Chemical Reaction Engineering

Lecture 12

Lecturer :

This course focuses on internal diffusion effects on heterogeneous reactions.

Internal diffusion: diffusion of the reactants or products from the external pellet surface (pore mouth) to the interior of the pellet. (Chapter 12) When the reactants diffuse into the pores within the catalyst pellet, the concentration at the pore mouth will be higher than that inside the pore and the entire catalytic surface is not accessible to the same concentration.
CAs C(r) CAb

Diffusion and reaction in a porous spherical catalyst pellets

The pores are a series of tortuous, interconnecting paths of pore bodies and pore throats with varying crosssectional areas. An effective diffusion coefficient is used to describe the average diffusion taking place at any position r in the pellet. The radial flux is based on the total area normal to diffusion transport. The effective diffusivity:

J pW De ! DA ~ X

DA

the bulk diffusivify pellet porosity (typical ~ 0.4) constriction factor (typical ~ 0.8) tortuosity (typical ~ 3.0)

Jp W ~ X

An irreversible isomerization reaction take places on the surface of the pore walls within the spherical pellet of radius R :

CAs
R

Ap B

Rate of A in at r = WAr area = r

W Ar v 4T r 2

Rate of A out at r - (r = WAr area = W Ar v 4T r 2 The mole balance over the shell thickness (r is:

r  (r

W Ar v 4T r 2

 W Ar v 4T r 2

r  (r

d  rA v 4T rm ( r v V c ! 0
2

where Vc is the mass of catalyst per unit volume; rm is the mean radius between r and r - (r

d  Ar r 2 W d  rA v r 2 v V c ! 0 dr

d W Ar r 2 d  rA v r 2 v V c ! 0 dr
For EMCD, or dilute concentration dC A W Ar !  D e dr

d

d A 2 r e dr d  rA v r 2 v V c ! 0 dr d where  rAd the rate of reaction per unit surface area; is Sa is the surface area of the catalyst per unit mass of catalyst typical value of Sa is 150 m2/g of catalyst
nth order surface reaction

d d  rA !  rAda S

n d  rAd k n C A !

dC A 2 d  De r dr n  r 2 V c knC A S a ! 0 dr

d 2 C A 2 dC A V c k n S a n  CA ! 0  dr 2 r dr De

d 2 C A 2 dC A V c k n S a n  CA ! 0  dr 2 r dr De
r N ! CA P! C As R d N 2 dN  2 d d
2

B.C. CA = CAC = constant CA = Cas

at r = 0 at r = R

Jn

V c k n S a R 2 C As ! De

n 1

2  Jn N n ! 0

B.C. N = finite value N=1

at P = 0 at P = 1

Dimensionless form of equations describing diffusion and reaction

The Thiele modulus, Jn

Jn
2

V c k n S a R 2 C As ! De

n 1

V k S RC As a surface reaction rate ! ! c n a a diffusion rate (C  0 ) D e As R

Jn o Jn q

internal diffusion limits the overall rate of reaction surface reaction limits the overall rate of reaction

For a reaction :

Ap B

If the surface reaction is rate-limiting with respect to the adsorption of A and desorption of B, and if species A and B are weakly adsorbed (low coverage) and present in dilute concentration, the apparent first-order rate law: d  rd k C !
A 1 A

B.C. d 2N 2 d N 2 n   J n N ! 0 N = finite value 2 d d N=1 V c k1 S a d 2N 2 d N 2 J1 ! R   J1 N ! 0 2 De dP P dP

at P = 0 at P = 1

small J1 medium J1 large J1 R r=0

A B ! 1 cosh J1P  1 sinh J1P P P

N = finite value at P = 0 N=1 at P = 1

1 sinh J1P N ! C A N! sinh J C As P 1

small J1: surface reaction control and a significant amount of reactant diffuses well into the pellet interior without reacting; large J1: surface reaction is rapid and the reactant is consumed very closed to the external pellet surface (A waste of precious metal)

Internal effectiveness factor:

(1) the relative importance of diffusion and reaction limitations (2) a measurement of how far the reactant diffuses into the pellet before reacting
L! actual overall rate of reaction rate of reaction if entire interio r surface were exposed to the external surface conditions (Cas)
mole (mass of catalyst ) v (time)

d  rA L!  rAs

observed reaction rate

d  rA v ( mass of catalyst ) M A L! !  rAs v ( mass of catalyst ) M As

mole time

M As

4 4 3 d TR 3 V c ! ( k1C As ) v S a v TR V c !  rAs v 3 3
surface area per unit mass of catalyst

first-order reaction

The actual rate of reaction: (the reaction at which the reactant diffuses into the pellet at the outer surface at the S.S.)

r !R

J1 ! R

V c k1 S a De

M A ! 4TRDeC As  1 coth J1  1 J
J M A 4TRDe C As  1 coth J1  1 4TRDeC As L! ! ! J1 coth J1  1 4 M As 4 d k1C As S a TR 3 V c  rAs v TR 3 V c 3 3 3 ! 2  1 coth J1  1 J J1
pp750 for J1 vs. L

dC A M A ! 4TR De r ! R ! 4TRDeC As dr
2

CA d C As r d R

dN ! 4TRDeC As d

!1

3 L ! 2  1 coth J1  1 J J1
R q J1 q L p 1

J1 ! R

V c k1 S a De

surface-reaction-limited

3 3 J1 "", (} 30) L $ ! J1 R

De , k1 V c S a

diffusion-limited reaction (external 1 diffusion will have a negligible effect on the overall reaction rate)

d  rA
L!

d 3  rA J ! 2  1 coth J1  1 d  rAs J1

d d  rA ! L  rAs ! L k1C As S a L$

3 R

De k1 V c S a

internal-diffusion-limited

How to increase the rate of reaction? (1) decrease the radius R (2) increase the temperature (3) increase the concentration (4) increase the internal surface area

d  rA !

3 R

De S a k1 C As Vc

Overall rate of reaction for a first-order reaction:

For reaction of order n, the Thiele modulus, Jn

Jn

V c k n S a R 2 C As ! De

n 1

When the reaction is internal-diffusion-limited ( J n "" ) :

2 L ! n 1

1/ 2

3 2 ! Jn n  1

1/ 2

3 R

De 1 n / 2 C As V c kn S a

When reaction order n is greater than 1: The effectiveness factor decreases with increasing concentration at the external pellet surface.

Application: use the effectiveness factor to calculate the true reaction order
Disguised/Falsfied Kinetics (the internal-diffusion-limited reaction)

d d nd  rA ! k n C As For a reaction

(measured reaction rate) ln -rA

slope = n apparent reaction order

From experimental results, we have:

ln CAs

d  rA L!  rAs
2 L ! n 1
1/ 2

n d d  rA ! L  rAs ! L k n S a C As

1 2 De S a n 1 / 2 k n 2 C As ( n  1) V c

When the reaction is internal-diffusion-limited ( J n "" ) :

3 Jn

2 d  rA ! n 1

1/ 2

3 3 n k n S a C As ! Jn R

(true reaction rate)

3 d  rA ! R

1 2 De S a n 1 / 2 d nd k n 2 C As ! k nC As ( n  1) V c

1 n d n ! 2

The relation between the apparent reaction order and the true reaction order

Apparent activation energy Vs. True activation energy

For a reaction, we obtain the experimental results and the apparent activation energy:

d d nd  rA ! k n C As

d k n ! Aapp e

E app RT

(measured reaction rate constant)

d  rA !

3 R

1 2 De S a n 1 / 2 d nd k n 2 C As ! k nC As ( n  1) V c

true rate of reaction

apparent rate of reaction

k n ! Atrue e

Etrue RT

d k n ! Aapp e

Eapp RT

3 ln R

2 De S a (n  1) V c

Eapp 1 n 1 / 2 Etrue nd Atrue 2 C As ! ln Aapp C As   RT 2 RT

Etrue ! 2 Eapp The relation between the apparent activation energy and the true activation energy

The importance of the internal-diffusion-limited reactions:

Disguised/Falsfied Kinetics (the internal-diffusion-limited reaction) When a reaction takes place and the rate of reaction is developed:

Eapp !
d d nd  rA ! k n C As

1 Etrue 2

apparent activation energy

nd !

1 n 2

apparent reaction order

If the pellet size became smaller and the reaction is no more internal-diffusion-limited Wrong reaction order and activation energy might be used for the design of reactor!

Runaway reaction conditions might occur and the exploding situation might happen!

Quick estimation of the rate-limiting step in a heterogeneous reaction

The internal effectiveness factor:

d  rA (obs ) 3 V c k1 S a ! 2  1 coth J1  1 J 1 ! R L! J d De  rAs J1 LJ12 ! 3 1 coth J1  1 J

the Weisz-Prater parameter

CWP !

observed ( actual ) rate of reaction rate of reaction evaluated at C As v rate of reaction evaluated at C As a diffusion rate

observed ( actual ) rate of reaction ! a diffusion rate (obs (obs  rd ) VkS  rd ) V kC S ! A v R2 c 1 a ! A v R 2 c 1 As a d d De DeC As  rAs  rAs
d  rA (obs ) V c R 2 ! DeC As
When CWP >>1; internal diffusion limited When CWP <<1; no diffusion limitations

Example
A first-order reaction A p B was carried out over two different-sized pellets. If the external mass transfer resistance is negligible, estimate the Thiele modulus and effectiveness factor for each pellet according to the following experimental results. What should the size of the pellet to eliminate the internal diffusion resistance?
easured rate of reaction 5 (mol/g cat s) v 10 3 15 Pellet radius (m) 0.01 0.001

Run 1 Run 2

J1 ! R

CW

d  rA (obs ) V c R 2 ! ! LJ12 ! 3 1 coth J1  1 J De C As

V c k1 S a De
J 11 ! 16 . 5 J 12 ! 1 . 65

2 d J coth J11  1  rA1 (obs ) R1 ! 11 2 J12 coth J12  1 d  rA 2 (obs ) R2

J 11 R ! 1 ! 10 J 12 R2
3 v 0.012 10J12 coth(10J12 )  1 ! 15 v 0.0012 J12 coth J12  1

LJ ! 3 1 coth J1  1 J
2 1

3 1 coth J1  1 J L! J12 J 11 ! 16 . 5
J 12 ! 1 . 65

L 1 ! 0 . 182 L 2 ! 0 . 856

Eliminating the internal diffuse resistance p L } 1

Assuming L = 0.95

3 13 coth J13  1 J 0.95 ! 2 J13

J 13 ! 0 . 9

J 11 R ! 1 J 13 R3

R 3 ! 5 .5 v 10  4 m

When both internal and external diffusion are important

CAs C(r) CAb

At steady-state:
the transport of the reactants from the bulk fluid to the external surface of the catalyst is equal to the net rate of reaction of the reactant within and on the pellet The molar rate of mass transfer from the bulk fluid to the external surface:

M A ! WAr ac (V
molar flux reactor volume external surface area per unit reactor volume This molar rate of mass transfer to the surface is equal to the net rate of reaction on and within the pellet:

d M A !  rAdexternal area  internal area

d M A !  rAdexternal area  internal area a c (V

internal area mass of catalyst

S a V b (V
mass of catalyst reactor volume
reactor volume

d M A !  rAd ac (V  S a V b (V d M A ! W Ar ac (V !  rAd ac (V  S a V b (V
usually small compared with the next term

W Ar ! k c C Ab  C As

d d d  rAd L ( rAs ) !

d d kc C Ab  C As ac ! L ( rAs ) S a V b
d d Assume a first-order reaction  rAs ! k1C As

kc C Ab  C As ac ! L ( k1C As ) S a V b

kc C Ab  C As ac ! L ( k1C As ) S a V b kc ac C Ab ! kc ac  Lk1S a V b
Lk1k c ac C Ab k c ac  Lk1S a V b

C As

d  rAd Lk1C As ! !

true rate of reaction

Reminding, the internal effectiveness factor (based on C As ) L! actual overall rate of reaction rate of reaction if entire interio r surface were exposed to the external surface conditions

The overall effectiveness factor (based on C Ab ) is defined as: ;! actual overall rate of reaction rate of reaction if entire interio r surface were exposed to the bulk conditions

Lk1C Ab d L  rAd 1  Lk1S a V b kc ac ! ! ;! d d k1C Ab  rAb 1  Lk1S a V b kc ac

Mass transfer and reaction in a packed bed reactor

Ac z=0 U z z+(z z=L

Ap B

At steady-state, the mass balance on A over the volume element (V=Ac(z is:
[rate in] - [rate out] + [rate of generation] = [rate of accumulation]

W Az z Ac  W Az

d z  (z Ac  r A V b Ac (z ! 0
WAz !  D AB

dW Az rd b ! 0 AV dz

the overall reaction rate within and on the catalyst per unit mass of catalyst:

dC Ab  UC Ab dz

d d  rA ! rAb v ; d d d first-order reaction,  rAb !  rAb S a ! kC Ab S a d  rA ! ;kC Ab S a

DAB

DAB

d 2C Ab dC Ab U  rd b ! 0 AV 2 dz dz

d 2C Ab dC Ab U  ;kC Ab S a V b ! 0 2 dz dz

DAB

d 2C Ab dC Ab U  ;kC Ab S a V b ! 0 dz 2 dz
If the axial dispersion is neglected, and the boundary condition at the entrance of the reactor:
 ( V b kS a ;z )

C Ab ! C Ab 0
U

at

z!0

C Ab ! C Ab 0 e
Example

A 2% NO-98% air mixture flows at a rate of 1 x 10-6 m3/s through a 2-in-ID tube packed with porous carbonaceous solid at a temperature of 1173K and a pressure of 101.3 kPa. The reaction is first-order in NO, calculate the weight of porous solid necessary to reduce the NO concentration to a level of 0.004%. NO  C p CO  1 N2 2

 r d ! kS a C NO NO
Our purpose: X = f (W)

C Ab 0  C Ab 2  0.004 X ! ! ! 0.998 C Ab 0 2

NO down the length of the reactor is: (when the axial dispersion is neglected)

dC Ab  ;kC Ab S a V b ! 0 dz
u ! UAc W ! V b Ac z

dC Ab ;kC Ab S a B.C. C Ab ! C Ab 0 at W ! 0 ! Dilute: I dW u 1 ; u ! u0

 kS a ;W C Ab ! C Ab 0 exp u0

 kS a ;W C Ab X ! 1 ! 1  exp C Ab 0 v0

L!

W!

1 v0 ln kS a ; 1  X
J1 ! R V c k1 S a De

X = f(W)

L ;! 1  LkS a V b kc ac
external transfer coefficient

3J1 coth J1  1 J12
1 1

L ! 0.167

Shd Red Sc !
2

Red !

Ud p (1  J )v

Sc !

v J kc d p d Sh ! D AB 1  J DAB

kc ! 6 v 10 5 m / s external diffusion resistance is important

L ;! 1  LkS a V b kc ac
6(1  J ) 4Tr 2 (1  J ) ! ac ! ! 500m 2 / m 3 4 3 dp kc ! 6 v 10 5 m / s Tr 3

L ! 0.167

; ! 0.059 internal diffusion resistance is important

v 1 W ! 0 ln kS a ; 1  X
1v10 6 m 3 / s 1 W! ln ! 450 g 10 3 2 2 (4.42 v 10 m / m s )(530 m / g )(0.059) 1  0.998

In this example, both internal and external diffusion resistance are significant. Which one is the rate-limiting step? See page 768 Table 12-1

Multiphase reactors
Two or more phases are necessary to carry out the reaction Examples (refer to Table 12-2 on page 769)
Slurry reactor Trickle bed reactor Fluidized bed reactor

Slurry reactors
reactant gas is bubbled through a solution containing solid catalyst particles solution may be either a reactant or an inert batch/continuous temperature control and heat recovery are relatively easy

An industrial slurry reactor used to convert synthesis gas (CO + H2) to a hydrocarbon wax by the Fischer-Tropsch synthesis.

25CO  51H 2 p C25 H 52  25 H 2O

Recycle gas catalyst Absorption from the gas phase into the liquid phase at the bubble surface Diffusion in the liquid phase from the bubble surface to the bulk liquid Diffusion from the bulk liquid to the external surface of the solid catalyst Internal diffusion of the reactant in the porous catalyst Reaction within the porous catalyst

product

Reactant gas

These steps are resistance to the overall rate of reaction.

Consider the hydrogenation of methyl linoleate to form methyl oleate in a slurry reactor:

L  H2 p O
Gas Absorption The rate of absorption of H2 per unit volume of linoleate oil is:

R A ! kb ab (C Ai  C Ab )
H2 concentration in the bulk solution mass transfer coefficient H2 concentration at oil-bubble interface bubble surface area

Transport to the catalyst pellet

The rate of mass transfer of H2 from the bulk solution to the external surface of catalyst pellet is:

R A ! k c a p m(C Ab  C As )
mass transfer coefficient external surface area of pellets mass concentration of catalyst H2 concentration at external surface of catalyst pellet

Diffusion and reaction in the catalyst pellet The rate of reaction per volume of solution:

d R A ! mL ( rAs )
internal effectiveness factor rate of reaction if the entire interior of the pellet were exposed to the reactant concentration at the external surface

The rate law

The rate law is (linoleate in the liquid phase is in excess):

d  rA ! kC A
At steady-state, all rates are equal:

d R A ! kb ab (C Ai  C Ab ) ! kc a p m(C Ab  C As ) ! mL ( rAs ) ! mLkC As

eliminate CAb, CAs

1 1 1 ! C Ai   RA k a b b k c a p m mL k

1 1 1 1 C Ai !   R A kb ab m k c a p kL

C Ai 1 1 1 1 !   R A kb ab m k c a p kL

C Ai 1 ! rb  rc  rr RA m
resistance to transport to catalyst surface

resistance to gas absorption

resistance to diffusion and reaction within the catalyst resistance to diffusion

C Ai RA rb

slope = diffusion and reaction resistance

C Ai RA

gas absorption control diffusion and reaction control

1 m
Which one is the rate limiting step? External diffusion? Internal diffusion? Surface reaction?

1 m

1 1  kc a p kL

Combination of the diffusion and reaction resistance

IF the particles are small and therefore resistance is surface reaction control: L } 1

rc  rr !

1 1 1  } k c a p kL k

resistance is independent of particle size

IF the particles are moderate and internal diffusion control, the internal effective factor is:
3 1 coth J1  1 large value of J1 J J12
J1 ! R

L!

L!

3 J1

V c kS a De

L!

6 dp

De V c kS a

rc  rr !

1 1  w d p resistance varies linearly with particle size. k c a p kL

IF the particles are moderate and external diffusion control:

1 1  rc  rr ! k c a p kL

1 rc ! kc a p

2 Td p 6 external area ! ! ac ! d p Vc mass of pellet T d 3 V p c 6

Sh ! 2  0.6 Re Sc
2

No shear stress between particles and fluid (diffusion to a particle in a stagnant fluid):

Sh ! 2

kc ! 2

D AB dp

rc !

1 2 w dp kc a p

Particles move with the fluid: increasing the stirring has no effect in increasing the overall rate of reaction Shear between particles and fluid

Sh ! 0.6 Re 2 Sc

kc d p D AB

d pU w v

U kc w d p

1 rc ! w d 1 .5 p kc a p

Shear between the particles and fluid is important: increasing the stirring increases the overall rate of reaction

ln rc  rr
s=1.5 ~ 2.0, external-diffusion-limited s=1, internal-diffusion-limited s=0, reaction-limited

ln dp The slope should be 0, 1, 1.5, 1.7 and 2.0. If the slope is between these values, this suggests that more than one resistance is limiting.

Example
A catalytic hydrogenation reaction is carried out in a slurry reactor. Hydrogen is bubbled up through the liquid and catalyst. The experimental data are shown in the table 12-5-1 on page 780. Determine the major resistance.

C Ai 1 ! rb  rc  rr A slurry reactor: RA m

C H 2i
 rH 2

1 ! rb  rc  rr m

C H 2i
 rH 2

H d2 H
 rH 2

1 ! rb  rc  rr m

CH 2i  rH 2

80Qm 40Qm

Henrys law

(rc + rr) rb

1 m

For 40 Qm pellet, the slope (i.e., the combination external and internal diffusion and reaction resistance) is (rc + rr) = 0.14; For 80 Qm pellet, the slope is (rc + rr) = 0.28

rc  rr 80 Qm rc  rr 40 Qm

0.28 !2 0.14

rc  rr w d p

Internal diffusion is the controlling resistance of the three resistance.

For 80 Qm pellet, the slope is (rc + rr) = 0.28; the intercept (i.e., the gas absorption resistance) is 0.08

C H 2i
 rH 2

1 m = 0.4 ! 0.08  0.28 m

C H 2i
 rH 2

! 0.84

rr 0.84  0.08 ! rb 0.08

Slurry reactor design example

A 2 m3 slurry reactor is used to convert methyl linoleate (ML) to methyl oleate (MO), which is the same reaction as the example in the previous slide. The molar feed rate of ML is 0.7 kmol/min. The partial pressure of H2 is 6 atm and the reactor is well-mixed. Calculate the catalyst charge necessary to achieve 30% conversion for a 60 Qm particle size.

From mass balance: (similar to CSTR) V !

FA 0 X  rA

At steady state, for a slurry reactor:

C Ai ! H d 2 ! 0.014 PH

1 C Ai ! rb  rc  rr  rA m
0.28 ! !2 0.14

VC Ai ! rb  FA 0 X m

rc  rr 80 Qm 1 rc  rr rc  rr 40 Qm

rc  rr 60 Qm ! 0.21
m ! 3.9 kg / m 3

the gas absorption resistance is 0.08

Trickle bed reactor

Gas and liquid flow (trickle) concurrently down a packed bed of catalyst particles ranging from 1/8 to 1/32 in. in diameter The pores of the catalyst are filled with liquid In petroleum refining, P = 34 ~ 100 atm; T = 350 ~ 425 C Used in process:
hydrodesulfurization of heavy oil stocks hydrotreating of lubricating oils other reactions

gas

liquid

The steps involving reactant A in the gas phase are: Transport from the bulk gas phase to the gas-liquid interface Equilibrium at the gas-liquid interface Transport from the interface to bulk liquid Transport from the bulk liquid to external catalyst surface Diffusion and reaction in the pellet Similar to slurry reactor...

gas liquid solid Assuming a first-order reaction in dissolved gas A and in liquid B, following similar procedures of a slurry reactor, for reactant gas A: CA

d  rA ! k reaction PA ! k reaction

1 C A( g ) H 1 ! C A( g ) H

(1  J ) V c (1  J ) V c 1 1 d  rA    Hk a kl ai kc a p LkC Bs g i
CA(g) CAb CAs

internal diffusion +rxn resistance external diffusion resistance liquid phase mass transfer resistance gas phase mass transfer resistance

 (1  J ) V c (1  J ) V c 1 1 d  rA    Hk a k l ai kc a p LkC Bs g i

1 ! C A( g ) H

d  rA ! k overall

for gas into pellet

C A( g ) ! k vg C A ( g )

Assuming a first-order reaction in dissolved gas A and in liquid B, for reactant liquid B:

1 1 ! CB (l ) d  rB  k a LkC As c p d  rB ! k overall for liquid into pellet C B ( l ) ! kvl C B ( l )

Mole balances on A and B:

dFA d ! rA !  k vg C A( g ) dW dFB d ! rB !  k vl C B (l ) dW
These equations are solved simultaneously.

Fluidized-Bed Reactor (FBR)

The fluid velocity is sufficient to suspend the particles, but not large enough to carry them out of the vessel. They can process large volume of fluid. They provide excellent solids mixing. The fluidized medium is either a liquid or gas Above the bed is a space, termed the disengaging section, to collect solids caught in the gas stream to fall back into the bed.

The Kunii-Levenspiel bubbling bed model

Bubble Wake phase Drift phase

As the bubbling rise, mass transfer of the reactant gases diffuse in and out of the bubble to contact the solid particles. The reaction product is formed. The product gases flow back into a bubble. The bubble reaches the top of the bed and the product is collected. Determine: The velocity at which the bubbles move through the column. The rate of transport of gases in and out of the bubbles.

From fluid mechanics:

I mf Q  0.72 ! 0.586] 3 V Ld g p
2 0.029

Vg V c

0.021

u mf !

(]d p ) 2 150 Q

?g ( V

 Vg )

A1  I

I mf

mf

0 1  0.3h d bm ! 0.652Ac (u0  umf ) .4 ub ! u0  u mf  0.71gd b / 2 d bm  d b ! exp D d bm t ] ! surface area of sphere of same volume

surface area of particle

From mass transfer:

u mf K bc ! 4.5 d b D1/ 2 g 1/ 4  5.85 d 5/ 4 b
I mf Dub ce ! 6.78 3 db cloud-to-emulsion
H !
1/ 2

bubble-to-cloud Fraction of the bubbles in the bed:

u0  umf ub  umf (1  E )

Volume of catalyst in the bubbles, Kb, clouds, Kc, and emulsion, Ke K ! 0.01 to 0.001 1 H 3(umf / I mf ) K e ! (1  I mf )  rc b K c ! (1  I mf ) E H ub  (u mf / I mf )

The catalyst weight necessary to achieve a given conversion is:

W!
where

V c Ac ub (1  I mf )(1  H )
k cat K R
1

ln

1 1 X

KR ! K b 

1 kcat  1 K bc K  c 1 kcat  K e K ce

kcat is the specific reaction rate

Chemical vapor deposition reactors

One of the key steps in the chip-making process is the deposition of different semiconductors and metals on the surface of the chip. Horizontal low-pressure CVD (LPCVD) operates at ca. 100 Pa.
process a large number of wafers without detrimental effects to film uniformity Re < 1 As the reactant gases flow through the annulus, the reactants diffuse from the annulus radially inward between the wafers to coat them.

LPCVD modelling
The reactant gas flows through the annulus between the outer edges of the cylindrical wafers and the tube wall. Silicon is to be deposited on wafers:

SiH 2 ( g ) m Si( s )  H 2 ( g )
CVD mechanisms: Rt

SiH 2( g )  S m SiH 2 y S SiH 2 y S p Si( s )  H 2 y S H 2 y S m S  H 2( g )

Mass balance on A: r Rw

W Ar v 2T rl

 W Ar v 2T rl

r  (r

d  2 v rAd 2T r ( r ! 0 v

d 1 d (W Ar r ) 2rAd ! r dr l

d 1 d (W Ar r ) 2rAd ! r dr l

d r d! ky A A
W Ar !  D AB dy A dr

1 d rdy A 2 ky A !0  r dr dr D AB l
!

r y ]! A Rw y AA

1 d d] 2 P  J1 ] ! 0 P dP d

] ! AI 0 (J1P )  BK 0 (J1P )

B.C.

]!

yA I (J P ) I0 is the modified Bessel function ! 0 1 2 y AA I 0 (J1 ) P = r/Rw 2 kR w

J1 = the Thiele modulus !

D AB l

L!

actual overall rate of reaction rate of reaction when entire wafer surface is exposed to the conditions in the annulus
Rw

dy d]   DAB A r ! RW (2TRwl ) P !1 d 2 2Tr  rAd dr  WAr r ! RW (2TRwl ) 2 I (J ) dP dr ! 1 1 ! !2 2 L! 0 2 ! 2 2 d d d d 2TRw  rAA 2TRw ( rAA ) 2TRw (ky AA ) 2TR / D AB l J1 I 0 (J1 )

the effectiveness factor

The value of the Thiele modulus affects the thickness of the deposition.