Fogler_ECRE_CDROM.

book Page 838 Wednesday, September 17, 2008 5:01 PM

838 Diffusion and Reaction Chap. 12

Consequently, the overall rate of reaction in terms of the bulk concentration

CAb is

–rA″ = Ω ( –r″Ab ) = Ω k″1 CAb (12-54)

where

Overall effectiveness η
factor for a Ω = ------------------------------------------ (12-55)
first-order reaction 1 + ηk″1 Sa ρb ⁄ kc ac

The rates of reaction based on surface and bulk concentrations are related by
–rA″ = Ω ( –r″Ab ) = η ( –r″As ) (12-56)
where
–r″As = k″1 CAs
–r″Ab = k″1 CAb
The actual rate of reaction is related to the reaction rate evaluated at the bulk
concentration of A. The actual rate can be expressed in terms of the rate per
unit volume, rA , the rate per unit mass, –r′A , and the rate per unit surface
area, –rA″ , which are related by the equation
–rA = –r′Aρb = –rA″ Sa ρb
In terms of the overall effectiveness factor for a first-order reaction and the
reactant concentration in the bulk
–rA = –rAb Ω = r′Ab ρb Ω = –r″Ab Sa ρb Ω = k″1 CAb Sa ρb Ω (12-57)
where again
Overall
η
effectiveness Ω = ------------------------------------------
factor 1 + ηk″1 Sa ρb ⁄ kc ac
Recall that k″1 is given in terms of the catalyst surface area (m3/m2 s).

12.5 Estimation of Diffusion- and Reaction-Limited

Regimes
In many instances it is of interest to obtain “quick and dirty” estimates to learn
which is the rate-limiting step in a heterogeneous reaction.
Fogler_ECRE_CDROM.book Page 839 Wednesday, September 17, 2008 5:01 PM

Sec. 12.5 Estimation of Diffusion- and Reaction-Limited Regimes 839

12.5.1 Weisz–Prater Criterion for Internal Diffusion

The Weisz–Prater criterion uses measured values of the rate of reaction,

–rA′ (obs), to determine if internal diffusion is limiting the reaction. This crite-
rion can be developed intuitively by first rearranging Equation (12-32) in the
form
ηφ12  3(1 coth1  1) (12-58)
Showing where The left-hand side is the Weisz–Prater parameter:
the Weisz–Prater
comes from CWP = η × φ12 (12-59)
Observed (actual) reaction rate Reaction rate evaluated at CAs
= -------------------------------------------------------------------------- × -----------------------------------------------------------------------
-
Reaction rate evaluated at CAs A diffusion rate
Actual reaction rate
= -----------------------------------------------
A diffusion rate
Substituting for
–r′A( obs ) –rAs ″ Sa ρc R2 –r′As ρc R2
η = --------------------- and φ12 = --------------------------
- = ----------------------
–r′As DeCAs DeCAs
in Equation (12-59) we have

–r′A( obs ) ⎛ –rAs ′ ρc R2⎞

CWP = --------------------- ⎜ ----------------------⎟ (12-60)
–r′As ⎝ DeCAs ⎠

–r′A( obs ) ρc R2
CWP = ηφ12 = ---------------------------------
- (12-61)
DeCAs

Are there any All the terms in Equation (12-61) are either measured or known. Consequently,
internal diffusion we can calculate CWP . However, if
limitations
indicated from the
Weisz–Prater CWP « 1
criterion?

there are no diffusion limitations and consequently no concentration gradient

exists within the pellet. However, if

CWP » 1

internal diffusion limits the reaction severely. Ouch!

Example 12–3 Estimating Thiele Modulus and Effectiveness Factor

The first-order reaction

A ⎯⎯→ B
Fogler_ECRE_CDROM.book Page 840 Wednesday, September 17, 2008 5:01 PM

840 Diffusion and Reaction Chap. 12

was carried out over two different-sized pellets. The pellets were contained in a
spinning basket reactor that was operated at sufficiently high rotation speeds that
external mass transfer resistance was negligible. The results of two experimental
runs made under identical conditions are as given in Table E12-3.1. (a) Estimate the
Thiele modulus and effectiveness factor for each pellet. (b) How small should the
pellets be made to virtually eliminate all internal diffusion resistance?

TABLE E12-3.1 DATA FROM A SPINNING BASKET REACTOR†

Measured Rate (obs) Pellet Radius

These two (mol/g cat s)
105 (m)
experiments yield an
enormous amount of
Run 1 03.0 0.010
information.
Run 2 15.0 0.001
† See Figure 5-12(c).

Solution
(a) Combining Equations (12-58) and (12-61), we obtain

–r′A ( obs ) R2 ρc
--------------------------------- = ηφ12  3(1 coth 1  1) (E12-3.1)
De C As

Letting the subscripts 1 and 2 refer to runs 1 and 2, we apply Equation (E12-3.1) to
runs 1 and 2 and then take the ratio to obtain

–r′A2 R22 φ12 coth φ12 – 1

---------------2- = ----------------------------------- (E12-3.2)
–r′A1 R1 φ11 coth φ11 – 1

The terms c , De , and CAs cancel because the runs were carried out under
identical conditions. The Thiele modulus is

–rAs ′ ρc
φ1 = R -----------------
- (E12-3.3)
De CAs

Taking the ratio of the Thiele moduli for runs 1 and 2, we obtain

φ11 R1
------- = ----- (E12-3.4)
φ12 R2

or

R 0.01 m
φ11 = ----1- φ12 = --------------------- φ12 = 10φ12 (E12-3.5)
R2 0.001 m

Substituting for 11 in Equation (E12-3.2) and evaluating –rA′ and R for runs 1 and
2 gives us

⎛ 15 × 105⎞ ( 0.001 )2 φ12 coth φ12 – 1

-⎟ --------------------  ---------------------------------------------------
⎜ --------------------- - (E12-3.6)
⎝ 3 × 105 ⎠ ( 0.01 )2 10φ12 coth ( 10φ12 ) – 1
Fogler_ECRE_CDROM.book Page 841 Wednesday, September 17, 2008 5:01 PM

Sec. 12.5 Estimation of Diffusion- and Reaction-Limited Regimes 841

φ12 coth φ12 – 1

0.05  ---------------------------------------------------
- (E12-3.7)
10φ12 coth ( 10φ12 ) – 1

We now have one equation and one unknown. Solving Equation (E12-3.7) we find
that
12  1.65 for R2  0.001 m

Then

11= 1012  16.5 for R1  0.01 m0

The corresponding effectiveness factors are

Given two experi-
mental points, one 3( φ12 coth φ12 – 1 ) 3( 1.65 coth 1.65 – 1 )
can predict the For R2 : η2 = ------------------------------------------ = ------------------------------------------------
- = 0.856
particle size where φ122 ( 1.65 )2
internal mass
3( 16.5 coth 16.5 – 1 ) 3
transfer does not For R1 : η1 = ------------------------------------------------
- ≈ ---------- = 0.182
limit the rate of ( 16.5 )2 16.5
reaction.
(b) Next we calculate the particle radius needed to virtually eliminate internal diffu-
sion control (say,  0.95):

3( φ13 coth φ13 – 1 )

0.95 = ------------------------------------------ (E12-3.8)
φ132

Solution to Equation (E12-2.8) yields 13  0.9:

φ13 ⎛ 0.9 ⎞
R3  R1 ------
-  (0.01) ⎜ ----------⎟  5.5
104 m
φ11 ⎝ 16.5⎠

A particle size of 0.55 mm is necessary to virtually eliminate diffusion control

(i.e.,  0.95).

12.5.2 Mears’ Criterion for External Diffusion

The Mears7 criterion, like the Weisz–Prater criterion, uses the measured rate of
reaction, –r′A , (kmol/kg cat s) to learn if mass transfer from the bulk gas
phase to the catalyst surface can be neglected. Mears proposed that when

Is external –r′A ρb Rn
diffusion limiting?
--------------------- < 0.15 (12-62)
kcCAb

external mass transfer effects can be neglected.

7 D. E. Mears, Ind. Eng. Chem. Process Des. Dev., 10, 541 (1971). Other interphase
transport-limiting criteria can be found in AIChE Symp. Ser. 143 (S. W. Weller, ed.),
70 (1974).
Fogler_ECRE_CDROM.book Page 842 Wednesday, September 17, 2008 5:01 PM

842 Diffusion and Reaction Chap. 12

where n  reaction order

R  catalyst particle radius, m
b  bulk density of catalyst bed, kg/m3
 (1  ) c (  porosity)
c  solid density of catalyst, kg/m3
CAb  bulk reactant concentration, mol/dm3
kc  mass transfer coefficient, m/s
The mass transfer coefficient can be calculated from the appropriate cor-
relation, such as that of Thoenes–Kramers, for the flow conditions through the
bed. When Equation (12-62) is satisfied, no concentration gradients exist
between the bulk gas and external surface of the catalyst pellet.
Mears also proposed that the bulk fluid temperature, T, will be virtually
the same as the temperature at the external surface of the pellet when

Is there a –ΔHRx ( –r′A ) ρb RE

temperature - < 0.15
------------------------------------------- (12-63)
gradient? hT 2Rg

where h  heat transfer coefficient between gas and pellet, kJ/m2 s K

Rg  gas constant, 8.314 J/mol K
HRx  heat of reaction, kJ/mol
E  activation energy, kJ/kmol
and the other symbols are as in Equation (12-62).

12.6 Mass Transfer and Reaction

in a Packed Bed
We now consider the same isomerization taking place in a packed bed of cat-
alyst pellets rather than on one single pellet (see Figure 12-10). The concentra-
tion CAb is the bulk gas-phase concentration of A at any point along the length
of the bed.

Figure 12-10 Packed-bed reactor.

We shall perform a balance on species A over the volume element V,

neglecting any radial variations in concentration and assuming that the bed is
Fogler_ECRE_CDROM.book Page 843 Wednesday, September 17, 2008 5:01 PM

Sec. 12.6 Mass Transfer and Reaction in a Packed Bed 843

operated at steady state. The following symbols will be used in developing our
model:
Ac  cross-sectional area of the tube, dm2
CAb  bulk gas concentration of A, mol/dm3
b  bulk density of the catalyst bed, g/dm3
v0  volumetric flow rate, dm3/s
U  superficial velocity  v0 /Ac , dm/s
Mole Balance A mole balance on the volume element (Ac z) yields
[ Rate in ]  [ Rate out ]  [ Rate of formation of A ]  0
AcWAz z  AcWAz zΔz  rA′ ρb Ac Δz 0
Dividing by Ac z and taking the limit as z ⎯⎯→ 0 yields
dWAz
– ------------- + r′A ρb = 0 (12-64)
dz
Assuming that the total concentration c is constant, Equation (11-14) can
be expressed as
dCAb
WAz  DAB -----------
-  yAb (WAz  WBz )
dz
Also, writing the bulk flow term in the form
BAz  yAb (WAz  WBz )  yAb cU  UCAb
Equation (12-64) can be written in the form
d2CAb dCAb
DAB -------------
2
- + rA′ ρb = 0
- – U ----------- (12-65)
dz dz

Now we will see The term DAB (d 2CAb /dz2 ) is used to represent either diffusion and/or
how to use and  dispersion in the axial direction. Consequently, we shall use the symbol Da for
to calculate the dispersion coefficient to represent either or both of these cases. We will
conversion in a
packed bed. come back to this form of the diffusion equation when we discuss dispersion
in Chapter 14. The overall reaction rate within the pellet, –r′A , is the overall
rate of reaction within and on the catalyst per unit mass of catalyst. It is a
function of the reactant concentration within the catalyst. This overall rate can
be related to the rate of reaction of A that would exist if the entire surface were
exposed to the bulk concentration CAb through the overall effectiveness factor :
–r′A = –r′Ab × Ω (12-57)
For the first-order reaction considered here,
–r′Ab = –r″Ab Sa = k″SaCAb (12-66)
Fogler_ECRE_CDROM.book Page 844 Wednesday, September 17, 2008 5:01 PM

844 Diffusion and Reaction Chap. 12

Substituting Equation (12-66) into Equation (12-57), we obtain the overall rate
of reaction per unit mass of catalyst in terms of the bulk concentration CAb :
–r′A   k″ SaCAb
Substituting this equation for –r′A into Equation (12-65), we form the dif-
ferential equation describing diffusion with a first-order reaction in a catalyst
bed:

Flow and first- d 2 CA b dCAb

order reaction in a Da --------------
2
- – Ωρb k″ SaCAb = 0
- – U ----------- (12-67)
packed bed dz dz

As an example, we shall solve this equation for the case in which the flow rate
through the bed is very large and the axial diffusion can be neglected. Young
and Finlayson8 have shown that axial dispersion can be neglected when

Criterion for –r′A ρb dp U0 dp

neglecting axial -------------------- « ----------- (12-68)
dispersion/diffusion U0CAb Da

where U0 is the superficial velocity, dp the particle diameter, and Da is the

effective axial dispersion coefficient. In Chapter 14 we will consider solutions
to the complete form of Equation (12-67).
Neglecting axial dispersion with respect to forced axial convection,

dCAb d2CAb
U -----------
- » Da -------------
-
dz dz2
Equation (12-67) can be arranged in the form

dCAb ⎛ Ωρb k″ Sa⎞

- = – ⎜ --------------------
----------- -⎟ CAb (12-69)
dz ⎝ U ⎠
With the aid of the boundary condition at the entrance of the reactor,
CAb  CAb0 at z  0
Equation (12-69) can be integrated to give
 ( ρb k″Sa Ωz ) ⁄ U
CAb = CAb0 e (12-70)
The conversion at the reactor’s exit, z  L, is

Conversion in a CAb  ( ρ k″S ΩL ) ⁄ U

packed-bed reactor - = 1–e b a
X = 1 – ---------- (12-71)
CAb0

8 L. C. Young and B. A. Finlayson, Ind. Eng. Chem. Fund., 12, 412 (1973).
Fogler_ECRE_CDROM.book Page 845 Wednesday, September 17, 2008 5:01 PM

Sec. 12.6 Mass Transfer and Reaction in a Packed Bed 845

Example 12–4 Reducing Nitrous Oxides in a Plant Effluent

In Section 7.1.4 we saw the role that nitric oxide plays in smog formation and the
incentive we would have for reducing its concentration in the atmosphere. It is pro-
posed to reduce the concentration of NO in an effluent stream from a plant by pass-
ing it through a packed bed of spherical porous carbonaceous solid pellets. A 2%
NO–98% air mixture flows at a rate of 1
106 m3/s (0.001 dm3/s) through a
2-in.-ID tube packed with porous solid at a temperature of 1173 K and a pressure of
101.3 kPa. The reaction
NO  C ⎯⎯→ CO  1--2- N2

is first order in NO, that is,

–r′NO  k″1 Sa CNO

and occurs primarily in the pores inside the pellet, where

Green Sa  Internal surface area  530 m2/g
chemical reaction
engineering
k″1  4.42
1010 m3/m2 s

Calculate the weight of porous solid necessary to reduce the NO concentration to a

level of 0.004%, which is below the Environmental Protection Agency limit.

Additional information:
At 1173 K, the fluid properties are
  Kinematic viscosity  1.53
108 m2/s
DAB  Gas-phase diffusivity  2.0
108 m2/s
De  Effective diffusivity  1.82
108 m2/s
Also see Web site The properties of the catalyst and bed are
www.rowan.edu/
greenengineering c  Density of catalyst particle  2.8 g/cm3  2.8
106 g/m3
  Bed porosity  0.5
b  Bulk density of bed  c (1  )  1.4
106 g/m3
R  Pellet radius  3
103 m
  Sphericity = 1.0

Solution
It is desired to reduce the NO concentration from 2.0% to 0.004%. Neglecting any
volume change at these low concentrations gives us
CAb0 – CAb 2 – 0.004
X = ------------------------
- = --------------------- = 0.998
CAb0 2

where A represents NO.

Fogler_ECRE_CDROM.book Page 846 Wednesday, September 17, 2008 5:01 PM

846 Diffusion and Reaction Chap. 12

The variation of NO down the length of the reactor is given by Equation

(12-69)
dCAb Ωk″Sa ρb CAb
-----------
- = – ------------------------------ (12-69)
dz U
Multiplying the numerator and denominator on the right-hand side of Equation
(12-69) by the cross-sectional area, Ac , and realizing that the weight of solids up to
a point z in the bed is
(Mole balance)
+ W  b Ac z
(Rate law)
+ the variation of NO concentration with solids is
(Overall
effectiveness dCAb Ωk″Sa CAb
-----------
- = – -----------------------
- (E12-4.1)
factor) dW v
Because NO is present in dilute concentrations, we shall take   1 and set
v = v0 . We integrate Equation (E12-4.1) using the boundary condition that when
W  0, then CAb  CAb0 :

CAb ⎛ Ωk″Sa W ⎞
X = 1 – ----------- = 1 – exp ⎜ – -------------------- ⎟ (E12-4.2)
CAb0 ⎝ v0 ⎠

where
η
Ω = ---------------------------------------- (12-55)
1 + ηk″Sa ρc ⁄ kc ac

Rearranging, we have

v0 1
W = --------------
- ln ----------- (E12-4.3)
Ωk″Sa 1 – X

1. Calculating the internal effectiveness factor for spherical pellets in which a

first-order reaction is occurring, we obtained
3
 ----2- (1 coth 1  1) (12-32)
φ1

As a first approximation, we shall neglect any changes in the pellet size

resulting from the reactions of NO with the porous carbon. The Thiele modu-
lus for this system is9

k″1 ρc Sa
φ1 = R ----------------- (E12-4.4)
De

where
R  pellet radius  3
103 m
De  effective diffusivity  1.82
108 m2/s
c  2.8 g/cm3  2.8
106 g/m3
9 L. K. Chan, A. F. Sarofim, and J. M. Beer, Combust. Flame, 52, 37 (1983).