Advanced Process Design

1. Heuristics
1.1. What are heuristics?
1.1.1. The rule of thumb
1.1.2. A statement concerning equipment sizes, operating conditions, and
equipment performance that reduces the need for calculations
1.1.3. Any approach to problem solving, learning, or discovery that employs a
practical method not guaranteed to be optimal or perfect, but sufficient for
the immediate goals
1.1.4. A short cut method
1.1.5. Reduces necessary calculations
1.1.6. Check consistency of your results
1.2. What to do to avoid going wrong?
1.2.1. Be mindful of your assumptions
1.2.2. Follow a structured thought process
1.2.3. Document assumptions in a way that’s tractable
1.3. this is of utmost importance as it gives credibility to our work and decisions even
in cases, when our solution is not optimal
1.4. Hierarchal Approach
1.4.1. Flow Diagram of the Hierarchical Approach

1.4.2. In practice it looks more like this

1.5. Heuristics for Reaction Path

1.5.1. Usually more than one way to produce a chemical
1.5.1.1. Established Process: one particular route represents the state of the
art, R&D, identify alternatives
1.5.1.2. New Process: different production pathways are identified at lab
scale
 1.5.2. Heuristics
1.5.2.1. Safety/environmental considerations
1.5.2.2. Economic considerations: evaluate the economic potential
comparing cost of raw materials with revenues from products
1.5.3. Example of Ethylene Glycol

1.5.3.1. Safety concerns

1.5.3.1.1. Both reactions are highly exothermic
1.5.3.1.2. Water spill into an ethylene-oxide could lead to a serious
accident
1.5.3.2. Two alternatives
1.5.3.2.1. Single step process using (more costly) chlorine and caustic
soda:

1.5.3.2.2. As ethylene-oxide is formed, react it with carbon dioxide to

form ethylene-carbonate, a much less active intermediate
that can be stored safely and hydrolysed to form the
ethylene-glycol product as needed:

1.6. Heuristics for Distribution of Chemicals

1.6.1. Selectivity
 1.6.1.1. Heuristic: for competing series or parallel reactions, adjust the
temperature, pressure, and catalyst to obtain high yields of desired
products

1.6.2. Example Allyl Chloride

1.6.2.1. Kinetic constants can be calculated using the Arrhenius equation

−E
1.6.2.1.1. k =k 0 e RT
1.6.2.2. Identify the right temperature range based on the kinetic data

1.6.2.2.1. Plot a log- log graph

1.6.2.2.1.1. The one where k1 is the highest is the right

temperature range
1.6.3. Heuristics for Equilibrium reactions (Reversible)
 1.6.3.1. When Q=K the reaction is at equilibrium
1.6.3.2. When Q<K, there are more reactants than products and the reaction
shift to the right
1.6.3.3. When Q>K, there are more products than reactants and the reaction
shifts to the left
1.6.3.4. Heuristic 1: If one of the reactants is cheap use it in excess to shift
the reaction to the right
1.6.3.5. Heuristic 2: In a gas phase reaction if the moles of products are less
than the moles of reactants operate at high pressure, if not operate
at low pressure
1.6.3.6. Reactive Distillation
1.6.3.6.1. For reversible reactions, consider conducting them in a
separation device capable of removing the products, and
hence, driving the reactions to the right.
1.6.3.7. Example of Methyl Acetate (MeAc)
MeOH+AcAcid↔MeAc+H2O
1.6.3.7.1. A conventional plant includes a reactor and separator

1.6.3.7.2. Intensified Plant: Reactive Distillation

where reaction shifts to right

1.7. Process Synthesis: Decisions on feed purification

 1.7.1. Diagram of the first decision that needs to be made

1.7.2. Impurity present in gas feed? → allow to enter the process

1.7.3. Impurity in liquid feed stream is also by-product → purify feed
1.7.4. Impurity present as azeotrope with the reactant → process it
1.7.5. Impurity is inert and can be separated easier from the product than from
the feed → let it pass through the process
1.7.6. Impurity affecting catalyst activity → remove
1.8. When to purge streams
1.8.1. Remove inert species D before reaction or after?

1.8.1.1. Heuristic 1: When nearly pure products are required, eliminate inert
species before the reaction operations when the separations are
easily accomplished and when the catalyst is adversely affected by
the inert. Do not do this when a large exothermic heat of reaction
must be removed
1.8.2. Insert a purge stream
1.8.2.1. Trace species are often introduced as impurities in feed streams or
formed in side reactions
1.8.2.2. They accumulate continuously unless a means is provided for their
removal (i.e., reaction, separation or purge)
1.8.2.3. Reaction and separation of trace species are costly, therefore use
purge when the species is not toxic
1.8.2.4. Heuristic 2: introduce a purge stream to provide exits for species
that:
1.8.2.4.1. Enter the process as impurities in the feed or are produced
by irreversible side-reactions
1.8.2.5. when these species are in trace quantities and/or are difficult to
separate from the other chemicals.
1.8.2.5.1. Lighter species leave in vapour purge streams, and heavier
species exit in liquid purge streams
 1.8.2.6. Heuristic 3: Do not purge valuable species or species that are toxic
and hazardous, even in small concentrations:
1.8.2.6.1. Add separators to recover valuable species OR Add reactors
to eliminate toxic and hazardous species
1.9. Possible heuristics for separations (liquid and vapour mixtures)
1.9.1. Image of the three heuristics

1.9.2. Illustrative Example on a Vapor separation

1.10. Distillation Columns

1.10.1. Heuristic Rules

1.10.1.1. This is restricted to simple columns (no heat integration)

1.10.1.2. Heuristics may be in conflict with each other
1.11. Heuristics for heat removal from and addition to reactors
 1.11.1. Illustrative example

1.11.2. Heuristic 1: For mild exothermic (or endothermic) reactions an adiabatic

reactor is usually the most cost-effective solution
1.11.3. Heuristic 2: For medium exothermic (or endothermic) reactions:
1.11.3.1. Circulate reactor fluid to an external cooler (or heater)
1.11.3.2. Use a jacketed vessel or cooling (or heating) coils
1.11.3.3. Consider the use of intercoolers (or inter-heaters)
1.11.4. Heuristic 3: For highly exothermic (or highly endothermic) reactions
consider
1.11.4.1. Use of excess reactant
1.11.4.2. Use of inert diluent
1.11.4.3. Use of cold (or hot) shots
1.12. Heuristics for pumping, compression and pressure reduction
˙
P2
1.12.1. Work done by pumping or compressing is given by Ẇ =∫ V̇ dP
P1
1.12.2. It is more efficient to pump a liquid then it is to compress a gas
1.12.3. If it is possible to condense the fluid without a refrigerant then the vapor
should be condensed, pumped, and then vaporized.
1.12.3.1. If not compress it
1.13. Tutorial: Hydrodealkylation of Toluene
1.13.1. Toluene + H2 → Benzene + CH4
2 Benzene ↔ Diphenyl + H2
1.13.2. The homogenous reaction takes place in the range from 621 °C (below
reaction too slow) and 704 °C (above hydrocracking takes place) and a
pressure about 3447 kPa (absolute). An excess of hydrogen is required to
prevent coking, and the reactor effluent must be rapidly quenched to 621
°C to prevent coking in the heat exchanger following the reactor
1.13.3. First Input Information
1.13.3.1. Reaction Information
1.13.3.1.1. Reactions
1.13.3.1.1.1. Toluene + H2 → Benzene + CH4
2 Benzene ↔ Diphenyl + H2
1.13.3.1.2. Inlet Temp >621°C P=3447 kPa (abs)
1.13.3.1.3. Relationships
moles of benzeneat reactor outlet
1.13.3.1.3.1. S=
moles of toluene converted
moles of toluene converted
1.13.3.1.3.2. x= reactor ¿
moles of toluene fed ¿
0.0036
1.13.3.1.3.3. S= 1.544
x <0.97
(1−x)
1.13.3.1.4. Gas Phase
1.13.3.1.5. No catalyst
1.13.3.2. Production of benzene: 265 kmol/h
1.13.3.3. Benzene purity > 0.9997
 1.13.3.4. Raw materials: Pure toluene at ambient conditions; H2stream
containing 95% H2 , 5% CH4
1.13.3.5. Constraints:
1.13.3.5.1. H2 /aromatic > 5 at reactor inlet
1.13.3.5.2. Reactor outlet < 704 °C
1.13.3.5.3. Rapidly quench reactor effluent to 621 °C
1.13.3.5.4. x < 0.97
2. Introduction to Process Simulations at Steady State
2.1. A Basic Process Flowsheet

2.2. What is it and what does it do?

2.2.1. Model-based representation of unit operations and processes in software
2.2.2. Avoids the most repetitive, routine, and heavy tasks
2.2.3. Covers different stages of process design, from research and
development to conceptual design and plant operation
2.2.4. Allows to explore alternative designs
2.3. What does it need and what will it give back?
2.3.1. Given
2.3.1.1. Process inputs
2.3.1.2. Set of specification
2.3.1.3. Thermodynamic model
2.3.1.4. Kinetic expressions
2.3.2. Solves
2.3.2.1. Mass balances
2.3.2.2. Energy balances
2.3.2.3. Equilibrium equations
2.3.2.4. Kinetics
2.3.3. Predicts
2.3.3.1. Operating conditions
2.3.3.2. Flow rates and compositions
2.3.3.3. Sizes of units
2.3.3.4. Capital and Operating Costs (CAPEX & OPEX)
2.4. How to start
2.4.1. If you do not know the composition of a stream start with a tear stream, in
the above flowsheet this could be between the mixer and heater 1
2.4.2. Solve one unit at a time
2.5. Sequential Modular Approach
2.5.1. Each block solved in sequence
 2.5.2. Unit operations have very detailed models, but limited flexibility
2.5.3. Softwares that use: Aspen PLUS, Aspen HYSYS

2.5.4. Process topoplogy

2.5.4.1. Identify the sequence of unit operation, recycle loops, and tear
streams
2.5.4.2. Initialize the flowsheet
2.5.5. Unit Operation
2.5.5.1. Solve mass and energy balances of each unit operation
2.5.6. Thermodynamic properties
2.5.6.1. Use thermodynamic models to predict physical properties (density,
phase equations, etc.)
2.5.7. Main Limitations
2.5.7.1. Slow convergence
2.5.7.2. Weak for highly recycled and highly integrated processes
2.5.7.3. Optimisation capability is very limited
2.6. Equation Oriented Approach (simultaneous)
2.6.1. Model expressed in one large system of algebraic equations
2.6.2. Unit operations have simplified models
2.6.3. Good for process optimisation
2.6.4. Software's that use this approach: gPROMS, GAMS

2.6.5. Process Topology and Unit Operation

 2.6.5.1. Initialize and solve a large system of non-linear equations
2.6.5.2. Usually the physical properties calculations is kept separate
2.6.6. Thermodynamic Properties
2.6.6.1. Use thermodynamic models to predict physical properties (density,
phase equations, etc.)
2.6.7. Main Limitations
2.6.7.1. Initialization and debugging may be challenging for large models
2.6.7.2. Computationally more expensive
2.7. Main Limitations and Caveats of Process Simulation
2.7.1. Process simulation is not a GOAL but a TOOL to reach another GOAL
2.7.2. Does NOT perform any critical analysis of the results
2.7.3. Does NOT compare design alternatives
2.7.4. Does NOT identify safety and environmental issues
2.7.5. Simulations may NOT reflect what is really happening in a plant
2.8. What is the usefulness of Process Simulators
2.8.1. Tools to create optimal process designs
2.8.2. Enable the steady-state and dynamic simulation of processes
2.8.3. Allows us to make better planning and optimization decisions with the
support of calibrated models
2.9. Examples of Process Simulators
2.9.1. Aspen Plus, Aspen-HYSYS (Aspen Technology), UNISIM (Honeywell
Process Solutions), CHEMCAD (ChemStations), PRO/II (Simulation
Sciences) and gPROMS (PSE)
2.10. Basic Computational elements
2.10.1. Component database
2.10.2. Thermodynamic solver
2.10.3. Flowsheet builder
2.10.4. Unit operation block solver (step by step)
2.10.5. Flowsheet solver
2.10.6. Data output generator
2.11. Steady State Simulation
2.11.1. Steady state refers to there being no accumulation of mass or energy over
the time period of interest

2.12. Choosing Fluid Package

2.12.1. Follow Eric Carlson’s recommendations from “Don’t gamble with physical
properties for simulations,” Chemical Engineering Progress, October 1996,
35-46.
2.12.2. Aspen HYSYS help: Property Package Selection Assistant
3. Reaction, Separation, and Recycle Streams
3.1. Introduction
3.1.1. Process design starts with the reactor
 3.1.2. Good reactor performance is of key importance for the economic viability
of the overall design and to minimize the environmental impact of the
process
3.1.3. In addition to the desired products, reactors produce unwanted byproducts
that:
3.1.3.1. Represent a loss of revenue
3.1.3.2. May have high environmental impacts
3.1.3.3. Can lead to a more difficult separation
3.1.4. Reactors can be classified as chemical or biochemical
3.1.5. Most reactors in industrial applications use a catalyst
3.1.5.1. Heterogeneous catalyst are the preferred choice because they don’t
have to be separated from the product stream
3.1.6. The issues that must be addressed for reactor design include:
3.1.6.1. Reactor type
3.1.6.2. Catalyst
3.1.6.3. Size
3.1.6.4. Operating conditions (temperature and pressure)
3.1.6.5. Phase
3.1.6.6. Feed conditions (concentration and temperature)
3.2. Reactor Performance
3.2.1. Conversion
reactant consumed ∈reactor
X= the reactor ¿
reactant fed ¿
3.2.2. Selectivity
desired product produced
S= (stoichiometry factor )
reactant consumed∈the reactor
3.2.3. Yield
Y=X ∙S
3.2.4. Process Yield
desired product obtained ∈process
Process Yield= ( stoichiometry factor)
reactant fed into process
3.2.5. Example

3.3. Ideal Reactors: Perfectly Mixed Reactors

3.3.1. Ideal batch reactors
3.3.1.1. Perfect mixing in the reactor
3.3.1.2. Concentration changes with time
3.3.1.3. The residence time is the same for all the reactor volume
3.3.2. Continuous Stirred Tank Reactor (CSTR)
 3.3.2.1. Perfect mixing in the reactor
3.3.2.2. Feed and product are both continuous
3.3.2.3. The residence time of individual fluid elements in the reactor varies
3.3.3. Plug Flow Reactor
3.3.3.1. Steady uniform flow
3.3.3.2. NO mixing along the direction of flow
3.3.3.3. Perfect mixing in radial direction
3.3.3.4. The residence time is the same for all fluid elements
3.4. Rate of Reaction

3.5. Types of reaction systems

3.5.1. Single reactions
3.5.2. Multiple reactions in series producing byproducts
3.5.3. Multiple reactions in parallel producing byproducts
3.5.4. Mixed parallel and series reactions producing byproducts
3.5.5. Polymerization
3.5.6. Biochemical Reactions
3.5.7. Note: the concentration of reactant in batch and PFR is higher than in
CSTR
3.6. Choice of Idealized reactor model
3.6.1. Single reaction

3.6.1.1. Rate of reaction is an increasing function of the feed concentration

3.6.1.2. A mixed-flow reactor requires a greater volume than an ideal batch
or plug-flow reactor to attain a certain conversion.
3.6.1.3. Ideal Batch or Plug Flow Reactor is preferred
3.6.2. Multiple Parallel Reaction

3.6.2.1. A batch or plug-flow reactor maintains higher-average

concentrations of feed than a mixed-flow reactor.
3.6.2.2. If a1 > a2 the primary reaction to PRODUCT is favoured by a high
concentration of FEED.
 3.6.2.3. If a1 < a2 the primary reaction to PRODUCT is favoured by a low
concentration of FEED.
3.6.2.4. a1 > a2, use a batch or plug-flow reactor
3.6.2.5. a1 < a2, use a mixed-flow reactor
3.6.3. Multiple Reaction is series

3.6.3.1. An optimum residence time exists to maximize the PRODUCT

selectivity
3.6.3.2. In the mixed-flow reactor, FEED and PRODUCT can leave the
immediately or remains for an extended period.
3.6.3.3. In a batch or plug-flow reactor every fluid element has the same
residence time
3.6.3.4. Use a batch or plug flow reactor to have a higher selectivity
3.6.4. Mixed Parallel and Series Reactions

3.6.4.1. As far as the parallel byproduct reaction is concerned, for high

selectivity, if:
3.6.4.1.1. a1 > a2, use a batch or plug-flow reactor
3.6.4.1.2. a1 < a2, use a mixed-flow reactor
3.6.4.2. The series byproduct reaction requires a plug-flow reactor. Thus, for
the mixed parallel and series system above, if:
3.6.4.3. a1 > a2, use a batch or plug-flow reactor
3.6.4.4. When a1 < a2: Some level of mixing between a plug-flow and mixed-
flow reactor will give the best overall selectivity.
3.6.4.5. This could be obtained by a:
3.6.4.5.1. series of mixed-flow reactors
3.6.4.5.2. plug-flow reactor with a recycle
3.6.4.5.3. series combination of plug-flow and mixed-flow reactors
3.6.5. Polymerization Reactions
3.6.5.1. In polymerisation reactions, monomers molecules are reacted
together to produce a high molar mass polymer. Two broad
categories, those that involve a termination step and those that do
not

3.6.5.2. The chain is terminated by steps such as the union of two radicals
that consume but do not generate radicals
3.6.5.3. Polymers are characterised by a distribution of molecular weight.
 3.6.5.4. The molecular weight determines the physical and mechanical
properties of a polymer and usually a narrow distribution is required
to have good quality product.

3.6.5.5. In a batch or plug-flow reactor, all molecules have the same

residence time and this will lead to a narrower distribution!
3.7. Design of a real reactor
3.7.1. Design of a real reactor is more complex than estimating the reactor
volume
3.7.2. Significant costs come from reactor internals
3.7.2.1. Mixers, agitators, baffles
3.7.2.2. Heat Transfer (jackets, coils, or external loops)
3.7.2.3. Catalyst
3.7.3. Non-ideal mixing and heat transfer in real reactors can be very difficult to
model and understand, with significant effects on process yields and
product purity.
3.7.4. Fluid dynamic simulations are useful to understand non-ideal behaviours
4. Heat Exchanger Networks
4.1. Solution methodologies
4.1.1. Composite curves
4.1.1.1. Determines the theoretical minimum amount of utilities (and
minimum transfer area)
4.1.2. Calculate the optimal HEN
4.1.2.1. Heuristics based on pinch analysis
4.1.2.2. Hybrid methods
4.2. Example: Temperature-enthalpy flow curve (T-H) for one hot and cold stream
4.2.1. Graphical representation

4.2.2. The point where the minimum temperature difference is met is the pinch
point, there is no heat exchanged here
4.2.3. Pinch analysis: thermodynamically based methods that guarantee
minimum energy levels in design of heat exchanger networks
4.2.3.1. No heat is transferred through the pinch
4.2.3.2. This makes the region above the pinch a heat sink region
4.2.3.3. The region below the pinch is the heat source
4.2.3.4. The rule is that heat is transferred from hot to cold streams only
4.2.3.5. SThot>TTcold+ΔTmin
4.2.4. Hands on Exercise

Assume ΔTmin=10°C
4.2.4.1. Composite Curve Construction

4.2.4.1.1. Slope is always the heat capacity

4.2.4.1.2. Hot streams on left side
4.2.4.1.3. Cold streams on right
4.2.4.1.4. Merging the streams: the area where the streams overlap
has a slope of the two heat capcities
4.2.4.2. Shifting technique for Minimum Energy Requirement
4.2.4.2.1. Set up shifted temperature intervals from the stream supply
and target temperatures by subtracting ΔTmin/2 to the cold
streams
4.2.4.2.2. In each shifted temperature interval. Calculate a simple
balance
4.2.4.3. Minimum consumption of utilities
4.2.4.3.1. Subtract ΔTmin/2 from the inlet and outlet temperatures of the
hot streams
4.2.4.3.2. Add ΔTmin/2 from the inlet and outlet temperatures of the cold
streams
4.2.4.4. Create cascade diagram

4.2.4.5.

4.2.4.5.1. The numbers are given by Q=FCP × (TS-TT)

4.2.4.6. Continued

4.2.4.7. Define the pinch point

4.2.4.7.1. Is defined as the most negative number in the brackets (7.5)
4.2.4.8. Add the 7.5 at the top of the cascade and recalculate (this is
showing the pinch point)
4.3. Hands on Exercise 2 with 6 streams

ΔTmin=20K
4.3.1. Solution Steps
4.3.1.1. Identify stream types
4.3.1.2. Calculate the shifted temperatures (Remember, subtract from hot
and add to cold ΔTmin/2)
4.3.1.3. Rank temperatures in descending order and identify intervals • Map
the streams
4.3.1.4. Calculate heat demands for each interval
4.3.1.5. Calculate the energy balance
4.3.1.6. Identify the pinch point and utility demand
4.3.2. Shifted Stream Temperatures
4.3.3. Map the streams

4.3.4. Heat demands per interval

4.3.5. Energy Balance and Pinch Point

4.3.6. Deciding Utilities

4.3.7. How utilities fit in the problem

4.3.8. Formulate an optimization problem to minimize the overall cost, yet

achieving the desired heat target
4.3.8.1. Objective function

4.3.8.2. Constraints

4.3.8.2.1. GAMS requires one variable to equal everything else

4.3.8.3. Constraints after relating utilities to relevant heat requirements
 4.3.8.4. Solving in GAMS gives

4.3.8.4.1. Shows our problem is correct because R6 is where we

identified pinch and there should be no heat transfer
4.3.8.5. We have not identified stream matching
4.3.9. Moving back to original temperatures

4.3.9.1. Start at the pinch

4.3.9.2. The CP inequality for individual matches
4.3.9.2.1. Above pinch: CPH≤CPC
4.3.9.2.2. Below pinch: CPH≥CPC
4.3.10. Stream Temperatures
4.3.11. Below the pinch

4.3.11.1. Number of hot streams must be greater than or equal to those of the
cold streams
4.3.11.2. Should split the cold stream to be able to match streams, if you don’t
you cant do the problem

4.3.11.2.1. Match the streams, 70 with 70, 94 with 94, 40 with 16.
4.3.11.2.2. Follows the FCP rule
4.3.11.3. The exit temperatures from the heat exchanger

4.3.11.4. Calculate the cooling requirements from the temperatures below the
exit temperature

4.3.11.4.1. To check you are doing it correctly the sum for the utilities
must be the same as you got in the cascade or for GAMS
4.3.11.4.1.1. This is satisfied as cooling water is 3000 kW
4.3.12. Above pinch formulation

4.3.12.1. Number of cold streams must be greater than number of hot streams
so must split the cold streams best bet is to split the stream with the
highest capacity

4.3.12.1.1. Must split streams so every stream has a match, try out for
why the streams should be split this way, it is a trial and error
problem and there is many answers for this problem don’t try
 to optimize

4.3.12.1.2. Notice the temperature of the hot utilities required, it is above

the temperature available for both high and low pressure
streams and only allows us the use of fuel which is
expensive
4.3.12.1.3. As long as the sum of utilities is the same it is correct but
there are infinite other solutions