Professional Documents
Culture Documents
- 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).
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
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
Products
Midpoints Endpoint
inhalation
Human
air population
process discharges dermal
water
soil
ingestion
1800
1600
1400
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
Human
mortality,
Chemical Emissions: Depletion of Damages to
processes CFCs, HCFCs ozone layer, ecosystems
radiation UV
Cl + O3 ClO + O2
ClO + O Cl + O2
O3 + O 2 O 2
Human and
ecological
Chemical Emissions: damages by
processes NOx VOCs Photochemical ozone or other
reactions oxidants
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
Xi + i H+ +
APi = (i/Mi)/(SO2/MSO2)
Ecological risk assessment: from defining the sources to estimating effects
ATMOSPHERE
HYDROSPHERE BIOSPHERE
LITOSPHERE
Products
Human and
ecological
Chemical Discharges: transport and toxicology:
processes HAPs, WWs, HWs fate of pollutants dose and
(immission) response
Toxic releases (air emissions, water effluents, solid wastes ) and chain of effects
Products
Chemical Discharges:
processes HAPs, WWs, HWs
FIRE
Feedstock Energy
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
Storage Refining
tank D/C
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):
Human and
ecological
Discharges: transport and toxicology:
HAPs, WWs, HWs fate of pollutants dose and
(immission) response
Environment
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 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
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 )
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