TK 4153

Perancangan Proses Teknik Kimia

[Chemical Process Design]

Kuliah 2
Perancangan Proses Basic Chemicals
Program Sarjana Teknik Kimia UNRI
Semester Ganjil 2018/2019
 Outline
 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.
 Development of Base-case Design
focusing on the most promising alternative(s)
from the synthesis tree.
 Preliminary Database Creation
 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
 Experiments
to check on crucial items above
 Preliminary Process Synthesis
Synthesis of chemical processes involves:
Selection of processing mode: continuous or
batch
Fixing the chemical state of raw materials,
products, and byproducts, nothing the
differences between them.
Process operations (unit operations) - flowsheet
building blocks
 Preliminary Process Synthesis
Synthesis steps
 Eliminate differences in molecular types
 Distribute chemicals by matching sources and
sinks.
 Eliminate differences in composition
 Eliminate differences in temperature,
pressure and phase
 Integrate tasks (combine tasks into unit
operations )
Continuous or Batch Processing?
 The Chemical State
 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.
 Process Operations
 Chemical reaction
 Positioning in the flowsheet involves many
considerations (conversion, rates, etc.), related to
T and P at which the reaction are carried out.
 Separation of chemicals
 Needed to resolve difference between the desired
composition of a product stream and that of its
source. Selection of the appropriate method
depends on the differences of the physical
properties of the chemical species involved.
 Process Operations
 Phase separation
 Flash drums (vapor-liquid separation)
 Decanters (liquid-liquid separation)
 Filters and centrifuge (liquid-solid separation)
 Change of temperature
 Change of pressure
 Change of phase
 Mixing and splitting of streams and branches
 Synthesis Steps
Synthesis Step Process Operation
Eliminate differences in Chemical reaction
molecular types
Distribute chemicals by Mixing
matching sources and sinks
Eliminate differences in Separation
composition
Eliminate differences in Temperature, pressure
temperature, pressure and and phase change
phase
Integrate tasks (combine tasks
into unit operations )
 Example
Vinyl Chloride Manufacture
1. Eliminate differences in molecular types
 1. Eliminate differences in molecular types
Selection of pathway to VCM (1)
Direct chlorination of ethylene:
C2H4 + Cl2 → C2H3Cl + HCl .... (1)
Advantages:
• Attractive solution to the specific problem denoted as Alternative 2
in analysis of primitive problem.
• 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
byproduct, which may not be sold easily.
1. Eliminate differences in molecular types
Selection of pathway to VCM (2)
Hydrochlorination of acetylene:
C2H2 + HCl → C2H3Cl ..... (2)
Advantages:
• This exothermic reaction is a potential solution for the specific
problem denoted as Alternative 3. 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%)
1. Eliminate differences in molecular types
Selection of pathway to VCM (3)
Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4 + Cl2 → C2H4Cl2 ....(3)
C2H4Cl2 → C2H3Cl + HCl ....(4)
(3) + (4) C2H4 + Cl2 → C2H3Cl + HCl ....(1)
Advantages:
• Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (1) 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 (2), which occurs spontaneously at 500 oC 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.
 1. Eliminate differences in molecular types
Selection of pathway to VCM (4)
Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O .... (5)
C2H4Cl2 → C2H3Cl + HCl .... (4)
(5) + (4) C2H4 + HCl + ½ 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
• Solution for specific problem denoted as Alternative 3.
Disadvantages:
• Economics dependent on cost of HCl
1. Eliminate differences in molecular types
Selection of pathway to VCM (5)
Balanced Process for Chlorination of Ethylene
C2H4 + Cl2 → C2H4Cl2 ..(3)
C2H4 + 2HCl + ½ O2 → C2H4Cl2 + H2O ..(5)
C2H4Cl2 → C2H3Cl + HCl ..(4)
(3)+(5)+(4) 2C2H4 + Cl2 + ½ O2 → 2C2H3Cl + H2O ..(7)
Advantages:
• Combination of Reaction Paths 3 and 4 - addresses
Alternative 2.
• All Cl2 converted to VC
• No by-products!
1. Eliminate differences in molecular types
Evaluation of Alternative Pathways
 Reaction Path (1) is eliminated due its low
selectivity.
 This leaves four alternative paths, to be
compared first in terms of Gross Profit.
1. Eliminate differences in molecular types
Computing Gross Profit
Reaction path (3) C2H4 + Cl2  C2H3Cl + HCl
Overall Reaction C2H4 Cl2 C2H3Cl HCl
Lb-mole 1 1 1 1
Molecular weight 28.05 70.91 62.50 34.46
lb 28.05 70.91 62.50 34.46
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 cent/lb VC
 1. Eliminate differences in molecular types
Computing Gross Profit
Gross Profit
Reaction
Overall Reaction (cents/lb of
Path VC)

(2) C2H2 + HCl → C2H3Cl -9.33

(3) C2H4 + Cl2 → C2H3Cl + HCl 11.94
(4) C2H4 + HCl + ½ O2 → C2H3Cl + H2O 3.42
(5) 2C2H4 + Cl2 + ½ O2 → 2C2H3Cl + H2O 7.68
 Preliminary Flowsheet for Path (3)

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.
2. Distribute the chemicals
A conversion of 100% of the C2H4 is assumed in
the chlorination
 2. Distribute the chemicals
 Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct
of HCl, according to Reaction Eqn. (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.
2. Distribute the chemicals
 The effluent stream from the pyrolysis operation is
the source for the C2H3Cl product, the HCl by-
product, and the C2H4Cl2 recycle
 2. Distribute the chemicals
 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.
 3. Eliminate Differences in Composition
 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.
 One possible arrangement is given in the next slide. The
data below explains the design decisions made.
3. Eliminate Differences in Composition

Other, possibly better configurations, will be discussed in Chapter 8

4. Eliminate differences in T, P and phase
5. Integrate tasks (tasks ⇒ unit operations)
 Assembly of synthesis tree
Reaction Distribution Separations T, P and Task
path of chemicals phase integration
changes





 Development of Base-case Design
Develop one or two of the more promising flow sheets from the
synthesis tree for more detailed consideration.
 Example 2:
Manufacture of Tissue Plasmonigen
Activator (tPA)
Manufacture of tPA
Manufacture of tPA
Process Synthesis Problem
1. Eliminated Differences in Molecular Type
1. Eliminated Differences in Molecular Type
Computing Gross Profit
Computing Gross Profit
Insert Reaction Operation into
Flowsheet
2. Distribute the Chemical
3. Eliminated Differences in
Composition
3. Eliminated Differences in
Composition
4. Eliminated Differences in
Temperature
5. Integrate tasks (tasks ⇒ unit
operations)
5. Task Integration – Reactor Section
5. Task Integration – Separation Section
tPA Synthesis Tree
 Process Creation - Summary
 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
• top-down approach.
• generates a “synthesis tree” of design alternatives.
• illustrated by the synthesis of the VCM and tPA processes.
 Development of Base-case Design
• focusing on the most promising alternative(s) from the
synthesis tree.