Study and Process Simulation
: International Journal of Chemical Reactor Engineering. N.p., 27 Aug. 2013. Web. 12 Feb. 2015.