Chemical Engineering & Processing: Process Intensification 175 (2022) 108904

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Chemical Engineering and Processing - Process

Intensification
journal homepage: www.elsevier.com/locate/cep

Investigation of isobutane dehydrogenation on CrOx/Al2O3 catalyst in a

membrane reactor
Ayşe Dilay Erdali a, Saliha Cetinyokus b, *, Meltem Dogan b
a
Gazi University, Institute of Science and Technology, Chemical Engineering, 06560, Ankara, Turkey
b
Gazi University, Faculty of Engineering, Chemical Engineering, 06570, Ankara, Turkey

A R T I C L E I N F O A B S T R A C T

Keywords: Isobutene is an important raw material for the production of additives that increase the octane number of
Isobutane dehydrogenation gasoline and reduce emissions, some polymeric materials and pharmaceuticals. Isobutane dehydrogenation,
Membrane reactor which is widely used in the production of isobutene, is an equilibrium-limited endothermic reaction. In this
CrOx/ Al2O3 catalyst
study, it was aimed to overcome the equilibrium conversions by using membrane reactor. First, Al2O3 supported
Reactor modeling
chromium-based catalysts were prepared by the impregnation technique. Characterization studies of catalysts
were carried out by DR..........-UV–vis, N2 adsorption/desorption, XRD and SEM/EDS analyses. Catalysts (6% Cr
by mass) were prepared at three different values of the contact time - 24, 48, 72 h mixing times. The highest
amount of monochromate was observed in the catalyst prepared during the mixing time of 48 h. Catalysts
containing 6%, 8%, and 10% Cr by mass (mixing time: 48 h) were also synthesized. When the chromium con­
centration increased above 8%, a decrease in the amount of monochromate was observed. Then, reactions were
performed with a catalyst containing 8% by mass of Cr, which was prepared in a mixing time of 48 h with the
highest amount of monochromate. The reactions were carried out in a Pd based membrane reactor system with
pure isobutane feed. The effect of reactor temperature was investigated at 550 ◦ C and 600 ◦ C (WHSV:0.3h− 1).
While no significant difference was observed between the conversion values at both reactor temperatures
(⁓90%), isobutene selectivity values were higher (⁓85%) at 600 ◦ C. It was observed that the high isobutene
selectivity values determined at 600 ◦ C were due to the high endothermic nature of the reaction. The reaction
was also carried out by changing the weight hourly space velocity at 600 ◦ C (WHSV:0.5h− 1). Although the
isobutane conversion values were close to each other (⁓90%), higher isobutene selectivity values (⁓90%) were
determined at 0.3h− 1. The presence of less hydrogen in the environment decreased the formation of the hy­
drogenation reaction of isobutane. This situation enhanced an increase in isobutene selectivity values. The shift
of the reaction towards the products also increased the selectivity of isobutene. It was observed that although the
amount of carbon (3 times more) formed at high retention times caused negative effects such as a decrease in the
surface area and closure of the pores, the active monochromate species preserved in the catalyst structure. It was
determined that the formed amorphous carbon did not cause the rapid decreases in activity and selectivity. The
results of the study showed that the equilibrium limitation could be overcome by removing hydrogen from the
reactor medium (equilibrium conversions:73% at 600 ◦ C, 53% at 550 ◦ C). The results of the modeling studies
carried out in the membrane reactor were found to be compatible with the experimental results.

1. Introduction dehydrogenation is an equilibrium-limited endothermic reaction. High

temperatures are required for high conversions. High temperatures
Isobutene, a product of isobutane dehydrogenation, is an alkene that cause coke formation and require frequent regeneration of the catalyst.
is widely used in industry. Isobutene can be used as a raw material for In addition, in the systems where the reaction is carried out, resistance of
rubbers, plastics and pharmaceuticals. Isobutene is also an important the reactor equipment and catalyst support material to high tempera­
raw material for the production of additives (ETBE, MTBE) that increase tures is expected, which increases the cost. Production of isobutene in
the octane number of gasoline and reduce emissions. Isobutane refineries has low efficiency. Catalyst life is short in processes such as

* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Cetinyokus).

https://doi.org/10.1016/j.cep.2022.108904
Received 21 August 2021; Received in revised form 11 March 2022; Accepted 21 March 2022
Available online 24 March 2022
0255-2701/© 2022 Elsevier B.V. All rights reserved.
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

commercial CATOFIN, Oleflex, STAR used in the production of iso­ solution and the support on the catalyst structure and activity was
butene. Catalyst development studies are gaining importance for investigated. It was determined that the amount of active mono­
isobutane dehydrogenation. Al2O3 supported chromium oxide catalysts chromate in the catalyst structure decreased with increasing Ca/Cr ratio.
are generally used for isobutane dehydrogenation in industry. Isobutene The isobutane reaction was investigated by Erol et al. [13] on hydro­
is produced by isobutane dehydrogenation using CrOx/Al2O3 catalyst at thermally synthesized CrOx/MCM-41 catalysts with different Cr content.
900 K, 40–50% isobutane conversion and approximately 90% isobutene It was determined that inactive α-Cr2O3 crystal formations increased
selectivity are obtained [1]. CrOx/Al2O3 catalysts are advantageous for with Cr content. In the catalytic tests carried out with the catalyst with
isobutane dehydrogenation due to their low cost, high activity and high 4% Cr content containing the highest amount of Cr6+, approximately
stability. Al2O3 is used in Cr catalysts for its support, high surface area 80% isobutene selectivity was obtained. It was shown that catalyst
and homogeneous distribution of the active ingredient at high temper­ deactivation was not caused by coke deposition, but by state change of
atures. In the study conducted by Fang et al. [2], isobutane dehydro­ Cr species.
genation was investigated on CrOx/Al2O3 catalyst, and the active centers Pd alloy membranes have high potential for hydrogen separation in
were determined as redox Cr2+ and Cr3+. It was shown that catalyst hydrogen dependent reactions. In the study conducted by Gallucci et al.
deactivation was caused by carbon deposited on the catalyst surface. [14], the advantages of using Pd-based membranes in different reactors
Cr6+ and Cr3+ in fresh and regenerated catalysts, and Cr2+ and Cr3+ were investigated. Pd membranes are the most researched and closest to
valences in the catalyst used in the reaction were determined. In another the market in hydrogen separation. It was determined that membrane
study conducted by Fridman et al. [3], it was shown that the chromium poisoning was reduced with the addition of other metals to the Pd
species in the catalyst structure depended on the type of support used in structure. In the study conducted by Rahimpour et al. [15], the use of
the catalyst and the synthesis method of the catalyst. This study palladium-based membranes in membrane reactors for pure hydrogen
demonstrated that the fresh CrOx/Al2O3 catalyst contained not only production was investigated. The advantages of Pd-based membrane
chromium species of ‘isolated’ mono/poly aluminum chromate(s), reactors were given in increasing the product yield, selectivity and
amorphous and crystalline Cr2O3 clusters with different sizes, but also overcoming the thermodynamic equilibrium limitation of the reactions.
chromium-chromate (Cr6+) species on the surface of Cr2O3 clusters and It is recommended to use palladium in alloys with other metals, espe­
aluminum chromium-chromate (Cr6+) species coupled with Cr2O3 cially silver, to increase hydrogen permeability [16–18].
clusters. In the study by Fridman and Xing [4], it was shown that Membrane reactors are reactors that perform catalytic reactions and
non-redox Cr3+ type chromium on Cr2O3 in fresh catalyst did not separation processes in one step. This combination reduces the number
contribute to the dehydrogenation activity. CrOx/Al2O3 catalysts were of reactors, the amount of catalyst and makes the process more efficient.
synthesized by Zhao et al. [5] using a porous MIL101 (Porous Chromium The use of membrane reactors in dehydrogenation reactions with
Terephthalate) precursor. It was shown that the activity of chromium equilibrium limitations is remarkable. The catalytic dehydrogenation
catalysts depended on the presence of Cr6+ and Cr3+ species in the reaction for the production of styrene from ethylbenzene was investi­
catalyst structure. High isobutene selectivity and good catalyst stability gated by Yu and Xu [19] in a Pd membrane reactor. The use of a
were detected in catalytic tests. Isobutane dehydrogenation on CrOx/­ membrane reactor was shown to significantly increased ethylbenzene
alumina catalysts with different chromium content was investigated by conversion and selectivity by removing hydrogen. Under the optimized
Baronskiy et al. [6]. Surface Cr3+s luminescence centers were detected reaction conditions, it was observed that the yield increased by 11.3% in
by photoluminescence spectroscopy in all samples. The maximum the membrane reactor. In the study conducted by Orekhova et al. [20],
amount of Cr3+s luminescence center was found for 1% CrOx/γ-Al2O3 conventional reactor systems and catalytic membrane reactor systems
catalyst. Isobutane dehydrogenation performance of CrOx/Al2O3 cata­ were investigated for oxidative and non-oxidative dehydrogenation of
lysts synthesized under different impregnation conditions was investi­ C2-C4 alkanes. It was noted that silicon-based selective membranes for
gated in fixed bed reactor by Zolotukhina et al. [7]. A series of catalysts oxidative dehydrogenation reactions were promising due to their oxy­
were synthesized at different impregnation pressures, and the applica­ gen permeability. A two-dimensional non isothermal mathematical
tion of vacuum was shown to reduce the catalyst surface area and reduce model was developed to simulate the propane dehydrogenation in a
the reaction activity. catalytic membrane reactor with tube-and-shell configuration by She­
Studies are also carried out to increase the dehydrogenation activity lepova et al. [21]. It was determined that the model correctly predicted
of isobutane, the stability of the catalyst and the amount of active the improved process parameters when the membrane thickness was 4
component. Al2O3 supported CrOx catalysts modified with Cu and Zn mm and the pore diameter was 0.4 nm. In the study by Sheintuch and
were synthesized by the impregnation method by Salaeva et al. [8]. It Nekhamkina [22], the main factor affecting the design of the membrane
was shown that Zn compounds reduced the catalytic activity, while Cu reactor in propane dehydrogenation was determined as catalyst and
compounds provided the formation of a higher amount of redox chro­ membrane deactivation due to coking. It was shown that it was neces­
mium species. The dehydrogenation of isobutane on Ca loaded CrOx/­ sary to keep the operating pressure below 5 bar, the catalyst temperature
Al2O3 catalysts was investigated by Wang et al. [9]. It was determined around 450–500 ◦ C and the membrane temperature at 200–250 ◦ C to
that the catalyst with 2% Ca loading by mass showed the highest ac­ prevent coking. In the study conducted by Ahn et al. [23], the dehy­
tivity. The reaction was investigated on a series of CrOx/alumina cata­ drogenation of ethane was investigated in a conventional fixed bed
lysts prepared at different K loading amounts with the same Cr content reactor (PBR) and a membrane reactor (MR) using two different silica
by Nazimov et al. [10]. It was stated that K particles interacted with membranes in the presence of Cr/ZSM-5 catalyst containing 5% Cr by
catalyst active sites at low reaction temperatures and caused chemi­ mass. Although ethane conversion and ethylene yield decreased with
sorption of water, which poisoned the active sites. increasing pressure, it was observed that hydrogen formation increased.
There are numerous literature studies investigating different aspects In the study by Wang et al. [24], titanium silicate (TS) was added to the
of CrOx catalysts on different supports for isobutane dehydrogenation. membrane structure to prevent the poisoning of palladium-based
In the study conducted by Deng et al. [11], mesoporous CaO supported membranes with hydrocarbons in hydrogenation or dehydrogenation
Cr-V based catalysts were synthesized by the impregnation method. reactions. Benzene conversion and phenol yield increased significantly
Different CrOx (0–4% by mass) and VOx (10% by mass) contents were with TS nanoparticles added to Pd membranes. In addition, membranes
included in the synthesized catalysts. Catalytic tests were carried out at coated with TS showed good stability in long-term catalytic tests (at
540 ◦ C, and the highest isobutene selectivity value (79%) was achieved 200 ◦ C, 100 kPa) for 110 h. The addition of TS also acted as a barrier to
with a catalyst containing 2% Cr and 10% V by mass. In the study by protect the Pd layer. The processes of ethane, propane and ethylbenzene
Dogan et al. [12], CrOx/AC catalysts were synthesized by the impreg­ dehydrogenation in catalytic membrane reactors were theoretically
nation technique, and the effect of the contact time of the metal salt compared in terms of efficiency and productivity by Shelepova and

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Vedyagin [25]. A two-dimensional non-isothermal stationary mathe­ impregnation method. Commercially available Al2O3 was used as cata­
matical model was applied. It was indicated that the heavier was a hy­ lyst support material. The effects of mixing time and chromium con­
drocarbon, the higher amount of by-products was formed. It was also centration on the catalyst structure were investigated in the application
demonstrated that since the contribution of the coke formation process of the impregnation method. Characterization studies were carried out
was being increased along with temperature, diminishing of the reactor with DR..........-UV–vis, XRD, N2 adsorption/desorption, SEM/EDS ana­
temperature by oxidation of flux hydrogen allowed enhancing the target lyzes. With the characterization studies, the structural properties of the
products’ yield. catalyst were determined and analyzes were carried out to determine the
Packed bed reactors are generally used in isobutane dehydrogena­ chromium oxide species in the structure. As a result of the character­
tion reactions, but these reactors have equilibrium limitations. The use ization studies, the reactions were carried out in the membrane reactor
of membranes in reactors increases isobutane conversion and isobutene with the selected catalyst. The reactions were performed at different
selectivity in isobutane dehydrogenation. And also, membrane usage reactor temperatures and at different weight hourly space velocities. In
reduces operating costs and provides hydrogen production [26]. In the addition, the results obtained by conducting a modeling study in the
study by Matsuda et al. [27], the reaction was investigated in a fixed bed membrane reactor were compared with the experimental results.
reactor and a membrane reactor using a silica membrane on a
commercially available chromium-based Al2O3 supported catalyst. 2. Experimental
Higher isobutene selectivity and yield were obtained in the membrane
reactor at all reaction conditions. Isobutane dehydrogenation was Experimental studies consisted of two parts, catalyst synthesis and
investigated in a fluidized bed membrane reactor by Kilicarslan et al. reaction studies. First, Cr-based catalysts were synthesized by the
[28]. A selective Pd composite membrane for hydrogen was prepared by impregnation technique using commercially available alumina support.
ELP (electroless plating) technique. The reaction was investigated on The effects of mixing time and Cr concentration on the catalyst structure
commercial CrOx catalyst. 40% isobutane conversion was determined at were investigated. Characterization studies of synthesized catalysts
450 ◦ C, and it was determined that Pd in the membrane structure were carried out with DR..........-UV–vis, N2 adsorption/desorption,
catalyzed the hydrogenation reaction and shifted the reaction in the XRD, SEM/EDS analyses. Then, by choosing the appropriate catalyst,
direction of the product. The reaction was investigated in a DD3R zeolite reactions for isobutane dehydrogenation were carried out in a Pd-alloy
membrane reactor in the presence of Cr2O3/Al2O3 catalyst by Bergh membrane reactor system at different reactor temperatures and weight
et al. [29]. It was observed that the equilibrium conversion was reached hourly space velocities (WHSV).
1.5 times by using Pd membrane in the reactor system on the CrOx/­
alumina catalyst prepared by impregnation. High hydrogen perme­
2.1. Synthesis of CrOx/ Al2O3 catalysts
ability and isobutene yield of 50% more than equilibrium value was
observed in the membrane reactor. It was stated that removal of
F-200 Al2O3, produced by BASF, was used as support material in the
hydrogen through the membrane reduced coke formation. It was indi­
catalyst. The diameter of the Al2O3 spheres used was 0.4 cm. Al2O3 is a
cated that the use of membrane reactors with a higher surface/volume
very suitable support material for dehydrogenation reactions of hydro­
ratio would increase the reactor performance. CrOx/MCM-41 catalyst
carbons due to its high breaking strength. The physical properties and
(3% Cr by mass) was hydrothermally synthesized and tested in a com­
chemical composition of the supplied alumina are presented in Table 1.
mercial Pd membrane reactor by Kilicarslan et al. [30]. It was shown
Cr(NO3)3⋅9H2O salt obtained from Merck was used as a chromium
that no side reactions were observed in 823 K, and the membrane only
source in the synthesis studies. Metal salt solution and Al2O3 were mixed
played a role in hydrogen separation. Dangwal et al. [31] investigated
in a magnetic stirrer at 400 rpm during all experiments. In the study
isobutane dehydrogenation in the presence of Pt/Al2O3 catalyst in a
where the mixing time of 24 h was examined as a parameter, the solu­
membrane reactor. It was stated that the use of membranes increased the
tion was mixed at room temperature for 23 h. Then it was stirred at 40 ◦ C
conversion and selectivity.
for 1 h, the temperature was increased to 60 ◦ C and the water of the
It is seen that modeling and optimization studies in membrane re­
solution was evaporated. The dried sample was placed in a quartz glass
actors in isobutane dehydrogenation reactions are also widespread. In
tube and calcined for 6 h at 600 ◦ C at 140 mL/min dry air flow. Ex­
these studies, the effects of many parameters on isobutane dehydroge­
periments were carried out at mixing times of 48 h and 72 h, as well as
nation can be evaluated and the most suitable operating conditions for
24 h of mixing time. In addition, experiments were carried out at
the reactions can be determined. In the study by Farsi et al. [32], the
different chromium concentrations (6%, 8% and 10% (by mass)) in
modeling of Pd/Ag based membrane reactors showing hydrogen selec­
order to examine the effect of metal concentration on the chromate
tivity for the reaction was studied. In the modeling optimized membrane
species in the catalyst structure. Since it is stated in the literature that
reactor, it was determined that the isobutane conversion increased by
high chromium concentrations cause a decrease in the activity in the
about 10.1% and the selectivity of isobutene by about 3.3% compared to
isobutane dehydrogenation reaction, 6–10% of chromium by mass has
the conventional reactor. In addition, it was observed that the methane
been studied. The operating conditions of the experiments in which the
formed as a result of side reactions decreased by 17.5% in the membrane
relevant parameters were examined are given in Table 2.
reactor. In another study conducted by Farsi et al. [1], the fluidized bed
Characterization studies were carried out to determine the effects of
reactor used in the Oleflex commercial process was modeled by placing a
mixing time and chromium concentration on the catalyst structure. With
Pd-Ag membrane plate in the reaction zone. Pt – Sn / Al2O3 catalyst was
N2 adsorption/desorption analysis (Quantochrome, Autosorb-1), pore
used in the reaction. The membrane reactor was modeled as heteroge­
diameter distribution curves of the support and catalysts were formed
neous and the isobutene yield increased by about 3.7% compared to the
conventional reactor system. Cetinyokus et al. [33] developed a reaction
rate expression on Cr/MCM-41 (3% Cr by mass) catalyst for isobutane Table 1
Physical properties and chemical composition of Al2O3.
dehydrogenation, and the activation energy was determined as 55
kJ/mol. The reaction system including a commercially supplied Pd physical properties chemical composition
membrane was modeled. Modeling and experimental results were Compound %, by mass
shown to be compatible with each other in 823 K. Surface area, m2/g 350 Al2O3 92.7
In this study, it was aimed to overcome the equilibrium limitation in Total pore volume, cm3/g 0.5 SiO2 0.02
isobutane dehydrogenation by using a perm-selective membrane reactor Density, kg/m3 769 Fe2O3 0.02
for hydrogen. First of all, Cr-based catalysts, which are desired to show Na2O 0.30
LOI (250–1100ºC) 6.96
high activity and high isobutene selectivity, were prepared by the

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Table 2 temperature range of 200–700 ◦ C. A set of permeability tests for the

Experimental conditions for catalyst synthesis. membrane were performed by using gas streams containing a mixture of
Experiment set in which the effect of mixing time on the catalyst structure was H2 with N2 (50:50) as well with pure H2 and N2 at different temperatures
investigated (in the range of 723–873 K) and also at different pressure differences. N2
Mixing Time(h) Cr(by mass)% Calcination Conditions did not pass through the membrane and H2 flux through the membrane
was correlated as expressed in the following equation.sure differences.
24 6% Dry air, 600 ◦ C, 6h
48
N2 did not pass through the membrane and H2 flux through the mem­
72 brane was correlated as expressed in the following equation.
Experiment set in which the effect of chromium concentration on the catalyst structure
was examined
PwH2h − PwH2l ( / )
JH2 = PM ; mol m2 .s (x : Pd coating thickness, 5 μm) (1)
Mixing Time(h) Cr(by mass)% Calcination Conditions x
48 6% Dry air, 600 ◦ C, 6h
When diffusion through the metal is the rate limiting step and
8%
10% hydrogen atoms form an ideal solution in the metal, the value of w
would also be expected to be as 0.5. The temperature dependence of the
permeability parameter PM was assumed in Arrhenius form as follows:
and their surface areas were determined. Chromate types and distribu­ ( )
( / )
tions in the catalyst structure were investigated by DR.......... -UV–vis PM = 1.80x10− 8 exp −
23
; mol m.s.Pa0.5 (2)
analyzes (Perkin Elmer Lambda 35). Compounds in catalyst structure RT
were determined by XRD analysis (Rigaku Ultima IV). With SEM/EDS The permeation activation energy (Ep) was found as 23 kJ/mol.
analysis (FEI brand Nova NANOSEM 430), the atomic ratios of the metal Results indicated that experimental H2 flux values agreed quite well
placed in the support structure were determined, and the morphological with the predictions of eq. (1) [33].
analysis of the support and catalysts was made. The membrane inside the reactor had a three-layer structure con­
sisting of Ni alloy porous material at the bottom, Pd-Ag alloy coating in
2.2. Reaction studies in membrane reactor the middle and Pd coating at the top. The schematic representation of
the membrane reactor is given in Fig. 1.
As a result of the characterization studies, reaction studies were The membrane was in a steel tube. The reactor consisted of a feed
carried out in the membrane reactor system with the selected catalyst. inlet, permeate and retentate outputs. Hydrogen was taken from the
The experimental setup basically consisted of isobutane and nitrogen lower chamber of the membrane tube. The membrane reactor was
tube, vertical tube furnace, membrane reactor, pressure gauges, mass placed in a vertical tube furnace. Nitrogen gas flow was used in the
flow meters and gas chromatography (SRI 8610C). The membrane experiment system to heat the system up to the operating temperature
reactor in the experimental setup was supplied from “REB Research & and to cool the system after the experiment was over. Pure isobutane
Consulting Hydrogen Separations and Membrane Reactors”. The mem­ feed was used in the experiments. In all tests, 20 g of catalyst was placed
brane reactor had 100% hydrogen selectivity and resistance in the in the annular space of the membrane reactor. The reaction was

Fig. 1. Schematic representation of the membrane reactor.

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

continued for 2 h. The gas mixture containing the reaction products was medium played an important role on the active chromium species (Cr6+)
analyzed in a gas chromatography (GC) instrument. The effect of reactor in CrOx/Al2O3 catalysts, and the color change provided an increase in
temperature on conversion and selectivity in membrane reactor system the active chromium species in the structure [3]. DR..........-UV–vis an­
was investigated. Reactions were carried out at 550 ◦ C and 600 ◦ C alyzes of catalysts synthesized by the impregnation method at different
(WHSV values were 0.3h− 1). Then, the weight hourly space velocity was mixing times are given in Fig. 3.
changed from 0.3h− 1 to 0.5h− 1 in the system and experiments were In Fig. 3, peaks originating from O–Cr(VI) bonds in dichromates
performed at 600 ◦ C. were observed in the 380 nm band. The peaks seen in the 430–460 nm
band indicated the O–Cr(VI) bonds in the polychromates in the struc­
3. Results and discussions ture [35]. The areas under the peaks was examined with the Digimizer
program and the highest value between the peaks at 380 nm was ob­
CrOx/Al2O3 catalysts were prepared by impregnation technique. The tained in the catalyst prepared during 48 h of mixing. The amount of
effects of mixing time and chromium concentration on the distribution monochromate in the catalyst prepared in 48 h of mixing time was found
of chromate species in catalyst synthesis were investigated. Character­ to be approximately 1.2 times the amount of monochromate in the
ization studies were made before and after the reaction. Reactions were catalyst prepared in 24 h of mixing time.
carried out in the membrane reactor at different reactor temperatures Synthesis studies were carried out at three different chromium con­
and different weight hourly space velocities(WHSV). By analyzing the centrations (6%, 8% and 10% Cr, by mass) after choosing a mixing time
product stream, isobutane conversion and isobutene selectivity values of 48 h in which highest amount of active chromates were obtained in
were determined, and the occurrence of side reactions was investigated. the catalyst structure. It is stated that the increase in the amount of
modeling studies were carried out, and the results were compared with monochromate positively affects the activity of the isobutane dehydro­
the experimental results. genation reaction. The activity of chromium oxide catalysts used in
dehydrogenation reactions is due to unsaturated redox Cr3+ species. It is
3.1. Characterization studies known that redox Cr3+ species are obtained by reduction of the initial
Cr6+ forms in the catalyst during the reaction [35]. DR..........-UV–vis
Commercially available Al2O3 was used as support material in the analyzes of catalysts prepared at different chromium concentrations
synthesis studies. The N2 adsorption/desorption isotherm of the Al2O3 during 48 h of mixing are given in Fig. 4.
support together with the pore size distribution is given in Fig. 2. Fig. 4 showed the presence of monochromate, dichromate and pol­
The isotherm seen in Fig. 2 was type IV adsorption isotherm ac­ ychromate peaks in catalysts prepared at all concentrations. The areas
cording to the BDDT (Brunauer-Deming-Deming-Teller) classification. under the peaks at 380 nm was also examined with the Digimizer pro­
In type IV isotherms, adsorption takes place in a multilayered manner gram and it was determined that the amount of monochromate was the
[34]. The formation of hysteresis was an indication of the presence of highest in the catalyst with 8% metal concentration by mass. For this
narrow slit-like pores in the structure. It can be seen from the pore reason, catalysts synthesized at 8% metal concentration and 48 h mixing
diameter curve that the average pore diameter of Al2O3 was about 38 Å. time were used in the reaction studies carried out in the membrane
The Single Point BET surface area of the support was calculated as 324 reactor. The pore size distribution curve of the catalyst at 8% metal
m2/g. concentration and 48 h of mixing time and the alumina support syn­
In order to examine the effect of mixing time on the samples pre­ thesized are given in Fig. 5.
pared by the impregnation method, catalysts were synthesized at 3 It can be seen from Fig. 5 that the pore size distribution curve in the
different mixing times. Catalysts synthesized at mixing times of 24 h, 48 catalyst widened. The presence of micropores smaller than 20 Å was less
h, 72 h containing 6% chromium by mass were calcined under the same in the support.
conditions (600 ◦ C, dry air flow). With the calcination process, the green SEM analyzes were carried out to investigate the surface morphology
color of the samples turned yellow. Color change was explained by of the catalyst. SEM photographs of Al2O3 support and catalyst are given
oxidation of chromium after calcination [35]. It is known that the color in Fig. 6. When Fig. 6 was examined, there was no great difference in
change in the catalyst is between yellow and green in the presence of support and catalyst surface morphologies. The bright regions in the
Cr3+ and Cr6+ species in the catalyst. It can be stated that the calcination catalyst synthesized by the impregnation technique showed the CrOx

Fig. 2. N2 adsorption/desorption isotherm and pore size distribution curve of Al2O3 support.

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 3. DR-UV–vis analyzes of catalysts prepared at different mixing times (6% Cr, by mass).

Fig. 4. DR-UV–vis analyzes of catalysts prepared at different chromium concentrations (mixing time:48 h).

structures. It can be said that the support structure tightened after 3.2. Reaction studies in membrane reactor
catalyst synthesis. In order to examine the distribution of chromium in
the catalyst, a mapping study was carried out with SEM/EDS analysis. Reaction studies were carried out in a reactor system with a Pd alloy
The mapping results are shown in Fig. 7. membrane tube. In the tests where the effect of reactor temperature on
It can be seen from Fig. 7 that the chromium distribution in the isobutane dehydrogenation was investigated, 20 g of CrOx/Al2O3 cata­
catalysts was homogeneous. The different sized dots in the mapping lyst was used and pure isobutane (40 mL/min) was fed to the system.
were due to the difference in chromate types. The smallest dots were Tests were conducted at atmospheric pressure for 2 h (WHSV=0.3 h− 1).
thought to belong to monochromates, and the largest to inactive Cr2O3 Reaction studies were carried out by changing the weight hourly space
crystals. The Cr/Al ratio (by mass) in the catalyst was calculated as 0.11 velocity (WHSV= 0.5 h− 1) at the reactor temperature selected as a result
by EDS analysis. The Cr/Al ratio in catalyst synthesis was determined to of the experiments carried out at different reactor temperatures.
be approximately 0.16 (by mass). It was seen that the analysis and Effect of Reactor Temperature on Conversion and Selectivity
synthesis values were close to each other. The smaller ratio in the Reaction studies were carried out at 550◦ C and 600◦ C reactor tem­
analysis can be explained by the inability of the chromium to be peratures for 2 h. Conversions and selectivities were calculated using the
analyzed by settling inside the pores. following equations.

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 5. Pore size distribution curves of alumina support and catalyst (mixing time:48 h, 8% Cr by mass).

Fig. 6. SEM photographs (a):support (b): catalyst (mixing time:48 h, 8% Cr by mass).

Fig. 7. Distribution of chromium in the catalyst by mapping (SEM/EDS).

7
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

( )
i − C4 H10, initial − i − C4 H10, exit 5 min. In the later stages of the reaction, propane selectivities not
isobutane conversion (%) = ( ) × 100 (3) exceeding 8% were observed at both reactor temperatures. It was seen
i − C4 H10, initial
that the isobutane hydrogenation reaction (R3) lost its importance as a
( ) result of the removal of hydrogen from the reaction medium by the use
i − C4 H8,exit
isobutene selectivity (%) = ( ) × 100 (4) of membrane at both reactor temperatures. In reaction studies carried
i − C4 H10,initial − i − C4 H10,exit
out at 550 ◦ C and 600 ◦ C, it was seen that propene selectivity increased
Fig. 8 shows the change of isobutane conversion values during the with the progress of the reaction, especially up to the 80th minute. This
reaction. showed that the cracking reaction of isobutane (R2) had gained
It was seen that there was no significant difference between the importance.
isobutane conversion values in the experiments carried out at two In the reactor system, a pressure difference of 70 kPa was created
different temperatures. In the tests carried out at 550 ◦ C and 600 ◦ C, it between the two sides of the membrane by applying vacuum inside the
was observed that the isobutane conversions were around 90%. It is membrane tube. In the previous study, it was shown that hydrogen flux
known that in isobutane dehydrogenation carried out in membrane re­ values determined at T = 550 ◦ C and T = 600 ◦ C for the pressure dif­
actors, the equilibrium limitation is overcome by removing H2 from the ference of 70 kPa were close to each other [36]. The close observation of
medium, thus higher conversions are achieved in the reaction. Conver­ the hydrogen amounts examined at the reactor exit (n600C/n550C ≈1.05)
sion values were determined higher in membrane reactors than in also showed that the operating conditions did not cause a significant
conventional reactors [31]. Equilibrium conversion values determined change in the hydrogen permeability. It was thought that the high iso­
by pure isobutane feed at atmospheric pressure at 550 ◦ C and 600 ◦ C butene selectivity values determined at 600 ◦ C were due to the high
were determined as 53% and 73%, respectively [35]. As can be seen, the endothermic nature of the main reaction.
equilibrium limitation was overcome with the use of membranes in the In the literature, it is stated that C formation reactions can occur at
study carried out at both reactor temperatures. The isobutene selectivity reactor temperatures above 450 ◦ C. The reactions listed below (R4-R6)
values determined at different reactor temperatures are given in Fig. 9. can be observed by the cracking of isobutene, propene and methane in
It was seen from Fig. 9 that the isobutene selectivity values were the medium [12].
higher in the reaction application where the reactor temperature was
i − C4 H8 ↔ C + 4H2 (R4)
600 ◦ C, compared to the study carried out at 550 ◦ C. The selectivity
values, which increased during the first 30 min at both reactor tem­
i − C3 H6 ↔ 3C + 3H2 (R5)
peratures, decreased after this minute. Possible side reactions when pure
isobutane is used as feed stream in isobutane dehydrogenation are CH4 ↔ C + 2H2 (R6)
shown below along with the main reaction.
Main reaction: It is known that olefins such as isobutene and propene adsorbed on
the catalyst surface in dehydrogenation reactions are more reactive than
i − C4 H10 ↔ i − C4 H8 + H2 ΔH = 117.0kJ/mol (R1) alkanes. When the adsorbed olefins are transported to the acidic centers,
Side reactions: the cracking reactions (R4, R5) took place. Therefore, the excess of
acidic centers on the catalyst surface increased the formation of unde­
i − C4 H10 ↔ CH4 + C3 H6 ΔH = 79.4kJ/mol (R2) sirable side reactions [13].
Under conditions where propane and propene selectivities are high,
i − C4 H10 + H2 ↔ C3 H8 + CH4 ΔH = − 45.0kJ/mol (R3)
methane selectivity is also expected to be high. However, very low
It has been shown in the literature that side reactions occur at high methane selectivities at both reactor temperatures were seen from
reactor temperatures [2,28]. In the study carried out, propene, propane Fig. 10. Low methane selectivities can be explained as the cracking of
and methane selectivities were investigated during the reaction in order methane causing C formation.
to examine the formation of side reactions (Fig. 10). Effect of weight hourly space velocity (WHSV) on conversion and
In Fig. 10, it was observed that propane, the second side reaction selectivity
product at 600 ◦ C, showed a high selectivity (approximately 45%) at the In the studies carried out at different reactor temperatures, the
beginning of the reaction, and the selectivity value decreased rapidly highest isobutane conversion and isobutene selectivity values were
after the 5th minute. At 550 ◦ C, propane formation decreased after about observed at 600 ◦ C. Experimental studies were carried out with a pure

Fig. 8. Isobutane conversion values determined at different reactor8temperatures (WHSV=0.3 h− 1, catalyst containing 8% Cr by mass).
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 9. Isobutene selectivity values determined at different reactor temperatures (WHSV=0.3h− 1, catalyst containing 8% Cr by mass).

isobutane feed of 76 mL/min (WHSV=0.5 h− 1) while keeping the reactor (R2). Fig. 13 showed low methane selectivities, methane decomposed to
temperature constant at 600 ◦ C. The variation of isobutane conversion form C.
values during the reaction in experiments carried out at two different It was seen that as the flow rate increased (WHSV=0.5h− 1), iso­
weight hourly space velocities is given in Fig. 11. butene selectivity values decreased. When the reactor exit compositions
In Fig. 11, it was seen that the conversion values determined as a of the reaction applications carried out at different WHSV values were
result of the reactions carried out at both weight hourly space velocities examined, in the case of WHSV=0.5h− 1, more hydrogen amount (n0.5/
were close to each other and around 90%. In the reaction study with a n0.3 ≈ 7) was observed during the reaction. This showed that the
high retention time (WHSV=0.3 h− 1), it can be said that the conversion hydrogen permeation through the membrane decreased at high flow
was slightly higher. High conversion values can be explained by the high rates. The first step in the transport of hydrogen from the metallic
contact time. In the literature, the equilibrium conversion determined membrane (solution-diffusion mechanism) is the adsorption of
by pure isobutane feed at 600 ◦ C at atmospheric pressure was 73% [35]. hydrogen to the metal surface. At high flow rates, hydrogen perme­
When the data in Fig. 11 was examined, it was observed that the equi­ ability values decrease due to the difficulty of performing the adsorption
librium conversions were overcome. The isobutene selectivity values step [23,39]. The presence of more hydrogen in the reaction medium
determined in the reaction carried out at different weight hourly space increased the formation of the hydrogenation reaction of isobutane (R3).
velocities in the membrane reactor are given in Fig. 12. This situation can be counted as one of the factors that cause a decrease
Fluctuations were observed in Fig. 12 as in Fig. 9. At least coversion in isobutene selectivity values. The shift of the main reaction towards
looked rather stable as function of time in Fig. 9. For consistency, the the products also increased the selectivity of isobutene under the con­
selectivity and conversion for catalyst is reported for gas phase products, ditions of rapid removal of hydrogen from the reaction medium
though this overestimates the selectivity at high conversions [37]. The (WHSV=0.3h− 1).
size of the plotted data points in initial isobutene selectivites vs initial It is known that one of the important causes of deactivation in cat­
isobutane conversions graph was larger than the error bars for conver­ alysts used in dehydrogenation reactions is the formation of coke [40].
sion and selectivity. When the selectivity values of different weight Dehydrogenation of isobutane in industry is generally carried out at high
hourly space velocities were examined, it was seen that the difference temperature in the range of 550–650 ◦ C. It is stated that this temperature
between the values at the beginning of the reaction was large, and the must be carefully controlled to avoid thermal stress on the catalyst,
difference decreased after the 60th minute. The isobutene selectivity which can cause irreversible damage and most importantly the loss of
values of the experiment with a weight hourly space velocity of 0.3 h− 1 selectivity by the formation of coke [41]. In addition, studies have
were higher. At WHSV=0.3 h− 1, the selectivity values, which were shown that side reactions such as C formation increase in the reactor at
determined to be approximately 100% around the 30th minute, high retention times as well as at high temperatures [32]. In dehydro­
decreased after this minute and decreased to approximately 60% at the genation reactions, the color of the catalyst turns black after the reac­
end of the reaction. Dehydrogenation reactions are quite complex due to tion, indicating the formation of coke in the catalyst [42,43].
the occurrence of side reactions such as cracking, polymerization and After the reactions carried out at different weight hourly space ve­
coke formation [38]. In isobutane dehydrogenation, it was shown that locities, the characterization studies of the catalysts were carried out.
side reactions increased due to cracking at high temperatures [32]. The The results of the DR..........-UV–vis analyzes of catalysts after reaction
variation of propene, propane and methane selectivities during the re­ are given in Fig. 14.
action are given in Fig. 13. In a study conducted in the literature, it was shown that mono­
In the experiments carried out when the weight hourly velocity was chromates in the catalyst structure positively affected the activity of
0.3 h− 1, the highest propane selectivity was seen at the 5th minute. At isobutane dehydrogenation reaction [35]. The activity of chromium
the 30th minute, the lowest (about 1%) propane selectivity was deter­ oxide catalysts in dehydrogenation reactions is due to the redox Cr3+
mined. This showed that the second side reaction (R3) lost its impor­ species present in the structure. Cr3+ species are obtained by reducing
tance after the 5th minute. In the study where the weight hourly space the initial Cr6+ forms in the catalyst’s structure during the reaction.
velocity was 0.5 h− 1, slightly high propane selectivity values were When Fig. 14 was examined, the maximum amount of monochromate
observed. It was seen that propene selectivity increased with the prog­ was seen in the catalyst with a weight hourly space velocity of 0.3h− 1.
ress of the reaction at both WHSV values. Increasing propene selectiv­ This showed that the monochromatic structures were more preserved in
ities indicated that the cracking reaction of isobutane gained importance the experimental conditions where the weight hourly space velocity was

9
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 10. Selectivity values determined at different reactor temperatures (WHSV=0.3h− 1, catalyst containing 8% Cr by mass) (a) 550 ◦ C (b) 600 ◦ C.

0.3h− 1. The areas under the peaks at 380 nm was examined with the between CO2 and H2 adsorbed to the metal oxide catalyst structure [44].
Digimizer program. After the experiment, 5.7 times more mono­
CO2 + H2 ↔ CO + H2 O ΔH = 41.3kJ/mol (R8)
chromate was detected on the catalyst with a weight hourly space ve­
locity of 0.3h− 1. When the CO and CO2 amounts at the reactor exit were examined,
In the literature, it was stated that transformation of dichromates the high amount of CO2 (nCO2,0.5/nCO2,0.3 ≈ 10) were seen at the reactor
(R7) formed during the reaction into monochromates occured when exit in the study where the WHSV value was 0.5h− 1. It was thought that
water was present in the reaction medium [13]. the reverse water gas shift reaction could not occur due to the difficulty
of adsorbing CO2 and H2 to the surface at low retention times. Mono­
H2 O + Cr2 O2−7 ↔ 2CrO2−4 + 2H + (R7)
chromates that provided high activity and selectivity could not be pre­
When the gaseous components in the reaction medium were exam­ served due to the absence of water in the reaction medium at low
ined, it was seen that the hydrogenation reaction of carbon dioxide retention times.
(reverse water gas shift reaction) was highly probable for the formation After the reaction at 600 ◦ C, N2 adsorption/desorption analyzes of
of water. This reaction (R8) takes place with the heterogeneous reaction the catalysts were carried out. The pore size distribution curves of the

10
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 11. Isobutane conversion values determined at different weight hourly space velocities (T = 600 ◦ C, catalyst containing 8% Cr by mass).

Fig. 12. Isobutene selectivity values determined at different weight hourly space velocities (T = 600 ◦ C, catalyst containing 8% Cr by mass).

catalyst after the reaction are presented in Fig. 15. 36.4; 41.8; 50.32; 55.16; 6.,6 and 65.32 were indexed as (012), (104),
It can be seen from Fig. 15 that there was a mesopore distribution (110), (113), (024), (116), (214) and (300), respectively [45]. From
between 20 and 100 Å in both catalysts. It was seen that a wider pore Fig. 16, characteristic peaks of inactive α-Cr2O3 crystals were seen at
size distribution curve was formed in the catalyst after reaction with 2θ=36.4◦ , 41.8◦ . It was shown that the peak of α-Cr2O3 at 36.4◦ was
WHSV=0.5h− 1. After the reaction, it was observed that the average pore more intense in the catalyst after reaction with WHSV=0.3h− 1. Other
diameter of the catalysts was around 37◦ A. The surface area values of the chromium oxide types in the structure could not be detected because
catalysts after the reactions are given in Table 3. they were in very small crystal structure [35]. Characteristic peaks for
It was seen from Table 3 that while the surface area values were close α-alumina (JCPDS no.71–1123) were 25. 59 o (012); 35.14 o (104), 37,
in fresh catalyst and the catalyst after reaction with WHSV=0.5h− 1, it 78 o (110), 43.36 o (113), 52,55 o (024), 57.52 o (116), 59 o (211), 61.5 o
decreased by about 44% in the catalyst after reaction with (122), 67 o (124), 68 o (030), 77 o (119). In the catalyst, α-alumina peaks
WHSV=0.3h− 1 compared to fresh catalyst. The color observed in the were clearly observed at 2θ=37.78◦ , 43.36◦ and 67◦ [46]. The peak at
catalyst after reaction with WHSV=0.3h− 1 suggested that the carbon 2θ=25.1◦ in the catalyst after reaction with WHSV=0.3h− 1 was an in­
deposition was excessive. When the used catalyst in the experiment with dicator of carbon deposition in the structure. This peak is defined spe­
WHSV=0.3h− 1 was removed from the membrane reactor, black color cifically for carbon [47]. The XRD diffraction patterns appeared to
was observed throughout the catalyst. For the catalyst after reaction support interpretations regarding the color of the catalysts after reac­
with WHSV=0.5h− 1, on the other hand, it was determined that the tion. SEM photographs of the catalysts before and after the reaction are
catalysts coming out of the non-membrane region were black in color. shown in Fig. 17.
The black color was thought to be due to carbon deposition on the When Fig. 17 was examined, it was seen that there were CrOx
catalyst. XRD analyzes were carried out to examine the components in structures in the bright regions above the Al2O3 support in the catalysts
the catalyst structure after the reaction. The XRD diffraction patterns of after reactions. After the reaction, bright regions were observed more
the catalysts before and after the reaction are shown in Fig. 16 clearly in the catalyst after reaction with WHSV=0.5h− 1, while the
comparatively. bright regions were less clear in the catalyst after reaction with
It is known that in XRD analysis, it is possible to detect only α-Cr2O3 WHSV=0.3h− 1. After the reaction, it was seen that the carbon deposition
crystals (JCPDS no. 38–1479) from the chromium oxide forms found in in the catalyst after reaction with WHSV=0.3h− 1 closed the pores and
the structure of the catalysts. Major peaks at values of 2ϴ: 24.62; 33.8; chromium. The carbon peaks in the catalysts after the reaction were

11
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

1
Fig. 13. Selectivity values determined at different weight hourly space velocities (T = 600 ◦
C, catalyst containing 8% Cr by mass) (a)WHSV= 0.5h−
(b)WHSV=0.3h− 1.

examined by EDS analysis, and it was determined that the amount of in the experiment performed at WHSV=0.5h− 1 compared to at
carbon in the catalyst after reaction with WHSV=0.3h− 1 was approxi­ WHSV=0.3h− 1.
mately three times higher than the amount observed in the catalyst after As mentioned before, when the reaction product olefins (isobutene,
reaction with WHSV=0.5h− 1. The results of the EDS analysis were propene) were adsorped to the catalyst surface, their decomposition was
consistent with the results of the XRD analysis and the catalyst colors faster than alkanes. Rapid removal of hydrogen from the reaction me­
observed after the reaction. dium at 600 ◦ C increased the probability of decomposition reactions
It was shown that increasing the retention time in the reactor also (R4-R6). When WHSV=0.3h− 1, a high rate of coke formation was
increased the formation of C. At the same reactor temperature, no C observed on the catalyst surface due to the low amount of hydrogen in
formation was observed, especially in the membrane region, at a low the reaction medium. It has been shown that high hydrogen fluxes can
retention time (WHSV=0.5h− 1). The results of the study also showed negatively affect catalyst stability and coke formation in membrane
that the removal of hydrogen from the reaction medium prevented the reactor applications where dehydrogenation reactions are carried out,
formation of the isobutane hydrogenation side reaction (R3). Charac­ and an optimum flux value that provides high conversion and selectivity
terization studies showed that there was less C deposition when the values should be determined [39]. The presence of more hydrogen in the
weight hourly space velocity was 0.5h− 1. When methane selectivities reaction medium reduced the coke formation for WHSV=0.5h− 1.
were examined, relatively high methane selectivities were determined SEM photographs of fresh catalyst and the catalyst after reaction

12
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 14. DR..........-UV–vis analysis results of catalysts after reactions carried out at different weight hourly space velocities.

Fig. 15. Pore size distribution curves of catalysts after reactions carried out at different weight hourly space velocities (T = 600 ◦ C).

It was stated in the literature that fibrous carbon formation occured on

Table 3
metal particles [2]. No metal formation was observed in the catalyst
Single Point BET surface areas of catalysts after reactions carried out at different
structure before and after the reaction. It was stated that the carbon
weight hourly space velocities.
deposited on CrOx/alumina catalysts was commonly amorphous [48,
Catalyst Single Point BET surface area (m2/g)
49]. It was also shown in the literature that the coke formed inhibited
Before reaction 280 the cracking reactions by blocking the regions active for the cracking
After reaction (WHSV= 0.3h− 1) 122 reactions, thus increasing the selectivity [50].
After reaction (WHSV= 0.5h− 1) 247
When the results of the studies carried out at different WHSV values
were evaluated together, it was determined that the amount of carbon
with WHSV=0.3h− 1 were given in Fig. 17. When the two photographs formed at high retention times caused negative effects such as a decrease
were compared, it was seen that there was no significant structural in the surface area and closure of the pores. Despite these disadvantages,
change. No fibrous carbon formation was observed in SEM photographs. the active monochromate species being preserved in the catalyst struc­
ture and the form of carbon formed did not cause the expected rapid

13
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Fig. 16. XRD diffraction patterns of catalysts before and after reactions carried out at different weight hourly space velocities (C:).

Fig. 17. SEM photographs of catalysts (x5000) (a) before reaction (b) after reaction (WHSV= 0.3h− 1) (c) after reaction (WHSV= 0.5h− 1).

decreases in activity and selectivity in the study with high retention where
time. JH2: hydrogen flux (mol /m2.s)
PM: permeability (mol/m.s.Pa0.5)
PH2h: hydrogen partial pressure in the high pressure region (Pa)
3.3. Modeling studies
PH2l: hydrogen partial pressure in the low pressure region (Pa) x:
membrane thickness (m)
Model equations were derived for the membrane reactor. The as­
w = 0.5, the ideal behavior of the membrane was determined. PM
sumptions in modeling studies are listed below:
values at 873 K were determined as 7.332×10− 10mol/m.s.Pa0.5. Mem­
brane thickness was 5 × 10− 6 m [30].
• The reactor is operating at steady state.
• Plug flow conditions are available in the catalyst bed.
• The temperature variation in the radial and axial directions in the
• There is no pressure drop through the catalyst bed.
catalyst bed is negligible.
• Gas components behave as ideal gas.
• The reaction takes place only on the catalyst surface. The reaction
• Total pressure is constant.
rate expression is adopted in the form below [51].
• The membrane provides only separation and is permeable only to
hydrogen. ⎛ ( ) ⎞
• The transport of hydrogen across the membrane is according to the CB RTx10− 5 CC RTx10− 5
′ − 5
⎜ kC A RTx10 − K ⎟
following equation: − rA = ⎜
⎝ ( )( )0.5 ( )0.5 ⎟
⎠
1 + K ′ CB RTx10− 5 CC RTx10− 5 + KH2 CC RTx10− 5
PwH2h − PwH2l
JH2 = PM
x (5)

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A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

Eq. (5) was derived from possible dehydrogenation mechanisms with

use of the general principles of the Langmuir-Hinshelwood approach.
The effects of deactivation and the overemphasis of certain reaction
conditions were ruled out. The parameters were estimated with the
Kinfit program by minimizing the sum of squares of the residuals (SSR)
between the measured and calculated compositions of the product
stream. The kinetic model was combined with an integral plug-flow
reactor model, and the minimization was performed by the Levenberg-
Marquardt method. The temperature dependence of the reaction rate
constant was described with an Arrhenius equation. The temperature
550 ◦ C was used as Tmean. The reparametrization was done to reduce the
correlation between the parameters. The adsorption equilibrium con­
stants were assumed to be temperature-independent. The equilibrium
constant of the dehydrogenation reaction was calculated from the
thermodynamic data in the Flowbat program [51,52].
The coefficients of Eq. (5) are given in Table 4. where CA is the
concentration of isobutane, R is the universal gas constant, CB is the
concentration of isobutene, and CC is the concentration of hydrogen.
The model (the alkane adsorbs dissociatively on a Cr-O pair) was
tested for the measured dehydrogenation data, and the results of the
parameter estimation. The lowest sum of squares of the residuals(SSR)
value of 24 was obtained. For the model, which assumed adsorption as
the rate determining step, the value of the isobutene adsorption term Fig. 18. Differential volume element for which model equations are derived. j:
was near 0. Thus, the model could be simplified to Eq. (5) by omitting A, B, C A: isobutane B: isobutene C: hydrogen NCr =0 j: A, B.
this term from the model [52].
solution program for solving ordinary differential equations with initial-
• Mass transfer limitations between catalyst particles and intra-
value problems. The solution is based on Runge-Kutta and Dormann-
catalyst diffusion limitations can be neglected.
Prince.
• The feed contains pure isobutane.
The conversion values obtained from the model results and the
• No side reactions.
experimentally determined conversion values are given in Table 5.
Table 5 showed a good agreement between the experimental and the
The differential volume element for which the model equations were
modeling results at 600 ◦ C, WHSV=0.3h− 1. Although side reactions
derived is shown in Fig. 18.
were neglected, it can be said that the agreement was remarkable.
The material balances written for isobutane, isobutene and hydrogen
in the differential volume element are given below (A: isobutane, B:
4. Conclusions
isobutene, C: hydrogen);
dCA In the study, Al2O3 supported chromium-based catalysts were pre­
− ν0 + RA ∗ ρ(1 − ε) = 0 (6)
dz pared by impregnation technique. It is known that the presence of high
amount of monochromate in chromium-based catalysts positively af­
− ν0
dCB
+ RB ∗ ρ(1 − ε) = 0 (7) fects the reaction performance. The effects of catalyst preparation con­
dz ditions on the monochromate species in the structure of the catalysts
were investigated. The reaction studies were carried out in the mem­
dCc PM (RT)n 2r1 brane reactor with the catalyst containing the highest amount of mon­
− ν0 − (CcH2h )n + Rc ∗ ρ(1 − ε) = 0 (8)
dz r0 2 x ochromate. In the experiments where the effect of mixing time on
The void fraction was (Ɛ) = 0.4 and the catalyst density was 1 g/cm3. chromate species was investigated, the highest amount of mono­
The MATLAB R2011a/ODE45 program was used in the joint solution of chromate was observed in the catalyst prepared in 48 h mixing time. In
the obtained ordinary differential equations. ODE45 is the first-line studies investigating the effect of metal concentration on the distribu­
tion of chromate species, a decrease in the amount of monochromate
was observed in catalysts with a chromium concentration above 8% by
Table 4 mass. The effect of reactor temperature on isobutane conversion and
The coefficients of Eq. (5) [51]. selectivity values was investigated at 550◦ C and 600◦ C
⎡ ⎤ (WHSV=0.3h− 1). No significant difference was observed between the
(− E ( 1 1
))
mol
k = Amean exp
′
− ⎣ ⎦ conversion values at both reactor temperatures (around 90%). Isobutene
R T Tmean (kgcatalyst )(s)(bar)
[ ]
selectivity values were determined higher at 600◦ C. While the isobutane
mol conversion values were close to each other in the studies carried out at
Amean = 0.0596 ± 0.0037
(kgcatalyt )(s)(bar) different weight hourly space velocities, higher isobutene selectivity
[
kJ
]
values were determined in the study where the WHSV value was 0.3 h− 1.
E = 141 ± 3
mol High carbon formation was observed in the study where the WHSV value
Tmean = 550[0 C]=823[K]
[ ]
(− 122 kJ )
mol
K = 2.1x107 exp [bar] Table 5
RT
Isobutane conversions determined from modeling and experimental studies.
[ − 3]
K = 22.90 ± 7.25 bar 2 Model Experimental
′

KH2 = 7.56 ± 2.19[bar− 1 ] 600 C,WHSV=0.3h

◦ − 1
%80 %83
1
600 ◦ C,WHSV=0.5h− %54 %59

15
A.D. Erdali et al. Chemical Engineering and Processing - Process Intensification 175 (2022) 108904

was 0.3h− 1 (approximately 3 times more than in the study where the [12] M. Dogan, S. Cetinyokus, E. Kirci, Investigation of isobutane dehydrogenation on
CrOx/AC catalysts, J. Gazi Univ. Faculty Eng. Archit. 33 (2) (2017) 455–467,
WHSV value was 0.5h− 1). Despite the high carbon formation, the
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monochromates were more preserved in the catalyst structure after the [13] Z. Erol, S. Cetinyokus Kilicarslan, M. Dogan, Investigation of Isobutane
reaction. It was shown that the average pore diameter (37 Å) did not Dehydrogenation On CrOx/MCM-41 Catalyst, Maced. J. Chem. Chem. Eng. 39 (1)
change in the catalysts after the reaction, while the surface area value (2020) 109–118, https://doi.org/10.20450/mjcce.2020.1842.
[14] F. Gallucci, E. Fernandez, P. Corengia, M. Annaland, Recent advances on
decreased by 44% in the catalyst with the highest carbon deposition. In membranes and membrane reactor for hydrogen production, Chem. Eng. Sci. 92
all reaction studies performed in the membrane reactor system, it was (2013) 40–66, https://doi.org/10.1016/j.ces.2013.01.008.
stated that the cracking reaction of isobutane was an important side [15] M.R. Rahimpour, F. Samimi, A. Babapoor, T. Tohidian, S. Mohebi, Palladium
membranes applications in reaction systems for hydrogen separation and
reaction. The absence of methane at the reactor exit was explained by purification: a review, Chem. Eng. Process. 121 (2017) 24–49, https://doi.org/
the cracking of methane and the formation of carbon. The compatibility 10.1016/j.cep.2017.07.021.
of the modeling and experimental results at 600 ◦ C was shown. The [16] M. Nordio, J. Melendez, M.S. Annaland, D.A.P. Tanaka, M.L. Tanc, F. Galluc,
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