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Solid/Liquid Separations

Selecting
Membrane Filtration
Systems
Wu Chen Proper design and scaleup of a membrane
Frank Parma
Anant Patkar filtration system requires an understanding
Adrienne Elkin and of the availability of membrane material,
Subrata Sen,
The Dow Chemical Co. pore size and module configurations.
These practical guidelines will help in the
selection process.

T
HE GROWING NEED FOR FINE FILTRATION Membrane classifications
in food and beverage manufacturing, biopro- Traditional filtration media such as filter cloth, wire
cessing and water treatment has placed mem- mesh or sintered metal have been used to remove parti-
brane filtration at the forefront of separation tech- cles measuring down to 1 mm. But, due to the lack of
nologies applied in the chemical process and related technology in manufacturing these media, they have
industries. However, membranes’ increasing preva- not been successful in filtering out finer particles. Ad-
lence in separation applications has not diminished vances in polymer technology have brought to market
the challenges users face when trying to design the many membranes with pore sizes down to a few
optimal membrane system. angstroms (10–10 m), opening the doors to what is now
Fundamentally, one must be familiar with the called membrane filtration.
availability of membrane materials, membrane pore Depending on the sizes of particles to be separated,
sizes and membrane module configurations (e.g., spi- membrane filtration can be classified as microfiltration
ral-wound vs. flat sheet). One must also consider sev- (MF), ultrafiltration (UF) or reverse osmosis (RO). There
eral crucial operating parameters during the mem- are no clear-cut boundaries among these categories. Nor-
brane evaluation and design phase, including module mally, MF refers to filtration of particles measuring ap-
geometry, flow patterns, flowrates (e.g., of the cross- proximately 0.05–1 µm. UF membranes reject particles
flow stream), shear rate, transmembrane pressure and measuring down to 30 nm (10–9 m). RO membranes are
cleaning strategies. In addition, pilot tests should be used to remove even smaller particles, such as sodium
conducted using membrane configurations that are ions, from the feed stream. Nanofiltration (NF), a rela-
similar to those of the full-scale system, in order to tively new term, has been employed for applications that
minimize problems during scaleup. Any attempts to fall within the boundaries of UF and RO.
design a membrane filtration system based on litera- MF membranes are rated by pore size, which is
ture data or small-scale laboratory tests alone will measured in microns. These ratings, however, are not
likely result in failure. always absolute. Membranes that have the same rating

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Table 1. Comparison of membrane filtration processes. Table 2. Commercially offered membranes.

Membrane Typical Typical ∆P, psi Supplier Membranes Offered


Process Pore Size Alfa-Laval PES, PS, RC, composite
Microfiltration 0.05–1 µm 5–50 Dow Chemical PES
Ultrafiltration 1–1,000 kD 7–100 Millipore PES, PVDF, RC, composite
GE Osmonics PAN, PES, PS,PTFE, PVDF, nylon, composite
Nanofiltration 0.01–1 kD 50–150
Reverse Osmosis 98–99% 120–1,200 Pall (Filtron) PES, PVDF, RC, ceramic, nylon
salt retention PTI PES, PAN, PS, PVDF, composite
Sartorius CA, PES, PP

may not exhibit identical rejection behaviors, due to differ- membrane suppliers typically offer a limited selection of
ences in membrane material, membrane microstructure, membrane materials (Table 2).
particle characteristics and membrane testing methods. Membrane filters are designed to filter very fine particles,
UF and NF membranes are rated using a term called which tend to form cakes with high resistance to flow. This
molecular weight cut-off (MWCO). The unit of measure can cause a rapid drop in the filtration rate with traditional
for MWCO is the Dalton (D). If a membrane does not dead-end filtration. The drop in filtration rate is especially
allow molecules with molecular weight of 100 g/mole or severe for compressible cakes formed by some biological
more to pass, then this membrane is considered to have a systems (e.g., bacterial cells from fermentation, broken cells
MWCO of 100 D. The MWCO is frequently expressed in after cell homogenization, mammalian cells after cell cul-
kD, where 1 kD = 1,000 Dalton. UF membranes are avail- ture). Thus, with membranes, crossflow filtration is normally
able in the range of 1–1,000 kD MWCOs. As in the case used to improve the filtration rate (Figure 1).
of MF, and for similar reasons, UF and NF membranes During crossflow filtration, the suspension flows at a
with identical ratings may not behave the same way. Man- high speed in the direction that is parallel to the filter sur-
ufacturers of UF and NF membranes use polymers with a face. This high flowrate provides greater shear at the mem-
defined molecular weight distribution, such as polyethy- brane surface, thereby preventing the solid particles from
lene glycol or dextrin, to evaluate membrane-rejection forming a cake, which permits a high filtration rate for a
characteristics. It is important to remember that the hydro- longer period of time.
dynamic radii of these extended polymers may be different
from those of the molecules one intends to separate. For Equipment options
example, proteins are usually globular and compact. In membrane filtration, the permeate (or filtrate) flows
Therefore, for complete rejection of a protein, one should through the membrane (in crossflow filtration, this flow is
use a membrane rated at one-fifth the molecular weight of perpendicular to the membrane surface), while the slurry
that protein (e.g., a 10-kD membrane should reject a 50- (or retentate) remains on the other side of the membrane.
kD protein completely). The filtration rate per unit membrane area is called perme-
For RO membranes, the rating is commonly listed as ate flux, commonly expressed in L/m2h.
percent (%) salt retention. Similar to UF and NF, the per- Due to the membranes’ small pore sizes and high medi-
cent removal depends on the type of salt and operating um resistance, the liquid flux is normally smaller than that
conditions. As the pore size decreases, the required driving seen in conventional filtration processes. A larger filtration
force (∆P) for filtration increases. A summary of mem- area is therefore necessary to achieve the required filtration
brane pore sizes and pressure drops for MF, UF, NF and
RO is presented in Table 1.

Membrane materials and modes of filtration


Although many membrane materials are discussed in lit-
erature, only a few are commercially available for large-
scale applications. Today, the most readily available mem-
brane materials for full-scale deployment are polyethersul-
fone (PES), polysulfone (PS), cellulose acetate (CA), re-
generated cellulose (RC), ceramic materials and sintered
metals. Less-commonly available materials are nylon,
polypropylene, polytetrafluoroethylene (PTFE), polyvinyli-
dene fluoride (PVDF), polyacrylonitriles (PAN) and com-
posites. Many other materials may have been developed,
but have not yet become commercially available. Due to ■ Figure 1. Shown are the two filtration modes: dead-end (left) and
difficulties in maintaining a wide array of product lines, crossflow (right).

CEP December 2004 www.cepmagazine.org 23


Solid/Liquid Separations

In this configuration, the retentate flows


across the membrane surface, while the per-
meate flows through the membrane to the col-
lection channels located at the edges of the
plates. Virtually any type of flat-sheet mem-
brane can be used. Some manufacturers fash-
a ion the flat sheets into cassettes that are easy
to replace and validate. However, in this case,
users would be limited to the membrane mate-
rials offered by the cassette suppliers.
Last, but not least, is the tubular arrange-
b ment (Figure 2d), which is used for polymer-
ic, ceramic or sintered-metal membrane fil-
ters. The advantages of ceramic or sintered-
metal filters are higher fluxes, greater toler-
ances to a broad range of operating conditions
(pH, temperature, solvents, pressure), ease of
cleaning and longer membrane life. Ceramic
d membrane modules tend to be more expen-
c sive, but are available in a wide variety of
pore sizes. Furthermore, their long lifecycle
■ Figure 2. Membrane element configurations: a)
spiral wound, courtesy of Dow Chemical Co.; b) hol- may result in lower long-term replacement
low fiber, courtesy of PCI Membrane Systems, Inc.; costs. Sintered-metal membranes are less
c) flat sheet, courtesy of Alfa Laval; d) tubular costly than their ceramic counterparts, but
ceramic, courtesy of Pall Corp. offer a limited selection of pore sizes.

capacity. One of the key issues in designing membrane fil- Membrane filter operation
ters is maximizing the filtration area, while avoiding the Crossflow rate and trans-membrane pressure (TMP) are
fabrication of very large equipment. two key parameters in the design and operation of a cross-
A membrane filtration system is composed of filter ves- flow membrane filtration system. Sufficient crossflow rate
sels in which a number of membrane modules are housed. is required to prevent concentration gradient buildup near
Four popular membrane module configurations are the spi- the membrane wall.
ral-type filter (Figure 2a), in which the membrane is spiral- Typical crossflow velocities for the cassette, hollow
wound and housed in a cylindrical casing. The retentate fiber, tubular and spiral configurations are, respectively,
flows in a direction that is parallel to the axis of the cylin- ~1–3 m/s, 1–5 m/s, ~5 m/s and ~3–8 gal/min (for a 2.5 in.
der and the permeate flows spirally into the membrane dia. × 40 in. long element). TMP controls the permeate
module’s central collection chamber. Today, spiral-type fil- flux. To this end, the following rule of thumb applies: The
ters are the most common and economic type of membrane higher the TMP, the higher the flux. It should be noted that
configuration, since they offer the highest membrane area crossflow rate and TMP are closely related. High crossflow
per footprint (space consumed in plant). However, these rates normally generate high TMPs, unless the back pres-
membranes are usually not suitable for systems with a high sure on the permeate side is properly controlled. Further, at
concentration of suspended solids. a given crossflow rate, the TMP cannot be decreased be-
Another module configuration that is frequently used in yond a certain value (which is dictated by the pressure drop
today’s industrial environment is the hollow fiber type (Fig- on the retentate side) without resulting in reverse flow
ure 2b). In this configuration, a bundle of hollow fibers (from the permeate to the retentate side) in part of the mod-
(with each fiber measuring 0.1–2 mm in internal diameter) ule. Reverse flow is particularly undesirable in spiral and
is contained within a shell. The retentate flows inside the some flat-sheet modules. Parameters, such as pH, tempera-
hollow fiber, while the permeate is collected on the shell ture and ionic strength of the medium may also be impor-
side. Hollow fiber membranes, like the spiral-wound mem- tant in some systems.
branes, are considered to be an economic option. However, The objective of membrane filtration has to be clearly
they are not recommended when solid particles are present. defined before attempting to optimize a filtration process.
Flat-sheet membrane systems, such as those shown in Often, the operating parameters (crossflow, TMP, pH, tem-
Figure 2c, comprise flat sheets of membranes that are at- perature, ionic strength) that result in the best filtration flux
tached to plastic plates, which provide mechanical support. may not permit optimal product passage. These parameters
Many plates can be stacked together to achieve a system must be carefully tested at the pilot scale to ensure success-
with a large filtration area. ful process design.

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Fouling is a major challenge in membrane filtration. It etc., that is intended for use on the production unit. It has
could be caused by blocking of the pores at the membrane been demonstrated over and over that membrane filter
surface or inside the membrane, constriction of the pores performance can be quite different — even for the same
by adsorption of particles, or chemical reactions occurring membrane type (e.g., a PVC membrane) that is conformed
on the membrane surface. The following techniques are to different module configurations (e.g., flat sheet vs. spi-
commonly employed to mitigate fouling: ral) or physical dimensions (diameter, length, height).
• providing high shear at the membrane surface Testing should establish the optimum operating parame-
• selecting a hydrophobic or hydrophilic membrane ters, process reproducibility, cleaning and sanitation meth-
based on the properties of the suspensions ods, as well as estimated membrane life under repeated
• operating the membrane under alternating conditions cycles of usage and cleaning.
(low pressure, different pH, temperature, etc.) The membrane filtration unit is normally designed
• coating the membrane with a fouling-resistant material. and built by companies that specialize in membrane sys-
If the process flux declines significantly, the membrane tems. Most membrane suppliers do not build complete
filter (and the system) should be cleaned. The frequency of systems. It is advisable to work closely with membrane
cleaning-in-place (CIP) is based upon the acceptable drop suppliers and system designers during the evaluation and
in membrane performance, the desired membrane life (fre- design phases, as experience still plays an important role
quent CIP may reduce membrane life) and regulatory con- in this technology. CEP

siderations. Commonly used chemicals for CIP include fil-


tered water (at room temperature or hot), base solutions
(usually sodium hydroxide), acids (phosphoric, nitric), de- WU CHEN is a senior specialist at The Dow Chemical Co. (B-1402, 2301 N.
Brazosport Blvd., Freeport, TX 77541; Phone: (979) 238-9943; Fax: (979)
tergents (ionic, nonionic) and chlorine (usually for applica- 238-0969; E-mail: wuchen@dow.com). He established a fluid/particle
tions under alkaline conditions). Multiple steps using dif- separation laboratory for Dow in Freeport for practical applications of
ferent reagents are often necessary to ensure efficient clean- fluid/particle separation technologies and has numerous publications
ing. One can obtain cleansing products designed specifical- about practical aspects of fluid/particle separation in journals,
conferences and books. Chen received his PhD in chemical engineering
ly for membranes from Ecolab, Alconox and Fibercorp, but from the Univ. of Houston (TX) and is an active member of the American
always consult the membrane manufacturer before writing Filtration and Separation Society (AFS), serving as society chair, board
cleaning protocols to ensure the chemicals are compatible member, as well as a speaker in numerous meetings. He is currently the
with the membrane materials. chair for the AFS Education Committee and a solid/liquid separation
course instructor for the ASME-AIChE continuing education program
Membrane sanitization may also be required when filter- (www.asme.org/education/shortco/aiche.htm).
ing products intended for food or pharmaceutical applica-
tions. Sanitation reagents include sodium hydroxide, nitric FRANK PARMA is a research specialist at The Dow Chemical Co., where he
acid, peracetic acid and chlorine. specializes in solid/liquid separations. In the past 15 years, he has
provided technical support for many Dow sites, both within the U.S. and
abroad. Parma’s recent focus has been on the application of solid/liquid
Selection of a filtration system separation technology for water treatment, especially in the area of water
Once a basic understanding of membrane filters is cap- and wastewater treatment chemicals. Parma received his BS in marine
tured, the process of selecting a membrane filtration sys- biology from Texas A&M Univ. (Galveston, TX). He is also an active
member of the AFS.
tem can begin.
1. Determine the separation goal. Since membrane fil- ANANT PATKAR is a senior specialist in the Bioprocessing R&D Group of The
tration systems are normally more expensive than tradition- Dow Chemical Co. (5501 Oberlin Dr., San Diego, CA 92121; Phone: (858)
al filters, ascertain whether membrane filtration is actually 352-4317; Fax: (858) 352-4602), where he engages in bioprocess
development, optimization and scaleup, with a primary focus on
necessary. Know the characteristics of the particles and liq- downstream processing. His industrial experience covers both microbial
uid, as well as the process conditions, such as temperature, fermentation and mammalian cell culture operations. Patkar received his
pressure and capacity requirement. PhD in chemical engineering from Purdue Univ.
2. Select a membrane pore size. One rule of thumb is to
ADRIENNE ELKIN, formerly a research engineer in the Bioprocessing R&D
select a membrane with a pore size one order of magnitude Group at The Dow Chemical Co., is currently employed by Merck & Co. She
smaller than the diameter of the particles to be separated. is experienced in downstream product recovery and purification process
However, this rule may not be true for all applications. development, scaleup and pilot-plant operation. Elkin received a BS in
Testing is therefore necessary. chemical engineering from Penn State Univ.
3. Ensure chemical compatibility. The suspension SUBRATA SEN is a R&D leader of Bioprocessing R&D Group at The Dow
should not attack the membrane and the membrane material Chemical Co. (Phone: (858) 352-4433; Fax: (858) 352-4602; E-mail:
should not be prone to fouling by the suspension. Small ssen@dow.com), where he spearheads the downstream recovery and
changes in operating conditions (pH, temperature) may im- purification operations. He received his BS in chemical engineering from
Indian Inst. of Technology (Kharagpur), and MS and PhD degrees in
prove chemical/membrane system compatibility. chemical engineering from Brigham Young Univ., specializing in flow
4. Perform pilot-scale tests. Conduct experiments physics and transport processes.
using the membrane material, pore size, configuration,

CEP December 2004 www.cepmagazine.org 25

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