Anatomy of a Chemical Manufacturing

Process
• Raw material storage • Purification
• Feed preparation • Product storage
• Reaction • Ancillary processes
• Product separation

Chemical Engineering Design

 Continuous and Batch Processes

• Continuous: 24 hours a day, 7 days a week with

downtime for maintenance, catalyst regeneration etc.

– Continuous process is economical for large scale production

• Batch processes: operate intermittently with some/all

process units shut down and startup frequently,
combination of batch reactor with continuous separation
– Batch processes are used for flexibility

Chemical Engineering Design

 Batch Processes: Advantages

• Allows multiple products in the same equipment

• Integrity of a batch is preserved, good for quality control

• Production rate is flexible

• Easier to clean and maintain sterile operation

• Easier to scale up

• Low capital for small scale production volumes

Chemical Engineering Design

 Batch Processes: Disadvantages

• Scale of production is limited

• Difficult to reach high production rate for achieving

economies

• Batch to batch quality varies

• Recycle and heat recovery are harder

• Asset utilization is lower

• More labor intensive

Chemical Engineering Design

 When to Chose Batch?

With high value small scale products

• Food products

• Pharmaceuticals products

• Personal care product

• Blended products with multiple grade

• Specialty chemicals

Chemical Engineering Design

 Conversion

• Conversion is a measure of the fraction of the reagent

that reacts. To optimize reactor design and minimize
byproduct formation, the conversion of a particular
reagent is often less than 100%.

Chemical Engineering Design

 Selectivity

• Selectivity is a measure of the efficiency of the reactor in

converting reagent to the desired product. It is the
fraction of the reacted material that was converted into
the desired product. If no byproducts are formed, then
the selectivity is 100%

• Selectivity is usually improved by operating the reactor at

low conversion

Chemical Engineering Design

 Yield

• Yield is a measure of the performance of a reactor or

plant.

Chemical Engineering Design

 Yield

• Plant yield is a measure of the overall performance of

the plant and includes all chemical and physical losses.

Chemical Engineering Design

 Use of Excess Reagent

• In industrial reactions the components are seldom fed to

the reactor in exact stoichiometric proportions. A reagent
may be supplied in excess to promote the desired
reaction; to maximize the use of an expensive reagent;
or to ensure complete reaction of a reagent, as in
combustion.

Chemical Engineering Design

 Recycles and Purges

• Processes in which a flow stream is returned (recycled)

to an earlier stage in the processing sequence are
common. If the conversion of a valuable reagent in a
reaction process is appreciably less than 100%, the un-
reacted material is usually separated and recycled.

• It is usually necessary to bleed off a portion of a recycle

stream to prevent the buildup of unwanted material.
Some portion of the stream must be purged to keep the
inert level within acceptable limits. A continuous purge
would normally be used. Under steady-state conditions:
– Loss of inert in the purge = Rate of feed of inerts into the system

Chemical Engineering Design

 Bypass
• A flow stream may be divided and some part diverted
(bypassed) around some units. This procedure is
often used to control stream composition or
temperature. Material balance calculations on
processes with bypass streams are similar to those
involving recycle, except that the stream is fed
forward instead of backward. This usually makes the
calculations easier than with recycle.

Chemical Engineering Design

 Stoichiometric Targeting

Reaction Separation

Feed- Desired
Product Yield Product Recovery
stocks Product(s)

Recycle Byproducts
and Wastes

Levels of Stoichiometric Targeting

Level I: Theoretical stoichiometric targets with full product
recovery
Level II: Actual stoichiometric targets without product losses
Level III: Actual stoichiometric targets with product losses

Chemical Engineering Design

Summary of Stoichiometric
Targeting

Overall Stoichiometric
Reaction

Reaction Yield Stoichiometric Calculations

Data Assuming Maximum Yield

Product Stoichiometric Calculations

Recovery/Separation Including Actual Yield
Data

Stoichiometric Calculations
Including Actual Yield and Separation Losses

Chemical Engineering Design

Problem 1. Stoichiometric Targeting of Ethanol
Production from Glucose
A new process is to be designed for the conversion of 150 MM kg/yr of
sugar to ethanol. The sugar is taken to be in the form of glucose
(C6H12O6) and is converted to ethanol (C2H5OH) through the following
overall fermentation reaction:
C6H12O6 → 2C2H5OH + 2CO2

a. Calculate the maximum theoretical stoichiometric target for ethanol.

b. Available experimental data (Krishnan et al., 1999) show that the actual
reaction yield that can be obtained is 0.46 kg ethanol/kg glucose. Determine
the actual stoichiometric target for ethanol.

c. In separating ethanol from the reaction mixture, it is expected to lose 5% of

ethanol with the wastewater stream. What is the actual stoichiometric target for
ethanol when the separation losses are accounted for?

Chemical Engineering Design

 Preliminary Economic Assessment:
Example
Quick check:
Price of product + by Product / kg  Price of raw
materials/kg

• Benzene (MW 78.11): $822/ton

• Ethylene (28.05): $1,100
• Ethylbenzene (106.167): $1800
• Styrene (104.15): $1,120.00

Chemical Engineering Design

 Case Study

Example :

Vinyl Chloride Manufacture

Chemical Engineering Design

 Case Study: Vinyl Chloride
Production
• Market analysis
• Plant location
• Process design (process creation/synthesis)
• Environmental awareness/waste treatment
• Plant safety
• Plant economics

Chemical Engineering Design

 Need assessment/Market analysis
• Plastic article import 2018-2019: 220707 million BDT(22071 crore
BDT) Total import $65bn)  4% of total import

• Major raw materials imported from abroad include polymers

of ethylene, polymers of propylene or of other; olefins,
polyacetal, and other polyether and epoxide resins, polymers
of vinyl, chloride or of other halogenated olefins, polymers
of styrene, amino-resins, phenolic resins and polyurethanes,
acrylic polymers, polymers of vinyl acetate or of other vinyl
esters, cellulose and its chemical derivatives, polyamides.

Chemical Engineering Design

 Need Assessment/Market Analysis
• Caustic soda (NaOH) is a basic chemical used in soap, glass, drugs,
paper & pulp, textile, leather, sugar, WTP and ETP etc industries in
Bangladesh.
• The demand of caustic soda has been increasing gradually, which for
the fiscal 2011-12 is predicted to be 1, 53,608 MT.
• Under this circumstance, there are only few chlor-alkali industries in
Bangladesh to produce this soda. The total production capacity is now
290 MT per day and 95,700 MT per year.
• The existing production capacity lagged behind the FY 2011-12's
demand by 38 per cent. The reason behind the lower production of
caustic soda is the lower demand of chlorine (Cl2), which is a bi-
product of the chlor-alkali plants in Bangladesh currently.
Developing a PVC granule-producing plant can create a scope for
the consumption of chlorine produced from local chlor-alkali plants.
Hossain, MI, Bangladesh. Int J Petrochem Sci Eng. 2017;2(5):155-156. DOI: 10.15406/ipcse.2017.02.00049

Chemical Engineering Design

 Plant location
• Location must be within Industry A : Chemicals Product
close proximity of • Caustic Soda NaOH
ethylene and chlorine • Sodium hypochlorite NaOCl
plant to minimize raw • Hydrogen Peroxide H2O2
material transportation • Calcium hypochlorite (Bleaching
cost powder) Ca(OCl)2
• Land price • Hydrochloric Acid HCl
• Wages • Chlorinated Paraffin Wax
• ChlorineCl2
• Utilities

Location Sreepur, Gazipur. The factory covers

approximately 15 acres

Chemical Engineering Design

PROCESS CREATION

Ref: Seider, Seader and Lewin (2009), Chapter 4

Process Creation
Chemical Engineering Design
 Schedule - Process Creation
• 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.

• Development of Base-case Design

– focusing on the most promising alternative(s) from the synthesis
tree.

Process Creation
Chemical Engineering Design
 Preliminary Database Creation
• Thermophysical property data
– physical properties
– phase equilibria (VLE, LLE, VLLE data)
– Property prediction methods

• Environmental and safety data

– toxicity data
– flammability data

• Chemical Prices
– e.g. as published in the Chemical Marketing Reporter

• Experiments
– to check on crucial items above

Process Creation
Chemical Engineering Design
 Preliminary Process Synthesis
 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.
 Synthesis steps -
1. Chemical reaction
2. Separation of chemical mixtures
3. Phase separation
4. Change of temperature
5. Change of pressure
6. Change of phase
7. Mixing and splitting of streams or batches 8.
8. Operations on solids, such as size reduction and
enlargement

Process Creation
Chemical Engineering Design
 Chemicals participating in VC
Manufacture
Molecular Chemical Chemical
Chemical weight formula structure

Acetylene 26.04 C2H2 H- CC- H

Chlorine 70.91 Cl2 Cl-Cl

Cl Cl
| |
H-C-C-H
1,2-Dichloroethane 98.96 C2H4Cl2 | |
H H
H H
C=C
Ethylene 28.05 C2H4 H H

Hydrogen chloride 36.46 HCl H-Cl

H Cl
C=C
Vinyl chloride 62.50 C2H3Cl H H

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (1)
 Direct chlorination of ethylene:
C2H4  Cl2  C2H3Cl  HCl (1)
Advantages:
– Occurs spontaneously at a few hundred oC.
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.

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (2)
 Hydrochlorination of acetylene:
C2H2  HCl  C2H3Cl (2)
Advantages:
– It provides a good conversion (98%) of C2H2 VC in the presence of HgCl2
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 C2H2 (2.5 100%)

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (3)
 Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4  Cl2  C2H4Cl2 (3)
C2H4Cl2  C2H3Cl  HCl (4)
C2H4  Cl2  C2H3Cl  HCl (1)
Advantages:
– Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (3.3) is
98% at 90 oC and 1 atm with a Friedel-Crafts catalyst such as FeCl3. This
intermediate is converted to vinyl chloride by thermal cracking according to
the endothermic reaction (3.4), which occurs spontaneously at 500 oC with
conversions as high as 65%
Disadvantage:
– Half of the expensive chlorine is consumed to produce HCl by-product,
which may not be sold easily.

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (4)
 Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
C2H4  2HCl  21 O2  C2H4Cl2  H2O (5)
C2H4Cl2  C2H3Cl  HCl (4)
C2H4  HCl  21 O2  C2H3Cl  H2O (6)
Advantages:
– Highly exothermic reaction (5) achieves a 95% conversion to C2H4Cl2 in
the presence of CuCl2 catalyst, followed by pyrolysis step (4) as Reaction
Path 3.
– Excellent candidate when cost of HCl is low
 Disadvantages:
– Economics dependent on cost of HCl

Process Creation
Chemical Engineering Design
 Selection of pathway to VCM (5)
 Balanced Process for Chlorination of Ethylene:
C2H4  Cl2  C2H4Cl2 (3)
C2H4  2HCl  21 O2  C2H4Cl2  H2O (5)
2C2H4Cl2  2C2H3Cl  2HCl (4)
2C2H4  Cl2  21O2  2C2H3Cl  H2O (3.7)
Advantages:
– Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
– All Cl2 converted to VC
– No by-products!

Process Creation
Chemical Engineering Design
 Evaluation of Alternative Pathways

 Reaction Path  is eliminated due its low selectivity.

 This leaves four alternative paths, to be compared first in terms of
Gross Profit.
Chemical Bulk Prices
Chemical Cost (cents/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

Process Creation
Chemical Engineering Design
 Computing Gross Profit
Reaction path  C2H4 + Cl2 = C2H3Cl + 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 Gross Profit
Overall Reaction
Path (cents/lb of VC)
 C2H2 + HCl = C2H3Cl -9.33

 C2H4 +Cl2 = C2H3Cl + HCl 11.94

 C2H4 + HCl + O2 = C2H3Cl + H2O 3.42

 2C2H4 + Cl2 + O2 = 2C2H3Cl + H2O 7.68

Process Creation
Chemical Engineering Design
 Further Justification

i. Ethylene route utilise chlorine which can directly be

supplied by the local chlor-alkali industries.

ii. Ethylene needed to produce VCM is also needed to

domestically produce the PE polymer granules, which are
also consumed in Bangladesh at a very large amount. A
common effort can be made to procure the ethylene for
both (PVC and PE) applications

Chemical Engineering Design

 Step 1. Input-output model (path 3)

Thermal cracking of C2H4Cl2 from chlorination of C2H4:

C2H4  Cl2  C2H4 Cl2

C2H4 Cl2  C2H3 Cl  HCl
C2H4  Cl2  C2H3Cl  HCl

Raw Materials Products

Process Flowsheet?
C2H4, Cl2 C2H3Cl, HCl

Process Creation
Chemical Engineering Design
 Step 2. Reaction Scheme

Cl2 HCl
113,400 lb/hr 58,300 lb/hr
C2H4Cl2
Direct HCl
Pyrolysis
Chlorination
C2H3Cl
C2H4Cl2
C2H3Cl
C2H4 C2H4 + Cl2 C2H4Cl2 C2H4Cl2  C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr

Process Creation
Chemical Engineering Design
 Step 2. Reaction scheme
• A conversion of 100% of the C2H4 is assumed in the chlorination
reaction.

Process Creation
Chemical Engineering Design
  Distribute the chemicals
• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct
of HCl, according to Eqn. (3.4).

• To satisfy the overall material balance, 158,300 lb/h of C2H4Cl

must produce 100,000 lb/h of C2H3Cl and 58,300 lb/h of HCl.

• But a 60% conversion only produces 60,000 lb/h of VC.

• The additional C2H4Cl2 needed is computed by mass balance to

equal:
[(1 - 0.6)/0.6] x 158,300 or 105,500 lb/h.

• Its source is a recycle stream from the separation of C2H3Cl from

unreacted C2H4Cl2, from a mixing operation, inserted to combine
the two sources, to give a total 263,800 lb/h.

Process Creation
Chemical Engineering Design
 Step 3. Recycle/purge scheme
• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct of
HCl

Process Creation
Chemical Engineering Design
 Step 4: Separation Scheme
• The product of the chlorination reaction is nearly pure C2H4Cl2,
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 C2H3Cl and HCl

• One possible arrangement is given in the next slide. The data

below explains the design decisions made.
Boiling point (oC) Critical constants

Chemical 1 atm 4.8 atm 12 atm 26 atm Tc,C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1

C2H3Cl -13.8 33.1 70.5 110 159 56

C2H4Cl2 83.7 146 193 242 250 50

Process Creation
Chemical Engineering Design
 Step 4: Separation Scheme

There may be other, possibly better alternative configurations

Process Creation
Chemical Engineering Design
 Reactor Temperature and pressure

• Reactor pressure and temperature levels:

– Chlorination reaction: 90oC, 1.5 atm is recommended, to eliminate
the possibility of an air leak into the reactor containing ethylene.
– Pyrolysis reaction: 500oC, 26 atm is recommended by the B.F.
Goodrich patent (1963) without any justification.
– The pressure level is also an important consideration in selecting
the separation operations, as will be discussed in the next synthesis
step.

Process Creation
Chemical Engineering Design
Step 5: Scheme for T, P and phase change

Process Creation
Chemical Engineering Design
 Integrate tasks (tasks  unit operations)

Process Creation
Chemical Engineering Design
 Assembly of synthesis tree
Reaction Distribution of Separations T, P and Task
path chemicals phase integration
changes




Process Creation
Chemical Engineering Design
 Development of Base-case Design
 Develop one or two of the more promising flowsheets from the
synthesis tree for more detailed consideration.

Process Creation
Chemical Engineering Design
 Waste Treatment
The by-products formed in the process are found in waste streams arising from EDC
Purification and Pyrolysis, as well as the Quench tank.
These waste streams come in two forms, liquid and vapor. The vapor wastes contain
more contaminants than the liquid wastes and this is due to the fact of the high
temperatures with which the reactors are run.

Chemical Engineering Design

 Waste Treatment Techniques
• These treatment technique include condensation, absorption/scrubbing,
flaring, and catalytic and thermal incineration.
• Condensation is the liquefication of contaminants by the use of low
temperatures. That is, the compounds to be removed from the gas phase
are cooled to a temperature at which their partial pressure in the gas
stream surpasses their dew point so that they turn to liquids. The liquids
are then packaged and are prepared for either selling or disposal.
• Flaring is another combustion technique that involves the direct burning
of an organic stream in an open flame
• Catalytic incineration involves the burning of the by-products using a
catalyst.
• Thermal incineration involves the burning of combustible wastes.

Chemical Engineering Design

 Selection of techniques

• One single treatment method would not be sufficient in

significantly reducing the waste streams and may create other
waste streams
• A combination of incineration, absorption, and scrubbing
technologies was selected.

Chemical Engineering Design

 Description of Waste Treatment
• The first step in this treatment method is to send all the liquid and vapor
wastes to the incinerator, where they are all combusted at a temperature of
1127 oC. Carbon dioxide (CO2), water (H2O), hydrochloric acid (HCl),
chlorine gas (Cl2), nitrous oxides (NOx) will be formed

• These products are then sent to an absorption column. This column uses
water as a solvent and removes HCl and H2O from the stream.

• From here the remaining products are sent to another absorption column,
this one using NaOH as the solvent. Here the NaOH removes the Cl2 and
forms a solution of sodium chloride and sodium hypochlorite, which is sold
to an industrial bleach production company. The CO2 is then sent to where
it will be sequestered.

• The NOx production is very minimal and in fact it is negligible. The NOx is
actually only about 7 x 10-4 percent of the waste streams.

Chemical Engineering Design