Fuel Processing Technology 194 (2019) 106104

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Fuel Processing Technology

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Research article

Effect of porous silica on the removal of tar components generated from T

waste biomass during catalytic reforming
⁎
Jun Kobayashia, , Katsuya Kawamotob, Noriyuki Kobayashic
a
Department of Mechanical Engineering, Kogakuin University, Tokyo, Japan
b
Graduate School of Environmental and Life Science, Okayama University, Okayama, Japan
c
Department of Materials Science and Engineering, Nagoya University, Aichi, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: Thermal gasification of waste biomass requires a method of tar removal from gasified gases, since the tar pro-
Waste biomass duced is at risk of obstruction of the piping of the gasification processes and failure of the subsequent power
Gasification generation processes. Using laboratory-scale fluidized bed gasifier and catalytic reformers, the characteristics of
Tar removal tar removal was investigated. A commercial Ni-based catalyst and several kinds of porous silica with different
Porous silica
surface areas were applied to the reforming reaction. Moreover, the feasibility of regeneration by air oxidation of
Reforming catalyst
both the catalyst and the porous silica was evaluated. In gasification and reforming experiments using woody
waste, application of porous silica led to lower levels of highly polymerized polycyclic aromatic hydrocarbons
(PAHs). The greater the specific surface area of the porous silica, the lower the concentration of PAHs. Carbon
deposited on the surface of the porous silica and the mass of the carbon deposit reached a maximum at a surface
area of 195 m2/g. When both the catalyst and the porous silica regeneration by air oxidation was performed,
hydrogen concentration was found to level off from the third reforming operation and the amount of total tar did
not increase after the second reforming operation. Our results showed that the catalyst and the porous silica is
likely to have good reforming activity even repeatedly regeneration condition.

1. Introduction conversion processes. In order to establish a highly efficient gasification

Flammable waste which includes biomass is regarded as a renew-
able energy resource in the same way as woody and agricultural bio-
mass. Gasification technology is one of the methods for effective utili-
zation of the waste biomass energy, since it will be possible to improve
the handling as fuel and the flammability in comparison with conven-
tional waste incinerators. The gasification of waste, moreover, has po-
tential for highly efficient energy production, since the fuel gases can be
applied to high-efficiency power generation such as gas turbine com-
bined cycle or fuel cell. [1–3] In order to promote the development of
the energy conversion, there is a need for a suitable gasification method
to make effective use of the gasified gas.
Many types of gasifiers, such as fluidized-bed [4–6], down draft [7],
and rotary kiln [8] types have also been proposed, and extensive re-
search and experiments continue to be conducted. Moreover, many
different methods of biomass gasification using steam [9,10], air
[11,12], oxygen [13] or CO2 [14] as gasifying agents, from low tem-
peratures below 973 K [15,16] to high temperatures over 1273 K
[17,18] have been investigated to develop the effective energy
process that produces convenient and clean fuel gases, we focused on
steam reforming using catalytic reaction at relatively low temperature.
It is reported that the method results in low sensible heat loss and is
useful not only for generating H2 rich gas but also for tar decomposi-
tion. ([19]; Swami et al., 2006; [20]) In recent studies on the applica-
tion of reforming catalysts for promote of tar removal and H2 produc-
tion, various catalysts have been suggested. Noble metals such as Pt,
Rh, and Pd [21,22], base metals such as Ni ([23,24]: [25]) and Co
[26,27] and mineral ores such as limonite, dolomite and olivine
[20,28,29] were evaluated. It has been shown that noble metal catalysts
have high activity in the decomposition of tar, but their high cost rules
them out as a first choice. Catalytic supports such as alumina, silica,
ceria, zirconia and alkaline earth metal compounds have also been in-
vestigated to promote the activity of base metal catalyst. [30,31] Our
research work has also shown CaO and alumina composite, used as a
catalytic support, is able to prevent Ni active sites from coking. [32,33].
To develop steam reforming using base metal catalysts such as Ni
under relatively low temperature condition, however, further tar re-
moval will be a significant issue. In case of high temperature

⁎
Corresponding author at: 2665-1 Nakano, Hachioji, Tokyo 192-0015, Japan.
E-mail address: jkoba@cc.kogakuin.ac.jp (J. Kobayashi).

https://doi.org/10.1016/j.fuproc.2019.05.027
Received 20 November 2018; Received in revised form 17 May 2019; Accepted 18 May 2019
0378-3820/ © 2019 Elsevier B.V. All rights reserved.
J. Kobayashi, et al.
gasification, in which most of tar will be decomposed, there is not only
above-mentioned heat loss but also possibility of erosion on furnace
walls by molten of alkali metal salts included in the biomass. Therefore,
achieving practical gasification requires sufficient ability of tar removal
under relatively low temperature condition. As one of the methods
independent on metal catalysts, tar capture and removal using porous
alumina (gamma alumina) has been studied, and several important
results have been achieved. [34–37] Tar removal performance using
porous alumina would prove to depend on Lewis acid sites rather than
its physical pore structure. From these studies, it is necessary to eval-
uate the function of porous material not only as the catalytic supports
but also as the materials contributed to tar removal. Small pores, which
are almost between 0.7 and 50 nm of pore diameter, will be suitable to
capture large hydrocarbon molecules contained in tar. [38,39] More-
over, a hydrophobic surface may have a strong affinity for organic
compounds. [40] In above-mentioned previous works, several types of
activated carbon and char were mainly applied to tar removal, so we
suppose that porous silica, which is an inorganic hydrophobic ad-
sorbent and mainly has mesopores, is highly effective in attracting tar
and has no effect from oxidizing agents. Moreover, it is thought that the
surface of porous silica will be hardly affected by poisoning chemical
compounds since the surface has few acidic sites.
The main purpose of this study is to investigate the influence of
porous silica on the removal of tar by combining reforming catalyst.
This study will demonstrate that the characteristics of the pore struc-
ture, such as the pore radius and specific surface area, of the porous
silica will in some way influence the decomposition and/or removal of
tar components. The feasibility of regeneration of both the catalyst and
the porous silica are also evaluated.
2. Experimental
2.1. Apparatus
A laboratory-scale gasification unit shown in the schematic diagram
of Fig. 1 was applied to the experiments. The system essentially consists
of two kinds of reactors in series: a primary reactor (gasifier) followed
by two secondary reactors (reformers) made of stainless steel. The ga-
sifier is designed as a fluidized bed-type (ID 37–75 mm, H 1360 mm)
and silica sand (mean particle diameter: 0.6 mm) is used as the fluidized
bed material The reformers are designed as packed bed types (ID
48 mm, H 1620 mm) and a packed bed of porous silica is placed on the
Fig. 1. Schematic diagram of experimental apparatus.
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Fuel Processing Technology 194 (2019) 106104
catalyst bed. All reactors are preheated with electric heaters. Three
thermocouples have been placed in the gasifier at distances of 50, 350,
and 650 mm above the distributor, to measure the temperature of the
fluidized bed, internally circulating particles and area near the outlet,
respectively. Two thermocouples more have been installed in each re-
former: one placed in the catalyst bed and the other placed about
20 mm below the bottom of the catalyst bed, to measure the tempera-
ture of the catalyst bed and the reformed gas, respectively. In this
system, feedstock is continuously supplied from the upper part of the
gasifier.
To perform the reforming process and catalyst regeneration si-
multaneously, two reformers are connected to the gasifier through
several valves that are used for switching between reforming and re-
generation. All pipelines are kept at around 523 K by means of in-
sulating jackets. The oxidizing agents are steam and simulated air
(mixed nitrogen and oxygen), preheated to around 550–600 K. This
mixture is supplied from the bottom of the gasifier. When the gaseous
mixture passes through the distributor, the feedstock and silica sand are
fluidized and mixed in the gasifier. This mixture is constantly heated by
the electric heater, since the thermal decomposition and volatilization
of the feedstock are endothermic. The produced gases and tar in the
gasifier pass through the cyclone, where unreacted char and fly ash are
removed, and then move on to the reformer. The tar and low hydro-
carbons are reformed by steam in the reformer, to be converted into
gases such as H2, CO and CO2.
2.2. Feedstock and packing material in the reformer
The ability of the hydrophobic and thermally stable porous silica to
promote tar removal and decomposition under steam reforming con-
ditions was investigated. In this study, five types of porous silica par-
ticles (Fuji Silysia Chemical Ltd.) with different porosities were used as
adsorbents for tar to assist its decomposition and/or prevent coking on
the catalyst. Their specific surface areas, total pore volumes and mean
pore diameters are shown in Table 1. The larger the surface area, the
smaller the mean pore radius. Here, the particle size of all porous silica
was around 1–3 mm in diameter. A comparison of these materials will
reveal how the fine pore structure of porous silica works.
As reported in our previous work [32,33], Ni-based commercial
reforming catalyst (ReforMax 330 LDP; Süd-Chemie Catalysts Japan,
Inc.) was also used in the experiments. This catalyst contains Ni at 11 wt
% and CaO at 13 wt%, with the balance being Al2O3. Its shape is a 10-
J. Kobayashi, et al. Fuel Processing Technology 194 (2019) 106104

Table 1 Table 4
Structural characteristics of porous silica. Experimental conditionsa (evaluation of catalyst regeneration by air oxidation).
Sample no. S1 S2 S3 S4 S5 Run no. 6 7 8 9 10 11 12 13

2 −1
Specific surface area [m ·g ] 71 107 195 280 430 Reforming reactor 1st 2nd 1st 2nd 1st 2nd 1st 2nd
Total pore volume [ml·g−1] 0.98 0.98 0.99 0.96 0.61 Feed rate [kg·h−1] 0.13 0.13 0.16 0.15 0.14 0.11 0.14 0.15
Mean pore diameter [nm] 48 31 16 13 5.9 Gasifier temp. [K] 1030 1030 1040 1040 1040 1030 1040 1030
Reformer temp. [K] 990 980 1040 1020 1040 1010 1020 1020
S/C [mol/mol] 2.0 2.0 1.6 1.7 1.9 2.4 1.9 1.7
ER [−] 0.14 0.14 0.11 0.12 0.13 0.17 0.13 0.12
Table 2
Maximum reformer 1110 1050 1070 1050 1100 1050 – –
Proximate and ultimate analyses of woody biomass.
temp. during air
Volatiles (wt% dry) 80.0 H (wt% dry) 5.9 oxidation [K]
Fixed carbon (wt% dry) 18.0 C (wt% dry) 51.4
a
Ash (wt% dry) 2.0 O (wt% dry) 40.7 The porous silica used in these experiments is S3.
Moisture (wt%) 9.0 N (wt% dry) < 0.1
HHV (MJ/kg dry) 20.5 Cl (wt% dry) < 0.01 reformer shown in Tables 3 and 4 is average of actual measured values
LHV (MJ/kg dry) 17.2 S (wt% dry) < 0.02
during each experiment. Gasification gas obtained by the gasifier has
been introduced into either of the reformers for about 2 h. The pro-
hole ring, with a diameter of 19 mm and height of 16 mm. The catalyst duced gas was passed through scrubbing bottles placed in an ice bath.
was pulverized and classified into 2–5-mm-diameter pieces for use in Tar and steam were condensed and deposited in the bottles. The con-
the experiments. densed tar components were extracted using n-hexane and analyses of
Woody waste from construction and demolition work in Japan was the extract as shown below were performed. After the tar was removed,
used as feedstock. The wood species perhaps is cypress or cedar but the the gas was passed through a series of gas analyzers. H2, O2, N2, CO,
details are unknown. That was pulverized by rotary cutter mill and CO2, CH4, C2H2, C2H4 and C2H6 were detected every 5 min using a
classified into 1–2-mm particles for experimental preparation. Micro-GC 3000 (Agilent Technologies). Qualitative and quantitative
Proximate and ultimate analyses of the feedstock are shown in Table 2. analyses of the removal tar containing PAHs were executed using
The composition of ash was low and that of volatile matter was very GC–MS (QP2010 Plus: Shimadzu, Ltd.), HPLC (LC-8020: Toso, Ltd.) and
high. Moreover, the feedstock contained > 40 wt% oxygen due to the FID-GC (GC-2014: Shimadzu, Ltd.). The deposited carbon content on
presence of cellulose and xylose. the catalyst and porous silica after the experiments were also measured
using a carbon determination unit (NC-22: Sumika Chemical Analysis
Service, Ltd.), and the nitrogen adsorption method at 77 K (Quadrasorb
2.3. Procedure
SI: Quantachrome Instruments) and X-ray diffraction (MultiFrex: Ri-
gaku Co.) was applied to pore structure and crystal structure analyses of
The experimental conditions for evaluation of porous silica and
these materials, respectively. In repeated experiments (Runs 6–13), the
regeneration of reformer are shown in Tables 3 and 4, respectively.
catalyst and porous silica in the other reformer was regenerated using
Here, the amount of steam injection was expressed as the parameter for
air at 1 l/min to remove tar and/or carbon deposits on these materials.
the S/C ratio (Molar ratio of steam/carbon in the feedstock [mol/mol]),
After regeneration was performed for about 2 h, the air in the reformer
while oxygen was expressed as ER (Equivalence ratio: ratio of actual
was purged with nitrogen.
oxygen supplied to total oxygen required to accomplish the complete
burning [−]).Since the feed rate fluctuated even when the rotary speed
of screw was constant, the mean feed rate (designated as 0.12 kg/h) was 3. Results and discussion
calculated after the experiments according to the amount of feedstock
actually supplied. The experiment of Run 0 was performed with catalyst 3.1. Effect of porous silica on catalytic reforming
only to compare with the results using both porous silica and catalysts
as shown in Run 1–5. When evaluating the regeneration of both catalyst Fig. 2 shows the average concentrations of the main components
and porous silica in Run 6–13, the amount of these materials was al- and light hydrocarbons below C2 in produced gases. Here, the con-
most same and 100 ± 1 g. centrations of the main components such as CO, CO2 and relatively low
Before starting the experiment, the gasifier and reformers were molecular weight hydrocarbon were fairly constant over time. In con-
preheated in a nitrogen atmosphere. After the temperature of these trast, the compositions of H2 and CH4 slightly decreased and increased
reactors reached the set value and was maintained for several hours, with lapse of time, respectively. Therefore, average composition for
feedstock was fed from the hopper through a screw feeder to the ga- each component during the experimental periods is shown. The main
sifier. Water for steam gasification was supplied with simulated air to a components showed almost the same concentration and were in-
preheater located upstream of the gasifier. These were heated and dependent of the specific surface area of the porous silica and its use or
evaporated through the preheater. Temperature of the gasifier and the non-use. Equilibrium compositions under similar conditions (1123 K,

Table 3
Experimental conditions (effect of pore structure).
Run no. 0 1 2 3 4 5

Feed rate [kg·h−1] 0.12 0.11 0.10 0.12 0.08 0.12

Gasifier temp. [K] 1030 1030 1030 1040 1020 1040
Reformer temp. [K] 1120 1130 1130 1120 1130 1120
S/C [mol/mol] 2.4 2.4 2.7 2.2 3.3 2.4
ER [−] 0.16 0.16 0.18 0.15 0.22 0.16
Reformer Porous silica Sample no. – S1 S2 S3 S4 S5
Weight [g] 0a 100 100 99 100 100
Catalyst Weight [g] 50 50 50 50 50 50

a
Non-porous alumina beads were used to a packed bed material instead of the porous silica.

3
J. Kobayashi, et al. Fuel Processing Technology 194 (2019) 106104

Fig. 2. Average composition of produced gas using catalyst and 5 kinds of the porous silica.

ER = 0.15, S/C = 2.6) based on our calculations are 46 vol% of H2,

21 vol% of CO2, 13 vol% of CO and < 0.1 vol% of CH4, and are roughly
in accordance with the experimental results in Fig. 2. This means that
the gasification and reforming reaction of woody waste closely ap-
proaches the reaction equilibrium, whether the porous silica is used or
not. On the other hand, hydrocarbon concentrations in the produced
gases, except for methane which can be synthesize through CO me-
thanation [41], were a little lower when using the porous silica with
catalyst, but varied according to the surface area. Under this set of
experimental conditions, the hydrocarbon concentrations tended to
decrease with increase in the surface area of the porous silica. The
reasons for this will be discussed in further detail in relation to carbon
deposits on the porous silica.
As an example, Fig. 3 shows each GC–MS chart of tar with or
without porous silica. It was found that a certain amount of dibenzo-
furan, fluorene and other PAHs were included in the tar when porous
silica was not used to the reformer. In contrast, it was suggested that the
amount of these PAHs remarkably reduced using porous silica com-
pared with intensities of GC–MS chart between Fig. 3(a) and (b).
However, certain amounts of naphthalene and anthracene/phenan-
threne have remained in the extract. Therefore, naphthalene, anthra-
cene, phenanthrene and pyrene are regarded as main indicators of the
tar removal. The quantitative evaluation results of these PAHs are
shown as follows.
Fig. 4 shows the concentrations of PAHs and total tar in the pro-
duced gases. These concentrations are the cumulative average values
and are indicated in the form of mass of material per unit volume of
nitrogen-free produced gas. Here, the concentrations in Runs 2 and 4
are relatively low because their ER and S/C values are higher than the
others. Concentrations of relatively heavy PAHs with > 3 benzene rings
were lower when using the porous silica, although the concentrations of
naphthalene using the porous silica was often higher than that without Fig. 3. GC–MS chart of collected tar with Run No. 0 and 3.
the porous silica. On the contrary, the concentrations of heavy PAHs
markedly decreased with increasing run number, i.e., surface area. On
materials in the reformer were observed after the gasification experi-
the other hand, when the porous silica was used, the concentrations of
ments. The carbon contents of the porous silica and the catalyst are
total tar decreased as compared with the case where the porous silica
shown in Fig. 5(a). This figure also indicates the concentration of total
was not used. The values reached a minimum when surface area was
tar as shown in Fig. 4. Here, units of carbon deposits are converted to
approximately 100–300 m2/g.
the same unit of tar concentration, which is mass of carbon par total
Previous work by co-author [42] reported that tar conversion using
amount of gasified gas without nitrogen, to enable comparison of
only the same catalyst as this study was about 84% although the ex-
carbon deposits with the total quantity of tar. Initially, there was almost
perimental conditions were slightly different. Assuming the relationship
no influence of the porous silica on the carbon deposit on the catalyst,
is maintained, tar conversion using both the catalyst and suitable
and the specific surface area little affected that on the catalyst. On the
porous silica such as S2-S4 would be calculated to be 95% or more.
other hand, the amount of carbon deposit on the porous silica changed
Carbon deposits on the silica surface were confirmed when the bed

4
J. Kobayashi, et al. Fuel Processing Technology 194 (2019) 106104

Fig. 4. Mean concentrations of PAHs and total tar in produced gases using catalyst and 5 kinds of the porous silica.

Fig. 5. Effect of carbon deposits on specific surface areas of the porous silica and change of porosity after experiments.

according to its surface area and reached a maximum at around 200
m2/g. This trend is almost the opposite to the behavior of total tar
concentration. It is supposed that the tar decomposes on the porous
silica and a part of that deposits as carbon-based material. Moreover it
is thought that above mentioned light hydrocarbon concentration de-
creases with decrease in tar concentration in the gas phase. Both the
amount of carbon deposit and tar concentration using the silica with the
largest surface were lower than these with the smallest surface area.
Fig. 5(b), on the other hand, shows that the surface area of the porous
silica after the experiments reduced when the original surface area
exceeded 200 m2/g. This tendency becomes more pronounced with
increase in the original surface area and the behaviors of total pore
volume is also similar as shown in Fig. 5(d). On the contrary, mean pore
radius of the porous silica scarcely changed as shown in Fig. 5(c). Here,
the volume of deposited carbons is calculated using graphite carbon
density (2.26 g/ml), and the amount is about 1/100 of the pore volume
or less. Therefore, it is considered that adsorbed tar and/or deposited
carbons did not fill the pore but blocked many pore entrance on the
outer surface. Consequently, the amount of carbon deposit on the
porous silica decreased. That explains the reason why mean pore radius
hardly changed but total pore volume decreased after the experiments.
Considering the size of benzene circle (about 0.5 nm), PAHs are rela-
tively large molecules and it seems likely to close the entrance of re-
latively small pores, which have large surface area.
Based on these results and conclusions, it was decided that the
porous silica with 195 m2/g (Sample No. S3) should be used in the
following experimental investigation on the repeated use of catalytic
materials.

5
J. Kobayashi, et al.
Fig. 6. Variation in produced gas composition with time and the effect of regeneration on the composition in produced gases (1st reformer).
3.2. Regeneration of catalyst and catalytic activity
The effect of regeneration on repeated reforming reactions was in-
vestigated using the abovementioned porous silica. Figs. 6 and 7 show
the variation in the produced gas compositions with time from Runs 6
to 13. The chief ingredients and low hydrocarbons in the produced
gases are shown in these figures.
Produced gas compositions at Run 6 were comparable to the results
for Run 3, but the concentration of H2 was higher and that of CH4 was
lower. After the first regeneration cycle (Run 8), the concentration of
H2 decreased and that of CH4 increased with time. After the second and
third regenerations, the concentration of H2 continued to decrease
slightly, but the concentrations of both gases showed little further
change. Thus, it was found that the performance of the catalyst and the
porous silica leveled off at the second regeneration or later, although
the performance was lower than with fresh materials.
The equilibrium concentration of H2 under 1030 K (about 50 vol%)
is higher than that under 1120 K, which is one of the reasons that H2
concentration at Run 6 was higher than that at Run 3. On the other
hand, the space velocity in the catalyst bed during Runs 6–12 was half
6
Fuel Processing Technology 194 (2019) 106104
of that at Runs 0–5, i.e., about 4000 h−1 (based on wet gas and ambient
temperature). The gasified gas therefore had sufficient residence time to
be reformed.
The performance of the steam reforming reaction slightly declined:
the concentrations of hydrocarbons increased with increasing number
of regeneration cycles, as seen in Figs. 6(b) and 7(b). However, time
course of these concentrations became plateau and continuous decrease
of the performance had been prevented by the regeneration. Im-
mediately after starting regeneration, temperature of the catalyst rose
up to 1100 K and then returned to preset temperature around 1000 K
within 30 min. Since high temperature period in the regeneration could
cause sintering of dispersed nickel fine particles on the catalyst surface,
it is thought that the catalyst regeneration using air oxidation results in
a little lower performance of the catalyst. In fact, compared between X-
ray diffraction patterns before and after experiment, there were no
peaks based on nickel crystal in fresh catalyst although the catalyst after
regeneration experiments clearly had the peaks as shown in Fig. 8.
However, half width of the peaks, which is proportional to the size of
nickel crystal, was almost same comparing used catalyst at Run No. 3
with that at Run No. 12. The result indicates that the nickel crystal size
J. Kobayashi, et al. Fuel Processing Technology 194 (2019) 106104

Fig. 7. Variation in produced gas composition with time and the effect of regeneration on the composition in produced gases (2nd reformer).

in the used catalyst is largely maintained even if catalyst regeneration is

Fig. 8. X-ray diffraction patterns of reforming catalyst (Fresh: unused catalyst,
Run No. 3 and Run No. 12: used catalyst without air oxidation after the op-
eration).
repeated. Sehested has reported that an increase in the nickel particle
size decreases the activity of a steam-reforming catalyst. [43] There-
fore, it is thought that the activity at the regeneration condition in this
work dose not decline much although that is slightly lower than the
fresh ones.
Figs. 9 and 10 show the effects of regeneration on the emission
behavior of PAHs and total tar in the produced gases. These con-
centrations were a little lower than those of Run 3. It was thought that
using twice the amount of the catalyst in Run 3 caused these results,
although the reforming temperature of Runs 6–13 was about 100 K
below that of Run 3. The concentrations of all PAHs and total tar
roughly increased after both the catalyst and the porous silica was re-
generated. However, increase in these concentrations has not been
continued and removal performance for the tar has been maintained
after the second regeneration. Comparing between the results of Run
No. 10 and 12, the concentrations of all PAHs and total tar decreased by
the regeneration although both gasification conditions such as S/C and
ER was almost similar. The results of Run No. 9 and 13 also indicated
similar tendency. Here, the results of Run No. 11 were excluded from

7
J. Kobayashi, et al.
Fig. 9. Mean concentrations of PAHs and total tar in produced gases while applying regeneration to the catalyst and the porous silica (1st reformer).
Fig. 10. Mean concentrations of PAHs and total tar in produced gases while applying regeneration to the catalyst and the porous silica (2nd reformer).
the comparison because both S/C and ER in the experimental condition
were higher than the others. From these tendencies, it seems that per-
formance of tar removal using porous silica would be maintained or
promoted by the regeneration treatment.
From these results for the regeneration experiments, continuous
reduction of the performances of both reforming and tar removal was
not confirmed although these performances slightly decline by re-
peating utilization and regeneration.
4. Conclusions
Gasification and reforming of woody waste using nickel catalyst and
porous silica were carried out under various conditions to clarify the
influence of porous silica on tar removal. The applicability of the re-
generation operation was also investigated. The following conclusions
were obtained.
1) Main components such as H2, CO, CO2 and CH4 were in-
dependent of the specific surface area of the porous silica as well as its
use or non-use. On the other hand, hydrocarbon concentrations in the
produced gases were slightly reduced when using the porous silica with
the catalyst and tended to decrease with increase in the surface area of
the porous silica.
2) The concentrations of relatively heavy PAHs were reduced when
using the porous silica, although there was no clear difference in
naphthalene concentration between use and non-use of porous silica,
and its concentrations fluctuated. Moreover, the concentrations of
heavy PAHs markedly decreased with increased surface area of the
porous silica. On the other hand, the concentration of total tar fell when
8
Fuel Processing Technology 194 (2019) 106104
using the porous silica, with its value reaching a minimum at a surface
area of around 100–300 m2/g.
3) The porous silica had almost no influence on the carbon deposits
on the catalyst. However, the amount of carbon deposited on the porous
silica reached a maximum when its surface area was around 200 m2/g.
This tendency was almost opposite to the concentration of total tar,
suggesting that the tar in the gasified gas decomposes and is deposited
as carbon.
4) The results of our regeneration experiments showed that the
performance of the catalyst and the porous silica almost leveled off after
the second regeneration, although the performance was inferior to the
fresh ones.
Acknowledgements
A part of this work was carried out by the joint research program of
the EcoTopia Science Institute, Nagoya University.
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