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“No Chemist ever goes undead. Being the bile of living decay is not only a degrading state
of being for them, but they know that every day they are releasing hydrogen sulfide, which
is going up into the air and producing pollution.”
--Disowned
Overview of the sulfur problem
• Fig 11.1 Sulfur cycle in the
environment as a result of human
activity (excluding volcanic eruption,
movement of sulfur into growing
plants and back out of decaying
plants.
• Vast majority of sulfur in the form of
gypsum or anhydrite.
• All fuels contain sulfur. When fuel is
burned, most sulfur turns into SO2. It
enters the atm, ppt, fall mostly into
oceans, become part of land mass by
geologic processes, enters back into
fossil fuel.
Essentially: S(s) + O2(g) SO2
The essential steps of the sulfur cycle are:
• Mineralization of organic sulfur to the
inorganic form, hydrogen sulfide: (H2S).
• Oxidation of sulfide and elemental sulfur (S)
and related compounds to sulfate (SO42–).
• Reduction of sulfate to sulfide.
• Microbial immobilization of the sulfur
compounds and subsequent incorporation
into the organic form of sulfur
• SO2 can be captured by various methods ( to
be discussed in this topic) in the form of
gypsum, then returned to landfill.
Sulfur in Coal
• Elemental sulfur is chemically-bound in coal,
and also in the form of small crystal iron pyrite
(FeS2, fool’s gold).
Absorber-stripper
combinations are
widely used to
remove HCs from
exhaust gas stream.
H2S Removal from Hydrocarbon
• Once H2S have been separated form other
components, it is normally reacted with oxygen in
controlled amount (by catalytic oxidation) to
oxidize to elemental sulfur:
1
H 2S O 2 S H 2 O (Claus Process)
2
but not
3
H 2S O 2 SO 2 H 2 O
2
Sulfur in HC Fuels
• Crude oil vary in their S content: low S are called sweet; high S
are sour.
• S in HC fuels (NG, propane, gasoline, diesel, etc) is converted
to SO2 during combustion & emitted to atm.
• Large oil burning facilities can have equipment to capture SO2,
but cars, planes, trucks do not.
• Therefore, must limit the amount of S in fuel to 0.05 wt %.
• S is removed from petroleum fractions by catalytic
hydrodesulfurization (HDS).
S removal from petroleum fractions by
hydrodesulfurization (HDS)
S (in HC) + H2
(Ni or Co catalysts promoted with Mo or W) H2S +
hydrocarbon
SO 2 0.5O 2 SO3
SO3 H 2O H 2SO 4
Example 11.3
• One of the largest copper smelters in the United States (Kennecott at Salt
Lake City) produces 320 000 tons of copper per year. The copper ore
smelted is principally chalcopyrite. If all the sulfur were admitted to the
atm as SO2, how much would be emitted? How much sulfuric acid would
be produced if all the sulfur were converted to acid?
Solution to Example 11.3
We know that we would produce 2 mols SO2 per mol of copper.
5
CuFeS 2 O 2 Cu FeO 2SO 2
2
MW SO2 = 64; Cu = 63; H2SO4 = 98
Comparing
this flow
diagram with
Fig 10.15, it
has no
stripper
because???
Sulfuric Acid
• It is the cheapest industrial acid. It has many uses.
• Largest use is production of phosphate fertilizers.
H2SO4 reacts with fluorapatite to produce raw
material for fertilizers.
Turbine hall
North elevation
South elevation
Class Exercise
• As in Example 11.2, amount of water can be
reduced by adding a reagent to water to
increase the solubility of the gas to be
removed.
• Go thru & discuss Example 11.5.
SO2 removal from lean gases
Flue Gas Desulphurization, FGD
Example 11.5 looks at using a dilute solution of NaOH
instead of straight water:
2NaOH + SO2 + ½ O2 Na2SO4 + H2O
Reactions (1) and (2) in scrubber, (2) and (3) in holding tank.
In fact, the aqueous chemistry of these systems is quite complex
Figure 11.13 (11.12) de Nevers
The dry FGD process has the following disadvantages when compared to limestone wet FGD
technology:
•For large units size, multiple absorber modules will be required, result ingin large inlet and outlet
ductwork and damper combinations.
•The process uses lime instead of limestone-based FGD systems. The availability of this reagent as to
be analyzed case-by-case and the reagent handling as to be adapted (e.g. Lime has to be stored in a
steel or concrete silo).
•Reagent utilization is slightly lower than for wet limestone systems to achieve comparable
SO2 removals. The lime stoichiometric ratio is higher than the limestone stoichiometric ratio (on the
same basis) to achieve comparable SO2removals.
•Dry FGD produces a waste, which does not have many uses (unlike gypsum). Nevertheless, new and
local applications could be identified where the dry FGD waste can be used.
•Combined removal of fly ash and waste solids in the particulate collection system precludes
commercial sale of fly ash if the unit is designed to remove FGD waste and fly ash together. In some
cases, FGD could be backfit after the existing electrostatic precipitator, which would allow the sale of fly
ash.
Wet-Dry System
The process is based on the reaction between hydrated lime
and the flue gases. The lime-based reagent is injected under the
form of milk of lime (in the case of lime spray dryer or semi-dry
process) or (humidified) powder (in case of dry processes). The
flue gas remaining heat dries the reagent and the solid reaction
product is collected by a downstream dedusting equipment (ESP
or baghouse filter).
Regenerative system and future
control devices
• Some kind of adsorbent/absorbent used to
capture SO2 from flue gas which can be
regenerated and produce pure SO2.
• Industry tries to further develop dry
limestone-based processes.
ALTERNATIVES TO “BURN AND THEN
SCRUB”
• Change to lower sulfur content fuel
• Remove sulfur from fuel
– Coal cleaning
– Solvent-refined coal
• Modify combustion process
• Don’t burn at all
SUMMARY
• Main sources of emissions are due to combustion of fossil
fuels and smelting of metal sulfide ores.
• Overall control strategy is to convert S to CaSO4∙2H2O and
return to landfill or make wallboard.
• For liq or gaseous fuel containing reduced S, convert to H2S,
then remove with weak alkaline soln, convert to S by Claus,
sell it or landfill.
SUMMARY
• For metal sulfide ore smelting which produces waste gas with
>4% SO2, convert it to sulfuric acid.
• For coal or high S oil in large power plants, exhaust gas
contain 0.1% SO2, treat with limestone/lime in forced FOS or
spray dryer, then convert to CaSO4∙2H2O, then to landfill or
wallboard plant.
• Other alternatives are being explored.
THANK YOU FOR YOUR ATTENTION