Fuel 85 (2006) 179–184

www.fuelfirst.com

A novel nickel/carbon catalyst for CH4 and H2 production from organic

compounds dissolved in wastewater by catalytic hydrothermal gasification
Atul Sharma a, Hiroyuki Nakagawa b, Kouichi Miura b,*
a
Shiga Prefecture Industrial Support Plaza, Inc., Shiga, Japan
b
Department of Chemical Engineering, Kyoto University, Kyoto 606-8501, Japan
Received 13 October 2004; received in revised form 9 February 2005; accepted 25 April 2005
Available online 21 September 2005

Abstract
A novel Ni/carbon catalyst recently developed by the authors was used to gasify organic compounds dissolved in the wastewater with TOC
concentration from 0.2 to 2%. The process removes the organic compounds by gasifying them into high calorific gases like methane and hydrogen.
The investigations were focused on the efficiency of the Ni/carbon catalyst in terms of carbon conversion, conversion of big organic molecules,
and catalyst deactivation due to sintering. The preliminary results showed that up to 99% carbon conversion can be achieved at 360 8C, and
20 MPa. A conversion mechanism was suggested which consists of: first, decomposition of big molecules to small molecules on the metal surface,
steam gasification of small molecules to produce CO and H2 followed by CO methanation and CO shift reaction to produce CH4 and CO2. The
catalyst was found to be highly active and stable and no sintering was observed even after 100 h of reaction time.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Nickel carbon catalyst; Hydrothermal gasification; Wastewater treatment

1. Introduction high concentrations. A typical electronic industry produces

Brown coals are important energy resources in the near
future because of their abundant deposits and distribution all
over the world. However, the water contents of brown coals are
very large in general: they reach as high as 60% by weight for
some coals. Therefore, dewatering (drying) is the first and
essential step in almost any brown coal utilization process [1,2].
In some of these processes, brown coals are treated under
hydrothermal conditions at 200–300 8C, where upgrading as
well as dewatering of brown coals are realized through the
decomposition of oxygen functional groups. It is preferable to
employ higher temperature for the treatment to be more
effective, but the amount of organic compounds leached out
from coal into the wastewater increases with increasing
treatment temperature [3]. This causes the loss of combus-
tible organic matter on one hand, and necessitates the
wastewater treatment on the other hand [4,5]. Similarly,
several industrial processes produce huge amounts of
wastewaters that contain organic compounds in small to
* Corresponding author. Tel.: C81 75 383 2663; fax: C81 75 383 2653.
E-mail address: miura@cheme.kyoto-u.ac.jp (K. Miura).
0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.04.035
about 5 ton/day of wastewater that contains about 2% total
organic carbon (TOC) concentration of organic compounds.
Similarly, palm oil mill industry in Malaysia produces about
30 MT/year of wastewater that contains about 0.3% TOC
concentration of organic compounds.
The treatment of wastewater is a serious issue not only from
environmental aspect but also due to loss of energy.
Wastewater containing organic compounds is generally treated
by the biological process (activated-sludge process), which
takes a long time and needs a large land. Apart from this
process gasification of organic compounds under hydrothermal
(HT) and/or supercritical water (SCW) condition has been paid
great attention, because it cannot only gasify the organic
compounds in the wastewater in a very short time but also
recover some fuel gas.
Several fundamental studies have been performed on the
gasification of organic compounds under HT and/or SCW
conditions. Yu et al. [6] has reported that glucose was gasified
at 600 8C and 34.5 MPa to produce H2, CH4, CO2, and CO
without catalysts. Xu and Anthal Jr [7] gasified a cornstarch
using an activated carbon catalyst to produce H2, CH4, and CO2
at 650 8C and 22 MPa. Schmieder et al. [8] succeeded in
gasifying several organic compounds including biomass at
600 8C and 25 MPa using KOH and K2CO3 as catalysts. The
experimental conditions employed by these researchers were
180 A. Sharma et al. / Fuel 85 (2006) 179–184
rather severe. Elliott [9–12] and his group has succeeded in
gasifying p-cresol completely at 350 8C and 20 MPa using a
Ni/Al2O3 catalyst that was selected from many candidates. His
group has also proposed a wastewater treatment process using
this gasification method. However, the Liquid Hourly Space
Velocity (LHSV) value realized by his group was 1 to 3 hK1,
which means that this process is not so effective. LHSV
governs the size of the reactor and eventually the plant and
running cost. A low LHSV means large reactor size and high
plant and running costs. Minowa et al. [13,14] has examined
the gasification of cellulose at 200–400 8C using several
catalysts. It was found that Na2CO3 is suitable to obtain water-
soluble components and that Ni-catalyst is effective to gasify
cellulose. As briefly reviewed, several trials have been made on
HT and SCW gasification. However, development of more
effective gasification methods based on highly active catalysts
is desired to apply HT and SCW gasification practically.
Recently, the authors have developed a novel Ni-supported
carbon catalyst [15–17]. The catalyst developed is a hard
spherical particle, supporting lots of Ni in highly dispersed state
on porous carbon support. This catalyst was successfully applied
to convert NO to N2 at 300 8C in gas phase without any reducing
agent [15]. Then the catalyst was applied to gasify organic
compounds dissolved in water under hydrothermal conditions.
Organic compounds such as sucrose, acetic acid, benzene,
toluene, and phenol were completely gasified to produce H2 and
CH4 at 350 8C and 20 MPa [16]. Based on the successful and
encouraging results of these studies, it was decided to investigate
the application of the above catalyst and process for treating
industrial wastewaters that contain organic compounds. How-
ever, developing an industrial process is full of challenges and
several issues must be investigated before a full-scale plant can
be considered. Among the several issues, the most important
issue is that of catalyst deactivation. The actual wastewater is
never a pure organic compound containing water but many
elements such as sulfur, chlorine and acids that deactivate and
some time destroy the catalyst and/or catalyst support are also
present. In addition, carbon based metal catalysts are also well
known for deactivation due to sintering and loss of surface area
due to carbon deposition. All the above issues affect the active
life of the catalyst and eventually the economics of the process.
In this paper, an improved novel Ni/carbon catalyst was
used to gasify organic compounds dissolved in the wastewater
with TOC concentration from 0.2 to 2%. The investigations
were focused on the efficiency of the Ni/carbon catalyst in
terms of carbon conversion, conversion of big organic
molecules, and catalyst deactivation due to sintering.
2. Experimental
2.1. Sample preparation
A wastewater from coal was produced during hydrothermal
treatment at 300 8C for 30 min of Loy Yang brown coal from
Latrobe Valley, Victoria, Australia. Hydrothermal treatment is
commonly conducted by adding extra water to the brown coal
prior to treatment. However, Loy Yang contains sufficient
inherent moisture (60–65%) to maintain hydrothermal con-
ditions during treatment at 300 8C. The wastewater produced
using this treatment method instead of traditional treatment with
extra water will have a significantly higher content of dissolved
organic matter, making it more suitable for gasification.
A detailed description of the dewatering process has been
described by Karin et al. [18]. The total organic carbon (TOC)
concentration was found to be 3000 ppm in the wastewater after
treatment. The amount of water was only 90 ml which was not
sufficient for 5 h run. Therefore, the wastewater was diluted to
2000 ppm (0.2%) of TOC concentration giving 150 ml of
wastewater for the gasification experiment.
A wastewater simulating a wastewater from an electronic
industry was prepared as per the organic compounds compo-
sition outlined in the industry’s effluent data sheet. The
wastewater contained phenol as a major organic compound.
The total TOC concentration was about 20,000 ppm (2%). The
simulated wastewater of 2% TOC concentration was prepared by
dissolving 26 g of phenol in 1 kg of water. In addition, an organic
water containing phenol corresponding to 2000 ppm (0.2%)
TOC concentration was also prepared to investigate the effect of
concentration on gas composition and gasification mechanism.
The samples were named as Loy Yang water (LYW), Industrial
water (IW) and Phenol water (PW), respectively.
An experiment supplying heavy water (D2O) of 99.9%
purity to the reactor was also carried out for 5 h to understand
the reaction mechanism.
2.2. Catalyst preparation
A meta-acrylic acid type ion exchange resin (Mitsubishi
Chemical, WK-11) was used as a starting material. It was
spherical in shape and its average diameter was about 0.5 mm.
About 20 g (50% water content) of resin as received was treated
in a beaker by 200 ml of aqueous ammonia solution (5 ml, 28%
conc.) containing 10.5 g of NiSO4$6H2O at room temperature
for 24 h. The amount of ammonia was adjusted to keep the
solution as a weak base (pH 8.8). The treated resin was then
washed by deionized water, followed by vacuum drying at 70 8C
for 24 h. The dried resin was heated in a nitrogen atmosphere at
the rate of 10 K/min to 500 8C to prepare the Ni/Carbon catalyst.
Fig. 1 shows a SEM image of the Ni/Carbon catalyst prepared. It
was very hard particle of 0.2–0.4 mm in diameter, maintaining
spherical shape. The amount of Ni supported by this method
surprisingly reached as high as 47 wt%, which was estimated
from the amount of ash of the catalyst. The BET surface area of
the 47% nickel containing particle was 170 m2/g and most of
pores were 1–10 nm in diameter. The apparent density was as
high as 1.9 g/cm3 because of high Ni content.
2.3. Apparatus and procedure
The experimental setup used for the catalytic hydrothermal
gasification (CHTG) has been described in detail elsewhere
[17]. However, we describe it here briefly. A small reactor
with 0.6 ml volume was charged with about 0.7 g of catalyst.
The wastewater from coal dewatering process and simulated
 A. Sharma et al. / Fuel 85 (2006) 179–184 181

Fig. 2. The carbon conversion, carbon balance and product gas yield for LYW,
Fig. 1. SEM image of the catalyst prepared.
IW and PW.
industrial wastewaters were continuously supplied to the
However, in case of IW, the carbon balance is about 94%. In
reactor by an HPLC pump at the rate of 0.5 ml/min which
addition, unlike LYW and PW gasification, C2H6 gas was
corresponded to 50 hK1 of liquid hourly space velocity
observed during the gasification of IW. These results suggest
(LHSV). The pressure inside the reactor was regulated at
that lower carbon balance for IW is probably due to the
20 MPa by use of a backpressure regulator. The reactor was
production of hydrocarbon gases larger than CH4 and C2H6 in
heated by an electric furnace. A thermocouple was inserted
molecular mass which could not be analyzed in this work.
below the reactor bed to regulate the bed temperature at 360 8C.
Fig. 3 shows gasification results for PW and IW water for 50
The effluent stream passing the backpressure regulator was led
and 200 h run time, respectively. The conversion, carbon
to a glass pot where all the products were collected. The
balance, gas yield, and composition are similar to those
gaseous product was then led to a gasbag through a valve
obtained in short time experiments. It is quite interesting to
equipped on the cap of the glass pot, and was analyzed by a
observe the formation of C2H6 in IW gasification when the only
Varian CP-4900 MicroGC equipped with Porapak Q and MS-
difference between IW and PW is the concentration of organic
5A columns. The liquid product was analyzed by a total
carbon. In IW, it is also worth to note that the yield of CO2 and
organic carbon analyzer (Shimadzu, TOC-5000A) to measure
H2 decreased in comparison to PW while CH4 remained same.
TOC and IC (inorganic carbon) concentrations of the treated
Fig. 4 shows the X-ray diffraction pattern of the fresh
water from which the carbon conversion of the organic
catalyst. Two broad peaks at 52 and 448 are attributed to
compound was estimated. XRD and TEM analysis were
metallic Ni, indicating that the crystallite size of Ni was very
made for the spent catalyst to investigate the change of
performance of the catalyst after extended reaction time. PW (0.2% TOC) gasification

Conv. CO2 CH4 H2 Cbalance

1.0
Yield, [mol/mol-C]

3. Results and discussion

Conversion, [-]

0.8
0.6
3.1. Gasification of wastewaters 0.4
0.2
Fig. 2 shows the carbon conversion, carbon balance and 0.0
0 10 20 30 40 50
product gas yield after CHTG of the LYW, IW, and PW
Time (h)
obtained at 360 8C after 5, 4 and 5 h of run time, respectively.
The LHSV value and the pressure employed were 50 hK1 and IW (2% TOC) gasification
20 MPa, respectively. The carbon conversion was about 99% Conv. CO2 CH4 C2H6 H2 Cbalance
for LYW and PW while it was about 95% for IW. Both LYW
1.0
Yield, [mol/mol-C]

and PW were about 2000 ppm TOC concentration, while IW

Conversion, [-]

0.8
was 20,000 ppm. The gaseous products detected were CH4, H2, 0.6
and CO2 for the gasification of LYW and PW while C2H6 was 0.4
also observed in the case of the gasification of IW. No CO was 0.2
detected. The carbon balance was obtained from the sum of 0.0
0 50 100 150 200
moles of carbon obtained as CO2, CH4 and C2H6 (in case of
Time (h)
IW). The carbon balance was 97, 94 and 99% for LYW, IW and
PW, respectively. The sum of the yields of CH4 and CO2 well Fig. 3. Product gases yield and carbon conversion during the 50 and 100 h run
coincided with the carbon conversion for LYW and PW. time for PW and IW waters, respectively.
182 A. Sharma et al. / Fuel 85 (2006) 179–184

Ni500fresh Ni500PW50h Ni500IW50h Decomposition of organic compounds

2
Ni C6 H5 OH C nNi/ C6 Hx KnNi C ð2KxÞH2 C H2 O (2)
Ni500PW50h

1.5
Reduction of NiO
Ni500IW50h Ni500fresh C6 Hx KnNi C 6NiO/ 6CO C ðx=2ÞH2 C ð6 C nÞNi (3)
Intenisty

1 Methanation reaction
Ni
NiO CO C 3H2 # CH4 C H2 O (4)
0.5
Water–gas shift reaction

0
CO C H2 O% CO2 C H2 (5)
30 35 40 45 50 55 60
2 theta
Overall reaction (not stoichiometric)
C6 H5 OH C H2 O/ CH4 ; C2 H6 ; H2 ; CO2 (6)
Fig. 4. XRD patterns of fresh and spent catalyst after 50 h.
Water oxidizes nickel according to reaction (1) and
small. The XRD profile of the catalyst after 50 h run time with
produces H2 and NiO. The organic compound is decomposed
0.2 and 2% TOC concentration are compared with the fresh
on the nickel particle surface to produces a complex consisting
catalyst profile in Fig. 4. The XRD profile of the catalyst after
of the decomposed organic compound and nickel as proposed
50 h run with IW does not show any significant changes.
by reaction (2). These complex intermediate molecules react
However, the catalyst after 50 h run with PW shows sharpening
with NiO formed by (1) to give CO, H2 and metallic Ni by
of peaks at 44 and 528 suggesting that the crystalline size of
reaction (3). The reactions (1)–(3) establish a redox cycle in
nickel particles increased. Also, an additional broad peak that
which carbon from organic compounds acts as reducing agent
was found to correspond to nickel oxide (NiO) appeared at 368.
to reduce NiO to Ni. The above reactions are main reactions
The formation of NiO suggests the oxidation of nickel either by
producing H2 and CO. The H2 and CO produced then reacts
oxygen from water or from dissolved oxygen in water. To
according to the methanation reaction (4) to give CH4 and H2O.
clarify the source of oxygen, an experiment was carried out
Methane may also be produced via decomposition reaction (2),
supplying heavy water (D2O) to the reactor for 6 h and the gas
but most of CH4 was judged to be formed by the reaction (4) as
collected was analyzed by a GC that can analyze D2.
was pointed out by Boudart [19]. In addition, the water–gas
Approximately, 14% of D2 was observed in the gas collected
shift reaction (5) also takes place, where CO reacts with H2O to
and no other gas was detected (balance was N2 purge gas).
produce CO2 and H2. The reactions (4) and (5) are judged to be
Fig. 5 shows the XRD profile of the catalyst after 6 h run with
in equilibrium under the experimental conditions employed
D2O. Broad peaks corresponding to NiO can be seen at 36 and
here. C2H6 may be formed either by decomposition of organic
428. These results confirm that nickel is oxidized by the oxygen
molecules over nickel surface (2) or by reaction (4). However,
from water to produce H2.
at the reaction conditions employed in the present study, the
formation of C2H6 by reaction (4) is less likely [19]. C2H6 may
3.2. Gasification mechanism
be formed by decomposition reaction (2) in both PW and IW
gasification. In case of PW, however, C2H6 formed may be
Based on the above results and by referring to the
further gasified to CO and H2 by reactions (3) and (4). This
mechanism proposed by Boudart [19] for the steam reforming
suggests that the reaction (3) is the slowest and hence rate
of CH4, the following reaction mechanism may be proposed.
controlling step of the overall gasification reaction.
Decomposition of water (oxidation of Ni)
Ni C H2 O/ NiO C H2 (1)
2

2 Ni500fresh Ni
Ni
1.5
Ni500fresh Ni500IW100h
1.5
Intenisty

Ni500D2O
Intensity

1
1
Ni Ni
NiO
0.5
0.5

0 0
30 35 40 45 50 55 60 30 35 40 45 50 55 60
2 theta 2 theta

Fig. 5. XRD profile of Nickel catalyst after 5 h experimental run with D2O. Fig. 6. XRD profile after 100 h with IW sample.

Fig. 7. TEM images of (a) fresh and (b) after 100 h.
The formation of NiO in PW can also be explained based on
the above mechanism. The catalyst developed in this study has
high content of nickel of highly dispersed particles as small
particles as 5–8 nm in diameter. The smaller the particle size,
the higher the number of active sites. The catalyst therefore, is
a highly active catalyst. When this nickel catalyst was used to
gasify PW which contained 2000 ppm of organic carbon,
transformation of Ni to NiO and increase in Ni particle size was
observed. However, when the same catalyst was used to gasify
IW sample containing 20,000 ppm of organic carbon, no
change in Ni to NiO was observed. This means that in case of
PW, NiO formed by reaction (1) is not totally reduced to Ni by
reaction (3) due to small concentration of reducing agent. On
the other hand, in case of IW, the concentration of reducing
agent is expected to be at least ten times as large as that of PW
and is sufficient enough to reduce all the NiO formed. This can
also be seen from the carbon conversion achieved for PW and
IW. In case of PW the conversion was 100%, while for IW the
conversion is about 94% and never reached 100%.
3.3. Performance of the catalyst
It is well known that carbon based metal catalysts show loss
of activity with time. There are many reasons for the catalyst
deactivation such as deactivation by sintering and phase
transformation, deactivation due to specific surface change due
to carbon decomposition during steam reforming. We
examined the activity of the catalyst for extended reaction
time of up to 200 h using IW sample which contained 20,
000 ppm TOC. The catalyst used is the same as one employed
IW (2% TOC) gasification
Conv. CO2 CH4 C2H6
1.0
Yield, [mol/mol-C]
Conversion, [-]
0.8
0.6
0.4
0.2
0.0
5 10 15
Time (h)
Fig. 8. Product gases yield and carbon conversion during the 25 h run at
100 hK1 LHSV to investigate the stability of the catalyst.
A. Sharma et al. / Fuel 85 (2006) 179–184 183
for the gasification of LYW and PW. Fig. 3 shows the changes
of product gas yields and carbon conversion during 200 h run
time. Both the carbon conversion and the gas yield were very
stable and steady up to 200 h, suggesting that the catalyst was
highly active even up to 200 h. After 100 h reaction time, XRD
and TEM measurements were made to observe the changes in
the catalyst. Fig. 6 compares the XRD patterns of the fresh
catalyst and the catalyst after 100 h. The main peak for Ni
showed no change in shape, suggesting that no sintering took
place. Also, no new peak was observed, indicating that no
phase transformation of Ni took place. TEM images also
confirm the results from XRD. Fig. 7 shows that the nickel
particles were still in the original size even after 100 h of use.
The catalyst BET surface area was also measured after 100 h.
The BET surface area after 100 h was 175 m2/g while the
initial BET surface area was 170 m2/g. These results suggest
that surface characteristics of the catalyst did not change at
least after 100 h of run.
The stability of the catalyst was investigated by carrying out an
experiment well below 100% conversion level. The same catalyst
and experimental conditions were employed except the LHSV
which was increased to 100 hK1. The increase in LHSV lead to
decrease in the conversion as expected due to reduced residence
time. Fig. 8 shows the conversion and gas yield profile during the
25 h run time. The conversion was 77% and was steady for 25 h
suggesting a good stability of the catalyst. These results show that
the Ni/Carbon catalyst is highly active and stable even after long
reaction time, proving that the present catalyst developed in this
study is more active and sintering resistant than other catalysts
reported in the literature [9–12].
4. Conclusions
H2 Cbalance
A novel Ni-supported carbon catalyst developed by the
authors was applied to treat wastewaters from coal dewatering
process and an electronic industry. The organic compounds in
each wastewater were almost completely gasified by use of the
catalyst at as low as 360 8C under 20 MPa at the liquid hourly
space velocity (LHSV) of as large as 50 hK1, producing
20 25 combustible gas rich in CH4 and H 2 in equilibrium
composition. The conversion mechanism was believed to
consist of: first, decomposition of big molecules on the Ni
surface to small molecules, steam gasification of small
184 A. Sharma et al. / Fuel 85 (2006) 179–184

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