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Documente Cultură
and
Gas- Liquid Solid Reactions
A. Gas Liquid Systems
Penetration theory
P. V. Danckwerts, Trans. Faraday Soc., 46 300 (1950).
P. V. Danckwerts, Trans. Faraday Soc., 47 300 (1951).
P. V. Danckwerts, Gas-Liquid Reactions, McGraw-Hill, NY (1970).
R. Higbie, Trans. Am. Inst. Chem. Engrs., 31 365 (1935).
pA
pAi
Bulk Gas
pAi = HA CAi
Bulk Liquid
CAb
x
x + x
L
x = G
x=0
x = L
Two-Film Theory
- Single Reaction in the Liquid Film A (g)
b B (liq)
P (liq)
kg -moles A
m
n
RA
=
k
C
C
mn A
B
m3 liquid - s
Closed form solutions only possible for linear kinetics
or when linear approximations are introduced
A( g ) bB (l ) P (l )
d2A
DA 2 r
dx
d 2B
DB 2 br
dx
at x 0 A A* at x A AL
dB
at x 0
0 at x B BL
dx
For r kmn Am B n
tD 2
* m 1
n
Ha @
D
k
A
B
=
A mn
L
tR m 1
1/ 2
q*
BL DB
bA* DA
C B
2C B
DB
RB
2
t
x
Penetration theory:
kL D1/2
Higbie model
t* - life of surface liquid
element
Danckwerts model
s - average rate of surface
renewal
RA'
D
kL @
= *
C C
RA'
D
kL @
2
= *
*
C C
t
'
A
R
k L =@ *
Ds
C C
Instantaneous
Fast (m, n)
Rapid pseudo
1st or mth order
Slow Diffusional
Very Slow
Characteristic
Reaction
Diffusion time
Reaction time
Diffusion &
Times
D
tD 2
kL
C CE
tR
r
1
tM
k L aB
tD<<tR kL=kL0
tD<<tR<<tM
tD<<tM<<tR
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Hatta Number :
Ei Number:
Enhancement Factor:
1
1
1
K L kL kg H
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B.
C.
D.
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S29
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: k v A mol m 3 cat.s A
TRANSPORT RATE
mol
m 3 react . s
Ag
: K 1 a B
A1
Ha
- Liquid - solid : k s a p Al As
- Gas - liquid
K l a B k s a p 1 B k v p
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Kinetic rate
: kv B mol m 3 cat.s
(per unit catalyst volume)
Rate in catalyst
(per unit reactor volume)
: kv p Bs 1 B mol m 3 react .s
Transport rate
(per unit reactor volume)
kls a p p kv 1 B
kg P
specific activity
S a
kg cat h
kg cat
x 3
catalyst concentration
m reactor
Sa
m v
m vmax
xmax
xmax
Clearly
is determined by transport limitations and
by
reactor type and flow regime.
m v
Sa
Improving
only improves
if we are not already transport S38
S39
S39
2-10
40-100
10-100
10-50
4000-104
150-800
S40
S41
S42
Starting References
1. P. A. Ramachandran and R. V. Chaudhari, ThreePhase Catalytic Reactors, Gordon and Breach
Publishers, New York, (1983).
2. Nigam, K.D.P. and Schumpe, A., Three-phase
sparged reactors, Topics in chemical engineering, 8,
11-112, 679-739, (1996)
3. Trambouze, P., H. Van Landeghem, J.-P. Wauquier,
Chemical Reactors: Design, Engineering, Operation,
Technip, (2004)
4. Dudukovic, Mills and Ramachandran, Course Notes
(1990s and 2000s)
Degree of Difficulty
Straightforward
Implementation
Insight
Straightforward
Very little
Significant
Reactor
Model
Reactor
Model
Macro distributions of
the gas, liquid and
solids
Heat exchange
Other types of transport
phenomena
Qin
Tin
Cin
Qout
Tout Product
Cout
Reactor
Reactor
Process
Reaction
Flow
Performance
Variables
Rates
Conversion
Flow rates
Kinetics
Selectivity
Inlet C & T
Transport Micro
Activity
Heat exchange
=f
Patterns
Macro
Liquid Phase
Solid-Phase
Plug-flow
Fixed
Reactor Type
Plug-flow
Back mixed
Mechanically
agitated
Plug-Flow
Back mixed
Bubble column
Ebullated - bed
Gas-Lift & Loop
Back mixed
Trickle-Bed
Flooded-Bed
(t)
QG
XL(t)
QL
0
XG(t)
or
t
QL
1 = G + L + C
Vr G
QG
- t / L
e
EL(t)
QG
VR = vG + VL + VC
G
(t)
Vr (1 G L )
QL
K1j Vj
j=2
Q1
K1j
C j
=
C1 equil.
Q1 +
K1j Vj
j= 2
p
K 1j Qj
j= 2
- H (k ) t
p
c
1 - XA = e
Hp(kc) = pdf for the stagnant phase
= e
0
Eext ( t ) dt
- (k W W / Q1 ) t
Eext ( t ) dt
Trickle - Bed
Bubble Column
Flooded - Bed
Plug-flow of gas
Backmixed liquid & catalyst
Batch catalyst
Catalyst is fully wetted
Plug-flow of gas
Plug-flow of liquid
Fixed-bed of catalyst
Catalyst is fully wetted
Key Assumptions
4. Plug-flow of liquid
5. Isothermal operation
6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
CB0 / C Al 1
DBL C B /D AL C Al 1
(Net input
(Input by Gas- - (Loss by Liquid- = 0
+
by
Liquid
solid Transport)
convection)
Transport)
Ql Al z Ql Al
k
a
A
Al Ar dz- k s a p Al As Ar dz= 0
l B
z dz
(1)
(2)
Conversion of Reactant B
(in terms of Reactor Efficiency)
Stirred Tank
Bubble Column
5. Isothermal operation
6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
A in liquid bulk:
bulk Analysis is similar to the previous case
For Reactant B:
(Net input
=
by flow)
(Rate of rxn of B
at the catalyst
surface)
(Note: No transport to
gas since B is nonvolatile)
C, D - Co current or
countercurrent two-phase
flow (plug flow or dispersed
flow) with exchange
between the phases and
stagnant phase.
Trickle-beds, packed or
empty bubble columns
E - Exchange between two
flowing phases, one of
which has strong internal
recirculation.
Empty bubble columns and
fluidized beds
C ig ( j ), T g ( J )
Gas Bulk
C iL ( j ), T L ( J )
Gas Film
N if,( j )
qif,( j )
Liquid Film
Cell Jth
X 0
N if,( j )
NR
d 2 Ci f
f
Di
ji
j
dx 2
j 1
d 2T f NR f
R j (H R )
2
dx
j 1
X 1
qif,( j )
X 0
C ig ( j 1 ), T g ( J 1 )
Liquid Bulk
Heat
Film
X 1
C iL ( j 1 ), T L ( J 1 )
Cif,Z0 C f Cb
i
i,Z m
Z 0 Z Z m
B.C.1D dC
i
NR
d 2 Ci f
Di
ji R j
2
dZ
j 1
f
i , z 0
dZ
k g (C C
g
i
g
i , z 0
Bim ,i c
*
g ,i
Bim ,i
Hi C
f
f
i , z 0
hi
f
0
dcif
p g ,i
m k g H ref ,i c *
g ,i
H ref ,i Cref ,i
Di
Solubility or Violability
ci
Hi H
f
ref
i
H Si
1
1
exp
( f
) H ref h f0
R
TZ 0 Tref
d 2T f
L
2
dZ
f
dT
B.C.1
L
dZ
dT f
B.C.2 L
dZ
hg T
g
out
Z 0
L
Z h
(T L TZf m )
h m
f
z 0
NR
j 1
( H r , j )( R j )
dCi f
( H s ,i )( Di )
dZ
i 1
NS
Z 0
Cells in series:
G and L mixed flow
Cell N
Cell j
Cells in
series-parallel
combination
Exchange
between
Upward and
downward
moving liquid
Cell 1
Liquid
Gas
Liquid
Gas
Prototype cell
Novel features
Non-isothermal effects in the gasliquid film and in the bulk liquid
Effect of volatility of the liquid phase
reactant on the interfacial properties
Gas-Liquid Reactor
Model
Non-Dimensionalized parameters
Variables
Cig
c g
Ci ,ref
g
i
and
Ci f
ci
Ci ,ref
f
TL
Tref
Tg
Tref
Qg
g
Qref
fi
L
uref
g
uref
H i ,ref
Reaction based
Bj
V ( a m ) ref
M j cell LL
Rj
Q C ref
H r , j C ref
L C pL Tref
Heat of reaction
parameter
Ha
2
j
2
R ref
j m
D ref C ref
Hatta number
E aj
RTref
Arrhenius
number
( H r , j ) Dref Cref
LTref
Heat of reaction
parameter
aV k
Lcell L
u ref A r
BiM ,i
Damkohler number
H k
m i ,ref g
Di
i C i , ref C ref
si
Di
D ref
Diffusivities
ratio
Biot number
hg m
Biot number
S ,i
(H S ,i ) Di Ci ,ref
LTref
Heat of solution
parameter
S
L
a glVcell L
mL C p , L m
Liquid heat
transfer number
S
g
a glVcell L
mg mC p , g
Gas heat
transfer number
Le L L C pL Dref
Lewis number
d B
d A
D
vk 2 A B
DA
k2 A B
B
2
2
dx
dx
Non-dimensionlizing
2
d b Ha
ab
2
dy
q
d a
2
Ha
ab
2
dy
where y x
D B
q B 0*
zD A A
2 k 2 B0
Ha
DA
2
d 2a
d 2b
q 2
2
dy
dy
E
E
Ha
tanh Ha
Ha bi
tanh Ha bi
k 2 Bi
Ha bi
1
2
Ha
For depletion of B bi q q 1
DA
tan( Ha bi )
Temp
.
Vaporization of B
Conc.
(Bim=1.5)
(Bim=0)
No vaporization
BiHg
Temp
Ha Rxn Temp.
BiHg
2 b
k
m hg
ref mCB
2
Ha
DA
No C reaction here
Shah, Y.T., Pangarkar, V.G. and Sharma, M.M., Criterion for supersaturation in gasliquid reactions involving a volatile product, Chem. Eng. Sci., 29, 1601-1612, (1974)
C
2C
C
Dax
u
R
2
t
z
dz
@z=0
Let
u0C0 uC Dax
Peax
uL
Dax
C
z
@z=L
C
0
z
C
1 2C C
R
2
t
Peax
d
@ = 0
1 C
C0 C
Peax
@ = 1
C
0
R
2
t
Peax
d
@ = 0
1 C
C0 C
Peax
@ = 1
C
0
Dax
k
a
A
Al k s a p Al As
l
l B
2
dz
dz
k s a p Al As c k1wAs
@z=0
dAl
ul Ali ul Al Dax
dz
@z=L
dAl
0
dz
L /U
characteristic convection time
2
Peax
plug flow
Peax0
Final Comments
To improve predictability of multiphase reactor
models and reduce the risk of scale-up, they
should be increasingly developed based on
proper physical description of hydrodynamics in
these systems.
Improved reactor scale descriptions coupled with
advances on molecular and single eddy (single
particle) scale will facilitate the implementation of
novel environmentally benign technologies by
reducing the risk of such implementations.
Reaction System
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References
1. Suresh, A.K., Sharma, M.M., Sridhar, T., Engineering
Aspects of Liquid-Phase Air Oxidation of
Hydrocarbons, Ind. Eng. Chem. Research, 39, 39583997 (2000).
2. Froment, G.F. and Bischoff, K.B., Chemical Reactor
Analysis and Design, Wiley (1990).
3. Levenspiel, O., Chemical Reaction Engineering, Wiley,
3rd Edition (1999).
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References
1.
2.
3.
4.
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