INTRODUCTION TO CREL
M.P. Dudukovic
Chemical Reaction Engineering Laboratory (CREL)
http://crelonweb.wustl.edu
Washington University Facts • The University is ranked 11th in 2005 USN&WR for full-
time undergraduate education
• $480 million was received in total research support, including $414 million in federal obligations. *
• The National Science Foundation ranked Washington University 6th among major private universities and 13th among all universities. *
• The University ranks 5th among all educational institutions receiving research support from the National Institutes of Health (NIH), and the School of Medicine ranks 3rd among all medical schools. *
• 2,911 total instructional faculty *
• 10,462 total full-time students *
• 3,357 total degrees awarded * The School of Engineering represents 25% of the Bachelor’s degrees
* Fiscal 2003 S1
INDUSTRIAL SPONSORS 2003/04
Sponsors
Collaborators
AIR PRODUCTS
BAYER
BP
CHEVRON TEXACO
CONOCO PHILLIPS
DOW
DUPONT
EASTMAN
ENI TECHNOLOGIE
EXXON – MOBIL
IFP
JOHNSON MATTHEY
PRAXAIR
SASOL
SHELL
STATOIL
TOTAL
UOP
Welcome to the
29th Meeting of the
Chemical Reaction Engineering Laboratory (CREL) and Industry
October 28, 2004
S2
Raw Materials Products
Non Renewable:
• Petroleum
• Coal
• Ores
• Minerals
Renewable:
• Plants
• Animals
Fuels
Materials
Plastics
Pharmaceuticals
Food
Feed
etc.
Chemical and
Physical
Transformations
Pollution
The domain of chemical engineering consists of
chemical and physical transformation of starting
materials to products
Key to economically and environmentally friendly process is
in choosing the right chemical transformations and being
able to scale them up.
S3
Use of Multiphase Reactor Technology
Dudukovic, Mills, Larachi, Catalysis Reviews, 44(1), 123-246 (2002)
G
G
S
S
S
G
G
G
G L+S
G
G
L
L
G
G
L
Petroleum Refining
Polymer
Manufacture
Environmental
Remediation
Syn & Natural Gas
Conversion
Bulk
Chemicals
Fine Chemicals
& Pharmaceuticals
Value of Shipments:
$US 637,877 Million
Biomass
Conversion
MeOH, DME, MTBE,
Paraffins, Olefins,
Higher alcohols, ….
Aldehydes, Alcohols,
Amines, Acids, Esters,
LAB’s, Inorg Acids, ...
Ag Chem, Dyes,
Fragrances, Flavors,
Nutraceuticals,...
Syngas, Methanol,
Ethanol, Oils, High
Value Added Products
De-NOx, De-SOx,
HCFC’s, DPA,
“Green” Processes ..
Polycarbonates,
PPO, Polyolefins,
Specialty plastics
HDS, HDN, HDM,
Dewaxing, Fuels,
Aromatics, Olefins, ...
S4
),()( bbb TCRCL
j
bbjjRbh TCRHTLj
),()()(
transport;kineticsf
00 P,C,T
P,C,T
product, Q
REACTOR PERFORMANCE = f ( input & operating variables ; rates ; mixing pattern )
REACTOR MOLECULAR SCALE EDDY/PARTICLE feed, Q
CHEMICAL REACTION ENGINEERING (CRE) METHODOLOGY: Multi-scale Quantification of Kinetic-Transport Interactions
S5
MOLECULAR SCALE (RATE FORMS)
Strictly Empirical Mechanism Based Elementary Steps
REACTOR SCALE
Axial Dispersion CFD Phenomenological Models
EDDY OR PARTICLE SCALE TRANSPORT
DNS / CFD Empirical Micromixing Models
PROCESS SCALE
Steady State Balances Dynamic Models for Control & Optimization
10-10 m
102 m
10-16 (s)
104 (s)
PFR/CSTR
Reactor performance affects number and size of separation units and overall
economics of the process
CREL Objectives
• Education and training of students
• Advancement of reaction engineering methodology
• Transfer of state-of-the-art reaction engineering to
industrial practice
CREL Funding
• General industrial CREL participation fees
• Federal grants
• Industrial mini-consortium
• Federal contracts
• Specific contract work
• Specific training
CHEMICAL REACTION ENGINEERING LABORATORY S6
CREL Activities
• Exploration of novel process concepts and of new
technology
• Development of improved multiphase reactor models
and validation of CFD models for multiphase reactors for
– Scale-up and design
– Troubleshooting
• Development of toolboxes and turn-key models and
training of personnel
CHEMICAL REACTION ENGINEERING LABORATORY S7
Sources of Novel Process Concepts 1. Conceptual ideas (Main source: Dr. Walter Knox)
• Biomass to syngas
• Syngas to vinyl acetate, methyl vinyl chloride, ethanol
• Propylene oxide from propane, oxygen and hydrogen
• Isobutane to p-xylene
• Methane to methanol
• Methane to ethanol
• Biomass and/or coal to hydrogen
• Methane to acetic acid
• Etc.
2. John Gleaves’ novel catalyst development for selective oxidations
(butane to maleic, propylene to acrolein, acrolein to acrylic), oxidative
hydrogenation (propane to propylene), epoxidation (propylene to
propylene epoxide), etc.
3. CEBC (Center for Environmentally Beneficial Catalysis – NSF ERC)
• Solid acid alkylation and acetylation
• Partial oxidation (cyclohexane to cyclohexanone and cyclohexanol or direct
to Acetic Acid)
CHEMICAL REACTION ENGINEERING LABORATORY S8
Novel Multiphase Reactor Technology
1. Microreactor Technology (Mikroglas - Invenios)
• Safe manufacture of explosive materials
• Determination of key process variables in oxidations
and other gas-liquid reactions
2. LOR (Liquid Oxidation Reactor Technology)
• Use of increased oxygen concentration (or pure
oxygen) in teraphthalic acid manufacture
• Extension of LOR to other oxidations
3. Biazzi Hydrogenation Technology
4. Ultra Short Contact Time Reactors and Reactor -
Regenerators
CHEMICAL REACTION ENGINEERING LABORATORY S9
Validation of CFD for Multiphase Systems and Improved
Model Development for Scale-Up, Design and Troubleshooting
• Bubble columns (slurry)
• Liquid-solid risers
• Moving beds
• Ebulated beds
Advances in CARPT-CT technology
Computer Automated Radioactive Particle Tracking (CARPT) and Gamma Ray
Computed Tomography (CT) yield the flow map of phase distribution and
velocity in various systems
Computer Automated Radioactive
Particle Tracking (CARPT)
High Pressure Bubble Column
• Gas-solid riser
• Stirred tanks
• Trickle beds
• Monoliths with two phase flow
• Etc
Process Applications
Computed Tomography (CT)
Normal Pressure Bubble Column S10
Scale-Up Models
• Optical probes (bubble dynamics)
• Mass transfer
• Real transfer
• Other
• Troubleshooting: Gamma ray
densitometry, tomography,
tracer methods
Point probes:
CHEMICAL REACTION ENGINEERING LABORATORY S11
3.56 m
Liquid/Catalyst Injection
to Center (N1-Center)
Liquid/Catalyst Injection
to Wall (N1-Sidewall)
9.66 m
Fresh Feed
0.46 m
Gas Tracer
Injection
Recycle
Syngas In
Syngas/Products Out
DET
1.83m
2.74m
0.61m
1.74m
1.52m
1.52m
2.74m
2
1
3
4
5
6
7 DET
DET
DET
DET
DET
DET
DET
DET
13.25m
W
N
S
E
r/R = 0.6 r/R = 0.35
24 tubes of
1” O. D.
Liquid/Catalyst Injection
to Center (N2-Center)
Liquid/Catalyst Injection
to Wall (N2-Sidewall)
DET
DET
Bubble Column Example
For sound scale-up and design strategy one needs validated CFD codes. CARPT-CT are used to develop an appropriate reactor flow and mixing model. CFD generated data are used to assess model parameters. Reactor flow and mixing model is coupled with the kinetic information.
Degaleesan et al., Chem. Eng. Sci., 51, 1967(1996); I&EC Research, 36,4670 (1997); Gupta et al., Chem. Eng. Sci., 56, 1117 (2001); Peng and Dudukovic, Chem. Eng. Sci. (submitted 2004).
CHEMICAL REACTION ENGINEERING LABORATORY
The CT Setup at CREL (Kumar, 1994)The CT Setup at CREL (Kumar, 1994)
Dzz
Drr
uz(r)
1-eL(r)
0 -R R
CT CT SCAN
CARPT
FLOW PATTERN
CFD + CARPT + CT
AFDU
0 100 200 300 400
1 0.8 0.6 0.4 0.2 0
Detector Level
1
0 100 200 300 400
1 0.8
0.6
0.4
0.2
0
Detector Level 6
Run 14.6
0.0
0.2
0.4
0.6
0.8
1.0
0 20 40 60 80 100
Time (sec)
No
rma
lize
d R
es
po
ns
e
Sim_L1
Exp_L1
Sim_L4
Exp_L4
Sim_L7
Exp_L7
Pressure = 50 atm
Temperature =250 Deg. C
Ug = 25 cm/s
0 20 40 60 80
100
1 0.8
0.6
0.
4
0.
2
0
7
6
5
4
3
2
1
Liquid
Tracer
Gas Tracer Gas
Gas
DET.
Data
Model
Prediction
time (s)
time (s)
time (s)
S12
Process Development, Turn-Key
Models, Tool Boxes
• Corn – to – ethanol for NCRC at SIUE (USDA
funded)
• Anaerobic digester design and operation (DOE
funded)
• Airlift reactor for photo induced algal growth
(CREL funded)
• Other proprietary contracts!
CHEMICAL REACTION ENGINEERING LABORATORY S13
Cells’ Movement
0 10 20 30 40 50 60 70 80 900
100
200
300
400
500
600
700
0 10 20 30 40 50 60 70 80 900
200
400
600
800
Time Series of Light intensity
experienced by the Cells in the reactor
Flow
Visualization
Airlift
Bioreactor Application:
Photobioreactor
Algal Growth
Exposur
e light
Light
distribution
H2O
O2
H+,e-, ATP
Light
Excitons
being
dissipated
as heat and
fluorescence
Reaction Center
Pigment
Complex
...
Physiologically Based
Photosynthesis rate model Dynamic Simulation
RIS
ER
19
cm
14.5 cm 2
00
cm
20 cm
16
5 c
m
0
10
20
30
40
50
60
0 100 200 300
Time, hr
Ce
ll
co
nc
en
tra
tio
n (
*10
6 c
ell
/ml)
EXP, Ug = 0.39 cm/s
Simulation of Wu
Ug=5 cm/s (this work)
Ug=1 cm/s (this work)
0
10
20
30
40
50
60
70
80
0 100 200Time, hr
Cell'
s C
oncentr
ation,
*106
cell/
ml
BC_5cms SC_1cmsSC_5cms DC_5cmsDC_1cms
(BC: Bubble Column; SC: Split airlift
column; DC: Draft tube airlift column)
Luo and Al Dahhan(2003)
S14
CREL Deliverables to Sponsors
• Annual report
• Annual meeting
• Copies of theses and reports prior to publication
• Training of personnel on CREL premises
• Joint proposals to federal funding agencies
• Networking with high quality institutions
• Access to unique experimental facilities
• Contract research work and reports
• Troubleshooting and consulting
• Opportunity to leverage resources
CHEMICAL REACTION ENGINEERING LABORATORY S15
CHEMICAL REACTION ENGINEERING LABORATORY
Need Enhanced CREL – Industry
Cooperative Efforts
Development of generic experimental and modeling tools for multiphase systems
Development of models and database for specific reactor types or for specific technology (mini-consortia, GOALI and other grants, sales and service contracts)
Development of new technology (research contracts with / without government involvement)
Closer ties on specific research projects (industrial co-advisors of student theses)
S16
To maximize value that CREL brings to sponsors
and provide for continuity of research we need to:
• Identify person(s) responsible for authorizing CREL
participation fee in each company
• Explore raising the fee to expand company participation in
multi-institutional or multinational effort (e.g. CEBC, NCL, etc.)
• Appoint an industrial executive advisory board to offer advice
on use of CREL general funds and spearhead special
initiatives
• Identify at each company people who can connect CREL to
company planned government funded initiatives (via DOE-ATP,
OIT, etc.)
• Give CREL and its partners a chance to participate in new
process development for the company.
CHEMICAL REACTION ENGINEERING LABORATORY S17
CREL Advisory Board
Selected representatives or participating companies are current
CREL advisors.
Company representatives advising D.Sc. Students are appointed
in addition as adjunct faculty.
Need Executive Advisory Board
•To define its role, functions, election of members
•To focus on enhancing CREL value to industry
•To enhance opportunities for CREL funding
CHEMICAL REACTION ENGINEERING LABORATORY S18
Initial Executive Advisory Board
•Hugh Stitt (Johnson Matthey)
•Bernie Toseland (Air Products)
•Tiby Leib (DuPont)
•Stan Proctor (Consultant / Ex-Monsanto)
Organizational meeting with all industrial representatives
Thursday, October 28, 2004
4:00 p.m.
CHEMICAL REACTION ENGINEERING LABORATORY S19
Radioactive Particle Tracking –
A good way to get velocity information in opaque systems
Huping, specify conditions
Are both draft tube columns
L – r differnece?
CHEMICAL REACTION ENGINEERING LABORATORY S20
N. Devanathan - CARPT - Bubble Columns
Y. Yang - CARPT - Bubble Columns
B.S. Zou - CARPT - Bubble Columns
S. Kumar - CT-CARPT - Bubble Columns
S. Limtrakul - CT-CARPT - Ebulated Beds
B. Sannaes - CARPT - Slurry Bubble Columns
S. Degaleesan - CARPT - Bubble Columns
J. Chen - CARPT-CT - Bubble Columns, Packed Beds
S. Roy - CARPT-CT - Liquid-Solid Riser
A. Kemoun - CARPT-CT - Riser, Stirred Tank
A. Rammohan - CARPT-CT - Stirred Tank
N. Rados - CARPT-CT - Slurry Bubble Columns
B.C. Ong - CARPT-CT - Bubble Columns
Acknowledgement of Significant Past CREL Contributions
K. Myers - Bubble Columns
R. Holub - Trickle Beds
B.S. Zhou - Tap Reactor Model
S. Pirooz - Plasma Reactors
V. Kalthod - Bioreactors
H. Erk - Phase Change Regenerators
A. Basic - Rotating Packed Bed
M. Al-Dahhan - Trickle Beds
J. Turner - Fly Ash and Pollution Abatement
S. Karur - Computational CRE
M. Kulkarni - Reverse Flow in REGAS
CARPT-CT
CFD, Reactor Models & Experiments Q. Wang - Bubble Columns
Z. Xu - Photocatalytic Distillation
K. Balakrishnan - Computational CRE
M. Khadilkar - CFD, Models, Trickle Beds
Y. Jiang - CFD, Models, Trickle Beds
J-H. Lee - Models, Catalytic Distillation
Y. Wu - Models (Trickle Beds,
Bubble Column)
Y. Pan - CFD (Bubble Columns)
P. Gupta - Models (Bubble Columns)
P. Chen - Bubble Columns
S21
ACKNOWLEDGMENTS
Department of Energy: DE-FC22 95 95051
DE-FG22 95 P 95512
CREL Industrial Sponsors: ABB Lummus, Air Products, Bayer, Chevron, Conoco, Dow Chemicals, DuPont, Elf Atofina, Exxon, EniTechnologie, IFP, Intevep, MEMC, Mitsubishi, Mobil, Monsanto, Sasol, Shell, Solutia, Statoil, Synetix, Union Carbide, UOP
CREL Colleagues and M.H. Al-Dahhan, J. Chen, S. Degaleesan,
Graduate Students: N. Devanathan, P. Gupta, A. Kemoun, B.C. Ong, Y. Pan, N. Rados, S. Roy, A. Rammohan, Y. Jiang, M. Khadilkar
Special Thanks to: B.A. Toseland, Air Products and Chemicals
M. Chang, ExxonMobil
J. Sanyal, FLUENT, USA
B. Kashiwa, CFDLib, Los Alamos
V. Ranade, NCL, Pune, India
S45 S22
2003 CREL ANNUAL MEETING
AGENDA
Thursday, October 28, 2004
Place: Washington University – Hilltop Campus (Knight Executive Center – Room 220)
8:30 – 9:00 a.m. Welcome and Introduction - M.P. Dudukovic
9:00 – 9:40 a.m. The Importance of Fundamentals in the Future Directions for the Chemical
Industries - Kurt Vanden Bussche (UOP)
9:40 – 10:20 a.m. Utilizing Fundamentals in Design, Scale-up and Troubleshooting - Hugh Stitt
(Johnson-Matthey)
10:20 – 10:40 a.m. Coffee Break
10:40 – 11:20 a.m. Reactor, Process and Product Engineering via Flow Modeling - Vivek Ranade
(NCL)
*11:20 – 12:40 p.m. Introduction of Posters and New Technologies
12:40 – 2:00 p.m. Lunch
**2:00 – 4:30 p.m. Viewing of Posters, Discussion of New Technologies and Laboratory Visits
4:30 – 5:30 p.m. Future Directions and Needs (Industrial Participants Only)
5:30 – 6:00 p.m. Meeting of Industrial Advisory Board with CREL
6:00 – 6:45 p.m. Reception
6:45 – 8:15 p.m. Dinner
8:15 – 9:15 p.m. The Story of Chemical Reaction Engineering - O. Levenspiel (Oregon State
University)
9:15 – 10:00 p.m. Ad hoc Discussions
* New Technologies
Mikroglas Microreactor system (www.invenios.com)
Biazzi Hydrogenation Reactor – Direct scale up from lab to production size (www.biazzi.com)
**CREL Facility Tours
1. 1:45 – 2:30 p.m. S23