Environmental Studies

P. Balasubramanian
Department of Chemical Engineering
Universiti Teknologi PETRONAS
Malaysia
Recap
Equipment design
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Outcome
To applyamethodto control theatmospheric
emissions
Todesignawater treatment method
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Content
Atmospheric Emissions
Water treatment methods
Environmental Impact Assessment(EIA)
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Atmospheric Emissions
There are many types of emissions to
atmosphere
Thesecanbecharacterizedas
particulate(solidor liquid)
vapor and
Gaseousemissions
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Atmospheric Emissions
Industrial emissions:
PM10
PM2.5
Ozone
VOC
SOxand NOx
CO and CO
2
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Atmospheric Emissions
Industrial emissions of major concern are as
follows:
PM10:
Particulate material less than 10 m diameter is
formed as a byproduct of combustion processes
through incomplete combustion and through the
reaction between gaseous pollutants in the
atmosphere.
PM2.5:
Particulate material less than 2.5 m diameter
forms in the same way as PM10, but it can
penetratedeeper intotherespiratorysystemthan
PM10.
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Atmospheric Emissions
O
3
:
Ozoneisaveryreactivecompoundpresent inthe
upper atmosphereandthelower atmosphere.
Ozoneis danger to humanhealthandcontributes
totheformationof other pollutants.
VOCs:
A VOC is any compound of carbon, excluding
carbon monoxide, carbon dioxide, carbonic acid,
metal carbides or carbonates and ammonium
carbonate.
VOCs are major components in the formation of
smog.
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Atmospheric Emissions
Sox:
Oxides of sulfur (SO
2
and SO
3
) are formed in the
combustion of fuels containing sulfur and as a
byproduct of chemicalsproduction.
NOx:
Oxides of nitrogen (principally NO and NO
2
) are
formed in combustion processes and as a
byproduct of chemicalsproduction.
CO:
Carbon monoxide is formed by the incomplete
combustion of fuel and as a byproduct of
chemicalsproduction.
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Atmospheric Emissions
CO
2
:
Carbon dioxide is formed principally by the
combustion of fuel but also as a byproduct of
chemicalsproduction.
Therearefour mainproblemsassociatedwith
atmosphericemissions:
Urbansmog
Acidrain
Ozonelayer destruction
TheGreenhouseeffect
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Atmospheric Emissions
Urbansmog:
Urban smog is commonly found in modern cities
especiallywhereair istrappedinabasin.
It isobservableasabrownishcoloredair.
Theformationof urbansmogisthroughcomplex
photochemical reactions that can be
characterizedby:
VOCs + NOx + O
2
O
3
+ other
photchemical pollutants
Photochemical pollutants such as ozone,
aldehydes and peroxynitrates such as
peroxyethanoyl (or peroxyacetyl) nitrate (PAN)
areformed.
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hf
Atmospheric Emissions
Ozone and other photochemical pollutants have
harmful effects on living organisms and on
buildingstructures
High levels of these pollutants can cause
breathingdifficultiesandbringonasthmaattacks
inhumans.
Warm weather and still air exacerbate the
problem.
In addition to VOCs and NOx , the problem of
urban smog is made worse by particulate
emissionsandcarbonmonoxidefromincomplete
combustionof fuel.
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Atmospheric Emissions
Acidrain:
Natural precipitationis naturallyacidicwith
apHoftenintherangeof 5to 6caused by
carbonicacidfromdissolvedcarbondioxide
and sulfurous and sulfuric acids from
natural emissionsof SOxandH
2
S.
Human activity can reduce the pH very
significantly down to the range 2 to 4 in
extreme cases, mainly caused by emissions
of oxidesof sulfur.
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Atmospheric Emissions
Problemsassociatedwithacidraininclude:
damagetoplant life, particularlyinforests
acidification of water, leading to dead lakes and
streams, loss of aquatic life and possible damage
tohumanwater supply
corrosion of buildings, particularly those made of
marbleandsandstone.
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Atmospheric Emissions
Ozonelayer destruction:
Theupper atmospherecontainsalayer richinozone.
Ozone in the lower levels of the atmosphere is
harmful
Ozone in the upper levels of the atmosphere is
essential as it absorbs considerable amounts of
ultraviolet light that would otherwise reach the
earthssurface
The destruction of ozone is catalyzed by oxides of
nitrogenintheupper atmosphere
The result of ozone layer destruction is increased
ultraviolet light reaching the Earth, potentially
increasingskincancer andendangeringpolar species
Thisisaglobal effect that requiresglobal solutions
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Atmospheric Emissions
TheGreenhouseeffect:
Gases such as CO
2
, CH
4
and H
2
Oare present in low
concentrationsintheearthsatmosphere
These gases reduce the earths emissivity and reflect
someof theheat radiatedbytheearth
The effect is to create a blanket to keep the earth
warmer thanit wouldotherwisebe.
The problemarises mainly from burning fossil fuels
andclearingforestsbyburning.
Results:
Global temperaturesincrease
Leadingtomeltingof thepolar icecapsandglaciers
Rising sea levels, desertification of areas, thawing of
permafrost, increased weather disruptions and
changestooceancurrents
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Atmospheric Emissions
Sourcesof atmosphericpollution:
Incompletecombustionor fuel ashfromfurnaces,
boilersandthermal oxidizers
Incompletecombustioninflares
Solidsdryingoperations
Kilns used for high temperature treatment of
solids
Metal manufacture
Crushingandgrindingoperationsfor solids
Any solids handling operation open to the
atmosphere, andsoon.
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Atmospheric Emissions
Vapor emissions are even more difficult as they
have even more sources such as:
Condenser vents
Venting of pipes and vessels
Inert gas purging of pipes and vessels
Process purges to atmosphere
Drying operations
Incomplete combustion of fuel in furnaces, boilers and
thermal oxidizers
Incomplete combustion in flares
Application of solvent-based surface coatings
Open operations such as filters, mixing vessels, and so
on, leading to evaporation of volatile organic
materials
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Atmospheric Emissions
drumemptyingand filling, leadingto evaporation
of volatileorganicmaterials
spillagesof volatileorganicmaterial
process plant ventilation of buildings processing
volatileorganicmaterials
storagetankloadingandcleaning
road, rail andbargetankloadingandcleaning
fugitiveemissionsthroughgasketsandshaft seals
fugitive emissions from sewers and effluent
treatment
fugitive emissions fromprocess sampling points,
andsoon.
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Atmospheric Emissions
Inlarger plants, significant reductionsinVOCemissions
canusuallybemade
by controlling major sources, such as tank venting,
condensersandpurges, and
byinspectionandmaintenanceof gasketsandshaft seals.
The largest volume of atmospheric emissions from
process plants occurs from combustion producing
gaseousemissions. Suchemissionsarecreatedfrom:
furnaces, boilersandthermal oxidizers
gasturbineexhausts
flares
processoperationswherecokeneedsto beremovedfrom
catalysts (e.g. fluid catalytic cracking regeneration in
refineries), andsoon
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Example 1
Astoragetankwithavent toatmosphereisto
be filled at 25

C with a mixture containing

benzene with a mole fraction of 0.2 and
toluenewithamolefractionof 0.8.
Estimate the concentration of benzene and
tolueneinthetankvent:
a) at 25

C
b) correctedto standardconditionsof 0

Cand
1atm
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Example 1
Assume that the mixture of benzene and
toluene obeys Raoults Law and the molar
mass in kilograms occupies 22.4 m
3
in the
vapor phaseat standardconditions. Themolar
massesof benzeneandtolueneare78and92
respectively. The vapor pressures of benzene
and toluene at 25

Care 0.126bar and 0.0376

bar respectively.
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Example 1: Solution (a)
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Example 1: Solution (b)
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Example 2
Anairstreamcontainsacetonevapor. Estimate
thefollowing.
a) Theoutlet concentrationthat canbeachievedby
coolingto 35

Cat 1 atmpressure (coolingwater

temperature).
b) Theoutlet concentrationthat canbeachievedby
coolingto20

Cat 1atmpressure.
c) The outlet temperature to which the air stream
must be cooled to obtain an outlet concentration
of 20mgm
3
.
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Example 2
The concentrations should be quoted at
standardconditionsof 0

Cand1atm. It canbe
assumed that the molar mass in kilograms
occupies 22.4 m
3
at standard conditions. The
molar massof acetonecanbetakento be58.
Thevapor pressureof acetoneisgivenby:
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Example 2: Solution
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Example 2: Solution
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Control of Solid Particulate Emissions
to Atmosphere
The selection of equipment for the treatment
of solid particle emissions to atmosphere
dependsonanumber of factors
sizedistributionof theparticlestobeseparated
particleloading
gasthroughput
permissiblepressuredrop
temperature
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Control of Solid Particulate Emissions
to Atmosphere
There is a wide range of equipment available
for thecontrol of emissionsof solidparticles:
Gravitysettlers
Gravitysettlers useto collect coarseparticles and
maybeuseasprefilters.
Onlyparticlesinexcessof 100m canreasonably
beremoved.
Inertial collectors
Onlyparticles>50mcanbereasonably
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Control of Solid Particulate Emissions
to Atmosphere
Cyclones
Particlessize>5m.
Scrubbers
Scrubbers are designed to contact a liquid with the
particle-laden gas and entrain the particles with the
liquid.
They offer the obvious advantage that they can be
used to remove gaseous as well as particulate
pollutants.
Electrostaticprecipitators.
Electrostaticprecipitatorsareusedwherecollectionof
fine particles at a high efficiency coupled with alow-
pressuredropisnecessary.
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Control of Solid Particulate Emissions
to Atmosphere
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Table 1 Methods of control of emissions of solid particles.
Control of VOC Emissions to Atmosphere
The hierarchy appropriate for control of VOC
emissions:
Eliminateor reduceVOCemissionsat source
Recover theVOCfor reuse
Recover theVOCfor treatment anddisposal
Treatment and disposal of the VOC-laden gas
stream
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Control of VOC Emissions to Atmosphere
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Tank loading can be a significant source of
VOC emissions from atmospheric storage
tanks used for the storage of organic liquids
(Figure25.1)
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Control of VOC Emissions to Atmosphere
There are a number of ways in which such VOC
emissions can be prevented frombeingomitted from
storagetanks.
Figure 25.2 shows a simple technique involving a
balancingline.
The atmospheric storage tank in Figure 25.2 is fitted
with avacuum/pressurerelief systemto guard against
over-pressureor under-pressureof thestoragetank.
Now as the atmospheric storage tank is emptied and
the road tanker filled in Figure 25.2, the displaced
vapor from the road tanker is pushed back into the
atmosphericstoragetank.
In this way, displaced vapor fromthe road tanker is
preventedfrombeingreleasedtotheatmosphere.
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Control of VOC Emissions to Atmosphere
Themethodsof VOCrecoveryare:
Condensation
Membranes
Absorption
Adsorption
Once VOCs have been minimized at source and
recovery possibilities have been exhausted, then any
residual VOCneedstobedestroyedusing:
flares
thermal oxidation
catalyticthermal oxidation
gasturbines
bioscrubbers
biofiltration
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Control of VOC Emissions to Atmosphere
Control of sulfur emissions
Sources of atmospheric sulfur emissions from
theprocessindustriesare:
chemical production: sulfuric acid production,
sulfonationreactions, andsoon
smeltingprocesses: productionof copper
fuel processingoperations: fuel desulfurization
combustionof fuel: steamgeneration.
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Control of sulfur emissions
Atmospheric sulfur emissions can be
minimizedat sourcebyimprovingtheprocess
yields and desulfurization of fuels prior to
combustion.
Sulfur can be removed fromemissions either
asSO
2
or H
2
S.
Removal of theH
2
Scanbeby:
physical absorption
chemical absorption
gasificationof material followedbyH
2
Sremoval
partial oxidationtoelemental sulfur
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Control of sulfur emissions
Removal of SO
2
can be by:
absorption using sodium hydroxide
wet limestone scrubbing
WellmanLord process
or many other methods
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Control of oxides of nitrogen emissions
NOx(principallyNOandNO
2
) areproducedin
chemical production, metal and mineral
processingandcombustionof fuels.
NOx formed in combustion processes is by
three mechanisms (fuel, thermal and prompt
NO).
Noxemissions can be minimized at source by
increasing process yields in chemical
production, switching to a fuel with lower
nitrogencontent or minimizingNOxformation
incombustionprocesses.
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Control of oxides of nitrogen emissions
After minimizing the production of NOx ,
removal by either oxidation or reduction can
beconsidered.
NOx can be absorbed in hydrogen peroxide,
whichformsnitricacid.
Reduction is usually carried out using
ammonia.
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Control of oxides of nitrogen emissions
Flue gas emissions can be minimized at source
by:
increased energy efficiency at the point of use
increased energy efficiency of the utility system
improvements to combustion processes
changing fuel
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Example 3
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Control of combustion emissions
The major emissions fromthe combustion of
fuel areCO
2
, SOx, NOxandparticulates.
The products of combustion are best
minimized by making the process efficient in
its use of energy through efficient heat
recovery and avoiding unnecessary thermal
oxidation of waste through minimization of
processwaste.
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Summary
Fluegasemissionscanbeminimizedat source
by:
increased energy efficiency at the point of use
(e.g. better heat integration)
increased energy efficiency of the utility system
(e.g. increasedcogeneration)
improvements to combustion processes (e.g. low
NOxburners)
changing fuel (e.g. changing from fuel oil to
natural gas)
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Summary
Treatment of SOx: The various techniques that
canbeconsideredfor thetreatment of SOxare:
absorptionintoNaOH, CaCO
3
, water, andsoon
oxidationandconversiontoH
2
SO
4
reductionbyconversiontoH
2
Sandthensulfur
Treatment of Nox: The techniques used for
treatment of NOxare:
absorption into an NO-complexing agent or oxidizing
agent
reduction using selective non-catalytic or catalytic
processes
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Summary
Treatment of particulates: Theseinclude
scrubbers
inertial collectors
cyclones
bagfilters
electrostaticprecipitators
Treatment of CO
2
: If CO
2
needs to be separated from
the other combustion products for the purpose of
reducing greenhouse gas emissions, there are four
waysinwhichthiscan, inprinciple, bebrought about:
absorption(for example, usingamine)
desorption(for example, usingalumina, zeolite, etc.)
membrane
cryogenicseparation
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Conclusion
In this lecture, different types of atmospheric
emissions are discussed.
The control of VOC, SOx, NOx, and combustion
emissions are briefly presented.
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References
R. Smith, Chemical Process: Design and
Integration, Wiley, 2005.
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