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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 the old membranes in order to use them as filters


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


global effectiveness or permeability of the
This pilot plant is fed with secondary effluent
membrane element.
from a wastewater treatment plant at a flow rate
Peeling effectiveness (PE) is defined as the
ranging between 5 and 8 m3/h. It consists of three
product of the product recovery and the salt
separation stages: cartridge filtration, membrane
passage after the peeling process divided by the
filtration, and RO. The unit was specifically
operating pressure during the peeling:
designed by EMALSA and the main design
features are shown in Table 1.
P E - P R x S P 104
All pressure vessels were recovered from an
PP
earlier application in the seawater RO plant.
Fig. 2 shows a picture of the plant's main body, where PR is the product recovery for the element
depicting the pressure vessels for membrane (or conversion ratio, fraction of water feed flow
filtration. that permeates through the membrane, %), SP is
the salt passage (fraction of salts that permeate
through the membrane, %), and PP is the
3. Results and discussion pressure during the operation of peeling (bar).
The first stage in the project, membrane The higher the peeling effectiveness, the better
conditioning by peeling off the separation layer, the membrane will perform as a filter. Our results
was carried out with some 80 (8") elements are expressed in terms of the PE.
through chemical attack with a strong oxidant. In some tests, the peeling was done by soaking
the membrane in a bath, without recirculation,
These elements had been used earlier in a large
with no pressure in the system. In such cases, a
RO production plant for periods of time between
simplified peeling effectiveness (SPE) is defined
3 and 5 years. Amongst the oxidising agents that
as:
were tested, potassium permanganate proved to
be the most effective. Others were sodium hypo-
SPE = PR x SP
chlorite and sodium hydroxide. These results
have been previously reported [10]. Apart from the purpose of comparison
Our aim, after peeling off the separation layer between different tests, the absolute value of the
of the membrane, was to obtain an element PE can be useful as well. We can estimate a
capable of filtrating the suspended matter con- maximum value for it. According to the manufac-
tained in the effluent from wastewater treatment turer' s recommendations, the maximum recovery
plants, rather than separating salts at this stage. for a single element would be 15%, with our goal
Therefore, the mission of these elements was to for salt passage up to 100%; meanwhile, the
produce a large amount of water (high product pressure during the peeling process should be
flow rate or high conversion ratio) and produce kept to a minimum (say between 5 and 10 bar).
high salt passage. On the other hand, the Therefore, we can expect values for PE some-
operating pressure of the system when the peel- where between 150 and 300. The SPE, on the
ing reagent was recycled through the membrane other hand, should be around 15%.
is also a parameter of interest because that
pressure has a strong influence on the energy
3.1. Type of oxidant
consumption of the peeling process. The lower
the peeling pressure, the lower the energy The first rounds of tests were aimed at
consumption. Hence, these three effects are 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 3.2.1. Feed water quality
Table 2. The peeling mode refers to immersion o f The pilot plant was fed with secondary efflu-
the membrane in the peeling solution (Imm), or ent with turbidity measurements usually between
recirculation of the latter around the membrane 5 and 10 NTU, although peak values could reach
(Rec). 90 NTU. Suspended solids concentration ranged
It was soon concluded that potassium perman- between 10 and 30 mg/l SS. There are significant
ganate was more effective, in general terms, than • variations in quality throughout the day and
other oxidants when applied to peeling off the during the week. Conductivity ranged from 1500
active separation layer. PE values over 150, to 2500 gS/cm.
regarded as a good achievement for an element,
were easily obtained with this reagent. In addi-
tion, sodium hydroxide produced good results, 3.2.2. Process results
and its effect is due to be assessed in detail in The feed water flow rate to the cartridge
further tests. filters was between 5 and 8 m3/h, and the filters
In addition, it was obvious that recirculation operated between 4 and 5.6 bar. Turbidity in
of the oxidising solution around the membrane water could be reduced from a range of values
rather than soaking the membrane was more between 8 and 10 NTU down to values below 0.6
effective. SPE values were between 1 to 30% in NTU after membrane filtration. In the second
the former mode vs. values below 1% in the filtration stage, membrane filtration operated at
latter. some 14 to 24 bar, and produced 4 m3/h per each
tube when fed with 16 m3/h, including a recir-
3.2. Pilot plant operation culation stream taken from the reject at a rate of
After the membranes were properly con- 11 m3/h. Turbidity was reduced to 0.1 NTU.
ditioned, they were tested in the pilot plant. The Finally, the RO unit produced 6 m3/h water when
main results from the tests are described below. operating at some 32 bar, reducing conductivity
70 J.M. Veza, J.J. Rodriguez-Gonzalez / Desalination 157 (2003) 65-72

i
~i ~. ----Membranefiltration reject

i \
Fig. 3. Particle size distribution.
Particle size, microns

from an average 2000 ~tS/cm to around 30 #S/cm operating week. The specific action taken con-
(98.5% salt rejection). sisted of a short flushing time by increasing the
Overall separation efficiency was over 97% flow rate.
for suspended solids and over 98% for dissolved The cartridge filters were cleaned by a back-
solids where the global conversion ratio is 60%. wash procedure, whereas the membrane filters
Particle size is also relevant. Several samples were cleaned in two ways. A short time flushing
were taken and analysed for particle size distri- was carried out with reject water by increasing
bution (PSD). Particle sized varied typically from the water flow rate from the nominal 17 m3/h to
8 to 50 ~tm, as shown in Fig. 3. The graph corre- 19 m3/h every hour during 15 rain. On the other
sponds to particles measured in the reject stream hand, chemical cleanings were performed with
from the membrane filtration stage. alkaline detergent every 3 to 4 days during 1 h.

3.2.3. Operating features 3.2.4. Modes of operation


Amongst the operating features, fouling was After the rapid fouling was identified, one of
found as the most relevant drawback. The mem- the actions taken to overcome the problem was
branes had undergone rapid fouling both in the modifying the hydraulic regime used in the
cartridge and in the membrane filters, which cartridge and the membrane filters. First the
made it necessary to carry out frequent cleanings once-through flow mode was tested, and it
on both filtration steps. The fouling rate was produced intense clogging, as indicated by a fast
assessed by observing the decay in permeability rise in pressure drop (AP), or other indicators
of the membranes, using a sort of permeability (AP/Q2), which is similar to a friction factor.
parameter (estimated as the product flow rate After this poor performance, the plant design had
divided by the applied pressure, Qp/Pal),which to be modified to allow for recirculation of the
decreased during the operation of the membrane reject from filters in order to get a higher flow
filters, whereas permeability recovered after rate in the membranes. The filters were now
cleaning. The variations can be easily determined operating on a recirculation mode as depicted in
in the graph (Fig. 4), which refers to a 5-d 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 [2] C. Reith and B. Birkenhead, Membranes enablingthe
avoid deposition of solids. affordable and cost effective reuse of wastewater as
Although this project is still in progress, we an alternative water source, Desalination, 117 (1998)
feel that the preliminary results are promising, 203-210.
and all indications show that the proposed [3] G. Tchobanoglous, J. Darby, K. Bourgeous, J.
McArdle, P. Genest and M. Tylla, Ultrafiltration as an
process is feasible. Hence, a second use has been
advanced tertiary treatment process for municipal
identified and tested for old RO membranes,
wastewater, Desalination, 119 (1998) 315-322.
which may also contribute to improvements in [4] M. Wilfand M.K. Schierach, Improved performance
wastewater treatment. and cost reduction of RO seawater systems using UF
pre-treatment, Desalination, 135 (2001) 61-68.
[5] J.C. Armas et al., Desalination of municipal sewage
effluent with electrodialysis reversal in Tenerife,
Acknowledgments Proc. IDA, San Diego, 1999, pp. 279-285.
[6] P. Cote and D. Thompson, Wastewater treatment
The authors gratefully acknowledge the fund- using membranes: the North American experience,
ing provided by Empresa Mixta de Aguas de Las Water Sci. Technol., 41 (2000) 209-215.
Palmas SA (EMALSA) for this project, under the [7] N. Engelhardt, W. Firk and W. Wamken, Integration
steering committee led by J. Alday. The con- of membrane filtration into the activated sludge
tributions from O. Trujillo, A. Vega and C. Diaz process in municipal wastewater treatment, Water
de Durana, and R. Rodriguez on the operation of Sci. Technol., 38 (1998) 429-436.
the test and pilot plants were essential in the [8] J. Glater, S.K. Hong and M. Elimelech, The search
experimental stage. Thanks are also due to the for a chlorine-resistant reverse osmosis membrane,
Desalination, 95 (1994) 325-345.
staff from the analytical laboratory.
[9] S. Avlonitis, W.T. Hanbury and T. Hodgkies, Chlor-
ine degradation of aromatic polyamides,Desalination,
85 (1992) 321-334.
References [10] J.J. Rodriguez, V. Jim6nez, O. Trujillo and J.M.
Veza, Reuse of reverse osmosis membranes as a fil-
[1] El agua en Canarias, Consejeria de Obras Publicas, tration stage in advanced wastewater treatment,
Vivienda y Aguas, 1992 (in Spanish). Desalination, 150 (2002) 219-226.

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