Catalytic Membrane Reactors by Developing New Nano...
Transcript of Catalytic Membrane Reactors by Developing New Nano...
05-08-2013 / Page 1
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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: [email protected]
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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DEMCAMER’s Aim (I)
To develop innovative multifunctional Catalytic Membrane Reactors (CMR) Based on:
• new nano-architectured catalysts and • selective membranes materials
To improve the CMRs’: • performance • durability • cost effectiveness • sustainability:
• lower environmental impact • lower use of raw materials
Set up and validate pilot prototypes
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CMRs to be used for selected chemical processes: • Autothermal Reforming (ATR) • Fischer-Tropsch Synthesis (FTS) • Water Gas Shift (WGS) • Oxidative Coupling of Methane (OCM)
For the production of: • pure hydrogen • liquid hydrocarbons • ethylene
DEMCAMER’s Aim (II)
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DEMCAMER Partnership
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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1. TECNALIA, Spain 2. VITO, Belgium 3. UNICAL, Italy 4. TU/e, The Netherlands 5. ICP-CSIC, Spain 6. FhG-IKTS, Germany 7. BIC, Russian Federation 8. INERIS, France 9. RKV, German 10. CERPOTECH, Norway 11. HYBRID, The Netherlands 12. HYGEAR, The Netherlands 13. ABNT, Spain 14. QUANTIS, Switzerland 15. HÖGANÄS, Sweden 16. TOTAL RC, Belgium 17. TOTAL EP, France
Consortium Composition
University of Calabria
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Development of novel catalyst materials Development of innovative membranes Novel catalytic membrane reactors designed:
• on the basis of novel catalysts and membranes • using new reactor configurations • supported by simulation
Modelling and simulation at different levels: • materials (membranes and catalysts) • reactor prototypes • control system
Lab scale and prototype reactors testing and validation Life Cycle Analysis, industrial risk assessment study
Project Structure
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Partnership Synergies
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WP2. Industrial specifications [HYGEAR]
WP3. Catalysts development [CSIC] • Catalyst preparation • Catalyst characterisation • Activity test • Scale up
WP5. Lab scale reactors [TU/e] • Integration in CMRs • Testing of CMRs
WP6. Pilot prototype [HYGEAR] • Design of Pilot • Set up
WP7. Testing and Validation [ABNT] • FAT • Testing and validation
WP4. Membrane development [VITO]
• Material for membranes • Membranes support • Membranes development and
characterization
WP8. Modeling and Simulation [UNICAL] • Ab initio calculations • Transport in membranes • CMR simulations • Process simulations
• Pilot scale simulation
WP1
1. S
cien
tific
coor
dina
tion
[TU
/e]
WP1
0. D
isse
min
atio
n an
d Ex
ploi
tatio
n [U
NIC
AL]
WP1
. Man
agem
ent [
TECN
ALIA
]
WP9
. LCA
and
Saf
ety
issu
es [I
NER
IS]
Overview of the Work Structure
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New membrane materials and nano-architectured catalysts • improved properties • long durability • reduced cost
Better understanding of
• fundamental physicochemical mechanisms • relationship between structure/property/performance • manufacturing process of membranes and catalysts
Achieving radical improvements in membrane reactors’ • design • modelling • efficiency of configurations
Scientific and Technical Objectives (I)
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Scientific and Technical Objectives (II)
Validating reactor configurations • at semi-industrial prototype level • in all four selected chemical process (ATR, WGS, OCM, FTS) • for pure hydrogen, liquid hydrocarbons and ethylene production
Improving cost efficiency of reactors by
• increasing their performance • decreasing raw materials consumption • decreasing associated energy losses
Use of new raw materials (i.e. convert non-reactive raw materials)
Assessment of the four CMR developed processes’
• health and safety • environmental impact • a complete LCA of the developed technologies
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Development of catalytic materials Physicochemical characterisation Activity tests Scale-up and confirmation
Catalysts for ATR - WGS - OCM - FTS Reactions
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Development of novel materials and membranes for application in CMRs
MIEC membranes
Hollow fibres (H2 and O2 permeation)
Coatings (O2 permeation)
Metallic membranes (H2 permeation)
Zeolite membranes (H2 permeation and
water removal)
Membranes ATR - WGS - OCM - FTS Reactions
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Development of Materials for Novel Membranes
Perovskite powders for MIEC membranes Selection and manufacture of a wide range of feedstock powders for the
development of hollow fibres for O2 and H2 permeation Materials for inter-diffusion layers of metal based membranes Manufacture of Al2O3 and YSZ based powders for development of layers by
thermal spraying
before granulation after granulation
Optimisation of morphology by freeze granulation process
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Advantages: The membrane used as structure
directing agent can be readily removed at the end of the reaction, thus avoiding challenging purification procedures .
The method is simple, eco-friendly
and highly reproducible.
The method could be favourably extended to other microporous alumino-silicate of different topologies.
Nanocrystals having FAU-Y topology with uniform particles size distribution have been prepared in high yield through an organic-template-free hydrothermal synthesis by using a FAU membrane as structure directing agents.
Development of Materials for Zeolites
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Development of High-Quality Metallic Supports for MIEC, Zeolite and Metal-Based Membranes
Materials for metallic membrane supports • Different powder morphologies, finer particle sizes • Metal powders for surface layers in gradient structures Metallic membrane supports • Planar porous metallic supports for H2 permeation membranes • Gradient and homogenous structures with different strengths and porosities • Planar compacted metallic porous supports for O2 permeation membranes • Porous tubes
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Development of perovskite membranes by spinning and phase inversion methods
Structural characterisation: XRD and SEM analyses
MIEC Membranes for H2 and O2 Permeation
A-site B-site O2-
Permeation measurements
2θ
Inte
nsity
a.u
.
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Improvement of FAU membrane layer by anchoring of the zeolite seeds onto support
Permeation tests: single and mixed gas (dry and humidified)
Structural characterisation: XRD and SEM analyses
0
1000
2000
3000
4000
4 10 16 22 28 34 40 46 52 58 64 70
2 theta
Inte
ns
ity
, a
.u.
Zeolite Membranes for H2 and Water Separation
University of Calabria
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Selection of Catalytic Membranes Reactors components: • catalysts • membranes materials • supports • sealings
Integration of these elements into lab-scale reactors specifically
designed for ATR, WGS, OCM and FTS
Validation of the performance of lab-scale reactors Identification of best designs for pilot prototypes
Development of Lab-Scale CMRs
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Reactor Configurations - ATR
Reverse flow CMR concept for combined high-temperature O2 separation and autothermal reforming of methane
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Reactor Configurations - WGS
Micro-structured CMR concept
maximisation of membrane area complete process integration
unique mass and heat transfer capabilities
maximal energy and mass transfer efficiency
WGS reaction and hydrogen separation coupled in one single unit
CO + H2O ↔ CO2 + H2 ∆H𝟐𝟐𝟐
𝟎 = -41.09 kJ/mol
University of Calabria
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CO,CO2,H2
H2
Furnace
GC 6890 Agilent
CO, CO2, H2, H2O(Retentate)
MFCH2COCO2
H2O
Permeate
PermeatePure H2 Retentate
Feed
Pd-Ag membraneCatalytic bed
Membrane reactor scheme
Experimental laboratory-scale plant
MR TR
Temperature, °C 350-400
Feed Pressure, bar 7- 9 7.5
Permeate Pressure, bar 1 -
H2O /CO feed molar ratio 1
GHSV (gas hourly space velocity) 8,000; 14,700; 36,700 h-1
Feed composition (dry), % CO:H2:CO2:N2 = 46:48:5:1
No sweep gas was used
WGS in a Fixed-Bed Membrane Reactor in
University of Calabria
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Reactor Configurations - OCM
(modified from Caro et al., 2010)
CMR with packed-bed configuration
optimising operating parameters (CH4/O2 feed ratio, T) to achieve enhanced CH4 conversion, best C2 selectivity and C2 product yield
2CH4 + O2 → C2H4 + 2H2O ∆H298
0 = -141 kJ/mol CH4
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Shell
ReactionCompartment(Syngas Feeding)
Catalystparticles
Membranes for theselective H2O removal
Permeate Side:
H2O + Gas sweep
HC’s
HC’s
PermeateSide: H2O
PermeateSide: H2O
P1
P2
P1 > P2
ReactionCompartment
Membrane
Cross-section View: PBMR
PermeateSide: H2O
CatalystParticles
Shell
ReactionCompartment(Syngas Feeding)
Catalystparticles
Membranes for theselective H2O removal
Permeate Side:
H2O + Gas sweep
HC’s
HC’s
PermeateSide: H2O
PermeateSide: H2O
P1
P2
P1 > P2
ReactionCompartment
Membrane
Cross-section View: PBMR
PermeateSide: H2O
CatalystParticles
Reactor Configurations - FTS
catalytic membrane milli-reactor in-situ water removal
packed bed membrane reactor distributed feeding
in-situ water removal
Shell
ReactionCompartment(CO Feeding)
Membranes for thedistributed feeding of H2
Catalystparticles
H2 Feeding
HC’s + H2O
P1 P2
P1 > P2
CatalystParticles
ReactionCompartment
Membrane
Cross-section View: PBMR
H2CO
Shell
ReactionCompartment(CO Feeding)
Membranes for thedistributed feeding of H2
Catalystparticles
H2 Feeding
HC’s + H2O
P1 P2
P1 > P2
CatalystParticles
ReactionCompartment
Membrane
Cross-section View: PBMR
H2CO
Shell
ReactionCompartment(Syngas Feeding)
Catalystparticles
Membranes for theselective H2O removal
Permeate Side:
H2O + Gas sweep
PermeateSide: H2O
P1
CatalystLayer
ReactionChannel
Membrane
Cross-section View: CMM
PermeateSide: H2O
PermeateSide: H2O
P2
P1
P1 > P2
HC’s
HC’sShell
ReactionCompartment(Syngas Feeding)
Catalystparticles
Membranes for theselective H2O removal
Permeate Side:
H2O + Gas sweep
PermeateSide: H2O
P1
CatalystLayer
ReactionChannel
Membrane
Cross-section View: CMM
PermeateSide: H2O
PermeateSide: H2O
P2
P1
P1 > P2
HC’s
HC’s
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Modelling and Simulation (I)
For membranes: Study of zeolite membranes properties by means of molecular modelling
and quantum chemical calculations: • Identification of structure-function relationships at molecular level • Identification of the optimal procedure for evaluating the selectivity • Identification selectivity of gases
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
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For ATR: Develop a reliable dynamic model in a reverse-flow membrane reactor For WGS: Develop a phenomenological model for fluidised-bed membrane micro-
reactors • Develop a reliable 2D model for membrane micro-reactors • Compare fluidised bed and packed-bed membrane micro-reactors • Analyse 1D or 2D dimensionless models for fixed-bed membrane reactor
For OCM: Develop a reliable 1D detailed model for the study of hollow fibre MIEC
membranes reactors with packed-bed configuration For FTS: 2D simulations of a fixed-bed catalytic membrane reactor
Modelling and Simulation (II)
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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
Modelling and Simulation (III)
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Porous support
Pd-based layer1
3
4
Layer 1
Layer n
Layer 1
Layer n
Por
ous
supp
ort
Pd-based layer
Feed Side
Permeate Side
Me
mb
ran
e l
ay
ers
Bulk Diffusion
Desorption
Bulk-to-Surface
Surface-to-Bulk
Adsorption
MulticomponentMass Transfer
Gaseous Film
Pd-
base
d la
yer
Mass transferin the pores
MulticomponentMass Transfer
Ma
ss
tra
ns
f er
me
ch
an
i sm
s
Gaseous Film
Porous support
2
Phys
ical
syst
em
Mat
hem
atic
al d
escr
iptio
n
Model based on a multicomponent approach
Modelling Example (I) Transport in Metal-Based Membranes
University of Calabria
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Catalytic bed
Pd-Ag membrane
Retentate
PermeatePure H2
Feed
Pd-Ag MR Traditional
reactor
Temperature 300-450°C
Feed pressure 500, 1000;1500; 3000 kPa
Feed mixture composition
CO: H2O: CO2: H2: N2 =
31.25:31.3:25.5:33:1, % molar H2O/CO feed molar ratio 1
GHSV 10000 - 40000 h-1
0
0.5
1
CO C
onve
rsio
n, -
300 400 500Temperature, °C
TR
1500
10000 h-1
Modelling Example (II) WGS – Fixed-Bed Membrane Reactor
University of Calabria
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NATURAL
GAS
Steam Methane
Reforming
H2 (high purity)
CO2
WGS MR
H2 (high purity)
H2 purification
WGS HT
Traditional Process
H2
(high purity)
CO2
CO2 separation
CO2 separation
H2 purification
WGS LT
Membrane Integrated Process
Modelling Example (III) WGS Process Simulation
University of Calabria
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water
NG
Permeate (H2 highly pure)
RE
FOR
MIN
G
Retentate stream
WGS Membrane Reactor Integration
Alternative downstream post-treatments
H2
CO2
separation H2
purif
icat
ion
CO2 compression and storage
CO2 separation
WGS MR H
2 pu
rific
atio
n
H2 H2
WGS MR
Modelling Example (III) cont’d
University of Calabria
05-08-2013 / Page 31
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Design and setup of the pilot scale catalytic membrane reactors
Pilot reactors for ATR, WGS, OCM and FTS processes Depending on the working pressure all reactors will be designed and
manufactured according the “Pressure Equipment Directive” of the EC (97/23/EEC)
Overall system controls for the different reactor types will be designed and constructed to ensure automatic operation of the systems and safety aspects and control strategies developed according to Pilot scale modelling
All system components will be mounted into an enclosure and will undergo a Factory Acceptance Test (FAT) before being set into operation for validation and testing.
Pilot Scale Prototypes
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Testing and validation of the pilot scale prototype reactors
For testing and validating of the pilots, corresponding test plans and protocols will be defined including parameters and/or values that have to be derived from the tests, such as system efficiency, etc.
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
Pilot Prototypes Testing and Validation
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Life Cycle Assessment and Safety Issues
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
Proposal of recommendations for the safe operation of the CMR technology
Socio-economic analysis to evaluate the sustainability and feasibility of the CMR technology (process performance, environmental and safety constraints) compared to currently available technologies
Socio-Economic Analysis
Safety Constraints
Process Performance Constraints
Environmental
Constraints
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Environmental Life Cycle Assessment
• DEMCAMER will perform a robust environmental Life Cycle Assessment (LCA) of the new technologies to be developed (CMR) compared with the reference technologies (baseline)
• Within DEMCAMER, the LCA focuses on the following environmental impact categories over the entire life cycle of the processes:
− Greenhouse gas (GHG) emissions (climate change) − Non-renewable primary energy use − Direct and indirect impacts on human health − Direct and indirect impact on ecosystems − Water use (incl. water impact assessment)
Objectives of the Life Cycle Assessment
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Environmental Life Cycle Assessment
Reference technology (baseline) CMR technology
compared with
Objectives of the Life Cycle Assessment – Example of ATR-CMR