Multiphase Reactor Engineering

Vivek V. Ranade
Catalysis, Reactors & Separation Unit (CReST)
Chemical Engineering Division
National Chemical Laboratory
Pune 411008
vv.ranade@ncl.res.in
 OUTLINE

National Chemical Laboratory/ Catalysis, Reactors &

Separations Unit (CReST)

Multiphase Reactor Engineering

NCL Innovation Park

Closure

Multiphase Reactor Engineering

 NATIONAL CHEMICAL LABORATORY

NCL, India

www.ncl-india.org

Multiphase Reactor Engineering

 NCL AT A GLANCE

Premier CSIR Laboratory in Chemical Sciences

[CSIR: 38 Laboratories with Scientific Staff of ~ 5000]

Catalysis Chemical &

Polymers/ Materials Process
Organic Chemistry Engineering
Biotechnology

~ 275 Scientific staff + ~ 400 Ph.D. Students + ~350 Project

Assistants
Industrial contract research (GE, DuPont, Unilever, ICI.)
~ 400 publications, ~ 100 patents per year (~30 US patents)

Multiphase Reactor Engineering

 CHEMICAL ENGINEERING

Transform cheaper raw materials into value added

products (which meet customer requirements) without
compromising safety, environment and economics

Realize Engineering Innovation via Better Chemistry/

Catalysis & Process Synthesis, Better Process Equipment/
Reactors & Operating Protocols, Better Separation Processes
Multiphase Reactor Engineering
 CReST @ NCL

Catalysis, Reactors and Separations Unit (CReST)

Catalysis/ Catalytic Materials/ Reaction Kinetics
Reactor Engineering and Flow Modeling
Separations
Cell Engineering & Computational Biology

Develop Ways of Enhancing Transformations

What transformations are expected to occur?
How fast these changes will occur?
What is the best way to carry out these transformations?

Reactor, Process & Product Engineering

Multiphase Reactor Engineering
 REACTOR ENGINEERING

Link reactor performance to reactor hardware and operating

protocols

Multiphase Reactor Engineering

 OUR METHODOLOGY

Development & Creative Use of

Computational Models for Better
Reactor, Process & Product
Engineering

Multiphase Reactor Engineering

 INDUSTRIAL PROJECTS

FCC Regenerator Pulverized Coal Fired Boilers

Oxy Reactor Spacers for membrane modules
Thermo-siphon Reactor Nozzles for FCC riser reactor
SAN Co-polymerization Modeling of Multiphase Flows
reactor Optimization of Air Filters
PET Finisher Rotary Desiccant Wheels
Allyl Chloride Reactor Regeneration of DPO Reactor
Filament Interaction Optimization of Vortex Diodes
R2 Reactor Modeling of Rotary Cement
Suspension Kilns
Polymerization Carbonylation/ Chlorination

Multiphase Reactor Engineering

 Multiphase Reactor Engineering

Bubble Column Reactors

Stirred Reactors
Fluidized Bed Reactors
Trickle Bed Reactors
Rotary Cement Kilns
Micro-reactors
Ejector Loop Reactors

Multiphase Reactor Engineering

 Bubble Columns

Reactant Gas Drives Flow/ Mixing/ Reactions

Oxidation/ Hydroformylation/ Methanol from syngas/
Gas to liquid fuels/

Few Degrees of Freedom to Manipulate & Control

Flow and Mixing

Key Issues
Distributor design/ weeping
Back mixing/ internals
Solid loading
Scale-up

Multiphase Reactor Engineering

 Rectangular Column

Experiment Euler- Euler-Euler Experiment Euler- Euler-Euler

Lagrange Lagrange

Ug=0.14 cm/s Ug=0.73 cm/s

0.6
Vertical liquid velocity, m/s

0.6

Vertical liquid velocity, m/s

0.0
0.0

-0.6
-0.40 0.00 0.40 -0.6
Horizontal liquid velocity, m/s -0.4 0.0 0.4
Horizontal liquid velocity, m/s

Multiphase Reactor Engineering

 Plume Oscillation

Plume Oscillation Period: EE and EL Simulations

14.0
Wall pressure fluctuation measurements
E-E Simulations
12.0
E-L Simulations
0.70
Plume oscillation period, s

10.0 0.60

Bubble slip velocity, m/s

0.50
8.0
0.40

6.0 0.30

0.20
4.0
0.10

2.0 0.00
0.00 0.05 0.10 0.15 0.20
Column width, m

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Superficial gas velocity, cm/s

Multiphase Reactor Engineering

 Non-uniform Gas Sparging

Previous literature assume uniform gas distribution at

sparger (Joshi 2001) Open to
surroundings
Adjust lift coefficient
Adjust drag coefficient Gas-liquid
interface
Overhead
space

Sieve plate sparger

non-uniform sparging

Plenum Sparger

Bubble swarms oscillating on the sparger Only gas

Gas phase
plate at superficial gas velocity of 0.05cm/s

Multiphase Reactor Engineering

 Transient Flow/ Averaging

Gas holdup

Transient flow Time averaged flow

Ug = 0.20 m/s

Multiphase Reactor Engineering

 Simulated Results

0.4 0.5

0.35 0.45

Time averaged gas holdup, -

0.4
Overall gas holdup (-)

0.3
0.35
0.25 0.3
0.2 0.25

0.15 0.2
0.15
0.1 Uniform-BC Uniform-sparger (H=0.17m)
0.1
0.05 Non-uniform-BC Non-uniform-sparger (H=0.17m)
0.05
Experiment (visual) Experiment single-tip (0.16m)
0 0
0 0.1 0.2 0.3 0.4 0.5 -0.1 -0.05 0 0.05 0.1
Superficial gas velocity (m/s) Radial co-ordinate, m

Overall gas holdup Time averaged gas holdup at

H=0.17m and Ug=0.20 m/s

Multiphase Reactor Engineering

 Reaction Engineering in BCR
Reductive Alkylation of PPDA Mixing cell approach

Backflow
from CFD

Liquid phase: p-phenylenediamine (PPDA) + MEK

Gas phase: Hydrogen
Solid phase: Pt/Al2O3 catalyst
Multiphase Reactor Engineering
 Influence of Radial Baffles

Baffles reduce backflow upto 70%

20% increase in conversion

Multiphase Reactor Engineering

 Stirred Reactors

Impeller Dominated Flows

Approaches for handling impeller rotation

Dispersed Multiphase Flows are Ubiquitous

Inter-phase drag force
Particle Reynolds number
Volume fraction of dispersed phase
Prevailing turbulence
Coalescence & break-up

Essential to Predict Different Flow Regimes/

Distribution of Dispersed Phase
Multiphase Reactor Engineering
 Gas-liquid Stirred Vessels
100

Brucato et al. (1998)

Pinelli et al. (2004)

10
Bakker and van den Akker
(1994), Re= 200
Bakker and van den Akker
(CD-CD0)/CD0

(1994), Re= 500

1
Lane et al. (2005)

Brucato et al. (1998), with

modified constant
0.1
Volume Volume
Reynolds Number
fraction 5% fraction 15%
200
500 / *
0.01
800
50, with 500 m
-
solid particles
0.001
1 10 db/ 100 1000

Multiphase Reactor Engineering

 Gas-liquid Stirred Vessels

(a) Experimental, S33 flow (b) Predicted, S33 flow regime, (c) Experimental, VC flow (d) Predicted, VC flow
regime, Fl = 0.0788 and Fl = 0.0788 and regime, Fl = 0.026267 and regime, Fl = 0.026267 and
Fr = 0.3005 (mid-baffle) Fr = 0.6 (mid-baffle) Fr = 0.6 (mid-baffle) Fr = 0.6 (mid-baffle)

Multiphase Reactor Engineering

 Gas-liquid Stirred Vessels

10 10 10

0 0 0
2, % 2, % 2, %

(a) L33 flow regime (b) S33 flow regime (c) VC flow regime
Fl = 0.1114 and Fr = 0.3005 Fl = 0.0788 and Fr = 0.6 Fl = 0.026267 and Fr = 0.6
Experimental data (Bombac et al., 1997)

Multiphase Reactor Engineering

 Tall GL Stirred Vessels

(a) DFF flow regime, (Fl = 0.638 & Fr = 0.028) (b) DDF flow regime, (Fl = 0.438 & Fr = 0.0597) (c) DDL flow regime, (Fl = 0.163 & Fr = 0.430)

Multiphase Reactor Engineering

 Tall GL Stirred Vessels

0.25 Utip 0.25 Utip 0.25

1.6

% Change in mixing time

1.2

0.8

0.4

0
0 2 4 6 8 10
N, rps

Multiphase Reactor Engineering

 SOLID SUSPENSION
1
1

0.8 0.8

0.6 0.6

z/H

z/H
0.4 0.4

0.2 0.2

0
0
0 0.5 1 1.5 2 2.5 3
0 0.5 1 1.5 2 2.5 3
C/Cavg
C/Cavg
(a) With Brucato et al. (b) With modified (c) Comparison of predicted results
Brucato et al. (1998) (a) With Brucato et al. (b) With modified Brucato (c) Comparison of predicted results
(1998) correlation with experimental data (1998) correlation et al. (1998) correlation with experimental data
correlation

dp= 264 microns, dp/ 20, = 0.1, N= 20.0 rps and Utip= 6.283 m/s
dp= 135 microns, dp/ 9, = 0.15, N= 15.0 rps and Utip= 4.7124 m/s

1
1

0.8
0.8

0.6
0.6

z/H
z/H

0.4
0.4

0.2
0.2

0
0
0 0.5 1 1.5 2 2.5 3
0 0.5 1 1.5 2 2.5 3
C/Cavg
C/Cavg
(b) With modified (a) With Brucato et al. (b) With modified (c) Comparison of predicted results
(a) With Brucato et al. (c) Comparison of predicted results Brucato et al. (1998) with
(1998) correlation Brucato et al. (1998) with experimental data (1998) correlation
correlation correlation experimental data

dp= 390 microns, dp/ 35, = 0.12, N= 20.0 rps and Utip= 3.27 m/s dp= 655 microns, dp/ 63, = 0.12, N= 26.7 rps and Utip= 4.36 m/s

Multiphase Reactor Engineering

 Critical Suspension Speed

0.1 0.22 0.34 0.5

4

3
Standard deviation,

= 0.8
1

= 0.2

0
0 5 10 15 20 25 30
Using modified Brucato et al. correlation (Equation no. 15)
N, rps (Equation no. 10)
Using Brucato et al. correlation

Multiphase Reactor Engineering

 Liquid-phase mixing time

Uncertainties
Identification of the operating conditions at
Single phase which maximum in the mixing time occurs
Solid-liquid
Mixing time

Kraume (1992) : Maxima in the mixing

time at N = Njs

Harrope et al. (1997) : Maxima in the

mixing time at N < Njs

Micheletti et al. (2003) : Maxima in the

mixing time at N = 1/3 Njs
Impeller rotational speed

Delayed mixing in the top clear liquid layer responsible for the increased mixing
time over single phase

Multiphase Reactor Engineering

 Effect of suspension quality
Dimensionless mixing time (Ntmix)

300 6
Just pt-1 pt-3 5
off-bottom pt-5 pt-6
suspension

Maxima at
200 N = 5rps = 1/3 Njs

1
3
100 Complete
Suspension
Incomplete
suspension 0.2
Single-Phase
SL-20rps
0.16
0 SL-10rps

0 10 20 30 40 0.12

Impeller rotational speed, N (rps)

V/Utip
0.08

tmix (CL layer ) > tmix (slurry) tmix (CL layer ) tmix (slurry) 0.04

Liquid Velocity at Top Region 0

0 0.2 0.4 0.6 0.8 1
r/R

Multiphase Reactor Engineering

 TRICKLE BED REACTORS

Liquid
Gas Gas & Liquid Flow through Void Space = 26-48 %
90
Ar-P
80
total
70 total

Characterization 60
poly

Conversion, %
of Packed Bed 50

40

Wetting of Solid Flow Regimes & 30

, P, L, , Global Flow
Surface by 20
RTD Characteristics
Liquid 10

Mal-distribution, 573 593 613

Temperature, K
633 653

Channeling &
Mixing
HDS Reactor
0.47m/s t=0m t=0 0.48m/s t=4m t=2
4
Experimental s ms s ms
5
Experiments:
Simulation-28mm
3 Simulation-3mm

(b)
Suekane et al. 2 (a)
Vz/Vmean

0.02m/ 0m/s
0 AIChE J., 49, 1 s
1 0.48m/s t=6ms 0.9m/s t=10m
t=4 t=10
ms s ms
0

(d)
-1 (c)
-1 -0.5 0 0.5 1 0m/s 0m/s
4.5 x/r
0.18m/ t=18ms t=16 0.2m/s t=26ms t=24
Simulations Experimental Simulated s ms ms

(e)
(f)
0m/ 0m/s
s
0.26m/s t=32ms t=30 0.28m/s t-equi t=eq
ms ui

(h)
(g)
0
0m/s 0m/s

Multiphase Reactor Engineering

 GAS-SOLID FLOWS

Dense Bed Fluidization

Inter-phase forces
Nature of particles: glass, poly-propylene
Long time bubbling characteristics

Multiphase Reactor Engineering

 FCC RISER REACTOR

Converts Heavy Hydrocarbons into More Usable Products

Developed Model for Droplet Evaporation
Products to Fractionator
Drop, T Solid Particle, T1
Simulated Plant Data of
Derouin et al.(1997) & Ali et
Spent Gases
al. (1997)
Vapor Generated due to Contact Heat
Transfer

Reactor
80 90
80
80
Predictions
64 70
Plant Data
Spent Catalyst
Conversion & Yield, wt%

Regenerator 64 60
Regenerator
50
48
48 40
Riser 30
32
32
20
PredictedConversion,VGO 10
PlantConversion,
Predicted Conversion,VGO
16 PredictedYield,GVGO
Plant Conversion, VGO
asoline 0
16
P lant Yield,Gasoline
Predicted Yield, Gasoline
Feed Plant Yield, Gasoline

0
O

as
in

/1
VG

G
Regenerated Catalyst 00

ol

re
3.5 7 10.5 14 17.5 21 24.5 28 31.5 35

as

of

tu
Air

of
0

ra
G

X
0 3.5 7 10.5 14 17.5 21 24.5 28 31.5 35

pe
of

m
Riser Height, m

X
Steam

Te
Multiphase Reactor Engineering
ROTARY CEMENT KILN
Coating
Rotating kiln
Secondary Air
Exhaust gases

Radiation
Entrainment
Coal +
Primary Air
Melt
Clinker
Partially Calcined
Raw Meal Clinker Reactions Flame

Gain Insight & Enhance

Understanding by
Understand Key Issues Developing CFD Models:
Controlling Performance Comprehensive
of Pre-heaters, Calciner, Solutions of Mass,
Kiln and Cooler Momentum and Energy
Conservation

Create Easy to Use GUI

based RoCKS Evolve Guidelines for
Developing Reaction
Develop & Validate Engineering Models for
Reactions Engineering RoCKS
Models

Multiphase Reactor Engineering

 MICRO-REACTORS

1
Ugs = 0.4718 m/s Uls = .2831 m/s
0.9 Uls = .4718 m/s
Uls = .6134 m/s
0.8
Uls = .8964 m/s

Normalised Frequency
0.7

0.6

0.5

0.4

0.3
800
0.2

0.1

0
0 5.6 11.2 16.8 22.4 28 33.6 39.2 44.8 50.4 56
Bubble Length (mm)

Multiphase Reactor Engineering

 EJECTOR LOOP REACTOR

Nozzle/ Diffuser/ Reactor 7.E-03

Models
6.E-03

Without Holes
5.E-03

Gas Flow Rate (m3/s)

With Holes
4.E-03

3.E-03

2.E-03

1.E-03

0.E+00
6.E-04 7.E-04 8.E-04 9.E-04 1.E-03
Liquid Flow rate (m3/s)

Multiphase Reactor Engineering

 EVAPORATIVE COOLING

Different Regimes: T/ Physical

180
l
150 T = 80 C
Properties/ Surface

Evaporation Time (s)

120 T = 60 C

Simplified Model to Predict 90

Evaporation Time 60

30

0
0 3 6 9 12
Droplet Volume (l)

0.2
This Study
0.16 Crafton et. al (2004)

Heat Flux (W/mm2)

0.12

0.08

0.04

0
0 1 2 3 4 5
Droplet Diameter (mm)

Multiphase Reactor Engineering

 CRYSTALLIZATION

Ferrous Sulfate: Experiments + Modeling

n ( nG ) ln M
+ +n = ( L Lo) * B( L0 )
t L t

700
0.55
600 simulation

Concentration, kg/kg
0.5 expt
Size, micron

500
400 0.45

300 0.4
200
0.35
100
0.3
0
0 500 1000 1500 2000 2500 3000 3500
100 200 300 400 500 600 700 800 900 1000 Time, s
Number/size

Multiphase Reactor Engineering

 NCL INNOVATION PARK

Create Greater Impact on Industrial Practice

Provide End to End Solutions
Need to walk the last mile for greater impact

! "

100 NCL Innovation Park

Multiphase Reactor Engineering

 CReST - TRIDIAGONAL
$ # % #
% & Knowledge base/ new ideas/ System design/ scale-up data/
' ( proof of concept/ patents testing/ usable products

$ Models/ methodology/ validation/ Software tools/ engineering

) expertise/ capabilities solutions

&' * Models/ methodology/ validation/ Complex geometry/ capture

expertise/ capabilities trends/ engineering solutions

)+ New techniques/ new data/ Plant data/ scale-down

' , validate physical models models/ diagnostic support

Students (Ph.D./ Masters), Retail training/ course

# design courses/ assignments contents/ logistics/ support
Multiphase Reactor Engineering
 CLOSURE

Multi-scale Modeling and Experimental Capabilities

are Essential to Address Industrial Projects
Interoperability between various tools often facilitates
performance enhancement & engineering innovation

Tremendous Opportunities for Using Computations

for Better Reactor, Process & Product Engineering

Multiphase Reactor Engineering