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A Guide to

Cost-Effective Membrane Technologies for Minimising

Wastes and Effluents

Presented with the compliments of Accepta

This guide, produced by the Environmental Technology Best Practice


Programme is reproduced in accordance with Acceptas agreement with and
courtesy of the United Kingdoms Controller of Her Majestys Stationery Office
and the Queens Printer for Scotland.

www.accepta.com
GG54
GUIDE

COST-EFFECTIVE
MEMBRANE TECHNOLOGIES
FOR MINIMISING WASTES
AND EFFLUENTS
COST-EFFECTIVE
MEMBRANE TECHNOLOGIES
FOR MINIMISING WASTES
AND EFFLUENTS
This Guide was produced by the
Environmental Technology Best Practice Programme

Prepared with assistance from WS Atkins Consultants Ltd

With particular acknowledgement for contributions from:

CARDEV International Ltd


KALSEP Ltd
Koch Membrane Systems
Memtech (UK) Ltd
PCI Membrane Systems Ltd
Process Technology Group
Renovexx Technology Ltd
Royal Society of Chemistry
USF Acumem Ltd

Crown copyright. First printed March 1997. This material may be freely reproduced except for sale or advertising purposes.
Printed on paper containing 75% post-consumer waste.
SUMMARY

Waste reduces a companys profitability, and many businesses are now altering their processes to
minimise the impact of waste on their bottom line and on the environment. Annual cost savings
of up to 1% of overall company turnover are proving to be typical results of waste minimisation
programmes.

There are technologies commercially available that can help businesses to do this. This Guide
explains the basic principles of one of them, membrane technology. It examines the technologies,
explaining the basic principles of operation, discussing appropriate applications and assessing their
relative advantages and disadvantages. It also offers guidance to membrane selection and gives
specific Industry Examples of companies that have reduced costs by installing membrane separation.

Membrane separation is mature technology that is commercially available in the UK from a number
of equipment suppliers. The technology can be used to separate various mixtures of liquid materials
in a growing range of applications. Units are generally compact, and their modular construction
means that they can be scaled up or down easily.

There are three main types of membrane system commonly used in industry:

Ultrafiltration is widely used for: oil, water and emulsion separations; paint recovery; and
the separation of fats, oils or greases in the food industry.
Reverse osmosis and nanofiltration are used extensively for water purification,
desalination and disinfection.
Microfiltration is applied to maintain degreasing process solutions for metal particle
recovery/removal or to concentrate other particulate materials from liquids or slurries.

Correctly used membrane separation can provide financial savings and conserve resources.
Maximum benefits are obtained when one or both the output streams from the membrane system
are recycled or re-used, thereby reducing process materials requirement and minimising waste
disposal costs.

The benefits of using membrane separations are only fully realised by selecting technology that is
compatible with the application. This will involve consultation with technology suppliers, clear
identification of the substances present in process streams, an understanding of the strengths and
weaknesses of the membrane systems available and completion of a structured feasibility
assessment.

Membrane technology is flexible and adaptable. It is suitable for use in all sizes of industry.
This Guide illustrates a range of established uses, with special emphasis on the recovery or
conservation of resources that would otherwise be wasted.
CONTENTS

Section Page

1 Introduction 1
1.1 How to use this Guide 1
1.2 Industry Examples 2

2 Why minimise waste? 3

3 Why install a membrane separation system? 5

4 Membrane technology 8
4.1 Principles of membrane separation 8
4.2 Membrane structure 11
4.3 Where to use a membrane system 14
4.4 System configuration 14
4.5 Availability 17
4.6 Practical concerns 18

5 How to select a membrane process 23

6 Ultrafiltration 28
6.1 The technology 28
6.2 UK applications 28
6.3 Potential applications 30

7 Reverse osmosis and nanofiltration 31


7.1 The technology 31
7.2 UK applications 32
7.3 Potential applications 33

8 Microfiltration 34
8.1 The technology 34
8.2 UK applications 34

9 Other commercially available technologies 37


9.1 Pervaporation 37
9.2 Gas separation 37
9.3 Electrodialysis (ion exchange) 37

10 Future developments 38

Appendices
Appendix 1 Technical tables 41
Appendix 2 UK equipment suppliers 44
Appendix 3 Further reading 46
1 INTRODUCTION

The generation, treatment and disposal of wastes are significant factors contributing to the rising
cost of production. Companies today have to implement effective waste management measures in section
order to conserve resources and reduce costs. 1
Government policy1 on waste management emphasises that, in general, the elimination or
minimisation of waste at source is preferred to end-of-pipe treatments or disposal options.

Various technologies and techniques can be used to minimise waste. The Environmental Technology
Best Practice Programme has published several Good Practice Guides on waste minimisation and a
Guide introducing a range of alternative separation technologies. These publications are available
free of charge through the Environmental Helpline on 0800 585794.

This Guide focuses specifically on industrial-scale membrane separation technologies. These


technologies are particularly effective for the recovery and re-use of both water and raw materials
from process streams and can be an important component of any waste minimisation initiative.

1.1 HOW TO USE THIS GUIDE


Section 2 assesses the need for waste minimisation in both economic and environmental terms.

Section 3 provides information on the benefits of using membrane separation systems to recover
and re-use products and water.

Section 4 contains background information about membrane technology. It outlines the


fundamental process principles involved, describes the different membrane structures and modules
that are commercially available, and assesses where in the process a membrane system might be
located. Section 4 also offers advice on how to find a supplier. It examines membrane system
configuration and operation and also looks at various practical issues and concerns, such as fouling
and cleaning, membrane life and robustness, and capital and operating costs.

Reading Section 5 is essential if considering a membrane separation installation. It examines a


number of the issues involved in membrane selection and operation, and two decision trees
highlight the types of information needed and the decisions that have to be made to select the
optimum membrane system for any particular application.

Sections 6, 7 and 8 provide information in greater detail about the more commonly used
membrane systems: ultrafiltration; reverse osmosis and nanofiltration; and microfiltration. As well
as providing technical information, these Sections outline the various commercial applications of
these technologies in the UK.

Other commercially available technologies, and applications that have been developed overseas but
have not yet been widely applied in the UK, are described in Sections 9 and 10.

Detailed tables on membrane structures, information about UK membrane suppliers, and a list of
references and other relevant texts are provided in the Appendices.

1 Department of the Environment Circular 11/94, Environmental Protection Act 1990 Part II, Waste Management Licensing:
The Framework Directive on Waste.
1
1.2 INDUSTRY EXAMPLES
The six Industry Examples (see Table 1) on the loose-leaf sheets in the back of this Guide describe
successful membrane applications in UK businesses. Each Industry Example summarises the reasons
for the installation, provides a process description and details of operation, and outlines the resulting
benefits. These successful applications are intended to encourage other companies to consider the
section benefits of membrane technologies for minimising wastes and effluents.
1
Industry Company Title
Example

1 Houghton Vaughan Ultrafiltration in oil manufacturing

2 IMI Yorkshire Fittings Ltd Ultrafiltration in the metal forming


industry

3 LINPAC Containers International Ltd Removal of ink from water by


ultrafiltration

4 The Haworth Scouring Company Cleaning and recycling rinse water


using ultrafiltration

5 Tucker Fasteners Ltd Degreasing bath microfiltration

6 Gaffers Transport Ltd Vehicle wash water recovery by


microfiltration

Table 1 Good Practice Guide 54 - Industry Examples

2
2 WHY MINIMISE WASTE?

From an economic point of view, it is already clear that companies investing in cleaner technology
and waste minimisation programmes are gaining both financially and through improved efficiency.
Annual cost savings of up to 1% of overall company turnover are proving to be typical results
of waste minimisation programmes at well-organised companies.
section
Large cost savings can often be achieved from a reduction in water use and effluent disposal.
2
Industrial water supplies in the UK historically have been readily available, and the costs of
purchasing water and disposing of wastewater have been low.

This situation is now changing:

potable water costs are increasing;


wastewater discharge costs are escalating;
waste disposal contractors are increasing their charges;
mains water supply restrictions are likely in drought-affected areas.

The disposal of process effluent, for instance, usually constitutes an expensive industrial overhead.
If that effluent is discharged to the public sewer, charges will be levied in relation to its volume and
strength. An effluent treatment plant on site to prepare effluent for discharge to sewer, by
neutralising or removing contaminants, may be a further cost burden. When effluent is treated on
site, there will be overhead charges associated with operating treatment plant, disposing of
treatment residues and capital investment repayments.

Costs associated with water use and effluent disposal can be reduced significantly by initiating a
liquid waste minimisation programme. The benefits include reductions in:

purchased water requirements and the associated costs;


effluent volume and the associated costs of handling, treatment and disposal;
the level of effluent contamination (eg chemical oxygen demand, settleable solids) and the
associated charges.

Such a waste minimisation programme can also achieve further savings in the longer term because
on-site effluent treatment plant capacities required will be smaller, reducing both the capital
investment necessary and the associated operating cost.

WRAP - Waste Reduction Always Pays

It is important to consider re-use and recovery of raw materials, product and process water in any
waste minimisation scheme. A membrane separation system is an effective method for recovering
water and other substances for re-use.

Any reduction in process waste, particularly where it incorporates the recovery and re-use of water
and other resources, reduces the environmental impact of an industrial process. It is also worth
remembering that companies that are seen to adopt an environmentally friendly approach by
minimising their environmental impact may be at an advantage in the marketplace.

3
Have you considered the cost of waste disposal to your company and whether initiating a
waste minimisation programme will benefit your financial bottom line?

Before you consider investing in effluent treatment plant:

assess where the effluent volumes originate and what the major contaminants are;
consider what measures you can take to reduce the effluent volumes and major
contaminants and draw up an appropriate Action Plan.

Adopting a structured approach will help you to maximise the benefits.


section

4
3 W H Y I N S TA L L A M E M B R A N E
S E P A R AT I O N S Y S T E M ?

Membrane separation is one of many commercially available separation technologies and


techniques that can be used as part of a waste minimisation programme. However, membrane
systems are particularly effective for the recovery and re-use of both water and raw materials.
Incorporating a membrane system as part of a waste minimisation initiative could reduce costs,
increase competitiveness and reduce your companys environmental impact.

Membrane processes are capable of separating mixtures of materials. The membrane is a


thin physical barrier through which materials can either pass (the permeate) or be rejected and
section
retained (the retentate). The structure and characteristics of the membrane layer determine the
nature of the separation.
3
Membrane systems separate:
solids from gases solids from liquids
gases from gases gases from liquids
dissolved or colloidal materials from liquids liquids from liquids

The technology used for membrane processes is mature, and is in widespread use throughout the
world. It is used in applications as diverse as: water purification; food and beverage processing;
medical applications; and the high-value, low-volume separations common in the pharmaceutical
industry. Table A1 in Appendix 1 provides a list of typical applications for membrane separations.

The range of membrane process applications is increasing. Most current membrane systems were
installed to treat contaminated water streams to meet disposal constraints (Fig 1). However, such
examples do not emphasise the full benefits to business of membrane systems, as they often ignore
or accept the costs incurred for process water supply and subsequent disposal, ie:

the supply cost;


the cost of preparation to process specification, eg chemical addition, de-ionisation or
softening;
the disposal cost - most trade effluent consents incorporate a substantial charge component
for volume disposal;
the energy cost - especially if heating is required (although this can be minimised by heat
recovery).

Environment

Energy Resources Water Treatment Sewer discharge Waste disposal


B C D E F contractor
G

Waste
stream
Process
A Product

Cost = A + B + C + D + E or F or G

Fig 1 Process waste stream with no recycle


5
Also ignored is the fact that water is a potentially re-usable resource and that, in manufacturing and
processing, there are often opportunities for water recovery, either for recycling in the same process
or for use in a less discriminating secondary application. Typical examples of secondary uses are
vehicle washing or wash-down water.

Today, more companies are recognising the cost implications of water consumption and the benefits
of re-use rather than disposal. The cost of recovering, recycling and re-using valuable materials
contained in process waste streams is also becoming financially more advantageous as water supply
and effluent disposal costs increase. A major advantage of membrane separation technology is that
the separated substances are often recoverable in a chemically unchanged form and are therefore
easily re-used (Fig 2).

section Environment
3 Reduced
effluent
f
Reduced Reduced

Energy Resources
Recovery
B c
Water
d Re-use
Waste
Process stream Membrane
A Product E

Cost = A + B + c + d + E + f

Fig 2 Ideal process with recovery, re-use and reduced discharge

Membrane separation processes have a role to play in minimising wastes and, in some cases,
in maximising the recovery, recycling and re-use of raw materials, products or water. They can,
therefore offer, a distinct financial advantage when compared with other physico-chemical or
biological treatment processes.

Membrane separation technologies are particularly appropriate if you are:

paying for large quantities of process water;


discharging large volumes of water as waste, particularly if it contains materials that are
uneconomic or illegal to discharge;
are discharging materials of value which, if recovered, can be re-used in your process or,
alternatively, used by others.

Membrane separation units are compact and their modular construction means that they can be
scaled up or down easily. Their commercial availability as small-scale, free-standing units suitable for
use by small to medium-sized companies is progressively increasing. Furthermore, the technology,
in common with physico-chemical or biological treatment processes, is available as modular turnkey
(off-the-shelf) plant.

However, although membrane separation systems offer many positive features, you should be aware
that there are some potential drawbacks. Table 2 summarises the common characteristics of
industrial-scale systems.

6
Advantages Disadvantages
Applicable to a wide range of processes. Selection of compatible membrane essential.
Physical process with few moving parts. Generally low selectivity.
Simple connections and utility requirements. Membrane fouling is a common problem.
Can operate continuously or on demand. Membrane life is finite and may be short.
Often no additives required. Capital investment sometimes appears high.
Products can be recovered in an unchanged Some effluents are not suitable for conventional
chemical form. membrane separation technology, eg highly
Equipment is modular and compact. fouling liquids.
System can be scaled up or down easily and
integrated with other treatment processes.
Membrane properties can be varied.
Can be used for single- or multi-stage separation. section

Permeate quality often independent of feed stream 3


concentrations.
Physical disinfection performed automatically.
Table 2 Advantages and disadvantages of membrane separation systems

In general terms, membrane technology is suitable for many separation duties in industry, although
very high temperatures aggressive or fouling conditions necessitate more expensive and specialised
membrane systems.

A further important constraint when selecting membrane plant may, in some instances, be the
payback period when compared with todays water costs and with the cost of alternative
technology.

By applying membrane separations correctly, you can make financial savings and conserve
resources. You will obtain maximum benefit when you recycle or re-use one or both streams
from the membrane separations. This will reduce your process materials requirement and
minimise your waste disposal costs.

7
4 MEMBRANE TECHNOLOGY

4.1 PRINCIPLES OF MEMBRANE SEPARATION


Separating substances that are intimately mixed, typically requires energy in the form of heat or
mechanical work. Most industrial membrane separations use hydrostatic pressure as the driving
force for transport across a membrane structure. Both flow and pressure are induced by pumping.

Membrane separations can achieve:

concentration (removal of a diluting solvent such as water);


purification (separation of contaminants such as salts);
section fractionation (resolution into two or more component substances).
4
Pressure-driven membrane separations are typically concentration or purification processes.

There are two basic modes of presenting a membrane for separation: cross-flow mode or dead-end
(sometimes called cartridge) mode. These modes are illustrated in Fig 3. Cross-flow mode produces
two streams (the permeate and the retentate or concentrate). Dead-end filtration, however,
produces only a permeate stream because the concentrate is contained.

Cross-flow filtration Dead-end filtration

Permeate stream
Feed stream

Pressure

Feed stream
Pressure
Concentrated
Concentrate
retentate
stream

Permeate stream Permeate stream

Permeate Permeate
rate rate

0 Time 0 Time

1 Feed stream 1 Permeate stream 1 Feed stream 1 Permeate stream


+ 1 Concentrate stream + 1 Concentrated retentate

Fig 3 Cross-flow vs dead-end filtration modes

Cross-flow membrane processes are often characterised in terms of their concentration factor, for
example 10:1 (Fig 4).

8
1 drum
concentrate

Membrane
system
Concentration
factor
10:1

10 drums
untreated waste 9 drums
permeate

Fig 4 Cross-flow membrane concentration

Either or both of the products from a membrane separation may be of value as a resource.

section
Most common industrial-scale membrane separations are performed on liquid or semi-solid 4
applications using the microfiltration, ultrafiltration, nanofiltration or reverse osmosis technologies
described in later Sections. Membrane technologies for such separations are usually categorised
according to pore size, ie the sieving properties of the membrane.
Microfiltration (MF)
Ultrafiltration (UF)
Decreasing membrane pore size Nanofiltration (NF)
Reverse osmosis (RO)

Fig 5 illustrates how the sieving effect of decreasing pore size selectively retains different substances.

Suspended solids Bacteria


Proteins Sugars
Salts Water

Microfiltration membrane
Decreasing pore size

Ultrafiltration membrane

Nanofiltration membrane

Reverse osmosis membrane

Pure water

Fig 5 Sieving effect of decreasing membrane pore size

Reducing the pore size of a membrane increases the selectivity, but demands a higher driving
force to induce a given permeate flow rate per unit of membrane area (flux).

9
In reality, the boundaries between MF, UF, NF and RO membranes are not uniform as performance
specifications vary from supplier to supplier. For example, one suppliers loose nanofiltration
membrane may be equivalent to anothers tight ultrafiltration membrane. Fig 6 relates the relative
sizes of typical materials to common membrane separation processes.

Membrane plants are designed and sized on many parameters, but the overriding criterion is the
permeate flow rate per unit of membrane area (flux) through the membrane under operating
conditions.

Flux is typically expressed as volume or mass per unit membrane area per unit time, for example
litres/m2/hour. Temperature can affect flux significantly.

Operating at high flux levels means that less membrane area is required and economies can be made
in terms of capital, operating and membrane replacement costs.

The performance or efficiency of a membrane separation is determined by:


section
membrane selectivity;
4 permeate flux.

Reverse osmosis Ultrafiltration


Membrane
technology

Nanofiltration Microfiltration

Aqueous
Enzymes Paint pigment
salts

Lignosulphonate Yeast

Metal Synthetic
Viruses Bacteria
ions dye

Examples of Fats and oil


Wood resin Lanolin
common materials emulsions

Antibiotics Gelatin

Sugars Colloidal silica Blue indigo dye

Detergents Egg albumen

Flavours and Sewage


Latex
fragrances particulates

Size range:
Approx molecular 100 200 1 000 10 000 20 000 100 000 500 000
weight
Microns (logscale) 0.001 0.01 0.1 1.0

Membrane porosity
Hydrostatic pressure

Fig 6 Size separation capability of different membrane systems

10
4.2 MEMBRANE STRUCTURE
Membranes are made from a range of different materials and by different methods. The result is a
range of performance criteria and properties. Fundamentally, membranes are manufactured from
inorganic materials, eg alumina, zirconia or metal, or organic materials, eg carbon, cellulose or
complex polymeric molecules such as polysulphone or polytetrafluoroethylene (PTFE). Woven
polyester cloth membranes are also available. Properties and applications of synthetic membranes are
given in Appendix 1, Table A2.

Microscopically, membranes have a symmetrical or an asymmetrical cross-sectional structure.


Microfiltration typically uses symmetrical membranes (Fig 7); the remaining technologies (UF, NF and
RO) favour asymmetrical structures (Figs 8, 9 and 10) to maximise flux. An additional specialised
inner surface layer may be added to a membrane support matrix, producing a composite membrane
with specialised features.

Photograph courtesy of KALSEP Ltd

Photograph courtesy of KALSEP Ltd


section

10 m 100 m
Fig 7 Symmetrical membrane cross-section Fig 8 Asymmetrical membrane cross-section
Photograph courtesy of KALSEP Ltd

Photograph courtesy of KALSEP Ltd

100 m 100 m
Fig 9 Hollow-fibre asymmetrical membrane Fig 10 Flat sheet asymmetrical membrane
cross-section cross-section

The thickness of symmetrical membranes varies between 10 and 200 m. Asymmetrical or


composite membranes have a dense layer of up to 1.0 m supported on a layer up to 150 m thick.

Membranes are manufactured and supplied as tubes or sheets which are arranged into
modules of known membrane surface area per unit volume.

11
Commercial membrane modules typically come in four configurations (Figs 11 - 14).

Fig 11 Hollow-fibre module

Permeate collection holes

section Feed solution Concentrate

4 Feed solution
Permeate out
Concentrate

Feed flow Feed channel spacer


across feed
channel spacer Membrane
Permeate collection material
Covering
Membrane
Feed channel spacer
Adhesion line
Permeate flow (after passage
through membrane onto permeate
collection material)

Fig 12 Spiral-wound module

Fig 13 Tube module Fig 14 Plate-and-frame module

Operating units comprise a number of modules to give the required membrane surface area for
effective separation. Each module will have an inlet and an outlet, plus a permeate port and a
cleaning system if appropriate. Modules may be arranged in series or as parallel units, depending
on the application.

12
Common membrane module properties and applications are summarised in Table 3.

Membrane Typical module Common Relative


module packing density m2/m3 applications investment cost
Cartridge filters 800 - 1 000 Dead-end filtration Low
(depth filtration)
Hollow-fibre 600 - 1 200 Cross-flow ultrafiltration Low
Tube <100 Cross-flow filtration of high Very high
solids content streams
Spiral-wound 300 - 1 000 Cross-flow ultrafiltration, Low
nanofiltration, reverse osmosis,
pervaporation, gas separation
Plate-and-frame 100 - 600 Reverse osmosis, pervaporation, High
gas separation
Table 3 Typical characteristics of membrane modules

Hollow-fibre systems have a high membrane surface area per module, but must operate at low
section
hydrostatic pressure. Hollow fibres are typically less than 0.5 mm in diameter, so systems are more
prone to blockages unless pre-filtration systems are used.
4
Tubular membrane modules have a lower membrane surface area per module than hollow-fibre
units, but they can operate at higher pressures. Tubular membranes tend to be around 10 mm in
diameter and therefore need more space, but they are more robust.

Tubular membranes also have superior solids handling capabilities compared with spiral-wound,
plate-and-frame or hollow-fibre modules. Spiral-wound and hollow-fibre modules require a higher
standard of pre-filtration when solids are likely to be present. The suitability of tubular and hollow-
fibre or spiral-wound membrane systems for specific applications is summarised in Fig 15.

Tubular Hollow-fibre or spiral-wound

- Temp >45C
- Compressor
- Vibratory finishing - Mixed wastes condensate
- Aqueous cleaner
- Tanneries - Cutting oils - Dye penetrant
- Parts washer
- Fish waste effluent - Metal plating
- Edible oil rinse waters
- Laundries - Spent coolant
- Textile printers - Grinding swarf - Groundwater
- Photo-emulsion
- Abattoirs - Vehicle wash
- Rolling oils rinse waters
- Flexo inks - Cosmetic waste
- Evaporator
- Surfactants
- Waste hauliers condensate

- Die-casting - Dyehouses

Fig 15 Guide to applications for tubular and hollow-fibre or spiral-wound membrane systems

13
4.3 WHERE TO USE A MEMBRANE SYSTEM

Membrane separation can be introduced at any point in an industrial process line. It does not
have to be an end-of-pipe technology, although this is the most common application. The
most effective use of membranes is as part of a re-use/recycle loop integrated into the
manufacturing process.

End-of-pipe installations concentrate one or more components of the waste stream, thereby
allowing use of different disposal routes for the separation products. For example, where there is
an oil emulsion that cannot be discharged directly to sewer, an ultrafiltration plant can be used to
separate the water and soluble substances for sewer discharge and retain the insoluble fraction for
disposal elsewhere (Fig 16).

section Process Permeate to


Membrane
4 effluent sewer discharge

Concentrate to
waste contractor

Fig 16 End-of-pipe concentration

The ideal zero effluent scenario (Fig 17) is impractical at present for most industries because
operational difficulties become more significant as liquid waste volumes decrease.

Re-use
Permeate

Process
effluent Membrane

Concentrate
Recovery

Fig 17 Ultimate zero effluent scenario

4.4 SYSTEM CONFIGURATION

Membrane separations may be single-stage processes or part of a sequence of processes. Most


membrane systems require a pre-treatment stage to remove any solids that are likely to block
the membrane modules. Treatment may also be necessary before re-use of the separated
products from membrane systems (Fig 18).

Fig 18 illustrates the pre-treatment and post-treatment processes associated with membrane
separation.

14
Retentate
processing
Untreated (if required)
waste stream

Pre-treatment Permeate
Membrane
(varying post treatment
system
requirements) (if required)

Fig 18 Membrane system with associated processes

Many of the membrane systems currently in use are single-stage separations with no further
processing of permeate and retentate. However, if economic conditions continue to focus attention
on the recovery of resources from complex wastes, there will be an increase in the processing and
re-use of separation products. This can be achieved using a multi-stage process involving, for
example, ultrafiltration followed by reverse osmosis.
section
A membrane separation system can be made as complex as necessary, and may include flow 4
controls, heat exchangers, automatic cleaning cycles and ancillary equipment. In essence, however,
the basic plant is very simple and add-on items should be carefully justified. Fig 19 illustrates the
basic components of a membrane separation system, shown here on a pilot-scale unit.

Photograph courtesy of Memtech (UK) Ltd

Fig 19 Basic membrane separation system

Most commercial membrane plant comprise:

a feed tank;
a pump to induce flow and hydrostatic pressure;
membrane module(s) to carry out the separation;
permeate handling facilities;
reject stream handling (cross-flow filtration) or residue handling (dead-end filtration) facilities.

Many membrane processes also include:

a pre-treatment stage, eg solids screening or the removal of free oil;


storage for recovered resources, with further treatment depending on intended use;
a membrane cleaning facility that may be physical or chemical, automatic or manual;
upstream chemical dosing, eg a biocide or to induce flocculation or pH adjustment;
15
Retentate
processing
Untreated (if required)
waste stream

Pre-treatment Permeate
Membrane
(varying post treatment
system
requirements) (if required)

Fig 18 Membrane system with associated processes

Many of the membrane systems currently in use are single-stage separations with no further
processing of permeate and retentate. However, if economic conditions continue to focus attention
on the recovery of resources from complex wastes, there will be an increase in the processing and
re-use of separation products. This can be achieved using a multi-stage process involving, for
example, ultrafiltration followed by reverse osmosis.
section
A membrane separation system can be made as complex as necessary, and may include flow 4
controls, heat exchangers, automatic cleaning cycles and ancillary equipment. In essence, however,
the basic plant is very simple and add-on items should be carefully justified. Fig 19 illustrates the
basic components of a membrane separation system, shown here on a pilot-scale unit.

Photograph courtesy of Memtech (UK) Ltd

Fig 19 Basic membrane separation system

Most commercial membrane plant comprise:

a feed tank;
a pump to induce flow and hydrostatic pressure;
membrane module(s) to carry out the separation;
permeate handling facilities;
reject stream handling (cross-flow filtration) or residue handling (dead-end filtration) facilities.

Many membrane processes also include:

a pre-treatment stage, eg solids screening or the removal of free oil;


storage for recovered resources, with further treatment depending on intended use;
a membrane cleaning facility that may be physical or chemical, automatic or manual;
upstream chemical dosing, eg a biocide or to induce flocculation or pH adjustment;
15
heat exchangers to limit recirculating liquid temperatures in closed-loop systems;
downstream polishing technology such as ion exchange, activated carbon adsorption or
concentrate processing by pressure dewatering;
upstream flow balancing tanks;
downstream chemical addition to restore product formulation before re-use.

Examples of cross-flow membrane systems include:

simple batch concentration (Fig 20), typically used for applications where small-volume
batches are processed;
fed batch concentration (Fig 21), typically used for applications where large-volume batches
are processed;
two-stage operation (Fig 22), for example, ultrafiltration/reverse osmosis system used to
generate very high quality permeate.

section Membrane separations may be operated in continuous mode with downtime for cleaning, or
4 as a batch process. The feed stream may undergo a single pass through the membrane system
or it may be recirculated many times. Membrane system configurations, therefore, tend to be
application-specific in waste treatment, recovery and re-use situations.

Valve
Feed/ Cross-flow
concentrate Permeate
membrane
tank

Recirculation
pump

Fig 20 Simple batch concentration

Feed
Valve
Feed/ Cross-flow
concentrate Permeate
membrane
tank

Recirculation
pump

Fig 21 Fed batch concentration

16
Feed
Valve
Feed/ Reject stream Cross-flow
Final
concentrate membrane
permeate
tank (RO)

Cross-flow
membrane
(UF)
Recirculation
pump

Fig 22 Two-stage operation

Membrane processes may be turned on or off when required, although polymeric membranes
should not be allowed to dry out.
section

4
When an effluent consists of many different process streams, it may be necessary to isolate the
discrete stream that has a resource value to maximise the benefits of, and minimise the
interferences on, the membrane separation stage.

4.5 AVAILABILITY
As with any separation process, membrane units operate within defined specifications. Very few
membrane separation units for treating complex process effluent are, therefore, available turnkey
(off-the-shelf). A testing regime is needed to identify and optimise membrane selection and to
demonstrate the efficacy of the process to all parties involved.

The diversity of industrial activities in the manufacturing sector means that every potential
membrane application must be treated as unique until shown otherwise.

Industrial membrane systems are readily available in the UK from:

a limited number of membrane manufacturing companies that make membranes and


supply equipment, mainly for the larger applications;
dedicated membrane equipment suppliers who use membrane modules from other
manufacturers and offer a wide range of equipment for all size applications;
original equipment manufacturers (OEMs) who buy membrane modules from larger
companies and fabricate the necessary system hardware. These tend to be smaller companies
concentrating on turnkey modular plants that are competitive with other marketplace
technologies.
A non-exhaustive list of membrane equipment suppliers contacted during the preparation of this
Guide is given in Appendix 2.

17
4.6 PRACTICAL CONCERNS

Choosing the optimum membrane type and area (m2) is critical in achieving a cost-effective
separation.

The range of membrane systems available from different manufacturers is wide, and each has
unique characteristics. The key to the success and efficiency of any membrane separation plant is
to choose a membrane that is compatible with the application, ie one that will process the required
flow rate to the necessary quality, and that will work reliably under operational conditions to meet
process and financial targets.

However, there are several common apprehensions about incorporating membrane separations in
industrial applications. These include:

membrane fouling and associated cleaning regimes;


section membrane longevity and robustness;
4 capital and operating costs.

4.6.1 Fouling and cleaning


Membrane fouling causes a reduction in permeate flux because the flow resistance of the
membrane is increased. It occurs by three main mechanisms as illustrated in Fig 23:

physical blinding - blocking of the flow path by solid materials; particularly relevant to
hollow-fibre (Fig 11) and spiral-wound (Fig 12) modules;
concentration polarisation - formation of a resistive concentrated layer at the inner
membrane surface (leading to gel layer formation);
adsorptive fouling - interaction between macromolecules and the membrane surface,
resulting in chemical blocking of the pore structure.

Gel layer formation


Concentrate

Physical blinding

Adsorptive fouling

Permeate Flow direction

Feed

Membrane
Concentration
polarisation layer

Fig 23 Membrane fouling mechanisms

In any membrane separation, the observed flux changes with time because of reversible or
irreversible fouling (Fig 24).

18
Concentration
polarisation
Flux

Fouling

Time

Fig 24 The effect of concentration polarisation and fouling on flux over time

Fouling effects are minimised by: section

choosing a compatible membrane system; and 4


intermittent cleaning-in-place using either hydraulic, chemical or physical methods (or a
combination).

Physical blinding is minimised if a suitable screening stage is introduced prior to the membrane
module. However, the presence of solids is not a difficulty for some membrane systems that have
a positive backwash action using water or air, or that are operated in a dead-end mode (usually
microfiltration). An asymmetric membrane structure also reduces this effect. Cleaned permeate, air
or both are suitable for backwashing.

Hydraulic measures reduce concentration polarisation (and gel layer formation) by increasing
both scour and turbulence close to the membrane surface. Cross-flow systems, for example,
operate with a minimum flow velocity of around 2 m/s across the membrane area and can include
baffling (or, less commonly, pulsatile flow) to promote turbulence.

Adsorptive fouling remains a significant barrier to widespread membrane use in some


applications. Cellulose-based membranes exhibit a low fouling tendency but operate at a low flux,
whereas synthetic polymeric membranes initially have high fluxes but are susceptible to irreversible
fouling from, for example, proteins or silicates. Polymeric membranes with surface modifications
are becoming available. These can sustain higher fluxes with potentially fouling streams.
Alternatively, a range of chemical cleaning regimes are effective in restoring membrane flux in many,
though not all, applications.

Chemical cleaning may be manually initiated or automated. Typical chemical cleaning agents used,
either individually or in combination, include:

acids (strong or weak) or alkalis;


detergents;
enzymes;
chelating agents;
biocides.

Chemical cleaning typically generates effluent. This effluent, which contains process residues mixed
with spent cleaning agents (often corrosive or surface active), may need further treatment before
being discharged or removed from site by licensed waste disposal contractors.

19
In some instances, physical cleaning is an option. For example, a tubular system can be cleaned
easily by passing a sponge ball, polythene pig or equivalent through the modules to induce abrasion
and scour.

Cleaning-in-place (either chemical or physical) improves membrane system flux, but will not restore
the original flux levels. The attainable flux will decrease over time, demanding more frequent
cleaning, and the membrane module will need replacing when the required flow rate can no longer
be economically maintained. The rate of flux decline will vary and is related to membrane duty,
membrane characteristics, the cleaning regime and the nature of the feed stream.

A typical flux curve is shown in Fig 25.

Flux With cleaning


section

4
Without cleaning

Time

Fig 25 Flux vs time, with and without membrane cleaning

Membrane equipment suppliers will specify operating limits and cleaning regimes, and will list
substances to be excluded from the system.

4.6.2 Membrane life and robustness


Tubular modules and woven-cloth systems tend to have longer working lives (typically five years but
sometimes more than 15 years). Hollow-fibre modules may only last between six months and two
years as individual fibres burst under operational conditions, causing a progressive deterioration in
permeate quality with time.

In some cases, membrane suppliers may be able to offer a pro-rata guarantee on membrane life but,
in many cases, membrane life is directly related to membrane duty and equipment maintenance.
Membrane longevity and performance are, for instance, adversely affected by stressing the
membrane with abnormal temperatures, aggressive chemicals (eg oxidising agents), solvents or
other reactive chemicals such as silicone-based compounds (eg anti-foam agents). The effects of
such stressing may be irreversible or very difficult to rectify, necessitating replacement of the
membrane modules.

Prevention may be cheaper than cure. To achieve maximum performance, you should:

operate the process according to the suppliers instructions;


avoid intermittent hydraulic shocks;
avoid temperature shocks;
avoid allowing polymeric membranes to dry out;
exclude significant concentrations of corrosive, oxidising or solvent substances unless
the membrane is selected to resist such trauma.

20
4.6.3 Capital and operating costs

The capital cost of membrane processes is directly proportional to the technology type, the
membrane area required and the number of modules necessary to satisfy this requirement.

The diversity of potential membrane technology designs and commercial considerations makes
capital cost estimation a case-specific exercise that is best carried out by membrane system suppliers.
However, capital cost guidelines from one UK system supplier (expressed as cost per m2 of
membrane area) are given in Appendix 1, Table A3. This Table gives the cost range associated with
different systems. Tubular systems, for example, are more expensive to buy than spiral-wound or
hollow-fibre systems. This is because many more modules are required to give the membrane area
necessary to achieve the desired flux. Ceramic membranes are more expensive than polymeric
membranes.

For application-specific cost estimates, contact several membrane technology suppliers.


section

In common with effluent treatment equipment, a membrane system design represents a 4


compromise between capital cost and operating cost.

For a typical industrial membrane system, the capital cost, including automated cleaning
facilities, can be broken down approximately as follows2:

pumps 30%
replaceable membrane components 20%
membrane modules (housings) 10%
pipework, valves, framework 20%
control system 15%
other 5%

The operating cost of a membrane system is derived from:

the energy cost of maintaining the systems hydrostatic pressure and flow rate;
the expected membrane life;
the cleaning regime required;
site-specific factors, such as the labour requirement.

The energy consumption of a membrane system is directly related to flow rate and pressure
requirements (including piping and module head-loss), ie pumping cost is related to flow rate and
power.

High-power pumping systems give a higher flux and require a smaller membrane area. Conversely,
a system designed with lower pumping cost in mind will require a greater membrane area to achieve
a given flux. Membrane suppliers design systems that strike a balance between these capital and
operating cost factors.

Most microfiltration and ultrafiltration system applications operate at low pressures. The energy
consumed is, therefore, mostly associated with maintaining a minimum velocity of about 2 m/s
across the membrane surface. Nanofiltration and reverse osmosis operate at higher hydrostatic
pressures, but with lower flow rates.

2 Reprinted from Noble, R and Stern, S. Membrane Separations Technology - Principles and Applications. 1995.
21
ISBN 0-444-81633-X. Pages 38-39, with kind permission from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV
Amsterdam, The Netherlands.
A typical ultrafiltration design dissipates around 50 W/m2 at the membrane surface. Taking into
account other energy losses such as heat, or friction, then the total energy requirement, in kWh/m3
of permeate, can be determined as follows3:

Energy required = Emem/(Seff x J)


where Emem = energy at membrane surface (typically 50 W/m2)
Seff = system efficiency (typically 40 - 60%)
J = flux in litres/m2/hour

This energy requirement estimate does not include add-on loads such as preliminary treatments or
frequent cleaning. These will add to the energy consumption.

For example, a membrane system with a flux requirement of 40 litres/m2/hour, an expected system
efficiency of 50% and dissipating 50 W/m2 at the membrane surface will have the following energy
requirement:

section Energy required = 50/(0.5 x 40) watt hours (Wh) per litre
4 = 2.5 Wh/litre
or 2.5 kWh/m3 permeate.

Operating costs will vary from application to application, and are often dominated by capital
cost charges. For a typical system, excluding capital charges, the operating cost can be broken
down approximately as follows3:

replaceable membrane components 35 - 50%


cleaning 12 - 35%
energy 15 - 20%
labour 15 - 18%

If possible, where high hydrostatic pressures are used (except in small-scale, single-pass units)
membrane module pressure should be retained in a high pressure loop (with a concentrate bleed)
for maximum energy efficiency.

3 Reprinted from Noble, R and Stern, S. Membrane Separations Technology - Principles and Applications. 1995.
ISBN 0-444-81633-X. Pages 38-39, with kind permission from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV
Amsterdam, The Netherlands.

22
5 HOW TO SELECT A
MEMBRANE PROCESS

If you are to select a waste treatment technology that is appropriate to your business, you will need
to put in the necessary effort at the technical feasibility stage. In this way you will ensure that the
equipment chosen performs to a given specification and is a benefit to the company rather than a
liability. An integrated approach that considers all process inputs and outputs is the most
appropriate. This Section outlines some of the basic selection principles involved.

Your first task is to identify clearly those substances that are present in the effluent stream (including
those present only intermittently). You should therefore examine the resource inputs to the process,
including those introduced during cleaning regimes and any substances contained in the effluent
from other associated activities.

When selecting a membrane process you will need to consider:

whether the process will achieve the desired separation;


section
whether there is a valuable resource to be recovered from the process stream;
the specification required for recycled resources;
5
how much it costs in financial and environmental terms not to recover and recycle;
whether other separation processes might be more effective;
the volume and the physical and chemical characteristics of the stream to be treated;
any process-limiting factors or constraints.

To ensure you choose the most appropriate supplier of suitable technology from the many
competing technologies available, you will benefit if you:

have a clear idea of the issues involved in choosing costly waste treatment technology;
can specify a quality requirement for the recovered substances;
have a clear understanding of your current costs regarding waste disposal and resource
purchase.

To obtain maximum benefit from membrane separation (or any other separation technique),
you must understand your process, the waste stream(s) generated and the financial cost of
disposing of the waste stream in an acceptable manner.

Where water is the resource to be recovered using a membrane system, you should give careful
consideration to its intended re-use with respect to the dissolved solids content. The more porous
membrane filtrations such as microfiltration or ultrafiltration do not, for instance, remove ionic or
small to medium-sized organic molecules, and these will still be present in the permeate. This may
be important when considering the quality of water required for a particular re-use. For example,
if water is recycled to a process that constantly adds dissolved materials, then the dissolved solids
concentration of that water will rise - possibly to unacceptable limits.

Zero discharge concepts involving 100% water recovery are probably impractical at present. Closing
process loops inevitably increases the concentrations of dissolved materials in circulating waters,
possibly creating difficulties with high salt contents or biological growths. Under these conditions
either periodic batch removal or continuous low-rate removal of the circulating content is necessary
to prevent excessive concentrations that might compromise process efficiency.
23
Two criteria must be met for the successful selection and installation of a membrane process:

the intended separation must be technically feasible;


the intended separation must be economically feasible.

From a technical point of view, membrane separation is an effective solution for the concentration
or purification of many waste streams. However, the economics of waste stream recoveries and
treatments are often marginal unless high-value substances can be retained for re-use or sale.
Where a separation product is not re-used on site, the value of that product is dependent on finding
a purchaser. If you fail to find a product purchaser, you will incur waste disposal costs although, in
some cases, residues may be removed free of charge. For example, waste oil recovered from
ultrafiltration plants may be removed for use as fuel.

Your financial assessments must be carefully calculated to take these and other issues into account.

When evaluating the options, it is helpful to make forecasts for at least two cases, one assuming no
investment is made, and one or more assuming an investment is made. All the significant factors
affecting company cash flows must be considered for each case. These include:
section
capital cost;
5 working capital;
construction period;
start-up costs;
sales or savings forecast;
economic life;
tax rate, depreciation life and method;
inflation rate;
risks involved.

Although many of these factors are applicable to any investment, there are risks that are specific to
membrane processes, eg fouling. The size of a plant (and hence its capital cost) is determined by the
design flux. You can present an attractive economic case by assuming a high flux, but this may not
take full account of the occurrence and effect of fouling.

You should talk to the technology suppliers


Membrane technology suppliers have unique experience in selecting membrane types for
industrial applications and will be pleased to discuss opportunities for membrane system
installations. Such suppliers should be able to advise on feasibility and potential payback
periods. Most companies will give no-obligation quotations, although you may need to
finance some laboratory-scale investigations beforehand.

The decision trees in Figs 26 and 27 highlight the information and decisions necessary when
selecting the optimum membrane system for your application.

The first phase (Fig 26) involves understanding the nature of the process waste and the cost of its
disposal (the base case). This activity is site-specific, but there are many general texts that can help
(see Appendix 3). This first phase is a prerequisite for considering any modifications to, or
investments in, effluent treatment.

The second phase (Fig 27) illustrates the method by which you can evaluate whether membrane
separation technology is applicable to a particular waste stream that you have identified.

24
Identify
stream(s) for treatment
Identify and initiate waste
reduction measures
(Read Good Practice Guides)
Can process stream(s) be
minimised or eliminated by
waste reduction measures Yes
or clean technology?

No
Physical parameters*
Costs*
flow rate, max, min, average
water purchase
daily flow pattern
trade effluent charge
regulatory requirements
treatment cost
temperature
viscosity
pH
plant space availability
Characterise
flow stream(s)
Chemical composition* Resources*
COD Identify potentially valuable
identifiable organic species resources
suspended solids water section
ionic species
oils
colour
process chemicals/
raw materials 5
solids recovery
regulatory requirements reaction by-products
Formulate a
waste strategy

Consider options and


opportunities for
recycling/re-using materials

No Recycle/re-use Yes
opportunities identified

Establish resource quality


Concentration/separation
criteria*
for all streams for disposal
water purity
dry solids content
molecular composition
product quality
Membrane separation
technology possible
Talk to membrane
technology suppliers

* The lists shown here are examples

Fig 26 Membrane separation process decision tree


Phase 1: Data acquisition

25
Identify characteristics of the stream Specify performance reqirements
ie presence of oxidising agents, free oil, eg flow rate, product quality
solids, silicon compounds, organic solvents
temperature
pH
osmotic pressure

Select potential membrane system


eg microfiltration, ultrafiltration
nanofiltration
reverse osmosis
single or multi-stage treatment
pre-treatment processes
polishing treatment

Can membrane system meet required duty?

No
Liaise with membrane supplier(s)

Yes

section Commission laboratory-scale trials


confirm resource quality can be achieved
5 confirm likely membrane type/specification
required
make initial capital and operating cost
estimate
establish criteria for pilot-scale trials
estimate potential investment payback
period

Consider alternative
Laboratory trial results show treatment technologies
No No eg biological treatment
potential limiting factors may be overcome
investment payback period may be realistic physico-chemical
treatment
particle filtration
Yes
Pilot scale tests in situ
performance specifications may be achieved
for longer term testing under operational
conditions
to optimise technology and cleaning regimes
to confirm financial data
to confirm flux rates are acceptable and
reliable

Cost-benefit assessment
(see Table 4)

No
Assessment positive technology proved

Other factors Yes


Company
environmental policy Purchasing decision process
BS 7750 accreditation
Penalties of no change
Environmental image

Fig 27 Membrane separation process decision tree


Phase 2: Process evaluation and selection

26
Table 4 highlights the factors you should consider when carrying out a cost-benefit assessment of a
given technology option. Every site will also have unique characteristics that should be taken into
consideration when evaluating proposals.

As operational experience and knowledge is often application-based, it is a good policy to contact


more than one technology supplier during the feasibility stage.

Existing process - no change * Membrane process installed *


Water supply cost Reduced water supply cost
Energy cost Reduced energy cost
Chemical supply cost New chemical supply cost
Raw materials cost Reduced raw materials cost
(by including recovery/recycle)
Disposal cost of liquid effluent Reduced disposal cost of liquid effluent
Disposal cost of solid waste Reduced disposal cost of solid waste
Labour cost Labour cost
Transport cost, eg for raw materials, Reduced transport cost
waste for disposal
Capital cost of equipment
section
Membrane replacement cost
Cost of ancillary requirements, 5
eg pipework, holding tanks
Separated product value
Total Total
* Normally expressed either in /year or as specific indices such as /tonne of product. The latter approach is used to
accommodate production fluctuations when evaluating costs and overheads over an extended period.

Table 4 Detailed cost-benefit assessment of the membrane process evaluation and selection process

27
6 U L T R A F I L T R AT I O N

6.1 THE TECHNOLOGY


Ultrafiltration systems are typically operated in cross-flow mode, producing a permeate and a
concentrate.

Ultrafiltration separates solutes from solids, colloids, emulsions and macromolecules. Sugars, salts
and low molecular weight organics will pass through the membrane and be present in the
permeate.

Most common, small-scale plants are based on spiral-wound or hollow-fibre technology, although
tubular systems are available. Membrane materials are typically polymeric, eg polysulphone,
although other types are readily available.

Chemical cleaning is usually used for spiral-wound and hollow-fibre membranes. In the case of
tubular systems either chemical or physical (eg sponge balling) methods are used.

Ultrafiltration: typical characteristics


section
Mode: Cross-flow
6
Operating pressure: Hydrostatic 1 - 10 bar
Mechanism: Sieving, adsorption
Separation cut-off range: Solid/liquid: 0.005 - 0.1m
Solute/liquid: 10 000 - 200 000 MW*
Membrane type: Polymeric or ceramic asymmetric
(separating layer 0.1 - 1 m)
Membrane configuration: Spiral-wound, hollow-fibre, tubular

* MW = Molecular weight of material, commonly used to indicate relative size.

6.2 UK APPLICATIONS
Ultrafiltration is particularly well established in UK industry for the following applications:

general oil/water/emulsion separations;


electro-coat paint recovery;
separating fats, oils or greases in the food industry.

One of the largest markets for small-scale ultrafiltration plants is oil/water separation. UK industry
uses vast quantities of mineral and synthetic oils for lubrication, machining and preservation. Oily
wastewaters are routinely produced at engineering premises in the form of, for example,
compressor condensate and swarf drainings. However, typical discharge consents exclude or limit
the level of oil that can be discharged as effluent.

Oily wastewaters are usually disposed of by waste contractors. The conventional method of
treatment for high volume oily waters is to use interceptors which produce a liquid stream for
discharge and trap the oil for removal. However, interceptors take up a large amount of space and

28
may cause additional nuisance such as odour. In addition, the trapped oil must be removed
periodically.

Ultrafiltration systems, on the other hand, are compact units (Fig 28) that separate the oil and solids
fraction from a liquid feed with a concentration factor of around 10:1. The permeate generated
may be re-used for low-grade applications without further treatment (eg water can be used for
washing down). The concentrated oil fraction can be either removed as waste or reclaimed as fuel
oil (after acid cracking if necessary) (see Industry Example 1).

Ultrafiltration units of this type are often operated as batch processes, continually recycling the feed
until permeate removal is complete and a concentrate remains.

section

Courtesy Memtech (UK) Ltd


Fig 28 Small ultrafiltration unit

Ultrafiltration is not suitable for removing solids or water from mineral oils. Depth or surface
filtration systems that use glass fibre or cellulose elements are well established for this purpose, and
have a proven record in maintaining heavy machinery lubricating oils and cutting oils. They maintain
oil quality for prolonged periods, reducing both cost and the environmental burden.

Water-based, semi-synthetic (5% mineral oil) and 100% synthetic machining coolants are now
becoming available in the UK. Ultrafiltration can recover the aqueous phase of these coolants for
recycling. After a chemical dose has been made to replenish losses, the coolants can be recycled
indefinitely. In the case of synthetic coolants, the recovery level is almost 100%. However, for semi-
synthetic preparations, the mineral oil fraction is lost from the permeate, and a new dose is required
to maintain the formulation. The mineral oil-rich concentrate can be re-used or reclaimed for fuel.

When ultrafiltration membranes are used to treat oily waters (or similar) pre-treatment may be
required to remove free oil and any solids above 1 mm. Pre-treatment is generally achieved by
including an oil coalescer and removal system prior to the membrane feed tank.

Electrophoretic paint recovery and recycling is another proven ultrafiltration application, but it tends
to be restricted to large-scale painting operations, such as vehicle body surface coating.

Fats, oils and greases are a common problem in food industry effluent. Ultrafiltration is an effective
means of concentrating such materials for animal feed or disposal.
29
Ultrafiltration has also been used in cosmetics waste treatment. In some cases, surfactants in the
wastewaters from shampoo formulations can be separated for re-use in lower-grade applications
such as car washing detergents.

6.3 POTENTIAL APPLICATIONS


Ultrafiltration is used overseas in several applications not found in the UK, particularly in certain food
industry applications such as breweries.

One example of an alternative application is the use of membranes for treating abattoir
wastewaters. In South Africa, ultrafiltration followed by reverse osmosis has proved to be
commercially viable for this purpose when compared with existing technology such as anaerobic
digestion4. However, high-quality permeate re-use in an abattoir may require the addition of
disinfectant and a change in hygiene regulations.

section

4 Cowan, J, MacTavish, F, Brouckaert, C and Jacobs, E. Membrane Treatment Strategies for Red Meat Abattoir Effluents.
1992. Water Science and Technology 25, No 10.
30
7 REVERSE OSMOSIS AND
N A N O F I L T R AT I O N

7.1 THE TECHNOLOGY


Reverse osmosis (previously termed hyperfiltration) and nanofiltration separate water from water
solute mixtures. These processes operate in cross-flow mode at hydrostatic pressures that are
sufficient to overcome the osmotic pressure of the feed stream and induce a flux.

To obtain purified water, sufficient hydrostatic pressure must be produced to generate flux while taking
into account the osmotic pressure of any dissolved solutes present. If dissolved materials are present in
high concentrations, the required hydrostatic pressure becomes excessive and the process impracticable.

Reverse osmosis membranes are non-porous and separation is achieved mainly by solute solubility
differences in the membrane. The membrane rejects ionic substances and the passage of non-polar
molecules is restricted by low solubility in the membrane. Membranes are typically characterised by
their retention properties, for example 99% salt retention or 60% sucrose retention. Reverse
osmosis typically requires pre-treatment of the feed stream to remove solids and macromolecules,
and ultrafiltration is often used for this purpose.

Reverse osmosis: typical characteristics


Mode: Cross-flow
Operating pressure: Hydrostatic 15 - 60 bar section

Mechanism: Solubility/diffusion 7
Separation cut-off range: Solid/liquid <0.001 m
Solute/liquid <500 MW*
Membrane type: Polymeric asymmetric or composite
(separating layer 0.1 - 1 m)
Membrane configuration: Spiral-wound, tubular

*MW = Molecular weight of material, commonly used to indicate relative size.

Nanofiltration uses semi-porous membranes which retain larger molecules, but permit the passage
of small ions. There is some selectivity with regard to the ionic charge of molecules present. This
process is, therefore, intermediate between reverse osmosis and ultrafiltration.

Nanofiltration: typical characteristics


Mode: Cross-flow
Operating pressure: Hydrostatic 20 - 40 bar
Mechanism: Solubility/diffusion
Separation cut off range: Solid/liquid 0.001 - 0.01 m
Solute/liquid 200 - 20 000 MW*
Membrane type: Polymeric asymmetric or composite
(separating layer 0.1 - 1 m)
Membrane configuration: Spiral-wound, tubular

*MW = Molecular weight of material, commonly used to indicate relative size.


31
7.2 UK APPLICATIONS
Both reverse osmosis and nanofiltration are extensively used for water purification, desalination and
disinfection. Reverse osmosis in particular represents the ultimate membrane separation and is
required if high-quality permeates are needed for re-use (Fig 29).

The electronics industry is one in which high-quality water is required for the manufacture of printed
circuit boards, and reverse osmosis is typically specified for this purpose. Nanofiltration may also be
suitable for similar applications.

Photograph courtesy of PCI Membrane Systems Ltd


section

Fig 29 Reverse osmosis membrane system

Although reverse osmosis and nanofiltration are widely used for water treatment, they are not
commonly applied to industrial effluent streams in the UK. However, proven industrial applications
do exist:

Evaporator condensate recovery. Large-scale evaporators, particularly in the food


industry, typically produce a liquid stream contaminated with volatile organic compounds
and/or product. Such streams are amenable to full water-recovery using reverse osmosis or
nanofiltration.
Vehicle washes. Reverse osmosis is used to de-ionise potable water. The reject stream is
then used to wash the vehicles and the de-ionised water is used as the final rinse (to minimise
salt deposition). This application reduces water consumption but does not recycle
contaminated wash waters.
Currently, the cost of purchased water alone is rarely sufficiently high to provide an adequate
payback period on reverse osmosis systems installed to allow full water recycle. This situation
may change if water charges increase or if restrictions on water use become widespread.
Water treatment in the dyeing industry. Nanofiltration has been used in the dyeing
industry as an end-of-pipe process to remove colour and recycle high-quality water for re-use5.

5 Nielson, C. Union Filtration: Recycling of Waste Water from Textile Dyeing using Membrane Filtration. Membrane
Technology 55.
32
7.3 POTENTIAL APPLICATIONS
Reverse osmosis, in particular, has not been widely applied, primarily because of the long payback
periods associated with the equipment and todays relatively low purchase cost for water, in
comparison with other raw materials.

However, reverse osmosis is used in the USA to recover metal ions from metal plating rinse waters,
enabling the metals involved to be recycled. An example of this is the treatment of nickel plating
rinse water6.

Nanofiltration for the recovery of caustic and acid cleaning chemicals, particularly in the dairy and
brewery industries, is a developing technique with environmental benefits. It is discussed further in
Section 10.

section

6 Schoemann, J, van Standen, J, Saayman, H and Vorster, W. Evaluation of Reverse Osmosis for Electroplating Effluent
Treatment Water. 1992. Science Technology No 10.

33
8 M I C R O F I L T R AT I O N

8.1 THE TECHNOLOGY


Microfiltration is used to remove particulate matter from liquid streams. There is a considerable
overlap between this technology and surface or depth filtration. The latter techniques use glass
fibre or cellulose filters and the capital investment involved is usually lower.

However, microfiltration, when operated in cross-flow or dead-end mode, can process higher liquid
flows and recover the concentrate in a handleable form. Depth filtration on the other hand is
designed as a disposal-only technology.

Typically, microfiltration concentrates solids and oils from liquids or slurries.

Microfiltration is a very diverse technology and no firm definitions are possible because of the
indistinct boundary with depth filtration. This Guide considers only cross-flow microfiltration in any
detail.

Microfiltration is characterised by a high level of membrane diversity. Membranes tend to be


symmetrical but can be made from inorganic materials, eg ceramics or sintered metals, or organic
materials, eg carbon or synthetic polymers. Woven-cloth modules are also classified as membrane
systems (Fig 30). These systems build up a solids layer on the inner cloth surface, thereby providing
the fine particle filtration required.

section Microfiltration: typical characteristics


8 Mode: Cross-flow or dead-end
Operating pressure: Hydrostatic 1 - 4 bar
Mechanism: Physical sieving
Separation cut-off range: Solid/liquid 0.1 - 20 m
Membrane type: Usually symmetrical polymeric or ceramic, 10 - 150 m
thick
Membrane configuration: Spiral-wound, hollow-fibre, tubular, ceramic, inorganic

The variety of materials available for membrane manufacture - carbon, metal and ceramics - allows
the microfiltration of aggressive, corrosive, solvent-laden or high temperature streams.

8.2 UK APPLICATIONS
One example of microfiltration under severe conditions is the use of this technology to prolong the
life of immersion or spray degreasing baths used in the engineering and surface coating industries.

Typically, alkaline degreasing baths are operated at temperatures of more than 50C and become
progressively contaminated by the grease and oil removed from soiled components. This emulsified
grease and oil accumulates until the cleaning efficiency of the bath is compromised and the bath
solution is disposed of.

34
Photograph courtesy of Renovexx Technology Ltd
Fig 30 Woven-cloth membrane system

The effective operating life of a degreasing solution is proportional to the duty imposed and the
cleaning agents and contaminants present. In some instances, the solution may need to be replaced
daily and this constitutes a significant overhead in terms of chemical cost, heating and waste
disposal charges (see Industry Example 5).

Microfiltration, however, is an effective means of continuously removing oily contaminants and


solids from the degreasing solution. Pre-treatment is required to remove both free oil and large section

solids. The resulting fluid is then recycled via the membrane. The permeate, including additives 8
such as wetting agents and surfactants, passes through the membrane and is returned to the
process. The concentrate retained by the membrane is periodically removed for disposal. This
procedure increases the operating life of the degreasing solution many times over.

Small-scale units are available, either as dedicated side-stream installations servicing one unit, or as
portable units that are capable of refreshing several units.

Microfiltration is also applicable to other areas of the metals industry. The technology is capable of
removing particles down to 0.1 m. It is therefore an effective polishing step following the
treatment of metal plating wastes using conventional precipitation technology.

Woven polyester cloth membranes have proved successful in removing precipitated heavy metals
from metal-bearing effluent such as metal plating waste. Applications of this type tend to be end-
of-pipe concentration treatments and, in most cases, involve no recovery. However, recovery may
be an option. In one example, metal particles have been removed successfully from effluent
generated during the manufacture of printed circuit boards. This allows the permeate to be re-used,
thereby saving on the costs of water purchase, process water de-ionisation and wastewater disposal.

Glaze recovery in the ceramic industry is another good example of microfiltration membranes being
used to separate out an expensive material that can then be re-used.

Another interesting concept is recycling wastewater from commercial vehicle washing facilities,
especially as vehicle washing is often restricted by drought orders. Although recycling equipment
that uses conventional depth filtration and polishing is already available, microfiltration membranes

35
have now been proven as a first-stage treatment for recycling wash water. The resulting permeate is
then polished with activated carbon prior to re-use in the washing process (see Industry Example 6).

Common microfiltration applications include:

degreasing processes;
metal particle recovery/removal (printed circuit board manufacture);
metal plating wastewater treatment;
vehicle washes.

section

36
9 O T H E R C O M M E R C I A L LY
AVAILABLE TECHNOLOGIES

Other commercially available membrane techniques include:

pervaporation;
gas separation;
electrodialysis (ion exchange).

9.1 PERVAPORATION
Pervaporation is a drying technique. It uses a membrane that is highly permeable to water but
impermeable to other solvents. The water molecules from a liquid feedstock are adsorbed onto the
membrane surface and are then diffused through the membrane where they vaporise.

Pervaporation can give substantial advantages over the distillation of constantly boiling mixtures
(azeotropes) in terms of both cost and performance. Furthermore, pervaporation is a low-energy
process that requires only low temperatures and pressures.

Until recently, only polymeric pervaporation membranes were available and these tended to be
permeable to other solvents. However, zeolite membranes (eg alumina or zirconia) are now
available and these provide a very high selectivity (because of their regular pore size) and a high
water flux (because of their high porosity).

9.2 GAS SEPARATION


Gas separation using specialist membranes can be applied to the large-scale separation of nitrogen
from air and of other gases from chemical feedstocks. However, membrane gas separation in section

isolation is not suitable for the production of high purity gases. It is, therefore, mostly applicable to 9
high gas volume applications such as inert atmospheres.

9.3 ELECTRODIALYSIS (ION EXCHANGE)


Electrodialysis (ion exchange) membranes are used for process separations, eg for chlor-alkali cells,
and desalination and in the chemical industry. An electrodialysis system separates ionic substances
from aqueous or other uncharged components using the electrical properties of the membrane
combined with an applied electrical potential difference (see Fig 31). Mass separation is achieved on
the basis of the electrical charge, and the membranes may incorporate anion or cation exchangers as
integral components. So far, electrodialysis has not been used in the waste recovery arena as other
techniques, eg reverse osmosis, ion exchange and distillation, are favoured technologies.

D + C D + C D +
D = Treated stream
+ C = Concentrate
Na+ Na+ Na+
a
Cl Cl

NaCl

Fig 31 Electrodialysis
37
10 F U T U R E D E V E L O P M E N T S

Membrane units are in widespread process use in certain European countries and in the USA.
Original Equipment Manufacturers (OEMs) supply membranes for a wide range of industrial and
domestic applications. Examples include reverse osmosis for metal plating and vehicle washes, and
ultrafiltration for abattoirs and a wide range of small-scale domestic applications.

Multinational membrane suppliers have a good understanding of membrane technology


applications in different countries. But the legislation and water resource situation in certain
countries may demand more expensive solutions for minimising industrial water use and
discharge than in the UK.

Although technology for membrane processes is well established, the continual development of
new membrane materials is opening up new opportunities for their application.

One exciting new development is the application of nanofiltration to spent cleaning-in-place (CIP)
liquors for caustic and acid recovery/re-use. A proprietary chemically stable membrane type is being
used to recover 90% of caustic or acid from spent process solutions. The recovered, purified
chemical can be re-used indefinitely with a low top-up for losses. This represents an advance on
comparable microfiltration technologies in similar applications. A possible CIP recovery schematic is
given in Fig 32.

This technology is potentially suitable for use wherever caustic or acid cleaning is carried out on a
large scale, for example:

food industry - evaporator caustic recovery, dairy products CIP recovery;


breweries - bottle wash caustic recovery and other CIP applications;
textile industry - cotton mercerisation caustic recovery;
ion exchange regenerant recovery.
section

10 Chemical
make-up
tank

Caustic or
acid cleaning
chemical
storage tank
Cleaned
Process or permeate
bottle wash

Pump

Concentrate

Pump
Membrane
Buffer system
tank

Concentrated
waste to disposal

Fig 32 Stylised CIP chemical recovery membrane system

38
CIP membrane systems have been used in Europe since 1995. The systems are designed in a
modular fashion for large-scale users as well as small CIP or bottle washing installations.

Membrane filtration is already proven as a tertiary suspended solids/disinfection option for


wastewater treatment plants. However, an application currently under development is to use
membrane filtration in biological wastewater treatment plants to retain biomass within the
bioreactor system.

There are two major benefits of incorporating a membrane filtration stage downstream of a
bioreactor to capture and recycle biomass:

the constraints of the commonly used gravity settlement processes are eliminated, allowing
higher bioreactor biomass concentrations and resulting in more compact plant sizes and
accelerated removal rates;
high quality permeates can be obtained from industrial effluents that were previously difficult
to treat biologically.

Membrane units are available for both aerobic and anaerobic systems. Development work on
anaerobic processes using ultrafiltration has been carried out in South Africa, and commercial
membrane systems for the aerobic treatment of municipal and industrial effluents are available in
the UK.

section

10

39
section

10

40
Membrane Driving force for mass Type of membrane employed Separation mechanism Application
separation process transport of the membrane
Microfiltration Hydrostatic pressure difference: Symmetrical porous membrane with Sieving effect/adsorption Separation of suspended
50 - 200 kPa a pore radius of 0.05 - 2 m materials, eg pigments,

T E C H N I C A L TA B L E S
bacteria, blood

Appendix 1
Ultrafiltration Hydrostatic pressure difference: Symmetrical porous membrane with Sieving effect/adsorption Concentration, fractionation
200 - 1 000 kPa a pore radius of 0.005 - 0.1 m and cleaning of macromolecular
solutions, eg viruses, proteins,
emulsions, colloids
Reverse osmosis Hydrostatic pressure difference: Asymmetric membrane from Solubility and diffusion in the Concentration of components
1 000 - 10 000 kPa different homogeneous polymers homogenous polymer matrix with low molecular weight,
eg metal ions, aqueous salts
Dialysis Concentration difference Symmetrical porous membrane Diffusion in a Separation of components
convection-free layer with low molecular weight from
macromolecular solutions
Electrodialysis Difference in electrical potential Ion exchange membrane Different charges of the Desalting and de-acidifying
components in solution solutions containing neutral
components
Gas separation Hydrostatic pressure difference: Asymmetric membrane from Solution and diffusion in the Separation of gases and vapours
1 000 - 15 000 kPa a homogeneous polymer homogeneous polymer matrix
Pervaporation Partial pressure difference Asymmetric solubility membrane Solution and diffusion in the Separation of solvents and
up to 100 kPa from a homogeneous polymer homogeneous polymer matrix azeotropic mixtures
Table A1 Features of industrial membrane processes
41

A1
appx
A1
appx
42
7

Membranes Basic materials Manufacturing procedures Structures Application


Centre for Exploitation of Science and Technology (CEST). Water - Resource and Opportunity. March 1992. CEST.

Ceramic (and Oxides (usually alumina or Pressing and sintering of Pores of 0.1 - 10 m diameter Filtering of suspensions, gas
metallic membranes) zirconia), graphite, metal fine powders cleaning, separation of isotopes
powder

Stretched Polytetrafluoroethylene, Stretching of partially crystalline foil Pores of 0.1 - 1 m diameter Filtration of aggressive media,
membranes polyethylene, polypropylene perpendicular to their orientation cleaning of air, sterile filtration,
medical technology

Etched polymer films Polycarbonate Radiation of a foil and Pores of 0.1 - 10 m diameter Analytical and medical chemistry,
subsequent acid etching sterile filtration

Homogeneous Silicone rubber, Extruding of homogeneous foils, Homogeneous phase, Gas separations, carrier-mediated
membranes hydrophobic liquids formation of liquid films support possible transport

Symmetrical Cellulose derivatives, Phase inversion reaction Pores of 50 - 5 000 nm Sterile filtration, dialysis,
microporous membranes polyamide, polypropylene diameter membrane distillation

Integral asymmetric Cellulose derivatives, Phase inversion reaction Homogeneous polymer or Ultrafiltration, hyperfiltration,
membranes polyamide, polysulphone pores of 1 - 10 nm diameter gas separations, pervaporation

Composite asymmetric Cellulose derivatives, Application of a film to a Homogeneous polymer or Ultrafiltration, hyperfiltration,
membranes polyamide, polysulphone, microporous membrane pores of 1 - 5 nm diameter gas separations, pervaporation
polydimethyl-siloxane

Ion exchange Polyethylene, polysulphone, Foils from ion exchange resins or Matrix with positive or Electrodialysis, electrolysis
membranes polyvinyl-chloride etc sulphonation of homogeneous polymers negative charges

Polymeric sinter Polytetrafluoroethylene, Pressing and sintering of fine powders Pores of 0.1 - 50 m diameter Coarse filtration, gases or liquids
membranes polyethylene, polypropylene
Table A2 Properties and applications of synthetic membranes7
Cost parameter Technology Membrane types Cost guideline*
per m2 membrane
System capital cost RO, NF Spirals and tubes 350 - 1 100
UF, MF Hollow-fibre, spirals and ceramics 400 - 1 500
Replacement membrane cost RO, NF Spirals and tubes 60 - 140
UF, MF Hollow-fibre, spirals and ceramics 80 - 350
* Source: A UK membrane system supplier
Table A3 Cost guidelines - membrane system capital cost and replacement membrane cost

appx

A1

43
Appendix 2
UK EQUIPMENT SUPPLIERS

A limited number of companies manufacture membrane modules in the UK and overseas. These
companies may supply membrane equipment either directly or, in the case of overseas corporations,
through UK agents.

Membrane technology know-how is broad-based and a large number of OEMs include membrane
separation equipment in their equipment portfolio. Potable water applications are well understood
and turnkey technology is applicable for such uses. The use of membrane technology for process
or effluent separations is a more specialised field requiring a good understanding of membrane
characteristics and a wide experience of treating different effluent types. Furthermore, most
membrane technology suppliers tend to specialise in particular effluent areas, although some larger
companies supply technology across most industrial sectors (and usually have the benefit of overseas
experience).

A list of contacts for products and services is given overleaf. The list is not exhaustive and has been
compiled from information currently available to the Environmental Technology Best Practice
Programme. The listing of an organisation should not be regarded as an endorsement of its services
or products by the Programme. Similarly, the Programme makes no claim for the competence or
otherwise of any organisation not listed.

The list is regularly updated and is available free through the Environmental Helpline on 0800
585794. The Helpline has access to the Joint Environmental Markets Unit (JEMU) database of
suppliers of environmental products and services.

appx

A2

44
Membrane equipment suppliers with process separation experience
who are active in the UK*

Company Telephone Technology Specialist area


CARDEV International Ltd 01423 522911 UF Oil and machine coolant
recovery
Domnick Hunter Ltd 0191 410 5121 MF Dead-end microfiltration
Fileder Filter Systems 01622 691886 MF, UF Membrane supplier
KALSEP Ltd 01276 675675 MF, UF MF and UF in broad range of
process effluent
Koch Membrane Systems 01785 212565 MF, UF, NF, RO Separations for a broad range of
process effluent
Le Carbone (GB) Ltd 01273 415701 MF, UF, Ceramic membrane applications
Pervaporation Degreasing bath cleaning
Solvent dewatering
Memcor 01629 823811 MF, RO Separations for a broad range of
process effluent
Memtech (UK) Ltd 01792 310454 MF, UF, NF, RO Separations for a broad range of
process effluent
MPW Sierma Membrane +31 73 312555 NF CIP chemical recovery and re-use
Systems (Kiryat Weizmann,
European Agent)
PCI Membrane Systems Ltd 01256 896966 MF, UF, NF, RO Separations for a broad range of
process effluent
Renovexx Technology Ltd 01388 420181 MF Vehicle wash
Metal removal
General particle separations
Smart Chemical Co. Ltd 0181 331 8167 Pervaporation Solvent dewatering
Distillation replacement
USF Acumem Ltd 0151 423 8800 MF, UF Oil/water separation or similar
separations
* Membrane technology suppliers contacted during the preparation of this Guide.

appx

A2

45
Appendix 3
FURTHER READING

Membrane suppliers typically offer a range of brochures and information describing the basic
concepts of membrane separations as well as specific products. Such information is readily available
from the listed companies.

Mulder, Marcel. Basic Principles of Membrane Technology. 1991. Kluwer Academic Publishers.
ISBN 0-7923-0978-2.

Environmental Technology Best Practice Programme: Good Practice Guides:

Good Practice Guide (GG25) Saving Money through Waste Minimisation: Raw Material Use

Good Practice Guide (GG26) Saving Money through Waste Minimisation: Reducing Water Use

Good Practice Guide (GG27) Saving Money through Waste Minimisation: Teams and Champions

Good Practice Guide (GG37) Cost-effective Separation Technologies for Minimising Wastes and
Effluents

Details of how to obtain a copy of any of these publications can be obtained from the Environmental
Helpline on 0800 585794.

appx

A3

46
The Environmental Technology Best Practice Programme is a joint Department of Trade and
Industry and Department of the Environment initiative. It is managed by AEA Technology plc
through ETSU and the National Environmental Technology Centre.

The Programme offers free advice and information for UK businesses and promotes
environmental practices that:

increase profits for UK industry and commerce;

reduce waste and pollution at source.

To find out more about the Programme please call the Environmental Helpline on freephone
0800 585794. As well as giving information about the Programme, the Helpline has access to
a wide range of environmental information. It offers free advice to UK businesses on technical
matters, environmental legislation, conferences and promotional seminars. For smaller
companies, a free counselling service may be offered at the discretion of the Helpline Manager.

FOR FURTHER INFORMATION, PLEASE CONTACT THE ENVIRONMENTAL HELPLINE

0800 585794
e-mail address: etbppenvhelp@aeat.co.uk
World wide web: http://www.etsu.com/ETBPP/