dehydrogenation
I. Indirect and direct routes for conversion of methane into methanol and olefins
II. (Oxidative) dehydrogenation of propane and subsequent selective oxidation of propylene in a
propane/propylene mixture to acrylic acid (KT purpose)
III. Direct conversion of CO2 into dimethyl carbonate (DMC) and dimethylether (DME) and methanol (MeOH)
2
PROPYLENE MARKET & PRODUCTION
Among the olefins, PROPYLENE is the world’s second largest petrochemical commodity
63% Polypropylene
R.M. Pandia, Maximising Propylene Yields Conference, June 19-20th, 2013, Frankfurt, Germany 3
PROPYLENE MARKET & PRODUCTION
Refinery Fluid Catalytic Cracking (FCC) units also contribute to a significant portion
of global propylene supply (30%)
To intensificate production
routes aiming to the
ACTUAL TREND product of propylene as
primary product
4
PROPYLENE MARKET & PRODUCTION
Shale gas production in the USA is projected to increase from 20% of total production to over 50% by
2040
Ethane cracking may also become economically attractive in other parts of the world in the coming
years
6
PROPANE DEHYDROGENATION
CnH2m = CnHm + H2
100
1.1 bar 2 bar 4 bar 6 8 bar 10 bar
80
C3H8 conversion, %
60
40
20
0
500 600 700 800 900 1000 1100 1200
Temperature, K
The lighter is the feedstock, the higher is the The higher is the pressure, the lower is the
temperature for conversion conversion
7
PROPANE DEHYDROGENATION
100
Catalyst Pt-based
Propene Selectivity, % 80
Thermodynamic equilibrium
60
40
20
0
300 400 500 600 700 800 900
Temperature, °C
Necessity to use a catalyst to improve the selectivity to propylene, minimizing the formation of by-products
such a C2H6, C2H4 and CH4 and coke SELECTIVE DEHYDROGENATION
Necessity to operate at the lowest possible temperature, in order to further improve the selectivity
Results from numerical simulation 8
PROPANE SELECTIVE DEHYDROGENATION
CATOFIN process
Licensor : ABB Lummus
Cr2O3/Al2O3 catalyst
Parallel adiabatic fixed bed
Operation under slight vacuum (0.5 bar)
Temperature : 860-920K
Some reactors are on stream, others in
regeneration
OLEFLEX process
Licensor : UOP
Pt/Al2O3 catalyst
Adiabatic moving beds
Operation under slight pressure (2 bar)
Temperature : 820-890K
Continous regeneration
9
PROPANE SELECTIVE DEHYDROGENATION
10
MEMBRANE BASED PDH
H2 + Sweep gas
REACTOR REACTOR
P = 5 bara
P = 1 bara
P = 10 bara
Catalyst
13
MEMBRANE BASED PDH
90
80
Propylene Selectivity, %
70
60
50
T = 540°C
T = 540°C T = 540°C
MEMBRANE REQUIREMENTS
High hydrogen flux
18
MEMBRANE BASED PDH
Closed Architecture
catalyst
Reactant
membrane
Open Architecture H2
FEED
Reaction Reaction
Retentate
On the basis of experimental results up to now KT – Kinetics Technology has developed a process scheme
with integration in open architecture for 4 scenarios
Simulation of DH reactor employing catalyst kinetic expressions of literature for Pt based catalysts
Feed to DH reactor: 80%C3H8, 20% H2O. Methane, ethane, ethylene, butane, butene as by
products:
Due to little conversion in each reactor, we condider it as pseudoisothermal one and heated by
external electrical source for pilot plant, by molten salts for large scale concept
Pressure: 10 bara
20
G. Iaquaniello, E. Palo, Method for olefins production, EP Application 11160218.1, 29 March 2011
MEMBRANE BASED PDH
Purification section
21
MEMBRANE BASED PDH
First scenario T:500°C, WHSV: 6 h-1 Second scenario T:500°C, WHSV: 8 h-1
Overall Membrane surface = 334 cm2 Overall Membrane surface = 372 cm2
Third scenario T:530°C, WHSV: 6 h-1 Fourth scenario T:530°C, WHSV: 8 h-1
Overall Catalyst volume = 2.4 liters Overall Catalyst volume = 1.8 liters
Overall Membrane surface = 256 cm2 Overall Membrane surface = 256 cm2
The evaluation of membrane surface is under assumption of its ideal behaviour without
considering any fouling phenomena
22
CONCLUSIONS
Shale gas discovery as well as the huge increase in propylene demand in the uncoming years pushes
to the intensification of selective propane dehydrogenation process
Commercialized technologies cannot be scaled down to 1/5 of capacity owing to extremely high plant
complexity linked to catalyst regeneration procedure
The coupling of dehydrogenation reactor with a membrane for hydrogen separation could help to
substantially lower the reaction temperature, thus limiting but not avoiding the catalyst deactivation
The design of membrane assisted dehydrogenation reactor requires the optimization of several
parameters:
The reactor geometry should take into account the decoking procedure for the catalyst
23
ACKNOWLEDGMENT
EUROPEAN COMMISSION
IS GRATEFULLY ACKNOWLEDGED
FOR THE FINANCIAL SUPPORT
24
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