Hierarchy Of Conceptual

Process Design

Mihir P.Shah
DDU, Nadiad
 Process Intensification
The ability to drive a chemical process

From the limits of equipment…….

To the limits of Physics and Chemistry…

Why PROCESS INTENSIFICATION?

• The highest possible rate of chemical process is

determined by the chemical (Kinetics) and
Physical (Diffusion and Conductivity) limits.
• Whenever we use equipment that brings in
additional limitations, we decrease the
productivity further than necessary because of
– Speed of mixing
– Heat transfer rates
– Pressure resistance
What will be outcome of these limitations?

• Bigger equipment (High capital and operating

investments) to achieve same production
capacities
• Larger hold-up, which may also present high
risk factor (e.g. of dangerous intermediates)
• Scale-up errors (Non-flyers)
 What is the solution?
• Maximize the kinetics
• Maximize the driving forces
– Enhance mass and heat transfer by increasing the
TRANSFER AREAS
– Speed up transfer by` reducing the characteristic
length TRANSFER DISTANCE
How will you do it?
 By combine operation to drive equilibrium
 Vapor and Liquid Recovery system

This looks very similar to Onion Model we saw in last presentation

 Input Information
• The reaction and reaction conditions
• The desired production rate
• The desired product purity, price vs purity
• The raw material, price vs purity
• Information about rate of reaction and the rate of catalyst
Deactivation
• Any processing constraints
• Other plant and site data
• Physical properties of all components
• Information concerning the safety, toxicity, and
environment impact of the material involved in the process
• Cost data for by-products, equipment, and utilities
Reaction Information
 Reaction Information
• Consider any possibility of side reactions and
decide Yield and selectivity analysis for finding
economic conversion.
• Yield Economic Conversion
Chemist ? Chemical Engineer

For a series reaction

A B C

Remarks:
P: Max. yield of B, large
conversions, but appreciable
amount of C is produced
Q: small amount of C is
formed, much less A is
converted so large recycle
stream is required
Selectivity Calculation
 Conversion effect on profit
In Petrochemical section, the dominating factor is raw material cost
which is around 35 - 85% of total product cost.
There is always a trade-off between large selectivity losses and large
reactor costs at high conversions against large recycle cost at low
conversions.
• Catalyst Deactivation
– Lack of long-time runs on catalyst activity.
– Data on activity and selectivity is available
– Normal life of 1 to 2yrs.
• Production Rate
– maximum size (?)
• Depends on maximum size of major equipment
– maximize market share to reduce risk factor
– production rate may change during design
• Product purity
– price vs purity
• Raw materials
– Lab experiments are done with pure chemicals
– Impurities can be either inert or may react
– May change size of recycle stream
– Price vs grade
Other Plant and Site Data
 Level I
Batch vs Continuous
For a continuous process, one has to look at following points
Continuous Vs. Batch
 SIZE (Throughput)
BATCH CONTINUOUS
• Smaller throughput favors • Economics of scale favor
batch operations. continuous processes for
• As throughput increases, large throughput.
the required size of the
process equipment
increases, and the technical
difficulties of moving large
amounts of chemicals from
equipment to equipment
rapidly increase.
 Batch Accountability and Product
Quality
BATCH
• When the product quality of
each batch of material must
be verified and certified, batch
operation are preferred.
• This is especially true for
pharmaceutical and food
products.
• If working (Reprocessing) of
off-specification product is not
permitted, small batches are
favored.
CONTINUOUS
• Continuous or periodic testing
of product quality is carried
out, but some potentially large
quantities of off-specification
product can be produced. If
off-specification material may
be blended or stored in dump/
slop tanks and reworked
through the process when the
schedule permits, continuous
processes are favored.
 Operational flexibility
BATCH
• Often the same equipment
can be used for multiple
operations, for example, a
stirred tank can be used as a
mixer, then a reactor, then
as a stage of a mixer-settler
for liquid-liquid extraction.
CONTINUOUS
• Operational flexibility can be
built in to continuous
processes but often leads to
inefficient use to capital.
Equipment not required for
one process but needed for
another may sit idle for
months. Often continuous
processes are designed to
produce a fixed suite of
products from a well defined
feed material. If market forces
change the feed/product
availability/ demand, then the
plant will be “Retrofitted” to
accommodate the change.
 Standardized equipment – Multiple
Products
BATCH CONTINUOUS
• Often batch processes can be • The product suite or slate
easily modified to produce produces from continuous
several different products sing processes is usually fixed.
essentially the same Equipment tends to be
equipment. Examples of batch
designed and optimized for
plants that can produce 100
a single or small number of
different products are known.
For such processes the optimal operating conditions.
control and sequencing of
operations are critical to the
success of such a plant.
 Processing Efficiency
BATCH CONTINUOUS
• Operation of batch processes • Generally as throughput
requires strict scheduling and increases, continuous
control. Because different processes become more
products are scheduled back to efficient. For example, fugitive
back, changes in schedules have a energy losses are reduced, and
ripple effect and may cause
serious problems with product rotating equipment (Pumps.
availability for customers. If the Compressors etc.) operate
same equipment is used to with higher efficiency. Recycle
produce many different products, of unused reactants and the
then this equipment will not be integration of energy within
optimized for any new product. the process or plant is
Energy integration is usually not standard practice and
possible, so utility usage tends to relatively easy to achieve.
be higher than for continuous
processes. Separation and reuse
of raw materials is more difficult
than for continuous processes.
 Maintenance and operating Labor
BATCH CONTINUOUS
• There are higher operating • For the same process,
Labor costs in standard operating labor will be
batch plants due to lower for continuous
equipment cleaning and processes.
preparation time. These
costs have been shown to
be reduced for the so called
“Pipe less Batch Plants”.
 Feedstock Availability
BATCH CONTINUOUS
• Batch operations are • Continuous plants tend to be
favored when feedstock large and need to operate
throughout the year to be
availability is limited, for profitable. The only way that
example, seasonally. seasonal variations in feeds
Canneries and wineries are can be accommodated is
examples of batch through the use of massive
processing facilities that storage facilities that are very
expensive or if possible by
often operate for only part blending with the other
of the year. streams.
 Product demand
BATCH
• Seasonal demand for
products such as fertilizers,
gas-line antifreeze, deicing
chips for roads and
pavements, and so on, can
be easily accommodated.
Because batch plants are
flexible, other products can
be made during the “Off-
season”
CONTINUOUS
• Difficult to make other
products during the “Off-
Season”. However, similar but
different products, for
example, a family of solvents
can be produced using the
same processes through a
series of “Campaigns” at
different times during the year.
Each campaign may last
several months.
 Rate of reaction to produce products
BATCH
• Batch operations favors
processes that have very
slow reaction rates and
subsequently require long
residence time. Examples
include fermentation,
aerobic and anaerobic
wastewater treatment, and
many other biological
reactions.
CONTINUOUS
• Very slow reactions require
very large equipment. The
flow through this
equipment will be slow and
dispersion can be a problem
if very high conversion is
desired and plug flow is
required.
 Equipment Fouling & Waste
Generation
BATCH CONTINUOUS
• When there is significant • Significant fouling in
equipment fouling, batch continuous operations is a
operations are favored serious problem and is
because cleaning of difficult to handle.
equipment is always a Operating identical units in
standard operating parallel, one on-line and the
procedure in a batch other off-line for cleaning,
process and can be can solve this problem.
accommodated easily in the However, capital investment
scheduling the process. is higher, additional labor is
• Amount of waster required, and safety
generated will of higher problems are more likely.
quantity.
 Safety
BATCH CONTINUOUS
• Generally, worker exposure • Large chemical plants
to chemicals and operator operating continuously have
error will be higher (Per excellent safety records,
pound of product) than for and safety procedures are
continuous processes. well established. Operator
Operator training in training is still of great
chemical exposure and importance, but many of
equipment operation is the risks associated with
critical. opening equipment
containing chemicals are
eliminated.
 Controllability
BATCH CONTINUOUS
• This problem arises because • Generally, continuous
batch processes often use processes are easier to
the same equipment for control. Also, more work/
different unit operations research has been done for
and sometimes to produce these processes. For
different products. This complicated and highly
efficient scheduling of integrated plants, the
equipment becomes very control becomes complex,
important. The control used and operational flexibility is
for this scheduling is greatly reduced.
complicated.
 Input-Output structure
A diagram used the stoichiometry of the
main reaction path way to identify the feed
and product chemicals.
• Flow-sheet Alternatives Whether to recycle or to remove
Thumb rule: Desirable to recover >99% of all valuable materials
but #1: Might be cheaper to lose inexpensive reactants (e.g., air, water etc)
but #2: Recycle gaseous reactant and purge a gaseous impurity or by-product

Remarks: If the cost of separation is cheap (e.g., membrane), recycle

and purge might not be necessary.

33
• Level-2 decisions

34
• Purification of feeds
- Equivalent to purification stage in process
• If feed impurities are not inert and is present in significant amount (remove it)
• If feed impurity is in a gas feed (feed to process)
• If feed impurity is in a liquid feed is also a product or by-product (feed to process)
• If feed impurity is present in a large amount (remove it)
• If feed impurity is present as an azeotrope with a reactant (feed to process)
• If feed impurity is inert but is easier to separate from the product (feed to process)
• If feed impurities will create catalyst poison (remove it)

• Recover or recycle by-products

Toluene  H 2  Benzene  CH 4
2 Benzene  Diphenyl  H 2
Recycle: Oversize all equipment in the recycle loops
Remove: Increase raw material costs
35
Gas recycle and purge
• If we have light reactant, feed impurity or by-product
has a normal b.p. less than propylene (-48 C), use a gas
recycle and purge stream.
• Since lower boiling components are very difficult to
condense using high pressure cooling water, it is cheaper
to lose some gaseous reactants.

What not to recover?

• water, air
• Normally we try to use them fully or fed in excess

Remark: We should always consider the cost of pollutant

treatment.
36
Number of Product streams
1. List all components that are expected to leave the reactor.
2. Give destination code to them like in previous slide.
3. Order them by normal bp’s (A – Z; low boiler - high boiler)
4. Group neighboring components with the same destination.
5. No. of groups – no. of recycle streams= no. of product streams
Ex. How many product streams?

38
Ex. How many product streams for HDA process?

component b.p. Destination code

Hydrogen -253C recycle and purge

methane -161C recycle and purge
benzene 80C primary product
Toluene 111C recycle
Diphenyl 253C fuel_____________

Results: three product streams (4-1=3)

39
 Design Variables, Balances and Costs
• Design Variables
Design degrees of freedom

Typical design variables:

• Overall material balances

Focus on input/output flows

40
 • HDA example

Toluene  H 2  Benzene  CH 4
2 Benzene  Diphenyl  H 2

41
 • HDA example-cont

Given: PB  265 mol/hr benzene  7.65 105 ton/yr,

x  0.75, y PH  0.4, S  0.9694 (Douglas, 1988; p.521)
PB 265
Freshfeed Toluene: FFT    273.4 mol/hr
S 0.9694
Toluene  H 2  Benzene  CH 4
Diphenyl produced: PD  PB (1  S ) / 2 S  4.2 mol/hr
2 Benzene  Diphenyl  H 2
Extents:1 = 273.4 (PB /S, toluene consumed)
 2 =4.2 (PB (1-S)/(2S), diphenyl produced;
 1 -2 2 =PB )
Makeup Gas:
PB PB (1  S )
H2 : yFH FG    yPH PG
S 2S
P
CH 4 : (1-yFH ) FG  B  (1  yPH ) PG
S
P [1  (1  yPH )(1  S ) / 2] (1  S )
 FG  B & PG  FG  PB
S ( yFH  yPH ) 2S
Balance on H 2 : purged FE  yPH PG  198.7
PB PB (1  S )
reacted   2 69.2 42
S 2S
• Stream Tables

43
 • Stream Costs

Economic potential (EP) at level 2.

EP2= product value + by-product value - raw material costs

44
Remark: We have not considered the recycle cost yet.
• Summary: Flowsheet Alternatives

- purify the feed: probably not desirable

- recycle diphenyl: We must oversize all the equipment in the
diphenyl-recycle loop.
- recover some hydrogen: Is justified by determining the cost
of the recovery system.

45
Choice of Reactor

Remark: EP= values of products-raw materials costs

 Types of Reactions

Remark: There are a lot of more reaction

systems, e.g., mixed parallel and consecutive
reactions.
 Reactor concentration and temperature
• The objectives to design the reactor concentration
and temperature profiles are:
– O1. to improve selectivity (minimize the generation of
byproducts)
– O2. to increase economic potential (minimize reactor cost)
– O3. to facilitate downstream separation (decrease
separation cost)
– O4. to possess operability (handle production rate
changes)
• Remark: Certainly, there are cases which are
important to ensure complete conversion of
hazardous or corrosive material.
Reactor concentration - Single Reaction
• Single Reaction :

– use PFR (O2)

• Single Reaction :

– A/B=50/50 is most economic but with little operability

– If R is HK, make LK excess (Cheng and Yu)
– If B is HK and R is IK, make B excess (Cheng and Yu)
– Degree of excess depends on the relative
reactor/separator costs (Cheng and Yu, AIChE J, 2003,
49, 682.)
Remarks: Total Reaction Rate : k(T)CACBVR
Reactor concentration - Parallel Reactions

Ref: Ward et al. (IEC&R 2004, 43, 3957) discuss operating policies for parallel
reactions in plantwide control.
Reactor Type
Reactor Type
Reactor Temperature – Reversible Reaction

Endothermic (Ef>Eb): - high temperature favors equilibrium

conversion and also gives higher reaction rate
- set the temperature as high as possible
Exothermic (Ef<Eb): - low temperature favors equilibrium
conversion but high temperature gives higher reaction rate
- set the temperature high initially and decrease the
temperature as equilibrium approaches
Remember Chemistry
 Implication in reactor design – Reversible
and exothermic

Design series of reactors with

intermediate coolers and heat exchangers
Reactor heat Removal
More reactor heat removal
Reactor Pressure – Vapor Phase Reaction

• Irreversible single reactions:

– high pressure increases vapor density and thus gives higher
reaction rate (smaller reactor volume if given conversion)
• Reversible single reactions:
– 2A↔B
– An increase in the pressure shifts the reaction toward
compensating the pressure increase (RHS) and thus
increases the equilibrium conversion (Le Chatelier’s
principle).
– A ↔ 2B
– An increase in the pressure shifts the reaction toward
compensating the pressure increase (LHS) and thus
decreases the equilibrium conversion.
Summary of heat removal system
 Recycle Structure of Process

• No. of reactors If set of reactions takes place

Toluene  H 2  Benzene  CH 4 at different T and P or if there is
requirement of catalyst then
2 Benzene  Diphenyl  H 2 different reactors may required.

Remark: One reactor will do.

1150  1300 F and 500 psia

 Example of two reactors
Acetone  Ketene  CH 4
1
Ketene  CO  C 2 H 4 , 700  C and 1 atm
2
Ketene  Acetic Acid  Acetic Anhydride, 80  C and 1 atm
 Number of recycle streams
Do not separate two components and remix them at a reactor inlet!

How many steam groups? 7

product streams: 4 (A+B, D+E, F and J)
recycle streams: 7-4=3 (C, G+H and I)
 Examples:

In both this processes

find out number of
product streams and
recycle streams.

Acetic anhydride Process

Recycle structure of both processes

Acetic Anhydride:
Reactor : 2
Product streams : 2
Recycle streams : 2
Excess Reactants