PERFORMANCE STUDIES OF TRICKLE BED REACTORS

Mohan R. Khadilkar

Thesis Advisors: M. P. Dudukovic and M. H. Al-Dahhan

Chemical Reaction Engineering Laboratory

Department of Chemical Engineering
Washington University
St. Louis, Missouri

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 Objectives and Accomplishments

Examined the current state of the art in experimentation and

modeling of trickle beds critically and successfully answered
the often asked questions
1. Do upflow and downflow differ? When and Why ?
2. How to get reproducible scale-up data from small scale
reactors independent of flow mode?
3. To what extent can current models predict the observed
behavior?
Formulated the rigorous approach to trickle bed modeling on
pellet and reactor scale and illustrated the effectiveness of this
approach for prediction of steady and unsteady state performance
Examined experimentally and via models, unsteady state operation
in trickle beds and identified regions of, and, reasons for
performance enhancement

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 Performance of Trickle Bed Reactors

1. Comparison of Trickle Bed and Upflow Chemical Kinetics

Effect of Bed Dilution
Model Evaluation Fluid Dynamics

2. Rigorous Steady State Model

Phase Interaction
& Contacting
3. Unsteady State Performance Experiments

4. Rigorous Unsteady State Model Transport

Coefficients
5. Transient Fluid Dynamic Simulation
Reactor Design
& Scale-up

Performance

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Trickle Bed Reactors
Cocurrent Downflow of Gas and Liquid Catalyst Wetting Conditions in Trickle Bed Reactor
on a Fixed Catalyst Bed L iq u id Film o r R iv u le t
L iq u id Fille d p o re s
Operating Pressures up to 20 MPa
......
...
D ry Pe lle t
Operating Flow Ranges: ........ ...... ....... Ca p i l l a r y Co n d e n s a ti o n
High Liquid Mass Velocity (Fully Wetted Catalyst)
(Suitable for Liquid Limited Reactions)
Low Liquid Mass Velocity (Partially Wetted Catalyst) Limiting Reactant criterion:
DeB C Bi
(Suitable for Gas Limited Reactions) 1
Gas limited reaction if DeAC A*
GAS LIQUID
D C
Liquid limited reaction if eB Bi 1
DeA C A*

Flow Map (Fukushima et al., 1977)

10000

CATALYST SPRAY
BED WAVY
1000

Re(Gas)
TRICKLE PULSE
GAS 100

DISP .
BUBBLE
10
1 10 100 1000
LIQUID Re (Liquid)

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 FLOW REGIMES AND CATALYST WETTING EFFECTS

DOWNFLOW (TRICKLE BED REACTOR) UPFLOW (PACKED BUBBLE COLUMN)

PARTIAL WETTING COMPLETE WETTING

CATALYST
LIQUID
GAS

(Trickle Flow Regime) (Bubble Flow Regime)

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Motivation
To understand the differences between downflow and upflow operation.
Are upflow reactors indicative of trickle bed performance under different
reaction conditions?
To understand the effects of bed dilution with fines on reactor
performance
To develop guidelines for scale-up/scale-down of reactors for gas or
liquid reactant limited reactions

Objectives
Experimentally investigate the performance of downflow (Trickle Bed)
and upflow (Packed Bubble Column) reactors for a test hydrogenation
reaction
Study the effects of pressure, feed concentration, gas velocity and bed
dilution on the performance of both modes of operation
Evaluate available reactor models in comparison with experimental
data
Reaction Scheme: CH3
C CH2
CH3
HC CH3

Pd/Alumina
+ H2
Catalyst : 2.5 % Pd on Alumina
(cylindrical 0.13 cm dia.)
Fines : Silicon carbide 0.02 cm
Alpha-methylstyrene cumene
B (l) + A(g) P(l)
Range of Experimentation :
Superficial Liquid Velocity (Mass Velocity) : 0.09 - 0.5 cm/s (0.63-3.85 kg/m2s)
Superficial Gas Velocity (Mass Velocity) : 3.8 -14.4 cm/s (3.3x10-3-12.8x10-3 kg/m2s)

Feed Concentration : 3.1 - 7.8 % (230-600 mol/m3)

Operating Pressure : 30 - 200 psig (3-15 atm)
Feed Temperature : 24 oC

Limiting Reactant criterion:

DeB CBi
Gas limited reaction if 1
DeA C*A

DeB CBi
Liquid limited reaction if 1
DeA C*A

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 Experimental Setup

High Pressure
PC Timer
Gas Supply

PC
PC Distributor
Rotameter

Damper TT High Pressure

Gas Supply
PT

LT LT
LT Cooling
Jacket Saturators
Feed Tank HP Feed
Tank

DPT
Reactor
Vent
Solvent

PC

High Pressure TT
Vent Diaphragm Pump
PT

TT PT PC PC Rotameter
LC LT

Waste Tank Demister

Gas-Liquid
Separator

PC PC
Gas
Chromatograph

Computer

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 Downflow and Upflow Experimental Results under Gas and Liquid
Limited Conditions without Fines

1 1
UPFLOW 0.9 DOWNFLOW
0.8 UPFLOW
DOWNFLOW 0.8
Conversion(X)

0.7

Conversion(X)
CBi=7.8%v/v, P=30psig CBi=3.1(v/v)%,P=200psig
0.6 0.6 Liquid Limited 0.8
Gas Limited 8.8 0.5
0.4 0.4
0.3
0.2 0.2
0.1
0 0
0 100 200 300 400 0 50 100 150 200
Space time , s Space time, s

Downflow outperforms upflow due Upflow outperforms downflow due

to partial external wetting and to more complete external wetting and
improved gas reactant access to better transport of liquid reactant to
particles the catalyst

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 Downflow and Upflow Experimental Results under Gas and Liquid
Limited Conditions with Fines

1
0.9 DOWNFLOW
1
DOWNFLOW 0.8 UPFLOW
0.9

Conversion(X)
0.8 UPFLOW 0.7 CBi=3.18%(v/v), P=200 psig.
0.8
Conversion(X)

0.7 0.6
0.6 CBi=6.7 %(v/v), P=30 psig 0.5
0.5 7.5 0.4
0.4 0.3
0.3 0.2
0.2 0.1
0.1 0
0
0 50 100 150 200
0 50 100 150 200
Space time,s Space time,s

ABOUT EQUAL PERFORMANCE DUE TO COMPLETE WETTING

Fines Packing Procedure: Vol. of Fines ~Void volume (Al-Dahhan et al. 1995)

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 Effect of Pressure and Gas Velocity on Performance

1 1
p=30psig =4.0
0.8 p=100psig =1.5 0.8 Downflow
Conversion(X)

Upflow

Conversion (X)
p=200psig =0.8
0.6 0.6 P=100 psig, = 1

0.4 0.4

0.2 0.2
CBi=3.1%,Ug=3.8 cm/s
0 0
0 50 100 150 200 0 3 6 9 12
Space time,s Superficial Gas Velocity, cm/s

Transition to Liquid Negligible Effect of Gas Velocity

Limited Conditions

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Slurry Kinetics
1 # 1 p =3 0 p s ig , C B i=3 . 9 %

0.9 # 2 p =1 0 0 p s ig , C B i=3 . 9 9 %

0.8 # 3 p =2 0 0 p s ig , C B i=4 %
Conversion(X)
0.7 # 4 p =3 0 0 p s ig , C B i=3 . 4 5 %
0.6
0.5
0.4
0.3
0.2
0.1
0
0 100 200 300
Time (min)

LHHW FORM Pressure (psig) kvs K1 K2

(m iq./m3cat./s)
3
*(mol/m3 liq)r-1
kvsCamsCh2
r 30 0.0814 0 0 0

( 1 K1Cams K2Ccume )
100 1.14 4.41 11.48 1
200 0.022 0.0273 0.021 2

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El- Hisnawi (1982) model
REACTOR SCALE
L G
Reactor scale plug flow equations
Liquid phase gas reactant concentration
Direct Access
Access of Gas . of gas
Constant effectiveness factor .. . . . .. . .
via Liquid ..................... Dry Areas
.......................
to
Modified by external contacting efficiency .....................................
......................
. ..........

Allowance for rate enhancement on

Liquid Dry
externally dry catalyst Film
Direct access of gas on inactively wetted pellets.
L G

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Beaudry (1987) model
Pellet scale reaction diffusion equations DRY HALF-WET FULLY W ET

For fully wetted and partially wetted slabs

d 2C ' A d 2C ' A
2
(1 ) 2 A2C ' A 0, 0 x 1; 2
A2C ' A 0, 0 y 1
dx dy
Effectiveness factor weighted based on
contacting efficiency
Catalyst P ellet

Flowing Liquid
Overall effectiveness factor changes along
the bed length
CA
Evaluation of overall effectiveness with change in CB

concentration and contacting CB

CA
Overall Effectiveness factor at any location

o ( 1 ce )2 od 2 ce ( 1 ce )odw 2ce ow 0 2V/S

x y
1 0 0 1

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Upflow and Downflow Performance at Low Pressure
(Gas Limited Condition)
Experimental Data and Model Predictions

1
down,El-Hisnawi
0.9
upflow,El-Hisnawi
0.8
downflow,Beaudry
0.7
Conversion(X)

upflow,Beaudryi
0.6 downflow,exp
0.5 upflow,exp
0.4
0.3
0.2
0.1 Ug=4.4cm/s,Co=7.6%(v/v),p=30psig
0
0 100 200 300 400
Space time(s)

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Upflow and Downflow Performance at High Pressure
(Liquid Limited Conditions):
Experimental Data and Model Predictions

1
0.9 Ug=3.8cm/s,Co=3.1%(v/v),p=200psig
0.8
0.7
Conversion(X)

0.6
down,El-Hisnawi
0.5
up, El-Hisnawi
0.4
down, Beaudry
0.3
up, Beaudry
0.2
downflow,exp
0.1 upflow,exp
0
0 50 100 150 200 250
space time(s)

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Summary
DOWNFLOW OUTPERFORMS UPFLOW AT LOW PRESSURE.
(Hydrogenation of alpha-methylstyrene is a gas limited reaction.
Partial wetting is helpful in this situation.)

UPFLOW OUTPERFORMS DOWNFLOW AT HIGH PRESSURE.

(Hydrogenation of alpha-methylstyrene becomes a liquid limited
reaction. Complete wetting is beneficial to this situation.)

THE PREFERRED MODE FOR SCALE-UP (UPFLOW OR DOWNFLOW)

DEPENDS ON THE TYPE OF REACTION SYSTEM AS WELL AS ON THE
RANGE OF OPERATING CONDITIONS THAT AFFECT CATALYST WETTING.

FINES NEUTRALIZE PERFORMANCE DIFFERENCES DUE TO MODE OF

OPERATION AND REACTION SYSTEM TYPE , DECOUPLE
HYDRODYNAMICS AND KINETICS, AND HENCE ARE TO BE PREFERRED
AS SCALE-UP TOOLS.

THE TESTED MODELS PREDICT PERFORMANCE WELL

(although improvements in mass transfer correlations are necessary)

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 Drawbacks of Evaluated Models
Isothermal Operation
Liquid Volatility Effects not Considered
Coupling of Hydrodynamics and Transport Ignored
Fully Internally Wetted Pellets Assumed
Single Component, Dilute Solution Transport Assumed
Multicomponent Effects not Considered

Simplified Models Accounting for Some of the Above Effects

Pellet Scale (Level I) Model (Kim and Kim, 1981; Harold,1988)

Reactor Scale (Level II) Model (LaVopa and Satterfield,1988; Kheshgi
et al., 1992)

Extended Steady State Rigorous (Level III) Model

Test Reaction System: Hydrogenation of Cyclohexene

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 L-III Model Reactor Scale Equations (1-D)
Continuity
d L u IL L d G u IG G
N iGLa GL M i N iLSa LSM i N iGL aGL M i N iGS aGS M i
dz dz

Species
d
u IL LCiL N iGL aGL N iLS aLS
d
u IG G CiG N iGL aGL N iGS aGS
dz dz

Momentum
d dp
( G G u IG u IG ) G G g G FD ,Gas K GL (u IL u IG )
dz dz G
u IG
I
( N iGL aGL M i N iGS aGS M i )
Energy
d ( L u IL L H L ) d ( G u IG G H G )
E GL aGL E GS aGS E GAaGA
E GL aGL E LS aSL E LA aLA
dz dz

Fluxes Modeled by Multicomponent Stefan-Maxwell Formulation

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 L-III Model Catalyst Scale Equations
(Extension of Harold,1988)
Liquid Filled Zone Fully Externally Wetted,
Partially Liquid Filled Pellet
d
dx

N iLC i Ri ,liq

N iLC
CiLC C nc1
C
CtL
N tL {[ BL ]1[]
d C
dx

CiL }i , j
j 1

| Wet Zone | Dry Zone |

d N iLC H iLC 0

2
d
keL 2
TLC 0 0Lc
dx dx

Gas Filled Zone

d
dx
C

N iG i Ri , gas Intra-catalyst G-L Interface
Continuity of temperature,

C
C
N iG
CiG
C
N C
tG
nc

{[ BG ]1
d C
CiG }i , j mass and energy fluxes,
CtG dx
j 1
and equilibrium relations
d 2 C d N iG H iG
between compositions

C C

keG TG 0
dx 2 dx

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 Simulation Results: Multiplicity Effects
1.2
460
1 440
N=1 .4 , Wet (L-III)
420

T emperature, K
0.8 N=2 .8 , Wet (L-III)
Conversion

400 N=4 .5 , Wet (L-III)

0.6 380 N=6 .3 , Dry (L-III)

N=8 , Dry (L-III)
Wet Branch(Exp t) 360 N=1 1 , Dry (L-III)
0.4 Dry Branch (Exp t)
Wet Branch (L-II)
340
0.2 Dry Branch (L-II)
Wet Branch, (L-III)
320
Dry Branch (L-III)
300
0
0 0.05 0.1 0.15 0.2
0 5 10 15 Axial Location, m
Hydrogen Feed Ratio, N

Hysteresis Predicted Wet Branch Temperature Rise (~10-

Two Distinct Rate Branches Predicted 15 oC)
(As Observed by Hanika, 1975) Dry Branch Temperature Rise
Branch Continuation, Ignition and (~140-160 oC)
Extinction Points
Wet Branch Conversion (~30 %)
Dry Branch Conversion (> 95 %)

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Wet Branch Simulation
Reactor Scale Hydrodynamics
0.4 0.045
0.012
0.04

Liquid Velocity (m/s) and Holdup

0.35
Gas Velocity (m/s) and Holdup

0.035
0.3 0.01
0.03
0.25 Gas Velocity
Gas Holdup 0.025 0.008
0.2 N(H2 ),z=
Liquid Velocity 0.02 0 .0 1

Intracatalyst Flux, mol/m2s

0.15 Liquid Holdup N(H2 ),z=
0.015 0.006 0 .0 5
0.1 N(H2 ),z=
0.01 0 .1 5
N=2.8, Wet Branch (L-III)
0.05 0.005 0.004 N(ene),z
=0 .0 1
0 0 N(ene),z
=0 .0 5
0 0.05 0.1 0.15 0.2 0.002
Axial Location,m N(ene),z
=0 .1 5
N(ane),z
Reactor Scale Species Concentrations 0 =0 .0 1
N(ane),z
=0 .0 5
6500 16
-0.002 N(ane),z
=0 .1 5
6000 14
Concentration, mol/m3

-0.004
Concentration, mol/m3

5500 12
N=2 .8 , Wet Branch (L-III)
5000 cyclohexene 10
-0.006
4500 cyclohexane 8
0 0.5 1
hydrogen
4000 6
N=2.8, Wet Branch (L-III) Intracatalyst Coordinate, (x/)
3500 4

3000 2

2500 0 Pellet Scale Multicomponent

0 0.05 0.1 0.15 0.2
Axial Location,m
Flux Profiles

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Dry Branch Simulation Pellet Scale Pressure Profiles
Reactor Scale Hydrodynamics
0.35 100000 1.900E+05
99990 1.800E+05
0.3 99980 1.700E+05

99970 1.600E+05

Pressure, N/m2
Gas Velocity, m/s

z=0.01 m

Pressure, N/m2
0.25 99960 1.500E+05
z=0.03 m
1.400E+05 z=0.06 m
99950
1.300E+05 z=0.12 m
0.2 99940
1.200E+05 N=8, Dry Branch (LIII)
Gas Velocity, m/s 99930
1.100E+05
0.15 Pressure, N/m2 99920
1.000E+05
N=8, Dry Branch, (LIII) 99910 9.000E+04
0.1 99900 0 0.2 0.4 0.6 0.8 1
0 0.05 0.1 0.15 0.2
Intracatalyst Coordinate, ((x-)/(Lc-))
Axial Location

Reactor Scale Species Concentrations Pellet Scale Temperature Profiles

25 N=8, Dry Branch (LIII) 550

Concentration, mol/m3

20 500

T emperature, K
15 450

400 z=0 .0 1
10 z=0 .0 3
z=0 .0 6
hydrogen 350 z=0 .1 2
5 cyclohexene
cyclohexane N=8, Dry Branch (LIII)
300
0 0 0.2 0.4 0.6 0.8 1
0 0.05 0.1 0.15 0.2 Intracatalyst Coordinate, ((x-)/(Lc-))
Axial Location,m

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Intra-reactor Wet-Dry Transition

0.0003 420
Internal T ransition, N=7 (LII) 1
Fw (wetting)

Mole Fractions, Wetting Fraction

0.00025 FL (liquid flow) 400 0.9
Liquid and Vapor Flow, mol/s

YA (cyclohexene)
T emperature, K) 0.8
YB (hydrogen)

T emperature, K
0.0002 380 0.7 YC (cyclohexane)
0.6
0.00015 360 0.5
0.4
0.0001 340
0.3
0.2
0.00005 320 Internal T ransition, N=7 (L II)
0.1

0 300 0
0 0.02 0.04 0.06 0.08 0.1 0 0.05 0.1 0.15
Axial Location, m Axial Location, m

Abrupt drop in liquid flow Abrupt change in catalyst wetting

Temperature rise after liquid- Cyclohexene and cyclohexane
gas transition mole fraction shows evaporation
and reaction

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Summary

The reactor scale variation of phase holdups and velocities, multiplicity,

and temperature rise were successfully simulated by the developed
(LIII) model more rigorously than other models developed earlier
Both wet and dry branch temperature, conversion, and corresponding
fluxes were successfully modeled by the set of equations developed
Intra-pellet reaction-transport equations for the wet and dry zones in
presence of multicomponent interactions, evaporation, and
condensation were successfully modeled
The wet to dry transition prediction requires robust numerical
techniques to yield stable solution at pellet scale (for the LIII model),
but depicts the observed abrupt transition with a reactor scale (LII)
model

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