Module 1: Environmental Literacy:: Environmental Issues, Risk, Exposure, and Regulations

Module 1: Environmental Literacy:
Environmental Issues, Risk, Exposure, and Regulations
David Shonnard
Department of Chemical Engineering
Michigan Technological University
1
University of Texas at Austin Michigan Technological University
Module 1: Presentation Outline
 Educational goals and topics covered in the module

 Potential uses of the module in chemical engineering
courses
 Review of environmental impacts - Chapter 1
 Environmental and health risk assessment - Ch. 2
 Exposure calculations - Chapter 6
 Environmental regulations of interest to chemical
engineers - Chapter 3
2
Module 1: Educational goals and topics
Students will:
 be introduced to major environmental issues related
to chemical processing
 become familiar with the fundamentals of risk
assessment
 be introduced to the major environmental regulations
of interest to the chemical industry and the chemical
engineer
 become aware of the major pathways and routes of
exposure to industrial chemicals
3
Module 1: Potential uses of the module in
chemical engineering courses
 Design course: Introduce environmental literacy

and regulations before assigning projects
 Freshman Engineering: Introduction to issues

regarding environment / society / industry
4
Module 1:
Scope of environmental impacts (Ch 1)
Materials Materials Materials Materials

Life-
Energy Energy Energy Energy
Cycle
Stages
Raw
Chemical Product Use, Reuse,
Materials
Processing Manufacturing Disposal
Extraction
Pollution Pollution
Control Control
Wastes Wastes Wastes Wastes
Midpoints
global ozone smog acidifi- ecological Human health

warming depletion formation cation harm and ecosystem
damage
Endpoint
5
Module 1: U.S. Energy Flows, 1997
Annual Energy Review 1997, U.S. DOE, Energy Information Administration, Washington, DC, DOE/EIA-0384(97)
6
Module 1:
Global warming and related impacts
Materials Energy Cause and Effect Chain
Products
greenhouse
Chemical climate change; human mortality
gas emissions
Processing CO2, CH4, N2O sea level change or life
adjustments
N2 O
O3
CH4
CO2
CFCs
Contribution to global
Warming; Phipps, NPPC, Climate Change 1995, Intergovernmental Panel on Climate Change, WMO and
http://www.snre.umich.edu/nppc/ UNEP, Cambridge University Press, 1996.
7
Module 1:
Stratospheric ozone and related impacts
Products
Chemical ozone depleting ozone layer loss human mortality

Processing substances increase in uv or life adjustments
CFCs, HCFCs ecosystem damage
1.E+06
Toxics Release Inventory Data
1.E+06
8.E+05
6.E+05
4.E+05
2.E+05
0.E+00
1995 1996 1997
Year
Total On- and Off-site Releases
8
Module 1:
Smog formation and related impacts
Products
Chemical NOx and volatile photochemical human/ecological

Processing organic substances oxidation reactions damage from O3
and other oxidants
1 - Chemical & Allied Processing

2 - Petroleum & Related Industries
NOx VOCs 6 7
1
5
NOx 2
1997
Miscellaneous 4 3
3 - Metals Processing, 4 - Other Industrial Processes

5 - Solvent Utilization, 6 - Storage & Transportation
Transportation 7 - Waste Disposal & Recycling
7 1
2 3
6
4
Industrial Processes
VOCs 1997
Fuel Combustion
National Air Quality and Emissions Trends Report, 1997, U.S. EPA Office of Air Quality Planning and Standards, http://www.epa.gov/oar/aqtrnd97/chapter2.pdf
9
Module 1:
Acid rain / Acid deposition
Products
Chemical SO2 and NOx Acidification rxns. human/ecological

Processing & acid deposition damage from H+
emission to air
and heavy metals
SO2
6 7
5
Miscellaneous 1997
4 1 1 - Chemical & Allied Processing
2 - Petroleum & Related Industries
Transportation 3 - Metals Processing
4 - Other Industrial Processes
Industrial Processes 5 - Solvent Utilization
6 - Storage & Transportation
7 - Waste Disposal & Recycling
Fuel Combustion
3 2
National Air Quality and Emissions Trends Report, 1997, U.S. EPA Office of Air Quality Planning and Standards, http://www.epa.gov/oar/aqtrnd97/chapter2.pdf
10
Module 1:
Human health toxicity
Materials Energy
Products
Chemical Toxic releases to Transport, fate, Human health

Processing air, water, and soil exposure pathways damage; carcino-
& routes genic & non...
All Other EPCRA

Transport- Industries Toxic Rubber All Other
ation 16%
Equipment Waste and Miscel- Industries
RCRA laneous 23%
7% Chemical
Hazardous Petroleum Plastics and Allied
Chemical / Refining 3%
Waste Allied Products
Primary 3% 27%
Metals Products
51% Paper and
8% Primary
Allied
Metals
Products
Petroleum Electronic 22%
5%
Refining Equipment
Transport- Electronic
9% 9%
ation Fabricated Equipment
5% Metals 6%
Allen and Rosselot, 1997 6%
11
Module 1:
Risk assessment: important questions (Ch 2)
 What are the risks associated with a chemical,

manufacturing process, or use of a product?
 How is risk quantified by professional risk assessors?
 Is risk assessment used by government agencies to

regulate industry? (Yes!)
12
Module 1:
Risk assessment: introductory concepts
Risk = F(exposure x hazard)
Modules 1,2 Modules 1,2

Chapters 5,6 Chapters 2,5
Steps in risk assessment

» Hazard assessment
» Exposure assessment
» Dose/response relationships
» Risk characterization
13
Module 1: Hazard assessment
Indicators of chemical toxicology
Carcinogenic effects - Slope Factor (SF), Weight of Evidence (WOE)
classification
Noncarcinogenic effects - No Observable Adverse Effects Level (NOAEL),
Reference Dose (RfD), Reference Concentration (RfC), Permissible
Exposure Limit (PEL), Threshold Limit Value (TLV)
Sources of Data for Health Effects

1. The Material Safety Data Sheet - MSDS
2. NIOSH Pocket Guide to Chemical Hazards (www.cdc.gov/niosh.npg/gpdstart.html)
3. Integrated Risk Information System (IRIS) (http://www.epa.gov/ngispgm3/iris/index.html)
4. National Library of Medicine (ToxNet) (http://sis.nlm.nih.gov/sis1)
5. Casarett and Doull’s “Toxicology, the Basic Science of Poisons”, Macmillan
6. Patty’s Industrial Hygiene and Toxicology, John Wiley & Sons
14
Module 1: Exposure assessment (Ch 6)
 Occupational Exposure- exposure to people in the workplace

 Community Exposure- exposure outside the workplace
Different modeling approaches and assumptions
Exposure Assessment Methodology - Community Exposure

1. Identify all waste stream components and concentrations
2. Estimate release rates to the air, water, and soil
3. Choose proper exposure pathways (through environment) and routes
(into humans)
4. Determine exposure concentrations at the point of exposure to humans
using measurements or an environmental fate and transport model
15
Module 1: Exposure assessment - cont.
Multiple pathways
Exposure Routes are possible
1. Inhalation
2. Ingestion
3. Dermal (skin)
16
Module 1:
Exposure assessment - H2S release example
x = 300 m
Atmospheric
dispersion
Model, Ca
H=0m
Q  H2 
Ca  exp  2 
Q = 0.025 kg/s H2S
 y zv x  2 z 
Rural release, daytime neutral atmosphere, x<500m, v x=4 m/s yz = 0.01082 x1.78
0.025kg / s
Ca   7.17  10 6 kg / m3  1.71 mg / m3
 (.01082 (300 m) (4 m / s))
1.78
Rural release, nighttime stable atmosphere, x<500m , v x=2.5 m/s yz = 0.0049 x1.66
0.025kg / s
Ca   5.02  105 kg / m3  50.2 mg / m3
 (.0049 (300 m) (2.5 m / s))
1.66
17
Module 1: Dose/Response
How large a dose causes what kind of effect?

Effective Dose
(reversible) Toxic Dose Lethal Dose
(irreversible)
Crowl and Louvar, Chemical Process Safety: Fundamentals with Applications, Prentice Hall, 1990
18
Module 1: Risk Characterization
Carcinogenic
Risk Example
(inhalation route) Exposure Dose
(mg/kg/d)
(Ca  CR  EF  ED) 
Risk i =   SF 
 (BW  AT ) i
Result: # excess cancers per 106
cases in the population; Dose - Response Relationship,
10-4 to 10-6 acceptable Slope Factor (mg/kg/d)-1
Exposure Factors
CR = contact rate (m3 air breathed / day)
EF = exposure frequency (days / yr)
ED = exposure duration (yr)
BW = body weight (kg)
AT = averaging time (days) - 25,550 days for carcinogenic risk
19
Module 1: Environmental regulations:
the regulatory process (Ch 3)
Environmental Laws
• Clean Air Act of 1970
Rule Making
• publish proposed regulations
in the Federal Register
• receive public comment on

Administrative Agencies proposed regulations
• US Environmental Protection Agency
• publish regulations in the
Federal Register
Environmental Regulations
• National Ambient Air Quality Standards (NAAQS)
20
Module 1: Environmental regulations:
changes over time
Major Laws/Amendments Environmental Regulations
Bishop, “Pollution Prevention: Fundamentals and Practice”, McGraw-Hill, 2000
21
The 9 essential environmental regulations:
the manufacture of chemicals
Environmental Date Purpose of Key Provisions

Statute Enacted Legislation
Regulation of Chemical
Manufacturing
The Toxic Substances 1976 Assess the risks of Chemical manufacturers, importers, or
Control Act (TSCA) chemicals before they processors, must test new chemicals
are introduced into and submit a Premanufacturing Notice
commerce. (PMN) to EPA.
The Federal Insecti- Enacted, Assess the risks of pes- Before any pesticide can be distrib-
cide, Fungicide, and 1947 ticides and to control uted or sold in the U.S., it must be
Rodenticide Act Amended, their usage to minimize registered with the EPA.
(FIFRA) 1972 exposure.
The Occupational 1970 Control exposure to Companies must adhere to all OSHA
Safety and Health Act chemicals in the work- health standards (exposure limits to
(OSH Act) place chemicals) and safety standards
(physical hazards from equipment).
Requires companies to develop (ma-
terial safety data sheet (MSDS).
22
The 9 essential environmental regulations :
discharges to air, water, and soil
Regulation of Discharges
to the Air, Water, and Soil
Clean Air Act (CAA) 1970 Establish uniform ambient air National Ambient Air Quality Stan-
quality standards / control air dards (NAAQS) for CO, Pb, NO2,
pollution discharge. Address spe- O3, particulate matter, and SO2.
cific air pollution problems (haz- States must develop source-
ardous air pollutants, stratospheric specific emission limits to achieve
ozone depletion, and acid rain). the NAAQS.
Clean Water Act (CWA) 1972 Reduce pollutant discharges into National Pollutant Discharge Elimi-
the nation’s waterways (“zero dis- nation System (NPDES) permit
charge” goal). Make water bodies program. Permit holders must
safe for swimming, fishing, and monitor discharges, collect data,
other forms of recreation (“swim- and keep records of the pollutant
mable” goal). levels of their effluents.
Resource Conservation 1976 Regulate the “cradle-to-grave” Generators must maintain records
and Recovery Act generation, transport, and dis- of hazardous waste generation and
(RCRA) posal of both non-hazardous and transportation, and file this data in
hazardous wastes to land, en- biennial reports to the EPA.
courage recycling, and promote Transporters and disposal facilities
the development of alternative en- must adhere to similar require-
ergy sources based on solid waste ments for record keeping and
materials. monitoring the environment.
23
The 9 essential environmental regulations :
clean-up, disclosure, and pollution prevention
Clean-Up, Emergency
Panning, and Pollution
Prevention
The Comprehensive 1980 Identify and clean up hazardous EPA identifies potentially responsi-
Environmental Re- waste sites at industrial com- ble parties (PRPs) and notifies
sponse, Compensation, plexes, and federal facilities. EPA them of their potential CERCLA
and Liability Act is responsible for creating the Na- liability, which is strict, joint and
(CERCLA) tional Priority List (NPL). Amended several, and retroactive.
by the Superfund Amendments
and Reauthorization Act (SARA)
of 1986.
The Emergency Plan- 1986 1) to respond to chemical release Facilities must help state and local
ning and Community emergencies, and 2) compile an entities to develop emergency re-
Right to Know Act inventory of toxic chemical response plans, and report annually
(EPCRA – part of SARA) leases to the air, water, and soil to EPA data on toxic substances .
from manufacturing facilities.
Pollution Prevention 1990 Establish pollution prevention as Owners and operators of facilities
Act (PPA) the nation’s primary pollution that are required to file a Form R
management strategy with em- under the SARA Title III to report to
phasis on source reduction. Es- the EPA information regarding the
tablished a Pollution Prevention source reduction and recycling ef-
Information Clearinghouse. forts that the facility has undertaken
during the previous year.
24
Module 1: Recap

courses
 Review of environmental impacts - Chapter 1
 Environmental and health risk assessment - Ch. 2
 Exposure calculations - Chapter 6
 Environmental regulations of interest to chemical
engineers - Chapter 3
25
Module 2: Evaluating Environmental
Partitioning and Fate: Approaches based on
chemical structure - Chapter 5
David Allen
University of Texas at Austin
26
Module 2: Evaluating Environmental
Partitioning and Fate:
Approaches based on chemical structure
 Educational goals and topics covered in the

module
 Potential uses of the module in chemical
engineering courses
 Overview of property estimation methods
 Software demonstration
 Case studies
27
covered in the module
Students will:
 become aware of the chemical and physical properties that
govern a chemical’s environmental partitioning and fate
 be able to estimate properties that govern environmental
partitioning and fate based on chemical structure
 be able to perform mass balances to estimate environmental
partitioning and be able to design structures that have targeted
properties
 be aware of the limitations of structure-property estimation

methods
28
covered in the module (cont’d)
Properties covered:
 Properties used to estimate partitioning:
boiling point, vapor pressure, octanol-water partition
coefficient, bioconcentration factor, Henry’s law
coefficient, soil sorption
 Properties that govern environmental fate:
atmospheric lifetimes, biodegradation rates
 Typical values of properties
 Environmental partitioning calculations
29
 Design course: Use as a preliminary screen of

chemical products and raw materials
 Materials course/thermodynamics course:

Module on estimating properties
 Mass and energy balances course: module on

estimating mass partitioning in closed systems
30
Module 2: Chemical properties for
environmental decision-making
Table 5.1-1 Chemical properties needed to perform
environmental risk screenings
Environmental Process Relevant Properties
Estimates of dispersion and Volatility, density, melting
fate point, water solubility,
octanol-water partition
coefficient, soil sorption
coefficient
Persistence in the environment Atmospheric oxidation rate,

aqueous hydrolysis rate,
photolysis rate, rate of
microbial degradation
Uptake by organisms Volatility, lipophilicity,

molecular size, degradation in
organism
Human uptake Transport across dermal

layers, transport rates across
lung membrane, degradation
rates within the human body
Toxicity and other health Dose-response relationships

effects
31
Module 2: Property estimation methods based
on chemical structure
 Empirical approach based on exp. Data

» Specific to chemical classes
» Termed structure-activity relationships (SARs)
 Approaches in Ch 5
» Functional Groups (KOW, kOH, PBio)
» Bond Types (H)
» Molecular Connectivity (KOC)
» Linear Free Energy (kHyd)
32
Module 2: Property estimation methods based
on other properties
 Based on KOW, octanol-water partitioning

» BCF - bioconcentration factor
» LC50 - lethal dose 50% mortality
» S - water solubility of organic compounds
» KOC - organic carbon/water partitioning
33
Module 2: Functional groups
 KOW - octanol-water partitioning

Describes partitioning of organic pollutants between the
water phase and octanol
log Kow = 0.229 +  ni fi +  nj cj
n = number of functional groups of types i or

j
fi = contribution to log Kow of group i
cj = correction factor for functional group j
34
Module 2: Functional groups
1,1-Dichloroethylene example
the molecular structure, CH2= CCl2
one =CH2 group

one =CH- or =C< group
two –Cl (olefinic attachment) groups
log Kow = 0.229 + 0.5184 + 0.3836 + 2(0.4923) = 2.11

(no correction groups)
Experimental log Kow = 2.13
35
Module 2: Bond Types
 H - Henry’s law constant

water phase and air in the environment
-log H =  ni hi +  nj cj
n = number of bonds of types i or j

hi = contribution to H of bond type i
cj = functional group correction
factor
36
Module 2: Bond Types
1-propanol example
the molecular structure,
H H H
  
H–C–C–C–O-H
  
H H H
7 C-H bonds, 2 C-C bonds, 1 C-O bond, and 1 O-H bond

-log H = 7(-0.1197) + 2(0.1163) + 1.0855 + 3.2318 = 3.7112
w correction; - log H = 3.7112 - 0.20 = 3.5112
linear or branched alcohols
Experimental -log H = 3.55
37
Module 2: Molecular connectivity
 KOC - Organic carbon-water partition coeff.

water phase and natural organic matter in soils/sediments
log Koc = 0.531 + 0.62 +  njPj
1
 = 1st order molecular connectivity index
nj = number of groups of type j
Pj = correction factor for group j
38
Module 2: Molecular connectivity
1-hexanol example
the molecular structure,
CH3 – CH2 – CH2 – CH2 – CH2 – CH2 – O - H
 (1) (2) (2) (2) (2) (2) (1) - atom connectivity
(i,j) (1,2) (2,2) (2,2) (2,2) (2,2) (2,1) - bond connectivity
 = (I* j)-0.5
1
1
 = (1/2) + (1/4) + (1/4) + (1/4) + (1/4) + (1/2) = 3.41
log Koc = 0.531 + 0.62 +  njPj
log Koc = 0.53 (3.41) + 0.62 + (-1.519) = 0.91
Experimental log Koc = 1.01
aliphatic alcohol
39
Module 2: Correction Factors
Chemical structure provides an incomplete description of

molecular interactions leading to observable properties
Correction Factors for intermolecular forces

» Electronic interactions
» Multiple hydrogen bonding
» Substituent effects
40
Module 2: Software
EPIWIN collection of software programs -

Properties covered:
 Properties used to estimate partitioning: boiling point,
vapor pressure, octanol-water partition coefficient,
bioconcentration factor, Henry’s law coefficient, soil sorption
 Properties that govern environmental fate:

atmospheric lifetimes, biodegradation rates
41
Module 2, Case study 1:
Environmental partitioning case study
Water Compartment Only

1 kg Hexachlorobenzene (Hx)
105 m3 volume of water
10-3kg organic carbon / m3 water
0.1 kg fish / 100 m3 water
Human Exposure : Fish Ingestion

0.5 kg of fish consumed
Dose due to ingestion?
Concentration in the Fish (mg/kg)?
Mackay et al., “Illustrated Handbook of Physical-Chemical Properties and Environmental Fate for
Organic Chemicals”, Lewis Publishers, 1992
42
Module 2, Case study 1:
Mass balance equation for Hx 118-74-1
MHx  MHx ,W  MHx ,S  MHx , F  VW CW  VW  oc KocCW   F BCF CW
43
EPIWIN:
Software demonstration
Concentration in Water
MHx 6 5 kg Hx
CW   9.97  10  10
(VW  VW  ocK oc 103   F BCF 10 3 ) m3 Water
10-3 m3/L
105 m3 3,388 L/ kgOC 5,152 L/ kgF
10-3 kgOC/m3 10-1 kgF/ 102 m3
Concentration in Fish
3
L 5 kg Hx 3 m Water 5 kg Hx
CF  BCF  CW  (5152 )(10 3 )(10 )  5.2  10
kg Fish m Water L kg Fish
Dose to Humans
kg Hx
Dose  MF  CF  (0.5 kg Fish)(5.2  10 5 )  0.26 g Hx
kg Fish
44
Module 2, maleic anhydride 108-31-6
EPIWIN (estimates) vs ChemFate (data)
Properties EPIWIN ChemFate

Bioling Pt. (ÞC) 156.4 202
Melting Pt. (ÞC) -51.6 52.8
Vapor Press. @25ÞC (mm Hg) 2.97 .25
log KOW 1.62 -----
No data because
Water Solubility (mg/L) 4912 -----
MA hydrolyzes
H (atm•m3/mole) 1.9x10-6 ----- in 1 minute in
water
Biodegradation half life weeks -----
Hydrolysis half life ----- 1 minute
Atmos. Oxidation half life (d) 4.71 0.7
log KOC 0 -----
Bioconcentration Factor 0.546 -----
45
Module 2, Benzene 71-43-2
EPIWIN (estimates) vs ChemFate (data)
Properties EPIWIN ChemFate

Bioling Pt. (ÞC) 102.24 80.09
Melting Pt. (ÞC) -77.92 5.53
Vapor Press. @25ÞC (mm Hg) 34 95
log KOW 1.99 2.13
Water Solubility (mg/L) 2000 1790
H (atm•m3/mole) 5.39x10-3 5.55x10-3
Biodegradation half life weeks-months week
Hydrolysis half life ----- -----
Atmos. Oxidation half life (d) 5.5 10
log KOC 2.22 1.69
Bioconcentration Factor 0.94 1.0
46
Module 2: Recap

module
engineering courses
 Overview of property estimation methods
 Software demonstration
 Case studies
47
Module 3:
Evaluation of Alternative Reaction Pathways
Chapters 7 and 8
David T. Allen
University of Texas at Austin
48
Module 3: Outline

module
engineering courses
 Green chemistry concepts - atom efficiency
 Tier 1 environmental impact assessment
 Green chemistry expert system (software)
 Adipic acid and maleic anhydride cases
49
Students will:
 understand the hierarchical design-for-environment approach
for chemical processes
 learn qualitative and quantitative methodologies for Green

Chemistry
 be able to evaluate feedstocks, solvents, and alternative

reaction pathways; both economically and environmentally.
50
 Design course: Green Chemistry concepts and a

screening of chemical products and raw materials on
the basis of economics and environmental impacts
 Reactor design course: Waste and risk

minimization approaches
51
Module 3: Hierarchical design process for
pollution prevention
Design Stage P2 Tools Environmental Book

Evaluation Chapter
1. Reaction pathways, • Green Chemistry Tier 1 7, 8
conversions, and yields, • atom efficiency
raw materials, solvents
2. Flowsheet systhesis, Release estimation, Tier 2 8, 9

specific process units optimum choice of
defined • mass separating agents
• process units
• processing conditions
3. Detailed design • Process integration Tier 3 10, 11
methods
• multimedia environmental
fate modeling
• relative risk assessment
52
Module 3: Green Chemistry - Ch 7
 Guiding principles for reactions

» Simplicity
» Safety
» High yield and selectivity
» High energy and atom efficiency
» Use of renewable resources
» Recyclable reagents and raw materials
53
Module 3: Feedstocks and solvents
 Important considerations
» Human / ecosystem health properties
– Bioaccumulative?
– Persistent?
– Toxic?
– Global warming, Ozone depletion, Smog formation?
– Flammable or otherwise hazardous?
– Renewable or non renewable resource?
» Life cycle environmental burdens? - Ch 13, 14
54
Module 3:
Alternative
choices:
raw materials
Benzene
• fossil fuel source
• carcinogenic
Glucose
• renewable source
• non-toxic
55
Module 3: Alternative choices: Solvents
Supercritical CO2
Non-toxic, non-flammable, renewable sources
Selectivity enhancement with SC CO2
Water as alternative solvent (as a co-solvent with an alcohol)

Reaction rate enhancements
56
Module 3: Synthesis pathways
Reaction Type Waste Generation Potential
Addition Reaction • completely incorporate starting

Isobutylene + methanol  methyl tert-butyl ether material into product
C4H8 + CH3OH  (C4H9)-O-CH3
Substitution Reaction • stoichiometric amounts of

Phenol + ammonia  analine + water waste are generated
C6H5-OH+ NH3  C6H5-NH2 + H2O
Elimination Reaction • stoichiometric amounts of

Ethylbenzene  styrene + hydrogen waste are generated
C6H5-C2H5  C6H5-C2H3 + H2
57
Module 3: Atom and Mass Efficiency:
magnitude of improvements possible
Atom Efficiency
- the fraction of starting material incorporated into the desired product -
• Carbon - 100%
• Hydrogen - 7/9 x 100 = 77.8%
• Oxygen - 0/1 x 100 = 0%
• Nitrogen - 100%
Mass Efficiency (Basis 1 mole of product)

Mass in Product = (6 C) (12) + (7 H) x (1) + (0 O) x 16) + (1 N) x (14) = 93 grams
Mass in Reactants = (6 C) (12) + (9 H) x (1) + (1 O) x 16) + (1 N) x (14) = 111 grams
Mass Efficiency = 93/111 x 100 = 83.8%
58
Module 3: Software exploration
Green Chemistry Expert System
TOPIC
AREAS
• Green Synthetic Reactions - search a database for alternatives
• Designing Safer Chemicals - information on chemical classes
• Green Solvents/Reaction Conditions - alternative solvents / uses
- solvent properties
59
Module 3: Software demonstration
search Green Synthetic Reactions for adipic acid references
60
Module 3: Adipic Acid Synthesis
Traditional vs. New
Traditional Route - from cyclohexanol/cyclohexanone
Cu (.1-.5%)
C6H12O+ 2 HNO3 + 2 H2O C6H10O4 + (NO, NO2, N2O, N2)
V (.02-.1%)
hazardous
92-96% Yield of Adipic Acid
global warming
ozone depletion
• Carbon - 100%
• Oxygen - 4/9 x 100 = 44.4%
• Hydrogen - 10/18 x 100 = 55.6%
• Nitrogen - 0%
Product Mass = (6 C)(12) + (10 H)(1) + (4 O)(16) = 146 g
Reactant Mass = (6 C)(12) + (18 H)(1) + (9 O)(16) + (2 N)(14) = 262 g
Mass Efficiency = 146/262 x 100 = 55.7%
Davis and Kemp, 1991, Adipic Acid, in Kirk-Othmer Encyclopedia of Chemical Technology, V. 1, 466 - 493
61
Module 3: Adipic Acid Synthesis
Traditional vs. New
New Route - from cyclohexene

Na2WO4•2H2O (1%)
C6H10 + 4 H2O2 C6H10O4 + 4 H2O
[CH3(n-C8H17) 3N]HSO4 (1%)
90% Yield of Adipic Acid
• Carbon - 100%
• Oxygen - 4/8 x 100 = 50%
• Hydrogen - 10/18 x 100 = 55.6%
Product Mass = (6 C)(12) + (10 H)(1) + (4 O)(16) = 146 g
Reactant Mass = (6 C)(12) + (18 H)(1) + (8 O)(16) = 218 g
Mass Efficiency = 146/218 x 100 = 67%
Sato, et al. 1998, A “green” route to adipic acid:…, Science, V. 281, 11 Sept. 1646 - 1647
62
Module 3: Maleic Anhydride Synthesis
Benzene vs Butane - Mass Efficiency
Benzene Route (Hedley et al. 1975, reference in ch. 8)
V2O5
2 C6H6 + 9 O2 2 C4H2O3 + H2O + 4 CO2
(air) MoO3
95% Yield of Maleic Anhydride from Benzene in Fixed Bed Reactor

2(4)(12) + 3(2)(16) + 2(2)(1)
Mass Efficiency = (100) = 44.4%
2(6)(12) + 9(2)(16) + 2(6)(1)
Butane Route
(VO)2P2O5
C4H10 + 3.5 O2 C4H2O0 + 4 H2O
(air)
60% Yield of Maleic Anhydride from Butane in Fixed Bed Reactor

(4)(12) + (3)(16) + (2)(1)
Mass Efficiency = (100) = 57.6%
(4)(12) + 3.5(2)(16) + (10)(1)
Felthouse et al., 1991, “Maleic Anhydride, ..”, in Kirk-Othmer Encyclopedia of Chemical Technology, V. 15, 893 - 928
63
Benzene vs Butane - Summary Table
Chapter 8 Stoichiometry 1 $/lb 2 TLV 3 TW 4 Persistence 5 log
Material BCF 5
Air Water
(d) (d)
Benzene Process
Benzene [71-43-2] -1.19 0.184 10 100 10 10 1.0
Maleic Anhydride 1.00 0.530 0.25 ---- 1.7 7x10-4 ----
Butane Process
Butane [106-97-8] -1.22 0.141 800 ---- 7.25 ---- ----
Maleic Anhydride 1.00 0.530 0.25 ---- 1.7 7x10-4 ----
1 Rudd et al. 1981, “Petroleum Technology Assessment”, Wiley Interscience, New York
2 Chemical Marketing Reporter (Benzene and MA 6/12/00); Texas Liquid (Butane 6/22/00)
3 Threshold Limit Value, ACGIH - Amer. Conf. of Gov. Indust. Hyg., Inc. , www.acgih.org
4 Toxicity Weight, www.epa.gov/opptintr/env_ind/index.html and www.epa.gov/ngispgm3/iris/subst/index.html
5 ChemFate Database - www.esc.syrres.com, EFDB menu item
64
Benzene vs Butane - Tier 1 Assessment
(TLV Index)
Environmental Index (non - carcinogenic) = |
i
i |  (TLVi )1
Benzene Route
TLV Index = (1.19)(1 / 10) + (1.0)(1 / .25) = 4.12
Butane Route
TLV Index = (1.22)(1 / 800) + (1.0)(1/ .25) = 4.00
65
Benzene vs Butane - Tier 1 Assessment
EPA Index
Environmental Index (carcinogenic)= |  |  (Maximum toxicity weight)
i i
i
Benzene Route
EPA Index = (1.19)(100) + (1.0)(0) = 119
Butane Route
EPA Index = (1.22)(0) + (1.0)(0) = 0
66
Module 3: Recap

module
engineering courses
 Green chemistry concepts
 Tier 1 environmental impact assessment
 Green chemistry expert system (software)
 Adipic acid and maleic anhydride cases
67
Module 3: Explore
search Green Solvents/Reaction Conditions

Designing Safer Chemicals
68
Module 4:
Environmental Evaluation and Improvement
During Process Synthesis - Chapters 8 and 9
David R. Shonnard
69
Module 4: Outline
After the Input-Output structure is established, an environmental
evaluation during process synthesis can identify large sources
of waste generation and release; directing the attention of the
designer to pollution prevention options within the process

courses
 Identify and estimate emissions from process units -
Chapter 8
 Pollution prevention strategies for process units -
Chapter 9
70
Students will:
 estimate air emissions and other releases from process units
after developing a preliminary process flowsheet, using software
and hand calculations
 have a better understanding of the mechanisms for pollutant

generation and release from process units
 become familiar with practical pollution prevention strategies for

process units
71
Mass/energy balance course:

• criteria pollutant emissions from energy consumption
• emission of global change gases from energy consumption
• calculate emission factors from combustion stoichiometry
Continuous/stagewise separations course:

• evaluate environmental aspects of mass separating agents
Design course:
• pollution prevention strategies for unit operations
Reactor design course:

• environmental aspects of chemical reactions and reactors
• pollution prevention strategies for chemical reactors
72
Chapter 8
Identifying and estimating air emissions

and other releases from process units
1. Identify waste release sources in process flowsheets
2. Methods for estimating emissions from chemical processes
3. Case study - Benzene to Maleic Anhydride process evaluation
73
Module 4: Typical waste emission sources
from chemical processes - Ch 8
1. Waste streams from process units

2. Major equipment - vents on reactors, column separators, storage tanks,
vacuum systems, ..
3. Fugitive sources - large number of small releases from pumps, valves,
fittings, flanges, open pipes, ..
4. Loading/unloading operations
5. Vessel clean out, residuals in drums and tanks
6. Secondary sources - emissions from wastewater treatment, other waste
treatment operations, on-site land applications of waste, ..
7. Spent catalyst residues, column residues and tars, sludges from tanks,
columns, and wastewater treatment, …
8. Energy consumption - criteria air pollutants, traces of hazardous air
pollutants, global warming gases,
74
Module 4: Process release estimation methods
1. Actual measurements of process waste stream contents and flow

rates or indirectly estimated based on mass balance and
stoichiometry. (most preferred but not always available at design
stage)
2. Release data for a surrogate chemical or process or emission
factors based on measured data
3. Mathematical models of emissions (emission correlations, mass
transfer theory, process design software, etc.)
4. Estimates based on best engineering judgement or rules of thumb
75
Module 4: Emission estimation methods:
based on surrogate processes
Waste stream summaries based on past experience
1. Hedley, W.H. et al. 1975, “Potential Pollutants from Petrochemical

Processes”, Technomics, Westport, CT
2. AP-42 Document, Chapters 5 and 6 on petroleum and chemical industries,

Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
3. Other sources
i. Kirk-Othmer Encyclopedia of Chemical Technology, 1991-
ii. Hydrocarbon Processing, “Petrochemical Processes ‘99”, March 1999.
76
Module 4: Emission Factors -
major equipment
Table 8.3.2 Average Emission Factors for Chemical Process Units

Calculated from the US EPA L&E Database
Process Unit EFav ; (kg emitted/103 kg throughput)

Reactor Vents 1.50
Distillation Columns Vents 0.70
Absorber Units 2.20
Strippers 0.20
Sumps/Decanters 0.02
Dryers 0.70
Cooling Towers 0.10
77
Module 4: Emission factors -
fugitive sources; minor equipment
Ei (kg i / yr)  mi  EFav  N s  24  365
78
criteria pollutants from energy consumption
EFav (lb i / 10 3 gal)  ED(Btu / yr)

Ei (lb i / yr)  3
HV(Btu / 10 gal)  BE
AP-42, Chapter 1, section 1.3, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
79
CO2 from energy consumption
EFav (lb i / 10 3 gal)  ED(Btu / yr)

Ei (lb i / yr) 
HV(Btu / 103 gal)  BE
80
Module 4: Emission correlations/models -
storage tanks and waste treatment
Software Tools
Storage tanks
TANKS 4.0 - program from EPA - www.epa.gov/ttn/chief/tanks.html
Wastewater treatment
WATER8 - on Air CHIEF CD - www.epa.gov/ttn/chief/airchief.html
Treatment storage and disposal facility (TSDF) processes

CHEMDAT8 - on Air CHIEF CD
81
Module 4:
Benzene to MA Process
V2O5
2 C6H6 + 9 O2 ----------> 2 C4H2O3 + H2O + 4 CO2
MoO3

82
Module 4: Air emission and releases sources:
Benzene to MA Process
Source Identification
1. Product recovery absorber vent
2. Vacuum system vent
3. Storage and handling emissions
4. Secondary emissions from water out, spent catalyst,
fractionation column residues
5. Fugitive sources (pumps, valves, fittings, ..)
6. Energy consumption
83
Module 4: emissions from energy consumption:
Criteria pollutants (SO2, SO3, NOx, CO, PM)
Process data for energy consumption

• 0.15 lb fuel oil equivalent per lb Maleic Anhydride
product
• fuel oil #6 in a Normally Fired Utility Boiler
• 1% sulfur
• Boiler efficiency included in the energy usage data
AirCHIEF Demonstration
84
Module 4: emissions from energy consumption:
continued
SO 2
 157 lb SO2   1 gal # 6 0.15 lb # 6  lb SO 2 lb SO 2
1%S 
-3
 = 3.53x10 = 3.53
%S 10 gal #6
3
6.68 lb # 6  lb MA  lb MA 10 3 lb MA
SO 3
 5.7 lb SO3   1 gal # 6 0.15 lb # 6  lb SO 3 lb SO 3
1%S 
-4
 = 1.28x10 = 0.13
%S 10 gal #6
3
6.68 lb # 6  lb MA  lb MA 10 3 lb MA
NOx
67 lb NOx  1 gal # 6 0.15 lb # 6  -3 lb NOx lb NOx
 3  = 1.50x10 = 1.50
10 gal # 66.68 lb # 6  lb MA  lb MA
3
10 lb MA
CO
 5 lb CO  1 gal # 6 0.15 lb # 6  -4 lb CO lb CO
 3  = 1.12x10 = 0.11
10 gal # 66.68 lb # 6  lb MA  lb MA
3
10 lb MA
PM
 9.19 lb PM   1 gal # 6 0.15 lb # 6  = 2.06x10 lb PM lb PM
1%S 
-4
 = 0.21
%S 10 gal #6
3
6.68 lb # 6  lb MA  lb MA 10 3 lb MA
85
Module 4: Uncontrolled Air emission / releases
Benzene to MA Process (lb/103 lb MA)
Release Source Maleic Benzene Xylene Criteria CO2 Tars and
Anhydride Pollutants oxygenates
i
Methods used (MA)
Venting from
1 0.03 0.14
storage tanks
Absorber column
2 100 700 (CO) 972 20
vent
Vacuum system
2 0.02 0.02
vent
Fugitive
3 0.2 0.2 0.1
Emissions
Loading/unloading
4 0.2 2.0
operations
Wastes from
5 3.8 26.5
vacuum columns
Energy use
6 5.5 562
emissions
Total 4.2 102.3 0.1 705 1,534 46.5
1 Vertical fixed-roof tank; surrogate for MA is perchloroethylene; Ta nks 4.0 program from EPA –
www.epa.gov/ttn/chief/tanks/html
2 Hedley et al. 1975. Potential Pollutants from Petrochemical Processes. Technomic, West Port, CT
AP-42 chapter 6 section 6.14, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
3 Typical chemical industry emission factor from Berglund and Hansen, 1990.
4 Equation 8.3-4, chapter 8, Green Engineering textbook.
6 AP-42, Chapter 1, section 1.3, Table 1.3-11, Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
86
Module 4: Flowsheet evaluation -
n-butane to maleic anhydride
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 15, pp. 893-927. 1991

87
Module 4: Uncontrolled Air emission / releases
n-butane to MA Process (lb/103 lb MA)
Release Source Maleic n-butane Criteria CO2 Tars and
Anhydride Pollutants oxygenates
i
Methods used (MA)
Venting from
1 1.0
storage tanks
Absorber column
2 8.0 251.4 761 (CO) 1033
vent
Vacuum system
3 9.6
vent
Fugitive
4 0.2 0.2
Emissions
Loading/unloading
5 0.2
operations
Wastes from
6 3.8
vacuum columns
Energy use
7 2.9 600
emissions
Total 22.6 251.6 764 1,633
1 Vertical fixed-roof tank; Tanks 4.0 program within the Environmental Fate and Risk Assessment Tool (EFRAT)
(see module 6)
2 from stream information using a commercial process simulator, HYSYS
3 from emission estimation program in EFRAT using the emission factor for a vacuum distillation column.
4 Typical chemical industry emission factor from Berglund and Hansen, 1990.
5 Equation 8.3-4, chapter 8, Green Engineering textbook.
7 from emission estimation program in EFRAT using emission factors for energy consumption, AP-42, Chapter 1,
Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm , bituminous coal for electricity demand only 88
Module 4:
Tier 2 environmental assessment indexes
1. Energy: [total energy (Btu/yr)] / [production rate (MM lb/yr)]
2. Materials: [raw materials (MM lb/yr)] / [production rate (MM

lb/yr)]
3. Water: [process water (MM lb/yr)] / [production rate (MM lb/yr)]
4. Emissions: [total emissions and wastes (MM lb/yr)] / [production

rate (MM lb/yr)]
5. Targeted emissions: [total targeted emissions and wastes (MM

lb/yr)] / [production rate (MM lb/yr)]
89
Module 4: Benzene to MA Process
Conclusions from emissions summary
1. Chemical profile:
CO2 > CO > benzene > tars-oxygenates > MA
2. Toxicity profile:
Benzene > MA > CO > tars-oxygenates > CO2
3. Unit operations profile:
Absorber vent > energy consumption > vacuum system vent
- Pollution prevention and control opportunities are centered

on benzene, the absorber unit, and energy consumption -
90
Module 4: Chapter 9
Pollution prevention strategies

for process units
1. Material choices for unit operations
2. Pollution prevention for chemical reactions and reactors
3. Separation units: reducing energy consumption and wastes
4. Preventing pollution for storage tanks and fugitive sources
5. Case study applications -
• VOC recovery/recycle: effect of MSA choice on energy consumption
• Maleic anhydride from n-butane: MA yield vs reaction temperature
91
Module 4: Important issues regarding pollution
prevention for unit operations
1. Material selection: fuel type, mass separating agents (MSAs), air,

water, diluents, heat transfer fluids
2. Operating conditions: temperature, pressure, mixing intensity
3. Energy consumption: high efficiency boilers, operation of units to

minimize energy usage
4. Material storage and fugitive sources: storage tank choices and

equipment monitoring and maintenance
5. Waste generation mechanisms: understanding this will lead to

pollution prevention strategies
92
Module 4: Pollution prevention through
material selection - fuel type
Example Problem:
Calculate the annual uncontrolled SO 2 emissions to satisfy a steam energy demand of 10 8
Btu/yr with a boiler efficiency of .85 assuming Fuel Oil #6, #2, and Natural Gas.
#6 Fuel Oil #2 Fuel Oil Natural Gas
Emission Factor, EF
(lb/103 gal) 157S 143S 0.6 lb/106 scf
Sulfur Content, S % 0.84 0.24 ----
Heating Value, HV 8 8
1050x106
(Btu/103 gal) 1.48x10 1.30x10 Btu/106scf
Annual Emission, E
(lb SO2/yr) 105 31 .07
EFav (lb i / 10 3 gal)  ED(Btu / yr) EF(lb i / 10 6 scf )  ED(Btu / yr)

Ei (lb i / yr)  3 Ei (lb i / yr)  6
HV(Btu / 10 gal)  BE HV(Btu / 10 scf)  BE
93
material selection - water pretreatment
Reverse Osmosis
to prevent
10 kg sludge/kg ppt
RCRA waste 94
material selection - reactor applications
1. Catalysts:
• that allow the use of more environmentally benign raw materials
• that convert wastes to usable products and feedstocks
• products more environmentally friendly - e.g. RFG / low S diesel fuel
2. Oxidants: in partial oxidation reactions

• replace air with pure O2 or enriched air to reduce NOx emissions
3. Solvents and diluents :

• replace toxic solvents with benign alternatives for polymer synthesis
• replace air with CO2 as heat sinks in exothermic gas phase reactions
95
Module 4: Pollution prevention
for chemical reactors
1. Reaction type:
• series versus parallel pathways
• irreversible versus reversible
• competitive-consecutive reaction pathway
2. Reactor type:
• issues of residence time, mixing, heat transfer
3. Reaction conditions:
• effects of temperature on product selectivity
• effect of mixing on yield and selectivity
96
Module 4:
Pollution prevention for chemical reactions
k
1st Order Irreversible Parallel Reactions R 
p
 P
k
1.0 R 
w
W
0.9
0.8 kp/kw = 100 High

[P]/[R]o Conversion
0.7 t > 5(kp+ kw)-1
kp/kw = 10
0.6
High
0.5 Selectivity
kp >> kw
0.4
kp/kw = 1
0.3
Selectivity
Independent
[W]/[R] o
0.2 of residence
time
0.1 kp/kw = 10
kp/kw = 100
0.0
0 1 2 3 4 5
 = (k p+k w) t
97
Module 4:
1st Order Irreversible Series Reactions k kw
R 
p
 P 
 W
1.0
[R]/[R]o kp/kw = 100 kp/kw = 1
[P]/[R]o High
[W]/[R]o
0.8 Conversion
kp/kw = 10 kp/kw = 2
t > 5 kp-1
0.6 High
Selectivity
kp/kw = 2
kp >> kw
0.4
kp/kw = 1 Selectivity
kp/kw = 10
dependent
0.2 on residence
kp/kw = 100 time
0.0
0 1 2 3 4 5
= k p t
98
Module 4:
Reversible Series Reactions CH4 + H2O  CO + 3H2
Steam reforming of CH4 CO + H2O  CO2 + H2
R = CH4
P = CO
W = CO2
Separate and recycle waste to extinction

99
Module 4:
Pollution prevention - reactor types
1. CSTR:
• not always the best choice if residence time is critical
2. Plug flow reactor:

• better control over residence time
• temperature control may be a problem for highly exothermic reactions
3. Fluidized bed reactor :

• if selectivity is affected by temperature, tighter control possible
4. Separative reactors:
• remove product before byproduct formation can occur: series reactions
100
Module 4:
Pollution prevention - reaction temperature
k
1st Order Irreversible Parallel Reactions R 
p
 P
k
R 
w
W
For Ep > Ew, Ep was set to 20 (k
kcal/mole
p /k w) and Ew to 10 kcal/mole.
14
12 for Ep > Ew,

Ep>Ew
Ew>Ep Ep = 20 kcal/mole
10
Ew to 10 kcal/mole
8
6 for Ew > Ep,

Ep = 10 kcal/mole
4
Ew to 20 kcal/mole
2
0 E = activation
-100 -80 -60 -40 -20 0 20 40 60 80 100
T (K)
energy
101
Module 4: Pollution Bo CSTR
prevention - mixing effects Ao
k1
Irreversible 2nd order competitive-consecutive reactions A  B 
  P
k2
1 P  B W
0.95
Y = yield
0.9 = P/Ao
Yexp = expected
0.85 yield
 = mixing time
Y/Yexp 0.8 scale
0.75 Increased
mixing will
0.7 increase
observed yield
0.65
0.6
1.E-05 1.E-04 1.E-03 1.E-02 1.E-01
(k 1 Bo )(Ao /Bo )
102
Module 4: Pollution prevention -
other reactor modifications
1. Improve Reactant Addition:
• premix reactants and catalysts prior to reactor addition
• add low density materials at reactor bottom to ensure effective mixing
2. Catalysts:
• use a heterogeneous catalyst to avoid heavy metal waste streams
• select catalysts with higher selectivity and physical characteristics
(size, porosity, shape, etc.)
3. Distribute flow in fixed-bed reactors
4. Heating/Cooling:
• use co-current coolant flow for better temperature control
• use inert diluents (CO2) to control temperature in gas phase reactions
5. Improve reactor monitoring and control
103
for separation devices
1. Choose the best technology:
• take advantage of key property differences (e.g. volatility for distillation)
2. Choose the best mass separating agent:
• consider operability, environmental impacts, energy usage, and safety
3. Separation Heuristics
• combine similar streams to minimize the number of separation units
• separate highest-volume components first
• remove corrosive and unstable materials early
• do the most difficult separations last
• do high-purity recovery fraction separations last
• avoid adding new components to the separation sequence
• avoid extreme operating conditions (temperature, pressure)
104
example of mass separating agent choice
Gaseous Waste Stream
Toluene & Ethyl Acetate Vent ; 21 -Vent;
Absorber 99.8 %90%
recovery MSA Screening
of Toluene and Ethyl Acetate
193.5 kg/h each; 12,000 recovery of VOC 1. 857 chemicals
scfm, balance N2 2. Hansen Sol.
Vent
Par.
11.8  d  22
0  p  9.3
Absorption Distillation
0  h  11.2
Column Column 3. Tbp > 220 ˚C
50/50 Mass
Mixed Product 4. Tmp < 26 ˚C
5. 23 chemicals
remain
Absorption
Absorber oil
oil(C-14)
Make-up oil 10 – 800 kgmole/h
recycle
HYSYS
Flowsheet
Conditions for simulations
1. 10-stage columns,
2. 10 ˚C approach temperature for heat integration,
3. absorber temperature = 32 ˚C
105
Chemical Utility Rank
(Btu/hr)
Module 4: o-Dibromobenzene 1.37x10
6
6
1
Butyl benzoate 1.39x10 2
Pollution Nitrobenzene 1.41x10
6
6
3
o-Bromoanisole 1.42x10 4
prevention - Dibenzyl ether 1.42x10
6
5
6
results of
Diethylene glycol dibutyl ether 1.46x10 6
6
Diethylene glycol butyl ether acetate 1.46x10 7
mass
6
Octanioc acid 1.47x10 8
6
Ethyl cinnamate 1.48x10 9
separating
6
1-Bromo-4-ethoxy benzene 1.49x10 10
6
trans-Anethole 1.62x10 11
agent Diethylene glycol monobutyl ether

1-Methyl naphthalene
1.68x10
1.70x10
6
6
12
13
choice p-Chlorobenzoyl chloride
4-Chlorobenzotrichloride
1.75x10
6
6
14
15
1.75x10
6
Diethylene glycol monoethyl ether acetate 1.83x10 16
6
Quinoline 2.30x10 17
6
1-Decanol 2.37x10 18
6
2-Decanol 2.55x10 19
6
Hexadecane 3.39x10 20
6
Tetradecane 3.94x10 21
6
1,2,4-Trichlorobenzene 3.95x10 22
6
Dodecane 5.35x10 23
106
Storage Tanks
Emission Mechanisms; Fixed Roof Tank

LTOTAL = LSTANDING + LWORKING
Vent
Vapor pressure of liquid drives emissions
T - Weather, paint color/quality
P - Weather
Liquid - liquid throughput, volume of

Roof Column Level tank
107
Module 4: Storage tank comparison -
TANKS 4.0 Demonstration
Gaseous waste stream flowsheet ; pg 37
• Toluene emissions only
• 516,600 gal/yr flowrate of toluene
• 15,228.5 gallon tank for each comparison
Storage Tank Type Vertical Internal Domed External
Fixed Roof Floating Roof Floating Roof
Annual Emissions (lb)
White Paint 337.6 66.2 42.8

Grey (Medium) Paint 489.1 85.1 52.4
Heated (White) 313.5
Poor (Grey/Medium) 509.7 81.0 51.5
Pollution prevention strategies

• replace fixed-roof with floating-roof tank
• maintain light-colored paint in good condition
• heat tank to reduce temperature fluctuations
108
Module 4: Fugitive Sources -
pollution prevention techniques
109
Module 4: Flowsheet evaluation -
maleic anhydride from n-butane
Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 15, pp. 893-927. 1991

110
Module 4: Reaction rate parameters -
Maleic anhydride from n-butane
Principal Reaction
1. C4H10 + 3.5O2  C4H2O3 + 4H2O-HR,1 = 1.26x106 kJ/kmole
2. C4H10 + 4.5O2  4CO + 5H2O -HR,2 = 1.53x106 kJ/kmole
3. C4H10 + 6.5O2  4CO 2 + 5H2O -HR,3 = 2.66x106 kJ/kmole
Activation Energies Rate Equations

E1/R = 8,677 K
E2/R = 8,663 K (KDiss pO2 )1/2
r1  k1 1/ 2 pBut.
E3/R = 8,940 K 1  (KDiss pO2 ) K Sorp pO2
r3  k3 pBut.
KSorp pO2 1  KSorp pO2
r2  k2 pBut.
1 KSorp pO2
Schneider et al. 1987, “Kinetic investigation and reactor simulation…”, Ind. Eng. Chem. Res., Vol. 26, 2236-2241
111
Module 4: Fixed-bed reactor section -
100 MM tons/yr maleic anhydride process
112
Module 4: Case Study - reactor temperature:
Maleic anhydride from n-butane
100
90
80
70
60
(%) 50
40
30
20
10
0
370 380 390 400 410 420 430
Reactor Temperature (C).
n-butane conversion MA Yield MA-CO2 selectivity MA-CO selectivity
113
Module 4: Summary/Conclusions
1. Methodologies/software tools - process synthesis:

• emission factors
• surrogate process information from historical sources
• emission estimation software: TANKS 4.0, AirCHIEF 7.0, process
simulator packages,
• Tier 2 environmental assessment
2. Case studies:
• VOC recovery/recycle from a gaseous waste stream - effects of MSA
choice on energy consumption
• Maleic anhydride from n-butane - effect of reaction temperature on
conversion, MA yield, MA selectivity
114
Module 5:
Process Integration of Heat and Mass
Chapter 10
David R. Shonnard
115
Module 5: Outline
The environmental performance of a process depends on both the
performance of the individual unit operations, but also on the level
to which the process steams have been networked and integrated

courses
 Review of heat integration concepts
 Introduction to the tools of mass integration and
synthesis of mass exchange networks - Chapter 10
 Cast study - heat integration of the MA flowsheet
116
Students will:
 learn about efficient utilization of waste streams as raw
materials through application of source/sink mapping
 are introduced to graphical tools of mass exchange network

synthesis, composition interval diagrams and load line
diagrams.
 apply mass exchange network synthesis to simple flowsheets
117
Mass/energy balance course:

• dilute contaminant balance calculations around process units
• source/sink matching of energy streams
Continuous/stagewise separations course:

• applications to in-process recovery and recycle of contaminants
Design course:
• graphical design tools for mass integration of waste streams
118
Module 5: Analogies between process heat
and mass integration
Heat Integration
the optimum use of heat exchangers and streams internal to the
process to satisfy heating and cooling requirements.
Tools: 1. Temperature interval diagram
2. Heat load diagram (pinch diagram)
Mass Integration
the optimum use of mass exchangers and streams internal to the
process to satisfy raw material requirements, maximize production and
minimize waste generation (water recycle/reuse applications).
Tools: 1. Source/sink mapping and diagrams
2. Composition interval diagram
3. Mass load diagram (pinch diagram)
119
Module 5: Heat exchange networks -
key features
T - Heat Load Diagram
Heat exchange network • composite curves
• internal • pinch analysis
• external • minimum external utilities
[(mCp)1 + (mCp) 2]-1
89% reduction in
external utilities
Seider, Seader, and Lewin, 1999, “Process Design Principles”, John Wiley & Sons, Ch. 7
120
Illustrative example - before heat integration
per sec
1 kg/s, Cp = 1 kJ/(kg-˚C)
2 kg/s, Cp = 1 kJ/(kg-˚C)
per sec
121
per sec Temperature - load (pinch) diagram
Placement of
each load line 2 kg/s
vertically is Cooling load for
arbitrary external network,
160 kJ/s
Heat transfer
load by internal
network,
1 kg/s
140 kJ/s
Heating load for

external network,
30 kJ/s
10 ˚C minimum temperature
difference defines the pinch
122
Illustrative example after heat integration
82.4% reduction
in cooling utility per sec
140 kJ/s
transferred
per sec 46.7% reduction

in heating utility
123
Module 5: Mass integration:
objectives and methods
Methods objective is to prepare source streams to be
acceptable to sink units within the process or to waste
1. Segregation treatment
avoid mixing of sources Pollutant-rich Pollutant-lean
streams streams
2. Recycle
direct sources to sinks
3. Interception
selectively remove
pollutants from source
4. Sink/generator
manipulation
adjust unit operation
design or operation
El-Halwagi, M.M.1997, “Pollution Prevention Through Process Integration: Systematic Design Tools”, Academic Press
124
Module 5: Motivating example:
Chloroethane process before mass integration
Mass balance in
terms of CE, the
minor component
C 2 H5 OH  HCl  C2 H5Cl  H2 O
Chloroethanol (CE) is byproduct
C 2 H5 OCl
Objective is to reduce the

concentration of CE sent to
biotreatment to < 7 ppm and
a load of < 1.05x10-6 kg CE/s
125
Module 5: Motivating example:
Chloroethane process after mass integration
Interception
CE load to biotreatment =
2.5x10-7 kg/s
Recycle
126
Module 5: Mass Integration Tools:
Source-sink mapping
the purpose of source-sink mapping is to determine if waste streams
can be used as feedstocks within the process - direct recycle
Recycle source
“a” directly
A range of
acceptable
flowrates and
composition
for each sink ,
“S” or mix sources “b”
and “c” to achieve
the target flowrate
- composition
using a Lever Rule
- like calculation
127
Module 5: Source-sink mapping:
acrilonitrile (AN) process before recycle
catalyst
C3 H6  NH3 + 1.5 O2 
 C 3 H3 N  3 H 2O
0 ppm NH3
≤ 10 ppm NH3 0 ppm AN
required
may contain AN
450 ˚C,
2 atm
2-phase stream
always with 1
kg/s H2O but no
H2O in the AN
layer
mass fraction
of AN always
equal to 0.068
NH3 equilibrium NH3 partitioning
CW = 4.3 CAN CSTEAM = 34 CPRODICT
128
Module 5: Source-sink map
acrilonitrile (AN) process
Sinks for
water
Sources
for water
129
Module 5: Flow rates of condenser and fresh
water sent to Scrubber
Water Mass Balance
kg kg
0.5  x  y  6.2
s s
NH3 Balance
kg
0.8  0 ppm  x  14 ppm  y  0 ppm
s  10 ppm
kg
0.8  x  y
s
x = flow rate of condensate stream sent to Scrubber
kg kg H2 O kg AN
= 4.4 = 4.0 + 0.4
s s s
kg H 2 O
y = flow rate of fresh water sent to Scrubber = 1.0
s
130
Module 5: Mass balances on AN units for
remaining flow rates and compositions
Aqueous streams
from condenser
and distillation
From fresh
column
water supply
4.7 kg/s H2O
1.0 kg/s H2O
0.5 kg/s AN
0 kg/s AN
12 ppm NH3
0 ppm NH3
Scrubber
Gas stream
from condenser
0.5 kg/s H2O
to decanter
4.6 kg/s AN ? kg/s H2O
39 ppm NH3
? kg/s AN
? ppm NH3
131
Module 5: Flow rates and compositions
from Scrubber to Decanter
Water Mass Balance

kg kg kg kg kg H2 O
0.5  1.0  4.0  0.7  6.2
s s s s s
AN Mass Balance
kg kg kg kg AN
4.6  0.4  0.1  5.1
s s s s
NH3 Balance
kg kg kg kg
5.1  39 ppm  0.8  0 ppm  1.0  0 ppm  4.4  14 ppm
s s s s  23 ppm
kg kg kg kg
5.1  0.8  1.0  4.4
s s s s
And similarly for other units

132
acrilonitrile (AN) process after recycle
freshwater feed AN production rate
30% of original increased by 0.5
kg/s; $.6/kg AN and
350 d/yr = $9MM/yr
rate of AN sent to
biotreatment is 60% of original
85% of original
133
Module 5:
Mass exchange network (MEN) synthesis
1. Similar to heat exchange network (HEN) synthesis

2. Purpose is to transfer pollutants that are valuable from
waste streams to process streams using mass transfer
operations (extraction, membrane modules, adsorption, ..
3. Use of internal mass separating agents (MSAs) and external
MSAs.
4. Constraints
i. Positive mass transfer driving force between rich and lean process
streams established by equilibrium thermodynamics
ii. Rate of mass transfer by rich streams must be equal to the rate of
mass acceptance by lean streams
iii. Given defined flow rates and compositions of rich and lean streams
134
Module 5: Mass integration motivating example
- Phenol-containing wastewater
Outlet
streams
for recycle
or sale
Mass
separating
agents
to waste
water
treatment
- Minimize transfer to
waste treatment -
to wastewater
treatment
135
Module 5: Outline of MEN synthesis
1. Construct a composition interval diagram (CID)
2. Calculate mass transfer loads in each composition interval
3. Create a composite load line for rich and lean streams
4. Combine load lines on a combined load line graph
5. Stream matching of rich and lean streams in a MEN using the

CID
136
Module 5: Hypothetical set of rich and lean
streams - stream properties
Rich Stream Lean Stream
in out Stream in out

Flow y y Flow x x
Stream
Rate, kg/s Rate, kg/s
R1 5 0.10 0.03 L 15 0.0 0.14

R2 10 0.07 0.03
R3 5 0.08 0.01
Equilibrium of pollutant between

rich and lean streams
y = 0.67 x
137
Module 5: Composition interval diagram -
a tool for MEN synthesis
x scale matched to y scale using

y = 0.67 x
138
Module 5:
Mass transfer loads in each interval
Rich Streams
Region 1 and 2 = (yout  y in )   Ri = (0.08 - 0.1)  5 kg / s = - 0.1 kg / s
Streams i
Region 3 = (0.07 - 0.08)  (5 kg / s + 5 kg / s) = - 0.1 kg / s
Region 4 = (0.03 - 0.07)  (5 kg / s + 10 kg / s + 5 kg / s) = - 0.8 kg / s
Region 5 = (0.01- 0.03)  (5 kg / s) = - 0.1 kg / s
negative mass load denotes

transfer out of the stream
139
Module 5:
Composite load line for the rich stream
Region 1 & 2
Region 3
Region 4
Region 5
140
Module 5:
Combined load line for rich and lean streams
mass load to be
added to lean
stream externally
mass load to be
transferred
internally
Rich Stream can

be moved
vertically
mass load to be
removed from rich
stream by external
MSA
141
Module 5:
Stream matching in MEN synthesis
142
Module 5:
Heat integration of the MA flowsheet
-9.23x107 Btu/hr
9.70x107 Btu/hr 2.40x107 Btu/hr
Reactor streams
generate steam
-4.08x107 Btu/hr
Without Heat Integration
143
Module 5: Heat integration of
reactor feed and product streams
1.E+08
 min = 10 ūF
1.E+08 (795 ūF, 9.72x107 Btu/hr)
8.E+07
Internal load
9.251x107 Btu/hr
Q (Btu/hr)
6.E+07 (805 ūF, 9.72x107 Btu/hr)
4.E+07
(165.3 ūF, 0 Btu/hr)

2.E+07
(215 ūF, 0.468x107 Btu/hr)

0.E+00
0 100 200 300 400 500 600 700 800 900
External load Temperature (F)
0.468x107 Btu/hr
Hot Stream Cold Stream
144
Module 5: Heat integration of
absorber outlet and recycle streams
5.E+07
(400 ūF, 4.05x107 Btu/hr)
4.E+07
Internal load
3.E+07 2.321x107 Btu/hr (445.6 ūF, 4.05x107 Btu/hr)
Q (Btu/hr)
2.E+07
(228.1 ūF, 1.73x107 Btu/hr)
1.E+07 External load

 min = 15 ūF 1.73x107 Btu/hr
(100 ūF, 0 Btu/hr)

0.E+00
100 200 300 400 500
Temperature (F)
Hot Stream Cold Stream

145
Module 5: Maleic anhydride flowsheet
with heat integration
146
Module 5: Energy Duty Energy (Btu/hr)
Heat No HI HI
integration Compressor 1.52x107 1.52x107

-9.40x107 -9.40x107
summary Reactor (Er1)
Reactor (Er2) -9.40x107 -9.40x107
Reactor (Er3) -9.40x107 -9.40x107
Greater energy Rxn. prod. cooler (E4) -9.23x107
reductions are
Abs. out heater (E5) 2.40x107
possible when
steam generated Purge heater (E6) 2.36x106 2.36x106
from the reactors Condenser (E7) -8.81x106 -8.80x106
is used for the
reboiler, purge Reboiler (E8) 1.28x107 1.28x107
and feed heaters Recycle pump (E9) 2.50x104 2.50x104
Recycle cooler (E10) -4.08x107 -1.68x107
Feed heater (E11) 9.70x107 4.69x106
76.8% reduction Total Inputs 15.1x107 3.51x107
27.4% reduction Total Outputs 42.4x107 30.8x107
147
Module 5: Recap

module
engineering courses
 Review of heat integration concepts
 Introduction to the tools of mass integration and
synthesis of mass exchange networks - Chapter
10
 Cast study - heat integration of the MA flowsheet
148
Module 6:
Flowsheet Environmental Impact Assessment
Chapter 11
David R. Shonnard
Hui Chen
149
Module 6: Outline
After the flowsheet input output structure, unit operation designations,
and mass/heat integration have been completed, the last step in the
process to improve the environmental performance of a chemical process
design is to perform a detailed environmental impact assessment

courses
 Review of environmental impact assessment methods
 Application of Tier 3 environmental impact
assessment to a detailed flowsheet - Chapter 11
150
Students will:
 learn to apply a systematic risk assessment methodology to the
evaluation of chemical process designs
 integrate emission estimation, environmental fate and transport

calculation, and relative risk assessment to rank process design
alternatives
151
Process Design course:

• develop and use environmental objective functions to rank process
design alternatives
• rank process designs quantitatively based on environmental criteria
Transport phenomena course:

• Module on interphase mass transfer in the environment
152
Module 6: Essential features of environmental
impact assessment for chemical process design
Computationally efficient
 Environmental performance metrics quickly calculated using
output from commercial process simulators
Link waste generation and release to environmental impacts

 Environmental metrics linked to process parameters
Impacts based on a systematic risk assessment methodology

 Release estimates  fate and transport  exposure  risk
153
Module 6:
Systematic risk assessment methodology
National Academy of Sciences, 1983
1. Hazard Identification (which chemicals are important?)
2. Exposure assessment (release estimation, fate and transport, dose assessment)
3. Toxicity assessment (chemical dose - response relationships)
4. Risk Characterization (magnitude and uncertainty of risk)

Result: Quantitative risk assessment (e.g. excess cancers)
Atmospheric
dispersion
Model, Ca
Thibodeaux, L.J. 1996, Environmental Chemodynamics, John Wiley & Sons

154
Module 6: Quantitative risk calculation
Carcinogenic Risk Example (inhalation route)
Exposure Dose
(C  CR  EF  ED) 
Risk i =  a  SF 
 (BW  AT ) i
Dose - Response Relationship,

Slope Factor
Result: # excess cancers per 106 cases in the population; 10-4 to 10-6 acceptable
Disadvantage: Only a single compartment is modeled / Computationally inefficient

Highly uncertain prediction of risk
155
Module 6: Relative risk calculation
Carcinogenic Risk Example (inhalation route)
(Ca  CR  EF  ED) 
  SF 
 (BW  AT ) i
Relative Risk =
(Ca  CR  EF  ED) 
  SF 
 (BW  AT ) Benchmark
=
Ca  SFi
Ca  SF Benchmark
Result: Risk of a chemical relative to a well-studied benchmark compound
Advantage: If C is calculated for all compartments using a multimedia

compartment model, computationally efficient
156
Module 6:
Tier 3 Relative risk index formulation
Chemical Specific
Exposure Inherent Impact Parameter

Potential
[(EP)(IIP)]i
Dimensionless Risk Index ( Ii* ) =
[(EP)(IIP)]B
Benchmark Compound Chemical “i”
Process N
Emission
Process Index (I)   (Ii )  (mi )
*
Rate of
i1
Chemical,
i
157
Module 6: Airborne emissions
estimation
 Unit Specific EPA Emission Factors

Distillation/stripping column vents

Reactor vents

Fugitive sources
 Correlation (AP- 42, EPA)


Storage tanks, wastewater treatment

Fugitive sources (pumps, valves, fittings)
 Criteria Pollutants from Utility Consumption


Factors for CO2, CO, SO2, NOx,

AP- 42 (EPA) factors
 Process Simulators (e.g. HYSYS)
158
Module 6: Release estimates
based on surrogate processes
Waste stream summaries based on past experience
1. Hedley, W.H. et al. 1975, “Potential Pollutants from Petrochemical

Processes”, Technomics, Westport, CT
2. AP-42 Document, Chapters 5 and 6 on petroleum and chemical industries,

Air CHIEF CD, www.epa.gov/ttn/chief/airchief.htm
3. Other sources
i. Kirk-Othmer Encyclopedia of Chemical Technology, 1991-
ii. Hydrocarbon Processing, “Petrochemical Processes ‘99”, March 1999.
159
Module 6: Multimedia compartment
model formulation
Multimedia compartment model Processes modeled
• emission inputs, E
• 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

160
model input data
Spreadsheet
Environmental Property Unit Location Benzene Ethanol PCP
Molecular Weight g/mole C6 78.11 46.07 266.34
Melting Point °C C7 5.53 115 174
Dissociation Constant log pKa C8 4.74
Solubility in Water g/m3 C11 1.78E+2 6.78E+5 14
Vapor Pressure Pa C12 1.27E+4 7.80E+3 4.15E-3
Octanol-Water Coefficient log Kow C13 2.13 -0.31 5.05
Half-life in air hr C33 1.7E+1 5.5E+1 5.50E+2
Half-life in water hr C34 1.7E+2 5.5E+1 5.50E+2
Half-life in soil hr C35 5.5E+2 5.5E+1 1.7E+3
Half-life in sediment hr C36 1.7E+3 1.7E+2 5.50E+3
161
model typical results
Chemical Percentage (%)
(emission scenario) Total mass Air Water Soil Sediment

(kg)
Benzene (a) 1.98x104 99.59 0.29 0.12 1.0x10-3
Benzene (b) 1.41x105 4.48 95.17 5.5x10-3 0.35
Benzene (c) 6.86x104 20.61 1.61 77.78 5.8x10-3
Ethanol (a) 4.56x104 92.87 3.85 3.28 2.9x10-3
Ethanol (b) 7.35x104 0.22 99.7 7.8x10-3 0.08
Ethanol (c) 7.84x104 0.92 5.64 93.42 0.02
Pentachlorophenol (a) 2.07x106 0.26 2.56 97.07 0.11
Pentachlorophenol (b) 4.59x105 7.2x10-5 96.19 0.03 3.78
Pentachlorophenol (c) 2.39x106 2.9x10-4 0.54 99.44 0.02
(a) 1000 kg/hr emitted into the air compartment

(b) 1000 kg/hr emitted into the water compartment
(c) 1000 kg/hr emitted into the soil compartment
162
model typical results - interpretations
1. The percentages in each environmental compartment depend

upon the emission scenario
a) the highest air concentrations result from emission into the air
b) the highest water concentrations are from emission into water
c) the highest soil concentrations are from emission into soil
d) highest sediment concentrations are from emission into water
2. Chemical properties dictate percentages and amounts

a) high KH results in high air concentrations
b) high KOW results in high soil concentrations
c) high reactions half lives results in highest pollutant amounts
163
Module 6: Nine Environmental Impact /
Health Indexes
R ela tiv e R isk 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 zo n e D ep letio n
I O* D,i  ODP i
S m o g F o rm a tio n * MIR i
I S F,i 
MIR R O G
A cid R a in ARP i
I A* R, i 
ARP S O2
G W P = g lo b al w a rm in g p o ten tia l, N C = n u m b er o f c arb o n s a to m s, O D P = o zo n e
d e p letio n p o te n ta l, M IR = m a x im u m in c re m e n ta l rea c tiv ity , A R P = a cid rain p o ten tial.
164
Module 6: Nine Environmental Impact /
Health Indexes
R e la tiv e R is 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
I IN G 
In g e s tio n R o u te 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 it y C W , B en zen e HV B en zen e
In g e s tio n R o u te
Hum an C A , i HV
C a r c in o g e n ic it y I * C IN H  i
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 it y 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 l it y , L C 5 0 = l e t h a l c o n c e n t r a t io n 5 0 % m o r t a l it y ,
a n d H V = h a z a r d v a l u e f o r c a r c i n o g e n ic h e a lt h e f f e c t s .
165
Process Simulator Output
or Conceptual Design
List of Chemicals, Equipment specifications,

Utility consumption, Annual throughput
EFRAT
Physical Properties, Toxicology,
Weather, Geographical,
and Emission Factors Databases
Chemicals, Chemicals, Chemicals,

Equipment specifications, KH, KOW , LC50, HV,
annual throughput MIR…
Air Emission Chemical Partition Relative Risk Index

Calculator Calculator Calculator
Emission
Chemical I1 I2 In Rate Report
A . . . . .
B . . . . . MS Excel®
C . . . . .
n . . . . .
Multi-Criteria Decision Analysis
166
Module 6: Software tools for environmental
impact assessment of process designs
Environmental Fate and Risk Assessment Tool (EFRAT)

• links with HYSYS for automated assessments
WAste Reduction Algorithm (WAR)

• reported to be linked with ChemCAD
• US EPA National Risk Management Research Laboratory
Cincinnati, OH
Dr. Heriberto Cabezas and Dr. Douglas Young
US Environmental Protection Agency
National Risk Management Research Laboratory
26 W. Martin Luther King Dr.
Cincinnati, OH 45268
167
Module 6: Absorption - distillation process:
analysis of an existing separation sequence
Gaseous Waste Stream

Toluene & Ethyl Acetate Vent ; 21 - 99.8 % recovery
193.5 kg/h each; 12,000 of Toluene and Ethyl Acetate
scfm, balance N2
Vent
Absorption Distillation
Column Column
50/50 Mass
Mixed Product
Absorption oil (C-14)

Make-up oil 10 – 800 kgmole/h
HYSYS Flowsheet
168
Module 6: Unit-specific emission summary
UNIT OPERATION Mass Emission rate (kg/hr)
Flow Toluene Ethyl C-14 SOx NOx CO2 CO TOC
"METHOD" (kg/hr) Acetate
Absorption
Column "HYSIS" 19,840 0.002 128 4.23
Distillation "emission
Column factor" 259.1 0.019 0.007
Fugitive "emission
Sources factor" 259.1 0.062 0.062
Storage
Tank "correlation" 259.1 0.0014 0.0014
Reboiler
6
Energy (10 Btu/hr) 6.16 3.93 0.52 499 0.129 0.007
Total Emissions (kg/hr) 0.088 128.07 4.23 3.93 0.52 499 0.129 0.007
Where are the centers for energy 100 kgmole/hr Oil Flow Rate;
consumption and emissions? Oil Temperature = 82˚F; T=180˚F
169
Module 6: Risk index summary
Relative Risk Index (I*)

Compound I* GW I* OD I* SF I* AR I* ING I* INGC I* INH I* INHC I* FT
Toluene 3.34 0 0.9 0.0 1 0 1.0 0 0.02

Ethyl Acetate 2 0 0.3 0.0 9.7 0 3.3 0 0.04
SOx 0 0 0.0 1.0 0 0 0.0 0 0.00
NOx 40 0 0.0 0.7 0 0 0.0 0 0.00
CO2 1 0 0.0 0.0 0 0 0.0 0 0.00
CO 0 0 0.0 0.0 0 0 141.2 0 0.00
C-14 3.1 0 0.0 0.0 0 0 0.0 0 0.00
TOC 3.1 0 1.0 0.0 0 0 0.0 0 0.00
Which chemicals have the

highest impact indexes?
170
Module 6: Process environmental summary
100 kgmole/hr Oil Flow Rate; N
Oil Temperature = 82˚F; T=180˚F Process Index (I)   (Ii *)  (mi )

i1
All units in kg /yr

Emis s ion from IFT IING IINH IGW IS F IAR
utility 0.00E+00 0.00E+00 1.44E+05 5.21E+06 1.70E+02 1.27E+04
a bso rbe r 4.67E+04 1.08E+07 3.73E+06 2.36E+06 3.74E+05 0.00E+00
ta nk 3.36E+00 6.43E+02 2.55E+02 2.95E+02 1.09E+02 0.00E+00
distilla tio n c o lum n 5.06E+00 6.43E+02 3.60E+02 6.82E+02 3.12E+02 0.00E+00
fug itive 3.12E+01 5.30E+03 2.35E+03 2.90E+03 1.12E+03 0.00E+00
Emis s ion of IFT IING IINH IGW IS F IAR

Ethyl Ac e ta te 4.68E+04 1.09E+07 3.73E+06 2.24E+06 3.72E+05 0.00E+00
To lue ne 1.92E+01 1.22E+03 1.22E+03 4.07E+03 2.11E+03 0.00E+00
Te tra de ca ne 0.00E+00 0.00E+00 0.00E+00 1.15E+05 1.14E+03 0.00E+00
Ca rbo n dio x ide 0.00E+00 0.00E+00 0.00E+00 4.87E+06 0.00E+00 0.00E+00
Ca rbo n m o no x ide 0.00E+00 0.00E+00 1.44E+05 0.00E+00 0.00E+00 0.00E+00
Nitro g e n dio x ide 0.00E+00 0.00E+00 0.00E+00 3.40E+05 0.00E+00 6.39E+03
S ulfur dio x ide 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00 6.36E+03
TOC 0.00E+00 0.00E+00 0.00E+00 6.51E+02 1.35E+02 0.00E+00
171
Module 6: VOC recovery by
absorption into tetradecane (C14)
120
100
% Recovery of VOCs
80
60
40
20
Toluene Ethyl Acetate
0
0 100 200 300 400 500 600
Absorber Oil Flow Rate (kgmole/hr)
172
Module 6: Environmental index profiles
3000
2500
2000
Inde xe s
(kg /hr)
1500
1000
500
0
10 IINH
0
10 100 IAR
20
50
100
200 IGW
300
400
500
Abs o rbe r Oil Flo w Ra te (kg mo le s /hr)
173
Module 6: Interpretation of environmental
assessment results
Risk reductions at 50 kgmole/hr flow rate

 Global Warming Index - 41% reduction
 Smog Formation Index - 86 % reduction
 Acid Rain Index - small increase
 Inhalation Route Toxicity Index - 78 % reduction
 Ingestion Route Toxicity Index - 18 % reduction
 Ecotoxicity (Fish) Index - 19 % reduction
Absorber oil choice is not an optimum

 Oil selectively absorbs toluene, but ethyl acetate has a higher
value
Multiple indexes complicate the decision
174
Module 6: Maleic anhydride from n-butane
process flowsheet evaluation
 Use of EFRAT : evaluate the MA process

 Basecase (Dibutyl phthalate absorber oil) with and
without heat integration
 Simulate 3 case studies using heat integrated
flowsheet
» Dibutyl phthalate absorber oil
» Dibenzyl ether absorber oil
» Diethylene glycol butyl ether acetate absorber oil
175
Module 6: Maleic anhydride from n-butane:
Use of EFRAT on basecase flowsheet
 Follow the tutorial instructions given in the notebook!
 The SCENE file has been linked to a HYSYS case

file
 Add three additional emission sources
 Complete the relative risk assessment calculations
176
Module 5:
Heat integration of the MA flowsheet
-9.23x107 Btu/hr
9.70x107 Btu/hr 2.40x107 Btu/hr
Reactor streams
generate steam
-4.08x107 Btu/hr
Without Heat Integration
177
Module 5: Maleic anhydride flowsheet
with heat integration
178
effect of heat integration on risk indexes
1.E+10
1.E+09 72.2%
reduction
1.E+08
Remaining
Indexes are
1.E+07 unchanged
(kg/yr)
1.E+06
1.E+05
1.E+04
Heat Integration
IGW
ISF No Heat Integration
IAR IING
30.4% IINH
reduction Relative Risk Indexes IFT
179
effects of absorber oil choice
16.3% 42.1%
reduction 85.1%
reduction reduction
1.E+10
1.E+09
(kg/yr) 1.E+08
1.E+07
81.7%
1.E+06 reduction
1.E+05
1.E+04 DGBEA
Dibenzyl Ether
IGW
ISF Dibutyl Phthalate
IAR
IING
IINH
Relative Risk Index IFT
180
Module 6: Summary / Conclusions

courses
 Review of environmental impact assessment
methods
 Application of Tier 3 environmental impact
assessment to a detailed flowsheet - Chapter 11
» Heat integration of the Maleic Anhydride flowsheet
» Effects of absorber oil choice for the MA flowsheet
181

Module 1: Environmental Literacy:: Environmental Issues, Risk, Exposure, and Regulations

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Module 1: Environmental Literacy:: Environmental Issues, Risk, Exposure, and Regulations

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Module 1: Environmental Literacy:

Environmental Issues, Risk, Exposure, and Regulations

 Educational goals and topics covered in the module

 Design course: Introduce environmental literacy

 Freshman Engineering: Introduction to issues

Materials Materials Materials Materials

global ozone smog acidifi- ecological Human health

Chemical ozone depleting ozone layer loss human mortality

Chemical NOx and volatile photochemical human/ecological

1 - Chemical & Allied Processing

3 - Metals Processing, 4 - Other Industrial Processes

Chemical SO2 and NOx Acidification rxns. human/ecological

Chemical Toxic releases to Transport, fate, Human health

All Other EPCRA

 What are the risks associated with a chemical,

 How is risk quantified by professional risk assessors?

 Is risk assessment used by government agencies to

Risk = F(exposure x hazard)

Modules 1,2 Modules 1,2

Steps in risk assessment

Sources of Data for Health Effects

 Occupational Exposure- exposure to people in the workplace

Exposure Assessment Methodology - Community Exposure

How large a dose causes what kind of effect?

• receive public comment on

Major Laws/Amendments Environmental Regulations

Bishop, “Pollution Prevention: Fundamentals and Practice”, McGraw-Hill, 2000

Environmental Date Purpose of Key Provisions

 Educational goals and topics covered in the module

 Educational goals and topics covered in the

 be aware of the limitations of structure-property estimation

 Design course: Use as a preliminary screen of

 Materials course/thermodynamics course:

 Mass and energy balances course: module on

Persistence in the environment Atmospheric oxidation rate,

Uptake by organisms Volatility, lipophilicity,

Human uptake Transport across dermal

Toxicity and other health Dose-response relationships

 Empirical approach based on exp. Data

 Based on KOW, octanol-water partitioning

 KOW - octanol-water partitioning

log Kow = 0.229 +  ni fi +  nj cj

n = number of functional groups of types i or

the molecular structure, CH2= CCl2

one =CH2 group

log Kow = 0.229 + 0.5184 + 0.3836 + 2(0.4923) = 2.11

Experimental log Kow = 2.13

 H - Henry’s law constant

n = number of bonds of types i or j

7 C-H bonds, 2 C-C bonds, 1 C-O bond, and 1 O-H bond

 KOC - Organic carbon-water partition coeff.

log Koc = 0.531 + 0.62 +  njPj

Chemical structure provides an incomplete description of

Correction Factors for intermolecular forces

EPIWIN collection of software programs -

 Properties that govern environmental fate:

Water Compartment Only

Human Exposure : Fish Ingestion

Dose due to ingestion?

Concentration in the Fish (mg/kg)?

Properties EPIWIN ChemFate

Properties EPIWIN ChemFate

 Educational goals and topics covered in the