INTRODUCTION TO CREL - Washington University in …crelonweb.eec.wustl.edu/files/CRELMEETINGS/2004/Welcome.pdf · • Propylene oxide from propane, ... • Partial oxidation ... •To

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


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)


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


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:


3.56 m

Liquid/Catalyst Injection

to Center (N1-Center)


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.


to Center (N2-Center)


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!


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

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.


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


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.


Radioactive Particle Tracking –

A good way to get velocity information in opaque systems

Huping, specify conditions

Are both draft tube columns

L – r differnece?


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

Documents

INTRODUCTION TO CREL - Washington University in …crelonweb.eec.wustl.edu/files/CRELMEETINGS/2004/Welcome.pdf · • Propylene oxide from propane, ... • Partial oxidation ... •To