International Biodeterioration & Biodegradation 113 (2016) 195e200

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International Biodeterioration & Biodegradation

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

Study of sulfuric acid treatment of activated carbon used to enhance

mixed VOC removal
Seo-Hyun Pak, Mi-Jin Jeon, Yong-Woo Jeon*
Environmental Convergence Technology Center, Korea Testing Laboratory, Seoul 08389, South Korea

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

Article history: The objective of this work was to study the effect of sulfuric acid treatments of activated carbons on
Received 9 January 2016 single and binary VOCs adsorptions. Commercial activated carbon (AC) and 5, 10 vol% sulfuric acid treated
Received in revised form activated carbon (5S-AC, 10S-AC) were prepared. The physical-chemical properties of activated carbons
11 April 2016
were characterized by N2 adsorption-desorption isotherms, temperature-programmed desorption (TPD).
Accepted 11 April 2016
Measurements of the adsorption behavior of pure concentrations and mixture of benzene and toluene on
Available online 28 April 2016
activated carbon were a ow-typed xed bed system at room temperature under atmospheric pressure.
Of all samples examined, the 10S-AC exhibited the highest adsorption capacity for both benzene and
Keywords:
Adsorption
toluene, having both longer breakthrough and separation times. The adsorption amount of toluene and
Benzene benzene on 10-S-AC was increased by 18% and 47%, compared with that on the AC. This is attributed to
Toluene the surface oxygen group species of activated carbon and changes the porosity of adsorbents due to
Activated carbon sulfuric acid treatment.
Acid treatment 2016 Elsevier Ltd. All rights reserved.

1. Introduction Among these methods, adsorption using activated carbon is a

Volatile organic compounds (VOCs) are the common air pol-
lutants emitted mainly from chemical and petrochemical in-
dustries, which include most solvents such as thinner, degreasers,
cleaners, lubricants, and liquid fuels. The following VOCs have been
the most commonly reported: formaldehyde (CH2O), tetrachloro-
ethylene (C2Cl4), benzene (C6H6), toluene (C7H8), xylene (C8H10),
and acetaldehyde (C2H4O). These VOCs are hazardous to both hu-
man health and the environment, causing global warming,
destroying the stratospheric ozone layer, and contributing to
photochemical smog. Especially, many volatile organic compounds
are known to cause cancer in animals; some are suspected of
causing, or are known to cause, cancer in humans. U.S. EPA (Envi-
ronmental Protection Agency) describe the effects on human health
of specic VOCs (e.g. benzene, toluene) that are dened as haz-
ardous (Foster et al., 1992; Ramos et al., 2010; Yamamoto et al.,
2010; Beetseh and Oragbe, 2013; U.S. EPA). For these reasons,
various technologies for VOC removal have been investigated in
recent years, with treatments now including thermal oxidation,
bio-ltration, absorption, adsorption, and condensation.
* Corresponding author.
E-mail address: ywjeon@gmail.com (Y.-W. Jeon).
key technique that improves VOC adsorption, with increases in use
being due to its low cost, hydrophobic properties, high surface area,
and the microporosity of activated carbon which provides an
excellent VOC adsorption capacity (Mohan et al., 2009). In addition,
activated carbon surface can be chemically modied to acids or
bases to improve the hydrophobicity and thereby enhance the VOC
selectivity and adsorption capacity. Although physical properties
such as specic surface area and pore size affects the adsorption
capacity of the activated carbon, surface chemical properties also be
taken into consideration due to the presence of this particular
interaction with the adsorbate/adsorbent in the adsorption process
(Gauden and Wisniewski, 2007; Pastor-Villegas and Duran-Valle,
2002;,Swider and Rolison, 1999).
The chemically modication of activated carbons for adsorption
of various gases has been investigated by some scientists in the
literature. The modication of activated carbon using phosphoric
acid to improve VOC adsorption performance was investigated by
Kim et al. (2006). They reported that the amount of VOC adsorbed
on the activated carbon modied by impregnating with 1 wt%
H3PO4 was larger than that on puried activated carbon due to
chemical modication of its surface despite the decreased specic
surface area. Oh et al. (2006) reported on the variation of surface
properties due to a hydrochloric acid pre-treatment and on the
effect of loading metallic potassium and their salts on activated

http://dx.doi.org/10.1016/j.ibiod.2016.04.019
0964-8305/ 2016 Elsevier Ltd. All rights reserved.
196 S.-H. Pak et al. / International Biodeterioration & Biodegradation 113 (2016) 195e200
carbon after the surface transformation by acid.
As VOCs in industrial processes consist of at least two mixed
gases, many studies on the adsorption performances of binary or
multi-component gas systems have been applied to VOC control
and gas separation technologies. The adsorption characteristics of
binary components on an adsorbent are more complicated than
those for a single component, due to the difference in the adsorp-
tion capacity of the adsorbent for binary components (Lillo-
Ro denas et al., 2006; Park et al., 2001).
In this paper, the adsorption characteristics of a binary gas
system involving toluene and benzene on sulfuric acid treated
activated carbon (S-AC) are studied. As adsorption characteristics,
breakthrough curve and adsorption capacity were evaluated using
a ow-typed xed-bed system for the effect of acid treatment of
activated carbon during VOC adsorption. The purpose of this study
is to analyze the adsorption behavior of mixed VOCs on activated
carbon and sulfuric acid treated activated carbon for supplement-
ing the scant information regarding the adsorption of VOCs
mixtures.
2. Experimental
2.1. Materials
The activated carbon was obtained from Samchully Co. (Korea),
and the acid-treated carbon prepared by activation with a sulfuric
acid solution with NaOH (samples 5S-AC and 10S-AC) are compared
in this study. The activated carbon used is in the form of pellets
(mean particle diameter of 2 mm). Commercial activated carbon
was soaked in 5 wt% or 10 wt% sulfuric acid under stirring for 12 h
and then separated through vacuum ltration. The ltered carbon
was washed with deionized water until the pH of the ltrate was
stable. The treated samples were dried in the oven at 105
C for
24 h.
The adsorbent was spent with toluene and benzene (99.99%,
Sigma Aldrich, USA). Table 1 summarizes the characteristics of the
VOCs.
2.2. Characterization of materials
Nitrogen sorption analysis, temperature programmed desorp-
tion (TPD) were performed to examine the physical and chemical
properties and their impacts on the VOC adsorption capacity of the
activated carbons.
The physical properties were measured using N2 adsorption-
desorption isotherms (ASAP, 2020; Micromeritics, USA). The spe-
cic surface area, pore volume, and pore diameter distribution of
the activated carbons were examined by measuring the nitrogen
adsorption/desorption isotherms at 196
C. The specic surface
area was calculated using the Brunauer-Emmett-Teller (BET)
method. The micropore volumes were calculated using the t-plot
and Horvath Kawazoe (HK) methods. The pore size distribution was
calculated based on the density functional theory (DFT) method
using a slit pore geometry.
The changes of chemical properties by treatment of sulfuric acid
were examined by TPD analyzer (Autochem 2920 Analyzer,
Micrometritic, America). About 100 mg of the dry sample was
Table 1
Characteristics of VOCs.
VOCs Exposure limit (ppm) Molecular weight (g/mole)
Benzene 1 78.1
Toluene 50 92.1
weighted accurately and put in a quartz tube. The sample was
pretreatment at 200
C under helium gas for 6 h for drying and
degasing. After degasing, evolved amounts of desorbed gas
analyzed by thermal conductivity detector (TCD), while the tem-
perature was increased up to 600
C at a rate of 10
C/min.
2.3. Benzene and toluene adsorption studies
Adsorption experiments for a benzene and toluene were per-
formed, each at 150 ppm concentration in air. The benzene and
toluene adsorption studies were conducted in a continuous ow-
type xed-bed system under an atmospheric pressure system.
The experimental setup is schematically shown in Fig. 1. The total
ow rate was 6 L/min as it passed through an adsorbent column
(diameter: 20 mm). A cross-section area of the adsorption tower is
0.000314 m2, ow rate and residence time were 0.3 m/sec, 0.6 s
respectively.
The adsorption experiments were performed at room temper-
ature. The concentrations of toluene and benzene were measured
using the ame ionization detector of a gas chromatograph (GC;
2010 Plus, Shimadzu, Japan). A six-way valve was installed in the
gas chromatograph to analyze the concentrations of the VOC gases.
An Rtx-5 column was used, and the samples were injected into the
GC every 10 min during the adsorption of toluene and/or benzene
to obtain the breakthrough curves.
The breakthrough prole was measured by monitoring the
outlet concentration as a function of time. When the outlet VOC
concentration was measured for the rst time, the breakthrough
time was determined. The performance parameters were calcu-
lated as following. During adsorption, the amount of VOCs adsor-
bed by the activated carbon was determined using Eq. (1).
Ci  C
VOCs Removal Efficiency R; %  100 (1)
Ci
Ci: reactor inlet concentration of VOCs (ppm)
C: reactor outlet concentration of VOCs (ppm)
3. Results and discussion
3.1. Adsorption isotherms
The physical properties of the normal activated carbon and
sulfuric acid-treated activated carbon were measured using the N2
gas adsorption-desorption isotherms (Table 2 and Fig. 2). Following
IUPAC classication, the N2 adsorption-desorption isotherms of
normal activated carbon and sulfuric acid-treated activated carbon
were deemed to be type I (Fig. 2), thus conrming the typical
characteristics of porous activated carbon, which rapidly increase at
a lower relative pressure. The rst adsorption curve at relative
pressures P/P0 < 0.01 indicates the lling of micropores, and the
steepness of second adsorption curve at 0.3 < P/P0 < 0.4 was due to
mesopores having a narrow distribution. The nal condensation
curve of P/P0 > 0.8 was related to the presence of intercrystalline
mesopores. Note that the pore size distribution is also shown in Fig
Boiling point at 760 mmHg Density Vapor pressure (mmHg at 20
C) Polarity index
80 0.8 75 2.7
110.5 0.8 22 2.4
 S.-H. Pak et al. / International Biodeterioration & Biodegradation 113 (2016) 195e200
Fig. 1. Experimental apparatus for VOC adsorption system.
Table 2
The specic surface areas and pore volumes for commercial AC, 5S-AC, and 10S AC.
Adsorbent SBET (m2/g) SMic (m2/g) SExt (m2/g) Vtotal (cm3/g) VMic (cm3/g)
AC 1067 280 786 0.58 0.14
5S-AC 885 425 459 0.45 0.21
10S-AC 840 336 503 0.45 0.16
Note: SBET, SMic, Sext and Vtotal, VMic represent BET surface area, micropore surface
area, non-micropore (i.e., meso-and macropore) surface area, and total pore volume,
micropore volume, respectively.
Fig. 2. N2 adsorption-desorption isotherms (a) and pore size distributions (b) of AC, 5S-AC, and 10S-AC.
2, in which the pore system is seen to include large amounts of
micropores (0.7 nm) and mesopores (2e4 nm). Note that 5S-AC and
10S-AC have a more narrow and uniform pore size distribution.
Table 2 shows the BET surface areas and pore volumes for
commercial AC, 5S-AC, and 10S AC. The BET area of commercial
activated carbon was 1067 m2 g1, and the total pore volume and
micropore volume were 0.58 cm3 g1 and 0.14 cm3 g1, respec-
tively. In the case of sulfuric acid treated activated carbon, the BET
area and the pore volumes were decreased as compared to that of
the commercial activated carbon. These observed phenomena
might be due to the blocking of some of the pores by the formation
of new functional group by the oxidation reactions and the erosion
of carbon skeletal structure (Seredych and Bandosz, 2010). But the
micropore surface area and micropore volume were slightly
increased after acid treatment. The increase in the micropore sur-
face area and volume can be attributed to the gas generation from
the reaction between the acid and materials on carbon surface,
reopening the closed micropores and forming new micropores
(Tang et al., 2016).
197
3.2. TPD analysis
The decompositions of organic groups, including the oxygen
group of the activated carbon surface, were analyzed using tem-
perature programmed desorption (TPD). Generally, oxygen func-
tional groups of various types present slightly on activated carbon
surfaces. They can be created by treatment with liquid oxidants like
the acid solution. In this way the generated oxygen surface groups
are stable at room temperature, but they were decomposed by
releasing CO2 et al., when the carbon is heated to higher temper-
atures. Thus, the TPD peaks of CO2 in the elevated temperature
condition correspond to surface oxygen groups. For example, CO2 is
released by decomposition of carboxylic groups at 100e400
C
(Otake and Jenkins, 1993; Zielke et al., 1996), or lactone groups at
190e650
C (Zielke et al., 1996; Marchon et al., 1988). The quantities
of CO2 released during TPD analysis correspond to the total amount
of surface oxygen group. Thus, the TPD proles gives qualitative
information about surface oxygen groups.
The TPD analysis results are shown in Fig. 3. All samples dis-
played a peak at 300
C due to the organic groups on the surface of
activated carbon; the carboxylic and Lactone groups generally
produce CO2 at temperature range of 100e600
C, as it reports in
the above-mentioned literature. The amounts of CO2 generated for
AC, 5S-AC and 10S-AC were 0.01 mmol g1, 0.10 mmol g1 and
0.11 mmol g1, respectively. The CO2 generated from the organic
groups on the 10S-AC surface is somewhat higher than for AC and
5S-AC. This result means that the oxygen functional groups on
198 S.-H. Pak et al. / International Biodeterioration & Biodegradation 113 (2016) 195e200
Fig. 3. TPD spectra (a) and CO2 generated (b) for AC, 5S-AC, and 10S-AC.
activated carbon surface were created much more by the treatment
of sulfuric acid, and they existed as the more quantities when
processing with 10 wt% sulfuric acids than 5 wt%.
3.3. Single VOC
Fig. 4 shows the concentration curves (ppm) of VOC emissions
(toluene and benzene) for commercial AC, 5S-AC, and 10S AC. In
these results, the amounts of toluene and benzene adsorbed on 5S-
AC and 10S-AC were larger than on commercial AC. Notably, the
breakthrough time of 10S-AC increased compared to commercial
AC. Table 3 presents the breakthrough times and adsorption ca-
pacities (g/100 g) for AC, 5S-AC, and 10S-AC. All experiments were
carried out under the same conditions (i.e., weight of adsorbent,
ow rate in the bed, etc.), thus allowing the time data for the
breakthrough times and adsorption capacities to be compared. The
breakthrough times of toluene and benzene for 10S-AC was
240 min, which is 152 min longer than for the others. The
adsorption capacities of toluene for AC, 5S-AC, and 10S-AC were
10.4 g/100 g, 11.1 g/100 g, and 12.3 g/100 g, respectively; the cor-
responding adsorption capacities of benzene were 4.5 g/100 g,
5.04 g/100 g, and 6.6 g/100 g.
Results showed that 10S-AC had superior adsorption capacities
for toluene and benzene than either AC or 5S-AC. It was found that
the acid treatment signicant affects the adsorption of VOCs as it
increased the surface oxygen group species of activated carbon,
which based on the TPD analysis was observed to be the carboxyl
acid group. Overall, the amount of activated carbon adsorbed from
the toluene and benzene increased with the concentration of the
Fig. 4. Breakthrough curves for toluene (a) and benzene (b) adsorbed on AC, 5S-AC and 10S-AC.
H2SO4 solution. As such, the adsorption ability of activated carbon
for VOCs is thought to increase as the size of the carboxylic acid
group is increased. In addition, the adsorption ability for toluene is
higher than for benzene, since the relative pressure used for
toluene is higher than for benzene (Lillo-Rodenas et al., 2006).
3.4. Binary VOCs (benzene-toluene)
The results of the concentration curves (ppm) of VOC emissions
for activated carbon and sulfuric acid treated activated carbon are
shown in Fig. 5. The breakthrough curve for the adsorption of
benzene-toluene mixture obtained in this study is in agreement to
 denas et al., 2005). Initially,
this reported in the literature. (Lillo-Ro
the activated carbon was saturated with benzene; after 58 min,
toluene was detected from the outlet of the adsorption bed. For 5S-
AC, the toluene was detected from outlet of the adsorption bed after
90 min; for 10S-AC, toluene was detected after 96 min. These times
were determined to be the difference between the times at which
the toluene outlet concentrations separated, i.e., the separation
times of AC, 5S-AC, and 10S-AC were 58 min, 90 min, and 96 min,
respectively. This result was shown because of that the adsorption
capacity of toluene was higher than that of benzene, that 10S-AC
had superior adsorption capacities in the benzene-toluene mixture
due to the difference in the breakthrough characteristics of its bi-
nary components and the presence of an organic group on the
surface.
Thus, the results for 10S-AC, a chemically activated carbon,
present a high adsorption capacity for both benzene and toluene; in
addition, it has a high breakthrough time. Importantly, the
 S.-H. Pak et al. / International Biodeterioration & Biodegradation 113 (2016) 195e200
Table 3
Single adsorption capacity for benzene and toluene.
Sample Breakthrough time for Toluene (min) Toluene (g/100 g AC)
AC 204 10.4
5S-AC 216 11.1
10S-AC 240 12.3
Fig. 5. Breakthrough curves for toluene and benzene mixture adsorbed on AC (a), 5S-AC (b), and 10S-AC (c).
relationship between the size of the organic group or adsorption
properties and the separation time has been identied. From this
study, it appears that the higher the volume of narrow micropores
and more organic groups there are on the surface, the higher the
separation time.
4. Outlook
VOCs generally exist and can greatly aggravate indoor and out-
door air quality. Especially, toluene and benzene are very toxics due
to its carcinogenicity. Toluene, benzene and xylene are universal
pollutants emitted from indoor VOCs sources such as ooring
materials and furniture. Also, they are generated from outdoor
VOCs sources like the painting process using the paint and thinner.
Various carbon materials as adsorbent are considered as the tech-
nique for removal of VOCs due to its high efciency and stability.
However, traditional carbon materials can limit the utilization ef-
ciency. Development of new carbon materials which can be
treated with acid or base is thus a requirement. These research
results can be applied to the adsorption tower which is used to
adsorb VOC emissions in many industrial processes. Also, the car-
bon materials developed can be used as VOCs adsorbents in the
indoor environment. More advanced approaches for adsorption-
regeneration method are also essential to progress due to its ad-
vantages in process economics and energy minimization.
5. Conclusion
The adsorption of mixtures of benzene and toluene on activated
carbon and acid treated activated carbon was investigated in order
to determine the effect of organic groups on the surface on the
adsorption of these mixtures. The adsorption tests for single or
mixed VOC systems (toluene and/or benzene) on different types of
activated carbon were carried out in a ow-type xed-bed
adsorption system.
The amount of toluene and/or benzene adsorbed on acid treated
activated carbon was larger than on commercial activated carbon,
with this enhanced 5S-AC and 10S-AC adsorption performance
being attributed to the effect of having an increase in the organic
199
Breakthrough time for benzene (min) Benzene (g/100 g AC)
104 4.5
116 5.04
152 6.6
group on the surface and the narrow micropore volume that was
caused by the acid treatment.
Acknowledgement
The authors gratefully acknowledge the nancial support pro-
vided by the Korea Environmental Industry & Technology Institute
(KEITI) (2014000110013).
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