MULTI-PHASE AND CATALYTIC CHEMICAL

REACTORS DESIGN SIMULATION TOOL

Jack R. Hopper
Jamal M. Saleh
Sandeep Waghchoure
Sandesh C. Hegde
Niraj Ramachandran
Lamar University, Beaumont, TX 77710

Ralph W. Pike
Louisiana State University
Baton Rouge, LA 70803
 Overview of Advanced Process Analysis System

Advanced Process Analysis System

On-Line Optimization

Process control
Process Modification

Flowsheet Simulation Reactor Analysis Pinch Analysis Pollution Index

 OBJECTIVE

To develop a User Friendly Simulation Package for multi-

phase catalytic and non-catalytic reactor analysis as a
component for the Advanced On-line Process Analysis
System for Pollution Prevention
 REACAT REACTOR SIMULATION TOOL
FEATURES

 User Friendly input/ output interface

 Graphical and Tabular Data Output
 Extensive Selection of Reactor Models
 Component Material Balances for Gas, Liquid and
Catalyst Phase
 Total Energy Balance
 Prediction of reactor hydrodynamics such as
pressure drop, power consumption, catalyst wetting
factor and flow regimes
 Reactor Models with numerous Options
Classification of Homogeneous and Heterogeneous
Reactor Models

REACTION PHASE REACTOR MODEL

Homogeneous Plug Flow, CSTR, Batch

Heterogeneous:-

Catalytic
Two Phase
Gas-Catalyst or Packed-Bed or Fluidized-Bed
Liquid-Catalyst

Three Phase
Gas-Liquid-Catalyst Trickle-bed, Bubble Fixed-Bed
CSTR Slurry, Bubble Slurry,
3-Phase Fluidized

Non-Catalytic

Gas-Liquid Gas-Liquid CSTR, Gas-Liquid

Bubble Column
 Reactor Definitions

•Catalytic Packed Bed: Gas or Liquid Reactants flow over a fixed bed of
catalysts.

•Catalytic Fluidized Bed: The up-flow gas or liquid phase suspends the fine
catalyst particles.

•CSTR Gas-Liquid: Liquid and gas phases are mechanically agitated

•Bubble Gas-Liquid Bed: Liquid phase is agitated by the bubble rise of the
gas phase. Liquid phase is continuous.
 Reactor Definitions (Contd..)
•Trickle-Bed: Concurrent down-flow of gas and liquid over a fixed-bed of
catalyst. Liquid trickles down, while gas phase is continuous

•Bubble-Fixed Bed: Concurrent up-flow of gas and liquid. Catalyst bed is

completely immersed in a continuous liquid flow while gas rises as
bubbles.

•CSTR Slurry: Mechanically agitated gas-liquid-catalyst reactor. The Fine

catalyst particles are suspended in the liquid phase by means of agitation.
(Batch liquid phase may also be used)

•Bubble Slurry Column: Liquid is agitated by means of the dispersed gas

bubbles. Gas bubble provides the momentum to suspend the catalyst
particles.

•Three-Phase Fluidized Bed: Catalyst particles are fluidized by an

upward liquid flow while gas phase rises in a dispersed bubble regime.
 Reactor Types Included in the Reactor Simulation
Tool, ReaCat
Homogeneous Reactors:

Plug Flow

CSTR
Batch
 Reactor Types Included in the Reactor Simulation Tool,
ReaCat (Contd..)
Two-Phase Reactors:

Gas /Liquid
Catalytic Reactors Fluidized
Bed

Fixed Bed

Liquid

Gas-Liquid Reactors
Gas-
Liquid
Bubble
Gas Liquid
Column
Gas-Liquid
CSTR

Gas
 Reactor Types Included in the Reactor Simulation Tool,
ReaCat (Contd..)

Three-Phase Reactors:
Three Phase Catalytic Reactors

Liquid

Gas

Liquid Liquid Liquid

Gas Gas
Gas
Cocurrent Cocurrent Bubble Slurry Three-Phase Fluidized
Downflow Trickle Upflow Packed Column Column
Bed Bed

Liquid Gas-Liquid Catalytic CSTR

Slurry Reactor

Gas
 REACTION RATE MODEL OPTIONS

Power-law reaction rate or Langmuir- Hinshelwood model to

account for the adsorption effects.

Correlations to estimate the external mass transfer effects

and dispersion coefficients

Catalytic effectiveness factor estimation to account for intra-

particle resistance

Flow Regime Options

Isothermal and non-isothermal/non-adiabatic conditions

Multi-reaction systems with up to 30 reactions and 36

components
Industrial Examples of Multi-phase and Catalytic
Reactors

Catalytic Gas/ Liquid Fluidized-bed Reactor

• Fluid Catalytic Cracking
• Production of Allyl Chloride.
• Production of Phthalic Anhydride
• Acrilonitrile by the Sohio Process

Catalytic Fixed Bed Reactor

• Partial oxidation of O-xylene to Pthalic Anhydride
• Hydrogenation of Aromatics and Olefins
• Dehydrogenation of Ethylbenzene to Styrene
Industrial Examples of Multi-phase and Catalytic
Reactors
Three-phase Reactor:

Trickle-Bed
Catalytic hydro-desulfurization
Catalytic hydrogenation
Catalytic hydrocracking
Fixed-bed upward bubble-flow
Fischer-Tropsch
Coal liquefaction
CSTR Slurry
Hydrogenation of fatty oils and unsaturated fats.
Hydrogenation of acetone
Bubble-Slurry Column
Catalytic oxidation of olefin
Liquid-phase xylene isomerization
Three-phase fluidized Bed
Production of calcium acid sulfite
Coal liquefaction, SRC process
Industrial Examples of Multi-phase and Catalytic
Reactors
Gas-Liquid Continuous Stirred Tank Reactor:

 Oxidation of cyclohexane to adipic acid, cumene to cumene

hydroperoxide, and toluene to benzoic acid.

 Absorption of SO3 in H2SO4 for manufacture of Oleum

 Absorption of NO2 in water for the production of HNO3

 Addition of HBr to alpha olefins for the manufacture of alkyl

bromide.

 Addition of HCl to vinyl acetylene for the manufacture of

chlroprene.

 Absorption of butenes in sulfuric acid for conversion to

secondary butanol.
 Multi-phase Reactors- Advantages and
Disadvantages
Advantages Disadvantages

Catalytic Fixed  The fluid flow regimes  The intra-particle

Bed Reactor approach plug flow, so diffusion
high conversion can be resistance is very
achieved. high.

 Pressure drop is low.  Comparatively low

Heat and mass
 Owing to the high hold- transfer rates
up there is better radial
mixing and channeling  Catalyst
is not encountered. replacement is
relatively hard and
 High catalyst load per requires shut
unit of reactor volume down.
 Multi-phase Reactors- Advantages and
Disadvantages

Advantages Disadvantages
Catalytic  The smooth, liquid-like flow of particles  This violent particle motion of
Fluidized-bed allows continuous controlled operations particles tends to homogenize all
Reactor
with ease of handling. intensive properties of the bed.
 Near isothermal conditions due to the rapid Thus it is not generally possible to
mixing of solids. provide an axial temperature
gradient which might be highly
 Small Intra-Particle resistance leads to a
better heat and mass transfer rate. desirable in some instances.
 Erosion by abrasion of
particles can be serious.

 Particle attrition
 Three-phase Reactors- Advantages and
Disadvantages

Advantages Disadvantages

Trickle-  Gas and liquid flow regimes  Poor distribution of the

Bed approach plug flow; high liquid-phase
Reactor conversion may be achieved.
 Partial wetting of the catalyst
 Large catalyst particle, therefore,
catalyst separation is easy.
 High intra-particle resistance

 Low liquid holdup, therefore liquid  Poor radial mixing

homogenous reactions are
minimized.
 Temperature control is
 Low pressure drop difficult for highly exothermic
reactions

 Flooding problems are not  Low gas-liquid interaction

encountered. decreases mass transfer
coefficients.
 High catalyst load per unit reactor
volume.
 Three -phase Reactors- Advantages and
Disadvantages

Advantages Disadvantages

Bubble  High liquid holdup,  Axial back mixing is

Fixed- Bed therefore, catalyst are higher than trickle-
Reactor completely wetted, better beds, conversion is
temperature control, and no lower.
channeling problems.
 Feasibility of liquid side
 Gas-liquid mass transfer is homogeneous
higher than in Trickle bed reactions
due to higher gas-liquid
interaction.
 Pressure drop is high

 Flooding problems may

occur.
Three -phase Reactors- Advantages and
Disadvantages
Advantages Disadvantages

Slurry and  Ease of heat  Axial mixing is

3-phase Fluidized recovery and very high
Reactor temperature
control.  Catalyst
separation may
 Ease of catalyst require filtration.
supply and
regeneration  High liquid to solid
process. ratio may promote
liquid side
 Low intra-particle reactions.
resistance.
 Low catalyst load.
 High external
Mass transfer rate
(Gas-liquid and
Liquid Solid)
 Multi-phase Reactors- Advantages and
Disadvantages

Advantages Disadvantages

Gas Liquid  Very effective for viscous
Continuous liquids and at very low gas
Stirred rates and large liquid volumes.
Tank
Reactor  Best for system with large
heat effects because of
superior heat transfer
characteristics.
 Useful for slow reactions
requiring high liquid holdup.
 Both liquid and gas phase
are almost completely
backmixed.
 High power consumption per
unit volume of the fluid.
 Sealing and stability of Shaft
in tall reactors.

 Residence time of liquid and

extent of agitation can be
easily varied.
Comparison of Three Phase Trickle- Bed and
Bubble Fixed Bed Reactors

Characteristics Trickle- Beds Bubble Fixed-

Beds

Pressure Drop Channeling at low liquid No Liquid flow

flow rates maldistribution
Heat Control Relatively Difficult Easy

Radial mixing Poor radial mixing Good mixing

Liquid/Solid ratio Low High

Catalyst Wetting Partial wetting is possible Complete

wetting
Conversion High Poor due to
back mixing
Comparison of Three Phase Suspended Bed
Reactors

Characteristic CSTR Slurry Bubble Slurry Three- phase

Fluidized
Catalyst Attrition Significant Insignificant Insignificant
Mass and Heat Highest High High
Transfer
Efficiencies
Mechanical Difficult Simple Simple
Design
Catalyst Easy Easy Easiest
Separation
Power Highest Intermediate Lowest
Consumption

Catalyst Uniform Nonuniformity Nonuniformity

Distribution may exist may exist
Gas-Liquid-Solid Contact in Three-phase Reactors

Bubble Particle

External
Diffusion

Internal
Diffusion

Catalytic Surface
 Theory of Catalytic Gas- Liquid Reactions

A(G) + B(L) C

Gaseous reactant A reacts with non-volatile liquid reactant B on

solid catalyst sites.

Mechanism Of Three- Phase Reactions:-

Mass Transfer of component A from bulk gas to gas-liquid
interface
Mass transfer of component A from gas-liquid interface to bulk
liquid
Mass transfer of A& B from bulk liquid to catalyst surface
Intraparticle diffusion of species A& B through the catalyst pores
to active sites.
Adsorption of both or one of the reactant species on catalyst
active sites
Surface reaction involving at least one or both of the adsorbed
species
Desorption of products, reverse of forward steps .
Common Flow Regimes in Industrial Catalytic
Gas- Liquid Reactors

Catalytic Gas-Liquid Reactor Common Flow Regime

Cocurrent Down-Flow Fixed- Trickle-Flow

Bed

Cocurrent Up- Flow Fixed-Bed Bubble- Flow

Bubble Column Slurry Reactor Homogeneous Bubble- Flow

Three- phase Fluidized- Bed Bubble- Flow

Design Models For Catalytic Gas- Liquid Reactors
Flow Regime Gas-phase Liquid- Phase
Design Model Design- Model

Trickle Flow Dispersion Dispersion

Cocurrent
Down-Flow Fixed-Bed

CSTR Slurry, Continuous or Semi- CSTR CSTR/ Batch

Batch

Homogeneous Bubble- Flow Continuous Dispersion Dispersion

Bubble Column
Slurry Reactor

Homogeneous Bubble- Flow Semi- Dispersion Batch

Batch Bubble Column Slurry

Bubble Flow Dispersion Dispersion

Three- phase Fluidized Bed
Correlations Used for the Three-Phase Catalytic Reactors

Correlation Trickle-Bed Fixed Up-Flow CSTR Slurry Bubble Slurry 3-Phase

Fluidized
Pressure drop Larkins et al. Turpin &
1961 Hintington 1967 - - -
Ellman et al.
1988
L & G Holdup Sato et al. 1973 Fukushima & Galderbank Yamashita & Kim et al.
Ellman et al. Kuasaka 1979 1958 Inoue 1975 1975
1989 Achwal & Yung et al. Maselkar 1970
Stepanek 1976 1979

L-S Mass Van Krevelen Specchia et al. Sano et al. Kobayashi & Lee et. Al
Trans. Coeff. 1948 1978 1947 Saito 1965 1974
Dharwadker &
Sylvester 1977
L Dispersion Michell & Stiegel & Shah Deckwer et El-Temtamy
Coeff. Furzer 1972 1977 - al.1974 1979

G Dispersion Hochman & Mangartz &

Coeff. Effron 1969 - - Pilhofer 1981 -

Wall Heat Baldi 1979 Fair 1967

Transf. Coeff. - - -

Power Luong &

Consumption - - Volesky 1979 - -
Michel and
Miller 1962
Correlations Used for the 2-Phase Reactors

Gas Liquid Continuous Stirred Tank Reactor

1. Maximum Gas Flow rate (QGmax) – Zwietering (1963)

2. Bubble diameter (db) – Van Dierendonck (1970)
3. Gas holdup (G) - Van Dierendonck (1970)
4. Liquid side Mass transfer coefficient (kL) – Van Dierendonck (1970)
5. Liquid side Mass transfer coefficient (kL) for single bubbles - Hughmark(1971)

Catalytic Liquid Fluidized Bed

Mass Transfer Coefficient (KL) – Chu, Kalil and Wetteroth (1953)

Catalytic Gas Fluidized bed

1. Voidage at Minimum Fluidization (mf) – Broadhurst and Becker (1975)

2. Velocity at Minimum fluidization (Umf) – Kunii and Levenspiel (1969 )
3. Bubble Diameter (DB)- Horio and Nonaka (1984)
4. Mass Transfer Coefficients (KBC and KCE) – Kunni and Levenspiel (1969)
5. Coefficient for Axial Dispersion (DGA) – Yoshida,Kunii and Levenspiel(1969)
Calculation of Catalytic Effectiveness Factor

Catalytic Effectiveness Factor:

  1 (Coth3  1 )
 3

where
- Thiele Modulus

1st order reaction rate:

Spherical Pellet
  R kSap / De
3
  R kSap / De
Cylindrical Pellet 2

  L kSap / De
Slab Pellet
Catalytic Fixed-Bed Reactor - Design Model

Mass Balance around the catalyst

(kcac )i (CG  CS )i   ( Rnet )i

Gas-Phase component mass balance (Plug Flow model)

 UG dCGi  (kcac)i (CG  CS )i  0.0

dz
Gas-Phase component mass balance (Dispersion model)

2
DGi d C Gi
 UG dCGi  (kcac)i (CG  CS )i  0.0
2
d z dz

Energy Model
dT
UGGCpG   ( RjHRj )  UA(T  Ta )
dz
Catalytic Gas-Fluidized Bed Reactor- Design Model

Bulk Gas Phase( Bubble Phase):

Plug Flow:-
dCib
Ub  K BC (Cib  Cic )
dZ
With Axial Dispersion:
d 2Cib dC
Dga 2
 U b ib  K BC (Cib  Cic )
dZ dZ

Intermediate(Cloud- Wake) Phase:

K BC (Cib  Cic )   c ( R)iCloudPhase  K CE (Cic  Cie )
Catalyst (Emulsion) Phase:

K CE (Cic  Cie )   e ( R) iEmulsionPhase

Energy Balance:
dT NR
 gU bC pg   Rj * Hr j  U * a (Tambient  TRe actor )
dZ j 1
Catalytic Liquid -Fluidized Bed Reactor-Design Model

Liquid-phase component balance:

Plug Flow:-
dCiL (1)
U L  K L (CiL  CiS )
dZ
Dispersion:-
d 2CiL dCiL (2)
DLa  U L  K L (CiL  CiS )
dZ 2 dZ

Catalyst (Emulsion) Phase:

K L (CiL  CiS )  ( R ) iCatalystPhase (3)

Energy Balance:-
dT NR (4)
 LU LC pL   Rj * Hr j  U * a (Tambient  TRe actor )
dZ j 1
 Gas-Liquid Agitated Tank- Design Model
Gas-phase Component Mass Balance:

(QG / RT )( P i i  P o i )  VR * E * K L a ( P o i / H  C o Li )  0
or
Fgas / PT ( P i i  P o i )  VR * E * K L a ( Poi / H  C o Li )  0 (1)

Liquid-phase Volatile-Component Mass Balance:

QL (C i Li  C o Li )  VR * E * K L a( P o i / H  C o Li )  Rinet *VR  0 (2)

Liquid-phase Non-Volatile-Component Mass Balance:

(3)
QL (C i Li  C o Li )  Rinet *VR  0

Energy
F i i[Balance:
(Ti  To )   / 2(Ti 2  To 2 )   i / 3(Ti 3  To 3 )]  [VR * (HR j * Rj )]
i i

 U * A(Ta  To )  0
 Three-Phase Gas-Liquid Catalytic Reactor- Design Model
(Trickle-Bed, Fixed-upflow Bubble-Bed, Bubble Slurry Bed,
3-Phase Fluidized Bed)
Non-Volatile Liquid-phase mass balance:
2
DL , i C2L , i  UL dCL , i  ( Kcac )i (CL , i  CS , i )  0.0
d
dz dz

Volatile Liquid-phase mass balance:

2
Cg , i
DL , i C2L, i  UL dCL , i  ( KLag )i (
d  CL , i )  ( Kcac)i (CL , i  CS , i )  0.0
dz dz Hi
Boundary Conditions:

At Z=0  DL , i dCL , i  UL (CL , i  C i L , i )

dz
At Z=L dCL , i  0
dz
Gas-phase mass balance:

dCg , i Cg , i
 Ug  ( KLag )i (  CL , i )  0.0
dz Hi
Component mass balance around the catalyst:

dCg , i Cg , i
 Ug  ( KLag )i (  CL , i )  0.0
dz Hi
 Three-Phase Gas-Liquid Catalytic Reactor- Design
Model (CSTR Slurry)

Non-Volatile Component Liquid-phase mass balance:

QL(C i L , i  C o L , i )  VR (kcac )i (C o L , i  CS , i )  0.0 (1)

Non-Volatile Component Liquid-phase

o
mass balance:
QL (C i L , i  C o L , i )  VR ( KLag )i ( C g , i  C o L , i )  VR (kcac )i (C o L , i  CS , i )  0.0
Hi (2)

Gas-phase mass balance: o

i o C
QG (C G , i  C G , i )  VR (kLag )i ( G , i  C o L , i )  0.0 (3)
Hi

i  CS , i )around
 VR (the
ri )catalyst:
o
VR ( Kcac )i (mass
Component C L ,balance
(4)
 ReaCat Start up screen

Reaction Reaction Phase Menu

Reactor Type Reactor Type Menu

Inlet Temperature Rate Law

and Pressure,
Energy Model
Selection
Reaction Rate Constant

Physical Properties
of Components
Reactor Specifications

Reaction Stoichiometry Run

REACTION

Reaction
Phase Menu
REACTOR TYPE

Reactor Type Menu

Global Options
Physical Properties
Reaction Stoichiometry
Reaction Rate
Rate Constant
Reactor Specifications

Feed Composition Input

Heat Transfer Data for Non-isothermal cases

Graphical Output of the ReaCat Program
Reactor Flow-Sheeting
 ReaCat, Test Cases
Catalytic Gas Fluidized Bed

Multiple reaction system for the production of Phthalic Anhydride from naphthalene.

“Fluidization Engineering”; Kunii and Levenspiel.(1991, Butterworth- Heinman, P 298)

Literature ReaCat (1) ReaCat (2) ReaCat(2)

Plug Flow Plug Flow Plug Flow Dispersion

Conversion 97% 94.93 % 85.49% 81.26%

(1) – Experimental bubble diameter values has been used by the program

(2) – The correlation of Horio and Nonaka (1984) has been used to find the bubble

diameter.
 ReaCat, Test Cases

Continuous Gas-Liquid Stirred Tank Reactor

Liquid phase oxidation of o-xylene into o-methylbenzoic acid

by means of air.

Chemical Reactor Analysis and Design; G.F.Froment and

K.B. Bischoff (1979)

Literature ReaCat

Conversion 83.39% 83.95%

 ReaCat, Test Cases

Trickle-Bed

Liquid-phase oxidation of formic acid in the presence of CuO.ZnO

catalyst; Baldi et. Al. 1974, Goto and Smith (1975)

Experimental ReaCat (plug flow) ReaCat (Dispersion)

Conversion 88.5 % 91.0% 89.8 %

 ReaCat, Test Cases

Continuous Catalytic Gas-Liquid Slurry Stirred Tank

Reactor

Hydrogenation of Aniline to Cyclohexylamine (Supported Nickel

catalyst)

(Govindrao and Murthy, 1975; Ramachandran and Chaudari 1983 p.

303

Literature ReaCat

Reactor Volume 98 Liter 99 Liter

(46 % conversion of Aniline)

 ReaCat, Test Cases

Semi-Batch Catalytic Gas-Liquid Slurry Stirred Tank Reactor

Butynediol Synthesis by the reaction of gaseous acetylene with

aqueous formaldehyde in the presence of copper acetylide catalysts.
; Kale et. Al (1981)

Experimental ReaCat (1) ReaCat (2)

Conversion 62 % 61.0% 68.5 %

1) Adsorption at catalyst surface is taken into account by the program

2) No adsorption effects
Sulfuric Acid Production by Contact Process

SO2 + ½ O2 SO3

P' P '1 / 2  P 
r  So 2 O2  1 SO 3 
SO 2 2  K P P 1 / 2 
 A  BP '1 / 2  CP '  DP   P SO 2 O 2 
 1O 2 SO 2 SO 3 


W here
,
PS
O 2,PO,P
2 SO3=In
terfac
ialP
artia
lPre
ssu
reso
fSO,O
2 2
a
n dS O3(atm)

P'deno te
spartia
lpressu
re sofSO2andO2atz e
ro
conversionund e
rtotalpressu
rea
tth
ep o
intinthe
re
actor(atm)
-1
/2
K
P=Th
ermod
y nam
icEqu
ilib
riumC o
nstan
t,a
tm
L
og1K
0 P=51
29/T–4 .89 TinoK
6

C
onsta
n tsA
,B,C
,Da
refu
nctio
nso
ftem
pera
ture.
Parameters and Operating Conditions for the
Sulfuric Acid Contact Process

Inlet Temperature 787 oF

Inlet Pressure 19.4 Psia
Viscosity 0.09 lb/ft.hr

Reactor Dimensions:
Diameter 2.453 ft
Length 44 ft
Volumetric Flow Rate ( SCFM) 5439.174

Inlet Partial Pressures (Psia):

S02 11.08
O2 7.958
SO3 0.362

Catalyst Properties:
Density 33.8 lb/ft3
Particle Diameter 0.0405 ft
Bed Voidage 0.45
Graph of Temperature v/s Tube Length for Contact
Process
Graph of Concentration v/s Tube Length for Contact

Process
Graph of Conversion v/s Tube Length for the
Contact Process
 SO2 Conversion v/s Inlet Temperature

0.6

0.5
S O 2 C O N V ER SIO N

0.4

0.3 CONVERSION

0.2

0.1

0
700 750 800 850 900 950 1000

INLET TEMPERATURE (F)

 SO2 Conversion v/s Inlet Flowrate

0.7

0.6
SO2 CONVERSION

0.5

0.4

conversion
0.3

0.2

0.1

0
3000 3500 4000 4500 5000 5500 6000

INLET FLOWRATE (SCFM)

 CONCLUSION

A Package for multi-phase catalytic and non-catalytic

reactors has been developed which demonstrates the
capability to handle complex Material and Energy Balances
and associated correlations.

Features to Be Added:-

Add a utility to perform reaction rate optimization.

This is very useful when reaction rate is not
known.

Build a kinetic database of specific industries

such as Sulfuric Acid and Ammonium Phosphate.