Energy Convers. Mgmt Vol. 39, No. 1618, pp.

18531862, 1998
# 1998 Elsevier Science Ltd. All rights reserved
PII: S0196-8904(98)00058-2 Printed in Great Britain
0196-8904/98 $19.00 + 0.00

ENERGY SAVINGS IN CHEMICAL PLANTS: A VINYL

CHLORIDE CASE HISTORY

VITTORIO BRUZZI,$* MARCELLO COLAIANNI% and

LUCIANO ZANDERIGHI}
$
Via Assietta 31, Milano, Italy
%
EVC Italia Via della Chimica 5, 30175, Porto Marghera, Italy
}
Dipartimento di Chimica Fisica ed Elettrochimica, Universita di Milano, Via Golgi 19, 20133, Milano,
Italy

AbstractTo optimise the energy utilisation in the processes (and in particular in the chemical indus-
try) it is useful to identify (when possible) process congurations in which the driving forces are uni-
form and the entropy generation approaches zero when the size of the plant increases. Such ideal
congurations can be used as references and, to obtain practical plant ow diagrams, they have to be
modied, according to the peculiar features of the process and the plant, the economical factors and
the safety and environmental requirements. This paper presents, after a short methodological introduc-
tion, a vinyl chloride plant optimisation, based on such concepts and realised in the Porto Torres plant
by the European Vinyl Corporation. Vinyl chloride monomer (VCM) is obtained by ethylene dichloride
(EDC) cracking; furnace euents containing VCM, EDC, hydrogen chloride (HCl) and chlorinated
byproducts are processed through quench towers and a distillation train in order to separate the various
components. The key of the new technology is the distillation sequence, which is adjusted to make it
similar to the thermodynamically optimal conguration. Due to the new temperature levels of reboilers
and condensers, a better heat cascading and a reduction of the steam consumption are obtained. The
modication of the existing plant with a nominal capacity of 150,000 t/a has been realised using mainly
the existing columns and exchangers; a HCl distillation column and three heat exchangers have been
added; a new screw compressor allows the use of the existing cooling system. In a 10-day test run car-
ried out at 50% capacity after the modication of the plant a reduction of the steam consumption of
50% was achieved. # 1998 Elsevier Science Ltd. All rights reserved

INTRODUCTION
A clever approach to the study of energy saving in plants is to nd an ideal ow sheet in which
the driving forces are uniformly distributed along the process, so that, for a given productivity
of the plant, by increasing to innite the dimensions of the equipments both the driving forces
and the entropy generation go to zero. The reduction of the equipment dimensions to a real
value can be obtained by introducing uniformly distributed driving forces. The nal dimension
of the equipments is thus an economical problem of optimising the investment costs (size of the
plant) and the operating conditions (energy or better exergy consumption).
Ideal arrangements are useful reference points, even though rather complex and far from any
real application due to the constraints, always present in any plant, such as those due: econ-
omics, environmental, safety, toxicity and stability of the products, quality requirements, etc. In
the case of a plant revamping specic constraints are present, due to the existing plant arrange-
ments; nevertheless, good opportunities are oered sometimes by available equipments. The
approach based on ideal congurations is usual in mechanics or in other elds, but less usual in
chemical plant design.
It is important to point out that not in all cases it is possible to nd an ideal conguration
for a chemical plant; in many cases the irreversible phenomena allow indeed the achievement of
the target of the process, such as the selectivity for a given chemical reaction, when the reaction
equilibrium under given operating conditions is unfavourable.
The search for the ideal arrangements is particularly easy, and useful, for the separation pro-
cesses. At least in principle for any of such processes it is possible to nd many ideal arrange-
ments: some are strictly related to the use of work (such as membrane separation), others to

*To whom all correspondence should be addressed.

1853
1854 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS

heat supplies and rejections (distillation, evaporation, crystallisation, etc.). In the rst case the
entropy variation of the isoenthalpic separation is removed as heat produced by the separation
work; in the last one by a heat cascade from high to low temperature.
The energy, or exergy, needs of a chemical plant can be classied according their use as:
thermodynamic ones (necessary), that are function of the initial and nal states of the
transformation; these needs depend on the amount of the transformation and can be reduced
only by abandoning the transformation itself;
kinetic ones (useful), used for setting up driving forces well balanced and optimised accord-
ing to the equipment size;
inactive ones, due to the non-uniform distribution of the driving forces in the real arrange-
ment (useless, but sometimes inevitable); the largest energy savings can be obtained just by redu-
cing, according to the constraints, these deviations.
Studies for the practical application of the above principles to the distillations are available in
the literature; the main results of these studies and the suggestions proposed for the process de-
sign are summarised in the following.

Ideal and real binary distillations; purication columns

The idea of a reversible binary distillation was rst introduced by Benedict [1] and used in the
following by other authors [2, 3]; such distillation is performed under equilibrium conditions in
any point: this implies that heat is supplied continuously along the stripping section and
removed continuously along the rectifying section; the vapour and liquid molar ows are no
more constant along the distillation column and the working lines of the column form an envel-
ope which agrees with the equilibrium line.
The supplied and rejected heat in the case of an ideal distillation is shown in Fig. 1 for three
dierent binary mixtures: indeed in the gure the 1/T vs heat is plotted, where T is the vapour

Fig. 1. Thermal proles of a distillation column fed with two component mixtures and dierent compo-
sitions. The curves are the 1/T proles for reversible columns and the rectangles for columns at mini-
mum reux: light component rich feed (LRM): curve 0A1B1C1D; rectangle 0E1F1D; equi-molar feed
mixture (EM): curve 0A2B2C2D; rectangle 0E2F2D; heavy component rich mixture (HRM): curve
0A3B3C3D; rectangle 0E3F3D.
 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS 1855

liquid equilibrium temperature. In such a diagram the areas enclosed with the 1/T equilibrium
curves represent the entropy of feed separation that is the entropy subtracted from the streams
by the heat in an ideal column; in the case of a real column, with a minimum reux, the only
point in equilibrium is at the feed plate since in all other parts of the column are present driving
forces and the system is far from equilibrium. The entropy to be removed increases due to the
irreversibilities, such as for instance the heat supplied at the bottom and removed at the top by
the condenser, and is described in Fig. 1 by the rectangles dened by the temperature level of
the boiler and the condenser and the duty of the boiler. A discussion of ideal columns and a
detailed analysis of the entropy generations in real distillations are reported in [3].
The main suggestions for improving distillations with respect to the conventional design are:
to adjust the head and bottom conditions for a better match with the thermal levels of the
utilities available in the plant; this can be obtained by choosing a suitable operating pressure,
and/or by forming heat cascades (multiple eects), or by using vapour thermocompression;
to introduce more favourable thermal levels by using inter-coolers (when the feed is rich in
the heavy component) or inter-reboilers (when the feed is rich in the light component): diagrams
like those in Fig. 1 can give useful suggestions;
to reduce the pressure drop along the distillation column by using suitable internals; this is
important in the case of vacuum distillation when the pressure drop is of the same order of the
operating pressure.
A purifying column removes either light or heavy impurities from the main stream and, even
though the feed is multicomponent, the separation column can be treated as a binary one. For
removing light impurities (stripping columns) the energy consumption, evaluated in Fig. 1 as
entropy generation, is lower than for removing the heavy ones. In this last case practically all
the feed has to be evaporated; nevertheless, the exergy consumption can be restrained by a suit-
able conguration: for example the purication can be performed in two steps: a main column,
operating with a small temperature dierence, followed by a small nal column for the concen-
tration of the heavy impurities (see later the columns T4400 and T401).
The thermodynamic eciencies of conventional binary distillations are generally very low
(from 3% for purication columns to 1015% for the separation of an equi-molar mixture). A
saving of 50% in the energy utilisation can be obtained in many cases.

Ideal and real multicomponent distillation trains

Ideal ow sheet. For the separation of a mixture into its n-components, a set of distillation
columns (or a column train) must be used, and the rst problem to solve is the sequence, or the
arrangement, of the columns. Usually heuristic rules are followed, as those introduced by
Treybal [4]. It is important to keep in mind that the nal products often must be obtained as
distillates for quality reasons.
The best known heuristic rule suggests (see Fig. 2(a)) to separate the components in order of
decreasing volatility: the distillation train is composed by (n 1) columns; all the components
but the heaviest are obtained as distillates; each component is distilled only once, except the hea-
viest; for this reason this arrangement is often preferred, having generally the lowest energy con-
sumption among the conventional ones.
In Fig. 2(b) the components are separated in order of increasing volatility; the train includes
n 1 columns; all the components but the lightest are obtained as residues; the component A is
distilled twice. With a n component mixture A is distilled (n 1) times, B (n 2) and so on.
In the two above arrangements the key components are contiguous in order of volatility.
Such arrangements cannot be drawn to reversible ones by increasing the size of the equipment,
since the separation of the components one at a time does not allow to obtain equilibrium con-
ditions in all the points of the columns. Indeed, the compositions of the distillate and residue
cannot be chosen arbitrarily, but must follow the mass balance.
The arrangement for the reversible multicomponent train has been described by Petlijuk et
al. [5]; in any column the key components are those with the greatest dierence in volatility;
each column eliminates the least volatile from the top and the most volatile from the bottom; it
results the tree-like arrangement shown in Fig. 2(c), where each column exchanges liquid and
vapour with the near ones with a net stream ow to the right direction, or the separation direc-
 1856
BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS

Fig. 2. Some arrangements of distillation columns for a three-component separation.

 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS 1857

tion. In each column the heat is supplied gradually at the equilibrium temperature in the strip-
ping section and removed in the same way from the rectifying section. An alternative equivalent
scheme is reported in Fig. 2(d); in this case the number of columns is n 1, like in the cases
2(a) and 2(b).
Multicomponent ideal columns: vapour and liquid compositions. The compositions and the
stream ows in a multicomponent ideal column are function of the vapourliquid equilibrium
constants which are in turn a function of the stream composition and temperature (or pressure).
In the case of ideal mixtures with constant relative volatility the stream compositions can be
described as follows:
in the rectifying zone the liquid concentrations are in constant ratio, equal to that in the
feed, except for the heaviest one, the concentration of which decreases until zero at the top;
in the stripping zone the liquid concentrations are in constant ratio, equal to that in the
feed, except for the lightest one, the concentration of which decreases until zero at the bottom.
Similar behaviour have the concentrations of the vapour phase.
Simplied tree-like ow sheet. In Fig. 2(e) a plant scheme for the separation of a ternary mix-
ture ABC is reported: a pre-fractionator (AC) is followed by two binary columns (AB) and
(BC); such a scheme is similar to the ideal arrangement of Fig. 2(c); however, the features more
dicult to realise (heating and cooling along the column sections; liquid streams owing back
from the binary columns to the ternary one) have been eliminated. Nevertheless, the main ad-
vantages of the ideal arrangement are still present:
the column (AC) requires a smaller number of plates, a lower temperature dierence
between bottom and top, and very low reux;
the column (BC) has the same temperature at the top and the bottom as the corresponding
column of Fig. 2(a), but the distillate stream is lower, since part of component B is separated by
the column (AB);
the column (AB) operates at a lower temperature than the corresponding column in
Fig. 2(a), since C has been removed, and moreover it has a lower reux (the feed is rich in the
component A).
Obviously by simplifying the scheme, that is going from Fig. 2(c) to Fig. 2(e), some irreversi-
bilities have been introduced that increase the exergy consumption. Since part of B is obtained
as residue of the column AB this could be a drawback in the case if B has to be obtained as a
quality end product. The purication column has a very low temperature drop and can be
included in an heat cascade.
The introduction of heat exchangers along the stripping and rectifying sections can create
more opportunities, drawing the arrangement more close to the reversible one.

THE VCM CASE HISTORY IN PORTO TORRES

The previous technology
The vinyl chloride monomer (VCM) is obtained from 1.2. ethylene dichloride (EDC) by a
thermal cracking reaction
ClH2 CCH2 Cl 4CH2 CHCl HCl
giving VCM and hydrochloric acid (HCl) in equi-molar amount.
The plant is divided into three sections (see Fig. 3): (1) reaction, (2) VCM distillation, (3)
EDC distillation.
The ow sheet of the previous plant is reported in Fig. 4.
In the rst section (reaction) the endothermic cracking reaction takes place; it is carried out in
tubular reactors contained in re boxes (furnaces) at a pressure of about 7.5 bar; the conversion
is about 50% and the nal reaction temperature is about 770 K.
The reacted mixture in nearly equi-molar proportions of HCl, VCM and unreacted EDC,
containing traces of some impurities, is washed and quenched in a column by a liquid stream,
coming from a cooler which partially condenses the vapours from the column. From the bottom
a purge of very heavy products (mainly coke) is obtained, that is sent to the disposal treat-
ments.
1858 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS

Fig. 3. Block diagram of the VCM plant.

The euents from the quench system (a liquid and a vapour stream) enter the second section,
or VCM distillation train (T5400 and T5500), where gaseous HCl, liquid VCM, and liquid EDC
are obtained. The VCM is the expected product; the HCl is recycled to chlorination units and
the EDC is sent to distillation and then recycled.
Usually there are two versions for the VCM distillation section:
the rst one is equal to the scheme reported in Fig. 2(a): at the top of the rst column the
stream of pure gaseous HCl is obtained by reuxing liquid HCl, obtained by a refrigeration
unit. The residue is sent to a second column where VCM, as the distillate, and EDC, as the resi-
due, are obtained.
the second version is included in Fig. 4: it diers from the previous one since part of the
EDC from the bottom of the second column (T5500, VCMEDC) is sent, after refrigeration, to
the top of the rst column (T5400) in order to reduce the duty of the refrigeration unit and to
avoid the HCl reux. The steam requirement for the two columns is increased; the EDC recycle
has the eects of an absorption refrigeration unit.

Fig. 4. Previous VCM ow sheet.

 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS 1859

In the Porto Torres plant the last version was applied before the modication; the two col-
umns for VCM distillation were T5400 (HClVCM) and T5500 (VCMEDC).
In the EDC distillation section, third section, the following four columns were present:
T305 puries, at atmospheric pressure, the moist feed stream, coming from the EDC syn-
thesis plants, removing water and light impurities;
T4200 puries, at atmospheric pressure, the dry EDC stream coming from cracking, remov-
ing light impurities;
T4400 puries, at atmospheric pressure, the total feed sent to the cracking, removing heavy
impurities;
T401 concentrates, under vacuum, the heavy impurities obtained from the bottom of
T4400, allowing to recover residual EDC.
The arrangement of the two columns T4400 and T401 is the same as described in Section 1.2:
it avoids the fouling of the reboilers since chlorinated compounds have a low thermal stability
and could decompose producing coke. The column T4400 distils a large amount of EDC, but it
has a very low temperature dierence between the top and the bottom, because in the residue
the heavy impurities are very diluted in the main component. The steam consumption of the
other columns of this section are rather small: the columns T305 and T4200 are indeed used for
separating light impurities and T401 is a nal concentration column that, moreover, is heated
with the sensible heat of the condense of all the plant. All the separated impurities are sent to
disposal treatments.
In the previous process all the heat was supplied as steam, except the furnace, where fuel gas
was burnt. The total steam consumption was about 1.65 kg/kg of VCM produced.
The operating conditions of the columns are reported in the following Table 1.

Modied technology
The feed to the VCM distillation section (Fig. 5) can be assumed as a ternary mixture:
according to the proposed method, the modications were studied to get the scheme as similar
as possible to the simplied tree-like arrangement described in Section 1.2.3, taking into account
the two main constraints: the upper limit of distillation temperature of 420425 K, and the exist-
ing equipment to be utilised for the new process.
As for the EDC distillation section, any improvement of the sequence was not advantageous;
indeed the purication columns T305 and T4200 have little steam consumption (being stripping
columns) and modications were not attractive; the arrangement of T4400 and T401, chosen in
the past due to the low thermal stability of the chlorinated products, was already favourable for
the insertion of T4400 in a heat cascade.
In the previous scheme the quench of the reacted gases was performed in two oversized col-
umns, D5300 and D5320 operating in parallel, and the reux was obtained by cooling the over-
head vapours to the ambient temperature. In the new ow sheet the two columns are arranged
in series: the rst column (T5300) carries out the quench, and some heat is available at a tem-
perature over 420 K; the second one (D5320) works as a pre-fractionate for the separation of
the components of the ternary mixture HClVCMEDC; each column has its reux and heat is
available at two temperature levels. Since the height of both the existing columns, D5300 and
D5320, was not sucient for locating a stripping section some HCl, in the residue, and some
EDC, in the distillate, are present. As shown later, such dierences from the ideal design have a
minor inuence on the process.
The distillate from 5320, after cooling, goes to the HClVCM binary distillation, which is car-
ried out in the new column T5602, having a relatively small diameter (1.2 m at the top and

Table 1. Operating conditions of the columns with the previous technology

Column number T5400 T5500 T305 T4200 T4400 T401
Temperature (K)
Top 243 308 333 348 363 328
Bottom 353 423 373 363 378 363
Pressure (bar) 7.5 6 1.3 1.2 1.3 0.2
Duty (steam kg/VCM kg) 0.24 0.56 0.192 0.184 0.480
1860 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS

Fig. 5. Flow sheet of the modied VCM process.

1.3 m at the bottom); the distillation is performed with a reux of liquid HCl: the EDC recycle
has been eliminated; the distillate HCl is held in vapour phase; to avoid the replacement of the
existing refrigeration unit, a new compressor, working on the vapour feed, has been installed.
The pressure of the reaction section is still 7.5 bar and that of the HClVCM column is 12 bar.
The bottom temperature of T5602 is about 343 K and the relevant reboiler works with part
of the heat available at the top of the column T4400.
The HCl distillate from the column T5602 is pure and the VCM, from the bottom, is free of
HCl; since the VCM is obtained as a residue, it is necessary to perform a purication from any
heavy products; the existing T5500 is utilised for this purpose. In the previous arrangement this
column was used to distillate a feed containing a large amount of EDC; in the new scheme it is
used as a purication column, having as a residue heavy byproducts, diluted in EDC and VCM.
Actually the main impurity is the EDC, which was absent in the previous scheme, and now is
present in the distillate of the prefractionate. The column T5500 still uses sea water as a cooling
agent; the bottom temperature is now 343 K and the reboiler uses the heat available at the top
of T4400. The purity of the VCM obtained is signicantly improved due to the lower content of
EDC in feed.
The streams from the bottom of the prefractionator D5320, that contains a small amount of
VCM and HCl, and from the bottom of T5500 are distilled in the T5400 column, previously
used to distil HCl, obtaining EDC as the residue. The distillate of T5400 (a relatively small
stream containing HCl and VCM and some EDC) is recycled to D5320. The reboiler of T5400
is heated by steam and the condenser of the column is an air cooler. It is important to point out
that, in order to get high purity VCM, the reux of the T5400 column has to be evaluated on
the basis of the most volatile byproduct, that is on the component more dicult to separate
from VCM.
In Fig. 6 a comparison between the new arrangement of the VCM distillation section and the
tree-like simplied ow sheet, shown in Fig. 2(e), is reported. It has to be pointed out that, in
the new design, the stripping section of the column T5400 plays both the role of the stripping
 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS 1861

Fig. 6. Simplied tree-like distillation column arrangements compared to VCM distillation after modi-
cation.

section of the prefractionator (AC) and of the binary column (BC). Since the product VCM
must be obtained as a distillate an ideal prefractionator is not substantial.
The reboiler of T4400 receives the heat made available at high temperature in the quench sec-
tion.
The two columns T5400 and T5500 in the new arrangement are largely oversized and some
modications of the trays has been necessary.
The operating conditions of the columns in a test run performed after the plant modication
in March 1993 are reported in the following Table 2. The specic consumption of steam in the
test run (performed at half of the nominal capacity) was about 0.8 kg/kg of product against a
value of 0.6 of the design. The electricity consumption remains substantially unchanged due to
the more rational arrangement of the refrigeration.
The steam needs of T305 and T4200 are practically unchanged; the duty for T5400 is signi-
cantly lowered; for T4400 and T5602 the steam needs are reduced to a small amount, practically
only for the control. According to the design the heat needs of T401 should be fullled by reco-
vering the sensible heat from the condense of all the columns: indeed, due to fouling problems
in the reboiler of T4400, now the column is heated by steam, with a small increase in the exergy
consumption.

Project development
The project started in 1988, when a ow sheet very similar to that described in the previous
paragraph was proposed. In the following the ow sheet was developed into a process design by
the aid of computer simulations that conrmed the validity of the approach and allowed the
evaluation of all the parameters of the process.
The process design has then been submitted to a committee of experts in the VCM technology
in order to identify the possible weak points: behaviour of impurities, fouling of heat exchan-
gers, corrosion due to any possible presence of traces of water, that has high deviation from ide-
ality in mixture with the main components. For each point suitable solutions have been
identied and suggested.

Table 2. Modied technology; operating conditions of the columns

Column number T5602 T5400 T5500 T305 T4200 T4400 T401
Temperature (K)
Top 246 308 308 353 360 367 320
Bottom 343 423 343 373 366 375 350
Pressure (bar) 12 7.5 5 1.3 1.3 1.2 0.2
Duty (steam kg/VCM kg) 0. 0.12 0. 0.127 0.193 0.0475 0.312
1862 BRUZZI et al.: ENERGY SAVINGS IN CHEMICAL PLANTS

The process modication required only one new column, a new compressor and some new
heat exchangers.
The main problems found during engineering were mainly due to the unfavourable location
of the points to be thermally connected; reboilers with liquid circulation were adopted.
The revamping of the process, including the previously described modication, was realised in
1992 with a grant from the EEC (Energy General Direction; contr. EE 194/88/1 T); the test run
were performed in March 1993, substantially conrming the design data. Some of the engineer-
ing adopted solutions need adjustments (for instance the circulation in the reboiler of T4400)
and they are planned for beginning of next year.

CONCLUSION
By applying a process design procedure based on fundamentals of thermodynamics, that take
into account the minimisation of the entropy generation, or the minimisation of exergy con-
sumption, it has been possible to reduce the steam consumption of the VCM process from 1.65
kg/kg of VCM to 0.8 kg/kg of VCM, against a theoretically estimated value of 0.6.

AcknowledgementsThe process was developed with the contribution of V. Guerrini, and the start-up was performed
with the participation of F. Piga.

REFERENCES
1. Benedict, M., Trans. Am. Inst. Chem. Eng., 1947, 43, 41.
2. King, G. J., Separation Processes, McGraw-Hill, 1971.
3. Bruzzi, V. and Zanderighi, L., Entropie, 1983, 109, 79.
4. Treybal, R. E., Mass Transfer Operations, McGraw-Hill Co, N.Y., 1968.
5. Petlijuk, F. B., Platonov, V. M. and Slavinskij, D. M., Int. Chem. Eng., 1965, 5, 555.