11/1/2017

Department of Chemical Engineering

College of Engineering
University of the Philippines Diliman
First Semester, AY 2017-2018

ChE 141: Chemical Process

Development and Plant Economics

LECTURE 09
Heuristics for Process
Synthesis (Part 4)

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General Structure of the

Separation System
The general structure of the separation
system depends on the phase of the
reactor effluent stream.

Separation system for a

liquid reactor effluent.
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General Structure of the

Separation System

Separation system for a vapor

or a two-phase reactor effluent.
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General Structure of the

Separation System

Design VRS before LSS since VRS generates a

liquid stream that must be further purified.
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General Structure of the

Separation System
Promising alternative processes may have
better conversion or selectivity compared to
conventional processes, but the structures
of their separation systems are expected to
be very similar.

Do not start the separation system design

from scratch. Study the separation system
of the conventional process!

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General Structure of the

Separation System
Consider the formaldehyde production via
partial oxidation of methanol with air. Recall
that the reactor temperature and conversion
have been narrowed down to two combinations:

• 400°C and 88% conversion

• 300°C and 98% conversion

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General Structure of the

Separation System

400°C and 88% conversion

Higher annual profit of 15.38 million
dollars, but with methanol recycle.
Expecting higher capital and operating
costs of separation system.
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General Structure of the

Separation System

300°C and 98% conversion

Lower annual profit of 12.30 million
dollars, but without methanol recycle.
Expecting lower capital and operating
costs of separation system.
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Vapor Recovery System

In attempting to synthesize a vapor
recovery system, two decisions have
to be made:

1. Location of vapor recovery system

2. Types of vapor recovery systems

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Vapor Recovery System

Location of Vapor Recovery System

There are three choices for the location

of the vapor recovery system.

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Vapor Recovery System

Location of Vapor Recovery System

Place on the purge stream if significant

amounts of valuable materials are being
lost at the purge.

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Vapor Recovery System

Location of Vapor Recovery System

Place on the gas recycle stream if materials

deleterious to the reactor operation (e.g., catalyst
poison) or contributes to degradation of product
distribution are present on this stream.
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Vapor Recovery System

Location of Vapor Recovery System

Place on the flashed vapor stream if the first

two objectives have to be met. In this case,
the phase split and vapor recovery system
can be merged.
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Vapor Recovery System

Location of Vapor Recovery System

Do not use a vapor recovery system if neither

of the first two objectives are important.

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Vapor Recovery System

Types of Vapor Recovery Systems
The most common choices are:

1. Condensation
2. Absorption
3. Adsorption
4. Membrane separation process

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Liquid Separation System

In attempting to synthesize a liquid
separation system, the following
decisions have to be made:

1. Removal and destination of light ends

2. Separations by distillation
3. Distillation sequencing
4. Alternatives to distillation

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Liquid Separation System

Removal and Destination of Light Ends

Some light ends will be present on

the liquid leaving the phase splitter.
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Liquid Separation System

Removal and Destination of Light Ends
Remove the light ends by using a
distillation column with a partial
condenser or a stripper. The light
ends may be:

• Sent to the fuel gas header

If combustible components make up
the majority of the light ends stream

• Vented to the flare

If the light ends stream does not
have significant fuel value

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Liquid Separation System

Separations by Distillation
In general, distillation is the least expensive
means of separating mixtures of liquids.

If the relative volatilities of two components

with neighbouring boiling points on a liquid
mixture is less than 1.1 or so, group them
into a single component.

Develop the best distillation sequence for

the mixture, then separate the lumped
components by alternative methods.

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Liquid Separation System

Separations by Distillation
The feed composition and flowrate to the
distillation column are usually specified.
The specifications of the products are
usually known as well.

The operating parameters to be selected

by the designer include:
• Feed conditions
• Type of condenser
• Operating pressure
• Reflux ratio

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Liquid Separation System

Separations by Distillation
Feed Condition
It is adequate to set the feed to saturated
liquid conditions. This tends to equalize the
vapor rate below and above the feed.

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Liquid Separation System

Separations by Distillation
Type of Condenser
Most designs use a total condenser.

• Total condenser is necessary if the

distillate needs to be sent to storage.

• The distillate can be readily sent to a

higher-pressure distillation column
for further separation using a pump.

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Liquid Separation System

Separations by Distillation
Operating Pressure
The lower limit is set by minimum temperature
that can be achieved using air or cooling water.
• If the condenser will be a cooling water exchanger, the
bubble point of the overhead product should be 80C
above the cooling water temperature.

• If the condenser will be an air fin cooler, the bubble

point of the overhead product should be 150C above
the summer air temperature.

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Liquid Separation System

Separations by Distillation
Operating Pressure
The lower limit is set by minimum temperature
that can be achieved using air or cooling water.
• If the previous criteria would lead to vacuum operation,
set the pressure at atmospheric pressure.

However, if operating the column at atmospheric

pressure will result in thermal degradation of bottoms
product, operate the column at vacuum.

• When separating gases and light hydrocarbons, the

column is operated at high pressure with refrigeration.

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Liquid Separation System

Separations by Distillation
Operating Pressure
The lower limit is set by minimum temperature
that can be achieved using air or cooling water.

If a partial condenser is to be used,

• The previous criteria should be applied to the dew
point of the vapor product.
• The minimum operating pressure will be dictated by
the destination pressure.

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Liquid Separation System

Separations by Distillation
Operating Pressure
The upper limit is set by the following,
whichever is lower:

• The lowest temperature at which the

bottoms product undergoes thermal
degradation.

• The highest temperature that can be

achieved using high-pressure steam.

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Liquid Separation System

Separations by Distillation
Operating Pressure
As pressure is raised,

PROS
• Reboiler and condenser duties decrease.
• Column diameter decreases.

CONS
• Column height increases.
• Reboiler and condenser temperatures increase.

Distillation columns are typically operated

at the lowest possible pressure.
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Liquid Separation System

Separations by Distillation
Operating Pressure
Alternative decision algorithm, provided by
Seider:

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Liquid Separation System

Separations by Distillation
Reflux Ratio
As the reflux ratio is raised,

PROS
• Column height decreases.

CONS
• Column diameter increases.
• Condenser and reboiler duties increase.

There exists an optimum reflux ratio.

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Liquid Separation System

Separations by Distillation
Recall option 1. Methanol
has to be separated from
the formalin product. The
distillation column is
modelled in ChemSep
(free software).

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Liquid Separation System

Separations by Distillation

Capital cost (blue line) generally increases as

reflux ratio decreases. Increase in column cost is
faster than decrease in cost of other equipment.
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Liquid Separation System

Separations by Distillation

Operating cost (red line) decreases as reflux

ratio decreases due to lower utility (cooling
water, steam, electricity) consumption.
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Liquid Separation System

Separations by Distillation

The optimum number of trays is around 40,

where the total annualized cost is around
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4.56 million dollars.

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Liquid Separation System

Separations by Distillation
Option 1: With recycle
Annual profit = 15.38 – 4.56 (LSS)
= 10.82 million dollars

Option 2: Without recycle

Annual profit = 12.30 million dollars

The VRS for both options are almost similar

in cost. Hence, it is more profitable to
operate the partial methanol oxidation
process without methanol recycle!

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Liquid Separation System

Distillation Sequencing
For sharp splits of a three-component mixture,
either recover the lightest component first or
the heaviest component first, and then split
the remaining two components.

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Liquid Separation System

Distillation Sequencing
The direct sequence often requires less
energy because the light material (A) is
only vaporized once in the said sequence.

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Liquid Separation System

Distillation Sequencing
However, the indirect sequence can be more
energy-efficient if the feed contains a low
concentration of the light material (A) and a
high concentration of the heavy material (C).

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Liquid Separation System

Distillation Sequencing
As the number of components increases, the
number of alternatives increases very rapidly.

Number of components 4 5 6
Number of sequences 5 14 42

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Liquid Separation System

Distillation Sequencing
Example: Separation of four components via
distillation involves five different sequences:
Option First Second Third
1 A / BCD B / CD C/D
2 A / BCD BC / D B/C
3 AB / CD A/B C/D
4 ABC / D A / BC B/C
5 ABC / D AB / C A/B

Determine the most economic reflux ratio for

each column, then select the sequence with
the lowest total annualized cost.
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Liquid Separation System

Distillation Sequencing
To simplify the effort of evaluating the most
economic distillation sequence, heuristics for
column sequencing have been developed:

1. Remove hazardous components early to minimize

inventory of the said components as safety
consideration.

2. Remove reactive and heat-sensitive components

early to avoid problems of product degradation
during separation.

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Liquid Separation System

Distillation Sequencing
To simplify the effort of evaluating the most
economic distillation sequence, heuristics for
column sequencing have been developed:

3. Remove corrosive components early to minimize

corrosion problems and use of expensive material
of construction.

4. If thermal decomposition in the reboiler

contaminates the product, the finished product
cannot be taken from the bottoms of the columns.

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Liquid Separation System

Distillation Sequencing
Additional heuristics by Seider:

1. Remove thermally unstable, corrosive, or chemically

reactive components early in the sequence.

2. Remove final products one-by-one as distillates (the

direct sequence).

3. Sequence separation points to remove, early in the

sequence, those components of greatest molar
percentage in the feed.

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Liquid Separation System

Distillation Sequencing
Additional heuristics by Seider:

4. Sequence separation points in the order of

decreasing relative volatility so that the most
difficult splits are made in the absence of the other
components.

5. Sequence separation points to leave last those

separations that give the highest-purity products.

6. Sequence separation points that favor near

equimolar amounts of distillate and bottoms in
each column.

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Liquid Separation System

Distillation Sequencing
Example:
Consider the separation problem indicated in the figure,
except that separate isopentane and n-pentane are also
to be obtained with 98% recoveries. Use heuristics to
determine a good sequence of ordinary distillation units.

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Liquid Separation System

Distillation Sequencing
Additional Data:

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Liquid Separation System

Distillation Sequencing
Answer:

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Liquid Separation System

Other Liquid Separation Methods
Consider the following liquid separation
methods as alternatives to distillation:

1. Absorption and stripping

2. Liquid-liquid extraction
3. Adsorption
4. Crystallization
5. Evaporation

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Department of Chemical Engineering

College of Engineering
University of the Philippines Diliman
First Semester, AY 2014-2015

ChE 141: Chemical Process

Development and Plant Economics

LECTURE 09
Heuristics for Process
Synthesis (Part 4)

kcdeguzman/2014

25