Chemical Engineering Journal 231 (2013) 190–197

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Kraft mill lignin – A potential source of bio-adsorbents for gold recovery

from acidic chloride solution
Birendra Babu Adhikari a, Manju Gurung a, Shafiq Alam a,⇑, Balázs Tolnai b, Katsutoshi Inoue c
a
Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. John’s, NL A1B 3X5, Canada
b
Kruger Inc., 3285 Bedford Road, Montreal, Quebec H3S 1G5, Canada
c
Department of Chemistry and Applied Chemistry, Saga University, Honjo-1, Saga 840-8502, Japan

h i g h l i g h t s

 We developed environmentally benign and low cost adsorbent from kraft mill lignin.
 Specific gold selectivity and high gold uptake capacity of the adsorbent.
 Reduction of adsorbed Au(III) to elemental Au and formation of gold aggregates.
 Promising candidate for selective recovery of gold from base metals in aqueous environment.

a r t i c l e i n f o a b s t r a c t

Article history: The potentiality of lignin, obtained as a byproduct of kraft mill industry, for adsorptive preconcentration
Received 10 April 2013 and separation of Au(III) from acidic chloride media was investigated. Quantitative adsorption of Au(III)
Received in revised form 7 July 2013 from hydrochloric acid medium was achieved using crude lignin while no base metals were adsorbed on
Accepted 8 July 2013
it. Adsorption of Au(III) on lignin followed typical Langmuir monolayer adsorption and the maximum
Available online 16 July 2013
Au(III) uptake capacity of the material was found to be approximately 6.0 mol kg1 at 313 K. Increasing
temperature appeared to improve the amount of gold adsorbed in addition to enhancing the sorption
Keywords:
kinetics. The computed thermodynamic parameters demonstrated that the adsorption was a spontane-
Kraft mill lignin
Bio-adsorbent
ous process and was favorably governed by an endothermic reaction. A pseudo-first-order kinetic model
Gold explained the results of kinetic studies conducted at various temperatures and also allowed the estima-
Adsorption tion of activation energy of the adsorption reaction. The obtained value of activation energy indicated
Reduction that the sorption of Au(III) on lignin was a chemisorption process. The adsorbed Au(III) species was sub-
sequently reduced to metallic gold by the reducing functional groups present in the lignin matrix.
Because of its considerable gold uptake capacity and resultant formation of elemental gold aggregates,
kraft mill lignin is a promising candidate for gold recovery from acidic chloride media.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
Gold has been the foundation of monetary systems for thou-
sands of years. This precious metal has reputation of being used
by almost every society to symbolize power, beauty, purity and
accomplishment [1]. Besides being used as a financial backing as
currency, gold is most significantly used in jewelries. With techno-
logical advancement, gold has witnessed extensive use in electric
and electronic devices due to certain specific properties such as
high chemical stability and high conductivity of this highly valued
metal [2]. In recent years, the increasing consumption of gold for
high-tech industries has seen unprecedented growth; a trend that
is likely to continue [1]. Because of its increasing demand along
⇑ Corresponding author. Tel.: +1 709 864 2331; fax: +1 709 864 4042.
E-mail address: alam@mun.ca (S. Alam).
with the decreasing amount of natural gold resources, the price
of gold in the market has increased constantly [3]. Accordingly,
recovery and recycling of gold from various secondary sources
has received a considerable amount of interest, thereby making
such technology imperative for those concerned with the develop-
ment of sustainable societies.
In the last decade, there has been an increasing focus towards
hydrometallurgical processes for the recovery of valuable metals
from their secondary sources [4,5]. Some of the methods reported
in literature for the recovery of precious metals from aqueous solu-
tions include solvent extraction [6], ion exchange [7], chemical
precipitation [8], etc. These recovery processes are, however,
uneconomical and also energy and time consuming. Furthermore,
these processes generate huge amount of secondary waste from
the use of a large amount of chemical reagents, and treatment of
the resulting secondary waste or sludge becomes essential which

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.07.016
 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197
pose additional issues that must addressed. It is therefore very
important to develop cost-effective and environmentally benign
method for the recovery of gold from aqueous solutions. Tech-
niques which rely on adsorption, due to its high efficiency in a wide
range of metal ion concentration coupled with easy and sludge free
operation leading to easier recovery of the analyte, have shown to
be one of the most effective methods to recover metal values from
aqueous environments [9,10].
The leaching of metal values from various sources into aqueous
solution using suitable solvents and reagent is the first and essen-
tial step of wet processing of metals. In recent years, hydrochloric
acid containing chlorine gas (Cl2/HCl) has gained popularity for the
leaching of precious metals from secondary sources [11]. In this
leaching method, the leach liquor typically contains chloride and
chloro-complexes of several metals, which includes base metals
and precious metals [12]. The presence of a wide variety of metallic
species in many cases impedes the selective recovery of the target
metal(s). Consequently, selective separation of precious metals
from base metals is a strategic challenge [12]. Thus, there is an
increasing interest to develop efficient materials that ensure selec-
tive recovery of precious metals from such liquor. From the techni-
cal, economical and environmental points of view, much of the
current attention has been focused on adsorbents prepared from
various agricultural or industrial biomass wastes as they are cheap,
environmentally benign, biodegradable and renewable [13].
Lignin, a natural polymer derived from plant materials, is one of
the widely generated industrial biomass wastes. During the kraft
pulping process, lignin is separated from the cellulose fibers. The
cellulose is used for paper making, and the lignin and hemicellulose
that is dissolved in the pulping stage (known as ‘‘black liquor’’) is
sent to a recovery system. In the past years, several technologies
have been developed for the separation of lignin from black liquor,
and today commercial quantities are available. Lignin has an aro-
matic three-dimensional complex structure containing a number
of functional groups such as methoxy, hydroxyl, carboxyl, and alde-
hyde groups [14,15]. These properties of lignin reveal that it has a
potential to be used as a possible adsorption material in the re-
moval of heavy metals from wastewater. In fact, lignin has been
used for the removal of heavy metal ions from aqueous effluents
[16–21]. Previously, the lignin isolated from wood was condensed
with phenol to make lignophenol which displayed great potential
for the effective recovery of Au(III), Pd(II) and Pt(IV) from hydro-
chloric acid medium [22,23]. It was realized that utilization of this
industrial byproduct for adsorptive recovery of precious metals,
such as gold, would not only serve as a useful approach for prospec-
tive recovery of this valuable metal but also provide an economical
and environment friendly means for converting the byproducts of
pulping industries to sorption active materials. Consequently, the
current work concerns evaluating the adsorption behavior of kraft
mill lignin towards Au(III) from hydrochloric acid medium.
2. Experimental
2.1. Chemicals and instrumentation
Reagent grade chloride solutions of Au(III) (Ricca Chemical
Company) and Pt(IV) (Fischer Scientific) were used to prepare the
working solutions. Reagent grade chloride salts of other metals
used in this work were purchased from either Fischer Scientific
or Sigma Aldrich and were used in as received condition. Metal
concentration of the test samples was analyzed using a Perkin El-
mer Optima 5300 DV inductively coupled plasma optical emission
spectrophotometer (ICP-OES). The X-ray diffraction (XRD) spec-
trum of the Au(III) loaded lignin was recorded with Rigaku Ulti-
ma-IV XRD spectrophotometer in the Bragg-Brentano mode
setting.
191
2.2. Adsorption material
The lignin used throughout the study was kindly provided by an
eastern Canadian Kraft mill. According to the information pro-
vided, lignin in the Kraft process is obtained as follows. The lignin
in the wood chip is dissolved in a pressurized continuous digester
using a cooking liquor and heat. The cooking liquor, also called
white liquor, is a mixture of caustic soda, sodium sulphite and so-
dium carbonate. The dissolved lignin combined with the hemicel-
lulose and the unreacted chemical generates a solution called black
liquor. Lignin is then removed from the concentrated black liquor
using a precipitation process followed by a washing stage. In the
precipitator, the black liquor is mixed with carbon dioxide in a pipe
reactor where the pH is lowered to between 9 and 10, at which the
lignin precipitates. Subsequent washing removes the remaining
black liquor from the cake and converts the Na-lignin to H-lignin.
The washed and membrane pressed lignin is air-blown to further
increase its dryness. The average particle size of thus obtained lig-
nin is between 1 and 2 lm. It has nearly 96% lignin, 1.5% sugar,
>0.2% ash and nearly 1% S content. Elemental composition: C:
66.4%, H: 6.34%, N: <0.1%. The BET surface area of the provided
material was 1.17 m2 g1. Total pore volume was 1.11  102 cm3 -
g1 and mean pore diameter was 41.498 nm.
2.3. Adsorption experiments
The adsorption experiments performed as a means of evaluat-
ing the sorption behavior of lignin towards various metal ions were
carried out according to the conventional batch method. In a typi-
cal set, 15 mL test solution containing 0.2 mM (M = mol dm3) of
each metal ions were added to 0.02 g lignin in a 30 mL vial, and
the resultant heterogeneous mixtures were shaken at 200 rpm
speed in an air bath shaker for 24 h at 303 K. The samples were
subsequently filtered using whatman no. 40 filter and the concen-
tration of metal ions was determined by ICP-OES. From the mea-
sured initial and equilibrium concentration of the metal ions, the
percentage adsorption of various metals (% A) was evaluated using
the relation,
Ci  Ce
%A ¼  100 ð1Þ
Ci
where Ci and Ce are the initial and equilibrium concentrations of
metal ions in aqueous solution, respectively.
In an experiment to determine the effective adsorbent dose for
quantitative adsorption of Au(III), the experiments were conducted
using 10 mL of 0.2 mM Au(III) solution in 0.1 M HCl and the
amount of lignin added varied from 0.004 g to 0.025 g. The heter-
ogeneous mixtures were shaken at 200 rpm speed in an air bath
shaker for 24 h at 303 K. The samples were then filtered and the
residual concentration of Au(III) ions in the filtrate was determined
by ICP-OES.
The adsorption isotherm experiments were also carried out by
conventional batch method. For these series of experiments,
0.02 g lignin was mixed with 15 mL test solution in which the ini-
tial Au(III) concentration varied from 0.5 mM to 12.5 mM. The
experiments were conducted at four different temperatures rang-
ing from 298 to 313 K. At each temperature studied, the samples
were shaken at 200 rpm speed for 96 hours in an air bath shaker.
After equilibration, the samples were filtered and the Au(III) con-
centration of the initial and equilibrium samples were measured.
From the measured initial and equilibrium concentration, the
amount of Au(III) adsorbed on lignin (q, mmol g1) was calculated
from the equation,
Ci  Ce
q¼ V ð2Þ
W
192 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197

where W (g) and V (L) are the weight of the adsorbent and volume 100
of test solution, respectively. (a)
Adsorption kinetics experiments were carried out by shaking
the heterogeneous mixture of 0.2 g lignin with 150 mL test solu- 80
tion at three different temperatures ranging from 293 to 313 K.

% Adsorption
The experiments were conducted in a 300 mL Erlenmeyer flask
60
and the temperature was maintained either by using water bath
or by using air bath shaker. Definite volumes (10 mL) of the mix-
ture were sampled at different time intervals for the analysis of 40
residual metal concentration in the solution. From the measured
initial concentration and at time, t, the amount of metal adsorbed,
qt, was calculated by using the equation, 20

Ci  Ct
qt ¼ V ð3Þ
W 0
0 1 2 3 4 5 6
where Ci and Ct are the initial and remaining metal concentrations
3
at any time t, respectively. [HCl] (mol/dm )

100
3. Results and discussion
(b) Au(III)

3.1. Adsorption behavior of lignin towards various metal ions Pd(II)

80

First, a preliminary investigation pertaining to the adsorption Pt(IV)

behavior of lignin towards Au(III) was carried out by conducting
% Adsorption 60 Fe(III)
the adsorption test for single species of Au(III) on lignin at different
concentrations of the HCl medium and the results are shown in Co(II)
Fig. 1(a). Under the experimental conditions, quantitative adsorp-
tion of Au(III) on lignin was observed at lower HCl concentrations, 40 Ni(II)
which appeared to decrease gradually with increasing HCl concen-
tration and the percentage adsorption was reduced to 56% in 6.0 M Cu(II)

HCl. It is well documented that Au(III) exists as chloroanionic spe- 20

 Zn(II)
cies, AuCl4 , in the acid concentration region currently under inves-
tigation [9]. It is also a common phenomenon that the ether
functional groups are protonated in hydrochloric acid medium
leading to the formation of oxonium salt. As lignin is composed
of a number of ether linkages [14,15], the surface of the adsorbent
becomes positively charged due to protonation at ether groups of
the lignin matrix. Consequently, it is believed that adsorption of
Au(III) on lignin in hydrochloric acid medium takes place due to
anion exchange of chloride ion with chloroaurate anion followed
by electrostatic interaction of the anionic species of Au(III) with
oxonium centre of the adsorbent. The gradual drop in adsorption
ability of the material with increasing concentration of hydrochlo-
ric acid is therefore attributed to the competitive sorption of chlo-
ride ions with the chloroaurate anion. Nevertheless, these results
suggested the adequacy of lignin for adsorptive separation of
Au(III) from hydrochloric acid medium.
To test the selectivity of lignin towards the adsorption of Au(III)
from the mixture of some precious and base metal ions, trials were
carried out at different concentration of HCl medium, as presented
in Fig. 1(b). The results clearly illustrate that only the Au(III) was
selectively adsorbed on lignin for a wide range of HCl media.
Although the effect of increasing HCl concentration appeared to
be non-advantageous for Au(III) adsorption and the adsorbent dis-
played moderate adsorption efficiency in higher concentration re-
gion of HCl, the results are encouraging in terms of selective
adsorption of Au(III) from the multicomponent mixture. Given that
selectivity towards the target metal is one of the most important
factor to be considered in separation chemistry, lignin holds tre-
mendous promise for highly selective adsorptive separation of
Au(III) from acidic chloride media.
As previously stated, the adsorption of Au(III) on lignin is in-
ferred to be brought about primarily through ionic interaction-
the interaction between the positively charged centers of lignin
and negatively charged species of Au(III). Since the majority of base
metals exist as cationic species in the HCl media, the adsorbent
Pb(II)
0
0 1 2 3 4 5 6
[HCl] (mol/dm 3 )
Fig. 1. Effect of HCl concentration on percentage adsorption of: (a) Au(III) only and
(b) different metal ions on lignin. Weight of lignin = 0.02 g, volume of test
solution = 15 mL, concentration of metal ions = 0.2 mM each, shaking time = 24 h
at 303 K, shaking speed = 200 rpm.
exhibited little or no tendency to adsorb the base metals. Although
6 2
Pt(IV) and Pd(II) also exist as PtCl2 and PdCl4 species in hydro-
chloric acid media, these ions were not apparently adsorbed on lig-
nin thereby inferring the occurrence of a peculiar phenomenon for
the highly selective adsorption of Au(III) on lignin. This will be de-
scribed in later sections.
3.2. Effect of adsorbent dose on adsorption of Au(III) on lignin
Fig. 2 shows the effect of adsorbent dose on the adsorption of
Au(III) on lignin. As evident from this figure, the amount of Au(III)
remaining in solution decreases sharply with the addition of lignin
and approaches to zero when the S/L ratio- the ratio of weight of
lignin to the volume to test solution approached 0.8 g/L. Hence,
even a small amount of lignin is effective for preconcentration of
Au(III) from large volumes of solution.
3.3. Maximum Au(III) loading capacity of lignin and adsorption
isotherm
The maximum Au(III) loading capacity of lignin at different
temperatures was determined by adsorption isotherm tests and
the results are presented in Fig. 3. As evident from Fig. 3, the
amount of Au(III) adsorbed on lignin increased with increasing
 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197 193

40 where Ce is equilibrium concentration of metal ion remained in the

solution after adsorption, qe is the amount of metal ion adsorbed per
unit weight of the adsorbent (mmol g1), qm is the maximum
Au(III) remains in solution (ppm)

amount of metal ion adsorbed on the adsorbent (mmol g1) and b

30 is the Langmuir constant related to the energy of adsorption
(L mol1).
Fig. 4(a) shows the Langmuir plots obtained after treating the
equilibrium adsorption isotherm data according to the Eq. (4) for
20
adsorption of Au(III) on lignin at different temperatures. The vari-
ous parameters calculated from the equations of the straight lines
derived from the Langmuir isotherm plots are summarized in Ta-
ble 1. Evaluation of the data presented in Table 1 indicates that
10
the maximum Au(III) adsorption capacities of lignin obtained from
the Langmuir equation at different temperature are very close to
the experimental data obtained from the plateau region of Fig. 3.
0 In all cases, high regression coefficient values of >0.97 were ob-
0 0.5 1 1.5 2 2.5 tained, suggesting the adequate fitting of the experimental data
S/L ratio (g/L) for the Langmuir isotherms. The increasing value of the Langmuir
equilibrium constant (b) with increasing temperature reflects that
Fig. 2. Effect of adsorbent dose on adsorption of Au(III) with lignin. Initial the rise in temperature enhances the binding of Au(III) ions with
concentration of Au(III) = 0.2 mM, concentration of HCl medium = 0.1 M, shaking lignin.
speed = 200 rpm, shaking temperature = 303 K.
The Freundlich adsorption isotherm is commonly used to de-
scribe the adsorption characteristics for the heterogeneous surface
Au(III) concentration of the test solution and approached a con- according to the equation,
stant value at all temperatures studied, which is the maximum qe ¼ K F C 1=n
e , which on linearization gives,

Au(III) loading capacity of the adsorbent at a particular tempera-

ture. The amount of gold adsorbed on the adsorbent increased with
increasing temperature whereby the maximum Au(III) uptake 2.5
capacity of the lignin increased from around 2.9 mol kg1 at 298 K (a)
298 K–6.0 mol kg1 at 313 K indicating that increasing the temper- 303 K
ature above the ambient temperature was beneficial for adsorption 2
of Au(III) on lignin. 308 K
The equilibrium adsorption isotherm data were then treated 313 K
Ce /q (g/dm 3 )

according to well known Langmuir, Freundlich and Temkin iso- 1.5

therm models [24–26].
The Langmuir isotherm model describes quantitatively the for-
mation of a monolayer adsorbate on the surface of the adsorbent, 1
and it represents the equilibrium distribution of metal ions be-
tween the solid and liquid phases according to the equation,
qm bC e
qe ¼ 1þbC e
,which can be transformed to the linear form, 0.5

Ce 1 1
¼ Ce þ ð4Þ
qe qm b:qm
0
0 1 2 3 4 5 6
7 Ce (mmol/dm 3 )

6 1

298 K (b)
5 0.75
303 K
q (mmol/g)

log q e (mmol/g)

4
308 K
0.5
313 K
3
0.25
298 K
2
303 K 0
308 K
1
313 K -0.25

0
0 1 2 3 4 5 6 -0.5
C e (mmol/dm 3 ) -3 -2 -1 0 1
log Ce (mmol/dm3)
Fig. 3. Experimental plots for adsorption isotherm of Au(III) on lignin at different
temperatures. Weight of lignin = 0.02 g, volume of test solution = 15 mL, concen- Fig. 4. Equilibrium adsorption isotherm data treated according to: (a) Langmuir
tration of HCl medium = 0.1 M, shaking time = 96 h, shaking speed = 200 rpm. (Eq. (4)) and (b) Freundlich (Eq. (5)) equations.
194 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197

Table 1 computations related to the thermodynamic parameters for the

Langmuir equation and various parameters obtained from isotherm plots for sorption of Au(III) on lignin were based on the parameters obtained
adsorption of Au(III) on lignin at different temperatures.
from Langmuir isotherm model.
Temp. Langmuir equation qmax qmax b R2
(K) observed calculated (L mol1)
(mmol g1) (mmol g1) 3.4. Thermodynamics of Au(III) adsorption
298 y = 0.3331x + 0.1543 2.89 3.00 2.158 0.986
303 y = 0.2821x + 0.1121 3.41 3.54 2.516 0.973 The increase in qmax and b with increase in temperature indi-
308 y = 0.2075x + 0.0542 4.73 4.81 3.828 0.990
cates that Au(III) adsorption on lignin becomes increasingly
313 y = 0.1678x + 0.0384 5.91 5.95 4.369 0.981
favorable when the temperature increases from 298 to 313 K,
which also reflects the endothermic nature of the adsorption
process. Thermodynamic consideration of an adsorption process
1 is necessary to conclude whether the process is spontaneous or
log qe ¼ log K F þ log C e ð5Þ
n not. In order to quantitatively assess the thermodynamic
parameters associated with Au(III) adsorption on lignin, the cal-
where KF is the Freundlich isotherm constant (mmol/g), 1/n is a
culated values of the Langmuir equilibrium constant (b) at dif-
function of the strength of adsorption, Ce is the equilibrium concen-
ferent temperatures were treated according to the Van’t Hoff
tration of adsorbate (mmol) and qe is the amount of metal adsorbed
equation,
per gram of the adsorbent at equilibrium (mmol/g).
Fig. 4(b) shows the Freundlich plots obtained after retreating
the adsorption isotherm data according to the Freundlich Eq. (5) DG 0 DH 0 DS0
ln b ¼  ¼ þ ð7Þ
for adsorption of Au(III) on lignin at different temperatures. The RT RT R
adsorption intensity (1/n) and the Freundlich constant KF of the
adsorption process were accessed from the slope and the intercept where DG0, DH0 and DS0 are the standard free energy, enthalpy, and
of the Freundlich equations, respectively. The various parameters entropy changes associated with the adsorption process, respec-
obtained from Freundlich isotherm plots are presented in Table 2. tively, T, b and R are the temperature (Kelvin), Langmuir adsorption
Since KF is an approximate indicator of adsorption capacity [24], constant, and universal gas constant ( = 8.314 J mol1 K1),
these values obtained from Freundlich curve fitting are much low- respectively.
er than the experimental adsorption capacities for adsorption of According to Eq. (7), the plot of ln b against the inverse of tem-
Au(III) on lignin. Hence, Freundlich isotherm was not fitted well perature (1/T) yields a straight line with slope and intercept equal
with our experimental data. However, as the value of 1/n lower to – DH0/R and DS0/R, respectively. Fig. 5 shows the Van’t Hoff plot
than 1 represents the normal adsorption [24], it indicates that for the adsorption of Au(III) on lignin. The values of Gibbs free en-
the sorption of Au(III) on lignin at all temperatures studied is a nor- ergy (DG) at different temperatures were directly obtained from
mal sorption phenomenon. the relationship shown in Eq. (7). The values of DH0 and DS0 were
The Temkin isotherm model, which assumes that heat of calculated from the equation of straight line in Fig. 5 and are pre-
adsorption of all molecules in the layer would decrease linearly sented in Table 3. The positive value of enthalpy change (DH0) indi-
rather than logarithmic with coverage, is characterized by a uni- cates the endothermic nature of Au(III) adsorption on lignin
form distribution of binding energies [24] and is given by the matrix. While cation desolvation in the adsorption process in-
equation, creases the randomness of the system, adsorption of Au(III) species
on the adsorbent, on the other hand, decreases the randomness of
RT the system. The positive entropy change of this adsorption phe-
qe ¼ ln ðAT C e Þ; which on linearization becomes;
b nomenon is the indication of increase of randomness of the system
and contributes for spontaneity of the process. The free energy
RT RT changes during the adsorption process are all negative values
qe ¼ ln AT þ ln C e ð6Þ
b b and become more negative with increasing temperature, which
where AT is Temkin isotherm equilibrium binding constant (L/g), b
is Temkin isotherm constant, R is universal gas constant (8.314 J/
1.75
mol/K) and T is temperature.
The constants b and AT can be computed from the slope and
y = -4.7312x + 16.619
intercept of the equation of Temkin plots. However, the attempted R² = 0.9545
1.5
curve fitting of the equilibrium isotherm data with Temkin model
did not give satisfactory results (data not shown) indicating that
the experimental data did not fit well with this model. Hence, esti-
mation of isotherm parameters from this model was not carried 1.25
ln b

out.
From curve fitting, it has been found that Langmuir isotherm
model is best fitted with our experimental data. Hence, further 1

Table 2
0.75
Freundlich equation and various parameters obtained from isotherm plots for
adsorption of Au(III) on lignin at different temperatures.

Temp. (K) Freundlich equation 1/n KF (mmol g1) R2

0.5
298 y = 0.2941x + 0.2412 0.294 1.74 0.972 3.15 3.2 3.25 3.3 3.35 3.4
303 y = 0.3374x + 0.3107 0.337 2.04 0.990
308 y = 0.3683x + 0.4842 0.368 3.05 0.977
1/T×1000 (K -1)
313 y = 0.3337x + 0.5936 0.333 3.92 0.989
Fig. 5. Van’t Hoff plot for the adsorption of Au(III) on lignin.
 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197 195

Table 3 Table 4
Thermodynamic parameters for the adsorption of Au(III) on lignin. Adsorption rate constant and correlation coefficient from the pseudo-first-order
kinetic model at different temperatures.
Temp. (K) ln b DG (kJ mol1) DH0 (kJ mol1) DS0 (J mol1 K1)
Temp. (K) Rate constant (k1) (h1) R2
298 0.769 1.906
303 0.923 2.325 +39.34 +138.20 293 0.062 0.977
308 1.342 3.438 303 0.148 0.982
313 1.474 3.838 313 0.550 0.959

suggest that the adsorption process is spontaneous and becomes
thermodynamically more favorable at higher temperature.
3.5. Kinetics of Au(III) adsorption
The results obtained for adsorption of Au(III) on lignin as a func-
tion of time at different temperatures are presented in Fig. 6(a).
These results indicate that increasing temperature has a beneficial
effect on sorption kinetics. For every 10° rise in temperature from
293 to 303 to 313 K, there is a significant improvement on the rate
of adsorption. The process of adsorption was so sluggish at 293 K
that quantitative adsorption under our experimental conditions
was not achieved until 24 h. On increasing the temperature of
the system, equilibrium was attained with quantitative adsorption
0.4
(a)
0.3
qt (mmol/g)
within 6 h at 313 K whereas it took 20 h for the adsorption process
to come to the equilibrium with quantitative adsorption at 303 K.
The results of Au(III) adsorption on lignin as a function of time
for three different temperatures were analyzed in terms of pseudo-
first order kinetics model according to the equation,
k1
logðqe  qt Þ ¼ log qe  t ð8Þ
2:303
On rearranging,
 
q
ln 1  t ¼ k1 t ð8:1Þ
qe
where qe and qt are the amount of adsorbed metal (mol kg1) at
equilibrium and at time, t, respectively, k1 (h1) is the pseudo-
first-order rate constant and t is the shaking time (h).
Based on the Eq. (8.1), the rate constants (k1) can be determined
experimentally by plotting ln (1  (qt/qe)) vs t as shown in Fig. 6(b).
The plots corresponding to three different temperatures emerge
from the origin and are lying on proportional straight lines with
a correlation coefficient greater than 0.94. The rate constants at
293, 303 and 313 K were then evaluated from the slopes of equa-
tions of respective straight lines. The values of rate constants along
with their corresponding correlation coefficients are presented in

Table 4. From these values, it is apparent that there was nearly

0.2 2.5-fold increase in the reaction rate for a 10° rise in temperature
from 293 K to 303 K, and nearly 4-fold increase in the rate of
adsorption of Au(III) on lignin for an additional 10° rise in temper-
ature from 303 to 313 K.
0.1 293 K

303 K
3.6. Energy of activation for adsorption of Au(III)
313 K
0 The magnitude of the activation energy (Ea) can aid in under-
0 5 10 15 20 25 standing and predicting whether the adsorption process is physical
Time (h) or chemical. From the relationship between the rate constant and

0
0
(b)
-0.5
-0.5 y = -9.9856x + 31.217
R² = 0.9817
-1 E a = 83.02 kJ mol -1
-1
ln (1-q t /q e)

A = 3.6×10 13
-1.5 -1.5
ln k

-2 -2
293 K

303 K -2.5
-2.5
313 K
-3
-3
0 5 10 15 20 25 30
-3.5
Time (h) 3.1 3.2 3.3 3.4 3.5

Fig. 6. Effect of shaking time on the amount of Au(III) adsorbed on lignin at

1/T ×1000 (K -1 )
different temperatures: (a) experimental plots and (b) pseudo-first-order plot.
Initial concentration of Au(III) = 0.5 mM, concentration of HCl medium = 0.1 M, Fig. 7. Arrhenius plot for the pseudo-first-order rate constants of Au(III) adsorbed
shaking speed = 200 rpm. on lignin at different temperatures.
196 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197

reactions. The significantly high value of Ea and variation of reac-

(a) tion rate with temperature in the present case suggests that the
adsorption of Au(III) on lignin is an activated chemisorption pro-
cess in which the activation energy usually varies between 8.4
and 83.7 kJ mol1 [27]. Chemical adsorption of Au(III) has also been
reported with other biomass materials such as lysine modified
crosslinked chitosan [28].

3.7. Adsorption followed by reduction of Au(III) to elemental gold

It is worth mentioning that the Au(III) species adsorbed on lig-

Gold flakes
nin were simultaneously reduced to elemental gold and aggregates
of metallic gold were clearly visible in the equilibrium mixture as
shown in Fig. 8(a). Reduction of adsorbed Au(III) to elemental gold,
which is visually distinct in the equilibrium solution, was also con-
firmed from the X-ray diffraction (XRD) analysis of Au(III) loaded
5000 lignin presented in Fig. 8(b). The sharp peaks observed at 2h values
(b) (in degrees) 38.18, 44.39, 64.57, 77.54, 81.72, 98.13, 110.80 and
4000 115.26 in Fig. 8(b) correspond to the typical values of elemental
Intensity counts

gold. This confirms the reduction of Au(III) to elemental gold, indi-

3000 cating that the adsorption of Au(III) with lignin was accompanied
by reduction reaction. The adsorption coupled reduction of Au(III)
2000 to elemental gold has been reported with the adsorbents derived
from lignin [21], tannin [9], cellulose [29] etc. As compared to
Pt(IV) and Pd(II), Au(III) has significantly high reduction potential
1000
(ORP values: Au(III) = 1.00 V, Pt(IV) = 0.73 V and Pd(II) = 0.62 V)
[30]. It is believed that the higher potential of Au(III) to be reduced
0
20 40 60 80 100 120 to elemental gold is the driving force for selective uptake of Au(III)
Two-theta (degree) over Pt(IV), Pd(II) and base metal ions with lignin. Hence, the un-
ique adsorption behavior of Au(III) mentioned in Section 3.1 is
Fig. 8. (a) Gold flakes observed in the equilibrium mixture of Au(III) solution and due to the dual mechanism of adsorption and reduction of Au(III)
lignin and (b) XRD spectrum of Au(III) loaded lignin. species.
It is evident from the results of XRD that the redox reaction has
taken place between the lignin gel particles and chlorogold species.
temperature, an Arrhenius plot was obtained according to the 
Because the predominant chlorogold complex is likely the AuCl4
Arrhenius equation,
under our experimental conditions, the reaction for the reduction
k ¼ AeEa =RT ð8:2Þ of the chlorogold complex can be expressed as,
 
Which can also be written as, AuCl4 þ 3e ! Auð0Þ þ 4Cl ð10:1Þ
Ea Kuyucak and Volesky have proposed a reaction for the reduc-
ln ðkÞ ¼  þ ln ðAÞ ð9:1Þ
RT tion of Au(III) with adsorbents having abundant hydroxyl groups
where k is rate constant, Ea is activation energy (kJ mol1), T is abso- in which the hydroxyl groups are oxidized to carbonyl groups as
lute temperature (K), A is Arrhenius constant and R is universal gas [31],
constant.  
AuCl4 þ 3R  OH ! Auð0Þ þ 3RðOÞ þ 3Hþ þ 4Cl ð10:2Þ
Fig. 7 shows the relationship between the rate constants and
temperature according to Eq. (9.1). A straight line with slope The hydroxyl groups are very abundant in polysaccharides, lig-
Ea/R was obtained in the plot of ln k vs inverse of temperature, nin, tannin etc, and their participation in the reduction of Au(III)
from which the activation energy, Ea, was calculated as has been confirmed in many studies [9,21,29]. Consequently, it is
83.0 kJ mol1 from the slope of the straight line. As the forces in- strongly believed that in the redox chemistry of Au(III) to Au(0)
volved in physical adsorption are usually weak, the energy require- with lignin particles, the hydroxyl groups are oxidized to carbonyl
ments in adsorption processes involving physisorption of the groups. As gold catalyzes many organic redox reactions, the gold
adsorbate species are small and the activation energies are usually nanoparticles once formed could even catalyse the oxidation of hy-
no more than 4.2 kJ mol1. Chemical adsorption of adsorbate spe- droxyl groups and reduction of other Au(III) species leading to the
cies, on the other hand, involves forces much stronger than in improvement in gold recovery rate [32]. Based on these observa-
physical adsorption. Therefore, the activation energy for chemi- tions, we propose a generalized scheme for the chemistry of Au(III)
sorption is of the same magnitude as the heat of chemical sorption on lignin as shown in Fig. 9. As depicted in the figure, the

Fig. 9. Schematic presentation of chemistry of Au(III) adsorption and reduction on lignin particles.
 B.B. Adhikari et al. / Chemical Engineering Journal 231 (2013) 190–197

AuCl4 species of Au(III) are attracted onto the positively charged
surface of the adsorbent through electrostatic interaction. The ad-
 (1992) 1389–1400.
sorbed AuCl4 species then takes part in redox reaction with adja-
cent reducing groups (hydroxyl groups) and reduced gold
particles are formed. The metallic gold particles then tend to accu-
mulate through metallic bond formation, thus leading to the for-
mation of aggregates of metallic gold which become clearly
visible as gold flakes.
4. Conclusions
Kraft mill lignin exhibited remarkable selectivity for adsorption
of Au(III) over Pt(IV), Pd(II) and some base metal ions in hydrochlo-
ric acid medium. Adsorption of Au(III) on lignin followed typical
monolayer type of Langmuir isotherm and maximum Au(III)
adsorption of raw lignin reached a maximum of 6.0 mol kg1 at
313 K. The adsorption process is enthalpy driven, and increasing
the temperature above the ambient temperature appeared to be
beneficial for the adsorption of Au(III) on lignin. The adsorption
was found to follow pseudo-first ordered active chemisorption
with activation energy of 83 kJ mol1. The adsorbed Au(III) was
simultaneously reduced to elemental gold and metallic gold flakes
were observed in the equilibrium mixture. The formation of metal-
lic gold aggregates reveals an additional advantage of using lignin
as an adsorbent thereby facilitating the recovery of elemental gold
by simple incineration of the loaded adsorbent. To conclude, the
by-product of kraft mills has shown tremendous potential for bio-
reduction and recovery of gold ions. Hence, it can be exploited as
an effective material for adsorptive preconcentration and recovery
of gold from acidic chloride media. Although the adsorption capac-
ity was significantly increased, a higher rate of dissolution of the
lignin was observed at elevated temperature. Hence, crosslinking
of lignin to render it water insoluble and evaluate its adsorption
behavior towards Au(III) will be the focus of future work pertaining
to this research.
Acknowledgements
The present work was financially supported by the Natural Sci-
ences and Engineering Research Council of Canada (NSERC). The
authors also gratefully acknowledge the eastern Canadian Kraft
mill for the supply of raw lignin powder.
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