DESALINATION

ELSEVIER Desalination 157 (2003) 65-72

www.elsevier.com/locate/desal

Second use for old reverse osmosis membranes:

wastewater treatment

Jose M. Veza a*, Juan J. Rodriguez-Gonzalez b

"Departemento de lngenieria de Procesos, Universidad de Las Palmas de Gran Canaria (ULPGC), Campus Tafira Baja,
E-35017 Las Palmas de Gran Canaria, Spain
Tel. +34 (928) 451942; Fax +34 (928) 458975; email: jveza@dip.ulpgc.es
bEmpresa Mixta de Aguas de Las Palmas SA (EMALSA), Plaza de la Constitucion 2,
E-35003 Las Palmas de Gran Canaria, Spain

Received 29 January 2003; accepted 5 February 2003

Abstract
This paper describes some tests made with old seawater reverse osmosis (RO) membranes, modified to be reused
as filtration membranes. These modified membranes were then used to reduce suspended solids in the tertiary treatment
of municipal wastewater. The purpose of the tests was td establish the feasibility of recovering old (discarded)
membranes in order to reduce industrial solid waste, as well as reducing costs in new filtration membranes. The active
layer in the old RO elements was skinned offby recirculation of a potassium permanganate solution, which drastically
reduced the salt rejection properties of the membranes, down to 2%. The elements so conditioned were then used as
membrane filters inside pressure vessels, which had also been used in RO plants and recovered for a new purpose. The
pilot plant was designed to reduce both suspended and dissolved solids from wastewater secondary effluent, with a
production capacity designed for 6 m3/h. The reused membranes proved capable of reducing suspended solids (93.9%
average reduction in turbidity), and the overall separation efficiency reached 97%. The RO unit reduced 98.5%
conductivity at a 60% recovery ratio when operating at 32 bar. The filtrationmembranes developed a high pressure drop,
and must be cleaned quite often, both by flushing at high recirculation ratios and'by chemical cleaning. The cleaning
procedures must be optimised and reduced to a minimum.

Keywords: Membrane; Reverse osmosis; Reuse; Wastewater; Filtration

*Corresponding author.

Presented at the European Conference on Desalination and the Environment: Fresh Waterfor All, Malta, 4-8 May 2003.
European Desalination Society, International Water Association.
0011-9164/03/$- See front matter © 2003 Elsevier Science B.V. All rights reserved
PII: S 0 0 1 1 - 9 1 6 4 ( 0 3 ) 0 0 3 8 4 - 9
66 J.M. Veza, J.J. Rodriguez- Gonzalez / Desalination 15 7 (2003) 65- 72
1. Introduction
Water resources in arid or semi-arid regions
like the Canary Islands are scarce. The average
yearly rainfall is only 300 m m [1]. Water con-
sumption per capita is usually below 200 L/
person/d, and therefore, reusing water resources
is encouraged by water planners. After appro-
priate treatment, municipal wastewater is reused
mainly for irrigation purposes. Due to the
reduced consumption per capita, wastewater
usually features a high content in suspended
solids (SS). The concentration may reach
between 700 and 1000 mg/L SS, which is hard to
reduce in a conventional primary and secondary
treatment plant working on high organic and
solids loads. Therefore, a tertiary or advanced
stage must be set up in order to reduce suspended
solids. Besides, drinking water is sometimes
provided with a slightly saline content. Even
when salinity remains below permitted levels, it
may not be advisable for certain crops such as
bananas, greenhouse flowers, or vegetables such
as cucumbers or peppers; therefore, wastewater
must also be desalted in order to reduce an
acceptable degree of salinity.
On the other hand, there are many desali-
nation plants on the islands. All desalination
technologies are in use, including multi-stage and
multi-effect distillation, as well as vapour
compression and membrane technologies such as
reverse osmosis (RO) and electrodialysis (ED).
RO has been widely used over the last 20 years,
and therefore there are large stocks of used mem-
branes that are no longer appropriate for seawater
desalination because they have lost their original
properties due to fouling, aggressive cleaning
procedures, etc. In the largest plant in the islands,
Las Palmas III, there are over 4000 old mem-
brane (8") elements in stock.
Considering both these circumstances - - the
need to treat and reuse water, and the existence
of old used membranes - - leads to the driving
force in our research project: to try to condition
the old membranes in order to use them as filters
for suspended solids in tertiary wastewater treat-
ment rather than seawater desalination. Reusing
the old membranes in a second "lower quality"
application would provide advantages both from
an environmental viewpoint (less solid waste)
and from the economic side, since the costs for
wastewater plant operation are obviously
reduced, particularly due to cheaper filter
replacement.
The reuse of RO membranes as filters requires
a preliminary stage: the membrane elements must
be conditioned to separate the active layer. The
active layer must be "peeled oft" so that the salt
rejection properties of the membrane are reduced.
In fact, when these membranes are used for
filtration, we should aim for a high salt passage,
although with a high separation efficiency in
suspended solids.
Regarding membranes for municipal waste-
water treatment, their use has increased signifi-
cantly over the last 10 years. The main appli-
cation so far is wastewater final filtration in the
tertiary stage. Microfiltration (MF) or ultra-
filtration (UF) membranes may be used for
suspended solids separation [2,3]. On the other
hand, when the dissolved solids content in
secondary effluent makes it unsuitable for reuse,
some desalination is required, either with RO or
ED membranes [4,5].
Another application has been introduced more
recently: it is the growing popular use of
membranes as a means of separating biological
suspended solids within the secondary stage tank
in wastewater treatment plants. The devices are
called membrane bioreactors (MBR) [6,7]; the
membranes can be placed in an aeration tank,
therefore skipping the clarification tank, or they
can be placed in a separate tank for solids
separation. The membrane configuration used in
the applications is hollow fibre rather than spiral
wound.
Such a proposal of RO membranes con-
ditioned for reuse as filters has not been
 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72 67

Raw water Secondary

effluent
t ; Wastewater ~i ~~Wastewater I
',...-..,. treatment r..............................
,.! treatment r.............t
i-'(-Pr!mar-Y~.... L! se'c?'nd'a"!"Y)~J [ Tertiary
effluent

['CARYR~DO~I FIL'raAT,O.I Ii3ESA~'NArlo"1

-'1 FILTRATION "1/wit,membranesUSed
RO IF" II membranesWi
RO th .............
~[i

Fig. 1. Process diagram of the wastewatertreatment plant Fig. 2. Detail of the pilot plant showing the pressure
and test unit. vessels used for membrane filtration.

Table 1
Main design features for the pilot plant

Feed water pump 20 m3/hflow, 6 bar pressure

Cartridge filtration Two filters, 31 cartridges each, cartridge 5 cm diameter, 1 m length
membrane filtration pump 20 m3/hflow, 17 bar pressure
membrane filtration 3 pressure vessels, 6 elements each, 8" diameter
RO feed pump 8.4 m3/h flow, 31 bar max pressure
RO desalination 2 pressure vessels, 6 elements each, 8" diameter
Energy recovery device Turbochm:ger,8.7 m3/h flow

recorded. The closest references are related to 'brane elements were characterised and soaked in
chemical attack to the active layer by oxidants a recirculating oxidising solution. The second
such as chlorine or its derivatives [8,9]. In fact, stage was the performance assessment of the
when using RO membranes, the chlorine must be unpeeled membranes in a pilot plant consisting of
avoided in the feed water so as to protect the several filtration and separation steps.
active layer. On the contrary, our purpose is
precisely to separate the active layer by chemical
attack. 2.1. Test unit
The conceptual design of the project and the The preparation of the unpeeled membranes
test units is depicted in Fig. 1 where the pro- was carried out in a test unit, initially designed
cesses in the test unit are denoted. for performance evaluation of the membrane
elements. The unit was used for chemical oxi-
dation of the membrane active layer by recycling
2. Experimental
a solution o f oxidising agent; it consisted o f a
During the development of this project, two standard design: cartridge filter, high pressure
different experimental devices were used. For the positive displacement pump (up to 70 bar) and a
first stage (peeling off the membranes), a pressure vessel (8" diameter), capable for a single
conventional test unit was used where the mem- spiral-wound element.
68 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72
2.2. Pilot plant design
This pilot plant is fed with secondary effluent
from a wastewater treatment plant at a flow rate
ranging between 5 and 8 m3/h. It consists of three
separation stages: cartridge filtration, membrane
filtration, and RO. The unit was specifically
designed by EMALSA and the main design
features are shown in Table 1.
All pressure vessels were recovered from an
earlier application in the seawater RO plant.
Fig. 2 shows a picture of the plant's main body,
depicting the pressure vessels for membrane
filtration.
3. Results and discussion
The first stage in the project, membrane
conditioning by peeling off the separation layer,
was carried out with some 80 (8") elements
through chemical attack with a strong oxidant.
These elements had been used earlier in a large
RO production plant for periods of time between
3 and 5 years. Amongst the oxidising agents that
were tested, potassium permanganate proved to
be the most effective. Others were sodium hypo-
chlorite and sodium hydroxide. These results
have been previously reported [10].
Our aim, after peeling off the separation layer
of the membrane, was to obtain an element
capable of filtrating the suspended matter con-
tained in the effluent from wastewater treatment
plants, rather than separating salts at this stage.
Therefore, the mission of these elements was to
produce a large amount of water (high product
flow rate or high conversion ratio) and produce
high salt passage. On the other hand, the
operating pressure of the system when the peel-
ing reagent was recycled through the membrane
is also a parameter of interest because that
pressure has a strong influence on the energy
consumption of the peeling process. The lower
the peeling pressure, the lower the energy
consumption. Hence, these three effects are
combined in a single parameter to represent a
global effectiveness or permeability of the
membrane element.
Peeling effectiveness (PE) is defined as the
product of the product recovery and the salt
passage after the peeling process divided by the
operating pressure during the peeling:
P E - P R x S P 104
PP
where PR is the product recovery for the element
(or conversion ratio, fraction of water feed flow
that permeates through the membrane, %), SP is
the salt passage (fraction of salts that permeate
through the membrane, %), and PP is the
pressure during the operation of peeling (bar).
The higher the peeling effectiveness, the better
the membrane will perform as a filter. Our results
are expressed in terms of the PE.
In some tests, the peeling was done by soaking
the membrane in a bath, without recirculation,
with no pressure in the system. In such cases, a
simplified peeling effectiveness (SPE) is defined
as:
SPE = PR x SP
Apart from the purpose of comparison
between different tests, the absolute value of the
PE can be useful as well. We can estimate a
maximum value for it. According to the manufac-
turer' s recommendations, the maximum recovery
for a single element would be 15%, with our goal
for salt passage up to 100%; meanwhile, the
pressure during the peeling process should be
kept to a minimum (say between 5 and 10 bar).
Therefore, we can expect values for PE some-
where between 150 and 300. The SPE, on the
other hand, should be around 15%.
3.1. Type of oxidant
The first rounds of tests were aimed at
determining the effect of different oxidants as
 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72 69

Table 2
Comparison of peeling effectiveness for various oxidants

Oxidixing Dose, mg/L Peeling mode Peeling effectiveness, Simplifiedpeeling

reagent bar-X effectiveness, %
H202 + SS 1800 Rec 5 0.3
KMnO 4 180 Rec 23 1.3
KMnO4 180 Rec 121 7.3
KMnO4 360 Rec 49 2.9
KMnO4 360 Rec 48 2.1
KMnO4 360 Rec 252 11.1
KMnO4 900 Rec 268 16.2
KMnO4 1800 Rec 210 l 2.2
KMnO4 5472 Rec 445 29.4
KMnO4 8208 Rec 181 10.6
NaCIO 198.4 Imm 0.3
NaC10 198.4 Imm 0.1
NaCIO 6000 Rec + Imm 279 17.3
NaCIO + H2SO4 673.2 Imm 0.1
NaCIO + SDS 6500 Rec 8 0.5
NaOH 7680 Rec 376 19.2

peeling agents and produced results as listed in
Table 2. The peeling mode refers to immersion o f
the membrane in the peeling solution (Imm), or
recirculation of the latter around the membrane
(Rec).
It was soon concluded that potassium perman-
ganate was more effective, in general terms, than
other oxidants when applied to peeling off the
active separation layer. PE values over 150,
regarded as a good achievement for an element,
were easily obtained with this reagent. In addi-
tion, sodium hydroxide produced good results,
and its effect is due to be assessed in detail in
further tests.
In addition, it was obvious that recirculation
of the oxidising solution around the membrane
rather than soaking the membrane was more
effective. SPE values were between 1 to 30% in
the former mode vs. values below 1% in the
latter.
3.2. Pilot plant operation
After the membranes were properly con-
ditioned, they were tested in the pilot plant. The
main results from the tests are described below.
3.2.1. Feed water quality
The pilot plant was fed with secondary efflu-
ent with turbidity measurements usually between
5 and 10 NTU, although peak values could reach
90 NTU. Suspended solids concentration ranged
between 10 and 30 mg/l SS. There are significant
• variations in quality throughout the day and
during the week. Conductivity ranged from 1500
to 2500 gS/cm.
3.2.2. Process results
The feed water flow rate to the cartridge
filters was between 5 and 8 m3/h, and the filters
operated between 4 and 5.6 bar. Turbidity in
water could be reduced from a range of values
between 8 and 10 NTU down to values below 0.6
NTU after membrane filtration. In the second
filtration stage, membrane filtration operated at
some 14 to 24 bar, and produced 4 m3/h per each
tube when fed with 16 m3/h, including a recir-
culation stream taken from the reject at a rate of
11 m3/h. Turbidity was reduced to 0.1 NTU.
Finally, the RO unit produced 6 m3/h water when
operating at some 32 bar, reducing conductivity
70 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72
i
~i ~.
i \
Particle size, microns
from an average 2000 ~tS/cm to around 30 #S/cm
(98.5% salt rejection).
Overall separation efficiency was over 97%
for suspended solids and over 98% for dissolved
solids where the global conversion ratio is 60%.
Particle size is also relevant. Several samples
were taken and analysed for particle size distri-
bution (PSD). Particle sized varied typically from
8 to 50 ~tm, as shown in Fig. 3. The graph corre-
sponds to particles measured in the reject stream
from the membrane filtration stage.
3.2.3. Operating features
Amongst the operating features, fouling was
found as the most relevant drawback. The mem-
branes had undergone rapid fouling both in the
cartridge and in the membrane filters, which
made it necessary to carry out frequent cleanings
on both filtration steps. The fouling rate was
assessed by observing the decay in permeability
of the membranes, using a sort of permeability
parameter (estimated as the product flow rate
divided by the applied pressure, Qp/Pal),which
decreased during the operation of the membrane
filters, whereas permeability recovered after
cleaning. The variations can be easily determined
in the graph (Fig. 4), which refers to a 5-d
----Membranefiltration reject
Fig. 3. Particle size distribution.
operating week. The specific action taken con-
sisted of a short flushing time by increasing the
flow rate.
The cartridge filters were cleaned by a back-
wash procedure, whereas the membrane filters
were cleaned in two ways. A short time flushing
was carried out with reject water by increasing
the water flow rate from the nominal 17 m3/h to
19 m3/h every hour during 15 rain. On the other
hand, chemical cleanings were performed with
alkaline detergent every 3 to 4 days during 1 h.
3.2.4. Modes of operation
After the rapid fouling was identified, one of
the actions taken to overcome the problem was
modifying the hydraulic regime used in the
cartridge and the membrane filters. First the
once-through flow mode was tested, and it
produced intense clogging, as indicated by a fast
rise in pressure drop (AP), or other indicators
(AP/Q2), which is similar to a friction factor.
After this poor performance, the plant design had
to be modified to allow for recirculation of the
reject from filters in order to get a higher flow
rate in the membranes. The filters were now
operating on a recirculation mode as depicted in
Fig. 5.
 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72 71
0.24

increase in
permeability \ /¢~ A i*~

0,22
l/vv
O

0.20 decrease due [

lofouling [
Fig. 4. Permeability parameter
Day 1 4 Day2 ~ 4 Day3 ~. ~ ,4 Day'5 depicting membrane fouling and
0,18 recovery after cleaning.
Time

Cartridge
filtration Membrane Reverse Tertiary"
filtration osmosis effluent

................................ i ...................

Secondary Rejectrecycle "I ~ ~/-~

effluent - - ~/ zrx
Energy I J,
recovery / Fig. 5. Flow recirculation in pilot
' device J plant flow diagram.

4. Conclusions Membranes could be effectively peeled off,

This paper presents some results from a showing a high salt passage after the attack.
research project which is still underway, whose Potassium permanganate was found the most
ultimate aim is to try to determine the feasibility effective peeling reagent. The salt passage after
of reusing old seawater RO membranes with oxidising the separation layer reached 90% and
wastewater. A number of these old seawater above. A parameter to measure the effectiveness
membranes previously used for several years was denoted as "peeling efficiency".
were chemically attacked in order to separate the Due to the particulars of the unit, operating on
active layer, and convert them into a type of secondary effluent, particular attention must be
microfiltration membrane. Subsequently, these given to the fouling process in the membranes
membranes were actually tested with secondary and also to the backwashing and cleaning proce-
wastewater effluent from an activated sludge dures. Regular filter back-washing and membrane
treatment plant. The pilot plant consisted of cleaning must be carried out, and a major goal of
cartridge filtration, membrane filtration, and the project is to optimise these procedures. One
brackish water R e ; and the tests produced some main conclusion is that recirculation is required
promising results. both at the cartridge and at the membrane filters,
72 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72
in order to maintain a significant flow rate and
avoid deposition of solids.
Although this project is still in progress, we
feel that the preliminary results are promising,
and all indications show that the proposed
process is feasible. Hence, a second use has been
identified and tested for old RO membranes,
which may also contribute to improvements in
wastewater treatment.
Acknowledgments
The authors gratefully acknowledge the fund-
ing provided by Empresa Mixta de Aguas de Las
Palmas SA (EMALSA) for this project, under the
steering committee led by J. Alday. The con-
tributions from O. Trujillo, A. Vega and C. Diaz
de Durana, and R. Rodriguez on the operation of
the test and pilot plants were essential in the
experimental stage. Thanks are also due to the
staff from the analytical laboratory.
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