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J. Chem. T echnol. Biotechnol.

1998, 71, 180È186

Utilization of Bagasse Fly Ash Generated in the


Sugar Industry for the Removal and Recovery of
Phenol and p-Nitrophenol from Wastewater
V. K. Gupta,* Saurabh Sharma, I. S. Yadav & Dinesh Mohan
Department of Chemistry, University of Roorkee, Roorkee - 247 667, India
(Received 14 February 1997 ; accepted 26 August 1997)

Abstract : Bagasse Ñy ash, a waste generated in local sugar industries, has been
converted into a low cost adsorbent. The product so obtained has been charac-
terized and used for the removal of phenol and p-nitrophenol. Investigations
include the e†ect of pH, sorbent dosage, phenol concentration and the e†ect of
surfactants on the uptake of phenol and p-nitrophenol. The adsorption data
follow both Langmuir and Freundlich models. Isotherms have also been used to
obtain the thermodynamic parameters of the process. Some experiments have
also been performed with a view to recover phenols and have in-situ chemical
regeneration of the spent carbon column. ( 1998 SCI.

J. Chem. T echnol. Biotechnol. 71, 180È186 (1998)

Key words : bagasse Ñy ash ; phenols ; adsorption ; waste utilization ; wastewater


treatment ; sugar industry

1 INTRODUCTION ultraÐltration, electrodialysis, electrochemical degrada-


tion, Ñotation, etc.
The presence of phenol and phenolic compounds in Adsorption technology is currently being used exten-
water and wastewater has been of great public concern. sively for the removal of organic and inorganic micro-
Phenol is one of the most frequent contaminants in haz- pollutants from aqueous phases and since its Ðrst
ardous waste sites. Phenols can cause bad taste and introduction in the 1940s, activated carbon has become
odour in drinking water, even at low concentration. the water industryÏs standard for the reclamation of
Some phenolic compounds have been found to acceler- municipal and industrial wastewater to a potable water
ate tumour formation and to be ciliostatic. Phenols are quality.2 In view of the high cost and tedious procedure
introduced into surface water from industrial effluents for the preparation and regeneration of activated
such as those from the coal tar, gasoline, plastic, rubber- carbon there is a continuing search for low cost poten-
prooÐng, disinfectant, pharmaceutical and steel tial adsorbents.3h10 Recently, some cheap and very effi-
industries and domestic wastewaters, agricultural cient adsorbents from the wastes generated in some
run-o† and chemical spills. Nitrophenols are usually prime industries have been developed in this labor-
formed from the photodegradation of pesticides. atory.11h17 The sugar industry is one of the most
Various methods have been proposed for the treat- important agrobased industries in India. A signiÐcantly
ment of wastewaters containing organic and inorganic large volume of wastes, particularly in terms of sus-
pollutants. These processes are based on the principles pended solids, organic matter, press mud, bagasse and
of precipitation/coagulation, chemical oxidation, sedi- air pollutants, largely bagasse Ñy ash, is generated
mentation, Ðltration, adsorption, osmosis, ion-exchange, during the manufacture of sugar. Continuing our
research in this area5,14h17 we have used bagasse Ñy ash
* To whom correspondence should be addressed.
Email address : vkgcy=rurkiu.ernet.in for the removal and recovery of phenol and p-
Contract/grant sponsor : CSIR (Council of ScientiÐc and nitrophenol after converting it into a suitable adsorbent
Industrial Research), New Delhi, India. material.
180
( 1998 SCI. J. Chem. T echnol. Biotechnol. 0268-2575/98/$17.50. Printed in Great Britain
Removal of phenols from wastewater 181

MATERIALS AND METHODS solutions of sorbates of known concentrations were


placed in a thermostatic shaking assembly. After attain-
All reagents used were of AR grade. Stock solutions of ing the desired temperature, a known amount of
the test sorbates were made by dissolving p-nitrophenol adsorbent was added to each tube. The solutions in the
and phenol in double distilled water. various test tubes were separated from the sorbent
material and the concentrations of phenol and p-
nitrophenol were determined.
Equipment

pH measurements were made using a pH meter (model


RESULTS AND DISCUSSION
CT No. CL46 ; Toshniwal, India). X-ray measurements
were done by a Phillips X-ray Di†ractometer employing
The adsorbent developed from bagasse Ñy ash was
nickel Ðltered Cu-K radiations. The surface area of the
a found to be of the “LÏ type, based on an earlier classi-
sample was measured by a surface area analyser (Model
Ðcation,15 i.e. it lowers the pH when kept in deionized
QS-7 ; Quantasorb Surface Area Analyser). IR spectra of
water. It is quite stable in water, salt solutions, acids,
the sample were recorded on an infrared spectropho-
bases and organic solvents. The di†erent constituents of
tometer (Model (FTIR) Perkin Elmer 1600). The con-
the bagasse Ñy ash used in these investigations are
stituents of the prepared adsorbent were analysed
SiO È61É44, Al O È14É5, CaOÈ28É2, Fe O È4É86,
following the routine standard methods of chemical 2 2 3 2 3
MgOÈOÉ71 and LOlÈ17É12 percent by weight. The
analysis.18 Absorbance measurements were recorded on
x-ray di†raction pattern of the product provided d-
a DU-6, UV-VIS spectrophotometer.
spacing values which reÑect the presence of geothite,
mullite, haematite, kaolinite, a-quartz and gamma
Material development alumina.19 The surface area of the adsorbent as calcu-
lated by the BET method was found to be 440 m2g~1.
The waste material was obtained from a local sugar Figure 1 depicts the variation of adsorption with pH.
factory at Bijnor (U.P.), India. The material was treated Both phenol and p-nitrophenol are strongly adsorbed at
with hydrogen peroxide (100 volumes) at 60¡C for 24 h low pH values. There is no change in the uptake of
to oxidize the adhering organic matter. The resulting phenol and p-nitrophenol up to pH 8É0 and 6É0 respec-
material was then washed with distilled water, dried at tively, beyond which a sharp decline in adsorption is
100¡C and stored in a vacuum desiccator. The adsorb- observed. As such all subsequent studies were per-
ent was powdered, ground, and sieved to desired parti- formed at pH 4É0, which is the optimum value for both
cle size before use. the sorbates.
Sorption isotherms of phenol and p-nitrophenol, at
di†erent temperatures under optimum conditions, are
Adsorption studies
depicted in Fig. 2. The curves are regular and concave
to the concentration axis, thereby showing a positive
Sorption studies were conducted in a routine manner by
adsorption. It is observed that the initial removal is fast
batch technique. Isotherms were run by taking di†erent
concentrations of phenol and p-nitrophenol (10~4È
10~3 M) at desired temperature and pH. These concen-
trations were however decided after a good deal of
preliminary investigations. Stoppered glass tubes
(50 cm3) containing sorbate solutions and deÐnite
amounts of bagasse Ñy ash were stirred intermittently.
After 24 h the solutions were separated by Ðltration and
the uptake of phenol and p-nitrophenol was determined
spectrophotometrically at 270 and 380 nm respectively.
The e†ect of an anionic detergent, Manoxol-1B (conc.
10~5 M), on the removal of phenol and p-nitrophenol by
the adsorbent material has also been studied.

Kinetic studies

The adsorption kinetics of phenol and p-nitrophenol on


Fig. 1. E†ect of pH on the uptake of phenol and p-
bagasse Ñy ash was studied by the bath technique nitrophenol on bagasse Ñy ash (temp. \ 30¡C ; particle
(Finite Bath). A number of stoppered Pyrex glass tubes size \ 150È200 mesh ; adsorbent dose \ 10 g dm~3 ;
containing a deÐnite volume (10 cm3 in each case) of concn \ 5 ] 10~4 M).
182 V . K. Gupta, S. Sharma, I. S. Y adav, D. Mohan

Fig. 2. Adsorption isotherms of (a) phenol and (b) p-


nitrophenol on bagasse Ñy ash at di†erent temperatures
(pH \ 4É0 ; particle size \ 150È200 mesh ; adsorbent Fig. 3. Adsorption isotherms of (a) phenol (b) p-nitrophenol
dose \ 10 g dm~3). on bagasse Ñy ash at di†erent amounts of adsorbent
(pH \ 4É0 ; particle size \ 150È200 mesh ; temp. \ 30¡C).

in both cases and at higher concentration the uptake


gradually decreases from 95 to 72% and 100 to 75% for taken as an appropriate amount for all subsequent
phenol and p-nitrophenol respectively. A decrease in the investigations.
uptake of phenol/p-nitrophenol is also observed with The sorption data of phenol and p-nitrophenol have
increase in temperature, thereby indicating the pro- been correlated with Freundlich and Langmuir models
cesses to be exothermic in nature. (eqns (1) and (2)).
The uptake increases when larger quantities of
adsorbent are used (Fig. 3). In the case of phenol, the q \ K C1@n (1)
e F
uptake goes up by 3% when the quantity of adsorbent
used in doubled, i.e. the amount increases from Q0bC
q \ (2)
5 g dm~3 to 10 g dm~3. On increasing the amount of e 1 ] bC
the adsorbent further to 20 g dm~3, the uptake goes up
only by 4%. As such, 10 g dm~3 of adsorbent is quite where q is the amount of solute adsorbed per unit
e
appropriate. For p-nitrophenol the adsorption goes up weight of adsorbent, K , 1/n and b are the character-
F
by 3É5% when the amount of adsorbent is changed from istic constants, C is the solute phase and Q0 the solid
5 g dm~3 to 10 g dm~3. On further increase in the phase concentration corresponding to complete cover-
quantity of adsorbent to 20 g dm~3, the enhancement age of available adsorption sites.
in p-nitrophenol uptake is only 3É6%. There seems to be The adsorption capacity “K Ï is less for the phenolÈ
F
little e†ect on increasing the amount of adsorbent. In bagasse Ñy ash system than that for the p-nitrophenolÈ
this case also, 10 g dm~3 of the adsorbent has been bagasse Ñy ash system. The slope “1/nÏ, which reÑects the
Removal of phenols from wastewater 183

intensity of adsorption presents the same trend. The higher temperature. The negative values of enthalpy
Langmuir constant “Q0Ï decreases with increase in tem- change (*H) for the process suggest the exothermic
perature, thereby indicating the process to be exother- nature and the possibility of strong bonding between
mic in nature. The value of Q0 appears to be adsorbates and the adsorbent. A positive entropy of
signiÐcantly higher for the p-nitrophenolÈbagasse Ñy adsorption (*S) also reÑects the affinity of the adsorbent
ash system in comparison to phenol on the same material towards phenol and p-nitrophenol.
adsorbent (Table 1). Although wastewater may contain many contami-
The dimensionless separation factor,20 R as calcu- nants besides phenols, the presence of anionic detergent
lated from the Langmuir isotherm using the equation, is most likely to be encountered in various situations.
R \ 1/1 ] bC was found to be 0É73 and 0É79 respec- As such the uptake of phenol and p-nitrophenol in the
0
tively for phenol and p-nitrophenol. This indicates a presence of an anionic detergent Manoxol-IB (conc.
highly favourable sorption (R > 1). 1 ] 10~5 M) has also been studied. A decrease in the
The thermodynamic parameters obtained for the scavenging efficiency of adsorbent, in the presence of the
systems under investigation, using eqns (3), (4) and (5), detergent, is evident from Fig. 4. A similar decrease in
are given in Table 2. the uptake of phenols has been reported earlier.21
For practical application and designing of sorption
*G \ [RT ln K (3) reactors it is necessary to determine the steps involved

*H \ [R
C T T D
K
2 1 ln 2 (4)
in the process of adsorption which govern the overall
rate of removal. The same was done using the ingenious
T [T K treatment of Boyd et al.22 and Reichenberg.23
2 1 1
A quantitative understanding of the sorption
*G [ *H dynamics and other mechanistic aspects is possible with
*S \ (5)
T the help of the following expressions eqns (6)È(9)

Where K, K and K are the equilibrium constants at


1 2
30, 40 and 50¡C obtained from the slopes of the adsorp- F\1[
6 = 1
; exp
C
[D tn2n2
i
D (6)
tion isotherms at zero concentration. *G stands for n2 n2 r2
n/1 0
GibbÏs free energy change, *S entropy change and *H
enthalpy change for the process. Other terms have their 6 = 1
usual signiÐcance. or F\1[ ; exp[[n2Bt] (7)
n2 n2
The negative free energy values (Table 2) indicate the n/1
feasibility of the process and spontaneous nature of the
adsorption. Free energy increases with increase in tem- where F is the fractional attainment of equilibrium at
perature indicating, thereby, a decrease in adsorption at time “tÏ and is obtained by the use of eqn (8).

TABLE 1
Freundlich and Langmuir Constants for Phenol and p-Nitrophenol

Adsorbates Freundlich constants L angmuir constants

n K Q0 ] 106 (mole g~1) b ] 10~6 (1 mol~1)


F
30¡C 40¡C 50¡C 30¡C 40¡C 50¡C 30¡C 40¡C 50¡C 30¡C 40¡C 50¡C

Phenol 2É55 2É65 2É87 1É00 0É95 0É70 7É11 5É88 5É00 2É64 3É63 3É50
p-Nitrophenol 2É50 2É57 2É70 1É21 1É02 0É78 8É33 6É60 5É50 2É14 2É60 3É11

TABLE 2
Thermodynamic Parameters For Phenol and p-Nitrophenol

Adsorbates [*G (kJ mol~1) [*H (kJ mol~1) *S(J K~1 mol~1)

30¡C 40¡C 50¡C

Phenol 37É25 38É14 40É39 10É40 88É60


p-Nitrophenol 36É72 38É81 40É23 15É84 68É90
184 V . K. Gupta, S. Sharma, I. S. Y adav, D. Mohan

n \ 1, 2, 3 . . . . are the integers deÐning the inÐnite series


solution obtained by a Fourier type of analysis.
For every observed value of F, corresponding Bt
values as derived from eqn (7) have been obtained from
ReichenbergÏs table.23 The linearity test of Bt versus
time plots are employed to distinguish between con-
trolled rates of exchange.
At lower concentrations (O5 ] 10~4 M) the Bt versus
time plots deviated from linearity and did not pass
through the origin, signifying the adsorption to be Ðlm
di†usion while at higher concentrations (P1 ] 10~3 M)
the same were linear and passed through the origin,
indicating the adsorption to be particle di†usion in
nature for both the sorbates (data not shown).
The experimental conditions were set up for particle
di†usion as the sole rate-determining step to study the
thermodynamics of the sorption process. The energy of
activation, E , has been determined by applying the
a
Arrhenius type equation.

D \ D exp
C D
[E
a (10)
i 0 RT

The pre-exponential constant D (analogous to Arrhe-


0
nius frequency factor) gives the entropy of activation,
*Sj :

D \ 2É72d2
kT C D C D
exp
*Sj
(11)
0 h R

where d is the average distance between the successive


exchange sites and is taken as 5 Ó.
The D values for the phenolÈbaggase Ñy ash and p-
Fig. 4. E†ect of Manoxol-1B on the adsorption of (a) phenol i
and (b) p-nitrophenol. nitrophenolÈbaggase Ñy ash systems at di†erent tem-
peratures are listed in Table 3. It may be argued that
the e†ective di†usion coefficient, D in these systems, is
Q i
F\ t (8) mainly comprised of two components, which are due to
Q the simultaneous di†usion of the ingoing ions through
0
the pores of di†erent widths and di†erent electronic
n2Di Ðelds along the di†usion path. The di†usion within the
B\ \ time constant (9)
r2 pores of wider-widths and weaker retarding forces of
0
electrostatic interaction (particularly at the surface of
where Q is the amount taken up at time “tÏ and Q is the sorbent) accounts for the faster one and the one
t 0
the maximum equilibrium uptake, D is the e†ective dif- within the pores of narrower mesh widths and stronger
i
fusion coefficient of ion in adsorbent phase, r \ radius retarding forces, accounts for the slower component of
0
of the adsorbent particle assumed to be spherical and D . As the temperature increases, the contribution of the
i
TABLE 3
E†ective Di†usion Coefficients (D ), D , E and *Sj for Phenol and p-Nitrophenol at Di†erent Temperatures
i 0 a
Adsorbates E†ective di†usion coefÐcient D E [*Sj
0 a
D (cm2 s~1) (cm2 s~1) (kJ mol~1) (J K~1 mol~1)
i
30¡C 40¡C 50¡C

Phenol 7É9 ] 10~20 6É66 ] 10~20 5É54 ] 10~20 3É31 ] 10~19 3É61 2É68
p-Nitrophenol 3É07 ] 10~16 2É92 ] 10~16 2É47 ] 10~16 1É28 ] 10~15 3É60 3É44
Removal of phenols from wastewater 185

faster component of D decreases. It is because of the ment. In order to achieve this and to assess the practical
i
decreasing mobility of ingoing species at higher tem- utility of the adsorbent, column studies were performed.
perature which to some extent overcomes the inÑuence A glass column (40 ] 0É5 cm) was Ðlled with 0É500 g
of retarding forces. (size, 200È250 mesh) of bagasse Ñy ash. The column was
The log D versus 1/T plots for both the phenols are loaded with phenol as well as p-nitrophenol and the
i
linear in nature. This permits the use of the Arrhenius solutions percolated downwards at a Ñow rate of
equation for the determination of D and E from the 0É4 cm3 min~1. Desorption was tried with a number of
0 a
intercepts and slopes of the linear plots (Fig. 5). D eluting agents, viz. acids, NaOH, ethanol, methanol.
0
values are further used to calculate the entropy of acti- With acids the elution of phenol and p-nitrophenol was
vation for the sorption of phenol and p-nitrophenol quite small while the recovery with methanol and
(Table 3). It is found that the value of E is higher for ethanol was only 70È72% of the amount loaded.
a
the phenolÈbagasse Ñy ash system than for the p- Almost complete ( B 98%) desorption of phenols could
nitrophenolÈbaggase Ñy ash system. The negative *Sj be achieved with only 8% NaOH. This may be due to
values reÑect that no signiÐcant change occurs in the the formation of sodium salt of phenols which could be
internal structure of bagasse Ñy ash during the adsorp- readily removed.
tion of phenol and p-nitrophenol. It is further observed that the column loses about
2È8% of its adsorption efficiency, after the Ðrst run. A
Recovery of adsorbates and regeneration of adsorbent good deal of experimentation with various reagents
have shown that a treatment with 1 M HNO solution
3
Regeneration of the adsorbent and recovery of the at a Ñow rate of 0É4 cm3 min~1 restores the lost sorp-
adsorbate is an important process in wastewater treat- tion capacity to almost the original value. No loss is
however observed in subsequent runs and a column can
be used for 8È10 cycles without further regeneration.

Treatment of effluent

Wastewater obtained from a coal gasiÐcation plant


(data given below) were successfully treated on the
columns of this adsorbent material. The analysis of coal
gasiÐcation plant effluent is : pH \ 8É2, SSÈ250 ; phenols
2800 ; CODÈ1600 : and SCN~È130 ; CN~È0.5 ;
TOCÈ6305 and ammonia 7200 (mg dm~3). The efflu-
ent was just treated with a mild acid (to bring down the
pH), allowed to settle down for some time in a tank and
then fed to columns of bagasse Ñy ash. A typical run
was carried out using bagasse Ñy ash. Almost complete
removal of phenol from 50 cm3 of wastewater at pH 4É0
was possible with the column of bagasse Ñy ash (particle
sizeÈ200È250 mesh ; adsorbent doseÈ4É0 g ; Ñow rate
0É4 cm3 min~1). The data may be helpful in designing a
Ðxed bed adsorber for the treatment of adsorbate of
known concentrations if applied on a large scale.

CONCLUSIONS

Bagasse Ñy ash obtained from a local sugar factory is an


e†ective adsorbent for the removal of phenol and p-
nitrophenol. The uptake of p-nitrophenol is more than
that of phenol and is comparable to other
commercially-available adsorbents. The removal of
phenols by this adsorbent takes place via particle di†u-
sion mechanism.
The cost of production of the material15 is almost
half that of other commercially available adsorbents.
Fig. 5. Plots of log D versus 1/T for (a) phenol and (b) p- Phenols adsorbed on the columns of this material can
i nitrophenol.
be eluted quantitatively with 8% aq. NaOH. Exhausted
186 V . K. Gupta, S. Sharma, I. S. Y adav, D. Mohan

columns can be chemically regenerated by treating with 10. Chaney, R. L. & Hundemann, P. T., Use of peat moss
1 M HNO without dismantling. The adsorbent has also columns to remove cadmium from wastewater. J. W ater
3 Pollut. Control. Fed., 51 (1979) 17È21.
been used successfully for the removal of phenol from 11. Srivastava, S. K., Tyagi, R., & Pant, N., Adsorption of
wastewaters. heavy metal ions on carbonaceous material developed
from the waste slurry generated in local fertilizer plants.
W ater Res., 23 (1989) 1161È5.
ACKNOWLEDGEMENT 12. Srivastava, S. K., Pant, N. & Pal, N., Studies on the effi-
ciency of a local fertilizer waste as a low cost adsorbent.
W ater Res., 21 (1987) 1389È94.
The authors are very much thankful to CSIR (Council 13. Srivastava, S. K., Bhattacharjee, G., Tyagi, R., Pant, N. &
of ScientiÐc and Industrial Research), New Delhi, India Pal, N., Studies on the removal of some toxic metal ions
for providing Ðnancial assistance. from aqueous solutions and industrial waste. Part I :
Removal of lead and cadmium by hydrous iron and alu-
minium oxide. Environ. T echnol. L etters, 9 (1988) 1173È85.
14. Srivastava, S. K., Gupta, V. K., Mohan, D. & Pant, N.,
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