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Manuscript Number: APEN-D-16-07232

Title: CATALYTIC FAST GASIFICATION OF EFB USING NiO PROMOTED ZSM-5:

EFFECTS OF Ni LOADING, CATALYST-BIOMASS RATIO, TEMPERATURE AND FLOW RATE
FOR HYDROGEN PRODUCTION

Article Type: SI:Biomass feedstocks

Keywords: Catalyst; EFB; Gasification; Hydrogen; Nickel oxide; ZSM-5

Corresponding Author: Prof. Yun Hin Taufiq-Yap, Ph.D.

Corresponding Author's Institution: Universiti Putra Malaysia

First Author: Yun Hin Taufiq-Yap, Ph.D.

Order of Authors: Yun Hin Taufiq-Yap, Ph.D.; K. Y. Yap, MSc; S.H. Teo,
PhD

Abstract: In this research, 4 parameters was investigated. The effect of

Ni loading on ZSM-5 support catalyst was conducted first. Ni loading of
1%, 5%, 10% 15%, 20% supported on ZSM-5 was synthesised. Unpromoted ZSM-5
and bulk NiO was used as comparison point for the promoted catalyst.
Initial test parameters are conducted at 900°C with isothermal heating,
with a 5% O2 dilute He gas flow rate of 10 cm3 min-1, and 20 wt % of
catalyst - biomass ratio. The reaction was conducted until H2 is not
detected and the total H2 produced was recorded. The best catalyst
showing high H2 selectivity while using low Ni amount was selected for
the optimisation step. The optimisation step was then conducted using
different flow rates, gasification temperatures, and catalyst - biomass
loadings while maintaining the initial test parameters. The catalyst was
characterised using powdered x-ray diffraction (XRD), temperature
programmed reduction (TPR-H2) and energy dispersive x-ray spectroscopy
(EDX) for one of the catalyst synthesised.
5%NiO/ZSM-5 catalyst was found to have sufficiently high H2 selectivity
with the lowest amount of NiO loading, showing a 33.4% increase in H2
selectivity compared to the uncatalysed reaction. Comparing with the
20%NiO/ZSM-5 catalyst only shows a 6.3% increase in H2 selectivity.
Therefore, 5%NiO/ZSM-5 was used for the optimisation step. A lower flow
rate shows higher selectivity for H2 for the catalysed reaction. The
5%NiO/ZSM-5 catalyst shows 125.7% increase in selectivity compared to the
uncatalysed reaction at 5 cm3 min-1 flow rate. Lower gasification
temperature shows very low selectivity towards H2 for the uncatalysed
reaction. However, with the 5%NiO/ZSM-5 catalyst, H2 selectivity is 3.1
times higher than the uncatalysed reaction. Catalyst - biomass ratio
shows a linear increase in H2 selectivity with the increase in amount of
catalyst used.
Cover Letter

10 October, 2016

Applied Energy

Editor in Chief
Joann Whalen, Prof. Dr.

Dear Editor,

This manuscript talks about the various effects of parameter affecting hydrogen production
from conventional gasification of agricultural waste such as empty fruit bunches (EFB) of oil palm.
Intense agricultural activity produces large amount of biomass waste which can be converted into
energy various methods such as direct usage as fuel in boilers or in gasification. Using EFB directly
as a fuel is not efficient as using hydrogen as it has a considerable calorific value of 122 MJ/kg
compared to EFB with only 17.97 MJ/kg. This research shows the effective hydrogen production
from agricultural waste material by using catalysts.

Therefore, I wish to submit electronically the soft copy of the manuscript “Catalytic Fast
Gasification of EFB using NiO Promoted ZSM-5: Effect of Ni Loading, Catalyst – Biomass Ratio,
Temperature and Flow Rate for Hydrogen Production” for consideration for publication in the
Special Issue Applied Energy. I hereby would like to declare that the manuscript is original,
unpublished work and is not being considered for publication elsewhere.

I look forward to receive acknowledgement of its receipt at your end.

Thanks and best regards,

Yours Sincerely,

Prof. Dr. Yun Hin Taufiq-Yap

Coordinator
Centre of Excellence for Catalysis Science and Technology
Faculty of Science
Universiti Putra Malaysia
43400 UPM Serdang
Selangor, Malaysia.
Tel: +603-89466809, Fax: +603-89466758,

Email: taufiq@upm.edu.my
Highlights (for review)

 Fast gasification via isothermal heating was carried out

 High NiO loading catalyst shows reduced catalytic activity from sintering

 5%NiO/ZSM-5 show effective H2 production at 5 cm3 min-1, 900°C

*Manuscript
Click here to view linked References

1 CATALYTIC FAST GASIFICATION OF EFB USING NiO PROMOTED ZSM-5:

2 EFFECTS OF Ni LOADING, CATALYST-BIOMASS RATIO, TEMPERATURE AND
3 FLOW RATE FOR HYDROGEN PRODUCTION
4 K.Y. Yap1,2, S.H. Teo1,2 Y.H. Taufiq-Yap1,2*
5 1
Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia,
6 43400 UPM Serdang, Selangor, Malaysia
7 2
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang,
8 Selangor, Malaysia

9 Abstract
10 In this research, 4 parameters was investigated. The effect of Ni loading on ZSM-5
11 support catalyst was conducted first. Ni loading of 1%, 5%, 10% 15%, 20% supported on ZSM-
12 5 was synthesised. Unpromoted ZSM-5 and bulk NiO was used as comparison point for the
13 promoted catalyst. Initial test parameters are conducted at 900°C with isothermal heating, with
14 a 5% O2 dilute He gas flow rate of 10 cm3 min-1, and 20 wt % of catalyst – biomass ratio. The
15 reaction was conducted until H2 is not detected and the total H2 produced was recorded. The
16 best catalyst showing high H2 selectivity while using low Ni amount was selected for the
17 optimisation step. The optimisation step was then conducted using different flow rates,
18 gasification temperatures, and catalyst – biomass loadings while maintaining the initial test
19 parameters. The catalyst was characterised using powdered x-ray diffraction (XRD),
20 temperature programmed reduction (TPR-H2) and energy dispersive x-ray spectroscopy (EDX)
21 for one of the catalyst synthesised.
22 5%NiO/ZSM-5 catalyst was found to have sufficiently high H2 selectivity with the
23 lowest amount of NiO loading, showing a 33.4% increase in H2 selectivity compared to the
24 uncatalysed reaction. Comparing with the 20%NiO/ZSM-5 catalyst only shows a 6.3%
25 increase in H2 selectivity. Therefore, 5%NiO/ZSM-5 was used for the optimisation step. A
26 lower flow rate shows higher selectivity for H2 for the catalysed reaction. The 5%NiO/ZSM-5
27 catalyst shows 125.7% increase in selectivity compared to the uncatalysed reaction at 5 cm3
28 min-1 flow rate. Lower gasification temperature shows very low selectivity towards H2 for the
29 uncatalysed reaction. However, with the 5%NiO/ZSM-5 catalyst, H2 selectivity is 3.1 times
30 higher than the uncatalysed reaction. Catalyst – biomass ratio shows a linear increase in H2
31 selectivity with the increase in amount of catalyst used.
32 Keywords: Catalyst, EFB, Gasification, Hydrogen, Nickel oxide, ZSM-5

33 Introduction
34 Steady growth in human population worldwide demands accelerates the growth in the
35 agricultural and the energy production sector. Currently, most of the energy generated are
36 derived from the usage of fossil fuel. However, combustion of fossil fuels for energy
37 production releases harmful greenhouse gases which contributes to global warming [1]. An
38 alternative sustainable and clean fuel source is needed to cope with the increase of energy
39 demands without further increasing the damage done to the environment. Intensive agricultural
40 activities produces large amount of biomass waste which can be converted into a green and
41 sustainable source of energy. Intensive agricultural activity converts the carbon dioxide form
42 the atmosphere into solid biomass with the help of light energy via photosynthesis [2]. The
43 biomass can then be converted into energy while releasing carbon dioxide, completing the
44 carbon cycle. Energy derived from this manner doesn’t involve introducing huge amount of
45 carbon into the atmosphere unlike energy derived from fossil fuels. Traditionally, H2 is
46 produced by the steam – methane reforming reaction (SMR) (1). Derivation of H2 using this
47 method produces CO2 as a byproduct. Deriving H2 from fossil fuel leaves a carbon footprint.
48 𝐶𝐻4 (𝑔) + 𝐻2 𝑂 (𝑔) → 𝐻2 (𝑔) + 𝐶𝑂2 (𝑔) (1)
49 In the case for Malaysia, the intense agricultural activity in the oil palm plantation
50 produces large amount of EFB waste biomass. About 18 022 tonnes of EFB was produced in
51 Malaysia alone in the year 2007 [3]. According to the Malaysian palm oil board (MPOB), EFB
52 have been traditionally burned to obtain ash for fertiliser production. The open burning
53 practices have been ceased due to environmental concern and EFB is now currently used as
54 mulch back in the oil palm plantations. However, not all of the EFB produced will be used as
55 mulch as mulching only uses a small portion of the EFB produced. Disposing of EFB by other
56 means adds cost to the process, which indirectly promotes open burning by some plantations.
57 Biomass gasification is a process whereby biomass undergoes thermal decomposition
58 in the presence of a reactive atmosphere to produce gaseous products called syngas [4].
59 Gasification process can be looked as a method to upgrade a solid fuel to a more valuable and
60 a higher heating value fuel. The gasification process however, produces a large amount of tar;
61 also known as polyaromatic compounds; which can cause equipment failure in large scale
62 reactor by condensing inside piping at lower temperatures compared to the gasifier itself [5,6].
63 Tar have some degree of hydrogen locked within them which will, in turn, reduce the H2
64 selectivity of the gasification reaction.
65 Tar can be removed via 3 different kinds of method; mechanical cleaning, catalytic
66 cracking, and thermal cracking [7]. In this research, catalytic cracking and thermal cracking
67 method will be discussed. Thermal cracking involves the thermal decomposition of tar with
68 high temperature conditions, typically at temperatures above 500°C. However, temperatures
69 below 800°C will show very poor carbon conversion and is not feasible for hydrogen
70 production [8]. Catalytic cracking on the other hand produces higher amounts of hydrogen in
71 comparison with thermal cracking.
72 Parameters such as gasifying temperature, gasifying agent, gas flow rate, heating rates,
73 and many more parameters can be studied. Temperature plays an important role in determining
74 the products of the gasification process. Temperatures above 600°C favours the production of
75 gaseous product over tar due to the effects of thermal cracking [9]. At higher temperature, the
76 tar formation thermally degrades into lighter hydrocarbons and syngas. Previous studies have
77 shown that high heating rate of biomass steam gasification shows high conversion of biomass
78 into gaseous product [10]. The reason for this is with a lower heating rate, the biomass spend
79 a longer time at those lower temperatures which is favourable for the production of tar. The tar
80 will then condense elsewhere, leading to a lower biomass conversion to gaseous product. This
81 explanation also applies to conventional gasification with the usage different gasifying agents.
82 The type of gasifying agent used also determines the type of products used for
83 gasification. Using an inert gas such as N2 or He as a gasifying will favour the production of
84 tar. Using steam as a gasifying agent can increase the production of hydrogen dramatically
85 [11]. Steam gasification does this by taking advantage of a reaction known as the water-gas
 86 shift reaction (WGSR) (2). During steam gasification, the hydrogen gas is derived from water
87 in the form of steam. The high temperature steam then reacts with the CO gas formed during
88 gasification and produces more H2.
89 CO (g) + H2 O (g) → CO2 (g) + H2 (g) (2)
90 Using O2 or compressed air as a gasifying agent will result in a mixture of gaseous
91 product and tar depending on the ratio of O2 with biomass. The ratio of O2 with biomass is
92 represented as the equivalence ratio (ER). According to a study conducted on the gasification
93 of pine sawdust done by Hurley et al., an equivalence ratio of 0.30 produces the most amount
94 of combustible gaseous and a higher ER ratio generally produces lower tar [12]. While steam
95 gasification can greatly improve the hydrogen production during gasification, research into
96 conventional gasification is still needed as some old gasifiers does not have a method for steam
97 gasification. Steam gasification technology is not widely used as it requires an expensive high
98 temperature steam generator to add on to conventional gasifiers.
99 Many research has been done on catalytic gasification of model compounds of tar in a
100 lab scale batch reactor. This research aims to study the catalytic gasification of actual waste
101 materials. Parameters such as Ni metal loading on the ZSM-5 support catalyst, gasification
102 temperature, gas flow rate and catalyst – biomass loading on H2 selectivity for the gasification
103 of EFB biomass was studied.
104 .

105 Methodology
106 Biomass Preparations
107 Raw EFB Biomass was obtained from the Biorefinery plant in UPM. The fibre was air
108 dried outdoor thoroughly to remove moisture and fungal growth. The fibre was then grounded
109 with an industrial grinder and was sieved with a 250 µm powder.
110

111 Catalyst preparations

112 5 g of ZSM-5 zeolite (ammonium) with a Si:Al ratio of 30:1 from Alfa Aesar was used
113 as the support catalyst for all samples in this paper. The support catalyst was calcined
114 beforehand to convert the ammonium ZSM-5 zeolite into H-ZSM-5. 1 wt% of Ni was doped
115 onto the support catalyst via the wet impregnation method by weighing appropriate amount of
116 Ni(NO3)2 and dissolving it in 10 ml of deionised water. The HZSM-5 prepared earlier was then
117 added into the Ni(NO3)2 solution. The slurry was then stirred for 6 hours to ensure
118 homogeneous mixing. The slurry was then dried in an oven at 100°C for 12 hours to remove
119 the water content from the slurry. The dried slurry was then grounded into a fine powder and
120 was calcined at 600°C for 6 hours according to the TGA analysis of the catalyst precursor. The
121 above method was repeated for 5 wt% Ni, 10 wt% Ni, 15 wt% Ni, and 20 wt% Ni. The sample
122 synthesised was named 1%NiO/ZSM-5, 5%NiO/ZSM-5, 10%NiO/ZSM-5, 15%NiO/ZSM-5
123 and 20%NiO/ZSM-5 respectively depending on the amount of Ni was doped onto the ZSM-5
124 support catalyst.
125
126 Characterisations
127 The synthesised catalyst was characterised using X-Ray diffraction (XRD), Brunauer,
128 Emmett and Teller Surface Area Measurement (BET), and Temperature Programmed
129 Reduction (TPR) whereas the catalyst precursor before calcination was sent for thermal
130 gravimetric analysis (TGA). EDX analysis was conducted for the 1 wt% NiO/ZSM-5 catalyst
131 to prove the presence of Ni on the ZSM-5 support catalyst. Some EFB powder was sent for
132 CHNO ultimate analysis for composition determination.
133

134 Catalytic Performance Test

135
136 Fig. 1: Steel Piping reactor setup. 1) Thermocouple monitor, 2) Gasifying agent inlet, 3) K-
137 type Thermocouple, 4) Furnace heating zone, 5) EFB biomass, 6) Quartz wool, 7) Catalyst
138 bed, 8) Cotton wool filter, 9) Cold trap, 10) Ice bath, 11) Outlet towards QMS
139

140 All catalytic performance test was conducted using the steel piping reactor setup as
141 shown in Fig 1. EFB biomass with the weight of 0.3 g was used for all reactions in this paper.
142 The purpose of the quartz wool was to support and isolate the EFB biomass from the catalyst
143 inside the steel piping reactor setup. The quartz wool was also used to prevent the catalyst from
144 being blown upwards by the gas flow. Isothermal heating was used in this paper whereby the
145 furnace was preheated to the desired temperature beforehand prior to the start of the reaction.
146 All reaction are carried out with a flow of 5% O2 diluted in He. The steel piping reactor setup
147 was flowed with 5% O2 diluted He for 10 minutes to ensure that the whole reactor is saturated
148 with the reaction gas. The gas produced during the reaction was analysed in real time using an
149 online quadrupole mass spectrometer (QMS).
150 Initial catalytic performance test was conducted with all of the catalyst synthesised
151 including commercial bulk NiO using the following parameters:
152 • Gasification temperature: 900°C
153 • Flow rate: 10 sccm
154 • Biomass-Catalyst ratio: 20 % wt

155 Optimisation test

156 The catalyst that shows high H2 selectivity with the lowest amount of Ni loading during
157 the initial catalytic performance test was then selected for further optimisation tests.
158 Optimisation tests are conducted to investigate the effects of catalyst-to-biomass ratio, flow
159 rate and gasification temperature. The uncatalysed reaction was also conducted for the
160 following optimisation test for comparison.
161 1st optimisation test (catalyst-to-biomass ratio)
162 • Gasification temperature: 900°C
163 • Flow rate: 10 sccm
164 • Catalyst-biomass ratio: 5 wt%, 10 wt%, 15 wt%, 20 wt%
165 2nd optimisation test (flow rate)
166 • Gasification temperature: 900°C
167 • Flow rate: 5 sccm, 10 sccm, 15 sccm, 20 sccm
168 • Catalyst-biomass ratio: 20 wt%
169 3rd optimisation test (gasification temperature)
170 • Gasification temperature: 800°C, 850°C, 900°C
171 • Flow rate: 10 sccm
172 • Catalyst-biomass ratio: 20 wt%
173
174
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180
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182
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184
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186
187
188
189
190
191
192 Results and discussion
193 Catalyst Characterisation

194
195 Fig. 2: TGA analysis of 5%Ni/ZSM-5 catalyst precursor
196

197 The TGA analysis of the catalyst precursor was conducted to identify the temperature
198 needed for the prepared catalyst to be calcined in. In this case, 5%NiO/ZSM-5 catalyst
199 precursor was used as a sample to identify the temperature needed for calcination. According
200 to Fig. 2, the differential thermal gravimetry graph shows at temperatures of 550°C and above,
201 the change in mass of the precursor starts to tapers off. Temperature of 600°C was selected to
202 ensure that the temperature required for thermal decomposition is sufficient and not too high
203 that it will contribute to the sintering of NiO.

204
205 Fig 3: XRD analysis of synthesised catalysts
206 XRD analysis is used detect the presence of the desired dopant crystalline structure on
207 the synthesised catalyst. From Fig. 3 the crystalline structure of NiO (JCPDS No. 01-073-1523)
208 dopants increases in intensity as the NiO loading increases. The 1%NiO/ZSM-5 catalyst does
209 not show the presence of the NiO crystalline phase, possibly due to the possible of high
210 dispersion and low population of the NiO dopant on the ZSM-5 support catalyst surface. The
211 ZSM-5 support catalyst shows the characteristic peak for a ZSM-5 zeolite with Si:Al ratio of
212 30:1 (JCPDS No. 00-044-0002).

213
214 Fig 4: EDX spectrum for 1%NiO/ZSM-5
215

216 Fig. 4 shows the EDX spectrum for 1%NiO/ZSM-5. EDX analysis was conducted with
217 the 1%NiO/ZSM-5 catalyst to detect the presence of Ni on the catalyst surface.
218

219
220 Fig 5: TPR-H2 analysis of synthesised catalysts
221
222 Temperature programmed reduction from Fig. 5 of the synthesised catalyst shows 2
223 distinct peaks for the 5%NiO/ZSM-5, 10%NiO/ZSM-5, 15%NiO/ZSM-5 and 20%NiO/ZSM-
224 5 catalyst. The lower temperature peak corresponds to the reduction of the bulk NiO on the
225 surface of the ZSM-5 support catalyst. The higher temperature peak correspond to the NiO
226 particles shows the stronger interaction between the dopant and the ZSM-5 support catalyst.
227 This stronger interaction corresponds to the formation of very small NiO size [13]. As the NiO
228 loading increases, the formation of bulk NiO is preferred over the formation of very small NiO
229 particles due to sintering of NiO particles during the calcination process. This can be seen in
230 the peaks distribution where increasing NiO loading, the area under the graph for the peak at
231 higher temperature decreases. TPR analysis of the ZSM-5 support catalyst was included for
232 comparison purposes.
233 Table 1: Ultimate analysis of EFB

Material Elemental Composition (%)

C H N O*
EFB 39.4 6.02 1.39 53.19
234 *Calculated by difference
235

236 Table 1 shows the ultimate analysis of the EFB biomass fibre. CHNS analysis of EFB
237 shows that EFB is 6.02 % hydrogen which is approximately close to the values obtained by
238 other researchers [14]. This value is needed in calculating the selectivity towards H2 production
239 during the catalytic performance test.
240

241 Catalyst Performance Test

242 Effects of Different Nickel Loading on ZSM-5 Support

243
244 Fig 6: H2 selectivity, Effect of NiO loading on ZSM-5
245 Fig. 6 shows the H2 selectivity of the synthesised catalyst together with the uncatalysed
246 reaction, ZSM-5 support catalyst and bulk NiO for comparison basis. The uncatalysed flash
247 gasification of EFB shows a H2 selectivity of only 9.07% which also serves as a baseline for
248 comparison for the other catalyst tested. The ZSM-5 and the bulk NiO sample was found to
249 have a H2 selectivity 9.39% and 9.54% respectively. This shows that the unpromoted ZSM-5
250 support and the bulk NiO have very little catalytic activity towards the tar cracking reaction.
251 The bulk NiO shows higher H2 selectivity compared to the unpromoted ZSM-5 support due to
252 it being catalytically active towards the tar cracking reaction. However, due to its nature to
253 easily undergo coking, the bulk NiO does not produce a higher H2 selectivity compared to the
254 ZSM-5 supported NiO of higher load. Furthermore, the bulk NiO active sites are situated
255 throughout the entire surface area of the NiO particle. Since bulk NiO has a very low specific
256 surface area, the amount of active site is very low which explains its low H2 selectivity.
257 1%Ni/ZSM-5 catalyst expectedly shows approximately the same H2 selectivity compared to
258 the uncatalysed reaction. The 1% Ni loading on the ZSM-5 support is easily deactivated by the
259 formation of coke, hence showing a reduced selectivity towards H2 [15]. Furthermore, the
260 deactivated Ni particles occupies active sites on the ZSM-5 which also reduces the reactivity
261 of the catalyst as a whole.
262 The 5% NiO/ZSM-5 shows a 33.4% improvement in H2 selectivity compared to the
263 uncatalysed reaction. 5%NiO/ZSM-5, 10%NiO/ZSM-5, 15%NiO/ZSM-5 and 20%NiO/ZSM-
264 5 catalyst shows H2 selectivity upwards of 12% and above up to 12.87%. 5%NiO/ZSM-5
265 catalyst shows little effect due to deactivation compared to the 1%NiO/ZSM-5 catalyst because
266 of the higher amount of Ni present on the ZSM-5 support catalyst. NiO active site deactivation
267 might still occur but due to the high amount of active site, H2 selectivity is not greatly affected.
268 However, increasing the Ni loading on the ZSM-5 support catalyst does not increase the H2
269 selectivity proportionally, possibly due to agglomeration of the NiO particles at high
270 temperatures [16]. The difference in H2 selectivity between 5%NiO/ZSM-5 and
271 20%NiO/ZSM-5 is only 6.3% but the increase in NiO loading is 300%. Because of this, the
272 5%NiO/ZSM-5 catalyst was selected for the optimisation step.
273 By observing the reaction time, the uncatalysed reaction takes the longest time to reach
274 completion which is at 155.73 minutes. ZSM-5 support shows the fastest time for reaction
275 completion compared to the rest of the catalyst prepared. This observation is due to the way
276 the reaction was set up. The catalyst bed is positioned directly above the EFB biomass layer.
277 This means that the tar produced by the thermal decomposition of EFB biomass will come into
278 contact with the catalyst bed beforehand. The presence of the catalyst bed presents a barrier for
279 the tar to pass through before being able to condense somewhere cooler downstream of the
280 reactor. This means that the tar produced will be temporarily trapped by this layer and the tar
281 cracking reaction takes place. With the uncatalysed reaction, the tar produced will escape the
282 high temperature zone and condense at the cooler downstream part of the steel piping reactor
283 setup where thermal cracking still takes place but at a slower pace.
284 Replacing the catalyst bed with an active catalyst yields a totally different result. The
285 5%NiO/ZSM-5 catalyst shows the longest time to reach completion compared to the rest of the
286 catalysed reaction. It is surprising that a catalysed reaction would show a longer time for the
287 reaction to reach completion. This observation could be because the catalyst bed acts as a
288 barrier, trapping the tar produced and promotes the tar cracking reaction. Since there is only 5
289 wt% of Ni on the 5%NiO/ZSM-5 catalyst, the tar cracking reaction is slower compared to the
290 10%NiO/ZSM-5, 15%NiO/ZSM-5, and 20%NiO/ZSM-5 catalyst.
291 Higher Ni loading shows a shorter time for the reaction to reach completion because
292 the catalyst has more active sites available to catalyse the tar cracking reaction. Because of this,
293 the time for reaction completion reduces. However, there is a limitation on how much Ni
294 loading before it doesn’t show any effect. The 15%NiO/ZSM-5 and 20%NiO/ZSM-5 catalyst
295 produces almost consistent time for reaction completion, showing that Ni loading beyond 15
296 wt% doesn’t improve reaction completion time. One explanation for this is the increased Ni
297 loading produces highly agglomerated NiO particles on the ZSM-5 support catalyst. These
298 highly agglomerated NiO particles presents lower specific surface area compared to their non-
299 agglomerated counterparts.
300

301 Optimisation by using different catalyst to biomass loading

302
303 Fig 7: H2 selectivity, Effect of (5%NiO/ZSM-5) catalyst – biomass ratio
304

305 Fig. 7 shows the H2 selectivity for the 5%NiO/ZSM-5 catalyst with varying catalyst –
306 biomass ratio. The trend produced by the optimisation process shows an increasing H2
307 selectivity when higher amount of catalyst was used. Higher amount of catalyst used provides
308 a thicker catalyst bed which indirectly means a higher number of active sites available for the
309 catalytic tar cracking of 0.3 g of EFB biomass. The thicker catalyst bed indirectly increases
310 contact time of the tar with the catalyst, since the tar formation needs to pass through a thicker
311 catalyst bed. 5% wt catalyst – biomass shows an increase in the time taken for the reaction to
312 reach completion compared to the uncatalysed reaction. The presence of the catalyst bed
313 increases the tar residence time in the reactor by providing a barrier for which the tar needs to
314 pass through after being produced. The tar then adhere onto the catalyst and the tar cracking
315 reaction takes place. With higher catalyst – biomass ratio, the catalyst bed is now thicker. This
316 has more active sites per reaction compared to the 5% catalyst – biomass ratio. Because of this,
317 the time taken for the reaction to reach completion is shorter. Catalyst-to-biomass ratio of 15%
318 and above shows almost identical time needed for the reaction to reach completion. This shows
319 that thicker catalyst bed above 10% catalyst – biomass ratio does not play a role in decreasing
320 the time taken for the reaction to reach completion.
321

322 Optimisation by using different gasification temperature

323
324 Fig 8: H2 selectivity, Effect of gasification temperature
325

326 Fig.8 shows the H2 selectivity with different gasification temperatures. It is understood
327 that higher gasification temperatures generally shows higher H2 production regardless for the
328 catalysed or uncatalysed reaction. The catalysed reaction for 800°C manages to show a
329 significant improvement of 312% over the uncatalysed reaction. At 800°C, the gasification
330 reaction tends to produce more tar over gaseous compounds. The uncatalysed reaction produces
331 a lot of tar which will condense at cooler parts downstream of the reactor. This cause the time
332 taken for the reaction to reach completion to be shorter compared to the rest. Introducing a
333 catalyst that can catalyse the tar cracking reaction into the gasification process will significantly
334 increase the H2 selectivity. As the gasification temperature is subsequently increased from
335 800°C to 850°C and 900°C, the improvements for H2 selectivity between the uncatalysed
336 reaction and the catalysed reaction reduces. More gaseous products are produced compared to
337 tar at higher temperatures, making the differences in improvements between the uncatalysed
338 reaction and the catalysed reaction closer.
339

340

341

342
343 Optimisation by using different flow rate

344
345 Fig 9: H2 selectivity, Effect of different flow rate for gasifying agent
346

347 Fig.9 shows the H2 selectivity with different flow rate for gasifying agent. A lower flow
348 rate of O2 yields a higher selectivity towards H2 at the same time affecting the time taken for
349 the reaction to reach completion. A lower flow rate favours the production of tar which then
350 can then be catalytically cracked by the catalyst. The lower flow rate results in a lower ER
351 which increases tar formation. Furthermore, the lower flow rate also does not push the tar
352 downstream of the catalyst as much compared with a higher flow rate. This also means that the
353 tar has higher contact time with the catalyst which will in return increase the hydrogen
354 selectivity of the reaction. A higher flow rate will favour the production of gaseous product
355 because of the higher ER as a resultant from higher flow rate. The higher flow rate also pushes
356 the tar formation from the reaction downstream of the catalyst faster, resulting in a lower
357 contact time with the catalyst. This, in turn reduces the hydrogen selectivity compared to the
358 reaction with a lower flow rate. Looking at the time taken for the reaction to reach completion,
359 higher flow rate will result in a shorter time for the reaction to reach completion as compared
360 with a lower flow rate.
361

362 Conclusion
363 It can be seen that the 5%NiO/ZSM-5 catalyst shows a 33.4% increase in H2 selectivity
364 compared to the 1%NiO/ZSM-5 catalyst. Further increase in NiO loading only shows slight
365 increase in H2 selectivity. This is because at higher loading, NiO sintering is very significant
366 that it affects catalytic performance. Therefore, the increase in H2 selectivity is not proportional
367 to the amount of NiO used, hence 5%NiO/ZSM-5 catalyst was chosen for further optimisation.
368 Increasing catalyst – biomass ratio shows increasing H2 selectivity due to an increased
369 thickness of the catalytic bed. Lower gasification temperatures have huge impact on the
370 selectivity of H2 for the uncatalysed reaction whereas the catalysed reaction shows smaller
371 variations. Generally, a lower flow rate will result in a higher H2 selectivity for the catalysed
372 reaction. The difference in H2 selectivity between the catalysed reaction and the uncatalysed
373 reaction at lower flow rate is very significant. This experiment concludes that the
374 5%NiO/ZSM-5 catalyst has higher H2 selectivity at lower temperatures and flow rate when
375 compared to the uncatalysed reaction under the same conditions.
376

377 References
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