Stages in Catalyst development

Preparation

Screening
Reaction
network
Kinetics
Increasing:
time
money
reality

Trends:

Life tests
Scale-up

Parallel activities
Subcontracting

Catalysis and Catalysts - Catalyst Performance Testing

Transport Phenomena in
Packed-bed Reactor
PLUG FLOW

MIXING
DISPERSION

DIFFUSION
REACTION
TRANSPORT PHENOMENA
Catalysis and Catalysts - Catalyst Performance Testing

Catalytic Reaction Engineering

Stability

Mechanism

Kinetics

CATALYSIS
ENGINEERING

Reactor
Engineering

Transport
Phenomena
Catalyst

Catalysis and Catalysts - Catalyst Performance Testing

Classification of Laboratory Reactors:

Mode of Operation
LABORATORY CATALYTIC REACTORS
Steady state

Transient

Continuous flow

Batch

Plug flow
Integral

Semi-batch

Mixed flow

Discontinuous

Step

Pulse

Differential

Single pass
External
Riser reactor
Thermobalance
Packed bed

Catalysis and Catalysts - Catalyst Performance Testing

Recycle

Fluidization
Internal

Berty reactor
Fluid bed

TAP
Multitrack

Slurry

Classification of Laboratory Reactors:

Contacting Mode
PFR

CSTR

FBR

Riser

Riser
fluid recycle

Catalysis and Catalysts - Catalyst Performance Testing

FBR
contn. cat feed

Slurry/FBR
with recycle

Slurry/FBR
fluid + cat. rec.
5

Pep versus Rep

Pe

uLb
Dax

Pep

Catalysis and Catalysts - Catalyst Performance Testing

ud p
Dax

Maximum allowable particle diameter versus (1 - x)

n = 1, single phase, Pep = 0.5
Lb
8n
1

ln

d p Pep 1 x

dt
10
dp

10

dt = 50 mm

dt = 50 mm

dpd p(mm)
(mm)

Lb = 100 mm
1

dt = 5 mm

dt = 5 mm
Lb = 10 mm
0.1

dt = 1 mm

dt = 1 mm

Lb = 1 mm
0.01
0.01

0.1

1-x

(1 - x)
Catalysis and Catalysts - Catalyst Performance Testing

Catalyst size

Practical catalyst:
often: dp = 1 - 3 mm

large reactor needed

Option: dilution with inerts

Catalysis and Catalysts - Catalyst Performance Testing

Catalyst wetting in trickle-flow reactors

Determined by friction and gravity

particle diameter
viscosity
linear velocity (from LHSV and Lb)
Wtr

l ul
d p2 g

5 10 6

Example
LHSV = 2 m3 / (m3h)

Catalysis and Catalysts - Catalyst Performance Testing

Catalyst wetting in trickle-flow reactors, Example

LHSV = 2 m3/m3h

l = 10-6 m2/s
dp = 1 mm
10 6 ul
ul
Wtr 6

5 10 6
10 10 10

ul = LHSV.Lb = 2 Lb m/h

Lb > 90 mm
Catalysis and Catalysts - Catalyst Performance Testing

10

Maximum allowable particle diameter versus kinematic

viscosity for complete wetting in trickle-flow reactors
10

LHSV = 2 m3 / (m3h)

d p (mm)

L b = 1000 mm
1

L b = 100 mm
L b = 10 mm

0.1
1.00E-07

Wtr

l ul
d p2 g

5 10 6

Catalysis and Catalysts - Catalyst Performance Testing

1.00E-06

1.00E-05

(m2/s)

LHSV

v ,l
Vreactor

ul A ul

Lb A Lb
11

Dilution with Inerts

Hydrodynamics governed by
small inert particles
Kinetic performance governed by
catalyst extrudates

Catalysis and Catalysts - Catalyst Performance Testing

12

Maximum allowable particle diameter as a

function of the catalyst fraction in a diluted bed
10

Lb
nx

d p (mm)

= 100 mm

Lb
nx

0.1

= 10 mm

Lb
nx

= 1 mm

0.01
0.1

fraction catalyst (1-b)

xdiluted bed xundiluted bed

xundiluted bed

Catalysis and Catalysts - Catalyst Performance Testing

b n xdp bn xdp

0.05
1 b 2 Lb
2 L0
13

Effect of Catalyst/Diluent Distribution

in Decomposition of N2O
1.0

X(N2O)

0.8

0.6

0.4

0.2

0.0
600

650

700

750

800

850

900

T (K)

Catalysis and Catalysts - Catalyst Performance Testing

14

Laboratory Reactors
PFR:

CSTR:

larger amounts of catalyst and flows needed

deactivation not determined directly
direct rate data from conversions

FBR:

non-ideal behaviour
continuous handling of solids possible

TGA:

limited to weight changes

careful date interpretation needed
often mass-transfer limitations

Batch:

catalyst deactivation hard to detect

yields conversion and selectivity data quickly over large range

deactivation noted directly

small amounts of catalyst needed
simple
yields conversion data, not rates

Catalysis and Catalysts - Catalyst Performance Testing

15

Mass and heat transport effects

catalyst particles

Mass and heat transport phenomena

Extraparticle transport
Intraparticle transport

Catalyst effectiveness
Generalizations
Catalyst shape, kinetics, volume change

Observable quantities
Criteria - transport disguises - experimental

Catalysis and Catalysts - Catalyst Performance Testing

16

Liquid film

Gas film

Ts
T
cs

Bulk gas
(bubble)

Tb

Catalysis and Catalysts - Catalyst Performance Testing

cb

Bulk gas

Exothermic

Gas film

Bulk liquid

Endothermic

Exothermic

17

Gradients at Particle Scale

Gas/solid Reactor
Gas film

Ts

T
Cs

Tb

Cb

Bulk gas

Exothermic

Catalysis and Catalysts - Catalyst Performance Testing

Endothermic

18

Gradients at Particle Scale

Gas/liquid/solid Slurry Reactor

Liquid film
Bulk gas
(bubble)

Gas film

T
c
Bulk liquid

Exothermic

Catalysis and Catalysts - Catalyst Performance Testing

19

Isothermal - External Mass Transport

mass transfer

reaction

Ap k f c b cs Vp rv

rv ,obs rv (cs ) a' kf cb cs

No transport limitations if:

film layer

cb

cs cb

When?
How to determine cs?

cs
Catalysis and Catalysts - Catalyst Performance Testing

20

Isothermal - External Mass Transport

kf cb cs Ap
observed rate

Catalyst effectiveness: e
rate at bulk fluid conditions
rv (cb ,Tb ) Vp
Observable quantity:

rv ,obs
a' k f ( c b c s ) ( c b c s )
Ca

a' k f c b
a' k f c b
cb
10

rV = kVCn

-1

e 1 Ca 1 0.05
n

0.05
Ca
n

0.5

n=
0.1

0.01
0.001

0.01

0.1

Ca
Catalysis and Catalysts - Catalyst Performance Testing

21

Nonisothermal - External Transport

Mass:
Heat:

rv ,obs a' kf cb cs

( Hr ) rv ,obs a' hTb Ts

T and c coupled via

:max. T-rise over film

Catalyst effectiveness?

Catalysis and Catalysts - Catalyst Performance Testing

Ts
1 eCa
Tb

( H r )k f cb ( T )max

hTb
Tb

cs
1 Ca
cb

22

Nonisothermal - External Transport

General kinetics:

Ca small

Ea
rv (cs ,Ts ) kv (Ts ) f (cs ) kv (Ts )
e

exp
rv (cb ,Tb ) kv (Tb ) f (cb ) kv (Tb )
RTb

Tb

1 1 0.05
Ts

Series expansion:
Ea ( H r ) kf cb rv ,obs


0.05
b e Ca
h Tb
R Tb
k f a'cb

Catalysis and Catalysts - Catalyst Performance Testing

23

Isothermal - Internal Mass Transport

Slab
Mass balance, steady state diffusion & reaction

1st order irreversible: Deff

d 2c
kv c 0
dx 2

Boundary conditions: x L
x0

1.0

x+dx x

0.1

dc
0
dx

cosh( x / L)
c cs
cosh( )

0.8

c*

c cs

0.6

1.0
0.4

kv
L
Deff

2.0
0.2

10.0
0.0
1.0

0.8

0.6

0.4

0.2

Vp
Ap

1
a'

0.0

x*
Catalysis and Catalysts - Catalyst Performance Testing

24

Catalyst Effectiveness
Vp

dc
Ap
dx
observed rate
x L
i
0

rate without internal gradients rv ,chem (cs ,Ts ) Vp

rv (cs ,Ts ) Vp

rv (c,T )dV

Slab:

Deff

tanh

1st order
1

Limits:

i 1

0.1
0.1

10

Catalysis and Catalysts - Catalyst Performance Testing

25

Diffusion Control?
Kinetics unknown

effectiveness cannot be calculated

2

observedrate L rv ,obs
Wheeler-Weisz: i

' diffusionrate' Deff cs

2

n21

(nth order)

1st order
0th order

3rd order

Weisz-Prater Criterion:
2nd

order

rv ,obs L2 n 1
i

0.15
Deff cb 2
2

i 2
Catalysis and Catalysts - Catalyst Performance Testing

26

Nonisothermal - Internal Transport

Ts

Ts

cs

cs

Exothermal

Endothermal

similar profiles
c and T

determined by Prater number

i

( H r )Deff c s
p,eff Ts

Catalysis and Catalysts - Catalyst Performance Testing

Typical values:
0-0.3 (exothermal)

27

Nonisothermal - Internal Transport

Slab

Heat and mass balance, steady state

Effective conductivity
0.1-0.5 J/m.K.s

d 2c
Deff
rv
dx 2
d 2T
p,eff
rv ( H r )
dx 2

Boundary conditions:

xL

c cs

T Ts

x0

dc
dT
0
dx
dx

0
p,eff d 2T
d 2c
Deff

dx 2
(Hr ) dx 2

x+dx x

T Ts

( H r )Deff
cs c
p,eff

Prater number

T i ,max
Ts

Catalysis and Catalysts - Catalyst Performance Testing

(Hr )Deff cs
p,eff Ts

temperature and concentration

profile similar (scaling)
28

Nonisothermal - Internal Transport

Internal effectiveness factor:

E
rv (c,T )
k (T ) f (c )
k (T )
v

v
exp a
rv (cs ,Ts ) kv (Ts ) f (cs ) kv (Ts )
RTs
i

10

s= 10
i varied

0.6

Criterion:

0.4
1

Ea H r Deff cs rv ,obs L2

p ,eff Ts
R Ts
Deff cs

0.2
-0.2
0.1
0.1

Catalysis and Catalysts - Catalyst Performance Testing

Ts

1 1 0.05
T

10

s i i 2 0.1
29

Criterion bed T-gradient

Analogous to particle T-gradient:
2
Ea rV ,obs ( H r ) rt

RTw
b,eff Tw

1
1 rp

0.05
8 Bi h,w rt

Bi h,w

hw d p

b,eff

rV ,obs rv ,obs (1 b ) (1 b )

Compare with:

s i i 2
2
Ea

R Ts

0.05

H r Deff cs

p,eff Ts

Catalysis and Catalysts - Catalyst Performance Testing

rv ,obs L2 1

0.05
D c 2
eff s

30

Mass Transport Limitations?

Internal / External
Criterion: = 1 0.05

Internal transfer:

i 0.15

rv ,obs L2 n 1
i

0.15
Deff cb 2

External transfer:

0.05
Ca
n

Ca

Bi m
Ca
s

Bi m

Also:

while Bim>~10
s=1,2,3 (geometry)

Catalysis and Catalysts - Catalyst Performance Testing

rv ,obs
a' k f c b

kf d p
Deff

Weisz-Prater more severe than

Carberry criterion

31

Heat Transport Limitations?

Internal / External

Criterion: = 1 0.05

Series expansion of expression around 1 for slab, first order irreversible

reaction results in:

1
1 eCa

e 1 Ca exp b
n

External transfer:

b e Ca 0.05
strongest influence

Internal transfer:

s i i 2 0.1
External gradient criterion more
severe than internal gradient criterion

Catalysis and Catalysts - Catalyst Performance Testing

32

Heat Transport Limitations?

Internal / External

Largest T-gradient ?
Internal:

T Ts

Deff ( H r )

External: Ts Tb

p,eff

cs c

kf Hr
cb cs
h

For x=0 c=0 largest T-gradient

T e
T i

Bi
m
Bi h

Bi m e

Bi h
i

Industrial:
internal gradient largest

Ca

1 Ca

10-104

gas-solid
10-4-0.1 liquid-solid

Laboratory:
external gradient largest
external gradient negligible

Catalysis and Catalysts - Catalyst Performance Testing

33

Heat Transport Limitations?

External / Bed
Comparison of external and bed gradient

(neglecting wall contribution and bed dilution):

rv ,obs ( H r ) rt2 (1 b )

w
2

8b,eff Tw

rt p,eff
r
b e Ca
p b,eff

> 100

>1

s 2 (1 b )

1

8

~1

Bed gradient criterion more severe

than external gradient criterion
Catalysis and Catalysts - Catalyst Performance Testing

34

Summary Dependence rv,obs

Observed reaction rate:

rv ,obs rv ,chem (cb ,Tb ) e i rv ,chem (cb ,Tb )

1. Kinetics:

rv ,obs rv ,chem (c b ,Tb ) kv c bn

does not depend on L, n reaction order, Eaapp= Eatrue

2. Internal mass transfer: rv ,obs

rv ,chem

n 1
Ea
1
1
n 1

kv Deff cs cs 2 exp
L
L
2RTs

depends on: 1/L, (n+1)/2 reaction order, Eaapp= Eatrue

3. External mass transfer: rv ,obs

1 um
a' k f c b
c
1 m b
LL

depends on: L, flow rate, 1st reaction order, Eaapp= 0

How to check whether limitations are present?

Catalysis and Catalysts - Catalyst Performance Testing

35

Observed Temperature Behaviour

Catalysed steam gasification of carbon (coke) on Ni catalyst
5

Ni

C + H2O

CO + H2

Ea(kJ/mol)
0
61

1
0.75
r(obs)

p(H2O)=26 kPa
thermobalance
coked catalyst:
Ni/Al2O3

164
0.1

0.6
order n
0.01
0.9

1.0

1.1

1.2

1.3

1.4

1000/T
Catalysis and Catalysts - Catalyst Performance Testing

36

Apparent Rate Behaviour

Controlling process

Apparent
order

Apparent
activation energy

Dependence
L

Dependence u

Kinetics

Ea(true)

Internal diffusion

n 1
2

Ea(true)

1/L

External mass transfer

Lm-2 *

um *

Catalysis and Catalysts - Catalyst Performance Testing

37

Diagnostic Tests - Mass-Transport Limitations

1. Particle size variation
observed rate

egg-shell catalysts?

particle size

2. Flow rate variation at constant space time!

xA,1

xA,2

xA,3
x

A ,1

A,2

Catalysis and Catalysts - Catalyst Performance Testing

A ,1

A,2

A,3

A,3

38

Whats observed?

intraparticle limitation

0.1

Limiting case: Falsified kinetics

dp/mm
kv

0.38

activation energy: Ea(true)/2

0.01

1.4

2.4
0.001
1.90

1.95

2.00

rv ,obs
2.05

rchem

1
n 1
kv Deff cs
L

2.10

1000/T

reaction order (n+1)/2

wide pore silica
effect dp

Catalysis and Catalysts - Catalyst Performance Testing

particle size dependent

39

Proper Catalyst Testing

Adhere to criteria
Ideal reactor behaviour: PFR or CSTR
Isothermal bed
Absence of limitations: observables, diagnostic tests

Compare catalysts at low conversion;

For high conversions use feed/product mixtures
Compare selectivities at same conversion level

Catalysis and Catalysts - Catalyst Performance Testing

40

Consecutive irreversible first order reaction

ARS

CA

Concentration

0.8

CS

0.6
0.4

Same CR

CR

0.2

0
0

20

40

60

W /F

80

100

Catalysis and Catalysts - Catalyst Performance Testing

41

More Efficient Catalyst Testing

PC-controlled microreactor set-up
Parallel reactors in one oven:

Sixflow reactor set-up

Experimental design

ANALYSIS

P
MFC

FEED

MFC

VENT

MFC
MFC
MFC

SV
MFC

MFC
MFC
MFC

BPC

Catalysis and Catalysts - Catalyst Performance Testing

42