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DOI 10.1007/s11244-012-9917-9
ORIGINAL PAPER
1 Historical Developments
Chromiaalumina catalyst for the production of olefins has
been in use since the late 1930s. During World War II,
catalytic dehydrogenation of butanes over a chromia/alumina catalyst was practiced for the production of butenes
which were then dimerized to octenes and hydrogenated to
octanes to yield high-octane aviation fuel.
Dehydrogenation of butanes over a chromia/alumina
catalyst was first developed and commercialized at Leuna
in Germany and also independently by Ipatieff and coworkers at UOP [2, 3]. The first UOP-designed plant came
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1298
120
Demand, MM MTA
100
Ethylene
Propylene
80
60
40
20
0
1995
2000
2005
2010
on stream at ICI in Billingham in 1940 and was soon followed by two other units in Heysham in 1941 [4]. The
production of octenes by butene dimerization made use of
UOPs catalytic condensation process in which olefins are
dimerized, oligomerized, or alkylated over a solid phosphoric acid (SPA) catalyst, discovered by Schaad and
Ipatieff, and first commercialized in 1933 [5].
These pioneering efforts were soon followed by other
companies (e.g., Phillips Petroleums multitubular dehydrogenation reactor near Borger, Texas, in 1943 [4]).
However, the most significant development was that made
by Houdry using dehydrogenation under vacuum for higher
per-pass conversions and commercialized two stage butane
dehydrogenation chromia/alumina system, known as Catadiene process, for the production of butadiene [4].
The Houdry Catadiene process was used extensively for
the production of butadiene, either by itself (n-butane to
butadiene) or in conjunction with the Oxo-D catalytic
process for the oxydehydrogenation of n-butene to butadiene that was commercialized by what was then known as
Petro-Tex Chemical Corp. [6]. A similar oxydehydrogenation approach for the production of butadiene was followed by Phillips Petroleum in their O-X-D process [6].
Large quantities of butadiene have become available in
the market over the past 30 years, mostly as a byproduct
from the thermal cracking of naphtha and other heavy
hydrocarbons. The result from this market shift has been
the shutdown of all ad-hoc catalytic dehydrogenation units
for butadiene production in North America, Western Europe, and the Far East. However, over the past two decades
because of changing to lighter (ethane and LPG) feedstocks
for the ethylene plant crackers, rate of butadiene production growth has slowed below the demand growth creating
regional shortage of butadiene. Butadiene price has jumped
from $800/MT in 2005 to over $2000/MT in 2011. As a
result of this there is again increasing interest in on-purpose
butadiene production. In August 2011 Texas Petrochemical
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(TPC Group Inc) announced detail engineering study of onpurpose butadiene production utilizing their idled Oxo-D
plant. In 2011 Mitsubishi announced a development of
oxidative dehydrogenation process for butane dehydrogenation for the production of butadiene [7].
In the late 1980s, application of chromia/alumina catalysts was extended by Houdry to the dehydrogenation of
propane to propylene and isobutane to isobutene, and over
the two decades there were several new units were built for
this purpose. These units again operate on the same cyclic
principles as in the former Catadiene process, and the new
process application is named Catofin [8, 9]. The Catofin
process technology is currently owned by Sud-Chemie and
is offered by Lummus, A CBI Company.
In about 1959 an alternative chromia/alumina catalytic
dehydrogenation process was developed in the former
Soviet Union that avoided the use of the cyclic operation
by using a fluidized bed reactor configuration similar to the
fluid catalytic cracking (FCC) process used in refineries
[4]. However, back mixing common to dense fluidized bed
operations results in poor selectivity and increases the
formation of heavies, sometimes called green oils. Circulating regenerated catalyst is used to provide the heat of
reaction in the riser and spent catalyst is reheated by carbon
burn in a regenerator. A larger scale isobutane dehydrogenation unit using this principle was commercialized by
Snam Progetti in Saudi Arabia based on technology from
Yarsintez in Russia [10].
Lestor, Carson, and others at UOP during late 1960s and
early 1970s also worked on development of fluid-bed catalytic dehydrogenation employing chromia alumina catalyst but the technology was not commercialized [1114].
Chromia/alumina catalysts pose a significant health risk in
case of spillage or by exposure to the plant operators during
maintenance or catalyst changeover. Chromia/alumina
catalysts always contain a significant proportion of Cr(VI),
principally in the regenerated catalyst; Cr(VI) is a wellknown carcinogen and its adverse health effects have been
well documented [15, 16]. Chromia/alumina catalysts sinter much more rapidly than alumina when exposed to high
temperatures; the replacement of the mass of spent catalyst
often requires strenuous and lengthy use of manual labor
for such an operation [17, 18].
The dehydrogenation of ethylbenzene to styrene reaction proceeds over an iron or an ironchromium catalyst
that usually also contains potassium in the form of potassium carbonate, so that at elevated temperatures various
complex mixed carbonates and oxides are formed; e.g.,
KFeO2. Temperatures are elevated, in the order of 630 C,
and steam dilution is practiced to lower the partial pressure
of the reactants. Because the reaction is strongly endothermic various reaction stages are normally employed
with interheat and interstage addition of superheated steam.
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Kp
Kp P
100
C-C-C
Propane
90
80
C-C=C
Propylene
3 Light Olefins
In view of the successful application of Pt-based noble
metal catalysts to the dehydrogenation of heavy paraffins it
would seem that their extension to the production of light
olefins would be a trivial undertaking. In reality, this is not
the case.
Heavy paraffins are both valuable and highly prone to
cracking. Therefore, in order to maintain a high selectivity
and yield it is necessary to operate at relatively mild conditions, typically below 500 C and at relatively low perpass conversions and higher H2 partial pressure. While this
Mole %
70
60
50
40
C-C C
Methyl
Acetylene
30
20
10
0
627
C=C=C
Allene
727
827
927
1027 1127
Temperature, C
Fig. 2 Propane dehydrogenation equilibrium at 1.00 atm abs pressure
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1300
C-C-C
Propane
90
80
Mole %
70
C-C=C
Propylene
60
50
C-C C
Methyl
Acetylene
40
30
20
C=C=C
Allene
10
0
627
727
827
927
1027 1127
Temperature, C
Fig. 3 Propane dehydrogenation equilibrium at 0.23 atm abs
Pressure
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has proven to be equally useful for the catalytic aromatization of LPG fractions such as in the UOP CyclarTM process and for the catalytic dehydrogenation of light paraffins.
The combination of noble metal catalysts operating at
high severity in conjunction with CCR technology has made
it possible to design, build, and operate very large catalytic
dehydrogenation units that can produce light olefins, in
particular propylene and isobutylene, at high selectivities
and economically [23]. Not surprisingly, the world propylene production capacity based on the use of catalytic
dehydrogenation of propane has increased steadily over the
past 20 years [24] with 2010 production of propylene via
propane dehydrogenation at 3 million metric tons per year.
Use of the Oleflex process for the dehydrogenation of
ethane to ethylene has also been investigated but, to date,
the economics do not appear to be favorable because of the
low equilibrium conversion and the need to operate under
vacuum if a reasonable ethane conversion is to be expected.
The cost of fractionating ethylene in an ethane-ethylene
splitter is otherwise too high. Dow Chemical has recently
been awarded a patent [25] for the dehydrogenation of
ethane over a metal-mordenite catalyst complex at relatively low-conversions in which the product ethylene is
selectively recovered from the dilute ethylene-ethane
stream by alkylating it with benzene.
As mentioned earlier lower partial pressure of reactant
increases conversion achieved. Steam dehydrogenation is
based on the idea that by adding steam the partial pressure
of the paraffin can be lowered such that effectively the
conversion level could be as much as that obtained under
vacuum, but still operating at a superatmospheric level.
Two other potential benefits are that superheated steam can
be used as a heat carrier to supply heat for the dehydrogenation reaction and that steam interacts with coke deposits
to maintain the catalyst free of coke and active.
This approach is used by Phillips Petroleum in developing their STAR technology for isobutene dehydrogenation employing Pt-type catalyst and multi-tubular reactor
design. This reactor design resembles a typical steam
reformer that is operated until the catalyst deactivates as a
result of coke deposition. This reactor is taken out of service for catalyst regeneration while a spare muti-tubular
reactor is brought on-stream. The STAR technology is
currently owned and licensed by Krupp-Uhde.
Steam dilution is also employed in dehydrogenation of
ethylbenzene to styrene. Bricker and associates developed
steam stable catalysts for propane and isobutene dehydrogenation in a high steam environment [26, 27].
3.1 Process Chemistry
The main reaction in catalytic dehydrogenation is the formation of the mono-olefin from the corresponding feed
1301
Pt
n-Paraffin
A, Pt
A, Pt
Pt
nOlefin
n-Diene
A, Pt
iso-Paraffin
Pt
Pt = Platinum Site
Cracked Products
isoOlefin
Polymers
A,
Pt
Coke
A = Acid Site
Aromatics
A, Pt
Cyclo-Olefins
Pt
Cyclo-Paraffins
A,
Pt
n-Paraffin
Pt
A, Pt
A, Pt
isoParaffin
Cracked
Products
A, Pt
Pt
A, Pt
nOlefin
A
A
Pt
A, Pt
nDiene
Pt
nTriene
A
iso-Olefin
Polymers
A, Pt
Pt = Platinum Site
A = Acid Site
Coke
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Pt
Pt
nOlefin
n-Diene
Pt
nOlefin
Pt
n-Diene
Pt
n-Triene
Pt
Aromatics
1302
5
DEH-5
DEH-7
4
3
2
1
0
-1
-2
-3
-4
-5
20
40
60
80
100
120
140
Hours On-Stream
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5
4
DEH-5
DEH-7
3
2
1
0
-1
-2
-3
-4
-5
-5
-4
-3
-2
-1
In paraffin dehydrogenation employing a platinum catalyst, hydrogen is used as a co-feed to increase catalytic
stability by suppressing undesirable consecutive reactions.
Thus, hydrogen also improves selectivity to the desired
mono-olefins.
Reaction conditions, such as temperature, pressure, and
hydrogen-to-paraffin feed ratio, are determined on the basis
of chemical equilibrium analysis and testing of a reference
catalyst. The most important data to be analyzed in the
preliminary evaluation stage are the change of conversion
as a function of time and the change of selectivity as a
function of conversion. For instance, Fig. 7 shows the
conversions of C10C14 n-paraffins obtained with DeH-5TM
and DeH-7TM PacolTM dehydrogenation catalysts. DeH-7
catalyst is more stable than DeH-5.
The selectivity to the corresponding n-mono-olefins for
DeH-7 catalyst is equivalent to DeH-5 catalyst, as shown in
Fig. 8. The results indicate that DeH-7 has superior stability and activity to that of DeH-5 and maintains equivalent selectivity to DeH-5 catalyst. Therefore, using DeH-7
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K2
n-C7=
Reaction: n-C7
K3
n-C7==
Toluene
100
100
90
Experimental
Data
80
80
70
70
n-Heptadiene
Experimental
Data
60
60
50
n-Heptene
90
50
2
10
15
20
25
30
n-C7 Conversion, %
Fig. 9 Simulation of selectivity for dehydrogenation of n-heptane
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1304
Temperature
Equilibrium
Conversion
Conversion
Reheat
Isobutane/H2
Rx1
Reheat
Rx2
Rx3
50
Single-Stage Process
Three-Stage Process
Interstage Reheating
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Conversions, %
40
35
30
25
20
15
10
5
0
-150 -125 -100 -75 -50 25
25
50
Difference of Temperature
and Target Inlet Temperature, C
Fig. 11 Isobutane dehydrogenation
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4 Ethylbenzene Dehydrogenation
As mentioned earlier, the ethylbenzene dehydrogenation
reaction proceeds over an iron or an iron-chromium catalyst
that usually also contains potassium in the form of potassium
carbonate. The reaction takes place at 630 C temperature
and pressure is usually subatmospheric for improved perpass conversion. Steam dilution is practiced to further lower
the partial pressure of the reactants. Because the reaction is
strongly endothermic, various reaction stages with interheat
and interstage addition of superheated steam are normally
employed. Figure 16 illustrates a typical process scheme for
the dehydrogenation of ethylbenzene to styrene.
In an interesting variant of the conventional process,
part of the hydrogen that is produced in the first stage of
conversion is selectively reacted with oxygen over a separate bed of oxidation catalyst such that significant
amounts of heat are released internally within the reactor
system. The hydrogen oxidation catalyst is selected such
that there is practically no conversion or degradation of
either ethylbenzene or styrene to CO2 [37]. While this
process could be thought of as an oxydehydrogenation
process, in reality it is just a conventional dehydrogenation
coupled with an oxidative reheat step. The alternative
ethylbenzene dehydrogenation process, known commercially as SMARTTM (Styrene Monomer by Advanced
Reheat Technology), was originally called the Styro-Plus
process and initially demonstrated at Mitsubishi Chemicals, Kashima, Japan The SMART process is now licensed
jointly by UOP LLC and ABB Lummus Global Inc. In
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Hydrogen-Rich
Off Gas
Light End
Gas
Hydrogen
Recycle Gas
Reactor
Light End
Liquid
Separator
Stripper
Charge
Heater
Benzene
Alumina
Treater
Linear
Paraffin
Charge
Linear
Detergent
Alkylene
UOP
Detergent Alkylate
Process
Paraffin Recycle
Charge
Heater
Air
Heater
Reactor
on Stream
Reactor
on Purge
Gasifier
Fuel
Air
Reactor
on Reheat
Exhaust Air
Steam
Steam
H2 (Optional)
PSA
C3-C5
Paraffin
Cooler
Fuel Gas
Cold Box
Drier
Cooler
Flash
Drum
Product
Compressor
C3-C5 Cut
Halogenated dehydrogenation
Oxydehydrogenation
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1306
Reactor Section
Regeneration
Section
C
C
R
Heater Cells
To SHP
H2 Recycle
Fresh
& Recycle
Feed
Disengaging
Hopper
Dust
Collector
Lift Gas
Blower
R
Regeneration
Tower
R
Catalyst
Lift Lines
Lock
Hopper
Lock
Hopper
Flow
Control
Hopper
Surge
Hopper
Lift
Engager
Lift
Engager
Nitrogen
Lift Gas
H2
Lift Gas
been proposed. Apart from the apparent corrosion problems associated with the use of chlorine, other difficulties
readily come to mind owing to the relatively high cost of
chlorine, and even more so of iodine, and the need to either
dispose of or recycle vast quantities of hydrogen chloride
generated as a byproduct.
Oxydehydrogenation or oxidative dehydrogenation can
be considered in at least two different ways:
123
Net
Separator
Off Gas
As indicated earlier, oxydehydrogenation found successful commercial application in the conversion of nbutenes to butadiene, but not yet for the production of
ethylene or propylene.
1307
Benzene
EB Recovery
Column
Recycle EB
Fresh EB
Benzene/Toluene
Splitter
Fuel Gas
Off Gas
Recovery
Steam
Steam
SM Reactor
Section
Steam
Superheater
Condenser
Toluene
Separator
Waste
Heat
Exchanger
SM Product
SM
Column
Water
EB/SM
Splitter
Tar
The conventional choice in reactor design is the downflow packed bed. Reactants, either vapor or vapor plus
liquid, enter at the top of the catalyst bed and flow down
through the catalyst. The main characteristics of the
downflow reactor are:
Plug flow
Tendency for imperfect distribution of process flow
Relatively high pressure drop
Adiabatic: no temperature control
Inefficient use of the catalyst
Plug flow
Low pressure drop
Easy catalyst replacement
Adiabatic: no temperature control
Limited to single-phase operation
Plug flow
Intrinsically high pressure drop that requires special
catalyst shapes to minimize pressure drop.
Fabrication constraints of large tube sheets
Difficult to load and unload
Limited control of the reactor temperature profile
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1308
Radial
flow
Tubular
Fluidized
bed
7 Conclusions
Catalytic dehydrogenation of paraffins and of ethylbenzene
is a commercial reality in widespread use for numerous
applications. These include the production of light olefins,
heavy olefins, and alkenylaromatics. Oxydehydrogenation,
on the other hand, is still in the developmental stage but if
successful holds great promise due to the potential energy
savings of this process. For the production of heavy olefins,
selective paraffin dehydrogenation over noble metal catalysts has proven to be the preferred and dominant route.
When only one or two light olefins are desired, in particular propylene or isobutylene or perhaps a mixture of
propylene and isobutylene, catalytic dehydrogenation over
noble metal catalysts has acquired a significant and growing market share.
Finally, the choice of reactor plays an important role in
securing the success of a catalytic process. Pressure drop,
heat transfer, and the ability to move or to regenerate the
catalyst all must be taken into account in the process
development and design stages.
References
1. CMAI petrochemical conference, March 2324, 2011; Houston,
TX
2. Grosse AV, Ipatieff VN (1940) Catalytic dehydrogenation of
gaseous paraffins. Ind Eng Chem 32(2):268272
3. Universal dehydro process. Oil Gas J. 22 March 1947, p 179
4. Hornaday GF, Ferrell FM, Mills GA (1961) Manufacture of
mono- and diolefins from paraffins by catalytic dehydrogenation.
In: Kobe KA, McKetta JJ (eds) Advances in petroleum chemistry
and refining, vol 4. Interscience Publishers, New York
5. Egloff G, Davis RF (1951) Polymerization of mono-olefins with
solid phosphoric acid. XII international congress of pure and
applied chemistry, New York, NY, September 1013
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