Workshop DEMCAMER-CARENA

TU/e, Eindhoven, 30 January 2013

Design and Manufacturing of

Catalytic Membrane Reactors
by Developing New
Nano-architectured Catalytic and
Selective Membrane Materials
This project is supported by the European Community’s Seventh
Framework Programme Grant Agreement
Nº NMP3-LA-2011-262840

Duration: 4 years. Starting date: 01-July-2011

Contact: joseluis.viviente@tecnalia.com
Then present document reflects only the author’s views and the Union is not liable for any use that may be made of the information contained therein.

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 Workshop DEMCAMER-CARENA
Summary TU/e, Eindhoven, 30 January 2013

The aim of DEMCAMER is to develop innovative multifunctional

Catalytic Membrane Reactors (CMR) based on new nano-
architectured catalysts and selective membranes materials to improve
their performance, durability, cost effectiveness and sustainability
(lower environmental impact and use of new raw materials) over four selected
chemical processes:
 Autothermal Reforming (ATR),
 Fischer-Tropsch Synthesis (FTS),
 Water Gas Shift (WGS),
 Oxidative Coupling of Methane (OCM))
for pure hydrogen, liquid hydrocarbons and ethylene production.
Moreover DEMCAMER will bring the proof of concept of these novel CMRs
by the set-up and validation of pilot prototypes relevant for each process.

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 Workshop DEMCAMER-CARENA
Partnership TU/e, Eindhoven, 30 January 2013

This research is carried out by a multidisciplinary and complementary team

consisting of 17 top level European organisations from 10 countries: 8 Research
Institutes and Universities working together with representative top industries in
different sectors (from raw materials suppliers to chemical end-users).

University of Calabria

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 Workshop DEMCAMER-CARENA
Partnership Synergies TU/e, Eindhoven, 30 January 2013

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 Workshop DEMCAMER-CARENA
Scientific and Technical Objectives (I) TU/e, Eindhoven, 30 January 2013

 New membrane materials with improved separation properties, long

durability and reduced cost

 New nano-architectured catalysts with better performance and at reduced

cost

 Understanding the fundamental physicochemical mechanisms and the

relationship between structure/property/performance and manufacturing
process in membranes and catalysts, in order to achieve radical
improvements in membrane reactors

 Design, model and build up of novel more efficient membrane reactor

configurations based on the new membranes and catalysts

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 Workshop DEMCAMER-CARENA
Scientific and Technical Objectives (II) TU/e, Eindhoven, 30 January 2013

 Validating the new membrane reactor configurations, at semi-industrial

prototype level, in four selected chemical process (ATR, WGS, OCM, FTS)
for pure hydrogen, liquid hydrocarbons and ethylene production

 Improving the cost efficiency of membrane reactors by increasing their

performance, decreasing the raw materials consumption and the
associated energy losses

 Use of new raw materials (i.e. convert non-reactive raw materials)

 Assessment of the health, safety and environmental impact of the four

CMR developed processes, a complete LCA of the developed
technologies will be performed

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 Workshop DEMCAMER-CARENA

Catalytic Materials TU/e, Eindhoven, 30 January 2013

 Development of ATR - WGS - OCM - FTS catalysts

 Physicochemical characterisation of ATR - WGS - OCM - FTS catalysts
 Activity tests in the ATR - WGS - OCM - FTS reactions
 ATR – WGS – OCM - FTS catalysts scale-up and conformation

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 Workshop DEMCAMER-CARENA
Membranes Development (I) TU/e, Eindhoven, 30 January 2013

 Development of materials for MIEC, zeolite and metallic membranes

preparation

 Development of ceramic and metallic membrane supports and

interdiffusion layers

 Development and optimisation of MIEC membranes for O2 and H2

separation

 Development and optimisation of metallic membranes for H2 separation

 Development and optimisation of zeolite membranes for water

separation

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 Workshop DEMCAMER-CARENA
Membranes Development (II) TU/e, Eindhoven, 30 January 2013

Novel materials and membranes for application in catalytic reactors:

Hollow fibres
(H2 and O2
MIEC permeation)
membranes
Coatings (O2
permeation)

Metal membranes
(H2 permeation)

Zeolites
(water removal)

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 Workshop DEMCAMER-CARENA
Reactor Configurations (I) TU/e, Eindhoven, 30 January 2013

Autothermal Reforming (ATR)

reverse flow membrane reactor fluidised bed membrane reactor

H2
Air N2/H2O
CO2

500z

CH4 + H2O

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 Workshop DEMCAMER-CARENA
Reactor Configurations (II) TU/e, Eindhoven, 30 January 2013

Water Gas Shift (WGS)

Packed bed micro reactor Fluidised bed micro reactor

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 Workshop DEMCAMER-CARENA
Reactor Configurations (III) TU/e, Eindhoven, 30 January 2013

Oxidative Coupling of Methane (OCM)

Packed bed reactor

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 Workshop DEMCAMER-CARENA
Reactor Configurations (IV) TU/e, Eindhoven, 30 January 2013

Fischer-Tropsch Synthesis (FTS)

packed bed membrane reactor in-situ water removal
distributed feeding
HC’s

HC’s + H2O

Permeate
Side: H2O HC’s
Shell
Shell Side
:
rm eate sweep
P e s
+ Ga
H 2O
Permeate
Catalyst P1
Catalyst Side: H2O
particles
P1 particles P2
P2 Cross-section View: PBMR
Cross-section View: PBMR
Membrane
Membrane

P1 > P2 Reaction P1 > P2 Permeate

Reaction H2 Feeding Compartment Membranes for the
CO Side: H2O
Compartment Membranes for the H2 (Syngas Feeding) selective H2O removal
(CO Feeding) distributed feeding of H2 Catalyst
Particles Reaction
Catalyst Reaction Compartment
Particles Compartment

HC’s
catalytic membrane milli-reactor
in-situ water removal Permeate
Side: H2O HC’s
Shell
:
Side
rm eate sweep
Pe Gas
+
H 2O
Permeate
Catalyst P1
P1 Side: H2O
particles
P2 Cross-section View: CMM
Membrane

Reaction P1 > P2 Permeate

Compartment Membranes for the Side: H2O
(Syngas Feeding) selective H2O removal

Catalyst Reaction
Layer Channel

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 Workshop DEMCAMER-CARENA
Modelling and Simulation (I) TU/e, Eindhoven, 30 January 2013

For membranes:
 Study of zeolite membranes properties by means of molecular modelling and
quantum chemical calculations.
 Comparative analysis between the fundamental transport properties of Pd
and Pd-based alloys and the corresponding properties of new (non-Pd)
alloys formed from different metals

For catalysts:
 Search for the optimal catalyst’s structure for ATR, WGS, OCM, FTS by
correlation between their morphological and structural properties and their
catalytic performance

For Catalytic Membrane Reactor:

 Develop reliable models for the different process and reactor configuration.

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 Workshop DEMCAMER-CARENA
Modelling and Simulation (II) TU/e, Eindhoven, 30 January 2013

Evaluation of the membrane separation properties:

 Mathematical models describing the permeation in metal and zeolite
membranes
 Identification of elementary steps affecting the permeation through the
membrane and their influence on mass transport properties

Processes:
 Design of new processes integrated with catalytic membrane reactors
 Analysis of the performance of the integrated processes as function of the
operating conditions assuring the best performance of the whole integrated
process

Pilot scale:
 Modelling of the pilot scale reactors for ATR, WGS, OCM and FTS
 Definition and modelling of control strategies and control routines for the
pilot scale reactors

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 Workshop DEMCAMER-CARENA
TU/e, Eindhoven, 30 January 2013

Pilot Scale Prototypes

 Design and setup of the pilot scale catalytic membrane reactors for ATR,
WGS, OCM and FTS processes
 Overall system controls for the different reactor types will be designed and
constructed to ensure automatic operation of the systems. The design of
the system control will consider safety aspects and control strategies
developed according to Pilot scale modelling.

Pilot Prototypes Testing and Validation

 Testing and validation of the pilot scale
prototype reactors
 Results will be compared to the requirements
and specifications
 Test results will be used in Modelling and
Simulation to validate and improve the pilot
scale models and the system control
strategies, as well as for the LCA and the
accidental industrial risk assessment
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 Life Cycle Assessment and Safety Issues
Workshop DEMCAMER-CARENA
TU/e, Eindhoven, 30 January 2013

Assessment of socio-economic sustainability of the proposed technologies from an

environmental and safety perspective.

 Environmental Life Cycle Assessment

analysis of the CMR process
 Identification and evaluation of key safety
parameters and risk analysis Process Safety
Performance Constraints
 Proposal of recommendations for the safe Constraints
operation of the CMR technology
Environmental
 Socio-economic analysis to evaluate the Constraints
sustainability and feasibility of the CMR
Socio-Economic Analysis
technology (process performance,
environmental and safety constraints)
compared to currently available
technologies

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 Workshop DEMCAMER-CARENA
TU/e, Eindhoven, 30 January 2013

Thank you for your attention

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