Chapter 14 Membrane separation

Feed: consisting of mixture of two or more

components
Retentate: The part of the feed that does not pass
through the membrane
Permeate: The part that does pass through the
membrane
Sweep: Is a liquid or gas used to facilitate removal

Pore Resistance to flow

Ideal straight cylindrical: Poiseuille flow
Bioprocessing:Membrane Selection Criteria:
(1)Selectivity: The membrane must retain active
species and pass contaminants at targeted
specifications.(2)Biocompatibility: The membrane
should resist inactivation, pluging, and fouling by
biological species or solution components.
(3)Chemical inertness: Must tolerate use and
validatable cleaning and sterilization cycles.
(4)mechanical Stability: Must be able to withstand
pressures and temperatuires ranges employed

Real porous

Bulk Flow: Bulk Flow is pressure driven through semi permeable barrier

Gas Permeation
Liquid diffusion through porous membrane
The membrane, often dense but sometimes micro porous, is permselective for the low-molecular-weight species A. But if the membrane is dense, these species are absorbed at the surface and then trans

Solution-Diffusion for Liquid Mixtures

Porous membrane

Liquid Diffusion through Nonporous membrane

Nonporous Membrane

Gas Diffusion through porous membrane

Reverse Osmosis

Note the same could be derived for Gas Mixture

Dialysis: Sweep is fed

Gas Diffusion through nonporous membrane

Pervaporation: Phase on one side of the revaporation membrane is different from that on the other. Feed to the membrane module is a liuid mixture at P1. The retentate is enr

(c) If we apply a pressure P1 that is higher than

the sum of the osmotic pressure and P2. This
allows us to push the seawater through the
membrane in the reverse direction of normal osmosis.
Liquid diffusate (permeate) contains solvent, solutes of type A, and little or
none of type B solutes. Liquid dialysate (Retentate) contains solvent, type B
solutes, remaining type A solutes, and colloidal matter

Membrane Requirements for Biotechnology:(1)Preserve biological activity:Denaturation, proteolytic cleavage, or mishorming of protein
projects must be avoided.(2) Satisfy cGmp requiremments:may include biocompatibility, sterilizability, and flushout of extractables.(3)
Accommodate modes scales of operation. (4) Include batch operation. Filtration Challenges:(1)Integrated process: The process may
define the product. Filtration cannot be implemented or optimized in isolation, but must be approached as an integral part of the entire series of
fermentation, purification, and formulation steps.(2)Compressed development: Pressing market need for biotechnology products to prevent or
Chapter 17 Crystallization
treat public health problems drives accelerate timelines for development.(3)Limited raw materials: Only mL to L of fermentation or cell culture
broth may be initially available for filter selection, characterization, and optimization.(4)Variable fermentation or cell culture:Membrane
Crystallization is a solid-fluid separation in
which crystalline particles are formed from a filter operation must accommodate wide variations in sell culture and fermentation composition and productivity while providing consistent yield
and purity.(5) Operability:Filter operations that maximize the robustness of process operations must be selected to provide consistent purity
homogeneous fluid phase. Crystals are pure
chemicals, are obtained in a high yield with a and yield, resulting in an economical, vaildatable process.(6)Virus removal: Must reduce the virus to a level of less than on virus particle per
10^6 doses. Fouling:(1)Macromolecular sorption:Dissolved macromolecules introduced in the feed adsorb rapidly to membrane surfaces,
desirable shape.
Industry.(1)Solution crystallization: inorganic decreasing permeate rate in proportion to coverage.(2)Particle deposition:The first sublayer builds as colloids, slowly deposit, decreasing
salt is the solute crystallized, and water is the permeate flux as monolayer coverage is approached.(3)Sublayer rearrangement: Additional sublayer build, reducing the cross section for
solvent remaining as a liquid.(2)Precipitation: Crystal Geometry: In a solid, motion of molecules, atoms, or ions is restricted largely to oscillations about fixed positions. In amorphous solid,
these positions are not arranged in a regular or lattice pattern, where as in crystalline solids, they are. Amorphous solids are isotropic, i.e.,
Fast crystallization( not good) Organic
physical properties are independent of the direction of measurement; crystalline solids are anisotropic, unless the crystals are cubic in structure.
solutions.(3 Evaporation: Used in Organic
Bravais showed that only the 14 space lattices are possible. The 14 lattices can be classified into the seven crystal systems. Cubic, Tetragonal,
solutions .(4 Cooling: Used in Organic
Orthorhombic,
Monoclinic,
Hexagonal,
Triclinic.
Crystals
of a givena substance
and a given
exhibit
markedly
Crystal-size Distributions: Crystallizer magmas contain
a distbution
of crystalRhombohedral,
sizes and shapes.
It is highly
desiable
to cahraterize
batch of crystals
by ansystem
average
crystal
size and different
a crystal-size distrib
Size
techniques:(1)Electron
solutions.(5)Melt: Used when both components appearances when the faces grow at different rates.
microscope.(2)Optical.
of a homogeneous, binary solution have
(3)Laser Light.(4) Wire mash.
melting( freezing) points not far removed from
Distribution. (1)Differential.
(2)Cumulative
)

Different Mean Particle Sizes:

Arithmetic-Mean
Surface-Mean Diameter

Mass-Mean D

Solubility: For systems of water and soluble inorganic and organic chemicals, presents extensive tables of
solubility as a function of temperature, and heat of solution at infinite dilution and room temperature.
Solubility is expressed as a solubility product, Kc in terms of ion concentration.
Effect of Temperature: Solubility of most inorganic compounds increase with temperature, but a few
common compounds exhibit a negative or inverted solubility in certain ranges of temperature where
solubility decreases with increasing temperature. When solubility increases with temp. best method for
crystallization would be cooling. When solubility remains constant along with increase in temp. the best
method for crystallization would be evaporation. Solid compound with low solubility can be produced by
reacting two soluble compounds.

Volume-Mean Diameter

Kinetics and Mass: Steps-(1) Nucleation, (2) Mass transfer: Solute to surface, (3) Solute addition. Driving force for all three steps is supersaturation. Supersaturation: As crystals size decreases,
solubility noticeably increases, making it possible to supersaturate a solution if it is cooled slowly with agitation
Relative Supersaturation Nucleation: Primary nucleation requires high supersaturation and is the
principal mechanism in precipitation-RequiressS>>1-No forging matter (dust).
Secondary nucleation is the key in commercial crystallizers, where crystalline
Kelvin equation
surfaces are present and large crystals are desired.
Primary nucleation: Can be homogeneous or heterogeneous. Molecules in the solution first associate to
form a cluster. If a cluster gets larger enough to take on the appearance of a lattice structure, it becomes an
embryo. Further growth can result in a stable crystalline nucleus. The rate of homogeneous nucleation:
Secondary Nucleation: Nucleation in industrial crystallizers occurs mainly by
secondary nucleation caused by existing crystals in the supersaturated solution. It is
Chapter 15 Adsorption, Ion Exchange,
initiated by: (1) Fluid shear past crystal surfaces that sweep away nuclei. (2) Collisions
Chromatography
of crystals with each other. (3) Collisions of crystals with metal surfaces such as the
Adsorption, ion exchange and chromatography are
crystallizer vessel wall or agitator blades. The rate of secondary nucleation:
Crystal growth: Mass
sorption operation in which components of a fluid
phase are selectively transferred to insoluble, rigid
particles suspended in a vessel or packed in a
column. Ex Adsorption of gas species into a liquid
and penetration of fluid species into a nonporous
membrane are sorption operations. In sorption
Adsorption
molecules
or atoms
process, the process:
sorbed solutes
are referred
to or
as ions, in a gas or liquid, diffuse to the Precipitation: In solution crystallization, a liquid containing a
surface of a solid, where they bond with the solid surface or are held by weak
solute is cooled or partially evaporated; causing the solute to
intermolecular forces. Ion-Exchange process: ions of positive charge or negativeexceeds its solubility sufficiently to partially crystallize.
in a liquid solution usually aqueous, replace dissimilar and displaceable ions, calledPrecipitation is the opposite of solution crystallization.
counterion, of the same charge contained in a solid ion exchanger.
Precipitation involves solutes that are only sparingly soluble.
Chromatography: the sorbent may be a solid absorbent: an insoluble, nonvolatileFast crystallization, formed by changing pH, solvent,
Surface Area/Volume (solid Activated carbon(small pore): Surface Area, Sg, m2/g=>400-1200. Molecular-Sieve
liquid
adsorbent
contained
in
the
pores
of
a
granular
sold
support:
or
an
ion
Adsorbents: Most adsorb species from gases and liquids, but few have a sufficient sphere)
Zeolites: Pore Diameter, dp, =>3-10.Two types of Adsorption: (1) Physical
selectivity and capacity to qualify as serious candidates for commercial
adsorption(Physisorption):
physical adsorption from gas occurs when
Specific surface area of an adsorbent
is measured
adsorbents.
intermolecular
attractive forces between solid and gas molecules attractive forces
by adsorbing
gaseous
nitrogen,
using the BET
Specific
surface
area, in
area
between
solid
and
gas
molecules
are greater than those between gas molecules.
method
(Brenauer,
Emmett, and Teller). N2
per
unit mass
of adsorbent
BET equation
(2) Chemical
(Chemisorption): Involves formation of chemical bonds
adsorption is oftern called BET,
Operateadsorption
in a
betweenthe
adsorbent and adsorbate in a monolayer, oftern with a release of heat
vacuum (5 to 250 mmHg), Measures
that the heat of vaporization. Commercial adsorbents rely on physical
equilibrium volume of pure Nlarger
2 physically adsorbed
adsorption to achieve separation: solid catalysts rely on chemisorptions to catalyze
Measuring Pore Volume and Pore Distribution

For N2 adsorption, filling of pores depends

on the size of the pore. Kelvin Equation:

Physical meaning: Change in vapor pressure

due to the curved liquid-vapor interface.
Ion Exchange: one sorbate is exchanged for
a solute ion, gonverned by a reversible,
stoichiometic,
Monolayer Isotherms: (1) Freundlish Isotherm:
IonrXn.
exchange material:
(2) Langmuir Isotherm
(1)Natural
resins:Polysaccharides, (2)
Organic Polymer resins, (3)
(3) Binary Mixture(Langmuir Modification
Inorganic Materials(zeolites)

Pure-Gas Adsorption:

General Equation:

Linear Isotherms: When the amount of

adsorbed molecule is low, isotherms
are approximately linear (form of
Henrys law

Adsorption is an exothermic process:

What are the effects of temperature ?

Surface is lined with a particular binding substance and as a solution is

fed you get binding at different locations. Then you use a solvent to
wash away the separated mixture.