Membranes: a new separation technology for the …...Membrane solutions for energy efficient...

Membranes: a new separation technology for the purification of hydrogen and industrial solvents

J.F. Vente

Presented at the Lecture Dinner Meeting at AIChE“, Zoetermeer, 13 April 2010

ECN-L--10-009 April 2010

Membrane solutions for energy efficient separations www.ecn.nl

Membranes: a new separation technology for the purification of hydrogen and industrial solvents

Jaap Vente


ECN’s location


ECN’s main features

•

ECN develops and implements high-level knowledge and technology

for the transition to sustainable energy management.

•

Annual turnover of 70 M€

(>25% from private contract research)

•

10-15 international patents / year (revenues: 1.5 M€/yr)

•

Approx. 600 reports and publications each year

•

(Inter)national co-operation with companies, universities and research institutes


Trias Energetica: to a sustainable energy system

2.

Maximise the use of renewable energy sources

1.

Reduce demand (energy saving)

3.

Use fossil fuels in the cleanest possible way

Energy demand


Renew

ables

Ene

rgy

effic

ienc

y

Clean and efficient (fossil) fuels

Supply issuesDemand reduction

Trias Energetica

Solar

Wind

Biomass

H2

, Fuel CellsCO2

-capture

Buildings

Smart grids

Industry

System innovations

Presentator

Presentatienotities

Hoe zit ECN in elkaar en hoe speelt dat in op onderwerpen binnen gemeente. ECN …. ICT: enerzijds kan ICT je ook helpen vraagvermindering te realiseren. Denk aan het regelenen afstemmen van vraag en aanbod door ICT technologie. Industrie richt oa op restwarmtebenutting. Dit is ook een onderwerp die voor de ICT op termijn belangrijker kan worden. Denk aan mogelijkheden voor het maken van elektriciteit met warmte of koeling. Technologie die nu nog moeilijk zijn intrede maakt, maar wellicht door hogere temperatuureisen van computerapparatuur (waardoor restwarmte warmer wordt en waarevoller) op termijn wel haalbaar.


ECN role in technology development

Fundamental research

Lab-scale (1 kg/h)

Pilot-scale (100 kg/h)

Demonstration

Commercial

effort / €

total effortcooperation

ECN


Energy Efficiency in Industry


ECN Energy Efficiency in Industry

Upgrading industrial waste heatIndustrial Heat Technology Thermo-acoustic heat pump

(13 fte)

Chemical heat pump

Combined unit operationsProces Intensification HEX reactors

(9 fte)

Membrane reactors

Molecular separationsMolecular Separation Technology Materials, processes

(12 fte)

Systems development


Molecular Separation technology

SeparationSeparationraw materials

REACTOR

and..and..

and..and..

and..and..

clean air

contaminants

products

by products

recycle

clean water

ScheidingScheiding

SeparationSeparation


SeparationSeparationSeparationSeparationraw materials

REACTOR

and..and..

and..and..

and..and..

clean air

contaminants

products

by products

recycle

clean water

ScheidingScheiding


SeparationSeparationSeparationSeparation


Motivation•

474 PJ/year Energy use in NL (petro)chemical (NL≈2400 PJ/year)

•

Separation processes 190 PJ/year•

Exergetic efficiency 10%


Membranes


Membrane separation

Feed

Permeate 9-

20 mm

30 -

100 cm


Separation principle

Dissolution and diffusionDense materials• Amorphous polymers; • Crystalline metals and oxides

Size and affinityPorous materials• Amorphous sol-gel based inorganic materials• Crystalline zeolites and related

Membrane solutions for energy efficient separations www.ecn.nl13

Membrane utilisationWater treatment

•

Purification of drinking water•

Treatment of sewage water

Gas separations•

Hydrogen recovery

•

Natural gas production•

Hydrogen production

•

Air separationMedical applications

•

Kidney dialysesOthers

•

Purification of organic solvents•

Volatile organic component recovery


Porous Membranessa

lt/m

etal

ions

Pore sizeµm

Microfiltration

10-2

10-1

1

101

10-4

10-3

bact

eria

viru

s colo

ïdal

par

ticle

s

prot

ein

gase

s

Ultrafiltration

PervaporationGas separation

Nanofiltration Activities ECN-MST


Top view of intermediate layers(1) Course alumina

support: packing of 20 micron particles

1

(2) 600A layer: Regular packing of submicron particles

2

(3) γ

Al2

O3

layer; Dense packing of nano-particles

3


Tubular microporous membranes

4 nm pores

120 nm pores

Pores < 1nmZrO2

/TiO2

1000 nm


Membrane fabrication

suspension

coat

speed

“dry”

wet evaporation

septum

coat vessel

Coat Vessel

coatspeed

meniscus


Pervaporation membranes


What is pervaporationPervaporation is a membrane based separation technique

= permeation + evaporation= selective evaporation of liquids via a membrane= much more energy efficient than distillation

Feed Permeate

Membrane

Evaporation

Pervaporation


Commercial available PV membranesPolymers

•

Sulzer: PVA•

Vaperma: polyimide

Ceramics•

Mitsui, Mitsubishi: Zeolite A

•

Pervatech: Silica


SiftekTM Membrane by VapermaHydrophilic polyimide hollow fiber concept

Vapour permeation from the bore side

100m2

membrane area per module

Water-Rich Permeate

Dry Ethanol

Ethanol- Water

Vapour Mixture

Source


20m3/day Demonstration unitBio-ethanol dehydrationDistillation and membrane

Source


Developments in Zeolite A membranes (1)Manufacturing companiesMitsui Engineering and ShipbuildingHyflux in collaboration with BP and DalianHitachiInocermic together with GFTMitsubishi Chemical Company formerly BNRI

Crystalline microporous material3D –

architecture.

Source


Developments in Zeolite A membranes (3)

Source

1997

2000

2007

2008

Pervaporation 75ºC

Vapour Permeation 150ºC


Present challengesHigher application temperaturesHigher acid resistanceHigher stability in aggressive solventsLarger application window w.r.t. water contentEffective methanol removalResistance against condensation

Amorphous inorganic microporous networks

•

SiO2

•

Methylated SiO2

•

Ti/ZrO2

•

HybSi®: SiO2

with organic bridges


Large scale production

Coat robot Drying Carousel Welding robot

Furnace Module

http://www.sulzerchemtech.com/en/DesktopDefault.aspx/tabid-98/


HybSi® membranes from bridged precursorsStrategy:

replace Si—O—Si bonds by Si—C—C—Si bonds

Collaboration with Universities of Twente and Amsterdam (Ashima Sah, Andre ten Elshof, Hessel Castricum, Marjo Mittelmeijer), started in 2003

SiSiEtO

OEt

OEtOEt

OEtOEt

HNO3, H2O

SiO

SiSi

OSi

O

OOH

OSi

Si

Si

Si

OH

OHOH

OHSi

SiSi

SiHO OH

HO OH

HOOH


Precursor selection for improved performance

Precursors:Recipe 1: BTESE + MTESRecipe 2: BTESERecipe 3: BTESM

MTES BTESE BTESM

Hybrid layer


100

98

96

94

92

90

88W

ater

cont

ent i

n th

e pe

rmea

te (%

)6004002000

Time on stream (d)

25

20

15

10

5

0

Wat

er fl

ux (k

g/m

2 h)

6004002000Time on stream (d)

Performance HybSi® membranes, 150oC

Life time state-of-the-art Me-SiO2

Feed: 5 wt.% water in n-BuOH

J. Membr. Sci. 2008, 324, 111

Life time >650 days

Recipe 1

Recipe 2


Application testing - alcoholsFeed = 5 wt.% water in alcohol

T = 55 70 85 95 °C

100

80

60

40

20

0

Wat

er c

onte

nt p

erm

eate

(wt.%

)

Recipe 3 Recipe 2 Recipe 1

MeOH EtOH PrOH BuOH

ChemSusChem 2008, 2, 158


Acid stability

Feed : 5 wt.% water in n-BuOH0.005 –

0.5 wt.% HNO3Recipe 2

3.0

2.5

2.0

1.5

1.0

0.5

Wat

er fl

ux (k

g/m

2 h)


100

90

80

70W

ater

con

tent

per

mea

te (w

t.%)

0.005 0.05 0.5 wt% HNO3

Feed : 5 wt.% water in EtOH0.1 wt% HAcRecipe 3

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0W

ater

flux

(kg/

m2 h)


100

95

90

85

80

75

70

Wat

er c

onte

nt p

erm

eate

(wt.%

)

0.1 wt% HAc

Acid stability very promising


Origins of stability of hybrid silica-

More stable bonds

-

Higher crack propagation energy

-

Lower surface diffusion coefficient

-

Lower solubility

Vente Membranes bij Rhodia.pptx


How to use HybSi®?

Azeotrope separation, Debottlenecking, Capacity increase


Where to use HybSi®

Permeating species

Retained species Azeotrope (wt% retained species)

Water Acetonitrile 83.7

Water Ethanol 95.5

Water n-Propanol 71.7

Water t-Butanol 88.3

Water Methyl acetate 95.0

Water Methyl ethylketone 89.0

Water Tetrahydrofuran 95.0

Methanol Toluene 31.0

Methanol Methyl acetate 81.3

Methanol Tetrahydrofuran 69.0

Azeotropes


Hydrogen selective membranes


Hydrogen for ammonia production

Desulphurisation Membrane Reactor

Natural gas Steam

N2

Syngas(H2 + N2)

CO2 + H2OH2 H2 H2

Desulphurisation Membrane Reactor

Natural gas Steam

N2

Syngas(H2 + N2)

CO2 + H2OH2 H2 H2H2H2 H2H2 H2H2

New scheme including membrane reactor

ConventionalDesulphurisation

Reformer1

Reformer2 HT Shift LT Shift

CO2 removalMethanation

Natural gas

Steam Air

Syngas(H2 + N2)

CO2

Fuel gas

800 oC 980 oC480 oC 350 oC 200 oC

50 oC275 oC

H2OH2O

140 bar 30 bar

43 bar

Desulphurisation

Reformer1

Reformer2 HT Shift LT Shift

CO2 removalMethanation

Natural gas

Steam Air

Syngas(H2 + N2)

CO2

Fuel gas

800 oC 980 oC480 oC 350 oC 200 oC

50 oC275 oC

H2OH2O

140 bar 30 bar

43 bar


Membrane reactor: Concept

Steam reforming: CH4 + H2O 3 H2 + CO (ΔH = 206 kJ/mol)

Water-gas shift: CO + H2O H2 + CO2 (ΔH = - 41 kJ/mol)

CH4 + 2 H2O 4 H2 + CO2

Steam reforming: CH4 + H2O 3 H2 + CO (ΔH = 206 kJ/mol)

Water-gas shift: CO + H2O H2 + CO2 (ΔH = - 41 kJ/mol)

CH4 + 2 H2O 4 H2 + CO2CH4 + 2 H2O 4 H2 + CO2


Tokyo gas pilot demonstration


1,0E-10

1,0E-09

1,0E-08

1,0E-07

1,0E-06

1,0E-05

1,0E-04

0 2 4 6 8

time [days]

Perm

eanc

e [m

ol/m

2 sPa]

0

5

10

15

20

25

30

35

CH

4 co

nver

sion

incr

ease

Stable H2 permeance

No membrane

No membraneStable CH4 permeance

1,0E-10

1,0E-09

1,0E-08

1,0E-07

1,0E-06

1,0E-05

1,0E-04

0 2 4 6 8

time [days]

Perm

eanc

e [m

ol/m

2 sPa]

0

5

10

15

20

25

30

35

CH

4 co

nver

sion

incr

ease

Stable H2 permeance

No membrane

No membraneStable CH4 permeance

Depending on conditions CH4

conversion may increase with >30%

H2

/CH4

sel > 1000

Shift in equilibrium, membrane reactor testing


H2 transport in dense Pd alloy membranes

1.

Bulk diffusion2.

Adsorption of hydrogen molecules

3.

Dissociation into atoms4.

Absorption of atoms

5.

Diffusion of atoms6.

Recombination

7.

Desorption

CO2

H2OH2

H2 H2

H2

H

HH

H1

2

3 54 6

7

Pd alloy membrane

High pressure Low pressure

CO2

H2OH2

H2 H2

H2

H

HH

H1

2

3 54 6

7

Pd alloy membrane

High pressure Low pressure


ManufacturingTwo distinct approaches

Electroless plating

Dalian Institute of Chemical Physics

Worcester Polytechnic Institute

Energy research Centre of the Netherlands

Magnetron sputtering

Southwest Research Institute

SINTEF

http://www.dicp.ac.cn/englishvers/

http://www.wpi.edu/index.html


Electroless plating route

(3) Sequential reduction and deposition of metal ions.

(4) Alloying step by heat treatment

(1) Support pore size reduction

(2) Seeding of support

Membranes of up to 90 cm


Long term behaviour

Steam reforming reactor tests, CH4

20% / N2

20% / H2

O 60%Feed flow 2 –

10 Nl/min; Pfeed = 25 –

42 bar;

T = 530 –

590ºC;

ECN –

membrane made by electroless plating

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50

Duration [days]

Con

vers

ion

CH

4 [%

]

0,00

0,02

0,04

0,06

0,08

0,10

0,12

0,14

Flux

[mol

/m2s

]

MR expThermoH2 fluxCH4 flux


Towards implementation: drivers and challenges

Large-scalehydrogen

production

On-site H2production

H2 recovery &purification

Research market

Precombustiondecarbon.

Dehydro-genation

Carbon deposition

Lifetime T > 600 oC

reproduciblemembrane

Technological challenges

System integration

Membrane cost

Membrane flux

Lifetime T > 500 oC

Membrane cost

Market size

Market drivers

Efficiency

Lower investment

Lower investment & process integration

Efficiency& investment

Manufacturing capabilityLifetime at T > 400 oC


Technology transfer to the market (1)

Production procedure up to 90 cm tubes

High quality membranes:

-high selectivity (1000-7000)

-H2

permeance 32-48 Nm3/m2hbar0.5

at 450°C

Thin layer defect free membrane

on tubular ceramic support



Prototype hydrogen separation modules

Small scale:Single tube~40 cm2

Hydrogen flow: 0.15 -

1 Nm3/hUp to 70 bars

Partners:CRL Energy (New Zealand)University of the Basque Country (Spain)



Prototype hydrogen separation modules

To full length multi tubular (1/8

to 1/2

m2)Up to 6 Nm3/hrUp to 25 bar

Partners:Technip KTI (Italy)N-GHY (France)


Next steps, separation modules•

On site H2

production–

600 kWth, = 350 kWe

–

12 m2

membrane

•

Partnering for:–

Further scaling up

–

Commercialisation–

Marketing


www.hysep.comwww.hybsi.com

http://www.hysep.com/

http://www.hybsi.com/


Membrane Technology Group


www.hysep.com www.hybsi.com [email protected]

www.ecn.nl/memtech

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