Preliminary Database Creation

Preliminary Process Synthesis

Development of the Base-Case Design
O Understand how to go about assembling design data and
creating a preliminary data base.
O Be able to implement the steps in creating flowsheets
involving reactions, separations, and T-P change operations.
In so doing, many alternatives are identified that can be
assembled into a synthesis tree that contains the most
promising alternatives.
O Know how to select the principal pieces of equipment and to
create a detailed process flowsheet, with a material and
energy balance and a list of major equipment items.
On completing this part of the course, you should:
Preliminary Database Creation
to assemble data to support the design.
Experiments
often necessary to supply missing database items or verify
crucial data.
Preliminary Process Synthesis
top-down approach.
to generate a synthesis tree of design alternatives.
illustrated by the synthesis of processes for the manufacture of
VCM and tPA (refer to text book, pg. 94).
Development of Base-case Design
focusing on the most promising alternative(s) from the synthesis
tree.

Thermophysical property data
physical properties
phase equilibria (VLE data)
Property prediction methods

Environmental and safety data
toxicity data
flammability data

Chemical Prices
e.g. as published in the Chemical Marketing Reporter
Companies carry out market studies and have a basis for projecting market size and
chemical prices.
Chemical market reporter, newspaper provide up-to-date for chemical commerce,
but not reflect the market situation, just give a good starting point.
To get the better estimation, contact manufacturers directly.
For utility prices; steam, cooling water, electricity, it is desirable to estimate it during
process creation.

Design concepts result from experiments
Additional experiments at other conditions of
compositions, temp, pressures and
representative solvents.
Rates of reactions and catalyst life
estimations.
Aid in the selection and preliminary design of
separation operations.
Synthesis of chemical processes involves:
Selection of processing mode: continuous or batch
Fixing the chemical state of raw materials, products, and by-
products, noting the differences between them.
Process operations (unit operations) - flowsheet building blocks
Synthesis steps -
O Eliminate differences in molecular types
O Distribute chemicals by matching sources and sinks
O Eliminate differences in composition
O Eliminate differences in temperature, pressure and phase
O Integrate tasks (combine tasks into unit operations)

Decide on the raw material and product specifications (states):
Mass (flow rate)
Composition (mole or mass fraction of each chemical species
having a unique molecular type)
Phase (solid, liquid, or gas)
Form (e.g., particle-size distribution and particle shape)
Temperature
Pressure

Chemical reaction
To effect differences in the molecular types between raw material and
product streams.
Positioning in the flowsheet involves many considerations (conversion,
rates, side reactions, reactions in the reverse direction), related to T and
P at which the reaction are carried out.
Methods to remove or supply energy
Catalysts (competitive reaction rates and selectivity).
Separation of chemicals
needed whenever there is difference between the desired composition of
a product stream or intermediate stream and the composition of its
source. (separation is needed when there is impurities in raw materials,
or when products, byproducts and unreacted raw materials coexist in
effluent stream).
Choice of separations operations depends on the phase of the mixture
and differences in the physical properties of chemical species.
Distillation (volatilities are large differrent) (vapor-liquid separation);
Crystallization (melting point s are large different) (solid-liquid
separation)
Liquid liquid separation (difference in volatilities and melting points are
small): use solvent which is selective for some components (e.g. liquid-
liquid extraction).
Gases separation: adsorbent, absorbent, membrane separation



Phase separation
- Flash drums (vapor-liquid separation)
- Decanters (liquid-liquid separation)
- Filters and centrifuge (liquid-solid separation)
Throughout a chemical process, there are often:
- Change of temperature
- Change of pressure
- Change of phase
when enter or leave a process operation (e.g.
reaction and separation operations) or during
Mixing and splitting of streams and branches

Synthesis Step
O Eliminate differences in
molecular types
O Distribute chemicals by
matching sources and sinks
O Eliminate differences in
composition
O Eliminate differences in
temperature, pressure and
phase
O Integrate tasks (combine
tasks into unit operations and
decide between continuous
or batch processing)
Process Operation
Chemical reaction
Mixing
Separation
Temperature, pressure and
phase change

1. Continuous
- Dominant in chemical process industry (large-scale) for
manufacture of commodity chemicals, plastic and etc
- Combined chemical fed, processing and product removal
continuously
- When production rates are low, it is difficult to justify
construction of continuous plant comprised of small vessels and
pipes
2. Batch
- Small scale production rates, production of many specialty
chemical using batch processing
- Batch chemical fed before and product are removed after
processing
- Fed-batch combined fed and process continuously, product
removed after processing is finished
- Batch-product removal chemical fed before processing. Then
product is removed continuously as processing occurs
- Fed- batch and batch-product removal semicontinuous process
- The challenge in designing batch processing time and size of
vessel
Continuous and Batch
Continuous
Batch
Fed-batch
Batch-product removal
Example 1:




Vinyl Chloride Manufacture
Process Creation DESIGN AND ANALYSIS II - (c) Daniel R. Lewin 14

Chemical
Molecular
weight
Chemical
formula
Chemical
structure
Acetylene 26.04 C
2
H
2
H - C C - H
Chlorine 70.91 Cl
2
Cl-Cl


1,2-Dichloroethane


98.96


C
2
H
4
Cl
2
Cl Cl
| |
H-C-C-H
| |
H H

Ethylene

28.05

C
2
H
4
H H
C = C
H H
Hydrogen chloride 36.46 HCl
H-Cl

Vinyl chloride

62.50

C
2
H
3
Cl
H Cl
C = C
H H

Chemicals participating in VC Manufacture:
O Direct chlorination of ethylene:

Advantages:
Attractive solution to the specific problem denoted as Alternative
2 (analysis of primitive problem in chapter 1).
Occurs spontaneously at a few hundred
o
C.
Disadvantages:
Does not give a high yield of VC without simultaneously producing
large amounts of by-products such as dichloroethylene
Half of the expensive chlorine is consumed to produce HCl by-
product, which may not be sold easily.

HCl Cl H C Cl H C
3 2 2 4 2

(2.1)
O Hydrochlorination of acetylene:

Advantages:
This exothermic reaction is a potential solution for the specific
problem denoted as Alternative 3 (analysis of primitive problem in
chapter 1). It provides a good conversion (98%) of C
2
H
2
to VC in
the presence of HgCl
2
catalyst impregnated in activated carbon at
atmospheric pressure.
These are fairly moderate reaction conditions, and hence, this
reaction deserves further study.
Disadvantages:
Flammability limits of C
2
H
2
(LFL = 2.5; UFL = 100%)

Cl H C HCl H C
3 2 2 2

(2.2)
O Thermal cracking of C
2
H
4
Cl
2
from chlorination of C
2
H
4
:

Advantages:
Conversion of ethylene to 1,2-dichloroethane in exothermic reaction
(2.3) is 98% at 90
o
C and 1 atm with a Friedel-Crafts catalyst such
as FeCl
3
. This intermediate is converted to vinyl chloride by thermal
cracking according to the endothermic reaction (2.4), which occurs
spontaneously at 500
o
C with conversions as high as 65% (Alternative
2).
Disadvantage:
Half of the expensive chlorine is consumed to produce HCl by-
product, which may not be sold easily.

2 4 2 2 4 2
Cl H C Cl H C
HCl Cl H C Cl H C
3 2 2 4 2

HCl Cl H C Cl H C
3 2 2 4 2

(2.3)
(2.4)
(2.1)
O Thermal Cracking of C
2
H
4
Cl
2
from Oxychlorination of C
2
H
4
:

Advantages:
Highly exothermic reaction (2.5) achieves a 95% conversion to
C
2
H
4
Cl
2
in the presence of CuCl
2
catalyst, followed by pyrolysis
step (2.4) as Reaction Path 3.
Excellent candidate when cost of HCl is low
Also a solution for specific problem denoted in Alternative 3.
Disadvantages:
Economics dependent on cost of HCl

(2.5)
(2.4)
(2.6)
O H Cl H C O HCl 2 H C
2 2 4 2 2
2
1
4 2

HCl Cl H C Cl H C
3 2 2 4 2

O H Cl H C O HCl H C
2 3 2 2
2
1
4 2

O Balanced Process for Chlorination of Ethylene:


Advantages:
Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
All Cl
2
converted to VC
All HCl produced in the pyrolysis reaction is consumed in the
oxychlorination reaction
No by-products!
(2.5)
(2.3)
(2.7)
O H Cl H C O HCl 2 H C
2 2 4 2 2
2
1
4 2

HCl 2 Cl H C 2 Cl H C 2
3 2 2 4 2

(2.4)
2 4 2 2 4 2
Cl H C Cl H C
O H Cl H C 2 O Cl H C 2
2 3 2 2
2
1
2 4 2

Chemical Cost (cents/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0


Chemical Bulk Prices
Reaction Path O is eliminated due its low selectivity.
This leaves four alternative paths, to be compared first in
terms of Gross Profit.
Reaction path O
C
2
H
4
+ Cl
2
= C
2
H
3
Cl + HCl
lb-mole
1 1 1 1
Molecular weight 28.05 70.91 62.50 36.46
lb 28.05 70.91 62.50 36.46
lb/lb of vinyl chloride 0.449 1.134 1 0.583
cents/lb 18 11 22 18

Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC
Reaction
Path
Overall Reaction
Gross Profit
(cents/lb of VC)
O
C
2
H
2
+ HCl = C
2
H
3
Cl
-9.33
O
C
2
H
4
+Cl
2
= C
2
H
3
Cl + HCl
11.94
O
C
2
H
4
+ HCl + O
2
= C
2
H
3
Cl + H
2
O
3.42
O
2C
2
H
4
+ Cl
2
+ O
2
= 2C
2
H
3
Cl + H
2
O
7.68


Raw Materials
Process Flowsheet?
C
2
H
4
, Cl
2
Products
C
2
H
3
Cl, HCl
Cl
2
113,400 lb/hr
C
2
H
4
44,900 lb/hr
Direct
Chlorination
Pyrolysis
C
2
H
4
Cl
2
HCl
58,300 lb/hr
C
2
H
3
Cl
100,000 lb/hr
HCl
C
2
H
3
Cl
C
2
H
4
Cl
2
C
2
H
4
Cl
2
C
2
H
3
Cl + HCl C
2
H
4
+ Cl
2
C
2
H
4
Cl
2
800 MM lb/year @ 330 days/y 100,000 lb/hr VC
On the basis of this principal sink, the HCl sink and reagent
sources can be computed (each flow is 1,600 lbmol/h)
Next step involves distributing the chemicals by matching
sources and sinks.
A conversion of 100% of the C
2
H
4
is assumed in the chlorination
reaction.
Only 60% of the C
2
H
4
Cl
2
is converted to C
2
H
3
Cl with a byproduct of
HCl, according to Eqn. (2.4).
To satisfy the overall material balance, 158,300 lb/h of C
2
H
4
Cl
2

must produce 100,000 lb/h of C
2
H
3
Cl and 58,300 lb/h of HCl.
But a 60% conversion only produces 94,980 lb/h of VC and HCl.
The additional C
2
H
4
Cl
2
needed is computed by mass balance to
equal:
[(1 - 0.6)/0.6] x 158,300 or 105,533 lb/h.
Its source is a recycle stream from the separation of C
2
H
3
Cl from
unreacted C
2
H
4
Cl
2
, from a mixing operation, inserted to combine
the two sources, to give a total 263,833 lb/h.
The effluent stream from the pyrolysis operation is the source for
the C
2
H
3
Cl product, the HCl by-product, and the C
2
H
4
Cl
2
recycle.
Reactor pressure levels:
Chlorination reaction: 1.5 atm is recommended, to eliminate the
possibility of an air leak into the reactor containing ethylene.

Pyrolysis reaction: 26 atm is recommended by the B.F. Goodrich patent
(1963) without any justification. Since the reaction is irreversible, the
elevated pressure does not adversely affect the conversion. Most likely,
the patent recommends this pressure to reduce the size of the pyrolysis
furnace, although the tube walls must be considerably thicker and many
precautions are necessary for operation at elevated pressures.

The pressure level is also an important consideration in selecting the
separation operations, as will be discussed in the next synthesis step.

The product of the chlorination reaction is nearly pure C
2
H
4
Cl
2
,
and requires no purification.
In contrast, the pyrolysis reactor conversion is only 60%, and one
or more separation operations are required to match the
required purities in the C
2
H
3
Cl and HCl sinks.
One possible arrangement is given in the next slide. The data
below explains the design decisions made.

Boiling point (
o
C)
Critical constants
Chemical 1 atm 4.8 atm 12 atm 26 atm T
c
,C P
c
, atm
HCl -84.8 -51.7 -26.2 0 51.4 82.1
C
2
H
3
Cl -13.8 33.1 70.5 110 159 56
C
2
H
4
Cl
2
83.7 146 193 242 250 50


Boiling point (
o
C)
Critical constants
Chemical 1 atm 4.8 atm 12 atm 26 atm T
c
,C P
c
, atm
HCl -84.8 -51.7 -26.2 0 51.4 82.1
C
2
H
3
Cl -13.8 33.1 70.5 110 159 56
C
2
H
4
Cl
2
83.7 146 193 242 250 50

There may be other, possibly better alternative configurations, as
discussed in the following chapter.
Summary of synthesis steps:
1. Reaction path
2. Distribution of chemical
3. Separations
4. Temperature, pressure and phase change
5. Task integration
1. Heuristics are the rules of thumb which must be
obeyed for designing a process
2. Heuristics are used commonly by design team to
expedite the generation of alternative flowsheet in
preliminary process synthesis
Detailed for heuristics will be covered on topic 4
Develop one or two of the more promising flowsheets from the
synthesis tree for more detailed consideration.
1. Block flow diagram (BFD)
- Represent the main processing sections in terms of
functional blocks
- Diagram indicates overall material balances and
condition at each stage where appropriate
- The detail is helpful to summarise principal
processing section and appropriate to be used in
early design stages, where alternative processes are
usually under consideration
2. Process flow diagram (PFD)
- Provide more detailed view of process
- Display all major processing unit in the process
(including HE, pump, compressor), provide stream
info, include main control loops
- Preliminary PFD constructed using process simulator,
then more detailed prepared using software such as
AUTOCAD and Microsoft Visio
3. Processing unit
- Icon that represent units are links by line that represent the
process stream
- Unit for icon are taken from accepted standard (ASME: American
Society for Mechanical Engineers)
- Labeling refer textbook pg 103 (new version); pg 97 (old version)
4. Stream information
- Directed lines represent stream, with flow direction from left to
right wherever possible
- By convention, when streamline cross, the horizontal line shown
as continuous, vertical line broken
- Mass flowrate, P, T may appear on PFD directly, but more often
are placed in the stream table instead, for clarity
- See table 4.6 pg 104 (new version); table 3.6 pg 100 (old version)
5. Utilities
- Various utility streams are utilised for heating or cooling the
process stream
- For ex. See table 4.7 pg 105 (new version); table 3.7 pg 100 (old
version)

6. Equipment summary table
- Provides info for each equipment item in PFD (See
table 4.8 pg 105 (new version); table 3.8 pg 101 (old
version)
- Materials of construction (MOC) and operating T and P,
required for all units
7. Piping and Instrumentation diagram (P&ID)
- Design document transmitted by process design
engineers to engineers responsible for plant
construction
- To support start-up, operation of process and
operator training
- Contains item that do not appear in PFD such as
location and type of measurement and control
instruments, positioning of valves, size, schedule,
material of construction of piping etc.

8. Calculation supporting flow diagram
- The important calculation in flow diagram is mass
and energy balance for each process
- Other than that, engineer should know how to
calculate number of stages and reflux ratio for
distillation towers
- The calculation could been completed using process
simulators
- Complete simulation not justified until design team is
ready to begin detailed design
- Gradually, additional detail is added to the
simulation model. For ex.: number of stages and
reflux ratio are selected for the distillation column
and; material and energy balance are completed with
recycle streams that are not assumed to be pure

Process Flow Diagram (PFD) development is central
to the design task

The PFD depicts the process route, showing the flows of material
and energy between those process units that make up the plant.
It therefore

defines the role/task and operating conditions of each section or
unit in the process line
gives an overall view of the process route
allows an insight into the overall operability of the process
provides an initial assessment of potential sources of hazards
forms the template for subsequent material and energy balances

A well thought out PFD simplifies unit process design
and allows more accurate assessment of the overall
viability of the plant

There are usually two stages to developing the PFD,
namely:

operational specification
functional specification
Here, you decide upon the sections of the
process that would be needed to manufacture
the product. Typically, a proposed plant is
divided into the following sections:

raw material storage
feed preparation
manufacturing
separation
purification
effluent and waste treatment
product packaging and storage
These are shown in the following figure
In most cases, the required sections
would have been dictated by the
chosen process route. It is during
this stage of the design that you
should be alerted to:

where recycles may be required to
minimise wastage
materials handling and transport
requirements, and
where loss containment systems
(control) have to be installed
The result at this stage is the process
flowsheet
Next, using process knowledge together with information
obtained from the literature, you will have to provide details
about the kind and number of main process units that are
required to perform the various operations defined by the main
sections of the plant. By convention, you should include only
those units where composition, temperature or pressure changes
occur. To do this, you will need data on reaction kinetics,
physical and thermodynamic properties of the materials being
handled at each section of the process and to call upon your
knowledge about the capabilities of each type of processing
equipment.
Thus, it is during this stage of the PFD development, that you get an
indication of the:
probable materials of construction for each process unit
utilities (steam, water, electricity) that will be required
potential hazards that may occur at unit level
impact of each unit on other units in the plant
1. Create a detailed database by refining and adding to
preliminary database
2. A pilot-plant is constructed to confirm that the
equipment items operate properly and provide data
for detailed data bank and simulation model is
prepared
3. It is common to add transport and kinetics data, as
well as data concerning the feasibility of separation,
the identity of any forbidden matches in HE,
heuristic parameters and data for sizing equipment
4. Additional data for sizing equipment are typically
maximum pressure drops, tube lengths and baffle
spacing in HE, surface tension and drag coefficients
for estimating flood velocities, specification for tray
spacing in multistaged towers and residence times in
flash vessel and surge tanks
1. As detailed database is assembled, the needs for
pilot-plant testing become quite evident
2. For manufacture new chemical, pilot plant can
produce quantities of product suitable for testing
and evaluation by potential customers
3. Very few processes that include reaction steps are
constructed without some form of pilot plant
testing prior to doing detailed design calculation.
Though it is an expensive and time consuming step.
4. In connection with the need for laboratory
experiments, pilot plant test also help to identify
potential problem that arise from small quantities
of impurities in feed stream and etc
5. Pilot plant can also verify separation schemes
developed during process design
1. When part of simulation model exist, it is
common for design team to assemble a more
comprehensive model, one that enable team to
examine the effect of parametric changes on
entire process
2. When process simulator have not been used for
design, simulation model is created for
comparison with pilot plant data and parametric
studies
Preliminary Database Creation
needed to provide data to support the design.
Experiments
often necessary to supply missing database items or verify
crucial data.
Preliminary Process Synthesis
Selection of processing mode
Fixing the chemical state
Process operation
Synthesis steps:
- Top-down approach.
- Generates a synthesis tree of design alternatives.
Development of Base-case Design
Creating block flow diagram (BFD)/process flow diagram (PFD)
focusing on the most promising alternative(s) from the synthesis
tree.
Symbols (or elements of symbols) for use in conjunction with other symbols
Symbols (or elements of
symbols) for use in conjunction
with other symbols
Pumps and Compressors