Chemical Engineering and Processing 49 (2010) 367375

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensication
journal homepage: www.elsevier.com/locate/cep

Purication process design in the production of styrene monomer

Ismael Daz a,b, , Paul Langston b , Gabriel Ovejero a , Mara Dolores Romero a , Eduardo Dez a
a
Grupo de Catlisis y Procesos de Separacin (CyPS), Departamento de Ingeniera Qumica, Facultad de CC. Qumicas, Universidad Complutense de Madrid Avda.
Complutense s/n, 28040 Madrid, Spain
b
Chemical and Environmental Engineering, The University of Nottingham, University Park, Nottingham NG7 2RD, UK

a r t i c l e

i n f o

Article history:
Received 11 December 2009
Received in revised form 22 February 2010
Accepted 6 March 2010
Available online 12 March 2010
Keywords:
Styrene
Distillation
Extraction
Purication

a b s t r a c t
An economic study of two alternatives for styrene monomer purication based on equilibrium staged
processes is presented. For this purpose, the solubility of t-butylcatechol (TBC) in styrene and the
styrenewater liquidliquid equilibrium were experimentally determined. In terms of economics, a combined process extractiondistillation shows worse results than a conventional distillation process, for the
styrene purication, but this process could be suitable in a high energy cost scenario. Measured activity
coefcients NRTL model and UNIFAC predictive model were used for the process optimization.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, styrenebutadiene derived rubbers (SBR) are widely
used in tyres, toys and adhesives production. Because the synthesis
of these products has risen since the 1960s, the demand for natural rubber derived products has been replaced. The development
of synthetic rubber processing forced manufacturers to develop
new purication processes for both monomers (styrene and butadiene). Purication is needed because, although both monomers
are produced with a purity above 99%, traces of polar compounds
can deactivate the initiator of the polymerization reaction.
In the SBR production, both monomers usually react through
an anionic mechanism, called anionic or living polymerization,
because the ends of the polymer chains are charged, so they can
react with other compounds. But the anionic intermediates, which
propagate the polymerization, need an initiator. Organometallic
compounds are usually employed for this purpose because they can
react easily with the monomers to form the intermediate carbanions. One of the most common initiators is n-butyllithium, which
decomposes to form Li+ and CH3 CH2 CH2 CH2 (Fig. 2). These last
carbanions react with olens to form various polymerization intermediates, as can be seen in Fig. 1 [1].

Corresponding author at: Grupo de Catlisis y Procesos de Separacin (CyPS),

Departamento de Ingeniera Qumica, Facultad de C.C. Qumicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid, Spain.
Tel.: +34 91394411.
E-mail address: idiaz@quim.ucm.es (I. Daz).
0255-2701/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2010.03.006

But organometallic compounds are very sensitive to the presence of polar compounds which can react with them. For example,
water reacts with n-butyllithium to form lithium hydroxide and
butane. In this way, the initiator decomposes, so it is not longer
effective for starting polymerization. Therefore, it is necessary to
reduce impurities to less than 1 ppm for both monomers.
Styrene is usually passed over an alumina bed, which adsorbs
traces of water and t-butylcatechol (TBC) [2,3]. This last compound
is added to avoid the thermal autopolymerization (via radical
mechanism) of the styrene during transport and storage, because
it is an effective free radical scavenger in presence of oxygen. But
the problem is that the lifespan of alumina beds is very short, so
they must be replaced and the waste must be treated; this makes
the process quite expensive [4].
Due to the difference in normal boiling points of the three
compounds involved (water, styrene and TBC), the purication of
styrene can be performed through a distillation process. As styrene
thermal polymerization rate becomes important at temperatures
higher than 50 C [5,6], the distillation process must be carried out
at reduced pressure [7]. The main problem in distillation is the very
high energy consumption, because TBC is heavier than styrene so
a large amount of the monomer puried must be evaporated and
then condensed. For this reason, this paper proposes a new hybrid
purication system combining distillation and liquidliquid extraction in such a way that evaporation of the whole styrene stream
is not necessary. To accurately design or simulate both systems, a
reliable thermodynamic model is needed. Therefore, experimental phase equilibrium data of the binary systems styreneTBC and
styrenewater have been obtained and tted to the NRTL [8] activity coefcient model. These data have been compared with those

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I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Fig. 1. Scheme of the anionic polymerization.

predicted by the UNIFAC [9] group contribution model. Economic

feasibility studies have been carried out for both purication systems, showing noticeable differences. The calculations of capital
investments and operational costs were performed with the help of
ASPEN ICARUS software and information in the literature [1013].
2. Experimental measurements of equilibria
2.1. Materials
Styrene was used in analytical grade and was purchased from
SigmaAldrich. TBC was obtained from Fluka in HPLC grade. Milli-Q
water was used from a Millipore on site generator.
2.2. Procedure
To study the styreneTBC system, a magnetically stirred tank
(25 mL), placed in a thermostatically controlled bath was used
(Fig. 3). Initially the tank was lled with pure styrene and small
amounts of TBC were subsequently added, until a solid phase began
to appear. Once this second phase had appeared, the system was
left until equilibrium was reached (minimun time 2 h) and a sample
of the liquid phase was taken in order to analyze TBC content. Each
sample was analyzed using a PerkinElmer A/S gas chromatograph,
equipped with a 60 m 0.32 mm 1 m DB1 capillary column and
a ame ionization detector. Since TBC is solid at ambient conditions (melting point 50 C), solubility experiments in styrene were
carried out in the range 23 to 30 C. To study the styrenewater
system, liquidliquid equilibrium data were obtained from 3 to
80 C, in the same thermostatically controlled bath previously
employed. In this case, the stirred tanks were bigger (250 mL) and
were equipped with a syringe needle xed onto the bottle plug, in
order to take sample of both bottom (aqueous) and upper (organic)
phases, minimizing experimental errors. All the experiments presented herein, were carried out at least four times analyzing each
sample three times. Experimental errors for all measurements were
below 10% (standard deviation/average value 100).
The samples of the aqueous phase were analyzed by total
organic carbon analysis (SHIMAZDU VCSH). The styrene composition was calculated from the total organic carbon measured in
the aqueous phase. The water content in the organic phase was
analyzed by KarlFisher titration (Mettler DL32).

and melting point (Tfusion ), must be known. In the case of low

temperatures, the difference between ideal and real equilibrium
composition of the mixture is about 85%.
The experimental results presented herein have been also compared with the prediction of UNIFAC model. In terms of activity
coefcients of TBC in solution, the UNIFAC group contribution
method predictions, as well as NRTL equation tting, are shown in
Fig. 5. It can be seen that the lower the temperature, the higher the
deviation from UNIFAC model. At 23 C the difference between
the experimental and the UNIFAC predicted value is about 80%.

2.3.2. Styrenewater system

Fig. 6 shows the experimental equilibrium curve of the biphasic
region, along with the values obtained from NTRL tting, those predicted by UNIFAC method, and the literature values [15]. It can be
seen that, again, the NRTL model adequately ts the experimental
data. UNIFAC predictions are quite good for the aqueous phase, but
not for the organic phase. The experimental results are in reasonable agreement with literature data [15]. The differences between
them are assumed to be related to the analytical apparatus used.

2.3. Thermodynamic modelling

2.3.1. StyreneTBC system
Fig. 4 shows the experimental solubility data, along with the
supposed ideal behaviour of the mixture (solid line). Strong deviations from ideality are observed, which are expected from the
polar structure of catechol. As suggested by Prausnitz et al. [14],
the ideal solubility could be written as ln x2 = fus S/R(Tfusion /T 1),
where only pure component properties, entropy of fusion (fus S)

Fig. 2. Initiator deactivation because of moisture.

Fig. 3. Thermostatically controlled bath: (1) water bath; (2) temperature controller;
(3) magnetic stirrers; (4) tanks for liquidliquid equilibrium; (5) plug with xed
needle.

I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

369

Fig. 4. Experimental solubility of TBC in styrene.

2.3.3. Binary interaction parameters

Table 1 shows the binary interaction parameters of each mixture, obtained from the NRTL t. These values have been obtained
by tting the experimental data to a maximum-likelihood objective function in the form (1) by means of a typical BrittLuecke
non-linear tting algorithm:


2 
2
NP
NC 

Test,i Texp,i
xest,j,i xexp,j,i

+
Q =
i=1

2
NC 

yest,j,i yexp,j,i
j=1

Fig. 5. Activity coefcient of TBC in styrene solution.

T,i

y,j,i

j=1

x,j,i

(1)

where NP is the number of points tted, Test is the estimated value of

temperature, Texp is the experimental value of temperature,  T,i is
the standard deviation of the temperature data i, NC is the number
of components in the mixture, xest is the estimated value of liquid
composition, xexp is the experimental value of liquid composition,
 x,i is the standard deviation of the liquid composition data i, yest is
the estimated value of vapour composition, yexp is the experimental
value of vapour composition and  y,i is the standard deviation of
the temperature data i.
The average deviation in terms of activity coefcient for the t
presented in Fig. 5 is 8.2%. The tting of the T-x-x data for the system
styrenewater results in an average deviation (in terms of liquid
composition of styrene) of 2.4%.
The values in Table 1 have been implemented in ASPEN PLUS
commercial software [16] to investigate the process economics.

3. Economic evaluation of two-distillation process

Fig. 6. Styrenewater liquidliquid equilibrium.

Table 1
NRTL binary interaction parameter regressed.
 ij = aij + bij /T (K)

Styrene (i)TBC (j)

aij
aij
bij
bij

15.8
8.3
5446.5
2401.9
0.2

Styrene (i)water (j)

175.1
148.3
10,068.1
4874.9
0.3

Once a reliable thermodynamic model had been developed, it

was used in the styrene purication design. The assumed specication was 30,000 tonnes/year of styrene monomer in 8000 working
hours (3750 kg/h), with a nal composition of both water and
TBC below 1 ppm. First of all, we adopted a conventional twodistillation column scheme. This process is the simplest from an
engineering point of view, but it has the disadvantage that the
energy consumption is high, which is an important issue for the
future both environmentally and economically. Hence, an alternative combined extractiondistillation process, which reduces the
energy consumption, is investigated in Section 4.

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I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Fig. 7. Process with two vacuum distillation columns in series.

All economic assessments were performed in terms of minimum

economic cost (EC ) [17]:
Ec = Cv + Ct + (ir + im ) FC

(2)

where Cv are the process variable costs, mostly annual utility consumption, Cf are the annual xed costs, i.e. maintenance and wages,
FC is the xed capital investment, ir is the xed capital recovery rate
applied to FC , and im is the minimum acceptable rate of return on
FC . Cf is assumed to be 10% of FC , and ir + im is assumed to be 25% of
FC hence EC expression can be rewritten:
Ec = Cv + (0.35) Fc

(3)

Hence, in terms of economics, the lower the value of EC the

better.
In the distillation process shown in Fig. 7, the water is removed
rst through the top of the rst column (COLWAT) and TBC is
removed next at the bottom of the second one (COLTBC). Hence,
the time that free inhibitor styrene goes through the process is
minimized. In other words, the number of unit operations in which
styrene goes through without TBC is minimized, so minimal fouling
due to thermal polymerization of styrene is expected.
Firstly, the design was carried out by using the experimental thermodynamic information previously related (NRTL model).
Then, the results were compared with those obtained using the
UNIFAC thermodynamic model. One of the aims of this work is to
quantify the economic accuracy of choosing a good thermodynamic
model.
The pressure of the system is an important aspect which was
taken into account, because it was observed that the lower the
working pressure in the columns, the lower the energy consumption. The pressure of the rst column is not so critical, because most
of the energy is consumed in the second column, where styrene is
evaporated, as shown in Fig. 8. Several authors [5,6] report that the
thermal polymerization mechanism is important at temperatures
above 5085 C. Therefore, the pressure range studied herein is limited to 120 mmHg. Fig. 9 shows the vapour pressure of styrene as
a function of temperature. The column temperatures allowed low
pressure steam in the reboilers and cooling water in the condensers.
Air cooling would be an alternative. A summary of unit utility costs
used here is shown in Appendix A.
Using the experimental equilibrium data, the required purity
was achieved with: rst column (COLWAT) with 4 theoretical
stages (feed in stage number 2) and second column (COLTBC) with
3 theoretical stages (feed in stage number 2). It was observed that
reux ratio is not a sensitive factor for this separation, because of
the low number of theoretical stages. It seems that the addition or
removal of one theoretical stage is more signicant than an increase
or decrease of the reux ratio. Thus, the relux ratio was xed in a
low value of 0.01 (minimum reux ratio is very small), in order to
minimize operational costs.

Fig. 8. Total heat consumption as a function of total pressure of the columns (points
near coincident for different values of pressure in COLWAT).

However, the vacuum applied in the columns is also costly.

Industrial vacuum is usually carried out by means of ejectors. In
this case we have considered air ejectors, whose operational cost
is directly related to the amount of vapour to be removed from the
columns. The amount of air required is calculated as in Perry [18],
based on 1% leakage of total inlet owrate.
Thus, it was necessary to perform an economic study of both
capital and operating costs not only as a function of the different thermodynamic models proposed, but also as a function of the
column pressures.
When using the UNIFAC thermodynamic model, it was necessary to redesign the columns. In this case, the separation was

Fig. 9. Vapour pressure of styrene (ASPEN PLUS database).

I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

371

Table 2
Capital (D ) and operating cost (D /y) summary for two-distillation column process.
Component name

NRTL

UNIFAC

20 mmHg 120 mmHg 20 mmHg 120 mmHg

Capital investment (D )
Column (COLTBC)
Column (COLWAT)
Condenser (COLTBC)
Reboiler (COLTBC)
Reboiler (COLWAT)
Ejectors (COLTBC)
Reux pump (COLTBC)
Reux pump (COLWAT)
Condenser accum. (COLWAT)
Condenser accum. (COLTBC)
Condenser (COLWATa )
Total capital (D )
Operating costs (D /y)
Reboiler (COLTBC)
Condenser (COLTBC)
Ejectors (COLTBC)
Reboiler (COLWAT)
Condenser (COLWAT)
Operating costs (D /y)
Economic cost (D /y)
a

112,400
79,900
75,500
70,900
69,200
28,900
27,300
20,300
16,800
12,500

111,700
110,500
63,900
70,900
65,600
12,500
27,300
22,600
15,000
13,300

187,175
234,530
75,500
70,700
78,200
28,900
27,300
22,600
16,800
12,500

112,600
113,800
63,900
71,300
64,900
12,500
27,300
22,600
15,000
13,400

513,700

513,300

754,200

517,300

49,488
7952
5680
4448
176

46,888
7520
4080
13,472
176

49,480
7520
5680
4464
176

46,888
7520
4080
13,424
176

67,700

72,100

67,300

72,000

247,000

252,000

332,000

253,000

Neglected because design results in a very small condenser.

possible with 4 theoretical stages for TBC separation and with 7

theoretical stages for water separation.
In both cases, UNIFAC and NRTL, structured packings type BX
of SULZER were selected, attending to specialized literature that
recommends using packings instead of trays when working under
vacuum [19]. Structured packing has higher efciencies for systems
containing styrene (HETP = 8 ) than random packing.
Table 2 shows the economic results for the different designs.
The major product owrate, styrene, occurs at the top of the TBC
column, hence there is a high energy demand in its reboiler and
condenser. The reboiler utility is more expensive. The vacuum cost
is small in comparison with energy consumptions. It can be also
seen that the lowest EC is obtained at 20 mmHg but it is not sensitive
to pressure. UNIFAC overstimates capital costs by up to 15%. There
are negligible differences in operating costs. Fig. 10 highlight that,
as expected, COLTBC reboiler is the most signicant operational
cost.

Fig. 10. Operating cost summary for two-distillation column process at 20 mmHg.

Fig. 11. Cost summary for two-distillation column process for the design with NRTL.

Fig. 11 shows the variation of the process costs with the pressure. It can be seen that these are larger at 120 mmHg, mainly
because of energy consumptions. For the experimental thermodynamic model, the difference in EC with pressure are small. The
choice of column pressure is more likely to be made on grounds of
safety and control.
4. Economic evaluation of combined
extractiondistillation process
To design this process, a material separation agent has been
added. The aim is to eliminate the bottom product (TBC) by an
extraction process in order to avoid the complete evaporation of
the styrene stream. The selection between different extractants was
made taking into account the relative afnity for TBC and styrene.
Usually, TBC is sold as a saturated solution containing 85% TBC
and 15% methanol [20,21]. The reported specic value of solubility of TBC in methanol is 500 g/100 g [22]. The problem of using
methanol as extractant is that it is miscible with styrene, so the
binary methanolstyrene mixture would be homogeneous and not
suitable for liquidliquid extraction.
A compound which forms two liquid phases with styrene is
water, but the problem of water is that it can only dissolve 2 g of
TBC per litre [22].
So, taking into account the previous considerations, a suitable solvent for the proposed separation system, could be a
methanolwater mixture. This binary solvent can form two liquid
phases with water, while keeping a great afnity for TBC. In the
design of the process it was observed that with a feed of mixture
50/50 (w/w), the styrene can be puried, minimizing the consumption of methanol.
In the proposed scheme (Fig. 12), the inlet stream goes directly
to the LL extraction unit where the TBC is removed with the
methanolwater solvent. The extract outlet stream is then carried to a simple distillation unit (COL1, 3 theoretical stages) where
TBC is obtained from the bottom and the methanol and water top
stream is recirculated to the extraction unit. Although the styrene
is impuried with methanol and water (rafnate outlet stream) in
the extraction unit, these two last compounds can be easily separated from styrene in a distillation column (COL2, 7 theoretical
stages with a reux ratio of 0.35), where pure styrene is obtained
as a bottom product. The distillation column works at 120 mmHg
of pressure in order to avoid thermal polymerization. Low pressure
steam is used in the reboilers and cooling water is used in the condenser for COL1. COL2 requires using chilled water because of the
lower temperatures.

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I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Fig. 12. Combined process extractiondistillation for the purication of styrene monomer.

The inuence of the number of theoretical stages (NE ) in the

extraction column and extractant owrate (FE ) is the most important in terms of process EC . Therefore, the rst optimization study
investigated variations of NE and FE maintaining 7 stages in COL2.
Then, for the best pair of variables NE and FE , the optimization of
COL2 was carried out by the classical analysis of calculating operational and capital costs for different pairs of reux ratio-number of
stages required.
The extraction unit can operate with high NE and low FE , high
capital low operating costs, or vice versa. In the latter case the
operational costs of methanol would be higher which is the most
signicant variable for the extractiondistillation process.

4.1. Extraction optimization

Random packings of INTALOX ceramics rings of 1 in. of diameter
were assumed. For this kind of column an efciency of 2 stages/m
and a total capacity of 20 m3 /h m2 is assumed [18].
Capital (Fig. 13), operating (Fig. 14) and EC (Fig. 15) costs have
been calculated for different of NE FE . The minimum in EC determines the optimum design. It was necessary to manipulate the
reux ratio in COL2 to achieve purication. For each simulation,
the COL2 inlet composition was different so, for a column of 7
theoretical stages, the reux ratio employed should be different
(Table 3).
Fig. 13 shows that the capital costs strongly depend on the size of
the extraction column employed. The inuence of extractant ow
is smaller. Operating costs (Fig. 14) have a minimum value for an
extractant ow of 115 kg/h. Lower owrates require higher recirculation ows so the energy costs in COL1 increase. Higher extractant
ow also results in a high cost of the methanol used. The inuence
of NE over the operating costs is important too, showing that larger
extraction columns need less extractant to carry out the separation
(Fig. 15).

Fig. 13. Dependence of capital cost with NE at different FE .

4.2. Final column (COL2) optimization

Finally, the economic optimization COL2 was carried out in
terms of the classical representation of operating cost and capital as a function of the reux ratio (Fig. 16). Values of 115 kg/h for
Table 3
Reux ratio used in COL2 to achieve purity specications.
Extraction column theoretical stages
10
Extractanct ow (kg/h)
90

100

115
0.80
130
0.60

15

20

25

0.82
0.45
0.40

1.25
0.54
0.35
0.31

0.86
0.45
0.33
0.28

I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Table 4
Capital (D ) and operating
extractiondistillation process.

373

cost

Component name
Capital investment (D )
Column (COL2)
Column (COL1)
Extraction column
Condenser (COL1)
Reboiler (COL1)
Reboiler (COL2)
Condenser (COL2)
Reux pump (COL1)
Reux pump (COL2)
Condenser accumulator (COL1)
Condenser accumulator (COL2)
Ejectors (COL2)

Fig. 14. Dependence of operating costs NE at different FE .

(D /y)

summary

NRTL

for

the

combined

UNIFAC

133,100
110,500
96,000
66,300
65,100
63,500
53,800
22,700
22,700
16,500
15,000
12,500

133,100
110,600
96,000
62,100
65,800
65,300
53,800
22,700
22,700
16,500
15,000
12,500

Total capital (D )

677,700

676,100

Operating costs (D /y)

Methanol
Reboiler (COL1)
Reboiler (COL2)
Condenser (COL2)
Air for ejectors
Condenser (COL1)

62,560
16,437
15,373
4628
2903
2278

32,640
14,253
15,953
5072
2903
2037

Operating costs (D /y)

104,000

72,800

Economic cost (D /y)

341,000

309,000

extractant ow and 15 theoretical stages were xed for the extraction column. The optimum now is the design with the minimum
EC,COL2 (EC,COL2 = Cv,COL2 + 0.35FC,COL2 ). Thus, a column of 6 theoretical stages operating at a mass reux ratio of 0,53 would determine
an EC,COL2 around 130,000 D /y.
4.3. Final design, comparison with UNIFAC model

Fig. 15. Dependence of EC with NE at different FE (the maximum in the gure is the
minimum EC , the optimum design).

Fig. 16. EC as a function of the reux ratio for COL2.

The economic assessment was repeated using the UNIFAC thermodynamic model. The optimum was obtained with: FE = 60 kg/h,
NE = 15 and RRCOL2 = 0.77. The capital cost is similar to the NRTL
model and the operating cost are 30% lower as shown in Table 4.
It can be seen that the highest operating cost is due to methanol
(Fig. 17). That can be minimized by further purication of the distillate stream in COL2, obtaining pure methanol to be storage and
reused in the process. Thus, the operating cost would be reduce in
50,000 D /y but the capital cost (because of the distillation column
required) would increase in 200,000 D so the EC would increase too.

Fig. 17. Operating cost summary for extractiondistillation combined process.

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I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Table 5
Operational costs of different processes.
Process

Operating cost (D /y)

Adsorption (only accounted adsorbent material cost)

Distillation
Combined extractiondistillation (methanol outlet stream valuation not carried out)
Combined extractiondistillation (all outlet methanol reused in the process)

5. Conclusions
The purication of styrene monomer has been studied in order
to seek a new process with lower costs than the current method
(adsorption onto alumina). Economic assessments (capital and
operating) of two alternatives have been undertaken showing the
lowest costs for a conventional distillation process. Experimental measurements of the phase equilibria were undertaken which
signicantly improves the accuracy of the economics. Table 5 compares the EC of the two processes proposed with the current
purication process.
The relative high price of alumina (1000 D /tonne) as well as the
price of solid waste treatment, make the current process expensive. A consumption of 200 tonnes/y of alumina is estimated for
comparison.
The two-column distillation process is the most economic. Since
this process has a high energy usage, which may become more
signicant, a combined extractiondistillation process with lower
energy use is proposed.
This combined process is feasible and reduces energy consumption by 38%, however, the costs are higher mainly due to the
consumption of methanol. The capital needed is also higher than
conventional distillation because the required equipment would
be larger. In a future scenario of very high energy costs this process

Capital cost (D )

200,000
67,000
104,000
50,000

EC (D /y)

51,3000
678,000
878,000

24,7000
341,000
357,000

could be feasible. For the case where most of the methanol would
be puried and recirculated in the process (assuming zero cost of
methanol), the combined process would be even more appealing in
terms of operating cost. The operational costs of all processes presented here are much lower than the current adsorption process.
There are signicant differences in the nal results of EC for the
proposed processes when using different values of mutual solubilities of the various binary mixtures (experimental values or UNIFAC
predicted values).
Future research should investigate improving the combined extractiondistillation process with other extractants and
improvements by complex distillation designs (divided wall
columns, thermal coupling, etc.).

Acknowledgment
Financial support from Spanish Education Ministry (AP200602300) for a short stay in a foreign institution is acknowledged.

Appendix A.
See Table A1.

Table A1
Utility costs.
Utility description

Price

Cooling water (21 C, D /m3 ) [23]

Chilled water (10 C, D /m3 ) [24]
Steam (690 kPa, D /tonne) [23]
Compressed air (D /m3 ) [11]
Methanol (D /tonne) [25]

0.0145
0.225
8.18
0.0117
136

Table B1
Stream data for the two-distillation process at 20 mmHg (NRTL model).
Feed stream

Temperature ( C)
Pressure (mmHg)
Mass ow (kg/h)
Mass frac
Water
Styrene
TBC

Bottom COLWAT

25
20
3750

46
20
3745

0
1
0

0
1
0

Distillate COLWAT
9
20
5

Bottom COLTBC

Distillate COLTBC

47
20
5

0.225
0.775
0

10
20
3740

0
0.925
0.075

0
1
0

Table B2
Stream data for the optimized combined extractiondistillation process (NRTL model).
Feed stream
Temperature ( C) 25
Pressure (mmHg) 760
Mass ow (kg/h)3750
Mass frac
Water
Styrene
TBC
Methanol

0
1
0
0

Fresh
extractant
25
760
115
0.5
0
0
0.5

Extractant to
extraction column
60
760
415
0.372
0.043
0
0.586

Rafnate
stream
31
760
3806
0.001
0.985
0
0.014

Extract
stream
23,5
760
358
0.424
0.049
0.001
0.525

Bottom COL1
95,2
760
58.9
0.943
0
0.006
0.051

Distillate COL1
73
760
300
0.322
0.059
0
0.619

Distillate
COL2
26
120
71.0
0.043
0.19
0
0.767

Bottom COL2
87
120
3735
0
1
0
0

I. Daz et al. / Chemical Engineering and Processing 49 (2010) 367375

Appendix B.
See Tables B1 and B2.
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