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Integrated Design
1
st
Year
Semester II, Academic Session 2013-2014
EKC 111
Due date: 26 May 2014
(Group Project: 4 students in a group, you are requested to present your mass
balance spreadsheet to the lecturer)


1. Project Topic: Production of Methanol through hydrogenation of CO/CO2.

Methanol has been used as the feed for the production of acetic acid and
formaldehyde. The annual production of methanol grows by 4% per year. Generally,
the traditional methanol production technology features four main processes, which
is the purification of the feed stock materials (natural gas), reforming (to prepare
the synthesis gas), methanol synthesis and methanol purification. The three main
raw materials used are the natural gas comprised of 96% methane and trace amount
of hydrogen sulphide, stream as well as oxygen that used for oxygen blow auto-
thermal reforming in the reforming processes.
The existence of hydrogen sulphide in the methanol synthesis loop will greatly
reduce the catalytic activity in the steam reformer and reactor. Hence, the natural
gas contains low levels of sulphur compounds need to undergo a desulphurization
process to reduce the sulphur levels of less than one part per million. The
desulphurization process is operating at a temperature of 350C and pressure of 20
bar. The feed is channel through zinc oxide beds where hydrogen sulphide is
adsorbed:

Two steps of catalytic reforming process involved in order to prepare the synthesis
gas. Reforming is the process which transforms the methane (CH4) and the steam
(H2O) to intermediate reactants of hydrogen (H2), carbon dioxide (CO2) and carbon
monoxide (CO). In the first step, the natural gas and steam are supplied to the steam
reformer with catalyst bed of nickel at approximately 600C.

The reformed gas, which consists of gas mixture of hydrogen, carbon monoxide,
unreacted methane and un-decomposed steam leaves the steam reformer at 850C
and 25 bar and routed to oxygen blown auto-thermal reformer (ATR). The operation
in ATR is carried out under higher temperature (1000 C) and higher pressure (50
bar). Oxygen also being supplied to the reactor such that it can react with hydrogen
in order to lower the H2 to CO ratio:

In this process, the oxygen has also partially oxidizes methane to produce carbon
monoxide and hydrogen gas.

After removing excess heat from the reformed gas, the reformed gas will then enter
a flash column to remove the excess steam. The separation is occurred at 50C and
50 bar. The bottom product (water) will be removed and the top product (carbon
monoxide, carbon dioxide and hydrogen) will be then compressed to 80 bar before
entering at the top of the methanol production stage in the synthesis reactor.
Reformed gas is then routed into the methanol reactor (CO/CO2 hydrogenations) at
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approximately 230C such that hydrogen and carbon monoxide can react to
synthesis methanol in the presence of a highly selective copper based catalyst. Here
the reactants are converted to methanol-steam mixture product with composition of
68% methanol and 31% water, as shown below:

The product mixture (methanol, hydrogen, steam, carbon monoxide and carbon
dioxide) is then discharged at the bottom of the reactor. In fact, methanol conversion
is at a rate of 5%, the product mixtures are separated in the flash column (top
product: hydrogen, carbon monoxide and carbon dioxide; bottom product:
methanol, steam), operated at 10
o
C and 50 bar. There is a continual recycling
whereby the unreacted gases (hydrogen, carbon monoxide and carbon dioxide) are
recycled in the synthesis loop to increase the overall methanol conversion. The
methanol-water stream is then heated to 80C and sent to distillation column to
separate the water from the methanol. In this tower, a methanol-rich stream,
containing approximately 99.86% of methanol is taken as top product and sent to a
central methanol storage vessel. The water comes out as bottom product contains a
lot of impurities and need to be sent to wastewater treatment plant for further
treatment.































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1. Process Flow Diagram (PFD)



Figure 1: Block flow diagram for methanol process
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Figure 2: PFD for methanol process








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2. Problem Statement

In EKC 157 Chemical Engineering Drawing (Semester 1, 2013/2014) you were asked to
prepare a block diagram and PFD of a plant producing methanol through hydrogenation
of CO/CO2 based on the given proses description. The process description and the
sample block diagram as well as the PFD are attached. In this Integrated Design project
you are requested to perform a mass balance on a unit operation with non-reactive
process and a unit operation with reactive process.

2.1 Unit operation with reactive process, Autothermal Reformer (R-103 in PFD).

Assume reaction taking place with alkane conversion of 100%, hydrogen yield of 90%
and 25 % excess oxygen for alkane oxidation. Take a basis of 100 kmol/h and give the
mass balance values up to 4 significant figures.

Table 1: Inlet composition of R-103
Component Mass fraction
CO
2
0.1637
N
2
0.0019
CH
4
0.0658
C
2
H
6
0.0178
C
3
H
8
0.0066
C
4
H
10
0.0013
H
2
O 0.5058
CO 0.1727
H
2
0.0644


2.2 Unit operation with non-reactive process, Flash Separator (V-101 in PFD).
Assume 100 % water removal in Flash Separator.

2.2.1 Perform a mass balance on Autothermal Reformer and Flash Separator
individually based on the information given above using MS Excel.

2.2.2 Perform a mass balance integrating both the operation units.