Plant Design: Process Synthesis

Steps for Basic Chemicals

Professor Ir Ts Dr Sharifah Rafidah Wan Alwi

[email protected]

School of Chemical & Energy Engineering

Universirti Teknologi Malaysia
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Learning Outcome

 Implement the steps in creating flowsheets

involving reactions, separations
Click to edit title and T-P change
operations.
Edit text

 Select the principles pieces of equipment to

integrate the tasks together.
Copyright of Universiti Teknologi Malaysia
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How to synthesis a chemical product from

lab to industrial scale?
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Production of 100,000 lb/hr of Vinyl

Chloride (VC)
Monomer intermediate
for production of
polyvinyl chloride.
C2H3Cl
Widely used for rigid
plastic piping, fittings, and
similar products.
Extremely toxic
substance.
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5 Key Synthesis Steps

By Rudd, Powers and Siirola (1973)

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Step 1: Eliminate Differences in Molecular

Type
Evaluate possible reaction paths.
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5 Possible Reaction Pathways to Produce VC

R1. Direct Chlorination of Ethylene R2. Hydrochlorination of Acetylene R3. Thermal cracking of
dicholoroethane from chlorination
of ethylene
C2H4 + Cl2 → C2H3Cl + HCl C2H2 + HCl → C2H3Cl C2H4 + Cl2 → C2H4Cl2
C2H4Cl2 → C2H3Cl + HCl
C2H4 + Cl2 → C2H3Cl + HCl

R4. Thermal cracking of dicholoroethane from R5. Balanced Process for Chlorination of Ethylene
oxychlorination of ethylene
C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O C2H4 + Cl2 → C2H4Cl2
C2H4Cl2 → C2H3Cl + HCl C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O
C2H4 + HCl + ½ O2 → C2H3Cl + H2O 2C2H4Cl2 → 2C2H3Cl + 2HCl
C2H4 + HCl + ½ O2 → 2C2H3Cl + H2O

Which reaction pathway should we select?

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Evaluate & Rank the Options

What are the advantage and disadvantages
for each reaction pathways?
• Which yield positive gross profit?
• Which uses less energy?
• Which has higher conversion yield?
• Which do not produce unwanted byproducts?
• Which has less safety, health and environmental impact?
• Which requires less capital and operating costs?
• Which raw material is easier to be obtained?
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Weighted Average Value

Criteria Weightage Reaction Pathway 1 Reaction Pathway 2 Reaction Pathway 3

(A) Score (B) Mark (A x B) Score Mark Score Mark

Criteria 1
Criteria 2
Criteria 3
Total
*Score: 0 (worst) to 5 (best)

Highest Total Mark is the best Reaction Pathway to be selected.

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Reaction Pathway 1. Direct Chlorination of

Ethylene

Advantages:
• Attractive solution
• Occurs spontaneously at a few hundred celcius

Disadvantages:
• Low percentage of yield
• Producing large amount of byproducts (Dichloroethylene)
• Half of the expensive Cl is consumed
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Reaction Pathway 2. Hydrochlorination of

Acetylene

Advantages:
• Good conversion (98%)
• Moderate reaction conditions
• Temp : 150 ◦C, Catalyst: HgCl2, Pressure: 1 atm

Disadvantages:
• Flammability of C2H2
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Reaction Pathway 3. Thermal Cracking of Dichloroethane from

Chlorination of Ethylene

Advantages:
• Conversion Ethylene to Dichloroethane is 98% (90 ◦C , 1 atm, Catalyst: FeCl3)
• Conversion of intermediate is 65% (spont. at 500 ◦C)

Disadvantages:
• Produce HCl
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Reaction Pathway 4. Thermal Cracking of Dichloroethane from

Oxychlorination of Ethylene

Advantages:
• Highly exothermic reaction with 95% conversion (250 ◦C , Catalyst: CuCl2)
oxychlorinates ethylene 1,2-dichloroethane

Disadvantages:
• Economics dependent on cost of HCl
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Reaction Pathway 5. Balanced Process for Chlorination of

Ethylene

Advantages:
• Combines path 3 and 4
• All Cl2 converted to Vinyl Chloride
• No by-products
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Determine the Gross Profit (GP)/ Economic

Potential(EP) for each reaction pathways. Is it
profitable?

G.P. = SALES OF PRODUCTS – COST OF RAW MATERIALS

*Does not include utilities & operating cost
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Evaluating Economic Pote for Reaction Pathway 1 & 3

C2H4 + Cl2 = C2H3Cl + HCl

lbmol 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 30 18 35 25

Gross profit = Sales of Products – Cost of Raw Materials

Gross profit = [35(1) + 25(0.583)] – [30(0.449) + 18(1.134)]
= 15.69 cents/ Ib of vinyl chloride
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Evaluate Gross Profit for all Reaction Path

Reaction Overall Reaction Gross profit
path (cents/lb of
vinyl
chloride)
A negative
1 C2H4 + Cl2 = C2H3Cl + HCl 15.69 gross profit
means loss and
2 C2H2 + HCl = C2H3Cl -12.94 the reaction
path should be
3 C2H4 + Cl2 = C2H3Cl + HCl 15.69 rejected.
4 C2H4 + HCl + ½O2 = C2H3Cl + H2O 6.96
5 2C2H4 + Cl2 + ½O2 = 2C2H3Cl + H2O 11.32
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Evaluate all reaction path based on multi-criteria by using

weighted average approach
Criteria Weightage Reaction Reaction Reaction Reaction Reaction
(A) Pathway 1 Pathway 2 Pathway 3 Pathway 4 Pathway 5
Score Mark Score Mark Score Mark Score Mark Score Mark

Gross Profit 40% 5 2 5 2 3 1.2 4 1.6

Conversion
25% 1 0.3 3 0.8 4 1 3 0.8
Selectivity
Temperature 15% 4 0.6 3 0.5 4 0.6 3 0.5
Produce
20% 4 0.8 4 0.8 5 1 5 1
byproducts
Total
*Score: 1 (worst) to 5 (best)
  3.65   4   3.8   3.8

Reaction path 3 is selected as it has the highest points.

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Step 2: Distribute the chemicals by matching

sources and sinks.
Perform mass and energy balance.
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Reaction path 3
Cl2
HCl

C2H4Cl2
DIRECT
PYROLYSIS
CHLORINATION

C2 H4 C2H3Cl

DIRECT CHLORINATION PYROLYSIS

•operates at 90oC and 1.5 atm •operates at 500oC and 26 atm
•the pressure selected to prevent the •the pressure is recommended by the B.F.
leakage of air into the reactor Goodrich patent (1963) without any
•98% conversion of C2H4 to C2H4Cl2 justification
•the remainder byproduct is converted •60% conversion of C2H4Cl2 to C2H3Cl with
to C2H4Cl3 a byproduct of HCl
•at this stage, the loss is neglected •need to recycle back the unreacted C2H4Cl
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Step 2: Distribute the chemicals by matching sources and sinks

Perform Overall Mass Balance

Direct Chlorination
Pyrolisis

Cl2
HCl

C2H4Cl2
DIRECT
PYROLYSIS
CHLORINATION

C2H4 C2H3Cl
Target
100,000 lb/h
*For preliminary calculation, assume 100% conversion.
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Step 2: Distribute the chemicals by matching sources and sinks

Evaluating Gross Profit for Reaction Pathway 1 & 3

C2H4 + Cl2 = C2H3Cl + HCl

lbmol 1 1 1 1
Molecular Weight 28.05 70.91 Multiply
62.50 all 36.46
lb 28.05 70.91 by62.50
100,000 36.46
lb/lb of vinyl chloride 0.449 1.134 1 0.583
Cents/lb 30 18 35 25

Gross profit = Sales of Products – Cost of Raw Materials

Gross profit = [35(1) + 25(0.583)] – [30(0.449) + 18(1.134)]
= 15.69 cents/ Ib of vinyl chloride
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Step 2: Distribute the chemicals by matching sources and sinks

Perform Overall Mass Balance

Direct Chlorination
Pyrolisis

Cl2
HCl
113,400 lb/h 58,300 lb/h
C2H4Cl2
DIRECT
PYROLYSIS
CHLORINATION

C2H4 C2H3Cl
Target
44,900 lb/h 100,000 lb/h
*For preliminary calculation, assume 100% conversion.
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Step 2: Distribute the chemicals by matching sources and sinks

Mass Balance for Direct Chlorination Unit

58,300 lb/h
Cl2
158,300 lb/h HCl
98% conversion
(neglect the unconverted)
113,400 lb/h
C2H4Cl2 HCl
DIRECT
PYROLYSIS C2H3Cl
CHLORINATION
C2H4Cl2

C2H4
Target
C2H3Cl
44,900 lb/h
100,000 lb/h
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Step 2: Distribute the chemicals by matching sources and sinks

Mass Balance For Pyrolysis Unit Considering Recycle Stream

58,300 lb/h
Cl2 158,300 lb/h HCl
98% conversion 60%
(neglect the unconverted) conversion
113,400 lb/h
C2H4Cl2 HCl
DIRECT
PYROLYSIS C2H3Cl
CHLORINATION
C2H4Cl2

C2H4
Target
C2H3Cl
44,900 lb/h
100,000 lb/h
Pyrolysis Recycle Mass Balance 105,533 lb/h
(1-0.6) x 158,300 lb/hr = 105,533 lb/hr
0.6
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Reaction path 3

Energy Balance
52 × 106 Btu/hr 58,300 lb/h
Cl2 150 × 106 Btu/hr 158,300 lb/h HCl

113,400 lb/h
DIRECT C2H4Cl2 PYROLYSIS HCl
CHLORINATION 500oC C2H3Cl
90oC, 1.5 atm 26 atm C2H4Cl2

C2H4
C2H3Cl
44,900 lb/h
100,000 lb/h
105,533 lb/h
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Step 3: Eliminate Differences in Composition

Design separation units with suitable temperature and pressure.
 Distillation Distillation
58,300 lb/h 28
Tower Tower
HCl
Feed at saturate liquid 12 atm 4.8 atm

C2H3Cl
158,300 lb/h HCl
Cl2 100,000 lb/h
C2H3Cl
113,400 lb/h -26.2 oC 33 oC
DIRECT PYROLYSIS C2H4Cl2
C2H4Cl2
CHLORINATION 500oC
90oC, 1.5 atm 112 oC 26 atm

C2H4 Liquid at
Assign for the last column first. Set a pressure
44,900 lb/h Assignwhere:
for the next upstream column. Set93 aC pressure where: 146
Bubble o
o
C
Point, 6 oC
•The top product can be condensed by cooling water
•Pressure (avoid from
gradient the use of to low
high 100,000 lb/h C H Cl 2 3
105,500 lb/h C H Cl
refrigerant). •The condenser temperature
C H Cl
not too low
2 4 2
2 4 2

•The reboiler can heat up the bottom by•using MPS can 105,500
The reboiler heat lb/h
up the bottom by using LPS
Boiling Points and
•The operating CriticalisConstants
condition far from Tc and
•ThePoperating
c. condition is far from Tc and Pc.
Boiling Point (oC) Critical Constants
Normal
Boiling
Chemical
Point 4.8 atm 12 atm 26 atm Tc (oC) Pc (atm)
(1 atm, oC)

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
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Step 3: Eliminate Differences in Composition
Design separation systems with suitable temperature & pressure.
Distillation 58,300 lb/h Distillation
Tower HCl Tower
12 atm 4.8 atm

52 × 106 Btu/hr
C2H3Cl
150 × 106 158,300 lb/h
Cl2 100,000 lb/h
Btu/hr
113,400 lb/h -26.2 oC 33 oC
DIRECT C2H4Cl2 PYROLYSIS
CHLORINATION 500oC
90oC, 1.5 atm 112 oC 26 atm

C2H4
Liquid at
44,900 lb/h Bubble
Point, 6 oC 93 oC 146 oC
100,000 lb/h C2H3Cl
105,533 lb/h C2H4Cl2
C2H4Cl2

105,533 lb/h
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Step 4: Eliminate Differences in Temperature,

Pressure and Phase
Design utilities system (heating, cooling, pressure systems e.g. pump,
compressor, pressure reducing valve)
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DIRECT
CHLORINATION
Which PYROLYSIS
500oC
90oC, 1.5 atm configuration 26 atm
C2H4Cl2 C2H4Cl2
Begin State: is better? End State:
Require compressor to
90 oC, 1.5 atm 500 oC, 26 atm
Liquid Phase raise the pressure
Vapour Phase
DIRECT PYROLYSIS
Temp. Phase Temp. Pressure
Configuration 1 CHLORINATION 500oC
90oC, 1.5 atm Change Change Change Change 26 atm
C2H4Cl2 242 oC 242 oC 499 oC C2H4Cl2
Begin State: 1.5 atm 1.5 atm 1.5 atm End State:
90 oC, 1.5 atm Liquid Vapour Vapour 500 oC, 26 atm
Liquid Phase Phase Phase Phase Vapour Phase
DIRECT Temp. PYROLYSIS
Pressure Phase Temp.
Configuration 2 CHLORINATION 500oC
90oC, 1.5 atm Change Change Change Change 26 atm
C2H4Cl2 91 oC 242 oC 242 oC C2H4Cl2
Begin State: 26 atm 26 atm 26 atm End State:
90 oC, 1.5 atm Liquid Liquid Vapour 500 oC, 26 atm
Liquid Phase Phase Phase Phase Vapour Phase
Require pump to raise
the pressure
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Step 4: Eliminate Differences in Temperature, Pressure and Phase

Cl2

113,400 lb/h C2H4Cl2

DIRECT Temp. PYROLYSIS
Pressure Phase Temp.
CHLORINATION 500oC
90oC, 1.5 atm Change Change Change Change 26 atm
90 oC 91 oC 242 oC 242 oC 500 oC
C2H4 1.5 atm 26 atm 26 atm 26 atm 26 atm 500 oC
44,900 lb/h Liquid Vapour 26 atm
at b.p. at b.p.
P Distillation
Distillation
Tower 58,300 lb/h Tower
Temp. 12 atm HCl 4.8 atm
C2H3Cl
Change 100,000 lb/h
90 oC 170 oC Vapour at Dew Pt.
-26.2 oC 33 oC
4.8 atm 26 atm
Phase Temp.
P P
Change Change
6 oC
12 atm
Temp. 93 oC 146 oC
Change Liquid at
100,000 lb/h C2H3Cl
Bubble Pt. 105,533 lb/h C2H4Cl2
 150 x 106 52 x 106 33
Pumping Work 23 x 106 21 x 106 40 x 106
Btu/hr Btu/hr
66 Bhp Btu/hr Btu/hr Btu/hr
Cl2

113,400 lb/h C2H4Cl2

DIRECT Temp. PYROLYSIS
Pressure Phase Temp.
CHLORINATION 500oC
90oC, 1.5 atm Change Change Change Change 26 atm
90 oC 91 oC 242 oC 242 oC 500 oC
C2H4 1.5 atm 26 atm 26 atm 26 atm 26 atm 500 oC
44,900 lb/h 26 atm

P Distillation
Distillation
58,300 lb/h Tower
Calculate
Tower
12 atm HCl 4.8 atm
Temp. C2H3Cl
energy Change 100,000 lb/h

balance 170 Co
Phase Temp.
-26.2 oC 33 oC

90 oC 26 atm P P
Change Change
4.8 atm
6 oC
3.4 x 106 12 atm
Temp.
Btu/hr 93 oC 146 oC
Change 100,000 lb/h C2H3Cl
105,533 lb/h C2H4Cl2
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Step 5: Integrate Tasks

Allocate appropriate unit operations.
Try to integrate several processes together by using single unit operation
where possible.
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Condensor
Preheater
Cl2 Cooling
Water
113,400 lb/h C2H4Cl2 Steam
DIRECT Temp. Pyrolisis PYROLYSIS
Pressure Phase Temp.
CHLORINATION Evaporato Furnace 500oC
90oC, 1.5 atm Change Change Change Change 26 atm
Pump r
90 oC 91 oC 242 oC 242 oC 500 oC
C2H4 Direct 1.5 atm 26 atm 26 atm 26 atm 26 atm 500 oC
44,900 lb/hChlorination 26 atm
Reactor

Cooling
Spray Water Distillation
58,300 lb/h
Distillation
Tower
Tower
Quench 12 atm HCl 4.8 atm
Temp. C2H3Cl
Tank Cooler 100,000 lb/h
Change
90 oC -26.2 oC 33 oC
4.8 atm 170 C o
Phase Temp.
26 atm P P
Change Change PRV o
6 C
PRV
Cooling Refrigerant
Water 12 atm
Temp. Condensor 93 oC 146 oC
Change 100,000 lb/h C2H3Cl
Cooler 105,500 lb/h C2H4Cl2
P
PRV
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Steam
Cooling
Water
Cooling
Water

Distillation Distillation
Tower 58,300 lb/h Tower
12 atm HCl 4.8 atm
C2H3Cl
Cooling
100,000 lb/h
Water
Final flowsheet -26.2 oC 33 oC

after task
integration for Refrigerant
the vinyl- 93 oC 146 oC

100,000 lb/h C2H3Cl

chloride 105,500 lb/h C2H4Cl2

process.
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Summary: 5 Key Synthesis Steps

Evaluate possible reaction paths

Perform mass and energy

balance

Design separation
processes

Design utilities systems

Allocate unit operations

By Rudd, Powers and Siirola (1973)

Thank You!