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CHEMICAL PROCESS INDUSTRY

LECTURE 2

Process Creation

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.

Ref: Seider, Seader and Lewin (1999), Chapter 2

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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

Literature and Information Sources

Company context - employees, company files, open literature provide :
Product info (related), thermophysical properties, transport data,
flowsheets, equipment descriptions, process models.
National Laboratories and Research Institute Reports e.g. SRI International, NIST,
NIOSH.
Encyclopedias (technical, chemical process and technology).
Handbooks and Reference Books (Perry’s Chemical Engineer’s Handbook, CRC
Handbook of Physics and Chemistry)
Journals (Book format, electronic format)
Indexes (INSPEC, COMPENDEX, SCIENCE CITATION INDEX)
Patents (U.S. Patent Office www.uspto.gov/patft )
Auxiliary Studies (e.g. technical feasibility, marketing, business related)
Innovation (e.g 3M)

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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.
 Process operations (unit operations) - flowsheet building blocks
 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?

Continuous

Batch

Fed-batch

Batch-product removal

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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.
• Phase separation
• Change of temperature
• Change of pressure
• Change of phase
• Mixing and splitting of streams and branches

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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 and
temperature, pressure and phase change
phase
 Integrate tasks (combine tasks
into unit operations)

Process Creation

Example 1:

Vinyl Chloride Manufacture

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Assess Primitive Problem

• Process design begins with a primitive design problem that
expresses the current situation and provides an opportunity to
satisfy a societal need.
• Normally, the primitive problem is examined by a small design team,
who begins to assess its possibilities, to refine the problem
statement, and to generate more specific problems:
– Raw materials - available in-house, can be purchased or need to be
manufactured?
– Scale of the process (based upon a preliminary assessment of the
current production, projected market demand, and current and
projected selling prices)
– Location for the plant
• Refined through meetings with engineering technical management,
business and marketing.
• Brainstorming to generate alternatives

Example: VC Manufacture
• To satisfy the need for an additional 800 MMlb/yr of VCM, the
following plausible alternatives might be generated:
Alternative 1. A competitor’s plant, which produces 2 MMM lb/yr of
VCM and is located about 100 miles away, might be expanded to
produce the required amount, which would be shipped. In this case, the
design team projects the purchase price and designs storage facilities.
Alternative 2. Purchase and ship, by pipeline from a nearby plant,
chlorine from the electrolysis of NaCl solution. React the chlorine with
ethylene to produce the monomer and HCl as a byproduct.
Alternative 3. Since the existing company produces HCl as a byproduct
in large quantities are produced, HCl is normally available at low prices.
Reactions of HCl with acetylene, or ethylene and oxygen, could produce
1,2-dichloroethane, an intermediate that can be cracked to produce
vinyl chloride.

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 Eliminate differences in molecular types

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

Selection of pathway to VCM (1)

 Direct chlorination of ethylene:
C2H4 + Cl2 → C2H3Cl + HCl (2.1)

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 by-product,
which may not be sold easily.

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Selection of pathway to VCM (2)

 Hydrochlorination of acetylene:

C2H2 + HCl → C2H3Cl (2.2)

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%)

Selection of pathway to VCM (3)

 Thermal cracking of C2H4Cl2 from chlorination of C2H4:
C2H4 + Cl2 → C2H4Cl2 (2.3)

C2H4Cl2 → C2H3Cl + HCl (2.4)

C2H4 + Cl2 → C2H3Cl + HCl (2.1)

Advantages:
– Conversion of ethylene to 1,2-dichloroethane in exothermic reaction (2.3) 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 (2.4), 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.

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Selection of pathway to VCM (4)

 Thermal Cracking of C2H4Cl2 from Oxychlorination of C2H4:
(2.5)
C2H4 + 2HCl + 21 O2 → C2H4Cl2 + H2O
C2H4Cl2 → C2H3Cl + HCl (2.4)

C2H4 + HCl + 21 O2 → C2H3Cl + H2O (2.6)

Advantages:
– Highly exothermic reaction (2.5) achieves a 95% conversion to C2H4Cl2 in
the presence of CuCl2 catalyst, followed by pyrolysis step (2.4) 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

Selection of pathway to VCM (5)

 Balanced Process for Chlorination of Ethylene:
C2H4 + Cl2 → C2H4Cl2 (2.3)
C2H4 + 2HCl + 21 O2 → C2H4Cl2 + H2O (2.5)
2C2H4Cl2 → 2C2H3Cl + 2HCl (2.4)

2C2H4 + Cl2 + 21O2→ 2C2H3Cl + H2O (2.7)

Advantages:
– Combination of Reaction Paths 3 and 4 - addresses Alternative 2.
– All Cl2 converted to VC
– No by-products!

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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

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

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Preliminary Flowsheet for Path 

Cl2 HCl
113,400 lb/hr 58,300 lb/hr
Raw Materials C2H4Cl2 Products
Process Flowsheet?
HCl
C2H4,Direct
Cl2 Pyrolysis C2H3Cl, HCl
Chlorination
C2H3Cl
C2H4Cl2
C2H4 + Cl2 C2H4Cl2 C2H3Cl
C2H4 C2H4Cl2 C2H3Cl + HCl
100,000 lb/hr
44,900 lb/hr

• 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.

 Distribute the chemicals

• A conversion of 100% of the C2H4 is assumed in the chlorination reaction.

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 Distribute the chemicals

• Only 60% of the C2H4Cl2 is converted to C2H3Cl with a byproduct of HCl,
according to Eqn. (2.4).
• 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.

 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.

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 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.

 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.

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

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 EliminateBoiling
Differences
point (oC) in Composition
Critical constants

Chemical 1 atm 4.8 atm 12 atm 26 atm T c,°C Pc, atm

HCl -84.8 -51.7 -26.2 0 51.4 82.1

C 2H 3Cl -13.8 33.1 70.5 110 159 56

C2H 4Cl2 83.7 146 193 242 250 50

There may be other, possibly better alternative configurations, as discussed

in Lecture 4 (Chapter 5).

 Eliminate differences in T, P and phase

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 Integrate tasks (tasks ⇒ unit operations)

Development of Base-case Design

Develop one or two of the more promising flowsheets from the synthesis
tree for more detailed consideration.

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Homework II
• Review assigned projects, form the project team, and submit the project
design constraints and criteria
Project design: UMORE park is a 5,000-acre property located 25 miles southeast of the Twin Cities in Dakota County. The
university is envisioned to build an environmental friendly community in the next two to three decades focusing on
innovations in many areas for example renewable energy. Instead of changing agricultural land to metro blocks, we are
making this fake projects to study the feasibility of producing ethanol, butanol or PLA from this agricultural land. Students
are requested to estimate the annual agricultural products that can be generated from this land and provide an engineering
design of a process to produce the targeted product. Please work in a big team to generate the overall economic feasibility
study.
1. ethanol fermentation
2. ethanol distillation
3. butanol fermentation (ABE fermentation)
4. Butanol distillation
5. lactic acid fermentation
6. PLA production
Project design: Minnesota State Fair is one of the largest state fairs in the US and it attracts over one million visitors every
year. The organization committee “wants” to build a demonstration process to teach the general public how we can
convert our food waste oils to biodiesel. Please provide an engineering design of this project, working in a big
team to generate the overall economic feasibility study.
1. biodiesel proudction --- oil transesterification
2. biodiesel separation
3. glyceral utilization

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