Production of high purity hydrogen by ethanol steam reforming in membrane reactor

Article abstract of DOI:10.1016/j.cattod.2014.01.014

Production of hydrogen in the course of ethanol steam reforming (ESR) on bimetallic Pt-Ni and Pt-Ru nanocatalysts supported on detonation nanodiamonds (DND) was studied in conventional and membrane reactors. The highest hydrogen yield and purity were achieved in the case of Pt-Ru/DND catalysts at total metal content of 0.3% and atomic Pt/Ru ratio of 9/1. It is shown that realization of ESR process in the membrane reactor with simultaneous hydrogen removal through the Pd-Ru membrane produces hydrogen of high purity, free of any other gaseous products.

Full text of DOI:10.1016/j.cattod.2014.01.014

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Production of high purity hydrogen by ethanol steam reforming in
membrane reactor
a
a
a
b,∗∗
E. Yu. Mironova , M.M. Ermilova , N.V. Orekhova , D.N. Muraviev
,
a,c,∗
A.B. Yaroslavtsev
a
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky prospect 29, Moscow 119991, Russia
Analytical Chemistry Unit, Department of Chemistry, Universitat Autonòma de Barcelona (UAB), 08193 Bellaterra, Barcelona, Spain
Department of Chemistry, Lomonosov Moscow State University, GSP-1, Leninskie Gory, Moscow 119991, Russia
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 August 2013
Received in revised form
Production of hydrogen in the course of ethanol steam reforming (ESR) on bimetallic Pt-Ni and Pt-Ru
nanocatalysts supported on detonation nanodiamonds (DND) was studied in conventional and membrane
reactors. The highest hydrogen yield and purity were achieved in the case of Pt-Ru/DND catalysts at
total metal content of 0.3% and atomic Pt/Ru ratio of 9/1. It is shown that realization of ESR process in
the membrane reactor with simultaneous hydrogen removal through the Pd-Ru membrane produces
hydrogen of high purity, free of any other gaseous products.
2
5 December 2013
Accepted 8 January 2014
Available online xxx
©
2014 Elsevier B.V. All rights reserved.
Keywords:
Ethanol steam reforming
Pd-Ru membrane reactor
Nanodiamond-supported metal catalysts
1
. Introduction
biomass [10,11]. Subsequent biomethanol [12] or bioethanol [13]
steam reforming enables to produce hydrogen from the renewable
sources. These processes can be realized under far milder condi-
tions than, for example, those of methane steam reforming. The
bioethanol steam reforming seems to be more attractive due to the
During the last decade hydrogen has become to be one of the
most demanded products for the energy industry as very light,
powerful and environmentally clean fuel. At the same time, the
contradiction between wide prevalence of hydrogen-containing
compounds in the nature and its absence in free zero-valence state
complicates the development of hydrogen energy substantially.
Fuel cells (the low-temperature fuel cells, in particular) will become
in the nearest future the main devices for application in hydrogen
energy [1–3]. For the low-temperature fuel cells a special atten-
tion should be given to manufacturing of CO-free hydrogen because
of irreversible poisoning of the catalytic materials even by trace
amounts of carbon monoxide [4–7].
Reforming of carbon-containing materials (e.g., ethanol) can
be also considered as an efficient method for hydrogen produc-
tion [8,9]. Intensive development of renewable energy sources in
recent years has led to the design of technologies for production
of various biofuels (such as methane, methanol, and ethanol) from
lower toxicity of its aqueous solution (8–12% C H5OH) which can
2
be used directly for steam reforming [13].
Ethanol steam reforming (ESR) requires substantial energy con-
sumption, as follows obviously from the enthalpy value of the
reaction:
◦
C H5OH + 3H O ↔ 2CO + 6H , ꢀH298 = +173 kJ/mol
(1)
2
2
2
2
To increase the product yield the temperature needs to be increased
– however, this leads to formation of numerous undesirable by-
products [13]. This problem can be successfully solved with the
membrane catalysis which allows to remove hydrogen selectively
from the reaction zone [14]. Within the last decade a number of
communications dedicated to realization of steam reforming pro-
cess of alcohols in membrane reactors has been published [15–20].
The main advantages of such approach involve both the increase in
hydrogen yield and the production of high-purity hydrogen.
Quite a number of heterogeneous catalysts were offered by
different authors for ESR, in particular, Rh, Ru, Pd, Pt, Ni, Co, Cu
on alumina, silica, magnesia, zirconia or ceria [12,13]. One of the
problems is deactivation of the catalysts due to carbon deposition
at high temperature. The application of supports made from the
carbon-based materials (graphite, fullerenes, carbon nanofibers or
∗ Corresponding author at: A.V. Topchiev Institute of Petrochemical Synthesis,
Russian Academy of Sciences, Leninsky prospect 29, Moscow 119991, Russia.
Tel.: +7 9104812220; fax: +7 4956338520.
∗
∗ Corresponding author. Tel.: +34 935814860; fax: +34 935812379.
E-mail addresses: Dimitri.Muraviev@uab.es (D.N. Muraviev),
yaroslav@igic.ras.ru, yaroslav@ips.ac.ru (A.B. Yaroslavtsev).
0
920-5861/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2014.01.014
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2
nanotubes) may solve this problem due to their resistance to car-
bonization, high specific area, thermal stability and good adhesion
to metals [21]. Nanodiamonds can also be considered under this
approach.
0.3 wt%) mixed with granulated quartz (fraction 1–3 mm) were
placed into the reaction zone of the membrane reactor consisting
of two parallelepiped-shaped stainless steel compartments with
the following inner dimensions: 118 mm × 20.5 mm × 2 mm (reac-
3
The number of publications dedicated to application of nanopar-
ticles in catalysis is permanently growing [22–24]. Detonation
nanodiamonds (DND), or nanodiamonds produced by detonation
synthesis technique, represent diamond nanoparticles consisting
tion zone volume 4.5 cm ). The two compartments were divided
by a pinhole-free foil membrane of Pd–Ru alloy (6 mass% Ru;
118 mm × 20 mm × 50 ␮m). Two gaskets made of copper and of
graphite ensured that the gaseous streams flowing in the permeate
and the reaction zones did not mix with each other in the reactor.
Experiments in MR were carried out at the temperatures of 350
3
of carbon atoms in the sp -hybridization state [25,26]. The outer
DND surface is partially oxidized and contains a large number of
carboxyl, carbonyl, and hydroxyl groups. This allows the forming
of the surface complexes with transition metal ions, which can
serve as the precursors of active nanocatalysts for various reactions,
electrochemical sensors, etc. Due to the presence of various func-
◦
and 450 C. The flow of sweep gas on the permeate side (from
3
3
40 cm /min to 100 cm /min) allowed to perform hydrogen removal
from the reactor.
Each experiment was carried out within 3–5 h. Regeneration of
the catalysts between experiments was carried out by heating in
2
tional groups and high specific surface area (150–450 m /g), DND
◦
are characterized by clearly pronounced sorption properties and
can be used as not only support for metal nanocatalysts but also
for their own catalytic activity [27–29]. An additional important
advantage of DND is their relatively low cost (5 Euros per gram);
high thermal stability makes them applicable for such high tem-
perature catalytic processes as ESR. The activity of Pt, Ru, Ni, Pt-Ni,
and Pt-Ru nanoparticles supported on DND was studied for the first
time in a conventional tubular reactor [30].
The main goal of this study was the research of the membrane
catalytic process of high-purity hydrogen production using Pt–M
alloy (M = Ni, Ru) nanocatalysts deposited on DND in the presence
of the commercial dense Pd-Ru membrane with 100% selectivity
for hydrogen.
hydrogen for one hour at 450 C. The ethanol conversion degree,
X (%), the catalyst selectivity, S (%), and the yield of products, Yi
were calculated from the results of analysis by using the following
equations:
ϕ − ϕ
0
1
X =
Si =
× 100
× 100
(2)
(3)
(4)
(5)
ϕ
0
ϕi
ϕ − ϕ1
0
ϕH2
ϕH2 + 2ϕCH4
SH2
=
× 100
ϕi
Yi =
,
ϕ0
where ϕ0 and ϕ1 are the initial and the resulting ethanol concen-
2
. Methods and materials
trations, respectively; ϕ is the ESR product concentration (i = H ,
i
2
CO, CO , or CH ).
2
4
2.1. Preparation of catalysts and the procedure for catalytic
Hydrogen permeability of Pd-Ru membrane was measured
directly in the membrane reactor before and after the comple-
tion of ESR experiments with Pt-Ru/DND catalyst by feeding the
experiments
The catalysts were prepared by deposition of metal chlorides
flow of pure hydrogen to the reaction zone and the flow of argon
onto DND followed by IR radiation. A suspension of metal chlo-
rides (Pt with Ru or Ni where the Pt:Ru (Ni) ratio was 9:1) and DND
particles in dimethylformamide (DMF) was subjected to ultrasonic
dispersion for 10 min and dried to a constant weight. Resulting
powder was exposed to IR radiation for 2 min in an inert atmo-
sphere; the intensity corresponded to the temperature of 700 C.
The samples of catalysts with 0.3 and 10 wt% of Pt–Ru or Pt–Ni
alloys were prepared.
A traditional tubular stainless steel reactor (TR) of 7 mm diam-
eter was used for ESR in the plug flow apparatus. Samples of
catalysts (loading 0.3 g; metal content 0.3 wt%) mixed with gran-
ulated quartz (fraction 1–3 mm) were placed into the middle of
reactor tube (volume of catalyst bed 4.5 cm ). ESR was carried out
at temperatures from 350 C to 650 C with a carrier gas (Ar) flow
3
(
40 cm /min) to the hydrogen removal zone. Hydrogen permeabil-
ity constant was calculated by using equation:
Q × ı
[cm s bar−1/2] =
2
−1
J
ꢀ
ꢂ
(6)
ꢁ
ꢁ
S ×
P1 −
P2
◦
3
where Q is hydrogen flux through the membrane, cm /min; ı – the
thickness of membrane, cm; P1 – hydrogen partial pressure on the
input side of membrane, bar; P – hydrogen partial pressure on the
2
2
output side of membrane, bar; S – membrane area, cm .
3
2.2. Catalysts structure and morphology
◦
◦
3
The specific area and porosity of catalyst samples were mea-
sured by low-temperature nitrogen adsorption in the porometer
ASAP-2020N (Micromeritics Co., USA). The specific surface area was
determined by using BET method in the range of relative pressure
values from 0 to 1 using the equation for multimolecular steam
adsorption. The micrographs of the samples were obtained by using
a transmission electron microscope JEM-2100 (Jeol).
rate of 20 cm /min. The liquid mixture of ethanol and water with
the molar ratio of 1:3 or 1:9 was fed by infusion pump P-600 into the
evaporator. At the evaporator outlet ethanol and water vapors were
mixed with the carrier gas and then fed into the reactor. Vaporous
ESR products were condensed at the outlet of the reactor in a glass
receiver cooled to 0 C. Uncondensed vapors (water and ethanol)
were fed to LHM 8MD chromatograph with thermal conductivity
◦
◦
X-ray analysis of the samples containing 0.3 or 10% of metal
catalyst was performed using the diffractometer “Rigaku D/MAX
detector (t = 160 C, I = 80 mA, a column with Porapak-T stationary
phase, carrier gas He, flow rate 30 cm /min). Methane, CO, and CO2
3
2
200”, CuK␣1 radiation. The software package Rigaku Application
were analyzed in the same chromatograph with the use of the acti-
vated charcoal column. Hydrogen and methane were analyzed with
the use of Chrom-4 chromatograph with a thermal conductivity
detector and CaA Zeosorb stationary phase column. The obtained
data were treated by using Ecochrom program.
Data Processing was used for spectra analysis.
3. Results and discussion
The other series of experiments was carried out in the mem-
brane reactor (MR). The samples of catalysts (0.3 g, metal content
X-ray patterns of Pt-Ru/DND and Pt-Ni/DND samples with
10 wt% metal content are similar, both having the peaks
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Fig. 1. XRD pattern of Pt-Ru (10%)/DND catalyst. Assignment of Pt–Ru alloy reflexes
of X-ray patterns is indicated by numbers. Symbol “C” denotes typical DND lines.
corresponding to the diamond and Pt phases (Fig. 1). The coher-
ent scattering region for diamond particles is equal to 4.5 ± 0.5 nm.
For metal particles this value was equal to 11 ± 1 nm which is far
higher than that for DND. The results of TEM analysis of DND and
DND-Pt/Ru nanocatalysts are shown in Fig. 2a and b respectively.
As one can see, an average size of DND particles equals to ≈4.5 nm
(Fig. 2a), while for metal nanoparticles this value was found to
be about 3.5–4 nm for different samples. At the same time, some
particles with higher sizes can also be observed (Fig. 2b). The dif-
ference between TEM and X-Ray data is determined by the fact
that the intensity of X-ray reflections is higher for large particles.
X-ray reflection of Pt-Ru and Pt-Ni nanoparticles cannot be detected
when their content in the sample equals to 0.3% and the metal
particle size is below the detection level. A similar situation was
observed for the metal particles synthesized in the Nafion mem-
brane matrix [31]. At the same time, the sizes of DND particles
determined by using both methods appear to be quite close to each
other because DND size distribution is quite narrow.
It is well known that different facets of the crystal surface are
characterized by different structure, heat of adsorption, therefore,
they can display different catalytic activity [32]. At the same time,
deposition of metal nanoparticles on the structured surface may
lead to the different preferential orientation of a metal nanocrys-
tal. From this viewpoint it is important to know which facets
predominate on the surface of platinum alloy nanoparticles pre-
cipitated on DND support. X-ray diffraction analysis cannot answer
this question because of the random orientation of nanoparti-
cles, while the High Resolution Transmission Electron Microscopy
(
HRTEM) appears to be far more informative in this case. This
technique allows to determine the distance between interatomic
layers located on the nanoparticles surface. The most frequently
observed distances between interatomic layers was determined to
equal ≈2.8 A˚ (see Fig. 2b), which corresponds to (1 1 0) XRD reflec-
tions. They cannot be observed in the Pt X-ray pattern in accordance
with the extinction rule. 1.95 A˚ and 2.25 A˚ distances corresponding
to (2 0 0) and (1 1 1) reflections, respectively, are far less common.
The experimentally determined specific surface area of cata-
2
lysts containing 0.3% of metal was equal to 290 ± 5 m /g. After
the use of these catalysts in the ESR process this value reduced
Fig. 2. TEM micrographs for DND (a) and for Pt-Ru/DND catalyst with 0.3% metal
content (b). b’ – the copy of (b) with the lattice fringes.
2
to 155 ± 3 m /g. However, both of these values are quite low when
compared to that calculated for nanoparticles with an average size
2
of 4.5 nm (∼500 m /g). This discrepancy can be explained by the
partial aggregation of catalyst nanoparticles, which increases in the
course of catalytic cycle.
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Table 1
4
Comparison of hydrogen yields (in mol H2/mol C2H5OH) in tubular and membrane
reactors with Pt-Ni or Pt-Ru catalysts.
◦
T ( C)
350
3/1
450
3/1
C2H5OH/H2O ratio
9/1
9/1
Pt-Ni/DND
MR
TR
0.83
0.52
1.23
0.87
1.42
0.5
2.32
0.97
Pt-Ru/DND
MR
TR
1.6
0.25
1.32
0.58
2.22
0.99
2.76
1.47
not only by reactions (7), (10), and (12), but also by methanation of
ESR product, CO2:
CO + 4H ↔ CH + 2H O
(13)
2
2
4
2
It is known that Ni and noble metal catalysts deposited on oxide
supports show high activity in this reaction. One of the methods
allowing to suppress this reaction consists in decreasing the ethanol
partial pressure [33]. In fact, the use in our experiments of the
H O/ethanol ratio of 9:1 instead of 3:1 decreased methane yield
2
1
.5 times and increased hydrogen yield simultaneously.
With high ESR temperature one can suppose the proceeding
of direct DND interaction with water vapor. In order to evaluate
the possible influence of this process on the distribution of the
products, the blank experiment was carried under the same condi-
tions. The main products of this reaction were H and CO . Still, the
2
2
yields of these products were negligible in the temperature range
◦
3
50–530 C. Thus, the hydrogen yield was 30 times less in this case
◦
than for the ESR on the Pt-Ru/DND catalyst at 530 C.
о
Fig. 3. Temperature dependence of products distribution for ESR process in TR by
Table 1 shows hydrogen yield at 350 and 450 C for different
using Pt-Ni/DND (a) and Pt-Ru/DND (b) catalysts (H2O/ethanol ratio = 3).
water-to-ethanol ratios in the reaction mixture for ESR process car-
ried out in the tubular and membrane reactors. The total ethanol
conversion achieved 98–99% at 450 C in the case of the membrane
◦
The distribution of the ESR reaction products obtained in the
tubular reactor for Pt-Ni/DND and Pt-Ru/DND bimetallic catalysts
with water/ethanol ratio of 3/1 is shown in Fig. 3. The ESR by-
products can be formed according to the following side reactions
reactor.
The following features of ESR process were noted. The hydro-
gen yield increased with temperature and with an increase in the
water-to-ethanol ratio. In accordance with the thermodynamics
of the process both of these features seem to be quite natural. At
the same time, the total hydrogen yield in the membrane reac-
tor increased as a rule by a factor of 1.5–2 in comparison with
ESR in a traditional reactor. Hydrogen removal from the reaction
zone through a membrane resulted in a remarkable shift of the
equilibrium to the ESR products formation. In the course of our
experiments with the Pt-Ru/DND catalyst a hydrogen amount from
∼35% to 60% was selectively removed through the membrane (it is
known as the hydrogen recovery factor), thus increasing hydrogen
yield substantially in the course of ESR process.
[
12]:
C H5OH ↔ CH + CO + H
(7)
(8)
2
4
2
C H5OH ↔ CH CHO + H
2
3
2
C H5OH ↔ C H + H O
(9)
2
2
4
2
2
C H5OH ↔ 3CH + CO
(10)
(11)
(12)
2
4
2
C2H5OH ↔ C + CO + 3H2
C H5OH ↔ CH + C + H O
2
4
2
The products distribution for Pt-Ni/DND and Pt-Ru/DND
Strictly speaking, one cannot exclude the catalytic effect of the
membrane used in the process under consideration. We have car-
ried out the blank ESR experiment at 450 C in the membrane
bimetallic catalysts after ESR in a tubular reactor at the water-
to-ethanol ration 3:1 is shown in Fig. 3a and b. Formation of
acetaldehyde and ethane was not observed in the course of these
ESR catalytic processes. The use of Pt-Ni/DND catalyst in ESR pro-
cess at low temperatures results in substantially lower hydrogen
yields (Fig. 3a) in comparison with Pt-Ru/DND (Fig. 3b).
◦
reactor in the absence of catalyst. The conversion of ethanol was
lower than 1%. Most probably, this is due to the lower surface area
−
3
of membrane in comparison with that of nanocatalyst (1.3 × 10
2
vs. 280 m /g, respectively).
Pt-Ru/DND catalyst has an additional advantage providing a
much lower carbon monoxide concentration in the products mix-
ture. CO concentration in the products mixture was close to zero
It is evident that the nature of second component of the alloy
affects the productivity of membrane reactor. Pt-Ni/DND catalyst
gives higher CO yield and lower selectivity on hydrogen in com-
parison with Pt-Ru/DND. This appears to be the reason for lower
hydrogen recovery factor and, as a consequence, the lower hydro-
gen productivity of membrane reactor with Pt-Ni/DND catalyst.
In all cases the methane yield in membrane reactor increased
with an increase in hydrogen yield. This fact allows to suppose that
the C C bond breakage proceeds only after the preliminary partial
hydrogen elimination from the alcohol molecule. At the same time
the formed methane does not take part in further transformations.
◦
at the temperatures lower than 450 C (Fig. 3b). However, the
methane yield increased considerably with a temperature increase
for this catalyst. It is likely that a decrease in hydrogen selectiv-
ity for Pt-Ru catalyst with temperature (Fig. 3b) is observed due
to the increase in selectivity of this catalyst on methane at high
temperatures.
The CH4 by-product formation observed for noble metal ESR
catalysts supported on oxide carriers [12,13] could be explained
Please cite this article in press as: E.Yu. Mironova, et al., Production of high purity hydrogen by ethanol steam reforming in membrane
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2
. The use of the membrane reactor allows not only the production
of high purity hydrogen but also an increase in the efficiency of
ESR process.
3
. The high temperature ESR process is characterized by a lower
selectivity; however, when the process is carried out at 350 C
◦
in the membrane reactor it allows to produce hydrogen of high
purity which is about completely free from impurities.
Acknowledgements
The authors are grateful to Natalia Shundina (the Center for Col-
lective Use of Moscow Institute of Steel and Alloys) for the TEM
investigation of the samples. This work was supported in part by
the Ministry of Education and Science of Russian Federation, Grant
No 8841.
Fig. 4. Dynamics of hydrogen and methane yields for ESR on Pt-Ru/DND catalyst in
◦
membrane reactor at 450 C, H2O/ethanol ratio = 9, Ar flow rate in zone of hydrogen
3
removal 40 cm /min.
References
[
[
[
1] J.O.M. Bockris, T.N. Veziroglu, A solar-hydrogen economy for U.S.A., Int. J.
Hydrogen Energy 8 (1983) 323–340.
2] D.S. Scott, W. Hafele, The coming hydrogen age: preventing world climatic
disruption, Int. J. Hydrogen Energy 15 (1990) 727–737.
3] European Commission, Eur20719 EN –Hydrogen Energy and Fuel Cells – A
Vision of Our Future, Office for Official Publications of the European Commit-
tees, Luxemburg, 2003.
[
[
[
4] M. Rikukawa, K. Sanui, Proton-conducting polymer electrolyte membranes
based on hydrocarbon polymers, Prog. Polym. Sci. 25 (2000) 1463–1502.
5] V. Neburchilov, J. Martin, H. Wang, J. Zhang, A review of polymer electrolyte
membranes for direct methanol fuel cells, J. Power Sources 169 (2007) 221–238.
6] A.B. Yaroslavtsev, Yu.A. Dobrovolsky, N.S. Shaglaeva, L.A. Frolova, E.V. Gerasi-
mova, E.A. Sanginov, Nanostructured materials for low-temperature fuel cells,
Russ. Chem. Rev. 81 (2012) 191–220.
[
7] L. Carrette, K.A. Friedrich, U. Stimming, Fuel Cells: Fundamentals and Applica-
tions, Fuel Cells 1 (2001) 5–39.
Fig. 5. Temperature dependence of hydrogen permeability of Pd-Ru membrane
before and after ESR experiments and after membrane regeneration.
[8] F. Gallucci, E. Fernandez, P. Corengia, M. Sint Annaland, Recent advances on
membranes and membrane reactors for hydrogen production, Chem. Eng. Sci.
9
2 (2013) 40–66.
Membranes made on the basis of platinum metals are known to
be poisoned by carbon and carbon monoxide formed in the course
of ESR process. However, the use of Pt-Ru/DND catalyst in the mem-
brane reactor for 3–5 h in the flow mode did not lead to a decrease
in the product yield (see Fig. 4).
[9] J.R. Mielenz, Ethanol production from biomass: technology and commercial-
ization status, Curr. Opin. Microbiol. 4 (2001) 324–3299.
10] M.V. Tsodikov, A.V. Chistyakov, F.A. Yandieva, V.V. Zmakin, A.E. Gekhman, I.I.
Moiseev, Conversion of biomass products to energy sources in the presence of
nanocatalysts and membrane catalyst systems, Catal. Ind. 3 (2011) 4–10.
[11] M. Ni, D.Y.C. Leung, M.K.H. Leung, A review on reforming bio-ethanol for hydro-
gen production, Int. J. Hydrogen Energy 32 (2007) 3238–3247.
12] N. Bion, F. Epron, D. Duprez, Bioethanol reforming for H2 production. A com-
parison with hydrocarbon reforming, Catalysis 22 (2010) 1–59.
[13] N. Bion, D. Duprez, F. Epron, Design of nanocatalysts for green hydrogen pro-
duction from bioethanol, ChemSusChem 15 (2012) 76–91.
14] V.M. Gryaznov, Hydrogen permeable palladium membrane catalysts, Platin.
Met. Rev. 30 (1986) 68–72.
[
The membrane hydrogen permeability decreases by almost
two-fold after 50 h online in ESR process with planned regener-
ations of Pt-Ru catalyst in hydrogen every 3–5 h (Fig. 5). To prevent
the inhibition of ESR process, membrane reactor was subjected to
[
[
◦
the oxidative regeneration by the air flow at 450 C. As also seen
from Fig. 5, after regeneration the value of membrane permeability
returns to the initial level.
It is probable that a practically constant activity of the Pt-
Ru/DND catalyst in our experiment is explained by the sufficiently
high rate of hydrogen removal by argon flow.
The production of ultra-high purity hydrogen on the output zone
is the main advantage of this process when carried out in the mem-
brane reactor. The impurities content in hydrogen did not exceed
[15] B. Krishna, R. Nair, M.P. Harold, Hydrogen generation in a Pd membrane fuel
processor: productivity effects during methanol steam reforming, Chem. Eng.
Sci. 61 (2006) 6616–6636.
[
16] A. Basile, A. Parmaliana, S. Tosti, A. Iulianelli, F. Gallucci, C. Espro, J. Spooronen,
Hydrogen production by methanol steam reforming carried out in membrane
reactor on Cu/Zn/Mg-based catalyst, Catal. Today 137 (2008) 17–22.
[
17] A. Iulianelli, A. Basile, Hydrogen production from ethanol via inorganic mem-
brane reactors technology: a review, Catal. Sci. Technol. 1 (2011) 366–379.
[18] A. Iulianelli, S. Liguuori, T. Longo, P. Pinacci, A. Basile, An experimental study on
bio-ethanol steam reforming in a catalytic membrane reactor. Part I: Temper-
ature and sweep-gas configuration effects, Int. J. Hydrogen Energy 35 (2010)
0.01%. This result is related on the practically absolute selectivity of
3170–3177.
hydrogen permeability through the dense Pd alloy membrane [34].
[19] A. Iulianelli, A. Basile, An experimental study on bio-ethanol steam reforming
in a catalytic membrane reactor. Part II: Reaction pressure, sweep factor and
WHSV effects, Int. J. Hydrogen Energy 35 (2010) 3159–3164.
4
. Conclusions
[
20] P.K. Seelam, S. Liguori, A. Iulianelli, P. Pinacci, V. Calabrò, M. Huuhtanen, R.
Keiski, V. Piemonte, S. Tosti, M. De Falco, A. Basile, Hydrogen production from
bio-ethanol steam reforming reaction in a Pd/PSS membrane reactor, Catal.
Today 19 (2012) 42–48.
The study of steam ethanol reforming over Pt–Ni and Pt–Ru
alloys supported on DND was carried out in traditional and mem-
brane reactors. The following conclusions can be derived from the
obtained results:
[
[
21] N.N. Vershinin, O.N. Efimov, V.A. Bakaev, A.E. Aleksenskii, M.V. Baidakova, A.A.
Sitnikova, A.Ya. Vul’, Detonation nanodiamonds as catalyst supports, Fullerenes
Nanotubes Carbon Nanostruct 19 (2011) 63–68.
22] I.P. Suzdalev, P.I. Suzdalev, Nanoclusters and nanocluster systems. Assembling,
interaction and properties, Russ. Chem. Rev. 70 (2001) 177–210.
1
. The best results regarding hydrogen yield and purity are
achieved both in traditional and membrane reactors when using
Pt–Ru alloy catalysts deposited on DND surface (at total metal
content of 0.3% and Pt/Ru = 9/1).
[23] M. Hosokawa, K. Nogi, M. Naito, T. Yokoyama, Nanoparticle Technology Hand-
book, Elsevier, Oxford, Amsterdam, 2007, pp. 622.
[
24] B. Domènech, M. Mu n˜ oz, D.N. Muraviev, J. Macanás, Catalytic membranes with
palladium nanoparticles: from tailored polymer to practical applications, Catal.
Today 193 (2012) 158–164.
Please cite this article in press as: E.Yu. Mironova, et al., Production of high purity hydrogen by ethanol steam reforming in membrane
reactor, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.014

G Model
CATTOD-8861; No. of Pages6
ARTICLE IN PRESS
E.Yu. Mironova et al. / Catalysis Today xxx (2014) xxx–xxx
6
[
[
[
25] V.N. Mochalin, O. Shenderova, D. Ho, Yu. Gogotsi, The properties and application
of nanodiamonds, Nat. Nanotechnol. 7 (2012) 11–23.
26] I.I. Kulakova, Surface chemistry of nanodiamonds, Phys. Solid State 46 (2004)
reforming on metals of VIII Group on nanodiamonds catalysts in traditional
and membrane reactors, Chem. Listy 106 (2012) 1248.
[31] S.A. Novikova, G.Yu. Yurkov, A.B. Yaroslavtsev, Synthesis and transport proper-
ties of membrane materials with incorporated metal nanoparticles, Mendeleev
Commun. 20 (2010) 89–91.
6
36–643.
27] D. Su, N.I. Maksimova, G. Mestl, V.L. Kuznetsov, V. Keller, R. Schlogl, N. Keller,
Oxidative dehydrogenation of ethylbenzene to styrene over ultra-dispersed
diamond and onion-like carbon, Carbon 45 (2007) 2145–2151.
[32] K. Christmann, Introduction to Surface Physical Chemistry, Steinkopff/Springer,
Darmstadt/New York, 1991, pp. 274.
[
[
28] X. Sun, R. Wang, D. Su, Research progress in metal-free carbon-based catalysts,
Chin. J. Catal. 34 (2013) 508–523.
[33] Y. Ando, K. Matsuoka, H. Takagi, K. Kuramoto, Hydrogen production
from ethanol steam reforming over noble metal catalysts supported on
SiO2: mechanism of methane production and reaction conditions for
suppression of methane production, Bull. Chem. Soc. Jap. 85 (2012)
517–521.
29] E.A. Tveritinova, I.I. Kulakova, Yu.N. Zhitnev, A.V. Fionov, A. Lund, W. Chen, I.
Buyanova, V.V. Lunin, Catalytic conversion of C2–C3 alcohols on detonation
nanodiamonds and its modification, Russ. J. Phys. Chem. 86 (2012) 26–31.
30] M.M. Ermilova, M.N. Efimov, G.P. Karpacheva, E.Yu. Mironova, N.V. Orekhova,
L.M. Zemtsov, A.B. Yaroslavtsev, Hydrogen production by ethanol steam
[
[34] E. Wicke, H. Brodowsky, H. Zuchner, Hydrogen in palladium and palladium
alloys, Topics Appl. Phys. 29 (1978) 74–155.
Please cite this article in press as: E.Yu. Mironova, et al., Production of high purity hydrogen by ethanol steam reforming in membrane
reactor, Catal. Today (2014), http://dx.doi.org/10.1016/j.cattod.2014.01.014