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Light alkane dehydrogenation to light olefin technologies: A comprehensive

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Article  in  Reviews in Chemical Engineering · August 2015

DOI: 10.1515/revce-2015-0012

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Zeeshan Nawaz*
Light alkane dehydrogenation to light olefin
technologies: a comprehensive review
DOI 10.1515/revce-2015-0012
Received April 7, 2015; accepted June 11, 2015
Abstract: The dehydrogenation of light alkanes, especially
propane and butane, is widely exploited for the large-
scale production of corresponding olefins. The industrial
application of the direct dehydrogenation of light alkanes
is limited due to reaction and thermodynamic constraints.
The dehydrogenation of light hydrocarbons involves the
breaking of two carbon–hydrogen bonds with the simul-
taneous formation of a hydrogen and carbon-carbon dou-
ble bond selectively. It may appear to be simple, but their
endothermic nature and selectivity control at higher tem-
perature is difficult. The same technologies with minor
changes in process and catalyst were used for the produc-
tion of both propane and isobutane dehydrogenation. The
economic analysis of the available technologies based on
the specific consumption of feedstock, operational ease,
and capital investment indicates an internal rate of return
~25%. The attractiveness of light alkane dehydrogenation
is largely dependent on the difference in feedstock and
the price of olefins produced. The available technologies
and how they manage reaction constraints at commer-
cial scale have been compared. The possible solution for
improvement is by focusing on catalyst improvements
and the unique design of reactors.
Keywords: dehydrogenation catalyst; dehydrogenation
technology; isobutane; light alkane; olefins; propane.
1 Introduction
The demand for light olefins has increased since 1930 and
is still increasing. This is mainly because of its reactiv-
ity and serving as a building block for the production of
polymers, commodities, and specialty chemicals for daily
*Corresponding author: Zeeshan Nawaz, Olefins and Aromatics,
SABIC Technology and Innovation, Saudi Basic Industries
Corporation (SABIC), P.O. Box 42503, Riyadh 11551, Kingdom of
Saudi Arabia, e-mail: engr.dr.zeeshan@gmail.com,
zeeshan@SABIC.com
Rev Chem Eng 2015; aop
use. The tremendous socioeconomic development in the
second half of the 20th century has been sustained mainly
because of the availability of energy through oil and gas.
The natural fossil resources mostly consist of saturated or
aromatic hydrocarbons and do not contain any amount
of olefins. Therefore, conventional and on-purpose tech-
nologies are in demand for the production of light olefins.
Propylene is second to ethylene in the global business but
is mostly produced as a byproduct in steam crackers and
fluid catalytic cracking (FCC). The demand for propylene
is continuously growing due to economic development
across the globe. Alternative technologies for the pro-
duction of propylene with novel, lower-cost on-purpose
propylene are becoming popular (e.g. propane dehydro-
genation). Similarly, isobutane dehydrogenation to isob-
utene, an intermediate olefin for the production of high
octane oxygenates [i.e. methyl tert-butyl ether (MTBE)], is
widely produced via direct dehydrogenation.
The dependency on on-purpose olefins technologies
such as direct dehydrogenation increased than on conven-
tional technologies such as FCC and steam cracking due
to the increasing demand for refinery fuel. Both propyl-
ene and isobutylene are produced via direct dehydrogena-
tion in various petrochemical complexes (Hamid and Ali
2004). Olefins can also be produced by on-purpose reac-
tions, for example, in propane dehydrogenation, methane
to propylene, methane to olefins, metathesis, and syngas-
to-olefins. It is a major industrial chemical intermediate
that serves as one of the building blocks for a series of
chemical and plastic products. It was one of the initial pro-
cesses employed on an industrial scale for the production
of petrochemical. Commercial propylene is a colorless,
low-boiling, flammable, and highly volatile gas. Propyl-
ene is traded commercially in three grades: polymer grade
(PG) 99.5% or higher purity, chemical grade (CG) 90–96%
purity, and refinery grade (RG) 50–70% purity. PG is used
for polypropylene and propylene oxide m ­ anufacture. PG
propylene contains minimal levels of impurities, such as
carbonyl sulfide, which can poison catalysts. The prin-
cipal chemical uses of propylene are in the manufacture
of polypropylene, acrylonitrile, oxo-alcohols, propyl-
ene oxide, butanal, cumene, and propene oligomers.
Other uses include acrylic acid derivatives and ethylene-­
propene rubbers. CG propylene is used extensively for
2      Z. Nawaz: Alkane dehydrogenation technologies
most chemical derivatives (e.g. oxo-alcohols and acryloni-
trile). Global propylene demand is dominated by polypro-
pylene production, which accounts for approximately two
thirds of total propylene demand. It can also be used in
some chemical syntheses (e.g. cumene or isopropanol).
The most significant market for RG propylene is the con-
version to PG or CG propylene for use in the production
of polypropylene, acrylonitrile, oxo-alcohols, and propyl-
ene oxide. The major propylene consumers include the
manufacturers of mechanical components, containers,
fibers, film acrylonitrile acrylic fibers, ABS polymer pro-
pylene oxide propylene glycol, antifreeze, polyurethane,
oxo-alcohol coatings, plasticizer cumene polycarbonates,
phenolic resin acrylic acid coatings, adhesives, and super-
absorbent polymers.
During World War II, high-octane aviation fuel was
widely produced by the Germans via the catalytic dehy-
drogenation of butanes followed by dimerization and
hydrogenation (Bhasin et  al. 2001). The introduction of
oxygenated compounds as gasoline additives caused the
MTBE production to boom. The direct dehydrogenation
of paraffins (non-oxidative dehydrogenation route) is
exploited for the large-scale production of light olefins,
particularly isobutylene for MTBE production. The widely
available normal butane can be isomerized to isobutane
and then dehydrogenated to corresponding isobutylene.
Later, MTBE is produced by the liquid phase reaction
of isobutylene and methanol on a strong acidic resin
(Brockwell et  al. 1991). Isobutane dehydrogenation is an
equilibrium-limited and highly endothermic reaction and
generally carried out at 555°C–649°C with platinum- or
chromium-based catalysts (Craig and Spence 1986, Atkins
and Evans 1995, Olah and Molnar 2003, Wei et al. 2008,
Nawaz et al. 2009a–g). Equilibrium conversion and reac-
tion rate increases with temperature and lower pressure.
At the same time, higher temperature propagates cracking
and coking reactions ultimately reduce the selectivity to
corresponding olefins. On the contrary, coking deactivates
the catalyst and periodically burnt in oxygen-diluents
mixture to regenerate the catalyst and generate heat. To
maintain world-class competitiveness, it is necessary to
run the plant with less operating cost and high specific
butane consumption and at the same time increase pro-
ductivity. To realize this level of performance, it is crucial
to simulate and optimize the entire process.
The dehydrogenation of light paraffins is one of the
most complex chemical processes to achieve in the indus-
trial scale, as the thermodynamic equilibrium limits the
maximum conversion per pass and, at the same time,
the reaction is highly endothermic and requires a large
amount of heat. Dehydrogenation reaction stoichiometry
demonstrates that high pressures adversely affect the
­reaction. In spite of this, light alkane dehydrogenation
reactions generally are slow (Miracca and Piovesan 1999).
The problem is not limited to this, as cracking, aromati-
zation, and other side reactions are thermodynamically
and kinetically favored at designated reaction condi-
tions. Therefore, the side cracking products, those were
not removed by low-temperature recovery system (LTRS),
are recycled to the reactor with unconverted alkane. The
selectivity of the desired product is critical and it will
improve the specific consumption of feedstock. Equilib-
rium conversion increases at lower pressures or by shifting
the equilibrium by diluting (Miracca and Piovesan 1999,
Nawaz et  al. 2010a–h). To make the commercial process
economically attractive, it is advisable to increase the
conversion per pass at the point of maximum selectivity
of the desired product, so that recycling and downstream
processing will be cheaper. Coke is formed and is an inevi-
table aspect of dehydrogenation reaction that gradually
reduces catalyst activity; hence, periodic regeneration
by burning the coke in oxygen, air, or steam is essen-
tial (Miracca and Piovesan 1999, Nawaz et  al. 2­ 009a–g,
2010a–h, 2011a,b, 2012, Jie et al. 2010).
The strategic constraints of dehydrogenation technol-
ogies and their robustness are based on catalyst produc-
tivity and the heat management philosophy of the reactor.
In overall economics, feedstock represents a large portion
of total production cost, whereas the economics for dehy-
drogenation process is largely dependent on the price dif-
ferential between alkane and the corresponding alkene.
A comprehensive review of light alkane dehydrogenation
technologies by defining the optimal synergy between
catalyst design and reactor engineering is discussed.
2 Chemistry of dehydrogenation
Direct dehydrogenation (i.e. non-oxidative route to
light olefins) is discussed here. The dehydrogenation of
propane and isobutane to corresponding olefin reactions
has an activation energy of ~121–143 kJ/mol and can be
presented as (Airaksinen et al. 2002):
C 3 H 8 ↔ C 3 H6 + H 2
i − C4 H 10 ↔ i − C4 H 8 + H 2
The reactions are reversible, prone to volume expan-
sion and highly endothermic; therefore, higher tempera-
tures and lower pressure (under vacuum) favor forward
reactions. The most important aspect of light alkane
dehydrogenation is the energy requirement for the

endothermic reaction. Heat input to the reactor is one of
the main technological challenges, which differentiates
commercial reactor designs and processes from each
other in addition to the catalyst (Sanfilippo and Rylander
2009, ­Sanfilippo 2011). On the contrary, high temperature
promotes side reactions and coke formation and deacti-
vates catalyst (Miracca and Piovesan 1999, Nawaz et  al.
­2009a–g, 2010a–h). Figure 1 shows the equilibrium con-
version of propane and isobutane at 1 bar and at a temper-
ature between 500°C and 600°C (Sattler et  al. 2014a–c).
Figure 1 also shows the equilibrium conversion of oxida-
tive dehydrogenation of propane, where the oxygen-to-
propane ratio is 0.1 (Uhde STAR Process 2011, Nawaz et al.
2013a,b, Chu et al. 2014). It is known that the conversion
of the said reaction increases with the decrease in pres-
sure (Uhde STAR Process 2011). At similar temperature
and pressure, the dehydrogenation equilibrium level rises
with an increase in the number of carbon atoms and the
degree of the paraffin branching (Uhde STAR Process
2011, Nawaz et al. 2013a,b, Chu et al. 2014):
C 2 C 3  n − C4 < i − C4 < n − C 5 < i − C 5
In general, the C–H bonds of paraffins and olefins are
more reactive than C–C bonds; therefore, a suitable cata-
lyst for paraffin dehydrogenation is the one that favors
C–H over C–C bond cleavage to avoid side reactions (Uhde
STAR Process 2011). The complicating factor is the product,
the olefins, which are more reactive than their correspond-
ing paraffins and can easily lead to unwanted side and
secondary reactions. The hydrogen adatoms and/or CxHy
adspecies are required for alkane hydrogenolysis to occur
as catalyzed by platinum sites (Nawaz et  al. 2013a,b).
Cracking also results in the cleavage of paraffins to form
smaller hydrocarbons and occurs at dehydrogenation
70
60
Conversion (%)
50
40
30
20
10
500 510 520 530 540 550 560
Temperature (°C)
Figure 1: Propane, oxy-propane, and isobutane equilibrium conver-
sion as a function of temperatures at 1 bar.
Z. Nawaz: Alkane dehydrogenation technologies      3
reaction conditions, as generally it requires higher tem-
perature and pressure. It is slightly different in the sense
that dehydrogenation reaction requires a catalyst with
Brønsted and Lewis acidity and proceeds via the forma-
tion of a carbocation intermediate (Song et al. 2006, Yang
et  al. 2011). Isomerization is the arrangement of atoms
within a molecule via carbocation intermediate formation
over Brønsted acid site (e.g. during isobutane dehydroge-
nation, isobutene may transform to 1- or 2-butene and may
further dehydrogenate to 1-3-butadiene; Song et al. 2006).
3 Dehydrogenation catalysts
for C3–C4
Catalysis is pervasive for direct dehydrogenation reac-
tion. Many materials have been explored as catalysts
for light alkane, but, in practice, only two main types
of formulations are used: noble metal-based and metal
oxide-based catalysts (e.g. platinum-based catalysts and
promoted chromium-based catalysts; Airaksinen et  al.
2002, S ­ anfilippo and Rylander 2009, Sanfilippo 2011). As
reaction conditions are severe, catalysts are designed to
limit irreversible deactivation due to sintering, volatiliza-
tion, hydrothermal regeneration with oxidants, and mor-
phological or phase transformations, therefore allowing
several years of expected active life (Airaksinen et al. 2002,
Sanfilippo and Rylander 2009, Sanfilippo 2011). Plati-
num is the only precious metal that has been extensively
studied. On the contrary, among metal oxides, CrOx is
most prominent, having commercial applications for light
alkane dehydrogenation. Promising results have been
achieved through the use of gallium, indium, vanadium,
zinc, and molybdenum oxides (Miracca and ­ Piovesan
1999, Airaksinen et  al. 2002, Nawaz et  al. 2­009a–g,
­2010a–h, Sanfilippo and Rylander 2009, Sanfilippo 2011,
Sattler et al. 2014a–c). The unavoidable formation of coke
on the catalyst surface results in the progressive reduction
of catalytic activity and requires periodic regeneration.
Therefore, each catalyst undergoes a cycle of exposure
to alternating atmospheres: reducing during reaction
and oxidizing during regeneration, because the redisper-
sion of active metal by certain catalysts is also employed.
A suitable catalyst is the one that allows high reaction
rates and higher olefin selectivity and has longer stability
(Airaksinen et al. 2002, Sattler et al. 2014a–c). The main
570 580 590 600 types of dehydrogenation catalysts reported in the patent
and scientific literature are as follows:
(a) Platinum-based supported catalyst with promoters
(and Group VIII metals),
4      Z. Nawaz: Alkane dehydrogenation technologies
(b) Chromium oxide-based supported catalyst with
promoters,
(c) Vanadium oxide-based catalysts,
(d) Molybdenum oxide-based catalysts,
(e) Gallium supported oxide or included in zeolites,
(f) Carbon-based catalysts, and
(g) Other formulations.
3.1 P
 t-Sn-based catalysts (and Group VIII
metals)
The inspiration came from bifunctional supported metal
catalyst utilization for catalytic reforming, where noble
metal with acidic support provides the active sites needed
for isomerization, hydrogenation, dehydrogenation,
cyclization, and hydrocracking reactions. In contrast, for
dehydrogenation catalysts, acidic function must be mini-
mized to avoid side reactions. Generally, all noble metals
of Group VIIIB are active in the hydrogenation and/or
dehydrogenation of alkanes. Platinum was established to
be superior in the activation of paraffinic C–H bonds and
low activity to C–C cleavage. Accordingly, it was commer-
cialized by Universal Oil Products (UOP) in Pacol process
in 1968 and later in Oleflex in the early 1970s. Owing to
platinum low activity for hydrogenolysis but at the same
time deactivation due to carbon deposits, extensive inves-
tigation has been done to reverse the relationship between
particle size and the rate of hydrogenolysis (i.e. coking;
Monzon et al. 2003, Spivey et al. 2004, Song et al. 2006,
Yang et al. 2011). It is believed that the two processes that
cause the deactivation of platinum-based dehydrogena-
tion catalysts are (i) side reactions that lead to the coverage
of the active sites with coke and (ii) the high temperature
in the regeneration process that triggers the agglomera-
tion or sintering (Miracca and Piovesan 1999, Airaksinen
et al. 2002, Nawaz et al. 2009a–g, Sanfilippo and Rylander
2009, Nawaz et  al. 2010a–h, 2011a,b, 2012, Sanfilippo
2011, Zhang et al. 2012, Sattler et al. 2014a–c). Therefore,
the strength of the platinum-support interaction is impor-
tant and depends on Pt–O–M bond strength (where M rep-
resents the cation in the support). However, platinum can
be redispersed by the addition of low amounts of oxygen
and chlorine at ~500°C, when the interaction between
the support and the PtOx and PtOxCly mobile surface com-
plexes is produced (Damyanova et al. 1997).
High surface area alumina is the classical support
for most of the catalysts, including platinum-based dehy-
drogenation catalysts. However, it is acidic. Therefore,
promoters are used to curb acidity. Another strategy is
to use more stable polymorphs of alumina, such as θ- or
α-alumina, as it has relatively less Brønsted acid sites
than γ-alumina and lower surface areas. In the last two
decades, environment-friendly, non-corrosive, shape-
selective, and hydrothermally stable, solid acid catalysts,
zeolites, and zeolite supports have become popular for
dehydrogenation applications. The zeolites have Brønsted
and/or Lewis acid sites and well-defined pore structures.
The well-known initiation step is the direct protonation of
alkane by Brønsted acid sites (Miracca and Piovesan 1999,
Nawaz et  al. 2009a–g, 2010a–h, 2011a,b, 2012, 2013a,b,
Vaezifar et al. 2011). It has been observed and experimen-
tally proven that zeolite acid sites are not sufficient for
light alkane protonation to make alkoxy species mecha-
nism (Miracca and Piovesan 1999, Nawaz et al. 2009a–g,
2010a–h, 2011a,b, 2012, 2013a,b). Another possibility for
initiating cracking and dehydrogenation is the presence
of Lewis acid sites of zeolites. This is somehow attributed
to hydride abstraction from alkanes and the generation
of carbenium ion-activated complexes. The initial mono-
molecular processes, carbenium ion complexes, are then
involved in bimolecular hydride transfer, agglomeration
reactions.
It is believed that the crystal structures and strength
of the active sites of zeolites differ considerably; hence,
the access to active sites varies. Pt-Sn-based catalysts
supported on amorphous materials and/or zeolites for
light alkane dehydrogenation have been discussed in
many studies (Sattler et al. 2014a–c). The selection of tin
as a promoter has been explained in terms of beneficial
geometric and/or electronic effects (Faro et  al. 2003a,b).
In geometric effects, the size of platinum ensembles
decreases. In Pt-Sn contact in a solid solution or an alloy,
tin fills up the 5d band of platinum that leads to decreased
hydrocarbon interaction with platinum, thus lowering
the contribution of hydrogenolysis and coke formation.
Tin also modifies the electronic density of platinum by
positive charge transfer from Sn+ species (Nawaz et  al.
2013a,b). The presence of tin also helps in the availability
of desired platinum sites for dehydrogenation at reaction
temperatures and retards the Pt-Sn alloy formation. These
interactions are discussed in various studies (Weckhuysen
and Wachs 1996, Miracca and Piovesan 1999, Airaksinen
et al. 2002, Nawaz et al. 2009a–g, 2010a–h, 2011a,b, 2012,
2013a,b). Tin also reduces the acidity of the supports and
stabilizes the surface area. Therefore, we can infer that
the dehydrogenation performance of Pt-Sn-based cata-
lysts depends on platinum, tin, and support interactions
(Miracca and Piovesan 1999, Airaksinen et al. 2002, Nawaz
et al. 2010a–h, 2011a,b, Zhang et al. 2012). The deactiva-
tion of platinum-based catalyst during propane dehydro-
genation is mainly due to the aggregation of platinum

particles and carbon deposition (Weckhuysen et al. 1998,
Faro et  al. 2003a,b). The presence of tin as promoters
facilitates the transfer of coke from active platinum sites
to support and stabilizes the catalytic activity for longer
durations. A numbers of other promoters, such as Na, Zn,
Ca, Cu, Mo, Ru, La, and Mg, have been studied, but their
role is reported to be controversial (Nawaz et al. 2011a,b).
In parallel to catalyst characterization, a lot of work has
been conducted on operating condition optimization for
dehydrogenation over platinum-based catalyst (Miracca
and Piovesan 1999, Nawaz et al. 2010a–h, Zangeneh et al.
2013). The characteristics of Pt-Sn-based catalysts have
been reported to be significant as listed below (Miracca
and Piovesan 1999, Airaksinen et  al. 2002, Nawaz et  al.
2009a–g, 2010a–h, 2011a,b):
–– Catalysts undergo a “double mechanism” aging
through coke fouling and sintering.
–– Catalyst can tolerate several percentages of coke
buildup, preserving enough catalytic activity and
allowing reaction time-on-stream of several hours
without regeneration.
–– The activity of catalyst is increased in the presence of
hydrogen, as it suppresses coking reactions.
–– The regeneration with oxygen/steam/air is possi-
ble. Moreover, platinum redistribution by chlorine
(through surface mobility of platinum-chloride inter-
action) reduces sintering.
3.2 Chromium-based catalysts
Chromium oxide-based catalysts for dehydrogenation
have been introduced by Frey and Huppke in the 1930s.
The popular formulations comprise chromium oxide. The
structure under different reaction conditions, the nature
of the active sites, the role of the support, the effect of
alkali metals, promoters, and the mechanism of the
dehydrogenation were studied (Airaksinen et  al. 2002).
Since the 1940s, chromium supported on alumina was
used for dehydrogenating butane to butenes and buta-
diene for various applications of commercially known
dehydrogenation. It is understood that the adsorption of
paraffin molecules takes place on Cr-O sites. A number of
surface species, including Cr6+, Cr5+, Cr3+, and Cr2+, have
been identified and their relative concentration seems
to be dependent on various factors, such as chromium
loading relative to the surface area, the calcinations treat-
ment, and the type of support. Generally, with weakly
bonded support, at lower chromium loading, isolated
CrO42- species predominate, whereas, at higher concentra-
tions, Cr-O-Cr species were prevalent due to the formation
Z. Nawaz: Alkane dehydrogenation technologies      5
of Cr2O3 crystallites. The recent spectroscopy evidence
discovered that surface Cr3+ species are produced at the
expense of Cr6+ species. Polychromate is more easily
reduced than monochromate, and a mixture of both Cr3+
and Cr2+ has been assumed as the active site for dehy-
drogenation reactions (Grunert et al. 1986, Cimino et al.
1991, Weckhuysen et al. 2000). Cr6+ or Cr5+ has not been
observed to be active for the dehydrogenation reaction,
although the reduction of these species by hydrogen
or alkane feed generates the precursor for active Cr3+
site formation (Bruckner et al. 1999, Nijhuis et al. 2004,
Mimura et  al. 2006). ­Furthermore, isolated and unsatu-
rated Cr3+ species, with two coordinative vacancies, are
formed on CrOx/Al2O3 catalysts during alkane dehydro-
genation. These fully coordinated Cr3+ species are highly
stable, whereas unsaturated Cr3+ species attempts to sta-
bilize bulk Cr3+ ions as octahedral environment and inac-
tive by adsorbing gaseous alkane molecules. Therefore,
optimum chromium loading is a critical factor in catalyst
design, as it holds a linear relationship below monolayer
coverage. Three different types of Cr3+ ions have been
detected through spectroscopy: (i) Cr3+ species formed by
the reduction of surface Cr6+/Cr5+ ions, (ii) isolated centers
of Cr3+ ions stabilized by the alumina surface, and (iii)
small amorphous Cr3+ clusters (invisible in X-ray diffrac-
tion; Weckhuysen and Schoonheydt 1999, Shi et al. 2008,
Fang et  al. 2015). Selectivity has been found insensitive
to chromium loading; during the induction period, highly
oxidized chromium species are being reduced to active
chromium species with lower oxidation states and low
selectivity. Later, the high selectivity of approximately
90% can be reached at a conversion of 55% (Weckhuysen
and Schoonheydt 1999, Shi et al. 2008, Fang et al. 2015).
Many researchers proposed the addition of CO2 as a
mild oxidant to improve the activity of chromium dehy-
drogenation catalysts; it removes the evolved hydrogen
through reverse water gas shift reaction without affect-
ing Cr3+ active sites, which effectively shifts the equilib-
rium toward product formation (Puurunen et  al. 2001,
­Michorczyk et al. 2010). In addition, high activity is also
dependent on the operating conditions and directly
proportional to reaction temperature and partial pres-
sure, whereas conversion is inversely proportional to
space velocity. Similar to platinum-based catalysts, CrOx
catalysts lose their activity faster due to the deposition
of coke and are deactivated in approximately 15–20 min
and required regeneration. Alumina supported CrOx
catalyst dissolution of active sites was due to the sin-
tering of alumina that may cause the entrapment of
the chromium species and the loss of alumina surface
area that reduces the ability to stabilize Cr6+ species
6      Z. Nawaz: Alkane dehydrogenation technologies
formed during the regeneration step (Wachowski et  al.
1994). Particularly, on γ-alumina support, entrapment
process is dominant, whereas, at elevated tempera-
tures, γ-alumina undergoes a thermodynamically driven
transformation to θ- or even α-alumina, and then it
considerably loses surface area. The said process can
be restrained by doping the support with silica, zirco-
nia, magnesia, or lanthana (Rossignol and Kappen-
stein 2001, Michorczyk et al. 2011). Cations having ionic
radius larger than Al3+, capable of affording high dopant
dispersion and tend not to dissolve in Al2O3, are effective
in preventing the formation of α-alumina. The oxidation
of Cr3+ to Cr6+ during regeneration helps in the redis-
persion of chromia crystallites. Alumina is by far the
most common support for a variety of chromium-based
catalysts: prepared by incipient wetness impregnation
of alumina with CrO3 or Cr(NO3)3 solutions, coprecipi-
tation of Al(OH)3 and Cr(OH)3 from Al3+ and Cr3+ solu-
tions, chromium compound deposited on alumina by
chemical vapor deposition also known as “atomic layer
deposition,” mesoporous CrOx/Al2O3 catalyst by using a
chromium-containing metal-organic framework filled
with an alumina precursor and subsequently combus-
ting the organic material, and the decomposition of
complexes including both alumina and chromium. All
these methods are followed by a calcinations step at
approximately 600°C. Thus, the nature of the support is
important not only for the mechanical properties of the
catalyst but also because of metal-support interaction.
The coinjection of hydrogen was also investigated for
chromium-based commercial catalysts for reducing the
deactivation rate (Nawaz et al. 2014).
The use of zirconia as an alternative support has been
investigated due to its low surface acidity and resistant
toward sintering (Fujdala and Tilly 2003). Zirconia as
support prevents the formation of Cr-Al mixed oxides but
deactivate faster. Fujdala and Tilley have reported the use
of a cothermolysis method involving several thermolytic
molecular precursors to produce a Cr/Si/Zr/O catalyst
capable of dehydrogenation at lower temperature (Fujdala
and Tilly 2003, Ma et al. 2012). A weak metal interaction
is observed with TiO2 support; a relatively high surface
area to stabilize Cr6+ sites is required for silica as support
­(Martyanov and Sayari 2008, Zhao et  al. 2013). Alkali
metals, such as K, Ca, Na, B, Rb, and Cs, are known to
promote chromium-based dehydrogenation catalysts.
These were attributed to stabilizing the structure of the
support, reducing surface acidity, and/or increasing active
chromium sites and dispersion (Sanfilippo and Miracca
2006). Some important features of chromium-based cata-
lyst are the following (Chaar et al. 1987):
–– Cr2O3 is thermodynamically stable even in excess O2
(regeneration environment).
–– Different chromium species form on fresh catalyst on
alumina-grafted Cr6+, soluble Cr6+, dispersed Cr3+, and
crystalline Cr2O3.
–– Cr6+ species are reduced completely during reduction.
–– Both Cr3+ and Cr2+, coordinative unsaturated Cr2+, play
a role in the catalytic activity.
–– The permanent deactivation of chromia-alumina
catalysts involves the formation of α-Cr2O3-4Al2O3 via
solid-state reaction.
Kilicarslan et  al. (2013) tried to improve chromium-
based catalyst performance using MCM-41 as support
and reported that the deactivation rate for isobutane
dehydrogenation is reduced. Characterization results
further demonstrate that Cr6+ percentage concentration
increased and chromium was well dispersed over the
MCM-41 ­(Kilicarslan et al. 2013). Pakhomova et al. (2012)
developed microspherical chromium oxide/alumina
catalyst (KDM) having superior performance and tested
the catalyst at fixed-bed reactor in laboratory scale and
in fluidized bed commercial-scale reactor for isobutane
dehydrogenation.
3.3 Vanadium oxide-based catalysts
Vanadium oxides are generally known for hydrocarbon
oxidation reactions and at the same time are exten-
sively investigated for oxidative dehydrogenation using
vanadium-magnesium mixed oxides (Russell and Stokes
1946, Wachs and Weckhuysen 1997, Carrero et al. 2014).
Monolayer coverage isolated vanadium species (crys-
tallites) are formed, such as the combination of V-O-
support (mixed oxides with Al, Zr, Ti, or Mg), V-O-V, or
VO, whereas hydroxyl groups (anchoring sites) should
present on the surface of the support to obtain a well-­
dispersed catalyst. Researches claim that vanadium
species bonded directly with γ/θ-alumina support are
active sites for dehydrogenation, whereas isolated active
site feed adsorption leads toward deactivation due to
coke formation. It is observed that vanadium oxide reduc-
tion with H2, CO, and CH4 never reaches completion, and
oxide species, including V3+, V4+, and V5+, remain present
on the catalyst surface. In generalized form, the nature
of the VxOy species and contribution from the electronic
structure of the support is the redox potential of the
active sites (Carrero et al. 2014). ­Al-Ghamdi (2013) inves-
tigated oxygen-free propane oxidative dehydrogena-
tion over vanadium oxide catalysts at 475°C–550°C and

disclosed promising results and proposed the said cata-
lyst for fluidized bed reactor (FBR).
3.4 Molybdenum oxide-based catalysts
Molybdenum oxide-based catalysts were also frequently
tested for hydrocarbon conversion reactions and first
reported for the dehydrocyclization of n-heptane in 1946
(Harlin et al. 1999). MoOx has been investigated for both
oxidative and non-oxidative dehydrogenation of alkanes.
The chemistry of molybdenum oxide is similar to vanadium
oxide, as it is also present in MoOx monomers, polymers,
or MoO3 crystallites. In the fresh catalyst, molybdenum is
present as Mo6+, and MoO3 is reduced during reaction to
active species Mo4+ and Mo5+ (Nesterenko et al. 2003). The
active material, molybdenum oxycarbide (MoOxCy), forms
on unsupported molybdenum oxide during butane dehy-
drogenation and demonstrates superior performance over
silica supports. Mixed metal oxide formation Al2(MoO4)3
crystallites leads to permanent deactivation and is pre-
vented by adding magnesium oxide. Overall, molyb-
denum-based catalysts deactivate and sintered rapidly
compared to other dehydrogenation catalysts.
Jibril et al. (2003) studied the oxidative dehydrogena-
tion of propane on alumina supported chromium-molyb-
denum oxide catalysts and investigated the reducibility
and changes of the nature of the lattice oxygen with chang-
ing molybdenum content in the catalysts and their effect
on olefin selectivities. The study also discussed the prom-
ising results on alkali metals (Li, K, and Cs) doping with
10 wt% Cr0.8Mo0.2 (alkali/CrMo weight ratio of 0–0.175;
Jibril et  al. 2003). Suppia (2012) investigated the change
of molybdenum oxide (supramolecular phase Mo36O112
and hexagonal phase h-MoO3) properties during oxidative
dehydrogenation. For MoOx, protonation phase encour-
ages the growth of the catalytic structure (Mo7O24) acting
as a nucleus creating the polyoxomolybdates having bulk
structural corner sharing pentagonal channels, whereas,
for MoVOx-based catalyst, amorphous phase was observed
having highly crystalline hexagonal phase (MoV2O8) and
tetragonal phase [(MoV)5O14] (Suppia 2012). Many dis-
tinct compositions, such as MgO-V2O5, MgO-MoO3, MgO-
V2O5-MoO3, and V2O5-MoO3, were prepared using sol-gel
chemistry, and an increase in both ODH conversion and
selectivity with molybdenum substitution on vanadium
sites was also observed (Pless et  al. 2004). They further
noticed that the vanadates were more active than the
molybdates at lower temperatures; however, the molyb-
dates exhibited higher selectivities at similar conversions
(Pless et al. 2004).
Z. Nawaz: Alkane dehydrogenation technologies      7
3.5 Gallium supported oxide
The dehydrogenation activity of supported gallium oxide
was reported in the late 1980s, and the exact nature of the
active sites is under debate. One of the explanations of
active site is weak Lewis acid sites formed by polymorphs
β-Ga2O3 (monoclinic structure, in which gallium atoms are
equally distributed between tetrahedral and octahedral
configurations; Liu et  al. 2008). Heterolytic dissociation
occurs where H-adsorbs on a Ga+ Lewis acid site and C4H9+
on neighboring oxygen (Xu et al. 2006). Xu et al. reported
GaO3/H-ZSM-5 catalyst dehydrogenation activity on both
Lewis and Brønsted acid sites (Xu et  al. 2007, Rodríguez
et  al. 2010). The density functional theory studies by
Liu et al. regarding propane dehydrogenation over Ga2O3
demonstrates that 100 surface activate the C–H bond by
abstracting a hydrogen and second hydroxyl group formed
via β-hydrogen elimination. The reduction of Ga2O3 is con-
troversial, as it has been reported that the reduction can be
promoted by the presence of easily reduced metals, such
as platinum and palladium, which can assist the reduc-
tion of Ga3+ to Ga+ and Ga0 at lower temperatures (Butt
et al. 1999). It is important to note that Ga2O is gaseous and
metallic gallium is liquid at approximately 500°C (Li et al.
2007). A number of studies have shown that the addition
of CO2 and water cofeeding enhances the olefin yield due
to reverse water-gas shift reaction (Shimada et  al. 1998,
Shen et  al. 2009). Different carriers have been also tried
for use in gallium oxide-based dehydrogenation catalysts
such as ZrO2, Al2O3, TiO2, SiO2, and MgO.
The dehydrogenation of propane in the presence of CO2
was investigated over ITQ-2 and MCM-22 supported gallium
oxide, and its performance is compared with zeolite sup-
ported catalysts and claimed higher selectivity to propyl-
ene and better stability (propylene yield of ~15%) due to
more open pore structures and weak strength of Brønsted
acid sites (Zheng et al. 2005, Wang et al. 2012). Alcantara-
Rodriguez et  al. studied mixed gallium/chromium oxide
pillared α-zirconium phosphate materials using a colloi-
dal suspension of the phosphate previously swelled with
vapors of n-propylamine for propane dehydrogenation
under oxidative and non-oxidative conditions and found
that the catalyst is more suitable in oxidative environment
(Alcantara-Rodriguez et al. 1999). The dehydrogenation of
ethane and propane using a platinum catalyst on a novel
Mg(Ga)(Al)O mixed oxide support was investigated, and
it was found that performance is strongly dependent on
gallium content in the support, optimum hydrogen addi-
tion, and coke suppression (Siddiqi et  al. 2010, Sattler
et al. 2014a–c). Platinum-promoted Ga/Al2O3 catalyst con-
sists of 1000 ppm Pt, 3 wt% Ga, and 0.25 wt% K supported
8      Z. Nawaz: Alkane dehydrogenation technologies
on alumina; a bifunctional active phase, in which coordi-
nately unsaturated Ga3+ species are active species and plat-
inum is a promoter, was presented (Sattler et al. 2014a–c).
The samples with varying platinum and gallium contents
were prepared and tested, and a stable promising perfor-
mance is noted with propane conversion ~32 wt% and pro-
pylene selectivity ~93 wt% in a long-term stability test of
approximately few weeks (Sattler et al. 2014a–c).
3.6 Carbon-based catalysts
Recently, carbon has been tested as support in various
catalytic applications because of its high surface area,
low cost, lightweight, and environment-friendly nature
(Zhang et  al. 2008). Carbon-based catalysts remain acti-
vate despite complete coke encapsulation and high tem-
perature. Accordingly, carbon nanotubes proved to be
catalytically active as radicals formed on the surface of
coke facilitate reaction. Researchers reported high selec-
tivity toward olefins ~85% in the oxidative dehydroge-
nation of light alkanes using nitrogen-doped carbon
nanotubes (Neylon et al. 1999). Neylon et al. studied the
activity of supported early transition metal (of groups 5
and 6, except niobium) nitrides and carbides for butane
dehydrogenation and obtained promising results com-
parative to platinum-based catalysts (Halasz et al. 1996).
Metal-free ordered mesoporous carbon catalyst was pre-
pared for direct dehydrogenation of propane to propylene,
demonstrating high activity, stability, and selectivity, in
comparison with nanostructured carbons (Liu et al. 2011).
The large surface area and the uniform pore size of mes-
oporous carbon were found useful for trapping and con-
verting propane (Liu et al. 2011). Pedersen (2013) studied
carbon supported metal (platinum/carbon) catalysts for
propane dehydrogenation; using a polyol process, the
catalyst was successfully prepared using carbon black,
graphite, and a conical platelet carbon nanofibers as
supports.
3.7 Other formulations
Despite the excellent performance of platinum and CrOx
catalysts in light alkane dehydrogenation to olefins, a
number of issues, including catalyst poisoning, high cost
of platinum, and environmental concerns associated with
chromium, have encouraged to search for alternatives.
Indium has similar catalytic properties to that of gallium
and is found similarly active for light alkane dehydrogena-
tion (Chen et al. 2011). Chen et al. tried to mix In2O3 with
other metal oxides for propane dehydrogenation (20%
In2O3 and 80% Al2O3) and obtained the highest propyl-
ene yield. Slower reduction was noticed, and Al2O3 and
ZrO2 were found suitable supports than SiO2 (Wenner and
Dybal 1948).
Supported iron oxides have been known for ethyl
benzene dehydrogenation since 1946. In late the 1990s,
its use was demonstrated for 1-butene dehydrogenation to
1–3 butadiene and Fe3+ (Stobbe et al. 1991, 1992, Boot et al.
1996, Yun and Lobo 2014). It is further observed that potas-
sium enhances catalytic activity and stabilizes the active
phase by forming KFeO2, which donates electrons to the
active iron species and prevents their reduction. Recently,
an active dehydrogenation catalyst was reported by incor-
porating Fe ions in the framework of ZSM-5 zeolites. The
activity was presumed because of the redox properties of
these sites (Fe2+ and Fe3+ redox cycle; Guisnet et al. 1992).
The conversion of light alkanes to aromatics over
zinc supported on H-ZSM-5 zeolites, where isolated Zn2+
species with tetrahedral orientation were active sites,
has received considerable attention (Eastman 1983, Mole
et  al. 1985, Wang et  al. 1993, Biscardi and Iglesia 1996,
Al-mutairi et  al. 2012). These stable species resided in
the cation exchange sites of the zeolite, where Al-bound
oxygen performs C–H cleavage and forms an Al–OH group
similar to other metals. Chen et al. investigated zinc titan-
ate and concluded that cubic Zn2TiO3 is an active species,
whereas others reported for silica support; Zn2+ Lewis acid
sites located on a trimembered siloxane ring are active
for alkane dehydrogenation (Chen et al. 1996, Airaksinen
2005, Chweitzer et al. 2014).
4 Dehydrogenation technologies
The focus of the research has been to find a method to
supply sufficient amounts of heat knowing the thermo-
dynamic limitations of dehydrogenation reaction yet to
manage the catalyst regeneration cycles. Different licen-
sors commercialized their work to deal with light alkane
dehydrogenation reactions and operated the reactor at
approximately ±50°C to the desired reaction tempera-
ture. The integration of such concepts with the choice of
catalyst is the basis for the industrial dehydrogenation
technologies developed. About eight known catalytic
dehydrogenation technologies and different heat import
approaches were compared and shown in Table  1 (Frey
and Huppke 1937, Burwell et al. 1960, ­Hornaday and Ferrell
1961, ­Al-Mutaz 1987, lmai et  al. 1989, Vora et  al. 1989,
Pujado and Vora 1990, Dunn et al. 1992, Sanfilippo 1993,
 Z. Nawaz: Alkane dehydrogenation technologies      9

Table 1: Industrially known dehydrogenation technologies.

Technology   CATOFIN   Oleflex   Uhde STAR   FBD   PDH   FLOTU/   SABIC

name process Tsinghua

Licensor/   CB&I-ABB   UOP LLC   Krupp-Uhde   Yarsintez-   Linde-BASF-Statoil   Tsinghua   SABIC

developer Lummus (Honeywell) Snamprogetti (Sintef) University
Reactor   Adiabatic fixed   Adiabatic   DH+ODH-   Fluidized bed   Isothermal fixed   Bimodal   Adiabatic fixed
bed moving bed adiabatic bed fluidized bed bed and FBR
Operation   Cyclic   Continuous   Cyclic   Continuous   Cyclic   Continuous   Cyclic
Feed   C3–C4   C3–C4   C3–C4   C3–C4   C3–C4   C3–C4   C3
Catalyst   CrOx/Al2O3 with   Pt-Sn/Al2O3   Pt-Sn/   CrOx/Al2O3   Initially Cr-based   Pt-Sn/SAPO-34   Pt-Sn/K/
alkaline promoter with alkaline ZnAl2O3/ with alkaline and now Pt SAPO-34
(Süd-Chemie) promoter CaAl2O3 promoter nanoparticle/
hydrotalcite Mg(Al)
O; Pt-Sn/ZrO2
Catalyst life   2–3 years   1–3 years   –   –   –   –   –
Heat import   From catalyst   Interstage   Catalyst tubes   From catalyst   Reactor heating   From secondary   (a) Tubes are
regeneration heating are placed in regeneration catalyst placed in
furnace section furnace and (b)
integrated FBR
with internal
regenerator
T (°C)   565–649   550–620   DH: 550–590,   535–590   ~590   570–610   560–600
ODH: ~600
P (bar)   0.3–0.5   2–3   5–6   0.5–1.5   ~1   0.5–1.5   0.1–6
Cycle time   15–30 min   –   8h   –   9h   –   15–30 min
Conversion (%)  C3: 48–65,   C3: ~25,   C3: ~40   C3: ~40,   C3: ~30   C3: 45–63,   C3: 48–65,
C4: 55–68 C4: ~35 C4: ~50 C4: 54–66 C4: 55–68
Selectivity (%)   C3: 80–88,   C3: 89–91,   C3: ~89   C3: ~89,   C3: ~90   C3: 89–91,   C3: 88–93,
C4: 89–93 C4: 91–93 C4: ~91 C4: 81–86 C4: 80–85
Development   Commercial   Commercial   Commercial   Commercial   Pilot plant   Pilot plant   –
stage
  Figure 2   Figure 3   Figure 4   Figure 5   Figure 6   Figure 7   Figure 8

DH, direct dehydrogenation; ODH, oxidative dehydrogenation.

Trifiro and Cavani 1993, A ­ l-Ghamdi et al. 1994, Atkins and
Evans 1995, Z ­ immermann and Verluis 1995, Ercan and
Gartside 1996, Iezzi and B ­ artolini 1997, L
­ uckenbach et al.
1997, Sanfilippo et  al. 1998, 2006, Miracca and Piovesan
1999, Scott 1999, Weckhuysen and Schoonheydt 1999,
Jensen et  al. 2000, Rokicki et  al. 2001, UOP 2001, 2004,
2013, Chaiyavech 2002, Tullo 2003, Gregor and Wei 2004,
Nijhuis et  al. 2004, Schindler et  al. 2004, Airaksinen
2005, CATOFIN 2005, 2007, 2013, Fridman and Urbancic
2005, Ghandhi et  al. 2005, Kallo et  al. 2005, S ­ anfilippo
and Miracca 2005, Urbancic et  al. 2005, CRI/SRL 2007,
Setoyama 2007, Caspary et  al. 2008, Fridman and
Romaine-Schmid 2009, Wei et al. 2009, Beesley and Wipp
2010, Miracca and Piovesan 1999, Nawaz et al. 2010a–h,
2011a,b, 2012, 2013a,b, 2014, Fridman and Urbancic 2011,
Oviol et al. 2012, Uhde STAR Process 2012, 2013, Chu et al.
2013, Honeywell 2013, Sattler 2014, Sattler et al. 2014a–c,
CCR Platforming and Oleflex 2015). Because the choice of
technology is usually based on heat supply options and
catalytic cycles, it is worth to discuss the following:
(a) Direct heating of the reacting mixture
–– Tubes in fired heater/furnaces
–– Adiabatic reactors in series with interstage heating
(b) Indirect heating by reactants/feed/catalyst
–– Batch-wise heating by reaction and heating steps
–– Circulating the catalyst itself and heating it in
another piece of equipment (e.g. regenerator)
(c) Removal of coke from catalyst by air or oxygen or steam
–– Alternating hydrocarbon feed to regeneration
atmospheres in the same reactor (several reactors
in parallel are required)
–– Circulating the catalyst between different vessels
(reactor or reactors and a regenerator).
The first butane dehydrogenation plant was designed by
UOP (USA) and ICI (England) in 1940. Soon after, other
companies, such as Phillips Petroleum, Houdry, Shell,
Gulf, and Dow, built similar products for dehydroge-
nation (Miracca and Piovesan 1999, Nawaz et  al. 2010
a–h, 2013a,b). Phillips Petroleum built a multitubular
10      Z. Nawaz: Alkane dehydrogenation technologies
dehydrogenation reactor in 1943, with an oxide hydro-
genation approach. Houdry designed dehydrogenation
process for butane with pressure less than atmospheric
conditions and higher conversions rates (Waddams
1980, Craig and Spence 1986, Dunn et al. 1992). Later, the
Petro-Tex Chemical Corporation, with the name Oxo-D,
commercialized this process. A variety of light olefins
were produced by thermal and catalytic cracking in
bulk quantity as byproduct, forcing to shutdown direct
olefin production in the 1970s. In the late 1980s, Eugene
Houdry extended the application of chromia-alumina
catalysts for the dehydrogenation of propane and isobu-
tene; they renamed the process CATOFIN, and approxi-
mately 10 units were commercialized (Dunn et al. 1992).
Out of these, two processes were particularly designed
for propane dehydrogenation to propylene, of approxi-
mately 250,000 MTA propylene capacities. The CATOFIN
technology used an adiabatic fixed-bed reactor at 570°C–
630°C and 0.5 bar, reported at 40–65% conversion. The
CATOFIN technology is currently owned by Clariant (for-
merly Süd-Chemie, as Süd-Chemie is merged in Clariant)
and license by ABB Lummus. Phillips Petroleum’s STAR
Krupp-Uhde (Steam Active Reforming) Process is based
on a fixed-bed fired-tube reactor, operating at a positive
super atmospheric pressure and isothermal temperature
conditions (Sanfilippo et al. 1998).
During the 1990s, a fluidized bed isobutane dehydro-
genation unit of approximately 450,000 MTA isobutylene
was commercialized by Snamprogetti in SDAF, Jubail,
Saudi Arabia, based on Yarsintez (Russian) technology
(Iezzi and Bartolini 1997, Luckenbach et  al. 1997, Setoy-
ama 2007). UOP commercialized a typical radial-flow adi-
abatic fixed-bed (or slowly moving bed) reactor design
using modified platinum-alumina catalysts for alkane
dehydrogenation, but the performance is unsatisfactory
due to number of reasons. BASF and Statoil also built
pilot plants for propane dehydrogenation named Linde
and Sintef, respectively. Recently, Mitsubishi Chemical
of Japan claimed a novel process for the oxidative dehy-
drogenation of alkane by using a fixed-bed reactor, but no
information was available through open resources (Scott
1999, CATOFIN 2013).
The product workup in the downstream sections for
all direct dehydrogenation technologies is quite similar.
Therefore, an effective design of the reaction system based
on optimum temperature profile for the reactor is most
important. It may be observed that the process is quite
energy intensive due to the endothermic nature of reac-
tion (Miracca and Piovesan 1999, Nawaz et al. 2010a–h).
The technical aspects of known dehydrogenation technol-
ogies are discussed in the following sections.
4.1 CATOFIN dehydrogenation technology
After changing few hands, now the CATOFIN technology
is licensed by CB&I-ABB Lummus and catalyst is sup-
plied by Clariant. Gas-phase reaction is carried out at
~560°C–610°C, in alternating cycles to achieve a continu-
ous operation, in three to eight parallel adiabatic reac-
tors (Dunn et al. 1992, Trifiro and Cavani 1993, Ercan and
Gartside 1996, Scott 1999, Bhasin et al. 2001, Tullo 2003,
Nijhuis et al. 2004, CRI/SRL 2007, CATOFIN 2013). In the
CATOFIN reactor, so-called “pseudo-steady-state” tem-
perature profiles were established under vacuum (0.3–
0.5 bar; ­Hornaday and Ferrell 1961, Al-Mutaz 1987, Rokicki
et  al. 2001, Urbancic et  al. 2005, Fridman et  al. 2009,
2011, Beesley and Wipp 2010). The process is relatively
complex, operating under quite harsh conditions, espe-
cially due to cyclic nature. The isobutane coming from
butamer unit (isomerization unit) is feed to the dehydro-
genation unit. The catalyst bed is covered with inert balls,
so that it can sustain in feed inlet thrust and distributed.
The diluted catalyst bed with inert solid particles provides
an energy reservoir without affecting reaction engineer-
ing constraints and pressure drop. Each reactor alter-
nates between dehydrogenation, purging, regeneration,
reduction, and evacuation steps, and the total cycle time
is between 15 and 30 min, so that the overall processes
work continuously. Therefore, at a certain time, a certain
number of reactors shall be performing dehydrogenation
reactions, whereas the other reactors are being regener-
ated or purged (Ercan and Gartside 1996). The catalyst bed
is heated by the regeneration mixture (air and methane),
and by the burning of coke, a part of heat is provided
by the preheated feed. The dehydrogenation reaction
time depends on the heat content of the system, which
decreases rapidly due to the endothermic dehydrogena-
tion reaction.
To achieve a certain level of catalyst bed temperature
at the middle and end of runs, fuel gas is added to the
reactor during the regeneration step. The temperature pro-
files of the reactors are complex due to the alternating reac-
tion-regeneration and other steps, decreasing temperature
during the reaction with time-on-stream and increasing
during regeneration. The CATOFIN process flow diagram
is shown in Figure 2. It comprises catalytic reactor section,
compressor section, and product recovery section (where
the product recovery at LTRS is achieved) and depro-
panizer (Dunn et  al. 1992, Trifiro and Cavani 1993, Ercan
and Gartside 1996, Scott 1999, Bhasin et  al. 2001, Tullo
2003, Nijhuis et al. 2004, CRI/SRL 2007, CATOFIN 2013).
Feed is preheated in charge heater and then the reac-
tion takes place in five fixed-bed reactors that operate on a

Figure 2: CATOFIN isobutane dehydrogenation process flow diagram.
cyclic basis. For the process with five reactors as shown in
Figure 2 at one time, two reactors are on dehydrogenation
reaction. At a certain time, bed temperature and catalytic
activity are not sufficient to sustain commercially required
conversion, which defines the end of reaction cycle
­(Al-Mutaz 1987, Fridman et  al. 2009). Over an extended
time, the catalyst ages and the activity decreases. This
affects the yield from the reactors; therefore, operating
process conditions are gradually adjusted to maintain pro-
duction with time. After the dehydrogenation step, said
reactors are purged with steam to remove all hydrocarbons
and then regenerated with air at 600°C–700°C. This step
is followed by evacuation and reduction with hydrogen,
and then again, dehydrogenation reaction begins. A cyclic
timing device actuated hydraulically to control the process
is used. The system is suitably interlocked to ensure safe
operation and gas-gas exchanger cools product isobutyl-
ene. Pressure drop across the bed defines the end-of-run
at ~0.3 kg/cm2 abs. The products are compressed in mul-
tistage compressor for the separation of byproducts, and
this separation is further enhanced by LTRS. In the com-
pressor section, the reactor effluent gas pressure is raised
from ~0.3 to ~12 kg/cm2 abs at ~40°C. Recirculation lines
are provided from each discharge to the suction of each
stage to prevent surging. At each stage, the compression
ratio is adjusted to the temperature below specified limit
to prevent polymerization. LTRS has multiple chillers
and cold box, where gas is cooled further to recover the
Z. Nawaz: Alkane dehydrogenation technologies      11
remaining C4’s, and the liquid from product gas separator/
flash drum is sent to the depropanizer. The stream passed
through the depropanizer, and pressure swing adsorption
(PSA) for lights and hydrogen recovery and the mixture
of isobutylene and unconverted isobutane are sent to the
MTBE synthesis unit. The typical reactor operating condi-
tions are shown in Table 2 (Al-Mutaz 1987, Dunn et al. 1992,
Trifiro and Cavani 1993, Ercan and Gartside 1996, Scott
1999, Bhasin et  al. 2001, Tullo 2003, Nijhuis et  al. 2004,
CRI/SRL 2007, Fridman et al. 2009, 2011, CATOFIN 2013).
Clariant is typically using terminologies of STD
(Standard) and HY (High severity) for chromium-based
cylindrical dehydrogenation catalysts depending on chro-
mium content. HY further demonstrated higher isobu-
tylene selectivity at higher isobutane conversion, and
Clariant claimed ~4% gain (Weckhuysen 1999, Fridman
and Urbancic 2005). CATOFIN conversion and selectivity
Table 2: Typical base case isobutane dehydrogenation process
conditions.
Operating pressure (bar)   0.25–1.2
Air/HC ratio   3.0–5.0
Hydrocarbon feed temperature (°C)  ~630–660
Conversion (%)   ~50–65
Selectivity (%)   ~83–93
Air compressor power (MW)   ~15
Regeneration air temperature (°C)   ~640–680
12      Z. Nawaz: Alkane dehydrogenation technologies
Table 3: Catalyst specifications.
Shape  
Diameter (mm)  
High (mm)  
Specific surface (m2/g)  
Specific pore volume (cm3/g)  ~0.05
Major components (%)  
 Cr2O3  
 Al2O3  
 MgO/K2O/ZrO2  
will change as the catalyst ages as well as the operational
severity mode. The general specifications of a commercial
Cr2O3/Al2O3 catalysts are shown in Table 3. The activity of
chromium-based catalysts is dependent on the chromium
loading, and both redox and non-redox Cr3+ are active in
dehydrogenation; the performance is further affected by
the process conditions and time-on-stream. In 2001, Süd-
Chemie commercialized a special formulation named
CATOFIN-ES (Extended Stability) that was chemically
stabilized to reduce the rate at which the catalyst aged
(Fridman and Urbancic 2005).
The active site can be described as a Cr-O pair, as both
the chromium and oxygen ions take part in the reaction,
whereas, in many kinetic modeling studies, the active
sites of the catalyst have been generally described as a
single ion. The well-known mechanism of isobutane dehy-
drogenation to isobutene over chromia catalyst is shown
below (Hornaday and Ferrell 1961, Sanfilippo 1993, 2011).
i − C4 H 10 ( g ) + Cr − O ↔ i − C4 H 9 …Cr − O … H
i − C4 H 9 …Cr − O … H ↔ i − C4 H 8 + H …Cr − O … H
H …Cr − O… H ↔ H 2 ( g ) + Cr − O
The experience gained through years of operation has
generated various ideas to boost the catalyst performance
and to improve reliability. Heat input to the catalyst bed has
been a critical limiting factor for direct dehydrogenation
processes and restricting the olefin production rate. This
issue is addressed by a novel approach of heat transfer to
the catalyst bed, taking advantage of cyclic operation and
reduction-oxidation mode. Recently, Clariant introduced
a concept of unique material heat-generating material
(HGM), as this inert material is added to the catalyst bed
to increase its heat storage capacity (Al-Mutaz 1987, Ercan
and Gartside 1996, Fridman et al. 2009, 2011, Oviol et al.
2012). HGM consists of Cu-Fe metal oxide material and has
the ability to produce heat in situ while remaining inactive
to the feed and products. During regeneration, metals are
oxidized by providing heat, as shown below (Weckhuysen
1999, Fridman and Urbancic 2005):
Pellet
Me + O2 → MeOx ∆H < 0
~3–6
~5
MeOx + H 2 → Me + H 2O ∆H < 0
200–260
The HGM is physically mixed or placed in the catalyst
bed at a particular level where the whole bed gets benefit
13–29 of its heat generation as follows (Beesley and Wipp 2010,
~65
­Hornaday and Ferrell 1961, Rokicki et al. 2001, Gregor and
2–3
Wei 2004, Urbancic et al. 2005):
–– Increase in olefin selectivity and reduction of mono-
mer factor by optimizing the catalyst bed temperature
profile.
–– Lower energy consumption by reducing the amount
of air used during the regeneration.
–– Reduction in the feed preheating temperature
increases olefin selectivity.
–– Catalyst life increases by minimizing the air inlet
temperature.
–– Increase in the number of reactors for dehydrogena-
tion mode.
4.2 Oleflex technology
The Oleflex process of UOP used a series of moving bed
reactors with interstage heating. It was first commercial-
ized in 1990 in NCP, Thailand (Chaiyavech 2002, UOP
2004). Initially, UOP faced problems in void blowing,
coking, metallurgical issues, polythionic acid, and heat
exchangers. Four different versions of catalysts were used
(Chaiyavech 2002). The UOP Oleflex dehydrogenation
process has three sections: reactor section, product recov-
ery section, and catalyst regeneration section as shown
in Figure 3 (Sanfilippo 1993, Heinritz-Adrian et al. 2008).
The reactor section consists of three or more radial-flow
(moving bed) reactors, charge heater for hydrocarbon feed
preheating, interstage heaters, and a feed-effluent gas-gas
exchanger (Chaiyavech 2002, UOP 2013). In the product
recovery section, the reactor effluents are cooled, com-
pressed, and sent to the cryogenic system for hydrogen (of
~90 mole% purity) and hydrocarbon separation/recovery.
Liquid hydrocarbons were sent to selective hydrogenation
to eliminate diolefins and acetylenes and then to de-etha-
nizer and propane-propylene splitter.
The process is mostly commercialized for the produc-
tion of PG propylene (Chaiyavech 2002, UOP 2013). The
continuous catalyst regeneration (CCR) section burns
coke over the catalyst and returns the regenerated cata-
lyst to the reactor. The process uses a Pt-Sn-based catalyst

Figure 3: UOP Oleflex propane dehydrogenation process.
(e.g. DeH-14, introduced in 2001) having high activity
and selectivity with lower attrition rates (Sanfilippo 1993,
­Chaiyavech 2002). The reaction runs at pressures ~1–3 bar
and temperatures ranging from 525°C to 705°C (Sanfilippo
1993, Chaiyavech 2002, UOP 2013). In CCR, the catalyst
after the burning of coke (Pt) is redispersed on the support
material by treating it with a chlorine-air mixture and oper-
ates continuously to obtain an uninterrupted production.
The cycle completes in 5–10 days. The product is recov-
ered by cooling/quenching, compressing, and drying the
reactor effluent; hydrogen is being separated cryogenically
from the hydrocarbons. In justifying the construction of
the propane dehydrogenation unit (as shown in Figure 3),
feasibility is to pay for propylene on a cost plus basis and
returning ~15–20% return on investment after production
cost, which is a major contribution in the polypropylene
manufacturing business. The average propylene selectiv-
ity and conversion at approximately 1000 days on stream
were ~83% and ~29%, respectively.
4.3 Uhde STAR Process (Thyssen-Krupp)
STAR is the acronym for Steam Active Reforming, the dehy-
drogenation technology initially developed by Phillips
Z. Nawaz: Alkane dehydrogenation technologies      13
Petroleum (now Conoco Phillips). Uhde acquired the tech-
nology, including the process know-how, patents, and cat-
alyst from Phillips in December 1999 (Jensen et al. 2000,
Uhde STAR Process 2013). The STAR Process was commis-
sioned for isobutylene at Coastal Chemical, Inc., Chey-
enne, WY, USA, in 1992 and at Polybutenos, Argentina, in
1994. The process was also commercialized for propylene
production at Propylene & Poly-propylene Company, Port
Said, Egypt, in 2006 by Uhde.
Propane feed, together with recycle propane and
steam diluents, is heated with the reactor effluent and
a fired preheater before injection to reformer-type dehy-
drogenation reactor. The intermediate product from the
reformer is cooled by condensate injection. Steam is also
injected to adjust the inlet temperature and the steam-to-
hydrocarbon ratio for the second reactor (oxy-reactor). The
injected oxygen shortly above the catalyst bed selectively
converts the hydrogen (selective hydrogen combustion),
which not only shifts the thermodynamic equilibrium of
the dehydrogenation reaction to higher equilibrium con-
version but at the same time provides the necessary heat
for further dehydrogenation (see Figure 1). Hot process gas
is cooled by exchanging heat for feed preheating, produc-
ing steam in the effluent boiler, and supplying heat for the
downstream separation section. The same catalyst is used
14      Z. Nawaz: Alkane dehydrogenation technologies
for the reformer and the oxy-dehydrogenation section.
The applied shift of the endothermic equilibrium by selec-
tive hydrogen combustion at the top segment of the oxy-­
reactor allows for more efficient utilization of catalyst
activity and helps in achieving higher conversion. Higher
space-time olefin yield allows smaller reactors and ulti-
mately reduces investment cost.
STAR claims higher productivity advantage due to
equilibrium shift by oxy-dehydrogenation (overall steam-
to-hydrocarbon ratio ~4.2), and at the same time, the
catalyst is stable and maintains its activity in a hydro-
thermal environment. The reformer inlet temperature
is ~510°C and the outlet temperature is ~550°C–580°C,
whereas the oxy-reactor outlet temperature is ~580°C.
The reformer operates at liquid hourly space velocity 4
and oxy-dehydrogenation at 6, adjusted by shorter tubes
with reduced amount of catalyst by ~30% (at 4–6 bar). An
effective design of the reactor section of STAR dehydroge-
nation process achieving optimized temperature profile
to achieve high space-time yields is shown in Figure 4
(Uhde STAR Process 2013). The process operates in the
presence of steam; therefore, the absolute pressure of the
reactor section is higher than the other technologies while
keeping the partial pressure of hydrocarbons low (and
thus high conversion).
The product mixture consisting of paraffins, olefins,
hydrogen, water, and CO2 in small quantity was com-
pressed for processing to pressures of 15–35 bar and sent
to the separation section. This section has compressors,
PSA, cryogenic unit, and fractionators. The process has
relatively higher suction pressure compared to the other
technologies, resulting in lower cost (Capex and Opex) for
Pre-heater Steam generation
STAR reformer
Heat recovery section
Oxy-reactor
Gas-gas exchanger
Figure 4: Uhde STAR Process dehydrogenation reactor section.
raw gas compression. The specific consumption of dehy-
drogenation plant typically makes up approximately 80%,
and STAR has the advantage of high conversion vs. high
selectivity and high recovery/high sophistication. The
reactor exit pressure is ~5 bar, which will allow sufficient
pressure drop to utilize the available heat. The steam pres-
ence in the system converts most of the coke to CO2, thus
allowing longer operation (i.e. ~7 h) and shorter regen-
eration cycle (i.e. 1 h). Therefore, 14.7% reactor capacity
is required to compensate regeneration, which is lowest
among other commercial technologies (Sanfilippo et  al.
1998, 2006, Jensen et al. 2000, Miracca and Piovesan 1999,
Nawaz et al. 2010a–h, Uhde STAR Process 2013).
The catalyst is platinum based on zinc and calcium
aluminate support with various promoters. The cata-
lyst for the process has demonstrated a lifetime of up to
7  years in commercial applications (Jensen et  al. 2000,
Sanfilippo et al. 2006, Uhde STAR Process 2013). Regener-
ation takes place only in the presence of steam and air and
without additional requirement for catalyst reactivation
(e.g. chlorination; Sanfilippo et al. 1998, Heinritz-Adrian
et al. 2008).
4.4 Fluidized bed dehydrogenation (FBD)
technology
An FBR-based dehydrogenation technology for C3–C5 olefin
production was developed in the former Soviet Union
during the 1960s by Yarsintez. Approximately two decades
before Yarsintez and Snamprogetti agreed to develop
it further, Snamprogetti licensed the first large-scale
LTRS/fractionator
compressor
Product mixture
Hydrocarbon feed

commercial unit in SADAF [a Saudi Basic Industries Cor-
poration (SABIC) affiliate], Jubail, Saudi Arabia (Zenz and
Othmer 1960, Sanfilippo 1993, Zimmermann and Verluis
1995, Sanfilippo and Miracca 2005, Sanfilippo et al. 2006,
Caspary et  al. 2008, Miracca and Piovesan 1999, Nawaz
et  al. 2010a–h). The technology is abbreviated as FBD-3
and FBD-4, where 3 for propane and 4 for isobutane.
In FBD, the catalyst solid particles are kept suspended
by feed gas/air using a distributor. Increasing the gas veloc-
ity, fluidization begins (minimum fluidization velocity
Umf ), the bed behaves like a liquid and bubbles are formed
(Umb); at gas velocity higher than the terminal velocity Ut
(i.e. the gas velocity exceeds that of free fall), the solid par-
ticles are blown away. The reactor behaves between fixed-
bed reactor and continuous stirred tank reactor (CSTR). In
the bubbling fluidized bed system, uniform temperature
and heat exchange such as CSTR, pressure drop through
the bed is equal to the weight per unit area of the bed and
independent of gas velocity. The high level of mixing of
the solid particles enhances both heat (high heat trans-
fer coefficient) and mass transfer phenomena. While
robust and mechanically strong, the catalyst is desirable
to avoid attrition. A significant dispersion of gas contact
times is expected and consecutive reactions decrease the
selectivity at increasing conversion. The back-mixing phe-
nomena is controlled by staging the fluidized bed [closer
to plug flow reactor (PFR)] by properly designed internal
baffles, approaching a series of CSTR, and a global PFR-
like behavior. As the direct dehydrogenation of alkane is
limited by equilibrium, a higher per pass conversion is
achieved by plug flow movement of the gas phase equal to
the reactor volume. The catalyst circulation is determined
by the amount of heat required by the reaction rather than
catalyst deactivation; therefore, the insertion of baffles
allows a substantial reduction in flow in comparison with
isothermal conditions.
The catalyst is chromium based supported on alumina
oxide similar to CATOFIN catalysts with relatively lower
active metal loading of ~15–19 wt% (Miracca and Piovesan
1999). The reaction heat is supplied by the heat capacity
of the circulating regenerated catalyst ( > 650°C), having a
residence time of ~10–30 min in the reactor and regenera-
tor (Sanfilippo et al. 2006). Consequently, the mechanical
life of the catalyst (loss by attrition) largely depends on
its circulation rate, although this loss can be compensated
by the continuous addition of catalyst in the regenerator
during operation without disturbing the hydrodynamics
and yield. The low pressure drop requires a much larger
cross-section or the addition of a diluent to maintain
such a low partial pressure of the reactants. A counter-
current flow of gas-solid in the reactor and regenerator is
Z. Nawaz: Alkane dehydrogenation technologies      15
Product Fuel gas
Sets of
cyclones
P=30 kPa
Regenerator
Reactor
Gδ=5.7 kg/m2-s °
Fuel
Air
Isobutane
feed @ 470°C
Fuel
Stripping
Stripping
nitrogen
dp=80 microns
nitrogen
Air Natural gas
Transfer lines
Figure 5: FBD reactor-regeneration system.
developed. Figure 5 shows the catalyst transfer between
the reactor and regenerator and feed, air, natural gas, and
nitrogen injects.
The significant difference of the Yarsintez-Snamprogetti
FBD technology with FCC reactor is that a small quan-
tity of coke is formed in FCC and is not enough to supply
the energy needed to heat the catalyst and to satisfy the
overall thermal balance. In FBD technology, some fuel
(natural gas) is added in the regenerator, and simplified
heat balance and catalyst circulation rate are given by
∆H glob [ kca l / h] = [ mcat × c p × ∆Tcat ]
= ∆H enth + ∆H reac + ∆H loss = ∆H fuel + ∆H coke
where ΔHglob is the global heat flux balance and the others
are the enthalpy change of the products minus reactants,
the reaction heat, and the heats of fuel and coke combus-
tion. mcat is the catalyst circulation rate in kg/h, cp is the
catalyst heat capacity (~0.22–0.29 kcal/kg/K), and ΔTcat
is the temperature difference of the catalyst entering and
leaving the reactor.
Before transferring regenerated catalyst from regen-
erator, absorbed oxygenated products are stripped from
the catalyst and reduced in stripping section at bottom of
regenerator. Gas distributors are installed in both reactor
and regenerator that ensure even gas distribution in cross-
sectional areas with a specific bubble size of ~20 cm that
displaces over 4 kg of catalyst and rising speed of 1 m/s
 16      Z. Nawaz: Alkane dehydrogenation technologies
that exerts intense force on the structure and shape of it
(Sanfilippo et al. 2006). The mechanical design of reactor
internals, regenerator internals, transfer lines, and
cyclones are the key to ensure mechanical reliability and
performance. The optimal design of the cyclones mini-
mizes the catalyst losses. Below are some important con-
siderations in reactor sizing for FBD technology (Miracca
and Piovesan 1999, Nawaz et al. 2010a–h):
–– The volume of the catalytic bed is determined by fix-
ing the space-time for the said amount of feed gas at a
given reaction temperature depending on the catalyst
activity.
–– This vessel diameter is dictated by superficial gas
velocity that has to stay between Umf and Ut (generally
for Geldart A powders,  < 1 m/s).
–– For required hydrodynamics, the bubbling regime
aspect ratio (height/diameter) is critical to avoid poor
distribution and poor heat/material exchange, with-
out high entrainment.
–– Catalyst circulation rate is dictated by the heat bal-
ance requirement.
4.5 P
 ropane dehydrogenation technology
(PDH) technology of Linde-BASF-Statoil
Linde-BASF-Statoil have also developed a PDH similar to
STAR technology, although limited information is avail-
able in open literature (Zimmermann and Verluis 1995,
Schindler et al. 2004, Caspary et al. 2008). Originally, the
catalyst was chromium supported on alumina oxide with
Regeneration mixture
BFW
Steam
Pre-heater
Figure 6: Linde-BASF-Statoil PDH reactors.
promoters consisting of compounds of alkali metals and/
or alkaline earth metals and compounds of metals from
the third and/or fourth subgroups, at least one cesium
metal compound promoter of ~0.1–10% by weight and
at least one zirconium metal compound of ~0.1–15% by
weight. Later, they changed to platinum supported on
Mg(Al)O (Zimmermann and Verluis 1995, Schindler et al.
2004, Caspary et al. 2008).
The reactor section includes three identical gas-fired
steam-reformer-type dehydrogenation reactors, as shown
in Figure 6. Two of these reactors operate for dehydroge-
nation, whereas the third reactor is on regeneration at that
time. The T-profile of the reactor is conceptually similar
to the previous designs (Zimmermann and Verluis 1995,
Schindler et al. 2004, Caspary et al. 2008).
4.6 FLOTU/Tsinghua dehydrogenation
technology
A highly selective and hydrothermally stable platinum-
based SAPO-34 supported catalyst was developed for
the first time by Nawaz et  al. at Tsinghua University,
Beijing, in 2009, under the supervision of Prof. Dr. Fei
Wei (Miracca and Piovesan 1999, Nawaz et  al. 2009a–g,
2010a–h, 2011a,b). The activity of platinum-based cata-
lyst is well known for the dehydrogenation, whereas its
dehydrogenation performance depends on platinum, tin,
and support interaction and lower Sn(0) and Pt-Sn alloy
concentrations, and these features were incorporated
­
using SAPO-34 as a support (weak surface acid sites;
Feed
Product downstream
Gas-gas
exchanger

Miracca and Piovesan 1999, Nawaz et  al. 2010a–h). The
platinum-support interaction were enhanced with better
platinum dispersion and inherent stability toward regen-
eration due to its silicon-based acid sites (Miracca and
Piovesan 1999, Nawaz et  al. 2010a–h). The role of tin as
a promoter is well defined for platinum dispersion over
various supports. Herein, a novel combination of Al2O3 with
SAPO-34 for Pt-Sn-based catalyst, which further improves
platinum dispersion, desired active platinum site concen-
tration (platinum anchored through SnOx) and ultimately
has an improved dehydrogenation capability (Nawaz et al.
2009a–g, 2010a–h, 2011a,b 2012). The catalyst was pre-
pared by a sequential impregnation method after adding
~20% Al2O3 with SAPO-34, improving the overall perfor-
mance. Above 91% of total olefin selectivity and approxi-
mately 34–45 wt% light alkane conversion were achieved
over Pt-Sn/SAPO-34 and Pt-Sn/Al2O3-SAPO-34 at weight
hourly space velocity 2–8 h-1, 1  atm, and ­ temperature
~585°C (Miracca and Piovesan 1999, Nawaz et al. 2010a–h).
The results were found promising by comparing
performance with other known zeolite-based catalysts
under identical operating conditions, and extensive
investigation using physicochemical techniques was
carried out to investigate superior performance (Nawaz
et  al. 2013a,b). The hydrothermal investigation demon-
strates superiority of support choice SAPO-34 (Miracca
and Piovesan 1999, Nawaz et  al. 2010a–h). The catalyst
shows excellent stability after mild steaming (nitrogen
mixed steam) for many continuous reaction-regeneration
(at ~600°C) runs. The physiochemical analysis of severe
hydrothermally treated samples helped to find reason
for activity loss during regeneration. Above 98% recov-
ery of catalyst activity after several regeneration was
obtained by the redispersion of platinum, and this credit
goes to the SAPO-34 due to its silicon-based stable acid
cites/­structure (Miracca and Piovesan 1999, Nawaz et al.
2010a–h, 2013a,b). Superior metal support interaction
helps to transfer coke to support and keep active sites
available for reaction (Miracca and Piovesan 1999, Nawaz
et al. 2010a–h, 2013a,b). The catalyst was pelletized and
used for pilot test.
The direct dehydrogenation of light alkanes is one
of the most economical routes to high-quality light
olefins but is complex due to the endothermic reaction
nature, equilibrium limitations, stereochemistry, and
reaction engineering constraints. The state-of-the-art
idea of bimodal particle (gas-solid-solid) FBR (GSS-FBR)
was introduced to overcome reaction barriers (Miracca
and Piovesan 1999, Nawaz et al. 2010a–h, 2011a,b, 2012,
2013a,b). Nawaz et  al. investigated propane and butane
dehydrogenation reaction using Pt-Sn/SAPO-34 and
Z. Nawaz: Alkane dehydrogenation technologies      17
Regenerator PDH reactor Olefins conversion
P
r
o
p
y
l
e
n
e
Steam
Propane Higher
olefins
Figure 7: Integrated setup of GSS-FBR with olefin interconversion
reactor for heat integration.
Pt-Sn/Al2O3-SAPO-34 catalysts at ~590°C in proposed GSS-
FBR, as shown in Figure 7 (Miracca and Piovesan 1999,
Nawaz et al. 2­ 010a–h, 2011a,b, 2012, 2013a,b). The inter-
esting results were obtained; both fixed-bed microreac-
tor and integrated bimodal particle FBR (GSS-FBR) were
compared and parametrically characterized (Miracca and
Piovesan 1999, Nawaz et  al. 2010a–h, 2011a,b, 2013a,b).
The GSS-FBR system consists of two catalysts, where one
catalyst serves for dehydrogenation (principal catalyst)
and the other catalyst (secondary catalyst) is almost inert
to dehydrogenation reaction and serves as a heat trans-
fer material. The reaction time of the principal catalyst
is ~6–8 h; therefore, it remains in the reactor, whereas
the secondary catalyst is moved to the regenerator and
after coke burning supplies heat for endothermic reac-
tion. In the integrated scheme presented in Figure 7, the
secondary catalyst (SAPO-34) further serves for olefin
interconversion (i.e. hexane to propylene) and then
regenerated. The GSS-FBR design and results were dis-
cussed in the author’s other publications (Miracca and
Piovesan 1999, Nawaz et  al. 2010a–h, 2011a,b, 2013a,b).
A significant enhancement in productivity is observed
owing to uniform heat transfer throughout the reactor
and the transfer of coke from the principal catalyst to the
secondary catalyst, which increases the principal cata-
lyst’s stability; the design has both economic and opera-
tional benefits (Miracca and Piovesan 1999, Nawaz et al.
­2010a–h, 2011a,b, 2012, 2013a,b). The GSS-FBR system
was successfully piloted at Tsinghua U ­ niversity, Beijing,
China, in late 2009.
Extensive investigation has been done before the
piloting of GSS-FBR for system hydrodynamics (using
18      Z. Nawaz: Alkane dehydrogenation technologies
cold model 2D fluidization apparatus) and catalyst attri-
tion (using ASTM standard air jet fluidized bed test D-5757;
Miracca and Piovesan 1999, Nawaz et al. 2010a–h, 2011a,b,
2012, 2013a,b). During the study, an attrition calculation
formula was developed, which explains the varying parti-
cle density and size distribution effect on attrition behav-
ior based on distinct fracturing mechanism (Miracca
and Piovesan 1999, Nawaz et al. 2010a–h, 2011a,b, 2012,
2013a,b). This varying particle density effect on attrition
behavior as disclosed by Nawaz et  al. is valid for all the
fluidized bed systems, as with the time catalyst size will
not remain the same, or its density may vary due to the
deposition of the product or byproducts, change of physi-
cal properties, and/or other contaminations. An inte-
grated process was proposed with GSS-FBR, where the
dehydrogenation reactor was attached to olefin intercon-
version reactor (higher olefins to lower olefins; Miracca
and Piovesan 1999, Nawaz et  al. 2010a–h). The second-
ary catalyst took heat from the regenerator (~650–700°C),
provided heat to the principal dehydrogenation catalyst
in the dehydrogenation reactor (~550–610°C), and finally
served as the catalyst for olefin interconversion reaction
(~480–520°C; Miracca and Piovesan 1999, Nawaz et  al.
2010a–h, 2011a,b, 2012, 2013a,b). The bimodal system
significantly improves principal catalyst holdup and well-
mixed hydrodynamics and its bubble braking mixing phe-
nomena improved the catalyst-feed interaction. The pilot
unit results significantly endorse the superiority of design.
4.7 SABIC dehydrogenation technology
SABIC as a leading petrochemical company is explored in
this chapter. Intensive work has been focused on reactor
design concepts and for the improvement of existing oper-
ating units using chromium-based catalysts. For propane
dehydrogenation, platinum-based catalysts were explored
due to their high selectivity for propylene. Selective zeolite
supported platinum-based catalyst compositions were
developed for light alkane, particularly for propane and
butane dehydrogenation; the catalyst composition con-
tains platinum, a tin component, a potassium component,
one or more additional promoter elements, and a silico-
alumino-phosphate (SAPO-34) molecular sieve zeolite
support or modified SAPO-34 (Nawaz et al. 2013a,b, Nawaz
2015). The catalysts were prepared by sequential impreg-
nation methods and observed the conversion of alkanes
~35% and selectivity ~94% for propylenes and ~84% for
butenes. The presence of a small concentration of potas-
sium with tin that modifies the surface electron density of
the final catalyst makes it more suitable for light alkane
dehydrogenation, and many efforts have been applied to
improve catalyst stability and olefin yield (Nawaz et  al.
2013a,b, Nawaz 2015).
Embedded dehydrogenation fixed-bed reactor
systems (EDFBRS) for the dehydrogenation of light
alkanes was proposed by Nawaz et  al. (2014), as shown
in Figure 8A. The system includes a furnace and further
includes embedded alkane feed preheating chambers,
regeneration mixture preheating chambers, at the top
portion of furnace, and two groups of reaction chambers,
all located within the furnace (Nawaz et al. 2014). The two
groups of reaction chambers can be switchable coupled
to an alkane feed and a regeneration mixture feed such
that an alkane can flow through one group of reaction
chambers, while a regeneration mixture flows through
the other group of reaction chambers. Therefore, the
reactor operates and produces in a continuous fashion.
The choice of catalyst can influence the operating phi-
losophy; for example, chromium-based catalysts are
highly active and achieve a high conversion of alkanes
B
Air/Fuel gas
Product
Fuel
EDFBRS
A Regeneration air
from pre-heater
Reactor
Reactor
Feed
Regenerator
Reaction/Regeneration
Feed
chambers
Nitrogen
Product
Product
Air/Fuel
Figure 8: SABIC Dehydrogenation Reactor Concepts (A) Embed-
ded Dehydrogenation Fixed Bed Reactor Systems (EDFBRS) for
dehydrogenating of light alkane; (B) Integrated FBR with internal
regenerator.

to alkenes but can be deactivated quickly, which can
require frequent regeneration (e.g. after approximately
8–20 min). On the contrary, platinum-based catalysts are
comparatively less active and require slower deactiva-
tion, and it can require regeneration after approximately
6–12  h of operation. Moreover, regeneration require-
ments are slightly different. EDFBRS has the flexibility
to manage all these aspects of frequency and intensity
of regeneration (Nawaz et  al. 2014). The design is not
only unique but has also the advantages of continuous
production from a single unit, lower heat losses as eve-
rything is in the furnace box, embedded preheaters for
reaction and regeneration, operational ease, and less
mechanical integrity issues. At one time, feed gas enters
the preheating chambers located at the top of furnace and
then enters the reaction chambers located in the high-
temperature zone of furnace. Similarly, the regeneration
gas mixture also enters the fixed regeneration preheating
chambers at the top of furnace and enters the catalyst bed
for regeneration. At a certain time, some of the chambers
filled with the catalyst were on regeneration and some
were on reaction.
Another unique design of an integrated FBR with
internal regenerator and a process for dehydrogena-
tion of paraffins to olefins is disclosed by Nawaz et  al.
(2014) (as shown in Figure 8B). The integrated FBR
reactor design provides an advantage of sharing regen-
erator heat to the reactor for endothermic reaction and
run the reactor substantially isothermal, lower catalyst
circulation, and lower attrition (Nawaz et al. 2014). Gen-
erally, the FBR dehydrogenation reactor has multiple
interdependent variables to control the process, as dis-
cussed in Section 4.4, for FBD technology, such as cir-
culation rate and/or regenerator temperature to control
reactor temperature, which further defines the catalyst
bulk density, holdup, or residence time. In the proposed
design, the interdependency of control variables was
no more present, and inherent design addresses these
issues, as only one lifts gas for catalyst circulation (i.e.
regeneration air and catalyst entered the reactor directly,
without having transfer line). Transfer lines for catalyst
movement from one equipment to another cause tem-
perature loss and considered as one of the major sources
of attrition. Integrated FBR has only one transfer line,
and it is enough to control circulation and holdup in
both risers. Overall, the process enhances feed conver-
sion and desired product selectivity, using chromium- or
platinum-based catalyst, as closer to plug flow behavior.
The design has better flexibility and control in operation
with less variables compared to other FBR dehydrogena-
tion technologies (Nawaz et al. 2014).
Z. Nawaz: Alkane dehydrogenation technologies      19
5 Summary
The price difference between paraffins and olefins,
with an increasing demand for olefins, keeps dehydro-
genation technologies drivers of profit that makes them
attractive for future research and commercialization. The
available technologies for the direct dehydrogenation of
light alkanes to olefins were discussed with respect to
catalyst and reactor design. Only known catalysts and
reactor concepts – those that were at least piloted or have
been potential candidate for commercialization – were
discussed. Most commercial processes only use chro-
mium- or platinum-based catalysts, while each technol-
ogy has uniqueness in the reactor features and operating
philosophy. The recent inventions address the catalyst
robustness issues related to higher selectivity with higher
conversion, high temperature stabilities, lower hydrog-
enolysis activity, and carbon deposition on support.
The process, in general, does not enjoy the plethora of
mechanistic subtleties that have engaged researchers to
develop sophisticated technologies. Achieving opera-
tional excellence is getting more and more vital due to
heat supply schemes for endothermic reaction and fre-
quent regeneration. Innovative ideas and pragmatic
approaches are required to improve the processes, oper-
ational efficiency, and cost-effective debottlenecking.
Moreover, the downstream of most light alkane dehy-
drogenation units is similar. Recent technologies were
presented with improved reactor design concepts having
integrated approaches for heat transfer to achieve better
performance. Recently, an extensive work in developing
dehydrogenation catalysts is about selective catalyst (e.g.
platinum-based zeolite supports catalyst). The design
philosophies for integrated fluidized bed having internal
regenerator and embedded fixed-bed furnace-type dehy-
drogenation reactors were discussed for their operational
superiority.
Acknowledgments: The author acknowledges the technical
support of colleagues who built the cultural background of
industrial dehydrogenation research in SABIC Technology
& Innovation at Riyadh.
Disclaimer: Moreover, the article may contain forward-
looking statements based on assumptions, knowledge-
based forecasts, known and unknown risks, uncertainties,
financial situation, development or performance, and
the estimates/designs presented here. Therefore, the
author or the company assumes no liability, whatsoever
to update these forward-looking statements or to confirm
them to future events or developments.
20      Z. Nawaz: Alkane dehydrogenation technologies
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Bionotes
Zeeshan Nawaz
Olefins and Aromatics, SABIC Technology
and Innovation, Saudi Basic Industries
Corporation (SABIC), P.O. Box 42503,
Riyadh 11551, Kingdom of Saudi Arabia,
engr.dr.zeeshan@gmail.com,
zeeshan@SABIC.com
Zeeshan Nawaz received his BE and MSc degrees with distinction
in Chemical Engineering from MUET Jamshoro in 2003 and UET
Lahore in 2006, respectively. He earned his doctoral degree (PhD)
in Chemical Engineering and Technology from Tsinghua University,
Beijing, China in 2010. He has been engaged in a number of cata-
lyst development, process and reactor design, and plant support
activities for alkane dehydrogenation since 2005 and patented
about 20 catalyst and process/reactor concepts. Working as a lead
scientist in SABIC Technology & Innovation, Saudi Basic Industries
Corporation (SABIC), he is involved in high-fidelity reactor mod-
eling, plant support, and various technology development activi-
ties, particularly alkane dehydrogenation, acetylene hydrogena-
tion, MTBE, ethylene oxide, ethylene glycol, and syngas conversion
to olefins. He won many awards and scholarships in his career,
including the NAYS Best Young Scientist (Chemistry) Award in 2011
and SABIC Syngas Technology Development Award 2015. Dr Nawaz
has more than 50 journal publications and editorial board member
in various reputed research journals of chemical engineering.