Novel process scheme for selective propane

dehydrogenation

C. Croppi, G. Iaquaniello, E. Palo, A. Salladini

Workshop on scale-up of Pd Membrane Technology

From fundamentals to Pilot demonstration
November 20th-21st, 2014, Petten, The Netherlands
 INTRODUCTION
European Project “CARENA”
Project full title: CAtalytic membrane REactors based on New mAterials for C1-C4 valorization

Project Acronym: CARENA (Coordinator: Mr. A. de Groot)

Duration period: 1st June, 2011 – 31th May, 2015

Main objective:
To develop and implement novel nano-structured materials and optimized membrane-reactor based chemical
processes to enable the efficient conversion of light alkanes and CO2 into higher valuable chemicals

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

37% Cumene, Acrylonitrile, Acrylic Acid, Isopropanol, Propylene Oxide, Oligomers

R.M. Pandia, Maximising Propylene Yields Conference, June 19-20th, 2013, Frankfurt, Germany 3
 PROPYLENE MARKET & PRODUCTION

Most propylene is produced by steam crackers (55%) as a by-product of ethylene

Refinery Fluid Catalytic Cracking (FCC) units also contribute to a significant portion
of global propylene supply (30%)

Other on-purpose propylene supplies contribute 15% of global propylene supplies in

the form of propane dehydrogenation (PDH), methanol-to-olefins (MTO), and
metathesis.

To intensificate production
routes aiming to the
ACTUAL TREND product of propylene as
primary product

4
 PROPYLENE MARKET & PRODUCTION

Why to maximize propylene production?

Shale gas advent in the USA

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

The amount of propylene produced in an

ethane-consuming steam cracker is about 10
times less than what is produced when
consuming naphta-range material

The shift towards shale gas would result in

constrained propylene supply for
petrochemical consumption and a potential
price increase

Increase in propylene demand

M. Imran, Petroleum Technology Quaterly, 2013, pg. 31-40 5

PROCESS SCHEME – CARENA PROJECT

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

Main limit of such technologies

Huge amount of carbonaceous

deposits on the catalyst leading Plant complexity and difficulty for
to periodic regeneration the scale down to 1/5 of capacity

SHIFT OF CHEMICAL EQUILIBRIUM

BY HYDROGEN REMOVAL UNDER
THE USE OF MEMBRANE BASED
REACTORS

Exhaust from gas turbine

Molten salts

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 MEMBRANE BASED PDH

H2 + Sweep gas

Sweep gas Basic unit : Reactor – Membrane - Reactor

It could be increaded depending on the level of

conversion to be reached
C3H8

REACTOR REACTOR

Target (base case):

30% propane conversion

With HRF of 70% and 12 reactors, about

100°C of temperature reduction

HRF: Hydrogen Recovery Factor

Results from numerical simulation 11

 MEMBRANE BASED PDH

P = 5 bara

P = 1 bara

Owing to detrimental effect of pressure on

chemical equilibrium, necessity to increase the
number of reactors to see appreciable gain

P = 10 bara

Results from numerical simulation 12

MEMBRANE BASED PDH

Catalyst

Membrane CHOICE OF OPTIMAL OPERATING CONDITIONS in terms

of Temperature, Pressure, Space Velocity and Feed
Catalyst/Membrane composition
Integration architecture FOR PROCESS SCHEME DEVELOPMENT

13
 MEMBRANE BASED PDH

CATALYST REQUIREMENTS – High selectivity - Influence of space velocity and pressure

100

90

80
Propylene Selectivity, %

70

60

50

P=1.1 bar- T=530°C P=1.1 bar- T=500°C P=1.1 bar- T=450°C

40
P=5 bar-T=530°C P=5 bar- T=500°C P=5 bar- T=450°C
P=10 bar-T=530°C P=10 bar- T=500°C P=10 bar- T=450°C
30
0 5 10 15 20 25 30
WHSV, h^-1
The higher pressure greatly affects the selectivity to propylene, in particular at higher temperature
The increase in space velocity is able to gain the loss of selectivity under pressure operation
Results from numerical simulation 14
 MEMBRANE BASED PDH

CATALYST REQUIREMENTS – High selectivity - Influence of space velocity and pressure

Highest conversion at lower WHSV values

Highest selectivity at higher WHSV values
Optimum WHSV = 6 ÷ 10 h-1

T = 540°C

Noticeable decrease in C3H8 conversion

Marked decrease in selectivity to propylene
T = 540°C
at highest pressure values

Results from experimental catalytic activity tests – University of Salerno 15

 MEMBRANE BASED PDH

CATALYST REQUIREMENTS – High stability - Influence of feed composition

At lower water content

Weak decrease of propane conversion
Weak decrease of selectivity to C3H6

T = 540°C T = 540°C

Importance to add steam to feed mixture in

order to reduce the extent of coke formation

Results from experimental catalytic activity tests – University of Salerno 16

 MEMBRANE BASED PDH

CATALYST REQUIREMENTS – High stability - Influence of pressure

Significant coke formation at high pressure

T = 540°C Reduction in coke selectivity

of about 25% under
reduction of temperature at
500°C

Results from experimental catalytic activity tests – University of Salerno 17

MEMBRANE BASED PDH

MEMBRANE REQUIREMENTS
High hydrogen flux

•Influence of type of membrane

•Influence of pressure

High stability on time on stream tests

•Influence of uncoming mixture

Results by SINTEF show a strong deactivation of the

membrane under propylene exposure

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 MEMBRANE BASED PDH

CATALYST/MEMBRANE INTEGRATION ARCHITECTURE

Closed Architecture
catalyst

Reactant

Permeate Sweep gas

Reactant

membrane

Open Architecture H2

FEED
Reaction Reaction

Retentate

Closed architecture under study by TECHNION 19

 MEMBRANE BASED PDH

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

Basic assumptions for pilot plant

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

Propane feed 2 kg/h with a conversion of 30%

Temperature: 500°C and 530°C

Pressure: 10 bara

WHSV: 6 and 8h-1

Hydrogen recovery factor from each membrane of 50% operating at 450°C

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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

Number of reactors = 10 Number of reactors = 11

Number of membrane = 9 Number of membrane = 10

Overall Catalyst volume = 4 liters Overall Catalyst volume = 3.3 liters

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

Number of reactors = 6 Number of reactors = 6

Number of membrane = 5 Number of membrane = 5

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

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 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:

Catalyst activity/selectivity and durability

Membrane durability
Choice of level of catalyst/membrane integration

The reactor geometry should take into account the decoking procedure for the catalyst

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ACKNOWLEDGMENT

EUROPEAN COMMISSION
IS GRATEFULLY ACKNOWLEDGED
FOR THE FINANCIAL SUPPORT

A SPECIAL THANK TO THE UNIVERSITY OF SALERNO PARTNER FOR

CATALYTIC ACTIVITY TESTS RESULTS

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