Advanced Membrane Reactors in Energy Systems ...gcep.stanford.edu/pdfs/kUXNHroC3cAssx6wJoz_Mg/Haije...Advanced Membrane Reactors in Energy SystemsAdvanced Membrane Reactors in Energy

Advanced Membrane Reactors in Energy Systems Development of novel membranes for membrane reactors.

Wim Haije Joop Schoonman Cor PetersWim Haije, Joop Schoonman, Cor Peters

www.ecn.nl

Advanced Membrane Reactors in Energy SystemsAdvanced Membrane Reactors in Energy Systems Development of novel membranes for membrane reactors.

Objective:

The purpose of this project is to develop H2 and CO2 membranes to allow combinations of natural gas reforming or WGS with H2 or CO2 separation in separation enhanced reactors, i.e. membrane reactors, for carbon-freeseparation enhanced reactors, i.e. membrane reactors, for carbon free hydrogen production or electricity generation.

2

The ECN TUD GCEP project layoutoverall efficiencies

economics

The ECN-TUD GCEP project layout

systemstudies

b

experimentalresults

reactorrequirements

reactordesign

membrane & catalyst

development

desired specificationsfundamental knowledgecharacterization

reactor testspatentsIP

materialsresearch

IPpublications

newdevelopments

T k 1 S t l i d th d i l ti E t d b ECNTask 1. System analysis and thermodynamic evaluations Task 2. Hydrogen membrane research & development Task 3. CO2 membranes research & development Task 4. Catalyst screening Task 5. Reactor modelling and design

Executed by ECNExecuted by TUD Executed by ECN+TUD Executed by ECN Executed by ECN

3

Task 5. Reactor modelling and design Executed by ECN

A li ti th l hN2, H2O

Application: the general scheme

Air

O 79% Npowerpowerplantplant

CH

O2, 79% N2

H2

HTS

Natural gasCH4, LTS

Reforming Shift H2/CO2separationseparation CO2

H2-MR: SR + WGS

4

CO2-MR: WGS only

A li ti th l hApplication: the general scheme

Hi h idH2O Catalyst particles

Membrane

or natural gasSyngas (CO,H2,CO2) Retentate

High-pressure sideH2O

CH4+H2O CO+3H2 CO+H2O H2+CO2 H2, H2O,(CO2,CH4, CO)

y p

MembranePermeate CO2

Low-pressure side

In steam sweep flowSteam sweep flow CO2 CO2 CO2 CO2

Low pressure side

5

Membrane developmentCO3-ions

• ECN: CO2 selective membranes (hydrotalcite): H2O

• TU Delft: Nano-structured ceramic membrane for perm selective H2 separation:

• TU Delft: Ionic liquids for CO2 separation:

NN CH3CH2

CH2

CH2

CH3 SO

OC

F

FF

C

F

F

F

SO

O

N+

6

Membrane development

Mechanisms of separation:

• Thermal assisted hopping ECNpp gof carbonate through the bulk lattice:

TUD• Molecular sieving:

• Affinity based

U

TUD- Dissolution-diffusion - Preferred adsorption

and exclusion: ECN

TUD

7

Characterisation and development of CO2 selective ceramic dense or porous membranes

Materials Science-HTC membranes

or porous membranes CO3-ions

Brucite layer

Mg6Al2(OH)16CO3·4H2O (lit.) H2O

CO2 transport channel??

Rhombohedral system:

8

a=b≈3Å c≈23Å mR3−


• Membrane material issues:- Thermal stability- Mechanical stability- Synthesis- Compositional windowCompositional window- (Micro)structure- Morphology

• Key question:- Porous or dense??

9

700

20oC

450oC


500

600

700 450oC

400oC

Lin

(Cps

)

300

400350oC

300oCInterlayer water out: ≈1.5 Å

10

100

200

300 C

100oC

01 089 0460 (C) H d t l it (M 0 667Al0 333)(OH)2(CO3)0 167(H2O)0 5 Rh b H 3 04600 b 3 04600 22 77200 l h 90 000 b t 90 000 120 000 P i iti R 3 (166)File: MG 50 pellet RT N2 after heattreatments.raw - Start : 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 4. sFile: MG 50 pellet 450 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 400 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 350 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. sFile: MG 50 pellet 300 N2 H2O.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 38. sFile: MG 50 pellet 100 N2 CO2.raw - Start: 5.000 ° - End: 80.000 ° - Step: 0.050 ° - Step time: 2. s

10

2-Theta - Scale8 10 20 30 40 50 60 70

In-Situ XRD:

HTC under

10

01-089-0460 (C) - Hydrotalcite, syn - (Mg0.667Al0.333)(OH)2(CO3)0.167(H2O)0.5 - Rhombo.H.axes - a 3.04600 - b 3.04600 - c 22.77200 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3m (166) N2/CO2/H2O

14

230°C


6

8

10

12

eigh

t (m

g)

Sample weight

CO2

Water

150°C 230°C

320°C440°C

Porous!!

0

2

4

6

0 1000 2000 3000 4000 5000 6000

We Porous!!

Time (s)

( )( ) ( )( ) OyHOxHOHCOAlMgOyHOxHOHCOAlMg Cads 2212324

1502212324 ... +⎯⎯ →⎯ ° (1)

Decomposition pathway from in-situ XRD + DRIFT, TGA/MS:

( )( ) ( )( ) OxHOHCOAlMgOxHOHCOAlMg C212324

230212324 . +⎯⎯ →⎯ ° (2)

( )( ) ( ) OHOAlOHMgMgCOOHCOAlMg C23223

32012324 3.3. +⎯⎯ →⎯ ° (3)

11

( ) OHCOOMgAlMgOOAlOHMgMgCO C2242

4403223 3.3.3. ++⎯⎯ →⎯ ° (4)

Neutron Diffraction on GEM, ISIS


Mg25,

Mg50

Mg90

Composition: Mg/Al=1.8 ⇒

Mg0 64Al0 36(OH)2(CO3)0 18·1.0 H2O

12

Mg0.64Al0.36(OH)2(CO3)0.18 1.0 H2O

Materials Science-Porous HTC membranes

Mechanical instability of these claylike materialsMechanical instability of these claylike materials automatically leads to supported membranes.

Two main routes:

•Applying a coating of HTC on a support•Applying a coating of HTC on a support

•Modifying the surface of the outer support layer to obtain CO affinity (basicity) providedlayer to obtain CO2 affinity (basicity) provided the pore size is small enough.

13


Prerequisite in the coating case is to be able to make small, nano sized, particles. Options:

C i it ti f M t l lt•Co-precipitation from Metal-salt precursors

•Exfoliation of HTC with formamide

•Sol-gel synthesis

•Emulsions (to be done)

Prerequisite for surface layer modification is finding the right, reactive, surface, the right

14

modifier and the right reaction conditions.


Co-precipitation:p p

Small particles 10-30 nm found in aggregates that are hard to disintegrate

15


Exfoliation:Exfoliation:

Mentioned in literature as aliterature as a method to peel off the brucite layers of HTCHTC.

Could not be reproduced: large aggregates

16


Sol-gel synthesis:Sol gel synthesis:

A large number of recipes have been tested with variations in precursors, solvent, pH, ratios, temperature etctemperature, etc.

All variants resulted in HTC plus impurity (reagents)plus impurity (reagents), some also yielded small, isometric, particles partly in

pH=8, particle diameter10-40 nm

17

aggregates.


Modification of the surface/walls of poresModification of the surface/walls of pores of a micro-porous support system

First experiments on green Boehmite

A bi t No HTC formed•Ambient pressure

•T 25 or 80 oC

Mg salts added

No HTC formed

Mg salts added.

Hydrothermal reaction @ 180oC HTC formedHighly crystalline

18


Conclusions:

Two ways to ‘affinity tuned’ porous membranes have to be further explored:

1.Nano particle based15

Size Distribution by Intensity

2.Modified surface based0

5

10

0.1 1 10 100 1000 10000

Inte

nsity

(%)

Size (d.nm)

To be done:

1.Prevent aggregation, formulate coating recipe, drying/calcination

2 U l t d f l i ti t

Record 301: SG1.4 2-butanol gel in its sol f iltered Record 302: SG1.4 2-butanol gel in its sol f ilteredRecord 303: SG1.4 2-butanol gel in its sol f iltered Record 304: SG1.4 2-butanol gel in its sol f ilteredRecord 305: SG1.4 2-butanol gel in its sol f iltered

2.Use real support, degree of precalcination etc.

Make small membranes via both routes and determine performance

19

Molecular sieving

A

Molecular sieving

AAtomic layer deposition:

BdInitial pore

C dH2Initial pore diameter

D

20

Molecular sievingMolecular sievingPrerequisites:

Monodisperse pore size•Monodisperse pore size distribution of the support

•MCM•MCM

•Hydrothermally stable membranemembrane

•Hybrid Al/Si oxide microporous films p(poster)

•ALD with stable oxideMCM:

mesoporous ceramic

21

pmembrane

Molecular sievingMolecular sieving

5 00E 02

6,00E-02

7,00E-02

N physisorptionSiO2

1 00E-02

2,00E-02

3,00E-02

4,00E-02

5,00E-02

Dv(

d)

[cc/

A/g

\]

40

50

60

70

80

90

t (cp

s)

N2 physisorption

0,00E+00

1,00E-02

0 10 20 30 40 50 60 70

Pore width (A)

0

10

20

30

40

10 15 20 25 30 35 40 45 50 55 60

2-Theta

Int

MCM LR order, d=3 nm

200

250

300

TEM

0

50

100

150

Int (

cps)

Proceed with ALD!

22

0 1 2 3 4 5 6 7 8 92-Theta

with ALD!

Dissolution Diffusion: Ionic LiquidsDissolution-Diffusion: Ionic Liquids

Abbreviation: [emim][Tf2N]

1-ethyl-3-methyl-imidazolium-bis-(trifluoromethylsulphonyl) imide

Abbreviation: [bmim][Tf2N]

1 b t l 3 meth l imida oli m bis(trifluoromethylsulphonyl) imide 1-butyl-3-methyl-imidazolium-bis-(trifluoromethylsulphonyl) imide

23

Dissolution Diffusion: Ionic Liquids

Cailletet Tube

Dissolution-Diffusion: Ionic Liquids

S lSample mixture

The number of phases can be observedThe number of phases can be observed visually

Adjustable Pressure and/or Temperature

Measuring Range 0.3-15 MPa, 250-450 K

Accuracy 0.03 MPa, 0.02 K

24


•The curvature in the CO2comparison of CO2, CO, H2, and CH4 solubilities in [bmim][Tf2N] 2solubilities & the linear solubilities of H2 and CH4suggest an optimal mid-range

12

14

16

H2 CO2

pressure for maximum separation efficiency.

• The opposite trends of 8

10

12

P, M

Pa

CH4

CO

ppsolubilities of CO2 and H2with temperature suggest operation at lowest possible

4

6

P

333.15 K353.15 K373 15 K

temperature for best separation.

•Absorption selectivity

0

2

0 0.1 0.2 0.3 0.4 0.5 0.6

mole fraction CO2/CH4/CO/H2

373.15 K393.15 K413.15 K433.15 K453.15 K

25

Absorption selectivity 5<CO2/H2<15


2μm

Architecture of an asymmetricasymmetric membrane support

26


27


P θγ cos4Δ50

14 P (1

dP γ=Δ

40

30P (b

ar)

12

10

8

10-9 m

ol m-2

80

bar)

γ = 30 mN/m γ = 50 mN/mγ = 70 mN/m

20

10

6

4

2Pa-1s

-1)

60

40

ce p

ress

ure

(b

γ

Target

10080604020t (min)

Bmim triflate: 37 5 mN/m !!20

0

Lapl

a Target

Thanks to ECN-EEI-MST:

Bmim triflate: 37,5 mN/m !!

28

806040200Laplace pore diameter (nm) Jaap Vente, Luci Correia, Johan Overbeek


Transport through IL membrane ≈ Solubility x p g yDiffusivity

To be done:

•Measure transport and derive diffusivity

•Determine absorption kineticsDetermine absorption kinetics

Furthermore:

•Measure multi gas absorption•Measure multi gas absorption

•Determine effect of steam (WGS)

29

•Determine IL vapor pressure @ 250-400oC

Thank you co-workers:

Virginie Feuillade

Yen Tran

Kostas Stoitsas Posters outside on:

Sona Raeissi Hybrid alumina-silica support

MCM materialsMCM materials

Ionic Liquids

WGS t l tWGS catalysts

Precursors coating materials/surface modification

30

materials/surface modification

Documents

Advanced Membrane Reactors in Energy Systems ...gcep.stanford.edu/pdfs/kUXNHroC3cAssx6wJoz_Mg/Haije...Advanced Membrane Reactors in Energy SystemsAdvanced Membrane Reactors in Energy