Application example:

INDUSTRIAL WASTE WATER RE-USE

MEMBRANA GmbH
Wuppertal, Germany
Norbert Selzer

www.liqui-flux.com
Content

Introduction of Membrana

Initial position of the Project

Pilot trials

Plant design

Operating experience

Summary and preview

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 SEPARATIONS MEDIA ENERGY STORAGE
High Performance Filtration Ion Exchange Membranes

INDUSTRIAL TRANSPORTATION
HEALTHCARE ELECTRONICS
& SPECIALTY & INDUSTRIAL
- Liquid filtration - Hemodialysis Rechargeable and Lead acid battery
- Degasification - Plasmapheresis Disposable separators
- Blood lithium battery
- Gasification
oxygenation separators
- Debubbling

Polypore separator

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Membrana’s core business

Healthcare
Dialysis membranes Oxygenation membranes

Industrial Separation
Membrane Contactors Filtration Modules Flat sheet membranes
4
History and status:

Part of Polypore-Group since 2002

Plant in Wuppertal, Obernburg Product launch
(Germany) and Charlotte, Liqui-Flux ®
North Carolina (USA)
2005

Leading manufacturer of Introduction of UltraPES
membranes for medical and capillary membrane
industrial application Start of 2000
®
MicroPES -membrane

~ 480 employees
1995 Membrana GmbH, Polypore 2002

Turnover > 100 Mio €/a Start of industrial
membrane (ACCUREL®) BU Membrana, Akzo 1988
Start of CUPROPHAN® membrane 1980
BU Membrana, Enka Glanzstoff 1960
worldwide leader in dialysis
Start of dialysis membrane 1974 Enka – Glanzstoff 1950
production
J. P. Bemberg, Vereinigte Glanzstoff Fabriken 1925
1965
J.P. Bemberg 1792

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Initial situation of the Project

Mix of waste water Parameter Range

from open sewer, TSS [mg/l] 500-750

with sewage from CSB [mg/l] 400-800

chemical, metal and Conductivity [µS/cm] 1200-2800

textile industry. Alkalinity [mg/l] 200 - 500

In winter diluted by rain Color [Co-Pt] 300-650

water. Temperature [°C] 7-30

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 Existing Waste Water Treatment Plant

Incl. tertiary treatment: Precipitation/Flocculation/Sedimentation/Sand filter

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Clean water quality

Quality requirements for

After existing WWTP
industrial re-use

Parameter Range Parameter Range

Turbidity [NTU] 2-10 Turbidity [NTU] <0,1

TSS [mg/l] 8-30 TSS [mg/l] ~0

CSB [mg/l] 20-60 CSB [mg/l] <=10

Conductivity [µS/cm] 1200-2800 Conductivity [µS/cm] 200 - 400

Color [Co-Pt] 10-60 Color [Co-Pt] <5

Temperature [°C] 7-30 Temperature [°C] -

pH 7,1-7,8 pH 7-8

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Pilot trials in 2 phases

Mechanical Biological cleaning Chemical treatment

cleaning Sand filter

Pilot Chemical Treatment

Phase B Phase A
UF Pilot system

Pilot RO

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UltraPES Membrane

Protective Separation
layer Support layer layer

Multifiber
P.E.T.® Technology

Membrane Characteristics
Membrane Type Hollow Fiber, Inside - Out
Membrane Material Polyethersulfone
Cross-section of the 3-layer structure Nominal Cut-off 80 kDa
Outer / Inner Diameter 1,25 / 0,8 mm
Burst Pressure > 12 bar

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Liqui-Flux® UF Module W02

Housing Material Glass Fiber Reinforced Plastic

Potting Material Polyurethane
Sealing Material EPDM, O-Ring
Connectors Victaulic (76.1 mm)
Shipping Weight 40 kg
Weight Filled With Liquid 135 kg
Membrane Surface Area 61 m2

Max. Working Pressure 4 bar

Max. Working Temperature 40 °C

pH-Range During Cleaning 1-13

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Pilot system in the field

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Phase A: Start of pilot trial

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Phase A: Stable operation achieved

Pilot trial - waste water Turkey 90 lmh; BW every 59 min; PAC 0,5 mg Al/l; CEB H2SO4

1000 10

900 9

800 8

700 7
TMF [l/h/m²/bar]

Turbidity [NTU]
600 6

500 5

400 4

300 3

200 2

100 1

0 0
07.04.2007 09.04.2007 11.04.2007 13.04.2007 15.04.2007 17.04.2007

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Phase B: Adjusting with the treatment of the WWTP

Simulation of overdosing in pilot sedimentation - UF 65 lmh; BW every 39 min; PAC 0,5 mg Al/l
1600
CEB NaOH + NaOCl,
CEB NaOH + NaOCl,
1400 10 min
10 min

1200
TMF [l/hm²bar]

1000

800

600

400

200

0
27.08.2007 27.08.2007 28.08.2007 28.08.2007 29.08.2007 29.08.2007 30.08.2007 30.08.2007 31.08.2007 31.08.2007 01.09.2007
00:00 12:00 00:00 12:00 00:00 12:00 00:00 12:00 00:00 12:00 00:00

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Filtrate quality in pilot trial

Parameter Range
Turbidity [NTU] <=0.01…0.02

SDI-15 [%/min] 2…2,5

TSS [mg/l] ~0 (detection limit)

COD [mg/l] 10-30

RO elements with high packaging ( 28 mil-Spacer )

were in stable operation without performance loss for weeks

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System design of UF&RO

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 System design of Ultrafiltration

Feed tank for approx. 30 min (nominal operation)

Dosing of coagulant and dynamic mixer

Coagulation pipe (inside feed tank) for
approx. 60 sec residence time

7 feed pumps for 7 UF-racks

Sieve basket filter, 200µm, automatic backwash,
synchronized with UF backwash

7 UF-Racks each with 76 modules , 4636 m²
membrane surface per rack

Backwash with UF-filtrate

CEB with RO-permeate

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 Operating experience I

From August until September 2007 the 7 UF and RO racks were started one after
another, one UF rack then one RO rack and so on.

At this point in time a good basis from the piloting was available to increase the flux
of the UF up to the scheduled value of 75 l/h/m² within a few weeks. At the beginning
the backwash interval was adjusted to 30 minutes and in several steps increased to
60 minutes. Transmembrane pressure (tmp) during filtration stayed below 0.2 bar
(2.9 psi).

The chemical enhanced backwash was adjusted several times to fit to the raw water
quality. The standard procedure now is cleaning with NaOH at pH >12 with addition
of 200ppm chlorine. After a backwash an acid step at pH 2 for rinsing out the caustic
follows.

During the start-up it was examined by sampling that all modules get the same
concentration of chemicals.

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 Operating experience II
Two events during the last 3 years required special activities.

In December 2007 the performance of the biological treatment in the WWTP

decreased and also a part of sludge came into the feed to the UF. Within a short
time the tmp increased to 0.8 bar and the system was stopped automatically.
Several backwashing steps could recover the flux only partially. Therefore the
caustic CEB was done two times at pH of 12.5 with a soaking time of 20 minutes,
which increased permeability to >500 l/h/m².

One year later, around New Year 2008/2009 an increase of the tmp took place
during several weeks until 0.6-0.7 bar were reached. The caustic CEB did not work
well. After checking the water analyses from the WWTP, which is done regularly by
the operating company, high values of metals (Al, Mn, 0.4-0.5 ppm) were obvious. A
CIP with citric acid for 1h at 38°C recovered the flux to a value in the range of the
start value.

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 Operating experience III

During 9 of 12 month in a year one CEB per day is satisfying. In case of high
contamination in the raw water the operator switches the CEB to every 12h and in
single cases to every 8h.

The filtrate quality is checked continuously regarding SDI-15 (<3) and turbidity (<0.1
NTU).

With this water quality the yield of the RO could be raised from 75% at the beginning
of the operation up to 85% today.

The final quality of product water has been maintained during the whole operation
time without any restrictions.

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 Summary and preview

By the combination of Inline-coagulation, Ultrafiltration and Reverse osmosis a
system design has been installed which works safely and economically despite the
changing load in the waste water from the different industrial companies.

The used Ultrafiltration membranes have been demonstrating their suitability by a
low fouling tendency and favorable cleaning properties.
In combination with a sophisticated module and system design, and an operation
adapted to the local situation, this process system obtains central importance in
industrial waste water recycling.

Alternatively to the pre-treatment from the existing system in this project
(sedimentation, gravel filter) for new systems, depending on the load of the water,
other process steps like flotation and sieve filter should be tested and considered.

UF system costs may be reduced by usage of modules with increased membrane
surface: 75sqm

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