Methanol Synthesis Plant Preliminary Design

CHEN 4500 Principles of Process Design

Dr. Hartounian
Group 2
Lazaro Dubrocq, 2016
Kevin Donnelly, 2016
Ryan Brenner, 2016
National Chemical Designs
New York, New York
November 16, 2015
Rev. 2

Glossary

Executive Summary
3
Assumptions
4
Amine Treatment of Liquid Hydrocarbons
5

Methane Steam Reforming

6

Partial Oxidation of Methane

6

Methanol Synthesis from Syn-gas

7

Preliminary Aspen Results

8

Works Cited
9

Block Flow Diagram-1

A1

Block Flow Diagram-2

A2

Block Flow Diagram-3

A3

ASPEN Program Values

xx

Executive Summary
A methanol synthesis plant was designed to produce 400,000 metric tons of
methanol per year with 99.5% purity from natural gas using conventional
technology. Methanol is produced from natural gas by first converting the
natural gas to syn-gas and then reacting it with a copper catalyst. In order to
prevent catalyst poisoning, hydrogen sulfide is removed from the natural gas
stream by an amine gas treating process which utilizes monoethanolamine
(MEA). Syn-gas is produced from both a reforming and partial oxidation
reaction. The syn-gas is then reacted over Topse MK-151 Fence copper
based catalyst to produce methanol. Methanol and water are separated from
the unreacted syn-gas in a flash unit. Next, water and other impurities are
removed from the methanol in distillation columns. The output of this design
is XXXX metric tons of methanol per year with 99.5% purity, satisfying the
design goals.

Assumptions
1. Pumps are 85% efficient
2. Compressors are 72% efficient
3. There is a pure feed of O2 available for the partial oxidation of methane
reaction
4. The hydrogen sulfide and carbon dioxide exhaust gas from the amine
gas treating process will be sold for profit to another company
5. The Methanol Synthesis plant can run 24 hours a day
6. There are 365 days in a year

Amine Treatment of Liquid Hydrocarbons

In the natural gas feed, it is assumed that hydrogen sulfide is also present at
a level of 15 ppm by volume. Hydrogen sulfide is a catalyst poison, and thus
needs to be removed to low levels. In order to remove the hydrogen sulfide
from the natural gas feed, an amine gas treating process is utilized.
Monoethanolamine (MEA) was chosen as the amine absorbent, because it is
the preferred solvent for gas streams containing relatively low
concentrations of H2S and CO2. One advantage to using MEA as the amine
absorber is the low molecular weight of MEA (61.09 g/mol) results in high
solution capacity at moderate concentrations. Additional advantages to using
MEA are its high alkalinity, and the relative ease at which it can be retrieved
from contaminated solutions (Khol, 1997). The optimal MEA concentration
was found to be 15 wt% from trial and error. The minimum amount of MEA
solution required to run the absorber was used. The principle reactions
occurring when solutions of monoethanolamine are used to absorb CO2 and
H2S are as follows (Khol,1997).
Ionization of water

++O H
H 2 O=H
Ionization of dissolved H2S

++ H S
H 2 S=H
Hydrolysis and ionization of dissolved CO2
+
+ H
C O2 + H 2 O=HC O3
Protonation of alkanolamine
[C2H7NO]NH2 + H+ = [C2H7NO]NH3+
Carbamate formation
[C2H7NO]NH2 + CO2 = [C2H7NO]NHCOO- + H+
The flow arrangement for the MEA acid-gas absorption process is shown in
Block Flow Diagram-1. The natural gas feed to be purified is passed
upward through the absorber, counter current to the MEA rich stream. The
MEA rich stream from the bottom of the absorber is then heated and fed to
6

the top of the stripping column. The acid gas that is removed from the
solution in the stripper is then condensed and flashed in order to separate
the exhaust gas, composed of hydrogen sulfide and carbon dioxide, from the
water. The water rich stream is then passed to the stripper in order to
remove the hydrogen sulfide and carbon dioxide form the amine rich
solution. Next, the MEA lean solution is cooled, because a lower temperature
of the MEA solution results in higher absorption of H2S, and returned to the
absorber to complete the cycle.

Methane Steam Reforming

After the removal of hydrogen sulfide from the natural gas feed, the syn-gas
production process begins with methane steam reforming. The steam
reforming of methane is comprised of three reversible reactions: the highly
endothermic reforming reactions (1) and (3), and the moderately exothermic
water-gas shift reaction (2) (Van Beurden, 2004):
C H 4 + H 2 O CO+3 H 2

H 298 K =+206 kJ /mol

(1)
CO+ H 2 O C O2 + H 2
C H 4 +2 H 2 O C O2+ 4 H 2

H 298 K =41 kJ /mol

(2)

H o298 K =+165 kJ /mol

(3)
During methane steam reforming over a nickel based catalyst, methane is
reacted with steam (reaction 1) between 800-1000 and 20.3-30.4 bar in a
highly endothermic reaction to form CO and H2 (Olah, 2006). In this design,
methane and steam are reacted at 800 and 20 bar over Topse RK-201
nickel based catalyst. The Topse RK-201 nickel based catalyst was chosen
due to the low cost of nickel. Part of the CO formed during reaction 1 reacts
with steam to yield more H2 and CO2 in what is called a water shift reaction.
The stoichiometric number (S) for the methane reforming is 3. This is far
from the desired value of 2 for methanol synthesis. However, this will be
adjusted during the partial oxidation of methane.
During the methane steam reforming, there are also ethane side reactions
given by the following equations (Gillan, 2013)

C2 H 6 +2 H 2 O CO+5 H 2
(1)
C2 H 6 +2 H 2 2 C H 4
(2)
CO+ H 2 O C O2 + H 2
(3)
Partial Oxidation of Methane
Next, the methane is reacted with insufficient oxygen in a process known as
partial oxidation. This reaction is exothermic, and typically operated at a
temperature between 1200-1500 oC (Olah, 2006). This design operates at
1200 and yields syn-gas with a stoichiometric number (S) of 2 which is
ideal for methanol synthesis from syn-gas. The principle reactions occurring
during the partial oxidation process are as follows
1
C H 4 + O2 CO+ 2 H 2
2

H o298 K =36 kJ /mol

1
CO+ O2 C O2
2

H o298 K =283 kJ /mol

1
H 2+ O 2 H 2 O
2

H 298 K =241kJ /mol

Methanol Synthesis from Syn-gas

The syn-gas product of the methane reforming and partial oxidation
reactions are heated, compressed, and then sent to the methanol synthesis
reactor. Methanol is produced from syn-gas over a heterogeneous catalyst by
the following reactions.

CO+2 H 2 C H 3 OH H 298 K =91 kJ /mol

C O2 +3 H 2 C H 3 OH + H 2 O H 298 K =50 kJ /mol
C O2 + H 2 CO+ H 2 O H 298 K =41 kJ /mol

(1)
(2)
(3)

The use of a copper catalyst lowers the operating temperature and pressure
of the methanol synthesis reaction. The methanol synthesis process utilizing
a copper catalyst is typically operated at a temperature between 200-300 oC
and 50.7-101.3 bar (Olah, 2006). For this design, the reaction is carried out
at 220 oC and 100 bar over the copper based catalyst Topse MK-151 Fence.
This catalyst is used because it is extremely active, stabile, and provides a
higher initial activity (Haldor Topsoe, 2015).
After the methanol synthesis reaction, the products are cooled to 50 oC and
then flashed in order to separate the water and methanol from the unreacted
syn-gas. Next, the unreacted syn gas is recycled to the methanol synthesis
reactor. 5% of the recycle stream is purged in order to prevent the buildup of
impurities. The methanol and water stream is then sent to a distillation
column where the water is separated from the methanol. Last, the distilled
methanol is passed to a second distillation column where the remaining
impurities such as CO and CO2 are removed.

Preliminary Aspen Results

46,461 kmol/hr methanol produced
46,461

kmol
Hr
operating days 1000 mol 32.04 g
1 kg
1metric ton
24
( 3650.97 )

hr
day
year
kmol
mol
1000 g
1,000 kg

= 13 million metric tons of methanol produced per year

Inlet flow
Natural Gas Feed: 51023.2 kmol/hr
51,023.2

kmol
Hr
operating days 1000 mol 16.6 g
1 kg
1 metric ton
24
( 3650.97 )

hr
day
year
kmol
mol
1000 g
1,000 kg

=
7 million metric tons of natural gas utilized per year
O2 Feed: 24168.5 kmol/hr
7 million metric tons of natural gas utilized per year

Reactor Operating Conditions

Methane Steam Reforming: 800, 20 bar
Partial Oxidation of Methane: 1200
Methanol Synthesis: 220 oC and 100 bar

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Works Cited
Feagan, R. A., Lawler, H. L., and Rhames, M. H., 1954, Petrol Refiner,
Vol. 22, June, p,167.
Gillan, Claire, Martin Fowles, Sam French, and S. David Jackson.
"Ethane Steam Reforming over a Platinum/Alumina Catalyst: Effect of Sulfur
Poisoning." Industrial & Engineering Chemistry Research Ind. Eng. Chem.
Res. 52.37 (2013): 13350-3356. Web.
Haldor Topsoe. (n.d.). Retrieved November 16, 2015, from
http://www.topsoe.com/products/mk-151-fencetm
Kohl, A., & Nielsen, R. (1997). Gas purification (5th ed.). Houston, Tex.:
Gulf Pub.
Olah, G.A. and A Goeppert, G.K.S. Prakkash, Beyond Oil and Gas The
Methanol Economy, New York, Wiley, 2006. Chapter 12 Production of
Methanol from Syngas to Carbon Dioxide, provided at the CHEN 4500
Courseworks web site.
Van Beurden, P. (2004). On the Catalytic Aspects of Steam-Methane
Reforming.

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