EVT524

EMISSION CONTROL TECHNOLOGY

TOPIC 5
CONTROL OF SULPHUR OXIDES
(SOx)
Outlines

1. An Overview of Sulphur Problem

2. Control of SO2 emission
3. Sulfur Control options
i. Desulfurization during combustion
 H2S removal from natural gas and petroleum
 S removal from petroleum
ii. Desulfurization during combustion
 Fluidized Bed Combustion (FBC)
 Integrated Gasification Combined Cycle
(IGCCS)

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An Overview of Sulphur Problem
H2S S SO2 SO3

H2S From natural gas

From anaerobic systems
Toxic, Highly odorous

SO2 Fossil Fuel combustion, S (in fuel) + O2  SO2

Base metal smelting, e.g.
CuFeS2 + 5/2 O2  Cu + FeO + 2 SO2

SO3 From oxidation of SO2, normally requires V2O5 or

other catalyst

Effects: Acid rain, sulfate aerosols (PM10) visibility

problems

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 An Overview of Sulphur Problem
S content in fossil fuels: 0-4%
 SO2 in flue gas: 5000 ppm
Note: Sweet crude oil 0.5% S, Sour crude 2-4% S

S content in mineral ores, e.g. CuFeS2 ,

Cu: 63.5 Fe: 55.8 S: 2 X 32
Thus, 64/183.3 ~ 33% S in ore

Correspondingly higher concentration in “roaster” gas

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1995 Criteria Air Emissions for Canada
1000 tons % of total

Industrial Sources 1950 73.47

Upstream Oil and Gas Industry 387
Petroleum Refining 141
Oil Sands 161
Non-ferrous mining and smelting industry 892

Non-industrial Fuel Combustion 566 21.33

Electric Power Generation 255

Transportation 136 5.12

TOTAL 2654 100

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 Air Quality Monitoring

Ambient air quality guideline (Malaysia)

Pollutants Averaging Concentration Concentration
(ppm) (µg/m3 )
Ozone (O3) 1 hour 0.1 200
8 hours 0.06 120
Carbon 1 hour 30.0 35
monoxide (CO) 8 hours 9.0 10
Nitrogen Oxide 1 hour 0.17 320
(NO2) 8 hours 0.04 -
Sulfur Dioxide 1 hour 0.13 350
(SO2) 8 hours 0.04 105
PM 10 24 hours - 150
12 months - 50
Total 24 hours - 260
suspended(TSP) 12 months - 90
Lead (Pb) 3 months 15 7
 Control of SO2 emission

 Desulfurization prior to combustion.

 Sulfur removal during combustion.

 Desulfurization of flue gas (post combustion–

flue gas desulfurization – FGD).

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Sulfur Control options
H2S Recover elemental S at high
concentrations, burn to SO2 at low
concentrations (pre-combustion
desulfurization)

SO2 Recover as H2SO4 at high

concentrations (more than a few %)

Capture as CaSO4 at low concentrations

(1000 – 5000 ppm)
(desulfurization post-combustion or
process)
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 H2S removal from natural gas and petroleum
Natural Gas

H2S in Natural Gas (NG), absorption with

mono-ethanolamine & stripping, Fig. 11.1,

S recovery from H2S by controlled catalytic oxidation:

H2S + ½ O2  S + H2O CLAUS PROCESS

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 H2S removal from natural gas and petroleum
 Mono-ethanolamine is a weak base reacted
and dissolved the H2S which is a weak acid.
Mono-ethanolamine is also simply known as
MEA.
 Cleaning process. The NG will pass
through absorber column (Figure) of
ethanolamine solvent and the H2S captured
by dissolving the gas into the MEA weak
base.
 Solvent recovery. The solvent-H2S
compound will pass into stripping column
and heated in gas-liquid separator. The
MEA recover and reuse for cleaning the
next incoming natural gas. 11
 Figure 11.1 (10.15) de Nevers

Note: Example of process in recovering of H2S in natural gas

using mono-ethanolamine (MEA) as weak base solvent.
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S removal from petroleum

Petroleum

S removal from petroleum fractions by

hydrodesulphurization:

S (in HC) + H2  H2S (Ni, Co, Mo, W catalysts)

H2S recovery follows as above. CLAUS PROCESS

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 Control of SO2 emission

 Desulfurization prior to combustion.

Desulfurization during combustion

 Desulfurization of flue gas (post combustion)

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 There are two types of SO2 emission

There are two types of SO2 emission which have

been differentiated based on the amount of the
gases emission:

 High concentration of gases SO2 - rich gases

Low concentration of gases SO2 – lean gases.

Note: High concentration more than 1% = more than 10,000 ppm.

Low concentration – between 1,000 to 5,000 ppm.

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 SO2 from rich gases
Fig. 11.4 (11.3) catalyst beds and absorption tower,
SO2 + ½ O2  SO3 (catalyst)
SO3 + H2O  H2SO4

Most H2SO4 used in fertilizer production:

phosphate rock + H2SO4  phosphoric acid  phosphate fertilizer
Double absorption plant are deployed to optimize adsorption of SO2
(see Figure).
but we still want to limit SO2 emissions to the atmosphere (less than
0.1% or <1,000 ppm):
- treat lean gases for SO2 removal (as CaSO4)
- modify process to reduce or eliminate lean gases in favor
of rich gases suitable for acid production.
(e.g. Inco-Sudbury)
Note: Phosphate rock in the form of Ca10F2(PO4)O6 not soluble in water –
reaction with sulfuric acids produced water soluble phosphoric acids
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Figure 11.4 (11.3) de Nevers

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 There are two types of SO2 emission

There are two types of SO2 emission which have

been differentiated based on the amount of the
gases emission:

 High concentration of gases SO2 - rich gases

Low concentration of gases SO2 – lean gases.

Note: High concentration more than 1% = more than 10,000 ppm.

Low concentration – between 1,000 to 5,000 ppm.

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 SO2 Removal

Purpose to remove SO2 in flue gas

stream (lean gas).
 Prior to combustion

 During combustion

 Post combustion (FGD)

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SO2 removal during combustion

Limited application even though

technologies have been developed over
the past decade.
 Fluidized Bed Combustion (FBC)

 Integrated Gasification Combined

Cycle (IGCCS)

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 Fluidised Bed Combustion
 Combustion of coal undertaken in a bed of inert
material – sand.
 Air blown up from beneath of the bed.
 Increasing of blown air cause particles suspended
in the air stream.
 Tube containing water used to tap heat from
combustion
 SO2 emission from the combustion by adding a
sorbent, i.e. limestone.
 The SO2 remain in ash and removed regularly
from the combustion chamber.
 Removal of SO2 achieved 80 – 90%
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Integrated Gasification Combined Cycle
System (IGCCS)
 Coal gasified under pressure with mixture of air
and steam.
 The resulting gas expansion within the chamber
used to turn turbine for electricity generation. The
waste heat from the gas turbine is then passed
through a second steam turbine.
 The sulfur present converted into H2S. The gas
stream then clean up from hydrogen sulfide gas.

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SO2 Removal

 Precombustion process
 During combustion
 Post combustion

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 Post combustion SO2 removal

 The most widely applied technologies in

Malaysia.
 Examples of application:
 Coal-fired electricity generation power plant
 Lynas advance material plant (LAMP)

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 Flue Gas desulfurization (FGD)

Scrubber system – Efficiency of trapping and

capturing depend on system design that is to
optimize contact between the dirty gas and the
liquid solvent.

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SO2 removal from lean gases
Flue Gas Desulphurization, FGD

Scrubbing techniques depend on approach to

maximize the contact between flue gas which is in
the gas phase and the solvent in the liquid phase.

There are three arrangement to maximise the contact

and optimise the chemical reactions:
a. Bubbler.
b. Spray chamber
c. Packed column

Fig. 11.5 (11.4) shows alternate arrangements

for wet scrubbing

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27
 SO2 Removal from lean gases
The Figure show arrangement for maximum
scrubbing a gas with a liquid.
Note for arrangement (a)-Bubbler
The gas is forced under pressure through
perforated pipes submerged in the scrubbing
liquid.
As the bubble rise through the liquid, they
approach chemical equilibrium with it.
If the liquid is deep enough and the bubbles are
small enough, this kind of device will bring the
gas close to chemical equilibrium.
Weakness high pressure drop.
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 SO2 Removal from lean gases

The Figure show arrangement for maximum

scrubbing a gas with a liquid.
Note for arrangement (b)- Spray chamber
In this arrangement, the gas flows up through an
open chamber while the scrubbing liquid falls from
a spray nozzles, much like the head of bathroom
showers, through the gas.
This arrangement main weakness is the lack of
liquid-gas contact.
Widely use because of its simplicity, low pressure
drop, and resistance to scale deposition and
plugging.
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 SO2 Removal from lean gases
The Figure show arrangement for maximum
scrubbing a gas with a liquid.
Note for arrangement (c)- packed column
Packed column similar to spray chamber,
except the open space is filled with solid material
that allows the liquid to coat its surface and run
down over it in a thin film.
The gas passes between pieces of solid material
and comes in good contact with the liquid films.
Better mass transfer per unit gas pressure drop
than either of the formers two.
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 Flue Gas desulfurization

There 3 types of solvent that are normally adopted

to trap and capture SO2 in the flue gas using
scrubber system.

Water as solvent (water scrubbing)

Base solution of NaOH (base scrubbing)

Limestone scrubbing (CaCO3)

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 SO2 Removal from lean gases
Water as solvent (water scrubbing)

Calculation to looks at scrubbing 106 scfm (standard cubic

feet per minutes) of flue gas with 1000 ppm SO2, using
H2O,

SO2 + H2O  H2SO3

Governed by the solubility of SO2 in water. 19,900 kg/s

of water to achieve 90% removal! Very large amount of
water. We end up with a large quantity of acidic water.

Note: Earlier coal-fired power plant adopted this method for

scrubbing SO2-problem has to deal with large amount of
acid solution.

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 Flue Gas desulfurization

There are three approach that can be applied to

trap and capture the SO2 lean gas emission.

Water as solvent (water scrubbing)

Base solution of NaOH (base scrubbing)

Limestone scrubbing (CaCO3)

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 SO2 removal from lean gases
Flue Gas Desulphurization, FGD

Sodium Hydroxide as scrubbing solution.

NaOH instead of straight water:
2NaOH + SO2  Na2SO3

This overall reaction proceeds via the dissolution of

SO2 first to make H2SO3, then neutralization.

From stoichiometry,
 49,200 ton/yr NaOH required; $34 million/yr! A lot
of money.
 The resulting effluent is not acidic but contains a
large amount of salt.
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 SO2 removal from lean gases
Flue Gas Desulphurization, FGD

 A complicating factor: CO2 also dissolves in water,

yCO2 / ySO2 ~ 20 in flue gas,

 solubility of CO2 is much lower

 but we still get [H2CO3] / [H2SO3] ~ 3

Thus we end up using NaOH also for the reaction:

2NaOH + CO2  Na2CO3 + H2O

Note: CO2 much more high concentration than SO2

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 SO2 removal from lean gases
Flue Gas Desulphurization, FGD

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

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

weak acid

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

strong acid

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. So it is not possible to avoid the

additional cost for NaOH. We need a cheaper reagent.

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 Flue Gas desulfurization

There are three approach that can be applied to

trap and capture the SO2 lean gas emission.

Water as solvent (water scrubbing)

Base solution of NaOH (base scrubbing)

Limestone scrubbing (CaCO3)

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 Limestone wet scrubbers and alternatives

 Forced-oxidation Limestone wet scrubbers

 Alternative
 Other wet system (lime and double alkali)
 Dry system
 Wet-dry system (spray dryers)

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SO2 removal from lean gases
Flue Gas Desulphurization, FGD
Forced-oxidation limestone wet scrubbing Fig. 11.6 (11.5
& 11.6)

(1) SO2 + H2O  H2SO3

(2) CaCO3 + H2SO3  CaSO3 + CO2 + H2O

(3) 2 CaSO3 + O2  2 CaSO4 (precipitate)

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)

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Fig. 11.6 (11.5 & 11.6) de Nevers

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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.

a. settling velocity of a spherical water droplet in air

b. fraction of water evaporated to saturate the gas
c. fraction of CaCO3 reacting per pass through
scrubber

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42
SO2 removal from lean gases
Flue Gas Desulphurization, FGD

Problems:
(largely overcome by recent systems)

1. corrosion due to Cl- buildup

2. solids deposition
3. poor reagent utilization
4. poor solid-liquid separation

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 Ca/S ratio in sulfur capture
Most common final form is CaSO4; Ca/S = 1

Typically 90-95% removal of SO2 is aimed at. Practice shows

Ca/S ~ 1.5 – 2 required; higher reagent and solids
handling costs.

Main reason:
CaCO3 (solid)  CaO (porous solid) + CO2 (gas)
CaO (porous solid) + SO3 (gas)  CaSO4 (solid)

Molar volume of CaSO4 is greater than the molar volume of

original CaCO3, pores plug up before all the CaO is
accessed by SO2.

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Limestone wet scrubbers and alternatives

 Forced-oxidation Limestone wet scrubbers

 Alternative
 Other wet system (lime and double alkali)
 Dry system
 Wet-dry system (spray dryers)

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 Alternative scrubbing chemicals
 Lime wet scrubbing; i.e. use Ca(OH)2 instead of
CaCO3

More reactive, but also more expensive.

 Ca(OH)2 is also known as hydrated lime,
quicklime.
 Similar to limestone the process is known as
throwaway processes.
 Normally CaO (lime) is added to the
oxidation tank and hydrates there to
Ca(OH)2.

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 Alternative scrubbing/capture systems

Double alkali
Scrub with soluble Na alkali
Na2CO3 + SO2  Na2SO3 + CO2
Then convert to insoluble Ca species in holding tank
Na2SO3 + CaCO3 + ½ O2  CaSO4 + Na2CO3

 In double alkali processes, the scrubbing step is done

with sodium carbonate or sodium bicarbonate
solution in the presence of low concentration of
calcium
 The application of double alkali is to avoid plugging
and scaling by insoluble calcium salts since sodium
salt is soluble in water.

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Figure 11.7 de Nevers
Double alkali scrubber

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 Alternative to force- oxidation
limestone scrubbing

Dry systems, Fig. 11.8 (11.7),

 Once through these systems were developed to avoid
dealing with wet sludge handling.
 The dry throwaway processes would have fewer
corrosion and scaling difficulties and would produce a
waste products much easier to handle and dispose of.

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Note : ESP = Electrostatic precipitator
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Alternative to force-oxidation limestone
scrubbers
 Dry alkaline particle into the gas stream,
where they react with the gas to remove SO2.
 The SO2-containing particle are then captured
in the particle collection device that the plant
must have to collect fly ash (particulate
matter) – either bag house or ESP.
 The chemical reaction
CaO + SO2 → CaSO3

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 Alternative to force- oxidation limestone
scrubbing
Wet-dry system-spray dryer
Basic principle of spray dryers.
 Spray dryers widely used in industries to spray
dried consumer products (which are heat
sensitive) such as milk powder based on principle
the suspended solid is dispersed as droplets into
a hot gas stream.
 The dispersion can be done by a high-pressure
gas-atomizing nozzle or a rapidly rotating(about
10,000 rpm) atomizing wheel.
 The hot gas is well above the boiling temperature
of water, so that the water in the droplets
evaporates rapidly.

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53
 Alternative to force- oxidation limestone
scrubbing
 The reagent slurry is dispersed as 10 – 50
µm drops, containing about 30 % (weight)
solids. The resulting dry particles are small
enough that most are carried along with the
gas stream.
 The SO2 dissolves in the water and reacts
there with dissolved Ca(OH)2.
 As the water evaporates from the drops, the
individual fine particles in them coalesce to
form porous particle from each drop.

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SO2 removal from lean gases
Alternatives to scrubbing:
 Change to a lower sulfur content fuel
 Remove sulfur from fuel.
 Coal cleaning. Normally used to remove pyritic sulfur
from pyritic coal dust, and separated by gravity
methods.
 Solvent refined coal. Catalytic hydrogenation that
use to remove S from petroleum applied to coal as
well. The coal is dissolved in a very strong solvent
prior to the desulfurization process.

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 SO2 removal from lean gases

Alternative to scrubbing (continued)

 Capture during combustion

 Fluidized bed combustion. At the pilot plant

stage – The fluidized bed combustor facilitated
with CaCO3 fluidized bed. SO2 formed reacted
with the CaCO3 to form CaCO4.
 Circulating fluidized bed combustion.

 Coal gasification, IGCC

(integrated gasification combined cycle)

 Don’t burn fuel with S, (burn less)

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 Fuel S
Coal: high (3-4%), low (<1%)

Diesel: high (0.5 – 1.5%), low (0.1%), now going

down to 500, 50 ppm?

Petroleum S can be reduced by hydrodesulfurization

Coal S
 Pyritic, FeS2, can be removed by crushing down to
100 microns and flotation, “washing”
 Organic, bonded to coal matrix, cannot be
removed

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