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CHE-396 Senior Design Membrane Separation

Membrane Separation and


Ultrafiltration

Syed Ali
Paul Boblak
Efrem Capili
Stanislav Milidovich

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CHE-396 Senior Design Membrane Separation

Table of Contents
Introduction … … … … … ..… … … … … … … … … … … … … … … … … … … … … … … ...1

FlowSheet. … … … … … ..… … … … … … … … … … … … … … … … … … … … … … … … .5

Process Operation … … … … … … … … … … … … … … … … … … … … … … … … … … .7

Limitations ..… … … … … … … … … … … … … … … … … … … … … … … … … … … … … 12

Decision Tree… … … … … … … … … … … … … … … … … … … … … … … … … … … … ..13

Theory on Design Parameters… … … … … … … … … … … … … … … … … … … … … .14

Properties … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 18

Examples.. … … … … … … … … … … … … … … … … … … … … … … … … … … … … … ..19

Costs … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … … 27

Alternatives … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .29

References … … … … … … … … … … … … … … … … … … … … … … … … … … … … … .31

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CHE-396 Senior Design Membrane Separation

Introduction

Membrane separation involves partially separating a feed containing a mixture of


two or more components by use of a semipermeable barrier (the membrane) through
which one or more of the species moves faster than another or other species. As shown
in Figure 1, the basic process of the membrane separation involves a feed mixture
separated into a retentate (part of the feed that does not pass through the membrane, i.e.,
is retained) and a permeate (part of the feed that passes through the membrane).

Feed
Mixture

Retentate

Membrane

Permeate

Sweep
(optional)

Figure 1: Basic Membrane Separation

Although the majority of time the feed, retentate, and permeate are usually liquid or gas,
they may also be solid. The optional sweep is a liquid or gas, used to help remove the
permeate.

Membrane Structures
Because the membrane must allow certain constituents to pass through, they must
have a high permeability to certain types of molecules. Membrane structures consist of
the following three basic types:

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CHE-396 Senior Design Membrane Separation

♦ Porous Membranes
Porous membranes are used in microfiltration and ultrafiltration.
The dimension of the pores (0.1~10um) mainly determines the separation
characteristics. High selectivities can be obtained when the size of the
solute is large relative to the pore size in the membrane. Microporous
membranes are similar to porous membranes and differ in regards to pore
dimension (50~500 angstrom). Refer to Figure 2.

Figure 2: Porous Membrane (separation of smaller species)

♦ Non-Porous Membranes
These membranes are capable of separating molecules of the same
size, gases as well as liquids. Non-porous membranes do not contain any
macroscopic pores. The transport is determined by the diffusion
mechanism, which means that components first must dissolve into the
membrane and then diffuse through the membrane due to a driving force.
Separation is due to differences in diffusivity and/or solubility. These
membranes can be found in gas separation. Refer to Figure 3.

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CHE-396 Senior Design Membrane Separation
Polymer

Figure 3: Non-Porous Membrane


♦ Carrier Membranes
In this type of membrane, separation occurs by a carrier molecule
transporting the desired component across the barrier. The carrier
molecule shows a very specific affinity to one component or class of
components in the feed, which means that high selectivity can be obtained.
Since the separation is completely determined by the carrier solute,
interaction of all types of components can be removed: gaseous or liquid.

Liquid
Carrier

Figure 4: Carrier membrane


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CHE-396 Senior Design Membrane Separation

Membrane Types
The membrane structures are made of various materials of natural or synthetic
polymers (macromolecules). The representative membrane materials and applications are
listed in Table 1.

Materials Membrane Separation Process


Plyproylene Microfiltration (MF)
Polysulfone Ultrafiltration (UF), Gas Separation (GS)
Polyimide Gas Separation
Polyamide Reverse Osmosis (RO)
Polyacrylonitrile Ultrafiltration
Cellulose Microfiltration , Ultrafiltration, Reverse
Osmosis

Table 1: Membrane Materials for Various Applications

Flowsheet
Membrane separation flow patterns are parallel flow, series flow and two-stage
flow. Parallel flow schematic is shown in Figure 5. It used when there is no need for a
high selectivity in either the permeate or retentate. The advantage is that it if one of the
stages gets clogged the entire process does not have to be stopped, where as in series or
stage this is not the case. Series flow is depicted in Figure 6 and is used for high
selectivity in the retentate. Two stage flow yields a higher selectivity in the permeate and
is shown in Figure 7.

Retentate

Feed
Permeate

Figure 5: Parallel Flow

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CHE-396 Senior Design Membrane Separation

Feed Retentate

Permeate Permeate

Figure 6: Series Flow

Retentate
Feed Retentate

Permeate

Figure 7: Two-Stage Flow

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CHE-396 Senior Design Membrane Separation

Process Operation

Membrane Separation Processes


The basic principles of membrane separation are used in many of the industrially
important membrane separation operations. The mode of membrane separation, an
example of its application, the driving forces, the permeates, and concentrates of the
different processes are described in Table 2.

Membrane Description Initial or Membrane Industrial Driving Permeates Concentrates


Separation Feed Phase Structure Application Forces
Dialysis Process for Liquid Porous membrane Hemodialysis Pressure/ Blood Waste metabolites,
selective (removal of waste Concentration etc.
removing of low metabolites, excess Difference
molecular weight body water, and
solids from a restoration of
solution electrolyte balance
in blood)
Gas Separation Component(s) of Vapor of Gas Nonporous Separation of air Pressure/ Oxygen Nitrogen
a gas are membrane Concentration
removed through Difference
a pressure
gradient
Liquid Extraction of a Vapor and/or Liquid membrane Recovery of zinc Pressure Wastewater Zinc
Membrane solute Liquid from wastewater Difference
Microfiltration Separation of Liquid or Gas Microporous Separation of Pressure Water, Solvents Suspended solids
organic and membrane suspended solids Difference
polymeric from liquid mixture
compounds with
micro pore ranges
of 50-500
angstrom
Pervaporation Component(s) of Liquid Nonporous Dehydration of Pressure Ethanol Water
a mixture diffuse membrane ethanol- water Difference
through, azeotrope
evaporate under a
low pressure, and
are removed by a
vacuum
Reverse Passage of a Liquid Nonporous Separation of Ions Pressure Water Salt Ions
Osmosis solvent through a membrane Difference
dense membrane
that is permeable
to solvent but not
solute(s)
Ultrafiltration Separation of Liquid Microporous Separation of Pressure Water, Low Colloid, High
polymeric membrane polymeric Difference molecular weight molecular weight
compounds from compounds from component component
aqueous solution aqueous solution

Table 2: Membrane Separation Processes with its Various Characteristics

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CHE-396 Senior Design Membrane Separation

Membrane Module Types and Their Characteristics


The various membrane materials described in the previous section are available in
one or more of the following modules: plate and frame, spiral-wound, tubular, and hollow
fiber.
♦ Plate and Frame
Process Description: In Figure 8, the arrows show the upstream and
permeate paths. The upstream leaves as the retentate and is enriched in
non-permeate. Permeates is collected from channels in support plates and
leaves enriched in the most permeable component.
Advantages: Easy to clean and replace membranes.
Disadvantages: Low membrane area per volume (a problem in high-
pressure application where pressure vessel costs are significant).

Figure 8: Plate and Frame Schematic

♦ Spiral-Wound Module
Process Description: The feed passes through membrane that is spirally
wound around the porous tube (refer to Figure 9). The membrane, feed
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CHE-396 Senior Design Membrane Separation

spacer, and permeate spacer are glued on three sides and terminates at its
fourth side into the porous pipe that collects the permeate. This module is
wrapped into a spiral and placed in a cylinder shell.
Advantages: Easy and inexpensive to adjust hydronomics by changing
feed spacer thickness to overcome concentration polarization and fouling.
Disadvantages: Low membrane area per volume. May become expensive
for high-pressures because extra high-pressure shells must be purchased.
By passing of feed may occur due to nonuniform wrapping of module
spiral.

(www.synderfiltration.com/technology/index.html)

Figure 9: Spiral Wound Schematic

♦ Hollow-Fiber, Capillary, and Tubular


Process Description: Hollow fibers (<0.5 mm diameter (D)), capillaries
(0.5-5 mm D), and tubes (5-15 mm D) can be configured in bore or shell
feed modules (refer to Figures 10 and 11). Packing density can be as high
as 50%. Positions of feed and permeate ports affect flow in the module.

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CHE-396 Senior Design Membrane Separation

High-pressure pressure applications tend to use shell feed, and low


pressures favor bore feeds.
Advantages: Eliminates bypassing when used in bore feed mode. Huge
membrane area per volume possible with fibers.
Disadvantages: Membrane formation is more complex because the
support and the selecting layer are formed as an integral cylindrical unit
during spinning for fibers and capillaries. To avoid excessive pressure
drop in bore for bore feed mode, large diameter fibers may be required in
some cases. Bypassing of feed in shell feed mode due to any
nonuniformities in fiber packing. Fouling due to high surface areas if feed
contains particulates or other foulants.

Figure 10: Bore Feed Schematic

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CHE-396 Senior Design Membrane Separation

Figure 11: Shell Feed Schematic

Table 3 lists the packing density (m2/m3), resistance to fouling, ease of cleaning, relative
cost, and main applications for each of the modules.

Plate and Frame Spiral-Wound Tubular Hollow-Fiber


Packing density, m2/m3 30 to 500 200 to 800 30 to 200 500 to 9,000
Resistance to fouling Good Moderate Very Good Poor
Ease of cleaning Good Fair Ecellent Poor
Relative cost High Low High Low
Main application D, RO, PV, UF, MF D, RO, GP, UF, MF RO, UF D, RO, GP, UF

Table 3: Characteristics of Membrane Modules

Pressure, temperature and flow rate each plays an important role in membrane
separation. At high-pressure difference, the concentration at the membrane surface will
reach a critical value where a cake or gel forms. Under these conditions, the volumetric
flux reaches a limiting value called a ceiling flux which is characteristic of the cross flow
rate and solute diffusion coefficient in the boundary layer. Further increases in pressure
not only will fail to provide additional flux, but can drive the precipitated layers into the
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CHE-396 Senior Design Membrane Separation

pores and irreversibly damage the membranes. Therefore, operating at pressures leading
to limiting flux behavior is not recommended. This precipitated layer is known as
concentration polarization that is accumulation of rejected non-permeated solute at the
interface of the membrane.
Operating at high-pressures can lead to damage of the membrane and low
pressures will not produce enough pressure difference to get the desired selectivity.
Similarly, the flow rates and fluid dynamics play a vital role. With suspension, shell-fed
hollow fiber and even spiral wound modules have a tendency to clog, while flat sheet and
bore fed tubular designs show the least tendency to clog under cross flow filtration.
Turbulent cross-flow velocities are required to avoid serious polarization and fouling in
some cases. Proper surface modification and management of fluid dynamics at
membrane surface are necessary to avoid fouling.
Temperature constraints occur due to the material of the membrane. If the
temperature is too high, the membrane may melt and be irreversibly damaged. Therefore,
it is necessary to verify that the operating temperature is suitable for the membrane. The
amount of membrane needed, sizing, depends on the selectivity that needs to be achieved.
Details on calculating total membrane surface area are discussed in the theory section.

Limitations
The following are some of the general limitations with membrane separations:
♦ Fouling which occurs because the membrane is clogged, this leads to
frequent cleaning
♦ Fluctuation in concentration is not handled well by the membrane
♦ Size of particles being separated; there is a molecular weight cut off
♦ Temperature and pH effects on diffusivity must always be considered
♦ 100-200 psi for porous membranes: collapse, blocks pores
♦ 200~1000 psi for non-porous membranes
♦ Temperature
♦ Melting Point
♦ Plastic membranes melt at 200°C
♦ Ceramic at higher temperatures
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CHE-396 Senior Design Membrane Separation

Decision Tree

Step 1: Step 2: Step 3:


Properties of Properties of Calculation of
Components in Feed Membrane Permeability

Step 6: Step 4:
Step 5:
Final Design and Membrane Design
Optimum Design
Costs Equations

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CHE-396 Senior Design Membrane Separation

Theory on Design Parameters


In this section, we will illustrate the equations involved with membrane
separations for porous and non-porous membranes. These equations will include
calculations for effective diffusivity, molar transmembrane flux, separation factor, and
the area of the membrane unit (transport equation).

Porous Membranes
• General Flux Equation
The mass transfer can be described by the molar transmembrane flux of the species i of:
Ni =Pmi / lm (driving force) = Pmi *(driving force)
Pmi * is known as the permeance of species i, which is defined as the ratio of permeability
(Pmi) to membrane thickness (lm) of a species.
• Molar Transmembrane Flux for Liquid Separations
For liquid separations, where liquid components exist on both sides of the membrane,
a modified form of Fick’s law can describe this phenomenon where the driving force is
concentration driven.

Ni = (Dei / lm) * (cio - ciL)

Where Ni = Solute transmembrane flux


cio Dei = effective diffusivity
lm = membrane thickness
ci = concentration of i in the solution

cif ci cip

Figure T-1

• Effective Diffusivity for Liquids


Dei =∈ * Di * Kri / τ

Where Di = ordinary molecular diffusion coefficient


of solute i in solution
∈ = volume fraction of pores in membrane
Kri = restrictive factor

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CHE-396 Senior Design Membrane Separation

τ = tortuosity

The restrictive factor(Kri) accounts for the effects of pore diameter(dp), when the ratio of
molecular diameter(dm ) to pore diameter(dp) exceeds approx. 0.01. This restrictive factor
can be approximated by Beck and Schultz with: Kri = [1 - dm/dp]4 where 1.0 ≥ dm/dp.

• Molar Transmembrane Flux for Gas Separations

For gas components on both sides of the membrane, the rate of component diffusion
can also be described by Fick’s Law, in terms of partial pressure driving force:

Ni = Dei * cm* (pio - piL)/(P* lm )

pif pio Where Ni = Solute transmembrane flux


Dei = effective diffusivity
lm = membrane thickness
cm = total conc. of gas mixture = P / RT
pil pip P = total pressure
pi = partial pressure

Figure T-2

• Effective Diffusivity for Gases

Dei =(∈ / τ ) * [ {(1/ Di ) + (1/ Dki )} ]

Where Di = ordinary molecular diffusion coefficient


of solute i in solution
Dki = Knudsen diffusivity
∈ = volume fraction of pores in membrane
τ = tortuosity

Knudsen diffusion takes into account the kinetic theory of gases applied to a straight
cylindrical pore. It depends on the temperature(T), molecular weight of the
component(Mi ), and diameter of the pore(dp ).

Dki = 4850 * dp * (T/Mi )1/2

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CHE-396 Senior Design Membrane Separation

Non-Porous Membranes
• Molar Transmembrane Flux for the Liquid Separation

Fick’s law in terms of concentration can also describe liquid mixtures, which are
concentration driven, Figure T-3.

Ni = (Ki*Dei/lm) * (cio-cil)

Where Ni = Solute transmembrane flux


cif Ki = Solubility of solute in mmbrane
c'io Dei = effective diffusivity
lm = membrane thickness
cio c'il cip ci = concentration of i in the solution

cil

Figure T-3

• Molar Transmembrane Flux for the Gas Separations

For gas mixtures, which are pressure driven, Figure T-4, the flux is described by:

NI = (Hi*Di/lm) * (pio-pil)
Or in the absence of boundary layer resistance,
pif Ni = (H i*Di/lm) * (xi * Pf – yi*Pp)
pio Where Hi = Henry’s Constant for species i
into a specified membrane
cio pil pip Pf = Pressure of the feed
Pp = Pressure of the permeate
Xi = mole fraction in retentate
cil yi = mole fraction in the permeate

Figure T-4

There are four flow modules that may describe the characteristics of the species entering
a membrane separator. The four modules are 1.Perfect mixing, 2.Counter current, 3.Co-
current, and 4.Crossflow. Walawender and Stern describe each module in detail. For ease
of calculation, the perfect mixing flow module was selected to illustrate the separation
factor and transport equation,

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CHE-396 Senior Design Membrane Separation

Perfect mixing flow patterns:

• Separation Factor

From the perfect mixing flow pattern, we can obtain the separation factor
Separation factor equation similar to relative volatility in distillation:
αA,B =(Ya / Xa) / (Yb/Xb)
For conditions where downstream pressure is negligible (or the ideal separation factor) :
αA,B * =HaDa/HbDb = Pma* / * Pmb*
For conditions where downstream pressure is not negligible:
αA,B = α A,B * *[XA(α A,B – 1) + 1 – r*αA,B ] / [XA(αA,B – 1) + 1 – r ]
Along with this relationship and the transport equations, the surface area of the
membrane can be calculated, thus the size of the membrane can be found.

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CHE-396 Senior Design Membrane Separation

Properties

Required data for gas permeation design


• Henry’s constant: is a property of each individual membrane and component used to
correct gas diffusion and it is obtained by performing experimental measurements on
a given membrane (Not to be confused with Henry’s gas constant). Use producer
reports for Henry’s constant determination.
• Diffusivity: is a property is a property of each individual membrane and it is also
experimentally determined. Use producer reports for Diffusivity determination.
• Membrane thickness: is a property of the membrane and is usually specified by the
manufacturer.

Membrane properties which must be given by manufacturers:


• α = Membrane Selectivity (Dimensionless)
• ε = Porosity (Dimensionless)
• τ = Tortuosity (Dimensionless)
• lm = Membrane Thickness (µm)
• d = Fiber diameter
• P = Pressure specifications
• T = Temperature specifications
• Pmi = Permeance of species i

Membrane properties found/required:


• Xi = Mole fraction of species i in retentate
• Yi = Mole fraction of species i in permeate
• Hi = Henry's Constant for species i
• Pmb = Permeability
• θ = Cut or Ratio of Permeate to Feed
• Am = Total membrane area
• ci = Concentration of species i
• Di = Ordinary molecular diffusion coefficient of solute i in solution
• Kri = Restrictive factor
• Dki = Knudsen diffusivity
• np = Moles of permeate

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CHE-396 Senior Design Membrane Separation

Examples
1.0 Design Example

• Design Problem

A mixture composed of 80% lights (CH4, CO, C2H4) and 20% acetone is fed into a
membrane separator at 500 lbmol/hr. A low-density polyethylene membrane is used for
carbon monoxide separation. The inlet temperature and pressure are 100°F and 150 psia,
respectively. The permeate (mostly carbon monoxide) is leaving at 15 psia.

Assume lights are mostly carbon monoxide due to similar molecular weight and diffusion
property. The related values for other components can be obtained in Perry’s Handbook.

• Analytical Analysis

The permeability of CO and acetone in the membrane is determined by

PmCO = HCO * DCO (D-1)


PmAce = H Ace * DAce (D-2)

Where H(CO) = 0.336*10-6 cm^3(STP)/cm^3-Pa, D(CO) = 0.332*10-6, cm^2/s, H(Ace) =


0.162*10-6 cm^3(STP)/cm^3-Pa, and D(Ace)=0.16*10-6 cm^2/s.
Note: The values of HAce, DAce were estimated by an inverse relationship of molecular
weight from Table 14.6 (Seader/Henley, 1998).

PmCO = 8.29* 10-13 lbmol-ft/ft2-h-psia PmAce = 1.93 * 10-12 lbmol-ft/ft2-h-psia

The membrane thickness was assumed to be

lm = 0.2*10-6 m = 0.66*10-6 ft

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CHE-396 Senior Design Membrane Separation

The permeance of each component is now calculated by the following equation

PmCO* = P mCO / lm 8.29* 10-13 / 0.66*10-6 ft = 1.256 * 10-5 lbmol/ft2-h-psia

PmAce* = 2.92* 10-6 lbmol/ft2-h-psia

Material balances for Acetone in this process is:

ZFAce * nf = YpAce * np + XRAceb * nb

where ZFace , YPAce,, and XRAce are the mole fractions of Acetone in the feed, permeate,
and retentate, respectively.

ZFAce = YPAce (nP/nF) + XRAce (nR/nF)

where θ = (nP/nF), and (1 - θ) = (nR/nF), which is just a ratio to simplify calculations.

XRAce = (ZFAce - YPAce * θ) / (1 - θ) = (0.2 - YPAce * θ) / (1 - θ) (D-3)

Similarly, for CO

XRCO = (ZFCO - YPCO * θ) / (1 - θ) = (0.8 - YPCO * θ) / (1 - θ) (D-4)


A separation factor given in Seader/Henley, 1998, is defined as

α =(YPCO / XRCOe) / (1-YPCO/1-XRCO) (D-5)

α = α* [(X RCO (α– 1) + 1 – rα ] / [XRCO (α – 1) + 1 – r ] (D-6)

where α* = PmCO* / PmAce* = 1.256* 10-5 / 2.92* 10-6 = 4.3

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CHE-396 Senior Design Membrane Separation

r = Ppermeate / Pretentate = 15/150 = 0.1

substituting the above numbers into D-3

α = 4.3*[(X RCO (α– 1) + 1 – .1α ] / [XRCO (α – 1) + 0.9 ] (D-7)

Transport equation are also given in Seader/Henley, 1998

YPAce*nF θ=Am* PmAce* * (XRAce * PR – YPAce*PP) (D-8)

YPCO* nF θ =Am* PmPCO* * (XRCO * PR – YPCO*PP) (D-9)

where Am is area of the membrane

Solving equations (D-3), (D-4), (D-5), (D-7), (D-8), and (D-9) simultaneously with
unknowns: XRAce, XRCO, YPCO, YPace , AM, and α. The variable θ is bounded between 0
and 1, so values of θ are selected in that range. The six equations with these six unknown
variables were solved simultaneously with a computer program such as Mathcad. The
following results are shown in the Membrane Cost Analysis section.

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CHE-396 Senior Design Membrane Separation

• Membrane Cost Analysis

Costs were calculated by using an average cost factor of $80/ft2 of membrane. This cost
takes into account purchase and installation costs for a given membrane.

θ XRAce Am,ft2 Cost

0.01 0.21 3.54*103 $280,000


0.2 0.232 7.29*104 $5,840,000
0.4 0.274 1.52*105 $12,200,000
0.6 0.331 2.42*105 $19,400,000
0.8 0.404 3.49*105 $27,900,000
0.99 0.489 4.75*105 $38,000,000

• Compressor Costs Analysis

First, the horsepower (hp) of the compressor must be determined. For this we use the
relationship described in Douglas on page 153. The equation is as follows:

3.03 *10 − 5   Pout γ 


hp = 
 
PinQin   − 1
 γ  
 Pin  

where Pin (lbf/ft^2) is the initial pressure, Pout (lbf/ft^2) is the final pressure, Qin
(ft^3/min) the flowrate into the compressor, and y has a value of 0.23 for complex gases.

The horsepower required to operate the compressor in this design problem is 760 hp from
the above equation.

Next, the brake horsepower (bhp) is obtained by introducing the compressor efficiency of
80%.

bhp = hp/0.8

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CHE-396 Senior Design Membrane Separation

The bhp for this problem is 950.

The purchase and instillation costs were obtained from Guthrie’s correlations described
in Douglas on page 573.

The purchase cost for required compressor is $552,000, while the installed cost is
$1,160,000, giving a total investment of $1,720,000.

• Annualized Total Cost Analysis


Annualized cost is based on a six year payback period.
Concentration of Acetone Annualized Annualized Annualized
In Retentate After Membrane Cost Compressor Cost Total Cost
Separation $ $ $
20.1 % $47,000 $287,000 $334,000
23.2 % $973,000 $287,000 $1,260,000
27.4 % $2,030,000 $287,000 $2,317,000
33.1 % $3,230,000 $287,000 $3,517,000
40.4 % $4,650,000 $287,000 $4,937,000
48.9 % $6,300,000 $287,000 $6,587,000

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CHE-396 Senior Design Membrane Separation

2.0 Membrane Book Example (Separation Process Principles,


Seader/Henley, 1998)

• Problem

A total of 20,000 scfm of air is compressed, cooled, and treated to remove moisture and
the compressor oil, prior to being sent to the membrane separator at 150 psia and 78ο F.
Assuming the air composition of 79% nitrogen and 21% oxygen. A low-density
polyethylene membrane in the form of a thin-film composite is being considered. If the
membrane skin is 0.2 µm thick, calculate the material balance and the area in ft2 for the
membrane as a function of the cut(fraction of feed permeated). Assume a pressure of 15
psia on the permeate side with perfect mixing on both sides of the membrane, such that
compositions on both sides are uniform and equal to exit compositions. Neglect pressure
drop and mass transfer resistance external to the membrane.

• Solution

Assume standard conditions are 0 C and 1 atm(359ft3/lbmol)

Nf = feed flow rate = 3,343 lbmol/h

For low-density polyethylene membrane, H(N2)=0.228*10-6 , D(N2)=0.32*10-6,


H(O2)=0.472*10-6 , and D(O2)=0.46*10-6 .

Calculates Permeability (Pmb).

Pmb = Hb * Db
P(O2) = 16.2 * 10-12 lbmol-ft/ft2-h-psia P(N2) = 5.43 * 10-12 lbmol-ft/ft2-h-
psia
A. Example for membranes: [Seader/Henley, 736] Cont.…

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CHE-396 Senior Design Membrane Separation

Calculates Permeance(Pmb*)
Pmb* = Pmb / lm lm = 0.2 µm = 0.66 * 10-6 ft
P(O2) * = 24.55 * 10-6 lbmol/ft2-h-psia P(N2) * = 3.58 * 10-6 lbmol/ft2-h-psia
Material balance equations:
For N2, Xfb * nf = Ypb * np + Xrb * nb

where n = flow rate in lbmol/h and the subscripts f, p, and r refer, respectively, to the
feed, permeate, and retentate. Let
θ= cut = np / nf, then (1- θ) = = nr / nf, (1)
Substituting the definition of θ in (1) gives

Xrb = (Xfb - Ypb * θ) / (1 - θ)=(0.79 - Ypb * θ) / (1 - θ) (2)

And similarly, for O2

Xra = (Xfa - Ypa * θ) / (1 - θ)=(0.21 - Ypa * θ) / (1 - θ) (3)

Separation factor:
Since both fluids are well mixed, then the following relationship can be used:
α A,B =(Ypa / Xra) / (1-Ypa/1-Xra) (4)

Transport equations:
The transport of A and B through the membrane of are Am, with partial pressures at exit
conditions because of perfect mixing, can be written as:
Ypb*np =Am* P mb* * (Xrb * Pr – Ypb*Pp) (5)
Ypa*np =Am* Pma* * (Xrb * Pr – Ypa*Pp) (6)

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CHE-396 Senior Design Membrane Separation

Where Am is the membrane area normal to flow, np, through the membrane. The ratio of
(6) to (5) is Ypa/Ypb, and subsequent manipulations lead to:

α A,B = α = 2.99 *[XrA (α– 1) + 1 – 0.299 ] / [XrA(α – 1) + 1 – 0.1 ]


(7)

Where r = Pp / Pr = 15 / 150 = 0.1 and αA,B * = αo 2,n2 = Pm,o2* /Pm,n2* = 2.99

Equations (3), (4), and (7) contain four unknowns: Xra, Ypa, θ, and αA,B = α. The
variable θ is bounded between 0 and 1, so values of θ are selected in that range. The other
three variables are computed in the following manner. Combine (3), (4), and (7) to
eliminate α and Xra. Solve (6) for the membrane area, Am. Alternatively, the three
equations can be solved simultaneously with a computer program such as Mathcad. The
following results were obtained:

θ Xra Ypa α A,B Am,ft2

0.01 0.208 0.406 2.602 22,000


0.2 0.174 0.353 2.587 462,000
0.4 0.146 0.306 2.574 961,000
0.6 0.124 0.267 2.563 1,488,000
0.8 0.108 0.236 2.555 2,035,000
0.99 0.095 0.211 2.548 2,567,000

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CHE-396 Senior Design Membrane Separation

Costs
The total capital costs for a membrane separation unit, and in particular the
ultrafiltration unit, include the costs for the membranes, pumps, a cleaning system,
piping, instrumentation, an electrical control panel, and a process tank. A distribution of
these costs are shown in Table C1, which were taken from Perry’s Chemical Engineers’
Handbook (7th ed.). Table C2 illustrates an estimation of the operating costs for the
membrane unit.

Cost Distribution % of Total Capital Investment


Membranes and membrane housing 17-40
Pumps, motors, etc. 15-9
Pipes, valves, and framework 35-31
Cleaning system 18-10
Control panel 15-10

Table C1: Total Capital Investment Distribution

a
The costs of a membrane unit are estimated by a correlation r (area) , where r and
a are empirical constants. The constants depend on the kinds of membranes and
equipments used, but can only be figured out by actual cases studied. For a preliminary
2
estimate, the cost of a membrane and its installation is $80/ft of membrane area. By
knowing that value, you can use the cost distribution in Table C1 to determine the total
capital investment.

Range of Variable
Expense Item Commonly Encountered
Energy consumption 0.5-5 kWh/m3 permeated
Cleaning chemicals and lost product $10-100/m2 membrane installed year
Membrane replacement 1-5 years at $20-40/m2; 10-20 years
at $200/m2
Operating, cleaning, and maintenance labor 2-3% of installed capital
Maintenance materials 0.6-0.06% of installed capital

Table C2: Operating Costs


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CHE-396 Senior Design Membrane Separation

The total cost for the membrane separation unit is equal to the operating plus the
total investment cost. Since a compressor is required for certain membrane operations,
annualized costs for this unit must also be calculated. Pricing for a compressor is given
by Guthrie’s correlation in Douglas’s Conceptual Design of Chemical Processes. To get
an annualized cost, just divide the total cost by the payback period. The total cost is
largely based on the cost of a membrane and its installation ($80/ft2). Because this is a
rough estimate, the pricing for your membrane unit can be estimated from vendors listed
in Table C3.

Sales Representative Equipment Manufacturer Type of Equipment


Tom Jordan
ABCOR Koch Membrane Systems Ultrafiltration
455 E. Eisenhower Romicon Membrane
Hazel Park, MI 48030 Systems
(313) 545-2400
A.T.A. Industries, Inc.
P.O. Box 250161 Ultrafiltration
West Bloomfield, MI
48325-0161
(313) 363-7214
Barrett & Burgess, Inc.
46901 Grand River Ave. Pace Ultrafiltration
Novi, MI 48050
(313) 348-3000
George R. Babb
B & K Environmental, Inc. Ultrafiltration
2712 Kraft S.E. & Reverse
Box 7 Osmosis
Grand Rapids, MI 49546
(616) 940-0030
Phil Wolfe
Enviro-Process Systems Enviro-Process Systems Ultrafiltration
P.O. Box 731
Bronxville, NY 10708
(914) 965-0599
James E. Giesel
P.O. Box 160 Marlin Diversified Ultrafiltration
Waters, MI 49797-0160

Table C3: List of Vendors

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CHE-396 Senior Design Membrane Separation

Alternatives
When ultrafiltration is not applicable for the separation of your system, other
forms of membrane separation could be used, such as those shown in Table 2 of the
process operation section. If membrane separation or separation by a barrier can not be
used for your system, alternative separation systems may be employed. Those systems
involve separation by phase addition or creation. Types of these separation operations
are illustrated in Table A1.

Separation Created or Separating Industrial


Operation Feed Phase added phase Agent Example
Partial Vapor and/or Liquid or Heat Recovery of H2 and N2
Condensation Liquid vapor Transfer (ESA) from ammonia
Flash Liquid Vapor Pressure Recovery of water
Vaporization Reduction from seawater
Distillation Vapor and/or Vapor and Heat Purification of
Liquid liquid Transfer (ESA) styrene
Extractive Vapor and/or Vapor and Liquid solvent (MSA) Separation of acetone
Distillation Liquid liquid & Heat transfer (ESA) and methanol
Absorption Vapor Liquid Liquid absorbant Separation of CO2 from
(MSA) combustion by absorption
w/ethanolamine
Stripping Liquid Vapor Stripping Vapor Steam stripping of naphtha
(MSA) kerosene, and gas oil from
crude distillation unit to
remove light ends
Liquid-Liquid Liquid Liquid Liquid solvent Recovery of aromatics
Extraction (MSA)
Evaporation Liquid Vapor Heat Evaporation of water from
Transfer (ESA) solution of urea and water
Crystallization Liquid Solid and Heat Crystallization of p-xylene
vapor Transfer (ESA) from mixture w/m-xylene
Desublimation Vapor Solid Heat Recovery of phthalic anhy-
Transfer (ESA) dride from noncondensible
gas
Leaching Solid Liquid Liquid solvent Extraction of sucrose from
(MSA) sugar beets w/hot water
Foam Liquid Vapor Gas Bubbles Recovery of detergents
Fractionation (MSA) from waste solutions

Table A1: Separation operations based on phase addition or creation

29
CHE-396 Senior Design Membrane Separation

The table gives a description of the separating agents involved with the operations, the
initial phase, the added or created phase, and an industrial example.
Separation by phase addition or creation involves the use of energy-separating
agents (ESA) and/or mass-separating agents (MSA). ESA consists of transferring heat or
shaft work to or from the mixture to be separated. An MSA may be partially immiscible
with one or more species in a mixture. It may also be miscible with a liquid mixture, but
may alter the partitioning of species between liquid and vapor phases. To facilitate a
more complete separation, an MSA may be used in conjunction with an ESA.

30
CHE-396 Senior Design Membrane Separation

References

Brandrup, J., Polymer Handbook, Second Edition, John Whiley and Sons, New York,
1975, p. III-229 to III-240

Douglas, James M., Conceptual Design of Chemical Processes, McGraw-Hill


Companies, Inc., 1988, p. 153-156, 573.

Matsuura, Takeshi, Reverse Osmosis and Ultrafiltration, American Chemical Society,


Philadelphia, 1985.

Meares, Patrick, Membrane Separation Processes, Elsevier Scientific Publishing


Company, New York, 1976.

Perry, Robert H. & Don W. Green , Perry’s Chemical Engineers’Handbook, 7th ed., The
McGraw-Hill Companies, Inc., 1997, p. 22-52 to 22-57.

Seader & Henley, Separation Process Priciples, John Wiley and Sons, New York, 1998,
p. 7-15, 713-772.

Wiley, John and Sons, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., New
York (1978-1984).

http://www.synderfiltration.com/technology/index.html

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