Beruflich Dokumente
Kultur Dokumente
Department of Industrial Chemistry, Faculty of Biological and Physical Sciences, Abia State University P.M.B. 2000
Uturu, Abia State, Nigeria.
2
Department of Pure and Industrial Chemistry, University of Port Harcourt, River State, Nigeria.
Accepted 20 April, 2007
Heavy metals constitute pollution problems to the environment and they are toxic to both man and
aquatic organisms. The passive removal of toxic heavy metals such as cobalt (II) (Co(II)), iron (II) (Fe(II))
and copper (II) (Cu(II)) by inexpensive biomaterials, termed biosorption, requires that the substrate
displays high metal uptake and selectivity, as well as suitable mechanical properties for applied
remediation scenarios. The kinetics and intraparticulate diffusivities for the adsorption of these metal
ions onto modified and unmodified maize cob was investigated. The amount of the metal ions adsorbed
increased as time increased. The trend of the sorption capacity was found to be Co(II) > Fe(II) > Cu(II)
for unmodified and Co(II) > Cu(II) > Fe for EDTA modified maize cob. The mechanism of adsorption of
the metal ions followed particle diffusion model. The pseudo-first order and pseudo- second order
kinetic equations were used to model the adsorption kinetics, with the second order giving a better fit,
2
as seen from the correlation coefficient (R ) which ranged from 0.2329 to 0.9958 for pseudo first order
and 0.9994 to 1.008 for pseudo-second order model. The applicability of the Elovich equation to the
sorption kinetics was also investigated. This work therefore shows that modified and unmodified maize
cob could be used to remove Co(II) Fe(II) and Cu(II) ions from waste water and also established their
mechanism of sorption.
Key words: Bioremediation, adsorption kinetics, heavy metal, maize cob.
INTRODUCTION
Cobalt, iron and copper are examples of heavy metals.
They are very toxic to both man and animal. They also
constitute pollution problems to the environment. When
these contaminants are found in effluent, they may increase fertility of the sediment and water column and consquently lead to euthrophication, which in open waters can
progressively lead to oxygen deficiency, algal bloom and
death of aquatic life (Asamudo et al., 2005).
Copper have been reported as one of the most widely
used heavy metal in electrical and electroplating Industries (Igwe and Abia, 2006). Since copper is an essential
metal in a number of enzymes for all forms of life, pro-
120
Table 1. Fraction of amount adsorbed as time increases for unmodified maize cob of
500m and 850m particle sizes.
Time (Min)
10
20
30
40
50
60
Ct/Co
Co
0.4959
0.4961
0.4964
0.4967
0.4969
0.4972
500 m
Fe
0.4380
0.4381
0.4386
0.4387
0.4389
0.4420
Cu
0.2228
0.2330
0.2363
0.2372
0.2500
0.2501
Co
0.4925
0.4977
0.4981
0.4983
0.4988
0.4997
850m
Fe
0.4269
0.4295
0.4314
0.4335
0.4338
0.4352
Cu
0.2407
0.2422
0.2464
0.2536
0.2686
0.2807
121
Table 2. Fraction of amount adsorbed as time increases for modified maize cob of 500
and 850 m particle sizes.
Tim (Min)
10
20
30
40
50
60
Ct/Co
Co
0.4838
0.4838
0.4839
0.4840
0.4839
0.4839
500 m
Fe
0.4771
0.4772
0.4774
0.4775
0.4776
0.4777
Cu
0.4785
0.4788
0.4791
0.4794
0.4794
0.4793
Co
0.4839
0.4840
0.4842
0.4843
0.4845
0.4847
850m
Fe
0.4776
0.4778
0.4781
0.4782
0.4783
0.4778
Cu
0.4789
0.4790
0.4792
0.4794
0.4794
0.4796
k1 (qe qt)
(1)
(2)
122
Table 3. Regression equations and R2 values for the pseudo- first order and pseudo- second order rate equations plot for the
metal ions adsorption on unmodified and modified maize cob of two particle sizes.
Unmodified
500m
850m
y = -0.0326x+1.2543
Y= -0.2162x+1.5859
2
2
(R = 0.9958)
(R = 0.8766)
Fe
Y= -0.0049x+2.4045
2
(R = 0.6756)
Y = - 0.013x+2.4717
2
(R = 0.9595)
Y= -0.0002x + 1.9643
2
(R = 0.9884)
Y= -0.0001x + 1.9502
2
(R = 0.0.2329)
Cu
Y= -0.0094x+3.0533
2
(R =0.9444)
Y = - 0.0003x + 1.9298
2
(R = 0.9576)
Co
Y = 0.001x + 0.0006
2
(R = 1.006)
Y = -0.0147x+3.0413
Y= - 0.0004x+ 1.9353
2
2
(R = 0.8990)
(R = 0.7332)
Pseudo Second Order
Y = 0.001x + 0.00005
Y = 0.001x+ 0.001
2
2
(R = 1.002)
(R = 1.001)
Fe
Y = 0.0011x+0.00017
2
(R = 1.002)
Y= 0.00011x+ 0.00038
2
(R = 1.008)
Y= 0.001x + 0.001
2
(R = 1.004)
Y= 0.001x + 0.002
2
(R = 1.008)
Cu
Y = 0.0019x+ 0.0065
2
(R = 0.9994)
Y= 0.0017x+ 0.0066
2
(R = 0.9994)
Y= 0.001x + 0.002
2
(R = 1.006)
Y= 0.001x + 0.002
2
(R = 1.005)
3.5
Co 500um
Fe 500um
2.5
Co 850um
Cu 500um
Fe 850um
Cu 850um
1.5
1
0.5
0
0
20
40
60
80
Co 500um
1.98
1.96
1.94
1.92
1.9
1.88
1.86
1.84
1.82
1.8
1.78
1.76
Fe 500um
Cu 500um
Co 850um
Fe 850um
Cu 850um
50
100
Time(min)
Y = 0.001x + 0.001
2
(R = 1.000)
Tim e (m in)
dqt/ dt =
Co
Modified
500 m
850 m
-5
Y = - 7.0x10 x + 1.8114 Y = - 0.0005x + 1.8153
2
2
(R = 0.6857)
(R = 0.9932)
(3)
Where:
k2 is the rate constant of pseudo second order adsorption
-1
-1
(mg min ) From the boundary conditions t=0 to t=t and
1/ (qe-qt)
1/ qe + kt
(4)
= 1/ k2 qe + 1 / qe (t)
-1
(5)
-1
123
Table 4. Kinetic constants for Pseudo First Order Model of the sorption process.
Metal
ions
Unmodified
500m
850m
-1
-1
K1 (min )
qe (mg/g)
K1 (min )
qe (mg/g)
0.0751
17.96
0.4979
38.54
0.0113
25.38
0.0237
296.28
0.0217
1130.58
0.0339
1099.77
Co
Fe
Cu
0.6
Cu 850um
Fe 850um
0.5
Co 850um
Cu 500um
t/qt
0.4
Fe 500um
Co 500um
0.3
0.2
0.1
0
10
20
30
40
50
60
Tim e(m in).
0.4
Cu 850um
0.35
Fe 850um
0.3
Co 850um
Cu 500um
t/qt.
0.25
Fe 500um
0.2
Co 500um
0.15
0.1
0.05
0
10
20
30
40
50
60
ho = k2 qe
Time(min).
(6)
1/ ho
1/ qe (t)
exp (- qt)
(8)
-1
t / qt
Modified
500m
850m
-1
-1
K1 (min )
qe (mg/g)
K1 (min )
qe (mg/g)
-4
-3
1.612x10
64.77
1.152x10
65.36
-4
-4
4.606x10
92.11
2.303x10
89.17
-4
-4
9.212x10
86.16
6.909 x10
85.08
(7)
-1
(9)
124
Table 5. Kinetic constants for Pseudo Second Order Model of the sorption process.
Metal ion
Unmodified
Modified
500m
qe
(mg/g)
Co
Fe
Cu
1000
909.1
526.3
h0
-1
-1
(g mg min )
3
16.67x10
3
5.88x10
3
0.15x10
K2
-1
-1
(g mg min )
qe
(mg/g)
850 m
h0
-1
(g mg
-1
min )
0.0167
0.0676
-4
5.42x10
1000
909.1
588.2
20.0x10
3
2.63x10
3
0.15x10
K2
-1
(g mg
-1
min )
0.02
3
3.18x10
-4
4.34x10
qe
(mg/g)
1000
1000
1000
500 m
h0
-1
(g mg
-1
min )
3
1.0x10
3
1.0x10
3
0.5x10
K2
-1
(g mg
-1
min )
-3
1.0x10
-3
1.0x10
-4
5.5x10
qe
(mg/g)
1000
1000
1000
850 m
h0
-1
(g mg
-1
min )
3
1.0x10
3
0.5x10
3
0.5x10
K2
-1
(g mg
-1
min )
-3
1.0x10
-4
5.0x10
-4
5.0x10
1200
Co 500um
1000
Fe 500um
Cu 500um
Co 850um
800
Fe 850um
Cu 850um
600
400
200
0
0
Co 500um
Fe 500um
Cu 500um
Co 850um
Fe 850um
Cu 850um
ln t
ln t
972
970
968
966
964
962
960
958
956
954
952
125
(10)
n+
]t / [M
n+
]eq
(11)
qt =Xi + K t
(12)
1
(13)
(14)
126
Table 6. Regression equations and R2 values for the Elovich equation and the intraparticle diffusion equation plots for
the metal ions adsorption on unmodified and modified maize cob of two particle sizes.
Elovich Equation
Metal
ions
Unmodified
Modified
500m
y = -1.4085x + 988.25
2
(R = 0.9282)
850m
Y= 7.1148x +970.87
2
(R = 0.8579)
500 m
Y = 0.1503x + 967.27
2
(R = 0.7458)
850 m
Y = 0.9017x + 965.47
2
(R = 0.8940)
Fe
Y= 3.1499x + 867.41
2
(R = 0.4801)
Y = 9.3608x +831.64
2
(R = 0.9877)
Y= 0.6751x + 952.51
2
(R =0.9522)
Y= 0.5168x +954.15
2
(R = 0.4107)
Cu
Y= 31.195x + 369.47
2
(R =0.9049)
Y = 0.7941x + 955.80
2
(R = 0.9136)
Co
Y =0.00014x + 1.6939
2
(R = 0.9265)
Y = 41.193x + 370.73
Y= 1.0856x + 954.45
2
2
(R = 0.7205)
(R = 0.9001)
Intraparticle diffusion equation
Y = 0.0072x + 1.6862
Y = 0.0002x + 1.6845
2
2
(R = 0.8566)
(R = 0.5123)
Fe
Y = 0.0035x+1.6374
2
(R = 0.4862)
Y= 0.0111x + 1.6199
2
(R = 0.9556)
Y= 0.0008x + 1.6778
2
(R = 0.9551)
Y= 0.0005x + 1.6786
2
(R = 0.4790)
Cu
Y = 0.0635x + 1.2829
2
(R = 0.9127)
Y= 0.0799x + 1.2884
2
(R = 0.7378)
Y= 0.0011x + 1.6789
2
(R = 0.9096)
Y= 0.0008x + 1.6794
2
(R = 0.8471)
Co
Y = 0.0008x + 1.6839
2
(R 0.8376)
Co 500um
Fe 500um
1.686
Fe 500um
Cu 500um
Co 850um
1.685
Cu 500um
1.4
1.2
Cu 850um
1
0.8
0.6
0.4
Co 850um
1.684
Fe 850um
Fe 850um
1.683
log R
log R
Co 500um
1.8
1.6
Cu 850um
1.682
1.681
1.68
0.2
0
1.679
0
0.5
1.5
log t
1.678
0
0.5
1.5
log t
127
Table 7. Kinetic constants for the intraparticle diffusion model of the sorption process.
Metal
ions
Co
Fe
Cu
Unmodified
500m
kid
49.42
43.39
19.18
a
0.0014
0.0035
0.0635
Modified
850m
Kid
48.55
41.59
19.43
500m
a
0.0072
0.00111
0.0799
Kid
48.36
47.62
47.74
a
0.0002
0.0008
0.0011
850m
kid
a
48.30
0.0008
47.71
0.0005
47.80
0.0008