Studies in Surface Science and Catalysis, volume 159

Hyun-Ku Rhee, In-Sik Nam and Jong Moon Park (Editors)

9 2006 Elsevier B.V. All rights reserved

457

Adsorption-desorption characteristics of modified activated carbons

for volatile organic compounds
Ki-Joong Kim a, Chan-Soon Kang a, Young-Jae You a, Min-Chul Chung a, Seung Won Jeong b,
Woon-Jo Jeong c, Myung-Wu Woo a, Ho-Geun Ahn a*
aDept, of Chemical Engineering and bjeonnam Techno Park, Sunchon National University,
315 Maegok-dong, Suncheon-si, Jeonnam, 540-742 Korea.
CDept. of Inform. & Comm., Chosun College Sci. & Techn., Seosuk-dong, Gwangju, Korea.
Modification techniques for activated carbon were used to increase the removal capacity by
surface adsorption and to improve the selectivity to volatile organic compounds (VOCs).
Modified activated carbons (MACs) were prepared by modifying the purified activated
carbon with various acids or bases. The effects of adsorption capacity and modified contents
on the textural properties of the MACs were investigated. Furthermore, VOC adsorption and
desorption experiments were carried out to determine the relationship between the adsorption
capacity and the chemical properties of the adsorbents. High adsorption capacity for the
selected VOCs was obtained over l wt%-H3PO4/AC (lwt%-PA/AC). As a result, MAC was
found to be very effective for VOC removal by adsorption with the potential for repeated use
through desorption by simple heat treatment.
1. INTRODUCTION
Several techniques for VOC removal have been investigated such as thermal incineration,
catalytic oxidation, condensation, absorption, bio-filtration, adsorption, and membrane
separation. VOCs are present in many types of waste gases and are often removed by
adsorption [ 1]. Activated carbon (AC) is commonly used as an adsorbent of gases and vapors
because of its developed surface area and large pore volumes [2]. Modification techniques for
AC have been used to increase surface adsorption and hence removal capacity, as well as to
improve selectivity to organic compounds [3].
In this study, the surface properties of modified AC (MAC) and its adsorption capacity for
VOCs were investigated. The effect of modified contents on adsorption performance was
studied. Furthermore, adsorption and desorption of VOCs was carried out to evaluate the
adsorption capacity and desorption characteristics after saturated adsorption.
2. EXPERIMENTAL

This subject is supported by the Ministry of Environment as "'The Eco-technopia 21 project".

t corresponding author Tel: +82-61-750-3583. E-mail: hgahn@sunchon.ac.kr

458

2.1. Preparation of MAC

The AC used in this study was a granular type (30-35 mesh) prepared from coconut shell.
The purified AC (PAC) was prepared by boiling the AC for 5 hr in a water bath. The acidic
and alkaline solutions for preparation of MACs were made with HNO3 (NA), H2SO4 (SA),
HC1 (HA), H3PO4 (PA), CH3COOH (AA), KOH (PH), and NaOH (SH). The AC was
modified into each solution according to the conventional wet process. The specific surface
area of the adsorbents was measured by BET method (ASAP 2020, Micrometrics, USA).
2.2. Measurement of VOC adsorption
The variation of concentration in the course of adsorption was continuously obtained as a
thermal conductivity detector (TCD) signal. Model gases were BTX (benzene, toluene and o-,
m-, p-xylene), alcohols (methanol, ethanol, iso-propanol), and methylethylketone (MEK). The
concentration of VOCs for adsorption was controlled by vaporizing VOCs in the saturator
with helium, which was maintained in the range of 10,000ppm - 15,000ppm. The temperature
in the saturator was maintained with a constant temperature vessel. Total VOC flow rate was
40ml/min as it passed through a U-type adsorbent column. Before adsorption experiment, the
MAC was pretreated for 1 hr in an adsorbent column of 250 ~ and 0.2g of the adsorbent was
used for each experiment. The VOC concentrations were monitored with TCD of gas
chromatograph. In addition, the MAC desorption characteristics were investigated by
temperature programmed desorption (TPD) technique.
3. RESULTS AND DISCUSSION

3.1. Modified effect of activated carbon

The prepared MAC adsorbents were tested for benzene, toluene, o-, m-, p-xylene, methanol,
ethanol, iso-propanol, and MEK. The modified content of all MACs was 5wt% with respect
to AC. The specific surface areas and amounts of VOC adsorbed of MACs prepared in this
study are shown in Table 1. The amounts of VOC adsorbed on 5wt%-MAC with acids and
alkali show a similar tendency. However, the amount of VOC adsorbed on 5wt%-PA/AC was
relatively large in spite of the decrease of specific surface area excepting in case of o-xylene,
m-xylene, and MEK. This suggests that the adsorption of relatively large molecules such as oxylene, m-xylene, and MEK was suppressed, while that of small molecules was enhanced. It
can be therefore speculated that the phosphoric acid narrowed the micropores but changed the
chemical nature of surface to adsorb the organic materials strongly.
The variation of amount of VOC adsorbed and the variation of BET surface area with
modified contents were shown in Fig. 1. The optimum modified content was l wt% for
benzene, toluene, p-xylene, methanol, ethanol and iso-propanol, but the amount of o-xylene,
m-xylene, and MEK adsorbed were decreased with increasing modified contents.
Interestingly, the amount of benzene, p-xylene, and ethanol adsorbed on l wt%-PA/AC was
1.5 to 2 times that on purified AC. The BET surface area of l wt%-PA/AC (1109m2/g) took
the maximum value.

459

Table 1. The prepared M A C s and their specific surface area and VOC adsorption on PAC and
various 5wt%-MACs
Aromatics

BET Surface
Area,,~,tm2/o~ Benzene

Sample

Alcohols

Tolomuene xylene xylene

PMeOH
xylene

EtOH

isoMEK
propanol

PAC

892

5.1

3.6

4.7

6.3

4.2

5.3

1.9

1.6

4.4

NA/AC

894

4.7

3.1

5.2

3.9

3.9

4.4

1.9

1.6

3.1

AA/AC

867

5.7

3.6

4.5

6.2

4.2

5.4

1.6

1.9

3.5

HA/AC

718

4.0

2.3

3.9

3.1

3.5

3.7

1.5

1.3

3.0

SA/AC

840

5.1

3.2

4.4

3.9

4.4

5.1

1.9

1.7

3.5

PA/AC

719

6.4

4.1

4.9

4.1

5.2

5.7

2.2

1.9

4.0

PH/AC

668

4.5

2.9

4.1

3.6

4.4

4.3

1.8

1.4

3.2

SH/AC

636

3.8

2.7

4.0

4.5

3.9

4.7

2.0

1.5

3.1

The reason for enhancement of adsorption

due to combination effect of increase of
BET surface area and chemical modification

- - - ~ I~-r ~

121
| *
I/\
'~

performance of PA/AC was considered to be

Area

+ Benzene
I "-0- Tcluene
I -'*- ~
I-"-r,,X~,~

E
88

1200

~000 __

--~.- ahard

8oo

by the treatment with PA. Consequently,

l wt%-PA/AC was determined to be a best
candidate

as an adsorbent for removing

benzene,

toluene,

p-xylene,

methanol,

09

<

~ ~, o

10

2oo4~176
m

ethanol, and iso-propanol. Therefore, l wt%PA/AC

was

investigate

used
the

as

the

adsorbent

adsorption

to

15

20

conterts [wt~o]

isotherm,

Fig. 1. Effect of modified contents on PA/AC.

adsorption and desorption performance.

3.2. Adsorption isotherms

Langmuir and Freundlich adsorption isotherms for toluene and M E K are shown in Figs. 2

0.25

.I.

o.2

1.6

0.15

,---., 1.2

0.1

0
E 0.8
E
,._.,,

l Oto,uene ~

0.05
0

0.2

0r 0 . 4
c
m

0.4

0.6

0.8

Ce[ mmol/L]

Fig. 2. Langmuir adsorption isotherm of

toluene and MEK on l wt%-PA/AC.

[Oto,uene

'

-2

-1.5

-1

-0.5

InCe[ mmol/L]

Fig. 3. Freundlich adsorption isotherm of

toluene and MEK on l wt%-PA/AC.

460
and 3, respectively. Langmuir and Freundlich isotherms expressed relatively well the
adsorption of toluene and MEK, indicating the dependence on both physical and chemical
adsorption. This analysis indicated that the adsorption capacity of MEK on l wt%-PA/AC was
larger than that of toluene.

3.3. Desorption performance by TPD

Fig. 4 shows the TPD experimental
results for l wt%-PA/AC with toluene and
MEK. The desorption characteristics of
l wt%-PA/AC with toluene and MEK were
determined by raising the room temperature
by 5~ /min to 300~ Maximal desorption
concentrations and temperatures of both
toluene and MEK were 1.13, 1.25 and 150 ~
100~ respectively. The toluene and MEK
adsorbed on l wt%-PA/AC was completely
desorbed when the adsorbent was heated in
an electric furnace. The temperature of the
adsorbent
was
programmed,
and
concentration of VOCs desorbed could be
controlled at some extents. The desorbed
efficiencies of toluene and MEK were
98.1% and 99.1%, respectively. Similar TPD

patterns were obtained even though the

adsorption-desorption
operation
was
repeated. It was therefore considered that the
adsorbents will be effective for repetition of
adsorption-desorption processes.
35O

3OO
1.2

25o
1.0

2oo

o 0.8
C.)

(~

0.6

E
too ~-

0.4
0.2
o.o ~
0

~" ~ ~ " " ~ ~~ ' ~ I0

2o

3o

4o

5o

0
60

Time on strean~min]

Fig. 4. TPD spectra from the desorption of

toluene and MEK on l wt%-PA/AC.

4. CONCLUSIONS
Adsorption capacity and desorption characteristics of modified activated carbon (MAC)
prepared with various acids and bases were investigated. Among the prepared MACs, PA/AC
showed the greatest adsorption capacity for benzene, toluene, p-xylene, methanol, ethanol and
iso-propanol due to chemical modification of its surface despite the decreased specific surface
area. Also, the maximum BET surface area with modified content of PA/AC showed l wt%PA/AC. The amount of VOC adsorbed on l wt%-PA/AC was larger than that on purified AC
excepting that of o-xylene, m-xylene, and MEK. The adsorbed toluene and MEK were easily
desorbed by heat treatment to 300 ~ suggested the possibility for repeated use. The findings
confirmed the potential of lwt%-PA/AC as a promising adsorbent for controlling VOC
emissions with low concentrations.

REFERENCES
[ 1] C.L. Chuang, P.C. Chiang, Chemosphere, 53, 17 (2003).
[2] D.J. Kim, W.G. Shim and H. Moon, Korean Jr. Chem. Eng., 18, 518 (2001 ).
[3] L. Guo, A.C. Lua, J. Porous Materials, 7,491 (2000).