1

CHAPTER 1
INTRODUCTION
1.0 Introduction
The conceptual design of a fixed bed reactor for the production of propylene for 100000
MTons/year is done by using propane dehydrogenation. According to Qing et al., (2011), the
world demand of propene is fast increasing due to the high demand for polypropylene,
acrylonitrile, propene oxide, cumene, phenol, isopropylic alcohol and many other propene
derivatives. Propane dehydrogenation is one of the techniques for on-purpose propene
production, and several propane dehydrogenations processes, such as Oleex and Caton, have
been commercialized.
Propane dehydrogenation is equilibrium limited and highly endothermic, which is usually
carried out at 500600 C and atmospheric pressure on platinum or chromium catalysts.
However, the dehydrogenation reaction is also accompanied by cracking and coking reactions at
such conditions. While cracking decreases the propene yield, coking deactivates catalyst. As a
result, periodic regeneration of the catalyst is required in industrial operation. Developing
dehydrogenation catalysts with high activity and selectivity as well as good stability against coke
formation remains a challenge.
The propane and/or butane dehydrogenation is the most economical route to propylene,
while it is very complex in thermodynamics and engineering constraints. Therefore, the numbers
of catalysts for both oxidative and direct propane dehydrogenation routes were proposed in last
two decades. Both platinum and chromium based catalysts were largely reported for the alkane
dehydrogenation. The chromium oxide based catalysts have been used in the absence of
hydrogen as a co-feed gas, and platinum-based catalysts were used in the presence of hydrogen.
While, platinum-tin-based catalysts were reported as the most promising catalytic formulation
for propane dehydrogenation. (Zeeshan Nawaz & Fei Wei, 2010)


2

1.1 Background and History
Propylene is an unsaturated organic compound having the chemical formula C
3
H
6
. It has
one double bond, is the second simplest member of the alkene class of hydrocarbons, and is also
second in natural abundance. The chemical structure of propylene is shown below: (Propene, n.d.)

Figure 1 : Propylene 2D structure Figure 2 : Propene-2D-flat.
Propylene is produced primarily as a by-product of petroleum refining and of ethylene
production by steam cracking of hydrocarbon feed stocks. Also, it can be produced in an on-
purpose reaction (for example, in propane dehydrogenation, metathesis or syngas-to-olefins
plants). It is a major industrial chemical intermediate that serves as one of the building blocks for
an array of chemical and plastic products, and was also the first petrochemical employed on an
industrial scale.
Commercial propylene is a colourless, low-boiling, flammable, and highly volatile gas.
Propylene is traded commercially in three grades:
1. Polymer Grade (PG): min. 99.5% of purity.
2. Chemical Grade (CG): 90-96% of purity.
3. Refinery Grade (RG): 50-70% of purity.
Propylene has a calorific value of 45.813kJ/kg. Also, propylene is used as a motor
gasoline component for octane enhancement via dimerization formation of polygasoline or
alkylation.
The boiling point and freezing point of propylene are -47.7 C and -185.3 C respectively.
Propylene is stored as a refrigerated liquid at -47C and transported by refrigerated vessels.
3

Tanks and pipes should be made of stainless steel or nickel alloys with suitable insulation. It can
be transported by tank trucks in the same manner as LPG.
Propane dehydrogenation is a catalytic process that converts propane into propylene and
hydrogen (byproduct). The yield of propylene from propane is about 85 wt%. The reaction by-
products (mainly hydrogen) are usually used as fuel for the propane dehydrogenation reaction.
As a result, propylene tends to be the only product, unless local demand exists for the hydrogen
by-product. PtSn-based catalysts supported on amorphous supports or zeolites for propane
dehydrogenation have been investigated extensively. The presence of Sn as a promoter helps in
dispersing Pt metal and largely suppresses coke forming reactions, and therefore significantly
improves catalytic performance.( Liu et al., 2011)

1.2 Application
Propene or propylene is the second most important starting product in the petrochemical
industry after ethylene. It is the raw material for a wide variety of products. Polypropylene is
needed for the production of films, packaging, caps and closures as well as for other applications.
Polypropylene is used to make straws, baby bottles and yogurt containers, as well as many of the
food storage containers sold in stores. Polypropylene plastics have a high melting point and are
often used to hold hot liquids. Polypropylene plastics are not considered harmful to our body.
Propylene glycol is considered generally recognized as safe (GRAS) by the U.S. Food
and Drug Administration, and it is used as an humectant, solvent, and preservative in food and
for tobacco products, as well as being the major ingredient in the liquid used in electronic
cigarettes. It is also used in pharmaceutical and personal care products. Propylene glycol is a
solvent in many pharmaceuticals, including oral, injectable andtopical formulations, such as
for diazepam and lorazepam that are insoluble in water, use propylene glycol as a solvent in
their clinical, injectable forms. Like ethylene glycol, propylene glycol is able to lower the
freezing point of water, and so it is used as aircraft de-icing fluid. It is similarly used as
automotive antifreeze. Water-propylene glycol mixtures dyed pink to indicate the mixture is
relatively nontoxic are sold under the name of an RV or marine antifreeze

4

Propylene carbonate is another product of propylene oxide. It combines PG and carbonic
acid to make a solvent that is colorless and odorless. This property makes it a useful solvent for
lithium batteries. It has a variety of other industrial applications, including the formulation of
cosmetics and as a plasticizer.
1.3 Raw material
Propane dehydrogenation converts propane into propylene and by-product hydrogen.
Dehydrogenation a reaction in which hydrogen is detached from a molecule .The reaction is
strongly endothermic, and therefore heat must be supplied to maintain the reaction temperature.
(The American Heritage Dictionary of the English Language, 2009) Propene is an saturated organic
compound having the chemical formula C
3
H
8
,while propylene is the second member of the
alkene series with chemical formula C
3
H
6
. Reaction by-products mainly hydrogen are usually
used as fuel for the propane dehydrogenation reaction. As a result, propylene tends to be the only
product, unless local demand exists for hydrogen. The propane dehydrogenation process may be
accomplished through different commercial technologies. The main differences between each of
them concerns the catalyst employed, design of the reactor and strategies to achieve higher
conversion rates.

1.4 Production and Technologies







Figure 1.1 : Block Flow diagram of Dehydrogenation of Propane

Fractional
Distillation
Column
Dehydrogenation
Reactor
Propane
Flue Gas
Propane
Hydrogen
Propylene
5

Figure 1.1 describes the flow process of dehydrogenation of propane to form propylene. The feed
which enters the reactor is propane at a high temperature between 798-978 K and at a low
pressure of about 1 bar with the presence of Sn/Pt catalyst to promote the reaction process. After
the reaction take place in the reactor the products and by-products are then distillated in a
fractional distillation column.Upon the reaction, unreacted propane and produced hydrogen gas
are recycled back to the reactor for the process to continue in a continuous cycle.
Table 1.3 : Parameters of Propane Dehydrogenation Process Technology
Process UOP Oleflex Uhde STAR
Reactor Type Adiabatic Isothermal
Total number of reactors 4 8
Duration of cycles Continuous 8 hours
Process Condition
Temperature (K) 798-978 755-894
Pressure (bar) 1-3 3-8
Propane conversion (%) 40 30-40
Selectivity to C3H6 90 80-90
CCR Yes No

Based on Kotanjac.,(2009), dehydrogenation is an endothermic equilibrium reaction that
is generally carried out in the presence of a noble- or heavy-metal catalyst such as platinum or
chromium.
C
3
H
8
C
3
H
6
+ H
2

The process is highly selective and overall yields of propene from propane of 90% are
claimed for commercially available processes. As a consequence of thermodynamics, higher
temperature and lower pressure increases olefin yield. However, increased process temperature
also causes pyrolysis (cracking) of alkane to coke in addition to its dehydrogenation, whereas
lower operating pressure increases selectivity. Coke formation wastes feedstock and deactivates
the dehydrogenation catalyst. By mixing the catalyst with inert material, much of the heat
liberated during coke oxidation can be captured and used to drive the endothermic
dehydrogenation. Dehydrogenation processes are operated near atmospheric pressure at around
500700C.
6

Table 1.3 compares two catalytic reaction systems using different technologies in the
dehydrogenation of propane namely the UOP Oleflex and Uhde STAR process. The OLEFLEX
process uses multiple side-by-side, radial flow, moving-bed reactors connected in series.The
reaction is carried out over platinum supported on stanum, under near adiabatic conditions. The
catalyst system employs UOP's Continuous Catalyst Regeneration (CCR) technology.CCR is a
process whereby the catalyst is continuously withdrawn from the reactor, then regenerated, and
fed back to the reactor bed. A series of lock hoppers, typically four complete lock hopper
arrangements, are used to move catalyst from the reactor to the regenerator and eventually back
into the reactor. The continuous catalyst regenerator makes it possible to manage the high
catalyst coking rate to achieve the constancy of the yields as this process id done in a high
temperature. The bed of catalyst slowly flows concurrently with the reactants and is removed
from the last reactor and regenerated in a separate section. The reconditioned catalyst is then
returned to the top of the first reactor.
Next is the Phillips Steam Active Reforming (STAR) process which uses a noble metal-
promoted zinc aluminate spinel catalyst in a fixed-bed reactor. The reaction is carried out with
steam in tubes that are packed with catalyst and located in a furnace. The catalyst is a solid,
particulate noble metal. Steam is added to the hydrocarbon feed to provide heat to the
endothermic reaction, to suppress coke formation, and to increase the equilibrium conversion by
lowering partial pressures of hydrogen and propane.
From the above,the UOP Olefex method is prefered to be used in our reaction
system.This is due to the UOP's Continuous Catalyst Regeneration (CCR) technology employed
in this process. This is because the constancy of the yields is achieved by the CCR section, which
ensures the reactors to be continuously supplied with freshly regenerated catalyst, and product
yields are maintained at fresh catalyst levels. Besides it also protects the catalyst and the
equipments resulting in maximum catalyst life and minimum maintenance requirement.Hence
this enables the coking process to be overcomed to a certain extent and retains a high selectivity
in the reaction process.Further more Oleflex process only requires 4 reactors for the reaction to
take place compared to STAR ,8 reactors.With this the production cost using Oleflex will be
much cheaper than STAR.

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1.5 Reaction Kinetics
1.5.1 Propane Dehydrogenation
The dehydrogenation reaction is considered as the main reaction (R1) governing propane and
hydrogen concentrations along the reactor. Both cracking and hydrogenolysis reactions may
occur by single or multiple CC bond rupture according to the catalyst formulation and operating
conditions. Acidic sites on the support promote cracking (R2) and coke formation reactions.
Dehydrogenation virtually occurs on all platinum sites, while hydrogenolysis (R3) occurs on low
coordination sites. Consequently, reactions (R2) and (R3) can represent the side
reactions.(Sahebdelfar et al.,2011)
Main Reaction
C
3
H
8
C
3
H
6
+ H
2
(R1)


Side Reaction
C
3
H
8
C
2
H
4
+ CH
4
(R2)
C
3
H
8
+H
2
C
2
H
6
+ CH
4
(R3)

According to Qing et al., (2011), LangmuirHinshelwood (LH) kinetic models for catalytic
propane dehydrogenation on Pt-Sn/Al
2
O
3
are proposed based on the reaction mechanisms that
take into account the one step or two-step dehydrogenation. Besides, LH establishes the kinetic
models by assuming different reaction mechanisms and rate-determining steps.
In the first mechanism, direct dehydrogenation of gas phase molecule to propene on Pt surface,
hydrogen dissociative adsorption, and propene desorption are involved.
Surface reaction (S1): C
3
H
8
+ 3S

C
3
H
6
S + 2HS
Adsorption (S2): 2HS

H
2
+ 2S K
3
=

Desorption (S3): C
3
H
6
S

C
3
H
6
+ S K
2
=

K
-1
K
a3
K
a2
8

In fact, this is a simple mechanism that lumps up all the possible dehydrogenation steps. By
assuming the surface reaction (S1) as the rate-determining step, the rate of propane conversion
is:
r
1
=

Where

atm
If the hydrogen adsorption (S2) is weak, the rate expression can be simplified to
r
2
=

In another mechanism, both propene and hydrogen adsorption are considered but
dehydrogenation is assumed to proceed step by step, i.e.
The first CH bond cleavage of propane (C1)
C
3
H
8
+ 2S

C
3
H
7
S + HS K=

The second CH bond cleavage of propane (C2)
C
3
H
8
+ S

C
3
H
6
S + HS K=

C
3
H
6
S

C
3
H
6
+ S
2HS

H
2
+ 2S
If the first CH bond cleavage of propane (C1) is the rate determining step, the rate expression
can be derived as:
r
3
=

k
-1
K
a2
K

-2
K
a3
9

If the second step with second CH bond cleavage of propane (C2) is the rate-limiting step, the
rate expression is:
r
4
=

By assuming negligible surface coverage of C
3
H
7
, or C
3
H
6
as the only dominating surface
species, or H atom as the only dominating surface species, the rate expression can be further
simplified to below
r
3-1
=

r
3-2
=

r
3-3
=

1.5.2 Propane Cracking
The side reaction considered is the cracking of propane to methane and ethylene (Ra, i.e.
C
3
H
8
CH
4
+ C
2
H
4

The cracking rate is assumed to be first order with respect to propane,
r
cracking
= k
2
P
C3H8
1.5.3 Coke formation and catalyst deactivation
Coke formation may from different paths, such as deep cracking of propane, polymerization of
olefins (mainly propene) and condensation of large molecules. The coke is mainly formed by
two mechanisms, i.e., deep cracking of propane that leads to graphitized carbon, and
polymerization that lead to polyaromatics. These two mechanisms are represented by The deep
10

propane cracking (R4) and the propene polymerization (R5) can be assumed to be first order
with respect to propane and propene.
C
3
H
8
3C + 4H
2
(R4)
nC
3
H
6
3nCH
0.5
+ 2.25nH
2
(R5)
As H
2
has definite influences on the coking rate, it should be included in the coking rate
equation. H
2
inhibits coke formation mainly by promoting propene desorption and decreasing the
surface coverage of propene, which lowers the rate of deep cracking or polymerization of
propene. Propene actually is the precursor for deep cracking and polymerization, and the
influence of hydrogen on the coking rate is assumed the same for both deep cracking and for
polymerization. Therefore, the coking rate on fresh catalyst is defined as:
r
co
=

where P
C3H6
and P
H2
are the partial pressures of propene and hydrogen. On partially coked
catalyst, the coking rate is
r
c
= a
c
r
c0

where ac is the activity of the catalyst for coke formation.
As usual, the rate of propane dehydrogenation is written as
r = ar
0

where r
0
is the rate on fresh catalyst, and a is the activity of the catalyst. The change of catalyst
activity with time generally takes the form
-

=
d
(pi,T)a
d
where d is the deactivation order and d the deactivation function, usually expressed in a LH
form. Assume that coke formation takes place on the same site for propane dehydrogenation, and
only one site is involved in the rate determining steps for both propane dehydrogenation and
11

coke formation, we have a first order catalyst deactivation and the same deactivation rate for
propane dehydrogenation and coke formation, i.e.
a
c
= a =

where Cc is the concentration of the active sites occupied by the coke and Cm is the total
concentration of the active sites. Therefore, equation of coking rate is rewritten as

r
co
Replacing Cc with Cm(1a) yields
-

a=

a k
d=

12

References
Sahebdelfar, S., Ravanchi, M.T., Zangeneh, F.T., Mehrazma, S., Rajabi, S., (2011). Kinetic study
of propane dehydrogenation and side reactions over PtSn/Al
2
O
3
catalyst. Chemical
Engineering Research and Design. 90(2012), 1090-1097.
Qing, L., Zhijun, S., Xinggui, Z., Chen, D., (2011). Kinetics of propane dehydrogenation over
PtSn/Al
2
O
3
catalyst. Appl. Catal. A 398, 1826.
Sahebdelfar S., Zangeneh F. T. , Dehydrogenation of Propane to Propylene Over Pt-Sn/Al2O3
Catalysts: The influence of operating conditions on product selectivity. Iranian Journal
of Chemical Engineering Vol. 7, No. 2 (Spring), 2010, IAChE, Catalyst Research Group,
Petrochemical Research and Technology Company, National Petrochemical Company,
Tehran, Iran.

Kotanjac .,(2009). Development of packed bed membrane reactor for the oxidative
dehydrogenation of propane. Gildeprint B.V., Enschede,_e Netherland.s

McGraw-Hill Concise Encyclopedia of Engineering. ( 2002 )by The McGraw-Hill Companies,
Inc.Retrieved from http://encyclopedia2.thefreedictionary.com/dehydrogenation on 4
October 2013.

The American Heritage Dictionary of the English Language, (2009). Retrieved from
http://www.thefreedictionary.com/propylene on 4 October 2013.

Propene, (n.d.). Retrieved from http://www.chemspider.com/Chemical-Structure.7954.html on 4
October 2013.