Determining the Kinetics of Liquid Phase Water-Gas Shift Reaction on Pt Catalysts

Dhairya D. Mehta1, M. Cem Akatay2, Eric A. Stach2, W. Nicholas Delgass1, Fabio H. Ribeiro1
2 1 School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907 (USA) School of Materials Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907(USA)

INTRODUCTION
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

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

KINETIC MEASUREMENTS
CO /cti,ation - &OR increases 2-0 ti"es on e1 osure to hi!h PCO (223ar) &his increased ,alue "aintained e,en after air e1 osure CO ro3a3l4 dri,es out 5S6 co,erin! the Pt7 increasin! the o3ser,ed &OR

EQUIPMENT OPERATION

/ll -inetic studies done after CO acti,ation Arrhenius Plot

-2 -3 -4.5

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

-5

Pt0o&'
Ea ) -6 ( ./&mol L8 (&OR9s-*)
-5.5 -6 -6.5 -7 -7.5 2.2 2.3 2.4 2.5 2.6 2.7 -3 -2 -1 0

'

) *0+30

L8 (&OR9 s-*)

-4 -5 -6 -7

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

,( ) *0+33

' ) 0+50

Reactor @eatures Stirred &an'nternals) Dip Tube, Gas Entrainment Impeller AOC: SST316 Pressure Ratin!) 340 bar (olu"e of Reactor) 500 ml

-8

&-*9 *:-0 B-*

L8 (P9 3ar)

EFFECT OF Mo
Catal4st ;< Pt9C Reaction Gas hase WGS LWGS Gas hase WGS LWGS &OR9*:-0 s-* :+*2= >+? :+> 0+2= ;: >

P D >: 3ar & D *2: C

&OR9 *:-0 s-*

Se"i - #atch O eration

Stea!4*State 5alue ;< Pt 2+2< Ao9C

&otal 'nlet @lo. D 0:: "l "in-* 'nlet Gas Co" osition *:< CO7 *:< H27 E:< /r

&OR for LWGS is an order of "a!nitude hi!her than !as- hase WGS TOR( PtMo / C ) Si"ilar ratio o3ser,ed for 3oth !as- hase WGS ~ 10 TOR ( Pt / C ) and Refor"in!
* Gas*phase 1GS T # e2trapolate! to 31GS $on!itions

0 0 50 100 150 (00 (50

T)160', P' ) 4 bar, P,( ) 4 bar, P' ( ) 0+( bar, P,( ) 5 bar
&i"e9 "in

COMPARISON OF ORDERS LWGS v/s WGS PROOF OF KINETIC CONTROL

%1ternal Aass &ransfer
6

Pt9C
CO2

PtAo9C
CO2 Gas WGS

'nternal Pore Ciffusion

Catal4st Cis ersion9 < (7 (8 &OR9*:-0 s-* 4+- 0+4 5+7 0+6
-0.4 -0.2 0

&OR9*:-0 s-*

5 4 3 2 1 0 0 500 1000 1500 2000

#e9ion o" peration

56Pt&' 16Pt&'

CO

CO

LWGS H2
0.2 0.4 0.6 -0.4 -0.2 0

H2
0.2 0.4

/!itation S eed9 r "

Boros 8o.a- Criterion - Similar T # obser:e! at !i""erent ;t+ 6 loa!in9 on $atal4st at same !ispersion+ Ensures that .ineti$s is the rate $ontrollin9 re9ime

CO Order) Co" etiti,e adsor tion .ith H2O CO2 Order) *+ Lo.er te" erature of o eration

CATALYST CHARACTERIZATION
Pt Content) Aeasured 34 'CP-O%S &est (Gal3raith La3s 'nc+) Pt Cis ersion) &rans"ission electron "icrosco 4 &%A '"a!es @R%SH FS%C Sa" les

2+ Hi!her ressure ran!e H2 Order) /ll the a3o,e three effects co" ensate for each other

CONCLUSION
@irst re orted -inetics for WGS in liquid hase refor"in! conditions

&he reaction "echanis" a

ears to 3e the sa"e for WGS and LWGS

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