Session 24

Curso Operaciones con

Transferencia de masa
Lina María González
19-427
Membrane Separation
Processes

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3
4
5
Membranes

https://www.youtube.com/wat
ch?v=5iRUYpIoN50
https://www.youtube.com/wat
ch?v=c0A56QlrYNs

• Desirable features of membranes

• Most common materials.
• Application of gas permeation and its materials.
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Diffusion mechanism
Many mechanisms have been proposed based on various interaction and diffusion processes. These
mechanisms are in broad terms distinguished by the ratio of the mean free path length l and the diameter
dp.

As the pore diameter becomes smaller the interactions of gas molecules and pore surface become larger.
Therefore, the state of the permeating gas molecule changes from a “gaseous state” to a “trapped state”. Gas
transport in membranes can occur through a number of possible mechanisms:
 Knudsen diffusion

In mesopores the mean free path of a gas molecule is larger

than the size of the pore. The interaction gas molecule-pore
wall is therefore more important than the interaction molecule-
molecule.

Surface diffusion

The transport in a microporous medium can be

described as a surface diffusion mechanism;
consequently the general Fick law can be applied:
 Gas - translational diffusion

Diffusing gas molecules have enough kinetic energy to escape

the surface potential….
…. but cannot readily do so because of the presence of a pore
wall on the other side. This is a mechanism in which there is a
combination of the Knudsen diffusion model and the surface
diffusion model.

Both surface diffusion and gas-

translation have contributions
Solid state diffusion

For solid-state permeation the molecules permeating through

the solid are considered to reside in solubility sites and to be in
equilibrium with the gaseous state.

Permeance = solubility x diffusivity

Gas permeation
Hollow-fiber or spiral-wound membranes

The feed gas is forced into the membrane

module under pressure.

Retentate, which does not go through the

membrane, will become concentrated in the
less permeable gas.

Retentate exits at a pressure that will be

close to the input pressure.

Cost: compression.
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 Permeation
• For gas permeation the steady-state general flux for gas A becomes:

𝑇𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑅𝑎𝑡𝑒 𝑃𝑒𝑟𝑚𝑒𝑎𝑏𝑖𝑙𝑖𝑡𝑦

𝐹𝑙𝑢𝑥 = = × (𝐷𝑟𝑖𝑣𝑖𝑛𝑔 𝐹𝑜𝑟𝑐𝑒)
𝑇𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝐴𝑟𝑒𝑎 𝑆𝑒𝑝𝑎𝑟𝑎𝑡𝑖𝑜𝑛 𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠

• where JA is the volumetric flux of gas A, is the molar transfer rate of gas which permeates
through the membrane
• yt,A is the mole frac A in the gas that transfers (or permeates) through the membrane
• ρA is the molar density of the solute in the gas transferring through the membrane
• A is the membrane area available for mass transfer
• PA is the permeability of species A in the membrane
• ΔpA, the driving force for the separation, is the difference in the partial pressure of A across
the portion of the membrane which does the separation
• tms is the thickness of the membrane skin which actually does the separation.
• The ratio PA/tms is known as the permanence, and is often the variable that is measured
experimentally.
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Permeation
𝐹𝑡 ∙ 𝑦𝑡,𝐴 Δ𝑝𝐴
𝐽𝐴 = = ℙ𝐴
𝜌𝐴 ∙ 𝐴 𝑡𝑚𝑠

• Since partial pressure = (mole fraction)(total pressure) or pA = yA p:

𝐹𝑡 ∙ 𝑦𝑡,𝐴 𝑝𝑟 ∙ 𝑦𝑟,𝑤,𝐴 − 𝑝𝑝 ∙ 𝑦𝑝,𝑤,𝐴

𝐽𝐴 = = ℙ𝐴
𝜌𝐴 ∙ 𝐴 𝑡𝑚𝑠

• where pr is the total pressure on the retentate (high pressure)

side
• yr,w,A is the mole fraction A on the retentate side at the
membrane wall
• pp and yp,w,A are the pressure and mole fraction at the wall on
the permeate (low pressure) side.
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 Gas Permeation of Binary Mixtures
• In binary mixtures: yB = 1-yA
• A: the faster permeating species
• The flux of the slower moving component B becomes:
𝑝𝑟 ∙ (1 − 𝑦𝑟,𝑤,𝐴 ) − 𝑝𝑝 ∙ (1 − 𝑦𝑝,𝑤,𝐴 )
𝐽𝐵 = ℙ𝐵
𝑡𝑚𝑠
• Usually:
• There is no concentration gradient on the permeate side perpendicular to the membrane;
thus, we replaced yp,w,A with yp,A
• Mass transfer rates in gas systems are high enough that the mole fraction at the membrane
surface is almost equal to the mole fraction in the bulk gas.

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Permeation mechanism
• Solution-diffusion:
Feed (high P)

Membrane
Low P
A
dissolves

A diffuses

ℙ𝐴 = 𝐻𝐴 ∙ 𝐷𝑚,𝐴
• Here, the permeability is:
• Where HA the gas solubility in the membrane and Dm is the diffusivity in the membrane

https://www.youtube.com/watch?v=08ZH7vwzzEg
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Permeation of gases in polymer membranes
• Small molecules such as helium
have high diffusivities but low
solubilities
• While large gas molecules such as
carbon dioxide have high solubilities
but low diffusivities.
• The resulting product, the
permeability P is relatively large for
both small and large molecules, but
has a minimum for molecules
around the size of nitrogen.

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Permeabilities
of gases in
various
membranes

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Selectivity
• If the driving forces are equal, gases with higher permeabilities transfer through the membrane at
higher rates:

ℙ𝐴
𝛼𝐴𝐵 = ℙ𝐵

• Calculate the selectivity of 2 systems according to the table data.

• αAB values of 20 and higher are preferred instead of the much more modest values commonly
employed in distillation.

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Binary Permeation in Perfectly Mixed Systems
• The simplest.
• The mole fracs and pressures on each side of the membrane are constant.: yp=yt
• We will also assume that the module has a high rate of mass transfer from the bulk fluid to the
membrane surface. This assumption makes yr=yr,w

𝐹𝑡 ∙ 𝑦𝑡,𝐴 𝑝𝑟 ∙ 𝑦𝑟,𝑤,𝐴 − 𝑝𝑝 ∙ 𝑦𝑝,𝑤,𝐴 ℙ𝐴 ∙𝐴∙𝜌𝐴

𝐽𝐴 = = ℙ𝐴 𝐹𝑃 ∙ 𝑦𝑃 = 𝑝𝑟 ∙ 𝑦𝑟 − 𝑝𝑝 ∙ 𝑦𝑝
𝜌𝐴 ∙ 𝐴 𝑡𝑚𝑠 𝑡𝑚𝑠

• And for B:
ℙ𝐵 ∙𝐴∙𝜌𝐵
𝐹𝑃 ∙ (1 − 𝑦𝑃 ) = 𝑝𝑟 ∙ (1 − 𝑦𝑟 ) − 𝑝𝑝 ∙ (1 − 𝑦𝑝 )
𝑡𝑚𝑠
• Make them iqual in Fp:

ℙ𝐴 ∙𝐴∙𝜌𝐴 ℙ𝐵 ∙𝐴∙𝜌𝐵
𝑝𝑟 ∙ 𝑦𝑟 − 𝑝𝑝 ∙ 𝑦𝑝 = 𝑝𝑟 ∙ (1 − 𝑦𝑟 ) − 𝑝𝑝 ∙ (1 − 𝑦𝑝 )
𝑦𝑝 ∙𝑡𝑚𝑠 1−𝑦𝑝 ∙𝑡𝑚𝑠
Rate transfer (RT) curve
• Solving for yr: 𝜌𝐴 ∙ 𝛼𝐴𝐵 𝑝𝑝
𝑦𝑝 −1 𝑝 1 − 𝑦𝑝 + 1
𝜌𝐵 𝑟
𝑦𝑟 =
𝜌 𝜌
𝛼𝐴𝐵 𝐴 − 𝛼𝐴𝐵 𝐴 − 1 ∙ 𝑦𝑝
𝜌𝐵 𝜌𝐵

• RT curve: relates the mole fractions on both sides of the membrane based on the RT parameters
and the driving force.
• It can take the place of an equilibrium expression for binary systems.
• This equation is applicable to other flow configurations if written in terms of yt and applied point-
by-point on the membrane.
• For a perfectly mixed separator values are constant: yr,sal=yr,prom=yr; yp,sal=yp y Fr=Fsal

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Completely mixed membrane module

• A single feed goes into a well-mixed chamber and two products are withdrawn.
• The more permeable species concentrates in the permeate product which is
analogous to the more volatile component concentrating in the vapor.
• However, the two products are not in equilibrium but are related by the RT
expression.
• Because of the geometric similarity, we can use an analysis procedure
analogous to that used for binary flash distillation.
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Completely mixed membrane module

• The overall mole balance and the mole balance on the more permeable
component?
𝐹𝑖𝑛 = 𝐹𝑝 + 𝐹𝑟 𝐹𝑖𝑛 ∙ 𝑦𝑖𝑛 = 𝐹𝑝 ∙ 𝑦𝑝 + 𝐹𝑟 ∙ 𝑦𝑟

• Combining and solving: 1 − 𝐹𝑝 𝐹𝑖𝑛 𝑦𝑖𝑛

𝑦𝑝 = − ∙ 𝑦𝑟 +
𝐹𝑝 𝐹𝑖𝑛 𝐹𝑝 𝐹𝑖𝑛
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The operating equation
1 − 𝐹𝑝 𝐹𝑖𝑛 𝑦𝑖𝑛
𝑦𝑝 = − ∙ 𝑦𝑟 +
𝐹𝑝 𝐹𝑖𝑛 𝐹𝑝 𝐹𝑖𝑛

• For the well-mixed gas permeator.

• θ=Fp/Fin known as the “cut,” is an important operating parameter.

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Reverse Osmosis (RO) https://www.youtube.com/watch?v=aVdWqbpbv_Y

• Osmosis

Osmotic pressure is the

• Osmotic pressure minimum pressure which needs to be
applied to a solution to prevent the
inward flow of its pure solvent across
a semipermeable membrane
• For dilute systems:

• For for water containing salts:

with T in °C and salt
24 concentration Cs in kg/m3
Reverse Osmosis (RO)

• The mass flux of solvent:

• The mass solute flux:

https://www.youtube.com/watch?v=aVdWqbpbv_Y 25
Concentration polarization

• The mass flux of solvent:

• It is posible to asume linear π=ax:

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Concentration polarization
• We define the concentration polarization modulus M in terms of the wt
frac

• The mass flux of solvent :

• The solute flux:

• Essentially the same procedure used to solve for the concentrations in gas
permeators will be used.

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Concentration polarization
• Setting the equations equal, we obtain:

• It is convenient to define the selectivity of the membrane α′ as:

• Solving for xr:

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RT curve
• Since RO often operates with high retention of solute and thus very low
values of xp, it is useful to simplify RT for small xp.
• As xp → 0, becomes:

• Usually, α′ρsolv(pr − pp) >> 1 and

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 The operating equation
• Balance:

• Solving for xp: Operating equation

• Alternative:

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Rejection coefficient R

• RO data are often reported as the rejection coefficient R:

Rejection coefficient R
• The rejection coefficient when there is no concentration polarization (M = 1) is
called the inherent rejection coefficient R°.
• We can find a relationship between retention R at one set of conditions and R at
another set of conditions for well-mixed systems.

• If the pressure difference (pr –pp) is the same in the two runs, then:
Rejection coefficient R
• When R is known, we can solve the RT Eq. (17-24a) simultaneously with operating
Eq. (17-23) for a completely mixed system:

• which is a very convenient and simple solution.

• Alternatively, we can solve for xp:
Determination of Membrane Properties from
Experiments
• Experimental values of xp and xout can be used to determine α′ and M.
• First, an experiment is done in a very well mixed cell under conditions where
there is no concentration polarization.
• Solving for the selectivity, we obtain:

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Mass-Transfer Analysis to Determine Concentration
Polarization
• Once values for a′ are known, experiments can be done under conditions where
concentration polarization is expected.
• M can be determined by solving for M.

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M by mass transfer
• The differential mass balance for this simple situation using a Fickian analysis is:

Boundary conditions:
Mass transfer coefficients
• For turbulent flow in tubes (Re>20000):

• With:

• For laminar flow in a tube of length L and radius R with a bulk velocity ub:

• For laminar flow between parallel plates with a spacing of 2h:

Coeficiente de TdeM
• For flat membranes in a well-stirred turbulent tank:

• k is in cm/s, ω is the stirrer speed in radians/s, dtank is the tank diameter in cm, D is the diffusivity
in cm2/s, and the kinematic viscosity ν = μ/ρ is in cm2/s.
• Stirred tanks are a convenient laboratory configuration.
• Spiral-wound membranes are most commonly used for water treatment. The spacers in the feed
channel are designed to promote turbulence and increase mass transfer rates. Schock and Miquel
(1987) experimentally determined the following mass transfer correlation for typical spiral-wound
modules:

Here Ds is the diffusivity of the salt, and d = heightof feed channel.

Pervaporación

• Dehydration of organic-
water mixtures using
hydrophilic zeolite
membranes (for example,
Zeolite A, T)
• Concentration of dilute
organic mixtures using
hydrophobic zeolite
membranes (for example,
Zeolite ZSM-5 and
Silicalite)
• Separation of organic-
organic mixtures (for
example, Zeolite X, Y)

• Muy popular
• Permeación-Evaporación
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Fuerza impulsora
• La presión parcial local
en el lado de la entrada
(1):

• La de la salida (2):

• La fuerza impulsora:

¿Cómo aumentar la f.i.?

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Membranas
Hidrofóbicas. Ej: eliminar trazas de sustancias orgánicas en agua. De
hule de silicona.

Hidrofílicas. Ej: eliminar trazas de aguas en solventes orgánicos.

Acetato de celulosa, intercambio iónico, ácido poliacrílico,
polisulfona, zeolitas, etc.

No son porosas: solución-difusión.

Membrana que permee el compuesto más diluido!

Se pueden requerir sistemas híbridos para mejorar la pureza y

recuperación del producto de interés.

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Sistemas híbridos
• Pervaporación-destilación
Columna 1:

• Azeótropo de punto de ebullición mínimo

• Fondos: A puro
• Destilado cerca de la composición
azeotrópica

Pervaporador

• A permea preferiblemente
• Se recircula a la torre 1
• El retentado (con B) entra a la columna 2

Columna 2

• El destilado tiene la composición

azeotrópica y se recircula al pervaporador
• Fondos son esencialmente B puro

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Sistema simplificado

Si la selectividad es alta, el retentado

puede llenar las especificaciones de
pureza y sólo se necesita la columna 1

Etanol-agua
Membrana hidrofílica que deja pasar
agua en forma selectiva.

La bomba de vacío causa los mayores

costos de operación.

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Selectividad
• Para una separación binaria, se define
la selectividad:

• Con x y y fracciones peso de líquido y

vapor.
• No es equilibrio como la volatilidad
relativa, sino que representa velocidad
de transferencia.

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Velocidad de transferencia
• La ecuación anterior se puede expresar como:

• Si suponemos módulos de membrana bien mezclados en ambos lados, podemos sustituir yA por
yp y xA por xsal:

• Nos referimos al componente más permeable en el lado del permeado y del retentado.
• La selectividad debe corresponder a la T de operación y a la fracción xsal en el líquido.

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Curva de velocidad de transferencia
Concentración de agua en el permeado (yp)

yp

xsal concentración de agua en el retentado xsal

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Balances
• BdeM general y para la
sustancia más permeable.

• Ecuación de operación:

• Donde:

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Balances
• Balance de energía para un
sistema en e.e. y adiabático.

• Definimos el punto de
referencia como A líquido
puro a la Tref y suponemos
calor de mezcla despreciable:

• La entalpía del vapor:

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Cálculo de la temperatura
• Combinando:

• Si el sistema está bien mezclado podríamos asumir equilibrio térmico (Tp=Tsal). Si suponemos
arbitrariamente que Tp=Tsal=Tref, se obtienen las expresiones más simplificadas del balance de energía:

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Procedimiento solución pervaporación
Directo si se especifican la temperatura de salida o el
corte.

Corte:

• Calcular Tsal.
• Trazar curva de velocidad de transferencia, con valores arbitrarios de xsal,
calcular selectividad, calcular yp y ubicar el punto en la gráfica.
• Si se disponen de datos experimentales de xsal vs yp se grafican
directamente.
• Trazar la línea de operación y donde se corte con la de velocidad, será la
solución del problema.

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