Aspen Plus® Study to Enhance Benzene Production by Hydrogen

Purification at Dow’s Aromatic Plants in The Netherlands

Joana de Oliveira Moutinho1, Maria Diná Afonso1, Jan Tange2, Levien Everaert2
1
University of Lisbon, Instituto Superior Técnico, Chemical Engineering Department, CEFEMA, Lisbon, Portugal
2
The Dow Chemical Company, Herbert H. Dowweg 5, 4542 NM Hoek, The Netherlands

Abstract
This work studied the hydrogen purification in the cold box (Aromatics-2 facility) at Dow’s plant in The Netherlands,
with the main aim of rising the benzene production in 35% at the hydrogenation reactor (Aromatics-1 facility), whenever
the hydrodealkylation reactor is stopped.
A model of the cold box was developed by using the Aspen Plus® V8.0 software and it was validated based on the
plant process data, revealing deviations inferior to 10%.
Subsequently, three distinct scenarios were analysed by using the developed Aspen model. Case Study 1 corresponded
the current plant situation, in which the hydrodealkylation reactor is working. Case Study 2 represented the main goal of
this study, i.e. it considered the hydrodealkylation reactor stopped. Case Study 3 was similar to Case Study 2 but it
considered the washing column working normally.
In the three case studies, a cold box feed of 22,7 t/h and a hydrogen purity of 90% (v/v) were set. Sensitivity analyses
were conducted for Case Study 2 whereas Case Studies 1 and 3 were analysed by single simulations.
In Case Study 1, the heavies ended up in the ethane outlet stream, unlike Case Study 3, in which the heavies ended up
in the methane outlet stream. In Case Study 2, the methane stripper was dispensable and yet the model yielded trustworthy
results.

Keywords: Aspen; benzene production; cold box; hydrodealkylation; hydrogen purification; hydrogenation reactor.

1. Introduction • Development of a process model for the cold box unit

Currently, in Dow’s chemical plant at Terneuzen,
benzene is mainly produced by extraction from pyrolysis
gasoline (pygas). From Dow’s pyrolysis gasoline a
mixture mainly composed by benzene, toluene and
xylenes (BTX) is obtained and further treated to recover
benzene.
In a hydrogenation reactor (trickle bed reactor, TBR)
located at the Aromatics-1 facility (Aro.1), a
hydrogenation reaction takes place under a trickle flow
regime. This reactor is fed by a BTX liquid phase and a
gas phase consisting of 60% (v/v) hydrogen.
Benzene is separated from the TX mixture, the latter
of which is sent to the Aromatics-2 facility (Aro.2)
where it undergoes a hydrodealkylation reaction in order
to produce more benzene. Depending on benzene market
price and its production costs, every now and then the
hydrodealkylation reactor is shut down and the TX
mixture is sold in the market.
Nevertheless, if the purity of the hydrogen fed into
TBR would raise, it would allow to reduce the hydrogen
flow rate and to augment the BTX liquid flow rate,
which might in turn lead to the increase of the benzene
production rate simultaneously.
The main goal of this work was to investigate the
possibility of using the cold box unit (Aro.2), to purify
the 60% (v/v) hydrogen up to 90% (v/v), whenever the
hydrodealkylation reactor (Aro.2) is stopped. For this
plant scenario, the economics should be quite favourable
as the TX mixture might be sold in the market and the
benzene production might increase, as well. For this
purpose, several stages were performed, namely:
by using the Aspen Tech Process Modelling V8.0 -
Aspen Plus® V8.0 software;
• Validation of the developed Aspen model based on the
plant process data;
• Analysis of three plant scenarios using the developed
Aspen model.
2. Aromatics-2 facility[1]
This study focused on the aromatic plants and the
entanglements between their units. This work intended
to analyse the performance of the cold box unit (Aro.2),
and predict its impact on benzene production depending
on the flow rate of BTX fed into the hydrogenation
reactor (Aro.1). Thus, a sketch of the main processes
surrounding the cold box unit was drawn for a better
insight over the Aromatics-2 facility (Figure 1).
2.1 Hydrodealkylation process
The hydrodealkylation (HDA) is a commercially
viable process used for the production of benzene from
toluene and higher molecular weight aromatics. This
process consists of removing one or more alkyl groups
(-CH3) from the aromatic ring, and replacing them by
hydrogen atoms. It requires an excess of hydrogen, high
temperature, and moderately high pressures. The
hydrodealkylation process has an important role in
Dow’s aromatics business since it is the largest producer
worldwide, setting the ceiling to benzene market and
ensuring an outlet to the market or reuse of the TX
stream.

1

Figure 1 Schematic overview of the Aromatics-2 facility.
TX - toluene/xylenes mixture, HDA – hydrodealkylation. The
blue dashed line indicates the option to send high purity H2
from the cold box unit (Aro.2) to the hydrogenation reactor
(Aro.1), when HDA reactor is stopped.
In Terneuzen site, the HDA reactions that produce
benzene are the following:
C 7H 8 + H2 à C6H6 + CH4 (1)
(toluene) (hydrogen) (benzene) (methane)
C8H10 + 2 H2 à C6H6 + 2 CH4 (2)
(xylene) (hydrogen) (benzene) (methane)
C8H10 + H2 à C6H6 + C2H6 (3)
(ethylbenzene) (hydrogen) (benzene) (ethane)
Obviously, for HDA reactions to take place it is
necessary to feed certain flow rates of TX and hydrogen
into Aro.2. This hydrogen comes from the ethylene plant
towards the methanator, located at Aro.2 facility. The
HDA reactor is the final step of the aromatics facilities
wherein benzene production increases by means of the
hydrodealkylation reactions. Depending on the daily
market situation and the benzene production costs, the
HDA reactor might be shut down temporarily, meaning
that the TX mixture may be directly sold in the market
instead of reused at Aro.2 facility.
The outlet product from the HDA reactor is cooled
down through a chain of heat exchangers, allowing the
separation of a liquid phase rich in benzene. The gas
phase is purified in a washing column and a cryogenic
section, and in between these units, the gas phase
undergoes a pre-cooling and a drying process.
2.2 Cryogenic section
The cryogenic section contains all the cooling
equipments that maintain the process streams at negative
temperatures. Basically, it comprises the cooler no.2 and
the cold box.
The cold box unit consists of a box containing a
package of equipments, such as piping, distillation
columns, heat exchangers and instrumentation to
maintain liquids at extremely cold conditions. The space
between the equipments and the inner walls of the cold
box is filled with perlite insulation. To prevent the
formation of explosive gas mixtures and humidity, the
cold box is purged with nitrogen under a low pressure.
This procedure prevents humidity deposits, such as ice,
that would impair the insulating effect.
2
After leaving the dryer at 10°C and 53 bar, the feed
gas stream flows towards the cooler no.2, where it is
cooled down to -60°C in counter-current with respect to
the cold product streams rich in hydrogen, methane and
ethane, respectively. Figure 2 represents the flowsheet of
the cryogenic section.
The next cryogenic exchanger is called deep cooler
no.1 because it is located inside the cold box. This
equipment is responsible for cooling down the feed gas
to -91°C in counter-current with respect to the cold
product streams. After passing through the deep cooler
no.1, a condensate product is obtained.
Afterwards, the flow rate of condensate product is
slightly increased by using an ethylene chiller, which
uses ethylene as refrigerant. The ethylene chiller is the
cold source of the plant responsible for the refrigeration
needs due to heat gains throughout the process, and in
the dryer cooling. Thereby, the ethylene evaporation is
used as cold source for the cooling and liquefaction of
the process streams. In this apparatus, the ethylene
refrigerant is totally vaporized by removing the heat
from the feed gas stream. Then, the vaporized ethylene
is discharged to the suction vessel of the ethylene plant.
The separator no.1 is located downstream of the
ethylene chiller, and a flash separation takes place
therein. The liquid product that leaves the bottom of the
separator is rich in ethane and most hydrogen sulfide is
dissolved in this stream. This liquid stream is expanded
and then stripped in the methane stripper. It is
noteworthy that the hydrogen sulfide in the feed gas
stream does not entail troubles in the cryogenic section
since the quantity remaining after the drying process is
dissolved in the liquefied ethane and does not cause
cloggings during the re-evaporation.
Meanwhile, the gas stream that leaves the top of the
separator no.1 is rich in methane and hydrogen. Its
temperature has to diminish in order to raise the
concentration of H2 up to 90% (v/v). Thus, another
cryogenic exchanger, named deep cooler no.2, is used to
cool down the feed gas stream to -136°C by means of
the cold products streams rich in methane and hydrogen,
respectively. At this temperature, part of the methane in
the feed gas condenses and forms a new cooling agent.
Thereby, the product stream rich in liquid methane is
collected in the separator no.2 wherein the flash
separation takes place yielding two different products.
The gas stream that leaves the top of the separator is
rich in hydrogen with a purity in the range 90-95% (v/v).
The purified hydrogen flows back into the system
through the heat exchangers battery, being heated up
until it leaves the cryogenic section at 2°C. In the
meantime, the liquid product that leaves the bottom of
the separator, rich in methane, is expanded by a control
valve undergoing a pressure drop from 53 to 5,6 bar,
assisted by the pipe diameter increase from 3” to 10”.
Then, the methane product stream flows back to the deep
cooler no.2, where it is the main responsible for the
cooling effect. It is noteworthy that the outlet
temperature of the cryogenic exchanger deep cooler no.2
is determined by the quantity of the expanded methane.
In case a heavy refrigeration is needed in the plant, a
higher quantity of methane should be expanded. Further,
the methane cold product flows back through the several
heat exchangers, being heated up until it leaves the
cryogenic section at -1,8°C. Moreover, the recovered
methane from the methane stripper (stream 30) and from
the separator no.3 (stream 17) are added to the methane
product stream (streams 13 and 26).
On the other hand, the liquid product that leaves the
bottom of the separator no.1 is expanded and supplied to
the head of the methane stripper. In this equipment,
CH4/C2H6 separation takes place as the feed stream flows
in counter-current with vapour, via 5 trays, such that a
fraction rich in ethane is formed in the sump and a
fraction rich in methane is obtained at the top of the
column, where a pressure control valve maintains the
rectification system pressure. A fraction of the main feed
gas stream is used in the reboiler to deliver heat for the
rectification system.
The liquid product that leaves the bottom of the
methane stripper is rich in ethane and flows towards the
deep cooler no.1, where it plays the role of cold fluid
occurring its partial vaporization in counter-current with
the main feed gas stream. After partially vaporized, this
stream undergoes the final separation in separator no.3.
As aforementioned, the final flash separation of
CH4/C2H6 occurs, whereas the remaining methane
(stream 17) is added to the methane outlet stream
(stream 13). From the separator no.3, a bottom liquid
product rich in ethane is pumped towards the cooler no.2
(outside the cold box) where it is vaporized, leaving the
cryogenic section at 5°C. The ethane outlet stream heads
to the ethane cracking furnaces in the ethylene plant, to
be cracked.
Although the cryogenic section comprises the cold
box unit and the cooler no.2 right before it (feed of the
cold box), for the sake of simplicity the designation of
“cold box unit” stands for the whole cryogenic section
throughout most text.
In this study, the main purpose of the cold box unit
was to cool down the feed gas until the hydrocarbons,
CH4 and C2H6, become liquid and separate from H2 in
three distinct outlet streams. Moreover, the hydrogen
purity of the feed gas would increase to be reused in the
HDA reactor (Aro.2) or in the hydrogenation reactor
(Aro.1).
3. Modelling of Dow’s cold box unit
3.1 Materials
The model for Dow’s cold box unit was developed
by using the Aspen Tech software. The acronym
“ASPEN” stands for “Advanced System for Process
Engineering”. Aspen is a process simulation software
widely used in industry and known as an important tool
for chemical engineers, thus it is often used to conduct
simulations of chemical processes. Given a process
design and an appropriate selection of thermodynamics
models, Aspen uses mathematical models to predict the
process performance. Furthermore, this software
performs mass and energy analyses. Among the wide
variety of Aspen packages, Aspen Tech Process
Modelling V8.0 - Aspen Plus® V8.0 was selected to
conduct the current simulations since it is a steady state
process simulator and the most adequate for the level of
complexity of this specific process [2].
3
A few tasks had to be performed to build the process
model of Dow´s cold box unit, namely:
• Selection of the property method (NRTL modifications
of the PSRK-Predictive Redlich-Kwong-Soave
equation of state);
• Selection of the convergence tolerance (10-7) and
number of flash iterations (75);
• Identification of the relevant components involved in
the process [(hydrogen (H2); methane (CH4); ethane
(C2H6); ethylene (C2H4); hydrogen sulfide (H2S);
toluene (C7H8) and benzene (C6H6)];
• Design of the flowsheet diagram.
3.2 Flowsheet diagram
Many process data of Dow’s cold box unit was
required to run a realistic simulation by using the Aspen
Plus software, but there was a wide lack of available
information. To start building the process flow diagram
of the cold box, a few input parameters, such as the
temperature, pressure, and composition of the cold box
feed stream were demanded by the software. To get the
maximum relevant plant process data, it was essential to
use the tool Aspen Tag Browser, containing the majority
of the daily plant process data, named InfoPlus.21
(IP.21)[3]. Using the Aspen Tag Browser, the temperature
of 10°C and the pressure of 53 bar were specified for the
feed gas stream. However, the current composition of
the cold box feed stream was not available because there
was not a composition analyser in this zone neither
inside the cold box. The only available record of this
composition was found in documents from 1980, which
were certainly not updated, thus it was not used as
current process data, though a comparison would be
interesting.
Therefore, some samples were taken from the cold
box outlet streams, because the inside of the box was not
accessible for this kind of operations. The samples were
taken while the process was running smoothly, on
November 19, 2014. The composition of each outlet
stream was analysed and the data are listed the Table 1.
The required composition for the simulation input was
the composition of the cold box feed stream, which was
obviously related with the data of the outlet streams,
shown in Table 1. The total mass flow rate of each outlet
stream was selected from IP.21 data based on the
sampling date and time.
As a reminder, this simulation run in steady state,
and assumed that there were no mass losses in the cold
box, i.e. the mass flow rate of the fluid entering in the
cold box was equal to the sum of the mass flow rates
going out. Hence, the hydrogen (H2), methane (CH4) and
ethane (C2H6) mass flow rates (and respective
compositions) of the cold box feed stream were
calculated through their partial mass balances and
presented in Table 2. Although there were many
compounds in the process, the hydrogen, methane and
ethane represented over 99% (w/w) of the total mass
flow rate, meaning that the other compounds
concentrations were negligible. Thus, a major
simplification was assumed for the simulation, viz. the
cold box feed gas stream only contained the main
compounds in Table 2.
 As the main input parameters were obtained, Aspen based on the process operating conditions by the
could finally start building the cold box flowsheet with sampling date and time. The proposed overall process is
all the streams and blocks identified in Table 3. The represented in Figure 2.
inlets specifications set throughout the simulations, were

Table 1 Compositions of the cold box outlet streams (sampling on November 19, 2014).
Hydrogen outlet stream Methane outlet stream Ethane outlet stream
C (vol%) C (wt%) C (vol%) C (wt%) C (vol%) C (wt%)
H2 90,6 53,5 8,42 1,05 0,04 <0,01
CH4 9,09 42,6 82,0 81,1 7,15 3,75
C2H6 0,01 0,09 9,32 17,3 89,8 88,2
Others 0,29 3,75 0,24 0,63 3,02 8,03
Total 100 100 100 100 100 100

Table 2 Compositions and mass flow rates of the cold box feed stream.
Cold box feed stream
Qm (t/h) C (wt%) C (vol%)
H2 3,3 14,6 60,2
CH4 15,3 67,2 34,8
C2H6 4,1 18,2 5
Total 22,7 100 100

Figure 2 Aspen flowsheet of the cold box unit.

4
 Table 3 Blocks description according to Aspen library and their specifications.
Name Quantity Description Specifications
ΔPmain stream = 0,3486 bar ; ΔPH2 stream = 0,3486 bar ;
Cooler no.2 1 Multi stream heat exchanger ΔPCH4 stream = 0,16319 bar ; ΔPC2H6 stream= 0,16319 bar ;
Tmain stream= -60,5°C; TCH4 stream = -1,75°C; TC2H6 stream = 4,98°C
ΔPmain stream = 0,3486 bar ; ΔPH2 stream = 0,3486 bar ;
Deep cooler
1 Multi stream heat exchanger ΔPCH4 stream = 0,16319 bar ; ΔPC2H6 stream= 0,16319 bar ;
no.1
Tmain stream= -91,05°C; TCH4 stream = -65°C ; Vf C2H6 stream = 0,628
Deep cooler ΔPmain stream = 0,3486 bar ; ΔPH2 stream = 0,3486 bar ;
1 Multi stream heat exchanger
no.2 ΔPCH4 stream = 0,16319 bar ; Tmain stream= -140°C (DesignSpec)
Ethylene
1 Thermal and phase state changer ΔPmain stream = 0,3486 bar; Tout= -95°C (DesignSpec)
chiller
Reboiler 1 Thermal and phase state changer ΔP = 0 bar ; Q = -88,21 kW
Methane 1 Rigorous 2-phase fractionation
No. trays = 5 ; PTop= 6,92 bar; PBottom= 6,72 bar
stripper for single columns
Separator 3 Two outlet flash ΔP = 0 bar; Q = 0 kW
Pump 1 Pump Pout = 7 bar
Valve 1 Valve Pout = 5,6 bar
Mixer 3 Stream mixer ΔP = 0 bar
Splitter 1 Stream splitter ΔP = 0 bar ; Limit flow rate of S9 = 1136,1 kg/h

correspond to Figures 3-5, respectively, and they present

4. Model validation the individual flow rates deviations between Aspen
results and IP.21 process data of each outlet stream,
As aforementioned in section 3, a model of the cold together with the individual compositions calculated by
box unit was developed by the implementation of its Aspen.
process diagram (flowsheet). To assess if it was a
reliable approach of the cold box unit, a validation
procedure was conducted based on current plant process
data, i.e. the deviations between the IP.21 process
database and Aspen results were analysed.
≈
≈
4.1 Cold box mass balances ≈
Figure 3 Comparison of the hydrogen outlet stream flow rates.
To achieve a reliable approach of the cold box unit,
the first step was striving to obtain accurate mass
balances. As aforementioned in section 3.2, a few
samples were taken from the cold box outlet streams,
and their compositions were analysed. These data
combined with IP.21 process data for the total flow rate
of each outlet stream, allowed to predict the feed gas
composition of the cold box, used as the simulation Figure 4 Comparison of the methane outlet stream flow rates.
input.
In order to validate the model, Aspen results were
compared to the plant data (Figures 3-5) and their
deviations were calculated, as shown in Tables 4-6.
≈
Besides, some process data of the cold box were ≈
found in documents from October 1980. Although these ≈
data were not updated ever since, the compositions of Figure 5 Comparison ≈of the ethane outlet stream flow rates.
the outlet streams were predicted by using the
composition ratios (inlet/outlet) from 1980, and then Table 4 Deviations between Aspen results and IP.21 database
of the hydrogen outlet stream flow rates.
compared with the Aspen results. This validation was
not so accurate as the direct comparison with IP.21 Hydrogen IP.21 deviation
CAspen (wt %)
database whenever available. Anyway, it was rather outlet stream (%)
interesting to check that there were only significant H2 2,41 56,6
variations in the mass balance of the ethane outlet stream CH4 1,37 43,4
(Figure 5) since 1980 until the present. Tables 4-6 C2 H6 49,5 4,58x10-2
5 Total flow rate 0,69 100
 variation of the hydrogen outlet stream was acceptable
Table 5 Deviations between Aspen results and IP.21 database and the temperature distribution was validated.
of the methane outlet stream flow rates.
Methane outlet IP.21 deviation
CAspen (wt %) IP21
Aspen

stream (%) 20

Stream temperature (°C)

H2 46,5 0,6
CH4 0,37 82,8 0

C2 H6 5,05 16,7 -20

Total flow rate 1,07 100 -40

-60

Table 6 Deviations between Aspen results and IP.21 -80

database of the ethane outlet stream flow rates.
-100

Ethane outlet IP.21 deviation CAspen (wt %) -120

stream (%) Equipments path

-11
H2 100 1,52x10
CH4 21,5 2,94 Figure 6 Temperature distribution of the main process stream
C2 H6 9,82 97,1 through the cold box. Direction: outside → inside.
Total flow rate 8,55 100
IP21
Aspen

0

This analysis showed that accurate mass balances

Stream temperature (°C)

were estimated by Aspen for the cold box unit since -20

most deviations were lower than 10%. However, some -40

deviations were much higher than 10%. Anyway, the -60

components showing huge deviations corresponded to -80

minor fractions (< 5% (w/w)) of the streams as shown in -100

Tables 4-6, thus they did not have a significant effect on -120

the mass balances. In sum, the model was validated as it -140

yielded an excellent estimation of the cold box mass -160

balances. Equipments path

Figure 7 Temperature distribution of the methane process
4.2 Temperature distributions stream through the cold box. Direction: inside → outside.

The analysis of the temperature distributions along IP21

Aspen

Stream temperature (°C)

the cold box unit was also a validation criterion of the 20

developed model. Therefore, a comparison was carried 0

out between the Aspen results and IP.21 process data -20

concerning the temperatures of each process stream.
-40

The main process stream was analysed (Figure 6) up
to the temperature at which H2, CH4 and C2H6 were -60

separated in three distinct process streams that were -80

individually analysed, as well (Figures 7-9). Please
-100

remark, that not every temperature calculated by Aspen
had a corresponding temperature in IP.21 database for -120

Equipments path

comparison purposes.
The temperature results of the main process stream, Figure 8 Temperature distribution of the ethane process
Figure 6, indicates a perfect match of the IP.21 process stream through the cold box. Direction: inside → outside.
data, since this temperature was specified based on the
IP.21 database. On the other hand, the temperature IP21
Aspen

results of the methane and ethane process streams, 20

Stream temperature (°C)

Figures 7-8 respectively, represent an excellent match of 0

the current plant situation as the maximum temperature -20


deviation between the Aspen results and IP.21 process -40


data is solely about 13°C for the methane process -60


stream, and 7°C for the ethane process stream. -80


Finally, the temperature of the hydrogen process -100


stream revealed the highest deviations, which reached -120


20°C, at the cold box outlet, as highlighted in Figure 9. -140


In fact, the temperature of the hydrogen outlet stream -160


Equipments path


was the only process variable, i.e. it represented the sole
degree of freedom in the simulation. Obviously, the Figure 9 Temperature distribution of the hydrogen process
errors associated to the simulation merged on that stream through the cold box. Direction: inside → outside.
variable. Moreover, the measurement instruments bear
random and systematic errors. Still, the temperature
6
 4.3 Hydrogen purity
The Aspen results showed the increase of the
hydrogen purity in the cold box feed stream from 60%
(v/v) to 91,2% (v/v) in the hydrogen outlet stream.
According to IP.21 database, the hydrogen purity in the
hydrogen outlet stream was about 90% (v/v)
representing a deviation inferior to 5%.
5. Case Studies
This section presents the analysis of three distinct
plant scenarios by using the Aspen model implemented
and validated along sections 3 and 4 respectively.
The Case Study 1 corresponded to the current plant
situation, in which the whole Aromatics-2 unit including
the HDA reactor was working normally.
As previously introduced in section 1, the main aim
of this study was to confirm if it was viable to feed the
hydrogenation reactor (Aro.1) with high purity hydrogen
from the cold box unit (Aro.2), whenever the HDA
reactor (Aro.2) was stopped. In such a case, the
methanator outlet stream (Aro.2), only containing CH4
and H2, would be transported to the cold box through the
existent piping and equipments without any chemical
Table 7 Different parameters of the two simulation models.
Equipments outlet hot stream
Vapour fraction of 0,92
Ethylene chiller
Deep cooler no.2 Vapour fraction of 0,7
Deep cooler no.1 Vapour fraction of 0,95
*Minimum acceptable target, defined by the user.
5.1 Case Study 1
The Case Study 1 corresponded to the current plant
situation, in which the HDA reactor was normally
working, as well as each and every equipment in the
Aromatics-2 facility.
So far, the developed Aspen model had just
considered the main components, CH4/H2/C2H6. To get a
more realistic response from the model and predict how
the plant worked, it was mandatory to consider small
flow rates of heavies, namely benzene (C6H6) and
toluene (C7H8), in the cold box feed stream (Table 8).
Actually, these heavies were known to end up in the
ethane outlet stream, reinforcing the motivation of this
case study to verify if this fact was really predicted by
the model. Moreover, a small flow rate of hydrogen
sulfide (H2S) was also considered in the cold box feed
stream to prevent coking in the HDA reactor.
Table 8 Case Study 1 – feed flow rates and compositions of the cold box unit.
H2 CH4
Qm (t/h) 3,31 15,2
C (wt%) 14,6 67,1
C (vol%) 60,2 34,8
reaction or physical process since these equipments were
also stopped. This situation was analysed in Case Study
2.
Actually, no one knew if it was possible to forward
the methanator outlet stream to the cold box without
operating the washing column, one of the equipments
through which the flow should pass towards the cold box
unit. Thus, this work also analysed Case Study 3, which
was similar to the plant scenario of Case Study 2, except
that the washing column was normally working.
Since the washing column solvent only contained
traces of xylenes, the cold box model never considered
these compounds in any of the case studies.
It is worthwhile mentioning that all these case studies
implied variations of the composition of the cold box
feed stream in the Aspen model. Before proceeding with
the variations of the composition of the cold box feed
stream a few parameters were replaced in the original
model to get reliable results. Thus, a new model was
used to conduct composition variations and analyse their
effect on the cold box outlet streams. Table 7
summarizes the parameters of the original model that
were replaced leading to a new model.
Original model New model
Temperature of -95°C
DesignSpec
Variable: T (-200 to 0°C)
Target: H2 purity of 90% (v/v)*
Temperature of -91,1°C
Using the new model (Table 7), a single simulation
was run, considering the heavies in the cold box feed
stream, whereas its total feed flow rate remained
constant at 22,7 t/h.
5.1.1 Cold box mass balances
The composition of the cold box feed stream was
slightly different from the one set in section 3. Table 8
lists the feed flow rates, weight and volume percentage
compositions assumed in Case Study 1.
The easiest way to check the heavies evolution
through the cold box, is by observing the compositions
of the cold box outlet streams (Table 9). Assuming the
feed conditions of Table 8, most heavies ended up in the
ethane outlet stream indeed, as expected.
C2 H6 C6 H6 C7 H8 H2S Total
4,12 0,023 0,023 2,27x10-3 22,7
18,1 0,10 0,10 0,01 100
5,02 0,01 0,01 0,002 100
7
 Table 9 Case Study 1 – Aspen results for the operating conditions, flow rates, and compositions of the cold box outlet streams.

H2 CH4 C2H6 C6H6 C7H8 H2S Total

-3 -15 -17 -7
Hydrogen C (vol%) 90 10 9,16x10 7,73 x10 5,39 x10 1,75x10 100
outlet stream C (wt%) 53 46,8 0,08 1,76 x10-13 1,45 x10-15 1,74 x10-6 100
T = -2,8°C Qm (kg/h) 3228 2854 4,9 1,07 x10-11 8,85 x10-14 1,06 x10-4 6087
P = 52,3 bar Qm (t/h) 3,2 2,8 4,9 x10-3 1,07 x10-14 8,85 x10-17 1,06 x10-7 6
Methane C (vol%) 4,65 84,4 10,9 2,31x10-5 2,88x10-6 2,88x10-3 100
outlet stream C (wt%) 0,55 79,9 19,5 1,07x10-4 2,25x10-5 5,80x10-3 100
T = 1,7°C Qm (kg/h) 85,6 12368 3011 0,02 3,47x10-3 0,89 15466
P = 5,1 bar Qm (t/h) 0,1 12 3 1,16x10-5 3,47x10-6 8,97x10-4 15
Ethane C (vol%) 8,42 x10-11 2,8 95,6 0,75 0,64 0,11 100
outlet stream C (wt%) 5,58 x10-12 1,5 94,5 1,9 1,9 0,12 100
T = 4,9°C Qm (kg/h) 6,51 x10-11 17,5 1104 22,7 22,7 1,4 1168
P = 6,8 bar Qm (t/h) 6,51 x10-14 1,75 x10-2 1,1 0,023 0,023 1,4 x10-3 1,16

5.2 Case Study 2

The Case Study 2 represented the main goal of this
work. Unlike Case Study 1, in this plant scenario the
HDA reactor was stopped. This case study is sketched in
Figure 10, displaying the methanator outlet stream,
which was compressed and transported towards the cold
box unit through the existent piping and equipments
without suffering any chemical reaction or physical
process since these equipments were also stopped. The
high purity hydrogen leaving the cold box unit was
subsequently fed to the hydrogenation reactor located in
the Aromatics-1 facility. As sketched in Figure 10, the
green blocks were working normally, whilst the grey
blocks were shut down.
Figure 10 Schematic overview of Case Study 2 (Aro.2
facility): grey blocks stopped and green blocks working. LHC
I/II: ethylene plants; DC-MTH: methanator; GB1, 2:
compressors; DA-WASH: washing column; DC-HDA:
hydrodealkylation reactor; CB: cold box unit.
Using the new Aspen model, the plant scenario of
Case Study 2 technically meant to vary the composition
of the cold box feed stream. To observe the effect of the
composition variation on the cold box performance,
several sensitivity analyses were performed, in which H2
purity in the cold box feed stream varied from 0 up to
100% (v/v), whereas the total feed flow rate remained
constant at 22,7 t/h.
The sensitivity analyses revealed that the model
representing the plant scenario of Case Study 2, was
only valid from 22,4 up to 90% (v/v) of H2 in the cold
box feed gas.
5.1.1 Cold box mass balances
The Aspen results pointed out that up to 10% (v/v) of
H2 in the cold box feed stream, the separation of H2 and
CH4 did not occur at all because the model was dealing
with supercritical fluids. Besides, the model faced
convergence errors from 10 up to 22,4% (v/v) of H2,
thus it did not yield reliable results in that range.
The results of the sensitivity analysis are plotted in
the validity range of the model, Figure 11, that displays
the composition distributions of the cold box outlet
streams.
Figure 11 shows that the ethane outlet stream was
absent (null flow rate), since C2H6 was not taken into
account in this case study, as the HDA reactor was
stopped. The methane outlet stream revealed a realistic
composition distribution, starting with a high flow rate
of CH4, and gradually reducing as the flow rate of H2 in
the cold box feed stream increased. Last, but not least,
Figure 11 presents the expected response of the total
flow rate of the hydrogen outlet stream. The latter
gradually rose as the H2 purity increased in the cold box
feed stream up to 90% (v/v). Beyond 90% (v/v) of H2 in
the cold box feed stream, the total flow rate of the feed
stream exceeded 22,7 t/h and the results were
unrealiable.
The equipment mainly responsible for the increase of
H2 purity was the deep cooler no.2, in which a
DesignSpec varied the outlet temperature from -200 to
0°C to condense methane till a H2 purity of 90% (v/v)
was achieved. A constant H2 purity of 90% (v/v) was
achieved in the hydrogen outlet stream throughout the
model validity range. If H2 purity in the cold box feed
stream would exceed 90% (v/v), the deep cooler no.2
would presumably condense H2 instead of CH4, but as
8
this process would be unfeasible at the operating 5.1.4 Ethylene chiller
conditions specified, the separation of CH4/H2 would not
occur, i.e. everything that would enter into the cold box As Case Study 2 did not consider ethane neither
would end up in the hydrogen outlet stream. heavies in the cold box feed gas, the flow rate of
ethylene refrigerant fed to the cold box was lower than
24


in Case Study 1.
Total flow rates of the outlet

20
The Aspen results showed that the ethylene chiller
partially condensed the feed gas, only containing H2 and
streams (t/h)

16
Hydrogen
stream
CH4, in a small range from 22,4% up to 24,6% (v/v) of
12
Methane
H2 in the cold box feed stream (Figure 13). For hydrogen

stream

8
Ethane purities beyond 24,6% (v/v), the ethylene chiller could
stream

4

not proceed with CH4 condensation and just a cooling
process took place.
0

0
10
20
30
40
50
60
70
80
90
100

Purity of H2 (vol%) in the feed gas stream of the cold 3

Ethylene flow rate (t/h)

box

2,5

Figure 11 Case Study 2 - sensitivity analysis regarding the 2

flow rates of the cold box outlet streams.
1,5

Partial
1
condensation
5.1.2 Temperature distributions 0,5
Cooling

0

Figure 12 displays a constant response for the 0
10
20
30
40
50
60
70
80
90
100

temperature of the methane outlet stream, since this
Purity of H2 (vol%) in the feed gas stream of the
variable was specified in the model. Conversely, the cold box

temperature of the hydrogen outlet stream showed a
steep variation of about 100°C because it was the sole Figure 13 Case Study 2 - sensitivity analysis regarding the
refrigerant flow rate in the cold box unit.
process variable.
Anyway, in the range of H2 purity in the cold box
feed stream practically applicable in the plant (60%-75% 5.1.5 Methane stripper
(v/v)), the temperature presented a rather small variation,
meaning that it would be safe working within this range The Aspen results of the methane stripper were in
without significant disturbances of the hydrogen outlet close agreement with the ethylene chiller results, i.e.
stream temperature. since ethane was absent in the cold box feed stream, the
Hydrogen Stream
Methane Stream
stripper feed was null (Figure 14). Yet, small flow rates
10

across the methane stripper were noticed in a small
Outlet streams temperature

range from 22,4 up to 24,6% (v/v) of H2 in the cold box

-5

0
10
20
30
40
50
60
70
80
90
100
feed stream, corresponding to a minor condensation of
-20

CH4 in the ethylene chiller, as explained in section 5.1.4.
-35

(°C)

-50

-65

Top
Bottom
Feed

-80

3

Methane stripper flow rates

-95

-110

Purity of H2 (vol%) in the feed gas stream of the 2

cold box

(t/h)

Figure 12 Case Study 2 – sensitivity analysis concerning the 1

temperature of the cold box outlet streams.
0

5.1.3 Pressure distributions 0
10
20
30
40
50
60
70
80
90
100

Purity of H2 (vol%) in the feed gas stream of the
The Aspen results for the pressure distribution of cold box

each outlet stream revealed that there were no Figure 14 Case Study 2 - sensitivity analysis concerning the
substantial pressure variations if the purity of H2 in the flow rates of the methane stripper.
feed gas stream of the cold box varied because the outlet
streams pressures were specified throughout the cold
box unit. 5.2 Case Study 3

Actually, no one knew if it would be possible to

forward the methanator outlet stream towards the cold
box unit without operating normally the washing
9 column, thus Case Study 3 considered this equipment in
the flowsheet. It was somewhat similar to Case Study 2
but the compositions of the cold box feed stream were
obviously different in Case Studies 2 and 3, because in
the latter the washing column operated with a BTX
solvent, whereas in the former this equipment was
stopped.
Case Study 3 was also analogous to Case Study 1,
though it did not consider ethane neither hydrogen
sulfide in the cold box feed stream, both intending to
ascertain in which outlet stream the heavies from the
washing solvent would end up. Likewise Case Study 1, a
single simulation was run for Case Study 3.
Table 10 presents the composition of the cold box
feed stream, considering identical flow rates of heavies
in the Case Studies 1 and 3. Table 11 displays the Aspen
results for the flow rates and compositions of the cold
box outlet streams. Unlike Case Study 1, the heavies
ended up in the methane outlet stream, meaning that
they passed through the heat exchanger deep cooler
no.2. This equipment worked at the lowest temperature
of the cold box unit, hence plugging was likely to occur
under these harsh conditions.

5.2.1 Cold box mass balances

Table 10 Case Study 3 – feed flow rates and compositions of the cold box unit.
H2 CH4 C6 H6 C7 H8 Total
Qm (t/h) 4,05 18,62 0,027 0,027 22,7
C (wt%) 17,8 81,9 0,125 0,125 100
C (vol%) 63,3 36,6 0,01 9,5x10-3 100

Table 11 Case 3 – Aspen results for the operating conditions, flow rates, and compositions of the cold box outlet streams.

H2 CH4 C6H6 C7H8 Total

-13 -15
Hydrogen C (vol%) 90 10 3,1x10 1,7x10 100
outlet stream C (wt%) 53,1 46,9 7,1x10-12 4,8x10-14 100
T = 0,8°C Qm (kg/h) 3942 3481 5,2x10-10 3,5x10-12 7423
P = 52,2 bar Qm (t/h) 3,9 3,5 5,2x10-13 3,5x10-15 7
Methane C (vol%) 5,28 95 0,03 0,03 100
outlet stream C (wt%) 0,69 98,9 0,18 0,18 100
T = -1,7°C Qm (kg/h) 106,2 15134 27,7 27,7 15298
P = 5,1 bar Qm (t/h) 0,1 15 0,03 0,03 15
Ethane C (vol%) 3,5x10-14 4,5x10-10 4,29 95,7 100
outlet stream C (wt%) 7,7x10-16 7,9x10-11 3,66 96,3 100
T = 4,9°C Qm (kg/h) 2,0x10-21 2,1x10-16 9,7x10-6 2,5x10-4 2,6x10-4
P = 6,8 bar Qm (t/h) 2,0x10-24 2,1x10-19 9,7x10-9 2,5x10-7 2,6x10-7

6. Conclusions analyse three distinct plant scenarios, in which the H2

This work investigated the hydrogen purification in
the cold box (Aromatics-2 facility) at The Dow
Chemical Company plant in The Netherlands, with the
major aim of enhancing benzene production in 35% at
the hydrogenation reactor (Aromatics-1 facility),
whenever the hydrodealkylation reactor is shut down.
A cold box model was developed, by using the
Aspen Plus® V 8.0 software, that predicted reasonably
well the current plant situation, yielding mass balances
deviations with respect to the IP.21 process data below
10%. The sensitivity analyses revealed reliable and
stable responses of the model for the outlet streams
compositions. Another conclusion drawn from the model
validation was that the hydrogen purity increased from
60 to 91,2% (v/v).
Although the developed model was a good
representation of the cold box unit, it was not robust to
vary the feed gas composition and still yield stable
responses. Hence, a similar model was implemented to
Anyhow, the methane stripper did not yield reliable
temperatures of its outlet streams.
10
purity was set as 90% (v/v) in the hydrogen outlet
stream for a cold box feed stream flow rate of 22,7 t/h.
The Aspen results of Case Study 1, representing the
current plant scenario, confirmed that the heavies ended
up in the ethane outlet stream. The results also revealed
excessive ethane in the methane outlet stream.
In Case Study 2, the simulations revealed a reliable
performance of the cold box unit, i.e. whenever the
HDA reactor was stopped, the methanator outlet stream,
only containing H2 (60% (v/v)) and CH4, was fowarded
to the cold box unit to reach the desired H2 purity of
90% (v/v) and raise the benzene production in 35%. The
methane stripper was dispensable in this scenario.
The Case Study 3 had the same purpose as the Case
Study 2, but it considered the washing column working
normally. In such a case, the heavies ended up in the
methane outlet stream, instead of ending up in the ethane
outlet stream as in Case Study 1. This fact might lead to
plugging.
 As for the future work, to study the cold box List of symbols
performance beyond the model validity ranges, it is
suggested to test it by varying the split fraction flowing
Variable Description Units
into the reboiler and the H2 purity goal; inserting
design/geometry parameters in the equipments; and T Temperature °C
selecting distinct methods for the components physical P Pressure bar, barg
properties. To test the aim of this work in the field, it is vol%, wt%
recommended to identify the cold box start-up operating C Concentration
conditions, by feeding only H2 and CH4, to ascertain the Qm Mass flow rate kg/h, t/h
possibility of running the cold box unit while the washing Q Heat duty kW
column is stopped. Furthermore, it is essential to analyse Vapour -
the likelihood of plugging foreseen in Case Study 3. Vf fraction
in Inlet -
References
out Outlet -
1. Dow – Hydrogen purification unit, Terneuzen – vap. Vapour phase -
operating manual (Accessed 2014). -
2. Dow – IP.21 database Info Plus (Accessed 2014). liq. Liquid phase
3. Aspen Technology, Inc., Aspen Plus: Summary File
Toolkit. 1-208 (2012).
List of compounds

Acknowledgments Molecular Molecular

Compound
formula weight (g/mol)
The Dow Chemical Company is acknowledged for the
Benzene C6H6 78,11
followship granted to Joana Moutinho, the availability of
its facilities and the support of its staff, especially Wim Ethane C2H6 30,07
Kamperman, allowing her to successful carry out this Ethylene C2H4 28,05
work and write her Master thesis in Chemical
Hydrogen H2 2,02
Engineering.
Hydrogen sulfide H2S 34,08
Methane CH4 16,04
Toluene C7H8 92,14
Xylenes C8H10 106,16
Water H2O 18,01

11