Chemical Reaction Engineering (CRE),

Environmental Protection and

Sustainable Development
M.P. Dudukovic
Chemical Reaction Engineering Laboratory (CREL)
Washington University in St. Louis, MO 63130, USA
Presentation at the First South East European Congress of
Chemical Engineering (SEECCHE1)
Beograd, Serbia, September 25-28, 2005

Introduction
Role (Current and Future) of CRE
Importance of Multiphase Reactors
Conclusions

S1

http://crelonweb.che.wustl.edu

SLIDE 1. It is a special privilege to speak in the auditorium of the

university I attended as an undergraduate student, in the very hall where
my bother Aleksander Sasha mesmerized students with his exciting
lectures in transport and reactions.
I will try today to convey to you as to why chemical reaction engineering,
which is at the heart of the chemical engineering discipline, is still very
important and why advances in CRE can help us in dealing with
environmental protection and development of more sustainable
technologies.

Key Factors Affecting the Environment and Sustainability

Total population

Agricultural practices
Mining practices
Energy utilization

Lifestyle

Recreational activities
Manufacturing practices

S2

SLIDE 2. The two key factors that affect the environment and
sustainability of our practices is the total number of people and their life
style.
Agricultural practices, clearing of forest for arable land, irrigation of
deserts, the extent of use of herbicides and pesticides, etc., obviously are
important.
Mining for finite mineral or energy resources, strip, deep shaft, etc., affect
the environment.
Energy utilization, drilling for oil in pristine areas and oceans, use of
hydroelectric power, etc., have environmental impact.
Recreational activities, such as country skiing or driving a snow mobile,
walking or using a dune buggy, have different environmental
consequences.
As important as all of the above are, it is the manufacture of products from
fuels to chemicals, plastics, pesticides that make alternate life styles
possible and that is the realm of chemical and process engineering, which I
wish to discuss.

The domain of chemical engineering consists of

chemical, physical and biological transformations
of starting materials to products
Raw Materials
Non Renewable:
Petroleum
Coal
Ores
Minerals
Renewable:
Plants
Animals

Chemical, Physical
and Biological
Transformations

Fuels
Materials
Plastics
Pharmaceuticals
Food
Feed
etc.

Pollution

CHEMICAL ENGINEERING is the profession in which a

knowledge of mathematics, chemistry and other natural sciences
gained by study, experience and practice is applied with judgment
to develop economic and environmentally acceptable ways of
using materials and energy for the benefit of mankind.
S3

SLIDE 3. In chemical engineering (or chemical processes) we deal with the

chemical and physical transformation of non-renewable and renewable
resources into a variety of products useful to man to which advanced
technological society like ours is absolutely addicted. It is self evident that
materials with new properties are created by the chemical change, i.e., by
the transformation in atomic content or configuration of a molecule. In the
process of accomplishing these transformations, we inadvertently create
undesirable changes which, if not checked, can result in pollution of the
environment. Both the degradation of the environment and heavy reliance
on non-renewable fossil based raw materials threatens to render our
technologies unsustainable over the long run.
To change this is the responsibility of chemical and process engineers who
are predominantly in charge of all such transformations.
Process engineers have always been aware of the 11th commandment
your process should make profit, so that the recently added 12th
commandment do not pollute is easier to implement if to do otherwise
leads to dire economic consequences, i.e., has a negative effect on the
fulfillment of the 11th commandment, which is an integral part of the
definition of chemical engineering.
Moreover, in assessing the environmental impact of our processes and/or
products we should include the life cycle analysis of the product to truly
understand the consequences of making it in the first place.

Pollution
Pollution
Energy
GNP
(Damage To =

Population
Energy
GNP
Population
Environment)

Pollution
- Depends on level of available technology
Energy
Energy
GNP

- Depends on the market forces

GNP
- Depends on economic growth
Population
Population - Depends on population growth
CHEMICAL REACTION ENGINEERING LABORATORY

S4

SLIDE 4. Let us take a brief global look as to the damage to the

environment created by our technological activities. The total pollution
generated can be, in the first approximation, expressed as a product of
four factors. 1) Pollution generated per unit of energy used, which
depends on the level of available technology and process efficiency, 2)
energy used for GNP generation which depends on market forces, 3)
GNP/per capita, which is affected by economic growth, and 4) total
population.

GLOBAL VIEW
Pessimistic Assessment
(consumption per capita ) (population)
Pollution
(process efficiency )
Optimistic Assessment
Pollution (1 - process efficiency ) (consumption per capita ) (population )

Time

Process Efficiency

Population

Consumption Per Capita

process inefficien cy

Time

Time (Investment)

CHEMICAL REACTION ENGINEERING LABORATORY

S5

SLIDE 5. One can further simplify this global view of the pollution
problem either into a pessimistic assessment that the total pollution
generated is the product of consumption per capita and population divided
by process efficiency. Or one can be an optimist and present the total
pollution as a product of consumption per capita, population and process
inefficiency = 1 process efficiency. Whichever view you take, it seems
self-evident that pollution can be reduced by controlling population
growth, and/or by reducing consumption per capita. In contrast, process
efficiency increases only asymptotically to unity. Hence, from the
pessimistic point of view that alone cannot provide a serious impact on
total pollution. One should also note that further increases in process
efficiency require considerable investment of capital and time. Improving
efficiency of one process may lead to inefficiency elsewhere. Hence, a
holistic systems approach and life cycle analysis are needed.

Most Effective Ways of Pollution

Prevention And Reduction
POPULATION GROWTH CONTROL
Not feasible due to political and religious opposition
REDUCTION IN PER CAPITA CONSUMPTION
Not feasible due to business interests expansion
needed to sustain the current world economic system.
THEREFORE
Pollution prevention and reduction via improved
technology
CHEMICAL REACTION ENGINEERING LABORATORY

S6

SLIDE 6. So, from the logical point of view, the best answer to preventing
pollution growth is control of population growth and reduction in per
capita consumption. The first approach, control of the population, is
anathema to two major religions and viewed as politically incorrect! The
second, reducing the consumption per capita, is anathema and heresy to
the free market and dreams of economic expansions that want even the
developing world to consume per capita as much as we do in the US! The
only remaining viable approach left is to take the optimistic viewpoint that
salvation will come via improved technology. Thus, as scientists and
engineers we must work on dramatic reductions in process inefficiency.
This, of course, as already stated, requires capital investment and time. As
voters we should fight for mandatory increases in process efficiencies
globally as this seems to be the only viable answer. Le us see now what we
have done so far:

Increased Profits, Government Regulation and

Public Pressure are Primary Motivators for
Better housekeeping practices in existing processes,
minimizations of wastes and spills with the goal of zero
emission.
End-of-the-pipe clean up via installation of processes for
clean-up and for recycling whenever possible with the goal of
total recycle.
Retrofitting existing processes for improved efficiency, waste
reduction and enhanced recycle with the goals of zero
emissions and total recycle.
Development of and installation of new more efficient process
technologies that minimize waste and pollution.
CHEMICAL REACTION ENGINEERING LABORATORY

S7

SLIDE 7. There are four accepted ways of pollution reduction and prevention listed in
order of increased capital expenditures. 1) Better house-keeping attempts to eliminate
obvious wastes, 2) end-of-the-pipe clean-up usually is the response to pubic pressure or
government regulations, 3) retrofitting of existing processes introduces better process
efficiency and thus reduces waste and pollution, 4) finally, it is the new technologies that
offer the best hope for minimization and prevention of pollution.
We should recall that better environmental practices are the result of increased
government regulations generated in response to the increased peer pressure from the
consumers and general public. Too little regulation increases pollution, too much stifles
business activity. Hence, a medium road must be taken. While often we hear about a
company acting responsibly to protect the environment, the truth is that the motivator is
always profits. Either one has to do it to stay in the business due to regulations, or to
prevent even more dramatic regulations. Or due to changing markets there is value to be
extracted from recycling. Or new technology expands the market.
Unfortunately, at present there is no incentive for companies to invest and take a risk with
new green technologies. The profit motive, in absence of global regulations, suggests as
optimal strategy to repeat the known technology at locations where labor is cheaper and
regulations less strict. It is a myth that new technology in chemical processes is favored,
as there are substantial risks in its implementation and no obvious rewards.

The Rich and The Poor

People
Total Population

Rich
0.97 billion

Poor
2.3 billion

Population Growth (% Annual)

0.5

1.8

Life Expectancy

78

58

Fertility Rate

1.7

3.7

Infant Mortality (Per 1000 Births)

5.4

82

Literacy

98

59

Environment
Surface Area (Sq KM)

35 million

32 million

Energy Use Per Capita (Kg Oil EQ)

5,350

508

Electricity Per Capita (KWH)

8,340

302

28,550

450

Economy
GNI Per Capita (US $)
Technology & Infrastructure
1,250

39

PCs Per 1000 People

Fixed & Mobile Phones (per 1000 People)

470

6.9

Paved Roads (% of Total)

93

13

Source: The World Bank Group

S8

SLIDE 8. Another reason while eventually we will have to embrace the

new efficient process technologies is the fact that the enormous gap
between the rich and poor nations must be bridged if we are going to avoid
serious social upheavals in the future. And using the current inefficient
technology will not do it since this is too wasteful in energy usage.
So to bring the standard of living of Asia and Africa to American level with
current technology is clearly unsustainable.
Let us plan considering only the new technologies, that we must start to
develop and implement proper understanding and application of reaction
engineering principles will be essential.
We should note, however, that in all the current and future methods of
pollution reduction, chemical reaction engineering plays a pivotal role.
That is true in retrofitting activities, in end-of-the-pipe treatment and
certainly in the development of cleaner new green processes.

feed, Q

L (C b ) = R ( C b , Tb )
T ,C , P
Lh (Tb ) =

T , C 0 , P0

( H R j ) j R j (C b , Tb )

= f (kinetics ; transport

)
product, Q

REACTOR PERFORMANCE

= f ( input & operating variables ;

rates

mixing pattern )

,-.,-

,-.,0 #
! "#

'

&

# '"

$# %

"

& "( '% #

! "'

"' '(

'% #

,-/

,-1 #
%

$ " #

"
'" ' *

'% # )
'
+ '"

SLIDE 9. Let us now consider why CRE is so important. The CRE methodology provides
a scientific basis for quantifying the chemical reactor performance, as measured by
volumetric productivity, selectivity, material and energy efficiency and environmental
impact as a function of input and operating variables, kinetic and transport rates and
mixing and flow pattern. An appropriate model of the reactor must be multi-scale in
character and describe a wide range of length and temporal scales. The molecular scale
events determine the mechanism and kinetic rates. Their description is rapidly moving
from the empirical to transition theory and quantum mechanics based calculations.
Micro and meso-scale, such as transport in a turbulent eddy or in a single catalyst
particle, determine local transport effects on the reaction rates and provide the source
terms in the species mass and energy balance equations. Their description is being
advanced from the empirical to DNS/CFD type models. To complete the reactor model,
which rests on mass and energy conservation laws, a reactor flow pattern must be
assumed or calculated. These descriptions are usually still at the primitive ideal reactor
level, for reasons to be described later, and need to be addressed. Full dynamic model
based process control and optimization also rests on a reliable reactor model.
Clearly, the choice of the reactor and how it operates affects the number of separation
units needed upstream and downstream and has a profound environmental impact.
Those that practice CRE at the high level control wastefulness better than those who are
using an ad-hoc approach to reactor design.

Environmental Acceptability,
as Measured by the E-Factor
Product tons
Industry

per year

Waste/product
ratio by weight

Oil refining

106 108

~ 0.1

Bulk chemicals

104 106

<15

Fine chemicals

102 104

5 50

Pharmaceuticals

100 - 103

25 - > 100

CHEMICAL REACTION ENGINEERING LABORATORY

S10

SLIDE 10. The enclosed table illustrates the so-called E factor of various
industries. Clearly, those that practice CRE at the high level produce the
fewest undesirable products per unit desired product. So-called high tech
industries, which are really high value added industries, like the electronic
industry used to be and pharmaceutical industry is now, have terribly high
E-factors and are not high tech at all from the environmental standpoint.
The other point that should be understood is that the so-called principles of
green chemistry are just one of the prerequisites for a green process.
Whether the process will be successful or not, depends on selection of
proper reactor type and its proper operation. A great number of new
processes is often abandoned due to inability to scale up reliably. Hence,
understanding of the multi-scale aspects of reaction engineering is lacking.

10

My First Assignment
as a Process Engineer (1967)
CARBON
FEED
MANHOLE
COVER

EUROPEAN (GERMAN) PROCESS:

CARBON + SULFUR
C
2S

electric arc

CS2
gas product

CARBON DISULFIDE
CS2

REACTOR: REFRACTORY
LINED KILN WITH
GRAPHITE ELECTRODES

LIQUID
SULFUR

LIQUID
SULFUR

HOT
ZONE
GRAPHITE
ELECTRODE

CHEMICAL REACTION ENGINEERING LABORATORY

S11

SLIDE 11. To illustrate the pivotal role of reaction engineering in

pollution prevention let me use an example from personal experience. My
first assignment as process engineer was to expand the capacity for
production of rayon fibers which utilized carbon disulfide as a solvent. In
Eastern Europe at that time, an expired German patent (that utilized coke
contacted by liquid sulfur in a refractory kiln heated by an electric arc
between two graphite electrodes) was the state-of-the-art technology for
production of CS2. Please, note that atom efficiency is 100% so the process
is from that point of view better than producing CS2 from methane and
sulfur, as the practice was and is in the US! The reactor operated
essentially at atmospheric pressure and our task seemed very simple to
replicate the design of the existing kilns in order to increase the plant
capacity. As we inspected the kilns in operation we soon discovered that
the existing manhole was not for cleaning purposes during shutdowns, as
we originally surmised.

11

Glowing Red Hot Coal !!!

Poisonous Gases !!!

2
3

4 '" ! 5 ( 6
6
6

THAR
THAR IT BLOWS !!!
Reactor Clearly Environmentally Unfriendly !

SLIDE 12. Without any warning often that manhole cover would open up
and discharge the glowing coal (coke) all over the place together with a
mass of toxic gases. You could not run for cover when the eruptions
happened because you would lose the respect of the operators then. So you
had to sort of look over your shoulder and nonchalantly say Thar it
blows!. This environmentally unfriendly reactor had very dire health
consequences for the operators who were exposed to this on a daily basis
since each kiln erupted about once a week and there were 5 of them!

12

+ (*
!" #

%
#

&

+ (*

'

(
)*

%
+(*

(*
9
!:
5
+
= !

;< %
% ;
&
#
'
% (

,- ./0
1

!5
$
#

&%
*

0"1
/-560
7
#

(
&%

#
*

2 %
34

;5

3
8

SLIDE 13. The point is that the reactor was selected poorly for the
process. It was the wrong reactor. Nevertheless, when we suggested that a
fluidized bed reactor with pre-volatized sulfur feed would not have a hot
spot problem and would be stable and work reliably, our suggestion was
dismissed as too risky (sounds familiar)? The aversion towards the risk of
adopting a new technology (not to replace but even to expand the plant
capacity!) led to the order that we improve on the existing kilns. We redesigned the hot zone the best we could, only to achieve 1 blowout of the
new kilns on the average of once in two weeks as opposed to one in every
five days for the old ones. That was considered a great success by our
management (they achieved their goal of increased capacity). So I came to
the US in the hope that reaction engineering here would be done right! I
was proven wrong. There is a morale and epilogue to the story. The old
kilns are now out of business.

13

Syn & Natural Gas

Conversion

Petroleum
Refining

MeOH, DME, MTBE,

Paraffins, Olefins,
Higher alcohols, .

Bulk
Chemicals
Aldehydes, Alcohols,
Amines, Acids, Esters,
LABs, Inorg Acids, ...

Fine Chemicals
& Pharmaceuticals
Ag Chem, Dyes,
Fragrances, Flavors,
Nutraceuticals,...

S14S2

HDS, HDN, HDM,

Dewaxing, Fuels,
Aromatics, Olefins, ...

Value of Shipments:
$US 637,877 Million
Uses of Multiphase
Reactor Technology

Biomass
Conversion
Syngas, Methanol,
Ethanol, Oils, High
Value Added Products

Polymer
Manufacture
Polycarbonates,
PPO, Polyolefins,
Specialty plastics

Environmental
Remediation
De-NOx, De-SOx,
HCFCs, DPA,
Green Processes ..

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 14. We need to recognize that the above example involved a

multiphase reactor and that multiphase reactors are important in all
process industries and contribute significantly to the national product. All
chemical, petrochemical, pharmaceutical and other manufacturing
industries use them.

14

REACTOR SCALE MODELS FOR CONTACTING OF TWO MOVING PHASES

Ideal Reactor Concepts:
G
1
A)

B)

Plug Flow (PFR)

U1
K

U2

2
1

Stirred Tank (CSTR)

C) Axial Dispersion Model

U1

U2

D) Need More Accurate Flow & Mixing Description Via

Phenomenological models based on:

1) CFD Models (Euler-Euler Formulation)
2) Experimental Validation: Holdup Distribution and Velocity Field

L
G
S

!
-- .

/
/

"#$%& $'()'*
&+++,
--/

L+S

" "0 *
%''%, 11*
&, &%$(%12
S15

SLIDE 15. In all of these technologies it is the chemical reactor, in which

chemical transformation takes place that is at the heart of the process. For
proper quantitative description of reactor performance it is important to
properly describe how are species brought into contact on smaller scale, by
flow and mixing. For example, when we have a reactor system with two
moving phases it is important to be able to describe the flow pattern of
each. In the past we relied on ideal reactor assumptions of treating each
phase as being either in plug flow or perfectly mixed. When reality did not
conform to these assumptions the axial dispersion model is often used to
match experimental observations but almost always lacked predictability.
To really advance the design, scale-up and operation of these reactors, we
must be able to describe the flow pattern and phase contacting better. We
need a better description via phenomenological models that capture the
physics of the flow. We need such models to be based on CFD calculations
which are experimentally validated. Everyone who has dealt with
multiphase flows will recognize the necessity of experimental validation of
the existing CFD codes due to uncertainty of closures used. The difficulty
lies in the opaque character of all multiphase systems of industrial interest
in which laser based diagnostic systems do not work. This can be
overcome by use of radioactive source based techniques introduced in our
laboratory. Thus, the modern approach to reactor modeling
requires:a)capturing the physics of flow by experimental means, b)using
CFD models and validating the results experimentally, c)completing
physically based engineering models for flow and mixing..
15

7 '"8
: ' % ;:%
OLD REACTOR: MIXER-SETTLER
WITH EXTERNAL RECYCLE PUMP

%9
# ' ' %
/-3"
--/ -3

5 "( ' %
%
#
<
" "/! "3 4
"" .3 /5

PRODUCT
t 40 min

HC
HF RECYCLE
with a pump !!
NEWER REACTOR: LIFT
PRINCIPLE: NO RECYCLE PUMP
PRODUCT

t 30 sec

HC

HF INTERNAL
RECYCLE
no pump !!
no leaky seals !!
Still HF is there!!

"" ""/
"

"/ - "
-3 !
>

SLIDE 16. Let us consider the application of CRE to the alkylation as an

example that illustrates the need for the multi scale approach to the problem.
The original process used stirred tanks (mixer settlers with heat exchanger) in
which HF used as the catalyst was recycled with the external pump. The
hydrocarbon parafin-olefin mixture and HF form two liquid phases. Low
concentration of olefins had to be maintained for good selectivity so micromixing
and point of introduction of olefins feed are reaction engineering issues. Many
stirred tanks in parallel are used. However, the process is environmentally
unfriendly due to HF use and leaky seals on the pump and reactor mixing shaft.
For that particular chemistry a lift type reactor, that avoids the rotating shafts,
and accomplishes mixing by utilizing the buoyancy force created in the mixture
of a light and heavy phase is to be preferred.
Quantum jump in technology, and its environmental friendliness, occurs with the
invention of super-acid catalyst, that can be contained on porous solid support,
and with solid acid catalyst deposited on solid support. New reactor
configurations suitable to deal with deactivating solid catalyst are now required.
We focus here on the liquid-solid riser arrangement. Proper reactor modeling
needed for scale-up can only be done if information on solids volume fraction
(holdup) distribution and solids velocity and mixing, as well as that of the liquid,
is known. This information is necessary to be coupled with kinetics of the
reaction and deactivation.

16

Radioactive Particle Tracking

(CARPT) Provides Solids
Velocity and Mixing Information

0 "
"
*76'! ,

"

Cold Flow Model

5. "
"
*
6'(&''! ,

"

0,,=
>,,=
3
4

Computer Tomography (CT)

Provides Solids Density Distribution

Tracer Studies Confirm Liquid In Plug Flow

(N > 20)
!""#$%

!""&$

'###

SLIDE 17. By building a prototype cold flow model of the riser, one can
execute appropriate studies to obtain the needed information and validate
the CFD code that can be used to predict liquid and solid mixing and
holdup distribution. Liquid tracer studies (with KCl as tracer and
electroconductance probes) quickly reveal that liquid is essentially in plug
flow (N > 20). At the time of this study in 2000 the prevailing assumption
was that solids are uniformly distributed and are in plug flow. The slip
velocity was assumed to be correlated with mean solids holdup via
Richardson Zaki correlation. This information proved inadequate for
precise design.
Our Computer Aided Radioactive Particle Tracking Facility (CAPT) was
then used to obtain full information about solids flow and mixing pattern.
An array of 28 2 NaI detectors monitors the motion of a single radioactive
particle (containing Sc 46) of the same size (2 mm) and density as the solids
used in the riser at a sampling frequency of 50 Hz. Gamma ray computer
tomography, with a single Cs 137 source and a fan beam of NaI detectors
that rotate 360 around the riser, yield the density distribution in various
planes.

17

#: #

'

#'"')
&

,A-

<!

' %# 2 '

/.

,D

+. '# '"F

,/

,--

"
'"5 '"
)
)
:# '"
' '% )
'
! #

D
/
.? -

.@

A-

'# '"F

' %# ' %:

-E
1
-E
?A

.DE
0

-E
?

./E
0

/E
1

-E
/A

DE
1

.A-A

&. '# '"F

-E
/
-E
,A
-E
,

#: #

-E
-A

'5 ?@ # ,>-- '# '"#

CB ,/A

'# '"F

":

: F

#/

@-

%)
'
"
% # ("F'
+ '"
"% '% G # %
'" '

D0A1?/,-

CB ,--

B 0- #

5 (
/A . ,-- #

'# '"F
,@

SLIDE 18. CARPT results reveal that a trajectory of a tracer particle

during its single sojourn through the riser is anything but a straight line!
Hence the individual particle does not experience plug flow but meanders
in a helical irregular path as it travels through the riser. However, upon
obtaining instantaneous velocities from 2000 trajectories of the tracer
particle and upon ensemble averaging them, a regular flow pattern with
solids rising in the middle and falling by the walls emerges. CFD
computations confirm that the instantaneous solids Eulerian velocities
form a complex 3D swirly pattern. Time averaging, however, confirms
CARPT results of solids rising in the middle and descending by the walls.
A quantitative comparison of time (ensemble) averaged axial solids
velocity from CFD and CARPT is in excellent agreement, as is the CFD
prediction of the CT determined time averaged solids holdup distribution.
Remarkably, solids kinetic energies determined by CARPT are also
predicted well by CFD. CARPT also provides diffusivities from first
principles from the Lagrangian particle trajectories.
This now provides the basis for a reactor flow pattern and mixing model
that can be coupled with kinetics of reactions and deactivation. The model
assumes liquid in plug flow, solids with their axial velocity profile and
superimposed eddy diffusivities. All parameters can be calculated from
CFD and are verified experimentally. Still the issue of how to introduce
olefins and keep their concentration low needs to be resolved.

18

$
/--

-E
1
'

: G

;: "

,A-

,--

')

H '

-E
/

-E
,

A-

,-

/-

?-

1-

# %"

B ,A
1

H '

'

: G

')

H '

'

2D = 0.26

-E
,

/I
2
S19 S2

#' %# J 0
0.18 2D 0.61

: G

')

2D

-E
?

-E
/

B -E
,A

# B , @??

-E
?

0-

-E
1

;: "

;: "

.1

A-

F#

#9

-E
1

.@

# B , 1D?

2D = 0.23

-E
?

H '

# B @DD

= 0.46

-E
/

-E
,

,-

/-

?-

# %"

B /-

#9

1-

A-

0-

,-

/-

F#

B -E
,-

?-

1-

# %"

B /?

A-

0-

F#

#9

B -E
/-

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 19. As a bonus from CARPT slides in the riser we obtain the
residence time distributions of solids which clearly show that solids are
much more backmixed than liquid. The RTD of solids is well represented
with 2-6 tanks in series, depending on the operating conditions CFD codes
are able to compute the RTD even in 2D axisymmetric simulation.

19

-/ /

!"

"!"-"

"

Drr ( ) = vr ( ) vr () d Dzz ( ) =
o

U z
r
o

z r ( ) o

vr ( ) vr () d + vz ( ) vz () d
o
?A-

B -E
1D
B /E
?0

?A

%8

%8

1-

B AE
/,

?-

?-/A-

B DE
-0

/A
/--

9-/ 4
4

- -/ 4
4

/,A
,A
-

B -E
1D
B /E
?0

,--

B AE
/,
B DE
-0

A-

-E
,

-E
/

-E
?

-E
1

" -5

%
S20 S2

,A-

-E
A

-E
0

-E
,

-E
/

-E
?

-E
1

-E
A

-E
0

" -5

&

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 20. Another bonus of the CARPT technique is the direct estimation
from first principles of the eddy diffusivity components. We see that axial
diffusivity is an order of magnitude higher than radial.

20


 
    
  
 
      

Dsz
UL

UL

UL

Dsz

US

Us
Deff

Us
ks 12
US

Dz
2

kLs 1

kLs

ADM

S21 S2

Dr
kLs

kLs 2

Two Zone

2-D Convection
Diffusion

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 21. Hence, now we have all the information ready to adopt any
level of reactor scale model that is needed. Moreover we have
experimental validation of CFD codes for modest scale-up factors.
However, we should not forget that we always need to worry
about phenomena on all scales. Dramatic reduction in deactivation rate is
possible via use of CO2 expanded solvent which may require use of a
different reactor type.

21

OLD APPROACH:

Scale-up In Size

NEW APPROACH:
Apply fundamentals on:
Molecular
Eddy / Particle
Reactor Scale

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 22. The previous example of alkylation illustrates well the reasons
as to why we must replace the old approach of reproducing the invented
chemistry in an ever larger equipment size (which is often unsuccessful) by
a new highly interactive modeling approach on all scales coupled with
needed experiments. This moves the process to commercialization faster
and meets the green processing requirements inherently as they are part of
the goals during process development.

22

REACTION ENGINEERING
Art

Science

Past & Present

Future

CHEMICAL REACTION ENGINEERING LABORATORY

S23

SLIDE 23. Thus, if we want to have high tech processes which will be
green, we must move reaction engineering from art towards science.
The days when the chemist found a magic ingredient (catalyst) for a recipe,
and the chemical engineer tried in earnest to get its full flavor expressed in
an available kettle, must be replaced by the coordinated effort of the
chemist to select the best catalyst and chemical engineer to provide it with
the best flow pattern and reactor.

23

BUTANE OXIDATION OVER VPO

O

n-butane

(VO)2P2O7

3.5 O2

+ 4 H2O

MAN

Active catalyst is a mixture of phases, including

-VOPO4, -VOPO4, -VOPO4 and (VO)2P2O7
Catalyst oxidation state is variable
O2
O2
V+3
V+4
V+5
HC
HC
Both heterogeneous and homogeneous reactions occur
[O]cat
O2
n-C4
MAN
COX, H2O
O2
Intrinsic rates affected by C4, O2, H2O, surface deposits, ...
OHOH~C-C-C~
:

<

S24

SLIDE 24. Another example of the need for better understanding of the
flow pattern in multiphase reactors is the celebrated green process of
butane oxidation to maleic anhydride with 100% carbon atom efficiency
which replaced the old benzene oxidation route. Catalyst investigations
revealed an intriguing mechanism involving variable catalyst oxidation
state. Attrition resistant catalyst was successfully made.

24

Circulating Fluid Bed (CFB) Reactor

Off-gas (COx, H2O,..)

Regen

Riser

Maleic Anhydride
Reduced
Catalyst

Main Reaction
O2

V+5

Air

Reoxidized
Catalyst

Solids
Flow
Direction

Catalyst Redox
Inert Gas
Butane
Feed Gas

V+3

O2
HC

V+4

O2
HC

V+5

Riser

CHEMICAL REACTION ENGINEERING LABORATORY

S25

SLIDE 25. This chemistry is then executed in a fluid bed-riser

combination to accommodate successive oxidation and reduction of the
catalyst. Yet, large scale operations apparently are not fully matching the
yield and productivity promise pointing to the importance of fully
understanding the contacting pattern in a multiphase reactor and its
changes with scale up.

25

Gas-Solid Riser

GAS-SOLID RISER

Gas-Liquid or Liquid Fluidized Bed

CARPT Detectors on Gas-Solid Riser

$

S26

SLIDE 26. In the systems with closed recirculation of solids it is difficult to

assess the solids recirculation rate and solids RTD. It is well known that
impulse injection of tracer leads to nonunique results for solids
recirculation rate and solids RTD. We have resolved this problem by using
the CARPT-CT technique by which with time of flight measurements in
the downcomer we can assess exactly the solids circulation rate. Moreover,
strategically locating detectors at entrance and exit of riser we get the
solids RTD and backmixing parameters. The experimental facility
consisting of a 6 diameter 26 foot riser is shown here. Detectors for
identification of particle trajectories in a fully developed region are also
shown.

26

OVERALL SOLIDS FLUX - TIME-OF-FLIGHT MEASUREMENTS

Solids Mass Flux (Gs) in the downcomer is :

Gs =

s s dA +
A

s' s' dA

s s s

Mean velocity can be calculated as

vs

H
t

average time of flight obtained for number of particle visits

Solid flux from
the hopper

Detectors to get
RTDs of the
sections in the
loop

Downcomer
Scintillation
detectors

H = 40 cm

Sc-46 radioactive particle

( 150 m , 2.55 g.cc-3 )

H= 2.2 m
Solids hold up

Radial Solids Hold Profile (Downcomer)

0.9
0.8
0.7

s = 0 . 59
-1

-0.5

0.6
0.5
0.4
0
0.5
Dimensionless Radius

1
S27

SLIDE 27. By tomography we establish that the solid holdup in the

downcomer is uniform and by time of flight measurement for our
radioactive particle we get the solids velocity. Thus, solids recirculation
flow is obtained.

27

Evaluation of Residence Time and First Passage Time Distributions

Distributions
from CARPT Experiments
Solids + air into
disengagement section

Typical
trajectory
of the
tracer

W
N
C
O

(3 ) C

(1 ) A

400

Riser

200

E
R

Lead shields

(2 ) B

600

Part of raw data from 3 detectors

800

Counts (#)

Solids
Solids from
from
hopper

Air inlet

20

30

40
Time (sec)

50

60

Time spent by the tracer between B-C should

not be counted in the residence time

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 28: In this slide we illustrate the ability of CARPT to determine

the residence time distribution time of solids in the riser. By monitoring
the appearance time of our tracer particle in the inlet plane of the riser and
in the exit plane of the riser, each monitored by a collimated scintillation
detector, we can determine the total time that the tracer particle spends in
the riser. For example, for the trajectory shown, the appearance A in the
inlet plane is not followed by tracer appearance at the exit plane but rather
by two additional consecutive appearances at the inlet plane B and C,
followed by tracer appearance at the exit plane, D. Hence, we know that
only time intervals A to B and C to D contribute to the residence time.
Only the time interval C to D contributes to the first passage time. Such
information is not available by conventional tracer studies where a
response to a pulse injection of multiple tracer particles is monitored.

28

FPTD versus Actual RTD

0.1

= 6.2

&

#!

'

()

!" #
!%

0.5

0.05

( = 13.52

0
5

0.04
0.03

&

()

= 2.3

+!,

'

0.5

0.01
0

( = 39.7

What is the true Dz ?

0
5

Differences in mean residence time of

66%:
Dimensionless variance by 170%

(!)
"(!( *

$
2

FPTD and RTD in FF regime

(shown)

Differences in

F -curve

Ugriser = 3.2 m.s-1 ; Gs = 30.1 kg.m-2.s-1

F - curve

0.15

Dispersion coefficient by 163%

FPTD and RTD in DPT

( not shown)
Differences:
Dimensionless variance by 195%
Dispersion coefficient by 207%
Bhusarapu et al., 2004, CREL Annual Report 04

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 29: To illustrate the distinction between RTD and FPTD, and point
out the confusion that may arise from impulse-response measurements
when it is unclear as to what is measured, we present this slide. Clearly the
mean residence time and the variance and, hence, the solids backmixing
inferred from the variance is vastly different, indicating that great caution
is advised when interpreting the results from the literature if people did
not use CARPT. This slide presents the probability density function (pdf)
for both the residence time distribution and first passage tracer
distribution at one operating condition. Even during first passage times
significant backmixing is detected. This information and the full blown
CARPT studies in the riser will provide the needed data base for validation
of riser models.
!

29

CARPT Single photon emission, point source tracking

Particle location inferred from number of rays detected in an assembly of
scintillation detectors Kondukov et al. (1964), Moslemian (1987), Devanathan (1991),
Degaleesan (1996).

':"# )'
'#
K
&

'# '".
':"

;:# '"%: "(

" :"L

'" ! # L

( ## '"
'" .
'
#
! '##.
'
'"

"# " " ':#

'# '"# &FF
+F
% "# " " ':#
'# '"#

"2 '

# &FF
+

"#

G
5 (

Constant r, variable
, equal volume cells

&FF
+F
.
)
) "
G < "
: ## 5
'
'"#

"# " " ':#

2'
# &FF
+F

v r = v x cos + v y sin
v = v x sin + v y cos
vz = vz
where cos =
M :G: " N
O: " #

(x1 + x2 )
(x1 + x 2 )2 + ( y1 + y 2 )2

: : "(
2'
# &FF
+F

Moslemian (1986);Devanathan (1990); Degaleesan ( 1996);Chaouki, Larachi, Dudukovic (1997);

A

Slide 30.
Using a pre-established algorithm, based on calibrated detectors,
instantaneous particle position is identified, filtered from the noise of gamma
radiation, and from successive two positions instantaneous velocity is identified
and assigned to the cell capturing the midpoint of two positions. Mean velocities
are evaluated by ensemble averaging the instantaneous velocities assigned to the
same cell. Appropriate turbulence quantities are obtained form the differences
of instantaneous and mean velocities.

30

Instantaneous Particle Traces FF Regime

1
+ !#) "

Ugriser = 3.2 m.s-1

36.7

Gs = 26.6 kg.m-2.s-1

36.1

36.1

35.4

35.4

34.7

34.7

34.1

34.1

33.5

33.5

32.8
-1 -.5 0 .5 1
x / R

32.8
-1 -.5 0 .5 1
y / R

37.4

37.4

36.7

36.7

36.1

36.1

35.4

35.4

34.7

. !

/
0

#+ )
1
!+ "

Z/ D

""

37.4

36.7

Z/D

/
0

Z/ D

. !

37.4

34.7

34.1

34.1

33.5

33.5

32.8
-1-.5 0 .5 1
x/R

32.8
-1-.5 0 .5 1
y/R

Zone of Investigation (Z/D) 33.5-36.7

Few times tracer passed through

the section straight, while many more
times tracer underwent internal
recirculation in the section.
Tracer downflow (negative axial
velocity) near the center(core region)
observed.
Span of residence times 0.1-100
sec! Three orders of magnitude !!

Bhusarapu et al., 2005a, Powder Tech., In review

CHEMICAL REACTION ENGINEERING LABORATORY

S31
Some of the typical trajectories of the tracer particle captured in
the riser section between 33.5 and 36.7 Z/D in the FF regime is depicted here. A
few trajectories are almost straight up and the particle travels upward at the
center of the column. Many more trajectories exhibit multiple loops including
strong tracer down-flow even close to the center of the column. The tracer
particle residence time in this section spans three orders of magnitude!! The
particle that moves straight up stays very short in the section, the one caught in
numerous down drafts stays very long. Only about 20% of the particles go
straight up without exhibiting downward velocities in the section of
interrogation.

31

High and Low fluxes Axial Velocity PDF

PDFs
High Solids Flux

Frequency

r / R = 0.94

*,
2$3 * * + !*
15
+ !
v

2$3 ) ( !#

!"
v

10

r / R = 0.44

20

2$3
v

10
5
0

20

5
0

1000

2000

0
-1000

1000

2000

-500

FF Regime

60
#
* #!,
% * !( 40

Z = 24

r / R = 0.07

15

No negative vels at center at

high fluxes

0
1000

500

Low Solids Flux

Frequency

2$3

40
$

r / R = 0.438

60

*+)
( + !#"
, #!% %

2$3

40

20

r / R = 0.938

,*
* ) !+ #

2$3

*+!

400

% ( !*

20

0
-1000

1000

200

0
-1000

1000

-1000

Clustering phenomenon
prevalent across CS low

600

##+ ,
( !, *

Z / D = 36

r / R = 0.063

60

0
1000

Frequency

250

,+(
2$3
, !) 200
v % " !)

%,

" % !"
# *!

20 2$3 ) * % !(
v

) , !(

15

15

10

10

100

50

1000

2000
$ 4

0
-1000

05 16 2$3

150

0
1000
2000
Axial velocity (cm/s)
4

70

' 16 v

-500

0
$

Z = 24

",

20 2$3

25

0
1000

500
$

70

Mainly near walls - high

DPT Regime

High Solids Flux

25

Bimodal in low, uni-modal at

high fluxes- center

Time-averaged vels are

negative near the wall - high
Downflow velocity in the
annulus increases with flux

' 1

CHEMICAL REACTION ENGINEERING LABORATORY

S32
This slide shows how the p.d.f. of axial solids velocity characterize
the flow dynamics. In the FF regime at high solids fluxes all solids flow up in the
center of the column, some down-ward flow is observed at r/R = 0.44 and much
down-ward flow at r/R = 0.94 close to the wall. In contrast, in the same FF
regime at low solids fluxes, a bimodal p.d.f. is observed at the center of the
column with many solid particles flowing downward even there, as well as at r/R
of 0.44 and near the wall. A very slow moving solids seem to be present at the
wall.
In the DPT regime one never observes negative or even small positive velocities
near the center of the column, with most of the downward flow occurring at the
wall. That downward velocity increases with solids flux.

32

Mean Velocity Field High Flux (FF Regime) - SNL

+
+

Bhusarapu et al., 2005b, I&ECR, In review

25 cm/s

+
-

50
4 m/s

45
40
35

Ug = 5.56 m.s-1

30
25

Gs = 144.5 kg.m-2.s-1

20

25 cm/s

15
10
5
0
-1

-.5 0
.5
X/ R

-1

-.5 0
.5
X/ R

-1

-.5 0
.5
X/ R

-1

-.5 0
.5 1
X/ R

Axi-symmetric with negligible radial and azimuthal velocities

Little axial variation fully-developed
Strong core-annular structure; Similar observations in DPT regime
CHEMICAL REACTION ENGINEERING LABORATORY

S33
The ensemble averaged solids velocity field for the Sandia riser at
high flux conditions is shown. Clearly the flow in the average sense is almost
axisymmetric and one dimensional. Solids rise in the middle and fall by the wall.
This is also observed at the CREL riser and at all other operating conditions.

33

Solids Backmixing RTD, TLDs

Bhusarapu et al., 2005b, I&ECR, In review

FF - Ugriser = 3.2 m.s-1; Gs = 26.6 kg.m-2.s-1

3

0.02

! $!
8
&

+ !% #
#!"

)(

m2/s

0.5

F- curve

2
1.5

0.015

!(
#

E (l/<l>), 1/cm

E (t/<t>), 1/sec

2.5
! $!

7
8

!
7
8

Core-annulus flow structure in

riser results in a RTD with
extended tail in the DPT
regime, while in the FF regime
it results in a hint of a dual peak
along with the extended tail.

" , !*
! * % ( !#
)(

0.01

M = 5.4
0.005

0.5
0

0
6

t/<t> (<t>= 1.19 sec)

l/<l>, (<l> = 358.4 cm )

Macromixing index decreases

with flux (not shown)

DPT - Ugriser = 5.49 m.s-1; Gs = 102 kg.m-2.s-1

1

.012
.01

E (t/<t>), 1/sec

! $!

!(
)+,

8
&

+! )
% !#

F-curve
E (l/<l>), 1/cm
l

+!

! $!

.008

0.5

'

7
8

.006

!
7
8

M =

)
! #
)+,

M = 9.6

.004
.002

Axial dispersion increases with

solids mass flux (not shown)

t/<t> (<t> = 10.1 s ec)

l/<l> (<l> = 1733 cm )

Mean of trajectory length

Characteristic length

Use of axial dispersion model

leads to wrong conclusions
regarding effect of operating
conditions on solids backmixing.
B

CHEMICAL REACTION ENGINEERING LABORATORY

S34
The core-annulus flow structure in the riser results in the RTD
with extended tail in the DPT regime and in a hint of a dual peak in the FF
regime along with the extended tail. As measure of backmixing one traditionally
takes the axial dispersion coefficient, but in actuality the macromixing index,
introduced by late professor Villermaux, is a much better measure of backmixing
and is obrainable directly from the tracetory length distributions determined by
CARPT.
The macromixing index decreases with flux indicating approach to plug flow.
Clearly, the use of the axial dispersion model leads to the wrong conclusion
regarding the effect of operating conditions on the extent of solids backmixing.

34

Solids Concentration FF, DPT Regimes

Bhusarapu et al., 2005a, Powder Tech. , In review

FF - Ugriser = 3.2 m.s-1; Gs = 26.6 kg.m-2.s-1

DPT - Ugriser = 4.5 m.s-1; Gs = 36.8 kg.m-2.s-1

0.08

Ug

0.07

In FF, a three layer stratification can

be seen with a gradual radial gradient.
In DPT too, a gradual radial gradient
of the holdup profile is observed.

0.06
Solids Holdup

Tomograms show a marked

difference in the holdup profiles.

0.05
0.04
0.03

Gs

m/s

kg/m2/s

3.2,
3.9,
4.5,
3.2,
3.9,
4.5,

26.6
30.1
32.1
30.1
33.7
36.8

- FF
- DPT
- DPT
- FF
- DPT
- DPT

0.02
0.01
0

0.13

0.27
0.4
0.53
0.67
Non-dimensional radius ( )

CHEMICAL REACTION ENGINEERING LABORATORY

0.8

0.93

S35.
Gamma ray CT scans show a remarkable difference in solids
distribution. In the FF regime a 3 layer structure is observed. In DPT regime a
thin layer of solids at the wall has experimentally decreasing solids holdup as one
moves inward to the center of the column.

35

SL36
Let us look now at the application of CARPT-CT in developing an
improved model for many of the bubble column uses. We have proven the
validity of this model for FT, methanol and DME synthesis. In process industry
bubble columns are operated at very high superficial velocity to increase their
productivity. These are buoyancy dominated churn turbulent flows.

36

D
%

'
' %

--/
%

-!

S37

"

SLIDE 37. This reminds us that successful contacting of gas reactants on a

solid catalyst in liquid solvent is needed. (The nice animation may not
work on the web site).

37

"

S38

SLIDE 38. To appreciate CARPT we show this brief animation that

exhibits the trajectory of the particle in a BC operated in churn turbulent
flow. The column on the right is operated at much lower gas velocity.
(We will repeat this separately at the end).

38

Reactor Model: Bubble Column Example

Flow and mixing model based on CARPT/CT validated CFD predicts tracer responses of
hot pilot plant AFDU in FT, DME and methanol synthesis
Gas

11.0

Data

Normalized Response

Pressure = 50 atm
Temperature =250 Deg. C
Ug = 25 cm/s

0.80.8

P
P

DET.

14.6
ModelRunSim_L1
Exp_L1
Prediction

0.60.6

Sim_L4
Exp_L4
Sim_L7
Exp_L7

0.40.4
00.0

20

"

time (s)

0.20.2

20
1

0.8

Liquid
Tracer 0.4

40

60

40Time (sec)
60

80

100

80

100

0.6

1-L(r)
Dzz

uz(r)

S39

time (s)
0

200

300

400

0.6
0.4

-R

100

0.8

Drr

'<
"

Detector Level 6

0.2

Gas

Detector Level 1

0.2

Gas Tracer

time (s)

0
0

100

200

300

400

SLIDE 39. Here we illustrate the development of a predictive flow pattern

model for bubble columns based on CT-CARPT data that were used for
validation of CFD codes. In churn turbulent flow parabolic gas holdup
profile drives the time averaged global scale liquid re-circulation in which
radial and axial eddy diffusivities are superimposed. The model is able.
with no adjustable parameters, to predict tracer responses for the liquid
and gas tracer measured at different elevations in an operating pilot plant
column at various processes.
This is important for design of bubble column for FT synthesis and
desulfurization of heavy fractions.

39

0 (>/
>
/ 3

1.00
0.95
0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00

4$ ; ??/
"
35>

A-

?-

/-

;:%2 '

1-

,-

<'. :%

-E
/

-E
1

-E
0

-E
@

&

.,./.?-

(a)

Ug, cm/s
P, Bar

.1"# '" ##

%:#

19 cm ID
12 cm/s

(b)

10
1

14
1

60.0

(e)

30
10

0.30
CT

<'. :%

-E
?A
-E
?

-E
/A
-E
/

-E
,A
-E
,
-E
-A
-

-E
/

-E
1
-E
0
"# '" ## %:#

Multiphase k-

-E
@

ASMM, DV
ASMM, SV

0.0
0.0
-20.0

-40.0

0.1

0.2

0.3

0.4

0.5

0.6

Dimensionless Radius

0.7

0.8

0.9

Two-fluid

0.25

20.0

-60.0

Two-fluid

40.0

1.0

T im e - a v e r a g e d H o l d u p

T im e -a v e ra g e d L iq u i d A x i a l V e l o c i ty , c m / s

-E
1

# ' %:

(d)

30
4

CARPT

-E
1A

S40
S2

(c)

30
1

ASMM, DV
ASMM, SV

0.20

0.15

0.10

44 cm ID
Ug = 10 cm/s

0.05

0.00
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

Dimensionless Radius

Implementation of Breakup and Coalescence Models

Peng (2004), Peng and Dudukovic (2004, 2005)

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 40. We have also obtained agreement with data in 3D churn

turbulent flow based on selecting a good estimate of bubble size. We
obtained a much better prediction of both liquid velocity and gas holdup
distribution by incorporating the BPBE into CFD calculations.

40

)
(
+ !&,

Time, 0
sec

S41
S2

/0
$- + ' &

(
.

19

Time,
sec

)
(
+ !&,

*
$- + ' &

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 41. Simulations of spreading of a tracer in the batch liquid, as well

as the passage of gas tracer, can be readily simulated in 3D once the flow
field is computed.

41

12 3 4516 1

12 -()

/47 36 2)35- )

88

@@*

%8 ,

Ug = 12 cm/s
Dc = 8

Ug = 10 cm/s
Dc = 18

@@*

%8 ,

*" ,

*" ,
S2
S42

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 42. From such simulations one can compute the eddy diffusivities
and compare with the CARPT data. Good agreement is obtained for axial
diffusivity in bubbly flow.

42

19cm

RISER

200 cm

19 cm

165 cm

RISER

14.5 cm

DOWNCOMER

200 cm
165 cm

20 cm

20
cm

Applications
Aerobic
Popular for cells with slow
growth rates
(Mammalian, algal cultures)
Extensively used for Effluent
treatment
Used as Fluidized beds with
immobilized bio mass
Anaerobic
Waste digestion, to produce
methane and hydrogen
Research Challenges
Complex multiphase flow
Oxygen transfer for aerobic
system
Spatial configuration/design
.#
E
:
,
/
,

,
,'

Slide 43 Airlift type of bubble columns with draft tube,

split and external leg are popular in many biological
applications. Optimal reactor selection may have an
effect on reactor productivity.
Let us illustrate this by considering micro algae growth
in such systems. This study was conducted by Professor
Al-Dahhan and his graduate student, Huping Luo, in our
CREL.

43

Interests in Microalgal/Cyanobacteria
High value products
Pigments (food color to immunoassays)
Biologically active substances (antiviral,
antifungal)
Polyunsaturated Fatty Acids (PUFA)

Biomass source
Single Cell Protein (human, livestock)
Food additives (alginates, xantan gums)

Renewable energy
Methane, biodiesel, ethanol or hydrogen

Wastewater and animal wastes treatment

CO2 Fixation

BB

Slide 44: Micro algae /Cyano bacterial cultures can

be used to produce high value added products, as
biomass source for food and feed, as renewable
energy source. Through the photo synthetic process
they fix carbon dioxide and release oxygen. So
availability of light is essential.

44

Problem Description
The major problem is light: its availability and its use efficiency
light intensity gradient in
a photobioreactor (PBR)
Cells Trajectory

Dark Center

Photolimitation
Photoinhibition

'

External
irradiance
Irradiance field I(x,y,z)

Mixing, which induce the beneficial flashlight effects,

can significantly enhance productivity

Bubbles

BC

Slide 45: Cells in their passage trough the reactor get

exposed to different levels of illumination. Too little
light leads to photo limitation, too much light to photo
inhibition. Proper mixing can significantly enhance the
beneficial flashlight effect.

45

Experimental setup

Application:
Photobioreactor

Flow Visualization

Velocity Profile
50

RISER

200 cm
165 cm

Exposure
light

Time, azimuthal and depth averaged axial

Velocity, cm/s

20 cm

14.5 cm

Light
distribution

DC 1cm/s

40

DC 5 cm/s
BC 2cm/s

30

BC 5 cm/s
BC 12 cm/s

20
10
0
0

Airlift Column

Cells Movement

10

20

30

40

50

60

70

80

90

600

200
0

10

20

30

40

50

60

0.6

0.8

Dimensionless Radial Position

60
50
40
30

EXP

20

Simulation of Wu
Ug=5 cm/s (this work)

10

Ug=1 cm/s (this work)

0
0

400

0.4

Draft Tube Column (DC)

vs. Bubble Column (BC)

-30

Cell concentration (*106 cell/ml)

19 cm

-20

700
600
500
400
300
200
100
0
0
800

0.2

-10

70

80

100

150

200

250

300

Time, hr

90

Time Series of Light intensity

experienced by the Cells in the reactor

50

Physiologically Based
Photosynthesis rate model

Dynamic Simulation
B>

SL46
Using CARPT one develops the velocity flow pattern of algae in the
system consisting of a riser and downer section. The ensemble averaged velocity
field becomes available as a function of air superficial velocity used. The shear
stress field is also developed.
In addition, for the first time, the illumination time distribution of the algae can
be calculated. Tomography provides the density profiles needed for proper
calculation of the Beer-Lambert effect. Coupling the illumination time history
with three basic states of the algae and algae kinetics ( not shown on the slide) one
can predict the reactor performance.

46

Cell'
s Concentration, *106
cell/ml

Dynamic Model -- Results ; Luo and Al Dahhan(2003)

80
70

(BC: Bubble Column;

SC: Split airlift column;
DC: Draft tube airlift
column)

60
50
40
30
20
10
0
0

BC_5cms
SC_5cms
DC_1cms

SC_1cms
DC_5cms

100

200

Time, hr

Simulation condition: External Irradiance: 250 E m-2 s-1; Initial Cells concentration:
8
106 cells/ml (BC: Bubble column; SC: Split column; DC: draft tube column.)

Note: This dynamic model approach can be extended to any

other physiologically based photosynthetic rate model and
more reliable irradiance distribution model
B?

S47:
Upon CFD validation, one can use the
combined reactor and cell model to predict cell
concentration in various reactor configurations to find out
that at the same constant volumetric average irradiance a
draft tube column is better than bubble column, and a
split column is far the best!

47

Particle trajectories

Plane including baffles

Vr , Vz plot :
Azimuthally Averaged Velocity vector

Vr

x Vz

(150 rpm) Reimp 12,345

Motor
Calibration
Rod

Single phase flow in STR :

results at a glance
Plane at bottom of the tank

Plane including baffles

Detector

Radioac
tive
Particle

Rammohan et al., Chem. Eng.

Research & Design (2001), 79(18),
831-844.

Blades

Disc
Baffles

Vr

, V

B@

SLIDE 48. Since stirred tanks are used in such a wide area of applications,
we have confirmed that CARPT is capable of faithfully capturing the mean
flow features, the intensity of vorticity and up to 80% of turbulent kinetic
energy in single phase flow, where CARPT data is compared to LDA, PIV,
etc. It takes only 16 hours for CARPT to obtain this information that takes
months for other techniques to acquire. But CARPT data can be obtained
in two and three phase flows where laser based techniques are useless.

48

Packed Bed With Two Phase Flow

Simulation Advances

Accounting for particle and

reactor scale wetting effect

Prediction of the porosity

distribution effect on flow
field
Description of multicomponent transport

G
L

Trickle-Bed

L
Packed-Bed

Ability to simulate periodic

operation
G

Packed -Bubble Flow

Cocurrent Downflow Countercurrent Flow Cocurrent Upflow

S49S2

Jiang et al., AIChE J. (2002),

Jiang et al., Catalysis Today (2001)
Khadilkar et al., Chem. Eng. Sci. (1999)

CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 49. Packed beds with two phase flow are also used extensively in
industry. We have made advances of being able to use commercial CFD
packages in modeling gas and liquid distribution in the bed given bed
voidage distribution. We can account for particle and reactor wetting
effects, describe multicomponent transport and simulate periodic
operation. CT has proven useful here.

49

Environmentally Beneficial
Catalytic Engineered Systems
TG1: Catalyst Design
and Preparation

TG2: Media and Catalyst

Supports

TG3: Experimental Design

and Advanced Measurements
CEBC U. of Kansas, U. of Iowa, CREL-WU

TG4: Multi-scale Process Model

- Quantum effects
- Molecular dynamics
- Rate theories
- Solvent thermodynamics and
kinetic effect
- Micromixing
- Multi-component transport
- Turbulence
- Mixing
- Computational fluid dynamics
- Reactor simulation
- Plant simulation
- Control
- Optimization

CHEMICAL REACTION ENGINEERING LABORATORY

CA

SLIDE 50. Based on the previously discussed concepts it is clear that

systems approach is needed in development of environmentally beneficial
catalytic engineered systems. We have joined the lead of the University of
Kansas, and with them and U of Iowa, entered into a partnership for
formation of a Center for Environmentally Beneficial Catalysis. CEBC
became a reality as one of the 4 new NSF ERCs on September 1, 2003.
The idea is to implement a highly interactive multiscale approach
consisting of experiments and modeling for development of new
environmentally beneficial catalytic processes.

50

! G# < ' '

! "5 '" " # '
"
'
" +
'%: '"'):"% # %#
#
! #': E !# "
'" G %'" )
) 5 5 %5" # " "% '
'"')
!
'" "(" "(
E

%5" # ;:
#
!'"
Molecular scale (e.g., discovery of green processes, improved
estimation of kinetic forms and constants, etc.)
Particle/Eddy scale (e.g., multi-component transport effects on
complex kinetics, etc.)
Reactor scale (e.g., full description of large scale flow patterns and
mixing, etc.)
'#
' # #
# "5
' 5 : ! # )'<# "%
' ;: "
!
E4"'< %( '))'<
"# "% ! # '" "( "% !
! "( # < !#
.: # ## " )
'
'
% '"')
'
)
'
" E "
'% #
# " ""'
% <!
"
! )'< ) %# "% ! # %# G: '"# "#:!# #
# &
" %
# " % %)
' 5 % '"')! '% #E
C

SLIDE 51. In conclusion, it seems clear that the best way to prevent
pollution is at the source. This requires the multiscale CRE approach
consisting of molecular, particle/eddy and reactor scale considerations.
Most reactor systems involve multiphase flows and we must validate CFD
codes for them before we can use them in design and scale up.

51

'" ": %
% '"G # % !";: # 7
"%
G ') '5%"(% )
' 5 % '"')
'% #
') ! "#
G# %
'
'% #E
!
(" :% ')
'" G: '"# ' ' : '"
5" '" "% %: '"% "%# '" ! 5 ')
('5 " " "% 5 )
:"%"(')
8
Fundamental CRE research
Generic research of various existing and new reactor
types
Development of sustainable technologies
(This in turn requires stable energy sources and
globalization of regulations).
CHEMICAL REACTION ENGINEERING LABORATORY

SLIDE 52 Gamma radiation based techniques like CT and CARPT are

capable of providing data for validating CFD codes and this gives rise to
phenomenological reactor models.
The magnitude of CRE contributions to sustainable technology depends on
the available funding of CRE research of various existing and new reactor
types. Reactor scale research must be kept alive and on par with
molecular scale discoveries.
Ultimately CRE contributions will depend on demand for it which is
related to development and implementation of sustainable technology.
A major activity in this direction requires globalization of environmental
regulations and solution to the energy question. Clean, stable preferably
sustainable energy sources must be found. This per se is the key issue of
green processing and is deserving of an Apollo type federally funded
research program.

52

3 0/
" 5" "3 4>3-3 -/ !! -3 4
4 3
-3 35 / !.- " "- 3 353"" 35-3
-?/ .35 3= "
8
" .3 /5"
)

65 )

), '' ": ":#:!

), *'' ": "::!'

)7 9

)/4

)) ,#;!#<="
5

377 /
)
2
5

)/
*

S53

3
)64(
2
5

2 > 3,
6
@
6
2 %
A
@ ?
3 %
5
73 (
2
?5
7 %
B

?
*
5

4
5

5
3 %
3
7

) 3
5

2)2
-1

7
@

1
@ ?

3
)
2
/-)6( -53
/ / 3
6 /
4

SLIDE 53. To develop experimental and modeling resources for advancing

state of the art descriptions of reactor scale flow patterns and mixing
requires a lot of resources. We at CREL were fortunate in the past to
enjoy government and industrial support. We also had excellent students
that worked with us. The future is less certain as molecular level research
is exclusively emphasized, and production facilities move off shore and
companies keep merging! However, as I illustrated today, reactor scale
advances are needed in addition to molecular scale discoveries to convert
green chemistry to green engineering and sustainable processes.
I am especially thankful to the National Science Foundation
for the engineering research center grant (EEC-0310689) for the Center
for Environmentally Beneficial Catalysis (CEBC) which made it possible to
put some of these ideas together, hopefully in a coherent way.

53

+
0

(
+ 0/*

F
F


    
  



     
     

1 C
!#"$&%')(+*-, .&/0(&/1$2*-3 (&, /4, /15#.+687)*-%1$:98/*;7
!=<>$?1(&/'98@A98/*4.6B39+(:'C*-, .&/298/15&, /94983D, /15E@A9+*-F1.4$4.&G .45H
!JIK3 (&/17C6983:.+6:7)*;(4* 9+LD.6LD*-F9+LD(B3;*B39+(:'C*-, .&/A98/15&, /949&3D, /152*;.M, /1$&%17)*-3D, (&GN43 (:'C*D, '9
377 /
3
7
7 3


)

,2
4

4
2
(

!3
- 3"
S54

5
5
5
5
)

(
-1

SL54
If you have a multiphase reactor modeling or scale up problem I
invite you to work with us.

54

CONVENTIONAL APPROACH:
End-of-the-pipe-clean-up,
improved house-keeping,
waste reduction, retrofitting,
recycle, environmentally
benign processing.

UNCONVENTIONAL INNOVATIVE IDEA DISCUSSED BY TWO

GENTLEMEN ABOVE: The only other solution is that, with the
help of genetic engineering, we may evolve into a species immune
to all this junk.
CC

SLIDE 55. Just to ensure that you can think outside the box let me inspire
you with this cartoon. Since all research money seems to be flowing into
the genome related research perhaps this unconventional idea is less far
fetched than you think.

55