Journal of The Institution of Engineers, Singapore

Vol. 45 Issue 6 2005

SYNTHESIS AND DESIGN OF CHEMICAL PROCESSES

Lim Kuan Howe1, Dennis1, N.V.S.N. Murthy Konda1 and G.P Rangaiah1*

ABSTRACT
The goal of this work was to critically examine two hierarchical procedures used by
Douglas [1] and Stanislav [2] for the conceptual design of chemical processes. Using the
Hydrodealkylation of Toluene (HDA) process as a case study, it was found that the
flowsheet developed using Stanislav’s procedure was more economical than the flowsheet
developed using Douglas’ procedure. The main advantage of Stanislav’s procedure is
that it is rich enough to allow all reasonable alternatives to surface, hence eliminating
the possibility of letting the best flowsheet slip through the mind of the engineer during
the design process. However, the drawback is that the process is more time consuming as
more options have to be enumerated. This disadvantage was circumvented in this study
by the formulation of a HYSYS-EXCEL interface using Visual Basic programming, which
essentially combines the simulation power of HYSYS with the spreadsheet capabilities of
EXCEL, thereby greatly shortening the time needed to evaluate a particular flowsheet.

INTRODUCTION
Process design involves not only technical knowledge but also a good dose of creativity.
With the increasing complexity of chemical processes and the invention of novel
operations (e.g. reactive distillation, membrane separations), it is not surprising that
numerous alternatives can be generated. The goal of the chemical engineer then, is to
choose the alternative that brings the largest economic benefits to the company. However,
even with the advent of powerful process simulation tools, it still remains a challenge to
develop an entire process flowsheet from the drawing block. Hence arises the need for a
systematic approach to plant design that would help the chemical engineer to arrive at the
best design in a logical fashion.

Douglas [1] suggested a hierarchy of decisions (Figure 1), which shall be referred to in
this paper as the conventional design procedure. Using this procedure to develop the
process flowsheet will help the designer to arrive at the final design using a stage-by-
stage method. At each stage, he generates new alternatives and evaluates those using
selected economic criteria. He then chooses the best alternative and proceeds to the next
stage where he will have to make another decision among the new alternatives that are
generated. Finally, he will arrive at the last stage where the final choice will lead to the
‘best’ alternative.

Stanislav [2] suggested a new hierarchy, also shown in Figure 1, which shall be referred
to in this paper as the modified design procedure. There are two key modifications from
1
Department of Chemical and Biomolecular Engineering, National University of Singapore,
Singapore 119260.
*
Author for correspondence; Email: chegpr@nus.edu.sg. Fax: (65) 6779 1936; Phone: (65) 6874 2187

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the conventional procedure. Firstly, the reactor design is considered as a separate stage of
the design procedure rather than as part of the recycle structure. Secondly, the decision to
recycle is left to the last stage of the hierarchy, just before the heat integration.

Figure 1: Conventional and Modified Design Procedures

The objective of this study is therefore to present a comparison of the conventional and
modified design procedures, the aim being to see which design hierarchy would help the
engineer to arrive at the ‘best’ process flowsheet in the shortest time. The HDA process is
used as the example in this study, which involves the extensive use of a process simulator
as well as sizing, costing and profitability analysis.

FLOWSHEET EVALUATION
In order to apply either of the two procedures listed in Figure 1, it is necessary to evaluate
the profitability of the different flowsheets generated at each stage of the procedure so
that we can select the most profitable alternative and proceed to the next stage. To
determine the profitability, the total capital investment and the annual cost of sales have
to be computed. These two components must in turn be calculated from various sub-
components including equipment cost, cost of land, site preparation, feedstock cost,
utility cost, labor cost, maintenance, operating overhead, depreciation, selling expense etc.
A summary of these computations is shown in Figure 2 and further details can be

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obtained from Seider et al. [3] as well as Turton et al. [4]. The problem however, is that
these computations are lengthy and even with the advent of commercial simulation
software, it still takes a substantial amount of time to arrive at the profitability of a
particular flowsheet e.g. the product selling price required to give a return on investment
of 20%. This was the reason why Douglas [1], in demonstrating the application of his
proposed design hierarchy, used shortcut calculations and estimates to determine the
profitability of the different flowsheets generated at each stage of the hierarchy. This
method, though time-saving, is undesirable because it might lead to the engineer
eliminating a potentially more economical flowsheet.

Figure 2: Profitability Analysis of a Flowsheet

Figure 3: Linking Object Libraries of HYSYS and EXCEL

To circumvent this problem, a special program was developed in this study to automate
the cumbersome process of determining the required selling price for a particular
flowsheet. This program is essentially an interface, which combines the process
simulation power of HYSYS with the spreadsheet capabilities of EXCEL by linking the

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object libraries of these two applications through Visual Basic as shown in Figure 3. With
this interface program, the time taken to evaluate a process flowsheet is thus greatly
reduced and as a result, the use of the design procedures becomes simpler and more
accurate.

The HYSYS-EXCEL interface is based in the EXCEL environment, the main page for
the HDA process as shown in Figure 4. On this screen, the interface captures the key
process simulation results from HYSYS and displays it in a user-friendly interface,
allowing the user to see at one glance whether all the key process constraints are satisfied.
This interface also allows the user to change the simulation parameters in HYSYS
directly from EXCEL. For example, the user can change the desired reaction conversion
rate on the EXCEL interface, which will automatically transmit the new input to HYSYS,
which will in turn run the simulation based on the new input and then send the new
simulation results back to the EXCEL interface.

Figure 4: Main View of HYSYS-EXCEL Interface for HDA Process Example

The main feature of the interface that allows it to speed up the evaluation of a process
flowsheet is its ability to size and cost equipment using macros in the EXCEL interface.
For example, sizing and costing a distillation column manually requires a lot of work
because iterative computations have to be done to obtain the column diameter which can

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give a vapor velocity that will not bring about flooding or entrainment. In addition,
calculations will also have to factor in the tray efficiencies. However, all these
calculations can be done automatically using macros in the HYSYS-EXCEL interface,
which will capture the necessary data from the HYSYS simulation, perform the iterative
calculations and compute the cost based on pre-entered cost equations. A similar
algorithm is followed for the other process equipment. Similarly, macros can also be
written for all the cost components in Figure 2 and hence, the profitability of a flowsheet
can be obtained at the click of a button. A view of the results that was obtained for a
HDA process simulation is shown in Figure 5 where the required selling price of benzene
to give a return on investment of 20% is seen to be $29.23/lbmol. The detailed results on
the equipment, utility and feedstock costs are also displayed in two other sheets in the
EXCEL interface. More details on features and programmability of this HYSYS-EXCEL
interface can be found in Lim [5].

Figure 5: Results View of HYSYS-EXCEL Interface for HDA Process Example

CASE STUDY: HYDRODEALKYLATION OF TOLUENE PROCESS

The HDA process was used as the case study in this work to compare the applications of
the conventional and modified design hierarchies. This process involves the conversion
of toluene to the more valuable benzene product, with methane and diphenyl as the by-
products. A production rate of 265 lbmol/hr of benzene at 99.99% purity was assumed.

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Process constraints can be found in Douglas [1]. The two non-catalytic vapor-phase
reactions are:

Reaction 1: Toluene + Hydrogen → Benzene + Methane

Reaction 2: Benzene ↔ Diphenyl + Hydrogen

Stage 1 of both the conventional and modified design hierarchies involves choosing
between a continuous and a batch process. In this case study, a continuous process rather
than a batch process was chosen for two reasons. Firstly, we are concerned with a plant of
a production capacity of 176x106 lb/yr. Such a large plant capacity would be more suited
to a continuous production. In addition, the benzene product is not a seasonal product
like fertilizers where demand is high only during certain periods of the year. Rather, we
expect the sales of a petrochemical product like benzene to go on throughout the year.
For this reason also, it is wiser to choose a continuous process.

The main difference between the two procedures arises in stage 2. In stage 2 of the
conventional procedure, we identify the input-output structure of the flowsheet and in
doing so, decisions are also made on which output streams to recycle. In contrast, for the
modified design procedure, no decisions on recycle are made at this stage of the
hierarchy. For the HDA process, the basic input-output structure with no recycle streams
can be developed as seen in Figure 6.

Figure 6: Input-Output Structure of HDA Process with no Recycle Streams

If one uses the conventional hierarchy, before designing the reactor sub-system in stage 3,
decisions would be made on which output streams from the process ‘black box’ in Figure
6 are to be recycled. For the case of the HDA process, benzene is obviously removed as a
product. Toluene is a valuable reactant and hence it should be recycled to the process.
Diphenyl is a by-product and a decision should also be made whether to remove or to
recycle it to the process. If diphenyl is removed from the process, there will be selectivity
losses of benzene to diphenyl and hence the toluene consumption rate and cost would
increase. Furthermore, there is the additional capital and operating costs associated with
the extra separation step of removing the diphenyl. However, it is also necessary to
consider the equilibrium constant of the by-product reaction. Finally, a decision is
needed as to whether there should be a recycle stream of the gas stream rich in hydrogen.
Here, a trade-off exists between the savings in fresh hydrogen feedstock and the
additional costs associated with the recycle compressor as well as the methane build-up
in the loop. It is possible to make rough calculations in order to estimate the economic

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potential of these alternatives and to make decisions on which streams to recycle.

Douglas [1] in doing so developed the input-output structure shown in Figure 7.

Figure 7: Input-Output Structure of HDA Process (Conventional Hierarchy)

Subsequent to the input-output structure, Douglas [1] continued with the stages in the
design procedure in Figure 1 and arrived at the flowsheet shown in Figure 8. This
flowsheet was re-simulated and evaluated in this work and the required selling price of
benzene to give a return on investment of 20% was found to be $29.25/lbmol benzene at
an optimum reactant conversion of 75%, similar to what was obtained by Douglas [1].

Figure 8: Flowsheet from the Conventional Design Procedure

The question arises with respect to the conventional procedure then as to how sure one
can be about the recycle decisions made in stage 2? At such an early stage of the
hierarchy, it might not be so easy to make decisions on which streams to recycle based on
simple heuristics or estimated calculations. It is more or less certain that toluene, being a
valuable feedstock should be recycled back to the process. However, the decision might

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not be so clear for diphenyl, hydrogen and methane because such recycle streams might
have a great impact on the design of the reactor and separation subsystems. For example,
if one had decided on recycling the hydrogen/methane stream at stage 2 of the hierarchy,
the possibility of replacing the stabilizer column with a simple flash unit due to the
elimination of methane build-up in the system might not have surfaced. This shows that
potentially more efficient designs of the reactor and separation subsystems could have
been missed if recycle streams were fixed a priori. In other words, the conventional
hierarchy of decisions is not rich enough to allow all potential designs to surface.

Figure 9: Modified Design Procedure with Additional Iterative Loop

In contrast, the modified design procedure avoids this flaw of the conventional hierarchy
by putting off the recycle decision to a later stage. In this manner, the reactor and
separation subsystems can be designed without any limitations and recycle decisions on
each output stream can be taken on its own merit i.e. whether recycling a particular
output stream will yield a cheaper flowsheet than the base flowsheet without any recycle
streams. However, we must not neglect the impact of a recycle stream on the reactor and
separation subsystem. For example, the decision to recycle diphenyl would mean that the
diphenyl concentration in the process would build up to an equilibrium level and
therefore the concern of increased selectivity losses at high reactant conversions is
eliminated. As such, the reactor system can be re-designed to operate at a higher optimal
reactant conversion. Therefore, it would be more appropriate to add an iterative loop to

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the modified hierarchy used by Stanislav [2] to reflect the re-consideration of the reactor
and separation subsystems whenever a new recycle stream is considered. This
modification is shown in Figure 9.

Applying the modified design procedure in Figure 9 to the design of the HDA process,
one would logically start by evaluating a flowsheet where diphenyl, excess toluene,
hydrogen and methane are all removed from the process. However, as previously
mentioned, the recycle of a valuable feedstock of toluene is almost certainly economical
and one might choose a flowsheet with only toluene recycle as the base case instead. This
was done in this study and the required benzene price of this flowsheet was evaluated to
be $42.05/lbmol benzene (at optimum reactant conversion of 95%). This price was then
used as the base price with which the next recycle decision can be compared.

Figure 10: Flowsheet from Modified Design Procedure

Next, the economic advantage of recycling diphenyl was examined and the simulated
flowsheet was found to give a benzene price of $40.20/lbmol (at optimum reactant
conversion of 98%). This price is lower than the base price and therefore, it is economical
to recycle diphenyl. The option of recycling hydrogen was then examined by
incorporating a recycle gas stream in the flowsheet with a membrane separator to remove
methane. This new flowsheet was found to give a benzene price of $29.31/lbmol (at
optimum reactant conversion of 98%). Hence, it is certainly economical to recycle the
excess hydrogen. It follows naturally then that one should next consider recycling
methane along with the excess hydrogen thus saving on the need for a membrane
separation unit. The results of this flowsheet showed a benzene price of $28.45/lbmol (at
optimum reactant conversion of 90%) and since this is lower than $29.31/lbmol, we
conclude that it is not worthwhile to separate and remove the methane from the recycle

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gas and the best flowsheet is that where toluene, diphenyl and flash gas (without further
separation) are all recycled. This flowsheet is shown in Figure 10. The main differences
between this flowsheet and that of Figure 8 are the elimination of the toluene column and
the operation of the reactor at a higher reactant conversion of 98%.

Hence, the results show that the flowsheet developed using the modified procedure is
more profitable than the flowsheet designed using the conventional procedure.
Specifically, for a desired return on investment of 20%, the required selling price of
benzene for the former flowsheet is $0.80/lbmole lower than the latter. The advantage of
using the modified hierarchy of decisions in Figure 9 is that one would systematically
consider all the possible recycle structures of the flowsheet, without the possibility of
missing out a better alternative if one had fixed a recycle decision a priori in stage 2 of
the hierarchy. This modified design procedure is richer than the conventional one in the
sense that it allows all possible alternatives to be included. This is an important
characteristic of an effective design hierarchy. On the other hand, as pointed out by
Kraslawski et al. [6], another important problem in process design and synthesis is the
strategy problem – whether a strategy can be developed to quickly locate the best
alternative without totally enumerating all the options. In this respect, the modified
procedure loses out to the conventional procedure because by not considering any recycle
streams in the first ‘run’ and the iterative loop made around the hierarchy with the
consideration of each new recycle stream, more time is taken in simulation and
evaluation of the different flowsheets. In contrast, in the conventional procedure,
heuristics, experience and shortcut estimations are used to fix recycle decisions early in
the hierarchy. As such, fewer alternatives have to be screened in detail and the ‘best’
alternative is quickly identified. However, the shortcoming of the modified hierarchy is
overcome by the advent of powerful simulation and costing programs such as the custom-
made HYSYS-EXCEL interface used in this study. Such software greatly speeds up the
process of simulating and costing a process flowsheet and hence time becomes less of a
concern. It becomes more important then for an effective hierarchy to be rich enough to
allow all alternatives to surface in the design process so that the most economical
flowsheet can be developed. As such, the modified design procedure shown in Figure 9
would be better than the conventional one.

CONCLUSIONS
Using the HDA process as an example, it was found that the modified hierarchy of
decisions provides a better way to develop a chemical process flowsheet. In the
conventional design procedure, recycle streams are fixed a priori and puts a constraint on
the design possibilities for the reactor and separation subsystems. In contrast, by leaving
recycle decisions to a later stage of the process, one can develop a base-case flowsheet
with no recycle streams first and then subsequently consider the individual economic
effects of the addition of different recycle streams. This is a relatively more time
consuming approach but it provides a more logical manner in developing a process
flowsheet and prevents the design engineer from missing out on any advantageous
modifications in the reactor or separation systems that could have been made had not a
decision to recycle been fixed in an earlier stage of the hierarchy. However, the

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application of a custom-made HYSYS-EXCEL interface will help to greatly reduce the

time needed for evaluating each alternative flowsheet generated during the procedure.

It is recommended to further test this modified design procedure by applying it to another

chemical process. One can also consider incorporating safety, environmental and process
control elements into the hierarchy of decisions. For example, diphenyl is known to cause
damage to the liver and the nervous system. In addition, it has high acute toxicity to
aquatic life. Hence, in the development of the input-output structure, it is necessary to
consider whether diphenyl should be removed or allowed to recycle to extinction in the
process. While designing complex flowsheets, it is also necessary to take into account the
process control considerations. The most profitable flowsheet would be of no use if it is
difficult to control. A reactor runaway or frequent off-specification production will make
the plant not only unprofitable but also an unsafe place to work in.

REFERENCES
[1] Douglas, J.M., Conceptual Design of Chemical Processes, New York: McGraw-Hill
(1988).

[2] Stanislav V.E., An Examination of a Modified Hierarchical Design Structure for

Chemical Processes, http://www.che.ttu.edu/classes/che5000/EmetsThesis.pdf (2003).

[3] Seider W.D., Seader J.D., Lewin D.R., Process Design Principles, New York: John
Wiley & Sons (1999).

[4] Turton R., Bailie R.C., Whiting W.B., Shaeiwitz J.A., Analysis, Synthesis, and
Design of Chemical Processes, New Jersey: Prentice Hall, PTR, Upper Saddle River
(2003).

[5] Lim D., Murthy Konda N.V.S.N., Rangaiah G.P., Synthesis and Design of Chemical
Processes, Department of Chemical and Biomolecular Engineering, National University
of Singapore (2004)

[6] Kraslawski A., Li X., Conceptual Process Synthesis: Past and Current Trends,
Chemical Engineering and Processing 43: 589-600 (2004)

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