Thermodynamics

in the production and purification of methanol

from methane
Jacob Hebert, Michael McCutchen, Eric Powell, and Jacob Reinhart
(Group 6)
Thermodynamics Review - Topics

Important Terms & Concepts

Models in CHEMCAD
Partial Oxidation
Steam Reforming
Water-Gas Shift
Methanol Synthesis
Methanol Purification
Important Concepts

Gibbs energy (G, G): denotes what happens

spontaneously, and to what degree
Enthalpy (H, H): relates to sensible heat
Entropy (S, S): commonly referred to as
disorder, universal entropy always increases
Chemical equilibrium (matters most at long time
scales and/or fast reactions!)
Significance of the Thermodynamic Model

There are many models allowing for good

approximations in a variety of situations
These models account for the non ideality
which arise when chemical interactions cause
unexpected effects.
 The Selection Process
Factors to be considered include:
Intermolecular bonding
Pressure and Temperature of the reaction
Phase separation
Molecular weights (for hydrocarbons)
 Choosing our model
N
Y
Use G-S T < 250 K Start

Y
H2 Y N Polar or Y Y
Use P-R Hydrocarbon Use sour
present Hydrogen Sour Water
or R-K-S C5 or lighter water system
bonding
N N
N
Y Y H2 Y Use
Use B-W-R
T < 250 K Use G-S present Electrolytes
or L-K-P electrolyte

N N
N
Y Y N N i
Use G-S P < 4 bar
P < 200 bar 0<T<750K experimental
or P-R T < 150C
data
N
N Y Y
Use UNIFAC to
Y estimate Two N Use Wilson, NRTL
Use R-K-S P < 350 bar Liq phases
interaction or UNIQUAC
parameters
N Y
Need more Select model that
Use NRTL
experimental gives best fit to
or UNIQUAC
data data

Towler, G., & Sinnott, R. (2008). Chemical engineering design principles, practice and economics of plant and process design. Amsterdam: Elsevier/Butterworth-Heinemann.
 Steam Reforming
CH4 + H2O -> CO + 3H2
Affected by temperature (higher temperature favors the
reaction)
Affected by pressure (lower pressure favors the reaction)
Very endothermic reaction

Ali, M. S., Zahangir, S. M., Badruddoza A. Z.

M., Haque M. R. (n.d.) A Study of Effect of
Pressure, Temperature, and Steam/Natural
Gas Ratio on Reforming Process for
Ammonia Production. Journal of Chemical
Engineering 23 1995-2005
http://www.banglajol.info/index.php/JCE/ar
ticle/view/5565
 Partial Oxidation
Methane and oxygen feed to reactor at 2:1 for methanol
synthesis preparation
Three different reactions can take place during partial
oxidation

A) CH4 + 0.5O2 CO + 2H2 H = -38kJ/mol

B) CH4 + 2O2 CO + 2H2O H = -803kJ/mol
C) CO + H2O CO2 + H2 H = -41kJ/mol

Choose reaction conditions to maximize Reaction A and

minimize Reactions B and C
Partial Oxidation: Reaction Enthalpies

http://www.bjb.dicp.ac.cn/jngc/2004/2004-04-191.pdf
1 kJ
CH4 + 2 O2 CO + H2 H = 38 mol
Selectivity for different reactions depends on temperature and pressure of reaction
Water-Gas shift reaction favors formation of CO and H2 and high temperatures
Partial Oxidation: Temperature Effect
Calculated equilibrium distribution
for CH4 : O2 molar feed ratio of 2:1

Partial oxidation favored over

complete oxidation at higher
temperatures

Above 1000K, methane conversion

and syngas selectivity >90% can be
achieved

Without catalyst, operating

temperature of 1400K is necessary
for reaction to occur

http://www.bjb.dicp.ac.cn/jngc/2004/2004-04-191.pdf
 Partial Oxidation: Pressure Effect
Despite excess feed oxygen, all
oxygen was consumed,
indicating a lack of inhibition
for total oxidation
Increase in moles of gas
molecules inhibit partial
Methane conversion at different pressures and different O:C ratios
oxidation at increasing pressure
http://www.bjb.dicp.ac.cn/jngc/2004/2004-04-191.pdf
Reduced conversion at high
pressure can be compensated
for by operating at higher O:C
ratios
 Water-Gas Shift
CO + H2O -> CO2 + H2
Slightly exothermic, but G and H vary with temperature
Low temperatures favor forward reaction
Pressure affects the reaction (even if it appears it should not)

John Kitchin, using values from the NIST Webbook http://matlab.cheme.cmu.edu/2011/12/12/water-gas-shift-equilibria-via-the- Chang, T., Rosseau, R. W., Kilpatrick, P. K., (1986).
nist-webbook/ Methanol Synthesis Reaction: Calculations of
Equilibrim Conversions Using Equations of State. Ind.
Eng. Chem. Process Des. Dev. 25 477-481.
Methanol Synthesis
temperature dependent, much
like most other reactions

CO + 2H -> CH3OH

exothermic reaction
strongly pressure dependent due
to the reduction in total moles
(high pressure favors the forward
reaction)

Chang, T., Rosseau, R. W., Kilpatrick, P. K., (1986). Methanol

Synthesis Reaction: Calculations of Equilibrim Conversions Using
Equations of State. Ind. Eng. Chem. Process Des. Dev. 25 477-481.
 Final Step: Separation
One of the most important steps where
thermodynamics plays a role.
The goal is to minimize energy loss
These losses are due to mixing as well as heat and
mass transfer
Thermodynamic properties and phase equilibrium
are notoriously hard to predict in methanol, water,
and hydrocarbon mixtures.
 Distillation
Differing boiling points among the species allows for a flash drum
followed by distillation

Two distillation columns are used to separate water and methanol

In a perfect system the thermodynamics would be controlled by

heaters and coolers with appropriate duties at each stage of the
columns, main issue is the cooling of mixture exiting at high
temperature

Thermodynamically distillation is a good separation process but

care must be taken to specify proper column specifications in order
to avoid unnecessary complications.
 Simple Example

http://www.scielo.br/scielo.php?pid=S0104-66322008000100021&script=sci_arttext
 Hydrate formation
At specific temperatures and pressures hydrate
formation can occur within the stream
Hydrates are solid crystalline compounds that are
created by natural gas compounds occupying the
empty lattice positions in a water structure

http://www.esrf.eu/UsersAndScience/Publicati
ons/Highlights/2009/materials/mat09
 Azeotropes
No Azeotropes in data for methanol, water,
and hydrocarbons
The closest azeotropic mixture is ethanol and
water
Care must always be taken when dealing with
separating a mixture that no azeotropes exist.
 Pressure Swing Adsorption
An easier separation process that deals with gases,
thermodynamically favored
Separates a gaseous species based off of the molecular
affinity for absorbent materials
High pressure adheres the gas to solid surface and low
pressure it is released
Very useful cleaning catalysts for hydrocarbons are zeolites

http://www.gazcon.com/sw13931.asp
 References - Models
Towler, G., & Sinnott, R. (2008). Chemical engineering design
principles, practice and economics of plant and process
design. Amsterdam: Elsevier/Butterworth-Heinemann.
 References Water Gas Shift and
Methanol Synthesis
Bustamante, F., Enick, R., Rothenberger, K., Howard, B., Cugini, A., Ciocco, M.,
Morreale, B. (2002). Kinetic Study of the Reverse Water Gas Shift Reaction in High-
Temperature, HIgh-Pressure Homogeneous Systems. Fuel Chemistry Division
Preprints 47(2), p. 663-664
Daza, Y. A. , Kent, R. A., Yung, M. M., Kuhn, J. N. (2014). Carbon Dioxide Conversion
by Reverse Water-Gas Shift Chemical Looping on Pervoskite-Type Oxides. Ind. Eng.
Chem. Res. 53, 5828-5837.
Park, S., Joo, O., Jung, K., Kim, H., Han, S. (2001). Development of ZnO/Al2O3
catalyst for reverse-water-gas-shift reaction of CAMERE (carbon dioxide hydrogenation
to form methanol via a reverse-water-gas-shift reaction) process. Applied Catalysis A:
General 211 p. 81-90
Chang, T., Rosseau, R. W., Kilpatrick, P. K., (1986). Methanol Synthesis Reaction:
Calculations of Equilibrim Conversions Using Equations of State. Ind. Eng. Chem.
Process Des. Dev. 25 477-481.
Kitchin, J. (2011) Water Gas Shit Via the NIST Webbook.
http://matlab.cheme.cmu.edu/2011/12/12/water-gas-shift-equilibria-via-the-nist-
webbook/
 References POX and Steam Reforming

Ali, M. S., Zahangir, S. M., Badruddoza A. Z. M., Haque M. R.

(n.d.) A Study of Effect of Pressure, Temperature, and
Steam/Natural Gas Ratio on Reforming Process for Ammonia
Production. Journal of Chemical Engineering 23 1995-2005
http://www.banglajol.info/index.php/JCE/article/view/5565
Lyubovsky, M., Roychoudhury, S., & LaPierre, R. (2005). Catalytic
partial oxidation of methane to syngas at elevated
pressures. Catalysis Letters. doi:10.1007/s10562-005-2103-y
Zhu, Q., Zhao, X., & Deng, Y. (2004). Advances in the Partial
Oxidation of Methane to Synthesis Gas. Journal of Natural Gas
Chemistry, 13, 191-203. Retrieved from
http://www.bjb.dicp.ac.cn/jngc/2004/2004-04-191.pdf
 References - Separations
Demirel, Dr Y., "Retrofit of Distillation Columns Using
Thermodynamic Analysis" (2006). Papers in Physical
Properties. Paper 6.
http://digitalcommons.unl.edu/chemengphysprop/6
Lide, D.R., and Kehiaian, H.V., CRC Handbook of
Thermophysical and Thermochemical Data, CRC Press, Boca
Raton, FL, 1994.
http://chemistry.mdma.ch/hiveboard/picproxie_docs/000506
293-azeotropic.pdf