ABSTRACT

Hydrodealkylation (HAD)
process of toluene to produce
benzene is widely used to
convert leftover toluene.
Benzene is produced to be used
in the manufacture of
cyclohexane, a precursor
material of nylon. This process
is simulated in ASPEN HYSYS
V9 to analyse the design,
material and energy balances,
and energy and utility
requirements. An economical
evaluation is also performed to
determine whether recycling of
raw material is economically
favourable or not.

Group M6:
Gwenal G. Bonnave
ADVANCED PROCESS Elisa Correa
Yolanda Hutabarat

DESIGN PROJECT
Made Sukma
Adriana Valarezo
HYDRODEALKYLATION OF TOLUENE PROCESS
December 2016
 TABLE OF CONTENTS

Table of Contents i
Index of Tables ii
Table of Figures iii
1 Hydrodealkylation of toluene without recycling process 1
a. Process Overview....... 1
i. Procedure and Methodology.. 1
ii. Description.. 1
iii. Process Diagrams and Streams Details..... 2
iv. Heuristics.... 4
b. Economic Assessment. 5
2 Hydrodealkylation of toluene with recycling process..... 7
a. Process Overview....... 7
i. Procedure and Methodology..... 7
ii. Recycling Process Description. 8
iii. Diagrams and Streams Details. 8
b. Economic Assessment... 10
c. Comparison between processes..... 11
3 Optimisation and Heat Integration ...... 12
a. Optimisation of Distillation Column 12
a. Heat integration. 13
i. Hot and cold streams of the system... 13
ii. Alternative Heat Exchanger Networks........... 14
4 References . 15
5 Appendix A (Hydrodealkylation of Toluene Without Recycling Process). A1
6 Appendix B (Hydrodealkylation of Toluene With Recycling Process) A4
7 Appendix C (Optimisation and Heat Integration). A8

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 INDEX OF TABLES

Table 1.1 Reactions within 103-PFR Unit....... 1

Table 1.2 Process Stream Specifications... 3
Table 1.3 Recap of the capital cost of equipment.. 5
Table 1.4 Operating Cost Estimation 6
Table 1.5 Revenue results. 6
Table 2.1 Process Stream Specifications 9
Table 2.2 Recap of the capital cost of equipment.. 10
Table 2.3 Operating Cost Estimation 10
Table 2.4 Revenue Economics Results... 10
Table 2.5 Economic comparison between processes costs. 11
Table 2.6 Summary of comparison between processes costs. 11
Table 3.1 Process streams description 13
Table 3.2 Utilities results from Aspen HYSYS Energy Analyzer. 14

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 TABLE OF FIGURES

Figure 1.1 Process Block Diagram toluene hydrodealkylation process... 2

Figure 2.1 Block Flow Diagram of Recycle System 8
Figure 3.1 Total cost of the distillation process for different reflux ratios. 13
Figure 3.2 Option 1 HEN from Aspen HYSYS Energy Analyzer... 15
Figure 3.3 Option 2 HEN from Aspen HYSYS Energy Analyzer... 15
Figure 3.4 Option 3 HEN from Aspen HYSYS Energy Analyzer... 15

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 APPENDIX A

HYDRODEALKYLATION OF TOLUENE WITHOUT RECYCLING PROCESS

Table A.1 Formulas used for equipment sizing A1

Table A.2 Calculations of the heat transfer surface area for the different heat A1
exchangers...
Table A.3 Calculations of the heat transfer surface area for the different heat A1
exchangers...
Table A.4 Calculations of the PFR and Flash Separator A2
Table A.5 Calculations for the Distillation Column modelled as pressure vessel... A2
Table A.6 Recap of the capital cost of equipment... A2
Table A.7 Actual utilities considered for cost estimation........ A3
Table A.8 Assumption Data for Estimating Operating Cost... A3
Table A.9 Operating Cost Estimation. A3
Figure A.1 Benzene Column Temperature Profile A4
Figure A.2 Toluene Column Temperature Profile................................................ A4
Figure A.3 Biphenyl Column Temperature Profile.................................... A5

APPENDIX B
HYDRODEALKYLATION OF TOLUENE WITH RECYCLING PROCESS

Table B.1 Calculations of the heat transfer surface area for the different heat A6
exchangers
Table B.2 Calculations of the PFR and Flash Separator. A6
Table B.3 Calculations for simple-stage centrifugal pump. A6
Table B.4 Calculations for the Distillation Column modelled as pressure vessels. A6
Table B.5 Calculations for simple-stage centrifugal pump. A6
Table B.6 Recap of the capital cost of equipment... A7
Table B.7 Actual utilities considered for cost estimation A7
Table B.8 Operating Cost Estimation A8
Table B.9 Case study for splitter fraction... A8
Figure B.1 Benzene Column Temperature Profile A9
Figure B.2 Toluene Column Temperature Profile. A9
Figure B.3 Biphenyl Column Temperature Profile A10
Figure B.4 Annual costs and profit for both systems A10
Figure B.5 Flow rates of all chemicals at inlets and outlets A10

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 APPENDIX C
OPTIMISATION AND HEAT INTEGRATION

a. Optimisation of Distillation Column

Table C.1 Distillation Column Cost (Without Condenser and Reboiler).. A12
Table C.2 Condenser Cost Estimation.. A13
Table C.3 Reboiler Equipment Cost Estimation.. A14
Table C.4 Operating (Energy) Cost Estimation... A15
Table C.5 CT, CC, and CO at various Reflux Ratios A16

b. Heat Integration
Table C.6 Option 1 results from Aspen HYSYS Energy Analyzer.. A16
Table C.7 Option 2 results from Aspen HYSYS Energy Analyzer A16
Table C.8 Option 3 results from Aspen HYSYS Energy Analyzer A16

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1. Hydrodealkylation of toluene without recycling process
a. Process Overview
i. Procedure and Methodology
The process was design to comply with the specifications given. It uses pure toluene and
hydrogen as raw material. The pressure drop is set to 20 kPa for the following unit: 102-Furnace,
103-PFR, and 104-Cooler. Two reactions occur in the reactor (details shown in Table 1.1). Rxn-1
is an exothermic reaction which produces the desired product, benzene, as the main product. For
both of reactions, the reaction rate coefficients are seemingly not too different hence the
temperature will not affect them notably and it is not necessary to maintain the temperature
constant (isothermal) that is why an adiabatic condition was chosen for plug flow reactor.

Table 1.1 Reactions within 103-PFR Unit

Rxn-1:
ra = (50000 exp (-2.3 x 105/RT)) Ctoluene Chydrogen0.5
Toluene + Hydrogen Benzene + Methane
Rxn-2: rc = (59870 exp (-2.13 x 105/RT)) Cbenzene2 (2.553 x
2 Benzene Biphenyl+ Hydrogen 105 exp (-2.1x 105/RT)) Cbiphenyl Chydrogen)

The separation and purification process is composed by a flash separator and three distillation
columns. The flash separator is used to separate highly volatile compound and operates at 1000
kPa. The first column (106-Stabilizer Column) is used to remove all the trace of hydrogen and
methane remaining. The output of this column is expected to recover at least 95% of the benzene
from the input stream. The second column (107-Benzene Column) is used to separate the benzene
as the main product. The benzene purity is specified to be more than 95%. The third column (108-
Toluene Column) is applied to separate toluene and biphenyl. Both toluene and biphenyl must be
recovered with minimum value of 95%.

ii. Description
The toluene hydrodealkylation process was performed in a total of 9 unit operations. The
hydrodealkylation reaction takes place in an adiabatic plug flow reactor (PFR) at high temperature.
Beyond this station the stream circulates through a series of distillations to achieve a high purity of
benzene, which is the actual desired product of this process.
Initially, the feed stream at ambient temperature and assumed to come from a pipeline with a
pressure of 3500 kPa composed of toluene and excess hydrogen is heated in a furnace (modelled
as a heater) to increase the temperature to 725 oC to favour the reaction to be taking place in the
PFR. The reactor was chosen to operate adiabatically. However, even with a conversion of 90.46%,
still at the outlet stream of the PFR it is possible to find unwanted biphenyl in considerable
proportions. Hence the necessity to use three distillation columns in the simulation.
The next unit operation is a 105-Flash Separator to remove components that are volatile such as
methane and hydrogen. However, because of the conditions set in the separator (~35 oC, 1000
kPa) are significantly lower comparing with the PFR output (820.4 oC, 3460 kPa), the stream flows
through a cooler and then a control valve to adjust the parameters. This significant drop of pressure
alters the phase of stream from gaseous only to a mixture of liquid and gas phases and allows a
better separation in unit 105-Flash Separator.
The bottom product leaves the 105-Flash Separator at 35.15oC and 1000 kPa to enter the first
distillation column (106-Stabilizer Column). To avoid pressure drops that could require more use
of energy, the reboiler and condenser pressures in the first column are set to the same value as
the feed (1000 kPa). The main goal in this unit operation is to get rid of any amount of hydrogen
and methane left, both of which are highly volatile compounds. For this reason, it is best to use a
partial condenser to reduce the amount of heat needed to remove in the condenser and to avoid
extremely low temperatures in it. The column was set with specifications that would assure to
accomplish the goal. In this case, those were a component recovery of 100% in the distillate for
both methane and hydrogen, the reflux ratio of 1, and benzene molar flow of 40 kmol/hr at the
bottoms.

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 The output flow from the reboiler of the first column becomes the feed of the next column, where
the focus is to obtain the desired product benzene as much as possible. The benzene product
exiting the second column (107-Benzene Column) need to achieve the purity specification of 0.95
(molar fraction). To ensure this, the column was set with a specification of benzene component
recovery of 0.99 and reflux ratio of 2, resulting in a benzene purity ~0.99 molar fraction. This column
uses a total condenser because there is no highly volatile component in the feed and because the
desired product, benzene, is produced in the top of column. Pressure parameters where set to
1000 kPa for the same reason as the previous one.
Finally, with mainly biphenyl and unconverted toluene in the bottom stream, the flow goes to a
third column (108-Toluene Column). Toluene being the priority for recycling purposes, it is required
a 95% recovery of both components. Since toluene is the lightest, a component recovery of 99%
in the distillate is set for this compound. This condition was enough to comply additionally with
biphenyl requirement after setting a reflux ratio of 1.5 and column pressures of 800 kPa.
Overall for this process simulation, the results obtained successfully met the requirements and
expectations. A flowrate of 40.12 kmol/hr of benzene with a purity of 98.71% is achieved. However,
it is important to point out that the operations from the columns can be improved by changing the
number of stages. Reducing the number of stages from the suboptimal set points of 8, 20 and 25
respectively; could significantly reduce the energy demand without disturbing the process
requirements.

iii. Process Diagrams and Streams Details

7
16 18
Toluene
1 4 5
2 3 105-FLASH
101-MIXER 102-FURNANCE 103-PFR 104-COOLER
SEPARATOR
Hydrogen

15 17 8
6
11 9

106- STABILIZER
13

COLUMN
107- BENZENE
RECOVERY
107- BENZENE
RECOVERY

14 12

Figure 2.1 Process Block Diagram toluene hydrodealkylation process

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 Table 1.2 Process Stream Specifications
Stream Name Unit Toluene Hydrogen FEED Hot Feed Out PFR Cold PFR To FLASH Out L
Stream Number [-] 1 2 3 4 5 6
Vapour Fraction [-] 0 1 0.73 1.00 1.00 0.75 0.77 0.00
Temperature [C] 25 25 24.16 725.00 820.43 40.00 35.15 35.15
Pressure [kPa] 3500 3500 3500.00 3480.00 3460.00 3440.00 1000.00 1000.00
Molar Flow [kgmole/h] 58 160 218.00 218.00 218.00 218.00 218.00 51.19
Mass Flow [kg/h] 5344.17 322.56 5666.73 5666.73 5666.55 5666.55 5666.55 4355.01
Std Ideal Liq Vol
[m3/h] 6.14 4.62 10.76 10.76 11.15 11.15 11.15 4.86
Flow
Heat Flow [kJ/h] 771594.67 -223.94 771370.73 14198616.06 14198462.07 -906148.33 -906148.33 2685945.44
Molar Enthalpy [kJ/kgmole] 13303.36 -1.40 3538.40 65131.27 65130.53 -4156.64 -4156.64 52466.75
Molar Fraction
Benzene [-] 0 0 0.00 0.00 0.20 0.20 0.20 0.80
Toluene [-] 1 0 0.27 0.27 0.03 0.03 0.03 0.11
BiPhenyl [-] 0 0 0.00 0.00 0.02 0.02 0.02 0.08
Hydrogen [-] 0 1 0.73 0.73 0.51 0.51 0.51 0.00
Methane [-] 0 0 0.00 0.00 0.24 0.24 0.24 0.01
Total Molar
[-] 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Fraction
Stream Name Unit Purge C1 Cond V C1 Cond L Reb C1 Cond L C2 Reb C2 Cond C3 L Reb C3
Stream Number [-] 7 8 9 10 11 12 13 14
Vapour Fraction [-] 1.00 1.00 0.00 0.00 0.00 0.00 0.00 0.00
Temperature [C] 35.15 159.87 159.87 188.09 179.16 251.88 199.89 371.18
Pressure [kPa] 1000.00 1000.00 1000.00 1000.00 1000.00 1000.00 800.00 800.00
Molar Flow [kgmole/h] 166.81 1.73 0.00 49.47 40.12 9.35 5.19 4.16
Mass Flow [kg/h] 1311.54 103.32 0.00 4251.69 3140.70 1110.99 472.84 638.15
Std Ideal Liq Vol
[m3/h] 6.29 0.13 0.00 4.72 3.56 1.16 0.54 0.62
Flow
Heat Flow [kJ/h] -3592093.78 89334.10 0.02 3977016.78 2908839.87 1207914.54 244090.05 1173078.57
Molar Enthalpy [kJ/kgmole] -21534.46 51731.90 67051.01 80398.31 72510.98 129180.85 47005.96 282137.71
Molar Fraction
Benzene [-] 0.02 0.69 0.93 0.81 0.99 0.04 0.08 0.00
Toluene [-] 0.00 0.02 0.06 0.11 0.01 0.52 0.92 0.01
BiPhenyl [-] 0.00 0.00 0.00 0.08 0.00 0.44 0.00 0.99
Hydrogen [-] 0.67 0.06 0.00 0.00 0.00 0.00 0.00 0.00
Methane [-] 0.31 0.23 0.01 0.00 0.00 0.00 0.00 0.00
Total Molar
[-] 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Fraction

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 iv. Heuristics
The Heuristics considered for this process are from Seider, Seader, Lewin & Widagdo;
2008.
Overall Process:
Heuristic 6 By-products that are produced in reversible reactions, in small quantities, are
usually not recovered in separators or purged. Instead, they are usually recycled to
extinction.
Biphenyl is an unwanted by-product. It acts as an impurity of the toluene stream when it is
recycled. In spite of this, the presence of this substance could lead to depress the second
series reaction which is undesirable since the reaction is reversible. To avoid the
accumulation of the biphenyl product in the stream, the purging stream may be applied in
this system as well.
Heuristic 5 Do not purge valuable species or species that are toxic and hazardous,
even in small concentrations.
Although the process is designed to purge hydrogen and methane, an alternative should
be considered such as using it as a fuel for the process furnace.
For PFR Unit:
Heuristic 21: To remove a highly-exothermic heat of reaction, consider the use of excess
reactant, an inert diluent, and cold shots.
The excess use of H2 as reactant is to prevent the carbon deposition and absorb the heat
produced during the process since the hydrodealkylation reaction is highly exothermic
(Lewin, 2004).
Heuristic 4. Introduce purge streams to provide exits for species that enter the process
as impurities in the feed or are produced by irreversible side-reactions when these species
are in trace quantities and/or are difficult to separate from the other chemicals.
Methane appears as an impurity. To avoid its accumulation in the process, a purging stream
could be introduced inside the hydrogen-methane recycle system.
Heuristic 7 For competing series or parallel reactions, adjust the temperature, pressure,
and catalyst to obtain high yields of the desired products. Initially obtain kinetics data and
check this assumption before developing a base-case design.
Choosing a PFR will avoid the reactant concentration drop which is undesirable to multiple
reaction in series, as opposed to a mixed-flow model or CSTR.
For Distillation Column:
In this process, the volatilities and the molar masses of the components play a much more
important role than the composition ratios of the streams. Hydrogen is the only corrosive
component and it is the lightest one as well, therefore, it is removed first.
Hydrogen (A), methane (B), benzene (C), toluene (D) and biphenyl (E); from the most
volatile and lightest to the least volatile and heaviest (direct sequence); have been separated
using the sequence AB/CBE C/BE B/E. Therefore, the following heuristics are the ones
that could be applied to the design:
Heuristic 4: Sequence separation points in order of decreasing relative volatility so that
the most difficult splits are made in absence of other components.
Heuristic 2: Sequence separation to remove, early in the sequence, those components
of greatest molar percentage in the feed.

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 Heuristic 5: Sequence separation points to leave those separations that give the highest-
purity products.
Heuristics 2 applies for the case of benzene which is being removed before removing
toluene and biphenyl as this compound is the largest fraction in the product effluent. As can
be seen in the stream compositions, this heuristic also applies for the following operations
because of the unfeasibility of an equimolar separation. Heuristic 4 supports the overall
separations taking place, since all the units removed the most volatile component first.
Heuristic 5 is considered because despite benzene is our desired product, toluene and
hydrogen are expected to be recycled in the next part of the simulation. Therefore, the need
to have the streams with high purity of those components.
For Heat Exchangers:
Heuristic 10 Attempt to condense vapour mixtures with cooling water.
In this system, there are four-unit heat exchangers for cooling process (three units are
distillation column condensers). All the processes utilize cooling water as the cooling fluid
agents.
Heuristic 25 Unless required as part of the design of the separator or reactor, provide
necessary heat exchange for heating or cooling process fluid streams, with or without
utilities, in an external shell-and-tube heat exchanger using counter-current flow. However,
if a process stream requires heating above 750oF (~400oC), use a furnace unless the process
fluid is subject to decomposition.
At the 3rd column reboiler, since the hot steam provided is at 260oC, it is necessary to use
a furnace in order to meet the process requirements.
b. Economic Assessment
Cost Evaluation
The major part of calculations is carried out with the equation 6.15 and the table 6.6 taken
from Sinnott and Towler, 2008:
= +
This correlation is used for preliminary estimations. This first appraisal give the Project
Engineering team an idea of the costs. Detailed further evaluations must be carried out to
pursue the economic analysis. Nonetheless, this correlation allows us to know if further
analyses are worthwhile and to approximately estimate the profitability.

Moreover, pipes, small devices, control room and other facilities are ignored in this study.
The case study does not take into account the evaluation of the field, the environment and
special constructions related to the area. Finally, measure of implementations, norms and
HSE issues are not considered in the evaluation of costs.
Table 1.3 Recap of the capital cost of equipment
Proportion of the
Type Name Ce global cost of
equipment
104-Cooler $ 13,355.66 2.4
Condenser-COL1 $ 10,014.77 1.8
Coolers Condenser-COL2 $ 10,862.98 2.0
Condenser-COL3 $ 10,103.50 1.8
Reboiler@COL1 $ 10,475.05 1.9
Reboiler@COL2 $ 13,442.28 2.4
Heaters
Reboiler@COL3 $ 68,617.00 12.5
Furnace $ 250,786.49 45.6
Plug Flow Reactor 102-PFR $ 56,831.11 10.3
Flash separator 105 - Flash Separator $ 34,499.01 6.3
T-100 $ 22,372.93 4.1
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 Distillation T-101 $ 29,234.75 5.3
Columns T-102 $ 13,091.46 2.4
(Vessel Only)

T-100 (Packing, pall

$ 1,817.83 0.3
rings)
Trays and packing
T-101 (Packing, pall
$ 3,450.25 0.6
rings)
T-102 (Packing, pall
$ 589.46 0.1
rings)
Sub-total Equipments $ 549,544.53 100

As can be seen in Table 1.3, the main contributor to the capital cost is the furnace used to
favour the reaction taking place in the PFR by increasing temperature. The PFR only
accounts for 10.3% of the total equipment's cost. We consider this value to be extremely low,
as it is commonly the most expensive equipment. This is because we are considering the
reactor as an empty pressure vessel and we are not taking into consideration the internal
structure, accessories, control instruments and catalysts.

Operating Cost Estimation

Operating cost estimation is done based on the several assumptions (more detail see -
Appendix A). The main contributor to the production cost are the raw materials which
account for almost 95% of the total see - Table 1.4 (and for more detail operating cost
estimation see Appendix A), whereas the rest comes from the utility cost. This result
strengthens the idea that recycling the unconverted reactant will significantly reduce the
production cost. This will be considered in the next section. Typically, about 80-90% of total
cost of production is taken by raw materials (Sinnot and Towler, 2008). The obtained
percentage value for the raw material cost is higher than that. However, it has to be noticed
that in these calculations, the operating costs are calculated based upon the variable cost
only, without considering to the fixed costs nor electricity plant requirements.
Table 1.4 Operating Cost Estimation
Type of Utility Cost per year($/year) % Cost
Fresh Reactants $40,336,183.21 95.5
Hot Fluid (HP Steam) $ 153,102.03 0.4
Cooling Fluid (Cooling
$ 25,519.80 0.1
Water)
Electricity - 0.0
Fuel (Natural Gas) $ 1,716,816.43 4.1
Total Operating Cost $42,231,621.47 100.0

The revenue comes from the sales of benzene only coming out of the condenser on the
second column, which complies with the purity criteria of at least 95%. The values obtained
can be seen in the Table 1.5. Assuming the plant has an availability of 85% from a total of
365.25 days/year, we obtain 310.5 operating days/year, and thus, 7451 operating hours.
Considering this, the revenue can be calculated as follows:
Total Benzene Production = Benzene Production (kg per hour) x Operating hours
Total revenue = Total Benzene Production x Benzene Price
Table 1.5 Revenue results
1. Total Revenue
1.1 Total Revenue [USD/year] 52,653,751.38
2. Operating Cost (Cost of Raw Material+Cost of Utility)
2.1 Cost of Raw Material [USD/year] 40,336,183.21
2.2 Cost of Utility [USD/year] 1,895,438.262
2.3 Operating Cost [USD/year] 42,231,621.47

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 3. Capital Cost
3.1 Capital Cost [USD] 549,544.53
3.2 Annual Capital Charge Ratio (ACCR) [-] 0.0365557
3.3 Annual Capital Charge (ACC) [USD/year] 20,089.01
4. Total Annualized Cost
4.1 Total Annualized Cost (TAC) [USD/year] 42,251,710.48
5. Margin
5.1 Gross Profit [USD/year] 10,402,040.90
5.2 Net Profit [USD/year] 7,281,428.63

There are some strategies we could point out to enhance the profitability of the plant. First
would be to introduce a recycling system to reduce the cost of raw materials. This will be
analysed in more detail in the next section. As mentioned in the heuristics part, to recycle
by-products may lead to an improvement in the production rate of benzene.
The purging stream of gas mixture contains hydrogen and methane. This stream could be
used to fuel the furnace. However, we should be careful when working with high percentages
of hydrogen, as it could be explosive, in which case a special tank should be designed to
feed it.
The heat integration can also be applied to reduce the utility cost. This plant has several
heat exchanger units whose heat could be exchanged between each other instead of
employing additional heating or cooling sources from external utilities. This possibility will be
assessed in more detail in the last part of this report. Additionally, the quenching strategy
could be implemented to utilize heat produced within system. The effluent stream from the
PFR output, whose temperature is extremely high, may be used as a heat source for the
feed stream. This could reduce not only the operating costs of energy but also the capital
cost due to the furnace high price. Another idea is by using expander or a pressure recovery
turbine rather than using pressure relieve valve to adjust the pressure before inlet stream to
105-Flash Separator.
2. Hydrodealkylation of toluene with recycling process
a. Process Overview
i. Procedure and Methodology
The second part of this simulation, the synthesis of the toluene hydrodealkylation process
with recycle stream, is built from the previous simulation and two of the recycle units are
added to recycle the remaining toluene and hydrogen to the system. To produce a similar
production rate of benzene, this system requires significantly lower fresh feed.

As the additional for the 1st part of the simulation, this system has employed recycle streams
of hydrogen and toluene. The remaining hydrogen will be separated from the product in the
flash separator unit. Purging is implemented using unit splitter (60% purge stream, 40%
recycle stream). A case study using ASPEN HYSYS V9 is done to ensure whether this value
is optimal or not to achieve the desired value of production rate of benzene. The study is
done by varying the flow ratio between 0.2 0.8 and the details of this results can be seen
in APPENDIX A. Based on the result, the production rate has not significantly changed from
36-38 kmol/hour. However, it is important to remember that the recycle stream will also
contain a certain amount of methane as the by-product of the process. Purging will be
needed to avoid its accumulation. Therefore, the flow ratio of 0.4 is the most suitable value
to have the maximum production rate of benzene while diminishing the accumulation of
methane in process system.
The flowsheet is equipped with additional equipment: (1) a compressor unit to adjust the
pressure of the hydrogen and methane gaseous mixture before recycling them back into the
system. (2) a pump unit to increase the pressure of toluene that is recovered from the toluene
column to the desired value (3500 kPa).

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 The system is composed by three distillation columns. The first column (106-Stabilizer
Column) is to remove all the trace of hydrogen and methane that remains in the system. This
is achieved by setting the reflux ratio (2); methane/hydrogen recovery (100%); and benzene
recovery (99%). The second column (107-Benzene Column) is to separate the benzene as
the main product. The benzene purity is specified to be more than 95%. This is achieved by
setting the reflux ratio to 3.0 and benzene recovery to 96%. The third column (108-Toluene
Column) is applied to separate toluene from mixture so it can be recycled. Both toluene and
biphenyl must be recovered with a minimum value of 95%. This is attained by setting the
reflux value to 1.5 and toluene recovery to 99%.

ii. Recycling Process Description

The recycling process flowsheet is built based on the previous part of the process, by the
addition of a recycle stream of hydrogen and toluene. To have a similar production rate of
benzene as the 1st part, it only requires 50 kmol/hour of fresh toluene and 100 kmol/hour of
hydrogen. The conversion of reaction 1 is about 63.2%; whereas the conversion of reaction
2 is about 344.2% due to the application of recycle stream. Hydrogen and methane which
are separated in 105-Flash Separator Unit will be recycled back into the system at the
desired operating pressure (3500 kPa) using a compressor unit.
The first column, 106-Stabilizer Column, has 8 stages, the operating pressure is about 1000
kPa and the operating temperature is between 125-196oC. This column produces a liquid
bottom product that is free from hydrogen and methane. In addition, the recovery of benzene
is of 99%, which exceeds the minimum requirement of the column. Benzene as the main
product is separated from the process within unit 107-Benzene Column. This column (20
stages) is assumed to operate at 1000 kPa and within a temperature range of 180-223oC.
The product specification is achieved with a purity of benzene of 95.5% which exceeds the
minimum requirements and the production rate of benzene is about 37.2 kmol/hour. The third
distillation column, unit 108-Toluene Column (25 stages), is operated at 800 kPa and at a
temperature between 200 and 353oC. This column could recover more than 99% of toluene
as the distillate product and 100% of biphenyl as bottom product. This toluene will be then
be recycled using pump in order to achieve the operating pressure of 3500 kPa.

iii. Diagrams and Streams Details

Figure 2.1 Block Flow Diagram of Recycle System

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 Table 2.1 Process Stream Specifications
Fresh Fresh Mix Hot Cold Cwater Out V-to
Stream Name Unit Out PFR Cwater In To Flash Purge
Toluene Hydrogen Feed Feed PFR Out Recycling
Stream Number [-] 1 2 3 4 5 6 7 8 9 10 11
Vapour Fraction [-] 0 1.00 0.69 1.00 1.00 0.69 1.00 1.00 0.7 1.0 1.0
Temperature [*C] 25 25 91.4 725 787.5 40 15.0 40 36.1 36.1 36.1
Pressure [kPa] 3500 3500 3500.0 3480 3460.0 3440 101.3 81.325 1000.0 1000.0 1000.0
Molar Flow [kgmole/h] 50.0 100.0 246.5 246.5 246.5 246.5 9753.1 9753.1 246.5 175.1 105.0
Mass Flow [kg/h] 4607 202 7893.2 7893 7893.0 7893 175703.4 175703 7893.0 1669.5 1001.7
Std Ideal Liq Vol Flow [m3/h] 5.30 2.89 13.8 13.82 14.2 14.18 176.1 176.06 14.2 7.2 4.3
Molar Enthalpy [kJ/kgmole] 13303.36 -1.3996 213.3 66092.34 66090.5 -10777.8 -286997.9 -285055 -10777.8 -31715.3 -31715.3
Molar Fraction
Toluene [-] 1 0 0.30 0.30 0.11 0.11 - - 0.11 0.00 0.00
Hydrogen [-] 0 1 0.56 0.56 0.38 0.38 - - 0.38 0.54 0.54
Benzene [-] 0 0 0.01 0.01 0.17 0.17 - - 0.17 0.01 0.01
BiPhenyl [-] 0 0 0.00 0.00 0.02 0.02 - - 0.02 0.00 0.00
Methane [-] 0 0 0.13 0.13 0.32 0.32 - - 0.32 0.44 0.44
Total Molar Fraction [-] 0 0 1.00 1.00 1.00 1.00 0 0 1.00 1.00 1.00
H2/CH4 C1 Cond Cond L Toluene
Stream Name Unit Recyling Out L C1 Cond L Reb C1 Reb C2 Reb C3 Cond C3 L
Recycling V C2 Recycling
Stream Number [-] 12 13 14 15 16 17 18 19 20 21 22
Vapour Fraction [-] 1.0 1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Temperature [*C] 36.1 180.8 36.1 125.3 125.3 196.4 180.1 223.9 353.0 200.8 203.3
Pressure [kPa] 1000.0 3500.0 1000.0 1000.0 1000.0 1000.0 1000.0 1000.0 800.0 800.0 3500.0
Molar Flow [kgmole/h] 70.0 70.0 71.4 1.4 0.0 70.1 39.0 31.1 4.5 26.6 26.6
Mass Flow [kg/h] 667.8 667.8 6223.6 48.2 0.0 6175.4 3068.7 3106.7 678.1 2428.6 2428.6
Std Ideal Liq Vol Flow [m3/h] 2.9 2.9 7.0 0.1 0.0 6.9 3.5 3.5 0.7 2.8 2.8
Molar Enthalpy [kJ/kgmole] -31715.3 -26682.2 40546.3 -12454.4 55179.8 70594 71625.9 72599.7 263191.8 46585.5 47073.0
Molar Fraction
Toluene [-] 0.00 0.00 0.38 0.04 0.21 0.39 0.05 0.81 0.06 0.94 0.94
Hydrogen [-] 0.54 0.54 0.00 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzene [-] 0.01 0.01 0.55 0.29 0.78 0.55 0.95 0.05 0.00 0.06 0.06
BiPhenyl [-] 0.00 0.00 0.06 0.00 0.00 0.06 0.00 0.14 0.94 0.00 0.00
Methane [-] 0.44 0.44 0.01 0.58 0.01 0.00 0.00 0.00 0.00 0.00 0.00
Total Molar Fraction [-] 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

Page |9
 b. Economic Assessment
Cost of Equipment Evaluation
The calculations are carried out under the same assumptions and equations of Part 1.
Table 2.2 Recap of the capital cost of equipment
Type Name Ce Proportion of the global
cost of equipment
104-Cooler $ 14,356.36 1.7%
Condenser-COL1 $ 10,038.39 1.2%
Coolers Condenser-COL2 $ 11,229.58 1.3%
Condenser-COL3 $ 10,506.90 1.2%
Reboiler@COL1 $ 10,790.13 1.3%
Reboiler@COL2 $ 12,389.57 1.5%
Heaters
Reboiler@COL3 $ 95,505.42 11.2%
Furnace $ 283,273.36 33.2%
Pump P-100 $ 3,348.02 0.4%
Compressor K-100 $ 56,911.17 6.7%
Plug Flow Reactor 102-PFR $ 56,831.11 6.7%
Flash separator 105 - Flash Separator $ 34,499.01 4.0%
Distillation Columns T-100 $ 52,144.01 6.1%
(Vessel Only) T-101 $ 98,298.96 11.5%
T-102
$ 94,991.61 11.1%
Trays and packing T-100 (8 trays) $ 1,817.83 0.1%
T-101 (20 trays) $ 3,450.25 0.5%
T-102 (25 trays) $ 589.46 0.4%
Sub-total Equipments $ 853,878.02 100.0%

Operating Cost Estimation

Based on the calculation of utility required for the whole process and the requirement of fresh
toluene (50 kmol/h) and hydrogen (100 kmol/h), the total of operating cost is about $35,270,999
per year with the detailed calculation is shown in Table 2.3.
Table 2.3 Operating Cost Estimation
Type of Utility Total Price % Cost
(USD/h)
$ 3,915.98 81.5%
Fresh Reactants
$ 544.32 11.3%
$ 9.76 0.2%
Hot Fluid (HP Steam)
$18.09 0.4%
$ 3.51 0.1%
$ 0.02 0%
Cooling Fluid (Cooling Water)
$ 0.71 0%
$ 0.33 0%
$ 0.36 0%
Electricity
$ 9.79 0.2%
-
Fuel (Natural Gas) -
$ 299.8 6.2%
Total Operating Cost $ 4,802.7 100%
$ 35,785,368 USD/year

Table 2.4 Revenue Economics Results

1. Total Revenue
1.1 Benzene Price [USD/kg] 2.25
1.2 Benzene Production [kg/h] 2,906.10
1.3 Operating hours [hours/year] 7,451.10
1.4 Total Benzene Production [kg/year] 21,653,658.85
Total Revenue [USD/year] 48,720,732.41
2. Total Operating Cost
2.1 Total Cost of Raw Material [USD/year] 33,234,171.35
2.2 Total Cost of Utility [USD/year] 2,551,196.57

P a g e | 10
 Annual Capital Charge (ACC)
2.3.1 Life time of plant [year] 40
2.3
2.3.2 Interest Rate [%] 2
2.3.3 Annual Capital Charge Ratio (ACCR) [-] 0.036555748
Annual Capital Charge (ACC) [USD/year] 31,214.15
Total Annualized Cost (TAC) [USD/year] 35,816,582.07
3. Total Profit
Profit = Revenue - TAC [USD/year] 12,904,150.34

c. Comparison between processes

As mentioned beforehand, the usefulness of the third column within the process without recycling
stream has not be proven. Actually, there is no need to separate toluene from biphenyl at the end
of the process if they are both wasted. Therefore, in order to compare the two processes, namely
with and without recycle, two options are considered: (1) The third column is removed; or (2) Main
recovered by-product (biphenyl) is sold. Although, the removal of the third distillation column seems
to be a good option (especially for Part 1), the second option is chosen. The reboiler outlet of the
third column gives the flow rate of the by-product that can be sold with a high purity. Assuming that
the current selling price of biphenyl is 2.58 USD/kg [Source: molbase database of chemicals], values
from the two processes are summarized in the following table.
Table 2.5 Economic comparison between processes costs
Parameter Unit System without Recycle System with Recycle Difference
Byproduct selling - Biphenyl
Biphenyl purity % 0.99 0.97 -3%
Biphenyl (sold) kg/h 633.66 654.87 3%
Sales USD/year $ 12,181,288.69 $ 12,589,076.25 3%

Although there is a decrease in purity when the recycle is added, the flow rate of biphenyl
produced rose by 3%. Finally, figures of selling are the same rough size. Selling biphenyl puts
again the process without recycling at a disadvantage.
If the 3rd distillation column was omitted in this design, the production and purity of benzene could
increase to 47.47 kmol/h and 99.9%, outperforming the original design (37.2 kmol/hour and 95.5%).
Since it is possible to calculate the requirements of toluene and hydrogen needed to produce the
same amount of benzene, this plant only requires ~39.2 kmol/hour toluene and ~78.4 kmol/h of
hydrogen. This is less than the amount required by the recycle system with the 3rd column (50 kmol/h
of toluene and 100 kmol/h of hydrogen). In addition, the capital cost of the 3rd column could be saved
as well.
The summary of comparison for both processes is shown on Table 2.6.
Table 2.6 Summary of comparison between processes costs
Parameter Unit System without Recycle System with Recycle Difference
Requirement of Fresh Raw Materials
Hydrogen (raw material) kg/h 5,344 4,607 -14%
Toluene (raw material) kg/h 323 202 -37%
Capital Cost
Total Capital Cost USD $ 549,138.08 $ 853,878.02 55%
Annual Capital Charge (ACC) USD/year $ 20,074.15 $ 31,214.15 55%
Operating Cost
Total Cost of Raw Material USD/year $ 40,336,183.21 $ 33,234,171.35 -18%
Total Cost of Utility USD/year $ 1,895,438.26 $ 2,551,196.57 35%
Total Operating Cost USD/year $ 42,231,621.47 $ 35,785,367.92 -15%
Total Profit
Total profit USD/year $ 7,281,439.03 $ 12,904,150.34 77%
Total Energy Consumption
Consumption of the whole plant MW 0 13.7 -
Conversion of reaction

P a g e | 11
 Reaction 1 % 90.45982 63.2 -30%
Reaction 2 % - 344.2 -
Benzene Production
Total Production Rate of Benzene kg/h 3,140.70 2,906.1023 -7%
Purity of the product % 98.53 95.5 -3%
Waste Production / compound
Benzene (wasted) kg/h 363.07 139.39 -62%
Toluene (wasted) kg/h 457.74 34.53 -92%
Biphenyl (wasted) kg/h 0.04 0.02 -54%
Hydrogen (wasted) kg/h 225.06 114.45 -49%
Methane (wasted) kg/h 841.57 761.31 -10%

As mentioned earlier, the largest proportion of operating cost is occupied by raw material cost
(Figures B.4 and B.5 in appendices). From Table 2.6 above and, the reduction of raw material
thanks to the recycling process, results in decreasing the total operating cost about 15%.
Additionally, after calculating the total amount of each compound produced and wasted, the process
with recycle allows to significantly reduce every need in terms of raw material, as well as the amount
of wasted chemicals see Table 2.6. The disposal of chemicals and waste treatment could be very
costly depending on the nature, the toxicity of the compounds and the complexity of the mixture
e.g. if it needs further pre-separations and not only burning. In conclusion, the savings in terms of
chemicals not wasted and less raw materials needed make it possible to largely counterbalance the
slight reduction (about 7%) in the production rate of benzene between the first and second
considered processes.
Overall, even if the capital cost of the first process (without recycle) is obviously smaller than for
the second one, hence it impacts the increase of annual capital charge (ACC) for about 55%. The
economy in term of fresh raw material allows the process with recycle stream clearly more profitable.
The net profit is improved by 77 % (Table 2.6). This shows us that the operating cost has a more
significant impact on the profitability of the plant than the capital cost.
3. Optimisation and Heat Integration
a. Optimisation of Distillation Column
The optimisation of distillation column is done by performing various simulations at different
number of trays. The aim is to minimise the total cost ($/year) of the distillation column by finding
an optimal reflux ratio. The Total Cost (CT) is given by the sum of the Capital and Operating Costs
(CC and CO), where CC is the purchase cost of equipment (CE), and CO considers the cost of steam
and cooling water. The data used to calculate CE is partially given by Table 6.6 on Sinnot & Towler,
2008 and from the design of the column. Using equation 6.15 from the previous reference, C E = a
+ bSn, the purchase costs of the equipment is determined. The calculations go as follows:
Cost of Trays
The column is designed with Sieve trays. This gives a cost of purchase for each tray based on the
column diameter D, where D = f(NStages). Then,
Ctray = 100 + 120 (D)2.0 = $ per tray
Therefore, CE1 will just be Ctray multiplied by the number of stages or CCE1 = Ctray * NStages

Cost of Column Reboiler and Condenser

The cost of these units is calculated as U-tube shell and tube heat exchangers. The estimative is
taken from the unit duty at different number of stages.
Unit Duty = f(NStages) =A U (T1-T2)/ln(T1/T2)
CE2,3 = 10000 + 88 (A)1
Cost of Column Tower
For this part, the equipment is considered a vertical stainless-steel pressure vessel. In this case
the cost is calculated in the following manner:
V = h D , where is the wall thickness.
m = Vss
CE4 = -10000 + 600 (m)0.6

P a g e | 12
 Then, the Capital Cost is given by: CC = CCE1 + CCE2 + CCE3 + CE4

From Sinnot & Towler, 2008 the price of steam and cooling water is set to $0.14/kmol and $0.02/
1000 kg respectively. The estimative is also taken from the unit duty at different number of stages.
Cost of Steam
V = Q/Hv260, where Q = f(NStages) is the reboiler duty. Then, CO,S = 0.14 * V
Cost of Cooling Water
V = Q [CpW T]-1, where Q = f(NStages) is the condenser duty. Then, CO,W = 0.02 * V/1000

The Operating Cost is calculated assuming 40 years of operation giving us:

CO = [CO,S + CO,W ] * Operating hours
Finally, the Total Cost is given just by CT = CC +CO
The column distillation was found to have a minimum reflux ratio, Rmin = 0.5318. Since Rmin is
found at an infinite number of stages, in the simulation it was determined when the reflux ratio did
not vary as the number of stages was increased significantly. For different values of the reflux ratio,
it was possible to notice a decreasing trend in the values of the Operating Cost as the reflux ratio
was reduced. The Capital Costs values coming from equipment sizing were the highest when the
reflux ratio was set close to the upper and lower limits, still they only represented around 1-15% of
the Total Cost. Under these conditions, the optimal number of stages is 24 with a reflux ratio of
0.614. At this point, the column consumes reasonable amount of utilities without sacrificing
performance or cost. Also, the objective function CT ($/year) = 34403 RR + 46400 expresses the
best the Total Cost as function of the reflux ratio as can be seen in Figure 3.1.

250000.000
Total Cost Capital Costs

Energy Costs Rmin

200000.000
Ropt Linear (Total Cost)
CostS ($/year)

150000.000

100000.000 CT = 34403 RR + 46400

50000.000

0.000
0.500 0.700 0.900 1.100 1.300 1.500 1.700 1.900
Reflux Ratio
Figure 3.1 Total cost of the distillation process for different reflux ratios

b. Heat Integration
i. Hot and cold streams of the system
Table 3.1 Process streams description
Stream Temp Stream Temp
Unit Operation Utilities Type Used [C] [C] Type of Stream
Inlet Outlet
Condenser@COL1 Cooling Water 173.2 125.3 Hot
Condenser@COL2 Cooling Water 181.0 180.1 Hot
Condenser@COL3 Cooling Water 201.8 200.8 Hot
104-COOLER@Main Cooling Water 787.5 40.0 Cold
102-FURNACE@Main Fired Heat (1000) 91.4 725.0 Hot
Reboiler@COL1 HP Steam 191.9 196.4 Hot
Reboiler@COL2 HP Steam 215.1 223.9 Hot
Reboiler@COL3 Fired Heat (1000) 291.1 353.0 Hot
P a g e | 13
Minimum utilities requirement
The minimum utilities required are the targets from Aspen HYSYS Energy Analyzer shown
below in Table 3.2.
Table 3.2 Utilities results from Aspen HYSYS Energy Analyzer
Current Target
Type
[kJ/h] [kJ/h]
Fired Heat (1000) 1.82E+07 3.434E+05
HP Steam 6.074E+06 6.025E+06
Total Hot Utilities 2.428E+07 6.368E+06
Cooling Water 2.468E+07 0
Air 0 1.448E+06
LP Steam Generation 0 3.793E+06
MP Steam Generation 0 1.534E+06
Total Cold Utilities 2.468E+07 6.775E+06

ii. Alternative Heat Exchanger Networks

To reduce the energy consumption in the plant, three alternative HENs have been proposed
where cost savings were based on the Energy Analyzer results. From the composite curve, the
pinch point is approximately 198oC.

In HEN 1 the hot and cold utilities are reduced by 71% and 70% respectively. This is achieved
by using the hot stream coming from the PFR to provide additional energy to heat up the mixed
feed. Done by 4 additional heat exchangers, removing and transferring heat, operating above and
below the pinch point (~300 oC and ~135 oC). This manages to reduce the need of Fired Heat at
the 102-Furnace, and for the PFR outlet stream to be cooled down from 502 oC instead of 787.5
oC which minimized the need of cooling water consequently. This design Total Cost is

$8.88E+08/s, 21% less than the base case.

In HEN 2, the hot and cold utilities are reduced by 60% and 59% respectively. Here the transfer
of heat from the PFR outlet stream is used to its full potential. This design employs 5 heat
exchangers where all of them remove and transfer heat from this stream above the pinch point
(~300 oC). In this design, it provides additional heat for the 102-Furnace and the reboiler of the
third column, consequently minimizing Total Cost to $5.14E+08/s, 54% less than the base case.

For HEN 3, the hot and cold utilities are reduced only by 8% both. The PFR outlet streams
energy is only used for the third column reboiler. With only one additional heat exchanger, it
removes heat at 300oC and the pinch principles are used to the minimum. Thus, high proportions
of cooling water are needed to cool it down and no complimentary heat is provided to the heating
units. Still, the total Cost is $9.19E+08/s, a 18% decrease from the base case.

From this analysis, it has been shown that the use of the PFR outlet stream for the 102-
Furnace is imperative to reduce the utilities consumption. In other words, when having a stream
at greatly high temperature, the best use of the pinch principle is to remove the heat when the
effluent is still quite hot (above pinch). Still, economic-wise is better to employ additional heat
exchangers to save utilities to the best possible, rather than the most in this plant. The HEN
options discussed can be seen in Figures 3.2, 3.3, and 3.4.

P a g e | 14
 Option 1

Figure 3.2 Option 1 HEN from Aspen HYSYS Energy Analyzer

Option 2

Figure 3.3 Option 2 HEN from Aspen HYSYS Energy Analyzer

Option 3

Figure 3.4 Option 3 HEN from Aspen HYSYS Energy Analyzer

4. References
Towler, G.P. & Sinnott, R.K., 2008. Chemical engineering design: principles, practice and economics of
a plant and process design, Amsterdam: Elsevier/Butterworth-Heinemann.
Seider, W.D. et al., 2010. Product and process design principles: synthesis, analysis, and evaluation,
New York: Wiley.
Anon, biphenyl 92-52-4 Precursor & Downstream _ Compound Dictionary. biphenyl 92-52-4 Precursor
& Downstream _ Compound Dictionary. Available at: http://www.molbase.com/en/precursor_92-52-4-
moldata-1410008.html [Accessed December 16, 2016]
Lewin, D.R., 2004, Simulation of The Toluene Hydrodealkylaition Process, [Accessed November 8,
2016]

P a g e | 15
 APPENDIX A
HYDRODEALKYLATION OF TOLUENE WITHOUT RECYCLING PROCESS
Sizing
This sizing aims at calculating only certain dimensions of each apparatus to evaluate the
coefficient S necessary to determine the cost in the next section. The precise sizing of each
unit will not be covered here. As an illustration, in order to obtain the cost of the furnace, the
supplied duty is only necessary.
Table A.1 Formulas used for equipment sizing
Formula
Equipment

= , =
ln( )
Heat Exchangers

U coefficient is fixed at 500 W/m2C for coolers and 1000 W/m2C for heaters.

=
Plug Flow Reactor
304 = 8027/3

Table A.2 Calculations of the heat transfer surface area for the different heat exchangers
Energy
A
Duty
Type Name T(LMTD)
kJ/h W m2

102-FURNACE 13427245.3 3729790.369

Reboiler@COL1 1430015.21 397226.4474 73.58291355 5.398351713
Heater
Reboiler@COL2 3087102.52 857528.4785 21.9222193 39.11686435
Reboiler@COL3 562002.345 156111.7624

104-Cooler 15068982.4 4185828.438 219.5411328 38.13252109

Condenser-COL1 40855.5611 11348.76697 135.2463238 0.167823666
Coolers
Condenser-COL2 2679033.59 744175.9975 151.7713131 9.806543571
Condenser-COL3 366122.203 101700.6119 172.9368704 1.176158811

Table A.3 Calculations of the heat transfer surface area for the different heat exchangers
Energy
A
Duty
Type Name T(LMTD)
kJ/h W m2

102-FURNACE 13427245.3 3729790.369

Reboiler@COL1 1430015.21 397226.4474 73.58291355 5.398351713
Heater
Reboiler@COL2 3087102.52 857528.4785 21.9222193 39.11686435
Reboiler@COL3 562002.345 156111.7624

104-Cooler 15068982.4 4185828.438 219.5411328 38.13252109

Condenser-COL1 40855.5611 11348.76697 135.2463238 0.167823666
Coolers
Condenser-COL2 2679033.59 744175.9975 151.7713131 9.806543571
Condenser-COL3 366122.203 101700.6119 172.9368704 1.176158811

P a g e | A1
 Table A.4 Calculations of the PFR and Flash Separator.
Type Name Diameter Length Shell mass
Plug Flow m m kg
102-PFR
Reactor 0.75 6.791 3262.4
105 Flash
Flash Separator 0.6096 3.3528 1309.2
Separator

Table A.5 Calculations for the Distillation Column modelled as pressure vessels.
Number of
Type of Diameter Height Shell mass
Name stage
Column
m - m kg
Distillation 106-STABILIZER Packed - PALL
Columns 0.48 8 2.5 770.4
COLUMN
107-BENZENE COLUMN Packed - PALL 0.66 20 2.5 1061.4
108-TOLUENE COLUMN Packed - PALL 0.27 25 2.5 438.7

Equipment Cost Estimation

Table A.6 Recap of the capital cost of equipment

Proportion
Parameters of the
Type Name Ce global cost
of
a B S n equipment
$
104-Cooler 10000 88 38.1325 1 2.4
13,355.66
$
Condenser-COL1 10000 88 0.1678 1 1.8
10,014.77
Coolers
$
Heat exchangers

Condenser-COL2 10000 88 9.8065 1 2.0

10,862.98
$
Condenser-COL3 10000 88 1.1762 1 1.8
10,103.50
$
Reboiler@COL1 10000 88 5.3984 1 1.9
10,475.05
$
Reboiler@COL2 10000 88 39.1169 1 2.4
13,442.28
Heaters
$
Reboiler@COL3 53000 69000 0.1561 0.8 12.5
68,617.00
$
Furnace 53000 69000 3.7298 0.8 45.6
250,786.49
$
Plug Flow Reactor 102-PFR 15000 560 3262.4277 0.6 10.3
56,831.11
Pressure vessels

105 - Flash $
Flash separator 10000 600 1309.1774 0.6 6.3
Separator 34,499.01

$
T-100 10000 600 770.4031 0.6 4.1
22,372.93
Distillation $
T-101 10000 600 1061.3680 0.6 5.3
Columns 29,234.75
$
T-102 10000 600 438.6992 0.6 2.4
13,091.46

Distillation
Trays and packing Type
Column*
$
T-100 Packing Pall rings 0 4000 0.4545 1 0.3
1,817.83
$
T-101 Packing Pall rings 0 4000 0.8626 1 0.6
3,450.25

P a g e | A2
 $
T-102 Packing Pall rings 0 4000 0.1474 1 0.1
589.46
$
Sub-total Equipments 100.0
549,544.53

Utilities Requirement
The utility requirement is calculated using model unit heater and cooler duties in
ASPEN HYSYS V9.
Table A.7 Actual utilities considered for cost estimation.
Temperature Inlet Temperature Pressure
Utility Total Required
(oC) Outlet (oC) (kPa)
Cooling Water 15 40 101.325 171,248.5 kg/hour
High Pressure Steam 260 260 4609 146.76 kmol/hour
Fuel Oil (Assumed) - - - 16.45 GJ/hour
Electricity - - - 0 kW

Operating Cost Estimation

Table A.8 Assumption Data for Estimating Operating Cost
Availability 85 % Toluene 0.85 $/kg
Operating Days 310.5 days Benzene 2.25 $/kg
Operating Hours 7451 Hours Hydrogen 2.7 $/kg
Efficiency of furnace 85 % Price of Chemicals Steam 0.14 $/kmol
and Utilities
Cooling Water 0.02 $/1000 kg
Fuel Oil 14 $/GJ
Electricity 0.10 $/kWh

Table A.9 Operating Cost Estimation

Units
Type of Amount of Cost of Cost per year %
Information of Price $/unit
Utility Utility Purchase ($/year) Cost
Utility
Fresh Toluene 5344 kg/h 0.85 USD/kg $4,542.54
$40,336,183.21 95.5
Reactants Hydrogen 323 kg/h 2.7 USD/kg $ 870.91
Hot Fluid Reboiler@COL1 45.6781952 kmol/h 0.14 USD/kmol $ 6.39
$ 153,102.03 0.4
(HP Steam) Reboiler@COL2 101.090188 kmol/h 0.14 USD/kmol $ 14.15
USD/1000
104-Cooler kg/h 0.02 $ 2.80
140046.247 kg
Cooling USD/1000
Q-condenser-COL1 kg/h 0.02 $ 0.01
Fluid 459.787751 kg
$ 25,519.80 0.1
(Cooling USD/1000
Q-condenser-COL2 kg/h 0.02 $ 0.55
Water) 27347.3704 kg
USD/1000
Q-condenser-COL3 kg/h 0.02 $ 0.07
3395.16191 kg
Electricity kW 0.1 USD/kWh $ - - 0.0
102-FURNACE 13427245.3 kJ/h 14 USD/GJ $ 18.80
Reboiler@COL3 562002.345 kJ/h 14 USD/GJ $ 0.79
Fuel
Total Duty 13989247.7 kJ/h 14 USD/GJ $ 19.58
(Natural $ 1,716,816.43 4.1
Gas) Total Consumed
Fuel (assume: 16.4579384 GJ/h 14 USD/GJ $ 230.41
eff.85%)
Total Operating Cost $42,231,621.47 100.0

P a g e | A3
Temperature Profile of Distillation Column

Figure A.1 Benzene Column Temperature Profile

Figure A.2 Toluene Column Temperature Profile

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Figure A.3 Biphenyl Column Temperature Profile

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 APPENDIX B
HYDRODEALKYLATION OF TOLUENE WITH RECYCLING PROCESS

Sizing
The methodology and formulas applied in this part have been explained in the previous section.
The result of equipment sizing for the system with recycle is described in the following tables.
Table B.1 Calculations of the heat transfer surface area for the different heat exchangers.

Type Energy / Duty A

Name
W m2
102-FURNACE 4.51E+06 Furnace type - duty is sufficient
Reboiler@COL1 5.91E+05 65.9 8.98
Heater
Reboiler@COL2 1.10E+06 40.4 27.15
Reboiler@COL3 / Furnace 5.46E+05 Furnace type - duty is sufficient
104-Cooler 5.26E+06 212.6 49.50
Condenser-COL1 2.65E+04 121.4 0.44
Coolers
Condenser-COL2 1.07E+06 152.8 13.97
Condenser-COL3 5.00E+05 173.5 5.76

Table B.2 Calculations of the PFR and Flash Separator.

Type Name Diameter Length Shell mass
Plug Flow m m kg
102-PFR
Reactor 0.75 6.791 3262.4
105 Flash
Flash Separator 0.6096 3.3528 1309.2
Separator

Table B.3 Calculations for simple-stage centrifugal pump.

Name Flow rate
Pump m3/h L/s
P-100
3.60101309 1.000281413

Table B.4 Calculations for the Distillation Column modelled as pressure vessels.
Diameter Number of trays Height Shell mass
Name
m - m kg
Distillation
106-STABILIZER COLUMN 0.65 8 5.4864 2284.3
Columns
107-BENZENE COLUMN 0.9 20 10 5764.9
108-TOLUENE COLUMN 0.6096 25 14.02 5474.4

Table B.5 Calculations for simple-stage centrifugal pump.

Name Driver power
Compressor kJ/h kW
K-100
3.52E+05 9.79E+01

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 Equipment Cost Estimation

Table B.6 Recap of the capital cost of equipment

Parameters Proportion of
the global
Type Name Ce
a b S n cost of
equipment
104-Cooler 10000 88 49.5040742 1 $ 14,356.36 1.7%
Condenser-COL1 10000 88 0.43624594 1 $ 10,038.39 1.2%
Condenser-COL2 10000 88 13.9724856 1 $ 11,229.58 1.3%
Condenser-COL3 10000 88 5.76017109 1 $ 10,506.90 1.2%
Heat
exchangers Reboiler@COL1 10000 88 8.97872922 1 $ 10,790.13 1.3%
Reboiler@COL2 10000 88 27.1541571 1 $ 12,389.57 1.5%
Reboiler@COL3 /
53000 69000 0.54575036 0.8 $ 95,505.42 11.2%
Furnace
Furnace 53000 69000 4.51069291 0.8 $ 283,273.36 33.2%
Pump P-100 3300 48 1.00028141 1.2 $ 3,348.02 0.4%
Compressor K-100 8400 3100 9.79E+01 0.6 $ 56,911.17 6.7%
102-PFR -15000 560 3262.42771 0.6 $ 56,831.11 6.7%
105 - Flash Separator -10000 600 1309.17743 0.6 $ 34,499.01 4.0%
Presure
T-100 -10000 600 2284.26628 0.6 $ 52,144.01 6.1%
vessels
T-101 -10000 600 5764.85533 0.6 $ 98,298.96 11.5%
T-102 -10000 600 5474.42961 0.6 $ 94,991.61 11.1%
Distillation
Number of trays
Column
T-100 8 100 120 0.65 2 $ 1,205.60 0.1%
T-101 20 100 120 0.9 2 $ 3,944.00 0.5%
T-102 25 100 120 0.6096 2 $ 3,614.84 0.4%
Sub-total Equipment $ 853,878.02 100.0%

Utilities
The utility requirement is calculated using model unit heater and cooler duties in ASPEN
HYSYS V9.
Table B.7 Actual utilities considered for cost estimation.
Temperature Inlet Temperature
Utility Pressure (kPa) Total Required
(oC) Outlet (oC)
Cooling Water 15 40 101.325 228,900 kg/hour
High Pressure
260 260 4609 199 kmol/hour
Steam
Fuel Oil - - - 21.4 GJ/hour
Electricity - - - 101.5 kW

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 Operating Cost Estimation

Table B.8 Operating Cost Estimation

Units
Type of Amount Total Price
Information of Price $/unit % Cost
Utility of Utility (USD/h)
Utility
Fresh Toluene 4607 kg/h 0.85 USD/kg $ 3,915.98 81.5%
Reactants Hydrogen 202 kg/h 2.7 USD/kg $ 544.32 11.3%
Hot Fluid (HP Reboiler@COL1 69.7 kmol/h 0.14 USD/kmol $ 9.76 0.2%
Steam) Reboiler@COL2 129.2 kmol/h 0.14 USD/kmol $18.09 0.4%
104-Cooler 175703 kg/h 0.02 $ 3.51 0.1%
Cooling Fluid
Q-condenser-COL1 884 kg/h 0.02 $ 0.02 0%
(Cooling USD/1000 kg
Q-condenser-COL2 35629.8 kg/h 0.02 $ 0.71 0%
Water)
Q-condenser-COL3 16683.3 kg/h 0.02 $ 0.33 0%
109-Pump 3.6 kW 0.1 USD/kWh $ 0.36 0%
Electricity
110-Compressor 97.9 kW 0.1 USD/kWh $ 9.79 0.2%
102-FURNACE 19104111 kJ/h 14 USD/GJ -
Fuel (Natural
Reboiler@COL3 2311413.3 kJ/h 14 USD/GJ -
Gas)
Total Consumed Fuel 21.4 GJ/h 14 USD/GJ $ 299.8 6.2%
$ 4,802.7 100%
Total Operating Cost $ 35,785,368 USD/year

Table B.9 Case study for splitter fraction

Ratio
Production flow
Case number Purge/Recycle
rate
streams
- - kmol/h
Case 1 0.2 36.45459
Case 2 0.25 36.83962
Case 3 0.3 37.2236
Case 4 0.35 37.61788
Case 5 0.4 37.93275
Case 6 0.45 <empty>
Case 7 0.5 38.74755
Case 8 0.55 38.5466
Case 9 0.6 38.77026
Case 10 0.65 38.50607
Case 11 0.7 37.84918
Case 12 0.75 37.46652
Case 13 0.8 36.31884

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Temperature Profile of Distillation Column

Figure B.1 Benzene Column Temperature Profile

Figure B.2 Toluene Column Temperature Profile

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 Figure B.3 Biphenyl Column Temperature Profile

Comparison Between Processes (Recycle and Non-Recycle Processes)

Annual cost and profit for both systems

System without Recycle System with Recycle
$45,000,000

$40,000,000

$35,000,000

$30,000,000
USD/year

$25,000,000

$20,000,000

$15,000,000

$10,000,000

$5,000,000

$0
Annual Capital Total Cost of Raw Total Cost of Utility Total operating Net profit
Charge (ACC) Material cost
Type

Figure B.4 Annual costs and profit for both systems

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 Flow rates of raw materials, product, byproducts and waste
6000

5000 System without Recycle System with Recycle

4000

3000
kg/h

2000

1000

0
Hydrogen Toluene Total Biphenyl Benzene Toluene Biphenyl Hydrogen Methane
(raw (raw Production (sold) (wasted) (wasted) (wasted) (wasted) (wasted)
material) material) Rate of
Benzene
Type

Figure B.5 Flow rates of all chemicals at inlets and outlets

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 APPENDIX C
OPTIMISATION AND HEAT INTEGRATION
a. Optimisation of Distillation Column

Equipment Cost Calculation

Table C.1 Distillation Column Cost (Without Condenser and Reboiler)

Column Tower Trays

NSTAGE Reflux Ratio Diameter (m) Height (m) Ratio Vol (m3) Shell mass (kg) Cost ($) Cost ($)
9 64.436 2.50 6.30 2.52 1.27 10053.72 141198.40 7650.00
10 5.889 0.94 6.10 6.48 0.47 3657.93 72431.33 2060.40
11 3.670 0.80 5.50 6.91 0.36 2794.78 60139.10 1936.47
12 2.223 0.90 6.00 6.67 0.44 3446.99 69545.41 2366.40
13 1.954 0.90 6.00 6.67 0.44 3446.99 69545.41 2563.60
14 1.416 0.90 6.50 7.22 0.48 3734.24 73458.85 2760.80
15 1.349 0.85 6.30 7.41 0.44 3418.26 69147.02 2800.50
16 1.059 0.75 6.08 8.11 0.38 2910.79 61871.68 2680.00
17 1.039 0.85 4.96 5.84 0.35 2691.20 58567.64 3173.90
18 0.861 0.80 6.30 7.88 0.41 3217.19 66319.79 3182.40
19 0.855 0.78 6.65 8.53 0.43 3311.02 67647.70 3287.15
20 0.740 0.75 6.00 8.00 0.37 2872.49 61302.77 3350.00
21 0.738 0.79 6.72 8.51 0.44 3388.77 68736.60 3672.73
22 0.663 0.78 6.60 8.46 0.42 3286.13 67296.88 3806.18
23 0.662 0.78 6.90 8.85 0.44 3435.50 69386.21 3979.18
24 0.614 0.75 7.20 9.60 0.45 3446.99 69545.41 4020.00
25 0.614 0.77 7.50 9.74 0.48 3686.36 72815.20 4278.70
26 0.583 0.76 7.80 10.26 0.49 3784.03 74124.75 4402.11
27 0.563 2.00 13.50 6.75 2.18 17234.94 198928.23 15660.00
28 0.563 2.00 17.07 8.53 2.76 21791.09 230501.98 16240.00
29 0.552 2.00 17.68 8.84 2.86 22569.35 235619.38 16820.00
30 0.552 2.00 18.29 9.14 2.95 23347.60 240666.67 17400.00

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 Table C.2 Condenser Cost Estimation

Process Stream Utility

NSTAGE Duty (W) Inlet (C) Outlet (C) Inlet (C) Outlet (C) Area(m2) Cost ($)
9 18707402.46 181.27 180.27 15 40 244.61 31525.61
10 1948313.96 181.27 180.27 15 40 25.48 12241.82
11 1333949.26 181.27 180.27 15 40 17.44 11534.90
12 920920.58 181.27 180.27 15 40 12.04 11059.65
13 843484.96 181.27 180.27 15 40 11.03 10970.55
14 689923.01 181.27 180.27 15 40 9.02 10793.86
15 670964.66 181.27 180.27 15 40 8.77 10772.04
16 588145.93 181.27 180.27 15 40 7.69 10676.75
17 582597.03 181.27 180.27 15 40 7.62 10670.36
18 531348.79 181.27 180.27 15 40 6.95 10611.39
19 530808.49 181.27 180.27 15 40 6.94 10610.77
20 496764.38 181.27 180.27 15 40 6.50 10571.60
21 496306.33 181.27 180.27 15 40 6.49 10571.07
22 474909.52 181.27 180.27 15 40 6.21 10546.45
23 474736.07 181.27 180.27 15 40 6.21 10546.25
24 461054.97 181.27 180.27 15 40 6.03 10530.51
25 461046.12 181.27 180.27 15 40 6.03 10530.50
26 452210.78 181.27 180.27 15 40 5.91 10520.33
27 446699.70 181.27 180.27 15 40 5.84 10513.99
28 446540.58 181.27 180.27 15 40 5.84 10513.81
29 443144.46 181.27 180.27 15 40 5.79 10509.90
30 443217.11 181.27 180.27 15 40 5.80 10509.99

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 Table C.3 Reboiler Equipment Cost Estimation

Process Stream Utility

NSTAGE Duty (W) Inlet (C) Outlet (C) Inlet (C) Outlet (C) Area(m2) Cost ($)
9 18749107.69 215.80 262.20 260 260 1212.33 116685.47
10 1990695.73 216.96 262.20 260 260 130.78 21508.36
11 1376769.42 217.54 262.21 260 260 91.15 18021.02
12 963822.85 218.31 262.21 260 260 64.52 15677.99
13 886307.26 218.31 262.21 260 260 59.33 15221.34
14 732839.51 218.53 262.21 260 260 49.20 14330.03
15 713799.91 219.56 262.21 260 260 48.67 14283.13
16 631089.03 219.61 262.20 260 260 43.08 13791.17
17 625584.14 219.95 262.20 260 260 42.93 13777.68
18 574279.89 219.97 262.21 260 260 39.38 13465.18
19 573684.98 220.21 262.19 260 260 39.59 13484.20
20 539533.66 220.22 262.21 260 260 37.14 13268.35
21 539354.06 220.23 262.21 260 260 37.14 13267.99
22 539354.06 220.40 262.21 260 260 37.24 13277.50
23 517665.37 220.40 262.21 260 260 35.75 13146.00
24 503901.71 220.49 262.21 260 260 34.85 13066.58
25 504275.80 220.53 262.21 260 260 34.90 13070.77
26 494979.56 220.60 262.21 260 260 34.28 13016.93
27 489436.83 220.65 262.21 260 260 33.93 12985.46
28 489021.02 220.58 262.21 260 260 33.86 12979.97
29 485784.98 220.68 262.21 260 260 33.69 12964.72
30 486014.57 220.68 262.21 260 260 33.71 12966.12

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 Table C.4 Operating (Energy) Cost Estimation

Condenser-COL2 (Cooling Water) Reboiler - COL2 (HP Steam)

NSTAGE Reflux Ratio Duty (W) q (kg/hr) Cost ($/hr) Duty (W) q (kmol/hr) Cost ($/hr)
9 64.436 18707402.46 53969.07 1.08 18749107.7 2212.11 309.70
10 5.889 1948313.96 5620.70 0.11 1990695.7 234.87 32.88
11 3.670 1333949.26 3848.32 0.08 1376769.4 162.44 22.74
12 2.223 920920.58 2656.77 0.05 963822.9 113.72 15.92
13 1.954 843484.96 2433.37 0.05 886307.3 104.57 14.64
14 1.416 689923.01 1990.36 0.04 732839.5 86.46 12.10
15 1.349 670964.66 1935.67 0.04 713799.9 84.22 11.79
16 1.059 588145.93 1696.74 0.03 631089.0 74.46 10.42
17 1.039 582597.03 1680.74 0.03 625584.1 73.81 10.33
18 0.861 531348.79 1532.89 0.03 574279.9 67.76 9.49
19 0.855 530808.49 1531.33 0.03 573685.0 67.69 9.48
20 0.740 496764.38 1433.12 0.03 539533.7 63.66 8.91
21 0.738 496306.33 1431.80 0.03 539354.1 63.64 8.91
22 0.663 474909.52 1370.07 0.03 539354.1 63.64 8.91
23 0.662 474736.07 1369.57 0.03 517665.37 61.08 8.55
24 0.614 461054.97 1330.10 0.03 503901.71 59.45 8.32
25 0.614 461046.12 1330.07 0.03 504275.80 59.50 8.33
26 0.583 452210.78 1304.58 0.03 494979.56 58.40 8.18
27 0.563 446699.70 1288.69 0.03 489436.83 57.75 8.08
28 0.563 446540.58 1288.23 0.03 489021.02 57.70 8.08
29 0.552 443144.46 1278.43 0.03 485784.98 57.32 8.02
30 0.552 443217.11 1278.64 0.03 486014.57 57.34 8.03

P a g e | A15
 Table C.5 CT ,CC , and CO at various Reflux Ratios
Reflux ACC Operating Cost Total Cost
NSTAGE
Ratio ($/year) ($/year) (k$/year)
9 64.436 10701.31 2315618.60 2326.320
10 5.889 4016.80 245845.63 249.862
11 3.670 3427.65 170021.55 173.449
12 2.223 3682.01 119019.94 122.702
13 1.954 3675.58 109446.29 113.122
14 1.416 3793.12 90491.99 94.285
15 1.349 3646.52 88140.51 91.787
16 1.059 3372.62 77925.13 81.298
17 1.039 3264.64 77245.22 80.510
18 0.861 3547.97 70908.84 74.457
19 0.855 3610.71 70835.39 74.446
20 0.740 3382.97 66617.52 70.000
21 0.738 3668.21 66595.22 70.263
22 0.663 3628.55 66586.02 70.215
23 0.662 3713.64 63916.58 67.630
24 0.614 3729.51 62216.71 65.946
25 0.614 3862.72 62262.75 66.125
26 0.583 3921.77 61114.80 65.037
27 0.563 8496.20 60430.25 68.926
28 0.563 9663.72 60379.01 70.043
29 0.552 9863.62 59979.27 69.843
30 0.552 10061.71 60007.56 70.069

b. Heat Integration
Table C.6 Option 1 results from Aspen HYSYS Energy Analyzer
OPTION 1 Current [kJ/h] Target [kJ/h] Design 1 Savings
Total Hot Utilities [kJ/h] 2.428E+07 6.368E+06 7.06E+06 71%
Total Cold Utilities [kJ/h] 2.468E+07 6.775E+06 7.46E+06 70%
Total Cost [$/s] 1.12E+09 2.49E-02 8.88E+08 21%

Table C.7 Option 2 results from Aspen HYSYS Energy Analyzer

OPTION 2 Current [kJ/h] Target [kJ/h] Design 2 Savings
Total Hot Utilities [kJ/h] 2.428E+07 6.368E+06 9.82E+06 60%
Total Cold Utilities [kJ/h] 2.468E+07 6.775E+06 1.02E+07 59%
Total Cost [$/s] 1.12E+09 2.49E-02 5.14E+08 54%

Table C.8 Option 3 results from Aspen HYSYS Energy Analyzer

OPTION 3 Current [kJ/h] Target [kJ/h] Design 2 Savings
Total Hot Utilities [kJ/h] 2.428E+07 6.368E+06 2.23E+07 8%
Total Cold Utilities [kJ/h] 2.468E+07 6.775E+06 2.27E+07 8%
Total Cost [$/s] 1.12E+09 2.49E-02 9.19E+08 18%

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