chemical

engineering
Science,
Printed in Great Britain

Vol.

43,

No.

8, pp. 2073-2078,

E xtended

re a c tor

wLl!L2sOY/8x$3.w+O.w
Pergamon Pressplc

1988

conc ept

D.W. Agar

for

dyna mic

D e N O x d e sign

and W. Ruppel

BASF AG, Ludwigshafen,

West

Germany

Abstract
An analysis

of chemical
reactors
according
to their
use of internal
and external
heat
and mass
reactor
with
periodically
transfer
reveals
a new reactor
configuration
- a chromatographic
reversing
flow_
The application
of this
configuration
in the
removal
of nitrogen
oxides
from
stack
gases
by selective
catalytic
reduction
with
ammonia is described_
The new reactor
offers
high NOx-removal
rates
without
ammonia slip
emissions
and ameliorates
problems
associated
with
the fluctuations
and distribution
of the
gas.
The detailed
kinetic
modelling
and preliminary
experiments
used to establish
the feasibility
of the process
are presented.
The necessary
criteria for the use of this
new reactor
type and its
relationship
to the catalytic
heat
regeneratorreactor
are discussed.

In many of the chemical

reactors
used in heterogeneous
catalysis,
the chemical
reaction
itself
is only one of several
processes
taking
place.
In addition,
one often
has internal
and external
mass and heat
transfer
processes,
which
can be of critical
importance
for
reactor
performance
and in subsequent
processing
steps.
Distinctive
reactor
types
can be distinguished
according
to
the dominant
transport
process:
whether
it involves
heat or mass, whether
it is primarily
interwhether
it is diffusive
or convective
and its
direction
relative
to the fluid
nal or external,
stream
(I).
Such an analysis
yields
an interesting
analogy:
given
a reactor
with
a certain
heat
transfer
configuration,
it is almost
always
possible
to find
a corresponding
system
for
mass
transfer.
A generalised
reactor
consists
of three
basic
components:
the fluid
being
processed,
the catalytic
phase responsible
for carrying
out the reaction
and the vessel
in which the reaction
occurs
(Fig.
1). The catalytic
phase
has thermal
(heat
capacity,
conductivity)
and perhaps
adsorptive
properties
in addition
to catalysing
the reaction(s).
Similarly
the vessel
wall
can
be permeable
to heat or mass and have ports
through
which convective
transport
takes
place.
In a
tubular
reactor,
the
individual
properties
of the catalytic
phase
and the wall
can be distributed
appropriately
along the reactor
length.
The recently
deveIoped
catalytic
heat regenerator
(2) represents
a reactor
in which the thermal
properties
of the catalytic
phase are exploited_
By using the catalyst
as a thermal
buffer
it is
able to assume
the function
of a heat
exchanger,
with the simplification
and savings
that
this
entai Is.
The reactor
utilises
the well-known
dynamic
behaviour
of thermal
waves
in exothermic
systems
to achieve
reaction
temperatures
greatly
in excess
of the steady
state
adiabatic
values.
By periodically
reversing
the flow direction,
the heat
of reaction
is retained
within
the
bed
and used to heat up the incoming
feed
gas.
The reactor
is especially
suitable
for
non-autotherma1 systems,
i.e.
dilute
gases,
and has already
been employed
commercially
in sulphuric
acid
production.
An analogous
system
involving
equivalent
mass transfer
processes
can also be envisaged,
in which
the adsorptive
properties
of the catalytic
phase
are utilised
instead
of its
heat
capacity
(3).
Reactants,
rather
than heat,
are retained
within
the bed by means of their
selective
adsorption
- a concept
we11 known from chromatographic
reactors
(4)
In order
to prevent
a breakthrough
of
the reactant
being
adsorbed,
the reactant
is supplied
discontinuously
to the feed
and the flow
is periodically
reversed
(Fig.
2).
For the
simple
bimolecular,
irreversible
and isothermal
reaction
illustrated,
a typical
cycle
comprises
four
phases.
In the
first,
the
reactant
being
adsorbed
(B) is introduced
in excess
and forms
a front
within
the
bed,
which
gradually
moves
toward
the exit.
In this
phase
the other
reactant
(A) is completely
converted_
In the
second
phase,
no B is supplied
- A, however,
continues
to react
with
the excess
B previously
adsorbed.
The original
breakthrough
front
continues
its
chromatographic
progress
down the
reactor
and a
second
front
is formed
due to the removal
of adsorbed
B via the reaction
and due to its
desorption.
The net effect
is a diminishing
zone of B moving through
the reactor,
reflecting
a complex
interaction
between
adsorption,
desorption
and
reaction.
The third
phase
is a repeat
of the
first,
but with a reversal
of the flow direction_
The existing
B zone is overtaken
by and submerged beneath
the new front
formed by the excess
B now being
supplied,
thus
producing
a defined
state
symmetric
to that
at the end of the
first
phase.
The fourth
phase
is identical
to the
second
except
that
the flow
is reversed.
Following
the fourth
phase,
the cycle
is repeated.
In
2073

D. W. AGAR

2074

Fig.

1: Generalised

reactor

scheme

and W.

for

RUPPEL

heterogeneous

E5

catalysis

=&A

Fig_

2:

Simplified
reversing

flowsheet
flow

of

a chromatographic

reactor

with

periodically

1X0S.V.

= 1300

h-1

T = 300 C

-z
5:

600-cl
3
400-

%L3 = 900 ppm

200-

Nttg-Beladung:0.24 Gew. "b

Fig_

3:

Measurement

and caIculation
of NH
adsorption
behaviour
on denitration
catalyst.
The
curve
shows the
calculated
results
?of breakthrough
experiment
at 300
C and
1 bar
on 77
cm3 post-desulphurisation
4 mm pitch
monolithic
catalyst
with S.V.
= 1 300 Nm3/m
cat-h.
At t = 0,
900 ppmV NH
were
added
to the
carrier
gas
(N +3% 02)
being
passed
through
the
monlithic
element.
Alter
total
breakthrough
(t
= 7 260
s)
NH
was
cut
off
and
the
adsorbed
ammonia
allowed
to
desorb.
The breakthrough
times
fbr
5 8 ppmV NH
measured
in
the
reactor
outlet
using
a rough
indicator
method
were
5 400
s for
adsorpt?on
and
9 900
s for
desorotion.

Extended

E5

contrast
occurs

reactor concept

to the
usual
chromatographic
over the whole cycle
and removes

for dynamic

DcNOx

there
is no
reactor,
the adsorbed
component

design

2075

regeneration
phase,
from the system.

the

reaction

To control
the duration
of the phases
one can either
follow
the B front
in the first
and third
phases
or the
level
of A in or before
the
reactor
exit
during
the
second
and fourth
phases.
the remaining
phases
are of fixed
duration,
the interval
Regardless
of which option
is selected,
being determined
by reactor
design.
The following
criteria
must be fulfilled
if the reactor
is
to function
properIy:
the adsorption
must be selective
and high enough to yieId
reasonable
cycle
times
1.
this
means uptake
in excess
of 0,l % by wt.
- for typical
industrial
catalyst
loadings,
2.
the rate
of adsorption
must be comparable
to the.rate
of reaction
- to ensure
that
suitable
breakthrough
fronts
are formed
the rate
of desorption
must be slow
3.
ideally
it is rectangular
with 2, defines
the form of the adsorption
isotherm,
- this,
the reaction
must be irreversible
and free
of side reactions
4.
- the absence
of a reactant
in the end zone would lead to reverse
reaction.
The high residence
time of the adsorbed
component
could
cause
difficuIties
with
otherwise
negligible
sidereactions.
The chromatographic
reactor
with
periodically
reversing
flow
offers
two interesting
features:
the high level
of one reactant
in the middle
of the reactor
(corresponding
to the temperature
in
the catalytic
heat regenerator)
and the exclusion
of this
reactant
from the product
stream.
Both
characteristics
are of interest
in gas purification
processes
in which an impurity
is removed
by
the
insensitivity
of the reactor
reaction
with an externally
introduced
component_
In addition,
to the fluctuating
concentration
values
common to such problems
makes
it attractive_
A periodic
catalytic
process
with flow reversal
has already
been described
for
the
removal
of traces
of
oxygen from nitrogen
and argon by the addition
of hydrogen
(5).
Another
suitable
reaction
is the
seIective
catalytic
reduction
of nitrogen
oxides
in stack
gases
using
ammonia,
the so-called
SCR
reaction
- an important
measure
in air pollution
control
(6).
The SCR reaction

is

described

by the

equation:

4 NO + 4 NH3 + O2 -

4 N2 + 6 Ii20

The reaction
is carried
out on a variety
of catalysts,
usually
based
on titanium,
vanadium
and
at temperatures
between
280 and 420 C. Various
configurations
are
possible
tungsten
oxides,
depending
on the
sequence
in which
dust
remova1,
desulphurisation
and
denitrification
are
carried
out.
The arrangements
differ
in the form and activity
of the catalysts
used,
the reaction
temperature
and the energy
demand3
A typical
coal-fired
power station
in West Germany can
achieve
NO values
of around
1 000 mg/m
(calculated
as NO basedo&-51~g~$$!~~h
redulre;;&
firing,
measures
alone.
In the
Federal
Republic
of Ger Any
SCR
coal-fired
power
stations
of 300 MW or more achieve
NO emissions
of 200 mg/m3 or less.
processes
represent
the only proven
technology
available
for this
purpose.
As ammonia emissions
of ammonia has to be very carefully
matched
to the flow and NO
may not exceed
5 ppmV, the supply
together
with dramatic
fluctuations
in gas amount
concentration
in the gas. Analytical
problems:
distributions
in the
massive
reactors
and composition
and the
difficulty
of obtaining
even
makes the operation
of SCR reactors
a formidable
task.
involved,
It has been known for some time that
the SCR catalysts
can adsorb
considerable
amounts
of ammoa fact
which
must
be taken
into
account
when developing
control
procedures
(7,8).
The
nia,
chromatographic
reactor
with periodic
flow
reversal
enables
this
otherwise
complicating
factor
to be used to the processs
advantage.
To establish
the feasibility
of using
such a reactor,
the
adsorption
of amnonia on commercially
available
denitrification
catalysts
was studied
experimenBreakthrough
and desorption
curves
measured
at technically
realistic
temperatures
and
tally.
space
velocities
confirmed
model results
derived
from the ammonia adsorption
behaviour
assumed
in kinetic
models
of the SCR reaction
(Fig.
3).
For fine
monoliths
(with
channels
of 4 mm or
less)
the rate
of adsorption
could be shown to be comparable
to the space time velocity
and much
faster
than the rate
of desorption.
The amount of ammonia adsorbed
(0,29
% by weight
for
a gas
phase
ammonia concentration
of 2000 ppmV and a typical
post-desulphurisation
catalyst)
and the
absence
of ammonia decomposition
or oxidation
with oxygen also fulfilled
the necessary
criteria.
a dynamic
model of the chromatoHaving established
rough values
for the adsorption
parameters,
graphic
reactor
with
periodic
flow reversal
was developed
for
the
SCR system
on the
basis
of
kinetic
data derived
from an extensive
study of SCR process
data
using
a well
established
model
(9) capable
of describing
dynamic
and steady
state
behaviour
over a large
concentration
range.
The system,
which is assumed
to be isothermal,
can be represented
by the following
equations:
Ammonia adsorption
SCR reaction:
fluid

phase

G . -$$i
yi

mass balance:
= z4 _ Mi _ Nil5

=y;
z=o

NH3
NH3X

+
+

X _
NO +

NH3X
l/4 02-N

3/Z

H20

(1)
(2)

D. W. AFAR and W.

2076

catalyst

phase

dN.

mass
2

QK

1
j=l

Ni

x1

E5

RUPPEL

balance:
(41

vij-wj

Ni /x=0=

Ni (x=6=

Pi

13; . dci

ax

(5)

(Ci

*E

yi)

ammonia
dq
r7Z

adsorption:
=

r-D-.

$S

0,6

reaction

+Z

Qk

(simplification

jf,

Vi5

warranted

(6)

WJ

by catalyst

physical

. ( P,,,H

- (1 - q) -

properties)

=
and

adsorption

Ammonia adsorption:
SCR-reaction:

kinetics:
w1
w2

=
=

k,(T)
k*(T)

. q - pNo

9)

(7)

ad.
(8)

This non-linear
boundary
value
problem
is solved
numerically
usi ng an implicit
finite
difference
The mesh points
and the time
step
interval
are auto smatically
adjusted
to match the
method (10).
stable
and
movement of the adsorption
and reaction
fronts.
This procedure
1eads to a numerically
which
is especially
suited
for
the
simulat ion of wavefront
phenomena_
The
flexible
algorithm,
solution
of the equations
gives
the concentration
profiles
for NO and ammonia in the gas phase
and for the adsorbed
ammonia along
the
length
of the reactor
and across
the catalyst
wall
as a
shown illustrates
a complete
half-cycle,
i.e.
up to the
function
of time (Fig.
4). The sequence
point
at which the flow would be reversed,
taken
to be when the NO level
in the reactor
outlet
reaches
100 ppmV.
the reaction
is confined
to a small
zone at the front
of the
During
the phase
with ammonia,
This behaviour
reflects
the high diffusional
reactor
and in the outermost
layer
of the catalyst.
The ammonia is only
adsorbed
downstream
of
resistances
within
the fine
pores
of the catalyst.
the
reaction
zone
and gives
a breakthrough
front
much less
influenced
by diffusion
than
the
a time designed
to prevent
ammoreaction_
When the ammonia supply
is cut off after
67 minutes,
the ammonia level
in the gas phase drops
off
almost
immediania emerging
in the reactor
outlet,
tely
to a low level_
A NO front
is formed
which steadily
proceeds
down the reactor,
exhausting
the adsorbed
ammonia reserves
as it goes.
The downstream
end of the
adsorbed
ammonia
profile
scarcely
moves at all due to the slow desorption
characteristics.
The example
demonstrates
the basic
feasibility
of the process.
The mean NO conversions
and NH
slip
values
obtained
( >99
% and <I
ppmV respectively)
are well
below those
required
and th$
cycle
interval
(150 mins.)
is realistic_
Reactor
operation
is controlled
by the measurement
of a
single
parameter
- NO - and avoids
the necessity
of measuring
very low levels
of ammonia slip
at
By virtue
of the ammonia stored
on the catalyst,
the process
is relatively
high NO conversions.
A further
advantage
is its
suppresinsensitive
to fluctuations
in gas flow and concentrations.
sion
of the
effects
of irregular
ammonia
distributions
over
the
reactor
cross
section.
The
requirement
for fine
monoliths
to attain
the necessary
adsorption
rates
means that
the process
is most suitable
for use with dust
free
systems
following
the desulphurisation
stage.
The lower
temperatures
employed
and the higher
conversions
demanded
in this
arrangement
also
favour
use of
the
reactor
could
also
be constructed
as a
the
reactor
in this
configuration.
In practice,
rotating
monolith
cylinder
with four
zones
corresponding
to the four
cycle
phases,
in order
to
It would also
be advantageous
to concentrate
the
obviate
the need for switching
high gas flows.
adsorptive
properties
of the catalyst
where they are most effective
- in the reactor
end zones
and in the centre
of the catalyst
wall.
By using
chromatographic
retention
and,
in effect,
integrating
the reaction
stoichiometry
over
successive
cycles,
the chromatographic
reactor
with periodic
flow reversal
permits
almost
total
stochastic
input
conditions_
NO conversion
without
ammonia slip
emissions,
even with non-ideal,
Furthermore,
the analytical
requirements
for
reactor
control
are much less
exacting
than
those
In common with
the
catalytic
heat
regenerator,
employed
for
reactor
operation.
steady
state
the reactor
utilises
non-catalyand in contrast
to most previous
work with periodic
processes,
Both reactor
types
involve
clearly
tic,
macroscopic
catalyst
properties
to improve
performance.
defined
physical
behaviour,
facilitating
reactor
design
and both entail
boosting
the value
of a
making
them
especially
suitable
for
reaction
parameter
within
the
central
reactor
section,
dilute
gas systems.

E5

Extended

reactor concept

for dynamic

DeNOx

i= N O
t = 3950

t -

Fig.

4:

Development
of NO and NH concentration
profiles
the gas cc.1 and on the zatalyst
(q) during
one
cycle
of &actor
operation.
T = 300 C, P = 1
S.V.
= 1 300 Nm/m
cat-h,
gas velocity
= 0,34
post-desulphurisation
monolithic
catalyst
with
pitch.

7800

in
half
bar,
m/s
4 mm

design

2077

2078

D.

W. AGAR and W. RUPPEL

E5

Notation:
a
C.

k
G

ki
k
ppd
ml
N
:
t
T
i

X
Y.
zi

channel
width ,
m
concent rat ion
of the species
i in the3gas
phase ,
kmol /m3
total
ads ohase
concent rat ion .
kmol /m
di f fusion
coef f icient ,
mL/s
speci f ic
mass f lux
in the gas phase ,
kg/m2 . s
rate constant
for react ion
j , kmol /bar . kg
cat -s
_,
equi l ibr ium
constant
for ammonia
adsorpt ion ,
bar
molecular
weight
of species
i , kg/km01
mean molecular
weight
of the gas phase ,
kg/kmol
speci f ic
molar
f lux of species
i in the catalyst ,
kmol /m2 . s
par t ial
pressure ,
bar
adsorbed
ammonia
as a fract ion
of the saturat ion
value
t ime ,
s
temperature ,
OK
kinet ic
rate expression
for react ion
j def ined
by equat ions
catalyst
wal l width
coordinate ,
m
mass
fract ion
of species
i in the gas phase
catalyst
bed length
coordinate ,
m

Greek
P
s
vi j

Pk

(1)
(2)
(3)
(4)
(5)
(6)
(71
(81

(9)

(ID)

let ters
gas f i lm mass
t ransfer
coef f icient
fo5
saturat ion
ammonia
adsorpt ion ,
kmol /m
hal f -breadth
of the catalyst
wal l ,
m
stoichiomet r ic
coef f icient3for
species
catalyst
bed densi ty ,
kg/m

species
cat .

i,

i in reaction

7 and

8,

kmol /kg

Subscr ipts
and
e
ef fect ive
i species
j react ion

m/s

cat -s

Superscr ipts

0 inlet

D . W . and Ruppel ,
W. ,
1988 ,
Erwei ter tes
Reaktorkonzept
zur
Entwicklung
neuer
MethoWar,
den der Reakt ionsfuhrung ,
Chemie-Ingenieur-Technik ,
to be publ ished
1985 , Unsteady
processes
in catalytic
reactors,
Studies
in Surface
Science
Mat ros ,
Yu . ,
and Catalysis ,
22
Agar ,
D-W . ,
Rumel ,
W. ,
Holder ich ,
W.
and
Drews ,
R. ,
(BASF
AG) ,
1988 ,
Verfahren
zur
Entst ickung
von Rauchgasen ,
German
patent
appl ied
for , Dec .
1987
J . and Lander
S.H. ,
1986 ,
Coca ,
Doing
chemist ry
in the
gas
chromatograph ,
Chemtech
16
(l l),
682 - 689
Agar ,
D-W . ,
Jaeckh ,
C . and Gal lei ,
E. .
(BASF
AG) ,
1985 ,
per iodisches
Verfahren
zur Feinreinigung
von Iner tgasen ,
German
patent
no . DE 3 401 197
Kot ter ,
M. ,
Lintz ,
H . -G . ,
and Weyland .
F. ,
1986 ,
selekt ive
Redukt ion
von St ickoxiden
in
Rauchgasen
- Stand
der Technik
und neue Wege ,
Chem . -Tr ig . -Tech . ,
58 (8) , 617 - 623
Zenz ,
J. and Helber ,
F. ,
(STEAG
AG) ,
1987 ,
Verfahren
zum AbschKden
von St ickoxiden
aus
Rauchgasen ,
German
patent
no . DE 3 604 045
Ase ,
H . and Koyanagi ,
M. ,
1987 ,
per iodic
cont rol
of catalyt ic
deni t r i f icat ion
systems
in
Internat ional
federat ion
of automatic
cont rol ,
10 th .
Congress ,
refuse
incinerator
plant ,
Munich
1987 ,
VDI /VDE-Gesel lschaf t ,
DDsseldorf ,
Vol .
2 , 326 - 331
Miyamoto,
A., Yamazaki,
Y., Hattori,
T. ,
Inomata
M . and Murakami ,
Y. ,
1982 ,
Study
on the
pulse
react ion
technique
- VI kinetics
of the reaction
of NO wi th
NH3 on vanadium
pent -

oxide
Butt,
tor

catalyst,
J.B.,

Journal

Weng ,
H.S.
dynamics ,
Chemical

of Catalysis,

74,

122 - 155

and Eigenberger ,
G. ,
Engineer ing
Science ,

1975 ,
Catalyst
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poisoning

and

f ixed

bed

reac-