Performance of catalyst in PDH with optimum operating conditions

Author/date
Catalysts Used Pt-Sn/Al2O3 Cr2O3/Al2O3 Pt-based catalyst
Radial moving bed
Reactor Fixed-bed reactor Fixed-bed reactor
reactor
Langmuir– Langmuir– Langmuir–
Reaction Kinetics Hinshelwood Hinshelwood Hinshelwood
mechanism mechanism mechanism
Conversion 48% 35% 34.48%
Selectivity 83% 82% 85.69%
Yield 36% - 30.34%
0.039 g coke/ g 0.029 g coke/ g 0.0416 g coke/ g
Coke content
catalyst catalyst catalyst
rate 6 9 9

General factors that will affect propane dehydrogenation reaction:

Effects of mass and heat transports on the reactions:
- When catalyst weight/volume flow rate ratio (W/F) ratio is large (e.g. >50 gmin/mol), for
same W/F ratio, conversion will be different
-When the W/F ratio is smaller than 50 gmin/mol, the influence of external transport can be
neglected.

Effect of reactor Inlet temperature (RIT)

-When weighted average inlet temperature (WAIT) increases, propane conversion and
propylene yield also increase. However, higher WAIT also promotes side reactions such as
cracking and coking, resulting in lower propylene selectivity.

Effect of reaction temperature

- Since the reaction is endothermic, an increase in temperature enhances the conversion of
propane due to both kinetic and thermodynamic factors.
- At higher temperature one may expect a larger decrease in propylene selectivity due to non-
catalytic gas-phase reactions bringing about coke formation and catalyst deactivation.

Effect of Hydrogen to hydrocarbon (H2/HC) molar ratio

- Higher hydrogen to hydrocarbon ratios resulted in higher propylene selectivity at the
expense of lower propane conversion.
-Increase in partial pressure of hydrogen has not only decreased the thermodynamic driving
force of the reaction, but also kinetically reduced the rate of dehydrogenation reaction due to
the competition of hydrogen with propane for the platinum active sites
-At higher propane conversion, reduction of molar ratio will increase propane conversion and
propylene selectivity.
-However, Low H2/HC molar ratio would accelerate the catalyst deactivation by coking.
Effect of Catalyst Circulation Rate (Us)
- Propane conversion and propylene selectivity increase with the increase of Us.
- Increase of Us has increased the catalyst regeneration rate and reduced the reaction
exposure time of the catalyst due to the lesser coke content and higher catalyst activity
- Increase of propylene selectivity with the increase of Us might be attributed to the lower
propane concentration in the reactor which promotes the hydrogenolysis reaction

Effect of Weighted Hourly Space Velocity (WHSV)

- Conversion decreases with WHSV at specified temperature.
- Total selectivity increases with WHSV, because a decline in residence time cause a
decrease in side reactions.
-Space time yield increases when WHSV increases. However, higher space velocities should
result in the shift to the kinetic-controlled regime and decreasing propane conversion which
means higher cost of separation and feed recycle, which is not desirable.
Effect of coking and cracking
- Coking leads to catalyst deactivation.
- Cracking decreases reaction selectivity.
Reaction Kinetics
https://pubs.rsc.org/en/content/articlelanding/2013/cy/c2cy20488f#!divAbstract
-Kinetic modelling of propane dehydrogenation was done using the Langmuir–Hinshelwood–
Hougen–Watson (LHHW) approach
This experimental results and kinetic analysis suggest that the most probable reaction model
(III-4, see Table 2) for propane dehydrogenation over Pt–Sn/Al2O3 is the following:
- Non-dissociative adsorption of propane on the catalyst (step 2).
- Dehydrogenation yielding propene (which remains adsorbed on the catalyst surface) and
simultaneous desorption of hydrogen (step 4).
- Propene desorption from the catalyst surface (step 9).

https://www.researchgate.net/publication/251618296_Kinetics_of_propane_dehydrogenation
_over_Pt-SnAl_2O_3_catalyst
In this mechanism, both propene and hydrogen adsorption are considered but
dehydrogenation is assumed to proceed step by step.
 If the first C–H bond cleavage of propane (II1) is the rate-determining step, the rate
expression is as follows:

By assuming negligible surface coverage of C3H7 as the only dominating surface species,
rate expression can be simplified to (M2-1)

Comparison between Reactors

Author/Date Type of reactor Feed ratio PressureTemperature

Residence timeWHSV ConversionSelectivity Yield Rate
Fixed bed reactor 19% 90% 18% 13
Ziaka 2010 H2/C3H8=0.2 3psig 540°C 2 secs -
Catalytic dehydrogenation membrane reactor 25% 95% 30% 7
Fixed bed reactor 22% 95% 21% 10
Nawaz 2010 H2/C3H8=0.25 - 590°C - 5.6h^-1
Fluidized bed reactor 26% 98% 25% 6
Yee 2014 Radial moving bed reactor H2/C3H8=0.2 2-36psig 620°C - 2.2h^-1 34.48% 85.69% 30.34% 6

Types of Reactors Advantages Disadvantages

Fixed bed reactor  High conversion rate  Rapid deactivation of
per weight of catalyst
catalyst.  Require use of at least 2
 Easy to build. reactors
 More contact  Difficult temperature
between reactant and control.
catalyst than in other  Temperature gradients may
types of reactors. occur.
 More product is  Catalyst difficult to replace.
formed due to  Channeling of gas stream
increased can occur, leading to
reactant/catalyst ineffective regions in the
contact. reactor.
 Low cost of  Side reactions possible.
construction,  Heat transfer to or from
operation, and reactor can be difficult.
maintenance.
 Effective at high
temperatures and
pressures.

Fluidized bed reactor  Even temperature  Require a sub-atmospheric

 distribution pressure to allow its
eliminates hot spots. successful operation which
 Catalyst is easily will restrain WHSV and
replaced or affect rate of
regenerated. dehydrogenation
 Allows for  Expensive to construct and
continuous, maintain.
automatically  Erosion of reactor walls may
controlled occur.
operations.  Regeneration equipment
 More efficient for catalyst is expensive.
contacting of gas and  Catalyst may be deactivated.
solid than in other  Can't be used with catalyst
catalytic reactors. solids that won't flow freely.
 Large pressure drop.
 Attrition, break-up of
catalyst pellets due to impact
against reactor walls, can
occur.

Moving bed reactor  Allow continuous  Flow of solids not easy to

operation and maintain
transfer of catalyst  Poor heat transfer
into and from characteristics
reaction zone  Fluid reactant may bypass
 Operation can be catalyst bed
carried out at sub-  Solid distribution difficult to
atmospheric pressure maintain
 provides a  Stagnation may occur
continuous  Attrition, break-up of
replacement of de- catalyst pellets due to impact
activated catalyst against reactor walls, may
 Easy to regenerate occur
catalyst
 Have plug flow
characteristics
 Low catalyst
handling cost
 High conversion rate
 Good selectivity

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/PBR/PBR.html
http://encyclopedia.che.engin.umich.edu/Pages/Reactors/FBR/FBR.html
http://encyclopedia.che.engin.umich.edu/Pages/Reactors/MovingBed/MovingBed.html