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Desalination 191 (2006) 35–44

Drinking water reclamation from palm oil mill effluent (POME)


using membrane technology
A.L. Ahmad*, M.F. Chong, S. Bhatia, S. Ismail
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
Seri Ampangan, 14300 Nibong Tebal, Penang, Malaysia
Tel. +60 (4) 593-7788; Fax: +60 (4) 594-1013; email: chlatif@eng.usm.my

Received 15 March 2005; accepted 24 June 2005

Abstract
Palm oil mill effluent (POME) is the largest pollutant discharged into the rivers of Malaysia. POME is a brownish
liquid waste and has high turbidity, color, chemical oxygen demand, oil and grease resulting from high organic matter
content and suspended solids. The removal of these pollutants is required in reclaiming the drinking water from POME.
Membrane technology (ultrafiltration and reverses osmosis) coupled with coagulation/flocculation as pretreatment was
used to reclaim drinking water from POME. The analyses of the reclaimed water shows that the water quality complied
with the drinking water standard set by the US Environmental Protection Agency. The performance of the membranes
with coagulation/flocculation showed great potential to reclaim drinking water from POME with 78% water recovery.
The present studies with chemical cleaning show that membrane fouling was reversible and primarily due to cake
formation.

Keywords: Drinking water; Ultrafiltration; Reverse Osmosis; Water reclaiming

1. Introduction European countries, water is recovered by mem-


brane filtration and is reused in agricultural
Water shortages, deterioration of water qual-
irrigation, greenhouse horticulture, cooling pro-
ity, and environmental constraints have led to an
cesses, and industry including food and beverage,
increased interest of recovering and recycling
paper, poultry and textiles [1]. In Feb 2002, the
water in many parts of the world. In many
Singapore government started to reclaim water
from the sewage water for drinking and general
*Corresponding author. use instead of buying from other sources [2]. An

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Seoul, Korea,
21–26 August 2005.

0011-9164/06/$– See front matter © 2006 Published by Elsevier B.V.


doi:10.1016/j.desal.2005.06.033
36 A.L. Ahmad et al. / Desalination 191 (2006) 35–44

independent poll by Forbes Research in October minerals and heavy metals is required in the
2002 showed an overwhelming level of reclaimed reclamation of drinking water from POME.
water acceptance among Singaporeans, with 82% In recent years, membrane technologies such
indicating that they were prepared to drink it as microfiltration, ultrafiltration (UF), nanofil-
directly, while 16% were prepared to drink it in- tration and reverse osmosis (RO) have become a
directly through mixing with reservoir water. more attractive for drinking water treatment
Malaysia is the largest producer and exporter compared to conventional clarification. The main
of palm oil [3]. However, the large amount of advantages of membranes technology are [7]:
crude palm oil produced also resulted in large compact process and plant, separation based on
amounts of palm oil mill effluent (POME) where size exclusion, invariable quality of produced
40.2 mil t of POME containing 38.2 mil t of water, constant production and water quality
water was discharged in the year 2004. With this independent of feed water quality, easy auto-
statistics, the palm oil mill industry in Malaysia mation and absence of bacterial regrowth and
was identified as the one that produces the largest residual toxicity.
pollution load into the rivers throughout the UF is a well known membrane technology
country [4]. based on pore size that can retain macro-
POME is a colloidal suspension of 95–96% molecules or high-molecular-mass compounds as
water, 0.6–0.7% oil and 4–5% total solids [3]. It well as colloidal and suspended matters. UF also
has high turbidity and color resulting from high excludes bacteria and viruses, which allows its
organic matter content and suspended solids. The application for water disinfection, producing
typical characteristic values of POME and the drinkable water as the permeate of the process
drinking water standard set by US Environmen- [8]. However, UF passes metal ions, aqueous
tal Protection Agency (USEPA) are given in salts, sugar and nonprotein nitrogen through the
Table 1 [5]. The removal of organic matter is membrane into the permeate [9].
required because [6]: RO utilizes a membrane that selectively
C colored water is unattractive/unacceptable to restricts the flow of solutes while permitting the
the consumers flow of solvent. RO membranes have pore
C results in coloring of clothes during washing diameters less than 10 Å where the solvent is
C can cause odour and taste forced through the membrane by pressure and the
C causes high chemical oxygen demand (COD) undesired co-products frequently pass through the
and biological oxygen semand (BOD) membrane by diffusion [9]. Therefore, RO is
C increases corrosion and biofilm growth in the most important in areas where portable water
distribution network demand has outstripped natural supply because it
C it is a precursor to the formation of disin- is able to reject all the solutes that UF fails to
fection by-products when water is disinfected. achieve.
The major drawback of the membrane appli-
POME also contains trace amount of minerals cation technology is flux decline due to mem-
and heavy metals [4]. The comparison made brane fouling. Membrane technology combined
between the qualities of POME with the drinking with pretreatment by coagulation and flocculation
water standard set by the USEPA in Table 1 to reduce and control fouling has been adopted by
shows that POME could not be used as drinking many researchers [6]. The coagulation process
water if it is not treated. Therefore, a proper neutralizes or reduces the charge on the sus-
treatment method to remove the organic matter, pended particles. This allows the van der Waals
A.L. Ahmad et al. / Desalination 191 (2006) 35–44 37

Table 1
POME characteristics of every stage of treatment and drinking water standards set by the USEPA

Parameter POME Pretreatment Ultrafiltration Reverse osmosis USEPA standard

pH 4.7 6.63 6.63 6.63 6.5-8.5


Color, color units 151 128 54 ND 15
Odor, threshold odor number 300 150 70 ND 3
Turbidity, NTU 11,000 34 0.65 0.02 <0.5
COD, mg/L 50,000 15,000 12,400 88 NR
Total dissolved solids, mg/L 20,500 8,850 6,640 130 500
Oil and grease, mg/L 4,000 80 ND ND 0.3
Nitrogen (organic), mg/L 750 748 710 0.50 NR
Ammonia nitrogen, mg/L 35 37 30 0.50 NR
Al, mg/L 3.9 0.52 0.34 ND 0.05–0.2
K, mg/L 2,270 1,169 360 5.45 NR
Mg, mg/L 615 589 181 2.74 150
Ca, mg/L 439 421 129 1.95 NR
Fe, mg/L 46.5 13.53 0.07 ND 0.3
Mn, mg/L 2 1.24 0.44 ND 0.05
Cu, mg/L 0.89 0.11 0.11 0.03 1.3
Zn, mg/L 2.3 0.08 0.04 0.01 5

ND, not detectable; NR, not required.

force of attraction to encourage initial aggre- 2. Experimental


gation of colloidal and fine suspended materials
2.1. Pilot plant experimental set-up
to form microflocs. Flocculation is the process of
bringing together microfloc particles to form POME samples used in this research were
large agglomerates by physically mixing or obtained from the United Oil Palm Mill, Sungai
through the binding action of flocculants, such as Kecil, Nibong Tebal, Malaysia. The membrane-
long chain polymers [10]. based pilot plant for POME treatment with a
The objective of this study was to reclaim and 500-L capacity, designed at the School of Chemi-
recover the drinking water from POME using cal Engineering, Universiti Sains Malaysia, was
membrane technology (UF and RO) coupled with used to perform the experiments. Raw POME
chemical and physical (coagulation/flocculation) (70EC) was cooled to room temperature (25EC)
treatments as pretreatment. A series of pilot- before being subjected to a series of treatments
plant-scale experiments was conducted using the which included coagulation/flocculation and
optimized operating parameters to collect the membrane separation (UF and RO) as shown in
reclaimed water. The quality of the reclaimed Fig. 1. The optimum operating conditions shown
water was checked to ensure the reclaimed water in Fig. 1 with 78% water recovery were first
met the drinking water standards set by the determined by preliminary laboratory and pilot
USEPA. plant tests, which are presented elsewhere [3].
38 A.L. Ahmad et al. / Desalination 191 (2006) 35–44

Fig. 1. Flowchart of membrane-based pilot plant for POME treatment.

The raw POME was transferred to a chemical by adjusting the pressure control valves. The feed
tank where the coagulant, modified industrial- flow rate and the flow velocity were set at 1 m3/h
grade alum, Envifloc 40L, was added at a dosage and 0.1 m/s, respectively (Reynolds number =
of 0.05 v/v. pH was adjusted to 5.5–6.5 by using 6155).
industrial-grade potassium hydroxide 65% During the experiments, permeate flow rate of
(NaOH). The mixing speed was set at 50 rpm for each membrane unit was periodically measured.
60 min to allow the formation of microflocs. The The temperature was maintained at 25EC by
flocculant, (Envifloc 20S)/potable water-grade using water-cooled heat exchangers. The
cationic polymer (0.1%), was added to the mix- permeate flux (Jv) was calculated using Eq. (1):
ture at a dosage of 0.015 v/v with a stirring speed
of 10 rpm for 30 min. The sludge was removed
from the supernatant (pretreated POME) by using (1)
a filter press (not shown in Fig. 1).
The pretreated POME was pumped to the PCI- where Qp is the permeate flowrate (L/h) and A is
Memtech B1 tubular module PVDF (ES625-type) the effective filtration area (m2) of the membrane.
UF membrane unit. This module was fitted with
a membrane of nominal molecular weight cut-off
2.2. Membrane cleaning procedure
(MWCO) of 200,000 g/mole with 18 flow chan-
nels. The inner diameter of each tube was The UF and RO membranes were cleaned
12.7 mm and length was 1200 mm. The effective after each experiment by using a chemical clean-
area for filtration was 0.9 m2 and could be ing method. The UF membrane was circulated
operated up to maximum pressure of 6 bar. The with clean water to flush out POME. The mem-
transmembrane pressure for UF was maintained brane was circulated with 0.1% w/w of sodium
at 2 bar by adjusting the pressure control valves. hydroxide for 30 min and then was soaked with
The feed flow rate and the flow velocity were set the same solution for 2 h to remove organic
at 0.8 m3/h and 0. 1m/s, respectively (Reynolds matter that might be adsorbed on the PVDF mem-
number = 5000). brane. The membrane was then rinsed with clean
The permeate collected from the UF unit was water followed by circulating with 2% w/w nitric
fed into the RO unit to produce permeate with acid for 30 min to remove any inorganic fouling.
drinking water standards. This PCI-Memtech B1 The RO membrane was circulated with clean
tubular module TFC (AFC99-type) RO mem- water followed by circulating with weak nitric
brane with 99.9% NaCl retention and with a acid solution (0.3% wt) for 30 min. Both mem-
0.9 m2 effective filtration area was operated up to branes were flushed with clean water to remove
a maximum pressure of 60 bar. The transmem- the remaining nitric acid by monitoring the flush
brane pressure for RO was maintained at 45 bar water pH value. A cleaned membrane should
A.L. Ahmad et al. / Desalination 191 (2006) 35–44 39

have a flush water pH value of 6.5–7.5. Although CECIL 1000 series spectrophotometer (Cam-
both membranes were cleaned at the circulation bridge, UK). Oil and grease were measured using
flow rate of 0.5 m3/h with the pressure control the Soxhlet extraction method, total organic
valve fully opened, permeate of cleaning agents nitrogen was measured by the Macro–Kjeldahl
at low flux was observed. This shows that pore method and the ammonia nitrogen was measured
cleaning was also carried out besides surface using a preliminary distillation step followed by
cleaning. The temperature was maintained at the titrimetric method with standard sulfuric acid
25EC by using water-cooled heat exchangers. The titrant, 0.02 N. Minerals and heavy metals were
efficiency of the cleaning procedure for both measured by using the atomic absorption spec-
types of membrane was checked by repeating trometric method with a direct air–acetylene
clean water flux tests and comparing results with flame and the inductively coupled plasma
the initial clean water flux evaluation. method. The details of all the analytical methods
followed were based on procedures given in the
2.3. Analysis APHA, Standard Method for the Examination of
Water and Wastewater [13].
The quality of the water after each stage of
treatment was analyzed to investigate the ability
of the pilot plant to reclaim water with drinking 3. Results and discussion
water quality. The parameters analyzed were
physical (turbidity, color, odor, total dissolved 3.1. Permeate quality
solids and pH) and chemical (COD, oil and The visual observations of the process from
grease, total nitrogen, ammonial nitrogen, mine- Fig. 2 show that the quality of the water improved
rals and heavy metals). Other parameters such as from each stage of treatment in terms of color,
microorganisms, disinfection by-products, disin- odor and turbidity. At the final stage of treatment,
fectants, radionuclides and organic chemicals RO produced odor-free, clear water. The chemi-
were not analyzed due to the negligible amount in cal analyses of the permeate water in Table 1
POME as reported in the literature [5,11,12]. show that USEPA drinking water quality stand-
Turbidity was measured by WTW a turb ards were met. The treatment of POME in the
350IR turbidity meter, pH was measured using a present studies gave more than 99% removal of
Mettler Toledo 320 pH meter, the color was COD, total dissolved solids, nitrogen (organic),
determined by spectrophotometry at a wavelength and almost 99% removal of ammonia nitrogen.
of 410 nm with the Cecil 1000 series spectro- The proposed treatment method completely
photometer (Cambridge, UK) in a 10-mm adsorp- removed the color, odor, turbidity, and oil and
tion cell; odor was determined by using the grease with a final pH of 6.63. The minerals and
threshold odor test where the sample was diluted heavy metals analysis according to Table 1 shows
with odor-free water until the least definitely per- a great reduction in their concentrations and well
ceptible odor was achieved. Total dissolved below the maximum contaminant level (MCL) set
solids were measured by evaporating the filtrate by the USEPA for drinking water standard. The
of the sample to dryness in a weighed dish and analysis of the reclaimed water quality shows that
dried to constant weight at 180EC. The increase the reclaimed water met most of the specifi-
in the dish weight represented the total dissolved cations with USEPA drinking water quality
solids. standards [14]. The COD reading (88 mg/L) of
COD was measured by using the colorimetric the reclaimed water was due to the presence of
method at a wavelength of 600 nm with the trace amounts of dissolved organic matter from
40 A.L. Ahmad et al. / Desalination 191 (2006) 35–44

(a) (b) (c) (d)

Fig. 2. Quality of water after each stage of treatment using pilot-plant-scale analysis. (a) Raw POME. (b) Supernatant after
chemical physical pretreatment. (c) Permeate of ultrafiltration. (d) Permeate of reverse osmosis (drinking water).

(a)

(b)

Fig. 3. Permeate flux for 24 h filtration and its recovery by chemical cleaning. (a) Ultrafiltration: transmembrane pressure,
2 bar; feed flow rate, 0.8 m3/h; flow velocity, 0.1 m/s; temperature, 25EC. (b) Reverse osmosis: transmembrane pressure,
45 bar; feed flow rate, 1 m3/h; flow velocity, 0.1 m/s; temperature, 25EC.
A.L. Ahmad et al. / Desalination 191 (2006) 35–44 41

(a) (b)

(c) (d)

(e) (f)

Fig. 4. Ultrafiltration membrane. SEM images of the cross sectional view: (a) new membrane, (c) fouled membrane, (e)
cleaned membrane (200× magnification); and surface view: (b) new membrane, (d) fouled membrane, (f) cleaned (10 k×
magnification).
42 A.L. Ahmad et al. / Desalination 191 (2006) 35–44

(a) (b)

(c) (d)

(e) (f)

Fig. 5. RO membrane. SEM images of the cross sectional view: (a) new membrane, (c) fouled membrane, (e) cleaned
membrane (500× magnification); and surface view: (b) new membrane, (d) fouled membrane, (f) cleaned membrane (10k×
magnification.
A.L. Ahmad et al. / Desalination 191 (2006) 35–44 43

palm oil fruits which are nontoxic. Since the show an absence of pore blockage after chemical
USEPA drinking water standard does not specify cleaning of the membranes. Figs. 4b and 5b show
the COD value, it is difficult to make a compari- the surface view of the new membrane for UF
son based on the COD. However, further analysis and RO, respectively. Cake formation was ob-
of the organic composition of the reclaimed water served after the filtration process (Figs. 4d and
(responsible for COD value) should be done to 5d). Figs. 4f and 5f show that the cake layer was
ensure the quality of the reclaimed water. removed after chemical cleaning of the
membranes.
3.2. Membrane performance
Fig. 3(a) and (b) show the permeate flux 4. Conclusions
behavior for UF and RO, respectively. The opti- The present studies indicate that UF and RO
mum operating conditions used in the filtration membrane technology coupled with coagulation/
are based on repeated experimental studies re- flocculation as pretreatment successfully re-
ported in previous work [3] at shorter filtration claimed drinking water from POME with 78%
times (1–2 h). Both Fig. 3(a) and (b) show a water recovery. The chemical analyses proved
similar trend where the permeate flux decreased that the quality of the reclaimed water from
from the initial flux value within seconds until the POME complied with drinking water standards
next chemical cleaning to restore the initial set by the USEPA. The membrane technology
performance of the membranes. The rates of per- significantly reduced the values of all parameters
meate flux decline were different for both UF and (color, odor, turbidity, total dissolved solids, oil
RO. The UF membrane flux decreased to about and grease, minerals and heavy metal) to the
50% of the initial flux after 6 h. In contrast, the values well below the MCL set by the USEPA.
RO membrane flux decreased to about 50% of the The performance of the membranes with
initial flux after 23 h. This phenomenon indicates coagulation/flocculation showed a great potential
that UF is more prone to fouling due to the for reclaiming drinking water from POME. The
increase of membrane resistance resulting from present studies with chemical cleaning show that
cake formation. membrane fouling, primarily due to cake forma-
Chemical cleaning after 24 h of operation tion, was reversible. This cake layer could be
increased the permeate flux effectively to the easily removed when the membranes were
initial level for both UF and RO membranes. The cleaned with chemicals, and membrane perfor-
deposit on the membrane surface was removed, mance was restored to its initial state.
and the flux after cleaning was 90.83% and The membrane technology used in the present
88.39% of the initial flux value for the UF and studies gave a very positive outcome of being a
RO, respectively. This indicated that the fouling method to reclaim drinking water from POME.
was primarily cake formation without pore block- Therefore, for future studies, the overall capacity
age of the membrane itself. This phenomenon and performance of the system combined with
was observed in the SEM images of the cross cost analysis should be done to study if the option
sectional and surface view for UF and RO shown is viable on a commercial scale.
in Figs. 4 and 5, respectively. Figs. 4a and 5a
show the cross sectional view of the new mem-
brane used for UF and RO, respectively. Both Acknowledgement
membranes after usage did not show any pore The authors would like to gratefully acknowl-
blockage (Figs. 4c and 5c). Figs. 4e and 5e also edge the Federal Land Development Authority
44 A.L. Ahmad et al. / Desalination 191 (2006) 35–44

Foundation (Yayasan Felda) of Malaysia for their water treatment by ultrafiltration of surface water and
financial support. its application to China, Desalination, 170 (2004)
41–47.
[8] J.M. Arnal, M. Sancho, G. Verdú, J. Lora, J.F. Marín
and J. Cháfer, Selection of the most suitable ultra-
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