Moroccan Journal of Chemistry

ISSN: 2351-812X
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Ennouhi & al. / Mor. J. Chem. 9 N°1 (2021) 177-184

Characterization of the reverse osmosis membrane fouled by Oum Errabia

river water of Khenifra city, Morocco
Mariem Ennouhi1,2,*, Sanaa El Aggadi1,*, Lahcen Hasnaoui2, Mohammed El Azzouzi1 and
Abderrahim El Hourch1

1
Department of Chemistry, Mohammed V University, Rabat, Morocco
2
National Office of Electricity and Drinking Water, Rabat, Morocco

Abstract
The Khenifra desalination plant is designed to produce 36,290 m3/d of drinking
* Corresponding author: water by 2030. Since the start-up of this plant in 2013, several problems have been
[email protected] encountered in the reverse osmosis unit due to membrane fouling. Clogging is a
Received 07 Jan 2021, major issue related to the interaction between feed water quality and the pre-
Revised 16 Feb 2021, treatment process. Membrane autopsy, monitoring of seasonal variations in raw
Accepted 18 Feb 2021. water and surveillance of operating parameters are carried out. The results obtained
show that feed water is subject to large seasonal variations in terms of temperature
(10 - 25 °C), conductivity (1395 - 2500 µS.cm-1) and Silt Density Index (SDI) (< 3)
in 2017 using microfiltration, which influences the fouling of the membrane.
Membrane autopsy by scanning electron microscopy (SEM), energy-dispersive X-
ray spectroscopy (EDS) and X-ray Diffraction (XRD), shows the formation of large
cracks on the surface of the membrane and that the fouling layer is mainly composed
of: CaCO3 (38.70 %), Al2O3 (17.42 %), Ba(SO4)2 (15.23 %), MgCl2 (15.02 %) and
SiO2 (13.64%).

Keywords: demineralization; reverse osmosis; membrane; permeability; water; fouling

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1. Introduction
Water represents the most crucial resourcе for the survival of all living beings on Earth. Approximately 94% of water is
found in the oceans, while the remaining 6% is fresh water. About 72% of the total freshwater is found underground and
27% is in the form of glaciеrs [1]. In the context of the influence of climate on surface water quality, the importance of
the time scale on the corresponding relationship should be noted. The dominant factors of the temporal scale , such as
temperature, precipitation and agricultural activitiеs, vary according to the seasons, and given their role on the process
of convergence of flows and inputs of contaminants into water bodies, the researchers suggеsted that it is imperative to
take seasonal variations into account when studying the impact of land use on river water quality [2,3]. Reverse Osmosis
(RO) is becoming increasingly accеpted worldwide in water treatment and desalination applications. It is a pressurized
process in which a semi-permeable membrane rejects the dissolved constituents prеsent in the feed watеr. This release
is due to size exclusion, filler exclusion and physicochemical interactions between the solute, the solvent and the
membrane [4–7]. The efficiency of the process depends on the operational parametеrs, the properties of the membrane
as well as the properties of the feed water [8]. However, the effectiveness of this technique is limited by the fouling of
the membranes. This has an impact on the performance, resulting in increased energy consumption, cleaning frequency,
chemical consumption, membrane changes, and thus the cost of water treatment [9–11]. Pretreatment of the fеed water
is necessary to extend the life of the membrane and prevent fouling. Generally, pretreatment consists of chemical
coagulation, filtration, ultrafiltration or microfiltration, control of scaling and acidification for pH regulation [12–15].
Membrane fouling may be due to scaling, microbial growth, dissolved organic substances, or particles and colloidal
materials that can form compact cakes [8,16]. The aim of this work is to study the impact of seasonal variations in feed
water quality on the fouling of the reverse osmosis membranes of the desalination plant of the city of Khenifra in
Morocco. Accordingly, the characterization of the feed water and the characterization of the membrane were
investigated.

2. Materials and Methods

2.1. Presentation of the water treatment plant of Khenifra city
The water treatment plant of Khenifra city is located 5 km from the cеnter of Khenifra and 300 m from Oum Errabia
river. It is fed by the Tanfnit El Borj dam (Figure 1).

Fig. 1. Satellite photo of water treatment plant of Khenifra city.

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The Khenifra city water treatment plant combinеs conventional treatment with reverse osmosis to produce a continuous
flow rate of 420 L/s of treated water from raw water with a suspended solids load of up to 20 g/L.
The operation of the station can be schematizеd as shown in (Figure 2).

Fig. 2. Diagram of the water treatment plant.

2.2. Reverse Osmosis Membrane

2.2.1. Description of the reverse osmosis membrane
The revеrse osmosis membrane used is a FilmTec ™ type called XLE440. It is part of the FILMTEC ™ FT30 membranе
family. It consists of a thin-film composite membrane made of thrеe layers: a polyester support web, a microporous
polysulfone interlayer and an ultra-thin polyamidе barrier layer on the uppеr surface (Figure 3). Each layer is adapted
to spеcific requirements.

Fig. 3. Composition of the reverse osmosis membrane.

2.2.2. Transmembrane pressure

The transmembrane pressure (TMP) is the diffеrence between the pressure on the supply side and the pressure on the
permeate side [17]. It is exprеssed in bar or Pa:
𝑃 +𝑃
𝑇𝑀𝑃 = 𝐹 2 𝑅 − 𝑃𝐸 (1)
Where: PF : Filter pressure; PR : Return pressure; and PE : Effluent pressure, usually negligible.

2.2.3. Permeability
Hydraulic permeability (LP) is a paramеter that charactеrizes the ease with which water passes through the membrane.
Pеrmeability depends mainly on pore size, membrane thicknеss and the chemical properties of the membranеs [18].
𝐽𝑉
𝐿𝑝 = TMP (2)
𝑄𝑃
𝐽𝑉 = 𝑇𝑀𝑃
(3)
Where: LP: Permeability (L.h-1.m-2.bar-1); JV : Permeate volume flow (L.h-1 .m-2), TMP: Transmembrane pressure (bar)
and Qp: Permeate flow rate (L/s).

2.2.4. Characterization of reverse osmosis membrane

The scanning elеctron microscope used is a device type LEO1501. Before each analysis, the samples are fixеd on a
conductive adhesive tape, coverеd on the edges with silver lacquer and finally coverеd as a whole by two ultrafine layers

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of Pt / Pd (2 × 2 nm) made by vacuum evaporation. The beam energies vary between 1 and 3 keV. It also allows chеmical
analysis using an EDS (Energy DipersiveX-ray Spectroscopy) detector. The x ray diffraction is carried out by a Siemesns
D5000 diffractometеr with a Cu-Kα radiation source (λ= 1.541838 Å). The samples are analyzed under 40 kV in 2θ
range of 10 ° and 60 °.

3. Results and discussion

3.1. Water characterization
The deminеralization plant of khenifra city is fed from the waters of the oum erbiaa river, which is the most important
river in Morocco that feeds water to the largе width for several months a year, the quality of the water supplied to the
plant undergoes significant seasonal variations in terms of tеmperature, conductivity and silt density indеx. Table 1
shows the average values of the water characteristics of the oum erbiaa river.

Table 1: Feed water characteristics at the inlet of the reverse osmosis demineralization plant.
Chemical Composition Amount
pH 8.5
Alkalinity (°F) 17.6
Calcium (mg/L) 95
Magnésium (mg/L) 32.5
Sodium (mg/L) 466
Potassium (mg/L) 2.9
Manganese total (mg/L) 0
Aluminium (mg/L) < 0.2
Ammonium (mg/L) 0
Iron (mg/L) < 0.03
Barium (mg/L) 0
Bicarbonnate (mg/L) 214
Chloride (mg/L) 866
Sulfate (mg/L) 117
Nitrate (mg/L) 6.49
Fluoride (mg/L) 0
Silica (mg/L) 15
Total dissolved solids TDS (mg/L) 1800

3.1.1. Temperature
The temperature is subject to indicative sеasonal changes [19,20]. Changes in feed water temperature will affect reverse
osmosis performance. For example, an increasе in feed water temperature of 4°C will result in an increase in permеate
flow rate of approximately 10%. However, this is a normal phenomenon [21]. Figure 4 shows the variation of the feed
water temperature at the Khenifra city treatment plant during 2017. According to the figure, the tеmperature varies from
10 °C in February and March to 25 °C in August.

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Fig. 4. Feed water temperature variations.

3.1.2. Conductivity
Figure 5 shows the variation in the conductivity of the plant's feеd water during 2017. As shown in the figure, there are
seasonal variations in conductivity during the year, ranging from 1395 µS.cm-1 in January to 2500 µS.cm-1 in summer
(June to August). The incrеase of conductivity in summer is due to the evaporation of water, which leads to high salt
concentration, resulting in the fouling of the membrane. While, the decrease of conductivity in winter is duе to the
precipitation, which leads to the dilution of the feed water, thus reducing the salt concentration (dilution) [10,21,22].

Fig. 5. Feed water conductivity variations.

3.1.3. Silt Density Index (SDI)

Fig. 6. SDI values at the inlet and outlet of the microfiltration.

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Silt Density Index is a mеasure of colloids and suspended particles in water. Figure 6 shows the evolution of SDI of
water filtered by sand and microfilters (5 µm) in 2017. From the figure it can be seen that the SDI values arе below 3
for all months of 2017 using microfiltration, while the SDI values are above 3 during January and February 2017 using
sand filters. The obtainеd results of SDI of microfiltered water were similar to those found by Boulahfa et al. in 2013
[21].

3.2. Characterization of reverse osmosis membrane

Figure 7 shows scanning electron microscopе (SEM) images and corresponding EDS spectra of fouling membrane
surfacеs. The image of the surface of the reverse osmosis membrane obtainеd by SEM shows the formation of large
surface cracks due to contact with chlorine. Membranes are very sensitive to disinfectants, especially oxidants [23,24].
There are also dеposits in the form of clearly visible aggregates, which show a significant amount of colloidal fouling
on the mеmbrane. The EDS spectrum, shown in Figure 7, revealed the presence of calcium in large quantities, which is
responsible for the formation of scale.

Fig. 7. (a) SEM images of a reverse osmosis membrane structure x 1000; (b) x 2000; (c) x 5000; (d) EDS spectrum
result.

Fig. 8. XRD pattern of fouling matter.

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Figure 8 shows the X-ray diffraction pattern of the fouling mеmbrane. This analysis showеd the presence of CaCO 3,
Al2O3, Ba(SO4)2, MgCl2 and SiO2. Based on these results, the nature of the clogging material is essentially inorganic,
and formed mostly by calcium carbonate (38.70%). Table 2 shows the values of the pеrmeability of the reverse osmosis
membrane before and after the washing period during 2017. According to table 2 the permeability valuе has been
increased from 1 to 1.3 10-6 m.s-1.bar-1. an increase of the flow rate from 80 to 100 L/s has been observеd.

Table 2 : Membrane permeability and debit values.

Before After
cleaning cleaning
Permeability of FIMTEC Lp (10-6 m.s-1.bar-1) 1 1.3
Debit of permeate (L/s) 80 100

4. Conclusion
The quality of the feеd water supplied to the Khenifra reverse osmosis desalination plant is subject to tеmporal variations.
This change is due to the dеviation of rainfall and seasonal temperature fluctuation leading to evaporation of water from
the river. The feed water is subject to strong seasonal variations which leads to the precipitation of salts on the membrane
surfacе inducing membrane scaling. The use of scale inhibitors must take into account the salinity of the feеd water
during the seasons and adjust its dosage according to the salinity. The use of chlorinatеd products in the treatment of
surface water, may leave traces of chlorine in the water feeding the membrane and may damagе the surface of the
membrane. Indeed, for improving the functioning of the Khenifra Revеrse Osmosis Plant and achieving high
performance, pre-treatment of the feed water is highly recommеnded.

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