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Treatment of landfill leachate by reverse osmosis

Article  in  Water Research · February 1999

DOI: 10.1016/S0043-1354(98)00240-1

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 Wat. Res. Vol. 33, No. 3, pp. 647±652, 1999
# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
PII: S0043-1354(98)00240-1 0043-1354/98 $19.00 + 0.00

TREATMENT OF LANDFILL LEACHATE BY REVERSE

OSMOSIS
ANGELO CHIANESE*, ROLANDO RANAURO and NICOLA VERDONE
Department of Chemical Engineering, University of Rome ``La Sapienza'', 00184 Rome, Italy

(First received February 1998; accepted May 1998)

AbstractÐThis paper deals with an experimental study describing the treatment of land®ll leachate by
means of a pilot-scale reverse osmosis unit. Leachate streams with a CO parameter in the range of 0±
1749 mg lÿ1 have been adopted. The ¯ux rate of the permeate through the membrane decreased linearly
with the COD factor. The rejection coecient of COD was practically independent of the COD value,
but was signi®cantly a€ected by the applied pressure. By operating at 53 atm, COD rejection values
around 98% were obtained. Finally, the e€ect of COD on the separation of some heavy metals was
investigated. For most metals this in¯uence was negligible. Only the rejection coecient of Zn
decreased signi®cantly upon increasing the COD of the leachate stream. # 1998 Elsevier Science Ltd.
All rights reserved

Key wordsÐreverse osmosis, leachate treatment

INTRODUCTION in¯uence of the pressure on the RO unit perform-

Leachates from municipal solid waste land®ll
sites are de®ned as hazardous waste water.
Their disposal is recognized as one of the most
dicult tasks associated with the operation of
land®lls.
In the 70's and 80's many studies have been
devoted to comparative evaluations of the disposal
treatments employed. Chian et al. (1976) reported
that reverse osmosis (RO) is the most e€ective oper-
ation in reducing the chemical oxygen demand
(COD) in leachate water. In recent years, the exper-
imental works by Krug and McDougall (1989),
Kinman and Nutini (1991), and Bilstad and
Madland (1992), have demonstrated the feasibility
of using reverse osmosis technology for leachate
disposal. In particular, it has been shown that
leachate can be puri®ed by RO from both organic
and inorganic compounds. Values of the rejection
coecient referred to COD parameter and heavy
metal concentrations higher than 0.98 and 0.99,
respectively, were reported.
In spite of much experimental work reported in
the literature, at lab and industrial scale, a systema-
tic investigation on RO performances under various
sets of operating conditions has not yet been per-
formed. As a matter of fact, the determination of
the minimum operating pressure which assures the
required puri®cation of leachate water is of great
economical importance and so a clear picture of the
*Author to whom all correspondence should be addressed.
[Tel.: +39-6-44585-X928; Fax: +39-6-4827453; E-mail:
angelo@impchim.ing.uniromal.it].
ance is required.
The main aim of the present work has been to in-
vestigate the performance of the leachate disposal
by an RO unit using a wide range of operating
pressures and of the COD level of the leachate.
EXPERIMENTAL
The experimental work has been carried out by using an
apparatus at pilot scale here described and a leachate from
the municipal land®ll of Pietramelina (Perugia, Italy).
The considered land®ll, established in 1994, has an area
of 40000 m2 and is located in a hilly region where the
average annual amount of rain is rather high (400 mm).
The leachate production could be up to 5000 l hÿ1. Its
chemical analysis is reported in Table 1. Since the plant
was built recently, a high value of the leachate BOD
would be expected. The relatively low BOD value
observed can be explained by considering that part of the
waste organic fraction is previously eliminated to produce
`compost'.
In order to investigate both the COD and heavy metals
separation, RO experiments were carried out feeding the
pilot plant with mixtures of an aqueous solution of some
chosen heavy metals (Zn, Cu and Cd) and samples of lea-
chate water withdrawn from the Perugia municipal land-
®ll. The COD values were varied by dilution. The leachate
was pre-treated by micro®ltration in order to eliminate the
suspended solids.
The experimental set-up, shown in Fig. 1, consists essen-
tially of a 50 l process tank (S-1), a high pressure recircula-
Table 1. Leacheate analysis
COD (mg/l) 3840
BOD (mg/l) 1200
BOD/COD 0.33
pH 8
Na (mg/l) 1800
Metals (Na except) (mg/l) <0.5

647
648 Angelo Chianese et al.
Fig. 1. Experimental set-up.
tion pump (PV-1), a spiral RO membrane (RO-1) and the
interconnecting piping.
Both the permeate and concentrate streams were re-
cycled to the process tank, having measured their ¯ow-
rates by means of two rotameters (FI-1, FI-2). A constant
temperature was attained in the feed tank by two trim
coolers (E-1, E-2). Between the booster pump (PC-1) and
the process pump two basket ®lters (F-1) provided the
continuous ®ltration of the stream fed to the RO mem-
brane.
The pH value of the liquid in the process tank was
adjusted to a value of 6 by addition of HCl, in order to
operate at the typical pH conditions of the land®ll lea-
chate achieved after the pre-treatment operations. The
spiral RO membrane was a 2.5 inch element supplied by
DOW Italia, SW30-2521 type. For all the runs the operat-
ing temperature was maintained at 2820.28C.
Throughout each run samples of permeate and concen-
trated streams were withdrawn and analyzed. The concen-
trations of the metals were measured by using the atomic
absorption spectrophotometer Philips 9200, whose accu-
racy is 0.1 ppm. The analysis of COD, carried out accord-
ing to the 1964 ASTM standard procedure, was performed
with an accuracy of 215 mg lÿ1.
RESULTS AND DISCUSSION
The ®rst series of experiments was devoted to
examine the e€ect of the operating pressure on the
permeate ¯ux rate through the membrane for values
of COD in the range between 0±1749 mg lÿ1. The
results obtained have been plotted in Fig. 2. At a
constant value of COD and salts content, the ¯ux
rate increased linearly upon increasing the operating
pressure, as expected. In fact, according to the sol-
ution-di€usion model (Lonsdale et al., 1965) that
excludes convective ¯ow, the steady-state per-
meation ¯ux of the solvent (water) through the
membrane for a dilute solution, Jw (m3 hÿ1 mÿ2), is
given by:
Pw
Jw ˆ …DP ÿ Dp† …1†
l
where DP and Dp are the transmembrane pressure
and the osmotic pressure di€erence between the
feed and permeate at the membrane surface (atm)
and the ratio Pw/l is the pure water permeability
constant, with l the membrane thickness (m) and
Pw the speci®c hydraulic permeability
(m3 hÿ1 mÿ1 atmÿ1) given by the relationship
(Mallevialle et al., 1996):
 w,mcw,m V
D w
Pw ˆ …2†
RT
where Dw,m is the water di€usion coecient
(m2 hÿ1), cw,m is the water concentration in the
membrane (m3 mÿ3), Vw is the water partial molar
volume (m3 kmolÿ1), R the gas constant, 0.08206
(m3 atm kmolÿ1 Kÿ1), and T the absolute tempera-
ture (K).
The experimental data are well ®tted by straight
lines (correlation>0.998) which have di€erent inter-
cepts and slope values in a close range.
 Treatment of land®ll leachate by reverse osmosis
Fig. 2. Permeate ¯uxes vs pressure.
This means that the in¯uence of leachate COD
and sodium content on the osmotic pressure is
strong, while it is quite negligible on the water per-
meability. The average slope of the straight lines ®t-
ting the measured permeate ¯uxes as function of
the operating pressure indicates a pure water per-
meability constant equal to 0.795  103 m3 hÿ1 mÿ1
atmÿ1 (sd 0.0163). This value is related to the struc-
ture of the used membrane. However, it is in the
range of the values in the literature for the same
range of applied pressure (Sourirajan, 1970).
The osmotic pressure values, calculated extrapo-
lating the straight lines for zero ¯ux, increase from
0 to 6.56 atm almost linearly upon rising the con-
centration of the leachate, that is the content of
both COD and sodium salts.
The osmotic pressure due to COD was evaluated
based on the assumption that the contributions of
inorganic salts and organic compounds in the lea-
chate are additive with respect to the overall osmo-
tic pressure. In order to determine the sodium salts
contribution, the sodium content was attributed to
sodium chloride and sodium sulphate in the molar
ratio reported in Krug and McDougall (1989). The
values of the osmotic pressure p due to each salt
were calculated by the general equation for dilute
solutions (Klotzi and Rosemberg, 1986):
p ˆ gcRT
Table 2. COD and salts contribution to osmotic pressure
COD (mg/l) SALTS (mg/l)
0 0
335 411
633 808
912 1149
1265 1604
1749 2226
649
where c is the solute concentration (kmol mÿ3), n is
the number of ions from dissociation and g is the
osmotic coecient. In general g is a function of the
solution composition; in this work, values of g coef-
®cients of the two considered salts were calculated
by ®tting by means of equation 3 the experimental
data of their diluted solutions reported in
Sourirajan (1970): values of 0.937 and 0.762 for
sodium chloride and for sodium sulphate, respect-
ively, resulted.
Assuming that the concentration of solute in the
permeate is negligible, the di€erence of osmotic
pressure within the membrane is coincident with the
osmotic pressure in the concentrated solution.
The values of the osmotic pressure due to the
two salts determined by equation 3 and those due
to COD, calculated as the residual contribution to
the overall osmotic pressure values, are shown in
Table 2. The overall osmotic pressure appears to be
mainly a€ected by COD. It means that the re-
duction of the permeate ¯ux, observed upon
increasing the leachate concentration, is essentially
due to the presence of the organic compounds
described by the COD parameter. The estimated
values of osmotic pressure of COD increase linearly
with the COD content according to the following
relationship (correlation index 0.990):
…3† p ˆ 0:00311
COD …4†
pTOT (atm) pSALTS (atm) pCOD (atm)
0.00 0.00 0.00
1.09 0.28 0.81
2.50 0.53 1.97
3.73 0.75 2.98
5.43 1.05 4.38
6.56 1.46 5.10
650 Angelo Chianese et al.

Fig. 3. COD rejection vs pressure.

where a phenomenological coecient (atm l mgÿ1) the equation:

appears. DP ÿ Dp
A second series of experiments has been carried R ˆ 0:991 …6†
DP ÿ Dp ‡ 0:469
out in order to evaluate the e€ect of the operating
pressure on the COD rejection coecient de®ned where Dp is the experimental osmotic pressure for
as: the considered COD.
cp The form of equation 6 is that usually assumed
Rˆ1ÿ …5† to express the relationship between the rejection
cf
coecient and the applied pressure di€erence across
where cf and cp are the solute concentrations, i.e. a membrane. As is well known, with increasing DP,
the COD, of the feed and the permeate streams, re- R tends toward an asymptotic value, lower than 1.
spectively. In the present case the R's asymptotic value is
In preliminary runs we ascertained that, in the equal to 0.991.
pressure range examined here, R is almost indepen- Equation 6 can be used to determine the mini-
dent of the COD of the feed stream but signi®- mum pressure required to achieve the maximum
cantly dependent on the operating pressure. COD allowed in the permeate stream.
Figure 3 shows that the COD rejection coecient Finally, we have carried out a further series of
increases from 96 to 98%, upon increasing the experiments to investigate the in¯uence of COD of
applied pressure from 20 to 53 atm. The value of R the leachate on the removal by RO of heavy metals.
obtained here at 20 atm, that is 96%, is slightly We have examined the operation yield with respect
lower than that one reported in Kinman and Nutini to the behavior of three heavy metals, Zn, Cu and
(1991), equal to 97%. In this latter work, however, Cd, whose requirements for the discharge of the lea-
the COD in the feed stream was 888 mg lÿ1, while chate are very di€erent, that is 500, 100 and
the reported results are referred to a COD equal to 20 mg lÿ1, respectively, according to Italian regu-
1749 mg lÿ1. lation. The adopted concentration of these metals
The experimental data reported in Fig. 3 can in the feed stream, equal to 20 mg lÿ1, is higher
be well ®tted (correlation index 0.994) by means of than the usual ones in the leachate. This choice was
performed to obtain a residual concentration well
Table 3. Removal of the three examined heavy metals from aqu- detectable by the used analytical instrument.
eous solutions at two COD contents The obtained results, reported in Table 3, lead to
Removal [%] the following observations:
20 atm 53 atm ± the removal of the three examined metals by
with with RO in the absence of organic contaminants is
without 1265 mg/l without 1265 mg/l always higher than 98%, in agreement with the
COD COD COD COD data reported in the literature;
Cu 99.2 98.5 99.2 98.7 ± the COD of the leachate water lowers the
Zn 98.1 97.2 98.3 97.3 removal of Cu and Zn, but to a di€erent extent. In
Cd 99.6 99.5 99.6 99.5
particular, operating with solutions with increasing
 Treatment of land®ll leachate by reverse osmosis
Fig. 4. Zn rejection vs pressure.
values of COD in the range 0±1265 mg lÿ1, we
notice an increase of the unremoved amount of Cu
of about 86% at 20 atm and of 63% at 53 atm. For
Zn by operating in the same COD range, on the
contrary, it has been observed increasing values of
the unremoved amount of metal of 48% and 59%
at the two operating pressures, respectively;
± the removal of Cd by RO is always higher than
99.5%, thus it is not a€ected by the presence of or-
ganic compounds in the aqueous solutions.
The major e€ect of COD on the zinc and copper
ions behavior can be explained by a greater com-
plexation of these ions with the organic compounds
with respect to the cadmium ions. It is, in fact, well
known that the complexation of an ion can greatly
increase its transfer within the membrane
(Menjeaud et al., 1993).
The Zn removal trend vs the RO operating press-
ure is shown in Fig. 4 in correspondence of three
di€erent COD values investigated. By ®tting the ex-
perimental data the following equation (correlation
index 0.981) to predict the Zn rejection as a func-
tion of the leachate organic compound content has
been derived (correlation index 0.981):
ÿ5
R ˆ …0:996 ÿ 1:92  10
…DP ÿ Dp†

COD† …
…DP ÿ Dp ‡ 0:0428†
CONCLUSIONS
The experimental work here reported, carried out
at pilot plant scale, has allowed the evaluation of
the in¯uence of COD of the leachate on the per-
formances of a RO unit used for leachate disposal.
651
The permeate ¯ux is signi®cantly reduced with
increasing COD up to 1749 mg lÿ1. On the basis of
the experimental data a relationship between the
osmotic pressure and the COD value has been
ascertained.
The pressure has an advantageous e€ect, as
expected, on the COD rejection, which increases
from 96 to 98% when the operating pressure is
increased from 20 to 53 atm.
The in¯uence of the COD of the leachate on the
rejection of heavy metals is related to the nature of
the metal. Among the investigated metals, Cu and
Zn exhibit a signi®cant removal, while Cd removal
seems not to be a€ected by the presence of organic
compounds in the leachate.
Finally, the rejection coecients obtained for Zn
at various values of COD and pressure has been
well predicted by a four parameters version of the
usual relationship assumed for the rejection coe-
cient estimation.
REFERENCES
Bilstad T. and Madland M. V. (1992) Leachate minimiz-
ation by reverse osmosis. Wat. Sci. Tech. 25(3), 117±
120.
Chian E. S. K., Asce M. and De Walle F. B. (1976)
Sanitary land®ll leachates and their treatment. Am. Soc.
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Kinman R. N., Nutini D. L. (1991) Reverse Osmosis
Treatment of Land®ll Leachate. In 45th Purdue
Industrial Waste Conference Proceedings. Lewis
Publishers, Inc., Chelsea, Michigan, U.S.A., pp. 617±
622.
Klotzi M., Rosemberg R. M. (1986) Chemical
Thermodynamics. The Benjamin/Cummings Publishing
Company, Inc., p. 436.
Krug T. A., McDougall S. (1989) Preliminary Assessment
of a Micro®ltration/Reverse Osmosis Process for the
Treatment of Land®ll Leachate. In 43rd Purdue
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Industrial Waste Conference Proceedings. Lewis
Publishers, Inc., Chelsea, Michigan, U.S.A., pp. 185±
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