C OAL T O M ET H A NO L D ES I G N
R E P O RT
METHANOL SYNTHESIS
UNIVERSITY OF
C A L I F O R N I A , S A N D I E G O,
9500 GILMAN DR., LA
JOLLA, CA 92093
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1. Executive Summary
Methanol synthesis was completed with syn gas from the water gas shift reactor. Aspen model simulation Ryield
combined with a flash and column distillation produced 1580 Mtonnes of methanol. A column distillation height and
diameter were calculated to be 38 feet and 3 feet, respectively. Methanol AA purity will need to be continued in the future
to separate the ethanol-methanol binary mixtures to AA specifications. Kinetic rate equations were given in cited articles
to be used for LHHW reaction model in Aspen for a Rplug reactor. At this time A Ryield reactor is used to synthesis
methanol.
Hydrocarbons derived from petroleum, natural gas or coal is essential to modern life and its quality. The bulk of the
world’s hydrocarbons are used as fuels for propulsions, electrical power generation, and heating8. Oil reserves are
diminishing and market prices soaring as a primary form of energy in the world. Alternative fuel sources and fuels must be
explored. Recent market fluctuation in the price of crude oil and other financial incentives are helping to attract internal
investments to exploring alternate energy sources. Methanol derived from the gasification of coal shows many promises
in areas of improved environmental carbon capture, production of a variety of synthetic fuels, and in 2008 financial profits
are becoming a reality.
A preliminary engineering design report investigating coal processing to methanol production at 5000Mtonne per day
capacity is presented. An economic, environmental and process safety evaluation of the production plan is underway.
Aspen process modeling simulation is used to verify the chemical engineering feasibility of coal to methanol.
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Hougen-Watson (LHHW) kinetic model have been partly completed. The LHHW parameters are used in the ASPEN
simulation RPlug model to specify a plug flow reactor during the synthesis reactions. A Flash and Distillation column were
used to refine methanol to the AA requirements. Based on the provided data and Aspen calculations preliminary reactor
sizing, column sizing have been completed. Economic analysis for the synthesis and refining phase will be completed in
the final design report.
Commercial technologies, processes, and plants currently in use throughout the world are discussed. The technologies
critical factors for consideration in a coal to methanol plant are explored. Comparing the simulation results and the
research a recommendation of a reliable technology is given.
Environmental and process safety during the synthesis, refining, and by product removal have been researched. Catalyst
life is an important factor designing by product removal. Recommendations will be provided based on this research.
Alternatives and improvements will be presented.
Based on the Aspen flow diagram, technology research and material balances annual utilities cost and capital investment
will be completed in the final report.
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KineticFactor [ DrivingForce]
(eq3.1) ri ' =
[ Adsorption]
f
k ps' , A 3 K co f co f H32/ 2 − 1/CH2 3OH°
( f H 2 K p1 )
(eq.3.2) '
rCH 3OH , A 3
=
K
(1 + K co fco + K co 2 f co 2 ) f H1/22 + H1/202 f
KH 2
H 20
It is of the form stated in equation 3.1a kinetic factor, driving force and adsorption expressions. The kinetic Factor follows
the Arrhenius rate law
(eq3.0) k = A exp[− Ea /( RT )]
Limits on the model are low pressures, kinetic factors > 0, Ea > 0. The equilibrium stated in the AICHe is valid for a
temperature range of 373K – 676K for the equilibrium relationship in equation 3.4.
1 P y 1 11284
(eq3.4) ln K p 2
= ln CH 3OH
2
= ln CH 3OH
2 2
= −32.918 +
psia PCO PH 2 yCO yH 2 P T (K )
Aspen simulation software has two models for handling kinetics. Following LHHW parameters given by Gaaf et al, the
RPlug model and be used to simulate the three reactions A, B, C.
Other design bases are separation principles heuristics for binary mixture separation. After the methanol synthesis,
whether a Rplug or Ryield reactor was used by product gases need to be separated from methanol, ethanol, water liquid
mixture. Ethanol is added in as a mass balance of 1:100 of methanol produced and produced by the following reaction.
A flash or knock out drum removes CO2 and CO excess and recycles back to WGS. Further separation of alcohols from
water and lastly methanol from ethanol are based on the relative volatilities of the binary components. No azeotropes
exist within this system allowing for theoretically perfect separation. Column sizes in diameter and height may limit
production of 5000mtone/day of methanol. Calculations are currently used with 3000Mtonnes/day of coal feed and once
the final yield is know this will need to be scaled up. At scale up reactor size and column size will be limited by structural
limits.
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3.2 Technology Selection Criteria and Considerations
Design considerations during the methanol synthesis and refining processes are syngas cooling, acid gas removal, in
particular carbon dioxide. The catalyst deactivates primarily because of loss of active copper due to physical blockage of
the active sites by large by-product molecules; poisoning by halogens or sulfur in the synthesis gas, which irreversibly
form inactive copper salts; and sintering of the copper crystallites into larger crystals, which then have a lower surface
area-to-volume ratio1.
Fixed Bed technology is a adiabatic quenched low pressure plug flow reactor. The reactor is catalyzed with a Cu/Zn/Al
mesh interface. The surface area is several hundred square feet per kilogram catalyst. There are inherent inefficiencies
from the cooling of the syngas feed to the heating of the reaction core. The raise and fall of temperature structurally
weakens materials of construction. However, this technology is known for the reliability.
Isothermal steam raising reactors were developed by Lurgi. They are made up of tubes packed with catalyst and cooling
water into steam on the shell. This allows for near isothermal conditions. Conversion is limited by equilibrium.
Synetix, formerly ICI, systems produced nearly 61% of the worlds methanol production with adiabatic quenched plug flow
reactors.
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5. PFD with Stream Tables synthesis and refining
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7. Major Equipment with Sizing for Cost Estimation
Methanol synthesis will require a plug flow reactor similar to the ICI adiabatic quench reactor. Sizing and number of
reactors required to meet capacity will be completed on final report.
Distillation column will be needed for methanol refining to meet AA specifications. Current distillation column can produce
1500 mtonnes of methanol with a feed stock of 3000mtonne of coal. Scale up processes will be limited by column
structural height. Prelimary size has been calculated to be:
• 3 foot diameter
• 38 foot height
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Reference:
2) G.H. Gaaf, “Comparison of two-phase and three phase methanol synthesis processes,” Chemical Engineering
and Processing 35 (1996) 413-427.
3) G.H. Gaaf, “Kinetics of Low-Pressure Methanol Synthesis,” Chemical Engineering Science vol 43 (1988) pp
3185-3195
5) H. Fogler, Elements of Chemical Reaction Engineering, 4th ed, Prentice Hall, 2005, pp 1021 – 1026
6) G.A. Olah, A. Goeppert, G.K.S. Prakash, Beyond Oil and Gas: The Methanol Economy. Wiley-VCH, Weinheim,
2006.