Steam Reforming of Bagasse To Hydrogen and Synthesis Gas Using Ruthenium Promoted Niefe/Geal O Nano-Catalysts
Steam Reforming of Bagasse To Hydrogen and Synthesis Gas Using Ruthenium Promoted Niefe/Geal O Nano-Catalysts
Steam Reforming of Bagasse To Hydrogen and Synthesis Gas Using Ruthenium Promoted Niefe/Geal O Nano-Catalysts
ScienceDirect
journal homepage: www.elsevier.com/locate/he
article info
abstract
Article history:
Bagasse conversion to H2, CO and light gaseous hydrocarbons was performed in a batch
micro reactor under 850 C and atmospheric pressure in the presence of unpromoted and
ruthenium promoted NieFe/geAl2O3 nano catalysts. The nano catalysts were prepared
29 May 2016
with 12 wt.% Ni, 6 wt.% Fe and 0.5 to 2 wt.% Ru loadings via microemulsion technique. The
catalysts were extensively characterized using ICP, XRD, TPR, BET, TEM and H2 chemi-
sorption techniques. XRD patterns confirmed formation of NieFe alloys on the catalysts.
Ruthenium increased dispersion of active metal clusters by 44.6% and consequently
Keywords:
improved the reducibility of the catalysts. The addition of 1 wt.% Ru increased the total gas
Biomass gasification
yield, the yield of hydrogen, the yield of carbon monoxide and the carbon conversion ef-
Steam reforming
Hydrogen
2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Nickel
Iron
Ruthenium
Introduction
Nowadays, the most important challenges associated with the
emission of greenhouse gases to the atmosphere and shortage
of fossil fuels has developed research on the use of biomass
and agricultural waste in energy conversion processes [1e3].
The catalytic gasification of biomass has been studied
worldwide as a way to produce hydrogen recognized as a
potential energy carrier from renewable sources at various
temperatures and pressures [4]. Different biomass gasification
methods such as pyrolysis, supercritical water gasification
and gasification via biomass steam reforming have been
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
The catalytic steam reforming of biomass has been investigated with various supported noble and base metal catalysts.
Both noble metals (e.g., Pd, Pt, Ru, Rh) and base metals (e.g.,
Co, Ni, Cu) have been investigated with various supports for
steam reforming of biomass [10e12].
In particular, Ni catalysts have been widely studied for the
steam reforming of tar because of their low cost and high
activity for CeC, OeH and CeH bonds cleavage in the hydrocarbons to be reformed. Ni catalysts also accelerate the water
gas shift reaction in order to remove adsorbed CO from the
surface [13,14]. Also, iron based and promoted catalysts are
attractive for researchers in gasification fields of study. The Fe
modified cobalt catalysts have been applied widely for the
steam reforming of oxygenates. Because of high oxygen affinity, Fe can increase the catalyst coverage with oxygen
atoms during the steam reforming reactions. This property
makes iron a good choice for catalytic reforming of oxygenates [15e19]. However, these catalysts suffer rapid deactivation as a result of coke deposition, sintering of metal particles
and carbon fouling at high temperatures. Essential factors
that describe the high catalytic activity of the nickel based
catalysts are small crystallite size and high degree of dispersion of nickel particles on the supports [20,21]. A proven
method to improve the activity and coke resistance of supported nickel catalysts is to dope it with promoter metals
especially noble ones. Effect of noble metals including Pt, Pd,
Rh and Ru, on the performance of Ni/CeO2eAl2O3 catalyst in
cedar wood biomass steam gasification have been examined.
Among these noble metals, the addition of Pt was most
effective even when the loading amount of added Pt was as
small as 0.01 wt.%. Ruthenium recently has been used as
active metal and promoter of catalysts in several types of
gasification especially supercritical water gasification. This
metal showed significant performance in gasification [22,23].
This interesting effect has been related to its specific electron
arrangement. So, it seems that Ru also can be a very beneficial
promoter on a catalyst for bagasse steam reforming.
In this work, bagasse was used as biomass feedstock for
catalytic gasification via steam reforming in presence of
ruthenium promoted NieFe/geAl2O3 catalysts. Catalysts with
different ruthenium contents were prepared by microemulsion method. The promotional effects of ruthenium on
the catalytic activity of NieFe/geAl2O3 catalyst in steam
reforming of bagasse are widely investigated.
Experimental
Materials and reagents
The bagasse biomass as feedstock was supplied from HaftTappe Industries. The material was washed, grinded and
sieved to achieve particle sizes up to 1 mm. Precursors,
Ni(NO3)2.6H2O, Fe(NO3)3.9H2O, n-Butanol, Tetrahydrofuran
(THF) and n-Hexane were purchased from Merck company.
Ruthenium
nitrosyl
nitrate
solution,
Ru(NO)(NO3)3,
with1.5wt.% ruthenium and a density of 1.07 g/ml was purchased from Sigma-Aldrich Company. Hydrazine hydrate and
Triton X-100 were purchased from Chem-Lab Company.
Conndea Vista Catalox g-alumina as support with 212.4 m2/g
Catalyst characterization
The metal loadings of the calcined catalysts were verified by
an Inductively Coupled Plasma Atomic Emission Spectroscopy
(ICP-AES) system.
Temperature programmed reduction (TPR) with H2 was
performed in the fixed bed flow reactor. The TPR profiles of
samples were recorded from room temperature to 850 C for
50 mg of catalysts under 30 ml/min flow of H2 and Ar mixture,
with H2/Ar molar ratio of %5. The heating rate was 10 C/min
and the temperature was maintained at 850 C for 30 min after
it reached 850 C. The consumption of H2 was monitored
continuously with TCD gas chromatograph equipped with
frozen acetone trap to remove the water from the effluent gas.
The amount of H2 consumption was estimated from the peak
area in the TPR profiles.
Catalyst formula
12%Ni- 6%Fe on geAl2O3
0.5%Ru-12%Ni- 6%Fe on geAl2O3
1%Ru- 12%Ni- 6%Fe on geAl2O3
1.5%Ru- 12%Ni- 6%Fe on geAl2O3
2%Ru- 12%Ni- 6%Fe on geAl2O3
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
Reaction setup
Fig. 1 shows the reaction setup. As shown, the reaction was
performed in a fixed bed reactor made of a quartz glass tube
with 800 mm long and 10 mm internal diameter. Quartz wool,
feed and catalyst bed was fixed in the center of the reactor.
The reactor was located inside a tubular furnace with 20 mm
ID and 200 mm OD with total heating length of 700 mm. The
furnace temperature was controlled using an electrical heater
and a PID temperature controller and measured using a K-type
thermocouple. Argon was used as inert carrier gas with
exactly 30 ml/min flow rate using mass flow controller. Water
was injected into the reactor using a syringe pump with
desired flow rate. Reaction time, temperature and water flow
rate were 30 min, 850 C and 0.6 ml/min, respectively. The
product leaving the reactor was condensed and separated into
liquid and gaseous fractions. The liquid fraction was collected
in a liquid trap of ice-salt bath and the gaseous fraction was
collected over a sodium chloride saturated brine solution in a
graduated column. The volume of collected gases was
measured from displacement of the solution in the column.
Before bagasse loading, the catalysts were reduced by
hydrogen with 30 ml/min flow rate at 450 C for 2 h. The
reactor was allowed to cool down at the end of each experiment. The quality and quantity of produced gaseous mixture
Catalysts characterization
The results of the chemical analysis (Ni, Fe and Ru) of the
calcined catalysts confirmed that the metal contents of the
catalysts were rather similar to the targeted metal contents as
shown in Table 3.
Catalysts reducibility in H2 atmosphere was determined by
TPR experiments. The TPR spectra of the calcined catalysts are
shown in Fig. 2. In the TPR spectra of Cat1eCat5 catalysts, the
low temperature peaks (570e660 K) are typically related to the
reduction of nickel oxides, weakly interacting with the support [24,25]. The second peaks (700e800 K) are assigned to the
reduction of small ferrous oxide species and nickel oxide in its
neighborhood [19]. The catalyst has been prepared by microemulsion of Ru, Ni and Fe on the Al2O3 as support. Due to the
small amount and well association of Ru with Ni and Fe, the
existing of RuOx cluster is not expected, as can be ascertained
by TPR spectra. It is more likely for the microemulsion catalyst
that Ru species are well associated with Ni, mostly forming
the RueNi clusters. The reducibility of Ni-oxides was
improved by forming RueNi clusters via microemulsion Ru
with Ni onto Al2O3 [26]. As shown in this figure, the addition of
Ru to the unpromoted NieFe/geAl2O3 catalyst shifts the low
temperature peak to the lower temperatures (the peak temperature decreases from 695 for Cat1 to 575 K for Cat5). The Ni
species reducibility was promoted by Ru addition due to
hydrogen spillover effect. These results also support that the
interaction between Ru and Ni species plays important roles
on the high activity in the gasification via steam reforming of
biomass which will be shown in the next sections. Also,
NiAl2O4 phase reduction peak becomes visible at 970 K for the
Cat4 and Cat5 catalysts. This phase reduction becomes difficult and causes decrease of Ni active surface metal particles. It
was suggested that, the small Ni metal clusters more strongly
interact with alumina [20e28]. The TPR peak temperatures
and the area under the peaks are shown in Table 4. The area
under the peaks can be attributed to reduction degree of
different catalysts. As shown, the addition of Ru increased the
TPR peak area and H2 consumption which can increase the
surface active metals available for steam reforming and other
gasification reactions.
XRD patterns of calcined Cat1eCat5 catalyst are shown in
Fig. 3. For all the catalysts the peaks at 2q values of 37.02 and
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
N
C
H
S
O
0.69
58.1
6.45
0.19
34.57
Cat1
Cat2
Cat3
Cat4
Cat5
Expected values
(mass fraction %)
Ni
Fe
Ru
Ni
Fe
Ru
12
12
12
12
12
6
6
6
6
6
e
0.5
1
1.5
2
11.8
11.8
11.8
11.7
11.7
5.9
5.9
5.9
5.8
5.9
e
0.5
1
1.4
1.9
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
695
631
616
586
575
18.5
19.1
20.8
21.0
21.7
Cat1
Cat2
Cat3
Cat4
Cat5
Reaction
Stoichiometry
Enthalpy
(kJ/mol)
Pyrolysis
180
300
142
71
213
778
310
230
Partial
oxidation
Steam
reforming
212
190
188
186
184
183
Total pore
volume (ml/g)
XRD results
dp (nm)
0.52
0.47
0.46
0.44
0.42
0.41
e
4.1
4.0
3.8
3.7
3.2
Water-gas shift
Methanation
64
41
211
(12)
(13)
CH4 / C 2H2
(14)
2 CO 4 C CO2
(15)
C H2O 4 CO H2
(16)
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
Fig. 4 e TEM images and particle size distributions for Cat1, Cat3 and Cat5 catalysts.
295
315
325
333
362
25.1
30.5
34.7
37.3
44.6
3.85
3.79
3.62
3.49
3
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
references
Fig. 7 shows the LHV values calculated using the gasification data. The results show that LHV increased by factor of
0.35 with addition of 1 wt.%Ru due to increasing %CO and %H2
contents in the produced gas.
Statistical analysis
The reported data are the averages of several observations for
each experiment in order to make results more statistically
confident. Also, the accuracy of data was studied through ANOVA
(analysis of variance). Statistical level was 5% with p < 0.05.
Conclusion
A series of supported NieFe catalysts promoted with different Ru
contents were synthesized and characterized. Their performances for gasification via steam reforming of bagasse were
investigated. It was found that addition of 1 wt.% Ru to the NieFe
catalysts, significantly increases the total gas and H2 production
yields but addition of Ru more than 1 wt.%, doesn't have
considerable effects. This can be attributed to smaller particle
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8
Please cite this article in press as: Jafarian S, et al., Steam reforming of bagasse to hydrogen and synthesis gas using ruthenium promoted NieFe/geAl2O3nano-catalysts, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.261