2016/17 H83PS1 Process Simulation 1

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Department of Chemical and Environmental Engineering

Faculty of Science and Engineering
LEVEL:
3
MODULE:
Simulation 1 (H83PS1)
ASSIGNMENT:
HYSYS modelling of synthesis loop
ISSUE DATE:
1st November 2016
SUBMISSION DATE:
Monday 21st November 2016 (4:00 PM)
Submission
(1) This handout with all questions answered is needed for hardcopy submission.
(2) The e-copy of simulation file must be uploaded to Moodle before the completion of
the given time frame. Name the files as below:
Simulation file:
your name_ID.hsc
LECTURER:

Dr Nusrat Sharmin

To be completed by the student

Name:

Date submitted:

Course:

Student Signature:

Certification: I certify that the whole of this work is the result of my individual effort
and that all quotations from books, periodicals, etc. have been acknowledged.
_____________________________________________________________
_________________
To be completed by the lecturer:
Comments:
Part 1 (14%)

Part 2 (11%)

Mark/Grades

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COURSEWORK 2 (25%)
Instruction
Follow the instructions given in the handout. Use the appropriate equipment for changing the operating
conditions when moving from one stream to the next. Assume zero pressure drop in equipment
UNLESS otherwise stated; and do not worry about information that are not mentioned in the
handout. Leave everything at default unless specified. Also, for all values not given, provide
an initial estimate and optimise it later if needed. At any mixing point or recycle, ensure the
consistencies in units, use any heater, cooler, pump or compressor if needed.
Project Tender
You are being offered the opportunity to take over the management of a design of a process for the
manufacture of synthesis gas from natural gas for International Chemicals Incorporated (ICI), after the
termination of the services of the previous company working for ICI, Emek Projects Ltd (EPL). The
original EPL design was shown in Appendix A.
Your design should produce synthesis gas with a molar ratio of H 2 to N2 of 3:1, to be used in the future
for ammonia production, assuming a basis of 12,000 kg/h of methane as feed, at a cost of 10
cents/kg. The main by-product of the process is CO 2, which has a market value of 10 cents/kg provided
that it can be produced at a purity of at least 98 mol%.
Table 1: Product specifications and revenues (NOTE: These are the DESIRED specifications of
the PRODUCTS from the process which can maximise the profit)
Product
Specification
Revenue
Synthesis
(a) A molar ratio of hydrogen to nitrogen To be sold for the production of ammonia
gas
of 3 (ideally, this ratio needs to be 3:1);
(b) no water; (c) CO and CO2 under 1
ppm each; (d) minimum inert (Argon
and CH4).
Carbon
CO2 should be supplied at a pressure in
There is no upper limit in the production rate
dioxide
the range 15-50 bar, with a purity of at
that can be accommodated. The revenue on
least 98 mol%; there are no restrictions
CO2 that meets the above specifications is
on its supply pressure, provided it is a
$0.1/kg. In the event that any of the
liquid.
specifications are not met, the gas is
considered a waste stream that needs to be
safely disposed of, at a cost of $0.05/kg*.
Water
Water can be reused in the process,
There is no upper limit in the production rate
provided its purity is greater than 99.5
that can be accommodated. While product
mol%, and at temperature less than 50
that meets the above specifications does not
o
C. There are no restrictions on its supply generate revenue, note that in the event
pressure, provided it is a liquid.
that any of the specifications are not met,
this stream is considered a waste stream
that needs to be safely disposed of, at a cost
of $0.05/kg*.
*Note that the waste disposal unit can accept streams at any temperature, pressure and composition.

Table 2: Costs of raw materials

Raw material
Specification
Natural Gas
Up to 12,000 kg/h (288 T/day) of pure methane is available at 15 bar and 30oC, at
a cost of $0.1/kg.
Steam
An unlimited supply of 15 bar saturated steam is available, at a cost of $0.02/kg.
This needs to be supplied both to the reformer (Reformer Steam) and the
oxidation reactor (Combustion Steam).
Air
An unlimited supply of air is available for free, at 1 bar and 30oC. The composition

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of air is: 78.08 mol % nitrogen, 20.95 mol % oxygen, 0.94 mol % argon and 0.03
mol % carbon dioxide.
Production process in details
A possible route to ammonia is from natural gas. The process involves two main parts: Part 1 - the
reaction section, and Part 2 the separation section.
Part 1:
Tips: Use an appropriate fluid package to simulate this operation. Then, create a template from
your flowsheet and save as a template.
Synthesis gas generation (see Appendix A): The objective of this section is to produce as much
synthesis gas as possible, and to ensure its purity. The specifications for synthesis gas are: (a) a molar
ratio of hydrogen to nitrogen of 3 (ideally, this ratio needs to be 3:1 in the NH 3 converter feed); (b) no
water; (c) CO and CO2 under 1 ppm each; (d) minimum inert (Argon and CH4). To achieve these
objectives, the following steps are employed:
1) The methane is combined with reformer steam, preheated in the heater E-101 and then fed to the
reformer, in which most of the methane is converted to hydrogen. The reformer is modelled as an
isothermal PFR with kinetic reactions (the effluent temperature is set to be equal to the feed
temperature). In the EPL design, the operating temperature is selected as 700 oC.
Note that PFR is in the Common tab of the HYSYS palette; for simulating a PFR, after
the connections, under Parameters, assume zero pressure drop, insert the reaction set,
and under Rating, use a volume of 1 m3 and length of 1 m.
The following reactions take place in the reformer:
Rxn-1:
Rxn-2:

CH4 + H2O 3H2 + CO

CO + H2O CO2 + H2

According to Parisi and Laborde (2001), reaction rates for these two kinetic reactions are as follows:

[ ( )]
[ ( )]

( )] P

r CH = k 1 exp

E1
E1 '
PCH P H O k 1 ' exp
RT
RT

r CO= k 2 exp

E 2
E2 '
PCO P H O k 2 ' exp
PCO PH
RT
RT

( )]

CO

P3H

kmol/m3-s

kmol/m3-s

In the above equations, the species partial pressures are expressed in atm, T is the temperature in
K, and that -rCO holds for T > 860 K. Parisi and Laborde (2001) provide kinetic parameters as
follows: E1 = E2 = 16,000 kJ/kmol,
-212,336 kJ/kmol,

k2

k 1 = 200 kmol/m3-s,

= 100 kmol/m3-s,

k 1 ' = 9.229010-12 kmol/m3-s, E1=

k 2 ' = 4,316 kmol/m3-s, E2= 49,655 kJ/kmol.

Tips: Simulate all kinetic reactions as Kinetic reaction, key in the Stoichiometric
Coefficient, on the basis of Partial Pressure and Overall Rxn phase; what you need to
do to specify the kinetic reaction is to key in the k and E values for the forward and
reverse reactions)

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2) The reformer effluent is combined with air and more steam in such a way as to try to ensure a 3:1
mixture of hydrogen and nitrogen in the resulting synthesis gas. This mixture is reacted in the
oxidation reactor, often referred to a secondary reformer, modelled as an adiabatic PFR with
heterogeneous catalytic reaction, where the oxygen in the air generates additional hydrogen. In
addition to Rxn-1 above, the following reaction also take place in the oxidation reactor:
Rxn-3:

CH4 + 2O2 CO2 + 2H2O

According to Wolf et al (1997), the reaction rate for the above reaction takes the mathematical
form:

1000 exp
r CH =
4

P
( 32000
RT )

CH 4

PO

kmol/m3-s

(1+ K C H PC H + K O PO + K C O PC O + K H O PH O )
4

Note that in the above equations, the species partial pressures are expressed in kPa and T is the
temperature in K. Wolf et al (1997) provide kinetic parameters as follows:

K C H =1.1 106 exp (EC H / RT ) , ECH =32,200 kJ /kmol

4

K O =1.1 10 exp ( E O / RT ) , EO =28,400 kJ /kmol

2

K C O =1.5 104 exp (EC O /RT ) , E CO =32,900 kJ /kmol

2

K H O =5.3 exp (E H O /RT ) , EH O =27,300 kJ /kmol

2

Tips: Model the above reactions as Heterogeneous catalytic reaction, on the basis of
Partial Pressure, and Overall reaction phase; what you need to do is, under the
Reaction Rate tab, to challenge yourself to fill in the Numerator and Denominator
sessions)
3) Since the first two reaction steps generate CO, which would poison the ammonia synthesis
catalyst, shift reaction steps are employed to convert the CO to CO 2. Both of these reactors are
modelled as adiabatic kinetic reactors. The first shift reactor, High-temperature (HT) shift, is fed the
oxidation reaction effluent. It is possible to install a heat exchanger to modify its inlet temperature,
as is done for the LT shift, where the heat exchanger E-102 reduces the feed temperature to 500 oC.
The following kinetic reaction takes place in the shift reactors, which are PFRs:
Rxn-4:

CO + H2O CO2 + H2

The same kinetic form is used as before, but, as stated in Parisi and Laborde (2001), the kinetic
parameters are slightly different, since the shift reaction is carried out at lower temperatures:

r CO= k 2 exp

( ERT )] P
2

CO

P H O k 4 ' exp
2

( ERT ' )] P
4

CO 2

PH

kmol/m3-s

In the above equation, the species partial pressures are expressed in atm, T is the temperature in K,
and that the above kinetic holds for T < 860 K. Parisi and Laborde (2001) provide kinetic
parameters as follows: E2 = 16,000 kJ/kmol,

k 2 = 100 kmol/m3-s,

k 4 ' = 7,594 kmol/m3-s,

E4= 54,053 kJ/kmol.

4) Any remaining CO is converted back to methane in the methanator, modelled as adiabatic PFR
reactor. In the methanator, Rxn-1 takes place, with the same kinetics. The operating temperature
needs to be low enough to ensure that the reverse reaction dominates. In the design, the
methanator feed temperature is selected as 250 oC.

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Part 2:
Start a new simulation and register the components appearing in this part 2 simulation using a
different appropriate fluid package. After entering the simulation environment, install the template
created for Part 1 as a sub-flowsheet.
5) The water produced in the previous reaction steps is removed. One possible implementation involves
cooling using E-104 to 40 oC to condense the water in the stream, and its removal largely using the
flash vessel, V-100. Residual water is removed via S-14 using adsorbing beds, modelled using a
separator, X-100 (i.e. only water as liquid is removed via S-14).
TIPS for component splitter: Equalize all stream pressures and specify vapour fraction as
1 for top product, and 0 for bottom product).
6) The CO2 produced in the previous steps is removed. One possible implementation, suggested by
EPL, involves simply cooling the effluent from X-100 using E-105, condensing out most of the CO 2 in
flash vessel V-101 as by-product, and then total removal of the residual CO 2 using adsorbing beds,
X-101. Decide the flash temperature (V-101) to be used for effective removal of CO 2.

Questions
Simulation:
1. Simulate the process using HYSYS. Save and upload this HSC case fil in the format of File1-your
name.hsc. [13%]
2. Use the ADJUST, SET, SPREADSHEET functions where necessary to achieve the desired product
specifications as shown in Table 1. Wait for a considerable amount of time for converging.
Save and upload this HSC case fil in the format of File2-your name.hsc. [13%] [6%]

Answer the following questions:

3. Which thermodynamic models were used in the template and the main flow sheet? Justify your
selections. [2%]

4. Did you manage to produce synthesis gas, CO 2, and water with the desired specifications as shown
in Table 1? If yes, briefly describe how you did that; if no, justify your reasons. [2%]
5. What is the temperature of the stream entering flash column (V-101)? What are the factors to be
considered while setting specifications for flash column output? Hint. Assume that the cost of
operating the special equipment modelled using splitter are known. [2%]

2015/16 H83PS1 Process Simulation 1

Appendix A: The Original EPL Design for Synthesis Gas Production

Heater

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