DESALINATION

ELSEYIER Desalination 108 (1996) 247-253

Waste water treatment by membrane processes -

New development in ultrafiltration, nanofiltration and
reverse osmosis
R. Rautenbach*, K. Vossenkaul, T. Linn, and T. Katz
Institut fiir Verfahrenstechnik der Rheinisch-Westftilische Technische Hochschule Aachen, Turmstrasse 46,
52056 Aachen, Germany. Tel.: +49-241.805470; Fax.: +49-241-8888252

Received 2 September 1996; accepted 6 September 1996

Abstract

A significant improvement of the quality of biologically treated municipal waste water with respect to
pathogenic bacteria and viruses and phosphate concentration is possible by a combination of precipitation/
ultrafiltration. But economically feasible is such a process only for an extremely low specific energy
consumption and, simultaneously, moderate specific investment costs. Worldwide, there are several groups
concerned with the development of such systems. In close cooperation with the Rochem company, Germany, we
developed a new ultrafiltration module meeting these requirements. This module has been tested on pilot plant
scale (9 mVh permeate) since October 95 with the sand-filtered effluent of the municipal waste water treatment
plant Berlin Ruhleben. The major results will be discussed. The second example concerns dumpsite leachate
treatment by a combination “reverse osmosis-nanofiltration-crystallisation-high pressure reverse osmosis”.
This combination achieved a water recovery rate of 97% with a very low overall power consumption (-8,3
kWh/m3 permeate] and far lower investment costs than comparable evaporation processes.

Keywords: Waste water treatment; Membrane processes; Ultrafiltration; Nanofiltration; Reverse osmosis
_

1. Removal of phosphate and pathogenic took and still undertake great efforts in order
bacteria from biologically treated municipal to improve the water quality of lakes and
waste water rivers,
Compared to 1960-1970, quality has
Environmental quality is recognized as an improved and this despite increased
essential part of our quality of life. population density and increased industrial
Accordingly, we - of course as a still fairly production rate. Necessarily municipal
prosperous industrialized country - under- wastewater treatment has been developed to
rather high standards. But still a further
Presented at the Second Annual Meetin of the Euro ean
Desalination Society (EDS) on Desa f’mation an dpthe improvement, especially with respect to the
Environment, Genoa. Italy, October 20-23, 1996. removal of pathogenic bacteria and viruses, is
required.
*Corresponding author.

001 l-9164/97/$17.00 Copyright Q 1997 Published by Elsevier Science B.V. All rights reserved.
PZI SO01 l-9164(97)00032-5
248 R. Rautenbach et al. /Desalination 108 (1996) 247-253

membrar - , permeate channel

/I\- module

I
pressure vessel
spacer
Fig. 1. Ultrafiltration as polishing step in municipal
waste water treatment. Fig. 2. Crossectional view of the Rochem UF module.

Of special interest in this context are

ultrafiltration or microfiltration as polishing
step after biological treatment of municipal
waste water (Fig. I). We ourselves prefer
ultrafiltration to microfiltration since ultra-
filtration guarantees the retention of bacteria,
viruses and substances such as precipitated
phosphate. In addition, a blocking of the
membrane pores as is observed sometimes in
microfiltration is unlikely in case of
ultrafiltration [I].
The advantages of the combination bio-
Fig. 3. Module arrangement of the UF pilot plant Berlin
reactor/ultrafiltration compared to biology/
Ruhleben.
sedimentation are well known and in small
scale units for biological treatment of
industrial effluents or dumpsite leachate this Table 1
combination can be considered as state of the Main features of the Rochem UF module
art. The advantages are:
- Significantly increased specific capacity _ Choice of cross flow or dead end operation
(space-time-yield) because of the high - Variable feed channel height - adaption to high or
biomass concentration (20-25 g/l instead low concentrations of solids in the feed possible
_ Flushing of the debris (gel layer) in intervals by air
of 4-5 g/l> [2]
_ Trouble-free operation (for example, no injection (bubble formation)
- High water recovery rate (>98.5%) since air injection
separation problem in case of foam-sludge. allows the separation of concentrated solids and
permeate is not required for flushing
The disadvantage of the conventional - Easy membrane replacement
- Easy module assembly
tubular UF systems with flow velocities of
about 4 m/s is the high specific energy
consumption of about 10 kWh/m’ permeate.
This is no problem in special cases such as
leachate treatment but prohibitive for the filtration stages only if the specific energy
treatment of municipal waste water. Here consumption can be reduced to about 0.3-0.5
ultrafiltration can replace the sedimentation/ kWNm3 [3].
 R. Rautenbach et al. /Desalination 108 (1996) 247-253 249

Worldwide there are a number of research Table 3

teams tackling this problem. We ourselves Distribution of operational costs (in %) calculated for a
permeate flux of 90 Vm2.h
developed in cooperation with the Rochem
company a new UF-module, based on the
DTF nanofiltration module. In the new Capital costs 50-60
Precipitation chemicals 3-5
module (Figs. 2 and 3) the feed channel is Maintenance 10-15
formed by 2 membranes and completely free Chemicals 8-12
of obstacles. Flow pattern is “straight Energy 4-8
through”. The key data of the module are Membrane replacement 12-16
summarized in Table 1.
Originally this module has been developed
for the treatment of water with high
concentrations of suspended solids at still
relatively low specific energy consumptions. 3. Reverse osmosis/nanofiltration/ high
But it has been successfully operated in dead pressure reverse osmosis for a zero-
end mode. In intervals, the cake formed on discharge treatment of dumpsite leachate
the membrane has been flushed out by
switching to cross flow mode and air bubble Nanofiltration is a still relatively new
injection for several seconds [4]. pressure driven membrane process. Regarding
Table 2 summarizes the results obtained in driving force and rejection of organic
an 8-week experiment with the effluent of the components in aqueous solutions, nano-
municipal waste water treatment plant Berlin filtration is somewhere between reverse
Ruhleben. In this case, UF was placed behind osmosis and ultrafiltration (Table 4).
sedimentation and a sandfiltration, i.e. just as
a polishing step. Estimated specific costs of Table 4
this UF step (including capital costs) are 0.35 Driving force and selectivity of reverse osmosis.
DM/m3 permeate. With such a cost figure, nanofiltration and ultrafiltration
large scale applications of UF, replacing
sandfiltration seem feasible. Pressure (driving Cut-off
Table 3 shows the distribution of operating force), bar g/m01
costs for the ultrafiltration process. The major
part are capital costs and membrane Reverse osmosis 30-200 <200
Nanofiltration 1 O-40 200-l ,000
replacement. Since these costs are directly
Ultrafiltration 2-10 l,OOO-100,000
connected to the permeate flux of the
ultrafiltration the total operating costs are
reduced if permeate flux can be increased.
Consequently enhancement of permeate flux
is a major task of membrane and module Like reverse osmosis, nanofiltration is
development - of cause at moderate energy based on solution-diffusion as major transport
consumption. mechanism. But contrary to reverse osmosis
nanofiltration membranes contain fixed
Table 2 (negatively) charged functional groups. As a
Key data of the UF pilot plant Berlin Ruhleben consequence, the selectivity of NF for
monovalent and bivalent anions is
Feed pressure, bar 0.7-2.0 significantly different. Table 5 shows results
Permeate flux, Vm2.h 90 of experiments with binary aqueous solutions.
Time or filtration cycle, min 60
Specific energy consumption, kWh/m3 0.2-0.3
Typically the rejection for chlorides and
Recovery rate, % 90-98 nitrates is about 50%, but for sulfates 96-98%
[51.
250 R. Rautenbach et al. /Desalination IO8 (1996) 247-2S3

Table 5 osmosis and nanofiltration is only of

Characteristics of reverse osmosis and nanofiltration quantitative nature; Whereas components of a
membranes
molecular mass of about 150 kg/kmol are
almost totally rejected by reverse osmosis, the
Reverse osmosis Nanofiltration
“cut-off” of nanofiltration is above 300
kg/km01 .
Membrane Reject. Membrane Reject.
rate, % rate, % Essentially based on the special feature of
nanofiltration - the significantly different
Chloride (monovalent)
rejection of mono- and bivalent anions - we
FilmTec FT30SW 99.1 FilmTec NF45 55 developed a new process for dumpsite
Desal3S 99.2 Desal5K 50 leachate treatment.
Toray UTC80 99.4 Toray UTC60 60 Dumpsite leachate is a direct consequence
Nitto NTR759H 99.5 Nitto NTR7450 50
of rainfall. The average leachate production
Sulfate (bivalent) of a dumpsite in western Europe is about 5
FilmTec FT30SW >99.8 FilmTec NF45 98.5 m3/ha.d. According to Fig. 5, leachate
Desal5K 96.4-98 contains a rather complex mixture of
components but mainly inorganics.
Fig. 6 shows the flow diagram of the
treatment process. The 2-stage RO is
operating at 60 bar and 120 bar in the first
loo , ,.. 1
stages and 60 bar in the second stages. The
concentrate of the 120 bar unit is treated by a
combination of NF/crystallisation. At
moderate transmembrane pressure differences
of 20-50 bar the nanoflltration unit produces
a permeate containing mainly chlorides. This
permeate can be concentrated further without
0 L__.___~._._.....____~_______~_~_~
, ~ j :X-l i danger of scaling by a 200 bar HPRO.
I i i ; i i i I Essential for the process is the operation of
-201
0 om am am 0.~ am 000 a07 am the NF/crystallizer cycle in the range of
supersaturation with respect to calcium sulfate
feed concentration Na ,SO, [WI
and at high concentrations of organics. For
Fig. 4. Influence of sulfate feed concentration on
this reason the success of the process depends
chloride rejection [6]. to a large extent on a proper module design -
the modules must be insensitive to fouling
and the presence of crystals. Such modules
have been developed by Rochem, Germany
In a number of cases this different rejection (Fig. 7). Stacks of rectangular membrane
of mono- and bivalent anions permits the cushions and matching spacer plates are
realisation of the Donnan Effect: In a arranged in series in the pressure vessel in
multicomponent system containing among such a way that stagnant areas are avoided and
others sulfate and chloride ions, the chloride internal friction losses are minimized. Feed
rejection in shifted towards negative figures flow is strictly parallel to the vessel axis, the
with increasing concentration of the sulfate velocity in the feedsite module channels is
ions (Fig. 4) - chlorides are forced into the about 1.5 m/s.
permeate with increasing sulfate con- In cooperation of the Rochem company
centration. and the Institute fur Verfahrenstechnik,
With respect to organic dissolved RWTH Aachen, the process has been installed
components, the difference between reverse and tested on a technical scale at the dumpsite
 R. Rautenbach et al. / Desalination 108 (1996) 247-253 251

iitrogen compounds Qlssdvd sdids

7
2.15g
components

Fig. 5. Average composition of

dumpsite leachate [7].

Fig. 6. Flow diagram of the process combination

ROMFlcrystallisation.

Fig. 8. Nanofiltration blocks at the dumpsite Ihlenberg.

Ihlenberg. A nanofiltration stage consisting of

4 blocks with 9 modules each and total
r ,T~: ^, ! . “ “zw;*:-p.irrc’-4’ _’ :
membrane area of 180 m* (Fig. 8) has been
;;,,‘“- ,

added to the existing RO-HPRO combination

Fig. 7. Rochem DFT-module. and commissioned in September 1994. The
252 R. Rautenbach et al. /Desalination 108 (1996) 247-253

unit is designed for the treatment of about 4 The rejection rate for sulfates is 92-95%,
m3/h RO concentrate of a concentration factor for the dissolved solids (conductivity) 20-
of 30%. Table 6 lists the data for other relevant
parameters. Interesting are the high rejection
CFv RO = (+~l VR)Ro = 10 of organics (COD) of about 92% and the
unexpected high rejection of about 40% for
Depending on the concentration factor of NH3/NH4+.
the 60 and 120 bar RO-stage, the NF-stage At the dumpsite Ihlenberg (Table 7) the
achieves a further concentration specific energy consumption of the NF and
the subsequent 200 bar RO stage is 32
CFv NF = ( CF / CR),, = 10-20 kWh/m3 permeate. This figure is a direct
consequence of the untypical leachate
A sludge consisting of organics, composition of the Ihlenberg dumpsite.
precipitated inorganics and water is
discontinuously withdrawn from the bottom
of the crystallizer/sedimentation tank.
With the added concentrate of the Table 6. Analysis of the dumpsite leachate and the
rejection rates of nanofiltration
subsequent 200 bar HPRO stage this
concentrate is disposed of at Ihlenberg by
Parameter Feed Permeate Reject.
solidification with fly ash and final storage at
rate
the dumpsite.
Cleaning of the NF-modules consists of
BSB, mg/lO2 480 280 41.67
flushing with feed at zero transmembrane CSB, mg/lO2 17,000 700 95.88
pressure difference for 30 seconds every hour Ammonia, m&l 3,350 1,420 57.61
and an alcaline cleaning every 250-300 Sulfate, mg/l 31,200 2,345 92.48
hours. Chloride, mg/l 12,760 17,730 -38.95
Fig. 9 shows the results obtained in the Calcium, mg/l 2,670 187 93.00
Magnesium, mg/l 1,030 72.7 92.94
operation period September/December 94. Sodium, mg/l 10,900 5,010 54.04
After startup, an average permeate flow rate of PI-I 6.3 6.4 _
3.6 m3/h is a achieved at transmembrane Conductivity, l&/cm 61 43 29.5
pressure differences of, initially 20 bar,
increasing to 40 bar before cleaning.

i 3500
1
; 3000

+ 2500

4 2000 rej. r. conductlvll

permeate flow
rej. r. sulfate

OJ LO
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400
operation time [h ]

Fig. 9. Operation data of the NF-plant on dumpsite Ihlenberg.

 R. Rautenbach et al. /Desalination 108 (1996) 247-253 253

Table 7. Specific energy consumption of the Ihlenberg In ultrafiltration, research and development
leachate treatment plant (capacity: 50 m3/h dumpsite concentrate on module design aiming at low
leachate) specific energy consumption and -
simultaneously - low investment costs with the
Part of plant Permeate Specific energy special aim of replacing sedimentation/
flow rate consumption
m3lh Process Total
sandfiltration in municipal sewage treatment
stage plant plants.
kWhlm3 kWh/m3 In reverse osmosis/nanofiltration, research
permeate feed and development concentrate on shifting the
limits of processes to very high water
RO/high pressure RO recoveries, i.e. the development of “almost
60-bar RO 35 4 2.8 zero discharge” processes. As shown in the
HD-RO 11 17 3.74
second example, this is also strongly related to
NF/high pressure RO module development.
NF 2.7 32 1.73
RO

Water recovery: 97.40% Total plant: 8.27

References

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[41 H.-J. Altmann, J. Dittrich, R. Gnirss, R. Peter-
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[51 R. Rautenbach, Membranverfahren. Umdruck zur
Vorlesung
4. Conclusions
[61 G. Schneider, Trennverhalten von Nanofiltrations-
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The two examples discussed in this paper [71 R. Rautenbach and Th. Linn, Desalination, High-
illustrate the steadily increasing impact of pressure reverse osmosis and nanofiltration, a
membrane processes on modern waste water “zero discharge” process combination for treatment
of waste water with severe fouling/scaling
treatment and, vice versa, how the
potential, 31 May 1995.
requirements of individual separation
problems intensified research and develop-
ment.
An especially rapid development can be
presently noticed for ultrafiltration/micro-
filtration and for RO/nanofiltration i.e.
processes which are commonly considered as
rather well developed.