Characterization and application of activated carbon produced by

H
3
PO
4
and water vapor activation
T. Budinova
a,

, E. Ekinci
b
, F. Yardim
b
, A. Grimm
c
, E. Bjrnbom
c
, V. Minkova
a
, M. Goranova
a
a
Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str. Bl. 9, 1113 Sofia, Bulgaria
b
Department of Chemical Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey
c
Department of Chemical Engineering and Technology, Division of Chemical Reaction Engineering, The Royal Institute of Technology,
Stockholm, Teknikringen 42, SE-10044 Stockholm, Sweden
Received 24 January 2006; received in revised form 18 May 2006; accepted 20 June 2006
Abstract
Activated carbons have been prepared from woody biomass birch by using various activation procedures: a) treatment with phosphoric acid
and pyrolysis at 600 C in inert atmosphere, b) the same as in (a) followed by steam activation at the same temperature and c) treatment with
phosphoric acid and direct pyrolysis in a stream of water vapor at 700 C. The surface area and the porosity of the activated carbons were strongly
dependent on the treatment after impregnation with H
3
PO
4
(pyrolysis in inert atmosphere, steam pyrolysis or combination of both).
Activated carbon, prepared by impregnation with phosphoric acid followed by steam pyrolysis (steam activation) had highly developed porous
structure and the largest surface area among all prepared carbons (iodine number 1280 mg/g and BET surface area 1360 m
2
/g). The adsorption
capacity of this sample for Hg(II) from aqueous solution was studied in varying treatment conditions: contact time, metal ion concentration and
pH. The adsorption followed Langmuir isotherms and the adsorption capacity for Hg(II) at 293 K was 160 mg/g.
2006 Elsevier B.V. All rights reserved.
Keywords: Activated carbon; Woody biomass birch; H
3
PO
4
activation; Steam activation; Hg adsorption
1. Introduction
Utilization of biomass from forestry and agricultural wastes
as a fuel or a raw material for production of activated carbons is
steadily increasing particularly in countries rich in forest and in
agricultural countries with vastly available biomass by-products
[1]. Numerous studies have been devoted to preparation of low-
cost high quality carbon adsorbents for purification of water and
air, as well as various chemical and natural products. The appli-
cation of high-surface area carbons in gas separation, medicine
and catalysis is also well known. Of particular interest is the
preparation of low-cost activated carbons based on biomass for
purification of water from heavy metals such as Hg, As, Zn, Pb,
and Cd [2].
There are two major activation methods in preparation of
activated carbons: physical and chemical. The physical method
involves two stage processes of pyrolysis (carbonization) of the
raw material in inert atmosphere and activation of the solid
residual product (char) at high temperatures (9001000 C) in
the presence of carbon dioxide or steam. Traditional method of
chemical activation with H
3
PO
4
consists in impregnation of the
raw material with water solution of the acid followed by
pyrolysis in inert atmosphere at temperatures between 350 and
600 C [310]. Important advantages of the chemical activation
compared to the physical activation are lower treatment tempe-
ratures and shorter treatment time. In addition activated carbons,
obtained by chemical activation possess large surface area and
well-developed microporosity, which can be controlled and
maintained in narrow ranges. Preparation of high quality acti-
vated carbons by chemical activation with H
3
PO
4
has been
studied using various low-cost biomass materials, such as co-
conut shell [11], sugar cane wastes [12], Arundo donax cane
[13], nutshells [14], peach stones [15], and apple pulp [16,17].
We have studied agricultural wastes as raw materials for the
preparation of activated carbons for various applications, such
Fuel Processing Technology 87 (2006) 899905
www.elsevier.com/locate/fuproc

Corresponding author. Tel.: +359 2 9606145; fax: +359 2 8700225.

E-mail address: goriva@orgchm.bas.bg (T. Budinova).
0378-3820/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2006.06.005
as adsorbents in liquid and gaseous phases, catalysts and sup-
port for catalysts applying simple one-step process of pyrolysis
in presence of steam. This method, developed in our laboratory
in The Bulgarian Academy of Sciences, is a feasible alternative
to the well established but more expensive two-step process of
consecutive carbonization and high-temperature activation of
the solid product from the carbonization [39].
The aim of the present work is to study the feasibility of the
preparation of high quality activated carbons by using combina-
tion of chemical activation with H
3
PO
4
and physical activation
with steam pyrolysis. The feasibility of using carbon adsorbents
based on woody biomass birch for removal of Hg(II) from
aqueous solutions has also been studied.
2. Experimental
2.1. Raw material
2.1.1. Biomass raw material
Woody biomass birch (BW) with particle size in the range
from 0.5 to 1 mm was used as a raw material for preparation of
activated carbon. The average proximate and elementary
analyses of the initial material are shown in Table 1.
2.2. Preparation of activated carbons
2.2.1. Impregnation with phosphoric acid, H
3
PO
4
The biomass precursor was mixed and kneaded overnight at
room temperature with phosphoric acid solutions with concen-
tration of 20 or 50 wt.% using varying weight ratios of acid
solution:precursor (1, 1.5, and 2).
2.2.2. Treatment after impregnation with phosphoric acid
The impregnated samples were further treated thermoche-
mically to prepare the activated carbons. Stainless steel reactor
with a diameter of 30 mm and a length of 45 mm was used for
the thermochemical treatment, which was performed in three
different ways as follows:
2.2.2.1. Thermal activation by pyrolysis in inert atmosphere.
The impregnated samples were heated with a heating rate of
3 C/min in inert atmosphere of nitrogen to a final heat treat-
ment temperature 600 C and kept at this temperature for a
period of 1 h (samples denotation N600-1).
2.2.2.2. Activation with consecutive pyrolysis in inert atmo-
sphere and in presence of steam. After treatment as in Section
2.2.2.1 the samples were submitted to additional pyrolysis at the
same temperature in a flow of steam (120 ml/min) for 1 h
(samples NS600-1).
2.2.2.3. Activation with steam pyrolysis. The impregnated
samples were directly pyrolized in a flow of steam at 700 C for
2 h (samples S700-2).
After being cooled, all prepared carbons were washed suc-
cessively several times with hot water until the pH became
neutral and finally washed with cold water to remove the ex-
cessive phosphorus compounds. The washed samples were
dried at 110 C to obtain the final products.
2.3. Characterization of the activated carbons
2.3.1. Iodine number
The surface areas of the activated carbons were characterized
by the adsorption capacity towards iodine determined using a
standard method (DIN 53582).
2.3.2. Surface area and porous structure
The surface area and the porous texture of the carbons were
characterized using adsorption of nitrogen at 77.4 K in conven-
tional volumetric equipment. The nitrogen adsorptiondesorp-
tion isotherms were used to determine the following parameters:
specific surface area S
BET
(according to the BETequation), total
pore volume V
tot
(calculated from the nitrogen uptake at relative
pressure of 0.95), total micropore volume V
micro
, according to
simplified equations [1820], total mesopore volume V
mes
(determined by subtracting the micropore volume from the total
pore volume), mean pore radius r
p
(calculated using the total
pore volume and the BET surface area, assuming a cylindrical
pore model), the micropore size distribution parameter X
o
(the
half-width of the distribution curve maximum according to
simplified equations [1820]).
2.3.3. Oxygen-containing functional group
The contents of oxygen-containing functional groups with
varying acidity were determined by the Boehm's method of
titration with basic solutions of different base strengths
(NaHCO
3
, Na
2
CO
3
, NaOH, and C
2
H
5
ONa). For this purpose
the samples were agitated for at least 16 h with 0.05 N solutions
of the four bases. The remaining amount of Na
+
ions in the
solution was determined by adding an excess of standard HCl
solution and back titration of the residual HCl [21,22]. The total
content of the basic functional groups in the samples was deter-
mined with titration of 0.05 N HCl [23].
2.3.4. IR spectroscopy
The carbon samples were analyzed using FTIR spectroscopy
(using Bruker IFS 113V). The samples were mixed with potas-
sium bromide and the mixture was pressed into pellets to be
used in the analysis.
2.4. Mercury adsorption
The adsorption capacities of the activated carbons towards
Hg(II) ion were determined using aqueous solutions of the metal
Table 1
Proximate and ultimate analyses of birch wood used as a raw material in this
work
Proximate analysis (wt.%) Ultimate analysis, maf (wt.%)
Fixed
carbon
Volatiles Ash Moisture Hydrogen Carbon Nitrogen Oxygen
(diff.)
12.0 81.2 0.2 6.6 5.6 48.4 0.2 45.8
900 T. Budinova et al. / Fuel Processing Technology 87 (2006) 899905
ion. The stock solution (1000 mg/l) of Hg(II) was prepared by
dissolving the necessary amount of HgCl
2
in distilled water. The
adsorption capacity was determined by the following procedure:
10 mg of the carbon sample was added to 50 cm
3
of the aqueous
solution of HgCl
2
with varying concentrations from10 to 40 mg/
l. The initial and the equilibrium concentrations of the mercury
in the solution were determined spectrophotometrically (using
Specord UVVIS) with rhodamine [24]. Effect of pH on Hg(II)
removal was studied using Hg(II) concentration of 20 mg l
1
.
3. Results and discussion
3.1. Chemical composition of the activated carbons
The chemical compositions of the activated carbons obtained
in this work by impregnation with 50% H
3
PO
4
, impregnation
ratio (acid solution:biomass sample) R=1.5 and activation by
various pyrolysis treatments are shown in Table 2. As expected all
carbon samples have much higher contents of carbon and ash and
lower contents of oxygen and hydrogen compared to the initial
biomass material. The oxygen content of the sample treated only
by pyrolysis in inert atmosphere is the highest. The residual
phosphorous content in this sample is also the highest.
The samples subjected to steam pyrolysis alone and parti-
cularly in combination with pyrolysis in inert atmosphere have
undergone deeper carbonization. It seems that combination of
chemical and physical activation has accelerated the chemical
changes in the material and facilitated the removal of hydrogen
and oxygen resulting in increased carbon content.
3.2. Oxygen functional groups
The oxygen functional groups are very important character-
istics of the activated carbons because they determine the surface
properties of the carbons and hence their quality as ion exchan-
gers, adsorbents, catalysts, and catalyst supports. The contents of
oxygen-containing functional groups with various acidity
strength: carboxylic (analyzed with titration of NaHCO
3
), carbo-
xylic in lactone-like binding and some phosphorous-containing
acidic groups of intermediate strength (determined with the diffe-
rence between the consumption of NaHCO
3
and NaCO
3
), phe-
nolic hydroxyl groups (determined with the difference between
NaOH and Na
2
CO
3
consumption) and carbonyl groups (deter-
mined with the difference between NaOEt and NaOH consump-
tion) as well as the total amount of the basic groups, determined
with titration of HCl, are presented in Table 3. The content of
carboxylic groups is much higher in the sample pyrolyzed only in
inert atmosphere i.e. obtained by chemical activation. The sample
NS600-1 activated by consecutive pyrolysis in inert atmosphere
and in presence of steam has much lower contents of carboxylic
and lactonic groups and somewhat higher contents of hydroxyl
and carbonyl groups. The contents of lactonic, hydroxyl and car-
bonyl groups in the samples activated either by pyrolysis only in
nitrogen or only in steam are similar.
The content of basic groups is much lower in carbon, ob-
tained by chemical activation (pyrolyzed in nitrogen, sample
N600-1), than in the samples obtained by activation in presence
of steam (NS600-1 and S700-2). The chemically activated
carbon has also the lowest value of pH, 4.5, which is consistent
with the highest content of carboxylic groups in this sample and
the contents of lactones, lactoles and phosphorous-containing
acidic groups. Highest content of basic groups is found in the
sample activated by consecutive pyrolysis in inert atmosphere
and in presence of steam. The pH of the carbon activated by
steam pyrolysis is highest, 6.5, which is also consistent with the
lowest content of carboxylic groups in this sample (under the
detectable limits). The nature of the functional groups detected
on the surface of the carbons prepared in this study suggests that
they are polyfunctional cationites.
3.3. Effect of the H
3
PO
4
concentration on the surface properties
of the activated carbons
The adsorption capacities towards iodine of activated carbons
prepared from biomass impregnated with H
3
PO
4
with two dif-
ferent concentrations (20 and 50%), R=1.5 and various thermo-
chemical activations are shown in Table 4. The concentration of
phosphoric acid has influenced significantly the adsorption
ability of the samples. Increasing the concentration of H
3
PO
4
from 20 to 50% (while maintaining constant ratio of solution
volume to sample mass) resulted in almost 30% increase in the
adsorption capacity.
The carbons activated with steam and particularly those acti-
vated by pyrolysis only in steam had higher adsorption capacities
Table 2
Chemical composition of samples of activated carbons prepared by impregnation
with water solution of H
3
PO
4
with concentration of 50% and impregnation ratio
R 1.5 (acid solution:precursor) followed by pyrolysis in different conditions
Samples Thermochemical
treatment
C H N P O Ash
After impregnation
with H
3
PO
4
(wt.%, maf
a
) (wt.%,
mf
b
)
N600-1 Pyrolysis in nitrogen,
600 C, 1 h
86.33 2.77 0.20 2.20 8.50 5.61
NS600-
1
Consecutive pyrolysis
in nitrogen and steam,
600 C, each 1 h
94.84 1.48 0.20 0.14 3.34 3.36
S700-2 Pyrolysis in steam,
700 C, 2 h
92.43 1.80 0.20 0.07 5.50 3.36
a
maf moisture and ash free.
b
mf moisture free.
Table 3
Amounts of various oxygen-containing functional groups (meq g
1
) of activated
carbons, prepared by impregnation with 50% H
3
PO
4
and impregnation ratio
R=1.5 followed by pyrolysis in different gaseous atmospheres
Samples
a
Acidic surface functional groups Basic
surface
functional
groups
pH
Carboxyl Lactonic Hydroxyl Carbonyl
N600-1 0.744 0.126 0.480 2.234 0.083 4.5
NS600-1 0.124 0.034 0.572 2.530 1.100 5.9
S700-2 BDL
b
0.123 0.422 2.255 0.902 6.5
a
For the conditions under pyrolysis see Table 2.
b
Below detection limit.
901 T. Budinova et al. / Fuel Processing Technology 87 (2006) 899905
than those, activated by pyrolysis only in nitrogen. Thus the ad-
sorption capacity for iodine was increased from 720 mg/g iodine
for the sample impregnated with 20% phosphoric acid and acti-
vated by pyrolysis in nitrogen to almost a double value, 1280mg/g,
by applying higher concentration of phosphoric acid, 50%, and
steam pyrolysis.
3.4. Effect of the impregnation ratio on the surface properties
of the activated carbons
Table 5 shows the dependence of the adsorption capacity of
the activated carbons on the impregnation ratio R (weight ratio
acid solution:initial biomass) at 50% H
3
PO
4
and various ther-
mochemical activation. In the selected experimental conditions
the use of impregnation ratio 1.5 resulted in the highest adsorp-
tion capacities. Lower ratio, 1, which is economically and envi-
ronmentally advantageous, seems also to be less detrimental for
the adsorption capacity of the carbons.
3.5. Surface area and pore structure
Table 6 presents the surface areas and pore structures of
carbon samples prepared in this work. The surface area is
determined both by adsorption with iodine (iodine number) and
by nitrogen adsorption isotherms at 77 K (BET surface area).
The pore structure is characterized with the volumes of the
micro- and mesopores, V
micro
and V
meso
, as well as the total pore
volume, V
tot
, calculated using methods recommended in the
literature [1820]. The half-width for the micropore distribution
curve maximum X
o
and the mean mesopore radius r
p
is also
presented in the table.
The data in Table 6 show the strong effect of the activation
procedure on the surface area and the pore structure of the
carbons. Carbons with high BET surface areas, 1290 and
1360 m
2
/g, are obtained by activation with steam(after pyrolysis
in nitrogen, NS600-1, or only with steam after the impregnation
with phosphoric acid, S700-2). The surface area of the carbon
activated by pyrolyzed only in nitrogen is much smaller
(S
BET
=761 m
2
/g).
Table 6 illustrates also the positive effect of combination of
treatment with phosphoric acid with steam activation on the
formation of carbons with large surface areas and well-deve-
loped porous structures.
It is known that phosphoric acid causes chemical changes in
the precursor facilitating formation of activated carbon at lower
temperatures. H
3
PO
4
has two important functions; it promotes
the pyrolytic decomposition of the initial material and the for-
mation of cross-linked structure. The decomposition is promoted
by the catalytic effect of phosphoric acid on the bond cleavage
reactions. The cross-linking is due to interactions between the
acid and the organic material in the precursor leading to for-
mation of phosphate linkages between the fragments in the
biopolymer [38].
It is also known that water vapor has the ability to penetrate
into solid materials and facilitate distillation, desorption and
efficient removal of volatiles from them [25]. The enhancement
of the removal of volatiles in the steam pyrolysis results in
significant increase of the pore volume, the surface area and the
adsorption capacity of the carbons obtained in presence of steam.
The results in Table 6 show indeed that the carbons prepared
by both impregnation with phosphoric acid and steam activation
(NS600-1 and S700-2) have much larger surface areas and pore
volumes, V
micro
, V
meso
, and V
tot
, compared to the those prepared
by pyrolysis only in nitrogen (N600-1).
Comparison of the iodine numbers and the BETsurface areas
of the carbons in Table 6 suggests that steamactivation promotes
formation of narrower micropores in the carbons. It is known
that there is a correlation between the adsorption capacities
towards iodine and/or the BETsurface areas for adsorbents with
surface areas less than 1000 m
2
/g [26]. Samples with much
larger surface areas and significant amount of narrow micro-
pores may, however, have lower iodine numbers, due to lower
access of iodine in the narrow pores. This may indeed be ob-
served in Table 6. The BETsurface area 761 m
2
/g of the carbon
obtained by pyrolysis in nitrogen (N600-1) has been increased to
1290 m
2
/g by additional pyrolysis in steam (sample NS600-1)
and to almost double surface area (1360 m
2
/g) for the sample
pyrolyzed directly in presence of steam (S700-2). The iodine
Table 5
Influence of the impregnation ratio R (acid solution:initial biomass) on the
adsorption capacity for iodine (mg/g) of carbons obtained by impregnation with
50% H
3
PO
4
and various thermochemical activations
Impregnation
ratio R
Iodine number (mg/g)
N600-1 NS600-1 S700-2
1 860 1080 1100
1.5 916 1200 1280
2 720 950 1006
For details about the thermochemical activation see Table 2.
Table 6
Surface areas and porosity characteristics of activated carbons obtained by
impregnation with 50% H
3
PO
4
, impregnation ratio R=1.5 and different
thermochemical activation
Samples I
2
number
(mg/g)
S
BET
(m
2
/g)
V
micro
(cm
3
/g)
V
meso
(cm
3
/g)
V
tot
(cm
3
/g)
X
o
(nm)
r
p
(nm)
N600-1 900 761 0.297 0.321 0.618 1.16 1.6
NS600-1 1200 1290 0.471 0.468 0.939 0.70 1.5
S700-2 1280 1360 0.485 0.541 1.026 0.64 1.5
Thermochemical activation of the samples is as in Table 2.
Where:
V
micro
and V
meso
are total micro- and mesopore volumes.
V
tot
total pore volume.
X half-width of the micropore distribution curve maximum.
r
p
mean mesopore radius.
Table 4
Iodine numbers of activated carbons prepared by impregnation with different
H
3
PO
4
concentrations and impregnation ratio R=1.5
Samples Thermochemical activation after
impregnation with H
3
PO
4
Iodine number (mg/g)
20% H
3
PO
4
50% H
3
PO
4
N600-1 Pyrolysis in nitrogen 720 916
NS600-1 Consecutive pyrolysis in nitrogen
and steam
940 1200
S700-2 Pyrolysis in steam 1006 128
902 T. Budinova et al. / Fuel Processing Technology 87 (2006) 899905
numbers of the same samples do not show, however, proportio-
nal increase; they change from 900 mg/g for the carbon obtained
by pyrolysis in nitrogen to only 1200 mg/g by additional steam
pyrolysis and to 1280 mg/g for the carbon obtained by only
steam pyrolysis. These results confirm that narrower micropores
have been developed in the samples obtained by steampyrolysis.
The smaller width of these narrow pores makes them accessible
for nitrogen, but not for iodine. Hence increased values of BET
surface area in such carbon samples do not correspond to similar
increase in the iodine numbers.
The micropore volumes of the samples vary from 47 to 50%
of the values of the corresponding total pore volumes determined
at p/ po=0.95 (by Gurvith's rule). The micropore size distri-
bution of the samples activated with steam pyrolysis is similar
(NS600-1 and S700-2). It shows prevailing supermicroporosity;
the half-width for the micropore distribution curve maximum X
o
is 0.64 and 0.70 nm (Table 6).
The enhancement of the formation of micro- and mesopores
and the increase of the pore volume by activation with steam are
favorable for the adsorption properties of the carbons. The
presence of well-developed mesostructure ensures sufficient
access to the micropores too.
3.6. IR spectroscopy
Fig. 1 shows FTIR spectra of carbons, prepared by impreg-
nations with H
3
PO
4
followed by pyrolysis in different gaseous
atmospheres. The band found at 1579 cm
1
in the carbon ob-
tained by pyrolysis in inert atmosphere has been shifted to 1578
in the carbon obtained by consecutive pyrolysis in nitrogen and
steam and to 1566 in the sample obtained with only steam
pyrolysis. This band is assigned to ring vibrations in large
condensed aromatic skeletons, generally found at 1580 cm
1
in
solid carbonaceous systems [27].
A broad band between 1300 and 900 cm
1
with a maximum
at 11161142 cm
1
was observed in all spectra. This band is an
indication for the presence of phosphorous and oxygen com-
pounds in the samples. Adsorption in this region is usually found
in oxidized carbons [28] and carbons activated with phosphoric
acid [29].
The broad bands at 13001000 cm
1
have been assigned to
CO stretching in acids, alcohols, phenols, ethers and esters
[28,29]. Due to overlap of the adsorption bands from various
oxygen and phosphorous compounds in this region, an unam-
biguous assignment is difficult.
The bands in the interval 13001000 cm
1
for carbons, ob-
tained by steampyrolysis or by consecutive pyrolysis in nitrogen
and steam are similar (Fig. 1). It seems that steam activation of
samples impregnated with H
3
PO
4
leads to decomposition of
the phosphoric compounds (see also the content of P in the
carbon samples in Table 2). The absorption at 1300900 cm
1
with the peak at 12201180 cm
1
was tentatively assigned to
the following phosphorous species: hydrogen-bonded P_O
[30,31], OC stretching vibrations in POC of aromatics [30]
and P_OOH [31].
The peak at 1720 cm
1
is usually assigned to C_O stret-
ching vibrations in ketones, aldehydes, lactones and carboxylic
groups. The weak intensity of this peak for carbon, obtained by
consecutive pyrolysis in nitrogen and steam suggests that this
carbon contains small amount of carboxylic groups, which is in
agreement with the data in Table 3 presenting the oxygen
functional groups in the carbons.
3.7. Adsorption of mercury
3.7.1. Effect of contact time and Langmuir isotherm
Fig. 2 shows the effect of contact time on the adsorbed
amount of Hg(II) from solutions with 10, 20, 30, 40 mg/l initial
concentrations of Hg(II). The figure shows that the adsorption
increases sharply at short contact times and slows down with
approaching equilibrium. Most of the metal ions were removed
from the solutions within the first 20 min. At low initial concen-
trations of mercury the equilibrium was obtained in a period of
1020 min; 3040 min contact time seems sufficient for higher
concentrations of metal ions.
The linearized Langmuir sorption model was applied to the
experimental data. The model is frequently used to assess
Fig. 1. IRspectra of activated carbons prepared by impregnation with phosphoric
acid with concentration of 50% and impregnation ratio of 1.5; pyrolysis
treatment: 1 in nitrogen (sample N600-1); 2 in nitrogen and steam
consecutively (NS600-1); 3 with steam (S700-2).
Fig. 2. Effect of the contact time and the initial Hg(II) concentration in the water
on the adsorption of Hg(II) on carbon S700-2; pH 5.0; amount of carbon in the
solution 10 mg/50 ml.
903 T. Budinova et al. / Fuel Processing Technology 87 (2006) 899905
adsorption from dilute solutions. This sorption model was used
to fit the isotherm relationship [32,33]
C
e
=q
e
1=Q
o
b C
e
=Q
o
1
Where: C
e
is the equilibrium concentration (mg/l), q
e
is the
amount of Hg(II) adsorbed at the equilibrium per biomass mass
unit (mg/g), Q
o
and b are characteristic Langmuir parameters.
Q
o
is the maximum adsorption capacity (mg/g); b is the energy
of adsorption.
The linear plot of C
e
/ q
e
versus C
e
shows that the adsorption
obeys the Langmuir isotherm model (Fig. 3).
Q
o
and b values are determined from the slope and the
intercept of the plot. The isotherm is well-fitted (R=0.99967) by
the Langmuir equation. The adsorption capacity of the carbon,
obtained by impregnation with 50% phosphoric acid at R 1.5
and steam activation was 160 mg/g, which is similar or higher
than the adsorption capacity of other carbons: 154 mg/g for
carbon from coir pith [34], 110 mg/g for peanut hull carbon,
124 mg/g for CAC granular activated carbon [35] and some
modifications of furfural carbon adsorbents, 174 mg/g for
carbon obtained from furfural by steam pyrolysis, 154 mg/g for
carbon, obtained by steam pyrolysis of mixture of furfural and
apricot tar and 134 mg/g for carbon obtained from furfural by
activation with air [36].
3.7.2. Effect of pH
The pH of the aqueous solution has strong effect on the
adsorption of metal ions on the carbon surface.
The adsorption depends on the nature of the surface of the
adsorbent and the type of the species in the water solution,
which is in contact with it. It has been observed that activated
carbons of surface functional groups with basic character are
most suitable for mercury(II) adsorption [36]. The type of the
species of Hg(II) in the water solution, depends strongly on the
pH. In presence of chloride ions and in absence of carbon
increasing pH of the solution does not lead to precipitation of
Hg(II) as hydroxide due to the formation of chloride complexes
of Hg(II): HgCl
+
, HgCl
2
, HgCl
3

, and HgCl
4
2
[39]. Thus
the chloride ions decrease efficiently the degree of hydrolysis of
Hg(II) ion by blocking some of the co-ordination positions.
Three uncharged species probably exist in neutral water sys-
tems: HgCl
2
, HgClOH and Hg(OH)
2
. Knocke and Hemphill
have found that in the presence of Cl

the predominant Hg
species at pH>4 is Hg(OH)
2
and at pH<4 it is HgCl
2
[37].
Fig. 4 shows the effect of pH on the adsorption of mercury
(II) on the carbon S700-2, which has neutral character of the
surface (pH 6.5). The mercury(II) adsorption increases sharply
between pH 2 and 5.5 of the solution, attains a maximum
value at approximately pH 6 and is almost constant at higher
pH values.
The influence of pH on the Hg(II) adsorption may be
explained as follows: at low pH both the adsorbent and the
adsorbate are positively charged resulting in electrostatic repul-
sion between them. Besides, the H
+
ions, which are available in
high concentrations at lower pH of the solution, compete with
the positively charged Hg(II) ions for the adsorption sites, thus
also hampering the adsorption of Hg(II).
The mercury adsorption may include formation of surface
complexes with the participation of the functional groups on the
surface of carbon. Hg(OH)
2
species may be retained in the pores
of the adsorbent by chemisorption involving formation of sur-
face complexes. The latter may be formed also by ion exchange
between H
+
and Hg(II) ions from the solution. The following
complexes may be obtained:
C
x
OH
2
Hg
2
C
x
OHg
2
2H

2
2C
x
OH

Hg
2
C
x
O
2
Hg
2
2H

3
4. Conclusions
Combination of chemical and physical activation seems to be
promising for preparation of carbon adsorbents for water puri-
fication. Activated carbons prepared by impregnation of woody
biomass birch with phosphoric acid followed by pyrolysis in
different gaseous atmospheres (nitrogen, consecutively nitrogen
and steam and only steam) have been compared. The properties
Fig. 3. Langmuir plot for adsorption of Hg(II) on carbon sample S700-2,
obtained by impregnation of woody biomass birch with 50% phosphoric acid at
R=1.5 and pyrolysis in presence of steam; Hg(II) concentration: 1040 mg l
1
;
contact time, 1 h; carbon amount 10 mg/50 ml.
Fig. 4. Effect of pH on Hg(II) removal by carbon S700-2 at contact time 1 h;
carbon concentration, 10 mg/50 ml; Hg(II) concentration, 20 mg/l.
904 T. Budinova et al. / Fuel Processing Technology 87 (2006) 899905
of the activated carbons were strongly dependent on the condi-
tions for preparations, concentration of phosphoric acid solu-
tions, impregnation ratio and the gaseous atmosphere in the
pyrolysis. The largest surface area, 1360 m
2
/g, and well-deve-
loped porous structure in the carbon were achieved by applying
steam pyrolysis to the impregnated precursor. The pore volume
was increased from 0.618 cm
3
/g to 1.026 cm
3
/g by replacing
nitrogen atmosphere with steamin the pyrolysis. The presence of
steam contributed also to efficient decrease of the content of
phosphor in the product (from 2.2 to less than 0.2 wt.%) and
good adsorption properties for removal of Hg(II) from aqueous
solution; the adsorption capacity was 160 mg/g.
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