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Liquid Phase Water-Gas Shift Reaction (LWGS)

CO + H2O(l) CO2 + H2

Water-Gas shift (WGS) - H2 roducin! reaction in Refor"in!

O#$%C&'%S * &urno,er Rate (&OR) in liquid hase conditions

2 Co"arison of inetics .ith !as-hase WGS

CO /cti,ation - &OR increases 2-0 ti"es on e1osure to hi!h PCO (23ar)

&his increased ,alue "aintained e,en after air e1osure

CO ro3a3l4 dri,es out 5S6 co,erin! the Pt7 increasin! the o3ser,ed &OR

/ll inetic studies done after CO acti,ation

-7.5

-7

-6.5

-6

-5.5

-5

-4.5

-3 -2 -1 0 1 2 3

L8(

&OR9s-*)

L8 (P9 3ar)

KINETIC MEASUREMENTSKINETIC MEASUREMENTSKINETIC MEASUREMENTSKINETIC MEASUREMENTS

EQUIPMENT OPERATIONEQUIPMENT OPERATIONEQUIPMENT OPERATIONEQUIPMENT OPERATION

INTRODUCTIONINTRODUCTIONINTRODUCTIONINTRODUCTION

Catal4st Reaction &OR9*:-0 s-*

;< Pt9CGas hase WGS :*=

LWGS >? :>

EFFECT OF MoEFFECT OF MoEFFECT OF MoEFFECT OF Mo

Dhairya D. Mehta1, M. Cem Akatay2, Eric A. Stach2, W. Nicholas Delgass1, Fabio H. Ribeiro11 School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907 (USA)

2 School of Materials Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907(

Determining the Kinetics of Liquid Phase Water-Gas Shift

Reaction on Pt Catalysts

Reactor @eatures

Stirred &an

'nternals Dip Tube, Gas

Entrainment Impeller

AOC: SST316

Pressure Ratin! 340 bar

olu"e of Reactor 500 ml

Arrhenius Plot r!ers o" #ea$tion % Pt&'

'( ) *0+30

' ) 0+50( ) *0+33

-8

-7

-6

-5

-4

-3

-2

2.2 2.3 2.4 2.5 2.6 2.7

L8(

&OR9s-*)

&-*9 *:-0 B-*

Pt&'Ea ) -4 4 ./&mol

Pto&'Ea ) -6 ( ./&mol

-

@undin! for this research has 3een ro,ided 34

%1ternal Aass &ransfer 'nternal Pore iffusion

&OR for LWGS is an order of "a!nitude hi!her than !as-hase WGS

Si"ilar ratio o3ser,ed for 3oth !as-hase WGS

and Refor"in!* Gas*phase GS T# e2trapolate! to GS $on!itions

T)160', P' ) 4 bar, P() 4 bar, P'(

) 0+( bar, P() 5 bar

CO Order Co"etiti,e adsortion .ith H2O

CO2 Order * Lo.er te"erature of oeration

2 Hi!her ressure ran!e

H2 Order /ll the a3o,e three effects co"ensate for each other

@irst reorted inetics for WGS in liquid hase refor"in! conditions

&he reaction "echanis" aears to 3e the sa"e for WGS and LWG

Ao "odifies the inetics for WGS and LWGS in a si"ilar .a4

-0.4 -0.2 0 0.2 0.4 0.6

Pt9C

Gas WGS

LWGS

;< Pt 2< Ao9CGas hase WGS 0=

LWGS ;: >

( / )~ 10

( / )

TOR PtMo C

T OR P t C

0

1

(

3

4

5

0 50 100 150 (00 (50

&

OR9*:-0

s-*

&i"e9 "in

P D >: 3ar

& D *: C

&otal 'nlet @lo.

D 0:: "l "in-*

'nlet Gas Co"osition

*:< CO7 *:< H27 E:< /r

Stea!*State alue

PROOF OF KINETIC CONTROLPROOF OF KINETIC CONTROLPROOF OF KINETIC CONTROLPROOF OF KINETIC CONTROL

Catal4st isersion9 < &OR9*:-0 s-*

5Pt&' (7 4+- 0+4

1Pt&' (8 5+7 0+601

2

3

4

5

6

0 500 1000 1500 2000

&OR9*:-0

s-*

/!itation Seed9 r"

#e9ion o"

peration

-0.4 -0.2 0 0.2 0.4

PtAo9C

COMPARISON OF ORDERSCOMPARISON OF ORDERSCOMPARISON OF ORDERSCOMPARISON OF ORDERS LWGS v/s WGSLWGS v/s WGSLWGS v/s WGSLWGS v/s WGS

CONCLUSIONCONCLUSIONCONCLUSIONCONCLUSION

CO2CO2

CO CO

H2 H2

Boros 8o.a Criterion - Similar T# obsere! at !i""erent ;t+ loa!in9 on $atalst

at same !ispersion+ Ensures that .ineti$s is the rate $ontrollin9 re9ime

Pt Content Aeasured 34 'CP-O%S &est (Gal3raith La3s 'nc)

Pt isersion &rans"ission electron "icrosco4

&%A '"a!es

@R%SH

FS%

Sa"les

CATALYST CHARACTERIZATIONCATALYST CHARACTERIZATIONCATALYST CHARACTERIZATIONCATALYST CHARACTERIZATION

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