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The CARENA project from Membrane to Process
ICCMR12
Szczecin, 23th of June 2015
Arend de Groot
• Need to turn to novel feeds such as light alkanes (C1 – C4), coal and biomass
• But …light alkanes are difficult to activate and transform directly and selectively to added value products
Increasing dependence on oil
PAGE 3
The CARENA project 1st of June 2011 - 1st of June 2015
Topic: Membrane Reactors
Sum-up
1) Scale-up: membrane reactors to the next level 2) Team-up: Bringing membrane and process together 3) Step-up: From materials to methods 4) Clean-up: Finding our way in process and reactor design 5) What’s up?
Bringing membrane reactors to the next level
Selected highlights from the CARENA project
Scale-up
CARENA processes (1) Membrane reactor design for Acrylic Acid from Propane
Propane
Crude AA
CO2
Propane dehydrogenation
Propylene oxidation
AA absorption
CO2 removal CO oxidation
O2 unit
H2
Membrane Reactor
Membrane
Catalyst
CARENA processes (2) Methanol production using a membrane reactor
• Methanol synthesis (traditional):
Prereformer Reformer
Natural gas
Steam Steam
Syngas for methanol synthesis
m=(H2-CO2)/(CO+CO2) = 2.1
Methanol synthesis
ATR
Oxygen
Cooler
Water
Integrated Membrane
reactor ATR
Natural gas
Steam Heat from GT exhaust and ATR-effluent
H2 permeate
Syngas retentate incl. CH4
Oxygen (ASU)
Syngas for methanol synthesis
m=(H2-CO2)/(CO+CO2) = 2.1
Methanol synthesis
Methanol
GT
• Methanol synthesis with Membrane Reactor
CARENA applications Overview of routes
Syngas
Methanol
Propylene Propane Acrylic acid
DMC
CO2
Ethylene
MeOH
CH4
C
C
C
C
Testing of combination of membrane and catalyst
C
C
Non integrated membrane reactor concept
Desulphurizer
R-01
H2 + (sweep steam)
Demi water
Natural gas
M-01AM-01B
R-02
M-02
Hot oil boiler water
Flare
stack
TIC
TIC
FIC
PIC
c.c.Fuel gas Fuel gas
c.c. AirAir
PIC2 STAGE OF REFORMING REACTION AND MEMBRANE SEPARATIONORGANIZED IN AN OPEN ARCHITECTURE
Nitrogen
FIC
FIC
REFORMER
Pd-based MEMBRANE
Non integrated membrane reactor concept
ECN
MRT
NGK
40%
45%
50%
55%
60%
65%
70%
590 600 610 620 630 640 650
Me
than
e c
on
vers
ion
, %
Reformer temperature, °C
RMM based on ECN membrane
RMM based on MRT membrane
without membrane
nmem dcat Acat
nbaffles
Integrated membrane reactor concept (closed architecture)
Efficient combination of reaction and separation:
Methane conversion and baffles
Feed pressure: 30 bar S/C=3
Permeate pressure: 5.5 bar
Feed Sweep
Permeate
Retentate
Fuel
Flue gas
Sweep
PermeateFeed
Retentate
00
z
r64 136.5
782.8
127.266.530
68.573.5
85.5
75.5
Øi = 4
Øe = 8
Øi = 10
Øe = 14
120
156.6
R1
R2R3
R4R5R6 R7 R8
R9R10
555.8
• SR-enhancement demonstrated • 1.6 Nm3/hr hydrogen for 55% methane conversion at 550oC • H2-purity 95% membrane selectivity improvement required • Long term testing terminated due to burner failure
Integrated membrane reactor concept Testing of integrated membrane reactor:
Summary:
Reactor scale-up aspects Status after CARENA Next step
Cost aspects: - Reactor cost - Membrane cost
- Membrane area per vessel
volume optimized - Scale-up: 1500 euro/m2
- Reactor and membrane < 4000 euro/m2
Integration aspects: - Heat distribution to
catalyst and membranes
- reaction/separation combination
- Integration in process
- Heat supply in catalyst section,
lower Tmem
- R-M-R configuration
- Heat supply by gas turbine
- No further optimisation - Multi (R-M), fluidynamic
optimization, sweep gas - Demonstration heat by GT
& other thermal medium
Operational aspects: - Operation P/T - H2-production level - H2-purity - Methane conversion - Lifetime - Feed quality - Maintenance
- 10 barg - 20 Nm3/hr - 99,5% - 54% - 2,000 hours - NG - Modular approach
- High P (40 bar) - > 10.000 Nm3/hr - > 99,99% - > 95% - > 15,000 hours - - - -
Non-integrated membrane reactor concept
Summary:
Integrated membrane reactor concept Reactor scale-up aspects Integrated membrane reactor
Status after CARENA Next step
Cost aspects: - Reactor cost - Membrane cost
- Membrane area per vessel volume
optimized - Scale-up: 1500 euro/m2
- Reactor < 5000 euro/m2
Integration aspects: - Heat distribution to
catalyst and membranes - reaction/separation
combination - Integration in process
- Optimized radial T-profile
- 5 baffles
- Heat supply by fully ntegrated burner
- Homogeneous T for
membranes - Multi-baffle
Operational aspects: - Operation P/T - H2-production level - H2-purity - Methane conversion
Lifetime - Feed quality - Maintenance
- 7 bar demonstrated - 1.6 Nm3/hr - 95% - 54% - 800 hours (tested) - Pure methane - Not addressed
- High P (40 bar) - > 200 Nm3/hr - > 99% - > 95% - > 40,000 hours - NG - Maintenance plan
Two membrane reactor concepts
• Novel issues adressed to scale-up
• Experimental results obtained
• Techno-economic evaluation results for MeOH production
Scale-up
Bringing membrane and process together
Team-up
Operating window defined by the membrane
Operating window defined by the process
17
• Methanol: Mismatch between operating window of membrane and reaction
0
20
40
60
80
100
0 50 100 150 200 250 300
Pre
ssure
(b
ar)
Temperature ( C)
Polymeric
membrane
Ceramic
membrane
Re
ac
tor CO2
H2O
CH3OH
H2
Operating window
Desired
Selectivity
More T resistant membrane needed
More active catalyst needed
Performance insufficient
Methanol
Confidential CARENA - Workshop - PETTEN, 29 April 2015
Zeolites SOD and LTA (LUH) MOF
iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported polymers
Other: amorphous SiC,
Innovative membranes
Zeolites (SOD and LTA) MOF
iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported polymers
Other: amorphous SiC
For an overview please check the list of publications on
www.CarenaFP7.org
Innovative membranes Innovative membranes
Step-up:
Towards application of membranes
21
M6 M18 M32
Toward application of membrane Manufacture of tubular dense membrane
Toward application of membranes Long term testing Pd-membranes
• Long term testing under steam methane reforming – Aim for stable performance of H2-producing membrane reactor (27 bar,
450oC, S/C=3):
• Permeance stability: Constant hydrogen production rate
• Stability in membrane selectivity: Constant H2-purity level
• Leakage mechanism:
Increasing amount of nano-scale defects (Knudsen-regime) vs time
Synchrotron-based FTIR • Pd membranes studied during PDH: effect of adsorbed species – DLS/SINTEF/ECN
High Resolution XRD
X-ray Absorption Spectroscopy
• New HTM: hydrated versus non hydrated – DLS/SINTEF
• MOF membranes: "breathing effect" – DLS/Leibniz University
• OTM for air separation: effect of T on lattice parameters – DLS/CNRS-IRCE
• OTM for air separation: chemical changes during in situ operation – DLS/CNRS-IRCE
200 400 600 800 1000 1200
0,40
0,44
0,48
0,52
0,56
Temperature (K)
3,98
3,99
4,00
4,01
4,02
4,03
Mesh P
ara
mete
r (Å
)
Ba0.5
Sr0.5
Co0.8
Fe0.2
O3-
PO2
= 21 kPa
In situ sample
environment
designed within
CARENA project
The evolution of mesh
parameters (black) &
oxygen vacancies (blue)
Structural defect characterization
Towards application of membranes Rational design of membranes
24
Ab initio calculation of different aspects:
• Permeance of hydrogen • Hydrogen dissociation on Pd surface • H2 and propylene coverage • Competitive adsorption SMR
Towards application of membranes Modelling and experiments to clarify impact of stresses
Creep modelling of BSCF membrane in operating condition
Grain size Stress
h Flux
measurement
P.F
Source
Permeation
AE sensor
Flow meter
AE signals acquisition & processing
Pressure gauge
MEMBRANE
Experimental set-up for gas permeation coupled with AE
Tubular membrane L=155mm
int/ext=7/10 mm)
Optimised membrane permeation cell designed at the IEM for acoustic measurements
Constraints :
Filtration process
Gas flow
Pressure/Vacuum
Temperature…
AE source:
Deformations - Dislocations
Phase transformation
Evolution of defects
Leakage, desorption,
swelling…
Towards application of membranes In operando characterization
Sintering
Membrane testing
> 5g
Calcination Pecchini method Pelletizing 10g
Design ?
-Size matching - Mechanic strength - Thermal expansion mismatch
High risks Poor gain of
knowledge
ABO3-δ
27
•MACRO KINETIC APPROACH •APPARENT KINETIC RATE
Towards application of membranes Rational design
Towards application of membranes Rational design
•Kinetic parameters measurements (SSITKA) -NEW •NEW model of oxygen transport in membrane •Rational design by predictive modeling
Sintering
ABO3-δ
> 5g
Calcination Pecchini method Pelletizing 10g
•Fast (no membrane testing) •MICRO KINETIC APPROACH •INTRINSEC KINETIC RATE
28
3) Step-up: from novel material to methods • Fabrication methods • Long-term behavior • Fundamental studies & modelling • Shortening the development cycle
Message: • Addressing wide range of issues to bring technology to
maturity requires concerted approach
Linked to application
Finding our way in process and reactor design
Clean-up
O2 CO2 ✔ CO + O2
✖
“Membrane reactor” for selective CO oxidation
Propane
Crude AA
CO2
Propane dehydrogenat
ion
Propylene oxidation
AA absorption
CO2 removal CO oxidation
O2 unit
H2
Membrane Reactor
Membrane
Catalyst
CO + 1/2O2 CO2 CO + 1/2O2 + (C3H6) CO2 + (C3H6)
Pt@S-1
Pt/S-1
Effect of the encapsulation
• Pt ~11 nm; D: 11.4%
• Pt ~9 nm; D: 10.4%
CO oxidation in presence of C3H6
Selective CO Oxidation - Objectives
• A build up of CO in the propane recycle feed will have a detrimental effect on the propylene oxidation catalysts.
• Therefore CO has to be selectively removed in the presence of propane.
• JM tasked with the development of a membrane catalyst.
• Each catalyst particle to be coated in a selective membrane layer to only allow CO to the active site.
• CO is oxidised to CO2 on the catalyst while propane is unaffected as it cannot permeate the membrane.
“Membrane reactor” for selective CO Oxidation • A stable zeolite coated oxidation catalyst has been produced that
selectively oxidises CO in the presence of propane.
• Key parameters for the production of the zeolite identified and a reproducible preparation method has been devised
• Tested in single-tube reactor at Arkema
• The catalyst has been scaled up to 5mm coated pellets.
35
Conceptual design for membrane reactors
Complex combination:
Very different alternative designs possible
Membrane reactor technology not to be discarded unless all designs found unsuitable
Requires structured approach
Catalyst
Membrane Heat exchange
36
Content: Module types Packed-bed membrane reactors
Catalytic-membrane reactors
Fluidized- or slurry-bed membrane reactors
37
Example: Pd membrane assisted Steam Methane Reforming
Leve
l of
suit
abili
ty
38
Leve
l of
suit
abili
ty
• Not enough heat exchange
• Transmembrane ∆p too high
• Requires flexible membrane
Example: Pd membrane assisted Steam Methane Reforming
Conceptual design for membrane reactors
39
Example: Pd membrane assisted Steam Methane Reforming
Leve
l of
suit
abili
ty
Expected difficulties to have enough heat exchange.
Conceptual design for membrane reactors
40
Leve
l of
suit
abili
ty
All criteria fulfilled!
Example: Pd membrane assisted Steam Methane Reforming
Conceptual design for membrane reactors
Some take-away messages:
• Coping with a changing world
• Change of scope in scaling-up
• Need to cooperate (inside/outside)
Sum-up
CARENA: Progress made on many aspects from membrane to process
What’s up?
WORKSHOP: CATALYTIC MEMBRANE REACTORS, WHAT'S NEXT? DATE: 29-30 APRIL 2015 VENUE: ECN, PETTEN, THE NETHERLANDS
c
Visit our website at: www.CarenaFP7.eu
The CARENA project is funded through the EU FP7 program under Grant Agreement no: 263007
Carena
Zeolites SOD and LTA (LUH) MOFs iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported SPEEK
Other: amorphous SiC,
Innovative membranes
SiO
OO
NH2
SiO
OO
NH2
SiO
OO
NH2
LTA nutrients
OH OH OH
In-situ growth
60 °C, 24 h
LTA
LTA SiO
OO
NH2
SiO
OO
NH2
SiO
OO
NH2
Toluene
110°C, 1h
SiEtO
OEtOEt
NH2
SiEtO
OEtOEt
NH2
Toluene
110°C, 1h
LTA nutrients
In-situ growth
60 °C, 24 h
2000
2500
3000
3500
4000
4500
5000
Separation factor
FluxS
ep
ara
tio
n fa
cto
r
LTA 2-layered LTA 3-layered LTA
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
Flu
x / k
g h
-1 m
-2
Zeolites SOD and LTA (LUH) MOF’s
iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported SPEEK
Other: amorphous SiC,
ZIF-8/ZnO/α-Al2O3 membrane
(reproducible on/in 5cm long industrial
supports)
An innovative Approach for the
Preparation of Confined ZIF-8 Membranes
by Conversion of ZnO ALD Layers,
M. DROBEK,& al, J. of Membr. Sci. 475
(2015) 39
Innovative membranes
Zeolites SOD and LTA (LUH) MOF’s iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported SPEEK
Other: amorphous SiC,
50 µm
(a) (b)
10 µm 10 µm
10 µm
(d) (c)
Al2O3 support
ZIF-95 layer
0.28 0.30 0.32 0.34 0.36 0.38 0.40 0.42 0.44
0.0
5.0x10-7
1.0x10-6
1.5x10-6
2.0x10-6
2.5x10-6
3.0x10-6
Pe
rme
an
ce
/ m
ol m
-2s
-1P
a-1
Kinetic diameter / nm
H2
N2 CH4
ZIF-95 pore size estimated
from crystal structure data
CO2 C3H8
Innovative membranes
Zeolites SOD and LTA (LUH) MOF’s iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported SPEEK
Other: amorphous SiC,
Innovative membranes
Zeolites SOD and LTA (LUH) MOF(CNRS IRC, CNRS IEM) iPOSS membranes Dense ceramic hydrogen
transport membranes
Ceramic supported SPEEK
Other: amorphous SiC,
New materials and sintering study: Ca doped Ce1-xCaxNbO4+
A = Y, Yb, Tm doped SrCe1-x-yZrxAyO3-
Tow
ard
s th
e a
pp
lica
tio
n
Fabrication of asymmetric membranes: A doped SrCe1-x-yZrxAyO3-
Flux and transport models: Ca doped Ce1-xCaxNbO4+
A = Y, Yb, Tm doped SrCe1-x-yZrxAyO3-
Potential of HTM for SMR, PDH
Flux measurements of asymmetric membranes in simulated PDH: A doped SrCe1-x-yZrxAyO3-
Mechanical study of porous supports: A doped SrCe1-x-yZrxAyO3-
Innovative membranes