SOX CONTROL

Introduction

Fuel desulfurization

Flue gas desulfurization

Limestone scrubbing
Lime scrubbing
Dry scrubbing
Activated carbon adsorption

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 INTRODUCTION
2/3 of SOx in the US is from what source?

In natural gas most of the sulfur is in the form of

H2S, which is easily separated from the other
constituents of the gas.

In oil(liquid petroleum), the sulfur is chemically

combined with the hydrocarbon compounds;
normally it cannot be removed without breaking
chemical bonds.
Here the sulfur is concentrated in the higher boiling
fractions of the oil, so the same crude oil can yield a low-
sulfur gasoline (avg. 0.03% S) and a high -sulfur heavy fuel
2

oil(0.5-1% S)
 INTRODUCTION
In coal, much of the sulfur is also in the form of
chemically bound sulfur, but some coals have a
large fraction of their sulfur in the form of small
crystals of iron pyrite, FeS2 .
When the fuel is burnt, almost all the sulfur in the fuel,
whether chemically bound or pyritic, is converted to sulfur
dioxide and carried along with stack gas.

The other important source of sulfur attributable to

humans is the processing of sulfur-bearing ores. The
principal copper ore of the world is chalcopyrite,
CuFeS2
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 INTRODUCTION

2 categories of control methods:

Fuel desulfurization
Flue gas desulfurization

Within these categories, dozens of methods have

been demonstrated. Only a few examples are
presented here.

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 FUEL DESULFURIZATION
Oil and natural gas:
A desulfurization unit removes organic sulfur via a catalytic
reaction with hydrogen:
( HC containing S) H 2 Ni
or HC H 2 S
Co catalyst

Next, in the Claus process, H2S is reacted with O2 from

the air in controlled amounts to oxidize it only as far as
elemental sulfur and not as far as SO2.
1
H 2 S O2 S H 2O
2
Some H2S is oxidized to SO2 , and then SO2 and H2S oxidize
and reduce each other to form elemental sulfur.
The elemental sulfur can be sold for use in the production of
sufuric acid or landfilled if there is no nearby market for it.5
 FUEL DESULFURIZATION
Although the Claus process is simple enough, there are a variety
of ways of carrying it out and the details can be complex.
Hundreds of such plants operate successfully throughout the
world; every major petroleum refinery has at least one.

Because elemental sulfur is inert and harmless and because

reduced sulfur in the form of hydrogen sulfide and related
compounds can be easily oxidized to sulfur or sulfur dioxide, the
entire strategy of the petroleum and natural gas industries in
dealing with reduced sulfur in petroleum, natural gas and other
process gases is to keep the sulfur in the form of elemental sulfur
or reduced sulfur(e.g.H2S).
O2 in the air is cheap and so can always move in the oxidation direction at a
low cost.
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In contrast H2 is an expensive raw material so moving in the reduction
direction is expensive.
 Sulfur in hydrocarbon fuels( natural gas, propane, gasoline,
jet fuel, diesel fuel, furnace oil) is normally converted to SO 2
during combustion and emitted into the atmosphere.

Large oil-burning facilities can have equipment to capture

that SO2, but autos, trucks and airplanes do not. The
only way to limit the SO2 emissions from these sources is to
limit the amount of sulfur in the fuel. For this reason
the Clean Air Act of 1990 limits the amount of sulfur in
diesel fuel to 0.05% by weight

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 FUEL DESULFURIZATION
Coal
30-70% of sulfur in coal is in mineral form, which can
be removed via washing or other physical cleaning.

Organic sulfur in coal, however, must be removed via:

Chemical desulfurization (costs money)
Gasification (costs energy, but coal can then be burned in
gas-turbine steam-turbine plants, which are more efficient
than coal-fired steam plants)

Can switch from high-sulfur eastern coal to low-sulfur

western coal
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 SO2 REMOVAL (FLUE GAS
DESULFURIZATION)
SO2 scrubbing, or Flue Gas Desulfurization processes can be
classified as:
Throwaway or regenerative, depending upon whether the
discovered sulfur is discarded or recycled.

Wet or dry, depending upon whether the scrubber is a liquid

or solid.

Regenerative processes have not become popular

because of their cost and complexity, and lack of
markets for the products.
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SO2 REMOVAL (FLUE GAS
DESULFURIZATION)

10

Wark, Warner & Davis, 1998

 THROWAWAY PROCESSES
Limestone scrubbing
Oldest and most widely used FGD process in US.
Used for most new installations.
Here limestone slurry is contacted with the flue gas
in the spray tower. The SO2 is absorbed into
limestone (CaCO3) slurry, where it reacts to form
calcium sulfite (CaSO3) and calcium sulfate (CaSO4).
CaCO3 ( s ) H 2O 2 SO2 Ca 2 2 HSO3 CO2 ( g )
CaCO3 ( s ) 2 HSO3 Ca 2 2CaSO3 CO2 H 2O

Can achieve removal efficiencies of ____90%_______.

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In scrubbing tower:
CaCO3 ( s ) H 2O 2SO2 Ca 2 2 HSO3 CO2 ( g )

In effluent hold tank (EHT):

CaCO3 ( s ) 2 HSO3 Ca 2 2CaSO3 CO2 H 2O

Net reaction:

Excess oxygen in the flue gas and EHT oxidizes

CaSO3 to CaSO4 (gypsum, a naturally-occurring
mineral).
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LIMESTONE SCRUBBING

13

de Nevers, 2000
LIMESTONE SCRUBBING
System operates countercurrent:
Scrubbing slurry (water with finely ground limestone) is
sprayed and falls down.
Flue Gas containing SO2 travels up.
SO2 is absorbed into slurry droplets, where it reacts to
form CaSO3.

Other designs use packing or a bubbler to

facilitate gas/liquid contact.

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LIMESTONE SCRUBBING
Scrubber tower configurations:

15

de Nevers, 2000
16
LIMESTONE SCRUBBING
Advantages
The absorbent is abundant and inexpensive

Has a wide range of commercial acceptance

Disadvantages
Scaling inside the tower

Equipment plugging

corrosive

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LIME SCRUBBING
Lime Scrubbing
Similar to limestone scrubbing, but lime [Ca(OH) 2] is more
reactive than limestone

Net reactions:

CaO H 2O Ca (OH ) 2
SO2 H 2O H 2 SO3
H 2 SO3 Ca (OH ) 2 CaSO3 .2 H 2O
1
CaSO3 .2 H 2O O2 CaSO4 .2 H 2O
2

Can achieve removal efficiencies of ___95%_. 18

LIME SCRUBBING
Advantages:
Better utilization of reagent

More flexibility in operation

Disadvantages:
High cost of lime relative to limestone

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DRY SCRUBBING

Direct injection of pulverized lime or limestone

into the flue gas

Dry adsorption of SO2 occurs and the particles

are collected in a baghouse

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DRY SCRUBBING
Advantages:
Low capital cost

Low maintenance cost

Disadvantages:
High reagent cost ( including transportation)

Waste disposal problems(leaching of soluble

sodium salts)

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ACTIVATED CARBON ADSORPTION

Carbon catalyzes reaction of SO2 to H2SO4,

preventing desorption of SO2

Carbon can be regenerated by water washing,

producing a dilute sulfuric acid stream that can
be neutralized and discarded

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