11/11/2016 KeyprinciplesandapproachesinwetlimestonescrubbingPowerEngineeringInternational

Key principles and approachesin wet-limestone scrubbing

Brad Buecker of Kiewit Power Engineers, USA, outlines the fundamental principles of wet-limestone scrubbing and its importance in
controlling pollution from coal red plants. The specic method will depend on factors such as the market for by-products and access to
high-quality limestone.

Brad Buecker, Kiewit Power Engineers, USA

Environmental personnel in many countries recognize the importance of controlling pollutant emissions from coal red power plants. A
primary pollutant is, of course, sulphur dioxide (SO2). Scrubbing is by far the most common method to remove SO2 from ue gas, where
many new scrubbers will utilize wet-limestone technology because of the reliability ofthe process.

This article outlines a number of fundamental principles of wet-limestone scrubbing, which will hopefully prove useful to plant personnel who
may be asked to plunge into unfamiliar territory. Critical aspects of operation include ensuring proper SO2 removal at all times, maximizing
reagent utilization and minimizing scale build-up on scrubber components.

Chemistry Fundamentals
A generic ow diagram of a spray-tower, wet-limestone scrubber is illustrated in Figure 1. The process is a classic example of an aqueous
acid-base chemistry reaction applied on an industrial scale, where alkaline limestone slurry reacts with acidic SO2.

Figure 1: Generic wet-limestone FGD process ow diagram for an open spray tower

Sulphur dioxide is rst absorbed into the liquid phase as it contacts the slurry sprays.

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SO2 + H2O <=> H2SO3

Some theoretical chemists argue that true H2SO3 does not exist and that SO2 retains its molecular character and is surrounded by water
molecules. However, when SO2 is added to water the pH drops, which suggests this equation is reasonable and that the following
dissociation reaction is accurate.

H2SO3 <=> H+ + HSO3 <=> H+ + SO3-2

Another argument for the formation of H2SO3, and its dissociated products bisulphite (HSO3) and sulphite (SO3-2) ions, comes from the fact
that the principal component of limestone, calcium carbonate (CaCO3), is only slightly soluble in water but will dissolve almost completely in
well-designed scrubbing systems.

CaCO3 + H+ Ca+2 + HCO3

Combining these three equations illustrates the simplied but fundamental wet-limestone scrubbing process.

CaCO3 + 2H+ + SO3-2 Ca+2 + SO3-2 + H2O + CO2

In the absence of any other reactants, calcium and sulphite ions will precipitate as a hemihydrate, where water is actually included in the
crystal lattice of the scrubber byproduct.

Ca+2 + SO3-2 + H2O CaSO3H2O

Proper operation of a scrubber is dependent upon the eciency of the above-listed reactions. Control of pH via reagent feed is very
important. Many wet-limestone scrubbers operate at a solution pH of around 5.6 to 5.8. A too-acidic scrubbing solution inhibits SO2 transfer
from gas to liquid; while an excessively basic slurry (pH > 6.0) indicates overfeed of limestone.

Oxygen in the ue gas greatly inuences chemistry. Aqueous bisulphite and sulphite ions react with oxygen to produce sulphate ions (SO4-2).

2SO3-2 + O2 2SO4-2

Approximately the rst 15 per cent mole of sulphate ions co-precipitates with sulphite to form calcium sulphite-sulphate hemihydrate
[(0.85CaSO30.15CaSO4)H2O]. Any sulphate above the 15 per cent mole ratio precipitates with calcium as gypsum.

Ca+2 + SO4-2 + 2H2O CaSO42H2O

Control of by-product chemistry oers interesting challenges, particularly in spray towers that have internal devices to enhance gas-liquid
contact. Experience has shown that operation in either a completely oxidized state (no calcium sulphite-sulphate hemihydrate in the
scrubbing slurry) or a completely non-oxidized state (no gypsum in the slurry) minimizes scaling of internal scrubber components.

An often critical factor regarding the choice of oxidized or non-oxidized by-product involves the handling characteristics and commercial
value of the solid. Calcium sulphite-sulphate hemihydrate is a soft material that tends to retain water. It has little value as a chemical
commodity

For this reason, many scrubbers are equipped with forced-air oxidation systems to introduce additional oxygen to the scrubber slurry. A
properly designed oxidation system will convert all of the liquid sulphite ions to sulphate ions.

Sulphate, of course, precipitates with calcium as gypsum, which forms a cake-like material when subjected to vacuum ltration. Generally, 85
per cent to 90 per cent of the free moisture in gypsum can be extracted by this relatively simple mechanical process. High-purity, dried
synthetic gypsum has become a favourite material of wallboard manufacturers.

Critical Scrubber Design Issues

An important concept regarding spray tower scrubbers is the liquid-to-gas (L/G) ratio. The proper amount of slurry must be present to allow
SO2 to pass from the gas phase to the liquid phase. In the United States, the common unit of measurement for the L/G ratio is gallons per
minute (gpm) of slurry per 1000 actual cubic feet per minute (acfm) of ue gas, where a baseline rule-of-thumb was once 120 gpm/acfm (16.1
lpm/m3).

The L/G ratio is strongly inuenced by the eciency of liquid/gas mixing within spray towers. First and second-generation scrubbers typically
contained internal trays or packing to enhance mixing and lower the L/G ratio. Unfortunately, these internal mixing devices served as
excellent locations for scale build-up and deposit formation. As packing fouls, tower dierential pressure increases, which may lead to a unit
derating or perhaps even a forced outage.

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Spraying technology has improved for scrubber applications, and open spray towers are now becoming popular,1 or at most with one tray
section. Nozzle design and alignment are critical in these systems, as droplet size and spray patterns must be optimized to provide the best
contact and to prevent channeling of the ue gas. That the spray nozzle design has become much better2 is the key to this development.

Limestone utilization in the scrubber is another important issue. If the limestone reacts poorly in the system, overfeed is required for
adequate SO2 removal. This of course results in excess reagent usage. Limestone costs for large scrubbers may reach or exceed a million
dollars per year, so loss of reagent because of poor utilization can be rather expensive.

Factors that inuence utilization include limestone quality, limestone grind size, residence time of the reagent within the scrubbing system
and performance of slurry separation devices. Limestone reactivity is important with regard to scrubber operation. The chemical make-up of
the reagent has a large inuence on scrubber eciency. In my experience, I have found that limestones containing 94 per cent or more
CaCO3 are very reactive, given of course that they are ground properly.

But not all plants are near high-quality limestone sources. Often, a stone may contain greater than 90 per cent total carbonate, but 10 per
cent or more exists as dolomite (MgCO3CaCO3), in which the magnesium is bonded with calcium in the crystal lattice. While pure MgCO3
dissolves quickly in scrubber solutions, and provides liquid alkalinity, dolomite is rather non-reactive, and tends to pass through the system
untouched. Utilities without access to high-purity limestone may need to enhance slurry reactivity with additives. One choice in the past was
adding magnesium salts.

Magnesium compounds, other than dolomite, generally dissociate quickly in scrubber solutions, whereupon the magnesium increases the
solution alkalinity and enhances the transfer of SO2 from the initial liquid phase to a reaction product with calcium. A popular organic
additive is adipic acid (hexanedioic acid), as shown in Figure 2, or the less rened material dibasic acid (DBA), which is a mixture of adipic,
glutaric, and succinic acids.3

Figure 2: The general structure of adipic acid

Like magnesium, these chemicals also increase the liquid phase alkalinity, where concentrations of a few hundred parts per million often are
sucient to achieve suitable results. In the US, DBA manufacturing has declined, so some utilities have had to switch to sodium formate as an
additive.

By-product disposal greatly inuences scrubber design. Most ue gas desulphurization (FGD) systems are of the forced-oxidation type to
produce a gypsum by-product. A primary motivating factor for gypsum production is the potential sale of the material to wallboard
manufacturers.

Preparation of gypsum for sale requires drying on a vacuum drum or belt lter, where often a fresh water wash is utilized to remove
dissolved chlorides. Forced oxidation normally produces at gypsum crystals that dewater quite readily, in which the gypsum forms a cake-
like material with perhaps 10 per cent moisture.

The drum in Figure 3 has an internal, mechanically applied vacuum, such that as the drum rotates through the slurry by-product contained in
a vat below, the solids adhere to the lter cloth while the liquid passes through for collection and reuse in the scrubber or disposal. The drum
rotates counter-clockwise in the view shown. Not shown is a fresh water wash header on the far side located just above the vat. The water
spray reduces the chloride content of the gypsum to less than 200 mg/l, which is a requirement from the wallboard manufacturer. In some
cases, the manufacturer may request a chloride limit of 100 mg/l.

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Figure 3: Gypsum cake being scraped from a vacuum lter

When by-product sale is not an option, forced oxidation may still be a good technique, as gypsum handling is very straightforward compared
to inhibited or partially-oxidized material. Gypsum can be easily loaded into dump trucks for disposal in a landll. Some utilities own enough
land for by-product retention ponds to be excavated and lined to serve as evaporation ponds so that liquid discharges are not an issue. In
this case, forced oxidation may be counter-productive.

Another important component of spray towers is the mist eliminator section or sections. Mist eliminators are vital to remove particulates that
would otherwise exit the scrubber through the stack. Typically, the mist eliminator is of a chevron-vane design, which forces the ue gas to
make several turns before exiting the scrubber.

Particulates impact upon the vanes and lodge on the material. Mist eliminators must be equipped with a water washing system to remove
accumulated particulates, but the wash system requires special care in the design phase. Poor nozzle patterns or low wash rates will allow
material to completely bridge areas of the packing. Alternatively, excess washing can upset the water balance in the scrubber.

FGD Chemistry Monitoring

Large manuals have been written on FGD analytical techniques, and space limitations prohibit a full discussion of these techniques here.
Thermogravimetry is an excellent technique for monitoring the gypsum, calcium sulphite-sulphate hemihydrate, and CaCO3 content in
scrubber solids,4 and in many cases it works well for limestone analyses.

Limestone reactivity testing, where limestone samples are treated with acid in a controlled environment, can provide valuable data on the
quality of the material. Ion chromatography is an excellent technique for monitoring chloride concentrations in the scrubber liquor, as
chloride is a primary corrosive agent in FGD systems.

On-line pH monitoring is a standard technique, where instrument reliability has improved over the years. Slurry densities and suspended
solids concentrations, and limestone grind sizing, are other important tests that can easily be performed in the laboratory.

New Scrubbing Technologies

Several other scrubbing technologies, some of which have been around for a decade or more, are gaining prominence.5 One of these is the
Chiyoda process (CT-121TM, Figure 4), in which the incoming ue gas is quenched and then directed into a slurry bath. Sulphur dioxide reacts
with the slurry, while being sparged with air to convert the by-product to gypsum. The clean gas bubbles out of solution, ows through riser
tubes to the outlet plenum, and then exits to the stack.

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