Process Synthesis

Instructor: Dr. Chandra Mouli M.R.

Chemical Engineering Department

 Process Synthesis Steps
1. Eliminate differences in molecular types (chemical
reactions)
2. Distribute chemicals by matching sources and sinks
(mixing)
3. Eliminate differences in composition (separation)
4. Eliminate differences in temperature, pressure and phase
(temperature, pressure and phase change)
5. Integrate tasks: combine operations into unit processes.

Example: Vinyl Chloride Production

 Process creation: Case study
Consider the need to manufacture vinyl chloride,
a monomer intermediate for the production of
polyvinyl chloride (PVC)

VC PVC
H Cl
CHCl CHCl CHCl
C=C
CH2 CH2 CH2
H H
Extremely toxic. Industrial plants must be designed
carefully to satisfy government health & safety
regulations.

3
 Process creation: Case study
Consider an opportunity to satisfy a new demand, on
the order of 0.8 billion lb/yr, for VC monomer in a
petrochemical complex in Shuaiba with existing plant
capacity of 1 billion lb/yr.

VC monomer is a commodity chemicals that is

produced continuously, rather than batch, virtually
everywhere.
Raw Materials Process Desired Product
Possibly (C2H4Cl2) Flowsheet ? (C2H3Cl)

4
 Feed availability (1/3)
Purchase and ship, by pipeline from a nearby plant,
chlorine (Cl2) from the electrolysis of NaCl
solution.React Cl2 with:
a) ethylene (C2H4) to produce the monomer (C2H3Cl)
C2H4 + Cl2  C2H3Cl + HCl
b) ethylene (C2H4) to produce 1,2-dichloroethane (C2H4Cl2),
which can be cracked to produce vinyl chloride (C2H3Cl)
C2H4 + Cl2  C2H4Cl2
C2H4Cl2  C2H3Cl + HCl

5
 Feed availability (2/3)
A nearby company produces large quantities of
HCl, at low cost. React HCl with acetylene
(C2H2):
C2H2 + HCl  C2H3Cl

6
 Feed availability (3/3)
Electrolyze available HCl to obtain H2 and Cl2.
React Cl2 according to:
C2H4 + Cl2  C2H3Cl + HCl

• Produce ammonia by reacting H2 with N2

• Produce methanol by reacting H2 with CO

7
Chemicals involved in VC
manufacturing

8
 Preliminary process synthesis
Step 1: Eliminate the difference in molecular
type through chemical reaction.

 Investigate different reaction pathways for

the best process.

9
 Reaction path 1
Direct chlorination of ethylene.
C2H4 + Cl2  C2H3Cl + HCl .......(1)

Advantages:
– The reaction occurs spontaneously at a few hundreds degrees
Celsius.
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 gas is consumed to produce HCl
by-product, which may not be sold easily.

10
 Reaction path 2
Hydrochlorination of acetylene
C2H2 + HCl  C2H3Cl…....(2)

Advantages:
– Exothermic reaction.
– Provides a good conversion (98%) at 150°C in the presence of
HgCl2 catalyst impregnated in activated carbon at atmospheric
pressure.
– Moderate reaction conditions (150°C and atmospheric pressure)
Disadvantages:
– Flammability limits of C2H2 (LFL = 2.5 → UFL = 100%)

11
 Reaction path 3
Thermal cracking of dichloroethane (C2H4Cl2) from
chlorination of Ethylene (C2H4):
C2H4 + Cl2  C2H4Cl2......................(3)
C2H4Cl2  C2H3Cl + HCl.................(4)
________________________________________________
C2H4 + Cl2  C2H3Cl + HCl............ (1)
Features:
– Rxn (3) is exothermic, with ≈98% conversion to 1,2-
dichloroethane at 90°C and 1 atm with FeCl3 catalyst
– Rxn (4) is endothermic. Thermal cracking occurs
spontaneously at 500°C with conversions of 65%.
– Half of the expensive chlorine is consumed to produce HCl
by-product, which may not be sold easily.
12
 Reaction path 4
Thermal cracking of C H Cl from Oxychlorination of C H :
2 4 2 2 4
C2H4 + 2HCl + ½ O2  C2H4Cl2 + H2O........... (5)
C2H4Cl2  C2H3Cl + HCl...................................(4)
______________________________________________
C2H4 + HCl + ½ O2  C2H3Cl + H2O............. (6)
Advantages:
– Highly exothermic Rxn (5) achieves 95% conversion to
C2H4Cl2 in the presence of CuCl2 catalyst, followed by
cracking in Rxn (4)
– Excellent candidate when cost of HCl is low
Disadvantages:
– Economics dependent on the cost of HCl

13
 Reaction path 5
Balanced Process for Chlorination of Ethylene:
C2H4 + Cl2  C2H4Cl2……………………...…….(3)
C2H4 + 2HCl + ½ O2  C2H4Cl2 + H2O……….(5)
C2H4Cl2  C2H3Cl + HCl……………………......(4)
____________________________________________________
2C2H4 + Cl2 + ½ O2  2C2H3Cl + H2O……....(7)
Advantages:
– Combination of reaction path 3 and 4
– All Cl2 converted to VC
– No by-products other than water.

14
 Reaction pathway screening
Decision I: Reaction path 1 is eliminated due to
low selectivity.

The other 4 reaction pathways will be screened

base on “gross profit analysis”.

15
Gross profit analysis−chemical
prices
Chemical Cost (¢/lb)
Ethylene 18
Acetylene 50
Chlorine 11
Vinyl chloride 22
Hydrogen chloride 18
Water 0
Oxygen (air) 0

16
 Gross profit analysis – Reaction path 3
C2H4 + Cl2  C2H4Cl2......................(3)
C2H4Cl2  C2H3Cl + HCl.................(4)
_____________________________________
C2H4 + Cl2  C2H3Cl + HCl............ (1)

Gross profit = 22(1) + 18(0.583) - 18(0.449) - 11(1.134) = 11.94 cents/lb VC

17
 Gross profit summary

Gross profit for reaction path 2 is negative

– Acetylene is very expensive compared to ethylene
– How would the gross profit vary with the price of HCl?
18
 Reaction pathway screening
(cont’d)
Decision II: Reaction Path 2 is eliminated due to
negative gross profit.

– This leaves three alternative paths

 Develop preliminary flow sheets

19
 Synthesis tree
1 Direct chlorination of ethylene ✗ Low selectivity

2 Hydrochlorination of acetylene ✗ Gross profit<0

Synthesis Thermal cracking of dichloroethane (C2H4Cl2) from

3
tree chlorination of ethylene (C2H4)

Thermal cracking of C2H4Cl2 from oxychlorination of

4
C2H4

5 Balanced process for chlorination of ethylene

20
 Preliminary process synthesis
Step 2: Distribute the chemicals.

Raw
Materials Chemical Plant Products

(sources) (sink)

21
 Preliminary flowsheet for path 3
800 million lb/year @ 330 days/y ⇒
– ~100,000 lb/hr VC = 1,600 lbmol/h

– Next step involves distributing the chemicals by

matching sources and sinks

22
 Preliminary flowsheet for path 3
distributing the chemicals by matching sources
and sinks

23
 Preliminary flowsheet – mass
balance
VC: 100,000 lb/hr = 1,600 lbmol/h
HCl: 1,600 lbmol/h = 58,300 lb/hr
Cl2: 1,600 lbmol/h = 113,400 lb/hr
C2H4: 1,600 lbmol/h = 44,900 lb/hr

24
 Preliminary flowsheet for path 3
Only 60% of the C2H4Cl2 is converted to C2H3Cl with a
byproduct of HCl, according to Rxn (4)
C2H4Cl2  C2H3Cl + HCl.................(4)

25
 Preliminary flowsheet for path 3
To satisfy the overall material balance, 158,300 lb/h
of C2H4Cl2 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 =
[(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 un-reacted C2H4Cl2, from a mixing operation, the two
sources are combined, to give a total 263,800 lb/h

26
 Preliminary flowsheet for path 3
The effluent stream from the pyrolysis operation is the
source for the C2H3Cl product, the HCl by-product, and
the C2H4Cl2 recycle

27
 Preliminary flowsheet – reactor P
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.
– High pressure to reduce the size of the pyrolysis furnace;
although the tube walls must be thicker and many precautions
are necessary.

The pressure level is also an important consideration in

selecting the separation operations

28
 Preliminary process synthesis
Step 3: Eliminate the difference in chemical
composition by separation.
Raw Chemical Plant
Materials Products
Physical Chemical Physical
Treatment Treatment Treatment

29
 Eliminate difference in composition
Needs for separation:

– 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 sinks.

30
 Separation system – path 3
What are the basis for design sequence?

31
 Separation sequence alternatives
Seq-1 Seq-2 HCl
HCl
C2H3Cl
HCl
HCl C2H3Cl
C2H3Cl C2H4Cl2
C2H4Cl2

C2H3Cl
C2H4Cl2 C2H4Cl2

HCl

HCl
C2H3Cl C2H3Cl Seq-3
C2H4Cl2

C2H4Cl2 32
 Separation sequence alternative
The large difference in volatility is a driving force for
separation, and an important parameter in decision
making for the optimal separation sequence.

33
 Separation conditions
Column 1: P = 12 atm, recommended by the patent
– P = 1 atm, boiling point of HCl is very low, i.e. very
costly refrigeration is necessary.
– P = 26 atm, same as reactor P.
Column 2: P = 4.8 atm, recommended by the patent.

HCl
C2H3Cl

HCl
C2H3Cl
C2H4Cl2

C2H4Cl2
34
Synthesis tree

35
 Preliminary process synthesis
Step 4: Eliminate the difference in T, P, Phase.

36
 Preliminary process synthesis
Step 5: Task integration.

37
Assembly of synthesis tree






38
Development of base case design

39