Green Engineering, Process Safety

and Inherent Safety: A New Paradigm

David R. Shonnard, Ph.D.
Department of Chemical Engineering
Michigan Technological University

Hui Chen, Ph.D.

Chemical and Materials Engineering
Arizona State University

SACHE Faculty Workshop

Sheraton Hotel and ExxonMobil, Baton Rouge, LA USA
September 28 – October 1, 2003
1
 Presentation Outline

• Introduction to Green Engineering (GE) and Inherent Safety

(IS)
– GE definition, concepts, principles, and tools
– IS concepts and tools
– Similarities and differences between GE and IS

• Environmentally-Conscious Process Design Methodology

– A hierarchical approach with three “tiers” of impact assessment
– A case study for maleic anhydride (MA) process design
– Early design methods and software tools
– Flowsheet synthesis, assessment, and software tools
– Flowsheet optimization - comparison of process improvement
– Summary of environmentally-conscious design methods

2
 What is Green Engineering?

Design, commercialization and use of processes

and products that are feasible and economical
while minimizing:

• + Risk to human health and the environment

• + Generation of pollution at the source

US EPA, OPPT, Chemical Engineering Branch, Green Engineering Program

3
 Why Chemical Processes (USA)?

• Positives
– 1 million jobs

– $477.8 billion to the US economy

– 5% of US GDP

– + trade balance (in the recent past)

– 57% reduction in toxic releases (`88-`00)

• Chemical and Engineering News, Vol. 80, No. 25, pp. 42-82, June 24, 2002
• US EPA, Toxics Release Inventory (TRI) Public Data Release, 2000

4
 Why Chemical Processes (USA)?

• Environmental Challenges
– Manufacturing industries in the US (SIC codes 20-39) 1/3 of
all TRI releases
– Chemical/Petroleum industries about 10% of all TRI
releases
– Increase of 148% of TRI wastes managed on-site (`91-`00)
– Chemical products harm the environment during their use
– Energy Utilization – ~15% of US consumption

• US EPA, Toxics Release Inventory (TRI) Public Data Release, 2000

• US DOE, Annual Energy Review, 1997.

5
 Energy Use: U.S. Industry

SIC Code 1015 BTU/yr

29 Petroleum/Coal Products 6.34

28 Chemicals / Allied Products 5.33
26 Paper / Allied Products 2.67
33 Primary Metals Industries 2.46
20 Food / Kindred Products 1.19
32 Stone,Clay and Glass 0.94
24 Lumber / Wood Products 0.49
Numbers represent roughly the % of US annual energy consumption

Annual Energy Review 1997, U.S. DOE, Energy Information Administration, Washington, DC, DOE/EIA-0384(97)
6
 Pollution Prevention (P2) vs.
Pollution Control (PC)

Traditional Process
Products
Raw Materials,
Energy Chemical
Process Pollution
Control
Wastes

Greener Process Higher income,

Products
Raw Materials, Higher operating costs
Energy
Modified
Chemical Pollution
Control Lower PC costs
Process
Wastes
Recycle

7
 Examples of Green Engineering

• Chemical reactions using environmentally-benign solvents

• Improved catalysts
– that increase selectivity and reduce wastes
– that improve product quality and reduce environmental impacts
– that process wastes into valuable products
• Separations using supercritical CO2 rather than R-Cl solvents
• Separative reactors that boost yield and selectivity
• Fuel cells in transportation and electricity generation
• CO2 sequestration
• New designs that integrate mass and energy more efficiently
• Process modifications that reduce emissions
• Environmentally-conscious design methods and software tools.

8
Environmentally-Conscious Design

• Methods and tools to evaluate environmental consequences of

chemical processes and products are needed.
– quantify multiple environmental impacts,
– guide process and product design activities
– improve environmental performance of chemical processes and
products

• Environmental impacts
– energy consumption - raw materials consumption
– impacts to air, water - solid wastes
– human health impacts - toxic effects to ecosystems

• Economic Performance
– costs, profitability

9
 Tools of Environmentally-Conscious
Chemical Process Design and Analysis

Chemical Process Properties Chemical Process Models

• thermodynamics • simulation
• reactions • waste generation and release
• transport

Environmental Fate Properties Environmental Fate Models

• databases • single compartment
• estimation • multi-media
E-CD
Environmental Impacts Models
Hierarchical Design • midpoint vs endpoint
• normalization
• valuation
Process Optimization
• multi-objective Process Integration
• mixed integer • mass integration
• non-linear • heat integration

10
 Principles of Green Engineering

The Sandestin Declaration on

Green Engineering Principles

Green Engineering transforms existing engineering

disciplines and practices to those that lead to
sustainability. Green Engineering incorporates
development and implementation of products,
processes, and systems that meet technical and cost
objectives while protecting human health and welfare
and elevates the protection of the biosphere as a
criterion in engineering solutions.
Green Engineering: Defining the Principles, Engineering Conferences 11
International, Sandestin, FL, USA, May 17-22, 2003.
 Principles of Green Engineering

The Sandestin GE Principles

1. Engineer processes and products holistically, use systems analysis, and
integrate environmental impact assessment tools.
2. Conserve and improve natural ecosystems while protecting human health and
well-being
3. Use life-cycle thinking in all engineering activities
4. Ensure that all material and energy inputs and outputs are as inherently safe
and benign as possible
5. Minimize depletion of natural resources
6. Strive to prevent waste
7. Develop and apply engineering solutions, while being cognizant of local
geography, aspirations, and cultures
8. Create engineering solutions beyond current or dominant technologies;
improve, innovate and invent (technologies) to achieve sustainability
9. Actively engage communities and stakeholders in development of engineering
solutions

Green Engineering: Defining the Principles, Engineering Conferences 12

International, Sandestin, FL, USA, May 17-22, 2003.
Definition of Inherent Safety (IS)

A chemical manufacturing process is described

as inherently safer if it reduces or eliminates
hazards associated with materials used and
operations, and this reduction or elimination is a
permanent and inseparable part of the process
technology. (Kletz, 1991; Hendershot, 1997a, b)

13
 IS Concepts

• Intensification - using less of a hazardous material

Example: improved catalysts can reduce the size of
equipment and minimize consequences of accidents.

• Attenuation - using a hazardous material in a less hazardous

form. Example: larger size of particle for flammable dust or a
diluted form of hazardous material like aqueous acid rather
than anhydrous acid.

• Substitution - using a safer material or production of a safer

product. Example: substituting water for a flammable solvent
in latex paints compared to oil base paints.

14
 IS Concepts (cont.)

• limitation - minimizing the effect of an incident.

Example: smaller diameter of pipe for transport of
toxic gases and liquids will minimize the dispersion
of the material when an accident does occur
• Simplification - reducing the opportunities for error
and malfunction. Example: easier-to-understand
instructions to operators.

15
 Comparison between IS and (GE)

Strategy/Tenet Inherent Green

Example Concepts
(Based on IS) Safety (IS) Engineering (GE)
Substitution Reaction chemistry, Feedstocks,
Catalysts, Solvents, Fuel selection √√√√ √√√√

Minimization Process Intensification, Recycle,

Inventory reduction, Energy efficiency, √√√ √√√√
Plant location

Simplification Number of unit operations, DCS

configuration, Raw material quality, √√√√ √√√√
Equipment design

Moderation (1) Conversion conditions, Storage

[Basic Process] conditions, Dilution, Equipment √√√√ √√√
overdesign

Moderation (2) Offsite reuse, Advanced waste

[Overall Plant] treatment, Plant location, Beneficial √√√ √√√
co-disposal

√√√√ = Primary tenet/concepts √√√ = Strongly related tenet/concepts

√√ = Some aspects addressed √ = Little relationship 16
 Similarities between (GE) and (IS)

• Benign and less hazardous materials.

• Both focus on process changes.

• Improving either one often results in improving the

other.

• Both use a life-cycle approach.

• Both are best considered in the initial stages of the

design.

17
 Differences between GE & IS

• Focus on a different parts of the product life cycle.

• Focus on different aspect of EHS (environmental,

health and safety) field and may conflict in
application.

• Environmental impacts are more numerous than

safety impacts.

18
 Presentation Outline

• Introduction to Green Engineering (GE) and Inherent Safety

(IS)
– GE definition, concepts, principles, and tools
– IS concepts and tools
– Similarities and differences between GE and IS

• Environmentally-Conscious Process Design Methodology

– A hierarchical approach with three “tiers” of impact assessment
– A case study for maleic anhydride (MA) process design
– Early design methods and software tools
– Flowsheet synthesis, assessment, and software tools
– Flowsheet optimization - comparison of process improvement
– Summary of environmentally-conscious design (ECD) methods

19
 Scope of environmental impacts

Pre-Chemical Chemical Post-Chemical

Manufacturing Stages Manufacturing Process Manufacturing Stages
• Chemical reactions • Final product manufacture
• Extraction from the
• Separation operations • Product usage in commerce
• Material storage • • Reuse/recycle
Loading and unloading • • Treatment/destruction
Material conveyance • • Disposal
environment •
Waste treatment processes • Environmental release
Transportation of materials •
Refining of raw materials •
Storage and transportation •
Loading and unloading
• Airborne releases wastewater releases • Solid/hazardous waste • Toxic chemical releases
• Energy consumption • Resource depletion

Environmental/Health Impacts
• Global warming • Ozone layer depletion • Air quality – smog • Acidification • Ecotoxicity
• Human health effects, carcinogenic and non carcinogenic • Resource depletion
20
 Tools of Environmentally-Conscious
Chemical Process Design and Analysis

Chemical Process Properties Chemical Process Models

• thermodynamics • simulation
• reactions • waste generation and release
• transport

Environmental Fate Properties Environmental Fate Models

• databases • single compartment
• estimation • multi-media
E-CD
Environmental Impacts Models
Hierarchical Design • midpoint vs endpoint
• normalization
• valuation
Process Optimization
• multi-objective Process Integration
• mixed integer • mass integration
• non-linear • heat integration

21
 Hierarchical Approach to E-CD

Process Design Stages Environmental Assessments

Level 1. Input Information Simple (“tier 1”)

problem definition toxicity potential, costs

Level 2. Input-Output Structure

material selection reaction pathways

Levels 3 & 4.
“tier 2” – material/energy
recycle separation system
intensity, emissions, costs

Levels 5 - 8. “tier 3” – emissions,

energy integration detailed evaluation environmental fate, risk
control safety
Allen, D.T. and Shonnard, D.R.
Douglas, J.M., Ind. Eng. Chem. Res., Green Engineering : Environmentally
Vol. 41, No. 25, pp. 2522, 1992 Conscious Design of Chemical Processes,
Prentice Hall, pg. 552, 2002. 22
 Early vs Detailed Design Tasks
Chen, H., Rogers, T.N., Barna, B.A., Shonnard, D.R.,, Environmental Progress, in press April, 2003.

Initial design task

Process synthesis and base case Equipment sizing

flowsheet development Economic assessment
Environmental assessment
1. Reaction pathway evaluation
2. Solvent selection
3. Technology selection Scaled gradient analysis
4. Equipment selection

Process Multi-objective
Iterate simulation optimization

PDS Life cycle assessment

Improved base Optimum

case flowsheet

Early Design Detailed Design 23

 Hierarchical Approach to E-CD

Process Design Stages Environmental Assessments

Level 1. Input Information Simple (“tier 1”)

problem definition toxicity potential, costs

Level 2. Input-Output Structure

material selection reaction pathways

Levels 3 & 4.
“tier 2” – material/energy
recycle separation system
intensity, emissions, costs

Levels 5 - 8. “tier 3” – emissions,

energy integration detailed evaluation environmental fate, risk
control safety
Allen, D.T. and Shonnard, D.R.
Douglas, J.M., Ind. Eng. Chem. Res., Green Engineering : Environmentally
Vol. 41, No. 25, pp. 2522, 1992 Conscious Design of Chemical Processes,
Prentice Hall, pg. 552, 2002. 24
 Case Study:
Maleic Anhydride (MA) Production

Level 1. Input / Output Information

Benzene Process n-Butane Process

V2O5-MoO3
VPO
2C6 H 6  9O2  2C4 H 2O3  4CO2  4 H 2O 2C4 H10  7O2  2C4 H 2O3  8 H 2O
2C 6 H 6  9O 2  12CO  6 H 2 O 2C 4 H 10  9O2  8CO  10 H 2 O
2C 6 H 6  15O 2  12CO 2  6 H 2 O 2C 4 H 10  13O2  8CO2  10 H 2 O
C 4 H 2 O3  O 2  4CO  H 2 O C 4 H 2 O3  3O2  4CO2  H 2 O
C4 H 2O3  3O2  4CO2  H 2O C 4 H 2 O3  O2  4CO  H 2 O

Benzene conversion, 95% n-butane conversion, 85%

MA Yield, 70% MA Yield, 60%
Air/Benzene, ~ 66 (moles) Air/n-butane, ~ 62 (moles)
Temperature, 375°C Temperature, 400°C
Pressure, 150 kPa Pressure, 150 kPa

25
 MA Production:
Early Design Costs

Level 1. Input / Output Information

“Tier 1” Economic analysis (raw materials costs only)

Benzene Process

(1 mole/0.70 mole)  (78 g/mole)  (0.00028 $/g) = 0.0312 $/mole of MA

MA Yield Bz MW Benzene cost

N-butane process
has lower cost
n-Butane Process
(1mole/0.60 mole)  (58 g/mole)  (0.00021 $/g) = 0.0203 $/mole of MA

MA Yield nC4 MW nC4 cost

Assumption: raw material costs dominate total cost of the process

26
 MA Production:
Environmental Impacts

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis

• Based on Products and Byproducts from the Reactor

• Alternative “tier 1” assessment approaches

– Toxicity and stoichiometry
– Toxicity, other impact potentials, and stoichiometry
– Toxicity, other impact potentials, stoichiometry, and
environmental fate
– Toxicity, other impact potentials, stoichiometry,
environmental fate, and pollution control.

27
 MA Production:
IO Assumptions

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis
CO2, H2O, air,
traces of CO, MA
benzene, n-butane

Pollution
Unreacted
Benzene Control
or 99% control
n-butane
Benzene CO, CO2 , H2O, air, MA
or
n-butane
Product
Reactor
Recover
99% MAyrecovery
Air MA, CO, MA
CO2 , H2O 50x106
air lb/yr
28
 Emission Estimation

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis

• Emissions to Air
– Emission factors from US EPA
• Reactors, separation devices
• Air ClearingHouse for Inventories and Emission Factors
• Air CHIEF http://www.epa.gov/ttn/chief/index.html
– CO, CO2 generation from the reactor
• Benzene process
– Benzene: 0.07 moles benzene / mole MA
– CO + CO2: 4.1 moles / mole MA
• n-butane process Conversions,
– n-butane: 0.25 moles benzene / mole MA Yields
– CO + CO2: 1.7 moles / mole MA

29
 Environmental /
Toxicity Properties

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis

• Environmental/Toxicological Properties
– Estimation Software
• EPI (Estimation Program Interface) Suite
• http://www.epa.gov/oppt/exposure/docs/episuite.htm
• Henry‘s constant, partitioning, degradation, toxicity
– Online Database
• Environmental Fate Database
• http://es.epa.gov/ssds.html

Compilation in: Appendix F.

Allen, D.T. and Shonnard, D.R., Green Engineering : Environmentally- Conscious Design
of Chemical Processes, Prentice Hall, pg. 552, 2002

30
 Environmental Fate Calculations

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis
Multimedia Processes modeled
compartment • emission inputs, E
model • advection in and out, DA
• intercompartment mass transfer,Di,j
• reaction loss, DR

Model Domain Parameters

• surface area - 104 -105 km2
• 90% land area, 10% water
• height of atmosphere - 1 km
• soil depth - 10 cm
• depth of sediment layer - 1 cm
• multiphase compartments

Mackay, D. 1991, ”Multimedia Environmental Models", 1 st edition,, Lewis Publishers, Chelsea, MI

31
 Impact Indicator Calculation

Level 1. Input / Output Information

“Tier 1” Environmental Impact Analysis
Carcinogenic Risk Example (inhalation route)

(Ca  CR  EF  ED) 
 SF

 (BW  AT ) 
i
Relative Risk =
(Ca  CR  EF  ED) 
 SF

 (BW  AT ) 
Benchmark

Exposure
=
Ca  SFi Factors
Ca  SF Benchmark

Multimedia compartment model Carcinogenic Slope Factor, SF

concentration in air (toxicological property)
32
 Indicators for the
Ambient Environment

Level 1. Input / Output Information The TRACI method and software

contains a comprehensive listing
“Tier 1” Environmental Impact Analysis of impact categories and indicators.
R e la tiv e R is k In d e x E q u a tio n
G lo b a l W a r m in g
I G* W , i  GWP i

*
MW C O2
I G W ,i  N C
MW i
O z o n e D e p le tio n
I O* D,i  ODP i

S m o g F o r m a tio n * MIR i
I S F, i 
MIR R O G
A c id R a in * ARP i
I A R, i 
ARP S O2
G W P = g lo ba l w a rm in g po ten tia l, N C = n u m be r of ca rbo n s a to m s, O D P = o zo ne
d e p letion p o te nta l, M I R = m a x im u m in cre m en ta l rea c tiv ity , A R P = a c id ra in p o tentia l.
Compilation impact parameters in: Appendix D.
Allen, D.T. and Shonnard, D.R., Green Engineering : Environmentally-
Conscious Design of Chemical Processes, Prentice Hall, pg. 552, 2002 33
 Indicators of Toxicity

Level 1. Input / Output Information The TRACI method and software

contains a comprehensive listing
“Tier 1” Environmental Impact Analysis of impact categories and indicators.
R e l a t i v e R i s k In d e x E q u a tio n
H u m a n T o x ic ity * C W , i LD 5 0, To lu en e
In g e s t io n R o u te
I IN G 
C W , To lu en e LD 5 0,i
H u m a n T o x ic ity * C A , i LC 5 0 , To lu en e
In h a la t io n R o u t e
I IN H 
C A , To lu en e LC 5 0, i
Hum an C W ,i HV i
I * C IN G 
C a r c in o g e n ic ity C W , B en zen e HV B en zen e
In g e s t io n R o u te
Hum an * C A , i HV i
C a r c in o g e n ic ity I C IN H 
C A , B en zen e HV B en zen e
In h a la t io n R o u t e
F is h T o x ic ity * C W , i LC 5 0 f , P C P
I FT 
C W , P C P LC 5 0 f , i
L D 5 0 = le t h a l d o s e 5 0 % m o r t a lit y , L C 5 0 = le t h a l c o n c e n t r a t io n 5 0 % m o r t a lit y ,
a n d H V = h a z a r d v a lu e f o r c a r c in o g e n ic h e a lth e f f e c t s .
34
 Indicators for MA Production
N
Level 1. Input / Output Information Process Index (I)   (Ii *)  (mi )
“Tier 1” Environmental Impact Analysis i1

Chemical Benzene n-butane

IFT (kg/mole MA) 5.39x10-6 2.19x10-6

IING “ 3.32x10-3 3.11x10-3

n-butane
IINH “ 8.88x10-2 3.93x10-2
process
ICING “ 1.43x10-4 0.00 has lower
environ-
ICINH “ 1.43x10-4 0.00
mental
IOD “ 0.00 0.00 impacts
IGW “ 2.01x10-1 1.17x10-1

ISF “ 3.04x10-5 4.55x10-6

IAR “ 0.00 0.00

35
 Hierarchical Approach to E-CD

Process Design Stages Environmental Assessments

Level 1. Input Information Simple (“tier 1”)

problem definition toxicity potential, costs

Level 2. Input-Output Structure

material selection reaction pathways

Levels 3 & 4.
“tier 2” – material/energy
recycle separation system
intensity, emissions, costs

Levels 5 - 8. “tier 3” – emissions,

energy integration detailed evaluation environmental fate, risk
control safety
Allen, D.T. and Shonnard, D.R.
Douglas, J.M., Ind. Eng. Chem. Res., Green Engineering : Environmentally
Vol. 41, No. 25, pp. 2522, 1992 Conscious Design of Chemical Processes,
Prentice Hall, pg. 552, 2002. 36
 Case Study: MA Production

Level 3-8. Flowsheet Synthesis and Evaluation

“Tier 3” Environmental Impact Analysis

• Based on an initial process flowsheet created using

“traditional“ economic-based design heuristics.

• “tier 3” assessment
– Emissions estimation from units and fugitive sources
– Environmental fate and transport calculation
– Toxicity, other impact potentials, environmental fate and
transport, and pollution control.

37
Integrated Process Simulation and
Assessment Method and Software

SCENE
PDS Report
Stream
information
SGA Report

HYSYS
EFRAT
Environmental
AHP
indices
DORT
Economic
Manipulated variables indices

OPTIMIZER Objective function

HYSYS – a commercial chemical process simulator software, EFRAT – a software for

calculating environmental impacts, DORT - a software to estimate equipment costs and
operating costs, AHP (Analytic Hierarchy Process) – multi-objective decision analysis, PDS
– Process Diagnostic Summary Tables, SGA – Scaled Gradient Analysis
38
Initial Flowsheet for MA from n-C4

Compressor
Air Reactors

Pump

n-Butane
Vaporizer

Off-gas
Off-gas
MA

Distillation
Absorber column

Solvent

39
Process Diagnostic Summary Tables:
Energy Input/Output for nC4 Process
Available Available
Energy flow % of total
Stream temperature Pressure
(MM Btu/hr) energy
(In,Out)(?F) (In,Out)(psia)
Input
Air 77 14.696 0.0000 0.00%
n-Butane 50 22.278 -0.0424 -0.11%
Make-up solvent 95 18.13 0.0004 0.00%
Solvent pump 472.87~472.96 1.2505~18.13 0.0107 0.03%
Air compressor 77~167.18 14.696~22.278 3.9588 9.92%
n-Butane vaporizer 50~50.004 22.278 1.0059 2.52%
Reactor feed heater 160.62~770 22.278 29.8800 74.90%
Reboiler 472.87 1.2505 5.0774 12.73%
Total 39.8908 100.00%
Output
Absorber off-gas 120.53 18.275 2.0033 1.80%
Distillation off-gas 95.043 0.3897 0.0002 0.00%
Crude MA 95.043 0.3897 0.0368 0.03%
Reactor 1 770 23.6340 21.29%
Reactor 2 770 23.6340 21.29%
Reactor 3 770 23.6340 21.29%
Reactor off-gas cooler 770~230 18.943 26.8940 24.23%
Solvent subcooler 234.95~95 18.13 7.1588 6.45%
Condenser 95.043 0.3897 4.0202 3.62%
Total 111.0153 100.00%

40
Process Diagnostic Summary Tables:
Manufacturing Profit and Loss, nC4

Name Total ($/yr) % of total cost

Revenue
Maleic anhydride 21,258,236 100.00%
Total Sales Revenue 21,258,836 100.00%

Manufacturing Expenses
Raw Materials
n-Butane cost 4,760,866 55.80%
Make-up solvent 81,343 0.95%
Utilities
Cooling water (tower) 159,913 1.87%
Electricity (on site) 679,014 7.96%
Steam (50 psig) 58,014 0.68%
Steam (600 psig) 580,303 6.80%
Natural gas 2,212,796 25.93%
Total Manufacturing Expenses 8,532,249 100.00%

41
 Process Diagnostic Summary Tables:
Environmental Impacts, nC4

k Ik Process Index
Normalization I 
Iˆk
N
National Index
Chemical IFT IING IINH ICING ICINH IOD IGW ISF IAR
Sulfur dioxide 0.00E+00 0.00E+00 1.49E+01 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 1.35E+02
TOC 1.36E-02 1.49E-02 6.62E+01 0.00E+00 0.00E+00 0.00E+00 4.11E+03 4.24E+02 0.00E+00
Carbon dioxide 4.36E+02 0.00E+00 8.91E+01 0.00E+00 0.00E+00 0.00E+00 6.09E+07 0.00E+00 0.00E+00
Carbon monoxide 1.90E-01 0.00E+00 1.65E+07 0.00E+00 0.00E+00 0.00E+00 2.33E+05 2.03E+03 0.00E+00
Dibutyl phthalate 7.70E+01 1.00E+02 3.01E+00 0.00E+00 0.00E+00 0.00E+00 2.56E+02 0.00E+00 0.00E+00
Maleic Anhydride 5.10E+02 7.27E+05 0.00E+00 0.00E+00 0.00E+00 0.00E+00 3.49E+04 0.00E+00 0.00E+00
n-Butane 6.98E-02 0.00E+00 2.38E+05 0.00E+00 0.00E+00 0.00E+00 6.97E+04 0.00E+00 0.00E+00
Nitrogen dioxide 2.10E-01 0.00E+00 2.89E+03 0.00E+00 0.00E+00 0.00E+00 4.09E+06 0.00E+00 7.16E+04
Totals 1.02E+03 7.27E+05 1.67E+07 0.00E+00 0.00E+00 0.00E+00 6.54E+07 2.46E+03 7.17E+04
Contribution to IPC 1.55% 0.34% 86.63% 0.00% 0.00% 0.00% 4.85% 0.14% 6.50%
IPC 6.13E-04
Weighting Factors

Process composite index global warming 2.5

IPC   (INk  Wk ) ozone depletion
smog formation
100
2.5
k acid rain 10
Source: Eco-Indicator 95 framework for life cycle assessment, carcinogenic 5
Pre Consultants, http://www.pre.nl noncarcinogenic 5
42
ecotoxicity 10
Flowsheet for MA Production from n-C4:
with Heat Integration.

Compressor

Air
Reactors

Pump
n-Butane

Vaporizer
Off-gas
Off-gas
MA

Distillation
Absorber column

Solvent

43
 Scaled Gradient Analysis

Flowsheet Optimization:
Scaled Gradient Analysis (SGA):

Rank Order Parameter, rj Proximity Parameter, pj

i = i-th unit operation i = i-th unit operation
j = j-th design variable j = j-th design variable

 
I i   I i x j x j
rj   x j pj 
 i 
x j
i
 I i x j x j
i

Douglas, J. M., “Conceptual Design of Chemical Process,” McGraw-Hill, New York (1988).

44
SGA: variable changes and scale factors

Flowsheet Optimization:
Scaled Gradient Analysis (SGA):

Incremental Scale
Design variable Unit
change factor
1 Change the recovery of MA in the absorber unitless 0.01 0.1
2 Increase the solvent inlet temperature in absorber ºC 5 10
3 Change recovery of MA in the distillation column unitless 0.018 0.1
4 Change the feed ratio of air to n-butane unitless 5 10
5 Change the reactor pressure kPa 10 30
6 Change the reaction temperature ºC 5 20
7 Change reflux ratio in distillation column unitless 0.1 0.5
Change minimum approach temperature of heat
8 ºC 5 10
exchanger between reactor feed and off-gas
Change minimum approach temperature of heat
9 ºC 5 10
exchanger between recycle solvent and distillation feed

45
Optimization using the Genetic Algorithm
Chen, H., Rogers, T.N., Barna, B.A., Shonnard, D.R.,, Environmental Progress, in press April, 2003.

Flowsheet Optimization:
B e g in
Genetic Algorithm
P o p u la tio n

Generations, 100
In itia liz a tio n

F itn e s s

Population Size, 100

E v a lu a tio n

S e le c tio n

Mutation Probability, 0.04

C ro sso v e r N o

M u ta tio n

C o n v e rg e n t?

Y es

S to p
46
Optimization Results: n-butane Process

AHP Ranking is the Objective Function

Operating conditions
Unit Range Value
Reflux ratio unitless 0.8~1.3 1.27
Reactor inlet temperature C 390~410 399.55
Reactor inlet pressure kPa 153.8~173.8 153.80
Recycle solvent flow rate kgmol/hr 170~230 230.00
Feed ratio of air to n-butane unitless 60~70 62.30
Indices
Unit Value Unit Value
IFT kg/yr 8.00E+02 IGW kg/yr 4.05E+07
IING kg/yr 6.60E+04 ISF kg/yr 2.04E+03
IINH kg/yr 1.59E+07 IAR kg/yr 5.46E+03
NPV MM$ 5.14 IPC unitless 5.38E-04

47
Optimization Results: n-butane Process

NPV is the Objective Function

Operating conditions
inlet temperature C 390~410 399.08
Reactor inlet pressure kPa 153.8~173.8 153.80
Recycle solvent flow rate kgmol/hr 170~230 230.00
Feed ratio of air to n-butane unitless 60~70 62.10
Indices
Unit Value Unit Value
IFT kg/yr 8.01E+02 IGW kg/yr 4.05E+07
IING kg/yr 6.61E+05 ISF kg/yr 2.04E+03
IINH kg/yr 1.60E+07 IAR kg/yr 5.48E+03
NPV MM$ 5.14 IPC Unitless 5.40E-04

48
Optimization Results: n-butane Process

IPC is the Objective Function

Operating conditions
Unit Range Value
Reactor inlet temperature C 390~410 390.00
Reactor inlet pressure kPa 153.8~173.8 153.80
Recycle solvent flow rate kgmol/hr 170~230 230.00
Indices
Unit Value Unit Value
IFT kg/yr 8.242E+02 IGW kg/yr 4.066E+07
IING kg/yr 6.773E+05 ISF kg/yr 1.921E+03
IINH kg/yr 1.509E+07 IAR kg/yr 5.384E+03
NPV MM$ 4.730 IPC unitless 5.112E-04

49
Optimization Results: Benzene Process

AHP Ranking is the Objective Function

Operating conditions
Unit Range Value
Reflux ratio unitless 0.81~1.3 1.28
Reactor inlet temperature C 375~395 375.00
Reactor inlet pressure kPa 147~177 147.00
Recycle solvent flow rate kgmol/hr 100~160 160.00
Feed ratio of air to benzene unitless 66~76 66.11
Indices
Unit Value Unit Value
IFT kg/yr 1.66E+03 ICINH kg/yr 3.89E+04
IING kg/yr 7.18E+05 IGW kg/yr 4.59E+07
IINH kg/yr 4.70E+06 ISF kg/yr 5.91E+03
ICING kg/yr 3.89E+04 IAR kg/yr 3.78E+03
NPV MM$ 3.44 IPC unitless 9.24E-02

50
Optimization Results: Benzene Process

NPV is the Objective Function

Operating conditions
Unit Range Value
Reflux ratio unitless 0.8~1.3 1.30
Reactor inlet temperature C 375~395 375.00
Reactor inlet pressure kPa 147~177 147.00
Recycle solvent flow rate kgmol/hr 100~160 159.96
Feed ratio of air to benzene unitless 66~76 66.00
Indices
Unit Value Unit Value
IFT kg/yr 1.66E+03 ICINH kg/yr 3.881+04
IING kg/yr 7.18E+05 IGW kg/yr 4.60E+07
IINH kg/yr 4.72E+06 ISF kg/yr 5.91E+03
ICING kg/yr 3.88E+04 IAR kg/yr 3.77E+03
NPV MM$ 3.49 IPC unitless 9.24E-02

51
Optimization Results: Benzene Process

IPC is the Objective Function

Operating conditions
Unit Range Value
Reactor inlet temperature C 375~395 395.00
Reactor inlet pressure kPa 147~177 177.00
Recycle solvent flow rate kgmol/hr 100~160 130.18
Feed ratio of air to benzene unitless 66~76 66.00
Indices
Unit Value Unit Value
IFT kg/yr 1.49E+03 ICINH kg/yr 2.37E+04
IING kg/yr 8.56E+05 IGW kg/yr 5.31E+07
IINH kg/yr 7.99E+06 ISF kg/yr 4.31E+03
ICING kg/yr 2.37E+04 IAR kg/yr 5.81E+03
NPV MM$ -2.13 IPC unitless 5.67E-02

52
 Continuous Improvement of Design
Performance

benzene
process
design

n-butane
process
design

53
 Summary / Conclusions

• A systematic and hierarchical approach for EC-D of

chemical processes is shown.
• The EC-D approach is applied to a case study design for
MA production from either benzene or n-butane.
• A number of computer-aided tools are available to facilitate
EC-D.
• This approach yields a continuous improvement in both
economic and environmental performance through the
designs process.
• Early design assessment methods are validated using
detailed design and optimization results.

54
 Acknowledgements

• EPA Contract 3W-0500-NATA – OPPT, Green Engineering

Program

• NSF/Lucent Technologies Industrial Ecology Research

Fellowship (BES-9814504)

• National Center for Clean Industrial and Treatment

Technologies (CenCITT)

55