Page : 1 of 107

KLM Technology Rev: 02

Group
Practical Engineering Engineering Solutions Rev 01 Mar 2014
Guidelines for Processing
Plant Solutions Rev 02 April 2014
www.klmtechgroup.com

KLM Technology Group Co Author

P. O. Box 281 Kolmetz Handbook
Rev 01 Mochamad Adha Firdaus
Bandar Johor Bahru,
80000 Johor Bahru,
of Process Equipment Design Rev 02 Apriliana Dwijayanti
Johor, West Malaysia
MEMBRANE TECHNOLOGY Editor / Author
SELECTION, SIZING AND Karl Kolmetz
TROUBLESHOOTING

(ENGINEERING DESIGN GUIDELINES)

TABLE OF CONTENT

INTRODUCTION 4

Scope 4

General Design Consideration 5

DEFINITION 18

NOMENCLATURE 21

THEORY OF THE DESIGN 23

Diffusion 23

History 25

The Membrane-Based Industry 26

Definition and Mechanism 27

Membrane Preparation 28

Membrane Modules 33

Driving Force and Fluxes 43

 Page 2 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Principle of Membrane Separation Process 44

Membrane Applications 46
i. Microfiltration 50
ii. Ultrafiltration 53
iii. Reverse Osmosis 54
iv. Gas Separation 62
v. Pervaporation 76
vi. Other Techniques 82

Membrane Fouling 84

APPLICATION 65

Application 1: Performance of a membrane system in liquid separation 86

Application 2: Performance of a membrane system in gas separation 90

REFEREENCE 99

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 3 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

LIST OF TABLES

Table 1: Applications of membrane separation system 6

Table 2 : Common polymers used in membranes 10
Table 3: Permeabilities of various gases in membranes24
Table 4: Preparation of Porous Membrane 30
Table 5: Charateristic of Module 40
Table 6. Membrane separation45
Table 7: Membrane Separation Technologies 46
Table 8: Membrane Gas – Separation Areas 69

LIST OF FIGURES

Figure 1: Membrane classification9

Figure 2: Principal types of Membrane 12
Figure 3: Spiral-wound Module 34
Figure 4: Hollow-fiber Module 36
Figure 5: Plate-and-Frame modules 38
Figure 6: Tubular Module 39
Figure 7: Range of Applicability 47
Figure 8: Typical retention of microfiltration 50
Figure 9: Comparison of Scanning Electronic Micrograph (SEM) Analysis 51
Figure 10: (a) Dead-end Filtration and (b) Cross-flow Filtration. 52
Figure 11: Osmosis and reverse osmosis: (a) osmosis, (b) osmotic equilibrium,
(c) reverse osmosis 55
Figure 12: Performance Characteristics 57
Figure 13: Water and Salt Fluxes 59
Figure 14: Salt Rejection 59

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 4 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Figure 15: Concentration and fluxes in reverse-osmosis process 60

Figure 16: Mechanisms for Permeation 64
Figure 17: Diffusion for variety of permeants 67
Figure 18: Permeability of any membrane 68
Figure 19: Spiral wound elements and assembly 71
Figure 20: Ideal flow patterns in a membrane separator for gases: (a) complete
mixing, (b) cross-flow, (c) countercurrent flow, (d) co-current flow. 73
Figure 21: Process flow for complete mixing case 74
Figure 22: Schematic of the basic pervaporation process 77
Figure 23: The pervaporation separation of acetone - water 78
Figure 24: Integrated distillation / Pervaporation plant 80
Figure 25. (a) Facilitated Transport and (b) Coupled Transport 83

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 5 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

INTRODUCTION

Scope

The separation, concentration, and purification of molecular mixtures are major unit
operations in the chemical industries. Efficient separation processes are needed to achieve
high-grade products in the food and pharmaceutical industries, to suuply communitites and
industry with high-quality water, and to remove or recover toxic or valuable components
from industrial effluents. For this task a multitude of separation techniques such as
distillation, precipitation, crystallization, extraction, adsorption, and ion exchange are used
today. More recently, these conventional separation methods have been supplemented by
a family of processes that utilize semipermeable membranes as separation barriers.

Membranes and membrane processes were first introduced as an analytical tool in

chemical and biochemical laboratories, and they developed very rapidly into industrial
products and methods with significant technical and commercial impact. Today,
membranes are used on a large scale to produce potable water from seawater, to clean
industrial effluents and recover valuable constitutents, to concentrate, purify, or fractionate
macromolecular mixtures in the food and drug industries, and to separate gases and
vapors. They are also key components in energy conversion and storage systems, artificial
organs, and drug delivery service. (13)

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 6 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

General Design Considerations

The membranes used in the various applications differ widely in their structure, their
function, and the way they are operated in a separation process. However, all membrane
processes share several features that make them particularly attractive tools for the
separation of molecular mixtures. The separation is performed by physical means at
ambient temperature without chemically altering the constituents. This is important for
applications in artificial organs and in many drug delivery systems, as well as in the food
and drug industries or in downstream processing of bioproducts where specific separation
tasks, and membrane processes are often technically simpler and more energy effiicient
than conventional separation techniques and are eqully well suited for large-scale
continous operations as for batchwise treatment of very small quantities.

Key property of a membrane is permselectivity, which is determined by differences in the

transport rate of various components through the membrane. The transport rate of a
component through a membrane is determined by the structure of the membrane, the size
of the permeating component, by the chemical nature and the electrical charge of the
membrane material and permating component, by the driving force due to the chemical or
eletrochemical potential gradients, that is, concentration pressure and electrical potential
differences.

Some driving forces such as pressure, temperature, and concentration gradients act
equally on all components. The use of different membrane structures and driving forces
has resulted in a number of rather different membrane processes such as reverse osmosis,
micro- and ultrafiltration, dialysis, electrodialysis, donnan dialysis, pervaporation, and gas
separation. The versality of membrane structures and functions makes a precise and
complete definition of a membrane difficult.

Generally, a membrane can be defined as a barrier that separates two different regions
and controls the exchange of matter, energy, and information between the regions in a very
specific way. The term “membrane” described in two very different items, first one is
biological membranes, which are part of a living organism, and the second is synthetic
membranes. Synthetic membranes are not nearly as complex in their structure or function

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 7 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

as biological membranes. They are usually less selective and energy-efficient but have
significantly higher chemical, thermal, and mechanical stability.

Today membranes are used on a large technical scale in three distinct areas : First,
including applications in which the use of membranes is technically feasible, but where they
must compete with conventional separation processes on the basis of overall economy.
This, for instance, is the case in seawater desalination and the treatment of certain
wastewater streams. Here, membranes must compete with distillation and biological
treatment, respectively.

The second area includes applications for which alternative techniques are available, but
membranes offer a clear technical and commercial advantage. This is the case in the
production of utlrapure water and in the separation of certain food products. Finally, there
are applications where there is no reasonable alternative to membrane processes. This is
the case in the certain drug delivery systems and artificial organs.

Since the 1960s, membrane science has grown from a laboratory curiosity to a widely
practiced technology in industry and medicine. This growth is likely to continue for
sometime, particularly in the membrane gas separation and pervaporation separation
areas. Membranes will play a critical role in the next generation of biomedical devices,
such as the artificial pancreas and liver. The total membrane market grew from $10 million
to the $1 – 2 billion level in the 30 years prior to 1994. Spectacular growth of this magnitude
is unlikely to continue, but a doubling in the size of the total industry to the $2 – 4 billion
level during the decade following is likely. Some industry use membrane system for their
process. Membrane types will be discussed detail in theory section.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 8 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Table 1: Applications of membrane separation system

Type of membrane Applications

Reverse Osmosis  Desalinization of brackish water
 Treatment of wastewater to remove a wide variety of
impurities
 Treatment of surface and ground water
 Concentration of foodstuffs
 Removal of alcohol from beer and wine

Dialysis  Separation of nickel sulfate from sulfuric acid

 Hemodialysis (removal of waste metabolites, excess
body water, and restoration of electrolyte balance in
blood)

Electrodialysis  Production of table salt from seawater

 Concentration of brines from reverse osmosis
 Treatment of wastewaters from electroplating
 Demineralization of cheese whey
 Production of ultrapure water for semiconductor industry

Microfiltration  Sterilization of drugs

 Clarification and biological stabilization of beverages
 Purification of antibiotics
 Separation of mammalian cells from a liquid

Ultra-filtration  Pre-concentration of milk before making chees

 Clarification of fruit juice
 Recovery of vaccines and antibiotics from fermentation
broth
 Color removal from kraft black liquor in paper making

Prevaporation  Dehydration of ethanol-water azeotrop

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 9 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
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Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

 Removal of water from organic solvents

 Removal of organics from water

Gas permeation  Separation of CO2 or H2 from methane and other

hydrocarbons
 Adjustment of the H2/CO ration in synthesis gas
 Separation of air into nitrogen and oxygen enriched
streams
 Recovery of helium
Recovery of methane from biogas
Liquid membrane  Recovery of zinc from wastewater in the viscose fiber
industry
 Recovery of nickel from electroplating solutions

Membrane separations represent a new type of unit operation. The membrane acts as a
semipermeable barrier and separation occurs by the membrane controlling the rate of
movement of various molecules between two liquid phases, two gas phases, or a liquid and
a gas phase. The two fluid phases are usually miscible and the membrane barrier prevents
actual, ordinary hydrodynamic flow.

Classification of membrane processes

1. Porous membrane
a. Gas diffusion. The rates of gas diffusion depend on the pore sizes and the
molecular weights.
b. Microfiltration (MF). This refers to membranes that have pore diameters from 0.1 to
10 m. It is used to filter suspended particulates, bacteria or large colloids from
solution.
c. Ultrafiltration (UF). This refers to membranes having pore diameters in the range
20-1000 Å . It can be used to filter dissolved macromolecules, such as proteins
and polymers, from solution.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 10 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

d. Reverse osmosis (RO). The membrane pores are in the range of 5-20 Å in
diameter, which are within the range of the thermal motion of the polymer chains.
e. Dialysis

2. Tight (nonporous, or dense) membrane Here the permeants are sorbed into the
membrane material under the influence of their thermodynamic potential and pass it as
a result of a driving force exerted:
a. Gradient of vapor pressure pervaporation (feed is liquid) vapor permeation (feed is
vapor)
b. Pressure gradient gas permeation (feed & permeant are gases) reverse osmosis
(feed & permeant are liquids)
c. Temperature gradient thermoosmosis
d. Concentration gradient dialysis (osmosis, liquid permeation) pertraction
e. Gradient in electric potential electrodialysis (ion-selective membrane)

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 11 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Membrane Production Application

structure method separation Application

Expended films Microfiltration

Template leaching Pore membrane Ultrafiltration
Phase inversion Dialysis
Nucleation track
Compressed powders

Symmetrical Diffusion Gas pemeation

membrane Extrusion membrane Pervaporation

Ion-selective
Casting Electrodialysis
membrane

Phase Pore membrane Microfiltration

inversion Ultrafiltration

Asymmetrical Composite coatings Diffusion Reverse osmosis

membrane Interfacial polymerization membrane Gas permeation
Plasma polymerization
Pervaporation
Diffusion
Precoat membrane Reverse osmosis
technique
Ultrafiltration
Pore membrane

Liquid Support matrix Diffusion Liquid

membrane Double emulsion membrane membrane
processes
Figure 1: Membrane classification

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 12 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Membrane Materials

Almost all industrial membrane processes are made from natural (wool, rubber, cellulose)
or synthetic polymers. At low temperatures typically below 100C, idealized polymers can
be classified as glassy or crystalline. Glassy type is brittle and glassy in appearance and
lacks any crystalline structure while the crystalline type is brittle, hard, and stiff with a
crystalline structure. If the temperature of a glassy polymer is increased the glass transition
temperature (Tg) may be reached where the polymer becomes rubbery. If the temperature
of a crystalline polymer is increased, the melting temperature (Tm) is reached where the
polymer becomes melted.

Most polymers have both amorphous and crystalline regions that is a certain degree of
crystallinity that varies from 5-90%, making it possible for some polymers to have both a Tg
and Tm. Membranes made of glassy polymers can operate below or above Tg while
membrane of crystalline polymers must operate below Tm.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 13 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
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Table 2 : Common polymers used in membranes

Polymer Type Glass Transition Melting Temp. Characteristic

Temp. oC o
C
Cellulose triacetate Crystalline 300  Consist of a thin dense skin
0.1 – 1.0 µm (permslective
layer)

Polyisoprene/natural rubber Rubbery -70

Aromatic polyamide Crystalline 275  Long-term thermal stability
 High resistance to solvent
 Some are easily fabricated
into fibers, films, and sheets

Polycarbonate Glassy 150  Thermoplastic

 Can be extruded into various
shapes

Polyimide Glassy 310 – 365  Tough, amorphous polymer

 High resistance to heat and
excellent wear resistance

Polystyrene Glassy 74 – 110  Linear, amorphous, highly

pure polymer 1000 unit
 Can be annealed (heated and
then cooled slowly) convert to
a crystalline polymer

Polysulfone Glassy 190  Easily spun into hollow fibers

 High strength
Polytetrafluoroethylene Crystalline 327  Highly crystalline polymer
 possess exceptional thermal
stability
 Can be formed into sheet,
films, and tubing

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 14 of 107
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Practical Engineering MEMBRANE TECHNOLOGY
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Types of Membrane

A membrane is a discrete, thin interface that moderates the permeation of chemical species
in contact with it. This is interface may be molecularly homogenous, that is, completely
uniform in composition and structure, or it may be chemically or physically heterogenous,
for example, containing holes or pores of finite dimensions. A normal filter meets this
definition of a membrane, but, by convention, the term membrane is usually limited to
structures that permeates dissolved or collodial species, whereas the term filter is used to
designate structures that separate particulate suspensions. The principal types of
membrane are shown schematically in Figure 1.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 15 of 107
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Practical Engineering MEMBRANE TECHNOLOGY
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Symmetrical Membrane
Nonporous Dense Electrical Charged
Microporous Membrane
Membrane Membrane

Anisotropic Membrane
Loeb-Sourirajan Liquid Membrane
Membrane Composite Membrane

Liquid Filled
Pores

Polymer
Matrix

Figure 2: Principal types of membrane (Baker, 2004)

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 16 of 107
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Practical Engineering MEMBRANE TECHNOLOGY
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Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Synthetic membranes show a large variety in their physical structure and the materias they
are made from. Based on their structure they can be classified into four groups :

 Porous membranes.
 Homogenous solid membranes.
 Solid membranes carrying eletrical charges.
 Liquid or solid films containing selective carriers.

Furthermore, the structure of membranes may be symmetric, that is, the sturcture is
identical over the entire cross section of the membrane, or it may be asymmetirc, that is,
the structure varies over the cross section of the membrane. The materials used for the
preparation of membranes can be polymers, ceramics, glass, metals, or liquids. The
materials may be neutral or carry electrical charges (for example, fixed ions).

1. Isotropic Microporous Membranes.

A porous structure represents a very simple form of a membrane, which closely resembles
the convetional fiber filter as far as the mode of separation is concerned. Separation of the
various components is achieved strictly by a sieving mechanism with the pore diamteres
and the particle sizes being the determining parameters.

Porous membranes can be made from various materials like ceramics, graphite, metals,
metal oxides, and various polymers. The structure can be symmetric, that is, the pore
diameters do not vary over the membrane section, or asymmetric, that is, the pore
diameters increase drom one side of the membrane to the other, typically by a factor of 10
to 1000. The techniques for the preparation of porous membranes can be rather different
and include simple pressing and sintering of polymer or ceramic powders, irradiation and
leaching of templates, as well as phase-inversion and polymer precipitation proceudres or
sol – gel conversion techniques.

A microporous membrane is very similar in its structure and function to a conventional filter.
It has a rigid, highly voided structure with randomly distributed, interconnected pores.
However, these pores differ from those in a conventional filter by being extremely small, of
the order of 0.01 – 10 μm in diameter. All particles smaller than the largest pores, but larger

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 17 of 107
KLM Technology Kolmetz Handbook
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Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
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Processing Plant
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www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

than the smallest pores are partially rejected, according to the pore size distribution of the
membrane. Particles much smaller than the smallest pores pass through the membrane.
Thus separation of solutes by microporous membranes is mainly a function of molecular
size and pore size distribution. Generally, only molecules that differ considerably in size
can be separated effectively by microporous membranes like in ultrafiltration and
microfiltration.

2. Nonporous Dense Membranes.

Nonporous, dense membranes consist of a dense film through which permeants are
transported by diffusion under the driving force of a pressure, concentration, or electrical
potential gradient. The separation of various components of a solution is related directly to
their relative transport rate within the membrane, which is determiend by their diffusity and
solubility in the membrane material. An important property of nonporous, dense
membranes is that even permeants of similar size may be separated when their
concentration in the membrane material (for example, their solubility) differ significantly.
Most gas separation, pervaporation, and reverse osmosis membranes use dense
membranes to perform the separation. However, these membranes usually have an
asymmetirc structure to improve the flux.

3. Electrically Charged Membranes.

Eletrically charged membranes can be dense or microporous, but are most commonly
microporous, with the pore walls carrying fixed positively or negatively charged ions. A
membrane with positively charged ions is referred to as an anion-exchange membrane
because it binds anions in the surrounding fluid. Similarly, a membrane containing
negatively charged ions is called a cation-exchange membrane. In a cation-exchange
membrane, the fixed anions are in electrical equilibrium with mobile cations in the
interstices of the polymer. On the contrary, the mobile anions are more or less completely
excluded from the cation-exchange membrane because of their electrical charge, which is
identical to that of the fixed ions.

Separation with charged membranes is achieved mainly by exclusion of ions of the same
charge as the fixed ions of the membrane structure, and to a much lesser extent by the

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 18 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

pore size. Due to the exclusion of the anions, a cation-exchange membrane permits
transfer of cations only. Anion exchanger membranes carry positive charges fixed on the
polymer matrix. Therefore, they exclude all cations and are permeable only to anions.

Films carrying charged groups are referred to as ion-exchange membranes. They consist
of highly swollen gels carrying fixed positive or negaitve charges. The properties and
preparation procedures of ion-exchange membrane are closely related to those of ion-
exchange resins. The separation is affected by the charge and concentration of the ions in
solution. For an example, monovalent ions are excluded less effectively that divalent ions
and, in solutions of high ionic strength, selectivity decreases.

Although there are a number of inorganic ion-exchange materials, mostly based on zolites
and bentonites, these materials are rather unimportant in ion-exchange membranes
compare to polymer materials. Electically charged membranes are used for processing
electrolyte solutions in electrodialysis. They aare also used as ion-conducing separators in
batteries and fuel cells.

4. Asymmetric Membranes.

The transport rate of a species through a membrane is inversely proportional to the

membrane thickness. High transport rates are desirable in membrane separation
processes for economic reasons, therefore, the membrane should be as thin as possible.
Conventional film fabrication tehcnology limits manufacture of mechanically strong, defet-
free films to about 20 μm thickness. The develoment of novel membrane fabrication
techniques to produce asymmetric membrane structures was one of the breakthroughs of
membrane technology during the past 30 years.

Asymmetric membranes consist of an extremely thin surface layer supported on a much

thicker porous, dense substructure. The surface layer and its substructure may be formed
in a single operation or formed separately. The separation properties and permeation rates
of the membrane are determined exclusively by the surface layer, the substructure
functions as a mechanical support. The advantages of the higher fluxes provided by
asymmetric membranes are so great that almost all commercial processes use such
membranes.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 19 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

In a symmetric membrane the structure and the transport properties are identical over the
entire cross section, and the thickness of the entire membrane determines the flux. In
asymmetric membranes structural and transport properties vary over the membrane cros
section. An asymmetric membrane consists of a 0.1 – 1 μm thick ‘skin’ layer on a highly
porous 100 – 200 μm thick substructure. The skin represents the actual selective barrier of
the asymmetric membrane. Its separation characteristics are determined by the nature of
the material or the size of its pores. The mass flux is determined mainly by the skin
thickness. The porous sublayer serves only as a support for the mosly thin and fragile skin
and has little effect on the separation characteristics or the mass transfer rate of the
membrane.

Asymmetric membranes are used primarily in pressure-driven membrane processes such

as reverse osmosis, ultrafiltration, and gas and vapor separation, since here the unique
properties of asymmetric membranes, that is, high fluxes and good mechanical stability,
can be utilized. Two techniques are used to prepare asymmetric membranes : One utilizes
the phase-inversion process, which leads to an intergral structre with the skin and the
support structure made from the same material in a single process, and the other resembles
a composite structure where a thin barrier layer is deposited on a porous substructure in a
two-step process. In this case barrier and uspport structures are generally made from
different materials.

5. Ceramic, Liquid, and Metal Membranes

This part implies that membranes material are organic polymers and, in fact, the vast
majority of membranes used commercilay are polymer based. However, interest in
membranes formed from less conventional materials has increased. Ceramic membranes,
a special class of microporous membranes, are being used in ultrafiltration and
microfiltration applications, for which solvent resistance and thermal stability are required.
Dense metal membranes, particularly palladium membranes, are being considered for the
separation of hydrogen from gas mixtures, and supported emulsified liquid films are being
developed for coupled and facilitated transport processes.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 20 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Liquid membranes are mainly used in combination with the so-called facilitated transport
which is based on “carriers” which transport certain components such as metal ions
selectivity across the liquid membrane interphase. Generally, it is no problem to form a thin
fluid film. It is difficult, however, to maintain and control this film and its properties during a
mass separation process. To avoid breakup of the film, some type of the reinforcement is
necessary to support such a weak membrane structure.

Two different techniques are used today for the prepartion of liquid membranes. First, the
selective liquid barrier material is stabilized as a thin film by a surfactant in an emulsion-
type mixture. In the second, a porous structure is filled with the liquid membrane phase.
Both types of membranes are used today on a pilot-plant scale for the selective removal of
heavy metal ions or certain organic solvents from industrial waste streams. They have also
been used rather effectively for the separation of oxygen and nitrogen.

Advantages and Limitations

In many applications membrane processes compete directly with the more conventional
techniques. However, compared to these conventional procedures, membrane processes
are often more energy efficient, simpler to operate, and yield higher quality products.
Furthermore, the environmental impact of all membrane processes is relatively low. There
are no hazardous chemicals used in the processes that have to be discharged and there is
no heat generation.

However, there are certain limitations to the application of membrane processes. A major
disadvantage of membranes, especially in water- and wastewater-treatment processes, is
that until today the long-term reliability has not completely been proven. Membrane
processes sometimes require excessive pretreatment due to their sensitivity to
concentration polarization, chemical interaction with water constituents, and fouling.
Membranes are mechanically not very robust and can easily be destroyed by a malfunction
in the operating procedure.

Another critical issure are the process costs. Generally, membrane processes are quite
energy efficient. However, the energy consumption is only part of the total process costs.
Other factors determining the overall economics of a process include the investment-
related cost, which is determined by the cost of the membranes and other process

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 21 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

equipment and their useful life under operating conditions, and various pre-and post-
treatment procedures of the feed solutions and the products. Plant capacity may also play
a role in total cost. While, for example, in distillation process usually a substantial cost
reduction can be achieved with an increase in the plant capacity, the scale – up factor has
only a relatively small effect on the process cost in desalination of water by reverse osmosis
or electrodialysis.

Depending on the composition of the feed solution and the required quality of the product
water, a combination of processes may be appropriate. For example, if ultrapure water for
certain industrial applications is required, a sequence of processes may be applied, such
as reverse osmosis, ion exchanger, UV sterilization, and microfiltration as a point-of-use-
filter to remove traces of particles. The environmental impact of all membrane processes is
relatively low. There are no hazardous chemicals used in membrane processes which have
to be discharged. In certain applications such as the purification of industrial effluents and
wastewaters or the desalination of brackish water there may be a problem with the disposal
of the concentrate. In these applications brine post-treatment procedures may be
necessary.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 22 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

DEFINITIONS

Back-flushing – A technique of pumping the permeate in the reverse direction through the
membrane.

Fouling – The potential deposition and accumulation of constituents in the feed stream on
the membrane . The deposition of material on the membrane surface and/or in its pores,
leading to a change in the membrane performance.

Flux – Flow of physical property in space (mass and energy). Amount of permeate, or of
any component in the permeate, that is transported through a membrane per unit of
membrane area and per unit of time.

Hollow-fiber – Consists of a bundle of hundreds to thousands of hollow-fibers.

Membrane – A selective barrier that allows the passage of certain constituents and retains
other constituents.

Permeability – Permeation of a gas or vapor through solid substance.

Permeate – The constituents that passes through the membrane.

Plate and Frame – A Membrane that consist of a series of flat membrane sheets and
support plates.

Rejection – Amount of particles that have been removed from the feed.

Retentate – The constituents that containing the retained components.

Scaling – Formation of chemical precipitates in membrane.

Spiral-wound – A Membrane where a flexible permeate spacer is placed between two flat
membranes sheet.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 23 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Tubular – Classification of membrane where the membrane are placed inside a support
porous tubes and placed together in a cylindrical shell to form the unit module.

Concentrate - The volume of liquid exiting a membrane system after flowing over the
membrane, not through it. It is expressed as feed less permeate; it is also called brine,
reject and retentate.

Feed - The volume of liquid entering a membrane system.

Housing - The part of the membrane filtration equipment holding spiral wound elements or
other types of membrane elements, also referred to as pressure vessel.

Pressure drop - The loss of pressure between inlet and outlet of a membrane system, a
housing (pressure vessel) or a membrane element.

Pressure osmotic - A theoretical value which highly impacts reality. The osmotic pressure
is a function of the content of salt and other low MW solutes. High MW solutes can
theoretically not contribute to osmotic pressure, but in reality a phenomena is experienced
which resembles osmotic pressure. The osmotic pressure of electrolytes and low MW
solutes can be calculated with some accuracy, but the "osmotic pressure" of high MW
solutes can only be determined by experimentation.

Bubble point pressure - Pressure at which a continuous stream of gas bubbles is

pressed through a liquid wet filter.

Bulk temperature - Temperature that exists in the bulk phase; in practice this
temperature is equal to the measured temperature.

Module - The smallest practical unit containing one or more membranes and supporting
structures (old terms to be replaced are permeator, membrane element).

Permeate - The portion of the feed passing through the membrane. Distillate can also be
used as a term to describe the “permeate” of membrane distillation, but it is better to use
“permeate” because it is commonly used in membrane literature.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 24 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

Pore size - Openings in a membrane; this term is preferred to “pore diameter” and “pore
radius”, because all pore shapes can be described by this term.

Porosity - The porosity is defined as the volume of gas that is trapped inside a
membrane divided by the total volume of the membrane;

Retention - The ability of a membrane to hinder a component from passing through it or to

retain a component in the fluid.

Retention coefficient - The degree of separation of a certain component from the solvent
by the membrane under defined operating conditions;

Permeability - The property or condition of being permeable. The rate of flow of a liquid
or gas through a porous material.

Diffusion-The passive movement of molecules or particles along

a concentration gradient, or from regions of higher to regions of lower concentration.
The spontaneous net movement of particles down their concentration gradient (i.e.
difference in the concentrations of substances or molecules between two areas).

Reverse osmosis (RO) - a water purification technology that uses a semipermeable

membrane. This membrane technology is not properly a filtration method. In reverse
osmosis, an applied pressure is used to overcome osmotic pressure, a colligative property,
that is driven by chemical potential, a thermodynamic parameter. Reverse osmosis can
remove many types of molecules and ions from solutions, and is used in both industrial
processes and the production of potable water.

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 25 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

NOMENCLATURE

A a constant,
Am membrane area,cm2;
Aw Solvent permeability constant (kg solvent/s m² atm)
As Solute permeability constant (kg solvent/s m² atm)
c Salt concentration (kg NaCl / kg H2O)
B variable in liquid separation
c1 Solute concentration in feed (g solute/L)
c2 Solute concentration in product (g solute/L)
cw2 the concentration of solvent in stream 2 (kg solvent/m3).
D Diffusion coefficent
Di diffusivity of the solute I in the solution
DKi Knudsen diffusivity (cm2/s) = 4850Dp (T / Mi)1/2
Dp diameter pores (m)
Dp pores diameter (cm)
F the total feed flow rate (cm3 (STP)/s)
Ji The flux of component i (m3 / m2)
Js Salt Flux (m3 / m2)
Jw A link to the pressure and concentration gradients across the membrane
K Henry’s law sorption coefficient
Kf restrictive factor
Mr Molecular weight
Nw Solvent flux (Kg solvent/s m²)
Ns Solute flux (Kg solute/s m²)
P Constant of Membrane Permeability
PMA Permeabilties component A, cm3(STP)/(s cm3 cm Hg)
PMB Permeabilties component B, cm3(STP)/(s cm3 cm Hg)
ph the total pressure in the high pressure (feed) side, cm Hg;
Pi Is a Constant of Membrane Permeability
pi(l) Partial pressure of the component at the other side
pi(o) Partial pressure of the component i
pl the total pressure in the low pressure or permeate side, cm Hg;
PMA the permeability of A in the membrane, cm3 (STP) cm/(s cm2 cm Hg);
q0 outlet reject flow rate (cm3 (STP)/s)

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.
 Page 26 of 107
KLM Technology Kolmetz Handbook
Group of Process Equipment Design Rev: 02
Practical Engineering MEMBRANE TECHNOLOGY
Guidelines for
SELECTION, SIZING AND
Processing Plant
Solutions TROUBLESHOOING April 2014

www.klmtechgroup.com (ENGINEERING DESIGN GUIDELINES)

qA the flow rate of A in permeate, cm3 (STP)/s;

qp outlet permeate flow rate (cm3 (STP)/s)
R Rejection (%)
t Membrane thickness (m)
T temperature (K)
v velocity rate (m³/m² s)
x0 the mole fraction of A in the reject side; and
yp the mole fraction of A in the permeate

Greek Leters

µ Viscosity fluid (Pa s)

α The membrane selectivity
αij The membrane selectivity
ɛ Membrane porosity / volume fraction of pores in the membrane
Δp the pressure difference across the membrane
Δπ the osmotic pressure differential across the membrane(atm)
π1 Inlet osmotic pressure (atm)
π2 Outlet osmotic pressure (atm)
ρ1 Inlet density (kg/m3)
ρ2 Outlet density (kg/m3)
Ɵ Fraction permeated
τ tortuosity

Superscript

A a constant,
D Diffusion coefficent
F the total feed flow rate (cm3 (STP)/s)
K Henry’s law sorption coefficient
P Constant of Membrane Permeability
R Rejection (%)

These design guideline are believed to be as accurate as possible, but are very general and not for specific design
cases. They were designed for engineers to do preliminary designs and process specification sheets. The final design
must always be guaranteed for the service selected by the manufacturing vendor, but these guidelines will greatly
reduce the amount of up front engineering hours that are required to develop the final design. The guidelines are a
training tool for young engineers or a resource for engineers with experience.

This document is entrusted to the recipient personally, but the copyright remains with us. It must not be copied,
reproduced or in any way communicated or made accessible to third parties without our written consent.