ADDIS ABABA UNIVERSITY

ADDIS ABABA INSTITUTE OF TECHNOLOGY

SCHOOL OF CHEMICAL AND BIOENGINEERING

Group Assignment II

Design of Fixed Bed Catalytic Reactor (adiabatic and Non-isothermal)

Process Engineering (PhD), Catalysis (ChEg 8101)

Group - I
By:
Name ID No

1. Tesfaye Kassaw GSR/7444/14

2. Wubshet Alemu GSR/0826/14
3. Yohannes Assefa GSR/6364/14

Submitted To: Dr.Eng. Nurelegn T.

Addis Ababa University

Addis Ababa, Ethiopia
February 21, 2022
Table of Contents
INTRODUCTION .......................................................................................................................... 1

1.1 Background ............................................................................................................................... 1

2. LITERATURE REVIEW ........................................................................................................... 3

2.1 Packed Bed Catalytic Reactor ............................................................................................... 3

2.2 Fixed Bed Catalytic Reactor ................................................................................................. 4

2.2.1 A Classification of Reactor Models................................................................................ 5

2.2.2 Mode of operation .......................................................................................................... 7

2.2.3 Advantages, disadvantage, limitation and overcoming the limitation............................ 9

2.2.4 Application of fixed bed catalytic reactor .................................................................... 13

2.2.5 Design Considerations .................................................................................................. 14

2.2.5.1 One-dimensional pseudo homogeneous model ......................................................... 14

3. Design, modeling and simulation of adiabatic and non-isothermal reactor.............................. 17

3.1 Discussion and recommendation for case 1 ........................................................................ 22

3.2 Discussion and recommendation for Case 2 Constant Ta ................................................... 25

3.3 Discussion and recommendation for Case 3 Co-Current Exchange ................................... 27

3.4 Case 4 Countercurrent Exchange ........................................................................................ 29

Reference ...................................................................................................................................... 31

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List of figures
Figure 2. 1: packed bed catalytic reactor……………………………………………………… 4
Figure 2.2: Expanded views of a fixed-bed reactor…………………………………………… 5
Figure 2.3: classification of FBCR models…………………………………………………… 6
Figure 2.4 Control volumes for (a) one- and (b) two-dimensional models…………………… 6
Figure 2.5: Fixed-bed catalytic reactors (FBCR) for two-phase reactions: modes of operation
(each rectangle or shaded area represents a bed of catalyst; each circle represents a heat
exchanger) ……………………………………………………………………………………... 8
Figure 2.6: Large particle has to be used (dp>1mm) …………………………………………... 12
Figure 2.7. Pressure drop along the length of reactor with different particle sizes……………. 15
Figure 3.1. polymath coding of adiabatic reactor……………………………………………….
21
Figure 3.2: Adiabatic conversion and temperature (a), and reaction rate (b) profiles…………...
22
Figure 3.3. Polymath coding with constant temperature heat supply……………………………
23
Figure 3.4. Profiles for constant heat exchanger fluid temperature (Ta); (a) temperature, (b)
conversion………………………………………………………………………………..........
24
Figure 3.5. Profiles for constant heat exchanger fluid temperature(Ta) for reaction rate…………
25
Figure 3.6: Profiles down the reactor for countercurrent heat exchange; (a) temperature, (b)
conversion, (c) reaction rate……………………………………………………………………
27
Figure 3.7: Profiles down the reactor for countercurrent heat exchange; (a) temperature, (b)
conversion, (c) reaction rate……………………………………………………………………
29

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List of Table

Table 2.1 applications of fixed bed catalytic reactor …………………………………………. 14

Table 3.1 Summary of parameter values …………………………………………………… 20

Table 3.2. polymath results of adiabatic reactor………………………………………………. 22
Table 3.3 Polymath result with constant heat supply…………………………………………...
24
Table3.4: Polymath result with co-current flow………………………………………………. 26
Table 3.5: Polymath result with counter-current flow………………………………………… 28
Table 3.6: Summary of Cases…………………………………………………………………
30

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 INTRODUCTION
1.1 Background
The discovery of solid catalysts and their application to chemical processes in the early years of
this century has led to the breakthrough of chemical industry. Since these days, this industry has
diversified and grown in a spectacular way, through the development of new or the rejuvenation
of established processes, mostly based on the use of solid catalysts (Brooks, 1991).

Many reactions are too slow to be commercially viable, no matter how much we desire the product.
Over the centuries, we have learned that adding a particular chemical, such reactions proceed at
commercially viable rates. We call that particular chemical a “catalyst.” A catalyst is a substance
that accelerates a specific reaction toward its equilibrium but remains unchanged after the reaction
achieves equilibrium. In catalysis, a rate expression will generally be based on the amount of
catalyst instead of a reactor volume. So, in case of a catalytic reaction over a solid catalyst in which
the rates are per mass of catalyst W. Fixed-bed catalytic reactors have been aptly characterized as
the workhorses of the process industries. For economical production of large amounts of product,
they are usually the first choice, particularly for gas-phase reactions (Worstell, 2014).

The first commercial application of a fixed-bed reactor occurred in 1831 when Peregine Phillips,
a British vinegar maker, patented a process for making sulfur trioxide by passing air and sulphur
dioxide, made by burning sulfur, over a hot bed of platinum sponge. The sulfur trioxide, formed
by the catalytic oxidation of the sulfur dioxide in the air, was subsequently dissolved in water
to form sulfuric acid, which, to this day, is the most widely used and important commercial acid.
Phillips saw the advantage of a solid catalyst that could be held in a container while reactants were
passed through it to produce the desired product. Since the catalyst is not consumed in the reaction
and is held in the bed, it can be used repeatedly as a continuous now of reactants is passed
over the bed of catalyst, without the need for separating and recycling the catalyst (Rase, 1990).

During the early 1800s, solid catalysts were just beginning to be studied and described by
distinguished chemists. In the ensuing years numerous catalysts were discovered, and most were
applied in commercial fixed-bed processes, making the fixed-bed reactor the dominant type for
solid catalysts. Since those early days, many special fixed-bed designs have been developed, but
all types of fixed-bed reactors fall into one of two major categories: adiabatic or nonadiabatic. The

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adiabatic design is always preferred when acceptable conversion and selectivity to the desired
product is possible. It is simpler and less costly than the nonadiabatic design, which requires heat
transfer along the bed between the reaction side and cooling or heating medium. For such heat
transfer to be effective, a high ratio of heat-transfer surface-to-reactor volume is required, usually
in the form of multiple small diameter tubes containing the catalyst and with the heat-transfer
medium flowing exterior to the tubes (Rase, 1990).

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 2. LITERATURE REVIEW
2.1 Packed Bed Catalytic Reactor

Reactant gas can be made to contact solid catalyst in many ways, and each has its specific
advantages and disadvantages. These may be divided into two broad types, the fixed bed reactors
and the fluidized-bed reactors. In passing through fixed beds, gases approximate plug flow. It is
quite different with bubbling fluidized beds where the flow is complex and not well known, but
certainly far from plug flow, and with considerable bypassing. This behavior is unsatisfactory from
the standpoint of effective contacting and requires much more catalyst for high gas conversion,
and greatly depresses the amount of intermediate which can be formed in series reactions. Hence,
if efficient contacting in a reactor is of primary importance, then the fixed bed is favored(Jansson,
1980).

Effective temperature control of large fixed beds can be difficult because such systems are
characterized by a low heat conductivity. Thus, in highly exothermic reactions hot spots or moving
hot fronts are likely to develop which may ruin the catalyst. In contrast with this, the rapid mixing
of solids in fluidized beds allows easily and reliably controlled, practically isothermal, operations.
So, if operations are to be restricted within a narrow temperature range, either because of the
explosive nature of the reaction or because of product distribution considerations, then the
fluidized bed is favored.

Fixed beds cannot use very small sizes of catalyst because of plugging and high-pressure drop,
whereas fluidized beds are well able to use small-size particles. Thus, for very fast reactions in
which pore and film diffusion may influence the rate, the fluidized bed with its vigorous gas-solid
contacting and small particles will allow a much more effective use of the catalyst. If the catalyst
has to be treated (regenerated) frequently because it deactivates rapidly, then the liquid-like
fluidized state allows it to be pumped easily from unit to unit. This feature of fluidized contacting
offers overwhelming advantages over fixed bed operations for such solids.(Jansson, 1980).

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 Figure 2. 1: packed bed catalytic reactor

2.2 Fixed Bed Catalytic Reactor

In a fixed-bed reactor the catalyst pellets are held in place and do not move with respect to a fixed
reference frame. Essentially all reaction occurs within the catalyst particles. When we need to
discuss both fluid and pellet concentrations and temperatures, we use a tilde on the variables within
the catalyst pellet. Material and energy balances are required for both the fluid, which occupies
the interstitial region between catalyst particles, and the catalyst particles, in which the reactions
occur(Publishing, 2011).

During any catalytic reaction the following steps occur:

1. Transport of reactants and energy from the bulk fluid up to the catalyst pellet exterior surface,
2. Transport of reactants and energy from the external surface into the porous pellet,
3. Adsorption, Chemical Surface Reaction, and Desorption of Products at the catalytic sites,
4. Transport of products from the catalyst interior to the external surface of the pellet, and
5. Transport of products into the bulk fluid.

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The coupling of transport processes with chemical reaction can lead to concentration and
temperature gradients within the pellet, between the surface and the bulk, or both.

Figure 2.2: Expanded views of a fixed-bed reactor

2.2.1 A Classification of Reactor Models

The process design of an FBCR involves exploiting the continuity (material-balance) and energy
equations to determine, among other things, the amount of a specified catalyst required for a given
feed composition, fractional conversion, and throughput; concentration and temperature profiles;
and the thermal mode of operation to achieve the objectives. The appropriate forms of these
equations, together with rate equations for reaction and heat transfer, constitute the main working
equations of a reactor model. Before using any particular model for calculations, we
describe a classification as a basis for consideration of models in general for an FBCR.

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 Figure 2.3: classification of FBCR models

Figure 2.4 Control volumes for (a) one- and (b) two-dimensional models

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1. In a “one-phase” or pseudo homogeneous model, intraparticle gradients are ignored, so that
everywhere in the catalyst bed, the value of concentration (CA) or temperature (T) is the same
as the local value for bulk fluid (CAb or T). The actual two-phase system (fluid and catalyst) is
treated as though it were just one phase.
2. In a two-phase or heterogeneous model, intraparticle gradients are allowed, so that, locally,
within the particle, (CA # CAb) and (T # Tb). The effects of these gradients are reflected in the
particle effectiveness factor, η or an overall effectiveness factor, Ω. If the reactor operates
nearly isothermally, a single value of η or Ω may be sufficient to describe thermal and
concentration gradients. However, if operation is non-isothermal, η and/or Ω may vary along
the length of the vessel, and it may be necessary to account explicitly for this behavior within
the reactor model. In a one-dimensional model, gradients of CA and T at the bed level are
allowed only in the axial direction of bulk flow. In a two-dimensional model, gradients at the
bed level in both the axial and radial directions are considered (Conesa, 2019).

2.2.2 Mode of operation

Adiabatic Operation
In adiabatic operation, no attempt is made to adjust T within the bed by means of heat transfer.
The temperature thus increases for an exothermic reaction and decreases for an endothermic
reaction. For a reactor consisting of one bed of catalyst (a single-stage reactor), this defines the
situation thermally. However, if the catalyst is divided into two or more beds arranged in series (a
multistage reactor), there is an opportunity to adjust T between stages, even if each stage is
operated adiabatically.

Non-adiabatic Operation
In non-adiabatic operation, heat transfer for control of T is accomplished within the bed itself. This
means that the reactor is essentially a shell-and-tube exchanger, with catalyst particles either inside
or outside the tubes, and with a heating or cooling fluid flowing in the shell or in the tubes
accordingly.

Isothermal conditions:

In isothermal process the temperature is constant at each point across the length of reactor

Non-isothermal conditions:

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 Figure 2.5: Fixed-bed catalytic reactors (FBCR) for two-phase reactions: modes of operation
(each rectangle or shaded area represents a bed of catalyst; each circle represents a heat
exchanger)

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2.2.3 Advantages, disadvantage, limitation and overcoming the limitation
The fixed bed or packed bed reactors are most commonly used for the study of solid catalysts. A
fixed bed reactor usually consists of a cylindrical vessel packed with catalyst pellets and is easy to
design and operate. The metal support grid and screen are placed near the bottom to support the
catalyst. Inert ceramic balls are placed above the catalyst bed to distribute the feed evenly.
Advantages of a packed bed or fixed bed reactor include ideal plug flow behavior, lower
maintenance cost, and reduced loss due to attrition and wear. Heat management is a very important
aspect of the design of a fixed bed reactor. Poor heat distribution may result in non-uniform
reaction rates and consequently low reactant conversion. Poor heat transfer may also result in the
generation of hot spots and thermal degradation of catalysts (Worstell, 2014)..

However, the situations are observed more in large fixed beds and for highly exothermic or
endothermic reactions when temperature control is difficult. The regeneration or replacement of
catalyst is also difficult in fixed bed reactors and the process needs to be shut down. Another major
disadvantage of a packed bed reactor is plugging of bed due to coke deposition which results in
high-pressure drop. A high-pressure drop is also observed for small beads or pellets of catalysts.
However, an increase in pellet size increases the pore diffusion limitation. Catalyst pellet sizes are
usually in the range of 1 to 10 mm. Non-uniform packing of catalysts can cause channeling of
fluids leading to poor heat and mass transfer. The column to particle diameter is maintained
between 10 to 20 to minimize channeling. The bed voidage is usually 70 to 90 %. Plug flow
behavior is ensured by maintaining the ratio of reactor length to catalyst particle diameter greater
than 50. The allowed pressure drop is less than 0.5-inch water per foot of bed depth. Usually, the
ratio of bed height to diameter is maintained at greater than 0.5. For better heat management for a
very highly exothermic (or endothermic) reaction, the multi-tubular reactor is used with catalyst
packed inside the tubes. The cooling (or heating) fluid flows through the shell side. The length is
limited by allowable pressure drop. The multi-tubular reactor has a high surface area for heat
transfer per unit volume.

Advantages Packed Bed Reactor

a) By using a packed bed reactor is a higher conversion per weight of catalyst than another
catalytic reactor.
b) The reaction rate is based on the amount of the solid catalyst rather than the volume of
the reactor.

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 c) Low operating cost and low maintenance by using this kind of reactor.
d) The process using a packed bed reactor operates continuously.
e) Little wear on catalyst and equipment.
f) Simple analysis
g) Little loss or attrition.
h) Only practical, an economic reactor at very high pressures.
i) The Usually, high ratio of catalyst to reactants long residence time complete reaction

Challenges/Limitations
For this reactor which is a packed bed, it consists of three aspects of limitation which are:
1. Temperature control.
2. Pressure drop.
3. Catalyst deactivation.

1. The first aspect is temperature control and the challenge that have to face are:
a. Endothermic reaction may die out.
b. Exothermic reaction may damage the reactor.
c. Selectivity control.

The ways that can be used is by choosing the suitable types of packed bed reactor.

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Single bed reactor multi-bed reactor multi-tube reactor

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2. The second aspect is pressure drop:
a) Friction between the gas and particle phase results in a pressure drop.
b) High-pressure drop will result in high compression cost.
c) Some systems have a low tolerance for pressure drop.
d) The pressure drop is mainly dependent on reactor length, particle diameter, void
fraction, and gas velocity.

Figure 2.6: Large particle has to be used (dp>1mm)

Porous Catalyst Particle:

 The particles are porous to increase the surface area of the catalyst.
 Reactants are transported inside the pores using molecular diffusion and adsorb to the
active sites where the reaction occurs.
 Products desorb and diffuse back to the bulk.
 Heat is transported by conduction
 intra-particle diffusion/conduction may be rate determining for large particle
3. Formation of carbon deposit deactivate the catalyst
Large carbon deposits may clog the tubes, causing hot-spots that damage the reactor.

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4. Catalyst regeneration is necessary
Disadvantages of Packed Bed Reactor
 Large temperature gradient or undesired thermal gradient may occur.
 Inefficient heat exchange
 Suitable for slow-or-non-deactivating processes.
 Poor temperature control.
 Channeling may occur.
 Unit may be difficult to service and clean.
 Swelling of the catalyst, deformation of the reactor.
 Regeneration or replacement of the catalyst is difficult- shut down is required.
 Pore diffusional problems intrude in large pellets

Overcoming the Disadvantages

a) Monolithic supports will overcome the problems of non-uniform flow patterns,
plugging high pressure for small pellets and pore diffusional problems,
b) Temperature control problems are overcome with:
 Recycle.
 Internal and external heat exchanges.
 Staged reactors
 Cold shot cooling
 Multiple tray reactor- fluid redistributed and cooled between stages and catalyst is
easily removed which varied from tray to tray.
 Use of diluents.
 Temperature self-regulation with competing reactions, one endo and one
exothermic.
 control by selectivity and temporarily poisoning the catalyst.

2.2.4 Application of fixed bed catalytic reactor

Catalytic processes are carried out in several types of reactors like fixed bed, moving bed, trickle
bed, two- and three phase fluidized beds, bubble columns, and stirred tanks. Examples of important
fixed bed catalytic processes with only one fluid phase are given in Table below. Other fixed bed
processes with particular catalyst designs exist as well.

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Several packed bed reactors are employed by the petroleum refining industries utilizing natural
gas as feedstock. Different compositions of synthesis gas (mixtures of carbon monoxide and
hydrogen) or syngas are important intermediate feedstocks for the production of large volume
chemicals such as ammonia, methanol, hydrogen and synthetic hydrocarbon liquids. The fixed bed
reactors used today are thus mainly large-capacity units due to the vast market demand.

Table 2.1 applications of fixed bed catalytic reactor

Basic Chemical Industry Petrochemical Industry Petroleum Refining

Primary steam reforming Ethylene oxide Catalytic reforming
Secondary steam reforming Ethylene dichloride Isomerization
Carbon monoxide conversion Vinyl-acetate Polymerization
Carbon monoxide methanation Butadiene (Hydro)desulfurization
Ammonia synthesis Maleic anhydride Hydrocracking
Sulfuric acid synthesis Phthalic anhydride
Methanol synthesis Cyclohexane
Oxo synthesis Styrene
Hydrodealkylation

2.2.5 Design Considerations

In addition to flow, thermal, and bed arrangements, an important design consideration
is the amount of catalyst required (W), and its possible distribution over two or more stages. This
is a measure of the size of the reactor. The depth (L) and diameter (D) of each stage must also be
determined. In addition to the usual tools provided by kinetics, and material and energy balances,
we must consider matters peculiar to individual particles, collections of particles, and fluid-particle
interactions, as well as any matters peculiar to the nature of the reaction, such as reversibility.

2.2.5.1 One-dimensional pseudo homogeneous model

Pseudo-homogeneous models are doing not account explicitly for the presence of catalyst, and The
basic model is the pseudo homogeneous one-dimensional model, which only considers transport
by plug flow in the axial direction.

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Pressure Drops
In addition to temperature and concentration distributions in the packed bed, the pressure drops
over the reactor is an important reactor characteristic. The pressure drop is rarely more than 10%
of the total pressure. Considering inaccuracies in the reaction rate expressions and the uncertainties
in the transport parameters, the pressure drop does not usually have a significant effect on the
overall model performance. Nevertheless, the pressure drop might be of great importance for
assessment of the reactor operation costs. Pressure drop is calculated according to the following
equation (Iordanidis, 2002):

𝑑𝑃 (1 − 𝜙)𝐺(1 + 𝜀𝑋) 150𝜇(1 − 𝜙)

=− [ + 1.75𝐺]
𝑑𝑧 𝑃 𝑇𝑜 3 𝐷𝑝
𝜌𝑜 (𝑃 ) ( 𝑇 ) 𝑔𝑐 𝐷𝑝 𝜙
𝑜

∑ 𝐹𝑖𝑜 𝑀𝑖 𝜋𝐷 2
Where, 𝐺 = (Mi = molecular weight of i and 𝐴𝑐 = (cross-sectional area)
𝐴𝑐 4

Figure 2.7. Pressure drop along the length of reactor with different particle sizes.

Reaction rate constant:

Reaction rate constant is affected by temperature and expressed by Arrhenius equation.

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 𝐸 1 1
𝑘 = 𝑘1 (𝑇1 )𝑒𝑥𝑝 [ ( − )]
𝑅 𝑇1 𝑇
𝑜
∆𝐻𝑅𝑥 1 1
𝐾𝑐 = 𝐾𝑐2 (𝑇2 )𝑒𝑥𝑝 [ ( − )]
𝑅 𝑇2 𝑇

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3. Design, modeling and simulation of adiabatic and non-isothermal
reactor
Case study: Production of Acetic Anhydride

Jeffrey’s in a treatment of the design of an acetic anhydride manufacturing facility, states the at
one of the key steps is the endothermic vapor-phase cracking of acetone to ketene and methane is,

He states further that this reaction is first-order with respect to acetone and that the specific reaction
rate is given by

-------------------eq (1)

where k is in reciprocal seconds and T is in Kelvin. It is desired to feed 7850 kg of acetone per
hour to a tubular reactor. The reactor consists of a bank of 1000 one-inch, schedule-40 tubes. We
shall consider four cases of heat exchanger operation. The inlet temperature and pressure are the
same for all cases at 1035 K and 162 kPa (1.6 atm) and the entering heating-fluid temperature
available is 1250 K. The heat-exchange fluid has a flow rate of 0.111 mol/s, with a heat capacity
of 34.5 J/mol·K.

A bank of 1000 one-inch, schedule-40 tubes, 1.79 m in length corresponds to 1.0 m3 (0.001 m3/tube
= 1.0 dm3/tube) and gives 20% conversion. Ketene is unstable and tends to explode, which is a
good reason to keep the conversion low. However, the pipe material and schedule size should be
checked to learn if they are suitable for these temperatures and pressures. In addition, the final
design and operating conditions need to be cleared by the safety committee before operation can
begin.

Case 1 The reactor is operated adiabatically.

Case 2 Constant heat-exchange fluid temperature Ta = 1250 K

Case 3 Co-current heat exchange with Ta0 = 1250 K

Case 4 Countercurrent heat exchange with Ta0 = 1250 K

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 𝑑𝑋 𝑟
1. Mole balance: = − 𝐹 𝐴 ---------------------------eq (2)
𝑑𝑉 𝐴𝑜

2. Rate Law: 𝑟𝐴 = 𝑘𝐶𝐴 -------------------------------eq (3)

34,222 1 1
By rearranging 𝑘 = 8.2𝑥11014 𝑒𝑥𝑝 [− ] = 3.58𝑒𝑥𝑝 [34,222 (1035 − 𝑇)]----eq (4)
𝑇

3. Stoichiometry (gas-phase reaction with no pressure drop):

𝐶𝐴𝑜 (1−𝑋)𝑇𝑜
𝐶𝐴 = --------------------------eq (5)
(1+𝑋)𝑇
 = 𝑦𝑎𝑜 𝛿 = 1(1 + 1 − 1) = 1
4. Combining yields
𝑘𝐶𝐴𝑜 (1−𝑋)𝑇𝑜
𝑟𝐴 = ------------------------eq (6)
(1+𝑋)𝑇
Before combining Equations eq (2) and eq (6), it is first necessary to use
the energy balance to determine T as a function of X.
5. Energy Balance:
a) Reactor Balance:
To simplify the mathematical model, major assumptions can be listed as follows:
 steady-state conditions;
 No phase change and no shaft work
 ideal gas behavior;
 the radial dispersions negligible;

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 Therefore, general energy balance is,
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑅𝑎𝑡𝑒 𝑜𝑓𝑓𝑙𝑜𝑤 𝑅𝑎𝑡𝑒 𝑜𝑓𝑤𝑜𝑟𝑘
𝑎𝑑𝑑𝑒𝑑 𝑡𝑜 𝑡ℎ𝑒 𝑙𝑒𝑎𝑣𝑖𝑛𝑔
𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑡𝑜 𝑡ℎ𝑒 𝑑𝑜𝑛𝑒 𝑏𝑦 𝑡ℎ𝑒
[ ]=[ ]−[ ] + 𝑠𝑦𝑠𝑡𝑒𝑚 𝑏𝑦 𝑚𝑎𝑠𝑠 − 𝑠𝑦𝑠𝑡𝑒𝑚 𝑏𝑦 𝑚𝑎𝑠𝑠
𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑤𝑖𝑡ℎ𝑖𝑛 𝑠𝑦𝑠𝑡𝑒𝑚 𝑓𝑟𝑜𝑚 𝑠𝑦𝑠𝑡𝑒𝑚 𝑜𝑛 𝑡ℎ𝑒
𝑓𝑙𝑜𝑤 𝑖𝑛𝑡𝑜 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡 𝑜𝑓
𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑡ℎ𝑒 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
[ 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 ] [ 𝑡ℎ𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 ]

𝑑𝐸𝑠𝑦𝑠𝑡𝑒𝑚
= 𝑄̇ − 𝑊̇ + ∑ 𝐹𝑖𝑜 𝐸𝑖𝑜 |𝑖𝑛 − ∑ 𝐹𝑖 𝐸𝑖 |𝑜𝑢𝑡
𝑑𝑡
𝑜
𝑑𝑇 𝑈𝑎(𝑇𝑎 −𝑇)+(𝑟𝐴 ′ )[∆𝐻𝑅𝑥 +∆𝐶𝑝 (𝑇−𝑇𝑅 )]
= -------------eq (7)
𝑑𝑉 𝐹𝐴𝑜 (∑ 𝜃𝑖 𝐶𝑝𝑖 +𝑋∆𝐶𝑝 )

b) Heat Exchanger:
We will use the heat-exchange fluid balance for co-current flow as our base case. We
will then show how we can very easily modify our ODE solver program (e.g.,
Polymath) to solve for the other cases by simply multiplying the appropriate line in the
code by either zero or minus one.
For co-current flow:
𝑑𝑇𝑎 𝑈𝑎(𝑇−𝑇𝑎 )
= ------------------------- eq (8)
𝑑𝑉 𝑚̇𝐶𝑝

6. Calculation of Mole Balance Parameters on a Per Tube Basis:

𝑘𝑔
7850( ) 1 𝑘𝑚𝑜𝑙 𝑚𝑜𝑙
ℎ
𝐹𝐴𝑜 = 𝑘𝑔 𝑥 1000 𝑇𝑢𝑏𝑒𝑠 = 0.135 = 0.0376
58( ) ℎ 𝑠
𝑘𝑚𝑜𝑙

𝑃𝐴𝑜 162𝑘𝑃𝑎 𝑘𝑚𝑜𝑙

𝐶𝐴𝑜 = = 3 = 0.0188 = 18.8 𝑚𝑜𝑙/𝑚3
𝑅𝑇 𝑘𝑃𝑎. 𝑚 𝑚3
8.31 (1035𝐾)
𝑘𝑚𝑜𝑙. 𝐾

𝐹 1 𝑚3 0.001𝑚3 𝑑𝑚3
𝑜 = 𝐶𝐴𝑜 = 2.0 𝑑𝑚3 /𝑠 𝑉 = 1000 𝑇𝑢𝑏𝑒𝑠 = 𝑇𝑢𝑏𝑒
= 1 𝑇𝑢𝑏𝑒
𝐴𝑜

7. Calculation of Energy Balance Parameters:

Thermodynamics:
𝑜
i) ∆𝐻𝑅𝑥 : At 298 K, using the standard heats of formation

𝑜 (𝑇 ) 𝑜 𝑜 𝑜
∆𝐻𝑅𝑥 𝑅 = 𝐻𝐵 (𝑇𝑅 ) + 𝐻𝐶 (𝑇𝑅 ) − 𝐻𝐴 (𝑇𝑅 )

𝑘𝐽 𝑘𝐽
= ((−61.09) + (−74.81) − (−216.67)) = 80.77
𝑚𝑜𝑙 𝑚𝑜𝑙

ii) Using the mean heat capacities

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 𝐽 𝐽
∆𝐶𝑝 = 𝐶𝑝𝐵 + 𝐶𝑝𝐶 − 𝐶𝑝𝐴 = (83 + 71 − 163) = −9
𝑚𝑜𝑙. 𝐾 𝑚𝑜𝑙. 𝐾

He at Exchange:

Energy balance. The heat-transfer area per unit volume of pipe is

𝜋𝐷𝐿 4 4
𝑎= 2
= = = 150 𝑚−1
(𝜋𝐷 /4)𝐿 𝐷 0.0266 𝑚

𝐽
𝑈 = 110
𝑚3 . 𝑠. 𝐾

Combining the overall heat-transfer coefficient with the area yields

𝐽
𝑈𝑎 = 16500
𝑚3 . 𝑠. 𝐾

Table 3.1 Summary of parameter values

𝑜 (𝑇 ) 𝑘𝐽 𝐽
∆𝐻𝑅𝑥 𝑅 = 80.77 𝑚𝑜𝑙 𝑈 = 110 𝑚3 .𝑠.𝐾

𝐽 𝑎 = 150 𝑚−1
∆𝐶𝑝 = −9
𝑚𝑜𝑙. 𝐾

𝑚𝑜𝑙 𝑑𝑚3
𝐹𝐴𝑜 = 0.0376 𝑉=1 = 0.001𝑚3
𝑠 𝑇𝑢𝑏𝑒
𝐶𝐴𝑜 = 18.8 𝑚𝑜𝑙/𝑚3 𝑜 = 2.0 𝑑𝑚3 /𝑠
𝐽
𝑈𝑎 = 16500 𝑇𝑜 = 1035𝐾
𝑚3 .𝑠.𝐾

𝑇𝑅 = 298𝐾 𝑚̇𝑐 = 0.111𝑚𝑜𝑙/𝑠

We will solve for all four cases of heat exchanger operation for this endothermic reaction example
in the same way we did for the exothermic reaction. That is, we will write the Polymath equations
for the case of co-current heat exchange and use that as the base case. We will then manipulate the
different terms in the heat-transfer fluid balance to solve for the other cases. We will start with the
adiabatic case where we multiply the heat-transfer coefficient in the base case by zero.

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Case 1: Adiabatic

We are going to start with the adiabatic case first to show the dramatic effects of how the reaction
dies out as the temperature drops. In fact, we are now going to extend the length of each tube to
make the total reactor volume 5 dm3 in order to observe this effect of a reaction dying out as well
as showing necessity of adding a heat exchanger. For the adiabatic case, we simply multiply the
value of Ua in our Polymath program by zero. No other changes are necessary. To illustrate how
an endothermic reaction can virtually die out completely, let’s extend the single-pipe volume from
1 dm3 to 5 dm3.

Figure 3.1. polymath coding of adiabatic reactor.

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Table 3.2. polymath results of adiabatic reactor.

Variable Initial value Final value

Cao 18.8 18.8
Cpa 163 163
Cpc 34.5 34.5
delCpc -9 -9
deltaH 7.414E+04 7.414E+04
Fao 0.0376 0.0376
mc 0.111 0.111
ra -67.304 -0.376
Rate 67.304 0.376
T 1035 904.8156
Ta 1250 1250
To 1035 1035
Ua 0 0
v 0 0.005
X 0 0.2817744

Figure 3.2: Adiabatic conversion and temperature (a), and reaction rate (b) profiles.

3.1 Discussion and recommendation for case 1

As temperature drops, so does k and hence the rate, –ra, drops to an insignificant value. Note that
for this adiabatic endothermic reaction, the reaction virtually dies out after 3.5 dm3, owing to the
large drop in temperature, and we observe very little conversion is achieved beyond this point.

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One way to increase the conversion would be to add a diluent such as nitrogen, which could supply
the sensible heat for this endothermic reaction. However, if too much diluent is added, the
concentration, and hence the rate, will be quite low. On the other hand, if too little diluent is added,
the temperature will drop and virtually extinguish the reaction.

Case II :Constant heat-exchange fluid temperature, Ta

We make the following changes in our program on line 3 of the base case (a)

𝑑𝑇𝐴 𝑈𝑎(𝑇 − 𝑇𝑎 )
= ∗0
𝑑𝑉 𝑚̇𝐶𝑝
𝑼𝒂 = 16,500 𝐽/𝑚3 /𝑠/𝐾
𝑎𝑛𝑑 𝑽𝑓 = 0.001 𝑚3

Figure 3.3. Polymath coding with constant temperature heat supply

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Table 3.3 Polymath result with constant heat supply

Variable Initial value Final value

Cao 18.8 18.8
Cpa 163 163
Cpc 34.5 34.5
delCpc -9 -9
deltaH 7.414E+04 7.414E+04
Fao 0.0376 0.0376
Mc 0.111 0.111
Ra -67.304 -16.48924
Rate 67.304 16.48924
T 1035 1114.093
Ta 1250 1250
To 1035 1035
Ua 1.65E+04 1.65E+04
V 0 0.001
X 0 0.9508067

a b

Figure 3.4. Profiles for constant heat exchanger fluid temperature (Ta); (a) temperature, (b)
conversion

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Figure 3.5. Profiles for constant heat exchanger fluid temperature(Ta) for reaction rate.

3.2 Discussion and recommendation for Case 2 Constant Ta

Just after the reactor entrance, the reaction temperature drops as the sensible heat from the reacting
fluid supplies the energy for the endothermic reaction. This temperature drop in the reactor also
causes the rate of reaction to drop. As we move farther down the reactor, the reaction rate drops
further as the reactants are consumed. Beyond V = 0.08 dm3, the heat supplied by the constant Ta
heat exchanger becomes greater than that “consumed” by the endothermic reaction and the reactor
temperature rises. In the range between V = 0.2 dm3 and V = 0.6 dm3, the rate decreases slowly
owing to the depletion of reactants, which is counteracted, to some extent, by the increase in
temperature and hence the rate constant k. Consequently, we are eventually able to achieve an exit
conversion of 95%.

Case 3 Co-current Heat Exchange

The energy balance on a co-current exchanger is

𝑑𝑇𝐴 𝑈𝑎(𝑇 − 𝑇𝑎 )
=
𝑑𝑉 𝑚̇ 𝑐 𝐶𝑝𝑐

with Ta0 = 1250 K at V = 0

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Table3.4: Polymath result with co-current flow

Variable Initial value Final value

Cao 18.8 18.8
Cpa 163 163
Cpc 34.5 34.5
delCpc -9 -9
deltaH 7.414E+04 7.414E+04
Fao 0.0376 0.0376
Mc 0.111 0.111
Ra -67.304 -4.899078
Rate 67.304 4.899078
T 1035 984.8171
Ta 1250 996.215
To 1035 1035
Ua 1.65E+04 1.65E+04
V 0 0.001
X 0 0.456201

a b

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 c

Figure 3.6: Profiles down the reactor for an endothermic reaction with co-current heat exchange;
(a) temperature, (b) conversion, and (c) reaction rate.

3.3 Discussion and recommendation for Case 3 Co-Current Exchange

In co-current heat exchange, we see that the heat-exchanger fluid temperature, Ta, drops rapidly
initially and then continues to drop along the length of the reactor as it supplies the energy to the
heat drawn by the endothermic reaction. Eventually, Ta decreases to the point where it approaches
T and the rate of heat exchange is small; as a result, the temperature of the reactor, T, continues to
decrease, as does the rate, resulting in a small conversion. Because the reactor temperature for co-
current exchange is lower than that for Case 2 constant Ta, the reaction rate will be lower. As a
result, significantly less conversion will be achieved than in the case of constant heat-exchange
temperature Ta.

Case 4 Countercurrent Heat Exchange

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For countercurrent exchange, we first multiply the Rhs. of the co-current heat-exchanger energy
balance by –1, leaving the rest of the Polymath program is the same.

𝑑𝑇𝐴 −𝑈𝑎(𝑇 − 𝑇𝑎 ) 𝑈𝑎(𝑇𝑎 − 𝑇)

= =
𝑑𝑉 𝑚̇ 𝑐 𝐶𝑝𝑐 𝑚̇ 𝑐 𝐶𝑝𝑐

Table 3.5: Polymath result with counter-current flow

Variable Initial value Final value

Cao 18.8 18.8
Cpa 163 163
Cpc 34.5 34.5
delCpc -9 -9
deltaH 7.414E+04 7.414E+04
Fao 0.0376 0.0376
mc 0.111 0.111
ra -67.304 -31.79235
Rate 67.304 31.79235
T 1035 1034.475
Ta 995.15 1249.999
To 1035 1035
Ua 1.65E+04 1.65E+04
v 0 0.001
X 0 0.3512403

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Figure 3.7: Profiles down the reactor for countercurrent heat exchange; (a) temperature, (b)
conversion, (c) reaction rate.

3.4 Discussion and recommendation for Case 4 Countercurrent Exchange

At the front of the reactor, V = 0, the reaction takes place very rapidly, drawing energy from the
sensible heat of the gas and causing the gas temperature to drop because the heat exchanger cannot
supply energy at an equal or greater rate to that being drawn by the endothermic reaction.

Additional “heat” is lost at the entrance in the case of countercurrent exchange because the
temperature of the exchange fluid, Ta, is below the entering reactor temperature, T. One notes
there is a minimum in the reaction rate, –rA, profile that is rather flat. In this flat region, the rate
is “virtually” constant between V = 0.2 dm3 and V = 0.8 dm3, because the increase in k caused by
the increase in T is balanced by the decrease in rate brought about by the consumption of reactants.
Just past the middle of the reactor, the rate begins to increase slowly as the reactants become
depleted and the heat exchanger now supplies energy at a rate greater than the reaction draws
energy and, as a result, the temperature eventually increases. This lower temperature coupled with
the consumption of reactants causes the rate of reaction to be low in the plateau, resulting in a
lower conversion than either the co-current or constant Ta heat exchange cases.

Table 3.6: Summary of Cases

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 Heat Exclusion X T(K) Ta

Adiabatic 0.28 905

Constant Ta 0.95 1114 1250
Co-current 0.456 985 996
Countercurrent 0.35 1034 995

Recommendation

As we have observed from the four case the constant energy supply reactor achieves a higher
conversion than the three cases. so it better to use the constant temperature energy supply system.

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Reference
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Iordanidis, A. A. (2002). Mathematical Modeling of Catalytic Fixed Bed Reactors. In Thesis.

Jansson, R. E. W. (1980). Electrochemical reaction engineering. In Chemical Engineering Science

(Vol. 35, Issue 9). https://doi.org/10.1016/0009-2509(80)80138-2

Publishing, N. H. (2011). Fixed-Bed Catalytic Reactors.

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Worstell, J. (2014). Adiabatic Fixed-Bed Reactors: Practical Guides in Chemical Engineering. In

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