Ind. Eng. Chem. Res.

2006, 45, 6405-6412 6405

APPLIED CHEMISTRY

Recovery of Gold(III), Palladium(II), and Platinum(IV) by Aminated Lignin

Derivatives
Durga Parajuli,† Hidetaka Kawakita,† Katsutoshi Inoue,*,† and Masamitsu Funaoka‡
Department of Applied Chemistry, Saga UniVersity, 1-Honjo, Saga 840-8502, Japan, and School of
Bioresources, Mie UniVersity, 1515 Kamihama, Tsu, Mie 514-8507, Japan

Conventional metallurgical processing of precious metals involves the use of large amounts of toxic chemicals.
Realizing a need to develop environmentally benign metallurgical technology for precious metals, we prepared
two types of adsorption gels, containing primary amine and ethylenediamine functional groups and abbreviated
as PA-lignin and EN-lignin, respectively, from wood powder. Both of these adsorption gels were found to
be effective for the adsorption of Au(III), Pd(II), and Pt(IV) from weak to strong hydrochloric acid media. In
contrast, base metals such as Cu(II), Fe(III), Ni(II), and Zn(II) were almost not adsorbed on either gel. The
above-mentioned precious metals were adsorbed on the gels according to the Langmuir adsorption model,
and the highest maximum adsorption capacity was observed for Au(III). The formation of ion pairs of metal-
chloro complex anions and protonated adsorption gels in acidic media was proposed to be the main adsorption
process. However, in the case of Au(III) adsorption, a reductive adsorption mechanism was confirmed to
occur by reference to XRD spectra and SEM images of the gels obtained after adsorption.

Introduction of these have been employed for commercial purposes.2-11

At present, precious metals such as gold, palladium, and
platinum are used extensively not only in traditional jewelry
materials but also as useful components in a variety of well-
known advanced applications such as electric and electronic
devices, catalysts, and medical instruments. Because these metals
are limited resources existing only in small amounts on Earth,
these metals must be effectively recovered from various wastes
for recycling and reuse purposes. From an economic point of
view, the recovery process should be such that the precious
metals are highly selectively separated from base metals such
as iron, copper, and zinc that often coexist with the precious
metals in disproportionate amounts.
The conventional and traditional processes used for the
separation and refining of precious metals consist of a series of
steps involving dissolution using aqua regia, conditioning, and
then precipitation, which is inefficient in terms of degree of
purification, yield, operational complexity, energy consumption,
and labor costs. To replace these traditional approaches, attempts
have been made in recent years to develop new processes
consisting of total leaching in hydrochloric acid containing
chlorine gas or hypochlorite, followed by solvent extraction and
ion exchange; such techniques have also been employed by
some refineries.1 In the new processes, solvent extraction
reagents or ion exchangers with high selectivities and high
loading capacities are strongly required to simplify the process
and decrease the costs. Toward this end, some new techniques
for precious metals recovery have been developed, and some
* To whom correspondence should be addressed. Address: Depart-
ment of Applied Chemistry, Saga University, 1-Honjo, Saga 840-8502,
Japan. Fax: +81-952-28-8591. Tel.: +81-952-28-8671. E-mail:
inoue@elechem.chem.saga-u.ac.jp.
† Saga University.
‡ Mie University.
10.1021/ie0603518 CCC: $33.50 © 2006 American Chemical Society
Published on Web 08/17/2006
However, the solvent extraction reagents and chelating resins
that have been developed to the date have not necessarily
accomplished satisfactory separation and recovery as expected.
In addition, such reagents and resins are expensive and are
detrimental for the environment.
To maintain a sustainable society, it must soon be acknowl-
edged that the majority of reagents, solvents, and resins produced
from petroleum should be replaced by environmentally benign
alternatives derived from biomaterials. From this perspective,
our focus is now toward developing adsorption gels for metal
separation from a variety of biomass wastes. At present, we
are developing different types of adsorption gels based on plant
lignin extracted from waste wood for the purpose of the selective
recovery of various precious metals.
Lignin is one of the main components of wood, furnishing
10-30% of its total structure. As shown in Figure 1, lignin is
an anomalous type of complicated polymeric material that
consists of dissimilar repeating units with different functional
groups such as hydroxyl, ether, and carbonyl.12 The separation
of lignin from cellulose, an interpenetrating component of
wood, is a difficult process. Despite these problems, the effective
separation of lignin without disturbing its three-dimensional
matrix is now possible because of the landmark contribution of
Funaoka et al.13-15
In previous work, we developed some novel adsorption gels
by chemically modifying lignin in wood through the immobil-
ization of catechol and phenol functional groups. Cross-linked
lignocatechol was found to be effective for the adsorption of
some heavy metals, especially lead(II), and base metals in acidic
pH ranges.16 Cross-linked lignophenol was found to be selective
only for gold(III) in strong hydrochloric acid medium.17,18
In the present work, we have incorporated primary amine
and ethylenediamine ligands onto cross-linked lignophenol to
prepare two types of aminated cross-linked lignophenol deriva-
6406 Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006
Figure 1. Chemical structure of lignin.
Scheme 1. Preparation of Cross-Linked Lignophenol
tives. These products were employed for the selective separation
of gold, palladium, and platinum from other coexisting metals,
taking into consideration the fact that these nitrogen-containing
soft base compounds have high selectivities to precious metals,
which are typically soft acids.
Experimental Section
Preparation of Cross-Linked Lignophenol. Raw wood powder
contains many extractives, which should be removed prior to the
preparation of lignophenol. For this purpose, 12 g of dried wood
powder was added to a mixture of 150 mL of ethanol and 300
mL of benzene (1:2 v/v ratio) and stirred thoroughly for 48 h
at room temperature, after which the mixture was filtered and
dried. From the extractive-free wood powder, lignophenol was
prepared according to the reaction shown in Scheme 1 as follows.
A 5-g sample of extractive-free wood powder was mixed with
50 mL of phenol in a 500-mL beaker, and the mixture was vig-
orously stirred mechanically for 5 min at 60 °C. The mixture
was then cooled to 30 °C, and 100 mL of 72 wt % sulfuric acid
was slowly added with constant stirring. The mixture was then
stirred vigorously until the viscosity reached a maximum and
then returned to the normal value, after which it was stirred
mechanically for an additional 1 h at 30 °C; this gave rise to a
homogeneous greenish brown mixture. After the mixture had
been centrifuged for 20 min at 2000 rpm, two separate layers
consisting of organic and aqueous phases were obtained. The
organic layer was retained, whereas the aqueous layer was dis-
carded. The product thus collected was added dropwise to 300
mL of diethyl ether in an ice bath with continuous stirring. After
a few additional minutes of stirring, the mixture was decanted,
and the lignophenol portion settled at the bottom. Then, the
entire ether portion was discarded, and the lignophenol portion
was dissolved in acetone and filtered to remove acetone-insolu-
ble impurities. The mixture of acetone and lignophenol was then
concentrated by vacuum evaporation, and the concentrated
solution was again decanted. The final product thus obtained
was identified as lignophenol by means of its FT-IR spectrum.
To make the lignophenol molecule rigid and water-insoluble,
it was cross-linked with paraformaldehyde as follows. A 5-g
portion of lignophenol was mixed with 50 mL of 72 wt %
sulfuric acid in a 300-mL eggplant flask, and the solution was
stirred for a few minutes. Then, 6.5 g of paraformaldehyde was
added, and the mixture was stirred continuously for about 24 h
at 100 °C. After the reaction mixture had cooled, 5% sodium
hydrogen carbonate solution was slowly added, and the overall
mixture was stirred for 3 h and then filtered. The obtained
residue was washed with hot water and then with 1 g/L
hydrochloric acid solution. Finally, the product was washed with
cold distilled water until neutral pH was achieved and then dried
at 90 °C for 48 h in a convection oven.
Preparation of Aminated Cross-Linked Lignophenol. Two
types of aminated cross-linked lignophenol, containing either
primary amine or ethylenediamine functional groups and denoted
as PA-lignin and EN-lignin, respectively, were prepared from
the cross-linked lignophenol using different aminating reagents.
(i) Preparation of PA-Lignin. PA-lignin was prepared
according to the reaction shown in Scheme 2. In a three-necked
flask, 5 g of cross-linked lignophenol was mixed with 200 mL

Scheme 2. Preparation of PA-Lignin
Scheme 3. Preparation of EN-Lignin
Table 1. Observed and Calculated Percentages of Different
Elements in PA-Lignin and EN-Lignin
observed calculated
PA-Lignin
H 5.32 5.80
C 61.78 67.69
N 3.30 3.83
EN-Lignin
H 6.39 7.05
C 72.72 70.58
N 4.71 8.23
of pyridine in an ice bath. Then, 30 mL of thionyl chloride was
added dropwise to the mixture in about 1 h. Afterward, the
mixture was stirred continuously for 5 h at 70 °C. The chlor-
inated product was washed with distilled water and dried for 5
h at 50 °C in a convection oven. Subsequently, 5 g of chlorinated
cross-linked lignophenol was placed in a three-necked flask and
kept in an ice bath. Then, 40 mL of 1.18 M ammonia (aqueous)
was added. After the mixture had been stirred for a few minutes,
100 mL of dimethyl formamide (DMF) was added, and the
resulting mixture was stirred continuously for 48 h at 75 °C.
The product obtained was washed with distilled water and dried
in a convection oven for 24 h at 50 °C.
(ii) Preparation of EN-Lignin. EN-lignin was prepared
according to the reaction shown in Scheme 3. In a 300-mL three-
necked flask, 5 g of cross-linked lignophenol was mixed with
50 mL of dimethyl sulfoxide (DMSO), and the solution was
stirred for a few minutes. Then, 8 g of sodium carbonate and
22 mL of ethylenediamine were added. The mixture was stirred
continuously for 24 h at 80 °C. Subsequently, the reaction
mixture was filtered, and the residue was washed first with 0.1
M hydrochloric acid solution and then with distilled water until
neutral pH was achieved. The product was collected and dried
in a convection oven for 24 h at 70 °C.
Identification of Aminated Lignin Gels. The amination of
cross-linked lignophenol was confirmed by FT-IR spectroscopy
and elemental analysis of the final products. The observed and
estimated percentages of different elements in PA-lignin and
EN-lignin are reported in Table 1. The percent contributions
of individual elements cited in Table 1 were evaluated from
the tentative structure of aminated cross-linked lignophenol.
From the observed and calculated percentages of nitrogen, the
degree of amination in EN-lignin was calculated as 46.53%
Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006 6407
and that in PA-lignin was calculated as 70.1%, according to
eq 1
percent amination )
observed weight percent of nitrogen
× 100 (1)
calculated weight percent of nitrogen
Surface Analysis. SEM micrographs of PA-lignin and EN-
lignin were recorded using a JEOL model JSM 5200 scanning
electron microscope operated at acceleration voltages of 20 and
30 kV, respectively. The images at a magnification of 500×
are shown in Figure 2a and b. From these images, it is clear
that the gel surfaces are relatively smooth and have a low degree
of porosity.
Metal Species for Adsorption Tests. For the preparation of
test solutions of Cu(II), Fe(III), Ni(II), Pd(II), and Zn(II),
analytical-grade chloride salts of the respective metals were
used. Analytical-grade HAuCl4‚4H2O and H2PtCl6‚6H2O were
used to prepare Au(III) and Pt(IV) test solutions, respectively.
Batchwise Adsorption Tests for Base Metals and Precious
Metals. As mentioned earlier, commercial recovery or separation
of precious metals is carried out from hydrochloric acid
solutions. Therefore, the adsorption behaviors of EN-lignin and
PA-lignin for Au(III), Pd(II), and Pt(IV) as well as for some
base metals were examined batchwise at varying concentrations
of hydrochloric acid. Similarly, the adsorption of behavior of
DIAION WA 30, a commercially available weakly basic anion-
exchange resin produced and marketed by Mitsubishi Chemical
Corp., containing dimethylamine functional groups incorporated
on matrixes of polystyrene, was tested under the same conditions
for comparison.
The adsorption tests of the precious metals Au(III), Pd(II),
and Pt(IV), as well as some base metals, from highly acidic
Figure 2. SEM images obtained at 500× magnification of (a) EN-lignin
and (b) PA-lignin. Acceleration voltage ) (a) 20 and (b) 30 kV.
6408 Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006
Figure 3. Proton adsorption properties of PA-lignin and EN-lignin.
media were conducted using solutions of nearly the same
molarity of individual metal ions dissolved in varying concen-
trations of hydrochloric acid solution. For the measurement of
the adsorption isotherm of Au(III), Pd(II), and Pt(IV), a range
of test solutions (0.3-6 mM) were prepared by dissolving
weighed quantities of the respective chloride salts in 0.5 M
hydrochloric acid solution. For each test, 15 mL of a test solution
was mixed with 20 mg of adsorption gel in a stoppered flask.
The flasks were then shaken in a thermostated shaker maintained
at 30 °C for 100 h to attain equilibrium, as discussed later.
The pH of the test solutions was measured by using a
Beckman model Φ-45 pH meter. The concentrations of hydro-
chloric acid before and after adsorption were measured by
titration using phenolphthalein as an indicator. The metal
concentrations in aqueous solutions before and after adsorption
were measured using a Shimadzu model AA-6650 atomic
absorption spectrophotometer and a Shimadzu model ICPS-100
III ICP-AES spectrometer.
Experiments on Breakthrough Followed by Elution Using
a Packed Column. Tests of breakthrough followed by elution
using a column packed with PA-lignin gel were carried out
using a column packed with 0.2 of g gel fitted with an EYELA
model microtube pump and a BIO-RAD model 2110 program-
mable fraction collector, the details of which are described
elsewhere.16 The feed solution was prepared by mixing equal
volumes of 0.4 mM Pd(II) and 4 mM Cu(II) solutions prepared
in 0.5 M hydrochloric acid. The packed column was conditioned
by passing distilled water through it for a few hours, followed
by 0.5 M hydrochloric acid. After about 12 h of conditioning,
the feed solution was pumped through the column at a flow
rate of 4 mL/h. Effluent samples for analysis were collected at
required time intervals using the fraction collector. After the
breakthrough of both metal ions, a mixture of 0.2 M thiourea
and 0.01 M hydrochloric acid solution was fed to carry out the
elution test. The concentrations of the two metal ions in the
effluent samples were measured using a Shimadzu model ICPS-
100 III ICP-AES spectrometer.
Results and Discussion
Protonation Capacities of EN-Lignin and PA-Lignin.
Adsorption tests using varying concentrations of hydrochloric
acid on EN-lignin and PA-lignin were carried out to determine
the protonation capacities of the gels. As shown in Figure 3,
for both gels, the adsorbed amount increases with increasing
concentration of acid until tending to reach a maximum value.
From these results, PA-lignin and EN-lignin were evaluated
to have maximum adsorption capacities for hydrogen ion of
0.90 and 0.98 mol/kg of dry weight of the gel, respectively.
Adsorption of hydrochloric acid on EN-lignin and PA-lignin
Figure 4. Kinetics of adsorption of Au(III), Pd(II), and Pt(IV) on (a) EN-
lignin and (b) PA-lignin. The kinetic data recorded after 5 h for Au(III)
are displayed in the insets of the respective figures. Initial metal concentra-
tion ) 0.5 mM, weight of gel ) 10 mg, volume of test solution ) 10 mL,
concentration of HCl ) 0.5 M, temperature ) 30 °C.
takes place according to the reactions described by eqs 2 and
3, respectively.
R-NH-(CH2)2-NH2 + 2HCl T
(R-NH2+-(CH2)2-NH3+)‚2Cl- (2)
R-NH2 + HCl T (R-NH3+)‚Cl- (3)
The protonated gels are paired with coexisting anions,
chloride ions in this case, which means that the higher the degree
of protonation, the higher the anion-exchange tendency of the
gels. Although EN-lignin consists of two amino groups, its
capacity is only slightly higher than that of PA-lignin, which
can be attributed to the low degree of amination in the former
case, as suggested from Table 1.
Kinetics of Adsorption of Au(III), Pd(II), and Pt(IV). The
adsorption kinetics of Au(III), Pd(II), and Pt(IV) on EN-lignin
and PA-lignin are shown in Figure 4a and b, respectively. As
is evident from these plots, in the case of Pd(II) and Pt(IV),
equilibrium was attained within a few hours. However, a strange
pattern was observed for Au(III). Unlike the usual adsorption
kinetics, a gradual decrease in the amount of Au(III) adsorbed
was observed at the initial stage of adsorption, and a gradual
increase was observed after 100-200 min of apparent steady
state. To explain this peculiar observation, the change in
concentration of Au(III) was tracked by means of UV spec-
troscopy.
The peculiar nature of Au(III) adsorption kinetics on EN-
lignin and PA-lignin can be seen from Figure 5. As shown in
this figure, although a gradual decrease in the concentration of
Au(III) was evaluated from the absorbance observed at 314 nm
[λmax for Au(III)], a gradual increase in total concentration of
gold with increasing time was observed from atomic absorption
spectrometry (AAS) measurements. The gradual decrease in
equilibrium concentration of Au(III) implies a gradual adsorption

Figure 5. Variation of total equilibrium concentration of gold and
equilibrium concentration of Au(III) observed during the kinetics study.
Initial metal concentration ) 0.5 mM, weight of gel ) 10 mg, volume of
test solution ) 10 mL, concentration of HCl ) 0.5 M, temperature ) 30
°C.
Figure 6. Percent adsorptions of different metal ions on (a) EN-lignin
and (b) PA-lignin gels at varying equilibrium concentrations of hydrochloric
acid. Initial concentration of metal ions ) 0.2 mM, weight of gel ) 20 mg,
volume of test solution ) 15 mL, temperature ) 30 °C, shaking time )
24 h.
of Au(III) ion onto the gel, conforming to the usual adsorption
kinetics. However, the peculiar case of the total gold concentra-
tion can be explained only in terms of the change in oxidation
state of some Au(III) once adsorbed, leading to the formation
of new ionic species, most probably Au(I), to which the gels
are not selective. For this reason, a pseudo-stationary state or
pseudo-equilibrium is observed in Figure 4a and b. This state
represents a state of equilibrium between adsorption of Au(III)
and elution of the new species. A further increase in the amount
of metal adsorbed, q, after some time ultimately leads to a true
equilibrium state. The final section of the kinetic curve most
probably represents the formation of elemental gold, as discussed
in detail in the following sections.
Batchwise Adsorption Test. Figure 6a shows the adsorption
behavior of EN-lignin for some metal ions at varying hydro-
chloric acid concentrations. It is clear that the gel is almost inert
toward Cu(II), Fe(III), Ni(II), and Zn(II), whereas it absorbs
Au(III), Pd(II), and Pt(IV). Likewise, Figure 6b shows the
adsorption behavior on PA-lignin at varying hydrochloric acid
Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006 6409
Figure 7. Percent adsorptions of different metal ions on Diaion WA 30 at
varying equilibrium concentrations of hydrochloric acid. Initial concentration
of metal ions ) 0.2 mM, weight of gel ) 20 mg, volume of test solution
) 15 mL, temperature ) 30 °C, shaking time ) 24 h.
Scheme 4. Adsorption Mechanism
concentrations. Also in this case, the percentage adsorption
observed for base metals is negligible, whereas there is marked
adsorption of precious metals. A number of anion-exchange
resins are reported to exhibit high selectivity to precious metals
over base metals, and some anion-exchange resin or gels have
been found to be selective only for precious metals.19-21
Although PA-lignin contains primary amino groups and EN-
lignin contains ethylenediamine groups, they are both found to
exhibit quite similar adsorption behaviors. However, the selec-
tivity orders for Au(III), Pd(II), and Pt(IV) are different as shown
in parts a and b of Figure 6; that is, the selectivity order observed
for EN-lignin is Au(III) > Pt(IV) > Pd(II), whereas that for
PA-lignin is Au(III) > Pd(II) . Pt(IV).
Au(III), Pd(II), and Pt(IV) form anionic chloride complexes
of the form AuCl4-, PdCl42-, and PtCl62-, respectively, at a
wide range of hydrochloric acid concentrations. According to
this principle, the adsorption of metal-chloro complexes on
PA-lignin is inferred to occur in terms of the anion-exchange
reactions expressed by eq 4 and 5 of Scheme 4, and that on
EN-lignin occurs by eq 6 of Scheme 4, where the coordination
numbers [4 for Au(III) and Pd(II) and 6 for Pt(IV)] are satisfied
by coexisting Cl- ions. Other metal ions such as Fe(III) and
Zn(II) also give rise to anionic chloro complexes over a wide
range of chloride concentrations, and it is well-known that they
are solvent-extracted with high-molecular-weight amines and
adsorbed on anion-exchange resins, as discussed later. However,
these ions are essentially not adsorbed on the present gels, which
should be clarified in future work.
Figure 7 shows a similar plot of percent adsorption vs HCl
concentration in the case of adsorption on DIAION WA 30
resin. The order of selectivity to precious metals was Au(III)
> Pt(IV) > Pd(II). This is the same order as obtained with the
PA-lignin gel. However, in contrast to the behavior for PA-
and EN-lignin gels, appreciable amounts of Zn(II) and Fe(III)
were adsorbed on WA 30 resin, whereas no adsorption of Cu-
(II) was observed on this resin. The marked increase in the
adsorption of Fe(III) from 2 M HCl is in accordance with the
start of the formation of FeCl4- resulting from the anion-
exchange adsorption of this species on the resin.22 From this
comparison, it is apparent that the PA- and EN-lignin gels
exhibit much better selectivities to precious metals than WA
30 resin, a commercially available resin.
Adsorption Isotherms of Au(III), Pd(II), and Pt(IV). As
both EN-lignin and PA-lignin were found to be effective in
6410 Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006
Figure 8. Adsorption isotherms of (a) EN-lignin and (b) PA-lignin for Au(III), Pd(II), and Pt(IV) from 0.5 M hydrochloric acid.
Figure 9. Elemental gold formed during adsorption of Au(III) observed
as a floating layer on the water surface in the beginning that develops
aggregates.
Scheme 5. Reduction of Aurate Ion by Aminated
Cross-Linked Lignophenol in Acidic Medium
the uptake of Au(III), Pd(II), and Pt(IV) ions over a wide range
of hydrochloric acid concentrations (Figure 6a,b), the adsorption
isotherms of these metal ions on EN-lignin and PA-lignin
were examined by conducting adsorption tests from lower (0.2
mM) to higher (6 mM) concentration of metal ions at constant
hydrochloric acid concentration (0.5 M), as shown in Figure
8a and b, respectively. From these plots, it is clear that, for
both adsorption gels, adsorption increases with increasing metal
ion concentration at low concentration, whereas a plateau region
is observed at high concentration irrespective of the metal ion
concentration, suggesting that Langmuir-type adsorption takes
place under the given conditions. From Figure 8a, the maximum
adsorption capacities of EN-lignin for Au(III), Pd(II), and Pt-
(IV) were evaluated as 3.08, 0.213, and 0.536 mol/kg of dry
gel, respectively. Similarly, from Figure 8b, the maximum
uptake capacities of PA-lignin for Au(III), Pd(II), and Pt(IV)
were evaluated as 1.95, 0.38, and 0.22 mol/kg of dry gel,
respectively. These results suggest that both of the lignin gels
exhibited the highest capacity for Au(III) with comparatively
lower values for Pd(II) and Pt(IV). The capacity of PA-lignin
is higher for Pd(II) than for Pt(IV), whereas the reverse is the
Figure 10. XRD spectrum of EN-lignin after adsorption of Au(III).
Figure 11. SEM image of EN-lignin after adsorption of Au(III) recorded
at 100× magnification shows gold aggregates that are larger than the gel
particles.
case for EN-lignin, which is in agreement with the selectivity
orders shown in Figure 6a,b.
Although both EN-lignin and PA-lignin were found to be
effective adsorbents for all of the precious metals tested, their
capacities for Au(III) are extraordinarily higher than those for
Pt(IV) and Pd(II). A more exciting result was observed, as
shown in Figure 9. The formation of gold particles was
confirmed by physical analysis of the gels after 24 h of shaking,
and larger aggregates of gold were observed after 100 h of
shaking. In Figure 9, as described later, a layer of fine gold
particles floating on the water surface was observed; the
layer formed aggregates upon further shaking and gradually
dropped to the bottom of the container. This result suggests
that the adsorption of gold on aminated cross-linked ligno-
phenol is accompanied by the reduction of Au(III) ion to Au-
(0), similar to the result observed in the adsorption of Au(III)
on cross-linked lignophenol.17,18 In the study of adsorption
kinetics, a gradual increase in the amount of adsorbed gold was
observed after the plateau region of pseudo-stationary state
(Figure 4a,b), which indicates that the gradual reduction of Au-
(III) takes place after a few hours of shaking. AuCl4- is a
powerful oxidizing agent in solution.23 In addition, polyphenolic
groups, which are the major constituents of lignin molecules,
are reported to reduce auric ion in aqueous acidic systems.24
Furthermore, the oxidation of amino groups present in the

Figure 12. (a) Breakthrough profiles of Pd(II) and Cu(II) from a column packed with PA-lignin. Feed concentration of Pd(II) ) 0.186 mM, feed concentration
of Cu(II) ) 1.914 mM, concentration of HCl ) 0.5 M, weight of adsorbent ) 0.2 g, temperature ) 30 °C, feed rate ) 3.933 mL/h. (b) Elution profiles of
Pd and Cu from a loaded column by a mixture of 0.2 M thiourea and 0.01 M hydrochloric acid solutions. Feed rate ) 3.94 mL/h.
aminated cross-linked lignophenol might take place as shown
in Scheme 5, which also contributes to the reduction of Au-
(III).25
To confirm the formation of metallic gold, analysis by means
of X-ray diffraction (XRD) and scanning electron microscopy
(SEM) of the adsorbent was carried out after the adsorption.
The 2θ values of the peaks as shown in Figure 10 were found
to precisely match those of gold, which verifies the formation
of elemental gold during the adsorption process. Similarly,
SEM micrographs of the adsorbents before and after adsorption
elucidated the morphology of the adsorbent along with that
of gold particles on the surface. The size of the gold particles
is observed to vary in SEM micrographs of the EN-lignin gel
taken after adsorption, as shown in Figure 11. At low con-
centrations of gold (0.2 mM), microscopic-level gold parti-
cles were observed, whereas at high concentrations, the micro-
scopic gold particles were found to form aggregates, resulting
in the formation of large gold particles that can be observed
visually.
Tests on Breakthrough Followed by Elution. The lignin-
based adsorption gels developed in this work were found to be
very selective for Au(III), and their capacities for Pt(IV) and
Pd(II) are also noteworthy. Between EN-lignin and PA-lignin,
PA-lignin exhibited a higher capacity for Pd(II), on the basis
of which PA-lignin was used for the mutual separation of trace
amounts of Pd(II) from a large excess of Cu(II) using a packed
column. As shown in Figure 12a, breakthrough of Cu(II) took
place immediately after the start of the feeding, whereas
breakthrough of Pd(II) took place after about 200 bed volumes.
After the complete breakthrough of Pd(II) ion, the elution test
was carried out using an aqueous mixture of 0.2 M thiourea
and 1 mM hydrochloric acid. Pd(II) was eluted in a high concen-
tration of about 10 times of the feed concentration, as shown
in Figure 12b. From the area of the breakthrough curve, the
maximum adsorption capacity was evaluated as 0.18 M/kg of
gel, which is about one-half of the value evaluated from the
adsorption isotherm; this might be due to the short contact time
in continuous flow because of the slow adsorption kinetics of
Pd(II). Nevertheless, chromatographic separation using PA-
lignin provides a promisingly effective technique for the sepa-
ration and preconcentration of trace amounts of Pd(II) from a
large excess of Cu(II).
Conclusion
The present study clearly establishes that both the PA-lignin
and EN-lignin gels developed in this work are effective
adsorbents for Au(III), Pd(II), and Pt(IV) over a wide range of
hydrochloric acid concentrations. The formation of stable anionic
Ind. Eng. Chem. Res., Vol. 45, No. 19, 2006 6411
chloro complexes of these metal ions and the protonation of
active functional groups of the adsorption gels in acidic medium
causing into the anion-exchange adsorption are concluded to
be the driving forces for the selective adsorption of precious
metals. Hence, these adsorbents can be specifically recom-
mended for the recovery of valuable metals from mixtures
containing the base metals.
Acknowledgment
Sasagawa Scientific Research Grant from The Japan Science
Society is gratefully acknowledged for partial financial support
of this work.
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ReceiVed for reView March 23, 2006
ReVised manuscript receiVed July 6, 2006
Accepted July 22, 2006
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