Acid Rain

Acidic particle emission, commonly termed "acid smut" or "acid fallout," is another cold-end problem. It is caused by
the production of large particulates (generally greater than 100 mesh) that issue from the stack and, due to their
relatively large size, settle close to the stack. Usually, these particulates have a high concentration of condensed
acid; therefore, they cause corrosion if they settle on metal surfaces.

The most common cause of cold-end problems is the condensation of sulfuric acid. This chapter addresses
problems incurred in the firing of sulfur-containing fuels. Sulfur in the fuel is oxidized to sulfur dioxide:

S + O2 = SO2

sulfur oxygen sulfur dioxide

A fraction of the sulfur dioxide, sometimes as high as 10%, is oxidized to sulfur trioxide. Sulfur trioxide combines with
water to form sulfuric acid at temperatures at or below the dew point of the flue gas. In a boiler, most of the sulfur
trioxide reaching the cold end is formed according to the following equation:

SO2 + 1/2 O2 = SO3

sulfur dioxide oxygen sulfur trioxide

The amount of sulfur trioxide produced in any given situation is influenced by many variables, including excess air
level, concentration of sulfur dioxide, temperature, gas residence time, and the presence of catalysts. Vanadium
pentoxide (V2O5) and ferric oxide (Fe2O3), which are commonly found on the surfaces of oil-fired boilers, are ef-
fective catalysts for the heterogeneous oxidation of sulfur dioxide. Catalytic effects are influenced by the amount of
surface area of catalyst exposed to the flue gas. Therefore, boiler cleanliness, a reflection of the amount of catalyst
present, affects the amount of sulfur trioxide formed.

The quantity of sulfur trioxide in combustion gas can be determined fairly easily. The most commonly used
measuring techniques involve either condensation of sulfur trioxide or adsorption in isopropyl alcohol. Figure 22-1 is
a curve showing the relationship of sulfur trioxide concentration to dew point at a flue gas moisture content of 10%.
Higher flue gas moisture increases the dew point temperature for a given sulfur trioxide-sulfuric acid concentration.
Cold-end metal temperatures and flue gas sulfur trioxide content can be used to predict the potential for corrosion
problems.

At the same sulfur content, gaseous fuels such as sour natural gas, sour refinery gas, and coke oven gas produce
more severe problems than fuel oil. These gases contain more hydrogen than fuel oil, and their combustion results
in higher flue gas moisture. Consequently, dew points are raised. With any type of fuel, corrosion and fouling
potentials rapidly increase below gas temperatures of 140 degrees F (60 degrees C), which is the typical water dew
point for flue gases.

Cold-end corrosion and deposition are usually much less severe in coal-fired boilers than in oil-fired units. Usually,
coal ash is alkaline, so it increases the pH of the deposits formed in cold-end sections. Thus, the extent of the
corrosive attack by sulfuric acid is diminished. Also, the high level of ash present when coal is fired results in a lower
concentration of acid in the ash particle. At the same sulfur content, coal firing dew points are generally 20-40
degrees F lower than oil firing dew points.

The most common cause of deposition within air preheaters is the accumulation of corrosion products. Most air
preheater deposits contain at least 60% iron sulfates formed by the corrosion of air heater tube metal. Therefore, a
reduced corrosion rate frequently reduces the fouling of air preheaters.