Topic 4:

Heuristic of Process Synthesis

Introduction

 Heuristics (Rules of thumb) used when generating alternatives that make up

the synthesis tree.
 Heuristics are easy to apply; they involves the setting of temperature,
pressure, excess amount of chemicals and so on.
 There are total of 53 heuristics.
 This enables several promising flowsheet(s) (base-case design) to be
generated rapidly with relatively little effort, which can be refined and
optimized through careful materials and energy balance analysis,
equipment sizing, and cost estimation using process simulator.
Raw Materials and Chemical
Reactions
Heuristic 1
 Raw materials and chemical reactions are often selected to protect the
environment and avoid the safety problems that area evident in MSDS.
 For these reason, societal needs are increasingly being formulated that call
for new processes to avoid or sharply reduce handling of hazardous
chemicals.
Distribution of Chemicals

In this distribution, decisions are made concerning:

 The use of one chemical in excess in a reaction operation
 The handling of inert species that enter in the feed streams
 The handling of undesired byproduct generated in side reactions
Excess Chemicals: Heuristic 2
 Important consideration is the degree in excess, as the unreacted excess
reactant is recycled, and this govern the costs of separation and
circulation.
 Other benefits of using excess reactant:
o For exothermic reactions, excess chemical serve the function of absorbing
heat of reaction and maintaining more moderate temperature.
o An excess of one chemical is also used to increase conversion of the other
(limiting) reactant when the extent of reaction is limited by equilibrium.
o Side reactions can be minimized by using excess of one reactant.
Inert Species: Heuristic 3
 Often impure feed streams contain significant concentration if species that
are inert in chemical reaction operations.
 An important decision concerns whether impurities should be removed
before or after reaction operation.
 Things to be considered:
o Cost of separation
o Sizing of reactor and separators
o Impact of inert on catalyst
o Temperature levels (exothermic reaction)
Purge Stream: Heuristic 4 & Heuristic 5
** Purge stream is a stream bled off to remove an accumulation of inert or
unwanted material that might otherwise build up in the recycle stream.
 In a continuous process, trace species (introduced as impurities in feed streams)
accumulate continuously unless a mean is provided for their removal.
 Selection of approach for removal of trace species:
I. Purge stream
 Used when the species are non-toxic and have little impact on the environment
 Also used for removing species present in large amount when their separation
from other chemicals in the mixture is difficult
 Cheaper in cost, where a portion of the recycle stream is bled off from the
process
 Purge/Recycle ratio being a key decision variable which directly affect the
operating cost (cost of raw materials loss, cost for recirculation)
II. Reaction and/or separation
 Used to recover/convert trace species in the stream, which is valuable/toxic/
environmental unfriendly
 Separation process: Adsorption, Absorption, Ion exchange, Membrane
separation
Recycle to Extinction: Heuristic 6
 Often small quantities of chemicals are produced in side reactions.
 If the reaction is irreversible, the side product must be separated away to
avoid build-up in process.
 If the reaction is reversible, the side product can be recycled to achieve
equilibrium conversion at steady-state, without remove from process.
 Avoid loss of chemicals
 Avoid insertion of separation operation
 This approach is effective when the equilibrium conversion of side reaction
is limited by a small chemical equilibrium constant (at operating T, P)
Selectivity: Heuristic 7
 When chemical reactions compete in the formation of a desired chemical,
the chemical conditions must be set carefully to obtain a desired
distribution of chemicals.
 Parameter to be considered:
o Pressure
o Temperature
o Ratio of feed chemicals
o Residence time
 If adequate selectivity cannot be achieved by adjust reaction conditions,
choosing the suitable catalyst play a key role.
 The chosen catalyst must permit the desired reaction to proceed more
rapidly at lower temperatures while reducing the rates of side reactions.
Reactive Separations: Heuristic 8
 Task integration, involves the combination of operations into process units.
 This heuristic combine reaction and separation together in a single process
unit.
 Examples:
o Reactive distillation
o Reactive absorption
o Reactive membrane separation
 Useful when deal with reversible reaction, where removal of a product is
possible to move the reaction in forward direction.
**In general, the optimal conversion for a reaction process need to take into
consideration economic balance between
o High reactor section cost at high conversion
o High separation section cost at low conversion
Separations
Separation Involving Liquid and Vapor Mixtures:

Heuristic 9, 10 & 11
 Selection of separation process is dependent on the phase of the stream to
be separated and the relative physical properties of its chemical species.
 Strategy recommended by Douglas (1988) with few heuristics:
 Certain separation devices (membrane separator) are not considered for
separation of liquids.
 To achieve partial condensation, cooling water is utilized initially, compared to
compression and refrigeration.
 Liquid separation are preferred over vapor separation.
 The choice of separator is influenced by the scale of process. Examples:
 Distillation is favored by economies-of-scale at large throughput
 Adsorption and membrane separation gaining favor as throughputs decrease
 If the reaction product in liquid phase,
o Liquid-separation system should be inserted in the flowsheet.
o Separators used: distillation and/or enhanced (reactive/azeotropic) distillation,
stripping, liquid-liquid extraction.
 If the reaction product in vapor phase,
o An attempt made to partially condense by cooling with cooling water or
refrigerant, to obtain a liquid phase and then send for liquid-separation system.
o The vapor phase is sent to vapor-recovery system which involves one or more of
following separations:
o Separators used: Cryogenic distillation, absorption, adsorption, membrane
separation and desublimation.
**A purge stream is added when necessary to remove trace inert that
concentrated in liquid/vapor phase and are not readily separated.
 If the reactor product is distributed between vapor and liquid phases,
combine the two flowsheets: Liquid-separation system and vapor-recovery
system
Separation Involving Solid Particles
 For streams involved solid phases or species that crystallize or precipitate,
several steps is necessary due to impossibility of removing dry solids directly
from a liquid/solution.
 When separating inorganic chemicals (especially in aqueous solution), the
stream is often cooled (decrease solubility) or partially evaporated
(increase concentration) to recover solids by crystallization followed by
filtration/ centrifugation, before drying.
 Slurries is concentrated by settling, centrifugation, or filtration, before drying.
 Three general mode of crystallization:
 Solution crystallization – chemical species are crystallized from a solvent
with an operating temperature far below the melting point of the crystals.
 Precipitation – fast solution crystallization that produces large numbers of
very small crystals, which usually refer to case where one product from two
reacting solutions is a solid with low solubility.
 Melt crystallization – two or more chemicals of comparable melting points
are separated at an operating temperature in the range of melting points.

 Crystallization is capable of producing very pure chemicals when

conducted according to the following Heuristics 12, 13 & 14.

 Prior to crystallization, it is common to employ evaporation to concentrate

a solution, particularly aqueous solution for inorganic chemicals. Apply
Heuristic 15 & 16, to minimize the operating cost.
 Solution crystallization produces a slurry of crystals and mother liquor, which
is partially separated by filtration or centrifugation into a wet cake and a
mother liquor.
 Important factors in selection of equipment:
o Moisture content of wet cake
o Solid content of mother liquor
o Fragility of crystals
o Crystal particle size
o Need for washing crystals
o Filtration rate

 Apply Heuristic 17 & 18, for selection of equipment for recovery of

crystal from solution.
 Wet cakes are then sent for drying process for removal of remaining
moisture. Selection of suitable dryer depends on:
o Type of feed
o Particle size

 Apply Heuristic19 & 20, in making preliminary selection of drying

equipment.
Heat Removal from and Addition to
Reactors
 Some of the approach for heat transfer affect the distribution of chemicals in
the flowsheet and are better considered after reaction operation positioned.

Heat Removal from Exothermic Reactors: Heuristic 21 & 22

 It is important to compute the adiabatic reaction temperature, the maximum
temperature attainable, in the absence of heat transfer.
 To achieve lower temperature, several alternatives are possible:
I. Use an excess of one reactant.
II. Use of an inert diluent, preferably with higher heat capacity to reduce
recirculation rate. The disadvantage of this approach, is the inert diluent may
present as impurity in the desired product.
**The heat is then removed in separator or by exchange with a cold process
stream or cold utility.
III. Use of cold shots. One of the reactants is cooled and distributed among
several adiabatic reaction operation in series.
IV. Diabatic operation. Heat is removed from the reaction operation in one of
the following ways:
 Cooling jacket is utilized or coils are installed, through which a cold process
stream/utility is circulated.
 Plug flow reactor/packed bed reactor that arranged like a shell-and-tube heat
exchanger design.
 Circulate a portion of the reacting mixture through an external heat exchanger.
V. Use of intercoolers. The reaction operation is divided into several adiabatic
stages with heat removed by heat exchangers placed between each
stage.

 The design team need to selects the acceptable temperature level and
flow rates of recirculating fluids which limits by:
o Rates of reaction, includes the need to avoid reaction runaway and catalyst
deterioration
o Materials of construction
o Temperature levels of available cold process streams and utilities
Heat Addition to Endothermic Reactors: Heuristic 23 & 24
 Similar approaches as exothermic reactors, but in the reverse way where
heat is added to the reaction instead of removed.
Heat Exchangers and Furnaces
 Heat exchange is commonly used in conjunction with separation and
reaction step to change the temperature and/or phase condition of a
process stream.
 Method of heat exchange:
o Heat exchange between two process fluids
o Heat exchange between a process fluid and a utility
o High-temperature heating of process fluid using heat from the products of
combustion in furnace
o Heat exchange within reactor or separator
o Direct heat exchange by mixing the two streams that are exchanging heat
o Heat exchange involving solid particles

 Heuristic 25-33 are useful in selecting an initial basis for heat exchange
method and operating conditions
Pumping, Compression, Pressure Reduction,
Vacuum and Conveying of Solids
Increasing the Pressure:
 To increase the pressure, the most important consideration is the phase state
(vapor, liquid or solid) of the stream.
 If the stream is gas,
o Heuristic 34 applies for determining the type of equipment (fan, blower or
compressor) should be used, based on the level of pressure increment.
o Heuristic 35 provides method to estimate the exit temperature after
compression and the power requirement when increasing the gas pressure by a
single stage of reversible, adiabatic compression.
o Heuristic 36 used to estimate the number of stages, N, required and the
inter-stage pressures.
**Multistage compression is required when the compression ratio is too high,
causing the exit temperature exceed the limit imposed by manufacture.
**When compressing a gas, the entering stream must not contain liquid, and the
exiting stream must be above its dew point, so as not to damage compressor.
 If the stream is liquid,

o Heuristic 37 applies to determine the type of pumps (centrifugal,

reciprocating, axial or rotary pump) based on the liquid flow rate and
pressure increase across the pump.

o Heuristic 38 provides an estimate on the pressure drop across pipeline,

control valves, and due to possible elevation, that must be included when
increase the liquid pressure to the desired level.

o Heuristic 39 estimate the theoretical pump power requirement.

**Unlike the case for gas compression, the temperature change across the
pump is small and can be neglected.
Decreasing the Pressure
 The pressure of a liquid or gas stream can be reduced with a single or more
throttle valve arrange in series.
 The adiabatic expansion of gas across a valve is accompanied by
decrease of temperature of the gas. Meanwhile the temperature change
for liquid is negligible.
 It is possible to recover energy in the form of shaft work that can be used
elsewhere by employing turbine-like device.
o Gas – expander, expansion turbine
o Liquid – power-recovery turbine

 Heuristic 40-42 provides rule for selection of device and estimation of

theoretical power.
Pumping a Liquid or Compressing a Gas: Heuristic 43
 It is almost far less expensive to pump a liquid rather than compress a
vapor, because volumetric flowrate, V of liquid is lesser
𝑃2
𝑊 = න 𝑉 𝑑𝑃
𝑃1

 The work for pumping liquid stream, typically two order of magnitude less
than compress gas stream.
 Two examples:
o If the low pressure stream is vapor and the phase state is also vapor, it is
almost preferable to condense the vapor, pump it and re-vaporize it, rather
than compress it.
o If the low pressure stream is liquid and high pressure stream is vapor, it is
preferable to increase the pressure first with a pump and then vaporize the
liquid, rather than vaporize the liquid and then compress it.
Vacuum
 Vacuum operation is common in crystallization, drying, evaporation, and
pervaporation operations.
 A vacuum system is used to remove the inleakage of ambient air, together
with any associated vapor in the process stream that passes through the
equipment.

 Heuristic 44-47 provide rules of thumbs:

o Selection of appropriate system based on vacuum level
o Estimation of inleakage air
o Total amount of air to be removed
Conveying Granular Solids

 Heuristic 48 provide rule of thumbs for selection of suitable equipment

for convey solid based on
o Stickiness
o Abrasiveness
o Particle size
o Density of the solid particles
Changing the Particle Size of Solids
and Size Separation of Particles
Heuristic 49-52
 Methods to accomplish changes in particle size
o Size reduction – crushing, grinding, disintegration
o Size enlargement – compression, extrusion, agglomeration
o Size separation device to obtain a narrow range of particle size
 Grindability is determined by hardness as measured by Mohs scale.
 Size of small particles is stated in terms of screen mesh according to ASTM.
Removal of Particles from Gases and
Liquids
 Heuristic 53 provide idea on selection of device for removal of particles
from gas and liquid stream
 Fine particles are most efficiently removed from
o Gas stream – cyclone
o Liquid stream – hydrocyclone
Considerations that Apply to the Entire
Flowsheet
 Flowsheet resulting from the 53 heuristics need additional development by
applying some general considerations that may able to improve the process
with respect to efficiency, simplicity and economics.
a) To increase second-law efficiency and reduce energy consumption, avoid, if
possible, the mixing of streams of different temperature, pressures or
compositions.
b) For a new process, determine how it differs from a similar conventional process
and pinpoint the advantages and disadvantages of new process, making
changes where disadvantages uncovered.
c) For a new process, determine the maximum production rate and yield, and look
for opportunities to increase them.
d) Carefully examine the flowsheet, looking for ways to eliminate equipment by
combining, rearranging, or replacing process steps.
e) Perform preliminary economic evaluation at different production rates and
corresponding plant sizes using simple scaling methods.