Applied ~/wwna/ En@wing Vol. 17. Nos. 8-10, pp. 879-888.

I997
c: European Communities 1997. Published by Elsevier Science Ltd
Pergamon Prmted in Great Britain
PII: S1359-4311(96)00075-O 1359-4311!97 Sl7.00 + 0.00

IMPROVED PROCEDURES FOR SEPARATING CRYSTALS

FROM THE MELT

D. Verdoes,* G. J. Arkenbout,* 0. S. L. Bruinsma,? P. G. Koutsoukos% and

J. Ulrichg
*TN0 Institute of Environmental Sciences, Energy Technology and Process Innovation, P.O. Box
342. 7300 AH. Apeldoorn, The Netherlands, tDelft University of Technology, Laboratory for
Process Equipment, Leeghwaterstraat 44, 2626 CA, Delft. The Netherlands, ZUniversity of Patras,
Institute of Chemical Engineering and High Temperature Processes, P.O. Box 1414, 26500, Patras.
Greece and 4University of Bremen, Abteilung Verfahrenstechnik:FB4, P.O. Box 330440, D-28334.
Bremen. Germany

Abstract-Innovative separation techniques like melt crystallization have the potential to fulfil two
important demands. namely: a significant reduction of energy consumption by the chemical industry. and
the production of high quality products required by industry. Several industrial applications of melt
crystallization have been realized but industry is still hesitating to fully commit its resources. One of the
most important reasons is that the most promising application of melt crystallization, the
suspension-based melt crystallization process, is still under development. For this reason this study had
the objective to improve equipment design and to establish optimal process conditions for the separation
of crystals from the melt, this being the essential step in crystallization from suspension. The ultimate aim
of the study was to test a pilot-plant for the application of melt crystalliration to an industrial problem.
In this paper, background information on melt crystallization processes and possible solid-liquid
separation techniques will be given. The content of the study is briefly discussed and experimental results
are given. JT# European Communities 1997. Published by Elsevier Science Ltd.

Keywords-Melt crystallization. energy saving. TNO-Thijssen wash column. purification. organic bulk
chemicals.

INTRODUCTION

Crystallization of organic materials from the melt is a separation technique enabling the
purification of chemicals at the cost of relatively low energy consumption compared to
conventional separation techniques like distillation. The separation potential of melt
crystallization is very high, due to the selectivity by which growth units are built into a crystal
lattice; in principle, a very pure product can be obtained in only one step. Consequently, the
energy requirement of melt crystallization is low because the large separation effect results in a
limited requirement for reflux. Moreover, the heat of transition in crystallization is 2-4 times less
than in distillation. Furthermore, azeotropic compositions containing water have to be overcome
in the distillation of several bulk chemicals of commercial interest by applying an entrainment
agent like di-isopropylether. This makes separation by distillation even more energy-intense.
Melt crystallization has advantages compared to crystallization from solution because no
solvent regeneration is required; hence energy consumption and environmental impact are
minimized.
In the chemical industry there is an increasing demand on purer products. This holds for fine
chemicals and pharmaceuticals, as well as for bulk chemicals, especially those that serve as basic
materials for polymers. Properties of polymers depend largely on the mean chain length of the
molecules, which can only be properly controlled when very pure reactants are used. The possibility
of upgrading bulk organic chemicals by melt crystallization has already been indicated for about
2.5 compounds, like acrylic acid, phenol and caprolactam, corresponding to a world capacity of
about 30 millions tons per year. The possibility of upgrading fine chemicals by melt crystallization
has already been demonstrated for more than 200 compounds on a laboratory scale using the zone
melting technique.

879
880 D. Verdoes ef nl.

heat melt

solid
layer
Fig. I. Principle of layer-based melt crystallization processes.

In those cases where a single-stage operation can yield the required separation duty, melt
crystallization is considered as an alternative for distillation [l]. A study performed by TN0 for
the Dutch situation indicated that in the case of caprolactam, phenol and dimethylterephtalate,
energy savings of 0.57, 2.35 and 4.64 GJ/ton respectively, or 50, 63 and 96%, respectively,
reductions of the present energy consumption are feasible when applying melt crystallization [2].
It can thus be concluded that innovative separation techniques like melt crystallization have the
potential to fulfil two important demands, namely: a significant reduction of energy consumption
by the chemical industry, and the production of high quality products required by industry. Several
industrial applications of melt crystallization have been realized but industry is still hesitating to
fully commit its resources. One of the most important reasons is that the most promising
application of melt crystallization, the suspension-based melt crystallization process, is still under
development. For this reason this study had the objective to improve equipment design and to
establish optimal process conditions for the separation of crystals from the melt, this being the
essential step in crystallization from suspension. The ultimate aim of the study was to test a
pilot-plant for the application of melt crystallization to an industrial problem. The study was
carried out by TN0 (The Netherlands) and the Universities of Delft (The Netherlands), Bremen
(Germany) and Patras (Greece). In this paper, background information on melt crystallization
processes and possible solid-liquid separation techniques will be given. A review on melt
crystallization processes is given in refs [3] and [4]. The content of the study is briefly discussed and
experimental results are given.

CONCEPTS FOR MELT CRYSTALLIZATION PROCESSES

Two essentially different concepts of melt crystallization process options can be distinguished.
The solid material can either be grown as a layer on a cooled wall or as crystals in suspension.
The principles of layer-based and suspension-based processes are presented in Figs 1 and 2,
respectively. The production rate of melt crystallization processes is mainly dependent on two

. . crystal
growth

suspension

‘\ . . . .. . .. . . separation/
‘\ puriication
‘\
‘\
‘\
‘\ product
i (liquid)
1 residue
t (remaining liquid)
Fig. 2. Principle of suspension-based melt crystallization processes.
 Improved separation of crystals from the melt 881

Table 1. Energy requirement (expressed in kJ primary energy per kg product) for layer-based and suspension-based melt crystallization
processes

Layer growth Layer growth Suspension growth

Compound (without washing) (with washing) Suspension growth (with heat pumps)

Naphthalene 2285 kJ/kg 1505 kJ/kg 514 kJ/kg 301 kJ/kg

Caprolactam 3821 kJ/kg 3517 kJ/ka 890 kJ/kg 492 kJ/kg

parameters: the surface area SA on which crystallization occurs and the growth rate G of the solid
phase. The layer-based option is characterized by a relatively low X4 (100 m2/m3) of the cooled
wall and relatively high G ( + 10 - 6-10 - 5 m/s). The total SA of crystals in suspension can measure
up to 10 000 ml/m’, implying that a relatively low G can be applied ( f 10-8-10-7 m/s) [4, 61. It
was shown that incorporation of impurities in the solid phase increases substantially with increasing
G [5]. Consequently, upgrading of the product requires more melting-crystallization cycles when
a high G is applied, which for economic reasons cannot be avoided in layer-based processes. This
affects the energy benefits of melt crystallization, as can be illustrated by the calculated energy
requirements of technical installations which were based on measured experimental data [5]. The
imaginary installations had a production capacity of 1000 kg/h, in which a 99 wt% feed of
caprolactam or naphthalene was purified to a 99.99 wt% product with a recovery of 91%. Table 1
gives the results of the calculations for the two types of melt crystallization processes.
Table 1 shows that the limitations with respect to energy requirement for layer growth processes
counterbalance the advantages of simplicity, easy scale-up and the absence of a separate solid/liquid
separation step for this technology, which is already applied in industry [4,7]. Suspension-based
processes are more promising from the energy point of view because large separation efficiencies
can be obtained in single-step operations. Significant reductions of the energy requirement of,
respectively, layer- and suspension-based processes seem possible by additional washing of the layer
and the application of heat pumps (see Table 1).
For the utilization of the energy-saving and purification potentials of suspension-based processes,
the complete separation of pure crystals from impure mother liquor is the essential step. Therefore,
the study focused on the development of a highly efficient solid-liquid separation technology in
suspension-based melt crystallization processes.

SOLID-LIQUID SEPARATION IN SUSPENSION-BASED PROCESSES

Solid-liquid (S-L) separation and washing of the product is important in suspension-based

processes because the impurities present in the adhering mother liquid contaminate the product.
In conventional devices, like filters and centrifuges, part of the impure mother liquor will remain
adhered to the crystal surface after the S-L separation and washing of the filter cake with pure
product usually leads to a number of practical problems. Thus the ideal separation device combines
S-L separation and washing in one apparatus. Wash columns fulfil this requirement.
Several types of wash column, differing in the transport mechanism of the crystal bed, have been
developed in the past. In forced transport wash columns, which are characterized by the formation
of a densely packed bed of crystals with a porosity of I 0.45, transport of the bed is forced by
pressure or mechanical means. In the scope of this study, a TNO-Thijssen hydraulic wash column
in which the bed was transported by means of hydraulic pressure was used. In gravity wash
columns, with relatively loosely packed beds with a porosity between 0.45 and 0.65, the crystals
were transported by gravity. Both types were operated continuously and pure melt was applied

Table 2. Characteristic parameters for gravity and forced-transport wash columns

Forced transport column Gravity column

Maxlmum capacity About 5000 kg/m’.h 1000-1500 kg/m’.h

Residence time of the crystals in the column < 10 min Many hours
Purification mechamsm Countercurrent washing Washing, sweating and (maybe) recrystallization
Loss of wash liquid No loss Considerable
Required crystal size 100-200 pm 500 pm
Maximum AT of feed and product < 15 c Probably 15-20 C
Compressible stress on crystal bed 0.5-10 bdr Negligible
882 D. Verdoes et al.

as washing liquid. Characteristic parameters for gravity and forced transport wash columns are
compared in Table 2.
The strong points of the forced transport wash columns are their relatively high capacities, the
compact equipment, the efficient washing process with no loss of washing liquid and the relatively
small required size of the crystals; disadvantages are the absence of extra purification mechanisms,
the limited allowable temperature difference between the feed and the product and the relatively
large compressive stress on the crystal bed. A feasibility study for the application of
suspension-based melt crystallization processes in combination with a hydraulic wash column for
10 organic chemicals is presented in ref. [8].
The advantages of a gravity wash column are that the long residence time of the crystals may
result in extra purification mechanisms, the somewhat larger temperature difference between feed
suspension and product [6], and the low compressive stress, which will be an advantage in the
processing of mechanically weak crystals. An important weak point of the gravity wash column
is the requirement of relatively large crystals, which implies that relatively large crystallizers will
be needed to grow crystals with the required dimensions. Other disadvantages are its relatively low
capacity, the loss of washing liquid and the relatively large size of the equipment.
In this study basic knowledge for both gravity and hydraulic columns were gathered in order
to obtain a better understanding of the phenomena governing the performance of both types of
column.

CONTENT OF THE STUDY

The study focused on further development of wash column technology for application in the area
of organic bulk chemicals. Caprolactam and phenol were selected as test systems of commercial
interest.
The applicability of a wash column as a S-L separation device coupled to a suspension
crystallizer does not only depend on the operational limits of the column but also on the size, shape
and size distribution of the crystals in the feed suspension. These parameters affect the permeability
of the crystal bed for the washing liquid and the mother liquor. In most cases a high permeability
will be preferred. The permeability increases with increasing crystal size and when the size
distribution is relatively narrow. The optimal shape is symmetrical in three dimensions (spherical
or cubic). ‘One-dimensional’ (needles) or ‘two-dimensional’ (plates) crystals can lead to a very
densely packed bed with a poor permeability.
In the first phase of the study data were collected which were necessary for testing a pilot-plant
for an industrial problem during the second phase. Two main tasks could be distinguished in the
first phase. The first task involved optimization of the quality of the feed suspension by
investigation of: upgrading the crystal size in a fluidized bed crystallizer; the effect of washing and
sweating on the purity of crystals; effects of operational parameters of a continuous suspension
crystallizer on the size, shape, size distribution and purity of the crystals; and agglomeration, which
is expected to affect the bed properties and the purification capacity. The second task was the
determination of the effects of operational parameters on the performance of wash columns. In
a gravity wash column, the operation is strongly dependent on the settling velocity of the crystals
which is mainly influenced by the crystallizer and the physical properties of the melt. In fact, the
only parameter of the gravity wash column which can be varied freely in a broad range is the reflux
ratio of the washing liquid, which will influence the production capacity and the purity of the
product.
The operation of a hydraulic wash column is more complicated because there are many
operational parameters which can influence each other. In contrast, however, it increases the
flexibility of the hydraulic wash column, where bed transport is realized by hydraulic pressure which
can be adjusted by means of the filtrate recycle loop. A diagram of the TNO-Thijssen hydraulic
wash column is shown in Fig. 3. Three regions can be distinguished during steady-state operation.
The first region, at the top of the column, contained the suspension as it left the crystallizer. In
the central zone, a packed crystal bed was formed due to the removal of mother liquor through
the filters. At the bottom of the column, a rotating knife scraped off the descending crystal bed.
The crystals were removed from the reslurry chamber underneath the knife and were subsequently
 Improved separation of crystals from the melt 883

--------WASH FRONT

r-Tk”CT

Fig. 3. Principle of TNO-Thijssen hydraulic wash column.

molten. The main part of this melt was removed as product and a minor part was sent back to
the reslurry loop. The pressure in the reslurry loop, which can be controlled with the product
control valve, caused part of the melt to re-enter the column in order to wash the crystal bed
countercurrently. The wash liquid freezed on the crystals because the feed crystals were colder than
the recycled melt. The wash liquid flow was controlled in such a way that freezing of the wash
liquid was completed before reaching the filters. In this way, no valuable product was lost and
clogging of the filters due to incrustation was prevented. A boundary becomes visible at the position
that the wash liquid was entirely frozen: the so-called wash front. The zone between the wash front
and the rotating knife was the third region, which was almost, or completely, free of impurities
due to the countercurrent washing and recrystallization of the wash liquid. The general control
strategy for hydraulic packed bed wash columns is described in refs [3, 6, 8, 91.
In the first phase of the study, the technical feasibility of a wash column as an efficient S-L
separation and washing device was tested. The operational limits of a hydraulic wash column were
investigated as a function of parameters like the habit of the crystals, the production capacity, the
wash front position, the height of the bed at the feed side, the pressure and the wash liquid flow
rate. As mentioned before, these parameters can influence each other mutually. At the end of the
first phase, general design criteria were derived for both the gravity and the hydraulic wash column,
based on the gathered experimental data.
During the second phase of the study, a pilot-plant for the application of suspension-based melt
crystallization and wash column technology to an industrial problem was tested. During this phase,
optimization of the wash column operation was carried out. The outcome of tasks which were
carried out in this study are highlighted in Section 5.

HIGHLIGHTS OF EXPERIMENTAL RESULTS

A fluidized bed crystallizer was built and tested successfully for the system caprolactam/water
using seed crystals of about 2 mm, obtained by cleaving raw caprolactam. It will be difficult to
develop a fluidized bed crystallizer for caprolactam/water with smaller seeds, e.g. originating from
a suspension crystallizer, due to the relatively high viscosity of the melt and the small difference
in density between crystals and melt. Growth rates between 10-h and lo-’ m/s, which is much
higher than in normal suspension crystallizers, were measured for melts containing 1.555 wt%
water. The purity of the unwashed crystals was dependent on the water concentration in the melt
but not on the growth rate. Values between 0.1 and 0.3 were found for the distribution coefficient
k,, which gives the ratio between the impurity concentrations in the mother liquor and the product.
The impurity content in the separated crystals could be reduced by about 50% using purification
techniques like washing and sweating.
Experiments were carried out in a 3-l laboratory-scale continuous suspension crystallizer in order
to study the effect of the residence time 5 and the suspension density M,, on the product. The crystal
884 D. Verdoes et al.

size of caprolactam increased with decreasing impurity concentration, increasing r and decreasing
MS,.An acceptable mass-based mean crystal size & between 700 and 1200 pm was obtained in all
cases. The phenol crystal size was hardly affected by z and MS,. An increase of the impurity
concentration from 1 to 10 wt% resulted in a reduction of d4, from 600 to 500 pm. The product
crystal sizes for caprolactam and phenol seemed suitable for application of a hydraulic wash
column. A larger crystal size is required for caprolactam since the viscosity of caprolactam melts
is much higher than for phenol.
The effects of two surfactants and the impurities aniline and nitrobenzene on the crystallization
for the system caprolactam/lO wt% water were studied. The size and purity of the crystals
decreased with increasing cooling rates. The presence of aniline, nitrobenzene and the surfactants
resulted in broader metastable zone widths, slower crystallization rates and larger crystals. Water
and an anionic surfactant stimulated the agglomeration of caprolactam, while aniline, nitrobenzene
and a cationic surfactant reduced agglomeration.
The tests of a pilot-plant-scale gravity wash column for caprolactam/water were not possible
since the settling velocity of the crystals was too low, due to the combination of a relatively small
crystal size and the relatively high viscosity of the melt. The design criteria and strategy for a gravity
wash column were reported. A technico-economic evaluation was carried out for the purification
of naphthalene from the solid-solution-forming mixture with thionaphthene using the developed
design strategy. The design of a plant for producing 20 000 ton/year naphthalene indicated that
thionaphthene can be reduced from 2.5 to 0.2 wt% with a reflux of 0.28 in a column 7.2 m high
at a naphthalene yield of 80%. This design will be checked by means of laboratory-scale
experiments.
A TN0 pilot plant, consisting of a 70-l continuous crystallizer coupled to a hydraulic wash
column, was used to demonstrate the technical feasibility of wash column operation. The optimal
crystallization conditions were derived from the 3-1continuous crystallization experiments. The size
and shape of the crystals in the 3-l and 70-l crystallizers were equal, showing that scaling-up from
laboratory to pilot-plant scale is possible. It was also possible to maintain a stable, but relatively
low, wash front of l-2 cm during a period of 5 h for the industrial phenol feed with 10 wt%
impurities. The purification efficiency of the wash column was compared with that of a
thermostated centrifuge using the analyses of six different impurities in samples of the product,
mother liquor and feed. The results of these analyses are given in Table 3, together with the
distribution coefficient k,,, which is equal to the ratio of the impurity concentration in the product
and the mother liquor. The lower the kd, the better is the removal of the impurity. The mother
liquor seems to contain less than 10 wt% impurities but this is caused by the fact that not all
impurities were analyzed.
Table 3 reveals that k, for impurities A-D is significantly lower than for impurities E and F for
both devices. The countercurrent washing in the wash column is especially effective for impurities
A-D, which show a eutectic behaviour. The measured k,, values of about 0.01 are typical for eutectic
impurities after crystal-melt separation in a hydraulic wash column. The removal of impurities
A-D in the wash column is remarkably good, despite the fact that the wash front was lower than
the minimum level of 2.5 cm required for maximum removal of eutectic impurities, that was found
in computer simulations [lo]. The superior separation efficiency of the wash column is less
pronounced for impurities E and F, due to the partial incorporation of these impurities in the
crystals by the formation of a solid solution. The applied centrifuge is probably not representative

Table 3. Impurity concentrations in mother liquor (ML) and product (P) of a hydraulic wash column and a centrifuge and the distribution
coefficient kl after experiments with the 70 litre crystallizer and an industrial feed containing 90 wt% phenol
Wash column Centrifuge

Impurity [Impurity] ML (wt%) [Impurity] P (wt%) kd [Impurity] ML (wt%) [Impurity] P (wt%) kd

A I .7067 0.0291 0.0170 I .5500 0.1663 0.1073
B 0.0200 0.0001 0.0036 0.0200 0.0020 0.1000
C 0.7100 0.0040 0.0057 0.6250 0.0575 0.0920
D 0.0847 0.0007 0.0080 0.0850 0.0055 0.0647
E 0.0950 0.0254 0.2675 0.0975 0.0333 0.3410
F 0.0157 0.0026 0.1641 0.0175 0.0033 0.1857
Total 2.6320 0.0618 0.0235 2.3950 0.2678 0.1118
 Improved separation of crystals from the melt 885

~feedmixture ’
0 mother liquor

- .+
4 ,_____
I I I /
-__----
/

0 3 6 9 12 15 16
Time after start-up (hours) -
Fig. 4. AZg,,,corresponding with the total concentration of aniline and nitrobenzene, for feed, mother
liquor and product samples from an experiment with the feed caprolactam/l wt% water/50 ppm
aniline/50 ppm nitrobenzene.

of large-scale industrial centrifuges, because the obtained k,s of 0.05-o. 1 are much lower than that
for many other centrifuges, where k, typically lies between 0.15 and 0.3. The above results indicate
that the separation of a 99 wt% phenol feed with a crystallizer and a wash column in a 99.9 wt%
product and a 90 wt% mother liquor is feasible. The recovery in this process is satisfactory
( t_ 91%). It is concluded that the separation efficiency of a hydraulic wash column is superior to
that of a centrifuge, especially for eutectic but also for solid-solution-forming impurities.
Caprolactam/water is a difficult system for wash columns due to the relatively high viscosity of
the melt. Nevertheless, a stable wash colunin operation was demonstrated for a period of 20 h for
a caprolactam feed with a 1 wt% water and 50 ppm aniline and nitrobenzene as impurities. The
product purity can be estimated because aniline and nitrobenzene can be detected using a UV
spectrophotometer. Figure 4 presents the absorbance at 290 nm (Azso), corresponding with the total
concentration of aniline and nitrobenzene, for the feed, mother liquor and product. It is shown
that the product purity increases with increasing running time and reaches a constant A?,,, level
15 h after start-up of the column. The A 190level of the final wash column product was even a little
lower than A?,, for a reference sample made from the raw caprolactam used for preparation of
the feed. This indicates that very pure caprolactam, maybe even purer than the original
caprolactam, has been produced. The fact that A190 for the mother liquor is higher than that of
the feed, indicating that the impurities are indeed concentrated in the mother liquor, confirms the
attained purification action.
The last phase of the study consisted of a production run using a 70-l continuous crystallizer
and an 8-cm diameter TNO-Thijssen hydraulic wash column with an industrial caprolactam feed.
The objectives of the production run were: to test the reliability of the operation of the suspension
crystallizer and the hydraulic wash column for a period of about 100 h; to prove that the separation
target, of splitting up the 99.9 wt% feed into a 99.99 wt% product and a 99.0 wt% residue, can
be satisfied; and to obtain the basic mass- and energy-balances for the design of a larger-scale plant.
The caprolactam recovery in the production run was about 91%.
Preliminary closed circuit experiments, which imply total recirculation of the product and mother
liquor streams to the feed of the crystallizer, revealed that the maximum production capacity of
the 8-cm wash column was at least 15 l/h, which corresponds with 3.25 tonnes per hour for a 1 m’
column. The conditions in the wash column indicated that higher capacities seemed possible but
this could not be proven due to limitations in the production capacity of the crystallizer. Analyses
of samples from the closed-circuit experiments indicated that the purification efficiency of the
crystallization-wash column process was more than sufficient to pass important quality tests on
water content and UV absorption at 290 nm for commercial-grade caprolactam.
A stable operation of the crystallization-wash column process was demonstrated without any
problem for a period of 100 h during the production run with the industrial feed. In the run, 1160 1
of the industrial feed was separated into 1055 1 of product and 10.5 1 of mother liquor. The
886 D. Verdoes et al.

purification efficiency in the production run will be determined on the basis of the analyses of the
feed, mother liquor and product samples. The results of the analyses are not available yet, but the
analyses of the samples from the preliminary closed-circuit experiments indicate that the separation
target will be satisfied.
A design for a melt crystallization-wash column process with a production capacity of 1 tonne
per hour was made on the basis of the data from the production run with the industrial feed. The
flow sheet for this imaginary installation is given in Fig. 5. The flow sheet was developed by
scaling-up the pilot installation consisting of a single suspension crystallizer and a single hydraulic
wash column, which is the same configuration as in the production run. The energy balance for
the flow sheet in Fig. 5 was set up by determination of the energy uptake by the pumps, motors,
tracing and heat exchangers. The difference in the energy efficiencies of electricity and steam were
taken into account by a conversion into primary energy. The assumed yields of electricity and steam
from primary energy were 38 and 85%, respectively. The total energy consumption for the flow
sheet, which is equal to the sum of the energy use of the pumps, motors and exchangers El-E3,
was calculated to be 154.1 kW primary energy. The capacity of the installation was 1 tonne
caprolactam per hour, which results in a specific energy consumption of 555 kJ/kg caprolactam
product with a purity of 99.99 wt%. It must be mentioned that the above energy balance was based
on the production run, which probably is not the most optimal situation from an energy point of
view, e.g. it is expected that an increase of the slurry density in the crystallizer and the application
of heat pumps can further improve energy efficiency. The slurry density in the production run was
about 13%, while it is expected that a slurry density of about 25% will be feasible in industrial
applications.
An increase of the slurry density in the crystallizer will reduce the flow through pump Pl and
the flow of the filtrate recycle to the crystallizer and thus of the energy use in exchanger E2.
Another, probably even more important, factor for energy efficiency is that the crystallization and
wash column process is very suitable for heat integration. The calculations revealed that about 30%
of the total energy consumption originates from melter El in the melting circuit of the wash
column. The heat withdrawn from the crystallizer by exchanger E4 is of the same order of
magnitude, while the temperature at which the heat is withdrawn in the crystallizer and the
temperature at which heat is needed to melt the crystals in melter El are relatively close. In such
a situation, a heat pump can be applied to integrate the cooling of the crystallizer with the melter
of the wash column. For comparable cases presented-in Table 1 it was shown that the total energy
consumption of a crystallization-wash column process could be reduced by 2045% with the
application of a heat pump [5]. It is therefore also very interesting to consider the use of heat pumps

. ,

mother
liquor

-
v1
I I Pl Ill P2
P6

T 8 .
1.
El
M2 0
product

I 1
P3

Fig. 5. Flow sheet for a suspension-based melt crystallization-hydraulic wash column process for a
capacity of I tonne purified product per hour. The scale-up is based on experimental data from the
production run with the industrial feed.
 Improved separation of crystals from the melt 887

in large-scale industrial installations where caprolactam is purified in a crystallization-wash column

process.
The standard purification technique for caprolactam in industry is distillation. Scraped thin-film
evaporators are used for the final distillation step in the conventional caprolactam separation train.
The energy use for this last distillation step was estimated to be 1254 kJ primary energy per kg
purified caprolactam by summing the energy use of pumps (16 kJ/kg), motors (116 kJ/kg) and the
reboiler/tracing (1122 kJ/kg). By comparing the energy used for distillation (1254 kJ/kg) and melt
crystallization (555 kJ/kg), it is revealed that the energy-saving potential of melt crystallization is
proven for the specific separation problem investigated.

CONCLUSIONS

The application of suspension-based melt crystallization as a separation technique has the

potential to fulfil two important advantages, namely: (1) this technique can lead to a significant
reduction of the energy consumption by the chemical industry, and (2) a single-step crystallization
is usually suited for the production of very pure products, which can be applied as basic materials
for the production of polymers, fine chemicals and pharmaceuticals.
Suspension-based melt crystallization processes are more promising from an energy point of view
than layer-based melt crystallization processes because large separation efficiencies can be obtained
in a single-step suspension crystallization. Suspension-based processes are suited for a further
reduction of the energy requirements by the application of heat pumps. The limitations with respect
to the energy requirements for layer-based processes counterbalance the advantages of simplicity,
easy scale-up and the absence of a separate solid-liquid separation step for this proven technology.
The complete separation of the pure crystals from the impure mother liquor is the essential step
for utilization of the energy-saving and purification potentials of suspension-based processes. Wash
columns are potentially the ideal separation devices, because solid-liquid separation and
countercurrent washing with pure melt is combined into one apparatus. A strong point of the
TNO-Thijssen hydraulic wash column is that scaling-up to an industrial plant is rather
straightforward. The capacity of the column can be increased by increasing the diameter of the
column and the number of filter tubes in such a way that the filtration area per tube remains equal
to the f 50 cm’ per filter tube in the smaller-scale wash column that was tested in the study.
This pilot-scale production run with the industrial feed has proven that a suspension-based melt
crystallization and wash column technology can be applied successfully to an industrial separation
problem. The proven technical feasibility of applying a TNO-Thijssen hydraulic wash column for
the solid-liquid separation and purification of phenol and caprolactam is a step forward in the
direction of the industrial application of suspension-based melt crystallization processes. The
attained state of development is an invitation for a larger-scale demonstration/implementation in
industry, as most of the technical uncertainties related to the nature of the process have been
resolved. The scaling-up potentials of the technology are good but can only be proven in a real
demonstration.

il~knoI~,k~ngc~nzmrs-In addition to financing by the Commission of the European Communities the study was also
sponsored by Novem (The Netherlands), Enichem (Italy) and TN0 (The Netherlands).

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