S O R P T I O N A N D D E S O R P T I O N OF D Y E S BY

SULFONATED COAL
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By Atul K. Mittal, 1 and C. Venkobacharz

INTRODUCTION

Wastewaters from dye-manufacturing factories and textile, paper, and

pulp industries are highly colored. Their discharge into river waters make
the water inhibitory to aquatic life, aside from causing visible pollution.
Dyes have a tendency to sequester metals, thus causing microtoxicity to fish
and other aquatic organisms. A wide variety of low-cost materials such as
flyash, clay minerals, coal, tire chippings, coconut shell powder and bio-
sorbents are being tried as viable substitutes for activated carbon to remove
different pollutants such as pesticides, heavy metals, and dyes (McKay et
al. 1987; Mittal and Venkobachar 1990; Muraleedharan and Venkobachar
1990; Poots et al. 1976; Surinova et al. 1983). The removal of dyes depends
upon their physical and chemical characteristics, as well as the properties
of the selected sorbents. To understand the nature of the chemical bonding
between dyes and sorbents during the sorption process, it is essential to
conduct desorption studies. The reversibility of adsorption of dyes can also
be determined by a simple mathematical equation. These studies provide
information on whether or not the sorbent material can be regenerated after
exhaustion. The present study focuses on sorption-desorption of dyes by
sulfonated coal, whose dye sorption potential was established by Mittal and
Venkobachar (1990).

EXPERIMENTAL
Bituminous coal from Giridih, Bihar, India, was sulfonated per the pro-
cedure of Michelson et al. (1975). This treatment was carried out by adding
600 mL of concentrated H2SO 4 for every 100 g of Giridih bituminous coal.
The mixture was heated in a water bath at 90~ _+ 2~ for 12 h, with
intermittent stirring. Subsequently, the coal was washed to remove the
loosely bound acid.
The sulfonated coal (SC) was pulverized and sieved to a geometric mean
(GM) size of 270 p~m, and used as sorbent for the removal of dyes. Two
basic dyes, rodamine-B (basic violet. 10, CI 45,170) and methylene blue
(basic blue. 9, CI 52,015), as well as an acidic dye, sandolan rhodine (acid
red 1, CI 18,050), were selected for these studies. Transmission spectra for
these dyes were run employing a Carry 17D, ultraviolet (UV)-visible spec-
trophotometer (made by Beckman).
Batch sorption experiments were conducted using a series of 50-mL re-
action mixtures containing 100 mg/L of dye solution to which different
1Lect., Dept. of Civ. Engrg., Motilal Nehru Regional Coll. of Engrg., Allahabad,
India.
ZProf., Dept. of Civ. Engrg., Indian Inst. of Technol., Kanpur-208016, India.
Note. Discussion open until September 1; 1993. To extend the closing date one
month, a written request must be filed with the ASCE Manager of Journals. The
manuscript for this paper was submitted for review and possible publication on May
20, 1992. This paper is part of the Journal of Environmental Engineering, Vol. 119,
No. 2, March/April, 1993. 9 ISSN 0733-9372/93/0002-0366/$1.00 + $.15 per
page. Paper No. 9918.
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J. Environ. Eng., 1993, 119(2): 366-368

 amounts of sorbent were added. After an equilibration time of 10 h (which
was determined earlier), the residual dye concentrations were found. For
desorption studies, the sorbent loaded with dye was separated from the dye
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solution and dried. This sorbent was resuspended in distilled water, or in

aqueous-based desorption agents such as 1 N H2504 or formic and acetic
acids. After attainment of new equilibrium for desorption, the aqueous-
phase concentration of the dye was determined spectrophotometrically.

RESULTS AND ANALYSIS

To predict the reversibility of adsorption of dyes from sulfonated coal, it
is essential to determine the sorption equilibria, and to write a mass balance
equation for desorption. The data for sorption of the three dyes fit the
Freundlich isotherm of the form
q = KC" . .................................................. (1)

where q = mg dye adsorbed per gram of SC; C = equilibrium dye con-

centration in mg/L; and K and n are the Freundlich parameters. The values
of these parameters are presented in Table 1 for different dyes.
The total amount of dye adsorbed is q r = q . w , where w = weight of
the adsorbent.
During desorption, the equilibrium sorption mixture was replaced by
distilled water or other aqueous-based eluants. The mass balance after the
desorption equilibrium is
qr = q'W + C'V' = K(C')".W + C'V' . ....................... (2)
where q' and C ' = new equilibrium values after desorption; and V' =
volume of solution in which dye is desorbed.
Solving (2), the desorbed dye concentration C' can be predicted. This
was done using the appropriate isotherm relationships for dye-SC systems.
The comparison of experimental values of dyes in distilled water with
those predicted using (2) facilitates the determination whether the sorption
is reversible or otherwise. If the experimental values agree well with the
predicted values, then the sorption is reversible. If there is no agreement,
then sorption reaction can be considered as slowly reversible.
From the data presented in Table 1, the nature of the binding of dyes to
the sulfonated coal can be understood. The basic dyes like rhodamine-B
and methylene blue did not desorb in distilled water, which indicates that
the sorption between these and sorbent is not by physisorption. Further,
the predicted desorption for these dyes is also negligible. However, sandolan
rhodine could be desorbed up to 17.5% in distilled water, indicating physical

TABLE 1. Sorption and Desorption of Dyes from Sulfonated Coal

ADSORPTION CYCLE DESORPTION CYCLE
Freundlich Predicted
parameters value Experimental Desorption (%)
[from
Per- Eq. (2)] i CH3COOH HCOOH
Sorbate cent K n (%) H20 1 N H2SO4 (100%) (100%)
(1) (2) (3) (4) (5) (6) (7) (8) (9)
Rhodamine-B 99.80 6.69 2 1.024 Traces 0.04 15.98 50.80
Methylene blue 99.80 85.62 0.06 0.10 0.05 0.51 1.90 21.78
Sandolan rhodine 96.00 6.69 0.5 0.34 17.55 0.25 0.35 41.25

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J. Environ. Eng., 1993, 119(2): 366-368

 sorption to be operative to some extent. However, the model-predicted
value was much less. Desorption of all dyes are negligible in 1 N HzSO4
acid medium, which rules out the possibility of ion exchange sorption via
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exchange of H + of sulfonated coal (RSO3H) by dye molecule. Significant

amount of desorption of all dyes, particularly in formic acid solution, is due
to the nonpolarity of the solvent. The formic acid solubilizes the dye mol-
ecule as a whole. The remainder appears to be chemically complexed, and
to have become an integral part of the sorbent.

CONCLUSION
Sorption of all three dyes employed onto sulfonated coal appears due to
chemical interactions. For sandolan rhodine, physical adsorption is also
operative. Methylene blue-loaded sorbent can be desorbed least, and those
loaded with sandolan rhodine desorbed maximum for eluants employed.
The mathematical model developed agreed well with experimental values
for the basic dyes only.

APPENDIX. REFERENCES
McKay, G., Ramprasad, G., and Mowli, P. (1987). "Desorption and regeneration
of dye colours from low cost materials." Water Res., 21(3), 375-377.
Michelson, L. D., Gideon, P. G., Pace, E. G., and Kutar, L. H. (1975). "Removal
of soluble mercury from wastewater by complexing techniques." VPI-WRRC Bull.
74, Virginia Water Res. Ctr., Virginia Polytech. Inst. and State Univ., Blacksburg,
Va.
Mittal, A. K., and Venkobachar, C. (1989). Studies on sorption of dyes by sulfonated
coal and Ganoderma lucidum. Int. J. Envir. Health, 31(2), 105-111.
Muraleedharan, T. R., and Venkobachar, C. (1990). "Mechanism of biosorption of
copper(II) by Ganoderma lucidum." Biotechnol. Bioengrg., 35(3), 320-325.
Poots, V. J. P., McKay, G., and Healy, J. J. (1976). "The removal of acid dye from
effluent using natural adsorbents. II." Water Res., 10(12), 1067-1070.
Surinova, S. I., Voronia, T. B., Klinkova, V. V., and Khoteleva, V. N. (1983). "Use
of brown coal for purifying coloured effluents." Solid Fuel Chem., 17, 73.

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J. Environ. Eng., 1993, 119(2): 366-368