Professional Documents
Culture Documents
Fixed-Bed Reactors
GERHART EIGENBERGER, Institut flir Chemische Verfahrenstechnik, Universitiit Stuttgart, Stuttgart,
Federal Republic of Germany
In additIOn to the standard symbols defined N energy required for coolant circulation.
m the front matter and on pp. 6-9 and 121- kW
t 23 of this volume. the following symbols are Nil Nusselt number
used: Q heat flow to be transferred. kW
Re Reynolds number
ap specific outer surface area of catalyst. Sc Schmidt number
m l lm 3 packing Sh Sherwood number (Eq. 2. to)
A flow cross-sectIOnal area, m 2 T temperature, K
c molar concentratton. mol/m 3 To feed gas temperature. K
Co feed concentratton. mol/m 3 U Circumference. m
cpG specific heat of reaction gas, kJ kg - I K - I Uw gas-catalyst heat-transfer coefficient.
c, specific heat of catalyst. kJ kg - I K - I Wm- 2 K- I
D diffusion coefficient. mlls t' G interparticle velOCity. m/s
dp catalyst particle diameter, m V volume flow rate. m 3 /s
dh hydraulic diameter (dh = 4 AI U). m VR reactor volume. m 3
11.2 Ergun coefficients (Eqs. 2.4. 2.5) II' migration velocity of reaction zone. mls
Gz mass-flow velocity. kgm-ls- I
= space coordmate, m
kG gas-catalyst mass-transfer coefficient. ZL reactor length. m
m/s ':1. w \\all heat-transfer coefficient.
L length of catalyst bed. m Wm- 2 K- 1
®
1. Introduction
Catalytic fixed-bed reactors are the most im-
portant type of reactor for the synthesis of large-
Heat
scale basic chemicals and intermediates. In these carrier
reactors, the reaction takes place in the form of
a heterogeneously catalyzed gas reaction on the
surface of catalysts that are arranged as a so-
called fixed bed in the reactor. In addition to the
synthesis of valuable chemicals, fixed-bed reac- Heat
tors have been increasingly used in recent years carrier
to treat harmful and toxic substances. For exam-
ple, the reaction chambers used to remove nitro-
gen oxides from power station flue gases consti-
tute the largest type of fixed-bed reactors as
regards reactor volume and throughput, while Figure 1.1. BaSIC type-; of catalytiC fixed-bed reactors
automobile exhaust purification represents by A) AdiabatiC fixed-bed reactor; B) Multitubular fixed-bed
far the most widely employed application of reactor
fixed-bed reactors.
With regard to application and construction,
It is convenient to differentIate between fixed- fixed bed that is surrounded by an outer insulat-
bed reactors for adiabatic operation and those ing jacket (Fig. 1.1 A). Adiabatic reactor designs
for nonadiabatic operation. Since temperature are discussed in Chapter 3.
control is one of the most important methods of Since the incoming reaction gases in most
influencing a chemical reaction, adiabatic reac- cases must be heated to the ignition temperature
tors are used only where the heat of reaction is of the catalytic reaction, adiabatic reactIOn con-
small, or where there is only one major reaction trol is often coupled with heat exchange between
pathway; in these cases no adverse effects on the incoming and exiting reaction gas resulting in
selectivity or YIeld due to the adiabatic tempera- so-called auto thermal reaction control. ThIS type
ture development are expected. The characteris- of reaction control offers certain specific features
tic feature of adiabatic reaction control is that and development perspectives, which are dis-
the catalyst is present in the form of a uniform cussed in Chapter 5.
Vol. B4 Fixed-Bed Reactors 201
Reactions with a large heat of reaction as well particular, fixed-bed reactors with a strongly
as reactions that are extremely temperature-sen- exothermic reaction exhibit an, at times, surpris-
sitive are carried out in reactors in which indirect ing operational behavior which is dIscussed in
heat exchange occurs via a circulating heat trans- more detail in Chapter 6.
fer medium integrated in the fixed bed. Within a production plant the reactor may
Since in most cases the task of the heat-trans- justifiably be regarded as the central item of ap-
fer cycle is to maintain the temperature in the paratus. However, compared to the remaining
fixed bed within a specific range, this concept is parts of the plant for preparing the feed and for
frequently described as an "isothermal fixed-bed separating and working-up the products, often it
reactor". However, isothermal reaction control is by no means the largest and most cost-inten-
does not provide optimum selectivity or yield in sive component. In many cases the achievable
all cases, and for this reason the concept of heat conversion in the reactor is limited for thermody-
exchangers integrated in the fixed bed is also be- namic (equilibrium) and kinetic reasons (selec-
ing increasingly used to achieve nonisothermal tivity). It is then usual to separate the material
temperature profiles. discharged from the reactor into products and
The most common arrangement is the multi- unreacted feed components (see Fig. 1.2), whic!1
tubular fixed-bed reactor, in which the catalyst is are recycled to the feedstock. This recycling pro-
arranged in the tubes, and the heat carrier circu- cedure involves costs
lates externally around the tubes (Fig. 1.1 B).
Fixed-bed reactors with an integrated heat sup- 1) For product separation
ply or removal are discussed in Chapter 4. 2) For recycle compression
Fixed-bed reactors for industrial syntheses 3) For repeated heating and cooling of the circu-
are generally operated in a stationary mode (i.e., lating matenal to the reaction temperature
under constant operating conditions) over pro- and the temperature of the separating device
longed production runs, and design therefore 4) Due to loss of product resulting from the
concentrates on achieving an optimum station- need to remove part of the circulatmg ma-
ary operation. However, the nonstationary terial to limit the amount of mert substances
dynamic operating mode is also of great im- or byproducts in the recycle stream (bleed
portance for industrial operation control. In stream).
Feed
l stream
Bleed
stream
Product
Figure 1.2. Reaction cycle for syntheSIS reactions With incomplete conversion
a) Fixed-bed reactor. b) Feed preheater; c) Exit cooler; d) ReCirculatIOn compressor. e) Separation column
202 Industrial Reactors Vol. B4
Iyst surface per cubic meter reactor volume) for ciently strong turbulence in random packing. As
reactions controlled by external mass transfer, a re ult the external gas - catalyst mass-transfer
the catalyst fraction I - E, where E = cubic me- resistance is small compared to the transport re-
ters of free gas space per cubic meter of reactor sistance in the catalyst pores.
volume, describing the void fraction of the fixed However, generally the thermal conductivity
bed. of the catalyst matrix is larger than of the gas.
The above requirements are to some extent This mean that the external gas - catalyst heat
contradictory, which has led to the proposition transport resistance exceeds the thermal conduc-
of a large number of different catalyst forms and tion resistance in the catalyst particles. The tem-
arrangements. However, only a few of the e have perature and concentration conditions estab-
proved really effective in practical operation . Ii hed in a pherical catalyst are illustrated for a
Suitable catalyst forms and arrangements in- partial oxidation reaction in Figure 2.2. The
clude random packings of spheres, solid cylin- conditions can be calculated from the model
ders, and hollow cylinders, as well a uniformly equation given in -+ Model Reactors and Their
structured catalyst packings in the form of Design Equation , pp. 141 - 142, under the as-
monoliths with parallel channels, parallel sumptions made there. An essential precondition
stacked plates, and crossed, corrugated-plate is that the catalyst particle i uniformly exposed
packets (Fig. 2.1). over its entire urface to a flow with uniform
temperature and concentration. This is, of
course, never the case in random packings. Fig-
ure 2.3 shows the local mas -transfer distribu-
2.1. Gas-Catalyst Mass and Heat
-.....
Transfer
-
;:. I kg gas per square meter of reactor cross sec-
tion per second. This loading produces a sum-
~
-' tr@
~ .
~
Boundary layer
Pellet radius-
Figure 2.3. Local mas -transrer distribution at the surrace
Figure 2.2. Temperature a nd concentration profiles ror a or ind ividual cylindrical or ring-shaped catalyst pellets in a
partial oxidation reaction in a spherical catalyst pellet fixed-bed packing
204 Industrial Reactors Vol. B 4
lysts is much more uniform , but they can also ~ 3.66 16.00 a
become limiting factors at high reaction rates.
This applies in particular to channel-type mono- 0 7.54 24.00 20
liths with narrow parallel channels. where the
Vol. B4 Fixed-Bed Reactors 205
10 2
D Re=600
• Re=1200
C> Re=1800
+ Re=2200
0
.-t
~ 10 1
ti
.
~
'"~
'"
10°L-__~-L~~WWUL~__L-~~~~~~~__L-~-W~
10- 4 10-3 10- 2 10-1
Z*=Zl/(dh · Re· S c ) _
Figure 2.5. BehavIOr of lhe dimensionless heal-transfer and mass-tran,fer coefficients over the dimensIOnless tube length
Nu ='w db/i.". Sh = kG d.ID
to further heat transfer and mass transfer. The for convective heat transport transverse to the
effiCiency of channel monoliths of equal cross- flow direction and for transverse mIXIng. which
sectional area but different shape therefore are discussed m more detail in the following sec-
decreases in the sequence: cIrcle. hexagon. tions.
rectangle. tnangle. ThiS is illustrated in Table t.
which gives the asymptotic dimensionless mass-
transfer and heat-transfer coefficients for tubes 2.2. Flow and Pressure Loss in
of the above cross sections. As Figure 2.5 shows. Fixed Beds
the asymptotic limiting value is established after
a flow length roughly corresponding to to times Conventional industrial catalyst forms differ
the hydraulic channel diameter. The asymptotic considerably as regards pressure loss. For exam-
limiting value from Table t can therefore be used ple. for equal mean dImensIOns and the same
to perform estimation calculations in conven- proportIon of empty space. random packmgs
tional industnal monolith catalysts with a large generally have a conSIderably higher pressure
length-to-diameter ratio. For more accurate cal- loss than monolith structures. and among these.
culations the radially and aXIally vanable veloci- corrugated structures have a hIgher pressure loss
ty. conCf'ntratJon. and temperature profiles must than monoliths with straight parallel channels.
also be taken into account [2.7]. Mass transfer and heat transfer are strongly cor-
In contrast to the monolith types discussed so related with the pressure loss. For reasons of
far. the flow conditions m corrugated-plate enelgy demand. the catalyst form for a given
monoliths (Fig. 2. t C) are turbulent under nor- process is chosen to combme the reqUIred mass
mal industrial velocities. The uniformity of the transport and heat transport with the lowest
mass-transfer distribution [2.8] depends on geo- pressure loss. However. It should be borne in
metrical parameters (wave form. amplitude. mind that the flow into the fixed-bed reactor
wavelength. angle of inCidence). The transfer (Fig. t. t) is generally achieved by means of a
coefficients are considerably higher than feed pipe and a distnbution hood These must
those of lammarly traversed channel monoliths therefore be constructed so that the fixed bed or
(Fig. 2.4 B). but the pressure loss IS also high. tube bundle is uniformly traversed. and the gas
These structures offer conSIderable advantages reSIdence time m each tube or each flow filament
206 Industrial Reactors Vol. 84
of the fixed bed is the same. This requirement can means of special devices and if necessary individ-
always be met simply if the pressure loss in the ually compensated for pressure loss.
fixed bed or tube bundle is substantially greater The pressure loss coefficient, (Eq. 2.2) can
than in the entrance hood. In this case it need be determined for typical packing forms, for ex-
only be ensured that the fixed bed is packed so ample, according to [2.9).
uniformly that no flow bypass is formed or, in
the case of a muItitube reactor, the pressure loss
is equalized in all the individual tubes of the bun-
2.3. Heat Transport Transverse to the
dle. Because the pressure loss increases with the
square of the flow velocity, a uniform distribu-
Flow Direction
tion of the flow then occurs automatically.
Obtaining a uniform flow distribution is sub- With nonadiabatic reaction control, heat
stantially more difficult If the pressure loss of the must be transported perpendicular to the flow
fixed bed is small. This holds in particular for direction through the fixed bed to the heat ex-
monolith reactors with straight, laminarly tra- change surfaces. At the usual mass flow rates of
versed channels (see Section 2.3). Gz = 1 kg m - 2 S- I, this heat transport takes
The Hagen - Poiseuille equatIOn is used to place mainly by convection, i.e., the fixed bed
calculate the pressure loss in laminarly traversed must be constructed so that flow components
monolith channels transverse to the main flow direction occur local-
ly. Monolith structures with straight parallel
(2.1)
channels are thus unsuitable for nonadiabatic re-
action control.
In catalyst packings transverse flow compo-
The pressure loss of packed tubes can be de- nents are automatically established as a result of
scribed either by means of a pressure loss coeffi- the nonuniform arrangement and the twisted
cient and the pressure drop equation flow around the pellets. Hollow and full cylin-
ders with a length-to-diameter ratio of 1 to 3 are
6p = (. ~. v~ (2.2) particularly effective in this respect.
2 Despite the fact that radial heat transport in
the form of twisted flow takes place mamly by
or by the Ergun equation:
convection. it is formally described by means of
(2.3) a so-called effective thermal conductivity I.,
transverse to the flow direction.
where for spherical packmgs: In addition to heat transport through the
fixed bed perpendicular to the maIO flow direc-
tIOn. the heat transport at the boundary between
(2.4)
the fixed bed and heat exchange surface IS also
decisive for the heat exchange. The latter heat
transport is generally described by a wall heat-
(2.5)
transfer coefficient :x w • in which the complex in-
terplay between convective flow at the tube wall
Thus the pressure drop depends very strongly and conduction transport by contact between
on the void fraction f. of the packmg. Of the the fixed bed and the heat exchange surface IS
standard forms for packed catalysts, hollow described 10 overall terms. Heat transport 10
cylinders ofthm wall thickness (r.:::: 0.6-0.8) are packed tubes has been investigated and discussed
therefore preferred to spheres (I: :::: 0.37 -0.4) and in detail [2.4). [2.10). However. the correlations
solid cylinders (r. :::: 0.35). for :x w and i., given in the literature do not ade-
The strong dependence of the pressure loss quately take account of the actual velocity distri-
on the void fraction underlines the importance of bution 10 packed tubes. Plug flow was generally
packing catalyst beds carefully to avoid bypass assumed. although the actual velocity profile is
flow due to local variations in the packing den- nonuniform with a pronounced slip at the wall
sity. For the same reason the tubes of multitubu- This IS due to the fact that the pellets make only
lar reactors for highly exothermic. selectivity- point contact With the wall. whereas they overlap
sensitive reactions are often filled uniformly by and cross over one another inSide the packmg.
Vol. B4 Fixed-Bed Reactors 207
the detenninatJOn of accurate heat-transport
parameters [2.12). [2.13).
Existing correlation equations for calculating
the heat-transport parameters were obtained
from heating or cooling experiments without re-
actions and assuming plug flow; they therefore
pennit only a semiquantitative evaluation. How-
ever. this is adequate for qualitative comparison
of catalyst structures.
single dominant reaction, the external gas-solid Using the above equations, reactor variants
mass transfer limits the reaction, since in this for catalytic off-gas purification with a given vol-
case the specific reaction kinetics have no In- ume now V were calculated in [2.11). The result
nuence. The relationships for a concentration c is shown in Figure 2.7. The pressure drop of the
of a key component A and a simple reaction fixed bed over the required reactor length is plot-
A + ... -+ products are outlined in [2.11). As- ted; the curve parameter is the hydrauhc diame-
suming mass-transfer limitation. the material ter d h of the monolith channel or packing bo-
balance for the key component along the now dy for different empty-tube gas velocitIes
path is v. = E . VG . According to Equation (2.11) the re-
quired fixed bed volume V. with square mono-
oc lith catalysts and a given throughput V depends
["1'
• c, oz
·-=-k G
'Q
p
·c (2.6)
only on d h , whereas the geometric arrangement
(small bed cross section A and long bed length
If the reactton has a conversion of 99 %, i.e .. ZL' or large bed cross section and short bed) has
an outnow concentration of 1 % of the innow no innuence on V•. However, the bed cross-sec-
concentratIOn, the length of the fixed bed ZL is, tional area A for a given gas throughput Ii deter-
by Integration. mines via
v= A '['G'£' (2.13)
V. d~ . [.
"" 1000 6
~ 1
V. =O.38-- (2.11) ::J
1/1
D 1/1
500
~ VG=O.5 m/s
a.. 6 .-----6 6
If Equation (2.1) is used for the pressure loss. 1 3 4
0
then for the laminarly traversed monohth chan- 0 1 2 3 4 5
Reactor length, m _
nel. from Equations (2.7) and (2.\0)
Figure 2.7. Pre"ure drop mer the lixed·bed length for a
catal)tlc combu,tlon reactor \\lth gIven throughput and
12.28 . '1 , 2
!'J.p = - - - - . 1'(', . /'
D . (2.12) 99°'0 converSIon J' ,I functIon of the h~drauhc catJlyst
diameter dh for dlilerent gas cmpt) -tube velOCItIes I r. [~ III
Vol. B4 Fixed-Bed Reactors 209
2.4.2. Catalyst Forms for Isothermal given in Figure 2.8 for some industrially Impor-
Operation tant filling and packing fonns in a tube of 50 mm
mternal diameter with a mass-flow velocity of
In addition to the previously discussed quan- Gz = 1 kgm- 2 s- l .
tities, the lateral heat-transport parameters of The dimensions of the packing bodies were
the fixed bed are further decisive parameters in chosen so that their specific external surface area
isothermal reaction control. As shown in Section a p is ca. 500 m 2 1m 3. Under these conditions hol-
2.3, heat transport can be characterized by the low, thin-walled cyhnders have clear advantages
effective thennal conductivity perpendicular to over other packmg fonns. exhibiting the lowest
the main flow direction ;., and the wall heat pressure loss and the highest thennal conductivI-
transfer coefficient ~w. Both quantities are ty. Only as regards wall heat transfer are they
strongly dependent on the filling or packing inferior to spheres or cylinders. However. good
fonn. Since transport in the industrially interest- wall heat transfer is apparently less deciSIve from
ing region mainly occurs by convection, they a reaction engineering viewpomt than good radi-
are approximately proportional to the mass al thennal conductivity, since the fonner can be
throughput. compensated by an appropriate temperature
For the purposes of overall companson. the profile of the heat-transfer medium. whereas the
corresponding characteristic parameters are radial thennal conductivity directly mfluences
3000 09
Dap
2500 nnn c
2000
~E
1 1500
;:;..
E
1000
"'~
500
rI I I I I I I
d e 9 h
30 300 o a." 50
25 250 mn A,
40
.6p/L
20
1 200
30
E
""E
0;- 15 ~ 150 "-
3
E 20 ~E
10 3 100 ~.
-<~ ~
05
ts
50 10 ci.
<l
0
b d e 9
Figure 2.8. SpecIfic ouler surface area lip' \old fraction 1:. efTt'Cll\e r"d'dl heal conductl\lt~ i,. wall heaHran,fer coeffiCIent
7 w• and pressure drop ~p for dllTerent paclmgs 10 a tuhe of 50 mm mternal d'ameler and an aIr ma"'O,,,\ \doclt)
G, = llgmO,s-' at ambIent cond,llOns
a) Glass spher.". d p = 5 mm. b) Glass spheres. dp = 10 mm. ci Rdschlg nngs. ceramIc. d. = 10 mm. d, = (, mm. 1= 11 ntnt.
d) RaschIg nngs. stamless steel. d. = 10 mnt. d, = 9 ntnt. 1= 11 mnt. e) Hollo" ceramIC c)hnders 01 ,rregul"r length.
d. = 9 mm. d, = 4 5 mm. I", 15 mm. t) Full cerdmlC C)hnde" of Irregular length. d. = 5 ntnt. I = 11 mm. gl ('"",ed
corrugated metal-plate paclmg (Suller Katapak) ",de channels. h) Crossed corrugated metal-plate paclmg. nam'"
chdnnels. I) Autontotl\e e,haust monohth. Cordtnth. square channels. d = 09 ntm
210 Industrial Reactors Vol. B4
c8
shape must be determtned by simulation of the Flue gas + NH J In
local two-dimensional flow through the packtng
[3.1].
The advantages of monohth catalysts with
Catalyst
t
straight, parallel channels for adiabatic reactors element
have already been referred to in Section 2.4.1.
Since monolith catalysts are usually produced
with a rectangular cross section. the fixed bed is
constructed by arranging these individual mono-
liths tn rows in the form of a large "box". Con-
ventional DENOX reactors for removing NO,
from power station flue gases are therefore de-
signed as rectangular chambers (FIg. 3.3). The
catalyst is often arranged in the form of several
layers in senes. the spaces between the individual
layers permitting cross-mixtng, so that the influ-
ence of nonuniform flow as weIl as any possible
local blockage of the next layer can be compen-
sated to some extent. Catalyst
Reference is made tn Section 2.2 to the Im- layers
portance of UnIform flow into and through Catalyst module
adiabatic fixed-bed reactors. ThIS is not easy Flue gas out
to achieve. particularly with low-pressure-Ioss Figure 3.3. Reaction chamber for removdl of mtrogen ox-
monolith reactors. and requires a careful deSIgn Ides from power station flue gas [3 2J
212 Industrial Reactors Vol. 84
of the inflow hood. On account of the low pres- volume of more than 1000 m 3 , are the largest
sure loss, unfavorable flow conditions in the out- adiabatic reactors, and the exhaust catalysts for
flow hood may also affect the flow behavior internal combustion engines, with a catalyst vol-
through the catalyst bed. ume of ca. 1 L, the smallest. Typical chemical
Figure 3.4 shows the velocity distribution m applications include the methanation of CO and
front of the monolith inlet for an industrially CO 2 residues in NH3 synthesis gas, as well as the
housed automobile catalyst [2.11]. Since the flow hydrogenation of small amounts of unsaturated
cannot follow the sudden widening of the inlet compounds in hydrocarbon streams. The latter
funnel, one third of the total cross section is tra- case requires accurate monitoring and regulation
versed at a velocity that is roughly three times the when hydrogen is in excess, in order to prevent
mean velocity. It can be estimated that, with uni- complete methanation due to an uncontrolled
form flow through the catalyst, half the catalyst rise in temperature, a so-called runaway (see
volume would be sufficient for the same mean Chap. 6).
conversion. Also, bends in the feedpipe can lead
to swirl-type components and thus contribute to
nonuniform flow. 4. Reaction Control with Supply or
Purely adiabatic fixed-bed reactors are used
mainly for reactions with a small heat of reac- Removal of Heat in the Reactor
tion. Such reactions are primarily involved in gas 4.1. Introduction
purification, in which small amounts of interfer-
mg components are converted to noninterfering In the majority of fixed-bed reactors for in-
compounds. The chambers used to remove NO, dustrial synthesis reactions, direct or indIrect
from power station flue gases, with a catalyst supply or removal of heat in the catalyst bed is
utilized to adapt the temperature profile over the
flow path as far as possible to the requirements
of an optimal reaction pathway. Here a clear
developmental trend can be observed, which is
illustrated schematically in Figure 4.1.
Development started with the adiabatic reac-
tor (Fig, 4.1 A), which on account of the adiabat-
ic temperature change could only be operated to
Mass flow give a limited conversion. Higher conversions
15 • • 204 kg/h were achieved at the same mean temperature lev-
o 0 70 kg/h
.. .. 35 kg/h el when several adiabatic stages were introduced,
with intermediate heating or cooling after each
stage. The sImplest form involves injecting hot or
cold gas between the stages (Fig. 4.1 8). For a
,.::,
u
constant tube diameter. the main disadvantages
o of thIS temperature control strategy are cross-
~
> sectional loading, which increases from stage to
stage, and the mixing of hot and cold streams.
4 6 8 10 which IS energetically unfavorable. The composi-
Diameter, e m - tion is changed by injection. which can have a
positive or negative effect on the desired reaction.
The next development was the replacement
of injection cooling by interstage heat exchang-
ers, through which the required or released heat
of reactIOn is supplied or removed (FIg. 4.1 C).
The development of reactors in which the
heat-exchange surfaces are integrated in the
fixed bed to supply or remove the heat of reac-
tion as close as possible to the reactIOn sIte
Figure 3,4, Velocity dl'tnbutlon In an Industnally housed occurred in parallel WIth the development of
dutomoblle catalyst [2 11) multistage adiabatic reactors WIth mtermediate
Vol. B4 Fixed-Bed Reactors 213
Feed gas ©
Inlerslage
heal
exchangers
®
Feed gas
l CD
-l
I Coolanl
I loop I
Heal
carrier
loop
___ JI
I
Coolanl
loop II
heating or cooling. The multi tubular fixed-bed Initially. the integration of heat exchange m
reactor (Fig. 4.1 D) constitutes the oldest and the fixed bed was utilized to ensure as Isothermal
still predominant representative of this class of a reaction control as possible. which IS why reac-
fixed-bed reactors. Here the catalyst packing is tors of the type shown m Figure 4 1 D are also
located m the individual tubes of the tube bun- commonly termed "isothermal reactors". They
dle. The heat-transfer medIUm is circulated are characterized by reaction tubes of 20 80 mm
around the tube bundle and through an external internal diameter and a carefully deSIgned
heat exchanger. in which the heat of reaction IS flow control of the liqUId heat-transfer medIUm.
supplied or removed. Whereas with endothermic With largely constant heat-transfer condltion~
reactions. circulatmg gas can be used as heat- throughout the tube bundle and maxImum tem-
transfer medium. for strongly exothermiC reac- perature changes of the heat-tran~fer medIum m
tions exclusively liquid or bOiling heat-transfer the tube bundle of a few degrees
media are used. Only In this way can the catalyst The latest concepb are aimed at establlshmg
temperature (e.g. m the case of partial oxida- a freely selectable (withm hmib) optimum tem-
tions) be held m the narrow temperature range perature profile over the tube length. ThIS re-
necessary for selective reaction control. qUires complex heat-transfer medIUm control
214 Industrial Reactors Vol. 84
with several sections and temperature levels (Fig. the equilibrium conditions. Intermediate cooling
4.1 E). or heating is used to displace the gas temperature
The stimulus for the developments outlined in the directIOn of higher equilibrium conver-
in Figure 4.1 was the need for total raw matenal sion. Typical examples include the synthesis of
utilization as regards both mass and energy. ThIS ammonia, sulfur trioxide, and methanol. In these
involves as main criteria the yield of primary end exothermic reactions the equilibrium conversion
products (maxImum), the yield of byproducts to the target product decreases with increasing
that must be removed and eliminated (mini- temperature. as shown in Figure 4.2 A. For a
mum), the thermal energy consumptIOn or re- given conversion x a temperature can therefore
covery, and the mechanical energy requirements be found at which the reaction rate, with respect
(gas compression, cIrculation of heat-transfer to the target product, becomes a maximum. This
medium). In addItion to the running costs, which temperature must be below the equilibrium tem-
are determined by the above criteria, the invest- perature but not so low that the reaction be-
ment costs are decIsive in an Investment decision, comes too slow for kinetic reasons. The points
and naturally rise sharply with increasing com- obtained in this way can be joined to form a
plexity of the reaction cycle. maxImum reaction rate curve (Fig. 4.2 B).
On account of cost degression the projected Since, in the case of adiabatic reaction con-
plant size and the subsequent degree of utiliza- trol the temperature increases linearly with the
tIOn as well as the technological sophistIcation achieved conversion ~x according to the equa-
are decIsive in calculating the product price. Sev- tion,
eral of the fixed-bed reactor vanants illustrated
In Figure 4.1 can. depending on the location of
the productIon site and the estimated output, be (4.1)
used for the same process. For example, multi-
stage adiabatic reaction systems with intermedi-
ate superheated steam feed, multi tubular reac- each adIabatic reaction pathway of an exother-
tors with circulating gas heating, and strictly mic reaction lies on a straight line of gradient
isothermal designs with multi tubular reactors ~T/~x (see FIg. 4.2A).
heated WIth molten salt are currently used for the A practicable reaction pathway for a multI-
endothermic synthesis of styrene from ethyl ben- stage adiabatic reaction can thus be derived from
zene. Also, exothermIC, equilibrium-limited reac- Figure 4.2 by joining straight-line sections for
tions such as methanol synthesis are carried out the adiabatIC reaction to vertIcal lines for the
in multistage adiabatic reactors with interstage temperature reduction due to indirect intermedi-
cooling as well as in multi tubular reactors. Over- ate cooling (Fig. 4.2C).
all, however, there is a trend towards the more The kinetically optimum reactIOn pathway
highly integrated deSIgns, which will accelerate with the smallest required catalyst volume results
WIth nSlng energy and raw matenal pnces. AdIa- when the trajectory follows, In a large number of
batIC multistage designs and reactors WIth heat small steps. the line of maxImum reactIon rate. In
exchange integrated in the fixed bed are dIS- practice. the apparatus and equipment expendi-
cussed in the following sections. Autothermal re- ture Involved in a large number of stages must be
actIOn control, In whIch the heat of reaction of weIghed up against the savings in catalyst. Con-
moderately exothermIC reactions is utilized to ventIOnal multIstage reactors for thIS class of re-
heat the Incoming feedstock. IS dIscussed sepa- actIOn therefore have three to five stages. FIgure
rately In Chapter 5. 4.3 shows the layout of an ammonia synthesis
reactor designed on this baSIS. For structural rea-
sons the heat exchanger is Incorporated between
the Inflow and outflow in the lowest part of the
4.2. Adiabatic Multistage Reactors with
pressure casing. The reactIOn gas then flows up-
Interstage Heat Transfer ward in the annular gap between the pressure
casing and the fixed beds, whereby It is further
Adtabatlc multistage fixed-bed reactors WIth heated and at the same time protects the pres-
intermedIate cooling or heating are nowaday, sure-beanng structural component, against ex-
used partIcularly where the reaction proceeds se- cessively hIgh fixed-bed temperatures. The three
lectively to gIve a single product but IS limited by adtabatlc fixed-beds are traversed from top to
Vol. B4 Fixed-Bed Reactors 215
® ® ©
1~
\
,,
,
tI .r::.abatic
..... V~:~~tlon .....
/" ....
Locus of .... ,
Feed path optimal ....
temperature
I
reaction rate
I .! I
Conversion. x _ x_ x_
Figure 4.2. EqUlhbnum hmltatlOn of exothermic reactions
A) Equlhbrium conversIOn as a functIOn of temperature. B) Optimum reactIOn rate curve. C) Improvement of conversIOn
by mterstage coohng
Steam
ll-l"'fl'I--- Water
Steam
~1--~4----Water
Stage
Clrcu(ating gas
Off-gas Feed
EXit
Condensation
coolers
Figure 4.3. Schematic of a multistage reactor for ammOnIa ,ynthesls
bottom. part of the heat of reaction bemg uti- Modern. adiabatic multistage reactors may
lized to generate steam In the two mtermediate thus become so complex that the question anses
heat exchangers. To start up the cold reactor. hot whether a multI tubular deSIgn accordmg to
gas must be added to the uppermost bed. for Figure 4.1 D or E does not represent the more
example through an external start-up preheater. favorable alternative. The required heat-ex-
Industnal adiabatic multistage reactors often change surface area in the case where heat ex-
differ in many details from Figure 4.3. although change is integrated in the fixed bed IS ~maller
they are of a comparable baSIC deSign. For exam- than In the case of free gas flow on account of the
ple, radially instead of aXIally traversed beds can positive effect of the catalyst packing. Further-
achieve a smaller pressure loss with a more fa- more, It does not involve any additional pre~~ure
vorable structural arrangement; heat exchange loss. and the optimum reacllon rate curve
with the cold feedstock can be effected by heat (Fig. 4.2 B) can be better approximated by con-
exchange surfaces mtegrated in the first catalyst trolhng the coohng temperature profile (see Sec-
bed; or a cold gas quench can be used to achieve tion 4.3.2.) than by a stepwise temperature re-
additional temperature regulation. duction
216 Industrial Reactors Vol. 84
On the other hand, a multistage arrangement away, although here too it is beginning to be
may be considered for structural, operating tech- recognized that a tight and uniform temperature
nology, or kinetic reasons in the following cases: control over the reactor cross section is advanta-
geous.
1) If, in the case of large single-train plants. sub-
division Into several individual items of ap-
paratus is necessary for reasons of transport
or construction
4.3.1. Heat Transfer Media for Fixed-Bed
2) If a catalyst must be replaced in individual
Reactors
stages at different times on account of differ-
ent catalyst compositions and/or aging
The first of the above requirements presup-
3) If a gradual addition of a reactant has kinetic
poses an assortment of heat-transfer media that
advantages compared to the total addition
covers the whole temperature range of interest
to the feed (here a suitably designed interme-
for gas-phase reactions in fixed-bed reactors. It
diate heat exchanger ensures a uniform distri-
IS convenient to distinguish between gaseous.
bution and mixing with the reaction gas
liquid. and vaporizing heat-transfer media.
stream)
Gaseous heat-transfer media in the form of hot
4) If the intermediate stages are used to extract
flue gases are used in the temperature range
a limiting product In the case of equilibrium-
above 500'C exclUSively to supply heat for en-
limited reactions; an example is the interme-
dothermic reactions.
diate absorption of SO) before the last stage
Conversely. vaporizing heat-transfer media
of the SO) synthesis
are used exclusively to remove heat from
5) With reaction temperatures above 300 'C in-
exothermiC reactions. Whereas formerly
termediate coohng can be performed directly
petroleum fractions such as kerosene (e.g., In
with boiling water. whereas In a fixed bed a
ethylene oxide synthesis) were more widely used.
high-temperature heat-transfer medium must
they have now been largely replaced by boihng
be used as coolant (see Section 4.3.1)
water on account of their flammability. lower
heat of vaporization. and the need to produce
steam in a downstream condenser/heat exchang-
4.3. Reactors with Heat Exchange er. Depending on the saturated vapor pres-
integrated in the Fixed Bed sure. the temperature range from 100 to 310 C
(100 bar) can be covered with boiling water. In
The aim of reaction control with heat ex- thiS range it is the preferred heat-transfer medi-
change integrated in the fixed bed using a um for evaporative cooling if an isothermal cool-
circulating heat-transfer medium is to maintain ing temperature is reqUired.
the catalyst temperature in a narrow optimum Locally vanable cooling temperature profiles
range under all operating conditions. With can be estabhshed most easily with hquid heat-
strongly exothermiC successive reactIOns. such as transfer media that do not vaporize in the intend-
partial oxidation, and partial hydrogenations. ed operating range. In order to avoid cavitation.
on account of the danger of a runaway reactIOn pressunzed water should be used only up to ca.
(see Section 6.2) this requirement can be met 220 C; heat-transfer oils cover the temperature
only If range up to 300 C. while above thiS temperature
salt melts are now used exclUSively in reaction
1) The temperature of the heat-transfer medium
technology [4.1). Compared to heat-transfer oils
IS close to the desired catalyst temperature
they have the advantage that they are incom-
2) Large heat-exchange surfaces arc available
bustible and stable. although they have the dis-
per unit catalyst volume
advantage that they solidify at about 200 C (ni-
3) A sufficiently large mass flow velOCity of the
trate melts) or 400 C (carbonate melts). The
reaction gases ensures good heat transport
temperature ranges of pOSSible heat-transfer me-
from the packing to the heat-exchange sur-
dia are compared in Figure 4.4. In addition to the
face
thermal stabihty. the energy IV per unit amount
With exothermic equihbnum reactions and of transported heat Q required to Circulate a
endothermiC reactions these requirements are heat-transfer medium IS an Important criterion
less stringent since these reactions cannot run- of choice
Vol. B4 Fixed-Bed Reactors 217
1000 I
I
I
800 I
I
I
I ~o
.c _ c: '"
600 I
.. ..'"
~~ 0
..'"
.. ..'"'"
I
I ..... E
o ..
1: E ~
....
:;-' 400 I
....
00 0 !D 0[i
I ~
>--
I 3 u:
I 3
200
The following equation has been derived for To test Equation 4.3 on a more realistic ex-
the evaluation of heat-transfer media without ample of the coohng of a multi tubular reactor, a
phase change [4.11]: quadratic tube bundle (cross section 1.5 x 1.5 m)
with fourfold passage of the coolant was de-
Q signed by using detailed equations for pressure
!!,:rc (l73 . cp drop and heat transfer [4.12] for vanous heat-
N036-~
(4.2)
transfer media. The heat release of 1650 kW in
1591 (37 x 43) tubes of 30 mm external diameter
and 4 m length corresponds to the conditIOns in
where Qis the heat flow transferred by the heat- a partial oxidation reaction. A temperature rise
transfer medium while Its temperature increases between feed and outlet of 11 Tc = 5 K was as-
by exactly I1Tc ' N IS the required pump power, sumed for the heat-transfer medIUm (additional-
and Q, cp ' and '1 are the density, specific heat ly 150 K for air and water vapor). Table 2 lists as
capacity, and viscosity of the heat-transfer medi-
results the required pump power N, the pressure
um. For liquid heat-transfer media, the equation
drop in the cooling cirCUIt I1p (whereby p = 1 bar
IS derived from the pressure drop in a turbulently
exit pressure was assumed for water vapor and
traversed, hydraulically smooth pipe. It is practi-
air), and the excess temperature of the reactor
cal to solve Equation (4.2) for the pump power' wall above the heat-transfer medIUm tempera-
. [Q
N- -
J2 75 (4.3)
ture I1Tw • assuming constant wall temperature
along the length of the tube. It was shown that
11T., the results of these more precise deSign equatlon~
for the hquid heat-transfer media can be corre-
Thus the reqUIred power vanes as almost the
lated with the equatIOn
third power of Q/11 Tc' The component '10 25;
c~ 75.
Q2, which depends only on the physical
properties of the heat-transfer medIUm, is plot- /Ii" =7800 [ - Q J2 73 -'1-
° P- (44)
ted as a functIOn of temperature in Figure 4.5. 11 T., c; 73 . ( /
o Diphyl THT
* BP Transcal N
... Water
x Air
• Water vapor
• Salt
• Sodium
• • • • • • • •
.. ..
.........
:
200.0 400.0
T.O(_
600.0 800.0
Figure 4.5. The matenal-specllic factor F = ~o "Ie; " . (1' for va no us heat-transfer medIa as a functIon of temperature
danger of a relatively large amount of hot salt transport behavior (Fig. 4.5). They are therefore
melt obviously exists. but tS reliably dealt with used exclUSIvely as flue gases to supply heat at
by experienced reactor construction companies. hIgh temperatures. However. large temperature
Special nitrate melts (HITEC) can be used m the dIfferences between the heat-transfer medium
temperature range 200 - 500 C. Gradual decom- and the reactor wall. with possible adverse effects
pOSitIOn begms above thiS temperature. which on the umformity of the heat supply. must then
can accelerate violently above 600 'C. Access of be accepted.
orgamc components to the melt (mtrate decom-
pOSitIOn) and of water (steam explOSIOn) must be
excluded [4.1). New salt melts. for example. 4.3.2. Reactor Designs
based on carbonates. are being developed for the
temperature range 400 -- 800 C. In this case It is As with adiabatic reactors. a prinCIpal task of
not so much the thermal stability of the molten reactor development is to produce uniform reac-
salt but rather the corrosion of the reactor mate- tIOn condItIOns over the whole reactor and main-
rtals that presents problems. tain such conditions durtng the entire operating
Gases are the only heat transfer media usable tIme. ThIS mvolves the conditIOns m the catalyst
over the entIre temperature range. but because of packing (residence time. catalyst concentratIOn
theIr low density they have an unfavorable heat and actIvity. heat transport) and in the heat-
Vol. B4 Fixed-Bed Reactors 219
® ® Steam
.J
Feed
water
J I Circulation Steam
turbine generator
Figure 4.8. Heat-transfer medIum control In tube-bundle fixed-bed reactors
A) Cross flo\\. B) Parallel flo\\
pending on the number of deflectIOns. with the Figure 4.9. Influence of the wolanl flo" dIrectIon and
result that the aforementioned problems do not flo" \elocll~ I. on the reactIon temperature profile
arIse. A) hothermal. BI ("ocurrcntll<",. ("I ("ountercurrcntll""
222 Industrial Reactors Vol. 84
® ® ©
t 750 100
I
r,\
720 \
I
80 I
I \
""~- 690 120
::J U
0
60
1 80
~ T,= T(=642K u
660 40 0
OJ
c. ~ 40
E ~ 20 ~
OJ
~ ~ 0
75 150 225 300 375 0
ZL' cm_
1.0 10
t
~~
10.8
>.
0.8 ~-~
.:; 0.6
:;::
.;( 0.4
o
Reactor length_ Reactor length_ Reactor length_
Figure 4.11. Influence of actIVIty profiles on the temperature profile of a strongly exothermic redctlOn
A) Catalyst with 66 % actIVIty 10 the front section of the tube and 100% actIVIty 10 the rear section of the tube 14 RI. B) Lmed<
(broken hne) and optimal catalyst actIVIty distributIOn (fuUlme) for hmltlng the maximum temperature to 370 C (simulation
result); C) Expenmental venficatlOn of B 14 101
be avoided if an activity profile is estabhshed by rear catalyst region. which may lead to excessive-
using a continuously varying mixture of catalysts ly high temperatures that can no longer be con-
with different activities (Ftg. 4.11 B. C) [4.10]. In trolled.
these cases the fully active entry region (relatlve In general. influencing the reaction course via
activity 1) IS designed so that the temperature control of the coohng stream (see p. 222) is more
rises to a preselected maximum value. In order to fleXible than incorporating catalysts of different
maintain the temperature at this value. the activ- activHies. Particularly WHh nomsothermal con-
ity in the following region is sharply decreased trol of the heat-transfer media. the reaction
and is then raised to a relative activity of 1 as the course can be influenced over a wtde range by
reaction rate drops due to the depletion of the means of the mflow temperature of the heat-
reactants. A smooth temperature profile can be transfer medIUm as well as by Its volumetnc flow
achieved even if the optimiLed activity profile ill rate.
Figure 4.11 B is only approximately reahzed
(Fig. 4.11 C).
The control of the maximum temperature by 5. Autothermal Reaction Control
using locally diffenng catalyst actlvitles presents
problems if the main reaction zone moves mto 5.1. Introduction
the regIOn of high catalyst activity due to changes
in the operating conditions. For example. m the The expressIOn autothermal reactIOn control
case of Figures 4.11 Band C. a decrease m the IS used WIth fixed-bed reactors if the heat of reac-
throughput may already result in reaction run- tIOn IS utilized to heat the reactor feed to the
away m the short. fully active front region ThiS IgmtlOn temperature of the catalyst Then. nei-
can be counteracted by reducmg the acttvity of ther addttlOn nor removal of heat occur~ durmg
this zone. Catalyst deactivation occurrmg dunng statIOnary operatIOn of the reactor. It thu~ fol-
operation may have more senous effects If. for lows that autothermal reaction control IS re-
example. the catalyst is pOisoned in a front mi- stncted to exothermiC reactlon~ m which a mod-
grating from the entrance to the rear. the mam erately large amount of heat tS produced A~ a
reaction zone finally migrates to the highly active measure of the heat release. the adiabatiC tem-
224 Industrial Reactors Vol. 84
/\~~
suitable only for an adiabatic temperature in-
crease> ca. 200 K. If the heat exchange is inte-
grated in the reactor (Fig. 5.1 B), then a better
heat transfer can be achieved mside the catalyst- -;11..:...
filled tubes as well as around the tubes as a result
~ )
of the transverse flow, so that also gases with a
somewhat lower adiabatic temperature rise can
be reacted autothermally. Overall, however, in- A
direct gas - gas heat exchange is a weakness of
this reactor concept. ~ )
® ©
T' T'
(.T_ T'_
Figure 5.2. Autothermal reactIon control wIth d,rect (regeneratIve) heat exchange for an Irre\erSlble reactIon [2 III
A) BasIc arrangement. B) Local concentratIon and temperature profiles pnor to no,," re\ersal on stead} state. C) VanatlOn
of outlet temperature wIth lime on steddy state
The main advantage of this form of reactIOn [2.11). Analogous to the Ljungstrom heat ex-
control IS the very effective regenerative heat changer. the rotation of the segmented fixed bed
exchange in the catalyst packing. which does not With a stattonary inlet. outlet. and flushing seg-
require any additional built-in components and ment leads to a penodtc change in the directIOn
permits autothermal reaction of gas mixtures offlow through the bed, which can be either axial
with an adiabatic temperature increase of less (Fig. 5.4A) or radial (Fig. 5.48).
than 20 K. The maIO application of autothermal
reaction control with periodically varying flow
direction is catalytic off-gas punfication, in par- 5.3. Reactor Behavior
ticular catalytic oXidation of small amounts
of combustible substances 10 exhaust air [2.11). Due to the direct couphng of the reactIOn
In addition this form of reaction control has with the heat exchange. autothermal reaction
been tested by MATROS et al. for equihbrium- control exhibits some speCific features as regards
limited exothermiC reactIOns such as S03' reactor behaVIOr that distinguish it from the be-
methanol. and ammonia synthesis. and has in havior of conventionally operated fixed-bed re-
some cases been employed on an mdustrial scale actors. Firstly. the autothermal procedure pre-
[5.1)-[5.3). supposes the eXistence of several statIOnary
In addition to the standard vanants shown in operating states (see Section 6.3). The "ignited"
Figure 5.2, a number of modifications ha ve been operatmg state is the demed state, for only then
proposed and apphed (Fig. 5.3). For example. IS so much heat released that the cold mflow can
the bed shown 10 Figure 5.3 A can be designed as be heated. In the "extingUished" state the reactor
a radial flow system, so that the hot region msu- cools to the inflow temperature. so that no fur-
lates itself. and a multlbed arrangement may be ther detectable conversion lakes place. The ob-
used to avoid flushing losses when reversing the ject of reaction control of autothermal reactors I~
flow direction, one bed bemg back flushed each to prevent extinctIOn of the reaction, but also to
time (Fig. 5.38). The arrangements of Figure 5.4 limit the n~e 10 the maximum temperature in the
offer an elegant pOSSibility of a valveless. contm- reactor due to the posItive thermal feedback hee
uous operation With an integrated flushing stage Section 6.3)
226 Industrial Reactors Vol. 84
® ®
T_
[Qjl
_T
lQ2]
® ®
Feed --........-++--~H----I Figure 5.4. Schematic of flow control WIth a rotatmg cata-
L---H_--I-+-__ Exit lyst bed [2 111
Purge
L-_ _ _' -_ _ _4 . - _
A) Axial-flow reactor; B) RadIal-flow reactor
The flushmg segment IS shaded.
Figure 5.3. AlternatIve arrangements for autothermal re-
actor desIgn wIth regeneratIve heat exchange
A) Radial flow concept. B) Multiple-bed arrangement
-2 ==-MXm~
deactIvation can also be Illustrated. DeactivatIOn
means a rise m the ignition temperature. In this
case autothermal operation exhibits a fortunate
tendency to self-stabIlization: the maximum
temperature adapts quasi-automatically to the
® rismg ignition temperature. so that total conver-
sion IS ensured over a large actIvity range. If the
catalyst activity IS too low. then extmction from
a state with highest maximum temperature oc-
t
....
curs rather abruptly In the case where the cata-
lyst IS deactivated by excess temperature. the self-
...; stabIlIzation of course leads to a VICIOUS cIrcle:
the higher the ma1(lmum temperature. the
greater the deactIvation. and the hIgher the max-
z_ Imum temperature. etc.
Figure 5.S. EqulvJlcnce of operating wIth perIodIcal now The mfluence of mert front and end zones.
reversal and Integrated countercurrent heat exchange which are frequently used WIth thIS type of reac-
A) Matros reactor. B) Temperature proliles In the Malro, tor. can also eaSIly be explained by means of
reactor wIth rapid now reversal. C) Countercurrent reactor
wIth catalyst at the wall. D) SchematIC concentratIon and
FIgure 5.6 A If the ignitIOn temperature IS Til
temperature profiles In natros and countercurrent reactors and the fixed bed of the reactor IS mert up to the
[211] pomt :: 2' then the catalytIC reactIOn can be mittat-
ed at the earlIest at ::2' the maxImum tempera-
the temperature that lIes .1. Tad below the maxi· ture tS thus raised from Til to T12 • compared to
mum temperature. the case of a contmuously active catalyst.
The gradient of the temperature curves below Figure 56 B shows the mfluence of the feed
the ignitIOn temperature can be derived from the concentration m the form of the adIabatic tem-
conditIOns of countercurrent heat exchange with perature rise on the temperature profile m the
axtal thermal conduction [2.11]: steady state. Accordmg to EquatIon (5 2). an m-
crease m .1. Tad broadens the temperature profile
and raises the maxImum temperature. whereby
the mcrease m the maxImum temperature above
(5.2)
the IgnItIOn temperature IS roughly proportional
to .1. Tad'
This allows a SImple graphical interpretatIon of The above discm.'IOn refers to countercur-
the influence of the operatmg parameters on the rent operatIOn and to the IImltmg ca,e of a "ery-
reactor behavior. rapId reversal of the flo\', dIrection. Normall)
228 Industrial Reactors Vol. B4
I z_
I
1:t\ z_
I
I
I
\.1
6. Stability, Dynamics, and Control of
Industrial Fixed-Bed Reactors
6.1. Introduction
Figure 5.6. The Influence of operaung parameters on reac-
tor behavIOr
A) Temperature and concentratIOn profiles for gases with
Stability. dynamics, and control of fixed-bed
different IgmtlOn temperatures 7;,. 7;,: B) Influence of the reactors with strongly exothermic reactIOns has
feed concentration c,. c,. In the form of an adiabatic tem- been studied in great detail since the early 1970 s.
perature flse /'; T'd [2 11 J The numerous publications could gIve the Im-
pression that this is a particularly critical reactor
type with a large potential risk. In fact, the oppo-
during operation with periodic flow reversal, the
site is true. Compared to a liquid-phase reactor
reactIOn zone first migrates a certain extent Into
of the same size. a fixed-bed reactor with a gas-
the reactor. As shown in Chapter 6, a relation-
phase reaction con tams a mass of reactants sev-
shtp for the front migration velocity II' can be
eral orders of magmtude smaller. There is there-
derived from the total energy balance around the
fore no danger of a runaway exothermic reactIOn
moving reactIOn front. and in the case of a large
due to reactants accumulatmg In the reactor, es-
temperature rise .1. T and a small adiabatic tem-
pecially as the heat capacity of the catalyst mass
perature increase .1. Tad' II' can be approximated
addItionally damps the uncontrolled tempera-
as follows:
ture rise.
/;. (lG' C
pG Nevertheless. Instabilities can arise m fixed-
I\' = - -.--------------. t'G (5.3)
r. . (!c, .C pC , + (1 - r.) . (!, C, bed reactors. particularly with strongly exother-
mic reactions. and can lead to excess tempera-
II' from the above equatIOn also corresponds to tures that can damage the catalyst and the reac-
the migration velocity of a temperature front in tor construction materials. Some causes of thIS
a packIng wtthout reactIOn traversed with a ve- are discussed below.
Vol. B4 Fixed-Bed Reactors 229
Fixed-bed reactors for industrial syntheses tice. however. these parameters are of only limit-
are generally operated over a long production ed Importance because they rarely take mto ac-
period with almost constant operating parame- count the pecuharitles of mdivldual cases. Sen~l
ters. The task of process control engineering is tive reactions such as partial OXidatIOn and
simply to keep these parameters optimal. In con- partlUl hydrogenatIOn are therefore generally
trast. for supply or disposal plants that have sev- tested 10 single-tube reactors of the same dimen-
eral users or suppliers 10 a production network. sions as those in the subsequent multltubular re-
there are frequent changes of feed matenal and actor. ThiS allows the range of parametnc sensI-
throughput which reqUIre fast. automatic reac- tiVIty to be determmed directly. RecalculatIOn of
tion control. Examples are fixed-bed reactors for the results for other tube diameters IS only POSSI-
syntheSIS gas production or off-gas treatment. ble to a hmlted extent due to the uncertamties In
the quantificatIOn of the heat-transfer parame-
ter~ (see SectIOn 2.3).
6.2. Parametric Sensith'ity An operatmg fixed-bed reactor can enter the
region of high parametric ~en~ltlVlty through
Parametric sensihvity IS the property typical changes 10 the catalyst propertie~ or operatmg
of all highly exothermiC reactions with high acti- conditions. Initially a few particularly sen~ltl\e
vation energy: small changes In the operatmg tubes of the bundle will runaway. I.e. the reac-
parameters can lead to large changes 10 the max- tion changes. for example. from a ~elective par-
imum temperature and yield. The reason IS the tial OXidatIOn to a total combu~tlon. and the tem-
exponential dependence of the reaction rate on perature rlse~ rapidly. In a multltubular reactor
temperature (Arrhenius law). Figure 6.1 ~hows WIth thou~ands of tubes every tuhe cannot be
calculated temperature profiles for partial oxida- eqUIpped with temperature-profile measure-
tion in a wall-cooled. fixed-bed reactor tube of ments: It is therefore likely that thl~ runaway WIll
typical dimensions. In Figure 6.1 A only the remam undetected. especlUlly if It involves only a
maIO reaction IS considered. while 10 Figure 6.1 B few tuhe~. Although temperatures > 1000 C
the total combustion to CO 2 and water IS addi- can often be reached In the cataly~t dUring ,uch
tionally taken into account. Since conSiderably runa\\ay~. they are generally safe proVIded the
more heat is liberated In the total combustIOn tuhe I~ surrounded by heat-transfer medium Be-
than in the desired maIO reactIOn. the sensitivity cause of the good heat transfer to the flUId the
IS increased conSiderably. As a measure of the tuhe temperature remam~ close to that of the
parametric sensitivity. Figure 6.1 C shows the heat-tran~fer medium. and melting of the tuhe
change in the maximum temperature Via the docs not occur. The mo~t certain method of de-
coohng temperature for case B. The sensitivity is tecting a runaway IS on-hne analYSIS of a product
only moderate at low coohng temperatures. formed 10 the runaway reaction. For example.
whereas above T, = 343 C small changes In CO 2 can he momtored 10 the off-gas dunng the
T, and also 10 other parameters such as runaway-sensitive syntheSIS of ethylene OXide. If
throughput. feed concentratIOn. or pressure Its concentration increases above a speCIfied lim-
lead to large changes in reactor behavIOr. Due to it. the reactor must he shut down and for a cer-
the unaVOidable differences between mdivldual tam penod cooled to a lower cooling tempera-
tubes. multltubular reactors cannot be operated ture hefore operation IS recommenced. The
m the range of high parametnc sensitivity. In thiS reason why lowermg the coohng temperature
case the coolmg temperature must be lowered to dunng operatIOn does not extmgUlsh the run-
ca. 340 C. and the tubes made longer to give a away reactIOn is dIscussed helow.
good conversIOn. This example emphaSizes the
reqUirement. discussed 10 Chapter 4. for makmg
the conditIOns m the tubes of the tube bundle and 6.3. Multiple Stationary States
m the cooling circuit as umform as pOSSible to
aVOId premature runaway reactIOn m indiVidual The term parametric ~ensltl\'lty applle, when.
tubes. accordmg to FIgure 6.1 D. a ~tate quantIty (Tmu)
In the literature there are numerou~ run- IS a ~mgle-valued functIOn of a control quantIty
away cntena with which operating ranges of (T,) However. In the runaway examples dIS-
high parametric sensitivity can be precalculated cussed III SectIOn 6.1 thIS dependence can also he
for known reaction kmetlcs [6.1] [6.3). In prac- multiple valued. Then the runaway occur~ not m
230 Industrial Reactors Vol. B4
0 ®
1000 1000
344(
600
u
0
f t 600
);'
'..: '..:
400
© ®
60 1400 1100
70 /0 \ ..,.00<1>
1200
1000 t
900
f 60"/ :
f 700
h 600 Main reaction
u
0 u
50 0 .... . /
600
M
~
....E
.....:: 500
.... ....
... .... "
ocP
40 _ o __ o~O"'o..o 400 ........ "No reaction
300 ..-
30L--L--...I..-~--~--' 200
300 320 340 400 500 600
Te,O(_ Tc,O(_
Figure 6.1. Parametnc sensitivity or a partial oxidation reaction m a fixed-bed reactor or typical dimensions as a runctlOn
or the coolant temperature Tc with T(z = 0) = Tc
A) Temperature profile over reaction length (main reactIOn only); B) Temperature profile mcluding total OXidatIOn as Side
reaction. C) Maximum temperature Tm .. and Yield as a runCtlOn orcoolant temperature Tc in case B: 0) Tm .. as a runctlon
or Tc ror both cases
a finite range of the control quantity, but on creases only linearly. Thus on exceeding a certain
exceeding a fixed limit Tel' often referred to as temperature limit. the heat release increases
the ignition limit (Fig. 6.2). Between ignition and more rapidly than the heat removal, and the re-
extinction of the runaway reaction (at Tc = TeE)' action ignites. On dropping below a second, low-
there is a hysteris region in which two stable sta- er temperature limit. the heat release becomes
tionary states are possible; at least one unstable less than the heat removal. and the reaction is
intermediate state must lie between them. Vari- extinguished. In fixed-bed reactors. this process
ous causes of multiple stationary states in fixed- of ignition and extinction is associated with a
bed reactors are known [6.4], [6.5]. Here, only local displacement of the main reaction zone.
the so-called thermal instabilities are discussed. This can be most readily demonstrated by the
They occur in exothermic reactions and arise be- example of an exothermic reaction in an adiabat-
cause the evolution of heat increases exponen- ic fixed-bed reactor.
tially with increasing temperature. while the heat Figure 6.3 shows the temperature profile for
removal at constant cooling temperature in- the catalytic total oxidation of ethane as a func-
Vol. B4 Fixed-Bed Reactors 231
700
680
660
f 640
~ 620
\
\
, .... ",,/""
>-'
600
....
"",,,,,,,"" .
..-.... No reactaon 580
..-I ""
I 560
I 8 12 16 20
I z.cm_
T[f To Figure 6,3. Measured aXIal temperature profile m the re-
re_ gIon of multIple steady states m an adIabatic fixed-bed
reactor for the OXIdatIon of ethane [6.6)
Figure 6.2. Igmtlon - extmctton hysteresIs in the regIOn of IgmtlOn from profile I to II a. extmctlon from II b to III
multIple steady states
Ignition occurs at T, = T" and extmctlOn at T, = T,. ure 4.9 (see p. 221). Another effect that can result
in multiple stationary states is single-grain insta-
bility (see --- Principles of Chemical Engineering.
ti~n of feed temperature. If thIs temperature is
p. 75-82). which in fixed-bed reactors is always
raIsed only slightly above the value for profile I,
coupled with the effect of the reverse axial back-
the reaction ignites in the rear portion of the
ward thermal conduction of heat [6.9) and inten-
reactor. Due to the axial thermal conduction in
sifies the above-mentioned hysteresIs behavior.
the developing steep temperature front. the main
Whether a fixed-bed reactor goes runaway
reaction zone moves slowly towards the entrance
due to high parametric sensitivity or whether the
and is stabilized in position II a. The feed temper-
reaction ignites on passing from a lower to a
ature must be lowered considerably to the value
higher stationary state. the results in practice are
of position II b before the reaction extinguishes
the same: the maximum temperature increases
completely to profile III upon a further slight
rapidly to an unacceptably high value. However.
I?wenng .of t.he feed temperature. A similar igni-
in the case of parametric sensitivity, decreasing
tIOn-extinctIOn behavior can also arise on
the cooling temperature or feed concentration
changing the throughput or the feed concentra-
during operation results in the maximum tem-
tion. The multiple stationary states [-II a and
perature returning to the safe range, whereas
II b -II [ are partly a result of the axial backward
when multiple stationary states are present. this
conduction of heat in the reaction front. This
need not be the case. If a certain limit IS exceeded
represents a positive feedback whIch stabilizes
on ignition. then the runaway reaction proceeds
either the ignited or the extinguished state.
towards the ignited stationary state. even If the
Mechanisms that transport heat from the end of
feed concentration or cooling temperature is
the bed to its beginning stabilize multiple station-
lowered considerably. Extinction of the reaction
ary states in a sImilar manner. These Include the
occurs only on passing below the extinction lim-
axial thermal conduction in the tube wall [6.7)
its. which particularly for strongly exothermic
and especially the influence of countercurrent
reactions lie far below the ignition conditions. In
cooling when the temperature of the coolant rises
this case, the best strategy is to switch off the feed
significantly [6.8). [n autothermal reaction con-
followed by inert gas purging, until all tempera-
trol (see Chap. 5). countercurrent cooling IS used
tures have fallen to uncritical values.
to stabilize the ignited state. which is desired in
this case. However. in the caseofstrongly exother-
mic reactions with a risk of runaway. counter- 6.4. Migrating Reaction Zones
current cooling should generally not be used. The
destabilizing effect of countercurrent cooling is The diSCUSSIOn in the prevIOus sections refers
demonstrated by the examples discussed in Fig- exclusively to the statIOnary state. i.e., the tem-
232 Industrial Reactors Vol. B4
700 161
safety risks can be assumed for fixed-bed reac-
tors:
1) Leaks which result in the release of large
600 amounts of gas or vapor and the formation of
121 explosive clouds
2) Leaks resulting in release of large amounts of
liquid heat-transfer media (oils, salt melts)
500
3) Occurrence of ignitable or decomposable gas
1
u
o
mixtures in the reactor
4) Melting of the reactor due to a runaway rea(-
,...: 400 tion
The safety aspects of liquid heat-transfer me-
dia are discussed in Section 4.3.1. Ignitable gas
300 mixtures can arise particularly during partial ox-
idation reactions. They are especially critical
where large packing-free volumes are present.
0.2 0.4 0.6 0.8 10 This is the case in the inflow and outflow hoods
z/L- of the reactor, while in the reactor tubes the cat-
alyst packing dampens the propagation of a
Figure 6.1. Mlgratmg combustion zone m the case of CO
oxidatIOn over nickel. caused by thermal deactivation of flame front due to its heat capacity. Complete
the catalyst [6.13) avoidance of ignitable mixture is generally not
possible in partial oxidations because at least
during mixing of the gas streams prior to the
640 reactor the ignition limit is exceeded locally.
600 Nevertheless, in the past, operation of fixed-bed
reactors with ignitable mixtures was avoided, ei-
I
""
560
520
ther by dilution with inert gas or by operating in
the nonstoichiometric range. The former re-
...... 480 quires additional efforts for heating, cooling,
and separation of the inert gas, while the latter
440
0 0.2 to gives only low conversions of the reactants in a
z/L- single pass. New developments in partial oxida·
Figure 6.8. Migrating reaction front during the synthesIs tion therefore aim for stoichiometric operation
of vmyl acetate over zmc acetate, caused by thermal dam· in the ignitable range [6.17]. A prerequisite for
age to the catalyst [6.14) this is pressure-resistant construction with check
a) 60 mm; b) 75 mm; c) 100 mm; d) 165 min valves and flame barriers so a possible that igni-
tion is confined to the interior of the reactor.
Melting of reactor tubes during runaway re-
mum. In the past, this was sometimes cited as a action is only to be feared in multi tubular reac-
good example of parametric sensitivity. The tors if the respective tube is not surrounded by
above discussion, however, shows that the cause heat-transfer medium. Thus. appropriate design
of the "runaway" reaction should rather be at- must ensure that running dry of reactor tubes
tributed to the dynamic influence of the migrat- cannot occur. In the case of corrosive reaction
ing combustion zone. gases, apparatus for the detection ofleaks caused
by corrosion must be provided, particularly
when pressurized or boiling water is used as
6.5. Safety Aspects coolant.
If the coolant circulation is interrupted dur-
Because of the small mass storage capacity ing an exothermiC reaction. the reactor must be
compared to liquid-phase reactors. the danger of shut down. Nevertheless, the heat storage capac-
sudden reaction of accumulated reactants in gas· ity of the catalyst and the heat-transfer medium
pha~e fixed·bed reactors is low. Leaving out the surrounding the tubes allows sufficient reac-
peculiarities of individual cases. the following tion time for controlled shutdown of the reactor.
Vol. B4 Fixed-Bed Reactors 235
This is shown by simulation calculations for a can be intensified by front migration phenomena
multi tubular reactor (Fig. 6.9) with a partial oxi- (Section 6.4) and can lead to thermal damage of
dation reaction. It was assumed that at t = 0 the reactor. This is particularly true of runaway-
either the circulating pump fails or that the regu- prone reactions such as partial hydrogenation
lating valve in the pipe to the steam generator with a large excess of hydrogen, which can
closes. As can be seen in Figure 6.9, there is a change from selective hydrogenation to com-
time span of 200 or 350 s, respectively before the plete methanation. This can be detected by on-
maximum temperature in the catalyst reaches line analysis of methane in the product.
unpermissably high values.
In large-volume adiabatic fixed-bed reactors,
local temperature maxima (hot spots) can form 6.6. Control of Fixed-Bed Reactors
due to nonuniform distribution of the flow or
inhomogeneities in the catalyst packing. They The control of fixed-bed reactors for chemi-
cal synthesis generally only involves maintaining
the operating conditions at the optimum values.
I Valve closure m,-O(at For runaway-prone reactions, this is supple-
t-- '=01 mented by an extensive measurement and con-
1.9
j trol system with built-in redundancy for giving
,.,,
Pump failure v, -0 (at '=01
alarm and shutting down the reactor. Slow
changes in catalyst activity during multistage
'/'
'" : adiabatic reactors are corrected by "manual" ad-
1 justment of the set value for the feed temperature
/' '
": : ..-----"\.- of each stage in multi tubular reactors or by the
, 1 _---- t.m,=-25% adjustment of the heat-transfer medium temper-
I~~~ _ _ _ - - - - - - - -
.'T--___ _ ature. The target is usually to keep the desired
:: T--- conversion constant. Mass flow control. feed
15
,, ,,
, 1 t.m,=+25%
stoichiometry control, control of the total pres-
sure (generally in the reactor outlet), as well as
o: :500 1000 1500 2000 feed temperature and heat-transfer medium tem-
200 350 perature control are therefore the most impor-
t.s_ tant automatic control circuits in fixed-bed reac-
® tors.
In the following, some special points con-
cerning the cooling temperature control of multi-
tubular fixed-bed reactors are considered. In a
multi tubular reactor with molten-salt cooling
(Fig. 6. t 0) the cooling temperature is controlled
by a control unit in the connecting channel to the
steam generator. In thiS way, varying amounts of
colder salt melt can be introduced into the circu-
lation system, with effective mtxmg taking place
In the circulating pump. This coohng circuit can
be unstable [6.3]. Since the reaction rate or liber-
ated heat QE increases exponentially wtth m-
creasing cooling temperature, while the heat re-
moved in the steam generator Q" increases only
025 050 075 100 linearly, the conditIOns shown in Figure 6. t t
z/L_ may occur in the desired state. On a slight in-
Figure 6.9. EfTect of disturbances In the coolant Circuit of crease of the cooling temperature above Te, ... '
a multi tubular reactor (Fig 610) with a partial OXidatIOn the coohng circUlt warms up since QF > Q", and
reaction [6 15] on dropping slightly below Tc:, ... cools down be-
A) Profile of maximum temperature With lime after change
of the valve poSitIOn (~J. after pump failure It, -+ 0). cause Q" > QE' Because of the large thermal in-
and after valve closure (m, -+ 0); B) Temperature profile ertia, however, the unstable operatmg pOint can
after failure of the coolant clrculallon pump easily be stabIlized vta the control Te (Ftg. 6.10).
236 Industrial Reactors Vol. 84
Coolant
0
0
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