Chemical Engineering and Processing 44 (2005) 1181–1187

Synthetic activated carbons for the removal of hydrogen cyanide from air
Terzić M. Oliver a,∗ , Krstić Jugoslav b , Popović Aleksandar c , Dogović Nikola a
a Institute for Medical and Technical Protection, Katanićeva 15, 11000 Beograd, Serbia and Montenegro
b Institute of Chemistry Technology and Metallurgy, Department of Catalysis and Chemical Engineering,
Njegoševa 12, 11000 Beograd, Serbia and Montenegro
c Faculty of Chemistry, Studentski trg 16, 11000 Beograd, Serbia and Montenegro

Received 15 November 2004; received in revised form 4 March 2005; accepted 11 March 2005
Available online 23 June 2005

Abstract

Copper containing and copper free synthetic activated carbons produced from porous sulfonated styrene/divinylbenzene resin were studied
for assessing the removal efficiency of HCN vapors from air. The pore structures and surface chemistry of these activated carbons were
analyzed through N2 physisorption at 77 K and X-ray photoelectron spectroscopy (XPS), respectively. Incorporation of copper into starting
material significantly increased HCN breakthrough times, but decreased benzene breakthrough times. The surface area and pore volume of
the adsorbents also decreased with incorporation of copper. Results of XPS analysis revealed partial or complete reduction of the starting
divalent copper on the surface of the adsorbents confirmed by the lack of formation of (CN)2 during the adsorption of HCN. The performance
of copper containing water vapor activated adsorbent was compared to the performance of ASC Whetlerite carbon.
© 2005 Published by Elsevier B.V.

Keywords: Activated carbon; Heat treatment; Porosity; Chromatography; Hydrogen cyanide

1. Introduction such as lack of control of carbonaceous starting materials,

Hydrogen cyanide (HCN) is an acutely poisonous com-
pound, which might enter the human body by breathing con-
taminated air. The HCN vapors are commonly released to the
air from various sources including vehicle exhaust emissions,
chemical processing, extraction of gold and silver from low-
grade ores, metal plating, steel, iron, and finishing industries,
petroleum refineries, and waste disposed of in landfills. The
best-known adsorbents for the removal of HCN from air are
the metal salts impregnated activated carbons. These materi-
als are usually obtained by wetting of the non-impregnated
carbon with a solvent containing the transition metal salt,
followed by drying. This method is used to produce ASC
Whetlerite carbons which contain salts of copper, chromium
and silver, and have been shown to be effective adsorbents
for removal of HCN, cyanogen chloride and hydrogen sul-
phide. However, these materials possess some disadvantages,
∗ Corresponding author. Tel.: +381 64 261 0995.
E-mail address: oterzic@eunet.yu (T.M. Oliver).
friability of active carbon support, complexity of impregna-
tion techniques [1–3], poor dispersion of impregnates in the
deeper pore system [4], and presence of hazardous chromium
species [5]. In order to overcome some of these shortfalls,
Barnes et al. [6] used approach based on the incorporation
of the desired metal(s) into the sodium carboxymethylcellu-
lose by ion exchange prior to carbonization and activation.
Although obtained materials showed some benefits, fibrous
nature of the precursor was retained and material exhibited
poor mechanical properties.
In this work, copper containing and copper free syn-
thetic activated carbons produced from porous sulfonated
styrene/divinylbenzene resin were studied for assessing the
removal efficiency of HCN vapors from air. It has been
shown that adsorbents of this kind have improved mechanical
characteristics of beads and can be prepared with tailorable
structural properties, including pore size distribution and sur-
face area [7,8]. Furthermore, the ion exchange properties of
the resin enable easy incorporation of significant quantities
of copper into the material as an active ingredient. Two pairs

0255-2701/$ – see front matter © 2005 Published by Elsevier B.V.

doi:10.1016/j.cep.2005.03.003
1182 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187
of adsorbents were synthesized by thermal decomposition of
starting resins being in H+ and Cu2+ form, respectively. Dur-
ing heat treatment, one sample from each pair of resins was
activated with water vapor. Nitrogen adsorption at 77 K has
been used to characterize the pore structure of the adsorbents.
The external surfaces of the adsorbents have been studied
using X-ray photoelectron spectroscopy (XPS). The perfor-
mances of synthetic activated carbons were evaluated by the
breakthrough data of HCN and benzene vapors and compared
with the performances of commercial non-impregnated BPL
carbon and ASC Whetlerite carbon produced from material
similar to BPL carbon by the common method. Along with
the breakthrough of HCN, eventual concurrent formation of
cyanogen (CN)2 was also monitored. Dynamic rather than
static measurements were chosen in view of the greater rele-
vance of the data to filtration systems.
2. Experimental
2.1. Synthesis
Macroreticular styrene/divinylbenzene sulfonic acid ion
exchange resin Amberlite 200 (registered trademark of
Rohm and Haas Company) in the Na+ form was washed
with distilled water in a column, converted to the H+ form
by passing through 2 mol/dm3 hydrochloric acid solution,
and rinsed with distilled water in order to achieve neutral
pH. This resin was used as the starting material for preparing
the pair of adsorbents denoted as carbonized amberlite
resin in H form (CAH). For obtaining the pair of copper
containing carbons, designated as carbonized amberlite
resin in Cu form (CAC), the resin was treated as described
above, saturated with a 0.5 mol/dm3 copper sulfate solution,
and rinsed with distilled water until no sulfate ions were
detected in the washing solution (via a barium chloride
test).
Heat treatments were performed in a horizontal metal tube
(3.40 cm diameter) with gas inlet, in a furnace modified for
temperature programming. For all samples, approximately
20 g of resin beads, dried at 105 ◦ C for 16 h, were placed
between quartz wool plugs in a tube. The adsorbents denoted
as CAH1 and CAC1 were prepared from resin samples apply-
ing the heat treatment procedure which included a 1 h heat
up to 200 ◦ C and 1 h hold at 200 ◦ C. Then, the temperature
was raised by 100 ◦ C increments during 0.5 h and held at the
new temperature for 0.5 h. The temperature rise cycle was
repeated until the final heat treatment temperature of 800 ◦ C
was reached. After holding 1 h at this temperature, the sam-
ples were allowed to cool down to room temperature over
next 18 h. During the entire heating and cooling procedure
the argon at 0.4 dm3 /min was passed through the tube.
The adsorbents denoted as CAH2 and CAC2 were pre-
pared in the same manner as previously described except that
after reaching 700 ◦ C the argon was replaced with the acti-
vation medium (mixture of argon and water vapor). These
samples were cooled in the argon atmosphere in the same
way as the first two samples. The total mass of water used
during activation process was 8.10 g, thus giving the flow of
5.4 cm3 /h at a superficial linear velocity of 0.595 cm/h. After
cooling, all samples were immediately placed in weighing
bottles and stored in a vacuum desiccator containing anhy-
drous CaSO4 .
2.2. Methods
The copper content in CAC samples was estimated by
atomic absorption spectroscopy after total oxidation of the
pulverized samples and nitric acid dissolution.
Cu 2p, O 1s, C 1s and Cu Auger XPS experiments were
carried out on a Kratos 300 ESCA instrument supplied with
data acquisition facilities. The instrument was calibrated
using C 1s XP spectra, which were assumed to be 284.6 eV
[9]. Chemical shift data has been used to study the oxidation
states of incorporated copper.
The nitrogen adsorption/desorption isotherms were mea-
sured at 77 K using a gas sorption apparatus Thermo Finnigan
Sorptomatic 1990. Carbon samples were outgassed 16 h at
300 ◦ C prior to the adsorption analysis. The various models
and appropriate software-WinADP version 4.0 CE Instru-
ments were used to analyze the obtained isotherms.
Breakthrough tests were carried out using an instrumen-
tal gas chromatography method for automatic determination
of the C6 H6 or HCN/(CN)2 concentration in a flow sys-
tem, as described earlier [10]. Breakthrough tests were per-
formed with inlet vapor concentrations of 10.00 mg/dm3 for
C6 H6 and 2.00 mg/dm3 for HCN. All measurements were
performed at (292 ± 1) K. The carrier gas was air with rel-
ative humidity RH = 45 ± 5% and volumetric flow rate of
0.172 dm3 /min. The ratio of concentrations at the outlet and
inlet of the adsorbent bed was monitored as function of time.
The activated carbon adsorbents used for comparison pur-
poses were a coal based, steam activated Chemviron BPL,
12–30 mesh, and Chemviron Whetlerite, 12–30 mesh. The
pore structures and surface chemistry of these activated car-
bons are described elsewhere [11,12].
3. Results and discussion
3.1. Synthesis
The yields (based on the weight of starting material) and
copper content (in mg/g of the adsorbent) for CAH and CAC
samples are presented in Table 1. It is obvious that in the case
of CAH2 and CAC2, a weight loss occurred indicating some
heterogeneous chemical reactions of oxidation of carbon with
water vapor at temperatures above 700 ◦ C [13]. The weight
yields for copper containing samples are higher than of their
corresponding copper free samples, as expected. In addition,
the copper content in CAC2 is higher than in CAC1 because
of higher loss of the organic part of the material.
 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187
Table 1
Weight yields and copper contents of the investigated carbons
Sample Weight yield (%) Copper content (mg Cu/g)
CAH1 36 –
CAH2 29 –
CAC1 46 256
CAC2 38 284
The particles of all synthesized activated carbons are
spheres of great physical integrity with slightly smaller
dimensions (mean diameter 0.18 mm) compared with the ion
exchange resin.
3.2. Surface chemistry
During heat treatment, the copper may be transformed to
CuO and/or be reduced to Cu1+ or Cu0 . The decomposition
of the pure copper sulfate occurs at about 700 ◦ C [14], but it is
found that interaction with the carbon surface leads to prema-
ture low temperature breakdown of the compound according
to the following equation [15]:
CuSO4 + C → Cu + CO2 + SO2
The results of the stoichiometric calculations based on the
assumptions that the effect of the copper on the decomposi-
tion is insignificant, and that all copper in the samples is in
zero state, are consistent with the small differences (4–5%)
in the weight loss observed between analogous samples of
the CAC and CAH carbons.
The XPS data confirmed previous assumption by showing
that the copper in both CAC samples is present predominantly
in the Cu0 state. The XPS scans of these samples, showing the
Cu 2p peak, and the Cu Auger spectrum, are almost identical
thus, only CAC1 scans are given in Figs. 1 and 2, respectively.
Accordingly, we can assume that in the samples inves-
tigated divalent copper is reduced with carbon during the
heat treatment of copper-containing resin. The introduction of
activation medium did not produce notable change in the state
Fig. 1. Cu 2p X-ray photoelectron spectrum of CAC1.
1183
Fig. 2. Cu Auger X-ray photoelectron spectrum of CAC1.
of copper. Although reduced copper could undergo oxidation
with water vapor, it retrieves zero state due to prolonged con-
tact with carbon surface under argon gas.
Nevertheless, activation did produce some changes in the
surface chemistry of the materials. The typical asymmetric
peaks of the C 1s core level XP spectrum obtained on the
(1)
CAH1 and CAH2 samples are given in the Figs. 3 and 4.,
respectively.
While XPS scan of CAH1 gives only the peak at 284.6 eV
assigned to graphitic carbon, the XPS scan shown in Fig. 4
evidences two additional peaks on the surface of the CAH2 at
286.0 and 287.3 eV for C O (phenolic, alcoholic or etheric)
and C O (carbonyl or quinone) functional groups, respec-
tively. Similar results are obtained with copper containing
samples. Obviously, the activation treatment performed with
a water vapor resulted in the chemisorption of oxygen on the
surface of the carbons [16].
3.3. Nitrogen adsorption
Fig. 5 shows the nitrogen adsorption/desorption isotherms
obtained with CAH and CAC samples. The predominant
Fig. 3. C 1s X-ray photoelectron spectrum of CAH1.
1184 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187

size distribution for mesopores was calculated according to

BJH method from desorption branch of isotherm. The val-
ues of Vmic are calculated using Horvath–Kawazoe equation
[17,19]. These results are in good correlation with values
obtained using the Dubinin–Radushkevich (DR) equation
[20] that has been shown to successfully describe the adsorp-
tion of vapors by microporous carbons.
It can be observed that in the synthesized samples specific
surface area, total pore volume, micropore volume and meso-
pore volume all increase significantly with activation. During
activation process, unsaturated carbon at the edge of the
graphite-like basal layers as well as the unorganized carbon
is burned out. The difference of burning speeds of different
parts of the layers cause an asymmetrical burning which
results in the development of microporous structure. The
Fig. 4. C 1s X-ray photoelectron spectrum of CAH2. widening of existing pores or/and burnout of walls between
adjacent micropores leads to an increase in the volume of
mesopores.
In the CAH samples, water vapor activation increases SBET
for 40%, while this increase in the CAC samples is 33%. On
the other hand, the activation increase of the total pore volume
is lower for CAH samples (23%) compared to the CAC sam-
ples (44%). In the CAH samples, increase in the volume is
obtained mainly in the micropore region (39% compared with
10% for the mesopore region), while in the CAC samples, sig-
nificant increase in volume (44%) is obtained in mesopore
region.
As can be seen from comparison of data for CAH1 and
CAC1, the incorporation of copper into the material caused
about 29% reduction of SBET , Vmic , and Vmes , while Vtot was
reduced for 32%.
The Horvath–Kawazoe distribution of micropores in the
Fig. 5. Adsorption/desorption isotherms of nitrogen at 77 K for the CAH carbons is shown in Fig. 6. It is shown that in the process of
and CAC carbons. activation, micropore distribution of carbons has not changed
significantly, especially in the case of CAH samples. In the
character of all these isotherms is type I [17] but with pos- both samples, about 70% of the cumulative micropore vol-
itive slope across much of the pressure range indicating the ume is attributed to the pores having pore half-widths between
presence of mesopores beside micropores in the materials. 0.2 and 0.3 nm. The median micropore half-widths for CAH1
Moreover, all isotherms exhibit a hysteresis loop usually and CAH2 are 0.252 and 0.253 nm, respectively. The incor-
associated with the filling and emptying the mesopores by poration of copper did not lead to significant change in the
capillary condensation. The shape of the loops is similar for median micropore half-width, only slightly decreased the
all samples. contribution of pores in the 0.2–0.3 nm region, and increased
The specific surface area (SBET ), total pore volume (Vtot ), in the 0.3–0.4 nm region. Therefore, it seems that copper only
micropore volume (Vmic ), and mesopore volume (Vmes ) are blocks the entry of micropores and do not enter into micro-
presented in Table 2. The specific surface area of sam- pores, otherwise the micropore distribution should change
ples SBET , was calculated according to Brunauer, Emmett, more significantly.
Teller method from the linear part of the nitrogen adsorp- The BJH poresizes plots for the samples are given in Fig. 7.
tion isotherms [18]. Vtot was given at p/p0 = 0.997. The pore Only notably change in the mesopore distribution obtained by
introduction of copper into the material (CAC1 versus CAH1)
Table 2 can be observed in the pores having half-widths between 1
Surface areas and pore volumes of investigated carbons and 5 nm. The volume contribution in this region decreased
Sample SBET (m2 /g) Vtot (cm3 /g) Vmic (cm3 /g) Vmes (cm3 /g) markedly, probably because copper jams those mesopores.
CAH1 446 0.472 0.220 0.251 Since the mesopore distribution in the whole did not undergo
CAH2 623 0.582 0.305 0.277 drastic change it can be assumed that that the finely divided
CAC1 320 0.322 0.156 0.192 elemental copper sits here uniformly dispersed in the matrix
CAC2 427 0.463 0.208 0.277
of carbon material.
 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187 1185

Fig. 6. The Horvath–Kawazoe micropore distribution of the CAH and CAC carbons.

3.4. Removal of HCN
The experimentally determined breakthrough curves of
HCN vapors, correlated with asymmetrical S-shaped curves
according to the modified Yoon–Nelson model [21], are
shown in Fig. 8.
The breakthrough time as well as the shape of the break-
through curve for HCN did not differ much among CAH
samples. The breakthrough curve was typically sigmoidal,
with a rapid initial increase in concentration followed by a
much slower asymptotic approach to the influent HCN level.
The breakthrough times were relatively short, as expected

Fig. 7. The BJH mesopore distribution of the CAH and CAC carbons.
1186 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187
Fig. 8. The breakthrough curves of HCN vapors (292 K, inlet concentration
2.00 mg/dm3 ) for CAH1, CAH2, CAC1, CAC2, BPL and ASC Whetlerite.
from the assumption that mostly weak physical adsorption of
HCN is taking place on the surface. The similar assumption
can be made with non-impregnated BPL carbon which fol-
lowed the trend of CAH carbons and showed poor ability to
remove HCN.
Incorporation of copper into the resin beads generally led
to an increase in the HCN breakthrough times. This was par-
ticularly obvious in the case of CAC2 compared to CAH2.
Furthermore, the concentration of effluent increased grad-
ually with time and the HCN breakthrough profile became
more inclined, suggesting chemical activity in the CAC sam-
ples. It is known that the copper, added to the activated
carbons, acts chemically with HCN towards formation of pre-
cipitate [22]. In the case of divalent copper, the precipitate is
copper (I) cyanide and the reaction is followed by the release
of (CN)2 :
2CuO + 4HCN → 2CuCN + (CN)2 + H2 O
Carbons impregnated with mono- or zero-valent copper
species do not have a tendency to produce (CN)2 upon expo-
sure to HCN:
CuO + HCN → CuCN + 21 H2
2Cu2 O + 2HCN → 2CuCN + H2 O
In the CAC pair of adsorbents, during HCN removal the
appearance of (CN)2 in the effluent stream was not observed.
This result is consistent with XPS data showing that the cop-
per is present on the surface of these adsorbents primarily in
the zero state.
The breakthrough time for HCN was much longer for
CAC2 than CAC1. According to the results listed in Table 2,
a heat treatment with water vapor caused significant increase
in Vmes as well as in the other parameters. Since the active
component copper appears to have an even distribution within
the mesopores of the material, this treatment also led to the
Fig. 9. The breakthrough curves of benzene vapors (292 K, inlet concen-
tration 10.00 mg/dm3 ) for CAH1, CAH2, CAC1, CAC2, BPL and ASC
Whetlerite.
increase of the active surface for HCN adsorption. That is
why the CAC2 carbon is much better adsorbent than CAC1
carbon even though the difference in the total copper content
is not significant (Table 1).
The performance of ASC Whetlerite was only slightly
better than the performance of CAC2 carbon. Although ASC
Whetlerite carbon possesses better textural characteristics
[11] than CAC2 carbon, it seems that relatively large
copper loading (28%) of CAC2 carbon compared to ASC
Whetlerite carbon (7%) is the major factor contributing
to the obtained results. In the case of ASC Whetlerite
along with breakthrough of HCN the evolution of (CN)2 is
detected.
3.5. Removal of benzene
(2)
The experimentally determined breakthrough curves of
benzene vapors, correlated with asymmetrical S-shaped
curves according to the modified Yoon–Nelson model [21],
are shown in Fig. 9.
Benzene is physically adsorbed in the micropores of the
(3) activated carbon and its breakthrough time depends very
(4) much on the adsorbent’s surface area and micropore vol-
ume. The order of the breakthrough times of benzene vapors
on the carbons generally followed the order of increasing
micropore volumes, as would be expected. The decrease in
surface area and micropore volume caused by the introduc-
tion of copper in the starting material (Table 2) resulted in
lower breakthrough times of CAC samples compared to the
corresponding CAH samples (Fig. 9). Thus, the role of cop-
per seems to be completely different for HCN and benzene
adsorption. In HCN adsorption copper acts as an active site for
the chemisorptions, while in benzene adsorption the presence
of copper diminishes the active adsorption area that provides
physisorption.
 T.M. Oliver et al. / Chemical Engineering and Processing 44 (2005) 1181–1187
4. Conclusion
The results of this work suggest that copper containing
synthetic activated carbons exhibit adsorptive and chemisorp-
tive properties. Identified method for the production of copper
containing carbons yielded hard, non-friable spheres with
mean diameter of 0.18 mm. Under the conditions used, the
water vapor activated sample produced a very encouraging
HCN performance which is comparable to the performance
of ASC Whetlerite carbons. The formation of poisonous
(CN)2 gas, common byproduct of removal by Cu(II) salts
impregnated activated carbons, is avoided without using envi-
ronmentally hazardous chromium in the composition of the
active phase of carbon. Copper is detected on the surface of
the adsorbent as predominantly Cu0 and appears to have an
even distribution within the mesopores of the material. The
ion exchange property of the starting resin enabled easy and
homogenous implantation of copper into the structure prior
to carbonization, while the activation was shown to affect the
accessibility of copper within the carbon particles.
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