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MEMBRANE ASSISTED
CRYSTALLIZATION
Prepared by :
Upasana Wadhwani
Guided by :
Dr. Bina Sengupta

INTRODUCTION
Crystallization is one of the oldest important separation and

purification process.
The crystallization process consists of two major events, nucleation
and crystal growth.
Supersaturation is the driving force for crystallization.
As a result crystals of different shapes and sizes are obtained.
The control of crystal size and shape constitutes one of the major
challenges in industries.
The interest in combining membrane operations and solution
crystallization is motivated by the aim to develop more efficient
crystallization processes.
Membranes, with their intrinsic characteristics of efficiency and
operational simplicity leads to significant innovation in both
processes and products.

Herman Kramer-Influence of solubility characteristics on experimental application and energy saving potential from
http://www.academia.edu/13279506/Membrane-assisted-crystallization

WHY MEMBRANES ?
Membranes are used due to their following properties:
Operational simplicity
High selectivity
Permeability for the transport of specific components
Compatibility between different membrane operations in integrated

systems
Low energetic requirement
Good stability under operating conditions
Environmental compatibility
Easy control and scale-up
Large operational flexibility

Enrico Drioli, Gianluca Di Profio, Efrem Curio. Membrane-Assisted Crstallization Technology-Vol 2;2013.

WORKING OF MEMBRANE ASSISTED CRYSTALLIZATION


Based on the utilization of hydrophobic micro porous membranes.
The double nature of the membrane impedes the passage of the contacted solutions

though the membrane in the liquid state allows the formation of a double
liquid/vapor interface on both the sides of the membrane.
A gradient of chemical potential between these two interfaces, due to a temperature
and/or concentration differences, is the driving force of the overall process.

Di Profio-Membrane crystallization technology: heterogeneous nucleation above the membrane surface from
http://www.itm.cnr.it/index.php/en/staff-2/2-non-categorizzato/95-highlights-di-profio-2

MAIN FEATURES OF MEMBRANE ASSISTED CRYSTALLIZATION

Well controlled nucleation and growth kinetics


Membrane surface promoting heterogeneous nucleation
Selection of polymorphic forms
Reduced energy consumption
Fast crystallization rates and reduced induction time

Enrico Drioli, Gianluca Di Profio, Efrem Curio. Membrane-Assisted Crstallization Technology-Vol 2;2013.

CONVENTIONAL CRYSTALLIZATION VS MEMBRANE


ASSISTED CRYSTALLIZATION
CONVENTIONAL
CRYSTALLIZATION

MEMBRANE ASSISTED
CRYSTALLIZATION

There is no control over the shape and size


of crystals formed.

Membranes help to form crystals of uniform


shape and size.

There is a large variation in product quality


and inflexibility of the process due to the
entanglement of different phenomena such
as primary nucleation, secondary
nucleation and so on.

Membrane assisted crystallization improves


the product quality due to membranes
intrinsic characteristics and also provides a
large operational flexibility.

The energy requirement is comparatively


large.

Energy requirement is comparatively low.

The product is not much stable under the


operating conditions.

Good stability under the operating conditions


and environmental compatibility.

Crystallization rates are relatively low as


compared to membrane assisted
crystallization.

Provides nucleation and crystal growth in


separate compartments and thus improves
the crystallization rates.

Enrico Drioli, Gianluca Di Profio, Efrem Curio. Membrane-Assisted Crstallization Technology-Vol 2;2013.

MEMBRANE ASSISTED CRYSTALLIZATION PROCESSES


Dialysis
Forward Osmosis
Membrane distillation
Reverse Osmosis

MEMBRANE ASSISTED CRYSTALLIZATION CONFIGURATIONS


Membrane Contactors
Membrane Reactors
Solvent evaporation membrane crystallizer
Antisolvent membrane crystallizer
Support liquid membranes
Membrane Templates

Enrico Drioli, Gianluca Di Profio, Efrem Curio. Membrane-Assisted Crstallization Technology-Vol 2;2013.

MEMBRANE DISTILLATION
Membrane distillation is a thermally driven process.
The hydrophobic nature of the membrane prevents the passage of

liquids through the pores, while allowing the passage of volatile


solvent in vapor phase
The temperature gradient across the two sides causes solvent
vapor to diffuse through the membrane and to condense on the
colder solution surface.
The transport mechanism is
broken down into three
steps:
1. Evaporation at the
membrane interface at
the feed side,
2. Migration of the
vaporized solvent
through the dry
membrane pores, and
3. Condensation on the
opposite distillate side.
Lawson, K.W. and Lloyd, D.R. Membrane distillation, J. Membr. Sci., 1997; 124:125.

ANTISOLVENT MEMBRANE CRYSTALLIZER


SCHEME 1
Solute and solvent are miscible.
Antisolvent evaporated in solution from another side.
Antisolvent mixes with the solvent and reduced solute solubility in solvent.
This creates supersaturation at feed side and results in solute

crystallization.

Stabile C,Caridi A,Curcio E, Drioli E.-Antisolvent membrane crystallization of pharmaceutical compounds.-J Pharm Sci.2009 Dec

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SCHEME 2
The antisolvent and the solvent are miscible.
A vapor pressure is generated between the two sides of the membranes by a

temperature difference
The solvent having higher vapor pressure, evaporates at a higher rate, thus
producing a certain degree of solvent/antisolvent demixing.
As the fraction of antisolvent in the mixture increases from the initial
composition, the lower solubility of the solute generates supersaturation and
a phase separation occurs.

Stabile C,Caridi A,Curcio E, Drioli E.-Antisolvent membrane crystallization of pharmaceutical compounds.-J Pharm Sci.2009 Dec

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APPLICATIONS

Application in Chemical field


Carbon Dioxide Recovery
Membrane based evaporation crystallization
Membrane crystallization in water treatment
Preparation of tubular membranes by Steam assisted crystallization

Application in Pharmaceutical and Biological field


MAC for recovery of pharmaceutical compound from waste streams
Trypsin crystallization by membrane based techniques
Crystallization of membrane proteins mediated by antibody fragments

[1] Ye, J. Lin, J. Shen, P. Luis, B. Van der Bruggen, "Membrane Crystallization of Sodium Carbonate for Carbon Dioxide Recovery
vol. 13, 2013;23622372
[2] Hajduk PJ and Greer J. A decade of fragment-based drug design: Nat Rev Drug Discov. 2007; 6:211-219 2005; 1171-1176.
[3] Konig A and Weckesser D. Membrane based evaporation crystallization

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THANK YOU

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