Chemical Technology and Sustainability

environmentally conscious design for chemical engineers

Objective: re-orient chemical engineering education to promote

the new paradigm of sustainability

Basis: a systemic approach (incorporated into existing courses),

with the appropriate scope (abstract ideas into definite problems)

- introduction: concerns and aware attitudes

- problem analysis (sources, effects)

Fernando Gutirrez
EUITI-QUIMICA INDUSTRIAL
media, scale and life cycles
and
TECHNICAL UNIVERSITY

(UPM) solutions (options, actions)

MADRID - Espaa 1- elimination and minimization
2- treatment technologies

- basics & examples (linking theory w industrial practice)

Summary of new concepts and paradigms in environmental engineering

- From pollution control and waste handling technologies after generation, to proactive
process integrated prevention (cleaner production, multimedia cross effects and reduction
approach at source, specially diffuse non-point-sources).

- From consideration of the environmental aspects of the manufacturing process, to

considering also the entire life cycle of a product.
- From a sole emphasis upon technological measures, to a broader scale perspective
which also encompasses non-tech measures
PC vs PP SM vs MM PE vs PU TE vs NT
Environmental technology (BAT) x . x . . . x .
Cleaner technologies (CP) . x . x x . x .
Sustainability (S) . x . x x x x x

Traditionally BAT are considered only pollution control (PC) technical (TE) measures (end-of-pipe technologies), that have generally
the inconvenients of shifting pollutants from one to another media (SM), and also aditional cost of production.
CP (cleaner production) can be viewed as a conceptual and procedural approach to industrial production (or process oriented, PE) with
the objective of the minimization or prevention (PP) of risks to humans and to the environment: primary emphasis ongoing to
systematic and integrated source reduction approach (MM), but oriented to production organizations.
The sustainability (S) paradigm, doesnt omit consumption and production structures at the societal level (attitudinal and other non
technical, NT, and product oriented, PU, measures), within a broader policy concept approaching on the entire organization of society
that involves industrialists, government authorities, educators and citizens to ensure sustainable societies. Such an approach in relation
to water, air, or soil pollution should be focused upon both of the reduction of emissions from industrial point sources, and non point
sources, with a multimedia approach (MM).
Integrated pollution prevention and control
ATMOSPHERE elimination
source reduction
recycle
treatment
HYDROSPHERE disposal

BIOSPHERE LITOSPHERE
Pollution prevention in the CPI through clean process
design merged with the interpretation phase of the life
cycle assessment:
LCA tool + system modeling & optimization techniques Multimedia minimization tetrahedron

Minimization actions (except discharge)

OPTIONS INTERNAL EXTERNAL

Source reduction & eco-design Selection, Recovery, Subproduct

PREVENTIVE [elimination, clean(er) product-ion/s, exchange
fugitive emissions]

Linear production model, pollution management, emission and immission limits

CORRECTIVE
Effluent control (end of pipe), Waste treatment, clean-up techs
abatement technologies (remediation of existing problems)
 Environmental problems are systemic and thus require a `systems approach,
at different levels, that provides a holistic view of the connections between
industrial practices and human activity, making them easier to identify and solve
(problem analysis: sources, effects; integrated problem solving: options and actions);
it can highlight the need for and advantages of achieving sustainability
The primary goal is to promote sustainable development at the global,
regional and local levels, and key issues include the use of resources,
ecological and human health, and environmental equity
(both intergenerational and inter-societal)
Sustainable development is only achievable if :
There are radical changes in our attitudes, in our institutions, and the way we work and
interact
Present rates of population growth, which cannot be sustained by available resources, are
brought under control
A safe and sustainable production pathway, which still have not found, is put into effect

Physical environment,
antrophosphere and
PRODUCTION AND CONSUMPTION (1) sustainability
Technology domain

WELFARE SUSTAINABILITY IMPACTS AND POLLUTION (2)

STANDARD (wants) vs QUALITY (needs) (equilibrium) Ecology domain
Economy domain (+ ?) Societal (1) Technical (2) (+ /-)
Problem analysis: sources and effects
Manufacturing industry is concerned with
processing materials and the laws of science
govern these operations;

two consequences follow from this:

raw materials and energy are needed to
effect transformations and waste is produced

The best that can be achieved is:

to minimize the use of resources and reduce
waste production;

and the first step in this attempting is to describe the

situation that currently exist because this is the basis
against
to know any
which
Getting futurethe
and understand improvement
problem . will be judged
Identifying waste generation sources .
Characterizing and targeting problem waste streams .
Identifying waste reduction alternatives .
Implementing the action plan.
 Production loads (discharge on the environment):
material (gases,liquids,solids), energy (heat,radiation,noise)

Depletion (resource consumption):

Raw materials (minerals, fossil fuels, renewables)
Perturbations (water, land use)
Pollution impacts: Air, Water and Soil
(levels: urban, regional, global)

Products
Midpoints Endpoint
inhalation
Human
air population
process discharges dermal
water
soil
ingestion

Raw materials Energy Environment

Scenery of impacts produced by the chemical industries (generalized)

 Global flows of selected materials (million tons/yr)

Minerals (1,2 t/capita)

Cement 890
Mica 280
Salt 190 Fossil fuels (1,6 t/capita)
Phosphate 120 Coal 3200
Lignite 1200
Metals (0,3 t/capita)
Oil 2800
Steel 780
Gas 920
Aluminum 97
Cooper 8,5
Zinc 7,0
Lead 3,4 Water (8200 t/capita)
Nickel 0,8
Flow 41.000.000
Tin 0,2
 Water resources in Europe

1800

1600

1400

cubic metres per capita (1995)

1200
long time resources
1000
total extraction
800 industry
water suply
600
agriculture
400

200

0
North South
 Global impacts: the climate change
Products

Human
mortality,
Chemical Emissions: Increases of Ecosystem
processes CO2 CH4 N2O CFCs temperatures, adjustments
sea level

Feedstock Energy Environment

Greenhouse emissions (cause and effects chain)

GWPi = iCidt / CO2CCO2dt

Greenhouse gases and contributions to global warming
Gas Source Emission ant Conc. prind Conc. prst Rsd. time Ef.radiative Cont.global
CO2 Fossil fuels,
deforestation 6000 Mt/yr 280 ppm 360 ppm 50-200 yrs 1 50%
CH4 Anaerobiosis,
mining, gas 300 Mt/yr 800 ppb 1700 ppb 10 yrs 58 12-19%
N2O Agriculture,
Industry 5 Mt/yr 285 ppb 310 ppb 140-190 yrs 206 4-6%
CFCs refrigerants,
solvent, aerosols 1 Mt/yr 0 0,7 ppb 65-110 yrs 4860 17-21%
O3 photochemicals
transport & ind. 22 ppb hours-days 2000 8%
 depletion of stratospheric ozone
Products

Human
mortality,
Chemical Emissions: Depletion of Damages to
processes CFCs, HCFCs ozone layer, ecosystems
radiation UV

Feedstock Energy Environment

Emissions destructive of ozone (cause and effects chain)

Cl + O3 ClO + O2
ClO + O Cl + O2

O3 + O 2 O 2

ODPi = (O3)i / (O3)CFC11

: f(persistence, Cl atoms, rate constants)
 Air quality: trophospheric ozone
Products

Human and
ecological
Chemical Emissions: damages by
processes NOx VOCs Photochemical ozone or other
reactions oxidants

Feedstock Energy Environment

Photochemical smog formation (cause and effects chain)

NO2 h NO + O O2 O3 NO NO2 + O2
VOC + NO NO2 + oxidation products

POCPi = MIRi/MIRROG
MIR: maximum incremental reactivity of organic gases
 acid rain
Products

Human and
ecological
Chemical Emissions: reactions of damages by H+
processes SO2 NOx acidification and and heavy
acid depositions metals

Feedstock Energy Environment

Acidification (cause and effects chain)

Xi + i H+ +

APi = (i/Mi)/(SO2/MSO2)
Ecological risk assessment: from defining the sources to estimating effects

MEDIUM Urban Regional Global

Atmosphere photo-chemical and acidification radiative effects

(CO,VOCs,NOx,SOx,NH3) (CO2,CH4,N2O, CFCs)
Hydrosphere wastewaters and eutrophication water resources, raw
(organics, ions NP) materials and energy
landfills, (consumption);
Litosphere
incineration soil & groundwater toxics to air, water, soil
(solid wastes) (diffuse pollution) (AH, pesticides, metals)

Impact scales and environmental compartments

ATMOSPHERE

HYDROSPHERE BIOSPHERE

LITOSPHERE

Multimedia pollution tetrahedron

Environmental assessment of chemicals
Characterization of risks include information on discharges,
environmental fate, the human exposures and its biological
response: Chemical risk = f ( hazard, exposure )

Products

Human and
ecological
Chemical Discharges: transport and toxicology:
processes HAPs, WWs, HWs fate of pollutants dose and
(immission) response

Feedstock Energy Environment

Toxic releases (air emissions, water effluents, solid wastes ) and chain of effects

Risk indexes can be expressed as the product of

inherent potentials (IP) and exposure (EP),
relative to one compound (r):
Ii = (EPIP)i /(EPIP)r I = miIi
Springs and inputs to the environment
The 1st step is to identify sources of potential contaminants,
and the 2nd is to inventory flows, concentrations and matrix
characteristics (gas, liquids, solids), by means of balances,
sampling or emission factors

Products

Chemical Discharges:
processes HAPs, WWs, HWs

FIRE
Feedstock Energy

TANKS Toxic releases (air, water, solids)

Process flow-sheet and design
In this stage we already know the basic equipment and flow streams, so we can
identify the potential sources:
primary (stack vents, fugitive) or secondary emissions (service use, evaporation)
aqueous effluents and solid wastes (all the outputs different to useful products)

Then, we evaluate discharges by direct measure, emission factors or modeling,

before characterizing their environmental impacts:
Measures for existing processes: discharges are calculated by multiplying
concentrations, volumetric flows and densities of the streams
Emission factors: databases for industrial sectors, combustion processes,
storage tanks and unit operations (www.epa.gov/ttn/chief/)
Emissions for unit operations and non point sources: E(g/h) = XVOCEFmM(kg/h)
Combustion: E(kg/year) = DE(energy/year)EF(kg/volume)HV-1(energy/volume)Ef-1
Cleaning losses: can be estimated as a fraction residual of the product based in
recipient characteristics, properties of substances and washing operation.

Models for estimating discharges: many design programs include methods

for calculating output streams (some being pollutants), while there are also
specific procedures for non conventional discharges (tanks, ponds)
 Table.- Factors for estimating emissions of process units and fugitives (averaged)
Process units: Fugitive emissions: Factor (g/hsource)
Organic Gas
Sources of vents EFm (g/kg) Source Service industries
Refineries
plants
Gas hydrocarbon 5,97 27
Valves Liquid light 4,03 11 20
Reactors 1,50 Liquid heavy 0,23 0,2 (all)
Hydrogen 8,3
Distillers 0,70 Pumps Liquid light 19,9 110 63
Liquid heavy 8,62 21 (liquid)
Absorbers 2,20 Compressors Gas hydrocarbon 228 630 204
Hydrogen 50 (all)
Strippers 0,20 Relief valves Gas hydrocarbon 104 160 188
Liquid 7 7 (all)
Decanters 0,02 Connections 1,83 0,25 1,1
Open lines 1,7 2 22
Dryers 0,70 Sampling All 15
Refrigeration Oil separators
towers 0,10 (open) 14600 kg/h for 330000 bbl/day

E.g.- Estimate the fugitive emissions from a organic chemical plant with 1400 valves (168 in gas services),
3048 connectors, 27 pumps (liquid), 20 pressure relief valves, 20 sampling points, y 21 open lines; all fluid
of the process constituted practically by volatile compounds.
Equipment number Emission factor (g/h) Emissions
valves (s. gas) 168 5,97 8,79 (6,9%)
valves (s. liquid) 1232 4,03 43,5 (34,3%)
connections 3048 1,83 48,9 (38,8%)
pumps 27 19,9 4,71 (3,9%)
relievers 20 104 18,2 (14,4%)
samplers 20 15 2,63 (2,2%)
open lines 21 1,7 0.31 (0,3%)
Total 127,0 t/year
case CH

study Storage
tank
Reactor Stripper

oxidation of cyclohexan to mixture alcohol/ketone

(for synthesis of adipic acid and nylon), Boiler Scrubbers
with a production of 100 million of pounds yearly
AC

Storage Refining
tank D/C

1,64 t CH + 0,13 t NaOH = 1 t A + 0,38 t C

1) Main sources of contamination and preliminary estimation of emissions:

EF Atmospheric contaminants Liquid
Sources effluents
(g/kg) A/C CH SO2 SO3 NOx PM CO
Reactor 1,5 (50%) (50%) (organic)
Stripper 0,2 (100%) (0%)
Decanter 0,02
1,6 g/kgP 0,8 g/kgP
Distiller 0,7
19 g/l 0,69 g/l 8 g/l 1,5 g/l
Scrubbers (NMHCs,COx,CH4) 8,4 g/kgP 34 g/kgP 200 g/kgP
Boiler (0,5 tfuel n6, 0,8 kg/l, 1%S / tP) 7,6 kg/tP 0,3 kg/tP 3,2 kg/tP 0,6 kg/tP
Fugitive 0,5 0,25 g/kgP 0,25 g/kgP
Cargo 0,15 g/kgP
L(lb/103gal):12SPM/T
Tank (2-3d 35x20ft, 80% filling) 0,5 g/kgP
white, Houston-TX
Total (g/kgP) 2 10 46 200

2) Metrics of environmental impacts:

- Material intensity: [(1,64+0,13) -1,38]/(1+0,38) = 0,28 kg/kg
- Energy intensity: 7 kBTU/ lb of product
- Water consumption: 30 gal/ lb of product
- Contaminants: 0,3 kg/ kg of product
 The impact values of the previous example are quite large, if compared
with other representative processes; thus there are high incentives for
improvement

Table.- Environmental indicators of some representative chemical processes

Int.material Energy Water Toxics Contaminants Cont+CO2
Product Process lb/lb kBTU/lb gal/lb lb/lb lb/lb lb/lb
Acetic acid Methanol
low pressure 0,062 1,82 1,24 0,00011 0 0,133
Acrilonitrile Amonoxidation
of propene 0,493 5,21 3,37 0,01514 0,00781 0,966
Maleic Oxidation of
anhydride n-butane 0,565 0,77 1,66 0 0 2,77
Sulphuric Pyrometallurgic 0,002 0,073 0,57 -0,65 -0,63 -0,04
acid Sulphur 0,001 -0,87 0,70 0,00195 0,00195 0,002
 Table.- Emission factors for air contaminants in power stations (US-EPA, 1998)
3 3
Contaminant Coal combustion (g/t) Fuel combustion (g/m ) Gas combustion (mg/m )
Arsenic 0,19 0,0158 0,00369
Cadmium 0,023 0,0477 0,00404
Chromium 0,12 0,1013 0,00176
Lead 0,19 0,181 0,00434
Mercury 0,038 0,0135 0,0115
Nickel 0,13 10,13 0,0579
Table.- Elimination eficiencies in municipal waste water treatment works (WWT)
Compound Volatilization Biodegradation Sedimentation Efluent
Triclhoroetane 73% 13% 1% 12%
Toluene 38% 48% 1% 13%
Diclhorobencene 19% 46% 7% 28%
Naphtalene 7% 53% 7% 32%
Anthracene 1% 47% 39% 14%
Pyrene 1% 14% 73% 12%
Dibutyl-phtalate 1% 27% 54% 19%
Phenol 1% 99% 1% 1%

Table.- Percentage estimates of remaining substances in deposits after emptying

Method of Viscosity and surface tension of the substances
Tipe of vessel
discharge Aqueous Surfactants Kerosenics Oily Viscous
Drum of steel 2,29 3,06 2,48 2,06 3
Pumping Plastic 3,28 NA 2,61 2,30 4
Drum with cover 0,403 0,485 0,404 0,737 1
Dumping Open 0,034 0,089 0,054 0,350 0,5
Bottom in step 0,019 0,048 0,033 0,111 0,1
Draining Cup of steel 0,034 0,058 0,038 0,161 0,2
Vitrified 0,033 0,040 0,040 0,127 0,2

E.g.- Estimate the wastes of cleaning empty drums (steel, 200 l), in a industry that buys 20000 kg/year of
hydrazine (viscosity similar to water, and emptied with a pump to a process tank):

Losses as drum residues (year) : 200000,0229 = 458 kg

Fate and behavior of chemicals in the environment
The 3rd step is to estimate immission levels as pollutants
disperse from the source (distribution and persistence in
the media), and the 4th is the number of people exposed
to these doses (to compare with environmental standards
like: RFC,RFD, LC50,LD50, TLV,PEL,REL, SF,WOE,HV)
Human and ecological toxicity is a function of the dose-response,
the 1st term being dependent of the mode of discharge, transport,
environmental fate and assimilation mechanism (exposure), while
responses of the organisms depend on chemical structures and
action modes (toxicology)

Human and
ecological
Discharges: transport and toxicology:
HAPs, WWs, HWs fate of pollutants dose and
(immission) response

Environment

Toxic releases (emissions, effluents, wastes): chain of effects

Exposures
The properties of distribution of substances between phases
(air, water, soil, biotic) and their persistence in environments
(aerial or aquatic reactions, metabolisms) permit to estimate
exposures: represent the amount in contact with humans and
are estimated from emissions with models of transport and fate;
the relation dose/exposure is called bioavailability.

Table.- Criteria for distributions and persistence

-1 -3
Volatility very volatil (10 ), volatil (10 ), moderate
3 -5 -7 -7
H(atmm /mol) (10 ), small (10 ) and non-voilatil (10 )
Solubility high (10000), soluble (1000), moderate
(S,ppm) (100), low (0,1) and insoluble (0,1)
Sorption in soil very strong (4,5), strong (3,5), moderate
(lg Koc) (2,5), low (1,5) and negligible (1,5)
Bioacumulation high potential (1000, lgKow4,3), moderate
EPIWIN (BCF) (250, lgKow3,5) and low (250, lgKow3,5)
Biodegradation fast (60, 1 week), moderate (30, 28 day),
(%, time) slow (30, 28 days), very slow (28 days)
 Predicts the concentrations stationary of substances in the
air (1), water (2), soil (3) and sediments (4), from constant
emissions in a defined region:
the balance of contaminants depends on the input levels (Ei),
advections (GAiCBi, DAi), transfer between compartments (Dij),
and chemical transformation (DRi); figure summarizes model,
emissions, transport and reaction parameters; solution of the
equations is complex, but we can use spreadsheets:
www.trentu.ca/cemc/models/VBL3.html Level III
E.g.- The bencene, ethanol and pentachlorophenol (PCP) are examples of contaminants with very diverse
properties (table), whose environmental fates in stationary state can be estimated with the Mackay model,
for the discharge of 1000 kg/h of each compound, in the three following scenery:
a) air emission, b) aqueous effluents, c) soil dumping

After introducing the environmental properties, the spreadsheet gives as result fugacities, concentrations,
and finally the quantities in each compartment (table). It could be pointed out:
1) the majority of contaminant would be found in the media where it has been discharged primarily
(with the exception of PCP emission, which has a low vapor pressure)
2) the quantities increase with the corresponding average lifetimes of each species

Input data:
Properties Bencene Ethanol PCP
Molecular weight (g/mol) 78,11 46,07 266,34
Melting point (C) 5,5 -115 174
Dissociation constant (pKa) 4,74
3 2 5
Aqueous solubility (g/m ) 1,7810 6,78"10 14
4 3 -3
Vapor pressure (Pa) 1,2710 7,8010 4,1510
Cf. Octanol-water (log Kow) 2,13 -0,31 5,05
2
Life average (h) Air 1,710 5,510 5,510
2 2
Water 1,710 5,510 5,510
2 3
Soil 5,510 5,510 1,710
3 2 3
Sediment 1,710 1,710 5,510
Results:
Scenery a b c a b c a b c
3
Total (10 kg) 19,7 139 28,7 45,6 73,2 78,3 2070 458 2390
Percentages (%) Air 99,95 4,66 67,63 92,89 0,22 0,93 0,25 0,00 0,00
Water 0,03 95,00 0,53 3,84 99,70 5,65 2,55 96,19 0,55
Soil 0,02 0,00 31,84 3,27 0,01 93,42 97,09 0,03 99,43
Sediment 0,00 0,34 0,00 0,00 0,07 0,00 0,11 3,78 0,02
Inhalation exposures

The simplified dispersion models (gaussian) estimates concentrations,

downwind (u, m/s), from continuous point emission (Q, g/s) at a height
of totally reflecting soil (h, m): C(g/m3)= Q/yzuexp[-(h/z)2]
Standard deviations can be calculated in function of of the distance,
atmospheric stability and local morphology: yz = axb
Area Atmosphere Distance a b
x 500 m 0,01082 1,78
Neutral x 500 m 0,04487 1,56
Rural x2000 m 0,0049 1,66
Stable x2000 m 0,01901 1,46
x 500 m 0,0224 2
Neutral x 500 m 0,394 1,54
Urban x 500 m 0,008 2
Stable x 500 m 0,34 1,37

E.g. : Effects of a ground level emission of hydrogen sulphide (25 g/s), on a

point 300 m downwind from the source, at day (u:4 m/s) and night conditions
(2,5 m/s), with air inhalation rate of 0,9 m3/h and hazard level RfC:42 mg/m3
Cd = 25000/(0,010823001,784) = 7,17 mg/m3 Cd/RfC1 (exposure: 6,45 mg/h)
Cn = 25000/(0,00493001,662,5) = 50,2 mg/m3 Cn/RfC1 (exposure: 45,2 mg/h)
Effects on the aquatic biota and dermal exposure
Toxic concentration from continuous effluents (g/s), sent to a sewerage
system (wwt) before being diluted in a free water stream (m3/s), can be
estimated by: SWC (ppm) = Effluent(g/s)(1-wwt)/Flow(m3/s)
E.g.: Estimate the potential impact on fish (LC50:20 mg/l), resulting from an
effluent of 34 kg/day of toluene to a sewer (primary-secondary treatments),
that discharges into a river with a minimal historic volume of 2,38 m3/s
SWC = (0,37 g/s)(0,13)/(2,38 m3/s) = 0,020 ppm (three order less than LC)

The doses adsorbed by human skin depend on the surface area (cm2),
permeability (cm/h), duration of event (h) and toxic concentration (mg/l).
The exposure is the result of the dose and frequency of events/year.
E.g.: Swimmer of medium size (1,94 m2), in river contaminated with 3 g/l
of trichloroethylene, during 15 days summer (0,5 h).
DA = SKpEdWf = 0,5 g/event Exposure: 7,5 g/year

lg Kp (cm/h) = -2,72 + 0,71lgKow -0,0061Mw = -1,8

lg Kow = 0,229 + nifi = 2,47 =CH- , =C n1 = 2 f1 = 0,3836

-Cl (olefin) n2 = 3 f2 = 0,4923
CCl2 = CHCl (Mw= 131,5)
Aquifers contamination
Underground transport depends on the environmental characteristics
and the chemical properties; the equation describes the distribution of
concentration with time, by the plume of contaminants originated from
instantaneous discharge (m) of non-reactive solutes in homogeneous
media: C(x,y,z,t)= m/[8(t)3/2(DxDyDz)]exp{-[(x-ut)2/4Dxt]-[y2/4Dyt]-[z2/4Dzt]}
The maximum concentration is in the plume centre (x=ut, y=0, z=0),
where the exponential term is the unity; the zone containing 99,7% of
contaminant is an elipsoid of dimensions: di=(2Dit)1/2 (from the centre).
Hydrodynamic dispersivity combines convection and diffusion: D=u+D*
(=0,1m for porous soils, u: interstitial velocity, D*: molecular difusivity)
E.g.: The rupture of a deposit discharges 100 kg of aqueous arsenic over
saturated soil were the flow of water is 50 cm/day; the diffusion coefficient
of arsenic: 2108 m2/s, and is not eliminated by precipitation or adsorption.
Estimate the location, size and concentration of the plume 90 days later of accident:
Location of the plume centre: (0,5 m/d)(90 d) = 45 m from the deposit (in the flow direction)
-8 2 2
Dx = (0,1 m)(0,5 m/d) + (210 m /s)(86400 s/d) = 0,0517 m /d
-8 2 2
Dy = Dz = (210 m /s)(86400 s/d) = 0,00173 m /d

dx = [20,051790] = 3,05 m (ahead and behind the centre)

dy = dz = [20,0017390] = 0,56 m (above, below and each sides)
3/2 3
Maximun concentration: C= m/[8(t) (DxDyDz) ] = 6,68 kg/m
Potential hazards
We can distinguish the exposure routes (inhalation, ingestion)
and the health effects (genotoxic and non-carcinogen)
The curves dose-response (bioassays) show different threshold
and sensibilities of the exposed populations: percent of incidence
per mgcontaminant/kgbodyday

100Table.- Criteria for persistence, bioacumulation and distributions of ecotoxicity

800 N of compounds
Solubility high (10000), soluble (1000), moderate Organics neutral -----------
(S,ppm) (100), low (0,1) and insoluble (0,1) Esters - - - - - - - - - - - - - -
600 Acids - . - . - . - . - . - . - . -
Sorption in soil Very strong (4,5), strong (3,5), moderate
50 Amines ---------------------
(lg Koc) (2,5), low (1,5) and negligible (1,5) Phenols - - - - - - - - - - - -
400 Aldehydes - . - . - . - . - . -.
Biodegradation fast (60, 1 sem), moderate (30, 28 d),
(%, tiempo) slow (30, 28 days), very slow (28 days) Lg(1/LC50)=algKOW-b
-1 -3
Volatility very volatil (10 ), volatil (10 ), moderate 200
3 -5 -7 -7
H(atmm10/mol) (10 ), small (10 ) and non-voilatil (10 )
Bioacumulation high potential (1000, lgKow4,3), moderate 0
-2 -1 0 1 2 3 4 5 6 7 8
(BCF)
Fig.- (250,
Curves lgKow3,5)
of toxic and low(%)
responses (250, lgKow
vs log 3,5)
(doses) lg LC50 (fish, 96h)
for two agents with different relative values (TD10,TD50)

genotoxics dont have safe thresholds; slope factors (SF) relates the
excess of deaths with the exposure: %= SF(mgkg-1day-1)
for non-carcinogens, chronic exposures are compared with the `safe
dose or concentration (RfX): hazard quotients
Considerations during the initial stages for selecting a process
Including both economical (added values) and environmental criteria: ideally the indexes
are compounded values of the emissions and measures of persistence, bioaccumulation
and toxicity, by using ratios of importance (low, moderate, high)
E.g.- Consider the two alternative routes for synthesis of methyl metacrilate:
acetone-cianhydrin (CH3)2CO + HCN + H2SO4 + CH3OH CH3-(C=CH2)-COOCH3
isobutene-metacrolein-oxigen): CH3-(C=CH2)-CH3 + O2 + CH3OH CH3-(C=CH2)-COOCH3

Stoichiometry, approximate costs and environmental data of materials in the synthesis of metacrilate
Persistence (average life) Bio-accumulation Factor toxic global
Compound i (kgrm/kgp) Pi (E/kg) aerial and aquatic (BCF)
TLV(ppm) Inhalation and ingestion
Route acetocianhydrin iPmp: 1,32 0,86 16600
Acetone -0.68 0,95 52 days Weeks 3,2 750 NA NA
Ac. cianhydric -0,32 1,48 1 year Weeks 3,2 10 1000 100
Methanol -0,37 0,14 17 days D-Weeks 3,2 200 10 10
Acid sulphuric -1,63 0,09 2 (est) 10000 1
Metacrilate 1,00 1,72 7 hours Weeks 2,3 100 (PEL) 10 10
Route isobutilene iPmp: 0,82 0,01 100
Isobutene -1,12 0,68 2,5 hours Weeks 12,6 200 (est) NA NA
Methanol -0,38 0,14 17 days D-Weeks 3,2 200 10 10
Pentane -0,03 0,25 2,6 days D-Weeks 81 600 NA NA
Acid sulphuric -0,01 0,09 2 (est) 10000 1
Metacrilate 1,00 1,72 7 hours Weeks 2,3 100 (PEL) 10 10

Life averages and bioaccumulation values were calculated with software EPISuite based in SAR models
(www.epa.gov/oppt/exposure/docs/episuite.htm); compared with the classification criteria of table 1 (scale 0-3),
practically all compounds have index 1 (moderate-low).

For toxicity we use subrogates as TLV or combined responses to dose and ingestion (global indexes could
be the highest of both); in this example, the greatest hazards are due to sulphuric and cianhydric acids and
we can see a preference for the route of isobutene (also with less costs of the raw materials).
Environmental index: i/TLVi or i(factor inhalation/oral)max
Valuation of toxic risks
Valuation of risks include information on potential hazards,
the routes and magnitude of exposures, and the population
affected: Chemical risk = f ( hazard, exposure )

Risk indexes are based in the concentration of contaminants

in air or water (Ci,c) after discharge of 1000 kg/h of substance
in the compartment (Mackay model)
these are converted in doses by multiplying concentration and
assimilation rates (standard factors: u= 20 m3/d and 2 l/day, for
inhalation or ingestion), by body weight (p: 70 kg):
Di = (Ci,mu/p)

finally, doses are transformed in risk with the previous hazard

parameters, and the indexes (INHXP, INGXP) result from the
comparison with two reference compounds (toluene, benzene)
in each case; all the input flows (mi) are aggregated to obtain
a global process index:
TPi = (Ci,c/Rfxi)/(CT,c/RfxT) IT = miTPi
CPi = (Ci,cSFi)/(CB,cSFB) IC = miCPi
 Waste VOC (toluene, ethyl acetate) is recovered by absorption with tetradecane and distillation; emissions
sources (absorber, condenser vents, deposits, fugitive and fuel) are estimated by a simulator (HYSYS) and
correlations (EFRAT), showing the effect of absorbent: VOCs capture but also service related emissions.
Indicators for 3 impact categories (equivalent factors) show a compromise between selective absorption and
fluegases, with significant reductions of IGW (42%) and ISF (82%), and modest increase of IA, at flow 50 kmol/h.

Absorbent flow Emissions (kg/h)

(kmol/h) Toluene AcEt CO2 CO TOC NOx SOx n-C14
0 193,5 193,5 0 0 0 0 0 0
10 119,9 185,9 37 0,013 0,001 0,05 0,41 4,28
20 53,1 178,4 74 0,027 0,001 0,11 0,81 4.83
50 0,97 160,4 183 0,066 0,003 0,26 1,99 4.67
100 0,02 128,1 360 0,129 0,007 0,52 3,39 4,23
200 0,02 59,9 714 0,257 0,013 1,03 7,82 4,13
400 0,03 1,70 1420 0,512 0,026 2,05 15,56 4,05

Indexes for:
20
2
Global warming (IGW /10 ) IA
1
Smog formation (ISF/10 )
c Acidification
0
(IA/10 )
a 15
IGW
s
e 10

s
t 5
u ISF
d
y 0 100 200 300 400
absorbent flow in the column ( kmol/h)
To evaluate toxicity in this example, we consider 3 relevant compounds: Toluene, AcEt, and Hexane as
a subrogate for products of incomplete combustion (TOC), none of them considered carcinogen.
Environmental concentrations are calculated from the standard emission of Mackay model (1000 kg/h),
as their potentials relative to reference compound (toluene) dont depend on emission levels (see table).
Figure shows variations of toxicity indexes for process (virtually identical), using the previously estimated
emissions; risks depend on absorption efficiency of toluene and acetate, while much less on TOC levels,
and these indexes could be minimized 39% operating at a flow of 50 kmolabs/h.

Compound Toluene Ethyl ac. Hexane Toxicity indexes by inhalation and ingestion
Physical properties
Molecular weight 92,13 88,11 86,17 IT 800
Melting point, C -95,0 -82,0 -95,3
Ratio of fugacity 1,0 1,0 1,0
P. vapor (25C), Pa 3800 12000 20000 600
Solubility, mg/l 550 80800 10
Log Kow 2,70 0,70 4,00 IINH , IING
Life average, h 400
Air 17 55 17
Water 550 55 550
Soil 1700 170 1700 200
Sediment 5500 550 5500
Concentration, mg/l
-7 -7 -7
Air 1,9710 4,3610 1,9710 0 100 200 300 400
-7 -6 -9
Water 4,0010 5,0010 1,5010 Absorbent flow (kmol/h)
Inhalation:
3
RfC, mg/m 0,4 0,2 The uncertainties in these analysis (estimation of emissions,
LC50, ppm 4000 3200 fate, exposures, effects), and particularly the use of different
INHTP 1,0 2,8 2,0 toxicity parameters (Rfx, Lx), must be taken into account as
Ingestion they introduce variations in the evaluations.
RfD, mg/kgd 0,2 0,9
On the other hand, the use of multicriteria indexes requires
LD50, mg/kg 5000 28700
also weighting factors to valuate their relative importance.
INGTP 1,0 2,8 6,510-4
Substance (i) Toluene (R) Ethyl acetate Hexane
Emission to air (standard environment)
1000 kg/h 1000 kg/h 1000 kg/h
Concentration stationary
Air (Ci,A) 197 ng/m3 436 ng/m3 197 ng/m3
Standard risk (Si,A) RfC (mg/m3) 0,4 0,2
LC50 (ppm) 4000 3200
Inhalation,
INHTPi= (Ci,A/Si,A)/ (CR,A/SR,A) 1,00 2,77 2,00
Concentration stationary
Water (Ci,W) 0,400 ng/l 5,02 ng/l 1,5110-3 ng/l
Standard risk (Si,W) RfD (mg/kgd) 0,2 0,9
LD50 (mg/kg) 5000 28700
Ingestion,
INGTPi= (Ci,W/Si,W)/ (CR,W/SR,W) 1,00 2,79 6,5810-4
Process emissions
(50 kg/h of absorbent) mi 0,97 kg/h 160,4 kg/h 0,003 kg/h
Global toxic index
IINH = mi INHTPi 445,3
IING = mi INGTPi 448,5

EPA hap-index MSDS