Study of methanol steam reforming and ethanol conversion in conventional and membrane reactors

Article abstract of DOI:10.1134/S0965544116110104

Research results for methanol steam reforming and ethanol conversion in a conventional and a membrane reactor in the presence of Ru–Rh/DND, LiZr₂(PO₄)₃, and Li_1.1Zr_1.9In_0.1(PO₄)₃ catalysts have been described. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and the BET method. The study of the catalytic properties of the catalyst composites has shown that the Ru–Rh/DND catalyst mostly mediates the dehydrogenation process, while LiZr₂(PO₄)₃ and Li_1.1Zr_1.9In_0.1(PO₄)₃ exhibit activity in both the dehydration and dehydrogenation reactions. The membrane process with a Pd–Ru alloy membrane provides a 20% increase in the hydrogen yield.

Full text of DOI:10.1134/S0965544116110104

ISSN 0965-5441, Petroleum Chemistry, 2016, Vol. 56, No. 11, pp. 1048–1055. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.A. Lytkina, A.B. Ilin, A.B. Yaroslavtsev, 2016, published in Membrany i Membrannye Tekhnologii, 2016, Vol. 6, No. 4, pp. 397–405.
Study of Methanol Steam Reforming and Ethanol Conversion
in Conventional and Membrane Reactors
A. A. Lytkina*, A. B. Ilin, and A. B. Yaroslavtsev
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
*e-mail: lytkina@ips.ac.ru
Received April 20, 2016
Abstract—Research results for methanol steam reforming and ethanol conversion in a conventional and a
membrane reactor in the presence of Ru–Rh/DND, LiZr (PO ) , and Li Zr In (PO ) catalysts have
2
4 3
1.1 1.9 0.1
4 3
been described. The samples have been characterized by X-ray diffraction, scanning electron microscopy,
and the BET method. The study of the catalytic properties of the catalyst composites has shown that the Ru–
Rh/DND catalyst mostly mediates the dehydrogenation process, while LiZr (PO ) and Li Zr In (PO )
2
4 3
1.1 1.9 0.1
4 3
exhibit activity in both the dehydration and dehydrogenation reactions. The membrane process with a Pd–
Ru alloy membrane provides a 20% increase in the hydrogen yield.
Keywords: membrane catalysis, NASICON, methanol steam reforming, ethanol conversion
DOI: 10.1134/S0965544116110104
INTRODUCTION
2
C H OH → C H OC H + H O,
2 5 2 5 2 5 2
(
4)
5)
0
Aggravated environmental problems have raised
interest in the use of renewable raw materials, promis-
ing types of which are biomass and bioalcohols result-
ing from the primary processing of biomass (metha-
nol, ethanol). Bioalcohols can be used as precursors
for producing hydrogen or a number of valuable prod-
ucts, such as hydrocarbons, ethers, aldehydes,
ketones, hydrogen, etc. [1]. The reforming of alcohols
whose molecules are much more reactive than meth-
ane molecules occurs at low temperatures [2–6].
In addition to target reaction (1), methanol steam
reforming (MSR) is characterized by the occurrence
by methanol decomposition (2) and reaction of the
produced CO with water (3):
ΔH2
= –88.48kJ mol;
98K
dehydration to ethylene:
C H OH → C H + H O,
2
5
2
4
2
(
0
ΔH2
= + 28.99 kJ mol;
98K
dehydration to acetaldehyde:
C H OH → CH CHO + H ,
2
5
3
2
(6)
0
ΔH2
= + 17.36 kJ mol;
98K
methanation:
C H OH → CH + CO + H ,
2
5
4
2
(7)
0
ΔH2
= +33.16 kJ mol;
98K
CH OH + H O ↔ CO + 3H ,
3
2
2
2
(1)
(2)
(3)
and steam reforming:
0
ΔH2
= 49.7 kJ mol,
98K
C H OH + H O → 2CO + 4H ,
2
5
2
2
(
8)
9)
CH OH ↔ CO + 2H ,
0
3
0
2
ΔH2
= +239.31 kJ mol;
98K
ΔH2
= 90.2 kJ mol,
98K
C H OH + 3H O → 2CO + 6H ,
2
5
2
2
2
(
0
CO + H O ↔ CO + H ,
2
2
2
ΔH2
= +157.0 kJ mol.
98K
0
ΔH2
98K
= −41.2 kJ mol.
In addition, the dehydrogenation of the reaction
products and catalytic crosslinking can occur to form
valuable extended-chain hydrocarbons. Depending
on the target product, catalysts with different struc-
tures and compositions are used for alcohol conver-
sion.
Ethanol conversion products can be much more
diverse. Ethanol conversion can occur via a few alter-
native pathways:
dehydration to diethyl ether (DEE):
1048

STUDY OF METHANOL STEAM REFORMING
1049
Typically, hydrogen is produced using metal cata- (even in small amounts of ~1 wt %) leads to an
lysts supported on various supports. It was shows that increase in the mechanical stability of the membrane
noble metals, such as Rh, Ir, Pt, Ru, and Pd, exhibit during thermal cycling in hydrogen [42].
high activity in alcohol reforming [7]. Furthermore,
The aim of this study was to examine the MSR and
Rh is regarded as one of the most active metals in the
ethanol conversion processes implemented by mem-
series of noble metals [8]. The authors of [9–13] also
brane catalysis. Of particular interest was to compare
consider Ru as a promising catalyst for steam reform-
the two processes; in one of them, hydrogen is the
ing and oxidative steam reforming. Since the use of
main product, while in the other, the hydrogen yield is
noble metals in catalysis is limited to their high cost
low; however, the use of membrane catalysis makes it
[
14], of considerable interest are catalysts with a low
possible to change the ratio of the conversion prod-
ucts.
content of noble metals [15] and materials composed
of a few metals [15–17].
An important problem is the improvement of the
selectivity and coking resistance of the composite. In
this respect, novel carbon materials, such as nano-
tubes, graphene, and detonation nanodiamonds
EXPERIMENTAL
Catalyst Synthesis, Physicochemical Investigation,
and Catalytic Test Procedures
(
DNDs), are attracting close attention; the unique
properties of these materials make them suitable for
use as catalyst supports [6, 18, 19]. DND nanoparti-
cles consist of a core with a diamond lattice and an
amorphous carbon shell. In addition, the DND sur-
face contains a large amount of oxygen-containing
functional groups that provide high adsorption prop-
erties of this material [20].
The Ru–Rh/DND catalyst was prepared by the
reduction of metal precursors (ruthenium(III) chlo-
ride and rhodium(III) chloride) at room temperature
in a liquid phase using 0.5 M NaBH as a reducing
4
agent. The amount of the precursor was calculated
according to the total metal content in the material
A promising type of alcohol conversion catalysts after complete reduction (7.5 wt %) and an atomic
are complex phosphates [21, 22]. Materials with a ratio of 1 : 1. The synthesized catalyst was exposed to a
NASICON-type (NA Super Ionic CONductor) struc- H (5%)/Ar atmosphere (20 mL/min) at 350°C for 3 h
2
ture are compounds with a general formula of to reduce the metals.
A B (ZO ) , where A is typically an alkali or alkaline
x
2
4 3
The LiZr (PO ) and Li
Zr In (PO ) com-
1.9 0.1 4
2
4
1 ± 0.1
earth element, B is a polyvalent element (Zr, Ti, Sc,
etc.), and Z is phosphorus or silicon. Their structure is
composed of edge-linked BO octahedra and ZO tet-
pounds were synthesized by the Pechini method [43–
4
5]. To this end, ZrOCl × 8 H O, citric acid, Li CO ,
2
2
2
3
6
4
and NH H PO were sequentially dissolved in a
4
2
4
rahedra. The voids of the framework formed by them
are occupied by the A cations [23–30].
deionized water–ethylene glycol mixture (10
:
2
mL/mL); after that, the solution pH was rapidly
Heterovalent substitution provides variation in the
number and strength of acid (Lewis and Brønsted) and
redox surface sites. The chemical and thermal resis-
tance of catalysts based on these compounds makes
them suitable for use under conditions where metal
catalysts undergo degradation.
One of the products of the above processes is ture.
hydrogen. A catalytic process version is membrane
catalysis, in which some of the products are selectively
adjusted to 5.5 by the addition of an ammonia solu-
tion. The resulting solution was sequentially subjected
to heat treatments at 95°С (24 h), 150°С (24 h), 350°С
(
4 h), and 750°С (10 h). To prepare LZInP, a weighed
portion of In O was dissolved in a minimum amount
2
3
of hot concentrated nitric acid and added to the mix-
The surface area and pore size of the synthesized
catalysts were examined by the BET method on an
separated or fed to the reaction mixture through a
membrane [5, 31–33]. In particular, the problem of
producing high-purity hydrogen can be effectively
solved using membrane catalysis owing to the selective
removal of hydrogen across a Pd-containing mem-
brane [34–36]. Other advantages of this method are
the possibility of shifting the thermodynamic equilib-
rium owing to the removal of the product. Therefore,
even if hydrogen is not the main product, the removal
of it can significantly change the process direction and
the product yield [5]. Compared with pure Pd mem-
branes, membranes made of some Pd alloys have a
number of advantages because they exhibit a higher
ASAP-2020N
instrument
(Micromeritics,
United States). X-ray diffraction (XRD) analysis of
the samples was conducted using a Rigaku D/Max-
2
200 X-ray diffractometer (CuK radiation). Spec-
α1
trum processing and qualitative analysis were con-
ducted using the Rigaku Application Data Processing
software package. Particle size (coherent scattering
region (CSR)) was determined from the XRD peak
widths using the Scherrer formula
kλ
d =
,
(10)
(
)
B − b cos θ
hydrogen permeability, strength, thermal stability, and where k = 0.89 is the Scherrer constant, λ = 1.5406 Å
catalytic activity [37–41]. The alloying of Pd with Ru is the wavelength of the radiation used, B is the peak
PETROLEUM CHEMISTRY Vol. 56 No. 11 2016

1050
LYTKINA et al.
Carrier gas
Quartz
Products
Quartz
Quartz + Catalyst
Methanol + water
Fig. 1. Diagram of a conventional flow reactor.
half-width at half-maximum (2θ), b is the instrumen-
tal broadening (2θ), and θ is the peak position angle.
Degree of conversion of alcohol X (mol %) was cal-
culated according to the analysis results using the fol-
lowing equation:
Transmission electron microscopy (TEM) images
were recorded on a JEM 2100 transmission electron
microscope at an accelerating voltage of 200 kV and a
point resolution of 0.23 nm. Micrographs of the sam-
ples were recorded using a Carl Zeiss NVision 40 scan-
ning electron microscope (SEM) equipped with an
electron probe microanalysis attachment. The accel-
erating voltage was 1 kV.
X = (ϕ – ϕ )/ϕ × 100,
0
1
0
where ϕ and ϕ are the initial and final concentrations
0
1
of methanol, respectively.
RESULTS AND DISCUSSION
Catalyst and Substrate Structural
and Morphological Characteristics
MSR and catalytic conversion of ethanol were con-
ducted in a conventional stainless steel tubular flow reac-
tor (Fig. 1). Reaction products were analyzed on LHM
The X-ray diffraction patterns of the Ru–
Rh/DND catalyst show broad peaks with maxima at
8MD (phase, Porapak T; carrier gas, He); Chrom-4
(
phase, CaA Zeosorb; carrier gas, Ar); and Kristallyuks
4
3.6° corresponding to the DND (Fig. 3a). The nar-
4
000M chromatographs (phase, HayeSep T 60/80 mesh, rower peaks are attributed to the Ru–Rh alloy for
SKT-6; carrier gas, He and phase, Mole Seive 5 A; carrier which the reflection peaks are located between the
gas, Ar); in the all cases, a thermal conductivity detector positions characteristic of the individual metals. The
was used.
unit cell parameter of the resulting alloy is 0.38044 ±
.0002 nm.
0
The catalyst with a weight of with 0.3 g was mixed
The XRD data for lithium zirconium phosphates
with quartz granules and placed at the center of the
reactor. Before each set of experiments, the metal cat-
showed that the LiZr (PO ) and Li Zr In (PO )
4 3
2
4 3
1.1
1.9 0.1
samples are composed of a single phase and corre-
spond to the monoclinic NASICON modification
alyst was in situ reduced with an H (5%)/Ar mixture
2
(
20 mL/min) at a temperature of 350°C for 3 h. The
(
Fig. 3b).
carrier gas was Ar or He (20 mL/min). For steam
reforming, a liquid mixture of methanol and water in a
molar ratio of 1: 1 was fed into an evaporator using an
Instilar1488 Dixion infusion pump at a flow rate of
According to SEM, the Ru–Rh/DND samples are
framework agglomerates with a size of 50–300 nm,
which are composed of significantly smaller particles
(
Fig. 4a). TEM data provide more information
2
mL/h and then mixed with the carrier gas stream. To
about these materials. The data show that the average
particle size of the metals in the studied composite is
study the catalytic conversion, ethanol was fed into the
reactor by passing the carrier gas through a bubbler
thermostated at 11°C.
5
–8 nm (Fig. 5). The particle size of the catalysts with
a NASICON structure varies in a range of 50–200 nm
The MSR and ethanol conversion reactions (Fig. 4b).
were also run in a membrane reactor. Catalyst samples
The table lists the specific surface areas of the syn-
0.3-g load) mixed with quartz granules (1–3 mm thesized catalysts and the average particle size of the
(
fraction) were placed in the reaction zone of a mem- composites determined by the BET method and cal-
brane reactor, which is schematically shown in Fig. 2. culated according to the XRD pattern linewidths
The reactor consisted of two stainless steel cylindrical (CSRs). The surface area of the Ru–Rh/DND sample
compartments separated by a dense membrane of a is determined by the degree of dispersion of the DND
Pd–Ru alloy (6 wt % Ru). The studied membranes because the content of DND in the composite is con-
had thicknesses of 12 and 70 μm. The reactor was siderably higher than that of the metals and the XRD
sealed using two gaskets made of copper and Gra- pattern lines corresponding to the Ru–Rh alloy are
phlex. The flow rate of the purge gas—argon—on the significantly narrower, thereby indicating that the par-
3
ticle size of this material is larger.
The specific surface areas of the catalysts based
on lithium zirconium phosphates vary in a range of
permeate and retentate side was 20 cm /min. Reaction
products were analyzed by the method described
above.
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STUDY OF METHANOL STEAM REFORMING
1051
Reactant vapor–carrier
gas mixture
Retentate
Catalyst mixed
with quartz
Copper gasket
Pd–Ru membrane
Graphlex gasket
Carrier gas
Permeate
Fig. 2. Diagram of a membrane reactor.
(a)
(b)
2
1
0
20
40
60
80
100
10
20
30
40
50
60
2Θ
2Θ
Fig. 3. (a) XRD patterns of the Ru–Rh/DND catalyst and (b) XRD patterns of (1) the LiZr (PO ) and (2) Li1.1Zr1.9In0.1(PO )
4 3
2
4 3
catalysts.
2
1
1–16 m /g (see table). The average particle sizes cal- CSR (table). This fact, along with the SEM data, sug-
culated from the BET data are 2—and more—times gests that a significant portion of the particles are
higher than the values determined by calculating the aggregated.
Specific surface area and characteristic particle size of the test catalysts, as calculated by different methods
Specific surface area,
Average particle size determined
from surface area, nm
Catalyst
CSR size, nm
2
m /g
Ru–Rh/DND
LiZr (PO )
289 ± 3
16 ± 1
11 ± 1
13 ± 1
49.4 ± 2.5
81.0 ± 4.0
20
87
2
4 3
Li Zr In (PO )
4 3
170
1.1 1.9 0.1
PETROLEUM CHEMISTRY Vol. 56 No. 11 2016

1052
LYTKINA et al.
200 nm
200 nm
(a)
(b)
Fig. 4. SEM micrographs of (a) the Ru–Rh/DND and (b) Li0.9Zr1.8In0.1Nb0.1P2.9Mo0.1O12 samples.
Catalyst Activity in Dehydrogenation
and Dehydration Reactions
to the appearance of about 3 vol % of a CO impurity in
the resulting hydrogen (Fig. 6, curve 2).
Conventional flow reactor. A comparative study of
the catalytic activity of the synthesized samples in the
The LiZr (PO ) and Li Zr In (PO ) samples
2
4 3
1.1
1.9 0.1
4 3
were used as ethanol conversion catalysts; they exhib-
ited activity in both the dehydration and dehydrogena-
tion of ethanol. This feature provides the occurrence
of ethanol conversion via a few alternative pathways:
dehydration to DEE, dehydration to ethylene, dehy-
drogenation to acetaldehyde, methanation, and steam
reforming. Other possible reactions are the dehydro-
genation of the reaction products and the catalytic
crosslinking of the resulting unsaturated hydrocar-
bons.
dehydration and dehydrogenation of C –C alcohols
1
2
in a conventional flow reactor was conducted.
A distinctive feature of DNDs is a high concentra-
tion of oxygen-containing groups on their surface [20].
According to the derived values, the degree of con-
version of methanol over the Ru–Rh/DND catalyst
was 85% at 300°С. With a further increase in tempera-
ture, the degree of conversion did not increase; how-
ever, the process became less selective for hydrogen.
In the case of the studied catalysts, the main prod-
ucts of the processes are acetaldehyde, hydrogen,
Figure 6 shows the temperature dependences of the
amounts of hydrogen and carbon monoxide produced
over the Ru–Rh/DND catalyst. At 330–350°C, the
hydrogen flux corresponds to a yield of 2.3 mol of
hydrogen per mole of fed alcohol, while the theoreti-
DEE, C hydrocarbons (ethylene and ethane pro-
2
duced in the hydrogenation of ethylene by hydrogen
during reaction), and C hydrocarbons. The formation
4
cally possible value is 3 mol/mol. At high tempera- of CO, CO
tures, in addition to the target reaction, methanol
undergoes decomposition by reaction (6), which leads
, and CH is also observed; however, the
4
2
1
250
200
150
100
50
2
0
1
50
250
350
T, °C
5
nm
Fig. 6. Flux of (1) hydrogen and (2) CO in the presence of
the Ru–Rh/DND catalyst.
Fig. 5. TEM micrograph of the Ru–Rh/DND sample.
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STUDY OF METHANOL STEAM REFORMING
a)
1053
(
(b)
4
1
3
0
0
0
0
.5
.4
.3
.2
1.0
0.8
0.6
0.4
0.2
0
2
1
3
0
.1
2
4
0
2
00
300
400
T, °C
500
120
220
320
T, °C
420
Fig. 7. Yield of (1) C hydrocarbons, (2) C hydrocarbons, (3) acetaldehyde, and (4) DEE in the presence of (a) the LiZr (PO ) and
2
4
2
4 3
(
b) Li Zr In (PO ) catalysts.
1.1 1.9 0.1 4 3
amounts of these products are negligible compared selective recovery of the reaction product—hydro-
with the main products.
gen—from the retentate zone leads to a shift of the
equilibrium position of the hydrogen-producing reac-
tions toward the products and to an increase in the
degree of conversion of the alcohol.
For lithium zirconium phosphate, the average
degree of recovery of hydrogen was 35%; in the case of
the Ru–Rh/DND catalyst, this parameter did not
exceed 15% (Fig. 9a). This difference can be attributed
to the fact that the Ru–Rh catalyst provides high
hydrogen fluxes, which lead to a significant increase in
the total flow rate of the reaction products along the
membrane and a change in the macrokinetics. Note
that the permeated hydrogen did not contain CO or
other impurities.
The LiZr (PO ) sample exhibits activity in the for-
2
4 3
mation of C and C hydrocarbons and DEE. Only
2
4
small amounts of acetaldehyde and hydrogen are
formed; this finding suggests that ethanol dehydration
reactions (4) and (5) are dominant reactions (Fig. 7).
The doping of lithium zirconium phosphate with
indium leads to a decrease in the acidity of the active
sites of the catalyst, which in turn leads to the inhibi-
tion of the dehydration function and an increase in the
hydrogen yield (Fig. 8). With an increase in tempera-
ture, the amount of acetaldehyde decreases apparently
because it is converted to hydrogen, methane, and car-
bon oxides.
In the case of MSR over the Ru–Rh/DND com-
posite in the membrane reactor, the process selectivity
for hydrogen also increased. The amount of carbon
monoxide produced in the conventional reactor was
about 3% at a temperature of ~330°C. In the mem-
brane reactor, this parameter decreased to 1%.
Membrane reactor. Figure 9 shows the temperature
dependences of the hydrogen flow rate in the presence
of the Ru–Rh/DND and Li Zr In (PO ) cata-
lysts. At high temperatures, for both catalysts, the
hydrogen yield in the membrane reactor was 20%
higher than that in the conventional flow reactor. The
1.1
1.9 0.1
4 3
In addition, an increase in the degree of conversion
of ethanol and in the activity in the formation of acet-
aldehyde is observed in the presence of the
Li Zr In (PO ) catalyst (Fig. 10). These effects
1.0
1.1
1.9 0.1
4 3
0
0
0
0
.8
.6
.4
.2
0
are attributed to a shift of the thermodynamic equilib-
rium caused by the removal of hydrogen through the
membrane; the shift contributes to the intensification
of the hydrogen-producing reactions.
2
1
CONCLUSIONS
A comparative study of the MSR and ethanol con-
version processes by conventional and membrane
catalysis has been conducted.
100
200
300
T, °C
400
500
For the Ru–Rh/DND catalyst, hydrogen is the
main product. At 330–350°C, the hydrogen flux cor-
responds to a yield of 2.3 mol of hydrogen per mole of
Fig. 8. Hydrogen yield in the presence of (a) the
LiZr (PO ) and (b) Li Zr In (PO ) catalysts.
2
4 3
1.1 1.9 0.1
4 3
PETROLEUM CHEMISTRY Vol. 56 No. 11 2016

1054
LYTKINA et al.
(a)
(b)
4
4
300
250
200
1
.6
3
3
1
1.2
1
1
50
0
.8
.4
0
100
2
0
2
5
0
0
2
00
250
300
350
200
300
400
T, °C
500
T, °C
Fig. 9. Hydrogen flow rates in (1) the retentate and (2) permeate zones, and (3) conventional reactor and (4) the total flux of
hydrogen in the membrane reactor in the presence of (a) the Ru–Rh/DND and (b) Li Zr In (PO ) catalysts.
1.1 1.9 0.1
4 3
fed alcohol, while the theoretically possible value is hydrogen from the retentate zone leads to an increase
mol/mol. At high temperatures, a CO impurity in in the MSR selectivity for hydrogen and a decrease in
the amount of 3 vol % is observed in the resulting the formation of CO. In the presence of
hydrogen. Li Zr In (PO ) , the degree of conversion of etha-
3
1.1
1.9 0.1
4 3
nol and the acetaldehyde yield increase owing to a
shift of the thermodynamic equilibrium. Hydrogen in
the permeate zone does not contain CO or other
impurities.
The LiZr (PO ) sample exhibits activity in the for-
2
4 3
mation of C and C hydrocarbons and DEE. Only
2
4
small amounts of acetaldehyde and hydrogen are
formed; this finding suggests that ethanol undergoes
conversion mostly through dehydration reactions. The
doping of lithium zirconium phosphate with indium
leads to a decrease in the acidity of the active sites of
the catalyst, which in turn leads to the inhibition of the
dehydration function and an increase in the hydrogen
yield.
ACKNOWLEDGMENTS
This work was supported by the Ministry of Educa-
tion and Science of the Russian Federation, agree-
ment no. 14.607.21.0033.
At high temperatures, for both catalysts, the hydro-
gen yield in the membrane reactor is 20% higher than
that in the conventional flow reactor. In the case of the
Ru–Rh/DND composite, the selective recovery of
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Translated by M. Timoshinina
PETROLEUM CHEMISTRY Vol. 56 No. 11 2016