PTL#3 Ideal Reactors and Transpor Mechanism

Advanced Transport Phenomena
Mass Transport: Composite Planar Slab
1
CONCENTRATION FIELDS, SURFACE MASS-
TRANSFER RATES & COEFFICIENTS
 Conservation Equations:
 Concentration fields are coupled by the facts that:
 Homogeneous reaction rates involve many local
species
 All local mass fractions must sum to unity (only N-1
equations are truly independent)
 Species i mass conservation condition may be written
as:
ri
�
+ div(m
&i'' ) = r&
i
'''
(i = 1, 2,..., N ),
�t
 r&
i
'''
 local mass rate of production of species i
2
 Since ri = ri, by virtue of total mass conservation:
r
�
+ div(m i ) = 0
& ''
�t
and the species balance becomes:
��i �
r � + v.gradi �= - div ( ji'',diff + ri ci ) + r&
i
'''
��t �
LHS  proportional to (Lagrangian) rate of change of
ifollowing a fluid parcel
RHS  ri ci is “forced” diffusion flux
3
 PDEs for i ( x, t ) coupled to each other, and to
PDEs governing linear momentum density rv(x,t) &
temperature field, T(x,t)
 All must be solved simultaneously, to ensure self-
consistency
 Simplest PDE governing  A ( x, t ) is Laplace
equation:
div ( grad A ) = 0
4
 Laplace eq. holds when there are no:
 Transients
 Flow effects
 Variations in fluid properties
 Homogeneous chemical reactions involving species A
 Forced diffusion (phoresis) effects
 In Cartesian coordinates:
�2 A �2 A �2 A

2
+ 2
+ 2
=0
�x �
y �
z 5
 Boundary conditions on i ( x, tare
) of two types:
 i along each boundary surface, or
 Some interrelation between flux m&i'',(e.g.,
& via
w i,w
heterogeneous chemical kinetics)
 Solution methods:
 Numerical or analytical
 Exact or approximate
 Solutions could be carried over from corresponding
momentum or energy transfer problems
6
ANALOGIES & ANALOGY-BREAKERS
 Heat-Transfer Analogy Condition (HAC) applies when:
 Fluid composition is spatially uniform
 Boundary conditions are simple
 Fluid properties are nearly constant
 All volumetric heat sources, including viscous

dissipation and chemical reaction, are negligible
 St
h , Nuh known as functions of Re, Pr, Rah, etc.
7
 Corresponding temperature field:
Tw - T
�T ( x , t ; Re, Pr,...)
* * *
Tw - T�
 Under HAC, the rescaled chemical species concentration
 A, w -  A
� * ( x* , t * ; Re, Sc,...)
 A, w -  A, �
 And corresponding coefficients, St and Num , will be
m
identical functions of resp. arguments.
8
 MACs:
 Species A concentration is dilute (
) A << 1
 specified constant along surface

A, w forced diffusion (phoresis)
 Negligible
 No homogeneous chemical reaction
 Analogy holds even when:

 Fluid flow is caused by transfer process itself (e.g., natural
convection in a body force field)
 Analogy to linear momentum transfer breaks down due to
streamwise pressure gradients
9
 MAC:
 Schmidt number Sc �n / DA plays role that Pr does for
heat transfer
 Mass-transfer analog of Rah is:
g  (  A, w -  A,�) L v3
Ram � 2
. �Grm .Sc
v DA
where  defines dependence of local fluid density on A:
1 ��u � 1 ��r �
 � � � = - � �
u ��
A �
p ,T
r ��
A �
p ,T
10
 Correction Factors for Analogy-Breaking Phenomena:
 Two analogy breaking mechanisms:
 Phoresis
 Homogeneous chemical reaction
 Have no counterpart in energy equation T(x,t)
 BL situation: Substance A being transported from
mainstream to wall
 A,w << A,∞
11
 Phoresis toward the wall:
 Distorts concentration profile

 Affects wall diffusional flux, - j A, w''
Num = F ( suction).Num,0
where Num,0 mass transfer coefficient without phoretic
enhancement; analogous to Nuh
F(suction)  augmentation factor
12

 F(suction) is a simple function of a Peclet number
based on drift speed, -c, boundary-layer thickness,
m,o, and diffusion coefficient, DA:
( -c )  m,0 � �( -c ) L �
�
Pesuction �� = � �
� D � A �DNum ,0 �
A
or
Pesuction �
( -c )
.
1
U Stm ,0
In most cases
Pesuction
F ( suction) @
1 - exp(- Pesuction )
13
 Homogeneous reaction within BL:
 A profile distorted, diffusional flux affected
Num = F ( reaction ) .Num,0

or
Stm = F ( reaction ) .Stm ,0
14

 F(reaction) depends on Damkohler (Hatta) number:
Dam �
tdiff
=
(  m ,0 / D )
2
�k ''' m2 ,0 �
=� �
tchem ( 1/ k ) � D �
''' �
�
A
where k”’  relevant first-order rate constant; time-1

can be rewritten using:
L D
 m ,0 = =
Num ,0 UStm,0
15

 For an irreversible reaction with A,w << A,∞
(
� )
1/2 1/2
� Dam / sin( Dam ) ( source)
F ( reaction ) @ �
( )
1/2 1/2
�
� Dam / sinh( Dam ) (sink)
(F(reaction)  1 when Dam  0)

Reaction augmentation factors  Hatta factors
 F(Reaction) = m,o /m
 If only heterogeneous reactions occur, analogy is

intact: Num = Num,0 16
QUIESCENT MEDIA
 Above conditions not sufficient in nondilute systems

 Mass transfer itself gives rise to convection normal to
surface, Stefan flow
vw m  A, w -  A,�
Bm � =
D 1 -  A, w
 vw fluid velocity @ interface
 Additional condition for neglect of convective transport
in mass transfer systems:
vw m  A, w -  A,�
= << 1
D 1 -  A, w
 Inevitably met in dilute systems
17
QUIESCENT MEDIA
 Stefan flow becomes very important when A,w ≠ A,∞, and
A,w  1
 e.g., at surface temperatures near boiling point of
liquid fuel
18
COMPOSITE PLANAR SLAB
 T continuous going from layer to layer, but not A
 Only chemical potential is continuous
 Two unknown SS concentrations at each interface
 Linear diffusion laws to be reformulated using a
continuous concentration variable

 Applies to nonplanar composite geometries as well
19
Mass transfer of substance A across a composite barrier: effect of piecewise

discontinuous concentration (e.g., mass fraction A(x))
20
 Continuous composition variable = -phase mass fraction of

solute A
 Corresponding mass flux through a composite solid (or liquid
membrane)
( D A ) overall

j ''
A, x =
�L �
()
(
�K A . D A ()
overall
)
�l �D r �. ,l
�A �
,l concentration-independent
l dimensionless equilibrium solute
A partition coefficients, (A()/A(l))LTCE, between phase  and
phase l (= …)
m,ef  stagnant film (external) thickness (resistance)
21
 Dilute solute SS diffusional transfer between two

contacting but immiscible fluid phases  in
separation/ extraction devices
 Modeled as through two equivalent stagnant films of
thicknesses m,ef () and m,ef ()
 In series, negligible interfacial resistance between them
 “Two-film” theory (Lewis and Whitman, 1924)
22
 KA()  overall interface mass transfer coefficient

(conductance)
 Satisfies “additive-resistance” equation
� ��  �
1 1
=� �+ � �
()
( ) ( )
( ) ( )
KA � D r /  �� D r /  �
{ �
1 4 44 2 4 4 43� 1 �4 44 2 4 4 43�
A m . eff A m , eff
Overall
mass transfer α-phase β-phase
resistance resistance resistance
(symmetrical replacement of  and  yields KA())
23
 Gas absorption/ stripping:

 One phase (say ) vapor phase
 K relevant partition coefficient; inversely
proportional to Henry constant, H:
(  A M ) solvent / M A �
p A = H .( x A ) solvent = H . �
� �
where M  solvent molecular weight
pA  partial pressure of species A in vapor
phase
24
 H  dimensional inverse partition (distribution)

coefficient
� (  ) RT � 1
 r
=� .
( ) �
� M �H
(if -phase (vapor mixture) obeys perfect gas law)
25
 Addition of reagents to solvent phase :
 Reduces m,ef ()
 Simultaneous homogeneous chemical reaction increases
liquid-phase mtc’s, accelerates rate of uptake of sparingly-

soluble (large H) gases
 Additive (B) in sufficient excess => pseudo-first-order
reaction ( linearly proportional to rA, with rate constant

- r&
A
'''
k”’)
26
 m(,eff) ;0
 m(,eff) =
F (reaction)
where
( Dam )
1/2
F ( reaction ) =
tanh( Dam)1/2
and
Dam �
(  2
m , eff ;0 /D ( )
A )
( )
1/ k '''
27
 When reaction is so rapid that the two reagents meet in
stoichiometric ratio at a thin reaction zone (sheet):
 Distance between reaction zone & phase boundary
plays role of  m(,eff) ( )
1 �DB B ,b �
F ( reaction ) � 1 + . � . �
b �DA  A,i �
B,b  concentration of additive B in bulk of solvent
i  concentration of transferred solute A at solvent
interface
 b gms of B are consumed per gram of A
28
Mass Transport: Diffusion with Chemical Reaction
29
QUASI-STEADY-STATE (QS) DIFFUSION
OUTSIDE ISOLATED SPHERE
 In completely quiescent case, diffusional mass transfer
from/ to sphere occurs at a rate corresponding to Nu m = 2
 If Bm ≡ vwm/D is not negligible, then:
ln ( 1 + Bm )
Num = 2
and Bm
Num ln ( 1 + Bm )
Fm ( Stefan " blowing ") � =2
Num,0 Bm
 Results from radial outflow due to net mass-transfer flux
across phase boundary
30
 vw may be established by physically blowing fluid through
a porous solid sphere of same dia => Bm  “blowing”

parameter
 vw is negative in condensation problems, so is Bm
 Suction enhances Num
31
 Pew,m  alternative blowing parameter, defined by:
u w m ,0
Pew,m �
and D
Num Pew,m
Fm ( Stefan blowing ) � =
Num ,0 exp ( Pew,m ) - 1
 Equivalent to correction factor for “phoretic suction”
32
 Stefan-flow effect on Num very similar to phoresis effect,
but with one significant difference:

 Phoresis affects mass transfer of dilute species, but
not heat transfer
 Stefan flow affects both Nuh and Num in identical
fashion, hence not an analogy-breaker

 Corresponding blowing parameters:
vw h vw h ,0
Bh = Pew,h �
 
33
and
Nuh ln(1 + Bh ) Pew,h
Fh ( Stefan blowing ) � = =
Nuh ,0 Bh exp ( Pew,h ) - 1
 Nuh same function of Bh (or Pew,h) & Pr, as Num is of Bm
(or Pew,m) & Sc
34
QS EVAPORATION RATE OF ISOLATED DROPLET
 Droplet of chemical substance A in hot gas
 Energy diffusion from hotter gas supplies latent heat
required for vaporization of droplet of size dp

 Known:
 Gas temperature, T∞
 Vapor mass fraction A,∞
 Unknowns:
 droplet evaporation rate ( &
m ''
= r v
w w or &
m p = p d pm )
&
2 ''
 Vapor/ liquid interface conditions (A,w, Tw)
35
 Assumptions:
 Vapor-liquid equilibrium (VLE) @ V/L interface
 Liquid is pure (A(l) = 1), surrounding gas insoluble in it
 dp >> gas mean free path
 Forced & natural convection negligible in gas
 Variable thermophysical property effects in gas
negligible
36
 Assumptions:
 Species A diffusion in vapor phase per Fick’s (pseudo-
binary) law
 No chemical reaction of species A in vapor phase
 Recession velocity of droplet surface negligible
compared to radial vapor velocity, vw, at V/L phase

boundary
37
 Dimensionless “blowing” (driving force)parameters:
 A, w -  A , �
Bm =
1 -  A, w
c p (T� - Tw )
Bh =
LA
where A,w = A,eq(Tw; p)
38
 Species A mass balance:

 m&A'' ,n continuous, and, in each adjacent phase, given
by:
mi = i mi + ri ci - Di ,eff r grad
&''
&''
 Since A(l) = 1, in the absence of phoresis:
m&A'' ,n = m&'' . A, w + j A'' ,n , w

m&
(applying total mass balance condition� n �
� ''
= 0)
�
39
 Since m& = r vw , and

''
j '' ��  A �
DA r � �
= -� �DA r
(  A, w -  A,�)
A, n , w � m
� �� n ��w
We can relate Bm directly to mass fractions of A as:
vw m  A, w -  A,�
Bm � =
D 1 -  A, w
40
 Similarly, energy conservation condition at V/L interface
leads to relation between Bh and T∞-Tw
m&'' LA = -q&n'' , w ( Fourier )

(neglecting work done by viscous stresses)
where LA  latent heat of vaporization
LA �hA ( Tw ) - hA( ) ( Tw ; p )
l
41
 Heat Flux:
�� T � �T� - Tw �
- q& ( Fourier ) = �
''
k� � � �k . � �
h �
n,w
�� n� �w �
 Mass Flux:
m& = 2
'' ( DA r )
.ln [ 1 + Bm ]
dp
 Relating the two:
m& =
''
&
qn ( Fourier )
''
=2
( k / cp )
.ln [ 1 + Bh ]
LA dp
42
 Driving forces are related by:
( 1 + Bh ) = ( 1 + Bm )
Le
where Le = DA/ [k/rcp] = Lewis number

 Yields equation for Tw
 Solution yields Bh, Bm
43
 Single droplet evaporation rate

�k � � c p ( T� - Tw ) �
m&p = 2p d p � 1+
.ln �
� �
�c � LA
�p � � �
 Equating this to
d � 4 � p ��
d
3
- �rl p � �� (overall mass balance on the entire droplet )

dt � 3 �2 ��
� �
 We find that dp2 decreases linearly with time:
� �r g
� � � c p ( T� - Tw ) �
�
�
d =d
2
p
2
p ,o �
-8� 1+
ln �
� �t
�
� �rl � � LA �
�
44
 Setting dp = 0 yields characteristic droplet lifetime:
d p2,0
tlife,vap =
� �r g
� � � c p ( T� - Tw ) �
�
�
8 �
� � 1+
ln � �
�
� �rl � � LA �
�
45
STEADY MASS DIFFUSION WITH SIMULTANEOUS
CHEMICAL REACTION: CATALYST PELLET
 Catalyst impregnated throughout with porous pellets
 To avoid having to separate catalyst from reaction product
 Pellets are packed into “fixed bed” through which reactant
is passed
 Volume requirement of bed set by ability of reactants to
diffuse in & products to escape

 Core accessibility determined by pellet diameter,
porosity & catalytic activity
46
 Assumptions in continuum model of catalytic pellet:
 SS diffusion & chemical reaction
 Spherical symmetry
 Perimeter-mean reactant A number density nA,w at R = Rp
 Radially-uniform properties (DA,ef, k”’ef, r, …)
 First-order irreversible pseudo-homogeneous reaction
within pellet
47
 SS nA(r) profile within pellet satisfies local species A
mass-balance:
0 = - div( j ) + r&
''
A
'''
A, eff
since
j @ - DA,eff r grad A
''
A
and
-r& '''
A, eff = k r A
'''
eff
48
 Then, nA(r) satisfies:

1 d �2 dnA � '''
2
. �r DA,eff �= keff nA
r dr � dr �
Relevant boundary conditions:
n A ( R p ) = n A, w
and
( dnA / dr ) r =0 = 0
49
 Applying species A mass balance to a “microsphere” of
radius , and taking the limit as  0:
� 1  ''' �
lim j A'' ,r = lim � 2 .� eff 4p r dr �
r& 2
 �0  �0 �4p 0
which, for finite ''' leads to:

r (o)
A
( dnA / dr ) r =0 = 0
50
 Once nA(r) is found, catalyst utilization (or effectiveness)
factor can be calculated as:
actual reaction rate within pellet

hcat �
reaction rate within pellet if n A ( r ) = n A, w
or Rp � �
� dn �
keff nA ( r ) 4p r dr � ( p p)
2
D
� A
� 4 R
�
''' 2
A, eff �
�
� � dr � r = Rp �
�
hcat = 0
=
'''
4p R 3
p � 4 p R 3
p
�
keff nA, w . '''
keff nA, w . � �
3 � 3 �
� �
51
 By similitude analysis:
nA �r �
c� = fct � ,  ��fct ( z ;  )
nA, w �R �
� p �
and, therefore:
1 �dc �
hcat = 2 � � = hcat (  )
 �dz � z =1
where the Thiele modulus, , is defined by:

-1/2
�DA,eff �
 �R p . � ''' �
�k �
� eff �
 2 relevant Damkohler number; ratio of characteristic
diffusion time (Rp2/DA,eff) to characteristic reaction time,52
-1
 c (z) normalized reactant-concentration variable,
satisfies 2nd-order linear ODE:
1 d � 2 dc � 2
z
� �=  c
z dz � dz �
subject to split bc’s:
c(1) = 1
( dc / dz ) 0 = 0
53
Solution to this two-point BVP:

sinh ( z )
c=
z sinh( )
or, explicitly:
nA ( r ) sinh (  r / R p )
=
nA, w ( r / Rp ) sinh( )
Catalyst-effectiveness factor is explicitly given by:
3 � 1 1�
hcat = .� - �
 �tanh   �
54
Catalyst effectiveness factor for first-order chemical reaction in a porous solid sphere
(adapted from Weisz and Hicks (1962))
55
hcat � 1 for  � 0
hcat � 3 /  for  >> 1
 Reaction only in a thin shell near outer perimeter of
pellet
 Alternative presentation of hcat : based on dependence on
F =  2h
�4p 3 �
( -rA,obs / M A ) / �3 Rp � 3 ( -r&A,obs / M A )
&
F� � �= .
( DA,eff nA,w / Rp )
 Independent of (unknown)
2
4p ( DA,eff nA, w R p )
keff'''
56
Catalyst effectiveness factor vs experimentally observable (modified) Thiele

modulus (adapted from Weisz and Hicks (1962))
57
 Following additional parameters influence hcat

E
Arr �
RTe
DA,eff nA,e ( -DH )
�
keff Te
n �reaction order
�DA, fluid �Nu m �
Bim �� .
�DA,eff � 2 �
�
�
� �
�
�k fluid �Nu h �
Bih �� . �
�k � 2
� eff � �
58
Representative Parameter Values for Some Heterogeneous Catalytic Reactions

(after Hlavacek et al (1969)) 59
TRANSIENT MASS DIFFUSION: MASS
TRANSFER (CONCENTRATION) BOUNDARY
LAYER
 Discussion for thermal BL applies here as well
 m @ 4 ( Dt )
1/2
 Thermal BL “outruns” the MTBL:

1/2
 h � �
= � � �( Le )
-1/2
 m �D �
 D <<  (Le << 1) for most solutes in condensed phases
(especially metals)
 Ratio holds for time-averaged penetration depth in
periodic BC case as well
60
CONVECTIVE MASS TRANSFER IN LAMINAR-
AND TURBULENT-FLOW SYSTEMS
 Analogies to Energy Transfer:
 When “analogy conditions” apply, heat-transfer
equations can be applied to mass-transfer by
substituting:
 � D,
Pr � Sc,
Nuh � Num
Sth � Stm ,
Rah � Ram
61
 Mass transfer of dilute species A in straight empty tube
flow (by analogy):

 A , w -  A ,b ( z )
 A, w -  A,b (0)
{ }
= exp -4x m .Nu m ( �) .F (entrance)
where
1 z
xm � . ( Sc �v / DA- mix )
Re.Sc d w
62
Nu m ( �) = �
0.023
� Re 0.8
Sc1/3
�
� (turbulent )
and
�� -8/3 1/8
1
�� + ( 7.60 x m ) � (laminar)
�
F (entrance) @ �
1 + ( z / d w ) � (turbulent)
-2/3
��
��
63
 Packed duct (by analogy):
dj A / (a ''' A0 dz )
Num ,bed �
(� / ( 1 -  ) ) . ( d p,eff ) �
DA r (  A , w -  A , b ) / � �
Since, in the absence of significant axial dispersion:
dj A = m&.d  A,b ,
64
We find:
 A , w -  A ,b ( z ) �
� �Num ,bed ( Rebed , Sc ) � z �
�
= exp �-6(1 -  ). � �. �
 A,w -  A,b (0) � �  Rebed .Sc �d p ,eff �
where
Num,bed Sc -0.4 @ 0.4 Re1/2
bed + 0.2 Re 2/3
bed
if 3 ≤ Rebed ≤ 104, 0.6 ≤ Sc, 0.48 ≤  ≤ 0.74
Quantity in square bracket = Bed Stanton number for
mass transfer, Stm,bed
65
In terms of Stm,bed
 A , w -  A ,b ( z )
= exp { - Stm,bed a ''' z}
 A, w -  A,b (0)
'''
where, as defined earlier, a (= 6(1-)/dp) interfacial
area per unit volume of bed
66

 Height of a transfer unit (HTU) is defined by:
 A , w -  A ,b ( z ) � z �
�exp �- �
 A, w -  A,b (0) � ( HTU ) �
 HTU  bed depth characterizing exponential approach to
mass-transfer equilibrium
67

In the case of single-phase fluid flow through a packed bed,
HTU = (a”’Stm,bed)-1
 Widely used in design of heterogeneous catalytic-flow
reactors and physical separators

 No chemical reaction within fluid
 Also to predict performance of fluidized-bed contactors,
using (Rebed) correlations
68

PTL#3 Ideal Reactors and Transpor Mechanism

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PTL#3 Ideal Reactors and Transpor Mechanism

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Advanced Transport Phenomena

Mass Transport: Composite Planar Slab

�2 A �2 A �2 A

 Fluid composition is spatially uniform

 Boundary conditions are simple

 Fluid properties are nearly constant

 All volumetric heat sources, including viscous

 No homogeneous chemical reaction

 Analogy holds even when:

 Correction Factors for Analogy-Breaking Phenomena:

 Two analogy breaking mechanisms:

 BL situation: Substance A being transported from

 Correction Factors for Analogy-Breaking Phenomena:

 Phoresis toward the wall:

 Distorts concentration profile

 Correction Factors for Analogy-Breaking Phenomena:

 Homogeneous reaction within BL:

 A profile distorted, diffusional flux affected

Num = F ( reaction ) .Num,0

 Correction Factors for Analogy-Breaking Phenomena:

where k”’  relevant first-order rate constant; time-1

 Correction Factors for Analogy-Breaking Phenomena:

(F(reaction)  1 when Dam  0)

 If only heterogeneous reactions occur, analogy is

 Above conditions not sufficient in nondilute systems

 Stefan flow becomes very important when A,w ≠ A,∞, and

 T continuous going from layer to layer, but not A

 Only chemical potential is continuous

 Two unknown SS concentrations at each interface

 Linear diffusion laws to be reformulated using a

continuous concentration variable

Mass transfer of substance A across a composite barrier: effect of piecewise

 Continuous composition variable = -phase mass fraction of

 Dilute solute SS diffusional transfer between two

thicknesses m,ef () and m,ef ()

 In series, negligible interfacial resistance between them

 “Two-film” theory (Lewis and Whitman, 1924)

 KA()  overall interface mass transfer coefficient

(symmetrical replacement of  and  yields KA())

 Gas absorption/ stripping:

 H  dimensional inverse partition (distribution)

 Addition of reagents to solvent phase :

 Reduces m,ef ()

 Simultaneous homogeneous chemical reaction increases

liquid-phase mtc’s, accelerates rate of uptake of sparingly-

reaction ( linearly proportional to rA, with rate constant

across phase boundary

a porous solid sphere of same dia => Bm  “blowing”

 vw is negative in condensation problems, so is Bm

 Suction enhances Num

but with one significant difference:

not heat transfer

 Stefan flow affects both Nuh and Num in identical

fashion, hence not an analogy-breaker

 Nuh same function of Bh (or Pew,h) & Pr, as Num is of Bm

(or Pew,m) & Sc

 Droplet of chemical substance A in hot gas

 Energy diffusion from hotter gas supplies latent heat

required for vaporization of droplet of size dp

 Vapor/ liquid interface conditions (A,w, Tw)

 Vapor-liquid equilibrium (VLE) @ V/L interface

 Liquid is pure (A(l) = 1), surrounding gas insoluble in it

 dp >> gas mean free path

 Forced & natural convection negligible in gas