PROPANE DEHYDROGENATION: REACTION ROUTES,

CATALYSTS, REACTOR CONFIGURATIONS AND LAB

TESTING

Mohamad Abou Daher

Youssef Al Ashkar
Isa Al Aslani
OUTLINE

• Motivation
• Different routes for propane dehydrogenation
• Proposed catalyst based on our selection criteria
• Suggested:
• Catalyst preparation and scale-up
• Textural and active sites characterization
• Deactivation and coke formation analysis
• Lab testing and kinetics study
• Recommendation
MOTIVATION

•ACS Catal. 2014, 4, 3357−3380

 MOTIVATION

Appl Petrochem Res 5, 377–392 (2015).

DIRECT PROPANE
DEHYDROGENATION
OVERVIEW

•  
• Electronic effect
• Strong and localized C-C and C-H bonds

• Geometric effect
• H can bond from all directions (1s orbital)
• Methyl group has one optimal bonding direction (sp3-hybridized carbon atom)
 SELECTIVITY

• Intermediates and products are more reactive than propane

• Stronger adsorption  higher activity but lower selectivity
• Weaker adsorption  lower activity but higher selectivity
TWO COMMERCIALIZED
CATALYST TYPES
• Pt-based catalysts
• CrOx-based catalysts
PT-BASED CATALYSTS
PROBLEMS WITH PT-BASED
CATALYST
• Coke formation
• Sintering

• Solution: promoters and good supports

SUPPORTS

• Most widely used: Al2O3 (alumina)

• High acidity results in serious cracking and coke formation
• Non-acidic metal oxides are added to counter that
• Other supports: Mg(Ga)(Al)O, Mg(Zn)AlOx, In/Mg(Al)O-x
• Enhanced structure, surface and electronic properties, and lower acidity
Higher stability and anti-coking capability
• Also possible: zeolites and nanocarbons
PROMOTERS

• Reason: reduce coke formation and sintering of Pt clusters

• Examples: Sn, In, Zn, Cu, Mn, and Fe
• Functionality: alter the structural, dispersion, and electronic properties of the catalyst
surface
• Example: In can poison the Brönsted acid sites, and thus prevent side reactions such as
isomerization and coke formation
 CROX-BASED CATALYSTS
• Mechanism
SUPPORTS

• Affect dispersion of active sites, electronic properties, and structure

• Most widely used: Al2O3 (alumina)
• Others: zirconia (ZrO2), mesoporous Al2O3, Zr-O, and CMK-3
• They all lack stability  promoters
PROMOTERS

• Examples: K, Ce, Ni, and Sn

• Alkali metals: K, Na, Ca, and Mg
• Poison acid sites and reduce deactivation rate and coke formation
• Drawback: they also poison Lewis acid sites
• Alternatively: transition metals like Sn, Ni, Ce, Sb, Co, and Bi
• affect dispersion, oxygen capacity, and surface properties of CrOx-based catalysts
REACTORS
• Fixed bed reactor
• Catofin process (CrOx/Al2O3)
• Moving bed reactor
• Oleflex process
• Fluidized bed reactor (FBD-4 reactor)
• Uses CrOx/Al2O3 catalyst
• High heat transfer efficiency
• Heat supplied by regenerated catalyst
• Downside: environmental effect
 MEMBRANE
REACTORS
• Push the reaction to the right.

• Main Limitations related to membrane

cost (Pt-based) and heat transfer
limitations.
 AUTOTHERMAL
• Thermodynamic
  Limitations

• Reduce the energy requirement

• SHC over single (Pt-based) or Multi-

catalyst systems (Requires special SOC: ).
OXIDATIVE DEHYDROGENATION (ODH)
• Drawbacks of direct dehydrogenation:
• equilibrium limitations
• necessitating high energy input as the reaction is endothermic
• coke formation that facilitates catalyst deactivation
•  The oxidative dehydrogenation (ODH) leads to:
• burning hydrogen (equilibrium shift)
• exothermic
• no coking

-
OXIDATIVE DEHYDROGENATION (ODH)

• But with oxygen:

• deep oxidation (poor selectivity)
• heat removal (overheating)
•  Use of mild/soft oxidants (CO2, N2O, SO2 and S2 gas)
OXIDATIVE DEHYDROGENATION (ODH) –
CO2
• Some catalyst systems were negatively affected by coupling with Reverse Water Gas Shift
reaction (RWGS) – reaction (2)
• However, this may result in additional coke deposition due to the increased CO partial
pressure.
 Catalyst Total
Catalyst Propylene Environmental Price lifetime Score
yield (0.35) Effect(0.1) (0.25)
(0.3) [%]

SELECTION 7.5Cr/Al2O3 55.18 10 75 6.67 41

20 Cr/Al2O3 37.53 5 80 13.33 37.6
CrZrOx   25.5 10 100 2.67 35.7
Go with Direct DH since it is
industrially adopted. PtSn/MgAl2O4 29.7 60 10 11 22.2
PtSnAl0.2/SBA-
55 60 10 20 33.75
15

PtIn/MgAlO- 67.6 60 7 100 61.4

600

Gaδ+Pt0/SiO2 31.6 60 10 67 39.66

PREPARATION: SUPPORT

1:4 ratio 20 mins pH 9-10

Niar Kurnia et al. Effect of Calcination at Synthesis of Mg-Al Hydrotalcite Using co-Precipitation
Method. The Journal of Pure and Applied Chemistry Research, [S.l.], v. 6, n. 1, p. 7-13, jan. 2017.
ISSN 2541-0733.
PREPARATION: CATALYST
• Sequential Impregnation:
InNO3 impregnated onto hydrotalcite
drying at 50 °C for 3h
drying at 120 °C for 2h
calcination at 550 °C for 4h
H2PtCl6 solution also impregnated
same procedure is repeated
 LAB TESTING
• GC for product analysis

• High-throughput catalyst testing

 TRANSPORT LIMITATIONS
Mass Transport
Heat Transport
KINETIC STUDY
• At various Compositions, T, P, WHSV and Tos

• Coke formation as function of Tos, T,

C*&CH3CC*

• Langmuir–Hinshelwood kinetic model

• Gives Insights on Catalyst performance (Yield

and Lifetime) and optimal operating conditions.
• For steady state runs operate at differential
conditions.
• Might need to dilute your catalyst.
TEMKIN REACTOR FOR
INDUSTRIAL CATALYSTS
• Industrial catalyst testing with lower
loading than PBR and lower testing time
than catalytic wall-reactor and BRETY-
reactor.

• Coupling Numerical and Experimental

Data.

• Form a global view of our catalyst

performance.
TEXTURAL CHARACTERIZATION

• Activity is to be measured by CO adsorption assuming CO/surface Pt=1 and quantified by

FTIR (other complementary techniques such as TEM).

• The catalyst acidity is characterized by using NH3-TPD

TEXTURAL CHARACTERIZATION (SEM)
TEXTURAL CHARACTERIZATION (XRD)
TEXTURAL CHARACTERIZATION (N2
ADSORPTION)
ACTIVE SITES CHARACTERIZATION (H2-TPR)
ACTIVE SITES CHARACTERIZATION (XPS)
ACTIVATION/
DEACTIVATION STUDIES
• Raman spectroscopy to study the effect of
feed composition and promoters on coke
formation and
• TGA for quantitative analysis.

• Monitor sintering after each air

regeneration(XRD and CO adsorption)
FUTURE WORK
• Investigate possible synergic effect of using
PtSnIn/MgAl(O) to couple the effectiveness of Sn in
producing smaller graphite crystallites.

• Similar effect was observed for cofeeding hydrogen, so it I

worth investigation.

• Study the effect of dichlorination

• Perform PDH using supported catalysts (e.g. packed

metallic foams).
THANK YOU
MOTIVATION
MOTIVATION
SEQUENTIAL IMPREGNATION

• Fast, inexpensive, final property and configuration controllable in advance

• However:
• hard to prepare high concentration catalyst
• Hard to obtain even dispersion of catalyst components on the surface
CO-PRECIPITATION

• Advantages:
• Homogeneity of component distribution
• Relatively low reaction temperature
• Fine and uniform particle size with weakly agglomerated particles
• low cost
• Disadvantages:
• Not a controlled process in terms of reaction kinetics
• Synthesized solids have uncontrolled particle morphology with agglomeration and incomplete
precipitation of the metal ions
COKE CHARACTERIZATION (TPO & TG)
ACTIVITY-STRUCTURE RELATIONSHIP
ACTIVITY-STRUCTURE
RELATIONSHIP
STABILITY-STRUCTURE RELATIONSHIP
OXIDATIVE DEHYDROGENATION
(ODH)
• Drawbacks of direct PDH:
• Equilibrium limitations
• necessitating high energy input as the reaction is endothermic
• coke formation that facilitates catalyst deactivation
•  The oxidation occurred with oxygen leads to no coking

-
OXIDATIVE DEHYDROGENATION
(ODH)
• Resulted hydrogen from the reaction is consumed by oxygen which makes the reaction:
• not limited by equilibrium
• high reaction rate and conversion levels can be achieved especially at high temperature and low
pressures
•  The purpose of using mild/soft oxidants (CO2, N2O, SO2 and S2 gas):
• resolve the problem of deep oxidation and heat removal associated with oxygen
OXIDATIVE DEHYDROGENATION
(ODH) – CO2
• Still endothermic 
• However, some catalyst systems were negatively affected by this coupled effect without
clear explanation provided in the literature.
OXIDATIVE DEHYDROGENATION (ODH) – CO2
• For this reaction to occur, the catalyst should have the affinity to adsorb CO2 and activate C-
H bond instead of C-C to avoid side reactions such as dry reforming.
OXIDATIVE DEHYDROGENATION (ODH) – CO2
TEXTURAL CHARACTERIZATION (TEM)
TEXTURAL CHARACTERIZATION (TEM)
TEXTURAL CHARACTERIZATION (N2
ADSORPTION)
ACTIVE SITES CHARACTERIZATION (NH3-
TPD)
ACTIVE SITES CHARACTERIZATION (NH3-
TPD)