FGD chemistry

[edit] Basic principles

Most FGD systems employ two stages: one for fly ash removal and the other for SO2
removal. Attempts have been made to remove both the fly ash and SO2 in one scrubbing
vessel. However, these systems experienced severe maintenance problems and low
removal efficiency. In wet scrubbing systems, the flue gas normally passes first through a
fly ash removal device, either an electrostatic precipitator or a wet scrubber, and then into
the SO2-absorber. However, in dry injection or spray drying operations, the SO2 is first
reacted with the sorbent, and then the flue gas passes through a particulate control device.

Another important design consideration associated with wet FGD systems is that the flue
gas exiting the absorber is saturated with water and still contains some SO2. These gases
are highly corrosive to any downstream equipment such as fans, ducts, and stacks. Two
methods that can minimize corrosion are: (1) reheating the gases to above their dew
point, or (2) choosing construction materials and design conditions that allow equipment
to withstand the corrosive conditions. Both alternatives are expensive, and engineers
designing the system determine which method to use on a site-by-site basis.

[edit] Scrubbing with a basic solid or solution

Schematic design of the absorber of an FGD

SO2 is an acid gas, and, therefore, the typical sorbent slurries or other materials used to
remove the SO2 from the flue gases are alkaline. The reaction taking place in wet
scrubbing using a CaCO3 (limestone) slurry produces CaSO3 (calcium sulfite) and can be
expressed as:

CaCO3 (solid) + SO2 (gas) → CaSO3 (solid) + CO2 (gas)

When wet scrubbing with a Ca(OH)2 (lime) slurry, the reaction also produces CaSO3
(calcium sulfite) and can be expressed as:

Ca(OH)2 (solid) + SO2 (gas) → CaSO3 (solid) + H2O (liquid)

When wet scrubbing with a Mg(OH)2 (magnesium hydroxide) slurry, the reaction
produces MgSO3 (magnesium sulfite) and can be expressed as:

Mg(OH)2 (solid) + SO2 (gas) → MgSO3 (solid) + H2O (liquid)

To partially offset the cost of the FGD installation, in some designs, the CaSO3 (calcium
sulfite) is further oxidized to produce marketable CaSO4 · 2H2O (gypsum). This
technique is also known as forced oxidation:

CaSO3 (solid) + H2O (liquid) + ½O2 (gas) → CaSO4 (solid) + H2O

A natural alkaline usable to absorb SO2 is seawater. The SO2 is absorbed in the water, and
when oxygen is added reacts to form sulfate ions SO4- and free H+. The surplus of H+ is
offset by the carbonates in seawater pushing the carbonate equilibrium to release CO2
gas:

SO2 (gas) + H2O + ½O2 (gas)→ SO42- (solid) + 2H+

HCO3- + H+ → H2O + CO2 (gas)

[edit] Types of wet scrubbers used in FGD

To promote maximum gas-liquid surface area and residence time, a number of wet
scrubber designs have been used, including spray towers, venturis, plate towers, and
mobile packed beds. Because of scale buildup, plugging, or erosion, which affect FGD
dependability and absorber efficiency, the trend is to use simple scrubbers such as spray
towers instead of more complicated ones. The configuration of the tower may be vertical
or horizontal, and flue gas can flow cocurrently, countercurrently, or crosscurrently with
respect to the liquid. The chief drawback of spray towers is that they require a higher
liquid-to-gas ratio requirement for equivalent SO2 removal than other absorber designs

Phosphogypsum refers to the gypsum formed as a by-product of processing phosphate

ore into fertilizer with sulfuric acid.

Phosphogypsum is produced from the fabrication of phosphoric acid by reacting

phosphate ore (apatite) with sulfuric acid according to the following reaction:
 Ca5(PO4)3X + 5 H2SO4 + 10 H2O → 3 H3PO4 + 5 CaSO4 · 2 H2O + HX
where X may include OH, F, Cl, or Br

Phosphogypsum is radioactive due to the presence of naturally occurring uranium and

radium in the phosphate ore.

Marine-deposited phosphate typically has a higher level of radioactivity than igneous

phosphate deposits, because uranium is present in seawater.[1]

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Laboratory-scale spray dryer.

A=Solution or suspension to be dried in, B=Atomization gas in, 1= Drying gas in,
2=Heating of drying gas, 3=Spraying of solution or suspension, 4=Drying chamber,
5=Part between drying chamber and cyclone, 6=Cyclone, 7=Drying gas is taken away,
8=Collection vessel of product, arrows mean that this is co-current lab-spraydryer

Spray drying is a method of producing a dry powder from a liquid or slurry by rapidly
drying with a hot gas. This is the preferred method of drying of many thermally-sensitive
materials such as foods and pharmaceuticals. A consistent particle size distribution is a
reason for spray drying some industrial products such as catalysts. Air is the heated
drying media; however, if the liquid is a flammable solvent such as ethanol or the product
is oxygen-sensitive then nitrogen is used.[1]

All spray dryers use some type of atomizer or spray nozzle to disperse the liquid or slurry
into a controlled drop size spray. The most common of these are rotary disks and single-
fluid high pressure swirl nozzles. Alternatively, for some applications two-fluid or
ultrasonic nozzles are used. Depending on the process needs, drop sizes from 10 to 500
µm can be achieved with the appropriate choices. The most common applications are in
the 100 to 200 µm diameter range. The dry powder is often free-flowing.[2]

The most common spray dryers are called single effect as there is only one drying air on
the top of the drying chamber (see n°4 on the scheme). In most cases the air is blown in
co-current of the sprayed liquid. The powders obtained with such type of dryers are fine
with a lot of dusts and a poor flowability. In order to reduce the dusts and increase the
flowability of the powders, there is since over 20 years a new generation of spray dryers
called multiple effect spray dryers. Instead of drying the liquid in one stage, the drying is
done through two steps: one at the top (as per single effect) and one or an integrated static
bed at the bottom of the chamber. The integration of this fluidized bed allows, by
fluidizing the powder inside a humid atmosphere, to agglomerate the fine particles and to
obtain granules having commonly a medium particle size within a range of 100 to 300
µm. Because of this large particle size, these powders are free-flowing.
The fines generated by the first stage drying can be recycled in continuous flow either at
the top of the chamber (around the sprayed liquid) or at the bottom inside the integrated
fluidized bed. The drying of the powder can be finalized on an external vibrating
fluidized bed.

The hot drying gas can be passed as a co-current or counter-current flow to the atomiser
direction. The co-current flow enables the particles to have a lower residence time within
the system and the particle separator (typically a cyclone device) operates more
efficiently. The counter-current flow method enables a greater residence time of the
particles in the chamber and usually is paired with a fluidized bed system.

Alternatives to spray dryers are:[3]

1. Freeze dryer: a more-expensive batch process for products that degrade in spray
drying. Dry product is not free-flowing.
2. Drum dryer: a less-expensive continuous process for low-value products; creates
flakes instead of free-flowing powder.
3. Pulse combustion dryer: A less-expensive continuous process that can handle
higher viscosities and solids loading than a spray dryer, and that sometimes gives
a freeze-dry quality powder that is free-flowing.

[edit] Spray dryer

SDX spray drying nozzles.

Schematic illustration of spray drying process.

A spray dryer is a device used in spray drying. It takes a liquid stream and separates the
solute or suspension as a solid and the solvent into a vapor. The solid is usually collected
in a drum or cyclone. The liquid input stream is sprayed through a nozzle into a hot vapor
stream and vaporised. Solids form as moisture quickly leaves the droplets. A nozzle is
usually used to make the droplets as small as possible, maximising heat transfer and the
rate of water vaporisation. Droplet sizes can range from 20 to 180 μm depending on the
nozzle.[2] There are two main types of nozzles: high pressure single fluid nozzle (50 to
300 bars) and two-fluid nozzles: one fluid is the liquid to dry and the second is
compressed gas (generally air at 1 to 7 bars).

Spray dryers can dry a product very quickly compared to other methods of drying. They
also turn a solution, or slurry into a dried powder in a single step, which can be
advantageous for profit maximization and process simplification.

[edit] Micro-encapsulation
Spray drying often is used as an encapsulation technique by the food and other industries.
A substance to be encapsulated (the load) and an amphipathic carrier (usually some sort
of modified starch) are homogenized as a suspension in water (the slurry). The slurry is
then fed into a spray drier, usually a tower heated to temperatures well over the boiling
point of water.

As the slurry enters the tower, it is atomized. Partly because of the high surface tension of
water and partly because of the hydrophobic/hydrophilic interactions between the
amphipathic carrier, the water, and the load, the atomized slurry forms micelles. The
small size of the drops (averaging 100 micrometers in diameter) results in a relatively
large surface area which dries quickly. As the water dries, the carrier forms a hardened
shell around the load.[4]

Load loss is usually a function of molecular weight. That is, lighter molecules tend to boil
off in larger quantities at the processing temperatures. Loss is minimized industrially by
spraying into taller towers. A larger volume of air has a lower average humidity as the
process proceeds. By the osmosis principle, water will be encouraged by its difference in
fugacities in the vapor and liquid phases to leave the micelles and enter the air. Therefore,
the same percentage of water can be dried out of the particles at lower temperatures if
larger towers are used. Alternatively, the slurry can be sprayed into a partial vacuum.
Since the boiling point of a solvent is the temperature at which the vapor pressure of the
solvent is equal to the ambient pressure, reducing pressure in the tower has the effect of
lowering the boiling point of the solvent.

The application of the spray drying encapsulation technique is to prepare "dehydrated"

powders of substances which do not have any water to dehydrate. For example, instant
drink mixes are spray dries of the various chemicals which make up the beverage. The
technique was once used to remove water from food products; for instance, in the
preparation of dehydrated milk. Because the milk was not being encapsulated and
because spray drying causes thermal degradation, milk dehydration and similar processes
have been replaced by other dehydration techniques. Skim milk powders are still widely
produced using spray drying technology around the world, typically at high solids
concentration for maximum drying efficiency. Thermal degradation of products can be
overcome by using lower operating temperatures and larger chamber sizes for increased
residence times.[5]

Recent research is now suggesting that the use of spray-drying techniques may be an
alternative method for crystallization of amorphous powders during the drying process
since the temperature effects on the amorphous powders may be significant depending on
drying residence times.[6][7]

[edit] Spray drying applications

Food: milk powder, coffee, tea, eggs, cereal, spices, flavorings, starch and starch
derivatives, vitamins, enzymes, colourings...

Pharmaceutical: antibiotics, medical ingredients, additives

Industrial: paint pigments, ceramic materials, catalyst supports, microalgae

[edit] Nano spray dryer

The nano spray dryer offers new possibilities in the field of spray drying. It allows to
produce particles in the range of 300 nm to 5 μm with a narrow size distribution. High
yields are produced up to 90% and the minimal sample amount is 1 mL.

[edit] References