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Once the process has been described, process engineer has to synthesize the flow sheet
which will give an overview of the whole process. Synthesizing flow sheet is also not a
very simple task. For it, process engineer has to consider various points. This whole task
of flow sheet synthesis has to be decided in different sub tasks. Generally these sub
tasks are considered as ‘decisions at different levels’ during flow sheet synthesis. These
different levels decisions include ‘Level-1 to Level-5’ decisions. After discussing these
various level decisions, flow sheet can be considered as well synthesized. In general this
level-1 to level-5 decisions is categorized as below:
Before discussing these different level decisions, it is needed to input some necessary
and important information to the process in order to take correct and proper decisions.
This input information required is as below:
Input Information
The starting point for any project / design problem is a data bank which defines the
basis of design. This information includes:
The degree of detail and depth required from each of the above heads is now discussed
below:
In general, several different reactions take place in any given process to be designed.
For better design, one should be familiar with all the relevant parameters of these
reactions such as
1. The stoichiometry
2. The range of industrially feasible temperature and pressure for carrying out the
reactions
3. The phase system of the reaction
4. Information regarding the product distribution v/s conversion & if possible, the
knowledge about preferred reactor temperature, molar ratio of reactants,
reactor pressure
5. Relationship between conversion and space velocity or residence time
6. For a catalyzed reaction process, it is necessary to have knowledge about state of
catalyst (like homogeneous, slurry, packed bed, power state etc.), deactivation
rate, regenerability of catalyst and the method of regeneration (coke burn /
solvent wash etc.)
While a majority of this information should be available from patent literature as well as
from in-house data bank, it is also a good idea to involve the in-house R & D / Chemists
for completing the above base.
2. Side Reactions:
All possible side reactions that occur and lead to the formation of by-products should be
known. In case of a plant with a recycle loop, the by-products will build up to high levels
unless a method for their continuous removal is devised. Armed with the complete
knowledge of the possible reactions that occur and their consequences, it is a relatively
easy task to synthesize a separation system and to avoid economic penalties as result of
negligence to these side reactions.
3. Maximum Yield:
While designing any process, the focus is always on trying different catalysts to identify
the most suitable one & establishing conditions which enables the process to operate at
maximum product yield. A word of caution: the operation at maximum yield condition
isn’t always one corresponding to the optimum economic conversion.
During a reaction scheme which involves concurrent reactions the strategy of achieving
the maximum amount of desired product may be accompanied by a significant
production certain undesired products that may have no use other than as fuel. In such
cases, a large amount of expensive reactant is consumed and converted into a
considerably low value product (equivalent to fuel). Instead, in such a case, a better
strategy could be to operate the process under such conditions as, which produce a
considerable amount of desirable product (but not necessarily at its maximum yield)
At this time we can define certain terms which will be used in the discussion to follow:
Selectivity & Selectivity loss as below:
Designer should try to estimate the economic incentive for determining the economic
optimum conversion even if such an approach requires some additional experiments
rather than just designing a process to operate at maximum yield.
4. Catalyst Deactivation:
This data is many times not available at the early stages of design. Also, to find the best
catalyst and then its deactivation rate is a time consuming process as some catalysts
have an operating life of 1-2 years before their deactivation begins requiring
reactivation / replacement. Thus to achieve the highest potential profitability, designer
should carry out sensitivity analysis of the total product cost to such uncertainty
(catalyst deactivation rate), and further experimental development program should be
prepared with help of these results.
5. Production Rate:
The rated design capacity of a plant depends upon the market conditions which
continually change. Before embarking on the design exercise, it is thus necessary, to
assess the target market share and corresponding business risk. Based on this risk and
opportunity analysis the rated design production capacity can be ascertained and the
project work can get underway.
The large production rates will require large size plant which in turn will require larger
investment, difficulties / restrictions during transportation of these large size plant and
equipments, higher risks during development of new technologies and larger
management costs.
The price of any product will change according to its purity. During early stages of
development of a new process, high costs will be incurred for producing a high purity
product, and this should be informed to the marketing department of the company so
that it does not raise the customer expectations to the unrealistic levels.
7. Raw Materials:
Trace amount of impurities in raw material can build up to large values in recycle loop,
unless some mechanism is built in to purge these regularly. The knowledge of
commercially available quality of raw materials is thus vital to enable the designer not
only to estimate the impurities brought in, their characteristics and effect on the
reaction and / or final product of interest (inert, unacceptable due to detrimental
effects, toxic, catalyst poison etc.) but also to incorporate an appropriately designed
purification / purge system.
8. Constraints:
While designing the process the designer is required to consider the constraints like, the
processing conditions operating within the explosive limits, materials polymerizing and
fouling the plant equipments, materials forming the coke and hence deactivating the
catalyst, materials causing the corrosion etc.
While erecting the new process at existing plant site, the design of the new process
should be compatible with the existing facilities at plant site. For this, costs of utilities
such as fuel supply, levels of steam pressure, inlet and outlet temperatures of cooling
water, refrigeration levels, electric power etc. as well as waste disposal facilities should
be available.
The conceptual designs are aimed to produce the new materials. In such design
exercise, physico-chemical data such as molecular weights, boiling points, vapor
pressures, heat capacities, heats of vaporization, heats of reactions, liquid densities, and
fugacity coefficients should be collected as these are sensitive to the total processing
costs.
This is the input information that must be provided during initial stage of project
development.
Continuous Process: Every unit is operating 24 hrs / day, 7 days / week throughout the
year before the plant is shut down for the maintenance purpose. They may be having
very few batch units, else otherwise operate continuously with large production rates.
Batch Process: It is started and stopped frequently where, units are filled with material,
perform the specified function for a specified time, then are shut down and drained
before being cleaned for the next cycle to begin. However, a few units here may be
continuous one such as when the products from batch process are stored for a while
and then fed to train of distillation columns which operate continuously.
1. Production Rates:
As a rule of thumb, continuous plants have capacity of greater than 50000 TPA while it is
less than 5000 TPA for batch process. Hence continuous plants operating at high
capacity require more accurate data base and incur higher design engineering costs. The
batch processes are simpler and being flexible, a variety of products can be produced in
the same processing equipment.
2. Market Forces:
Batch processes are suitable to produce the seasonal products, due to which the same
equipment can be further used to produce another product in next season which is
economical one rather than to use a continuous process for producing the seasonal
product which incurs large inventory cost in storing the product.
3. Operational Problems:
Generally, batch processes are more suited to slow reactions. Also for processes
involving material which tend to foul equipment needing frequent clean-ups, batch
processes may be in order since the plant is idle after every batch is drained and thus
cleaning down time can be factored in easily.
Compiled By Prof. Prasad Parulekar
4. Multiple Operations in a Single Vessel:
It is often possible to accomplish the several operations in a single batch vessel, while an
individual vessel is needed for each single operation in continuous plant. Also single
large vessel is required when multiple operations are carried out in single vessel; with
this we can obtain the economy of scale, while separate vessels are required when
individual vessel is used for an individual operation such as in continuous process.
Catalyst
Product
Feed
Heat Reactor Separator
Continuous Process
Product
Still
Feed
Heat
Heat
Reactor
Catalyst
Separator
Batch Process
For developing a conceptual design for a continuous process, following steps should be
followed:
For batch process, in addition to these steps, decisions should be taken for:
(i) Which units in the process should be batch and which should be continuous?
(ii) What processing steps should be carried out in a single vessel versus using an
individual vessel for each processing step?
(iii) When it is advantageous to use the parallel batch units to improve the
scheduling of the plant?
(iv) How much intermediate storage is required, and where should it be located?
Considering the overall process, the input is nothing but the raw material fed to process
and output is the product obtained from the process. Before adding other details to
design, it is necessary to calculate the raw material cost as it amounts to anywhere
between 83 to 85% of the total processing cost.
While developing the flow sheet, the thumb rule should be followed that, it is desirable
to recover more than 99% of all valuable materials. Basically, two different alternatives
for flow sheet always exist: One in which all reactants are first completely recovered and
then they are recycled, while in the other, where reactants are consumed by side
reactions due to presence of impurities while process occurs, the reactants are recycled
Feed
Product
Process
By-products
Streams
Purge
Feed
Product
Process
By-products
Streams
Once it is decided that process should be batch wise or continuous, the next level
decision is to decide the input-output structure of the flow sheet. At this level of
decision making, designer should consider the points such as-
Need to purify the feed streams before their entry in the process
Removing or recycling the reversible by-product
Using a gas recycle and purge stream
Recovery and recycling of some reactants
Predicting the possible number of product streams
The design variables for this structure and economic trade-offs associated with
these variables.
These points are briefly discussed below:
Purification of feeds:
While synthesizing the flow sheet, proper purification system must concurrently be
designed. For designing this purification system, certain guidelines should be followed:
Process alternatives:
Whatever decision we take, if we are not sure about them, then opposite decisions
should be considered, all such opposite decisions can be termed as process alternatives.
Cost of the process increases when feed containing large amount of inert or active
impurities is being handled as it requires design of a proper separation system whose
design criterion is not fixed.
If reversible by-product is to be recycled, all the equipments in that recycle loop should
be oversized in order to accommodate the equilibrium flow of the reversible by-
product. And if that by-product is removed from the process, economic penalty is
required to be paid as result of the increased raw material cost of reactant which was
converted to the reversible by-product.
e.g.
2 Benzene Diphenyl + H2
(By-product)
So here, the decision involves economic trade-off between raw material losses to less
valuable by-products and increased recycle costs.
It should be used when a light reactant and a light feed impurity or a light by-product
boil lower than propylene (- 48oC). This is because the lower-boiling point components
normally can’t be condensed at high pressure with cooling water i.e. both the high
pressure and refrigeration will be required. So in such cases, as gaseous reactants are
As per the design guidelines, we have to recover 99% of all valuable materials. But
certain materials like, air and water, which are less valuable than organic materials,
need not to be recovered and recycled. Usually, these components are used in excess so
as to achieve complete conversion of other reactant. But here also, one thing should be
kept in mind that, using excess amount of air means increasing the operating cost of
blower used to move the air. So the extent of excess used needs to be optimized.
The number of product stream depends upon the components that are expected to
leave the reactor; these components include the components in feed stream, reactants
and products appearing in every reaction. Once these are known, certain destination
codes are given to them as per their properties. This procedure can determine the
number of products stream. Certain list of destination codes and component
classification is as below:
1. Number of reactor systems required and need for separation between these
reactor systems
2. Number of recycle streams required
3. Need for using an excess of one reactant at the reactor inlet
4. Need for gas compressor and its cost
5. Operation method for reactor i.e., should it be adiabatic operation, or with direct
heating and cooling, or it is a diluent or heat carrier type
6. Need for shifting the equilibrium conversion and if it is then how
7. Effect of the reactor cost on the economic potential
Multiple reactors are required for reactions taking place at different T & P, or involving
different catalysts.
2 Benzene Diphenyl + H2
(By-product)
these both reactions occurs at 1150 – 1300oF and 500 psi., i.e. at same T & P condition,
hence only one reactor system is required while in the following reaction system,
Ketene CO + ½ C2H4
In this second process system, first two reactions occur at 700oC & 1 atm, while third
occurs at 80oC and 1 atm, i.e. at different T & P conditions, hence here in this case, 2
reactor systems are required.
For this reaction steps should be associated with the reactor number, then feed streams
with the reactor number, and similarly recycle streams can be associated with reactor
Acid Feed
Acid Recycle
Acetone
Feed
Reactor R1 Reactor R2 Separator
Product
Acetone Recycle
3. Excess Reactants:
Use of an excess reactant can shift the product distribution. e.g. production of isobutene
by butane alkylation.
In this reaction, excess of isobutene can improve the selectivity of isooctane, but this
excess should be optimum one so that, cost to recover and recycle the product does not
outweigh the benefit of improved conversion to isooctane.
Also use of excess can be used to shift the equilibrium conversion. This equilibrium
conversion can be shifted to the right side by using excess of reactant at reactor inlet.
Molar ratio of reactants at the reactor inlet is often s design variable. By carrying out an
economic analysis in terms of this variable alone, it is possible to arrive at the
economically optimum value of this design variable.
For evaluation of heat effects of reactor and equilibrium calculations, reactor flows
should be known.
RG yPH
H2 Feed
Purge
FG
Benzene, PB
Reactor Separator
FT FT (1-x)
FFT Diphenyl
Toluene
Feed FT (1-x)
Hence, material balance for limiting reactant at a mixing point before reactor is:
FFT + FT (1-x) = FT
FT = FFT / x
Other Reactant:
For this process, other reactant is H2. Its material balance can be calculated as-
MR = molar ratio of hydrogen to toluene at reactor inlet; Fresh feed hydrogen = yFH FG;
Recycle Hydrogen = yPH RG ;
Hence,
yFH FG + yPH RG = MR (FFT / x)
No rule of thumb is available for selecting the conversion, x or purge composition yPH or
molar ratio, MR for complex reactions. However for single reaction, x can be considered
as equal to 0.96 or 0.98xeq.
Reversible By-products:
Flow of by-product being recycled during a reversible reaction can be calculated using
equilibrium expression. For e.g., for HDA process, where Diphenyl is a by-product
produced by a reversible reaction:
2 Benzene Diphenyl + H2
(By-product)
The next decision to be taken is about operating condition of the reactor i.e. to be
operated adiabatically, or by direct heating or cooling, or using heat carrier. Depending
upon this only, further separation system of process can be designed. So for this,
estimation of reactor heat load and adiabatic temperature change is needed.
For a single reaction, generally all fresh feed gets converted. So here, heat load can be
calculated as
However, for complex reactions, extent of each reaction depends upon the design
variables as like conversion, molar ratio of reactants, T & P etc. Hence in this case heat
load is calculated as a function of these design variables.
This can be calculated by knowing heat load and flow rate through reactor as-
QR = F Cp (TR,in - TR,out)
When adiabatic operation is not possible, direct heating & cooling technique is to be
used. But also there is limitation for heat transfer surface area that can fit into a reactor.
What should be the magnitude of this area, for this, case of high temperature gas-phase
reaction is considered where heat transfer coefficient and temperature difference are
assumed as U = 20 Btu/ (hr.ft2.oF) and ΔT = 50oF, and hence area of heat load of 1×106
Btu/hr will be
The maximum heat transfer area that can fit in heat exchanger is about 6000 to 8000 ft 2.
Hence, when direct heating or cooling method is used, and a single heat exchanger is to
be used, the reactor heat load is limited to 6 to 8×106 Btu/hr.
Heat Carrier:
The adiabatic temperature change depends upon the flow through the reactor, and by
increasing the flow rate, temperature change can be moderated. So for moderating the
temperature change, recycle flow of reactant or product or by-product should be
increased, and if it is not possible, extraneous component is need to be added. In some
reactions, certain by-products are produced which act as heat carrier, and if such
component are allowed to leave the reactor, exit temperature of the reactor will be
increased & hence adiabatic reactor could not be used longer. To avoid this, recycle flow
should be increased. E.g., in HDA process, methane in gas-recycle stream acts as heat
carrier.
Equilibrium Limitations:
For industrial processes, equilibrium limitations are important. Hence the flows of
reversible by-products are estimated when they are recycled and allowed to build up to
their equilibrium levels at reactor outlet.
The process flows are first calculated as a function of design variables and then they are
put into equilibrium relationship to check whether the conversion that was selected
earlier is above or below the equilibrium value, if it is above then, result is of no
meaning.
In this level decision of flow sheet synthesis, we have to decide a separation system for
the process in order to recover gaseous and liquid components.
Liquid
Liquid
Reactor Separation Products
System System
Feeds
Liquid Recycle
Purge
Vapor
Phase Vapor
Split Recovery
System
Liquid
Vapor
Liquid
Liquid
Reactor Separation Products
System System
Feeds
Liquid Recycle
Gas Recycle
Purge
Vapor
Recovery
System
Vapor
Reactor Phase
System Split Liquid
Feeds
Location of VRS:
For this there are 4 choices-
1. VRS on the Purge stream
2. VRS on Gas recycle stream
3. VRS on Flash vapor stream
4. None (No VRS)
Type of VRS:
The decision where we need to decide the synthesizing system for liquid
separation includes:
Light Ends:
Some light ends will be dissolved in the liquid leaving the phase splitter and
normally some will be dissolved in liquid streams leaving the VRS. They must be
removed if they are contaminating the product. They can be removed by using
either of the following methods:
1. Drop the pressure or increase the temperature of a stream and remove the
light ends in a phase splitter
2. Use a partial condenser on product stream
3. Use a pasteurization section on product stream
4. Use a stabilizer column before the product column
If component forms an azeotrope with a reactant, we have the choice of recycling the
azeotrope or splitting the azeotrope and just recycle the reactant. Splitting the
azeotrope normally requires two columns and therefore it is expensive. However, if we
recycle azeotrope, we must oversize all the equipments in recycle loop to handle
incremental flow of extra components. No general heuristic is available to decide
between these two; hence both alternatives need to be evaluated on economical basis.
Applicability of Distillation:
Alternative to Distillation:
(a) Extraction
(b) Extractive Distillation
(c) Azeotropic Distillation
(d) Reactive Distillation
(e) Adsorption
(f) Crystallization
(g) Reaction
So these are the various points that we have to taken into consideration for
synthesizing the separation system for the flow sheet.
This is the final level decision to be taken during flow sheet synthesis. Here, we need to
identify the sources of waste heat available in process. These heat sources may be like
exothermic chemical reactions, distillation columns, boilers, condensers, hot waste
water, evaporator, etc. similarly, identify the process steps or unit operations,
equipments, where heat is required or to be removed., such as heat exchangers,
reactors, distillation columns, etc. Then heat exchanger network (HEN) should be
designed in such a way that the waste heat can be utilized for the operations which
requires the heat. In this way, we can reduce the utility load and the cost of utilities/fuel
can be reduced to some extent.
This is the way to synthesize the whole flow sheet for a particular process.
Introduction:
The carrying out chemical reactions to achieve the transformation which are desired
forms a large part of chemical engineer’s core skills. Choosing the right type of reactor
for converting the maximum of the input reactants into desired products, minimizing
the by-products/ wastes during reactions, deciding upon a reactor geometry which leads
to minimum effluent and assure minimum environmental footprint, and finally,
minimizing the energy required for this transformation are all considerations which go
into this decision making process. A correctly selected reactor type / geometry indirectly
translate into additional benefits further downstream and vice versa:
In case of the ammonia converter, the incoming gas stream flows down the
annular space between the reactor shell and the catalyst bed assembly thereby
simultaneously
a. Protecting the reactor shell from seeing the higher temperature at which the
reaction actually takes place
b. Using the exothermic heat of reaction to heat the incoming reactants to the
desired initial reaction temperature
c. Cooling the reaction mass to promote shift of the reversible reaction to the
right
Certain reaction conditions require the chemical engineer beyond the narrow confines
of the known models of reactors to specifically design reactor geometries which are best
suited for the peculiar reaction / energy considerations.
Most chemical engineering students would, at this point in their academics, be familiar
with the basic two models: continuous stirred tank reactor (CSTR) and the plug flow
reactor (PFR).
Under industrial conditions the concept of a CSTR is practically realized through the
following geometries:
Bubble column reactor in which a reactant in the gas phase rises after being
sparged from the bottom of a tower which is filled with a liquid with a bulk
downward flow, is an excellent approximation to a CSTR. Additional mechanical
agitation or use of column packing brings it closer to a true CSTR in performance.
This type of reactors with reaction between the fluidizing medium and the
fluidized solids also can be approximated as a CSTR. One of the most successful
practical applications of this idea is the ORTHO Reactor for FCC of Petroleum.
A heat exchanger may be added into loop to add or remove heat. The relative
ratio of recycle to the fresh ingredients decides the temperature rise. Additional
mixing apart from the re-circulating device may be provided by inline static
mixers.
A more common variation of this basic theme is a packed bed multi-tube type
reactor which allows heat transfer possibilities through the tube walls. This is
nothing but a shell and tube heat exchanger with tubes packed with catalyst
particles, the shell side carrying heating/cooling fluid as required by the reaction.
Alternatively, side heat exchangers are employed if adequate heat transfer is not
possible through walls. The multi-bed catalytic converter of the DCDA Sulphuric
acid manufacturing plant is a good example with waste heat boilers /
economizers / super heaters / interpass heat exchangers removing heat after the
reactants, SO2 and oxygen in this case, have reacted adiabatically in the catalyst
bed and a certain conversion has been achieved.
A R (desired)
A S (waste)
Where the ratio of the reaction rates is rR / rS = (k1 / k2) CAa1-a2
(i) if a1 > a2, keep CA high. Also,
A+B R (desired)
A+B S (waste)
where the ratio of the reaction rates is rR / rS = (k1 / k2) CAa1-a2 CBb1-b2
A R (desired) S (waste)
Minimize the mixing of streams with different compositions. Consider the option
of removing “R” from partially reacted stream before attempting further
conversion.
A R (desired)
A S (waste)
A R (desired) S (waste)
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