CONTROL OF SULFUR OXIDES

This family of pollutants contains the

infamous sulfur dioxide, produced in
prestigious amounts, and the lesser
produced sulfur trioxide.
 INTRODUCTION
• Control of PM and VOCs is mostly accomplished by
physical processes that do not involve change of
pollutants’ chemical nature, and changes into
harmless materials by combustion
• SOx and NOx cannot be economically collected by
physical means or rendered harmless by combustion.
• SOx control is largely by chemical means.
 As a Natural Secondary Pollutant
• In nature, decay of organic material creates hydrogen
sulfide gas. This reacts with oxygen to form sulfur
dioxide.
2 H2S + 3 O2  2 SO2 + 2 H2O
• It can also react with ozone:
H2S + O3  SO2 + H2O

“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).

• When burned, almost all is converted to SO2

and some SO3 and carried along in stack gas.
 Sulfur in Metal Processing
• Another important source
of SO2 is the processing of
sulfur-bearing ores.
• Copper ore is chalcopyrite,
CuFeS2.
• High T smelting converts
the sulfur to SO2 gas.
• Other ores are from lead,
zinc, nickel.
5
CuFeS 2  O 2  Cu  FeO  2SO 2
2
 Sulfuric Acid Plants
• Sulfur trioxide is produced by the oxidation of sulfur
dioxide, and this is then reacted with water to form
sulfuric acid. Some of the sulfur dioxide is released
into the atmosphere rather than being properly and
fully oxidized.
 Acid plant in Copperhill in 1912.
A sulfuric acid plant at a copper mine in PHOTO: Environmental Protection Agency
Copperhill, Tennessee. The landscape around the
mine and acid plant is all barren and dead as a
result of the factory's effluent. Fumes from
smelting copper for sulfuric acid have destroyed
all vegetation and eroded the land
Common copper containing minerals are sulfides
of copper and iron.
 Sulfur in Oil & Gas
• In natural gas, most sulfur is in form of H2S.
• In liq petroleum, oil shales, oil sands, sulfur is
chemically combined with HC compounds, can only
be removed by breaking the bonds.
• Since sulfur is removed in the refinement of
petroleum and natural gas, they are not major
sources of sulfur oxide pollution. (See Table 11.2)
Coal combustion
contributes 71% of the
total.
Coal + oil combustion =
86% of total.
Combustion from metal
(Used to be major source
before 1970) processing
have been controlled and
contribute only 2.7%.
• Sulfur containing gas streams most dealt with
in the industry belongs to three categories:
– Reduced sulfur
– Concentrated SO2 stream
– Dilute SO2 stream.
Removal of Reduced Sulfur Compounds
from Petroleum & Gas Streams
• Here we discuss the
technology to remove sulfur
from gas streams when sulfur
is present in reduced form.
• Reduction of sulfur to H2S
occurs in the processing of
sour crude oil & natural gas
and in fuel gas produced by
coal gasification.
 Example 11.1
• A flow of 108 scf/day of natural gas (~0.2%
average US consumption) contains 1% (10 000
ppm) H2S is treated as in Fig 10.15 to reduce H2S
conc to 4 ppm (the max allowable in US). Gas is
scrubbed at 100 atm, 20°C. Water is the
scrubbing agent. Est the required water flow rate.
• Calculations show that 148 kg/s of water is
needed to remove H2S!
• Need to find other scrubbing agent.
• H2S, SO2, SO3 are acid gases, which dissolves in
water to form H+ ions.
• An alkali is needed to remove the H+ so that less
water will be needed.
• Commonly used alkali are ethanolamines (mono-,
di-, or triethanolamine), sodium or potassium
salts of weak acids like carbonic or phosphoric.
• If the previous example is repeated using MEA,
the required liq flow rate is only 6.1 kg/s.
• There are hundreds of plants all over the
world uses this MEA system, not only for NG
but also H2S containing gases generated in
petroleum refining.
• Every major refinery has at least one of them.

IGCC at Puertollano in Central Spain

 Figure 10.15 de Nevers

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

The HCs are then

condensed. The
remaining gas
stream (containing
H2 and H2S) is
treated in a
refinery for H2S
removal

Schematic diagram of a typical Hydrodesulfurization (HDS) unit in a petroleum refinery

 REMOVAL OF SULFUR FROM RICH
WASTE GASES
• SO2 conc from smelting of metal sulfide ores range
from 2 – 40%. It can be economically treated in
sulfuric acid plants:

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

To produce 320 000 tons of copper per year:

320000 ton Cu 2  64 g/mol SO 2
  650000 ton/yr SO 2
year 63 g/mol Cu

From Table 11.2, if this plant did not capture

its SO2, it would be 3.2% of total US SO2
emissions!

If all were converted to sulfuric acid?

It would be roughly 2% of total US sulfuric acid production!

 Temperature-conversion relationship
of sulfuric acid production
• The rxn does not go to completion. It is exothermic, so
the % conversion at equilibrium is higher at low T.
• The rxn is normally done in 3 or 4 separate catalyst
beds with intercoolers in between (See chart in Fig
11.2).
• The preheated feed gas enters 1st catalyst bed at 420°C.
It then leaves the bed and cooled before entering next
bed. The exit gas from the final bed is ≈ 425°C (≈98%
converted to H2SO4). The remaining 2% of SO2 is vented
out to atm (lean gas stream).
In response to legal pressure to reduce SO2 emission, the resulting
gas is again contacted with water so that SO3 is absorbed. This is
called double contact or double absorption plants. It can convert
over 99.7% SO2 to H2SO4. See Figure 11.3 de Nevers.

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.

phosphate rock + H2SO4  phosphoric acid  phosphate fertilizer.

• Large scale production of H2SO4 is only feasible if

there is a nearby deposit of phosphate rocks. Why?
 Limitation of H2SO4 production
• It is uneconomic if conc of SO2 is too low (less
than 4%)
• Capital and operating cost depends of
volumetric flow rate of gas, not conc of SO2.
• If less than 4%, plants are not autothermal,
therefore needs external heat supply, adding
fuel cost & plant complexity.
 REMOVAL OF SULFUR FROM LEAN
WASTE GASES
• Large coal or oil-burning facilities typically
emits exhaust gas ≈ 0.1% SO2. Not
economically to convert to acid.
• Scrubbing with limestone water is the most
widely used method.
1
CaCO3  SO 2  O 2  CaSO 4  CO 2
2

• The process is called Flue Gas Desulfurization

(FGD).
 Example 11.4
SO2 removal from lean gases
Example 11.4 looks at scrubbing 106 scfm of flue gas with
conc 1000 ppm SO2, using H2O,
SO2 + H2O  H2SO3

Governed by the solubility of SO2 in

water. 3585 kg/s of water to achieve
90% removal! Very large amount of
water. We end up with a large quantity
of acidic water.
Problems of Absorption with water
• Requires large amount of water.
• Wastewater stream is saturated with SO2, may
reenter the atm.
• Aqueous solution would remove dissolved O2
from rivers, fishes suffer.
Flue Gas Desulfurization Process
 Battersea Plant of London Power
Company
• Read page
410 of
textbook.
Take 5! More pix of the previous dog!

Main boiler house

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

[This overall reaction proceeds via the dissolution of SO2

first to make H2SO3, then neutralization].

From stoichiometry, 44,700 tonne/yr NaOH required; $22

million/yr! A lot of money.
The resulting effluent is not acidic but contains a large
amount of salt.
 What problem might the power plant
encounter?
Comparing with in Example 11.1 and 11.2
• Volumetric flow rate is 1700 times that in the
H2S removal (14 times becoz of higher molar
flow rate, 120 times because of lower gas
density.
• Power cost to drive gas thru scrubber is 1700
times larger. Important to minimize P drop.
• No regenerator
 More problems…
• What to do with the salt cake? Detergent
manufacture & paper industry use pure
sodium sulfate.
• Salt cake is contaminated with fly as, must be
further purified.
• Salt cake is generally not accepted in landfill
due to high water solubility, landfill is well
protected from water infiltration.
 SO2 removal from lean gases
More problems… CO2

A complicating factor: CO2 also dissolves in water,

Conc CO2 is 120 times SO2 in flue gas,
It use up NaOH by this rxn:

2NaOH + CO2  Na2CO3 + H2O

 Solution to CO2 problem
We can try to adjust pH such that we dissolve SO2 but not
CO2

CO2 (g)  CO2 (aq) + H2O  H2CO3  H+ + HCO3-

SO2 (g)  SO2 (aq) + H2O  H2SO3  H+ + HSO3-

Based on the multiple simultaneous equilibria in water, find

H+ concentration that forces first equation to left, second
equation to right; 4 < pH < 6

But, this is acidic, not alkaline. To remove SO2 without

scrubbing CO2, we must use a weak acid.
 Figure 11.4 de Nevers
• For High P H2S removal: Use packed/plate towers.
• Three arrangements for scrubbing SO2 with a liquid:
• First arrangement: Simple
bubbler.
• High P drop.
• Plate type
distillation/absorption columns
are series of bubblers stacked
one above the other.
• Spray chamber
• Low gas P drop
• Difficult to approach
equilibrium because liq-gas
contact is low.
• Widely used becaoz
simplicity, low P drop,
resistance to scale
deposition and plugging.
• Packed column
• Better mass transfer per unit
of gas P drop.
 Forced-Oxidation Limestone
Scrubbing
• This is a wet process which can produce wallboard
grade gypsum. The process is based on the reaction
between a limestone
suspension and the flue gases. Scrubber
designers intend to promote maximum gas-liquid
surface area and residence time in order to perform
high removal efficiencies (up to 99%).
• The sulfur containing slurry is then oxidized to
produce solid FGD-gypsum which is removed from
the slurry by physical separation (filter, decanter...).
All the reactions required by the process are done in the scrubber, the physical
separation is the only step required outside the absorber.
Main advantages of FOLS process
• Use of limestone which is generally cheaper
than lime
• Marketable / Saleable by-product (wallboard
quality gypsum)
• Wet process (> higher contact between
reagent and flue gas)
• Well-known process, many engineering able
to design FGD unit
 Main disadvantages of FOLS process
• Molecular weight of limestone higher than for lime (>
more tons of reagent is required to achieve the
removal of 1 ton of SO2)
• Extra CO2 emission due to the reaction
between limestone and SO2
• Preparation of the reagent (suspension of micronized
CaCO3) use a lot of energy and milling step is more
complicated than lime based process. Use of
milled limestone is simple but milled limestone cost
is more expensive
• Wet slurry to be treated
• Low FGD-gypsum market in some regions
 SO2 removal from lean gases
Flue Gas Desulphurization, FGD
Forced-Oxidation Limestone scrubbing Fig. 11.5 & 11.6

(1) SO2 + H2O  H2SO3

(2) CaCO3 + H2SO3  CaSO3 + CO2 + H2O
(3) 2 CaSO3 + O2  2 CaSO4

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

• Principal chemical equilibria in a limestone

scrubber
 Fig. 11.6 (11.5 & 11.6) de Nevers

• Flue gas desulfurization details

 SO2 removal from lean gases
Flue Gas Desulphurization, FGD
Example 11.8 (11.6), demonstrates the application of
familiar mass balance and fluid mechanics principles to
the scrubber system in Fig. 11.6

- settling velocity of a spherical water droplet in air

- fraction of water evaporated to saturate the gas
- fraction of CaCO3 reacting per pass through scrubber
Figure (11.6) de Nevers
 SO2 removal from lean gases
Flue Gas Desulphurization, FGD
Problems:
(largely overcome by recent systems)
• corrosion due to Cl- buildup
• solids deposition, scaling, plugging
• poor reagent utilization
• poor solid-liquid separation
 Other approaches: Wet Processes
• Dual-alkali process
• Ammonia scrubbing
• Scrubbing by MgO Slurry
• Absorption by Sodium carbonate/Bicarbonate
solutions
• Citrate process
• Other scrubbing processes
 Dry Process
• Dry alkaline particles injection
• Use of Metal Oxides
 Figure 11.7 de Nevers
• Once through dry solids addition
Flowchart illustrates a Circulating fluidized bed
FGD system (CFB or dry process) with by-
products recirculation
Disadvantages of dry processes versus classical wet technologies

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

Manjung coal-fired power plant, in Malaysia

© Marc Roussel / Interlinks-Image