Complete Lecture Notes

Process Economics
Process Economics Process Design Slide 1

Based on: Analysis, Synthesis and Design of Chemical Processes, Third Edition by Turton, Bailie, Whiting and Shaeiwitz
Outline
• Capital Cost Estimation
• Cost of Manufacturing
• Economic Analysis
• Profitability Analysis

Capital Cost Estimation
• Types of estimate
• Adjusting for changes in size and time
• Estimating total plant costs
– Lang Factors
– Module Factor Approach

Types of Capital Cost Estimate

1. Order of Magnitude Estimate (Feasibility)
• + 40%, − 20%
• Block Flow Diagram
2. Study Estimate / Major Equipment
• + 30%, − 20%
• PFD , Equipment Cost Charts
3. Preliminary Design (Scope) Estimate
• + 25%, − 15%
• PFD , vessel sketches , equip. diagrams

Types of Capital Cost Estimate
4. Definitive (Project Control) Estimate
• + 15%, − 7%
• PFD , P&ID, all vessel sketches, equip. diagrams,
• 5. Detailed (Firm or Contractors) Estimate
• + 6%, − 4%
• Everything included: ready to go to construction phase

Cost of Estimate
Error
1
2
3
4
5
Cost of Estimate (Engineering time)

Estimating Purchased Equipment
Costs
• Vendor quote
– Most accurate
- based on specific information
- requires significant engineering
• Use previous cost on similar equipment and scale for time
and size
– Reasonably accurate
- Beware of large extrapolation
• Use cost estimating charts and scale for time
– Less accurate
– Convenient

Effect of Size (Capacity)

Keeping everything else the same (type of equipment, materials
construction, pressure rating), it is often found that the cost of two
pieces of the same equipment with different sizes (capacities) are
related by: ௡
‫ܥ‬௔ ‫ܣ‬௔
ൌ
‫ܥ‬௕ ‫ܣ‬௕
Where ‫ ܥ‬is the cost of the equipment, ‫ ܣ‬is the size or capacity of the
equipment, subscripts ܽ and ܾ refer to the two pieces of equipment
and ݊ is the cost exponent.
• Typically ͲǤͶ ൏ ݊ ൏ ͲǤͺ
• Often ݊ ൎ ͲǤ͸ (the six-tenths rule)
• An order-of-magnitude estimate of the total capital cost can be
obtained by taking ݊ ൌ ͲǤ͸ and scaling up (or down) with the
capacity (production rate)

Example 1
A floating head heat exchangers with area 100 m2 costs $92,000. How
much would a heat exchanger for a similar application cost if it had an
area of 50 m2 and n = 0.44?
Solution:
ହ଴ ଴Ǥସସ
ୟ ൌ ͻʹǡͲͲͲ ൌ ̈́͸͹ǡ͵ͲͲ
ଵ଴଴
• A 100 m2 exchanger costs less than two 50 m2 exchangers.

• This is sometimes called economy of scale.
• However there is a limit to the size of any piece of equipment

Effect of Time
• Inflation causes costs to rise over time.
• Cost indexes track changes in price over time.
– Chemical Engineering Plant Cost Index (CEPCI): Publically available;
widely used
– Marshall and Swift Process Industry Index (M&S): Widely used in the
past; no longer publically available
‫ܥ‬ଶ ൌ ‫ܥ‬ଵ ‫ܫ‬ଶ Τ‫ܫ‬ଵ
Where C = Cost, I = Value of cost index and 1,2 represent points in time at
which costs required or known and index values known
• Cost indexes are based on the cost of a “basket of goods” typical for
construction of chemical plants – see the following table.

Effect of Time
Nelson Farrar Refinery
Construction Index
(1946 value = 100)
Marshall and Swift

Process Industry Index
(1926 value = 100)
Engineering News – Record

Construction Index
(1967 value = 100)
Chemical Engineering
Plant Cost index
(1957 value = 100)

CEPCI Basis
Components of Index Weighting of Component (%)
Equipment, Machinery and Supports:
(a) Fabricated Equipment 37

(b) Process Machinery 14
(c) Pipe, Valves, and Fittings 20
(d) Process Instruments and Controls 7
(e) Pumps and Compressors 7
(f) Electrical Equipment and Materials 5
(g) Structural Supports, Insulation, and Paint 10
100% (61 % of total)
Installation Labor 22
Buildings, Materials, and Labor 7
Engineering and Supervision 10
Total 100

Example 2
The cost of a vessel in 1993 (CEPCI=359) was $25,000. What is the estimated
cost in 2007 (CEPCI=500)?
Answer:
‫ܫ‬ଶ଴଴଻ ͷͲͲ
‫ܥ‬ଶ଴଴଻ ൌ ‫ܥ‬ଵଽଽଷ ൌ ʹͷǡͲͲͲ ൌ ̈́͵ͶǡͺʹͲ
‫ܫ‬ଵଽଽଷ ͵ͷͻ

Example 3
Two heat exchangers were bought at different times for the same service
Exchanger A Exchanger B
Area 70 m2 130 m2
Cost $17,000 $24,000
Year 1990 1995
CEPCI 358 381
What is the estimated cost of a 80 m2 heat exchanger in 2007 (CEPCI = 500)?

Example 3 - Solution
First bring costs to 2007:
ହ଴଴ ହ଴଴
‫ܥ‬௔ ሺʹͲͲ͹ሻ ൌ ͳ͹ ൌ ̈́ʹ͵ǡ͹Ͷ͵ ‫ܥ‬௕ ሺʹͲͲ͹ሻ ൌ ʹͶ ൌ ̈́͵ͳǡͶͻ͸
ଷହ଼ ଷ଼ଵ
Then solve for n:
‫ ܥ‬ൌ ‫ܣܭ‬௡
̈́ʹ͵ǡ͹Ͷ͵ ൌ ‫ ܭ‬͹Ͳ ௡
̈́͵ͳǡͶͻ͸ ൌ ‫ Ͳ͵ͳ ܭ‬௡
͵ͳǡͶͻ͸ െ ሺʹ͵ǡ͹Ͷ͵ሻ
݊ൌ ൌ ͲǤͶͷ͸ͷ
ͳ͵Ͳ െ ሺ͹Ͳሻ
‫ܥ‬ ʹ͵ǡ͹Ͷ͵
‫ ܭ‬ൌ ௡ ൌ ଴Ǥସହ଺ହ ൌ ̈́͵ǡͶͳͶ
‫ܣ‬ ͹Ͳ
‫ ܥ‬ൌ ͵ǡͶͳͶ ͺͲ ଴Ǥସହ଺ହ ൌ ̈́ʹͷǡʹ͵ͷ

Installed Cost of Equipment

Purchase cost is the cost paid to the manufacturer or vender of
the equipment. Installed cost is greater (often 3 to 8 times
greater) because it also includes:
• Direct Project Expenses
• Equipment
• Material for installation
• Labor for installation
• Indirect Project Expenses
• Freight, insurance, and taxes
• Construction overhead
• Contractor engineering expenses
• Contingency and Fee
• Contingency
• Contractor fee
• Auxiliary Facilities
• Site development
• Auxiliary buildings
• Off-sites and utilities
Lang Factors
In the Lang Factor method, total installed cost (Total Module Cost, ‫்ܥ‬ெ ) is
estimated by multiplying the purchase cost of major equipment by a Lang
Factor:
Flang = 4.74 Fluid processing plant
= 3.63 Solid-Fluid processing plant
= 3.10 Solid processing plant
௡
‫்ܥ‬ெ ൌ ‫୐ܨ‬ୟ୬୥ ෍ ‫ܥ‬௣௜

௜ୀଵ
‫்ܥ‬ெ : Total Module Cost
‫ܥ‬௣௜ : Purchased Cost of each piece of major equipment

Module Factor Approach

‫ܥ‬஻ெ ൌ ‫ܥ‬௣௢ ‫ܨ‬஻ெ
‫ܥ‬஻ெ : bare module cost

‫ܥ‬௣଴ : purchased equipment cost for carbon steel and 1 atm
‫ܨ‬஻ெ : Accounts for pressure, materials of construction and installation cost.
‫ܨ‬஻ெ ൌ ‫ܤ‬ଵ ൅ ‫ܯܨ݌ܨʹܤ‬

Fp: pressure factor (= 1 for 1 bar)
FM: is the material of construction factor (=1 for carbon steel (CS))
The bare module cost ‫ܥ‬஻ெ can be determined if ‫ܥ‬௣଴ , ‫ܤ‬ଵ , ‫ܤ‬ଶ , ‫ܨ‬௣ and ‫ܨ‬௠ are
known. These can be determined from tables in Appendix A of the reference
textbook. For illustrative purposes, tables for heat exchangers are included in
these lecture notes. Data are for 2001 when the CEPCI had a value of 397.

B1 B2
Heat Exchangers Double pipe, multiple pipe, scraped wall, and
1.74 1.55
spiral tube
Fixed tube sheet, floating head, U-tube,
1.63 1.66
bayonet, Kettle reboiler, and Teflon tube
Air cooler, spiral plate, and flat plate 0.96 1.21
Process vessels Horizontal 1.49 1.52
Vertical (including towers) 2.25 1.82
Pumps Reciprocating 1.89 1.35
Positive displacement 1.89 1.35
Centrifugal 1.89 1.35


ଵ଴ ‫ܥ‬௣଴ ൌ ‫ܭ‬ଵ ൅ ‫ܭ‬ଶ ଵ଴ ‫ ܣ‬൅ ‫ܭ‬ଷ ଵ଴ ‫ܣ‬ ଶ
K1 K2 K3 Capacity Min size Max size

Scraped wall 3.7803 0.8569 0.0349 Area, m2 2 20
Teflon tube 3.8062 0.8924 -0.1671 Area, m2 1 10
Bayonet 4.2768 -0.0495 0.1431 Area, m2 10 1000
Floating head 4.8306 -0.8509 0.3187 Area, m2 10 1000
Fixed tube 4.3247 -0.303 0.1634 Area, m2 10 1000
U-tube 4.1884 -0.2503 0.1974 Area, m2 10 1000
Kettle reboiler 4.4646 -0.5277 0.3955 Area, m2 10 100
Double pipe 3.3444 0.2745 -0.0472 Area, m2 1 10
Multiple pipe 2.7652 0.7282 0.0783 Area, m2 10 100
Flat plate 4.6656 -0.1557 0.1547 Area, m2 10 1000
Spiral plate 4.6561 -0.2947 0.2207 Area, m2 1 100
Air cooler 4.0336 0.2341 0.0497 Area, m2 10 10000
Spiral tube 3.9912 0.0668 0.243 Area, m2 1 100

Pressure Factor ଶ
ଵ଴ ‫ܨ‬௉ ൌ ‫ܥ‬ଵ ൅ ‫ܥ‬ଶ ଵ଴ ܲ ൅ ‫ܥ‬ଷ ଵ଴ ܲ
Heat Exchanger Type C1 C2 C3 Range (barg)
Scraped Wall 0 0 0 P< 40
0.6072 -0.912 0.3327 40< P< 100
13.1467 -12.6574 3.0705 100< P< 300
Teflon tube 0 0 0 P< 15
Bayonet, fixed tube sheet, floating head, kettle 0 0 0 P< 5
reboiler, and U-tube (both shell and tube) 0.03881 -0.11272 0.08183 5<P<140
Bayonet, fixed tube sheet, floating head, kettle 0 0 0 P< 5
reboiler, and U-tube (tube only) -0.00164 -0.00627 0.0123 5<P<140
Double pipe and multiple pipe 0 0 0 P<40
0.6072 -0.912 0.3327 40<P<100
13.1467 -12.6574 3.0705 100<P<300
Flat plate and spiral plate 0 0 0 P<19
Air Cooler 0 0 0 P<10
-0.125 0.15361 -0.02861 10<P<100
Spiral tube (both shell and tube) 0 0 0 P<150
-0.4045 0.1859 0 150<P<400
Spiral tube (tube only) 0 0 0 P<150
-0.2115 0.09717 0 150<P<400

Materials of construction
Heat Exchanger Type Material of Construction FM
Double pipe, multiple pipe, fixed tube CS-shell/ CS-tube 1.0
sheet, floating head, U-tube, bayonet, kettle CS-shell / Cu-tube 1.3
reboiler, scraped wall, and spiral tube Cu-shell / Cu-tube 1.7
CS-shell / SS-tube 1.8
SS-shell / SS-tube 2.7
CS-shell / Ni alloy tube 2.7
Ni alloy, shell / Ni alloy-tube 3.7
CS-shell / Ti-tube 4.6
Ti-shell / Ti-tube 11.3
Air cooler CS tube 1.0
Al tube 1.4
SS tube 2.9
Flat plate and spiral plate CS (in contact with fluid) 1.0
Cu (in contact with fluid) 1.3
SS (in contact with fluid) 2.5
Ni alloy (in contact with fluid) 2.7
Ti (in contact with fluid) 4.6

Illustrative Example
Determine the bare module cost ‫ܥ‬஻ெ of a stainless steel shell-and-tube heat
exchanger in 2001 with a heat exchange area of 100 m2 rated for 100 bar
pressure.
Answer: B1=1.63; B2=1.66
K1= 4.8306; K2= −0.8509; K3= 0.3187
C1=0.03881; C2= − 0.11272; C3=0.08183
FM=2.7
ଵ଴ ‫ܥ‬௣଴ ൌ ‫ܭ‬ଵ ൅ ‫ܭ‬ଶ ଵ଴ ‫ ܣ‬൅ ‫ܭ‬ଷ ଵ଴ ‫ܣ‬ ଶ ‫ܥ‬௣଴ ൌ ̈́ʹͷǡ͵ͲͲ
ଵ଴ ‫ܨ‬௉ ൌ ‫ܥ‬ଵ ൅ ‫ܥ‬ଶ ଵ଴ ܲ ൅ ‫ܥ‬ଷ ଵ଴ ܲ ଶ ‫ܨ‬௉ ൌ ͳǤ͵ͺ
‫ܨ‬஻ெ ൌ ‫ܤ‬ଵ ൅ ‫ܯܨ݌ܨʹܤ‬ ‫ܨ‬୆୑ ൌ ͹Ǥͺ͵
‫ܥ‬஻ெ ൌ ‫ܥ‬௣௢ ‫ܨ‬஻ெ ‫ܥ‬஻ெ ൌ ̈́ͳͻͺǡͲͲͲ

Total-Module and Grass-Roots Costs

The total module cost includes contingency and fees at 15% and 3% of the
bare module cost respectively:
‫்ܥ‬ெ ൌ ͳǤͳͺ ෍ ‫ܥ‬஻ெ
The total module cost of grass-roots plants (a brand new plant site with no
existing facilities) can be determined by:
଴
‫ீܥ‬ோ ൌ ‫்ܥ‬ெ ൅ ͲǤͷͲ ෍ ‫ܥ‬஻ெ
଴
‫ܥ‬஻ெ is ‫ܥ‬஻ெ calculated with ‫ ݌ܨ‬ൌ ‫ܨ‬ெ ൌ ͳ (The additional cost of a grass-roots
facility should not depend on the pressure or materials of construction of the
major units.)

Summary
• In general, information about costs must be scaled

for capacity and time using appropriate cost
exponents and indices
• Total plant costs involve a variety of factors that
vary with equipment type, operating pressure, and
materials of construction.
• For additions to existing facilities, the total module
cost should be used but for totally new projects
grass roots costs are appropriate.

Outline

Outline
We consider three types of operating costs:
Direct Costs
• Vary with production rate but not necessarily directly proportional
Fixed Costs
• Do not vary with production rate but relate “directly” to production function
General Expenses
• Functions to which operations must contribute – overhead burden

Estimation of Manufacturing Costs

Direct Costs
• Raw Materials Fixed Costs
• Waste Treatment • Depreciation
• Utilities • Local Taxes and Insurance
• Operating Labor • Plant Overhead Costs
• Supervisory and Clerical Labor General Expenses
• Maintenance and Repairs • Administration Costs
• Operating Supplies • Distribution and Selling Costs
• Laboratory Charges • Research and Development
• Patents and Royalties

Manufacturing Costs
Direct Manufacturing Costs
Raw materials ‫ܥ‬ோெ
Waste treatment ‫ܥ‬ௐ்
Utilities ‫ܥ‬௎்
Operating labor ‫ܥ‬ை௅
Direct supervisory and clerical labor ͲǤͳͺ‫ܥ‬ை௅
Maintenance and repairs ͲǤͲ͸‫ܫܥܨ‬
Operating supplies ͲǤͲͻ‫ܫܥܨ‬
Laboratory charges ͲǤͳͷ‫ܥ‬ை௅
Patents and royalties ͲǤͲ͵‫ܯܱܥ‬
‫( ܫܥܨ‬Fixed Capital Investment) is ‫்ܥ‬ெ or ‫ீܥ‬ோ from capital cost estimation.

‫ ܯܱܥ‬is the cost of manufacture that we want to determine.

Manufacturing Costs
Fixed Manufacturing Costs
Depreciation ͲǤͳ‫ܫܥܨ‬
Local taxes and insurance ͲǤͲ͵ʹ‫ܫܥܨ‬
Plant overhead costs ͲǤ͹Ͳͺ‫ܥ‬ை௅ ൅ ͲǤͲ͵͸‫ܫܥܨ‬
General Manufacturing Expenses

Administration Costs ͲǤͳ͹͹‫ܥ‬ை௅ ൅ ͲǤͲͲͻ‫ܫܥܨ‬
Distribution and selling costs ͲǤͳͳ‫ܯܱܥ‬
Research and development ͲǤͲͷ‫ܯܱܥ‬

Manufacturing Costs
Adding everything up and solving for ‫ܯܱܥ‬:
‫ ܯܱܥ‬ൌ ͲǤʹͺͲ‫ ܫܥܨ‬൅ ʹǤ͹͵‫ܥ‬ை௅ ൅ ͳǤʹ͵ ‫ܥ‬௎் ൅ ‫ܥ‬ௐ் ൅ ‫ܥ‬ோெ
To determine the cost of manufacture, we must first determine:

• ‫ܥ‬ை௅ (cost of operating labor)
• ‫ܥ‬ோெ (cost of raw materials)
• ‫ܥ‬௎் (cost of utilities)
• ‫ܥ‬ௐ் (cost of waste treatment)

Cost of Operating Labor

଴Ǥହ
ܰை௅ ൌ ͸Ǥʹͻ ൅ ͵ͳǤ͹ܲଶ ൅ ͲǤʹ͵ܰ௡௣
NOL = the number of operators per shift

P = particulate processing steps
Nnp = non-particulate processing steps – compression,
heating/cooling, mixing, separation, and reaction
Liquid pumps and vessels are not included in the calculations.

This equation is based on data from chemical plants and refineries where the number
of particle processing steps is low. For units with more than 2 particle processing
steps ignore middle term and add 1 operator per particle processing step.

Example
How many operators are required for the DME process shown on the next slide?
What is the cost of operating labor (‫ܥ‬ை௅ ) if workers are paid $60,000/yr?

Example: DME Process

V-201 E-201 E-203 T-201 E-204 E-205 DME V-202 DME P-202 A/B E-206 T-202 E-207 V-203 P-203 A/B E-208
Feed Methanol DME DME DME Condenser Reflux DME Reflux Methanol Methanol Methanol Methanol Methanol Wastewater
Vessel Preheater Cooler Tower Reboiler Drum Pumps Reboiler Tower condenser Reflux Drum pumps Cooler
P-201 A/B Feed E-202 Reactor R-201
Pump Cooler Reactor

Example: DME Process
Equipment Type Included?
V-201 Feed Vessel Vessel ಊ
E-201 Methanol Preheater Heat exchanger ‫ض‬
E-203 DME Cooler Heat exchanger ‫ض‬
T-201 DME Tower Tower ‫ض‬
E-204 DME Reboiler Heat exchanger ‫ض‬
E-205 DME Condenser Heat exchanger ‫ض‬
V-202 DME Reflux Drum Vessel ಊ
P-202 A/B DME Reflux Pumps Pumps ಊ
E-206 Methanol Reboiler Heat exchanger ‫ض‬
T-202 Methanol Tower Tower ‫ض‬
E-207 Methanol condenser Heat exchanger ‫ض‬
V-203 Methanol Reflux Drum Heat exchanger ‫ض‬
P-203 A/B Methanol pumps Pumps ಊ
E-208 Wastewater Cooler Heat exchanger ‫ض‬
P-201 A/B Feed Pump Pumps ಊ
E-202 Reactor Cooler Heat exchanger ‫ض‬
R-201 Reactor Reactor ‫ض‬
Solution
ܱܰ‫ ܮ‬ൌ ͸Ǥʹͻ ൅ ͵ͳǤ͹ Ͳ ʹ ൅ ͲǤʹ͵ ͳʹ ଴Ǥହ ൌ ͵ǤͲͲ
If operators work five eight-hour shifts per week, 49 weeks per year:
(49 wk/yr)(5 shifts/operator/wk) = 245 shifts/operator/year
Total shifts per year = (365)(3 shifts per day) = 1095 shifts/year
1095 / 245 = 4.5 operators
Therefore 4.5 operators are required to staff a single position during continuous
operation.
Total number of operators:
͵ǤͲͲ ൈ ͶǤͷ ൌ ͳ͵Ǥͷ (round up to 14)
‫ܥ‬ை௅ ൌ ͸ͲǡͲͲͲ ൈ ͳͶ ൌ ͺͶͲǡͲͲͲ ̈́Ȁ

Cost of Raw Materials, Utilities,
and Waste Treatment
Costs of raw materials, utilities and waste treatment depend on what
fraction of the year the process is operational. Continuous plants commonly
shut down for two weeks or so each year for cleaning and maintenance. The
stream factor is the fraction of time each year that the plant is operational.
If the plant is shut down for two weeks each year, then the stream factor is
50/52≈0.96
The most reliable source of information is a quotation from a supplier. Costs

of a small number of commodity chemicals are published, for example in
the Chemical Market Reporter. Prices change due to market forces as well as
inflation.
Costs of utilities can be estimated based on demand.

Utilities - Steam
• Large chemical complexes generate high pressure steam and use excess
pressure to generate electricity
• Steam is typically available at multiple pressure levels at different cost
– Low (30 – 90 psi)
– Medium (150 – 250 psi)
– High (525 – 680 psi)
• Steam is usually saturated but may be superheated
• Steam can be used as a drive medium for compressors and pumps and
may be directly injected into processes.
• Some processes generate surplus heat that can be used to produce steam
that can be contributed to the steam network.

Utilities - Steam

Utilities – Cooling
• Cooling water is almost always available. Excess heat is removed by
evaporation in a large cooling tower. Cooling water is commonly available
at about 30 °C and warm cooling water returned to the network should
have a temperature no greater than about 50 °C. Cooling water is cheap
but not free.
• If it is necessary to cool a process stream below about 40 °C (allowing for a
10 °C temperature driving force), refrigerated (or chilled) water will be
required. If the cooling medium must be less than 0 °C, a refrigerant is
required. The cost of chilled water and low-temperature refrigerant is
significantly greater than that of cooling water.

Utilities - Cooling Water
Make Up and Chemicals

Evaporation +
entrainment loss
30°C 40°C
Process
Purge
Utilities
Utility Description Cost $/GJ Cost (other units)
Pressurized and dried air
Compressed air 6 barg (90 psig) $0.49/100 std m3
3.3 barg (50 psig) $0.35/100 std m3
LP (5 barg, 160 °C) 13.28
Steam MP (10 barg, 184 °C) 14.19
HP (41 barg, 254 °C) 17.70
Cooling Water 30°C to 40 or 45 °C 0.354
Electricity 16.8 $0.06/kwh
Fuel oil no. 2 14.2
Fuels Natural gas 11.1
Coal (f.o.b. mine mouth) 1.72
These values are out of date and are provided for general reference only.

Utilities
Utility Description Cost $/GJ Cost (other units)
Refrigerated water (5 °C) 4.43
Refrigeration Low temperature (−20 °C) 7.89
Very low temp. (−50 °C) 13.11
Waste Disposal Nonhazardous $36/tonne
(solid and liquid) Hazardous $200–2000/tonne
Primary (filtration) $41/1000 m3
Secondary (filtration + $43/1000 m3
Waste Water activated sludge)
Treatment Tertiary (filtration + $56/1000 m3
activated sludge +
chemical treatment)
The cost of wastewater treatment may be much higher depending on the

contaminants and their concentrations.

Summary
Cost of manufacture (COM) can be estimated if the
fixed capital investment (FCI) is known from capital cost
calculations and the costs of labor (COL), utilities (CUT)
and raw materials (CRM) can be estimated.

Outline

Outline
• Interest Rates
• Cash Flow Diagrams
• Annuities and Discount Factors
• Depreciation
• Taxation, Cash Flow, and Profit
• Inflation

Interest
• Simple interest neglects compounding, that is the fact that we earn
interest on our interest. The simple interest rate is designated ݅௦ . On an
investment of ܲ dollars, we earn ܲ݅௦ dollars in interest each year. After ݊
years we have received ܲ݅‫ ݊ݏ‬dollars in interest and the value of the
investment is ܲ ൅ ܲ݅‫݊ݏ‬
• Compound interest (݅) accounts for the fact that we earn interest on our
interest. On an investment of ܲ dollars, one year later we have ଵ ൌ ܲሺͳ ൅
݅ሻ and after ݊ years we have ୬ ൌ ܲ ͳ ൅ ݅ ୬ dollars.
Example: How much would I need to invest at 8 % p.a. to yield $5000 in 10
years?
ͷͲͲͲ
ܲൌ ଵ଴ ൌ ̈́ʹ͵ͳͷǤͻ͹
ͳ ൅ ͲǤͲͺ

Cash Flow Diagrams

• Timings and magnitudes of cash flows (incoming or outgoing) can be
respresented on a cash flow diagram.
– x-axis is time and y-axis is magnitude
– both positive and negative cash flows are possible.
• The direction (sign) of a cash flow depends on the entity that is
considered.
Example: I borrow $20k from a bank repay $400 monthly for 5 years.
For Bank For Me
$400 $20,000
1 2 3… 60
1 2 3… 60
$400
$20,000
Cumulative CFD
• A cumulative cash flow diagram can also be constructed.

Calculations with CFDs

Example: Suppose I invest $5k, $1k, $2k at End of Years 0, 1, 3, and withdraw
$3k at End of Year 4. Draw a cash flow diagram. How much is in the account if
the interest rate is 8%? How much would have to be invested in year 0 to
have the same amount in year 7?
$5,000
$2,000
$1,000
4 7
0 1 3
$3,000
‫ ଻ܨ‬ൌ ͷǡͲͲͲ ͳ ൅ ͲǤͲͺ ଻ ൅ ͳͲͲͲ ͳ ൅ ͲǤͲͺ ଺ ൅ ʹͲͲͲ ͳ ൅ ͲǤͲͺ ସ െ ͵ͲͲͲ ͳ ൅ ͲǤͲͺ ଷ ൌ

̈́ͻͲͻ͹
ͻͲͻ͹ǤͺͶ
ܲൌ ൌ ̈́ͷ͵Ͳͻ
ͳǤͲͺ ଻

Taxation and Depreciation
• Taxation is very complicated. Tax laws vary from country to country and change
from year to year.
• Depreciation refers to the fact that capital equipment wears out and loses value
over time.
• A company that buys capital equipment would usually prefer to charge the entire
expense against their profit in the year of the purchase to lower their tax bill that
year.
• Governments generally do not allow this, but instead require the company to
report depreciation as an operating expense over a certain number of years.
• Depreciation is also complicated. The simplest method is the so-called “straight
line” method, in which the depreciation is spread evenly over a given number of
years. For example, if a company invests $10 million in capital, They might be
allowed to claim that the capital depreciates by $2 million each year for five years.

Cash Flow and Profit

Adding everything up, we have:
– Expenses = COMd + dk
– Income Tax = (R – COMd - dk)t
– After Tax (net)Profit =(R – COMd –dk)(1 – t)
– After Tax Cash Flow = (R – COMd – dk)(1 – t) + dk + Investment
COMd: cost of manufacture excluding depreciation

dk: depreciation in year k
R: revenue from sales
t: tax rate

Example
A new chemical plant is going to be built and will require the following capital
investments (all figures are in $million):
Cost of land, L= $10.0
Total fixed capital investment, FCIL = $150.0
Fixed capital investment during year 1 = $90.0;
Fixed capital investment during year 2 = $60.0
The plant will start-up at the end of year 2
Working capital = $30.0 at end of year 2
Yearly sales revenue (after start-up), R = $75.0 per year
Cost of manufacturing excluding depreciation, COMd = $30.0 per year
Taxation rate, t = 45%
Interest rate, i = 10%
Straight-line depreciation over five years.
Salvage value of plant, S = $10.0 Assume an operating life of 10 years.
Determine the after tax cash flow, cumulative after-tax cash flow, discounted cash flow
and cumulative discounted cash flow for each year of the project

Example
Cumulative
Year Investment dk R COMd (R-COMd)(1-t)+dk Cash Flow
Cash Flow
0 (10) ── ── ── ── (10) (10)
1 (90) ── ── ── ── (90) (100)
2 (60+30)=(90) ── ── ── ── (90) (190)
3 ── 30 75 30 38.25 38.25 (151.75)
4 ── 30 75 30 38.25 38.25 (113.5)
5 ── 30 75 30 38.25 38.25 (75.25)
6 ── 30 75 30 38.25 38.25 (37)
7 ── 30 75 30 38.25 38.25 1.25
8 ── ── 75 30 24.75 24.75 26
9 ── ── 75 30 24.75 24.75 50.75
10 ── ── 75 30 24.75 24.75 75.5
11 ── ── 75 30 24.75 24.75 100.25
12 10+30=40 ── 85 30 24.75 64.75 165

Example
Cumulative Discounted Cumulative Discounted
Year Cash Flow Cash Flow
Cash Flow Cash Flow
0 (10) (10) (10.00) (10.00)

1 (90) (100) (81.82) (91.82)
2 (90) (190) (74.38) (166.20)
3 38.25 (151.75) 28.74 (137.46)
4 38.25 (113.5) 26.13 (111.34)
5 38.25 (75.25) 23.75 (87.59)
6 38.25 (37) 21.59 (65.99)
7 38.25 1.25 19.63 (46.37)
8 24.75 26 11.55 (34.82)
9 24.75 50.75 10.50 (24.32)
10 24.75 75.5 9.54 (14.78)
11 24.75 100.25 8.67 (6.11)
12 64.75 165 20.63 14.53

Summary
• Investment involves principal, interest rate, and time

• The timing of transactions is conveniently shown on a
Cash Flow Diagram
• Depreciation of equipment value impacts the amount of
tax that one pays
• Inflation reduces the power of investment and decreases
the buying power of future investments.

Outline

Outline
Typical CFD for a new project

Profitability Criteria
Non-discounted
Discounted
Comparison of large projects

Cash Flows for a New Project
1. Purchase Land
2. Build Plant (1 – 3 years typically)
3. Plant start-up (requires working capital)
4. Plant produces product and revenue
a. Depreciate capital over some number of years
b. Plant operates for some period of time – time over
which profitability analysis is performed
5. At the end of the project working capital, land,
and salvage value are recovered

Cash Flows for a New Project

Project life
Land
Plant start-up WC
S
Depreciation period
0 1 2 3 4 5 6 7 8 9 10 11 12
Land
FCIL
Cumulative Cash
Flow Diagram
WC
Low revenue in 1st year
after start-up
Non-discounted Profitability Criteria
Time
Payback Period (PBP): time required after start-up to recover FCIL
Cash
Cumulative Cash Position (CCP): worth of the project at the end of
the project life
Interest Rate
Rate of return on investment (ROROI):

ൌ
ሺ ୐ ሻ


Example: Determine the three non-discounted profitability criteria for
the plant discussed previously.
Solution:
Payback period (PBP):
From the problem statement, FCIL is $150 and land plus working capital is
$40. The PBP is the time after startup (year 2) when the cumulative cash
flow is −$40. From the data on the previous slide, This will happen
between year 5 and year 6 so the payback period is between 3 and 4
years. A more accurate value can be found by interpolating between the
two data points.
ܲ‫ ܲܤ‬ൌ ͵ ൅ ሺെ͹ʹǤʹͷ ൅ ͶͲሻΤሺെ͹ʹǤʹͷ ൅ ͵͹ሻ ൌ ͵Ǥͻͳ

Cumulative Cash Position:
This is the cumulative cash flow at the end of the project. From the data:
ൌ ̈́ͳ͸ͷ
Return on investment:
The average annual net profit is the total profit from ten years of
operation divided by ten years. From the data, from year 2 to year 12, the
starting position is െ̈́ͳͻͲ. The ending position (with working capital and
land excluded) is $125.
The average annual profit after startup is: ሺ̈́ͳʹͷ െ െ̈́ͳͻͲ ሻȀͳͲ ൌ ̈́͵ͳǤͷ
The FCIL is $150, so the ROI is: ̈́͵ͳǤͷΤ̈́ͳͷͲ ൈ ͳͲͲΨ ൌ ʹͳǤͲΨ


Discounted Profitability Criteria
• Discounted profitability criteria are calculated using discounted cash

flows. All cash flows are adjusted (discounted) to the same time,
usually the start of the project.
• For large capital projects, e.g., new plants or significant additions,
discounted criteria are always used.


Time
Discounted Payback Period (DPBP): time required, after start-up, to
recover FCIL with all cash flows discounted back to time zero.
Cash
Net Present Value (NPV): Cumulative discounted cash position at the
end of the project
Interest Rate
Discounted Cash Flow Rate of Return (DCFROR): interest or discount
rate for which the NPV of the project is equal to zero.

Example: Determine the three discounted profitability criteria for the
plant discussed previously.
Solution:
Discounted Payback period (DPBP):
Land ($10) is purchased in year 0 so there is no discount. Working capital
is purchased in year 2. The discounted value of working capital is
$30/(1.1)2=$24.8. We seek to find the point where the cumulative
discounted cash flow is equal to $34.8. This happens very near to year 8
so the DPBP is 8.0 years.


Net Present Value:
This is the cumulative discounted cash flow at the end of the project.
From the data:
ൌ ̈́ͳͶǤͷ͵
DCFROR:
This is the interest rate that makes the NPV equal to zero. By trial-and-
error (or interpolation, or Excel Solver, or any programming language) the
DCFROR is 11.8%.



Comparing Projects
For large projects over multiple years, discounted criteria
are almost always used. But which criteria is best?
Suppose there are three mutually exclusive alternatives
(only one can be chosen). Which is best?
Initial Investment NPV DCFROR

Project A $60 $11.9 14.3%
Project B $120 $15.2 12.9%
Project C $100 $15.6 13.3%
In theory the company maximizes shareholder value by

choosing the project with the largest NPV.

Summary
• There are two types of profitability criteria: discounted and
non-discounted.
• For both types there are three criteria based on time, cash, or
interest rate.
• For large projects over multiple years, discounted criteria are
almost always used.
• When comparing large, mutually exclusive projects, the best
criterion is NPV.

Heat Integration
Heat Integration Process Design Slide 1

Based on: Analysis, Synthesis and Design of Chemical Processes 3rd edition by R. Turton, R. C. Bailie, W. B. Whiting and J. A. Shaeiwitz Chapter 15
Heat Integration
• A chemical process typically has many material streams that must
be heated or cooled.
• Hot and cold utilities (e.g. steam and cooling water) are available,
but it is possible to save energy by matching streams which must
be heated with streams that must be cooled and transferring
heat directly between them. This is called heat integration.
• The heat integration scheme must satisfy the first and second
laws of thermodynamics
• A tradeoff between capital cost (i.e. number and size of heat
exchangers), process flexibility and operability, and energy
savings is always encountered.
• There is a systematic method for designing heat exchange
networks, which we will discuss in this topic.

Procedure
• Choose a minimum approach temperature
• Construct a temperature interval diagram
• Construct a cascade diagram
• Calculate the minimum number of heat exchangers
• Design the heat exchanger network

Example
Stream # Condition Flowrate, ‫ܥ‬௣ ݉‫ܥ‬
ሶ ௣ ܶ௜௡ ܶ௢௨௧ Q (kw)
݉(kg/s)
ሶ (kJ/kg °C) (kw/ °C)
1 Hot 10.00 0.8 8.0 300 150 1200
2 Hot 2.50 0.8 2.0 150 50 200
3 Hot 3.00 1.0 3.0 200 50 450
4 Cold 6.25 0.8 5.0 190 290 −500
5 Cold 10.00 0.8 8.0 90 190 −800
6 Cold 4.00 1.0 4.0 40 190 −600
Minimum approach temperature:

10°C

Example
Temperature interval diagram
Stream 1 2 3 4 5 6
݉‫ܥ‬
ሶ ௣ 8.0 2.0 3.0 5.0 8.0 4.0 kw/°C
σ ݉‫ܥ‬
ሶ ௣ ȟܶ
300 °C 290 °C (kw)
A 300
200 °C 190 °C
B –50
150 °C 140 °C
C –350
100 °C 90 °C
50 °C
D 40 °C
50
–50

Example
Energy cascade diagram
A
300
300
B
Cold Utility
−50
Hot Utility
250
QH=100 C
Pinch −350 Pinch
a b
D
50 QC=50

Procedure
• The temperature at the top of the highest-temperature zone
where cooling is required is called the pinch temperature.
• Heating may be required at multiple points above the pinch
temperature, and cooling may be required at multiple points
below the pinch temperature, but no cooling is required above
the pinch temperature and no heating is required below the
pinch temperature.
• In this example, the pinch temperature is at 100 °C for the hot
streams and 90 °C for the cold streams. (We could also call 90 –
100 °C the “pinch zone”.)
• To minimize utility consumption, we should not transfer energy
across the pinch.
• In this example, this means that no heat exchanger should
transfer energy from a hot stream with a temperature above 100
°C to a cold stream below 90 °C.

Example
A
300
300
B
Cold Utility
−50
Hot Utility
250
Q
C
QH=100
Pinch 350 Pinch
a b
Q
D
−50
QC=50

Example
A A
B B
Cold Utility
Cold Utility
Hot Utility
Hot Utility
C C
D D
(a) (b)
Some cascade diagrams do not have a pinch. In this case, only one utility
(hot or cold) is required.
Example
Minimum number of exchangers above the pinch
H. U. 1 2 3
100 1200 100 300
100 400 800 100 300
4 5 6
500 800 400
Above the Pinch

Minimum number of exchangers, Nmin,a=5
Example
Minimum number of exchangers below the pinch
2 3
100 150
100 100 50
6 C.U.
200 50
Below the Pinch

Minimum number of exchangers, Nmin,b=3
Example
• Unless there is an exact match between the energy demands of a
set of hot and cold streams, the minimum number of heat
exchangers above and below the pinch is given by:
Minimum number of exchangers = (Number of hot streams) + (Number

of cold streams) + (number of utilities) − 1
• In this example, because the heat demand of stream 6 exactly

matches the heat available from streams 2 and 3, one fewer than
this number of heat exchangers is required.
• Note that the matching performed at this point does not

necessarily correspond to the final heat exchanger network design.

Example
• To design the heat exchanger network, consider the regions above
the pinch and below the pinch separately.
• Start at the pinch and move away from the pinch.
• Directly above the pinch, match streams so that ݉ܿ ሶ ௣ǡ௛௢௧ ൑ ݉ܿ
ሶ ௣ǡ௖௢௟ௗ
to ensure that the minimum approach temperature is not violated.
• More than one matching may be possible. For example, in the
following figure, either stream 2 or stream 3 can be matched with
either stream 5 or stream 6.

Example
Design the heat exchanger network
Stream 1 2 3 4 5 6
࢓cሶ p 8 2 3 5 8 4
(a) 300 290
200 190
150 140
100 90
(b)
190
200 Q2 = 300 165
2 2
100 90
150 Q1 = 100 102.5
1 1
100 90

Example
• Continue to move away from the pinch.
• In this example, energy available in stream 1 is matched with energy
required in streams 4 and 5 in intervals A and B respectively.
• Additional energy required for stream 6 is supplied by the hot utility.
• Temperatures at the outlet and outlet of each heat exchanger are
determined by the energy balance.

Example
(c) 300 Q4 = 500 290
4 4
190
237.5 Q3 = 700 190
3 3 190
150
200 Q2 = 300 165
2 2
100 90
150 Q1 = 100 102.5
1 1
100 90
(d) 300 Q4 = 500 290

4 4
190
237.5 Q3 = 700 190 190
3 3 5 Q5 = QH = 100
150
200 Q2 = 300 165
2 2
100 90
150 Q1 = 100 102.5
1 1
100 90

Example
• Directly below the pinch, match streams so that ݉ܿ ሶ ௣ǡ௛௢௧ ൒ ݉ܿ
ሶ ௣ǡ௖௢௟ௗ
to ensure that the minimum approach temperature is not violated.
• In this example, the value of ݉ܿ ሶ ௣ for cold stream six (4 kw/ °C) is
greater than that of either hot stream 2 (2 kw/ °C) or hot stream 3
(3 kw/ °C). Thus if stream six is connected directly to stream 2, an
energy balance predicts that the temperatures of the two streams
will cross, which is impossible.
• The solution is to split stream 6 into two streams, each with half of
the flow rate and therefore half of the value of ݉ܿ ሶ ௣.
• One of theses streams is connected to stream 2 and one is
connected to stream 3. Cold utility provides the additional cooling
needed for stream 3.

Example
T(°C) Stream 2 hot (100 °C, ݉‫ܥ‬
ሶ ௣ =2)
Stream 6 cold (90 °C, ݉‫ܥ‬

ሶ ௣ =4)
Stream 6 cold (65 °C)
ൌ ͳȀሺ݉‫ܥ‬
ሶ ௣ሻ
Stream 2 hot (50 °C)
Q
Because we started at the pinch, the streams at the right hand side of
the exchanger already have the minimum approach temperature
difference (10 °C). Because the ݉‫ܥ‬ ሶ ௣ of hot stream 2 is less than the ݉‫ܥ‬
ሶ ௣
of cold stream six, the temperature difference decreases as energy is
transferred and eventually the stream temperatures cross. This is
consistent with the first law of thermodynamics but violates the second
law of thermodynamics and therefore is not feasible.

Example
Stream 1 2 3 4 5 6
࢓cሶ p 8 2 3 5 8 4
100 90
(a)
50 40
100 6 6
90
50 Q6 = 100 65
(b)
Temperature
50 Cross 40

Example
Split stream 6 into 2 equal parts
100 6 Q6 = 100 90 6
(c) 50 100 Q7 = 100 40
7 7 90
66.7 40
50
100 6 Q6 = 100 90 6
50 100 Q7 = 100 40
(d) 7 7 90
66.7 40
50
8 Q8 = Qc = 50
Example

Example
The problem can also be represented graphically on a composite temperature enthalpy
diagram, or “grand composite curve”.
On this diagram, the slope of each line segment has units of °C/kW and is equal to
ͳΤሺ݉‫ܥ‬ሶ ௣ ሻ for each interval. The diagram shows how the temperature rises or falls as
energy is transferred between streams.
Adding cold duty corresponds to moving the cold curve to the right. 50 kW of cold duty
are added so that the two curves remain 10°C apart at the pinch.

Example
Hot Streams
Temperature Temperature Enthalpy of hot streams in Cumulative Enthalpy of
Interval Temperature Interval (kw) hot streams (kw)
D 50 0 0
C 100 (2+3)(100−50)=250 250
B 150 (2+3)(150−100)=250 500
A 200 (8+3)(200−150)=550 1050
300 (8)(300−200)=800 1850
Cold Streams
Temperature Temperature Enthalpy of cold streams in Cumulative Enthalpy of
Interval Temperature Interval (kw) cold streams (kw)
D 40 0 0
C 90 (4)(90−40)=200 200
B 140 (8+4)(140−90)=600 800
A 190 (8+4)(190-140)=600 1400
240 (5)(290-190)=500 1900
Example
Composite Temperature Enthalpy Diagram
290
240
Temperature (°C)
190
Qh= 100kW
140
Hot Cold
90 ΔT= 10 °C
40
0 Qc= 50kW 500 1000 1500 2000
Cumulative Enthalpy (kW)

Example

Try it yourself
Consider a process with the streams listed in the table below with an
approach temperature of 20 °C.
• Construct a temperature-interval diagram for the process
• Construct an energy cascade diagram
• Calculate the minimum utility loads
• Calculate the pinch temperatures
• Design the Minimum Utility Minimum Number of Exchangers (MUMNE)
network for the process
• Construct the composite curve diagram
Stream # ݉‫ܥ‬ሶ ௣ ܶ௜௡ ܶ௢௨௧

(kw/ °C)
1 4 300 180
2 3 250 140
3 3 140 280
4 5 140 210

Answer
Stream 1 2 3 4
ሶ p
࢓c 4 3 3 5 kW/Ԩ Q
300 280
A 50
250 230
B 80
230 210
C -50
180 160
D -100
160 140
E 60
140 120
40 kW

Answer
A
Q = 50
50
B
Q = 80
130
C
Q = -50
80 Min hot utility = 20 kW
20 Min cold utility = 60 kW
HU D
Q = 20 Q = -100
E 60 CU
Q = 60 Q = 60

Answer
Above Pinch
1 2 HU
480 kW 270 kW 20 kW
420 20 270 20
Number of exchangers
3 4
above pinch = 4
420 kW 350 kW
Below Pinch
2
60 kW
60 Number of exchangers
CU below pinch = 1
60 kW

Answer
Design above pinch
300.0 280.0
4 4
236.7
3
267.5 210.0
2 2
180.0 140.0
250.0 230.0
1 1
180.0 140.0
Stream No. 1 2 3 4
MCp 4.0 3.0 3.0 5.0

Answer
Hot Streams
Temperature Temperature Enthalpy of hot streams in Cumulative Enthalpy of hot
Interval Temperature Interval (kw) streams (kw)
E 140 0 0
D 160 (3)(160−140)=60 60
C 180 (3)(180−160)=60 120
B 230 (4+3)(230−180)=350 470
A 250 (4+3)(250−230)=140 610
300 (4)(300−250)=200 810
Cold Streams
Temperature Temperature Enthalpy of cold streams in Cumulative Enthalpy of cold
Interval Temperature Interval (kw) streams (kw)
E 120 0 0
D 140 0 0
C 160 (3+5)(160−140)=160 160
B 210 (3+5)(210−160)=400 560
A 230 (3)(230−210)=60 620
280 (3)(280−230)=150 770

Answer
Composite Temperature Enthalpy Diagram
300
280
260
Temperature (°C)
240
220
200
180
Hot Cold
160
140
0 200 400 600 800 1000
Cumulative Enthalpy (kW)

Green Process Design
Green Process Design Process Design Slide 1

Based on: Green Chemistry and Engineering: A Practical Design Approach by Concepción Jiménez-González, David J. C. Constable
Outline
• Synthetic chemistry (synthetic route)
• Solvent selection
• Catalyst selection
• Bioprocesses
• Process intensification
• Life cycle inventory and assessment
• Closing thought: industrial ecology

Synthetic chemistry
Synthetic chemistry (or synthetic route) refers to
the pathway (or steps) taken to convert available
raw materials into a product. Typically each step
consists of reaction to form an intermediate
product followed by separation and purification.
Some chemical products are quite complicated
and many synthetic routes are possible. How can
we chose one that is environmentally friendly?

Metrics for synthetic chemistry

• Theoretical yield: (moles of limiting reactant (A)) × (stoichiometric
ratio:[C⁄A] desired product/limiting reagent) × (FW of desired product (C])
• Percentage yield: (actual yield)⁄(theoretical yield)×100%
• Atom economy (AE): (m.w. of desired product)/(sum of m.w of all
reagents)
• Reaction mass efficiency(RME): ((mass of product)/(mass of reactant))
• Mass intensity (MI): (total mass in reaction vessel (kg))/(mass of product
(kg))
• Mass productivity (MP): (1/MI)×100%= (mass of product (kg))/(total
mass in reaction vessel (kg)) )×100%
• And many others…

Example
A chemist reacts benzyl alcohol (10.81 g, 0.10 mol, FW 108.1)
with p-toluene sulfonyl chloride (21.9 g, 0.115 mol, FW 190.65)
in toluene (500 g) and triethylarnine (15 g) to give the sulfonate
ester (0.09 mol, 23.6 g FW 262.29). Calculate the values of the
five chemistry metrics listed on the previous slide.
+ → + HCl

Solution
ൌ ͲǤͳ ൈ ͳȀͳ ൈ ʹ͸ʹǤʹͻ ൌ ʹ͸Ǥʹ͵
ଶଷǤ଺
ൌ ൈ ͳͲͲΨ ൌ ͻͲǤͲΨ
ଶ଺Ǥଶଷ
ଶ଺ଶǤଶଽ
ൌ ൈ ͳͲͲΨ ൌ ͺ͹Ǥ͹Ψ
ଵ଴଼Ǥଵାଵଽ଴Ǥ଺ହ
ଶଷǤ଺
ൌ ൈ ͳͲͲΨ ൌ ͹ͲǤͻΨ
ଵ଴Ǥ଼ଵାଶଵǤଽ
ଵ଴Ǥ଼ଵାଶଵǤଽାହ଴଴ାଵହ
ൌ ൌ ʹ͵Ǥʹ Ȁ
ଶଷǤ଺
ଵ
ൌ ൈ ͳͲͲΨ ൌ ͶǤ͵Ψ
୑୍

Synthetic chemistry

Chemistry selection
Bond type Chemistry Chemistry Mass Energy Solvent
C-C Knoevenagel 14 10 9 10
Cyanation 8 7 8 6
C-acylation 4 6 9 6
C-alkylation 4 4 3 8
Grinard 1 1 2 4
C-H Hydrogenation 7 5 4 8
Borohydride 6 5 4 7
Lithal 5 3 1 4
C-O O-alkylation 6 8 10 8
Epoxidation 4 5 7 6
The higher the score, the better the chemistry.

Example
• An organic chemist wants to protect an
alcohol group. Analyze the synthesis step
below.

Example
• From the GSK green chemistry chart, an O-
alkylation is generally good.
• However, we still have to choose the right
solvent.
• Also, the formation of HBr will decrease the
mass efficiency.

Example
The BHC Company Synthesis of Ibuprofen. From

Cann MC, Connelly ME. Real World Cases in
Green Chemistry. American Chemical Society,
Washington, DC, 2000

Example

Solvent selection
• Define the problem (What will the solvent be used for?)
– Processing (reaction, separation, crystallization)
– Formulated product
– Washing
• Identify Search Criteria
– Physical properties
– Chemical properties
– EHS properties
– Operational and functional constraints
– Cost limitations
• Perform Search
– Computer database search
– Computer-aided molecular design
– Experience and expertise
• Verify results
– Simulation?
– Experiments
– Lab/pilot plant/plant

Solvent selection
Gani, R; Jimenez-Gonzalez, C; ten Kate, A; et al. A modern approach to solvent selection CHEMICAL
ENGINEERING Volume: 113 Issue: 3 Pages: 30-43 Published: MAR 2006

Solvent selection
GlaxoSmithKline’s
solvent selection guide

Solvent selection: example

Decaffeination of coffee beans
Coffee is one of the most popular beverages in the world, and has been known since
at least the 10th century. Caffeine can be removed from coffee beans by extraction
with a liquid solvent. The challenge is to remove the caffeine without changing the
flavor of the coffee by removing any other compound.
• Roselius (1908, US patent #897,840) marketed decaffeinated coffee beans using benzene (!)
as a solvent.
• Methylene chloride (dichloromethane) was used until the 1970s but concerns about toxicity
and the role of dichloromethane in depleting the ozone layer have lead to this solvent being
phased out as well.
• Ethyl acetate occurs naturally in many foods, especially fruits, and is completely digested by
humans. Therefore its toxicity has never been questioned. However it is produced
commercially from petroleum feedstocks and has the associated environmental impacts.
• Supercritical carbon dioxide has been demonstrated to be a very good solvent for caffeine
and to have little effect on the flavor and aroma of the coffee.
• In the Swiss water method, beans are contacted with green bean extract which contains little
caffeine. Caffeine is transferred to the extract and the extract is filtered with activated carbon
to remove the caffeine and recycled.

Find a more environmentally friendly alternative to replace
dichloromethane (DCM) as the solvent for this general reaction
system:


This problem was solved using the commercial software ICAS-ProCAMD, which
combines computer-aided molecular design with an extensive database of solvent
properties. The existing solvent DCM is used as a benchmark. The new solvent should
have the same performance as DCM but more favorable EHS attributes. The following
criteria, called R-indicies in the program, were adopted:
• R0 = 1: Solvent addition is needed to improve the miscibility of the reactants.
• R1 = 1: Reaction is taking place in the liquid phase.
• R2 = 278 K: Reaction temperature is 278 K.
• R3 = 1: Solvent needs to dissolve the reactants.
• R4 = 0: Solvent does not need to dissolve the products.
• R5 = 1: The solvent needs to have a phase split with water.
• R6 = 1: Solubility parameters are known.
• R7 = 1: Solvent must be neutral towards the compounds in the reaction system.
• R8 = 1: Solvent must not associate/dissociate.
• R9 = 1: Favorable solvent EHS properties are desirable.

Software screen captures


Solvents recommended by the computer program are
listed below. Solubility and reactivity properties can be
verified by experiment.

Catalyst selection
• Turnover frequency
The number of molecules converted by each catalytic site in a unit of time:
ൌ ሺ݊௥଴ െ ݊௥ ሻȀሺ‫݊ݐ‬ୡୟ୲ ሻ (s−1)
• Catalyst selectivity
The number of desired product molecules produced per molecule of reactant
converted:
݊௣ െ ݊௣଴
ൌ ߪ ൌ
݊௥଴ െ ݊௥
• Catalyst stability (half life)
Time required for the catalyst activity to reduce by 50%

Example
A chemist is studying noble and transition metal catalysts for the selective conversion
of furfural to furfural alcohol by hydrogenation. 2-methylfuran is an undesired
byproduct. To do this, a 0.2 molar solution of furfural in ethyl acetate (0.83 mL of
furfural in 50 mL of ethyl acetate) is fed through a packed bed containing 0.2 g of
catalyst at 90 deg C and 50 bar hydrogen pressure at a rate of 0.3 mL/min with a
residence time of 34 s. The effluent from the reactor is sampled and the mole fraction
of each species is shown in the table on the following slide. The density of the active
sites of the two catalysts A and B is estimated to be 8.5×10−5 and 11×10−5 mol/g
respectively. Estimate the turnover frequency, the selectivity and the catalyst half-life.
Which catalyst is preferred?
+H2O
Furfural Furfuryl alcohol 2-methylfuran
(96.1 g/mol) (98.1 g/mol) (82.1 g/mol)
Example
Fresh catalyst A Fresh catalyst B
Species Mole fraction (%) Species Mole fraction (%)
Ethyl acetate 97.74 Ethyl acetate 97.64
Furfural 0.41 Furfural 0.34
Furfural alcohol 1.18 Furfural alcohol 1.14
2-methylfuran 0.34 2-methylfuran 0.44
Water 0.34 Water 0.44
catalyst A after 1000 hrs catalyst B after 1000 hrs

Species Mole fraction (%) Species Mole fraction (%)
Ethyl acetate 97.84 Ethyl acetate 97.87
Furfural 0.84 Furfural 1.05
Furfural alcohol 0.84 Furfural alcohol 0.67
2-methylfuran 0.24 2-methylfuran 0.20
Water 0.24 Water 0.20

Solution
Calculations are shown only for fresh catalyst A:
୫୐ ଵ ୫୧୬ ଵ ୐ ୫୭୪ ୫୭୪
Reactant feed rate: ͲǤ͵ ୫୧୬
ൈ ଺଴ ୱୣୡ
ൈ ଵ଴଴଴ ୫୐
ൈ ͲǤʹ ୐
ൌ ͳǤͲ ൈ ͳͲି଺ ୱ
Conversion: ୫୭୪ୣୱ ୭୤ ୰ୣୟୡ୲ୟ୬୲ ୡ୭୬ୱ୳୫ୣୢ 1.18+0.34

ൌ 0.41+1.18+0.34 ൌ ͲǤ͹ͻ
୫୭୪ୣୱ ୭୤ ୰ୣୟୡ୲ୟ୬୲ ୤ୣୢ
୫୭୪ ଵ ଵ ଵ ୥
TOF: ͲǤ͹ͻ ൈ ͳ ൈ ͳͲି଺ ୱ
ൈ ଴Ǥଶ ୥ ൈ ଼Ǥହൈଵ଴షఱ ୫୭୪ ൌ ͲǤͲͶ͸ ିଵ
ଵǤଵ଼
Catalyst selectivity:
ଵǤଵ଼ା଴Ǥଷସ
= 0.776
Conversion after 1000 hours: 0.84+0.24

0.84+0.84+0.24 ൌ ͲǤͷ͸ʹͷ
୪୭୥ሺ଴Ǥହሻ
Half-life: బǤఱలమఱ ൈ ͳͲͲͲ ൌ ʹͲͶͳ
୪୭୥ బǤళవ

Solution
Property Catalyst A Catalyst B
Turnover frequency (s−1) 0.046 0.037
Selectivity 0.776 0.728
Half life (hr) 2041 1169
Catalyst A has a higher turnover frequency, a greater selectivity toward the desired
product, and a longer half-life. Therefore it is preferred.

Example
Cumene is produced from propylene and benzene. The total worldwide production
capacity of cumene is about 6 million tons/year. The conventional processes use solid
phosphoric acid (SPA) or aluminum trichloride as catalysts. SPA production is still
heavily predominant.
Several companies have been involved in the development of new zeolite-based

processes. The Mobil/Badger cumene process uses a novel zeolite catalyst developed
by Mobil that offers higher yield and product purity than the traditional processes
while eliminating problems with corrosion, catalyst handling, and disposal, such as
significant amounts of acid waste. The pilot plant results show a 100% propylene
conversion and nearly 100% selectivity over a period of 5000 h of operation.

Example
Ethyleneimines are important chemicals commercially for the production of
pharmaceuticals, coatings, and textiles. Ethyleneimine has been produced by the
dehydration of monoethanolamine (MEA) in the liquid phase using sulfuric acid and
sodium hydroxide (the Wenker process).
The Wenker process has very low mass productivity, however, and produces large
amounts of sodium sulfate waste (4kg/kg ethyleneimine). The vapor-phase process
using solid acid-base catalysts is more efficient than the Wenker process, provided
that the formation of undesirable by-products ( e.g., acetaldehyde, piperidine,
acetonitrile) is minimized. A new catalyst has been developed by Nippon Shokubai35
with 86% conversion of monoethanolamine and 81 % selectivity for aziridine.

Bioprocesses
• Broadly speaking, biochemical processes are chemical
processes that make use of biological agents such as enzymes
(biological catalysts), micro-organisims (MO) (such as bacteria
or yeast) or cultured animal cells to produce a chemical
product.
• Since biochemical reactions tend to use renewable feedstocks
and take place in water under mild conditions, biochemical
synthesis may be better for the environment. However this is
not always the case, and detailed analysis may be required to
compare biological and non-biological process alternatives.

Bioprocesses
Downstream
Industry Scale Processing Biocatalyst Types of Products
Complexity
Organic small
Basic chemicals Very large Low MO/enzymes
molecules
Organic small
Fine Chemicals Medium Medium MO/enzymes
molecules
Detergents Large Low MO Enzymes
Personal care MO/enzymes/mammalian Proteins and small
Small – medium Medium – high
products cells molecules
Conventional Organic small
Medium Medium – high MO/enzymes
pharma molecules
Biopharma Small High MO/mammalian cells Proteins
Proteins and
Food/feed Very large Medium MO/enzymes
others
Metals and metal
Metal mining Very large Low MO
compounds
Purified air, water,
Waste treatment Very large Low MO
and soil
MO: microorganism
Bioprocesses
Table 8.2 Annual Production Volumes of Major Bio-derived Products, 2005
Product Annual Production (tons) Product Annual Production (tons)
Bioethanol 26,000,000 L-Hydroxyphenylalanine 10,000
L-Glutamic acid (MSG) 1,000,000 6-Aminopenicillanic acid 7,000
Citric acid 1,000,000 Nicotinamide 3,000
L-Lysine 350,000 D-p-Hydroxyphenylglycine 3,000
Lactic acid 250,000 Vitamin F 1,000
Food-processing
100,000 7-Aminocephalosporinic acid 1,000
enzymes
Vitamin C 80,000 Aspartame 600
Gluconic acid 50,000 L-Methionine 200
Antibiotics 35,000 Dextran 200
Feed enzymes 20,000 Vitamin B12 12
Xanthan 30,000 Provitamin D2 5
L-Threonine 10,000

Example
7-aminocephalosporic acid (7-ACA) is an intermediate in the
production of several antibiotics in the cephalosporin class. It is
traditionally produced from cephalosporin C via non-biological
chemical reaction. Recently a biocatalytic route has been
proposed. Both routes are shown on the following slide. Which
route is more green?

Example
Chemical route
Biocatalytic route

Attribute Chemical Process
Example Biocatalytic Process
Renewability Cephalosporin C salt is derived from a fermentation. Reagents and Cephalosporin C salt is derived from a
solvents are not renewable. fermentation. Enzymes can be produced
from renewable feedstocks.
Toxics Dichloromethane-suspect human carcinogen.
PC13: Reacts violently with water, very toxic by inhalation. Highly
reactive.
PC15: Reacts violently with water, very toxic by inhalation. Highly
reactive.
Dimethyl aniline: limited evidence of carcinogenic effect, toxic by
inhalation, ecotoxic effects-aquatic.
Ammonia: corrosive, toxic by inhalation, explosive.
Chemoselectivity Protection/deprotection strategy required. Chemoselective.
Process safety PC13 and PC15: require special handling. Hydrogen peroxide is produced and may be
added, although there is
a very low risk associated with this.
Mass efficiency Requires about 50% of the mass of the
chemical synthesis.
Energy Chemical route requires considerable chilling (to -37 °C) to control Requires about 80% of the process energy
exotherms. of the chemical synthesis.
Complexity Batch operation with greater number of steps. Batch operation largely aqueous based
Reagent addition must be carried out with care to avoid with simple mixing operations.
worker exposures and process safety risks.

Example
The biocatalytic route is preferred.

Process intensification
Process intensification is a strategy for process
improvement in which engineers attempt to
reduce the size of equipment, number of pieces
of equipment, energy or solvent use by making
processing steps more efficient or combining
two or more processing steps in one unit.

Improving efficiency
• Mixers
– Static mixer
– Y-shaped jet mixer
– Vortex mixer
• Reactors
– Microreactors
– Spinning disk reactor
– Spinning tube-in-tube reactor
– Oscillatory flow reactor
• Separators
– Rotating packed bed
– Centrifugal liquid-liquid extractors
Combining Processing Steps
• Hybrid reactors
– reactive crystallization
– reactive distillation
– Membrane reactors
• Hybrid separations
– Membrane distillation

Example: Spinning disk reactor

• As the name suggests, a spinning disk reactor consists of a
spinning disk onto which reactant is deposited.
• The reactant forms a thin film on the disk and flows very
rapidly to the edge of the disk under high centrifugal force.
The high sheer rate produces excellent heat and mass transfer
rates.

Example: spinning disk reactor

Example: Spinning disk reactor

• Oxly et al. applied a spinning disk reactor to the following reaction which produces
an intermediate in the production of a pharmaceutical product:
• The two reactants exist in different phases and in a conventional reactor the
reaction rate is severely limited by the rate of mass transfer between phases.
• They found that the reaction time was reduced by 99.9%, the reactor volume was
reduced by 99%, the production of byproduct was reduced by 93% and the
reaction could take place at room temperature which reduced refrigeration costs.
Paul Oxley, Clemens Brechtelsbauer, Francois Ricard, Norman Lewis and, and Colin Ramshaw. Evaluation of Spinning Disk Reactor
Technology for the Manufacture of Pharmaceuticals Industrial & Engineering Chemistry Research 2000 39 (7), 2175-2182

Example: reactive distillation
• Methyl acetate is produced by the reaction of acetic acid with
methanol:
Acetic acid + methanol ↔ methyl acetate + water
• The conventional process consisting of at least nine major
units and associated pumps, intermediate storage vessels, etc.,
was replaced with a single reactive distillation column.
• The integrated process has only one fifth of the capital cost
and one fifth of the operating cost and energy consumption of
the conventional process.

Example: reactive distillation
Reactive Distillation
Conventional Process Process

Life cycle inventory and assessment

Example: 3-pentanone
3-pentanone is used in the manufacture of pharmaceutical and
fine chemical products. It is produced from propanoic acid.
(Nitrogen is used to purge byproduct gasses)
+ + CO2 + H2O
propanoic acid propanoic acid 3-pentanone
Propanoic acid is produced from carbon monoxide, ethylene and

water:
C2H4 + CO + H2O Æ propanoic acid

Ethylene is ultimately produced from crude oil or natural gas,
and carbon monoxide is ultimately produced from natural gas.
All of this information can be represented on a chemical tree,
which summarizes the amount of raw material required at each
step in the manufacturing process until we reach raw materials
that are taken from the earth.

Life cycle inventory/assessment

Level 1 Level 2 Level 3 Level 4 Level 5 Level 6
3-Pentanone Ethanecarboxylic acid Carbon monoxide Carbon dioxide Natural gas Natural gas
1,000 1,734 797 398 81.6 (unprocessed)
83.2
Nitrogen from air Air (untreated)
153 153
Oxygen from air Air (untreated)

67.9 67.9
Water for reaction Water (untreated)

106 106
Natural gas Natural gas

268 (unprocessed)
274
163 163
Ethylene Naphtha Crude Oil

702 716 737
790 790
Nitrogen Air (untreated)

156 216

Once all processing steps have been identified, the raw material
and energy requirements and the emissions to the environment
associated with producing a given quantity of the product can be
estimated.

464
Life cycle inventory/assessment
LIFE CYCLE INVENTORY AND ASSESSMENT CONCEPTS
Table 16.4 3-Pentanone Cradle-to-Gate Summary Including Energy-Related Emissionsa Table 16.4 (Continued)
3-Pentanone Total 3-Pentanone Total
Energy- Transportation 3-Pentanone Energy- Transportation 3-Pentanone
Total Process Total Process
Related 3-Pentanone GTG Related 3-Pentanone GTG
Raw Material (kg) Ethane 27.9 27.9 0 0
Air (untreated) 437 437 0 0 Ethanecarboxyli
8.67 x 10-3 8.67 x 10-3 0 8.67 x 10-3
Coal 229 0 229 0.0233 c acid
Crude oil 968 737 169 62.2 0.169 Ethylene 11.1 11.1 0 0
Natural gas 314 0 314 33.1 Ethylene
46.6 46.6 0 0
Natural gas carbonate
357 357 0 0
(untreated) High alkanes 0.0707 0.0707 0 0
Water Hydrogen 1.03 1.03 0 0
1058 1058 0 0
(untreated) CH4 13.6 9.17 4.27 0.202 0.216
Energy (MJ) Naphtha 14.0 14.0 0 0
Electricity 4190 4190 0 0.486 Nitrogen dioxide 0.984 0.984 0 0
DowTherm 1829 1829 0 1829 Nitrogen
0.643 0.643 0 0
Heating steam 7507 7507 0 580 monoxide
Direct fuel 6954 6954 0 0 NMVOC 12.5 6.31 4.83 1.32 0.640
Natural gas 8124 8124 0 0 NOx 10.8 2.43 4.52 3.84 0.808
Natural gas, Propane 0.0708 0.0708 0 0
2390 2390 0 0
refinery Propylene 2.30 2.30 0 0
Coal 0 0 0 0 Propyne 0.0167 0.0167 0 0
Coal, refinery 107 107 0 0 SOx 6.39 1.69 4.44 0.261 -0.138
Diesel 2693 0 2693 440 Total air
3160 1023 1925 212 617
Undefined 1194 1194 0 0 emissions
Heavy oil, Water Emissions (kg)
1009 1009 0 0
refinery 3-Pentanone 6.01 6.01 0 6.01
Hydro power, BOD 0.116 4.59 x 10-5 0.104 0.0119 -2.21 x 10-3
7.16 7.16 0 0
refinery BOD5 0.144 0.144 0 0
Nuclear power, C5 and higher 0.0151 0.0151 0 0
7.16 7.16 0 0 aLevel: 4 (cradle-to-gate data after energy requirement and transportation); basis: 100 kg; allocation: 1.00; date: 7/21/07.
refinery
Energy input 3.60 x 104 3.33 x 104 2693 2850 Not all inputs are raw materials.
Cooling water -2.24 x 104 -2.24 x 104 0 -2539
Refrigeration 36.0 36.0 0 0
Potential
-9,396 -9,396 0 -1227
recovery
Net energy
(Input, potential 2.66 x 104 2.39 x 104 2693 1622
recovery)
Air Emissions (kg)
1,3-Butadiene 0.139 0.139 0 0
3-Pentanone 11.0 11.0 0 11.0
Acetylene 0.0186 0.0186 0 0
Ammonia 3.29 3.29 0 0
Argon 2.43 2.43 0 0
Butane 0.0695 0.0695 0 0
Butene 0.241 0.241 0 0
C5 and higher 1.90 1.90 0 0
CO2 2883 771 1907 205 0
CO 110 108 0.332 1.13 0.175
Catalyst 1.00 x 10-3 1.00 x 10-3 0 1.00 x 10-3

Plant Bottle

Industrial ecology
• From open system to closed systems

• Type 1 : unlimited resources and waste
• Type 2 : limited resources and waste
• Type 3 : sun is the only external input


Chemical Process Safety
Chemical Process Safety Process Design Slide 1

Chemical Process Safety: Fundamentals with Applications by Daniel A. Crowl and Joseph F. Louvar
Outline
• Toxicology
• Toxic release
• Fire and explosions
• Pressure relief
• Hazard identification and risk analysis

Toxicology
• Entry route
– Ingestion
– Inhalation
– Injection
– Dermal adsorption
• Elimination
– Excretion
– Detoxification
– Storage in fatty tissue
• Effect, reversible or irreversible

– Cancer, chromosome damage, etc.

Toxicology
• Gaussian distribution can represent the

biological response to exposure to a toxicant.
• Dose(in logarithm)-Response(in probit or
probability) curve can show properties like ED
(effective dose), TD (toxic dose) and LD (lethal
dose).
• Based on LD, ED, or TD, the relative toxicity of
compounds can be determined.

Toxicology
• ED: effective dose
(minor, reversible
irritation)
• TD: toxic dose
(serious or
permanent damage)
• LD: lethal dose
(causes death)

Toxicology
• One of the most important references used

during an industrial hygiene study is the MSDS.
• TLV: Threshold limit value: maximum permitted
exposure.
• Time-weighted average concentration
ͳ ௧ೢ
ܹܶ‫ ܣ‬ൌ න ‫ݐ݀ ݐ ܥ‬
ͺ ଴
σ௡௜ୀଵ ‫ܥ‬௜
ሺെሻ௠௜௫ ൌ ௡
σ௜ୀଵ ‫ܥ‬௜ Ȁሺെሻ௜

Example
• Air contains 5 ppm of diethylamine (TLV-TWA
of 10 ppm), 20 ppm of cyclohexanol(TLV-TWA
of 50 ppm), and 10 ppm of propylene
oxide(TLV-TWA = 20ppm). What is the mixture
TLV-TWA and has this been exceeded?

Example
ହାଶ଴ାଵ଴
• ሺܶ‫ ܸܮ‬െ ܹܶ‫ܣ‬ሻ௠௜௫ ൌ ఱ మబ భబ =25ppm
ା ା
భబ ఱబ మబ
• And total mixture concentration is
5+20+10=35ppm>25, so the concentration is
exceeded

Example
• Determine the 8-hour TWA worker exposure if
the worker is exposed to toluene vapors as
follows. The TLV of toluene is 100 ppm.
Duration of exposure (hours) Measured concentration (ppm)
2 110
2 330
4 90
ͳͳͲ ‫ ʹ כ‬൅ ͵͵Ͳ ‫ ʹ כ‬൅ ͻͲ ‫ כ‬Ͷ

ܹܶ‫ ܣ‬ൌ ൌ ͳͷͷ‫݉݌݌‬
ͺ
Toxicology: Industrial hygiene

• Enclosure: enclose room or equipment and place under
negative pressure
• Local ventilation: Devices like fume hoods
• Dilution Ventilation: make sure that rooms are well-
ventilated.
• Wet methods: Use wet methods to avoid producing
hazardous dust
• Good housekeeping: Clean up spills promptly, provide
water for washing and cleaning, provide well-designed
sewer systems with containment
• Personal protection: Wear safety glasses, face shields and
aprons. Personal respirators should be used only
temporarily or in an emergency.
Toxic release: Source model
• Material release process which can result in
accidents in chemical plants.
• Basic source models
– Flow of liquid through a hole/pipes
– Flow of vapor through holes/pipes
– Flashing liquids
– Liquid pool evaporation or boiling

Toxic release and dispersion

• After release, airborne material is carried
away by the wind in a puff or plume.
Dispersion is affected by many parameters.
– Wind speed can make plume longer and narrower
– Atmospheric stability relates to vertical mixing of the air
– Ground conditions, buildings, water, trees will affect the
mechanical mixing
– Height of the release above ground level significantly
affects ground level concentrations
– Momentum and buoyancy of the initial material released
changes the effective height of the release

Toxic release

Modeling the release

• Result from material balance always depend
on eddy diffusivity, which depends on many
factors including weather conditions.
Therefore it is difficult to estimate.
• Methods for modeling dispersion after a toxic
release are discussed in your textbook.

Fires and explosions
• When fuel, an oxidizer, and and ignition source are present,
fire or explosion will occur.
• Flammable vapors have an lower flammability limit (LFL)
and upper flammability limit (UFL) which are usually
expressed as concentrations in volume percent in air.
• The limits for vapor mixtures can usually be estimated by
the following equations:
‫ܮܨܮ‬௠௜௫ ൌ ͳȀሾσଵ௜ୀଵ ‫ݕ‬௜ Ȁ‫ܮܨܮ‬௜ ]
ܷ‫ܮܨ‬௠௜௫ ൌ ͳȀሾσଵ௜ୀଵ ‫ݕ‬௜ Ȁܷ‫ܮܨ‬௜ ]
• This equation is not always accurate (see the textbook for
additional information). Flammability limits also depend on
temperature and pressure.

Fires and explosions

Test apparatus for
acquiring vapor
explosion data
(UFL and LFL)

Example
What are the LFL and UFL of a gas mixture composed of
0.8% hexane, 2.0% methane, and 0.5% ethylene by volume?
Is the mixture below combustible?
Volume Mole fraction on
LFLi (volume %) UFLi (volume %)
% combustible basis
Hexane 0.8 0.24 1.2 7.5
Methane 2.0 0.61 5.0 15
Ethylene 0.5 0.15 2.7 36.0
Total
3.3
combustibles
Air 96.7

Example
LFLmix=2.65%
UFLmix=13.0%
Since the mixture is 3.3% combustibles, it is combustible.

Explosion
• Refers to rapid energy release.
• The expansion of gas will result in shock wave
in front of the flame. If the shock wave is
faster than the speed of sound, then the
explosion is called a detonation. Otherwise it
is called a deflagration.
• The shock wave and subsequent wind (blast
wave) cause most of the structural damage.

Types of explosions
• Vapor cloud explosion (VCE)
– Usually the most dangerous and destructive type
of explosion
– Caused by a sequence of steps:
• Sudden release of a large quantity of flammable vapor
• Vapor disperses throughout the plant while mixing with
air
• Vapor cloud ignites

Types of explosions
• Boiling Liquid Expanding Vapor Explosion
(BLEVE)
– Most commonly caused by fire:
• A fire develops near a tank containing liquid
• Liquid starts to boil and tank becomes pressurized
• Tank ruptures due to high temperature and pressure,
releasing its contents as a vapor.
– This can then lead to either a toxic release or a
VCE

Preventing fires and explosions

• Inerting- reduce the oxygen concentration
– Vacuum purging (remove air under vacuum, requires that vessel can withstand
vacuum)
– Pressure purging (using an inert gas such as nitrogen)
– Sweep-through purging (for vessels rated not for pressure or vacuum)
– Siphon purging (first fill the vessel with liquid to minimize use of purge gas)
• Prevent static discharge
– Static discharge is the most common ignition source, but it is very difficult to
prevent
– Your textbook discusses methods to minimize the likelihood of static discharge.

Preventing fires and explosions
• Explosion proof (XP) area and equipment
– An explosion-proof area is one where explosive vapors
may be present; therefore all devices must be
explosion proof.
– Explosion-proof housings (for example, for electric
motors) are not designed to prevent explosive vapors
from entering but rather to contain an explosion and
prevent combustion from spreading.
• Ventilation: open air plants or local ventilation
systems.
• Sprinkler systems are effective at extinguishing
fires in many case.
Reliefs
• High pressure may rupture process equipment, so relief
methodology is important for process safety.
• There are some guidelines for specifying relief positions
– All vessels need reliefs, including reactors, storage tanks, towers, and
drums.
– Blocked-in sections of cool liquid-filled lines which are exposed to heat
or refrigeration need reliefs
– Positive displacement pumps, compressors, and turbines need reliefs
on the discharge side.
– Storage vessels need pressure and vacuum reliefs to protect against
pumping in or out of a blocked-in vessel, or against the generation of a
vacuum by condensation.
– Vessel steam jackets are often rated for low pressure steam. Reliefs
are installed in jackets to prevent excessive steam pressures due to
operator error or regulator failure.

Example
Specify the location of reliefs in the simple
polymerization reactor system illustrated on the
following slide. The major steps in this polymerization
process include (1) pumping 100 lb of initiator into
reactor R-1, (2) heating to the reaction temperature of
240°F, (3) adding monomer for a period of 3 hr, and (4)
stripping the residual monomer by means of a vacuum
using valve V-15. Because the reaction is exothermic,
cooling during monomer addition with cooling water is
necessary.

Example

Example

Example
• Reactor (R-1): A relief is installed on this reactor because, in
general, every process vessel needs a relief. This relief is labeled
PSV-1 for pressure safety valve 1.
• Positive displacement pump (P-1 ): Positive displacement pumps
are overloaded, overheated, and damaged if they are dead-headed
without a pressure-relieving device (PSV-2). This type of relief
discharge is usually recycled back to the feed vessel.
• Heat exchanger (E-1): Heat exchanger tubes can rupture from
excessive pressures when water is blocked in (V-10 and V-11 are
closed) and the exchanger is heated (by steam, for example). This
hazard is eliminated by adding PSV-3.
• Drum (D-1): Again, all process vessels need relief valves, PSV-4.
• Reactor coil: This reactor coil can be pressure-ruptured when water
is blocked in (V-4, V-5, V-6, and V-7 are closed) and the coil is
heated with steam or even the sun. Add PSV-5 to this coil.

Relief types

Blowdown drum

Relief sizing
• Relief design is difficult, and experimental data
are preferred for proper design.
• Reliefs must be designed to be the proper size,
neither too large nor too small.
• Unlike other pieces of process equipment, they
are not routinely used so they may not be
noticed or optimized by operators.
• However, when they are activated, they must
perform flawlessly.
• The textbook provides details about relief sizing.

Hazard Identification and Risk

Analysis
• HAZOP
• Risk assessment
• Event tree
• Fault tree

HAZOP
• Apply a number of guide words(as well as,
part of, more, other than…) to various parts of
the process design intention.

HAZOP-example
Guide Deviation Possible causes Consequences Action
word
No No cooling 1. Control valve fails 1. Temperature 1. Install back-up
closed increase in control valve, or
2. Plugged cooling reactor manual bypass
line 2. Possible valve.
Etc. thermal 2. Install filters to
runaway prevent debris
from entering
line
Etc.
More More 1. Control valve fails 1. Reactor cools, 1. Instruct operators
cooling open reactant builds on procedure
flow 2. Controller fails and up, possible
opens valve runaway on
heating

Risk assessment
Typical plots of (a) the failure rate μ, (b) the failure density f (t), (c) the failure probability
P(t), and (d) the reliability R(t).

Risk assessment
• μ: failure rate
• Reliability (probability of no failure in interval
between (0,t)): ܴሺ‫ݐ‬ሻ ൌ ݁ ିఓ௧
• Failure probability, ܲሺ‫ݐ‬ሻ ൌ ͳ െ ܴሺ‫ݐ‬ሻ ൌ ͳ െ ݁ ିఓ௧
• Failure density, ݂ሺ‫ݐ‬ሻ ൌ ݀ܲሺ‫ݐ‬ሻȀ݀‫ ݐ‬ൌ ߤ݁ ିఓ௧
• Mean time between failures(MTBF, or E), ‫ ݐ ܧ‬ൌ
ஶ
‫׬‬଴ ‫ ݐ݀ ݐ ݂ݐ‬ൌ ͳȀߤ
• Total reliability for units in series:
ܴ ൌ ς௡௜ୀଵ ܴ௜
Example
The water flow to a chemical reactor cooling coil is
controlled by the system shown in the table below,
find the overall reliability, failure probability, failure
rate and MTBF. Assume a one year period of
operation.
Component Failure rate
(faults/yr)
Control valve 0.6
Controller 0.29
DP cell 1.41

Answer
ܴ ൌ ςଷ௜ୀଵ ܴ௜ ൌ ݁ ି଴Ǥ଺ ݁ ି଴Ǥଶଽ ݁ ିଵǤସଵ ൌ ݁ ିଶǤଷ ൌ ͲǤͳͲͲ
ܲ ൌ ͳ െ ൌ ͲǤͻͲͲ
ߤ ൌ ͲǤ͸ ൅ ͲǤʹͻ ൅ ͳǤͶͳ ൌ ʹǤ͵ failures/yr
MTBF=1/μ=0.43 years

Event tree
• Provides information on how a failure can occur and
the probability of occurrence.
• Useful for providing scenarios on possible failure
modes.
• May be very large for realistic cases.

Event tree

Event tree
Suppose that a loss-of-cooling event occurs once a year.
Suppose also that the loss of coolant alarm fails 1 % of
the time it is placed in demand. This is a failure rate of
0.01 failure/demand. Also assume that the operator
will notice the high reactor temperature 3 out of 4
times and that 3 out of 4 times the operator will be
successful at reestablishing the coolant flow. Both of
these cases represent a failure rate of 1 time out of 4,
or 0.25 failure/demand. Finally, it is estimated that the
operator successfully shuts down the system if
necessary 9 out of 10 times. This is a failure rate of 0.10
failure/demand.

Event tree

Fault tree
• Can identify ways in which hazards can lead to
accidents. Flat Tire Top Event
OR
Tire Failure
Road
Debris
OR
Defective Worn
Tire Tire


Process Optimization
Process Optimization Process Design Slide 1
Formulation of Optimization Problem

The formulation of an optimization problem involves:
• A set of ܰ୚ୟ୰୧ୟୠ୪ୣୱ variables, ‫ݔ‬.
• The selection of a set of decision variables, ݀, from the set ‫ݔ‬.
• A measure of goodness called an objective function, ݂ ‫ ݔ‬.
• A set of ܰ୉୯୳ୟ୲୧୭୬ୱ equality constraints, ܿ ‫ ݔ‬ൌ Ͳ.
• A set of ୍ܰ୬ୣ୯ୟ୪ inequality constraints, ݃ ‫ ݔ‬൑ Ͳ.
• Lower and upper bounds on some or all of the variables, ‫ ݔ‬௅ ൑ ‫ ݔ‬൑ ‫ ݔ‬ு
A general optimization problem is stated as follows:
Minimize (or maximize) , ݂ ‫ ݔ‬, the objective function
with respect to (w. r. t.) ݀, the design variables
subject to (s. t.):
ܿ ‫ ݔ‬ൌ Ͳ, the equality constraints
݃ ‫ ݔ‬൑ Ͳ, the inequality constraints
‫ ݔ‬௅ ൑ ‫ ݔ‬൑ ‫ ݔ‬ு the lower and upper bounds

• Objective Function and Decision Variables
• The objective function is a measure of goodness. Often it is an
economic measure such as Net Present Value (NPV) or Total Annual
Cost (TAC)
• The objective function should be a function of all of the decision
variables and may also be a function of other variables in ‫ݔ‬.
• The decision variables are adjusted until the minimum (or
maximum) value of the objective function is found.
• Equality Constraints
• In process design, most of the equality constraints are the equations
that constitute the mathematical models of the process units. For
example, a distillation column may be described by hundreds of
material-balance, energy-balance and vapor-liquid-equilibrium
equations.

• Inequality Constraints
• Inequality constraints are expressions that bound the feasible region
of operation. For example, there are often limits on the maximum
temperature and pressure in a reactor, a minimum value for product
purity, etc.
• Lower and Upper Bounds
• Lower and upper bounds place limits on the values of the variables
themselves.
• They can be included with the inequality constraints, or listed
separately

Additional Vocabulary
• The combination of equality constraints, inequality constraints and lower
and upper bounds define the feasible region.
• A feasible solution is one that satisfies the constraints and bounds.
• If a feasible solution also minimizes (or maximizes) the objective function,
it is called a local optimal solution.
• Sometimes other local optimal solutions exist, with one or more being
global optimal solutions.
• If the objective function, equality constraints, and inequality constraints
are linear with respect to the variables ‫ݔ‬, the problems is referred to as a
linear programming problem.
• If the objective function or any of the constraints are nonlinear with
respect to ‫ݔ‬, then the problem is called a nonlinear programming
problem.
• An optimization problem with out any constraints or bounds is called an
unconstrained optimization.
• Likewise, if an optimization problem has any constraints or bounds, it is
called a constrained optimization.
• If the optimal value of a variable is away from a given constraint, the
constraint is called a slack constraint.
• If the optimal value of variable lies on a constraint, then the constraint is
called a binding constraint.
• In some cases, an objective function or constraint may be discontinuous
• In some cases, one or more decision variables may be integers, the most
common case being that they are binary integers, either one or zero. In
this case the problem is called a mixed-integer linear programming
problem or a mixed-integer nonlinear programming problem

Example: Beer Supply Problem

During the 2002Winter Olympics in Salt Lake City, Utah, a local
microbrewery received a rush order for 100 gal of beer containing 4.0 vol%
alcohol. Although no 4% beer was in stock, large quantities of Beer A with
4.5% alcohol at a price of $6.40/gal and Beer B with 3.7% alcohol priced at
$5.00/gal were available, as well as water suitable for adding to the blend at
no cost. The brewery manager wanted to use at least 10 gal of Beer A.
Neglecting any volume change due to mixing, determine the gallons each of
Beer A, Beer B, and water that should be blended together to produce the
desired order at the minimum cost.

Solution
Let VA = gallons of Beer A, VB = gallons of Beer B, and VW =gallons of water.
The optimization problem is stated as follows:
Minimize Cost ̈́ ൌ ͸ǤͶͲܸ஺ ൅ ͷǤͲͲܸ஻ ൅ ͲǤͲͲܸௐ
w. r. t. s. t.
ܸ஺ , ܸ஻ , ܸௐ ͲǤͲͶͷܸ஺ ൅ ͲǤͲ͵͹ܸ஻ ൅ ͲǤͲͲܸௐ ൌ ͲǤͲͶ ൈ ͳͲͲ
ܸ஺ ൅ ܸ஻ ൅ ܸௐ ൌ ͳͲͲ
ͳͲ ൑ ܸ஺ , Ͳ ൑ ܸ஻ , Ͳ ൑ ܸௐ
The problem can be simplified by solving the second equality constraint for ܸ஻ :
ܸ஻ ൌ ͳͲͲ െ ܸ஺ െ ܸௐ
Minimize Cost ̈́ ൌ ͳǤͶͲܸ஺ െ ͷǤͲͲܸௐ ൅ ͷͲͲ

w. r. t. s. t.
ܸ஺ , ܸௐ ͲǤͲͲͺܸ஺ ൅ ͲǤͲ͵͹ܸௐ ൌ ͲǤ͵
ܸ஻ ൌ ͳͲͲ െ ܸ஺ െ ܸௐ
ͳͲ ൑ ܸ஺ , Ͳ ൑ ܸ஻ , Ͳ ൑ ܸௐ
Solution
This is a linear
programming problem.
For linear programming
problems, the optimal
solution always lies at
the intersection of
constraints. The second
constraint can be re-
written:
ܸ஺ ൌ ͶǤ͸ʹͷܸௐ ൅ ͵͹Ǥͷ
And the problem can be
represented graphically.

Solution
We can calculate the value of the objective function at all intersections of
constraints:
VA (gal) VB (gal) VW (gal) % alcohol Cost ($)

37.50 62.50 0.00 4.00 552.50
10.0 90.0 0.00 3.78 514.00
88.89 0.00 11.11 4.00 568.90
Row 2 is not a feasible solution because it does not meet the constraint on
alcohol concentration. The feasible solution with the lowest cost is in row 1.
No water should be used.
Try it yourself
Process 1: A+BÆE
Process 2: A+2BÆF
Raw Material Maximum Available Cost (¢/lb)

lb/day
A 40,000 15
B 30,000 20
Process Product Reactant Requirements Processing Selling Price Maximum Production

(lb) per lb Product Cost of Product Level (lb/day)
1 E 2/3 A, 1/3 B 15 ¢/lb E 40 ¢/lb E 30,000
2 F 1/2 A, 1/2 B 5 ¢/lb F 33 ¢/lb F 30,000

Try it yourself
Define: x1=lbs/day A consumed
x2=lbs/day B consumed
x3=lbs/day E produced
x4=lbs/day F produced
Then the optimization problem can be formulated:
Maximize ܲ ൌ ͲǤʹͷ‫ݔ‬ଷ ൅ ͲǤʹͺ‫ݔ‬ସ െ ͲǤͳͷ‫ݔ‬ଵ െ ͲǤʹ‫ݔ‬ଶ
w. r. t. s. t.
‫ݔ‬ଵ ǡ ‫ݔ‬ଶ ǡ ‫ݔ‬ଷ ǡ ‫ݔ‬ସ ‫ݔ‬ଵ ൌ ͲǤ͸͸͹‫ݔ‬ଷ ൅ ͲǤͷ‫ݔ‬ସ
‫ݔ‬ଶ ൌ ͲǤ͵͵͵‫ݔ‬ଷ ൅ ͲǤͷ‫ݔ‬ସ
Ͳ ൑ ‫ݔ‬ଵ ൑ ͶͲǡͲͲͲ
Ͳ ൑ ‫ݔ‬ଶ ൑ ͵ͲǡͲͲͲ
Ͳ ൑ ‫ݔ‬ଷ ൑ ͵ͲǡͲͲͲ
Ͳ ൑ ‫ݔ‬ସ ൑ ͵ͲǡͲͲͲ
Example
The problem can be simplified by incorporating the constraints into the
statement of the objective function:
Then the optimization problem can be formulated:
Maximize ܲ ൌ ͲǤͲͺ͵͵‫ݔ‬ଷ ൅ ͲǤͳͲͷ‫ݔ‬ସ
w. r. t.
‫ݔ‬ଷ ǡ ‫ݔ‬ସ s. t.
Ͳ ൑ ͲǤ͸͸͹‫ݔ‬ଷ ൅ ͲǤͷ‫ݔ‬ସ ൑ ͶͲǡͲͲͲ

Ͳ ൑ ͲǤ͵͵͵‫ݔ‬ଷ ൅ ͲǤͷ‫ݔ‬ସ ൑ ͵ͲǡͲͲͲ
Ͳ ൑ ‫ݔ‬ଷ ൑ ͵ͲǡͲͲͲ
Ͳ ൑ ‫ݔ‬ସ ൑ ͵ͲǡͲͲͲ

Linear Programming
A linear process model can be written:
‫ ܡ‬ൌ ۹‫ܝ‬
A linear programming (optimization) problem can be written:
‫ ܬ‬ൌ ܎ ᇱ ‫ܠ‬
‫ܠ‬
ǣ
‫ ܠۯ‬൑ ‫܊‬
‫ ܠ ۯ‬ൌ ‫܊‬
‫ ܊ܔ‬൑ ‫ ܠ‬൑ ‫܊ܝ‬
Linear Programming problems can be solved in
matlab using the command linprog:
x=linprog(f,A,b,Aeq,beq,lb,ub)
Example
Solve the previous problem in Matlab. Note that although the
output x is a column vector, linprog requires that f, b, beq lb
and ub be row vectors.

Solution
The problem can be formulated in one of two ways. Using all
four variables:
f=-1*[-0.15 -0.2 0.25 0.28]
A=[]; b=[];
Aeq=[-1 0 0.667 0.5;
0 -1 0.333 0.5]
beq=zeros(1,2)
lb=zeros(1,4)
ub=[4e4 3e4 3e4 3e4]
J=-f*x
Answer: ‫ ݔ‬ᇱ ൌ ͵ͷͲͳͲ ʹͶǡͻͻͲ ͵ͲͲͲͲ ͵ͲͲͲͲ

‫ ܬ‬ൌ ͷ͸ͷͲ
Solution
Using only two variables:
f=-[0.0833 0.105];
A=[0.667 0.5;
0.333 0.5;
-0.667 -0.5;
-0.333 -0.5];
b=[4e4,3e4,0,0];
Aeq=[]; beq=[];
lb=zeros(1,2); ub=[3e4,3e4];
J=-f*x
Answer: ‫ ݔ‬ᇱ ൌ ͵ͲͲͲͲ ͵ͲͲͲͲ
‫ ܬ‬ൌ ͷ͸ͷͲ

Try it Yourself
Consider the following refinery production problem. Develop a
linear program to describe the problem and solve it in Matlab.
Solution
Let the variables be:
x1 = bbl/day of crude #1
x2 = bbl/day of crude #2
x3 = bbl/day of gasoline
x4 = bbl/day of kerosene
x5 = bbl/day of fuel oil
x6 = bbl/day of residual
The objective (to be maximized) is:
‫ ܬ‬ൌ െʹͶǤͳ‫ݔ‬ଵ െ ͳ͸‫ݔ‬ଶ ൅ ͵͸‫ݔ‬ଷ ൅ ʹͶ‫ݔ‬ସ ൅ ʹͳ‫ݔ‬ହ ൅ ͳͲ‫଺ݔ‬

Solution
The data in the table provide four linear equality constraints:

ǣ ‫ݔ‬ଷ ൌ ͲǤͺͲ‫ݔ‬ଵ ൅ ͲǤͶͶ‫ݔ‬ଶ
ǣ ‫ݔ‬ସ ൌ ͲǤͲͷ‫ݔ‬ଵ ൅ ͲǤͳͲ‫ݔ‬ଶ
ǣ ‫ݔ‬ହ ൌ ͲǤͳͲ‫ݔ‬ଵ ൅ ͲǤ͵͸‫ݔ‬ଶ
ǣ ‫଺ݔ‬ ൌ ͲǤͲͷ‫ݔ‬ଵ ൅ ͲǤͳͲ‫ݔ‬ଶ
The constraints can be written in vector-matrix form as Aeqx=beq,

where:
ͲǤͺͲ ͲǤͶͶ െͳ Ͳ Ͳ Ͳ Ͳ
ͲǤͲͷ ͲǤͳͲ Ͳ െͳ Ͳ Ͳ Ͳ
‫ ۯ‬ୣ୯ ൌ ‫܊‬ୣ୯ ൌ
ͲǤͳͲ ͲǤ͵͸ Ͳ Ͳ െͳ Ͳ Ͳ
ͲǤͲͷ ͲǤͳͲ Ͳ Ͳ Ͳ െͳ Ͳ
Solution
There are also upper bounds on some variables:

ǣ ‫ݔ‬ଷ ൑ ʹͶǡͲͲͲ
ǣ ‫ݔ‬ସ ൑ ʹǡͲͲͲ
ǣ ‫ݔ‬ହ ൑ ͸ǡͲͲͲ
All variables should be non-negative (i.e. greater than or equal to

zero).

Solution
The problem can be formulated in Matlab as follows:
f=-1*[-24.5 -16 36 24 21 10];

Aeq=[0.80 0.44 -1 0 0 0
0.05 0.10 0 -1 0 0
0.10 0.36 0 0 -1 0
0.05 0.10 0 0 0 -1];
beq=zeros(1,4);
lb=zeros(1,6);
ub=[1e6 1e6 24000 2000 6000 1e6];
A=zeros(1,6); b=0;
J=-f*x
Solution
The answer is:
‫ݔ‬ଵ ൌ ʹ͸ǡʹͲ͹ Ȁ
‫ݔ‬ଶ ൌ ͸ǡͺͻ͹ Ȁ
‫ݔ‬ଷ ൌ ʹͶǡͲͲͲ Ȁ ሺ ሻ
‫ݔ‬ସ ൌ ʹǡͲͲͲ Ȁ ሺ ሻ
‫ݔ‬ହ ൌ ͷǡͳͲ͵ Ȁ
‫ ଺ݔ‬ൌ ʹǡͲͲͲ Ȁ
‫ ܬ‬ൌ ̈́ʹͺ͸ǡ͹ͷͺȀ

Quadratic Programming
A quadratic programming (optimization) problem can be written:
ͳ
ൌ ܎ ᇱ ‫ ܠ‬൅ ‫ ் ܠ‬۶‫ܠ‬
ʹ
ǣ
‫ ܠۯ‬൑ ‫܊‬
‫ ܠ ۯ‬ൌ ‫܊‬
‫ ܊ܔ‬൑ ‫ ܠ‬൑ ‫܊ܝ‬
Quadratic Programming problems can be solved in

matlab using the command quadprog:
x=quadprog(H,f,A,b,Aeq,beq,lb,ub)
Example
A plasma etcher has a yield of good chips that is influenced by
pressure (‫ݔ‬ଵ ) and gas flow rate (‫ݔ‬ଶ ). Both ‫ݔ‬ଵ and ‫ݔ‬ଶ are scaled
variables (Ͳ ൑ ‫ݔ‬௜ ൑ ʹ). A model has been developed based on
operating data as follows:
ܻ ൌ െͲǤʹͳ‫ݔ‬ଵଶ ൅ ͲǤʹ‫ݔ‬ଶ ‫ݔ‬ଵ െ ͲǤͲͻ‫ݔ‬ଶଶ ൅ ͲǤͳͷ‫ݔ‬ଵ ൅ ͲǤͷ
Find the values of ‫ݔ‬ଵ and ‫ݔ‬ଶ that maximize the yield.

Solution
lb=[0 0]’;
ub=[2 2]’;
f=-[0.15 0]';
H=-2*[-0.21 0.2;0 -0.09];
x=quadprog(H,f,[],[],[],[],lb,ub)
Answer: ‫ ݔ‬ᇱ ൌ ͲǤ͹ͷͺͶ ͲǤͺͶʹ͹

‫ ܬ‬ൌ െͲǤͲͷ͸ͻ
ܻ ൌ ͲǤͷͷ͸ͻ
Nonlinear Programming
A general nonlinear programming problem can be written:
݂ ‫ݔ‬ଵ ǡ ‫ݔ‬ଶ ǡ ǥ ‫ݔ‬ேೇ

ǣ
݄௜ ‫ݔ‬ଵ ǡ ‫ݔ‬ଶ ǡ ǥ ‫ݔ‬ேೇ ൌ Ͳ ݅ ൌ ͳǡʹǡ ǥ ܰா
݃௜ ‫ݔ‬ଵ ǡ ‫ݔ‬ଶ ǡ ǥ ‫ݔ‬ேೇ ൑ Ͳ ݅ ൌ ͳǡʹǡ ǥ ܰூ
Constrained Nonlinear Programming problems can be solved in

Matlab using the command fmincon:
fmincon(FUN,X0,A,B,Aeq,Beq,LB,UB, NONLCON)

Example
Consider a modified version of the plasma etcher problem where
the etcher has a yield of good chips that is given by the following
equation:
ܻ ൌ െͲǤͳ‫ݔ‬ଵସ ൅ ͲǤʹ‫ݔ‬ଶ ‫ݔ‬ଵଶ െ ͲǤͲͻ‫ݔ‬ଶଶ െ ͲǤͳͳ‫ݔ‬ଵଶ ൅ ͲǤͳͷ‫ݔ‬ଵ ൅ ͲǤͷ
Find the values of ‫ݔ‬ଵ and ‫ݔ‬ଶ that maximize the yield.
Solution
y=@(x) -(-0.1*x(1).^4+0.2*x(2).*x(1).^2 ...

-0.09*x(2).^2-0.11*x(1).^2+0.15*x(1)+0.5);
lb=[0 0]; ub=[2 2];
[x fval]=fmincon(y,[1 1],[],[],[],[],lb,ub)
Answer: ‫ ݔ‬ᇱ ൌ ͲǤ͹͹͸͸ ͲǤ͸͹ͲͲ

‫ ܬ‬ൌ െͲǤͷͷͶʹ
ܻ ൌ ͲǤͷͷͶʹ

Example: Design of Heat Exchanger
In a petroleum refinery, 80,000 lb/hr of a light gas oil at 440 °F from a
sidecut stripper of a crude distillation tower is currently being cooled with
cooling water before being sent to storage. The heat lost could be used to
help preheat 500,000 lb/hr of the crude oil, which is available at 240 °F and
is being heated by other means at a cost of $3.00/million Btu. The plant
operates 8,200 hr/yr. Based on the following data, determine what should
be done, if anything. The savings in cooling water cost can be assumed
negligible.
Information:
• Average specific heat of light gas oil = 0:50 Btu/lb-°F
• Average specific heat of crude oil = 0:45 Btu/lb-°F
• Annualized cost of heat exchanger ($/year):
‫ܥ‬ு௑ ‫ ܣ‬ൌ ͲǤͺʹͶͺ ͳͳǤ͸͸͹ െ ͲǤͺ͹Ͳͻ ‫ ܣ‬൅ ͲǤͲͻͲͲͷ ‫ ܣ‬ଶ
for 200<A< 12000 ft2.
• For heat exchanger: ܳ ൌ ͲǤ͹ܷ‫ܣ‬οܶ௟௠ , ܷ ൌ ͵ͷ Ȁ ȉ ι ȉ ଶ
Solution
The objective function is the total annualized cost of the proposed retrofit
including the capital cost of the heat exchanger and the savings in energy
cost:
ͺǡʹͲͲ ൈ ͵ǤͲͲ ൈ ܳ
‫ܥ‬ሺܳǡ ‫ܣ‬ሻ ൌ െ ൅ ‫ܥ‬ு௑ ‫ܣ‬
ͳǡͲͲͲǡͲͲͲ
Four equality constraints can be written based on engineering knowledge:
Energy balances:
ܳ ൌ ͺͲǡͲͲͲ ͲǤͷͲ ͶͶͲ െ ܶ௅ீைǡ୭୳୲
ܳ ൌ ͷͲͲǡͲͲͲ ͲǤͶͷ ܶ஼ைǡ୭୳୲ െ ʹͶͲ
Heat transfer rate:
ܳ ൌ ͲǤ͹ ͵ͷ ‫ܣ‬οܶ୐୑
Definition of log-mean temperature-driving force:
ସସ଴ି்಴ೀǡ౥౫౪ ି ்ಽಸೀǡ౥౫౪ ିଶସ଴
οܶ୐୑ ൌ రరబష೅
಴ೀǡ౥౫౪
୪୬ ೅
ಽಸೀǡ౥౫౪ షమరబ

Solution
There are four equations and five variables (ܶ௅ீைǡ୭୳୲ , ܶ஼ைǡ୭୳୲ , ܳ, ‫ܣ‬, οܶ୐୑ ).
Therefore there is one decision variable, which must be selected from
among the set of variables. The best choice is ܶ௅ீைǡ୭୳୲ because it is easily
bounded and the other variables can be calculated explicitly once it is
specified. Thus the optimization problem can be formulated:
Minimize ‫ܥ‬ሺǡ ሻ
w. r. t. s. t.
ܶ௅ீைǡ୭୳୲ ܳ ൌ ͺͲǡͲͲͲ ͲǤͷͲ ͶͶͲ െ ܶ௅ீைǡ୭୳୲
ܳ ൌ ͷͲͲǡͲͲͲ ͲǤͶͷ ܶ஼ைǡ୭୳୲ െ ʹͶͲ
ܳ ൌ ͲǤ͹ ͵ͷ ‫ܣ‬οܶ୐୑
ସସ଴ି்಴ೀǡ౥౫౪ ି ்ಽಸೀǡ౥౫౪ ିଶସ଴
οܶ୐୑ ൌ రరబష೅಴ೀǡ౥౫౪
୪୬
೅ಽಸೀǡ౥౫౪ షమరబ
ʹͶͲ ൏ ܶ௅ீைǡ୭୳୲ ൏ ͶͶͲ
Solution
0
-20
-40
Annuualized Cost (1000$)
-60
-80
-100
-120
-140
-160
240 260 280 300 320 340 360 380 400 420 440
Exit Temperature of Light Gas Oil (°F)

Example
The following azeotropic distillation process is to be optimized to minimize
total annual cost.
Example
The decision variables are the composition of the recycle stream D2 (xD2),
the number of stages in the azeotropic column (N1), the azeotropic column
feed stage (NF1), the total number of stages in the recovery column (N2)
and the feed stage of the recovery column (NF2). Two constraints are that
the purity of the IPA must be xB1=0.999999 and the purity of the water must
be xB2=0.999.

Solution
The optimization problem can be formulated:
Minimize ୅ ሼ‫ݔ‬ሽ
w. r. t. s. t.
‫ݔ‬஽ଶ ǡ ܰଵ ǡ ܰிଵ ǡ ܰଶ ǡ ܰிଶ ܿ ‫ ݔ‬ൌ Ͳ (model equations)
‫ݔ‬஻ଵ ൌ ͲǤͻͻͻͻͻͻ
‫ݔ‬஻ଶ ൌ ͲǤͻͻͻ
Solution

Solution
Solution

Plantwide Process Control
Plantwide Process Control Process Design Slide 1

Based on: Plantwide Process Control by Luyben, Tyreus and Luyben
Introduction
• Fundamentals concepts of process control are
taught in the process control course.
• In this topic, we will discuss control of certain
unit operations, present a methodology of
plantwide process control, and illustrate the
methodology with examples.

Control of Unit Operations
• We will discuss decentralized control
structures for certain common unit operations:
• Distillation columns
• Flash units
• Chemical reactors
• Process-to-process heat exchangers

Control of Distillation Columns

• Distillation is the most widely-used method of separation in the
chemical process industries, and control of distillation columns
has received a great deal of attention.

• A simple two-product distillation column such as the
one shown in this figure has five control degrees of
freedom if the feed flow rate is fixed:
• Condenser duty (or cooling water flow rate)
• Liquid reflux flow rate
• Distillate product rate
• Reboiler duty (or steam rate)
• Bottom flow rate
• Three inventory variables must be controlled:
• Column pressure
• Liquid level in distillate receiver
• Liquid level in column bottom


• This leaves three control degrees of freedom. These
can be used to control
• Flow rate through the column
• Two compositions, usually one at the top of the
column and one at the bottom.
• Sometimes it is only important to control one
composition. In this case, another variable (usually
reflux ratio or boilup ratio) can be kept constant.


Control of a flash drum

Control of Chemical Reactors
• The two most common types of chemical reactors
encountered in the chemical process industry are well-
mixed (CSTR) reactors and packed bed (PFR) reactors.
These two reactor types will be considered in this
topic.
• For highly exothermic reactions, reactor temperature
control is critical for process safety.

Control of stirred reactors

• The most common choice is to manipulate the flow
rate of coolant to control the reactor temperature and
manipulate the reactor effluent flow rate to control
the reactor level. The throughput can be controlled by
manipulating the feed rate.
• If two or more reactants are mixed in the reactor, ratio
control may be used to control the other flow rates.
• If there is a vapor stream withdrawn from the reactor,
the vapor flow rate can be manipulated to control the
reactor pressure.
• If the reactor is jacketed, a cascade control structure
can be implemented based on secondary
measurement of the jacket temperature.
Control of stirred reactors

Control of process-to-process heat

exchangers
• Control of utility heat exchangers (steam, furnace, cooling water,
etc.) is straightforward: The utility duty is manipulated to control
the temperature of the process stream.
• Process-to-process heat exchangers (that result from heat
integration) are more difficult: if a single heat exchanger with no
bypass is employed, then there are no control degrees of
freedom.

Control of process-to-process heat
exchangers

Plantwide Control Design Procedure

• Establish control objectives
• Reactor and separation yield
• Product quality specifications
• Product grades
• Environmental restrictions
• Range of safe operating conditions
• Determine Control Degrees of Freedom
• Count the number of manipulated variables available
• In some cases, the process may need to be modified to
introduce additional manipulated variables
• Establish Energy Management System
• Remove excess heat of reaction from the process
• Transfer thermal disturbances to the utilities

• Set Production Rate
• Usually the production rate is set by flow-controlling one of
the reactant streams
• Note that a change in the production rate must be
accompanied by a change in some property of the reactor
(usually holdup, temperature or reactant concentration).
• Control Product Quality and Handle Safety, Environmental and
Operational Constraints
• Control Inventories (Pressures and liquid levels)
• Check Component Balances
• Verify that there is some way for all species to be consumed
or exit the process
• If a process has two or more reactants that are recycled, do
not flow-control more than one of them.


• Control Individual Unit Operations
• Control of common unit operations was discussed previously
• Relative Gain Array (RGA) and Singular Value (SV) analysis
can be used to suggest pairings between controlled and
manipulated variables for other units.
• Optimize Economics and Improve Dynamic Controllability
• If additional control degrees of freedom remain, they can be
used to improve controllability or improve dynamic
performance.
• Try to identify variables which, when maintained constant,
keep the process near the economic optimum point. This is
called self-optimizing control

Acyclic process

Acyclic process
Control structure for fixed fresh feed

Acyclic process
Control structure for on-demand product

Reactor-flash-recycle process

Control structure based on unit-by-unit design

"Snowball Effect"
• The control structure on the previous slide will work in some
cases, but it may suffer from what Luyben calls the "snowball
effect".
• Because the reactor level and temperature are maintained
constant, if we wish to increase the production rate, the only way
to achieve this is to increase the concentration of reactant in the
reactor.
• In some cases, this can result in dramatic increases in recycle flow
rate for relatively small changes in production rate. This is called
the "snowball effect"
• An alternative strategy is to control the flowrate in the recycle
loop to a constant value and change the production rate by
changing the holdup in the reactor.

Plantwide control structure to avoid the snowball effect.



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Process Economics

Process Economics Process Design Slide 1

Process Economics Process Design Slide 2

Process Economics Process Design Slide 3

Types of Capital Cost Estimate

Process Economics Process Design Slide 4

Process Economics Process Design Slide 5

Cost of Estimate (Engineering time)

Process Economics Process Design Slide 6

Process Economics Process Design Slide 7

Effect of Size (Capacity)

Process Economics Process Design Slide 8

• A 100 m2 exchanger costs less than two 50 m2 exchangers.

Process Economics Process Design Slide 9

Process Economics Process Design Slide 10

Marshall and Swift

Engineering News – Record

Process Economics Process Design Slide 11

(a) Fabricated Equipment 37

Process Economics Process Design Slide 12

Process Economics Process Design Slide 13

What is the estimated cost of a 80 m2 heat exchanger in 2007 (CEPCI = 500)?

Process Economics Process Design Slide 14

Process Economics Process Design Slide 15

Installed Cost of Equipment

‫்ܥ‬ெ ൌ ‫୐ܨ‬ୟ୬୥ ෍ ‫ܥ‬௣௜

Process Economics Process Design Slide 17

Module Factor Approach

‫ܥ‬஻ெ : bare module cost

‫ܨ‬஻ெ ൌ ‫ܤ‬ଵ ൅ ‫ܯܨ݌ܨʹܤ‬

Process Economics Process Design Slide 18

Process Economics Process Design Slide 19

Module Factor Approach

K1 K2 K3 Capacity Min size Max size

Process Economics Process Design Slide 20

Process Economics Process Design Slide 21

Process Economics Process Design Slide 22

ଵ଴ ‫ܨ‬௉ ൌ ‫ܥ‬ଵ ൅ ‫ܥ‬ଶ ଵ଴ ܲ ൅ ‫ܥ‬ଷ ଵ଴ ܲ ଶ ‫ܨ‬௉ ൌ ͳǤ͵ͺ

‫ܨ‬஻ெ ൌ ‫ܤ‬ଵ ൅ ‫ܯܨ݌ܨʹܤ‬ ‫ܨ‬୆୑ ൌ ͹Ǥͺ͵

‫ܥ‬஻ெ ൌ ‫ܥ‬௣௢ ‫ܨ‬஻ெ ‫ܥ‬஻ெ ൌ ̈́ͳͻͺǡͲͲͲ

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Total-Module and Grass-Roots Costs

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• In general, information about costs must be scaled

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Process Economics Process Design Slide 26

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Estimation of Manufacturing Costs

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‫( ܫܥܨ‬Fixed Capital Investment) is ‫்ܥ‬ெ or ‫ீܥ‬ோ from capital cost estimation.

Process Economics Process Design Slide 29

General Manufacturing Expenses

Process Economics Process Design Slide 30

‫ ܯܱܥ‬ൌ ͲǤʹͺͲ‫ ܫܥܨ‬൅ ʹǤ͹͵‫ܥ‬ை௅ ൅ ͳǤʹ͵ ‫ܥ‬௎் ൅ ‫ܥ‬ௐ் ൅ ‫ܥ‬ோெ

To determine the cost of manufacture, we must first determine:

Process Economics Process Design Slide 31

Cost of Operating Labor

ଵ଴ ‫ܨ‬௉ ൌ ‫ܥ‬ଵ ൅ ‫ܥ‬ଶ ଵ଴ ܲ ൅ ‫ܥ‬ଷ ଵ଴ ܲ ଶ ‫ܨ‬௉ ൌ ͳǤ͵ͺ

Typical CFD for a new project

ܲ‫ ܲܤ‬ൌ ͵ ൅ ሺെ͹ʹǤʹͷ ൅ ͶͲሻΤሺെ͹ʹǤʹͷ ൅ ͵͹ሻ ൌ ͵Ǥͻͳ