Modern Methods in Heterogeneous Catalysis Research

TRANSPORT PHENOMENA
10/31/08 Giulio Lolli
 Outline
2

  Part I - Theory
  Why Transport?
  Fundamental equations

  Unified approach to transport phenomena

  Boundary Layer approach

  Dimensionless numbers

  Part II - Practice
  Example: Methanol Synthesis

Transport Phenomena 10/31/08

 Further Reading
3

  Part I
  Bird, Steward, Lightfoot
  Transport Phenomena
  Asano Welty
Mass Transport Fundamentals of M,H&M Transfer
  Part II
  Handout
  Web: Document DB # 15375
  Perry’s Chemical Engineering Handbook

Transport Phenomena 10/31/08

4 Part I
Theory

Transport Phenomena 10/31/08

 Why Transport? Catalytic Process
5

  Thermodynamic
  Reaction Equilibrium
  Phase equilibrium:
adsorption/desorption
  Kinetic
  Reaction Kinetic
  Transport
  Reactants/Product to/
from the active sites
  Heat to/from the
Transport Phenomena 10/31/08
active site
 Transport Phenomena
6

Type of transport What is transferred

Specific direction x
  Momentum Transport   Kinetic Energy
∂!uy ∂T ∂CA
!τxy = −µ qx = −k jA,x =Law
  Newton’s −DA
nx ∂x ∂x ∂x
 
st
Heat Transport Thermal Energy
 
1 Law (Fluxes)
∂T ∂CA
qx = −k jA,x = −DA   Fourier’s Law
∂x ∂x
!
T! Mass
  !Transport
= −µ∇! u !   Chemical
!q = −k ∇T j!A =Energy
! A
−DA ∇C
) ∂CA
jA,x = −DA   Fick’s Law
! = −σ ∇ϕ
! A∂x
Φ
!
!q = −k ∇T j!A = −DA ∇C! A
2nd Law (variation in space-time)
Transport Phenomena 10/31/08
 !τxy = −µ qx
∂x
First Law of
Specific direction x
transport
7
st
Specific direction x
!τxy = −µ
∂!uy 1 q =Law
−k
x
∂T (Fluxes)
j = −D A,x A
∂CA
∂x
∂!uy ∂x
∂T ∂xA
∂C
!τxy = −µ qx = −k jA,x = −DA
∂x ∂x ∂x
1st Law (Fluxes)
!! !u
st
1 Law (Fluxes)
!
T! = −µ∇!
!u
−µ
T!q ==−k∇T
!
∇! j! ! A
= −DA ∇C
!q =
A
!
T! = −µ∇!
!u !
!q = −k ∇T ! A
j!A = −DA ∇C
! = −σ ∇ϕ
Φ ! A
! = −σ ∇ϕ
Φ ! A ! = −σ ∇ϕ
Φ ! A
2nd Law (variation in space-time)
2nd Law (variation in space-time)
D!u !
ρ = µ∇2!u+ρ!g − ∇p
nd Transport Phenomena
ρ
Dt
D!
u 2 !
= µ∇ !u+ρ!g − ∇p 2 Law (variation in sp
10/31/08
Dt
 Math 101- Gradient
8
Math 101 Nabla, Gradient
   
∂ ∂S
 ∂x   ∂x 
! ∂!  ∂S 
∇ =  ∂y  ∇S =  ∂y 
   
∂ ∂S
∂z ∂z

Math 102 Divergence, Laplacian

   
∂ ∂S
 ∂x   ∂x  ∂Vx ∂Vy ∂Vz
! ∂!  ∂S  ! !
∇ =  ∂y  ∇S =  ∂y ∇ · V = + +
    ∂x ∂y ∂z
∂ ∂S
∂z ∂z
Transport Phenomena 10/31/08
2 2 2
2 ∂ S ∂ S ∂ S
 ρ = µ∇ !u+ρ!g − ∇p
! = −σ ∇ϕ
Φ ! A Dt
Second
nd
Law of Transport
2 Law (variation in space-time)
9
DT 2
= µ∇ !u+ρ!g − ρC = k∇ T +µφu
D!u Navier-Stokes
ρ 2 !
∇p p  
Dt Dt
DT   nd
2 Fourier’s
ρCp
Dt
2
DCA
= k∇ T +µφ − r∆H u rxn
2
DC A = D A ∇ C A +νA r
Dt
= D ∇ C +ν r
A
2
Dt
A A 2 Fick   nd

Dϕ
Dt
2
= σ∇ ϕ Dϕ 2
= σ∇ ϕ
Fundamental equations of the system
Dt
D!u !
ρ = µ∇2!u+ρ!g − ∇p
Dt
Fundamental equations
Transport Phenomena 10/31/08
 ! ∂!  ∂S 
∇ =  ∂y  ∇S =  ∂y 
   
Math 102 – Divergence & Laplace
∂
∂z
∂S
∂z

10 Math 102 Divergence, Laplacian

   
∂ ∂S
 ∂x   ∂x  ∂Vx ∂Vy ∂Vz
! ∂!  ∂S  ! !
∇ =  ∂y  ∇S =  ∂y ∇ · V = + +
    ∂x ∂y ∂z
∂ ∂S
∂z ∂z

2 2 2
2 ! ! ∂ S ∂ S ∂ S
∇ S = ∇ · ∇S = 2
+ 2 + 2
∂x ∂y ∂z
Math 103 Substantial Derivative
   
∂ ∂S
 ∂x   ∂x  ∂Vx ∂Vy ∂Vz
! ∂!  ∂S  ! !
∇ =  ∂y  ∇S =  ∂y  ∇ · V = + +
    Transport∂x ∂y 10/31/08
Phenomena ∂z
∂ ∂S
 ∂z ∂z

2 2 2
∂ S ∂ S ∂ S
Math 103 – Substantial Derivative
2 ! !
∇ S = ∇ · ∇S =
∂x 2
+ 2 + 2
∂y ∂z
11
Math 103 Substantial Derivative
   
∂ ∂S
 ∂x   ∂x  ∂Vx ∂Vy ∂Vz
! ∂!  ∂S  ! !
∇ =  ∂y  ∇S =  ∂y  ∇ · V = + +
    ∂x ∂y ∂z
∂ ∂S
∂z ∂z

2 2 2
2 ! ! ∂ S ∂ S ∂ S
∇ S = ∇ · ∇S = 2
+ 2 + 2
∂x ∂y ∂z

DS ∂S ! ∂S ∂S ∂S ∂S
= + !u · ∇S = + ux + uy + uz
Dt ∂t ∂t ∂x ∂y ∂z

Transport Phenomena 10/31/08

 = σ∇2 ϕ
Dt
Equations of Motion
12
Fundamental equations of the system

D!u 2 !
ρ = µ∇ !u+ρ!g − ∇p
Dt
DT 2
ρCp = k∇ T +µφu − r∆Hrxn
Dt
DCA 2
= DA ∇ CA +νA r
Dt
! · (ρ!u) = 0
∇
Transport Phenomena 10/31/08
 Example
13

  Start-up in circular tube r

θ

  Cylindrical coordinates
z
  Only vz(r) ≠ 0

Example: startup in circular tube only uz (r) != 0

! "
∂uz ∂u
!!z 1 ∂ ∂uz
ρ + uz! = ∆p + µ r
∂t ! ∂z r ∂r ∂r

In S.S. conditions (∂/∂t = Transport

0) Phenomena 10/31/08
 Example
Example: startup in circular tube only u (r) != 0 z
14
! "
∂uz ∂u
!!z 1 ∂ ∂uz
ρ + uz! = ∆p + µ r θ
∂t ! ∂z r ∂r ∂r r

In S.S. conditions (∂/∂t = 0) z

! "
∂ ∂uz ∆p
r =− r
∂r ∂r µ

∂uz ∆p r"2 A" ∂uz

r" =− + " B.C. = f inite r=0
∂r µ 2 "r ∂r
∆p r2
uz = − +B B.C. uz = 0 r=R
µ 4
∆p # 2 2
$ Transport Phenomena 10/31/08
uz = R −r
4µ
 θ
r

1.0

0
0.0001
0.001
0.01
0.05
0.1

vz/vmax(r=0)
0.2
0.5 0.5
infinite

0.0
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
r/R

15 Transport Phenomena 10/31/08

 Numerical Solution
16

  Finite elements approach

  Software packages

  Fluent

  CFD

  Physics

  Set up the correct problem and boundary conditions

  Many times is not necessary to know the exact T,C,v

of every single point in your system

Transport Phenomena 10/31/08

 Boundary Layer
17

  All the phenomena happen in the boundary layer

  Everything
outside the boundary layer is in equilibrium
and constant
  The boundary layer is very “thin”
  The size of the boundary layer (δ) is smaller than the
characteristic size of the system
  Order of magnitude approach
  Taylor series
Transport Phenomena 10/31/08
 Reynold’s Number
18

Boundary layer approach

Reinolds Number
δ

D"u
ρ = µ∇2"u
Dt
!! !! ρux
ρu
∆u
≈µ
δ2
∆u
Re =
δ
x
! "2
µ
µ
ρux
≈ = 1/Re Re =
x ρux µ
Prandtl Number
Transport Phenomena 10/31/08
 δ µ ρux
≈ = 1/Re Re =
x ρux µ
Prandtl’s Number
Prandtl Number
19

uT = uδT /δ

DT
ρCp = k∇2 T δ
1/2 Dt
δT
!
∆T! !
∆T !
ρCp uT ≈k 2
x δT
δT k
ρCp u
δx
≈ 2
δT Cp µ
! "3
δT k
Pr =
δ
≈
Cp µ
k
δT Cp µ
≈ P r−1/3 Pr =
Transport Phenomena 10/31/08
δ k
 Dt
!
∆T! !
!
∆T
Schmidt’s Number…
ρCp uT
x
≈k 2
δT
Cp µ
20 δT
ρCp u ≈ 2
k
Pr =
! "3
x δT
k
δT k
≈ Re−1/2 δ
δ Cp µ
δC
δT Cp µ
≈ P r−1/3 Pr =
δ k
… As usual everything is
Schmidt Number
the same ρDA
δC Sc = ρD
µ µ
A
≈ Sc−1/3 Sc =
δ

Transport Phenomena 10/31/08

 Nusselt’s Number
21

Considering the
Considering the fluxes:
fluxes: δ

∂T δT
−k ∂T
qq =
= −k
∂x
= h∆T
= h∆T
∂x
!!
∆T!
! ! ≈ k!
! ∆T
hh!
∆T
∆T ≈k δ
δTT
hx
hx xx δδ KA x x δ
NNuu =
= ≈
≈ Sh = ≈
kk δδ δδTT
!"#$ !"#$
!"#$ !"#$ DA δ δC
!"#$
1/2
!"#$
Re1/2
Re 1/3
Prr1/3 Re1/2 Sc1/3
P
In general
In general Transport Phenomena 10/31/08
 Sherwood’s Number
22

Considering the
Considering the fluxes:
fluxes: δ

∂T δC
−k ∂T
qq =
= −k
∂x
= h∆T
= h∆T
∂x
!!
∆T!
! ! ≈ k!
! ∆T
hh!
∆T
∆T ≈k δ
δTT
hx
hx xx δδ KA x x δ
NNuu =
= ≈
≈ Sh = ≈
kk δδ δδTT
!"#$ !"#$
!"#$ !"#$ DA δ δC
!"#$
1/2
!"#$
Re1/2
Re 1/3
Prr1/3 Re1/2 Sc1/3
P
In general
In general Transport Phenomena 10/31/08
 hx x δ
Nu = ≈
k δ δT
In General…
!"#$ !"#$
Re1/2 P r1/3
23 In general

hx 1/3 KA x
Nu = = f (Re) P r Sh = = f (Re) Sc1/3
k DA


Re 1/2
Plate in laminar flow






2 + Re1/2 Sphere in laminar flow
f (Re) =

 0.8

0.005Re Packed bed in turbulent flow




· · · · · · · · · · · ·

Extension to macroscopic balances

) *
Transport Phenomena 10/31/08 *
Q̇ = q dA = A U ∆T 1/U = 1/h + s /k
 Extension to Macroscopic Balances
24

Transport Phenomena 10/31/08

 hx 1/3 KA x
Nu = = f (Re) P r Sh = = f (Re) Sc1/3
Overall Transfer Coefficient
k DA
25


Re 1/2
Plate in laminar flow






2 + Re1/2 Sphere in laminar flow
f (Re) =

 0.8

0.005Re Packed bed in turbulent flow




· · · · · · · · · · · ·

Extension to macroscopic balances

) * *
Q̇ = q dA = A U ∆T 1/U = 1/hi + si /ki
A

1/U = 1/hint + s/kmetal + 1/hext

Transport Phenomena 10/31/08
 Nu = = f (Re) P r
k
hx KA x
Nu = = f (Re) P r1/3 Sh =  = f (Re) Sc1/3
Log-Mean Temperature Difference
k D



A
Re 1/2
Plate
 

26
 


Re 1/2 2 + Re1/2
Plate in laminar flow Sphere

 f (Re) =



2 + Re1/2 
 0.8

Sphere in laminar flow
 0.005Re Packed
f (Re) = 

 


0.005Re 0.8 · · · ·flow
Packed bed in turbulent ········





· · · · · · · · · · · ·Extension to macroscopic balanc
)
Extension to macroscopic balances
Q̇ = q dA = A U ∆T
) A
* *
Q̇ = q dA = A U ∆T 1/U = 1/hi + si /ki
A 1/U = 1/hint + s/kmetal + 1/hext
∆T1 − ∆T2
1/U = 1/hint + s/kmetal + 1/hext ∆Tln =
ln (∆T1 /∆T2 )
Transport Phenomena 10/31/08
 Conclusions
27

  Momentum, Heat and Mass Transfer

  Highly inter-correlated
  Similar physical principles
  Similar driving force
  Similar mathematical formulas

  2ndorder PDE – numerical solutions

  Highly dependent from fluid-dynamic properties

  Simplifications
  Boundary layer
  Dimensionless numbers

Transport Phenomena 10/31/08

28 PART II
Methanol Synthesis

Transport Phenomena 10/31/08

 Methanol Production
29

  Produced from SynGas

  Catalyst Cu/ZnO-Al2O3
  Equilibrium limited
  P = 50 – 100 bar
  T = 200 – 300 ˚C

  Main Commodity
  20 Million ton/year
  Typical plant size is 1 Million ton/year
  12 m3/s

Transport Phenomena 10/31/08

 Catalyst specs
30
KATALCO 51-8
Methanol Synthesis Catalyst

Product Benefits • Long life as a result of the optimized formulation incorporating a patented
use of a fourth component MgO
• Low operating temperatures minimize the catalyst sintering rate
• High catalyst selectivity gives very low impurities in the crude product
• Close approach to equilibrium is achieved and maintained
• Easy to reduce and start-up

Product Uses • Synthesis of methanol from H2, CO and CO2 mixtures arising from steam
reforming of hydrocarbons, coal gasification or POx
General • KATALCO 51-8 is a copper catalyst on a ZnO-Al2O3 support with a MgO
Description promoter
Physical Properties (Typical) Chemical Composition (Typical)
KATALCO 51-8
Form Cylindrical pellet CuO: 64 wt%
Diameter 5.4 mm Al2 O3 : 10 wt%
Length 5.2 mm ZnO: 24 wt%
Bulk Density 1250 kg/m 3 MgO: 2 wt%
Crush Strength 80 kgf
(axial)
Shipping & • Avoid contact with skin and clothing. Avoid breathing dust. Do not take
Handling internally. Please refer to the relevant Material Safety Data Sheet for
further information.
• KATALCO 51-8 catalyst is available in non-returnable polythene lined
mild steel drums or bulk bags for easy loading.

Transport Phenomena 10/31/08

 Reactor types
31

Transport Phenomena 10/31/08

 Multi-Bed Reactor
32
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Transport Phenomena 10/31/08
!
 Reactor dimensioning
33

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Transport Phenomena 10/31/08
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Transport Phenomena 10/31/08
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Transport Phenomena 10/31/08
*%&' % ()(* 0.1
 
 )
'
 2 3  $
· · ·
·)*+ ,#, 0.005Re0.8


· · · · · · · · ! Packed) bed in turbulent
*XTZ)FD;)G8=>)* flow
4X)H4)FD;)

/External properties
Extension
- '



4
to macroscopic
2)*+ & )*+·3"
-.
$
#
'
· · · · · · · · balances
/'
· · · "'/&
)
[786<)D)+E7>86<);86<)=>:)?;:77E
)*+
37 )
)Extension to macroscopic balances ) * *
Q̇ = -56789:;86<)
q dA = A U ∆T #5)=:KD@ED=:)
1/U 1/hi =>:)
+ :V=:;6D@)si /ki CD77
Nusselt
A ) and Sherwood Numbers BDA=5;7 \
I) *
Colburn Factors *
)
Q̇ = q dA = A U ∆T ) 1/U = 1/hi + si /ki
1/U = 1/hint &A2'+"s/kmetal + 1/hext
+, ' ' #(0" .( $"'* ("')%&
%− ∆T2 ' '
$

∆T / 01 #
+,
∆Tln =1/U = 1/hint + s/kmetal + 1/hext
1 '
2)*+ 3,#, $!
ln % 3"1 /∆T2 )
(∆T )
-. ' ' "'$*$
∆T1 − ∆T2 ) 4 /'
∆Tln =. /- ' -. '
$
#

%
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01 ' ' "')#%
J& '!56. ) J
h = 725 2 h = 610 2
-56789:;86<)
) m sK J m sK
J
)h =mol725 2 ) h =mol610 2
)
k = 13.2 m sK k = & 2' " m sK
65.6
m2 s +, ' m 2's #(0"
) mol % mol
Transport Phenomena 10/31/08
)k = 13.2 m2 s k = 65.6 2
% 3" ms
 )
% / ! )%)(' # 1 ! (') %
* " -)
External Limitations
)
38
#7;)?@A5?=?)B5CC;:;DE;)F;6G;;D)67;)H@<)@DB)67;)I;>>;6)<=:C@E;
)
+'
&7+,- ! $ 234 % ! 5+,- &/ 56 ! #%')
(1
+ ' 5+,-
&.+,- ! ! (%#* , " .
($ .
8941 )
 No external limitations in terms of gas composition
&/ 56 ! *&/ ))) %
and temperature *0# profile
)%)* *0#
! Due
5+,-   to the turbulent flow regime
$( 234 -
)
#7;)?@<<)6:@D<C;:)5<)D96)@D)5<<=;M)9D>K)67;)7;@6)6:@D<C;:)<6@:6<
67;)75H7)7;@6)9C):;@E659D)5DJ9>J;BN)
Transport Phenomena 10/31/08
)
 Heat Exchanger
39

  1st bed 580  490 K

  35 MW power to take out
  Boiling water to produce low pressure steam
!"#$%&'()*+',"-#) )
  16 kg/s steam produced
!

  Shell tube heat exchanger: 2” (5cm) tubes

6:96

  hout=220 W/m2K 6:27

)";<=>=?@=<A)>=BC
)DEBFGHBG)@HGC)IAE>JKLDHGFM
6:25

  U ≈ 200 W/m2K 6:24

6:29

6:26

N!C'$
6:67

6:65

6:64

6:69

6:66
456 476 866 896 846 856 876 566 596
#OPQ

Transport Phenomena!"#$%&'()'*&+,-"./'0+-1'"/'-1&'2'3&45'.6'-1&'%&+,-.%)'
10/31/08
 Evaporation/condensation
5-22 HEAT AND MASS TRANSFER
40

For example, vapori

radiation and conve
result of heat absorb
the disengaging sur
Pr water ≈ 7
when the superheat
also occurs from falli
flashing of liquids su
Pool boiling ref
heating surface is su
is not flowing at any
motion of the bubbl
of pool boiling are p
fluid temperature is
collapse of the bubb
pool boiling, with bu
resulting in net vapo
The general shape
FIG. 5-10 Dukler plot showing average condensing-film coefficient as a func- to " tb, the tempera
tion of physical properties of the condensate film and the terminal Reynolds temperature and the
number. (Dotted line indicates Nusselt theory for Reynolds number < 2100.)
[Reproduced by permission from Chem. Eng. Prog., 55, 64 (1959).] metric relations tha
boiling curve was ori
[ J. Soc. Mech. Eng.
Transport
hµl / kl !l1/2 = 0.065(N 1/2 Phenomena
1/2 10/31/08
Pr)l Fvc (5-99a) one of the great dile
2 faced with at least s
 Heat Exchanger
41

  1st bed 580  490 K

  35 MW power to take out
  Boiling water to produce low pressure steam
  16 kg/s steam produced
  Shell tube heat exchanger: 2” (5cm) tubes
  hout=220W/m2K
  U ≈ 200 W/m2K

  Low pressure steam 1-2 atm 120˚C

  ΔTln= 140K
  Exchange Area 1300 m3 (about 2000 tubes)
  40 banks of 50 tubes (4-5 m in size)
Transport Phenomena 10/31/08
 Further Reading
42

  Part I
  Bird, Steward, Lightfoot
  Transport Phenomena
  Asano Welty
Mass Transport Fundamentals of M,H&M Transfer
  Part II
  Handout
  Web: Document DB # 15375
  Perry’s Chemical Engineering Handbook

Transport Phenomena 10/31/08

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