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Department of Inorganic Chemistry, Faculty of Chemistry, Maria Curie-Skodowska University, M. Curie Skodowska Sq. 2, 20-031 Lublin, Poland
Coaltec Energy USA, Inc., United States
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
a r t i c l e
i n f o
Article history:
Received 28 June 2016
Received in revised form 18 August 2016
Accepted 19 August 2016
Available online 20 August 2016
This article is dedicated to Professor
Zbigniew Hubicki on the occasion of his
70th birthday.
Keywords:
Biochar
Active carbon
Pyrolysis
Sorption
Desorption
a b s t r a c t
In the first stage on the effectiveness of various operating factors such as: adsorbent dose, contact time,
solution pH, initial concentration and temperature on the sorption of heavy metal ions of Cu(II), Zn(II), Cd
(II), Co(II) and Pb(II) were carried out using the commercial active carbon Purolite AC 20 and biochar. It
was found that the sorption capacity increases with the increasing phase contact time and concentration
of the initial solution. It was found that biochar removes more efficiently heavy metal ions from aqueous
solutions than the activated carbon. Sorption kinetic data provide a complex mechanism of sorption and
better fit of the pseudo second order model than the pseudo first order and the intraparticle diffusion
ones. In the second stage the desorption of the above mentioned heavy metal ions from the biochar
and commercial activated carbon was conducted. It was proved that biochar has excellent properties
and can be used as a sorbent of multi-use 0.1 M HNO3 was the best eluent for desorption of heavy metal
ions in the sorption/desorption studies in the third stage. In order to characterize the mechanism of
sorption/desorption for both biochar and activated carbon, the Brunauer Emmett Teller surface area
was determined and point of zero charge was measured. Moreover, the elemental analysis and the
Fourier transform infrared spectroscopy were applied. The thermogravimetric and derivative thermogravimetric analyses were conducted.
2016 Elsevier B.V. All rights reserved.
1. Introduction
Heavy metals produced by different branches of industry are
hazardous for health and life of humans and animals [13]. Of
Corresponding author.
E-mail address: d.kolodynska@poczta.umcs.lublin.pl (D. Koodynska).
http://dx.doi.org/10.1016/j.cej.2016.08.088
1385-8947/ 2016 Elsevier B.V. All rights reserved.
various methods used for their removal from waters and wastewaters adsorption proves to be the most effective [4]. For this aim
active carbons and biochars are successfully used.
Activated carbons (AC) are amorphous materials characterized
by expanded surface area, porosity and availability of appropriate
active centers which promotes absorption of gases and organic
compounds. The main feedstock for the preparation of activated
354
carbons is hard coal, due to its low production cost, good ion
exchange properties and ease spent sorbents degradation [5]. The
others include: peat, cellulose, fruit stones, nut shells, sugar cane
etc. [6]. The type of feedstock as well as operating conditions of
carbonization and activation processes affect physicochemical
properties of activated carbons, their selectivity and capacity
[5,7]. They are also widely used in: gas storage [8], catalysis [9],
medicine and environmental protection [10].
Biochar (BC) is a carbon-rich solid product obtained by pyrolysis
or gasification biomass in nitrogen atmosphere in the temperature
range 6231073 K. Properly selected gasification conditions such
as temperature, vapour residence time, heating rate allow to control the properties of the resulting biochar [11,12]. Gasification
allows for the reuse of agricultural solid wastes and wood, as well
as refinery wastes. The thermochemical processes by which biomass can be converted are: slow pyrolysis, fast pyrolysis, flash carbonization, hydrothermal carbonization (HTC), gasification and
torrefaction [1318].
Gasification and hydrothermal carbonization are the two most
efficient technologies to produce biochar. These methods are characterized by high efficiency and a wide range of materials. The HTC
method consumes less energy because it does not require drying of
biomass, such as slow pyrolysis [19]. As the optimal temperature
for the production of biochar, Lehmann [12] indicates 823 K. This
temperature allows to obtain good properties of biochar such as:
cation exchange capacity, carbon content, surface area and porosity. Biochar obtained at low temperatures is characterized by a
low adsorption capacity [20,21].
Suitable properties of biochar are decisive for its applications. In
bioenergetics biochar is used as a renewable fuel [22,23]. The use
of biochar for soil fertilization improves soil fertility by increasing
pH. It is also used for long-term storage of carbon dioxide [24,25].
Biochar obtained from wastes provides a cheaper alternative to
activated carbon and can be used to remove organic contaminants
such as: hormones, dyes, pesticides, herbicids and inorganic impurities such as heavy metal ions from aqueous solutions and
wastewaters [26,27]. There are numerous studies related to the
sorption of heavy metal ions Cu(II), Cd(II), Zn(II), Pb(II), Cr(VI) using
biochar obtained from: switchgrass, hardwood, corn straw etc.
[2830].
In the paper, the studies on sorption/desorption of heavy metals
from the dairy manure-derived biochar (BC) produced by Coaltec
Energy USA, Inc. and commercial active carbon (Purolite AC 20,
denoted also as AC) were carried out. Special attention was paid
to characterization of this new biosorbent (BC) and it was compared to the commercially activated carbon ion exchanger (AC).
Kinetic and adsorption studies of Cu(II), Zn(II), Cd(II), Co(II) and
Pb(II) were optimized and characterized. It is well known that desorption can be carried out using both mineral and organic acids.
Therefore in the second stage desorption studies were performed
and estimated. The washing method was applied using 0.11 M
HNO3, H2SO4 and HCl as eluents.
Table 1
Physicochemical characteristics of biochar and activated carbon.
a
b
Properties
BC
AC
3.95
59.42
15.11
9.8
29.12
0.82
0.82
115.5
58.763
0.074724
9.99
14.90
14.55
6.8
77.10
1.41
0.66
759.9
55.789
0.420963
355
logq1 qt logq1
k1 t
2; 303
t
1
t
qt k2 q22 q2
qt ki t1=2 C
(a)
983
BC
BC-Cu(II)
0.04
Absorbance [a.u.]
985
0.03
2119 2108
0.02
3728
1404
2299
3669
3148 2319
3384
0.01
0.00
4000
3500
3000
2500
2000
1412
1500
1000
500
-1
Wavenumber [cm ]
2.4. Calculations
(b)
0.020
AC
AC-Cu(II)
2110
3851
0.015
Absorbance [a.u.]
2688
3798
0.010
3323
2738
2111
0.005
1418
qt
C0 Ct V
m
%S
C0 Ct
100%
C0
1157
0.000
4000
3500
3000
2500
2000
1500
1172
1000
500
-1
Wavenumber [cm ]
Fig. 2ab. FT-IR spectra of BC (a) and AC (b) before and after the reaction with
200 mg/dm3 Cu(II) for 6 h at pH 5.
356
(b)
(a)
(c)
(d)
Fig. 3ad. SEM images of BC sample at (a) 10,000 and (b) 1000 magnifications and AC sample at (c) 10,000 and (d) 1000 magnifications.
%D
C des
100%
C0
(a)
50
45
The specific surface area is smaller for BC 115.5 m2/g than for
AC 759.8 m2/g. The measured values of surface area, pore size
and pore volume are listed in Table 1. The N2 adsorption/desorption isotherms (Fig. 4ab) of BC resemble the Type IV isotherm
and H3 hysteresis loop according to the IUPAC classification. The
hysteresis loop suggests the presence of mesopores (pores of the
width 20500 ) between the slits of the micropores and the possibility of capillary condensation in the pores [30]. The N2 adsorption/desorption isotherms of AC can resemble the Type I isotherm
with tendency to form a plateau at low relative pressures and predominance of micropores in the sorbent. After filling the micropores N2 adsorption is likely to continue in the mesopores [47,48].
In Fig. 5ab. the pore size distribution of BC and AC obtained from
N2 desorption isotherm curves is presented. The pore distribution
curves are in the range of micropores [49].
Point of zero charge (pHpzc) was determined with a graph of
DpH (pH1pH0) vs. pH0 (Fig. 6ab). For BC pHzpc is equal to 9.8
whereas for AC this value is 6.8. When the pH is less than pHzpc
the surface of the sorbent is positively charged which increases
the electrostatic repulsion between the sorbent surface and heavy
metal ions. Negatively charged surface is formed when the pH is
greater than pHzpc. Then the attraction increases between the sorbent surface and the Cu(II), Zn(II), Cd(II), Co(II) and Pb(II) ions.
Mohan et al. noted that at low pH increases the equilibrium pH
of the solution vs. the initial pH. As a result, it increases the sorption capacity of the sorbent. pH 5 is indicated as the optimum pH
sorption [50]. On the surface of BC and AC negatively charged functional groups are present that attract heavy metal cations.
However, the sorption process of metal ions is very complex. As
follows from the literature data the carboxyl (COOH), hydroxyl
(OH), phenol (ROH) groups are generally accepted as the main
groups contributing to coordination of heavy metal ions such as
Cu(II), Zn(II), Cd(II), Co(II) and Pb(II) etc. on the sorbent surface.
Complexation of metals with these ionized oxygen-containing
functional groups through ion exchange has been suggested as a
major mechanism for metal sorption by biochar. As the hydroxyl
and carboxylic groups on biochars surface became deprotonated
(COO and O) at the wide pH range, the formation of (COO)2M,
COOM+ and (O)2M, OM+ as well as (RO)2M occurs as
presented below:
357
40
35
30
Adsorption
Desorption
25
0.0
0.2
0.4
0.6
0.8
1.0
280
260
(b)
240
220
200
180
160
0.0
Adsorption
Desorption
0.2
0.4
0.6
0.8
1.0
358
(a) 0.0020
(a)
4
pH 1-pH 0
5
0.0015
0.0010
3
2
1
0.0005
0
2
0.0000
0
20
40
60
80
10
12
10
12
pH0
-1
100
(b)
(b)
0.004
0.003
1
pH 1-pH 0
3
Pore volume [cm /g A]
0.002
0
2
-1
6
pH0
-2
0.001
-3
0.000
0
20
40
60
80
100
(a)
0.14
100
TG
DTG
0.12
0.10
0.08
80
0.06
0.04
70
Weight [%]
90
0.02
60
0.00
0
200
400
600
800
1000
Temperature [C]
(b)
0,25
100
TG
DTG
0,20
0,15
90
0,10
85
Weight [%]
95
0,05
80
0,00
0
200
400
600
800
1000
Temperature [C]
(a)
(b)
40
359
40
50 mg/dm
50 mg/dm
3
35
35
100 mg/dm
100 mg/dm
150 mg/dm
30
25
200 mg/dm
25
qt [mg/g]
qt [mg/g]
150 mg/dm
30
200 mg/dm
20
15
20
15
10
10
50
100
150
200
B
250
300
350
400
50
100
150
200
250
300
350
400
Fig. 8ab. Effect of the phase contact time on Cu(II) adsorption on BC (a) and AC (b) for different metal ion concentrations (pH 5, shaking speed 180 rpm, temperature 295 K).
360
Table 2
Kinetic parameters for Cu(II), Zn(II), Cd(II), Co(II) and Pb(II) on BC.
c0
qexp
PFO
PSO
q1
k1
IPD
2
q2
k2
ki
R2
Cu(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
9.98
19.42
22.93
24.95
2.23
10.94
14.59
15.48
0.036
0.009
0.006
0.008
0.898
0.988
0.968
0.983
10.02
19.42
22.37
24.88
0.067
0.004
0.002
0.002
6.638
1.371
1.108
1.408
1.000
0.993
0.975
0.989
0.307
0.818
0.959
1.099
5.893
5.838
5.416
6.190
0.445
0.860
0.911
0.896
Zn(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
9.59
18.57
20.78
23.26
2.50
9.63
5.58
9.95
0.008
0.012
0.006
0.007
0.699
0.940
0.889
0.796
9.51
18.87
20.37
22.73
0.023
0.005
0.009
0.005
2.160
1.575
3.731
2.647
0.998
0.995
0.997
0.994
0.290
0.747
0.583
0.888
5.245
6.737
11.428
8.861
0.495
0.787
0.468
0.730
Cd(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
9.91
19.74
28.30
33.90
3.96
9.45
13.96
19.95
0.033
0.019
0.012
0.013
0.964
0.991
0.983
0.970
9.95
20.08
27.25
34.48
0.032
0.007
0.005
0.002
3.141
2.771
4.134
2.513
1.000
0.999
0.995
0.993
0.335
0.738
1.991
1.450
5.213
8.761
5.617
10.769
0.550
0.692
0.836
0.831
Co(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
7.97
14.16
16.60
20.23
3.40
7.00
6.14
9.07
0.017
0.007
0.008
0.008
0.983
0.948
0.788
0.957
8.00
13.83
16.34
19.96
0.020
0.006
0.007
0.004
1.289
1.125
2.030
1.691
0.999
0.988
0.995
0.988
0.286
0.533
0.539
0.696
3.684
4.983
7.740
8.276
0.654
0.783
0.539
0.696
Pb(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
9.96
19.86
28.67
37.80
10.98
7.31
4.20
3.86
0.015
0.028
0.012
0.014
0.540
0.635
0.569
0.767
9.97
19.84
28.74
37.88
0.811
1.155
1.730
0.027
80.558
455.56
1421.99
38.163
1.000
1.000
1.000
1.000
0.187
0.338
0.511
0.939
7.654
15.728
22.437
25.469
0.170
0.138
0.152
0.308
Table 3
Kinetic parameters for Cu(II), Zn(II), Cd(II), Co(II) and Pb(II) on AC.
c0
qexp
PFO
PSO
IPD
q1
k1
R2
q2
k2
R2
ki
R2
Cu(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
4.62
6.36
8.16
8.47
1.42
2.03
2.03
2.19
0.007
0.014
0.004
0.004
0.766
0.890
0.698
0.632
4.52
6.12
8.08
8.24
0.038
0.069
0.019
0.020
0.809
2.786
1.241
1.436
0.997
1.000
0.994
0.995
0.150
0.198
0.221
0.231
2.269
3.373
4.613
4.680
0.558
0.510
0.436
0.445
Zn(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
4.75
8.48
9.92
12.90
1.04
1.32
2.24
10.41
0.004
0.008
0.012
0.025
0.914
0.655
0.510
0.776
4.63
8.40
9.85
12.69
0.042
0.049
0.040
0.005
0.950
3.504
3.959
0.885
0.996
0.999
0.999
0.986
0.110
0.278
0.302
0.681
2.932
5.373
5.671
2.278
0.326
0.350
0.449
0.804
Cd(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
5.35
10.47
12.37
12.64
1.67
1.96
7.72
7.60
0.006
0.012
0.042
0.033
0.812
0.815
0.888
0.881
5.25
9.55
12.21
13.59
0.132
0.062
0.013
0.003
3.776
6.798
1.962
0.483
1.000
0.994
0.997
0.916
0.110
0.247
0.516
0.629
3.761
6.659
4.733
3.741
0.227
0.304
0.572
0.664
Co(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
4.64
5.47
6.45
6.90
1.84
1.13
1.95
1.69
0.016
0.006
0.021
0.013
0.960
0.867
0.848
0.974
4.66
5.38
6.01
6.91
0.038
0.041
0.262
0.040
0.827
1.231
10.91
1.902
0.999
0.998
0.995
0.999
0.168
0.137
0.415
0.193
2.173
3.335
2.231
4.102
0.638
0.364
0.672
0.429
Pb(II)
50 mg/dm3
100 mg/dm3
150 mg/dm3
200 mg/dm3
8.67
16.38
20.72
29.20
1.53
4.18
4.87
9.17
0.007
0.012
0.011
0.004
0.760
0.622
0.688
0.962
8.58
16.03
20.62
27.40
0.032
0.025
0.013
0.005
2.373
6.616
5.626
3.917
0.999
0.999
0.999
0.984
0.208
0.525
0.570
0.788
5.515
8.746
12.303
14.800
0.322
0.503
0.420
0.474
361
Table 4
Sorption capacities of AC and BC for Cu(II), Zn(II), Cd(II), Pb(II) and Co(II).
Adsorbent
Ion
Parameters
Cd(II)
Zn(II)
Cd(II)
Zn(II)
Pb(II)
8.69 mg/g
10.56 mg/g
9.68 mg/g
0.88 mg/g
22.82 mg/g
4.25 mg/g
2.4 mg/g
pH ranged
pH ranged
pH ranged
pH ranged
n.a.
n.a.
n.a.
n.a.
Pb(II)
Pb(II)
Reference
5.66.1
5.66.1
5.55.9
5.55.9
for
for
for
for
OG-AC
OG-AC
Mg-AC
Mg-AC
[55]
[55]
[55]
[55]
[56]
[56]
[57]
[57]
(b)
100
100
80
80
60
60
G
(a)
40
40
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
20
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
20
0
0
100
200
300
400
500
100
200
300
400
500
Fig. 9ab. Elution of Cu(II), Zn(II), Cd(II), Co(II) and Pb(II) from metal-loaded BC (a) and AC (b) using 0.1 M HNO3.
(b)
100
100
80
80
60
40
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
20
0
0,00
0,25
0,50
0,75
1,00
Concentration [M]
(a)
60
40
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
20
0
0,00
0,25
0,50
0,75
1,00
Concentration [M]
Fig. 10ab. Comparison between Cu(II), Zn(II), Co(II), Cd(II) and Pb(II) elution from metal loaded BC (a) and AC (b) using different concentrations of HNO3.
362
100
(a)
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
80
60
40
20
0
HNO3
H2SO4
HCl
(b) 100
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
80
60
40
20
0
HNO3
H2SO4
HCl
Fig. 11ab. Comparison between Cu(II), Zn(II), Co(II), Cd(II) and Pb(II) elution from
metal-loaded BC (a) and AC (b) using different desorbing agents at a concentrations
of 0.1 M.
100
Cu(II)
Zn(II)
Cd(II)
Co(II)
Pb(II)
80
60
40
20
0
1
Fig. 12. Comparison of between Cu(II), Zn(II), Co(II), Cd(II) and Pb(II) elution from
metal-loaded BC using 0.1 M HNO3 in three sorptiondesorption cycles.
4. Conclusions
1) Biochar (BC) and commercial active carbon (AC) were compared as far as sorption and desorption of Cu(II), Zn(II), Cd
(II), Co(II) and Pb(II) ions from aqueous solutions.
[17]
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[27]
[28]
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[31]
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