Synthesis of 1,3-Butadiene from 1-Butanol on a Porous Ceramic [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 Catalytic Converter

Article abstract of DOI:10.1134/S002315842003009X

Abstract: —A two-stage method was developed for the synthesis of 1,3-butadiene by dehydration of 1-butanol to a mixture of butenes on γ-Al₂O₃ granules prepared by self-propagating high-temperature synthesis (SHS) followed by dehydrogenation of the butene fraction to 1,3-butadiene using a porous ceramic catalytic SHS converter [Fe,Cr]/γ-Al₂O₃(K,Ce)/α-Al₂O₃. The dehydration of 1-butanol to the butene mixture proceeded almost completely at ~100percent selectivity on γ-Al₂O₃ granules obtained by SHS at 300°C, which is 50 degrees lower than on industrial gamma-alumina granules. The use of an original hybrid catalytic membrane reactor (HCMR) with selective removal of hydrogen from the reaction zone led to a ~1.3-fold increase in the yield of 1,3-butadiene at ultrapure hydrogen extraction of up to 16 mol percent of the total amount of the hydrogen product. The catalytic activity of the system did not decrease after 20 h of experiment, in contrast to its activity in the industrial process, where catalyst regeneration is performed every 8–15 min.

Full text of DOI:10.1134/S002315842003009X

ISSN 0023-1584, Kinetics and Catalysis, 2020, Vol. 61, No. 3, pp. 390–404. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Kinetika i Kataliz, 2020, Vol. 61, No. 3, pp. 366–381.
Synthesis of 1,3-Butadiene from 1-Butanol on a Porous Ceramic
[Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 Catalytic Converter
A. S. Fedotova, *, V. I. Uvarovb, M. V. Tsodikova, I. I. Moiseeva, S. Paulc, S. Heytec, P. Simonc,
M. Marinovad, and F. Dumeignilc
aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
bMerzhanov Institute of Structural Macrokinetics and Materials Sciences, Russian Academy of Sciences,
Chernogolovka, Moscow oblast, 142432 Russia
cUniversité de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, UMR 8181-UCCS-Unité de Catalyse et Chimie du Solide,
Lille, F-59000 France
dInstitut Chevreul, FR2638 CNRS, Bât. C6 Université Lille 1, Villeneuve d’Ascq, F-59655 France
*e-mail: alexey.fedotov@ips.ac.ru
Received April 25, 2019; revised September 27, 2019; accepted January 22, 2020
Abstract—A two-stage method was developed for the synthesis of 1,3-butadiene by dehydration of 1-butanol
to a mixture of butenes on γ-Al2O3 granules prepared by self-propagating high-temperature synthesis (SHS)
followed by dehydrogenation of the butene fraction to 1,3-butadiene using a porous ceramic catalytic SHS
converter [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3. The dehydration of 1-butanol to the butene mixture proceeded
almost completely at ~100% selectivity on γ-Al2O3 granules obtained by SHS at 300°C, which is 50 degrees
lower than on industrial gamma-alumina granules. The use of an original hybrid catalytic membrane reactor
(HCMR) with selective removal of hydrogen from the reaction zone led to a ~1.3-fold increase in the yield of
1,3-butadiene at ultrapure hydrogen extraction of up to 16 mol % of the total amount of the hydrogen prod-
uct. The catalytic activity of the system did not decrease after 20 h of experiment, in contrast to its activity in
the industrial process, where catalyst regeneration is performed every 8–15 min.
Keywords: heterogeneous catalysis, porous ceramic catalytic converter, self-propagating high-temperature
synthesis, catalytic membrane reactor, dehydration of biobutanol, dehydrogenation of butenes, monomer
synthesis, 1,3-butadiene synthesis, release of ultrapure hydrogen
DOI: 10.1134/S002315842003009X
INTRODUCTION
reactions, leading to quick coking of catalysts [4].
Therefore, the world’s leading scientific schools are
searching for alternative approaches to the develop-
ment of environmentally friendly and effective pro-
cesses for the production of 1,3-butadiene [5].
Since the early 20th century when S.V. Lebedev’s
work was published, alcohols have been the raw mate-
rials for the industrial production of 1,3-butadiene,
which is one of the main monomers for the synthesis
of artificial rubbers [1]. Today the general trend is
additionally a transition to renewable resources.
The synthesis of 1,3-butadiene was the subject of
many studies [2, 3]. Despite the rich history of the
development of methods for its synthesis, the selectiv-
ity of transformations still remains a challenge. As the
reaction is endothermal, it is necessary to maintain
high temperature in the reactor, which promotes side
1,3-Butadiene is the most important monomer
with global production of over 12 million t/year [6],
which is mainly used for the synthesis of butadiene-
styrene (28%) and polybutadiene (26%) rubbers
widely used in tire industry. Currently, 1,3-butadiene
is obtained by three main methods [7]: steam cracking
of paraffin hydrocarbons, where butadiene is a by-
product of ethylene production (more than 95% of
world production); catalytic dehydrogenation of
butane-butene fractions (less than 2%); and oxidative
and vapor-oxidative dehydrogenation of butenes (the
rest). Importantly, the monomer production includes
numerous stages, such as oil refining, organic synthe-
sis, separation of hydrocarbon mixtures, etc. Thus, all
the proposed methods for butadiene synthesis are cap-
ital intensive, and the use of fossil fuels as raw materi-
Abbreviations: GLC, gas-liquid chromatography; GC-MS, gas
chromatography-mass spectrometry; FID, flame ionization
detector; HCMR, hybrid catalytic membrane reactor; SHS,
self-propagating high-temperature synthesis; SEM-EDX, scan-
ning electron microscopy with energy dispersive X-ray spectros-
copy; TGA, thermogravimetric analysis; TPReduction-H ,
2
thermally programmed reduction with hydrogen; TEM, trans-
mission electron microscopy; XPS, X-ray photoelectron spec-
troscopy.
390

SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
391
als increases the environmental load on the produc-
1. EXPERIMENTAL
tion sites [8].
1.1. Synthesis of Porous Catalytic Materials
for the Production of 1,3-Butadiene from 1-Butanol
From the viewpoint of rational nature manage-
ment, the monomer synthesis should utilize the by-
products of alcohol fermentation, for example, 1-buta-
nol [9], by its dehydration to the butene fraction fol-
lowed by dehydrogenation to 1,3-butadiene.
1.1.1. SHS of γ-Al2O3 granules. To perform SHS of
the butene fraction from 1-butanol, γ-Al2O3 granules
were obtained. The fraction was synthesized from a gel
of a pseudoboehmite AlOOH structure using single-
action compacting at a pressure of 30–90 MPa fol-
lowed by sintering at 750°C in air for 1 h. The diameter
of the open pores of the synthesized sample deter-
mined with a mercury porometer and by the bubble
method was ~1–3 μm. The porosity of the samples
measured by hydrostatic weighing was ~40%.
1.1.2. Preparation of a tubular porous ceramic sup-
port based on α-Al2O3 by SHS. The raw material for
the preparation of a tubular porous ceramic support
was α-Al2O3 powder of a large fraction of “Electroco-
rundum white” with a particle size of 100 μm (Lit-
prom).
To increase the mechanical strength of the support
and its resistance to high temperature, powder addi-
tives of eutectic composition were introduced in the
initial α-Al2O3 powder: magnesium oxide (GOST
(State Standard) 4526-75, Krasnyi Khimik (Red
Chemist) plant) and silicon carbide in a ratio of 90 wt
% α-Al2O3, 3 wt % MgO, and 7 wt % SiC. During the
SHS, these compounds form active SiO2, which binds
α-Al2O3 particles with one another due to their trans-
formation into mullites, indialite (Mg2Al4Si5O18), and
spinel (MgAl2O4).
Butanol is now considered as a high-octane addi-
tive to gasoline fuel, whose technical characteristics
are significantly higher than those of ethanol. For this
reason, several large companies decided to develop
processes aimed at increasing butanol production
[10–12]. In addition, 1-butanol can serve as a raw
material for biofuel production [13, 14].
Butanol, like ethanol, can be synthesized by pro-
cessing sugar or starch of agricultural crops (first-gen-
eration biobutanol) and cellulose (second-generation
biobutanol). As the biobutanol market has already
reached 5 billion L/year [15], it is potentially of inter-
est for obtaining additional quantities of butadiene at
decentralized low-tonnage enterprises, which may be
important for regions remote from the sites of large
petrochemical plants. For example, in 2016, the pro-
duction of high-purity bio-1-butanol was commer-
cialized by Green Biologics (Great Britain) at its new
industrial facilities in Little Falls (Minnesota, United
States) [16].
It is also important that recently, the scientific basis
for breakthrough technologies for direct production of
1-butanol from ethanol has been developed, by per-
forming the reaction of EtOH in a supercritical state
with a record yield of 1-butanol of ~60% at 85–90%
selectivity, while the yield of 1-butanol in fermenta-
tion processes does not exceed 10% [12, 17, 18].
Therefore, the use of 1-butanol for the production of
synthetic rubbers may become another important
stage in the development of environmentally friendly
chemical industries based on renewable raw materials.
The powders were mixed in a ball mill for 1 h. The
finished mixture was subjected to single-action com-
pacting at a pressure of 30–90 MPa, sintered at 1300–
1450°C in air for 1 h, and cooled to room temperature
for 2 h.
At powder sintering temperatures in the range
1300–1450°C, a liquid phase of eutectic composition
forms, which contains magnesium oxide and silicon
carbide in the form of clinoenstatite, which wets Al2O3
particles, forming a strong porous support frame. For
easy recording of the catalyst composition, the tubular
ceramic support is denoted below as α-Al2O3 without
mentioning the additives.
The porous ceramic support is a tube with a dead
end to provide forced diffusion of gases through the
cylinder’s working surface from outer to inner wall,
and the other end of the tube has a hold-down nut for
hermetically joining the tubular support with the reac-
tor through a graphite gasket (Fig. 1). The tube chan-
nel is intended for introducing a hydrogen-selective
palladium-containing membrane and removing the
unchanged substrates and unfiltered reaction products
from the reactor [19].
One promising way to solve this problem is the use
of hybrid membrane catalytic technology. In this tech-
nology, the total energy of the process is reduced due
to a combination of stages in one device: the reaction
stage proceeding in the channels of a porous catalytic
converter obtained by self-propagating high-tempera-
ture synthesis (SHS) and the hydrogen separation
stage on a palladium-containing membrane integrated
into the cavity of the converter. Due to this, the
dimensions of the unit are significantly reduced, the
hardware design is significantly simplified, and high-
purity products can be obtained with higher yields at
the outlet of the reactor than in a conventional reactor
with a stationary bed of bulk catalyst. The efficiency of
this approach was confirmed by previous studies on
the production of ultrapure hydrogen in carbon-diox-
ide, steam, and mixed reforming of methane, ethanol,
fermentation products, and dimethyl ether [19–21].
The geometrical dimensions of the tubular support
were: total length 137 mm, working area length
KINETICS AND CATALYSIS Vol. 61 No. 3 2020

392
FEDOTOV et al.
120 mm, outer diameter of the tube 25 mm, and wall
thickness 7 mm.
The open pore size of the tubular porous ceramic
support was evaluated according to the capillary dis-
placement model based on the Laplace formula for the
cylindrical pore model using a mercury porometer and
by the bubble method [22]. The open pore diameter of
the support was 1–3 μm. The porosity measured by
hydrostatic weighing was more than 50%.
Fig. 1. Tubular porous ceramic support consisting of α-Al O .
2
3
The final two-stage calcination of all the samples
was performed in a muffle furnace at a temperature
rise rate of 10 deg/min, allowing them to stand at
500°C for 3 h and at 800°C for 2 h.
The composition of the prepared catalysts is given
in Table 1.
The tubular porous ceramic supports with a pre-
liminary deposited intermediate layer of γ-Al2O3,
formed in order to increase the pore surface, were
modified in a similar way, by molecular layering of a
colloidal solution of the precursor of the active com-
ponent on the pore surface. For this, a colloidal solu-
tion of a sol consisting of H2O (0.03 mol %), 1.5 M
1.2. Modification of the Tubular Porous Ceramic
Support with Iron-, Chromium-, and Manganese-
Containing Mono- and Bimetal Catalysts
To impart the catalytic properties necessary for
dehydrogenation of butenes to the tubular porous
ceramic support, it was modified with various active
components.
To determine the optimum composition of the cat-
alyst for butene dehydrogenation, model granular cata-
lysts were used in a flow reactor at the first stage of the
study: Mn/γ-Al2O3(K,Ce); Fe,Mn/γ-Al2O3(K,Ce)
(separate deposition of Fe and Mn); [Fe + Mn]/γ-
Al2O3(K,Ce) (combined deposition of Fe and Mn);
and [Fe + Mn]/γ-Al2O3(K,Ce) (separate deposition of
Fe and Cr).
Al(OPri)3, and acetylacetone (1.5 mol) in toluene was
applied by injecting it through the pores of the sample
at the first stage. After the sol was applied, the modi-
fied porous ceramic support was dried in a flow of air
in a drier at 120°С for 1 h, and then heat treatment was
performed in a thermal shock mode at 500°С for 30 min.
The amount of deposited γ-Al2O3 was evaluated from
the increase in the mass of the sample. The impregna-
tion step was repeated four times until the mass gain
reached 4–5 wt %. Then, K2O and CeO2 were applied
by separately impregnating the converter with aqueous
potassium carbonate and cerium nitrate.
The active Fe- and Cr-containing components
were separately deposited on the modified support
from the toluene solutions of the corresponding acetyl
acetonate complexes containing 7.2 wt % Fe(acac)3
and 7.4 wt % Cr(acac)3. To form Fe(III) and Cr(III)
oxides, the impregnated sample was calcinated in a
muffle furnace in an air flow at 500°C for 2 h, 600°C
for 2 h, and 800°C for 1 h. The amount of the depos-
ited components was determined by weight gain of the
sample after all stages of heat treatment.
The support was γ-Al2O3 (sphere 0.8 mm, Ssp =
205 m2/g) (SKTB Katalizator, Novosibirsk). In all the
cases, the initial γ-Al2O3 was first dried in a vacuum
drier at 100°C for 3 h, and then modifying additives
were introduced by separate impregnation of alumina
with aqueous solutions of potassium carbonate
(K2CO3) and cerium nitrate [Ce(NO3)3 · 6H2O].
These components were applied to a porous ceramic
support to suppress side reactions [23]. After the
impregnation, the thus modified support was dried in
a flow of warm air at 40°C, then in a drier at 120°C for
3 h and calcinated in a muffle furnace at 500°C for 4 h.
Then the precursors of active components were applied
to it in layers from aqueous and organic solutions.
Mn/γ-Al2O3(K,Ce). Manganese was deposited by
impregnating modified alumina with an aqueous solu-
tion of manganese acetate Mn(OAc)2 · 4H2O.
Fe,Mn/γ-Al2O3(K,Ce). At first, iron was applied
from aqueous iron nitrate Fe(NO3)3 · 9H2O; then, after
drying and thermal shock at 500°C for 30 min, manga-
nese was applied from aqueous manganese acetate.
The contents of the components of the [Fe,Cr]/γ-
Al2O3(K,Ce)/α-Al2O3 catalytic converters of dehy-
drogenation of the butene fraction are listed below:
[Fe+Mn]/γ-Al2O3(K,Ce). Iron and manganese
were simultaneously deposited from an aqueous solu-
tion containing iron nitrate and manganese acetate,
then dried and calcinated.
K2O CeO2 Fe2O3 : Cr2O3 = 1 : 1 γ-Al2O3 α-Al2O3
0.12 0.04
0.50
4.53
94.81
[Fe,Cr]/γ-Al2O3(K,Ce). Iron and chromium were
The sample of the porous ceramic support pre-
deposited by separate impregnation with a toluene or pared from α-Al2O3 and modified with the catalyti-
mixed toluene–benzene solution containing iron and
chromium acetyl acetonates Fe(acac)3 and Cr(acac)3.
cally active components is called below a “converter.”
The catalytic experiments used both the whole con-
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SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
393
Table 1. Composition of the model catalysts of dehydrogenation
Catalyst
Composition (oxides)
γ-Al2O3
Content, g
Content, wt %
Mn/γ-Al2O3(K,Ce)
18.80
0.32
0.21
2.11
87.69
1.48
K2O
CeO2
0.97
9.86
88.36
1.33
Mn2O3
γ-Al2O3
K2O
18.84
0.28
0.21
1.00
0.99
18.16
0.40
0.18
Fe,Mn/γ-Al2O3(K,Ce), sepa-
rate deposition of Fe and Mn
CeO2
0.96
4.70
4.65
85.52
1.90
0.85
11.73
90.30
1.50
Fe2O3
Mn2O3
γ-Al2O3
K2O
[Fe+Mn]/γ-Al2O3(K,Ce),
co-deposition of Fe and Mn
CeO2
(Fe,Mn)2O3
γ-Al2O3
K2O
2.49
17.80
0.30
0.16
1.46
[Fe,Cr]/γ-Al2O3(K,Ce), sep-
arate deposition of Fe and Cr
CeO2
0.80
7.40
(Fe,Cr)2O3
verter and the granules obtained by mechanical crush- was then preliminarily heated in an evaporator (15) to
ing (granular converter).
200°C. The space velocity of the vapor–gas mixture
Ar/1-BuOH = 2 fed into reactor 1 (23) was 228 h–1 at
a total pressure of 1 atm. The temperature in reactor 1
(23) was adjusted in the range T = 300–350°C.
1.3. Membrane-Catalytic Unit
The two-stage conversion of 1-butanol into 1,3-
butadiene was studied using the developed mem-
brane-catalytic unit (Fig. 2). The unit includes reactor
1 (23) for dehydration of 1-butanol into butenes and
reactor 2 (24) for their subsequent dehydrogenation to
1,3-butadiene installed in sequence.
The dehydration of 1-butanol ((pure grade), GOST
(State Standard) 6006-78 with amendments 1, 2) with
the formation of a butene fraction was performed by
feeding 1-butanol from a liquid dosing unit (6)
through a steel pipe to flow reactor 1 (23) filled with
commercially available γ-Al2O3 granules in one case
and with γ-Al2O3 granules prepared by SHS in the
other. Both processes were carried out under the same
conditions; the mass of bulk γ-Al2O3 was 20 g.
The butene fraction diluted with argon and
obtained in reactor 1 (23) was separated from the liq-
uid phase containing a small amount of unchanged
1-butanol and water formed during the dehydration in
a water-cooled separator (34). The dried argon–
butene mixture, preliminarily mixed with water to
reduce the partial pressure of butenes, went to the
dehydrogenation stage along a network of pipelines
through T-joints (37 and 10) into reactor 2 (24). Water
was supplied from a liquid doser (7) through a mixing
T-joint (11), and the mixture was heated in an evaporator
(16). Butenes were dehydrogenated to 1,3-butadiene on
the granules of model catalysts and on the synthesized
tube or granular converter in a hybrid membrane-cata-
lytic reactor (HMCR) (Fig. 3) the same to the one
described in [19]. The reactor was made of steel
20Х23Х18. The conditions of dehydrogenation corre-
sponded to the industrial conditions (except the mass
of the catalyst charge): mgr.cat. = 14.75 g; excess H2O:
×0, ×10, ×20, ×30; space velocity of the vapor-gas mix-
ture Qv-g = 597 h–1; T = 637°C; and Ptot = 1 atm.
The argon carrier gas was supplied at a flow rate of
3 NL/h from a gas distribution comb (1) through an
RRG electronic controller (Eltochpribor BUIP-1,
Russia) (4). The air required for the oxidative regener-
ation of catalysts is indicated on comb (1). Argon and
1-butanol were mixed in a mixer (13), and the mixture
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394
FEDOTOV et al.
4
8
2
3
5
9
10
Ar
11
14
GFR
Air
1
13
12
15
19
17
21
16
20
18
22
7
Liquid dosers
6
R
Е
А
C
Т
О
R
1
R
Е
А
C
Т
О
R
2
25
26
Gas discharge
23
24
41
40
34
43
39
38
37
Gas
chromatograph
32
31
33
27
28
29
35
36
42
30
Ar
44
Fig. 2. Diagram of a membrane-catalytic unit for the synthesis of 1,3-butadiene from 1-butanol. (1) Comb with inlet gases;
(2), (31) reducers; (3), (9), (12), (37), (38), (40), (42), (44) three-way valves; (4) gas flow regulator; (5), (10), (11), (14), (19),
(20), (41) T-joints; (13) mixer; (6)–(7) liquid dosers; (8), (28), (35) gate valves; (15), (16) preliminary heating furnaces; (17), (18),
(25), (26) thermocouples; (21), (22) manometers; (23) reactor with a Pd-containing membrane; (24) catalytic converter; (27),
(34) separators; (29), (36) containers with condensate; (30) cylinder with Ar; (32) fine adjustment valve; (33) flow meter; (39) gas
meter; and (43) gas chromatograph.
The gas mixture obtained at the outlet of reactor calibrated RI-550A IR spectrometer (Riken Keiki,
2 (24) and containing the desired 1,3-butadiene prod- Japan).
uct was separated from the liquid phase in a water-
The С1–С4 hydrocarbon gases were identified on a
cooled separator (27) and forwarded to the instrument
for online gas chromatographic analysis (43).
To evaluate the contribution of the material of an
empty reactor to dehydrogenation, a comparative idle
experiment was performed in it under the same condi-
tions as on the catalytic converters.
Crystallux-4000M chromatograph using a flame ion-
ization detector (FID) and helium as a carrier gas. The
following gas flow rates were determined: helium
30 mL/min; hydrogen 35 mL/min; and air
300 mL/min. An HP-PLOT/Al2O3 chromatographic
column was used (Agilent Technologies, United
States; 50 m × 0.32 mm, film thickness 8.0 μm). The
temperature was 120°C (column), 230°C (detector),
and 250°C (evaporator). The product concentration
was determined from the calibration curves using spe-
cialized NetChrom v2.1 software.
1.4. Method for Analysis of Reaction Products
The contents of hydrogen, carbon oxides, and
methane in the reaction products were determined
online by gas chromatography on a Crystallux-4000M
chromatograph (Meta-chrom, Russia) using a ther-
mal conductivity detector; the carrier gas was high-
purity argon with a flow rate of 10 mL/min; the
adsorption packed column was 1 m × 3 mm. The col-
umn packing was activated carbon SKT; the particle
size was 0.2–0.3 mm. The temperature of the column,
detector, and evaporator was 120°C. The gas concen-
The liquid organic products of the reaction in the
organic phase were identified by GLC on a Varian
3600 chromatograph (Varian Chromatography Sys-
tem, United States), FID, Chromatec SE-30 capillary
column, 25 m × 0.25 mm, Df = 0.33 μm. The tem-
perature conditions: 50°С (5 min), 10°C/min, 280°С,
Tinj = 250°С, Pinj = 1 bar, 1/200 flow division, helium
trations were found from the calibration curves using carrier gas. The internal standards: trifluoromethyl-
specialized NetChrom v2.1 software. The low concen- benzene for the alkane-olefin fraction and n-octane
trations of carbon monoxide were determined using a for the alcohol mixture. The residual content of
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SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
395
Ar + extracted
hydrogen
Thermocouple
Raw material
Converter
Main
products
Pd–Ru membrane
Ar into Pd–Ru-
membrane
Fig. 3. Hybrid catalytic membrane reactor for dehydrogenation of the butylene fraction with an installed tubular [Fe,Cr]/γ-
Al O (K,Ce)/α-Al O catalytic converter.
2
3
2 3
organic products in the aqueous phase was found from
the ratio of integrated signals by absolute calibration
using GC-MS.
1.6. Calculation Procedure
The process parameters were calculated by
Eqs. (1)–(6).
Conversion of butanol:
1.5. Structural Analysis Method
n
(1)
XBuOH
=
вutenes ×100%.
nBuOH
The carbon content in the spent catalyst was deter-
mined by thermogravimetric analysis (TGA) on an
SDT Q600 instrument (TA Instruments, United
States) (TG analyzer and differential scanning calo-
rimeter) in an air flow. The conditions of TGA: sam-
ple 26.2 g, heating rate 10°C/min, air flow rate
100 mL/min, temperature range 25–700°C.
Conversion of butenes:
n
(2)
(3)
Xbutenes
=
transf.butenes ×100%.
n
fed butenes
Yield of 1,3-butadiene:
n
n
The thermally programmed reduction with hydro-
gen (TPR-H2) of the initial [Fe,Cr]/γ-Al2O3(K,Ce)/
α-Al2O3 converter was performed on an AutoChem II
2920 Chemisorption Analyzer (Micromeritics, United
States). Experimental conditions: sample 0.2 mg,
composition of the gas mixture 5% H2 + Ar, gas flow
rate 50 mL/min, heating rate 10°C/min, temperature
range 25–1000°C.
x1,3-butadiene
=
1,3-butadiene ×100%.
fed butenes
Butanol selectivity of 1,3-butadiene:
n
1,3-butadiene
(4)
),
SBuOH
=
×100%.
nBuOH
−1
Productivity for 1,3-butadiene (L h–1
where the active components are Fe and Cr:
g
аct.comp.
The photomicrographs of the converters and the
distribution of elements on the surface were obtained
by scanning electron microscopy with energy disper-
sive X-ray spectroscopic analysis (SEM-EDX) on an
S-3600N instrument (Hitachi, Japan) with the follow-
ing operating parameters: accelerating voltage 20.0 kV,
200-fold resolution.
V1,3-butadiene
mact.comp.
(5)
ρ1,3-butadiene
=
.
Degree of hydrogen extraction on the palladium-
containing membrane:
n
(6)
Nhydrogen
=
extr. hydr. ×100%.
The structure of the material of the catalytic con-
verter and the distribution of elements on its surface
were studied by transmission electron microscopy on
a TEM TITAN Themis 300 instrument (FEI, United
States).
ntotal hydr.
In Eqs. (1)–(6):
nbutenes is the molar flow of butene products formed
during the dehydration of 1-butanol, mmol/h;
The surface analysis was performed by X-ray pho-
toelectron spectroscopy (XPS) on an Axis Ultra DLD
instrument (Kratos Analytical, Great Britain) with
monochromatic AlKα X-radiation (15 kV, 15 mA,
1486.6 eV). All the spectra were calibrated in energy
using the position of the C1s peak corresponding to
the C–C and C–H bonds at 284.8 eV.
nBuOH is the molar flow of 1-butanol fed for dehy-
dration, mmol/h;
ntransf. butenes is the molar flow of butenes trans-
formed during the dehydrogenation, mmol/h;
nfed butenes is the molar flow of butenes fed for dehy-
drogenation, mmol/h;
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396
FEDOTOV et al.
n1,3-butadiene is the molar flow of 1,3-butadiene
At 300°C, the conversion of 1-butanol was ~66%
on industrial γ-Al2O3 granules and close to 100% on
the γ-Al2O3 sample prepared by SHS (Table 2). It was
found that almost complete conversion of 1-butanol
on industrial γ-Al2O3 granules could be achieved only
at 350°C.
formed during the dehydrogenation of butenes,
mmol/h;
nextr. hydr. is the molar flow of hydrogen extracted on
the palladium-containing membrane, mmol/h;
ntotal hydr. is the total molar flow of hydrogen includ-
ing the extracted and nonextracted hydrogen,
mmol/h;
V1,3-butadiene is the molar flow of 1,3-buadiene that
formed during the dehydrogenation of butenes, L/h;
mact. comp. is the mass of the catalytically active com-
ponent deposited on the porous surface of the con-
verter, g.
It can be assumed that the increase in the conver-
sion of 1-butanol at 300°C on γ-Al2O3 granules syn-
thesized by SHS is due to the improved mass and heat
transfer of the substrate in the synthesized porous
material compared to those of industrial granules.
After the separation of the formed water and trace
amounts of unchanged 1-butanol in the separator, the
reaction products were forwarded, without prelimi-
nary gas purification and fractionation, to the second
reactor for dehydrogenation of the butene fraction into
1,3-butadiene.
Stage 2: Dehydrogenation of the butene fraction;
synthesis of 1,3-butadiene. The catalytic dehydrogena-
tion of the butene fraction to 1,3-butadiene is an endo-
thermal process, which proceeds in accordance with
the following equations [25]:
2. RESULTS AND DISCUSSION
2.1. Synthesis of 1,3-Butadiene
Stage 1: Dehydration of 1-butanol; synthesis of the
butene fraction. The catalytic dehydration of 1-buta-
nol leads to the formation of four butene isomers:
BuOH ꢀ(butene-1 + cis-butene-2
(I)
+ trans-butene-2 + iso-butene) + Н2О,
ΔН = 34 kJ/mol.
butene-1 ꢀ1,3-butadiene + Н2,
(II)
ΔН = 110 kJ/mol,
Our experiments on industrial γ-Al2O3 granules
and the sample obtained by SHS gave a butene frac-
tion that formed during the dehydration of 1-butanol
and contained predominantly butene-1 (Table 2). The
concentration of butene-1 depends on the process
conditions and the type of the catalyst used. In the
presence of commercially available γ-Al2O3 granules,
the concentration was 97% at 300°C. On the sample
prepared by SHS, the selectivity for butene-1 was
slightly lower, 83% at the same temperature, which is
probably due to the lower acidity of the active sites of
the synthesized material [24]. In addition to butene-1,
the butene fraction contained the cis-, trans-, and
branched isomers; when the temperature increased to
350°C, the proportion of the latter increased to 24%
for commercially available granules and to 63% for the
synthesized sample. This change in the isomer ratio
does not affect further dehydrogenation because all
the three isomers are converted into 1,3-butadiene
[25]. The by-products contained traces of hydrocar-
bons from hydrogenation, cracking, and isomerization
such as ethylene, propylene, butane, and isobutane, as
well as hydrogen. The total concentration of by-prod-
ucts did not exceed 0.12% (Table 2). Importantly, dib-
utyl ether was not detected in the products. This evi-
dently indicates that dehydration of 1-butanol mainly
cis-butene-2/trans-butene-2/iso-butene
(III)
ꢀ 1,3-butadiene + Н2, ΔН = 120 kJ mol.
The results of the idle experiment in a catalyst-free
stainless steel flow reactor showed that the side pro-
cesses of the destruction of the carbon skeleton of the
initial butene fraction were dominant and formed a
large amount of coke.
In order to find the optimum conditions, the pro-
cess was performed both in a flow mode (contactor)
using a conventional reactor with a bulk layer of gran-
ular catalyst and in a membrane mode (extractor)
using an original membrane-catalytic hybrid reactor
with an integrated hydrogen-selective palladium-con-
taining membrane [19].
To determine the optimum process conditions and
the composition of the butene dehydrogenation catalyst
at the first stage of the study in a flow reactor, the process
was studied in the presence of granular model catalysts:
α-Al2O3; Mn/γ-Al2O3(K,Ce); [Fe,Mn]/γ-Al2O3(K,Ce)
(separate deposition); [Fe + Mn]/γ-Al2O3(K,Ce) (co-
deposition); [Fe,Cr]/γ-Al2O3(K,Ce) (separate depo-
sition).
At first, comparative experiments were performed
on a tubular support based on α-Al2O3 and synthe-
occurred at various active centers remote from one sized by SHS and on manganese-containing model
another, which excludes the interaction of adsorbed catalysts. As a result, it was found that 20-fold dilution
butanol molecules with one another. Another reason of the reagents with water was optimum and led to an
for the almost complete absence of esterification approximately ninefold increase in the yield of 1,3-
products is the low partial pressure of the substrate butadiene compared with its yield in experiments at
[24, 26, 27]. The activity of the studied catalysts did lower dilution (experiments 5–20, Table 3). Twenty-
not decrease throughout the experiment (30 h).
fold dilution also decreased the concentration of
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397
Table 2. Composition of the products of dehydration of 1-butanol at 300 and 350°С on industrial γ-Al2O3 granules and on
granulated γ-Al2O3 synthesized by SHS
Industrial γ-Al2O3 granules
Granulated γ-Al2O3 synthesized by SHS
Component of product
mixture
300°С, XBuOH = 66% 350°С, XBuOH = 100% 300°С, XBuOH = 100% 350°С, XBuOH = 100%
С, vol %
С, vol %
С, vol %
С, vol %
Ethylene
Propylene
Butene-1
iso-Butene
trans-Butene-2
cis-Butene-2
1,3-Butadiene
Hydrogen
0
0
0
0
0
0
0.03
0.03
36.35
0.21
29.67
33.59
0
96.75
0.11
0.83
2.31
0
76.20
0.12
6.60
17.08
0
83.26
0.11
3.95
12.57
0
0
0
0
0
0.03
0.08
0.06
0.06
n-, iso-Butane
cracking and pyrolysis products approximately three- tion zone on a palladium-containing membrane gen-
fold. Thirty-fold dilution of reagents with water did erally promotes the process (Table 4).
not lead to a significant increase in the yield of 1,3-
In addition to the main dehydrogenation reaction,
butadiene, which is probably due to the competing
side cracking reactions occur at temperatures above
adsorption of water molecules at the active sites of the
600°C, forming mainly propylene, ethylene, and
catalyst (experiments 3, 4; 7, 8; 11, 12; 15, 16; 19, 20;
methane (Table 4).
Table 3).
Thus, the use of the developed two-stage scheme
An experiment was performed, using the obtained
optimum conditions for dilution of the butene fraction
with water vapor, on the preparation of 1,3-butadiene
on the synthesized [Fe,Cr]/γ-Al2O3(K,Ce) model cat-
alyst containing active components similar to those of
the industrial catalyst for dehydrogenation of the
butane–butene fraction (experiment 26, Table 4).
for conversion of 1-butanol into 1,3-butadiene allows
us to obtain a valuable monomer with high efficiency
from biomass fermentation products with simultane-
ous release of ultrapure hydrogen, which is a useful
raw material for organic synthesis and environmen-
tally safe fuel for hydrogen internal combustion
engines and fuel cells.
Importantly, the process occurring in the catalytic
channels of the converter significantly decreases the
intensity of coke formation. When the reaction is per-
formed on the granular converter, the catalytic activity
of the system decreases already after 20–30 min work.
In view of its higher stability compared to manga-
nese-containing catalysts in the process under study,
the iron-chromium-containing system was chosen for
the synthesis of the [Fe,Cr]/(K,Ce)γ-Al2O3/α-Al2O3
converter. According to experiment 26 (Table 4), the
yield of 1,3-butadiene on the synthesized integral con-
verter was 18.8% at ~19.2% selectivity based on the
initial 1-butanol.
The
palladium-containing
hydrogen-selective
HMCR membrane used in the dehydrogenation of the
butene fraction with integral converter remains clean
(Fig. 4a), but is carbonized after the experiment on the
granular converter of the same composition, which
lasts for the same period of time (Fig. 4b).
The significantly higher resistance of the integral
converter to surface carbonization was confirmed by
the thermogravimetric and structural analysis data.
The use of integral [Fe,Cr]/γ-Al2O3(K,Ce)/
α-Al2O3 converter in the mode of hydrogen extraction
from the reaction zone on a palladium-containing
membrane allows us to increase the 1,3-butadiene yield
and productivity ~1.3-fold (experiment 27, Table 3).
An increase in the yield of 1,3-butadiene in the case
of using the integral converter may indicate an
increase in the probability of the contact of substrate
molecules with the active surface during the reaction
in the forced diffusion mode in a limited space of the
catalytic channels of the converter.
3. STUDIES OF THE SURFACE
OF THE CATALYTIC CONVERTER
A TG analysis revealed insignificant carbonization
of the spent integral [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3
converter in the air flow (Fig. 5).
It was shown that dehydrogenation of butenes on
the [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 converter in the
The thermogravimetric data indicate that the
mode of ultrapure hydrogen extraction from the reac- degree of sample carbonization after 20 h was only
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398
FEDOTOV et al.
Table 3. Dehydrogenation of the butane fraction*
Selectivity
of formation of 1,3-
butadiene**, %
1,3-Butadiene output,
Experi-
ment no.
х-Fold dilution
with water of 1,3-butadiene, %
Yield
Catalyst composition
−1
L h–1
gact.comp.
1
2
3
4
Reactor without catalyst: idle
experiment
0
2.7
7.3
6.4
5.0
3.6
6.8
6.2
4.8
–
–
–
–
10
20
30
5
6
7
8
Tubular α-Al2O3 support
0
3.8
8.5
7.3
6.1
5.0
9.1
7.7
6.1
–
–
–
–
10
20
30
Modified industrial α-Al2O3 granules in a mode without hydrogen extraction (contactor)
9
10
11
12
[Fe+Mn]/γ-Al2O3(K,Ce)
0
1.4
9.5
8.8
8.7
2.0
10.4
9.6
0.2
1.1
1.1
1.0
10
20
30
9.2
13 [Fe,Mn]/γ-Al2O3(K,Ce)
0
2.4
10.0
11.8
12.4
3.5
11.5
13.7
13.9
0.3
1.2
1.5
1.5
14
15
16
10
20
30
17 Mn/γ-Al2O3(K,Ce)
0
1.3
8.5
1.8
8.8
0.1
0.9
1.0
1.1
18
19
20
10
20
30
9.2
10.1
11.6
10.4
21 [Fe,Cr]/γ-Al2O3(K,Ce)
20
1.1
1.6
2.0
9.0
8.3
Granulated modified converter in a mode without hydrogen extraction (contactor)
22 [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 20
Granulated modified converter in a mode with hydrogen extraction (extractor)
23 [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 20
Integral modified converter in a mode without hydrogen extraction (contactor)
4.2
9.2
7.8
11.7
24 [Fe,Cr]/(K,Ce)γ-Al2O3/α-Al2O3
0
1.7
13.1
18.8
2.0
14.6
19.2
0.2
1.6
2.3
25
26
10
20
Integral modified converter in a mode with hydrogen extraction (extractor)
27 [Fe,Cr]/(K,Ce)γ-Al2O3/α-Al2O3 20
* Process conditions: n = 66.90 mmol/h, Т = 637°С, Р = 1 atm.
2.9
23.2
23.7
butenes
tot
** Selectivity of formation of 1,3-butadiene based on the initial 1-butanol. The dash means that it was impossible to calculate the output
per gram of active component in the uncharged reactor and on alumina granules because of the absence of the active component.
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SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
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400
FEDOTOV et al.
(а)
(b)
Fig. 4. Hydrogen-selective palladium-containing membrane after the dehydrogenation of the butene fraction (a) using integral
[Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter and (b) on a granular converter of the same composition.
2
3
2 3
0.005 wt %. The oxidative regeneration was performed surface was determined before and after the catalytic
at 450–600°C.
tests using TEM-EDX analysis.
The dehydrogenation of the butene fraction into
1,3-butadiene for 20 h did not lead to a noticeable
decrease in the catalytic activity of the system. This is
an important advantage of the system over the indus-
trial catalyst for dehydrogenation of the butane–
butene fraction, which is generally regenerated every
8–15 min [28].
Therefore, we can conclude that the developed
[Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 integral converters
are stable against carbonization during dehydrogena-
tion of the butene fraction to 1,3-butadiene, which
makes them promising for practical applications. This
is in good agreement with the results of previous stud-
ies that showed that the carbon dioxide reforming of
methane was promoted in open catalytic channels of a
porous converter and had significantly higher resis-
tance to carbonization compared to the process in a
conventional flow reactor with a loaded granular cata-
lyst bed [19–21, 29].
On the initial catalyst, the iron- and chromium-
containing components were uniformly distributed
over the surface of the α-Al2O3 support, but some
regions contained distinct clusters with sizes of up to
100–150 nm containing highly dispersed particles of
metal-containing active components (Figs. 7a–7c).
In the spent converter, there were no visible
changes in the particle size of the deposited Fe and Cr
components. There was no surface carbonization,
which indicates high resistance of the sample to coke
formation during the dehydrogenation of butenes.
Figure 8 shows the Fe2p and Cr2p XPS spectra of
the initial [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 converter.
Only some part of the 2p3/2 spectrum was processed for
both metals after subtracting the background compo-
nent by the Shirley method. The spectra were identi-
fied using the database [30].
A SEM-EDX analysis allowed us to evaluate the
size factor and the distribution of active components
on the surface of the [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3
converter (Fig. 6a). The distribution of the K, Ce, Fe,
and Cr components on the support surface is quite
uniform (Figs. 6b–6f). The particle size does not
exceed 6 nm. The carbon content in the spent sample
is low, indicating slight coking of the catalyst during
the dehydrogenation of the butene fraction. The car-
bon distribution data presented in Fig. 6b refer to the
carbon of the organic-based fixing glue required for
fixing the sample on the stage of the electron micro-
scope.
99.99
99.97
99.95
99.93
99.91
99.89
99.87
99.85
50
150
250
350
450
550
650
Temperature, °С
Fig. 5. TG analysis in the air flow of the [Fe,Cr]/γ-
The active components of the [Fe,Cr]/γ-Al2O3
(K,Ce)/α-Al2O3 converter were visualized and spec-
trally identified and their particle size on the support
Al O (K,Ce)/α-Al O converter. The low peaks in the
2
3
2 3
temperature range 100–150°C correspond to water
desorption.
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SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
401
14653
30523 CK
0
0
0
5
100 nm
100 nm
(а)
(b)
KK
0
3
CrK
3
100 nm
100 nm
(c)
(d)
FeK
0
3
CeL
2
100 nm
100 nm
(e)
(f)
Fig. 6. Images of the (a) scanned surface of the spent [Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter and (b–f) distribution of active
2
3
2 3
components: (b) C, (c) K, (d) Cr, (e) Fe, and (f) Ce on it according to SEM-EDX analysis data.
HAADF
(а)
Fe
Cr
200 nm
200 nm
200 nm
(b)
(c)
Fig. 7. Images of the (a) scanned surface of the initial [Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter and (b), (c) distribution of (b)
2
3
2 3
Fe and (c) Cr particles and agglomerates on it.
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402
FEDOTOV et al.
(а)
(b)
Fe3+
Cr3+
740
730
720
710
700
595
590
585
580
575
570
Binding energy, eV
Binding energy, eV
Fig. 8. (a) Fe2p and (b) Cr2p XPS spectra of the initial [Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter.
2
3
2 3
(а)
(b)
Fe3+
Fe2+
Cr3+
740
730
720
710
700
595
590
585
580
575
570
Binding energy, eV
Binding energy, eV
Fig. 9. (a) Fe2p and (b) Cr2p XPS spectra of the spent [Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter.
2
3
2 3
It was found that, in accordance with the results of
The XPS studies of the spent converter indicate
that in addition to Fe3+, the Fe2+ component is pres-
ent, whose peak is localized in the energy region of
708.5 eV. It was found that the Fe2+ content was ~25%
of the total amount of iron in the sample. This suggests
partial reduction of iron with hydrogen during the cat-
alytic process.
There were no changes in the Cr2p spectrum after
catalysis. This means that chromium does not change
its oxidation state during the process and is in the Cr+3
state, as it was in the initial sample (Fig. 9b).
the decomposition of the Fe2p spectrum, iron is in the
oxidation state +3; the binding energy of the main
peak is 710.2 eV, and that of the satellite peak is 9.3 eV
higher.
The Cr2p spectrum contains a main peak with a
binding energy of 576.0 eV and four multiplet peaks.
The presence of these peaks suggests that the initial
converter contained chromium oxide Cr2O3 particles
in addition to iron oxides.
The data obtained in the decomposition of the
Fe2p spectrum (Fig. 9a) suggest the presence of
reduced forms of iron in the converter.
The data of programmed thermal reduction with
hydrogen showed the presence of a small peak
(0.00184 mmol/g) in the temperature range 494.5°C
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SYNTHESIS OF 1,3-BUTADIENE FROM 1-BUTANOL ON A POROUS CERAMIC
0
403
–0.0005
–0.0010
–0.0015
–0.0020
–0.0025
0
100 200 300 400 500 600 700 800 900 1000
Temperature, °С
Fig. 10. TPR-H profile of the initial [Fe,Cr]/γ-Al O (K,Ce)/α-Al O converter.
2
2
3
2 3
European Regional Development Fund; École centrale de
Lille; and Central Initiative Fund for financial support.
of the initial [Fe,Cr]/γ-Al2O3(K,Ce)/α-Al2O3 con-
verter. At these temperatures, Fe(III) oxide is partially
reduced to nonstoichiometric magnetite (Fig. 10):
FUNDING
(IV)
3Fe2O3 + H2 → 2Fe3O4 + H2O.
This study was supported by the Russian Science Foun-
dation (grant no. 17-13-01270).
The obtained result correlates well with the XPS
data, indicating that during dehydrogenation, the
spent sample is reduced with liberated hydrogen to
nonstoichiometric magnetite, in which some part of
Fe+3 ions are reduced to Fe+2.
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Translated by L. Smolina
KINETICS AND CATALYSIS
Vol. 61
No. 3
2020