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