392 Journal of the Japan Petroleum Institute, 46, (6), 392−395 (2003)

[Research Note]

Oxidation of Sulfur Dioxide to Sulfuric Acid over Activated Carbon

Catalyst Produced from Wood

Naonobu KATADA†1)*, Yusuke II†1), Munekazu NAKAMURA†2), and Miki NIWA†1)

†1)
Dept. of Materials Science, Faculty of Engineering, Tottori University, 4-101 Koyama-cho Minami, Tottori 680-8552, JAPAN
†2)
Faculty of Education and Regional Sciences, Tottori University, 4-101 Koyama-cho Minami, Tottori 680-8551, JAPAN

(Received June 9, 2003)

Sulfur dioxide can be removed from exhaust gases by oxidation to sulfuric acid over an activated carbon cata-
lyst in the presence of water. A manufacturing method for activated carbon was developed based on the steam-
ing of wood at relatively low temperature. The catalytic activity of the activated carbon produced from wood for
the oxidation of sulfur dioxide was compared with those of commercially available activated carbons. The car-
bon produced from wood showed high activity, but it was lower than that of a highly developed catalyst such as
activated carbon fiber. However, the potential utilization of waste wood as an environmental catalyst was clear-
ly demonstrated.

Keywords
Sulfur dioxide, Catalytic oxidation, Activated carbon catalyst, Waste wood, Sulfuric acid

1. Introduction was attempted5)∼8). Recent studies of several catalysts

Sulfur dioxide formed by the oxidation of sulfur
compounds in petroleum or coal burned as fuels causes
acid rain. Several methods for the removal of sulfur
compounds from the fuels or exhaust gases are utilized.
Oxidation and neutralization of sulfur dioxide in the
presence of oxygen, water vapor and calcium oxide
powder into calcium sulfate (gypsum) has been utilized
for a boiler using heavy oil1).
SO2 + 0.5O2 + CaO CaSO4 (1)
However, the use of gypsum has been limited in recent
years. Therefore, in civilized countries, gypsum
formed by this process is treated as an industrial waste.
Sulfur dioxide is oxidized into sulfuric acid over an
activated carbon catalyst in the presence of water2).
SO2 + 0.5O2 + H2O H2SO4 (2)
Therefore, the latter catalytic reaction has recently
drawn attention, because the formed sulfuric acid can
be utilized for industrial processes, so the harmful
waste, sulfur dioxide, can be recycled as a useful
resource, sulfuric acid3).
The study on the catalytic oxidation of sulfur dioxide
has a long history. The relationship between the sur-
face composition and catalytic activity was investigated
to propose a model of active site in early studies4).
Subsequently improvement of the trickle bed reactor
* To whom correspondence should be addressed.
* E-mail: katada@chem.tottori-u.ac.jp
such as activated carbon fiber9) and fluorocarbon-treat-
ed carbon3) have found quite high performance.
Production of activated carbon from wood has
recently become important for the utilization of waste
wood10),11). Conventionally, the production of activat-
ed carbon from wood has been carried out using a
reagent such as zinc chloride or water vapor at quite
high temperatures such as 1473 K12). The present
authors previously developed a method to produce acti-
vated carbon with high surface area by the water vapor
treatment of wood at a moderate temperature such as
1073 K13). Here we report the catalytic activity of the
activated carbon for the oxidation of sulfur dioxide.
2. Experimental
Table 1 shows a list of activated carbons used in
this study. The sample YS-1 was prepared according
to our previous patent13). Chips of sugi wood
(Japanese cedar, ca. 5 cm in length) were continuously
fed into a stainless steel reactor with 543 cm2 cross sec-
tional area at 5 kg･h−1. A gaseous mixture of water
vapor and nitrogen (7.50 mol･h−1 and 3.68 mol･h−1,
respectively) was also continuously supplied. The
wood was passed over a heated zone in which the tem-
perature was kept at 1073 K for ca. 20 min. In other
words, the water vapor treatment of sugi wood was car-
ried out at 1073 K for ca. 20 min in a nitrogen flow
containing 67 mol% of water vapor. The samples YS-

J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003

 393

Table 1 Activated Carbons Used in This Study

BET surface
Nomenclature Manufacturer Raw material
area [m2･g−1]
YS-1 Y.S. Engineering Ltd. Sugi wood (Japanese cedar)a) 659
YS-2 Y.S. Engineering Ltd. Waste wood from scrapped houseb) 677
YS-3 Y.S. Engineering Ltd. Waste wood from scrapped housec) 680
4SA Kuraray Chemical Co., Ltd. Coconut shell 958
4GG Kuraray Chemical Co., Ltd. Coconut shell 1047
PG-3 Cataler Corp. Coal 1240
G-BAC G-70R Kureha Chemical Industry Co., Ltd. Pitch from petroleum 1236
JXN Nippon Carbon Co., Ltd. Coconut shell 1144
HG Ajinomoto Fine-Techno Co., Inc. Coconut shell and coal 1143
GX Takeda Chemical Industries, Ltd. Coconut shell 1229

a) 1073 K, H2O : N2 = 0.67 : 0.33 (molar ratio). b) 1123 K, H2O : N2 = 0.67 : 0.33. c) 1123 K, H2O : N2 = 0.82 : 0.18.

2 and 3 were prepared from waste wood at 1123 K for

ca. 20 min in a nitrogen flow containing water vapor
(67 mol% and 82 mol% for YS-2 and 3, respectively).
Other samples were supplied commercially. Surface
area was determined from the adsorption capacity of
nitrogen at 77 K according to the BET (Brunauer_
Emmett_Teller) equation after evacuation at 373 K.
The activated carbon (3.8 g) was placed in a Pyrex
tube (30 mm i.d.) and evacuated at 318 K for 1 h.
After evacuation, the reactant mixture was directly sup-
plied to the catalyst bed, and the adsorption of sulfur
dioxide on the carbon surface took several hours to
reach saturation. The catalytic activity could then be
measured from the consumption of sulfur dioxide4).
In order to avoid this long equilibration period, the cat-
alyst bed was filled with a 0.5 mol･dm−3 aqueous solu-
Fig. 1 Conversion of SO2 over Various Activated Carbons in
tion of sulfuric acid to fully adsorb sulfuric acid. The Supplied Form
solution was soon exhausted. This pretreatment
method was adopted for quick evaluation of catalysts in
the previous studies3). After this pretreatment, a mix- mercially available samples showed initial conversions
ture of nitrogen, sulfur dioxide, oxygen and water of 40 to 80%, and slow degradation of the activity was
vapor was fed at rates of 1.9 × 10−4, 1.1 × 10−7, 1.3 × generally observed. The activity was apparently
10−5 and 1.9 × 10−5 mol･s−1, respectively, under atmos- independent of the surface area. The activated car-
pheric pressure, corresponding to a space velocity of bons prepared from wood (YS-1, 2 and 3) showed
ca. 1200 h−1 and initial concentration of sulfur dioxide higher activities. Especially, the samples prepared
of 500 ppm. The reaction was carried out at 318 K from waste wood (YS-2 and 3) showed initial conver-
under the trickle bed conditions, i.e., condensed water sions close to 100% under these conditions.
and sulfuric acid (reaction product and reagents The apparent rate of this reaction was affected by the
remaining after the pretreatment) formed liquid drops morphology of activated carbon generally in a trickle
in a gas flow. The remaining sulfur dioxide in the gas bed reactor, because the reaction occurs at the triple
flow at the outlet of the reactor was analyzed by an SOx phase interface between the liquid (water and produced
meter (Koritsu, KS-300). sulfuric acid), gas (oxygen and sulfur dioxide) and
X-Ray photoelectron spectroscopy (XPS) was per- solid (carbon) phases; so the macro porosity of the cat-
formed with a Physical Electronics Quanta SXM spec- alyst affected the accessibility of liquid drops and gas
trometer with Al Kα radiation (1486.6 eV) at 15 kV bubbles to the triple phase interface5)∼8). The conver-
and 6.36 mA to analyze the surface composition. sion was increased by milling the activated carbon into
fine particles (< 0.1 mm) in all cases. Figure 2 shows
3. Results and Discussion that the activated carbons prepared from wood (YS-1, 2
and 3) also showed the highest activity after milling,
Figure 1 shows the catalytic activities of various with 100% conversion under the experimental condi-
activated carbons as their supplied forms. The com- tions.

J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003

 394
Fig. 2 Conversion of SO2 over Various Activated Carbons
Milled into Fine Particles (< 0.1 mm)
The activity of carbon for this reaction is affected by
the macroporosity5)∼8), surface composition4) and hydro-
phobic/hydrophilic property3). Elemental analysis of
the surface by XPS showed a positive relationship
between the oxygen concentration and activity after
milling, as shown in Fig. 3. This is in agreement
with previous findings4), and therefore the high activity
of the activated carbon produced from wood can be
explained by the high oxygen concentration.
However, the origin of the high oxygen concentration
on the carbon produced from wood remains unclear.
In addition, the observed oxygen may be contained in
impurity metal oxides and functional groups such as
phenol, ketone, carboxylic acid and alcohol groups, and
the effects of these species was not been clear.
Further study is needed.
The activity of the activated carbons in the supplied
form was not related to the oxygen concentration.
This is presumably because the morphology of the car-
bon strongly affects the apparent reaction rate.
To evaluate the catalytic performance, the space
velocity was increased to ca. 2400 h−1 with constant
molar ratios of the reactants; the flow rate of sulfur
dioxide was increased to 2.2 × 10−7 mol･s−1 with the
catalyst amount of 3.8 g. The conversion over YS-3
was 69%, and the activity was stable within 5 h on the
stream (data not shown). Therefore, the reaction rate
was 4 × 10−8 mol･s−1･g-C−1. Also under these condi-
tions, the activity was higher than those of the commer-
cially available activated carbons, e.g., the conversion
of 4GG was 36%. The conversion of sulfur dioxide
on the best activated carbon fiber was ca. 93% at 303 K
in a gaseous mixture of 1000 ppm of sulfur dioxide
(double that of the present study), 5 mol% and 10
mol% of oxygen and water, respectively (same as in the
present study) with 5 × 10−4 g･min･cm−3 for the W
J. Jpn. Petrol. Inst., Vol. 46,
Fig. 3 Relationship between Surface Concentration of Oxygen
and Catalytic Activity of Activated Carbon before (○)
and after Milling (▲)
(weight of carbon)/F (total flow rate) ratio9); so the
reaction rate is calculated to be ca. 10−6 mol-SO2 s−1･g-
C−1. This is the highest activity reported for this reac-
tion. Although the reaction temperature was a little
different, the activity presently observed over the acti-
vated carbon produced from wood was approximately
1/20 of that over the activated carbon fiber.
Therefore, the activity per unit weight was lower than
that reported on a carefully designed catalyst such as
carbon fiber. However, from the view point of the uti-
lization of waste material, the present activated carbon
was easily produced from the waste wood, so the dif-
ference in the activity was not so large. The potential
utilization of waste wood as an environmental catalyst
was thus demonstrated.
4. Conclusion
High activity for the oxidation of sulfur dioxide was
observed over activated carbon prepared by the water
vapor treatment of wood. The potential utilization of
the waste wood as an efficient environmental catalyst
was thus demonstrated for the utilization of sulfur diox-
ide as a source of sulfuric acid.
Acknowledgment
This study was partly supported by a Grant-in-Aid
for Scientific Research from the Japan Society for the
Promotion of Science (No. 13650843) and a research
foundation from the Organization for Tottori Industrial
Promotion. The samples YS-1 to 3 were prepared by
Mr. Takazumi Shido and Mr. Ei-ichi Sugitani of Y.S.
Engineering Ltd.
No. 6, 2003
 395

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要   旨

木材から製造した活性炭触媒による二酸化硫黄の硫酸への酸化

片田 直伸†1)，井伊 祐介†1)，中村 宗和†2)，丹羽  幹†1)
†1)
鳥取大学工学部物質工学科，680-8552 鳥取市湖山町南 4-101
†2)
鳥取大学教育地域科学部，680-8551 鳥取市湖山町南 4-101

二酸化硫黄は水の共存下，活性炭触媒上で硫酸へ酸化するこ 販の活性炭の活性と比較した。木材から製造した活性炭は高い
とで排気中から除去できる。一方，著者らは比較的低温で木材 活性を示した。活性は活性炭素繊維のような非常に優れた触媒
を水蒸気処理することによる活性炭の製造方法を開発した。本 のものよりは低かったが，廃木材の環境触媒としての利用可能
研究では，木材から製造した活性炭の二酸化硫黄酸化活性を市 性が示された。

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J. Jpn. Petrol. Inst., Vol. 46, No. 6, 2003