Reaction selectivity

Irreversible !

B
1. Parallel reactions

A
C

2. Series reactions

3. Independent reactions

Catalysis Engineering - Selectivity

A
P

B
Q

Selectivity parallel reactions

B

Rate expressions

rB = k B c An
rC = kC c Am

kB
kC

Kinetic selectivity:

S=

Rate selectivity:

rBapp J B
=
rCapp JC

x =L

fluxes out of particle

Pore diffusion limitations:
Highest penalty on the highest order reaction
diffusion limitations may or may not be preferred
Equal order: no effect on selectivity

Catalysis Engineering - Selectivity

Shape selectivity: zeolites

Pore size of molecular dimensions: high penalty on branching
or bulkyness

Reactant selectivity

Transition state selectivity

branched alkenes cannot enter

ZSM-5, linear ones can

transition state does not fit

e.g. cis vs. trans products
in zeolite Beta

Product selectivity
p-xylene formation ZSM-5
DMA formation ZSM-5
Catalysis Engineering - Selectivity

Toluene disproportionation
De,rel.

De,rel.

>1000

CH3

H3C

CH3

1000

+
H3C

>1000

CH3
CH3

>1000

CH3

ZSM-5

CH3

strong effect diffusion limitation

transition state selectivity?
Catalysis Engineering - Selectivity

Selectivity series reactions

Rate expressions

rA = k B c A
rB = k B c A kC c B
First order, equal diffusivities

Pore diffusion equations:

d 2c B
= kC c B k B c A
De
dx 2
d 2c A
= k Bc A
De
dx 2

Solution -> concentration profiles -> particle rates -> production selectivity

Catalysis Engineering - Selectivity

Selectivity series reactions

Solution concentrations A and B inside slab

c A = c Ab

cosh(B x / L )
cosh(B )

local gas phase concentration

(no external limitations)

k B cosh(C x / L ) cosh(B x / L )
b cosh(C x / L )
c B = c Ab
c

+

B

cosh(
)
cosh(
)
cosh(C )
k
k

C
C
B
B

Local selectivity equals fluxes through external slab surface:

J
B
JA

x =L

dc B k B C tanh( C ) c BbC tanh( C )

=
=
b
1
dc A k B kC B tanh( B ) c A B tanh( B )

Integration yields concentration ratio (integrating factor)

Catalysis Engineering - Selectivity

Selectivity series reactions

Limiting cases (after integration)

b 1 S
S
c

S c A

1
=

c
S 1 c A 0

b
B
b
A

at reactor entrance

2. Both Thiele moduli large, tanh -> 1

b 1SS
c

S c A

1
=

c
S 1 c A0

b
B
b
B

Fraction A converted to B

1. Thiele moduli small, chemical control

0.8

1.

0.6

0.4

2.

0.2

0.0
0.0

0.2

0.4

0.6

0.8

1.0

Fraction A converted

Diffusion limitation always lowers selectivity intermediate

to be avoided !
Catalysis Engineering - Selectivity

Series reactions
maximum shifts to lower
conversion of A
Fraction A converted to B

0.8

1.

0.6

0.4

0.0
0.0

0.2

0.4

0.6

0.8

Fraction A converted

Catalysis Engineering - Selectivity

Q:
What is maximum yield B?
At what conversion of A?

2.

0.2

1.0

Selectivity independent reactions

A
P

B
Q

rB = k B c A

Rate expressions

rQ = kQ c P
first order, equal diffusivities

Pore diffusion model for slab gives:

c A = c As
cP = c Ps

cosh(B x / L )
cosh(B )
cosh(Q x / L )
cosh(Q )

tanh( i )
i

rBapp k B c Ab
c Ab
=
=S b
rQapp k P c Pb
cP

Limiting cases:
1. i small -> kinetic control
2. i large -> diffusion control

Catalysis Engineering - Selectivity

So:

i =

rBapp
=
rQapp

k B c Ab

c Ab
= S b
b
cP
k P cP

diffusion limitations always disfavours desired reaction

Independent reactions: distribution active phase

Becker & Wei J.Catal. 46(1977)372
uinform poisoning

pore mouth poisoning

10

Egg
shell

m = R

Egg
white

km
De,m

Egg
yolk

Uniform
0.1
0.1

p = R

10

40

kp
De,p

Criterion: longest catalyst life with effectiveness of 0.4 or higher

Catalysis Engineering - Selectivity

Temperature effects

Yield depends on S or

S=

Ea,undes
E
kdes
exp a,des

kundes
RT

largest Ea dominates

Ea,des > Ea,undes

Ea,des < Ea,undes
Catalysis Engineering - Selectivity

favourable
unfavourable

Series reaction example

Voge and Morgan I&EC PDD11 (1972)454
k1
k2
' coke'
C4=
C4==

Butene dehydrogenation:
Selectivity butadiene
at 35% conversion
100
90

Q:
does this result agree
with theory?

80
70
60
50

particle diameter / mm

Catalysis Engineering - Selectivity

10

Deactivation
Poisoning

no effect on accessibility

Homogeneous

equal or
lowers activity
Thiele moduli become smaller better selectivity

Pore mouth

diffusion resistance increase

fastest reaction most affected

Fouling
Homogeneous

Pore mouth

may affect accessibility (decreases Deff )

lowers activity
Thiele moduli become smaller/larger
selectivity ?
lower selectivity

Catalysis Engineering - Selectivity

lower selectivity

Reaction selectivity
Kinetics

Reaction conditions
Intrinsic selectivity
Adsorption

Reactor type

Shape effect

Zeolite type

Modifier/solvent

Selectivity
Diffusion limitations

Deactivation

Catalysis Engineering - Selectivity

Homogeneous
Pore mouth

By purpose or
To be avoided

Reaction modifiers
Selectivity control through selective adsorption
Series reactions A --> B --> C
Add component I with:
KA > KI > KB
Reaction stops after conversion of A
Examples
Hydrogenation of ethyne in ethene feed for polymerization (CO, H2S)
Functionalized alkynes to alkenes (N-compounds)
(Marieke Spee Utrecht)

Catalysis Engineering - Selectivity

Effect aging on three-way catalysts

de Soete, IFP
Desired:

2NO + 2CO

Undesired:

2NO + CO

NO conversion
to N2O

N2 + 2 CO2
N2O + CO2

Aging
Selectivity
declines by
deactivation:
kinetics effect

~400

~700

Temperature (K)

Additional catalytic component needed

Catalysis Engineering - Selectivity

1-Butene isomerization: Ferrierite

Mooiweer et al 1994

carbenium ion formation

dimerization
(oligomerization)
skeletal isomerization
diffusion branched isomers
highly hindered
cracking to isobutene upon
escape from matrix

C
C C C

C C C+

C
C C+ C

C
C C+ C

product shape selectivity

mild cracking activity
Catalysis Engineering - Selectivity

C H+
C C C

C C C+ C

C C C C

C
C

C
C C

C C C

Competitive adsorption
Selective hydrogenation aromatics
S.Toppinen,Thesis 1996
Ni-alumina trilobe catalyst
3 mm particles
40 bar H2
125oC
semi-batch reactor

CH3

CH2

CH3

CH3

Consecutive conversion
behaviour
rate constants ~ similar
adsorption constants
decrease

concentration / wt.%

30
25

CH3

20

CH3

15
10

H3C

5
0

space time / min.g.ml-1

Propose a rate expression to account for this effect

Catalysis Engineering - Selectivity

10

CH3

Competitive series reactions

effect on selectivity
Acetylene Hydrogenation:

butyne -> butene -> butane

A1
A2
A3

butyne and butene compete for the same sites

but:
K1 >> K2
resulting high selectivity for butene (desired) possible
even when k2 > k1
show this !
k1K1
since:
S1,2 =
k 2 K2

Meyer and Burwell (JACS 85(1963)2877) mol%:

2-butyne
22.0
cis-2-butene
77.2
trans-2-butene
0.7
1-butene
0.0
butane
0.1
Catalysis Engineering - Selectivity

Zeolite Beta: Meerwein-Ponndorf-Verley

reduction and Oppenauer oxidation
Creighton, van Bekkum 1996
4-tert-butylcyclohexanone + isopropanol

O
CH3
H C OH
CH3

Catalysis Engineering - Selectivity

cis-4-tert-butylcyclohexanol

OH

BETA
80 0C

CH3
C O
CH3

> 95% cis-isomer (fragrance intermediate)

transition state selectivity
molecular modelling

Zeolite Beta: Aromatic acylation

Van Bekkum
Classical route
CH3

Cl2

OH

CCl3
FeCl3

OH

OH

hv

OH

Catalytic route

OH

COOH

CH3
O2
cat.

H-Beta
OH

OH

C
OH

Yield >90%
no corrosive by-products
Catalysis Engineering - Selectivity

+ 3 HCl

+ H2O

Partial benzene hydrogenation

Ru-catalyst - clusters of crystallites
Slurry reaction, elevated pressures
Water-salt addition increases selectivity

+H
2

+ 2 H2

Ru

Salt-water

Adsorption / Desorption properties affected

Catalysis Engineering - Selectivity

Reaction steps - Catalyst modification

Adsorption: reactants concentration / positioning /

competition
Modifications by
support (deep HDS)
catalyst surface (enantiomers)
use other support (CH4 reforming)
change fluid phase
add fluid phase (cyclohexene)
shape selectivity, pore architecture
Desorption:
Facilitate desorption (Ga for H2 )
solvent choice (alkylation)

Catalysis Engineering - Selectivity

Multicomponent adsorption / inhibition

Langmuir adsorption

A =

K 1p A
1 + K 1p A + K i p i

Inhibitors / Competitors
Control adsorption/desorption !
Catalysis Engineering - Selectivity

Reaction steps - Catalyst modification

Surface reaction
Affect selectivity by
transition state confinement (acylation zeolites)
shape selectivity (membrane coating)
deliberate diffusion limitations (p-xylene, isobutene)
reaction coupling
transient operation

Catalysis Engineering - Selectivity

Catalyst and separation

methyl amines production
H.C.Foley et al. Chem. Eng. Sci. 49(1994)4771
ordinary Si-Al catalyst

MeOH + NH3
MMA
DMA

Carbon molecular sieve

layer (~ 0.5 nm pores)

Catalysis Engineering - Selectivity

MMA (0.4 nm)

DMA (0.45 nm)
TMA (0.5 nm)

Classical a-selective catalyst

turned into a selective by
a permselective coating

Composite catalyst: FCC

multifunctional
macropores

mesopores

zeolitic pores

low acidity
medium acidity
high acidity

resid
LCO/HCO
metal-porphyrins

gasoline/LPG

Ni
bulk

Catalysis Engineering - Selectivity

catalyst design
pore structure
catalytic functions
stabilization
strength
metal catchers

Alkylation of isobutane with 2-butene

catalyst: Beta
K.P.de Jong et al., ISCRE 1996
Reaction
C
C C
C

C
C

C
C

C
C

70-120oC

C
C

Side reactions
Dimerization/oligomerization
Product alkylation

Fouling, deactivation

Low olefin concentration

CSTR operation
Suitable solvent medium
Catalysis Engineering - Selectivity

Isomerization alkanes n=5,6,7

% conversion

Bifunctional catalyst:
H- Mordenite catalyst (500-550K)
Pt doping
100
H-Mor + Pt

H-Mor
0
time (h)

zeolite catalysed isomerization

hydrogenation to prevent coking
Catalysis Engineering - Selectivity