BINIVOX catalyst for hydrogen production from ethanol by low temperature steam reforming (LTSR)

Article abstract of DOI:10.1007/s12039-017-1388-x

Abstract: Nickel doped bismuth vanadate [Bi4(V0.90Ni0.10)2O11-δ;BINIVOX] calcined at 800°C (BINIVOX-800) catalyst is prepared by a solution combustion method. The catalytic activity study is carried in the temperature range of 250–400°C, and with the molar feed ratios of water: ethanol at 23:1 and 2.5:1. The study reveals an increase in the ethanol conversion and selectivity of carbon dioxide & hydrogen but a decrease in the selectivity of carbon monoxide and methane with an increase in temperature and water: ethanol mole ratio. Fresh and used catalysts are characterized using DTA, TGA, XRD and FTIR. XRD results reveal that the fresh catalyst is phase pure γ -BINIVOX. The phase purity and crystallinity of the catalyst is retained after 30 h of activity study. Graphical Abstract : Catalytic activity of nickel-doped bismuth vanadate (BINIVOX) powder for hydrogen production from ethanol via low-temperature steam reforming is reported here. Preliminary results show an increase in ethanol conversion and selectivity of carbon dioxide and hydrogen with temperature and water: ethanol mole ratio.[Figure not available: see fulltext.].

Full text of DOI:10.1007/s12039-017-1388-x

J. Chem. Sci.
© Indian Academy of Sciences
DOI 10.1007/s12039-017-1388-x
REGULAR ARTICLE
Special Issue on Recent Trends in the Design and Development of Catalysts and their Applications.
BINIVOX catalyst for hydrogen production from ethanol by low
temperature steam reforming (LTSR)
B PATIL, S SHARMA, H K MOHANTA and B ROY∗
Department of Chemical Engineering, Birla Institute of Technology and Science (BITS) Pilani,
Rajasthan 333 031, India
E-mail: banasri.roy@pilani.bits-pilani.ac.in
MS received 17 April 2017; revised 25 July 2017; accepted 17 August 2017
Abstract.
Nickel doped bismuth vanadate [Bi4(V0.90Ni0.10)2O11−δ;BINIVOX] calcined at 800 ◦C
(BINIVOX-800) catalyst is prepared by a solution combustion method. The catalytic activity study is carried
in the temperature range of 250–400 ◦C, and with the molar feed ratios of water: ethanol at 23:1 and 2.5:1. The
study reveals an increase in the ethanol conversion and selectivity of carbon dioxide & hydrogen but a decrease
in the selectivity of carbon monoxide and methane with an increase in temperature and water: ethanol mole
ratio. Fresh and used catalysts are characterized using DTA, TGA, XRD and FTIR. XRD results reveal that the
γ
fresh catalyst is phase pure -BINIVOX. The phase purity and crystallinity of the catalyst is retained after 30 h
of activity study.
Keywords. BINIVOX catalyst; catalytic activity; phase transition; crystal structure; thermal analysis.
1. Introduction
petroleum gasification, electrolysis, fermentation (bio-
logical ways), etc.7,8 Steam Reforming is a widely
practised synthesis route owing to its high process
efficiency and economic viability. Steam reforming is
usually carried out at temperatures higher than 550 ◦C.9
Low Temperature Steam Reforming (LTSR) is preferred
due to it incurring lower operational and fixed costs,
while, simultaneously offering high energy efficiency.
The renewable feedstock for hydrogen production
for steam reforming is usually lighter hydrocarbons
(methane, natural gas) and oxygenated hydrocarbons
(alcohols, bio-oils, organic acids), out of which, we have
used ethanol owing to its wide availability in India.10,11
Most common catalysts used for steam reforming are
nickel(Ni), cobalt(Co), iron (Fe), copper (Cu) (transition
metals), silver(Ag), gold(Au), platinum (Pt), rhodium
(Rh), ruthenium (Ru), palladium(Pd) (noble metals) as
active phase. Alumina, ceria, zirconium oxides are used
as supports usually.12–14
International Energy Outlook (IEO 2016) has predicted
that the world energy demand will rise from 540.5 to
815.0 quadrillion BTU by 2014, as the projection for
world population indicates that the 8 billion marker will
bereachedin2025whichis7billionin2012.1–3 Conven-
tional energy sources, in addition to their non-renewable
nature, pose various problems such as environmental
pollution (ozone depletion, global warming, acid rain,
radioactivedischarge)andhealthhazards(bronchialdis-
eases, malignancy, infant mortality), effects on human
health, agriculture, economy, and society are detrimen-
tal.4 Thus renewable energy sources, that are sustainable
and economic at the same time, are the need of the hour.5
Out of all the renewable energy sources, hydrogen is
garnering attention among environmental enthusiasts,
industrial and scientific community because of its non-
toxic nature, zero emission of a pollutant, high calorific
value (3100 kcal/kg) and a wide range of flammabil-
ity.6,7 Hydrogen is industrially manufactured by various
processes like catalytic partial oxidation, steam reform-
ing, dry reforming, decomposition of hydrocarbons,
This work focuses on an individual group of cata-
lysts called BIMEVOX which are complex oxides of
bismuth, a metal (different transition metals such as Ni,
Cu, Co, Mg, Zn, Fe, etc.) and vanadium. These catalysts
have high oxide ion conductivity.15 These catalysts have
*
For correspondence
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-017-1388-x) contains
supplementary material, which is available to authorized users.

B Patil et al.
been used earlier for partial oxidation of propylene in
Oxidizer
(Bismuth nitrate,Nickel
nitrate,vanadiumpentoxide)
Fuel
the vapour phase.16 This is the first time we are reporting
the application of these catalysts for hydrogen produc-
tion via steam reforming. The high oxygen conductivity
can help in reduction of carbon deposition and increase
water gas shift reaction and thus decrease the deactiva-
tion rate.
(Glycine)
Mixing
Ethanol
F:O= 1:1
Slurry
Overnightdrying at 60°C
Pest
300°C for 2 hours
This work centres on preparation, characterization
and activity study of BINIVOX [Bi4(V0.90Ni0.10)2O11−δ;
BINIVOX] catalyst. The catalytic activity study has
been performed at different temperatures and the var-
ied composition of feed consisting of ethanol and water.
The catalytic activity study is carried out by collecting
and analyzing gaseous and liquid samples with the help
of GC and HS-GC, respectively. Physical and chemical
properties of BINIVOX-800 catalyst (BINIVOX cal-
cined at 800 ◦C) are determined by characterizing the
powders using XRD, DTA, TGA, and FTIR.
Blackfluffy mass
Washing with DI Water
Wetslurry
Drying at 60oC for 12 hours
Dried Pure powder
Annealing at800oC for2 hours
BINIVOX -800
DTA,TGA
XRD,FTIR
2. Experimental
Catalytic Activity Study
2.1 Catalyst Preparation
Figure 1. Flowchart for the solution combustion synthesis
method used for the preparation of BINIVOX catalyst and the
corresponding characterizations.
BINIVOX-800 (Bi4[V0.9Ni0.1]2O11) catalyst is synthesized
by a solution combustion synthesis (SCS) method. Sto-
ichiometric amount of bismuth nitrate (Bi(NO3)3.5H2O)
(Rankem, LR grade, purity> 99%) (34.9 g), vanadium
pentoxide (V2O5) (Himedia, LR Grade, purity> 98%)
(2.9 g), nickel nitrate (Ni(NO3)2.6H2O) (QLS, AR Grade,
purity>99%) (1.04 g) as oxidizer and glycine (C2H5NO2)
(Rankem, LR Grade, purity> 99%) (9.3 g) as fuel (with oxi-
dizer to fuel ratio as 1:1) are mixed thoroughly with ethanol
in a 500 cc beaker. The mixture is left overnight for drying at
room temperature. The homogenous paste is heated to 300 ◦C
over a heating plate inside the fume hood to ensure security.
The mixture is self-ignited in one place and spread throughout
the beaker eventually, turning it into a black fluffy mass. The
obtained mass is washed three to four times with DI water to
remove the un-reacted salts and fuel and dried at 60 ◦C for 12
h. Finally, it is calcined at 800 ◦C for 2 h. This catalyst from
now on is called as BINIVOX-800. The SCS method has been
explained as a flowchart in Figure 1.
Fourier Transform Infrared (FTIR) spectroscopy analysis
of the catalyst is performed by a Perkin Elmer FrontierTM
within the wavenumber range of 400 to 4000 cm−1. The data
is averaged over 20 scans.
2.3 Catalyst Activity Study
Catalytic activity studies are conducted in a custom-made U-
tube packed bed reactor (inner diameter of 3/8 inch) sited
inside a muffle furnace. 2 g of the catalyst powder is loaded
into the reactor. Water: ethanol mixture of 2.5:1 and 23:1
mole ratio is preheated to 110 ◦C. Pure nitrogen gas (99.99
%) swept through the preheater and carries vapour to the reac-
tor. The vapour conducting ducts are maintained at 110 ◦C by
wrapping heating tape around them in order to avoid the con-
densation of the feed vapour. An ice cooled phase separator is
used to separate liquid and gaseous parts of the product com-
2.2 Catalyst Characterization
Simultaneous thermogravimetric and differential thermal ing out of the reactor. The gaseous products are analyzed at an
analysis (S- DTG; Shimadzu, DTG-60H) of the dried powder interval of each hour for 6 h. A gas chromatograph instrument
is carried out in the presence of air from 30 to 800 ◦C at a rate (Shimadzu gas chromatograph (GC - 2014)) with porapak as
of 5 ◦C per min rise in temperature. DTA data of the catalyst reference column and carbosphere as sample column with
is also collected during the cooling cycle from 800 to 200 ◦C. thermal conductivity detector (TCD) is used for the purpose.
The X-ray diffraction data of the fresh and used BINIVOX- The liquid products are collected at the end of 6 h and are
α
800 is acquired by Rigaku Miniflex II with the help of CuK
radiation (1.5 Å, 15 mA, 30 kV). The sample is scanned at with Flow Ionization Detector (FID). The schematic of the
2 ◦/min from 20 to 60◦.
experimental setup is shown in Figure 2.
analyzed by a GC- HS (Shimadzu model no.10) equipped

BINIVOX catalyst for hydrogen production
PG
EtOH-H2O
FURNACE
PRE-
HEATER
N2
Cylinder
PHASE
SEPER
ATOR
GAS
ANALYSIS
(GC-TCD)
REACTOR
LIQUID
ANALYSIS
(GC-FID)
LIQUID
COLLECT
CATALYST BED
Figure 2. Schematic of low temperature steam reforming experimental set up.
100.4
100.0
99.6
99.2
98.8
98.4
98.0
Cooling
(a)
(b)
100.0
99.9
99.8
Cooling
Heating
99.7
100.0
Cooling
Heating
99.9
99.8
99.7
Heating
200
400
600
800
0
200
400
600
800
Temperature(°C)
Temperature(°C)
Figure 4. DTA/TGA spectra for BINIVOX -800 (a) fresh
and (b) used catalyst.
Figure 3. DTA/TGA spectra for BINIVOX powder.
shows the DTA and TGA spectra for BINIVOX-800 (a)
fresh and (b) used catalyst. DTA spectra show that there
is no change in phase during heating and cooling both,
after 30 h of the experiment. TGA analysis shows that
there is a ∼ 0.24% and ∼ 0.26% decrease in weight
for the fresh and used catalyst, respectively. The change
in weight is observed only minimal (∼ 0.02%), which
could be attributed to C deposition (DTA has no peak)
on the catalyst. This indicates the stability (in terms of
phase content and activation) of the catalyst.
3. Results and Discussion
3.1 Characterization Results
3.1a S-DTG Analysis: Figure 3 show the DTA and
TGA profiles of the dried powder. Thermogravimetric
analysis shows that there is a ∼ 0.8% decrease in weight
at∼ 305 ◦CaccompaniedbyanendothermicDTApeak.
This could be attributed to the loss of surface moisture,
volatile organic materials and/or some Bi-V-O related
phase change.17 The exothermic DTA peak at ∼ 640 ◦C
may correspond to some phase change in the sample. 3.1b XRD Analysis: From the X-Ray diffraction
The DTA cooling spectrum devoid of any phase rever- spectra of the fresh and used samples (Figure 5), it could
sal peak indicates the stability of the catalyst. Figure 4 be inferred that the heat treated (800 ◦C for 2 h) catalyst

B Patil et al.
peak at 2770 cm−1 exhibits the presence of O-H stretch.
This corresponds to the moisture adsorbed by the cat-
alyst. Apart from these, the FTIR also shows peaks
in-between 995–1203 cm−1 set for the asymmetric V-O
stretching (VAS) of vanadate ions. The peak at 709 cm−1
corresponds to a symmetric V-O stretching (VS) of vana-
date ions. The peak at 478 cm−1 could be attributed to
the vibration of the Bi-O band of bismuth oxide.18,20
FRESH
USED
3.2 Catalytic Activity Study
Gaseous products obtained by steam reforming of
ethanol consist of hydrogen, carbon monoxide, carbon
dioxide and methane. The percentage (%) selectivity of
the individual products is calculated using the following
equations.21,22
xH
2
H2 selectivity (%) =
CO2 selectivity (%) =
CO selectivity (%) =
CH4 selectivity (%) =
× 100
(1)
× 100 (2)
× 100 (3)
× 100 (4)
20 25 30 35 40 45 50 55 60
3xCO
2
xCO
2
2 theta (degrees)
xCO + xC H + xCO
2
4
xCO
xCO + xC H + xCO
Figure 5. XRD spectra of the BINIVOX-800 catalysts,
fresh and used.
2
4
xC H
4
USED
478 cm-1
xCO + xC H + xCO
2
4
FRESH
(Bi-O)
Ethanol conversion = ((mol EtOHin − mol EtOHout)/
mol EtOHin) × 100
1050 1000 950
USED
(5)
Experimental results indicate that the selectivity
of the products attains steady state after five hours
and almost remains constant for next 20 h indicat-
ing that the catalyst is stable over 25 h which is in
accordance with the X-ray Diffraction and DTA/TGA
results.
1203-995cm-1
ѴAS(V-O)
FRESH
2870 cm-1
(O-H Stretch)
709 cm-1
Figure7showsthechangesinethanolconversion(%),
product selectivity (%) in the gaseous phase and carbon
(%) in the gas phase with temperature. As temperature
and the feed composition of water: ethanol (2.5:1 and
23:1 mole ratio) increase ethanol conversion increases.
The similar results have been established by Romero-
Sarria F et al.23 With the increase in steam content in
the feed to the reactor, there is enhanced C-C and C-
O bond cleavage. The lowest and the highest ethanol
ѴS(V-O)
3600 3000 2400 1800 1200 600
Wave number(cm-1)
Figure 6. FTIR images of the BINIVOX-800 fresh and
used catalysts.
18,19
The used conversion (42% and 75%) is observed at 250 ◦C, H2O:
γ
is essentially single-phase -BINIVOX.
catalyst (after 30 h of the experiment) shows almost no EtOH = 2.5:1 mole ratio and 400 ◦C, H2O: EtOH = 23:1
sign of degradation in terms of phase composition and mole ratio, respectively.
retains good crystallinity (within 10% of the fresh one;
Figures 7(b), 7(c), 7(d) and 7(e) reveal the rise of
Table S1) almost similar to the fresh one. These results the hydrogen and carbon dioxide selectivity and drop in
are in accordance with the DTA analysis.
carbon monoxide and methane selectivity with respect
to the temperature for both feed concentration. At the
3.1c FTIR Analysis: The FTIR spectra of BINIVOX- feed composition of H2O: EtOH = 23:1, the highest
800, before and after use are depicted in Figure 6. The hydrogen and carbon dioxide selectivity are recorded

BINIVOX catalyst for hydrogen production
40
35
30
25
20
15
10
5
75
70
65
60
55
50
45
40
50
(a)
(b)
(c)
45
40
35
30
25
H2O:EtOH=2.5:1
H2O:EtOH=23:1
H2O:EtOH=2.5:1
H2O:EtOH=23:1
H2O:EtOH=2.5:1
H2O:EtOH=23:1
20
240 270 300 330 360 390
240 270 300 330 360 390
Temperature (oC)
240 270 300 330 360 390
Temperature (oC)
Temperature (oC)
35
90
(d)
(f)
(e)
60
55
50
45
85
80
75
70
65
60
55
30
25
20
15
H2O:EtOH=2.5:1
H2O:EtOH=23:1
H2O:EtOH=2.5:1
H2O:EtOH=23:1
H2O:EtOH=2.5:1
H2O:EtOH=23:1
240 270 300 330 360 390
Temperature (oC)
240 270 300 330 360 390
Temperature (oC)
240 270 300 330 360 390
Temperature (oC)
Figure 7. Catalytic activity as a function of temperature for the BINIVOX-800 powder for low temperature steam reforming
of ethanol-H2O mixture at two different mol ratio; (a) ethanol conversion (%) (b) H2 selectivity (%), (c) CO2 selectivity (%),
(d) CO selectivity (%), (e) CH4 selectivity (%), and (f) C in gas product (%).
to be 50 and 35%, respectively at 400 ◦C, which are, C2H5OH+3H2O↔6H2+2CO2; ꢀH◦ = 173.3 kJ/mol
140 and 600%, respectively, larger than the selectivity
observed at the lowest reaction temperature (250 ◦C).
The lowest selectivity values of carbon monoxide and
methane are noticed to be 16 and 48%, respectively,
at 400 ◦C and water: EtOH= 23:1 mole ratio. Sup-
plementary word file is provided to show the carbon
balance.
Reportedly, at lower steam reforming temperature
(200 to 500 ◦C), ethanol undergoes the direct decompo-
sition yielding carbon monoxide, methane and hydrogen
(eq. 6).21,23,24
(9)
C2H5OH+H2O ↔ 4H2+2CO2; ꢀH◦ = 260 kJ/mol
(10)
Here, our results show that higher water: ethanol ratio
favours methane reforming and water gas shift reaction,
as expected.24–27
4. Conclusion
BINIVOX catalyst annealed at 800 ◦C can be used for
the production of hydrogen by low temperature steam
reforming of ethanol. The preliminary catalytic activ-
ity study shows the significant formation of hydrogen
and carbon dioxide in the product gas. Carbon dioxide
is observed to be produced at temperatures as low as
250 ◦C. There is an increase in the selectivity of hydro-
gen, carbon dioxide and a decrease in the selectivity
of methane and carbon monoxide with the increase in
reaction temperature and water: ethanol mole ratio. This
probably indicates methane steam reforming and water
gas shift reaction capacity of the catalyst at low tem-
perature. According to XRD and S-DTG analysis, the
γ
C2H5OH → CH4 + CO + H2; ꢀH◦ = 49 kJ/mol
(6)
That can be followed by methane steam reforming reac-
tion to produce carbon dioxide and hydrogen (eq. 7).
CH4 + 2H2O ↔ 4H2 + CO2; ꢀH◦ = 164.5 kJ/mol
(7)
At the similar low temperature, water gas shift reac-
tion can also take place (eq. 8).
CO + H2O → CO2 + H2; ꢀH◦ = −40 kJ/mol (8)
Higher reaction temperature (550 ◦C) favours direct fresh catalyst is a phase pure - BINIVOX and retains
ethanol steam reforming to produce carbon dioxide its crystallinity and phase purity till after 30 hours of
(and/or CO) and hydrogen (eqs. 9 and 10).
activity study.

B Patil et al.
γ
Supplementary Information (SI)
based -alumina catalysts for bioglycerol aqueous phase
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14. Doukkali M E, Iriondo A, Cambra J F, Gandarías I,
Jalowiecki-Duhamel, Dumeignil F and Arias P L 2014
The comparative peak width data of the fresh and used
catalysts are demonstrated in Table S1. The detailed
carbon balance related calculation procedure (flow rate,
Ethanol conversion and Carbon in gas and liquid phases,
etc.,) is provided in SI available at www.ias.ac.in/
chemsci.
γ
Deactivation study of the Pt and/or Ni-based −Al2O3
catalysts used in the aqueous phase reforming of glycerol
for H2 production Appl. Catal. A-Gen. 472 80
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Acknowledgements
The authors would like to thank the Department of Chemi-
cal Engineering, Birla Institute of Technology (BITS), Pilani,
Pilani Campus for providing the utilities to conduct the exper-
iments. Authors also would like to gratefully acknowledge the
department of physics BITS Pilani for conducting the XRD.
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