Sulzer Chemtech

0699 2803, Originalfoto: BASF AG

Fractional Crystallization


Fractional Crystallization
Fractional Crystallization

Crystallization is one of the most powerful purification methods available in pro-

cess engineering. Fractional crystallization is a stagewise separation technique Melt
that relies upon liquid-solid phase transition and enables multicomponent mix- r ate
s

Temperature
a
tures to be split into narrow fractions, ultimately leading to top purities of selected A se
para B sep
components, through the virtue of selectivity found in solid liquid equilibria. Frac- A solid
tes B solid + melt
tional crystallization is most frequently encountered in the separation of organic + melt
materials ranging from isomer separations to tar chemical mixtures and from A + B solid
organic acids to monomers. A Eutectic composition B

Figure 2a: Immediate implications that arise

from the eutectic phase diagram are that a
Fractional Crystallization single stage crystallization produces a pure
published equilibrium data, extensive crystalline component and that the yield is
from Melts from Solvents laboratory and pilot testing are prere- limited by the eutectic point.

Higher operating Lower operating quisites for successful process design.

Feed
temperature temperature The majority of binary and multicom-
Good selectivity Improved selectivity ponent systems form eutectics which Melt
theoretically allow crystallization of a melt + s
olid
Temperature

Higher viscosity Reduced viscosity

Moderate growth rate Enhanced growth rate
Compact equipment Larger equipment
No solvent recovery Solvent recovery
required
Figure 1: The influence of the liquid phase
structure on crystallization.
Liquid Phase Structure
Crystallization can be performed both
from melts and from solutions. The
addition of solvents generally reduces
the operating temperature and incre-
ases the selectivity of purification. The
presence of solvents leads to reduced
specific pure component in a single
step (Figure 2a). Even where solid
solutions occur (Figure 2b), separati-
on factors are often higher than those
attainable by distillation.
The phase diagrams clearly demon-
strate that pure A and pure B crystals
can in principle be obtained over a range
of temperatures and concentrations as
indicated by the corresponding free-
zing point curves. It is further evident
that any mother liquor, coexisting with
any species being crystallized, must
be less pure than the crystals them-
selves. In such cases, the crystalline
Solid
A Melt Solid B
Figure 2b: When both solids are completely
soluble in one another the system is said to
constitute a simple series of solid solutions.
Liquid and solid coexist in equilibrium in the
region between the freezing point curve and
the melting point curve, and it is within this
region that phase separation is effected.
p - NCB
m - NCB Product 0
0
0

viscosity and, in some cases, modifies

Temperature ( oC)

0
phase is covered by impure mother 0
crystal habit. On the other hand, the liquor which should be removed in or-
Feed
0
absence of a solvent involves smaller der to secure purity. For this reason 0

equipment volumes and does not re- the removal of residual mother liquor 0 0
0
quire additional equipment to recover 0
C B (% )

in order to secure a pure product is an 0 -0

the solvent. important operation both in large scale
0
Residue -0
tion o- N

0
00
plants and in the laboratory. 0
0
0
Phase Equilibria Melt crystallization does not require a
0
0
0
(%)
0
tra

0
Solid liquid phase equilibria are shown solvent. The feedstock is heated until 0 0 NCB
C oncen

0 0 p-
0 tion
in phase diagrams and classified as molten, and the melt is then cooled un- 00
0
0
cen
tra
eutectic or solid solutions. In multi- til partially frozen. Figure 3 shows how o - NCB C on
component systems many combina- the para isomer can be crystallized out Figure 3: Phase diagram of
tions of eutectic and solid solution be- of a molten mixture of nitrochloroben- Nitrochlorobenzene. Separation of the para
haviour are known. In the absence of zene isomers. isomer is shown.


Crystallization Techniques

Industrial crystallization features generation of crystals by nucleation, crystal

growth and the recovery of crystals from residual mother liquor. Both generation
and recovery of crystals can be performed either from suspension or through a
crystal layer.

Crystal Melt Cooled wall Crystal layer Melt

Figure 4: Figure 5:
Suspension crystallization. Individual crystals Layer Crystallization. Crystal mass is frozen
are freely suspended in liquid. Crystallization onto the cooling surface. Crystallization
proceeds by cooling the liquid. proceeds by cooling the crystal mass.

Crystallization in Suspension Layer Crystallization Two different systems are generally

With this technique a melt or a solu-
tion is cooled below saturation tempe-
rature. Crystals grow under adiabatic
conditions with supersaturation as dri-
ving force being present throughout the
liquid phase. A very special knowhow
is required to secure crystal shape,
crystal size and crystal size distribution.
Since the product from suspension
crystallization is a slurry, the separa-
tion of residual mother liquor from large
specific surface area is usually carried
out in dedicated equipment.
Crystals are allowed to grow onto a
cooled surface (Figure 5). Crystals
grow in a non adiabatic environment
in such a way that subcooling is sup-
plied through the crystal layer rather
than through the liquid phase. The
driving force results from the net ef-
fect of temperature and concentration
gradients across both solid and liquid
phase. Under these conditions crystal
growth rate is 10 to 100 times faster
than in suspension crystallization.
used:
– Static Crystallization: crystals are
grown from a stagnant melt.
– Falling Film Crystallization: the li-
quid is moved in relation to the solid
surface.
Crystallization from a falling film is a
proprietary technology of Sulzer Chem-
tech Limited.


Falling Film Crystallization

Phase 1: Crystallization
A crystalline layer is grown from a falling film of melt on the inside of a tube
which is cooled externally by a cocurrent falling film of a HTM.

Phase 2: Partial melting (Sweating)

The tube wall is heated to induce partial melting (sweating); the molten material
is drained off.

Phase 3: Melting
The remaining crystal layer is molten and collected as (intermediate) product.

Figure 6: Phases of operation of the Falling Film Crystallization.

Figure 7 is a simplified flow diagram.

Crystallizer At the beginning of the first phase,
the collecting tank is filled with molten
Feed feed. Both product and HTM circul-
tion pumps are started, and a layer of
Heating
medium frozen product begins to form in the
crystallizer. Consequently, the liquid
Cooling level in the collecting tank falls. When
medium
Intermediate it reaches a preset value, freezing is
storage stopped and the collecting vessel is
vessels drained through the residue line to the
HTM battery limit or, in multistage operation,
conditioning unit to intermediate storage vessels.
In the sweating phase which follows,
HTM circulation warm HTM is circulated. Sweat frac-
pump tion is collected until a preset level is
reached in the collecting vessel. It is
then pumped back to the respective
Collecting tank
Melt circulation pump storage vessel.
Residue Product
Figure 7:
Basic flow diagram.


During the third phase, the remaining Feed
solid layer is melted into the collecting
vessel and then transferred to the pro-
duct storage or, in multistage opera-
tion, used for the subsequent purifica-
Product
tion step.

Any degree of purity can be obtained Stripping Feed Recti-

by using the intermediate product as stage stage fication
stage
feedstock and repeating the procedure. Residue

In a similar way, the residue drained

off in the first phase may be further Figure 8: Mass flows in a three-stage process.
depleted by additional melt/freezing
processes to give enhanced yield.

Figure 8 illustrates a three-stage pro-

cess. In industrial application, the
number of stages varies between one
and seven.

Note: Staging does not require multiple

crystallizers. The steps run in sequen-
ce in a single crystallizer.

Figure 9:
Small capacity plant (10 tons/year). Fully
automated plant to produce high purity
hydrazine used as propellant for satellites.
The plant has been built for the European
Space Agency. 0691 2804


The Falling Film Crystallizer

Melt inlet Figure 10 shows the key piece of

Melt
Distribution equipment in the process. Basically it
consists of a system of vertical tubes.
However, there is a special feature;
HTM neither the shell side nor the inside of
Distribution the tubes is filled with liquid. Falling
Cooling/Heating films are used instead. The product
medium flows down on the inside surface of the
HTM
Falling film
tubes, whereas the liquid used for coo-
ling and heating is distributed to wet the
external surface of the tubes. During
freezing (phase 1), cold HTM is used to
Melt
Falling film
chill the tubes. Partial melting (phase 2)
is in-duced by raising the temperature
of the HTM, and the final melting (pha-
se 3) is achieved by applying higher
temperatures. The distribution system
is designed to equalize flow through
Collecting vessel the tubes. Optimum performance is
achieved through accurate control of
the heating and cooling profiles.
Figure 10:
Falling film crystallizer. Melt outlet

Phase 1 Phase 2 Phase 3

Crystallization Partial melting Melting
(sweating)
Figure 11: Process phases.
Temperature

Phase 1

Phase 2

Phase 3

Time
Figure 12:
Temperature-time profile of the Falling Film
Stage 1 Stage 2 Stage 3 Crystallization.


 0690 2814-3

Figure 13:
Installation of a crystallizer in an existing
plant.

Figure 14:
0696 2803 Acrylic Acid plant at BASF Antwerpen.


Static Crystallization

Static melt crystallization is a very simple Cooling/Heating medium

process using cooled plates immersed
in stagnant melt (Figure 16). The free-
zing process is time-controlled.

Melt inlet

Collector

Melt outlet

Phase 1 Phase 2 Phase 3 Phase 4

Crystallization Draining Partial melting (sweating) Melting
Figure 15: Process phases.

Figure 16 shows how the HTM tem-

perature is lowered according to a
program which has been established
by pilot tests. After a crystal layer has
formed, the melt is drained off and
sweating is induced in a way similar to
Temperature

the falling film process. The sweated

fraction is removed and the remaining
crystal layer is melted and passed to a
storage tank.
Phase 1 Phase 2 Phase 3 Phase 4
Time
Figure 16: Temperature-time profile.


Figure 17:
Paraffin plant at SCHÜMANN SASOL, Germany (100´000 tons/year).

Technical data and dimensions

Type 1 2 3 4 5 6 7 8 9

Effective volume m 3 1.8 3.5 7.6 10.4 18 26.1 35 42 50

Lenght* mm 1‘910 2‘910 4‘210 4‘910 4‘910 8‘060 8‘060 9‘460 9‘460

Width* mm 1‘020 1‘160 1‘510 1‘710 2‘700 2‘400 3‘090 3‘130 3‘640

Height* mm 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570

Weight (empty) kg 3‘200 5

‘600 10‘300 13‘500 21‘000 30‘500 39‘000 46‘000 54‘000

Heat transfer
liquid flow rate m3/h 16 35 70 95 165 240 315 380 450

* Overall dimensions incl. supports

All dimensions are for reference only and are subject to change.


Crystallization with Heat Pump Technology

Process and Equipment Description based on the

example p-Xylene
Basics
The process involves repetitive crystallization of the isomer
mixture. It is based on the principle of forming a crystal
layer on a cooled heat exchange surface. The solid is the
purified p-Xylene while impurities are concentrated in the
remaining melt. After the crystal layer is grown a heating
phase follows to sweat the crystal layer and to separate
adhering or trapped mother liquor. Finally the crystals are
melted off the tubes.

Falling film Falling film

refrigerant refrigerant
Crystallizer Crystallizer
Product Product Product Product
Residue Residue Residue Residue
Product pump Feed Productpump Feed

Refrigerant Refrigerant
separator separator
Compressor Refrigerant Compressor Refrigerant
pump pump

Aux. Aux.
Aux. Cond. Evap. Aux. Cond. Evap.

Cooling water Steam Cooling water Steam

Figure 18: Heat pump crystallization.

20
Case 1:
19-24% Prepurification 90-99% Fractional 99.7-99.9%+ 10
mixed p-Xylol
p-X Section p-X Crystallization p-X
Prepurification 0
Temperature ( oC)

Case 2: -10
Separation Co- 19-23% Prepurification 99-99.5% Fractional 99.7-99.9%+
lumns Section Crystallization -20
p-X p-X p-X

-30
Benzol
Case 3:
80-90% 99.7-99.9%+ -40
Toluene Toluene Dispropor- Separation Fractional
tionation Columns p-X Crystallization p-X -50
100 90 80 70 60 50 40 30 20 10 0
Benzene p -Xylene (%)

Figure 19: Flow diagrams of 3 different cases.. Figure 20: Phase diagram of p-Xylene.

10
Heat Pump Crystallizers
The key equipment of the process are
the heat pump crystallizers. Depen-
ding on the plant capacity two or more
crystallizers of equal size are used
per plant. These crystallizers are inte-
grated in the heat pump refrigeration
cycle. The crystallizers are designed to
allow switching between cooling with
liquid refrigerant and heating with re-
frigerant vapour. Whilst one crystallizer
operates in the crystallization mode as
an evaporator, the other one operates
in the sweating or melting mode as a
condenser.
The heat pump crystallizer basically
consists of a system of vertical ele-
ments used as heat transfer surface.
The isomer mixture enters at the top
of the elementes. Distributors put the
liquid in a falling film flow to the outside
surface of the tubes. The refrigerant for
cooling is distributed at the top through
an internal tube to wet the inside of the
crystallizer tubes.
In order to switch cooling/heating mode Low Energy and Investment Costs
at the end of the crystallization or mel- The heat pump concept improves p-
ting, the feeding of liquid refrigerant Xylene crystallization significantly:
and vapour to the crystallizers is stop-
1. Energy costs are reduced due to
ped. Remaining refrigerant is drained
the use of condensation enthalpy
into the receiver. The process is then
for crystal melting. And evaporati-
continued by heating the crystallizer
on energy is higher due to direct
containing the crystals and by cooling
cooling inside of the crystallizer
the other crystallizer to start with a new
tubes.
crystallization stage.
2. A minimum of equipment is re-
The compressor for the plant operates
quired since process energy is di-
in a defined pressure range. When the
rectly used within the crystallizer.
pressure exceeds the upper or lower
Refrigeration unit is only equipped
set point vapour is condensed or liquid
with auxiliary heat exchangers to
evaporated in an auxiliary condenser
eliminate excess energy and to fa-
and evaporator.
cilitate start-up.

Refrigeration
Liquid refrigerant is pumped from the
receiver to one crystallizer and is distri-
buted inside the crystallizer tubes. The
temperature level within the crystallizer
is controlled by a valve controling the
evaporation pressure. The low pres-
sure vapour flows then via the recei-
ver to the compressor. The vapour is
compressed to a point where it can be
condensed in the other crystallizer, to
sweat or melt the crystals. The con-
densed refrig-erant flows from the cry-
stallizer via a float valve, back to the
receiver. The refrigeration cycle is thus
completed.

Figure 21:
p-Xylene plant of
CESPA in Spain. 0698 2804-1

11
Combinations to Enhance Performance

Falling Film Crystallization – Static Crystallization

Falling Film Cry- Static

Feed stallization Crystallization

Residue
Product

Residue Feed Product

Static
Crystallization

Falling Film Cry-

stallization

0699 2805

Figure 22: Flow diagram of a plant combining falling film and static crystallization. Figure 24: Acrylic Acid plant at BASF,
Germany

Figure 25: Erection of static crystallizers for

Cristallization – Distillation
Paraffin plant in Germany.

Distillation Crystallization
Isomer
Mixture
Para-
Isomer

Ortho Isomer

Ortho Feed Para

Distillation

Crystallization

0699 2801-3
Figure 23: Flow diagram of a plant combining distillation and crystallization.

12
 0699 2804 0694 2816-6

Figure 26: Bisphenol A plant at Abbildung 28: Naphthalene plant a Jining, P. R China.
General Electric Plastics, Spain. (10´000 tons/years)

Figure 27:
Naphthalene plant
at Cindu Chemicals
in the Netherlands
(12´000 tons/year).

Figure 29:
Acrylic Acid plant at LG
Chemical, Korea
0693 2804 (20´000 tons/year). 0699 2802

13
Fractional Crystallization

Fractional crystallization is used to H H H

purify a wide variety of chemicals.
Plants have been supplied by Sulzer H C C
n
C H

Chemtech for products such as: H H H

OH
paraffin
COOH

p – cresol
O
benzoic acid
H H

N N
N H C H3
H H

H
hydrazine
O caprolactam
H C C CI
C H3
OH
CI
monochloro HO C OH
dichloro-
acetic acid
benzene
C H3

bisphenol A
H H
CI O
CI
H C C C
n
OH
H H H H
O
fatty acid
C C C

OH naphthalene
H C H3
nitrochlorobenzene
acrylic acid N O2

p-Xylene

More than 250 compounds

have been purified successfully in our C H3

test facilities.

General Characteristics of Crystal-
lization
– high selectivities due to regularity
of the crystal lattice
– high purities due to high selectivi-
ties
– reduced number of stages due to
high selectivities
– low operating temperatures due to – separation of mixtures forming
the nature of phase equilibria azeotropes
– reduced thermal degradation due – can replace chemical separation
to lower operating temperatures methods
– energy savings due to lower heats
of melting, lower operating tempe-
ratures and reduced number of sta-
ges

14
Characteristics of Sulzer Chemtech Crystallization Systems

Static Crystallization If you have a separation problem Bench Scale Test

– for medium to high product puri-
ties
– for small to large capacities
– the product is in liquid form
– simple and standardized equip-
ment
– no slurry handling, no filtration
– no moving parts, low maintenance
cost
– ease of scale up since commercial
equipment consists of a multip-
le of elements identical to those
used in pilot testing
– low labour cost due to micropro-
cessor control
– environmentally safe due to inert
gas blanketing and the absence of
solvents
feel free to consult our crystalliza-
tion specialists.
If crystallization is a possible solution
they will ask for a sample of crude ma-
terial for testing in our well equipped
laboratories.
Between 2 and 10 kg are sufficient to
carry out bench scale tests for a pre-
liminary assessment on crystallization
behaviour, product quality and process
feasibility.
Pilot Scale Test
100 to 800 kg are required for pilot
tests. As a result of these investiga-
tions, a detailed proposal can be sub-
mitted which will include a preliminary
process flow diagram, an equipment
list, and plant performance data.
It goes without saying: All work is
done on a strictly confidential basis.

Falling Film Crystallization

– for medium to very high product
purities
– for medium to large capacities
– the product is in liquid form 0690 2816-5
– no slurry handling, no filtration
Figure 30:
– no moving parts, low maintenance
Bench scale test unit.
cost
– ease of scale-up since commercial
equipment consists of a multip-
le of elements identical to those
used in pilot testing
– low labour cost due to automatic
control
– flexibility due to countercurrent
staging combined with predeter-
mined and carefully controlled 0690 2816-1
mass and energy balance
– ease of restarting the process Figure 31:
without any loss of time or pro- Falling film pilot test unit.
duction
– multipurpose plants
– environmentally safe due to inert
gas blanketing and the absence of
solvents
Figure 32:
Mobile pilot plant. 0693 2811

15
Headquarters Sulzer Chemtech Ltd, a member of the Sulzer Corporation, with head-
Sulzer Chemtech AG quarters in Winterthur, Switzerland, is active in the field of process engi-
P.O. Box 65 neering and employs some 1500 persons worldwide.
CH-8404 Winterthur, Switzerland Sulzer Chemtech is represented in all important industrial countries and
Telephone +41 (0)52 262 50 28 sets standards in the field of mass transfer and static mixing with its ad-
Fax +41 (0)52 262 01 82 vanced and economical solutions.
E-mail chemtech@sulzer.com
Internet www.sulzerchemtech.com
The activity program comprises:
North and South America • Process components such as trays, structured and random packings,
Sulzer Chemtech USA, Inc. internals for separation columns and reaction technology
4106 New West Drive
• Engineering services for separation and reaction technology such as
US-Pasadena, TX 77507
optimizing energy consumption, plant optimization studies, pre-engi-
Telephone +1 (281) 604-4100
neering for governmental approval, basic engineering
Fax +1 (281) 291-0207
• Separation and purification of organic chemicals by means of crystal-
Asia Pacific lization and membranes
Sulzer Chemtech Pte. Ltd. • Mixing and reaction technology with static mixers
Regional Headquarters
25 International Business Park • Tower field services
#03-28 German Centre
SG-60 99 16 Singapore
Telephone +65 6863 75 60
Fax +65 6861 15 16

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28.56.06.40-IV.06-50 - Printed in Switzerland