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CONTENTS
SECTION
INTRODUCTION/PURPOSE
SCOPE
FIELD OF APPLICATION
DEFINITIONS
ADIABATIC REACTORS
4.1
4.2
4.3
4.4
3
4
4
4
5.1
5.2
5.3
5.4
5.5
5.6
5.7
5
6
7
8
9
9
9
10
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TABLE
1
10
FIGURES
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INTRODUCTION/PURPOSE
Reactors can be categorized in many different ways. For the purposes of this
Process Engineering Guide, a very simple categorization based on thermal
characteristics is used as follows:
Adiabatic
Non adiabatic
These two generic descriptions are further subdivided by type to reflect the many
variants to be found in industry. This Guide provides brief notes on the typical
intrinsic characteristics of the various generic reactor types together with a
selection guide to help determine the most appropriate type(s) for any given
application.
Where the choice of reactor type interacts with the rest of the flowsheet, either
via changes to conversion, selectivity or heat recovery, it will be necessary to
optimize the design of the complete process.
SCOPE
This Process Engineering Guide sets out the selection factors and criteria to
enable process developers to choose the most appropriate type of reactor for
solid-catalyzed gas phase reactions. It does not cover the detailed reactor design
nor the modeling of the reactions or the reactor.
2
FIELD OF APPLICATION
DEFINITIONS
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ADIABATIC REACTORS
Adiabatic reactors are probably the commonest class of reactor where, other
than external heat loss/gain through the vessel wall, there is no other heat
addition or removal within the reactor vessel (although clearly there may well be
elsewhere in the flowsheet up or downstream of the reactor).
Adiabatic reactors are suitable for reactions with mild to moderate
thermochemistry (typical temperature change across the reactor no greater than
50C) and moderate variation of reaction rate with temperature (including byproduct formation rates). There can be control problems with kinetically limited
reactions where the reaction rate more than doubles for a 20 increase in
absolute temperature.
The catalyst is typically in the form of pellets or particles with characteristic size
in the range 2 - 6 mm to avoid excessive pressure drop. However, this can lead
to a significant diffusion limitation, the effects of which can be ameliorated in part
by use of ring or multi holed catalyst pellets.
Adiabatic reactors can be further sub-divided as follows:
Single Bed
Divided Bed
Moving Bed
Radial Flow
Single bed reactors should be used wherever practicable since these will always
offer the lowest vessel cost per unit volume of catalyst. Divided bed designs
should only be considered where the crush strength of the catalyst is significantly
lower than the imposed stresses. Moving bed designs tend to be mechanically
complex but can offer benefits where catalyst regeneration is a problem. Radial
flow reactors can be used beneficially where gas volumes are large and/or where
pressure drop is an issue.
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4.1
A reactor having a single undivided catalyst bed offers simplicity of design and
construction, ease of charging and discharging, low cost and potential for good
flow distribution.
Optimum bed aspect ratio is decided by an economic tradeoff between pressure
drop and vessel costs. If this gives an aspect ratio of less than 1, gas distribution
will be difficult and a radial flow reactor should be considered. The optimum will
vary if a full bore closure is required. In general, on large diameter vessels, full
bore closures should not be provided. Adequate access for catalyst charging,
discharging and inspection purposes can be gained via a 24" (or greater)
manway.
Note:
A larger diameter access should be considered if access to the vessel requires
the use of breathing apparatus.
On large diameter vessels, a full bore closure can increase the vessel cost
significantly whilst the joint can prove troublesome to seal.
Imposed stresses on the catalyst can be quite high in certain conditions. Janssen
(ref. Janssen, H A, "Versuche ber Getreidedruck in Silozellen", Z. Verein
deutscher Ingenieure, 39, No. 35, pp 1045-1049 (1895)) analysis can be used to
predict initial stresses quite accurately to compare with catalyst crush strength
results. In deciding between a single and multiple bed design, it is necessary to
consider all phases of the catalyst's life and to be aware of any sudden
reductions in catalyst strength which may occur during, for example, any catalyst
preconditioning process.
Where there is a risk of significant exotherms being generated in the catalyst bed
which would result in either an uneconomic set of design conditions or severe
damage to the pressure shell, it may be necessary to install either a heat shield
or a removable cartridge to provide a thermal barrier between the catalyst and
the vessel shell.
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4.2
Reactors having a divided catalyst bed with intermediate bed supports should
only be considered where catalyst strength is low and significantly less than the
imposed stresses imposed on the catalyst particles in service, or to overcome the
effects of channelling when very high conversions are needed. The option of a
single reactor shell with a divided bed should be compared to the provision of
several smaller single bed reactors in series to determine the optimum capital
cost. Examples are Cumene.
The internal structures necessary for the intermediate bed supports add
significantly to the cost of the vessel and restricts access for maintenance,
charging and discharging. In addition, the presence of any internal support pillars
tends to make uniform flow distribution difficult to achieve with inevitable
consequences on reactor performance.
4.3
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4.4
Non adiabatic reactors cover a very wide range of reactor designs which can be
subdivided into the following broad categories
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5.1
Boiling/condensing water
Molten salt
Hot oil
External firing (heating only)
FIGURE 1
To avoid wall effects and poor flow distribution, tube diameter should be at least
10 times the catalyst pellet diameter.
Generally tubular reactors are complicated and expensive compared to adiabatic
systems. Reactor diameter will be significantly larger for a given catalyst volume
and pressure drop (typically only 40 - 50 % of vessel cross sectional area can be
usefully used for catalyst).
It is important to ensure even flow distribution through tubes. This is best
achieved by checking that the pressure drop through tubes at the packing stage
is within specified tolerances. The use of orifice plates or similar devices to
artificially increase the pressure drop through catalyst filled tubes is
recommended to ensure good distribution if the pressure drop is too low.
Charging/discharging time can be significant for this type of reactor (especially if
this requires an inert atmosphere) and will always be significantly greater than for
a corresponding adiabatic reactor of the same catalyst volume.
Consideration has to be given to the implications of any leak resulting from failure
of a tube.
The main control variable is the heating/cooling medium temperature.
External firing is a special case for extremely endothermic reactions (e.g. steam
reforming of methane).
Designs are generally complex and limited to a limited number of specialist
manufacturers (e.g. salt cooled systems, lack of verified heat transfer correlations
for boiling of water on the outside of vertical tubes).
The choice of heating/cooling medium can raise issues in its own right (e.g.
flammability of some oils, solidification of molten salt systems). For liquid cooled
tubular reactors attention should be paid to the shell-side coolant flow distribution
to avoid dead zones which may give rise to reaction hot spots. For critical
systems the variation of heat transfer due to velocities and to the temperature
dependence of the physical properties needs to be considered. Provision for the
venting of inerts from under the top tube sheet should not be overlooked.
Possible catalyst life issues can arise depending on deactivation mechanism.
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5.2
Tube cooled reactors employ a catalyst packed around the outside of tubes
through which cooling the medium flows.
The issues are similar to those for tubular reactors with external heating/cooling
except:
(a)
(b)
The larger mean distance and greater variation in path length between the
catalyst and cooling surface leads to larger variations in the mean catalyst
temperature and hence the reaction rate than for tubular reactors.
(c)
The catalyst is packed on the shell side which makes charging and
discharging potentially complex and uniform flow distribution difficult to
achieve.
(d)
Designs can result in smaller reactor vessel diameters for a given catalyst
volume and pressure drop than for tubular reactors but catalyst handling
and flow distribution problems should not be underestimated.
Although less serious than in the case of a tubular reactor with external heating
or cooling, consideration has to be given to implications of any leak resulting from
failure of a tube and in particular how this will be detected.
5.3
Autothermal Reactors
Autothermal reactors are a specialist subset of tube cooled designs where the
heating/cooling medium is feed/product gas (see Figure 2). Use for fairly
exothermic reactions (e.g. MeOH synthesis).
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FIGURE 2
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5.4
Such reactors are usually configured as cold shot (quench) converter but hot
shot design is theoretically possible.
Cold shot reactors are generally used in similar applications to autothermal
reactors.
They are normally used for exothermic reactions although they can theoretically
be used for endothermic reactions, but most of the advantages are lost.
Cold shot reactors are used to avoid having to heat all of the feed gas to the
reaction initiation temperature.
The reaction is "quenched" and approach to equilibrium composition is altered by
injecting a quantity of cold (or hot) feed gas.
They are generally configured with divided beds with inter bed gas mixing - see
Figure 3. Lozenge arrangements are now no longer favoured.
Mixing of fresh feed gas with gas already in the reactor is critical to success.
Cold shot reactors are generally simpler and cheaper than tube cooled reactors.
Potentially slightly less than optimal catalyst use.
Several variables are available for control (more than with tube cooled design).
As with tube cooled reactors and some adiabatic reactors, cold shot reactors
usually require a separate start up heater.
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FIGURE 3
5.5
Such reactors comprise divided beds of catalyst followed by patten type heating
or cooling coils.
They are generally mechanically complex, usually with many penetrations of the
pressure shell.
Consideration should be given to consequences of tube failure.
Examples of the use of divided bed reactors with intercooling include sulfuric acid
converter and some aromatics reactors.
5.6
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The design lends itself to the provision of heating/cooling coils along the axis of
the vessel, across which the gas flows between passes through the catalyst.
Radial flow reactors avoid many of the catalyst handling problems associated
with tubular reactors.
5.7
Fluid bed reactors are suitable for very highly exothermic reactions.
They require very small catalyst particles to ensure fluidization.
Significant problems with attrition and dust generation are inevitable.
Fluid bed reactors are suitable for strongly diffusion limited reactions.
They are inherently prone to gas by-passing as bubbles flow up through the
catalyst bed.
They are suitable for heavily coking reactions with short time between
regenerations.
Good heat transfer is possible within the bed.
They are generally suitable for very fast non-equilibrium limited reactions.
Fluid bed reactors should be considered when one of the reactants is in the solid
state (e.g. coke).
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KEY:
Notes:
1
Only used for very endothermic reactions requiring very high process
temperatures (e.g. methane steam reforming, ethylene oxide etc.).
Stable reaction defined typically as one where the rate of the main or any
significant side reaction (including coking) doubles/halves for a change in
temperature of 20 or more.
Unstable reaction defined typically as one where the rate of the main or
any significant side reaction (including coking) doubles/halves for a
change in temperature of 20 or less.
This type of reactor can be used but the catalyst volume is rarely sufficient
to justify this type of system.
These reactors are particularly suitable because they offer the opportunity
to control conditions to maximize the approach to equilibrium.
10
Very close approach to equilibrium is not possible with this type of reactor
due to gas bypassing through the bed via bubbles.
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11
Small particle size catalyst (typically mean particle diameter 2 - 6 mm) are
suitable for strongly diffusion limited systems. Penalty is high pressure
drop.
12
Large catalyst pellets suitable for non diffusion limited systems or where
cost of pressure drop is high.
13
14
15
16
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