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Printed in Great Britain Pergamon Press plc
Abstract--The adsorption of four pollutants in aqueous solutions onto activated carbon has been studied.
The following solutes have been investigated, phenol, p-chlorophenol, sodium dodecyl sulphate and
mercuric ions. The kinetics were studied using an agitated batch adsorber and a model was proposed,
based on external mass transfer and pore diffusion. The model presented has a rapid analytical solution
and is based on the assumption of a pseudo-irreversible (rectangular) isotherm.
Key words--adsorption, carbon, mass transport, phenol, mercuric ions, sodium dodecyl sulphate,
p-chlorophenol
279
280 GORDON McKAY and MURAD J. BINO
C]c Reacted r* Ct
"N / -
O,
/ / Tie
.....Un,~ ~ i \ o0.~-.... . . . . .
/ \
Co Co Unreocted / "~ i
anectiolL between
Fig. 2. Connection be:ween bulk and
mql surf; "e cox
surface concentration porhcl, e ~ ' ~ Cen¢~ntration front
during the adsorption in batch tests,
Once k r is known, the equations (1) and (3) can be Fig. 3. Concentration profile in particle.
used to determine the concentration of the adsorbate
in the liquid phase C~ at the granular surface. This Each Cao was plotted on the isotherm and the
gives the value of the concentration Q~0 in the solid corresponding equilibrium value Q~0 was obtained.
phase which is assumed to be in equilibrium with C~¢o. The operating line for the above process was also
These equilibria are described for both high and low drawn by plotting the Cto, Q,~o values, determined
adsorbate concentrations in water by the equilibrium from the batch contact experiment, and C,.~ and
isotherms. Q,. ~ values were determined by extending the oper-
The adsorbent particle is regarded as a porous ating line to cut the isotherm (Fig. 2). Knowing the
solid. The subsequent description of the adsorption concentrations Ct0, Q~0, C, and Q, at any time, the
rate will therefore be based on the following assump- time dependent internal mass transfer coeffÉcient, k,
tions: values, were calculated by utilizing equations (1) and
(2) in the form,
(i) The adsorbate is transferred within the pores of
the adsorbate solely by means of molecular kf ( C , - C,)
k, = (6)
diffusion. p,(Q,,,-O,)
(ii) Adsorption equilibrium according to the iso-
The rate of adsorption on a carbon particle can be
therm is presumed between the pore water and
determined as follows:
the adsorbent throughout adsorption process.
In other words, the deposition rate of the (i) Mass transfer from the external water phase:
adsorbate molecules in the pore water on the
adsorbent surface is taken to be much higher = 4rrR 2kr(C, - C,). (7)
than their rate of diffusion. (ii) Diffusion in the pore water according to Fick's
(iii) The adsorbate concentration in the carbon is law:
independent of that in the water, i.e. the ad-
47rDeer C
sorption is irreversible. = ~ ~,~ (8)
(iv) The quantity of absorbate in the poore water
is much lower than that on the adsorbent per \rr R]
unit volume and can therefore be neglected. where D,fr is the effective diffusion coefficient in
Because of the external mass transfer resistance, the pore water.
the concentration of adsorbate in the water drops (iii) The velocity of the concentration-front is ob-
from value C0~ in the bulk to the equilibrium value tained from the mass balance on a spherical
C~tl at the surface. The concentration of adsorbate in element:
the pore water, therefore, decreases from C~0 to zero
at rt. The adsorbate in the pores is adsorbed in a N= -4nr~Y~p,(drr~. (9)
\at)
well-defined concentration front, moving with vary-
ing velocity from the particle surface inwards. A (iv) The average concentration in the particle is
concentration curve in the particle is shown in Fig. 3. given by:
The equilibrium concentrations C, and Q, were
determined as a function of the concentration Cto and
~ by substituting the value of kf from equation (4)
and the adsorption rate .~'(t) at different times in: Introducing dimensionless parameters:
+Z.(dq Co D,~t
C~t) = C,) Akr\ dt ]" (5) P, Yg' R2 (11)
W,R.2.2/3.--B
282 GORDON McKAv and MuaAo J. BINO
S---h= _ _ 1 dr/ (17) and this can be integrated using partial fractions
3(1 - r / ) dr according to the following form,
with the adsorption rate dr//d~ from the batch tests . +,oF(x .
one obtains the experimental values of Sh while from L\ 1 + a)aJJ
the rearranged equation (15)
I f I-(2- a)-I
dr/ 3(1 - Chr/)(1 -- r/)~/3 + ~larctan L ~ j
d--~= 1 -- [1 -- (l/Bi)](1 - r/)u3 (18)
the theoretical values Sh can be predicted. Thereby (26)
the concentration ¢ in equation (15) was replaced by
(1 - Chr/) which follows from the total mass balance The limits of integration in equation (26) are r = 0,
for the vessel. Here C h = WY~/LCo is the capacity r/=0, atx=l andr=z,r/=qandx=x
factor for the individual test. The value of the
effective diffusivity in the pores D ~ has been adopted r =~-~.~h{ln[(x3+aS)(2B--!)]+ln[(x + a)~]}
to give the best fit between experimental and theor-
etical data. 1 f [-(2 - a ) - ]
From adsorption tests presented in this paper it + ~larctanL a--~-~J
follows that the experimental and theoretical values
of any given system can be fitted with sufficient
accuracy introducing a constant diffusion coefficient
ar,tao[ ll (27)
--" 200-- ~
08 .
0.6
v 100 -
~;
0.,~ I I
20 40 60
Time (rain)
Table I. Film mass transfer and effectivepore diffusion coefficientsfor the adsorption of different
pollutants
Co W dp kr D~ Yt
Run Pollutant (mgdm -3 ) (g) (m) Ch (10 -4 ) (10 -~) (mgg -I )
I Phenol 200 0.85 428 0.515 1.0 2.0 206
2 Phenol 300 0.85 428 0.343 1.0 2.0 206
3 Phenol 400 0.85 428 0.257 1.0 2.0 206
4 Phenol 200 1.70 428 0.941 I.O 2.0 206
5 Phenol 300 1.70 428 0.687 1.0 2.0 206
6 Phenol 400 1.70 428 0.515 1.0 2.0 206
7 Phenol 500 1.70 428 0.495 1.0 2.0 206
8 Phenol 600 1.70 428 0.343 1.0 2.0 206
9 Phenol 300 1.70 605 0.625 1.0 2.0 200
10 Phenol 500 3.40 ' 605 0.786 1.0 2.0 200
II Phenol 326 1.70 303 0.644 1.0 2.0 210
12 Phenol 509 3.40 303 0.825 1.0 2.0 210
13 p-Chlorophenol 500 1.00 428 0.482 1.20 10.0 410
14 p-Chlorophenol 400 1.00 428 0.603 1.20 10.0 410
15 p-Chlorophenol 300 1.00 428 0.804 1.20 10.0 410
Adsorption of pollutants 285
500 -
Phenot.
450
CO = 5 0 0 mg dm - 3
~'~ wt : 1.79 g
E dp = 4 2 8 F m
'1o
E 400.
350
I I
o 50 loo 15o 200 2.50
Time (rain)
(ii) The diffusivity value may be either smaller or Table 2. Comparison of experimental and theoretical
larger than molecular diffusion coefficients in particle mass transfer coefficients for SDS and phenol
systems
the water phase.
Experimental Theoretical
(iii) The porosity has no recognizable effect on the Pollutant k,, t (m s- i) k,,~(m s-J)
transfer mechanism. Phenol 1.5 x 10-s I.I x 10-s
(iv) The adsorption rate (dn/dT) can be predicted 0.88 x I0 -5 0.88 x I0 -5
with a constant diffusion coefficient, Dc~, which 0.40 x 10-5 0.63 x 10-5
0.28 x 10 -5 0.35 x I0 -5
depends solely on the test system and can be 0.12 x 10 -5 0.23 x 10 -5
determined in a straightforward batch tests.
SDS 7.69 x I0 -7 9.00 x I0 -7
(v) The equilibrium isotherm is very important 5.00 x 10 -7 6.92 x 10 -7
and a constant value of a monolayer coverage, 4.1 x 10-7 5.69 x 10-7
3.31 x 10-7 4.82 x 10-7
Y*, can be used to fit experimental and 2.75 x 10-7 4.10 x 10-7
theoretical results.
CONCLUSION
-6.1
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