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
Methanol Synthesis #1 (Syngas)
Methanol Synthesis #2 (CO2)

CH4 + 2O2
CO + 2H2
CO2 + 3H2

CO2 + 2H2O
CH3OH
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, PreExponential 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)

EA = 1.25 x 105 (J mol-1)
K02 = 1.2 x 10-2 (Pa-1)

KH2O = 1.2 x 10-2 (Pa-1)

KCO2 = 5.0 x 10-3 (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 zincbased 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 zincbased 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
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