On the potential of Ni-based catalysts for steam reforming of methane in

membrane reactors

J.A.Z. Pieterse J.W. Dijkstra

J. Boon Y.C. van Delft

M. Ligthart E.J.M. Hensen

A. Pfrang R.W. van den Brink

Presented at the International Conference on Catalysis in membrane reators, June 2009,

Lyon, France

ECN-L-09-162 December 2005

ww

w.e

cn.n

l

On

the

pote

ntia

l of N

i-bas

ed c

atal

ysts

for

stea

m

refo

rmin

g of

met

hane

in m

embr

ane

reac

tors

J.A

.Z. P

iete

rse,

J.W

. Dijk

stra

, J.

Boo

n, Y

.C. v

an D

elft,

M. L

igth

art,

E.J

.M.

Hen

sen,

A. P

fran

g, R

.W. v

an d

en B

rink

201

/12/

2009

Hyd

roge

n M

embr

ane

reac

tors

for

pre-

com

bust

ion

CO

2ca

ptur

e

•D

evel

op, a

nd e

valu

ate

the

pote

ntia

l of P

d H

2m

embr

ane

reac

tors

for

CO

2ca

ptur

e in

nat

ural

gas

com

bine

d cy

cle

pow

er p

lant

PR

E-r

efor

mer

Com

bust

ion

cham

ber

Inte

grat

ed m

embr

ane

refo

rmer

com

bine

d cy

cle

301

/12/

2009

Mem

bran

e pr

inci

ple

•P

aral

lel r

eact

ion

and

H2

rem

oval

shi

ft eq

uilib

rium

tow

ards

hig

h co

nver

sion

s

•F

avor

able

heat

inte

grat

ion:

•No

low

tem

pera

ture

WG

S a

nd s

epar

atio

n se

ctio

ns n

eede

d

•Ref

orm

ing

at d

ecre

ased

tem

pera

ture

CO

2, H

2O,

(H2,

CO

, CH

4)M

embr

aneCO

+H

2O

C

O2+

H2

CH

4+H

2O

C

O+

3H2

Ret

enta

te

Per

mea

te (

incl

. H2)

H2

H2

H2

H2

Sw

eep

Nat

ural

gas

+ H

2O

Fue

l + a

irF

lue

gas

Com

bust

ion

Hea

tH

eat

Ste

am r

efor

min

g: C

H4

+ H

2O

3

H2

+ C

O (

∆H =

206

kJ/

mol

)

Wat

er-g

as s

hift:

CO

+ H

2O

H2

+ C

O2

(∆H

= -

41 k

J/m

ol)

CH

4+

2 H

2O

4

H2

+ C

O2

Ste

am r

efor

min

g: C

H4

+ H

2O

3

H2

+ C

O (

∆H =

206

kJ/

mol

)

Wat

er-g

as s

hift:

CO

+ H

2O

H2

+ C

O2

(∆H

= -

41 k

J/m

ol)

CH

4+

2 H

2O

4

H2

+ C

O2

CH

4+

2 H

2O

4

H2

+ C

O2

401

/12/

2009

Pro

cess

con

ditio

ns in

the

mem

bran

e re

form

er

Fee

d pr

essu

re 4

5 ba

r: a

vaila

ble

from

the

grid

Per

mea

te p

ress

ure

5-10

bar

:dr

ivin

gfo

rce

for

perm

eatio

n

Sw

eep

for

low

erin

gth

e m

embr

ane

surf

ace

area

Ste

amto

carb

on r

atio

≤

3

Use

suf

ficie

nt T

empe

ratu

re fo

r fa

vora

ble

kine

tics

:

Tra

de o

ff:

1)H

igh

T to

boo

st p

erm

eanc

e an

d lim

it co

stly

mem

bran

e su

rfac

e ar

eaan

d to

ob

tain

hig

h ca

taly

st a

ctiv

ity

2)T

oo h

igh

T in

crea

ses

desi

gn c

osts

and

lim

ited

ther

mal

sta

bilit

y of

mem

bran

e m

ater

ials

⇒fo

cus

on 5

00 –

600°

C

⇒W

hat a

bout

the

cata

lyst

act

ivity

and

sta

bilit

y?

501

/12/

2009

Obj

ectiv

e

•N

i-bas

ed c

atal

ysts

-U

sed

in in

dust

rial r

efor

min

g at

80

0 –

1000

°C-

Pro

ne to

e.g

. ca

rbon

form

atio

n•

Pre

ciou

s-m

etal

bas

ed c

atal

ysts

-M

ainl

y R

hodi

um-

Use

d/de

velo

ped

for

low

-te

mpe

ratu

re/p

ress

ure

refo

rmin

g an

d he

avy

feed

s -

Hig

h co

sts

0246810

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

O/C

H/C

400

°C5

00 °C

600

°C7

00 °C

Car

bo

n F

orm

atio

n

S/C

=3

Membrane effect: H 2 withdrawal

S/C

=2

DR

SR

Can

we

use

Ni c

atal

ysts

in th

e hy

drog

en-le

an m

embr

ane

ref

orm

ing

cond

ition

s or

sho

uld

we

rath

er lo

ok a

t Pre

ciou

s M

etal

cat

alys

ts ?

Is N

i act

ive

and

stab

le e

noug

h? �P

robl

em: m

embr

ane

oper

atio

ns, l

ower

H/C

, in

crea

sed

risk

carb

on fo

rmat

ion

601

/12/

2009

Exp

erim

enta

l app

roac

h1)

Act

ivity

: Ni v

ersu

s R

hca

taly

sts

•Det

erm

ine

whe

ther

hyd

roge

n pr

oduc

tion

rate

is

suffi

cien

t to

mat

chth

e hy

drog

en fl

ux o

f the

mem

bran

e�

1D m

odel

: use

hig

h pr

essu

re r

eact

ion

kine

tics

of N

i a

nd

Rh

cata

lyst

s an

d st

ate-

of-t

he-a

rt p

erm

eanc

eof

Pd

bas

ed

mem

bran

es

2) S

tabi

lity

test

ing

of N

i and

Rh

cata

lyst

s un

der

sim

ulat

ed (

low

H

/C)

mem

bran

e co

nditi

ons

�M

icro

flow

test

rig, 6

00°C

, 1 a

tm, H

/C=1

0 (7

.5%

CH

4,

22.5

%H

2O)

perio

dica

lly c

hang

ed to

H/C

=2.5

(1

.3%

CH

4,0.

14%

CO

,11.

6%C

O2,

16%

H2O

)

3) M

embr

ane

refo

rmer

test

ing

at h

igh

pres

sure

with

m

embr

ane

and

cata

lyst

S

wee

p

Tub

ular

mem

bran

e

Cat

alys

t

Sea

ling

Rea

ctor

out

erw

all

Sw

eep

tube

Clo

sed-

end

seal

ing

Fee

d

Ret

enta

te

Per

mea

te

701

/12/

2009

Str

uctu

reof

1-d

mod

el

Fee

d

Sw

eep

Ri

Mem

bran

eJ i

zz+

dz

Out

=

In

–

Per

mea

nce

+ r

eact

ion

z=o

z=L

T

)(z

,R

dzLW

T)

(z,

J

dzL

A-

(z)

F

dz)

(z F

reac

tions

ii

mem

ii

∑⋅

+⋅

=+

Fi(z

)F

i(z+

dz)

Fi=

feed

side

flux

of c

ompo

nent

i

z=le

ngth

coor

diat

e

Am

em=

mem

bran

esu

rfac

ear

ea

L =

mem

bran

ele

ngth

Ji=

mem

bran

eflu

x of

com

p. i

W=

cata

lyst

wei

ght

R=

reac

tion

rate

of c

omp.

I

T=

tem

pera

ture

Ref

orm

ing:

isot

herm

al

801

/12/

2009

at 5

00 d

eg C

, goo

d st

abili

ty,

but…

….

Com

mer

cial

Ni

Com

mer

cial

PM

H/C

=10 H

/C=

2.5

Res

ults

Sta

bilit

y

901

/12/

2009

But

, at

600

deg

C:

Com

mer

cial

Ni

Com

mer

cial

Pre

ciou

s M

etal

60708090100 0

1020

3040

Tim

e [h

r]

CH4Conversion (%)

Ni-P

RH

/C 1

0 H/C

2.5

0

20406080100

010

2030

4050

60T

ime

[hr]

CH4Conversion (%)

PM

-SR

H/C

2.5

H/C

10

Mod

est s

tabi

lity

loss

RA

MA

N: c

arbo

n

Dra

mat

icst

abili

ty lo

ss

afte

r ex

posu

reto

H/C

2.5

RA

MA

N: l

ittle

car

bon

CO

che

m: s

inte

ring

rela

ted

1001

/12/

2009

�P

repa

re s

erie

s of

Ni-M

gAl 2

O4

cata

lyst

s (M

gAl 2

O4:

bas

ic →

prev

ents

“C

”fo

rmat

ion,

use

d in

indu

stry

; dry

impr

egna

tion)

�P

repa

re s

erie

s of

Ni+

prom

otor

-MgA

l 2O

4ca

taly

sts

�C

hoic

e pr

omot

ors:

Lan

than

ides

par

ticul

arly

Lan

than

um

�C

hara

cter

ize

the

deac

tivat

ion

at 6

00°C

�F

ocus

on

carb

on

=> F

urth

er r

esea

rch

devo

ted

to th

e op

timiz

atio

n of

Ni c

atal

yst

1101

/12/

2009

Pos

sibl

e ro

le o

f Ln/

Lant

hanu

m in

pre

vent

ion

coki

ng

Ver

ykio

set

al.,

Mun

era

et a

l.

1. 2.Im

prov

ed s

team

sor

ptio

n,

to a

id th

e ga

sific

atio

n of

C w

ith s

urfa

ce O

H

3.S

tabi

lizat

ion

Par

ticle

siz

e

4.O

xyge

n bu

ffer

-‘O

’to

gas

ify C

pre

curs

ors

(Cer

ia)

Car

bon

form

atio

n

Car

bon

gasi

fica

tion

1201

/12/

2009

�19

Wt%

Ni (

9nm

par

ticle

), a

dded

2W

t% L

a, C

e,P

r,G

dan

d 8W

t% P

r, C

eby

se

quen

tial i

mpr

egna

tion:

no

sign

ifica

nt e

ffect

of L

nad

ditio

n on

sta

bilit

y�

8 W

t% L

a (c

lose

to th

eore

tical

mon

olay

er):

Effe

ct o

f Lan

than

ides

1301

/12/

2009

�La

st

abili

ty b

ut

con

vers

ion

activ

ity�

No

effe

ct o

f ele

ctro

nega

tivity

Ln=>

rol

e in

ste

am g

asi

ficat

ion

not i

ndic

ated

�R

ole

of g

asifi

catio

n of

‘’C

’’by

La

2O2C

O3

?

0102030405060708090

010

2030

40

Ni (

1:27

)

NiL

a_m

onol

ayer

cal

c (1

:10)

NiL

a_m

onol

ayer

not

cal

c(1

:10)

Con

vers

ion

(%)

->T

ime

on s

trea

m (

h)

�19

Wt%

Ni (

9nm

par

ticle

), a

dded

2W

t% L

a, C

e,P

r,G

dan

d 8W

t% P

r, C

eby

se

quen

tial i

mpr

egna

tion:

no

sign

ifica

nt e

ffect

of L

nad

ditio

n on

sta

bilit

y�

8 W

t% L

a (c

lose

to th

eore

tical

mon

olay

er):

A

B

Effe

ct o

f Lan

than

ides

H/C

10

H/C

2.5

8 w

t% L

a

Seq

uent

ial i

mpr

egna

tion

Co-

impr

egna

tion

A B

1401

/12/

2009

La2O

2CO

310

86 c

m-1

�N

i-MgA

l 2O4

and

2%La

Ni-M

gAl 2O

4: c

arbo

n of

hig

h gr

aphi

tic n

atur

e

�S

pent

Impr

egna

ted

8%La

:, lo

wer

am

ount

car

bon

(sup

port

ed b

y T

PO

exp

erim

ents

),

carb

on w

ith ‘’

less

gra

phiti

c na

ture

’’

=>

SR

use

d ca

taly

sts

char

acte

rized

sho

w s

mal

l am

ount

La 2

O2C

O3

and

low

am

ount

of

C

NiO

‘C’

‘C’

0

10

00

20

00

30

00

40

00

50

00

60

00

70

00

80

00 10

06

00

11

00

16

00

21

00

Ram

an s

hift

[cm

-1]

Relative Intensity (Arbitrary Unit)

spen

t2%

LaN

iMA

(A

)

grap

hite

(mer

ck)

fres

h 8%

LaN

i_C

O2

CA

LC(B

)sp

ent

8%La

Ni

(B)

spen

t 8%

LaN

i(A

)

La2O

2CO

3

Cha

ract

eriz

atio

n: R

AM

AN

1501

/12/

2009

Cha

ract

eriz

atio

n: T

PR

& X

PS

TP

R:

•La

impr

oves

the

redu

ctio

n of

Ni-

spec

ies,

wea

kens

the

inte

ract

ion

betw

een

Ni2+

ions

and

MgA

l 2O

4;

•S

mal

ler

Ni p

artic

les

?

XP

S:

•In

dica

tions

of p

rese

nce

of N

i2+in

La

-Ni p

hase

(La

2NiO

4or

LaN

iO3)

6.20

0.28

NiL

a(D

I)

La (

DI)

5.36

Ni (

DI)

Tot

al H

2co

nsum

ed(m

mol

x 10

2 )

Cat

alys

t

010

020

030

040

050

060

070

080

0

x563

648

5La

(D

I) ti

mes

5

180

672

215

285

515

NiL

a(D

I)

Ni (

DI)

MgA

l 2O4

H2consumption (a.u.)

Tem

pera

ture

(C

)

�B

enef

icia

l rol

e of

La

on th

e st

abili

ty o

f Ni c

atal

yst

is n

ot y

etso

lely

as

sign

ed to

gas

ifica

tion

of ‘’

C’’

by L

a2O

2CO

3

1601

/12/

20092030405060708090100

010

2030

4050

Dur

atio

n [d

ays]

Conversion CH4[%]

0,00

0,02

0,04

0,06

0,08

0,10

0,12

0,14

Flux [mol/m2s]

X C

H4

X T

herm

o H

2 flu

xC

H4

flux

Cat

alys

tin

mem

bran

ere

form

erte

stin

g53

0-59

0°C

; Pf 2

5-42

bar

afe

ed: C

H4/

H2O

= 1

/3 N

iLaM

gAl 2

O4

;3.8

µm

Pd/α

Al 2

O3,

35

cm

leng

th, O

D 1

.4 c

m, 1

55 c

m2 ,

co-

curr

ent

590°

C; P

f 29

bara

N2

swee

p 0.

05 m

l/min

, CH

4/H

2O =

1/3

•99

% c

onve

rsio

n po

ssib

le (

up to

70

% h

ighe

r th

an e

quili

briu

m c

onve

rsio

n)

•S

tabl

e m

embr

ane

oper

atio

n, s

tabl

e co

nver

sion

1701

/12/

2009

Cha

ract

eriz

atio

n ca

rbon

with

TP

R

0 1 2 3 4 5 6 7

020

0 40

0 60

0 80

0 10

00

1200

T (

°C)

TCD - Signal

top

0.22

wt%

m

iddl

e 0.

27w

t%

botto

m 0

.30w

t%

•Car

bon

is fo

rmed

with

cat

alys

t use

d in

mem

bran

e re

form

er

•Rol

e of

dep

lete

d hy

drog

en c

once

ntra

tion

to c

arbo

n fo

rmat

ion

uncl

ear

(sim

ilar

valu

es %

wt C

alo

ng r

eact

or

coor

dina

te)

•Diff

eren

t for

ms

of c

arbo

n: n

ot a

ll ca

rbon

con

trib

utes

equ

ally

tode

activ

atio

n; h

ighe

r st

eam

use

may

be

nece

ssar

y to

pre

vent

plu

ggin

g af

ter

exte

nded

per

iods

of o

pera

tion

Cα

Gum

Gra

phite

1.1

1.3

1.2

Top

Mid

dle

Bot

tom

Tot

al c

arbo

n(C

HN

S)

(wt%

C)

Mc

Car

thy,

198

2

Cat

alys

t col

lect

ed a

t 3 lo

catio

ns a

long

the

reac

tor:

Top

, Mid

dle

and

Bot

tom

1801

/12/

2009

Sum

mar

y

�‘’C

onve

ntio

nal’’

Ni-M

gAl 2O

4ha

ve s

uffic

ient

act

ivity

for

use

in s

team

ref

orm

ing

in m

embr

ane

refo

rmer

s

�P

rom

otio

n w

ith L

anth

anum

impr

oves

sta

bilit

y of

Ni-M

gAl 2O

4(a

lbei

t at t

he c

ost o

f act

ivity

)

�T

he r

ole

of L

a co

uld

be r

elat

ed to

the

form

atio

n of

La 2

O2C

O3

durin

g re

actio

n an

d su

bseq

uent

ga

sific

atio

n of

car

bon

prec

urso

rs b

ut m

ay v

ery

wel

l be

mor

e co

mpl

ex (

mor

e in

situ

cha

ract

eriz

atio

n pl

anne

d)

�G

ood

perf

orm

ance

Pd

mem

bran

es a

nd c

atal

yst i

n m

embr

ane

reac

tor

test

ing

(low

er a

mou

nt o

f cat

alys

t ne

cess

ary

to s

tudy

dea

ctiv

atio

n in

mor

e de

tail)

�O

utlo

ok�

Mem

bran

e re

acto

r te

stin

g:

�be

tter

dim

ensi

oned

cat

alys

t-m

embr

ane

surf

ace

area

test

ing

to s

tudy

cat

alys

t dea

ctiv

atio

n

�ch

arac

teriz

atio

n m

embr

ane

afte

r te

stin

g –

inte

ract

ion

cata

lyst

-mem

bran

e

�2D

reac

tor

mod

el :

heat

, mas

s tr

ansf

er, r

adia

l cok

ing

prof

iles

�C

hara

cter

izat

ion

of th

e sy

nerg

y N

i-La,

impr

ove

activ

ity

�8-

tube

mem

bran

e re

acto

r te

stin

g to

det

erm

ine

feas

ibili

ty o

f lar

ger

scal

e hy

drog

en p

rodu

ctio

n

1901

/12/

2009

Pro

cess

deve

lopm

entU

nit (

PD

U)

Dem

onst

ratio

n of

m

embr

ane

reac

tors

at s

cale

•M

ultit

ube

mem

bran

e re

acto

r•

8 tu

bes

of 5

0 cm

•M

embr

ane

refo

rmin

g an

d •

Mem

bran

e w

ater

gas

sh

ift•

Max

600

°C, 4

0 ba

r

Rea

ctor

Ven

tilat

ion

pipe

Cab

le p

anel

Gas

sup

ply

cont

rol p

anel

Rea

ctor

Ven

tilat

ion

pipe

Cab

le p

anel

Gas

sup

ply

cont

rol p

anel

2001

/12/

2009

Pro

cess

dev

elop

men

t Uni

t (P

DU

)

CH

4

N2

H2

CO

2

CO

H2

CO

2

CO

8x

H2O

N2

H2O

N2T

est r

ig

Mem

bran

e re

acto

r

T

est r

ig

Ret

ent

ate

Per

mea

te

Fee

d Sw

eep

H2O

Mem

bran

eC

ata

lyst

wat

er

wat

er=S

ampl

e po

int f

or g

as a

naly

sis

8x

8x

Ref

orm

ing/

shift

:

150/

400

l n/m

in w

et fe

ed fl

owra

te(2

.5/6

.7kW

th p

rodu

ct H

2)

Ope

ratin

gw

indo

w25

-400

%

Gas

mix

ing

and

pre-

heat

ing

Wat

er r

emov

alan

d ve

ntin

g

Gas

sam

plin

g on

allt

ubes

2101

/12/

2009

Ele

ctric

ove

n

Rem

ovab

letu

bes

Fla

nge

conn

ectio

nsto

test

rig

Man

ifold

ing

with

flexi

ble

conn

ectio

ns

Rea

ctor

des

ign

Sou

rce:

Sel

as/L

inde

Indu

stria

l SM

RP

DU

rea

ctor

des

ign

The

cur

rent

des

ign

of th

e m

embr

ane

reac

tor

is d

eriv

ed fr

om a

n en

visa

ged

full

scal

e st

eam

met

hane

ref

orm

er ty

pe r

eact

or w

ith m

embr

anes

inse

rted

into

the

reac

tor

tube

s. H

eatin

g is

don

e by

rad

iatin

g el

ectr

ical

ele

men

ts, m

imic

king

rad

iant

bur

ners

.

2201

/12/

2009

PD

U

Set

upw

ithm

embr

ane

reac

tor

Rea

ctor

tube

s

2301

/12/

2009

Ack

now

ledg

emen

ts

The

aut

hors

ack

now

ledg

e th

e fin

anci

al s

uppo

rted

of

Sen

terN

ovem

(EO

SLT

0301

5, E

OS

LT

0501

0 pr

ojec

ts)

and

the

Dut

ch M

inis

try

of E

cono

mic

Affa

irs (

EZ

).G

.D. E

lzin

ga

and

O. P

irgon

are

ackn

owle

dged

for

thei

r co

ntrib

utio

n in

the

cata

lyst

test

ing

and

D. M

eyer

, M. S

aric

and

R. S

umbh

araj

u fo

r th

eir

cont

ribut

ion

in th

e m

embr

ane

refo

rmer

test

s.