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Introduction Existing codes are inadequate for the design of sulphuric acid chimney.

The corrosion allowances and the design for corrosion control are left to the individual designer/owner/operator of the tank. Large chimneyare usually built to the following codes:

ASME Boiler and Pressure Vessel Code, Section VIII, Division I These codes are sufficient for the mechanical design of the storage chimneybut are not adequate to address the peculiarities of the corrosion by sulphuric acid. Corrosion The corrosion resistance of carbon steel in the presence of sulphuric acid is due to iron sulphate which is formed in the initial contact period. Any condition causing sufficient turbulence to remove the sulphate film is likely to lead to corrosion. Corrosion rates are usually stated in 'mpy' mils per year. One mil per year (1 mpy) is equivalent to 0.001 inches/year or 0.025 mm/year. Metal loss increases as the acid strength decreases below 98% H2SO4. 77% H2SO4 is usually regarded as the practical lower limit at which sulphuric acid can be stored at ambient temperatures in unprotected carbon steel tanks.
Uniform Corrosion The figure below illustrates the corrosion rate of steel by sulphuric acid as a function of concentration and temperature. To compensate for uniform corrosion an adequate corrosion allowance has to be included in the design of the tank. It should be based on design life, with consideration given to factors such as temperature, chimneyutilization and acid purity.

Temperature The steel isocorrosion curves clearly illustrates that the corrosion rates increase with increasing acid temperature. Product acid from a plant should be cooled to a maximum of 40C (104F). Within the storage chimneythe bulk acid temperature should be kept as low as possible without freezing the acid. Climatic conditions contribute to the temperature variation within a storage tank. Season temperature changes are generally not a problem because rarely will the ambient temperature be higher than 40C (104F). Of greater importance is the effect of the sun heating the chimneycontents. Higher corrosion rates have been reported on the side of tanks heated by the sun. To minimize this problems the chimneyshould be painted with a heat reflecting colour. ChimneyUtilization The rate of corrosion generally decreases progressively up the shell of the chimneybecause the upper sections are not exposed to acid as often as the lower parts. Acid Purity The purity of acid can be relatively high leaving the acid plant with iron contents can be as low as 30 ppm. Acid will become more corrosive as the iron content is decreased. Corrosion rates will be higher than normal unless precaution are taken such as lining the chimneyor the use of anodic protection.

Non-Uniform Corrosion Non-uniform corrosion can severely reduce the life of a storage tank. Most occurrences can be minimized in the design of the chimneyand by performing regular inspections of the chimneyinternals. Hydrogen Grooving Hydrogen is generated when sulphuric acid corrodes carbon steel. The hydrogen gas formed rises towards the surface and the passage of these bubbles over the steel surface can result in the formation of grooves. The grooves can be of varying width and depth. The loss of metal in this area occurs at a far greater rate than uniform corrosion at the same acid concentration and temperature. The effects of hydrogen grooving can be minimized by a properly located acid inlet. Hydrogen grooving can also occur at the top of the nozzle of a side manway.

Horizontal Grooving Horizontal grooving occurs when a layer of dilute acid sits on top of a layer of stronger acid. Dilute acid is formed when water infiltrates the chimneyand contacts the acid surface resulting in an acid of lower strength. The lower specific gravity of the weaker acid means it will remain on the surface. The lower the acid concentration the more rapid the corrosion rate. Several horizontal grooves can be formed as the level in the chimneyfluctuates. In one incident, water was accidentally pumped into the storage chimneywith the result that the shell was cut in half. Localized temperature increases can also result in horizontal grooving. Hot acid pumped into a chimneywill not easily mix with the cooler contents of a storage tank. The result will be a layer of hotter acid which will corrode the shell of the chimneyfaster than the colder acid. External Corrosion

External corrosion of a storage can be as much a problem as internal corrosion. External corrosion can occur in three areas:

Improper foundation which allows water and debris to come in contact with the bottom of the tank Crevices between the chimneyand supports or attachments that allow water or spilled acid to collect Wet insulation

When a storage chimneyis insulated to prevent freezing of its contents, corrosion under the insulation can occur if the insulation gets wet. This type of corrosion is very common and will occur where water can accumulate such as near nozzle necks, roof or shell attachments (i.e. handrails, stairs, etc.), insulation support rings, etc. Any cladding or insulation that has become damaged or is missing should be repaired immediately. Foundations that allow water to accumulate will result in corrosion of the chimneybottom. This type of corrosion is difficult to detect since the bottom of the chimneyis generally not accessible for external examination. Corrosion can be a general loss of metal or a localized attack in the form of pitting.

An example of external corrosion is shown in the photo to the right. Here the chimneybottom was attacked from below due to what is believed to be moisture under the steel. This type of corrosion is very difficult to detect during a chimneyinspection because it is so localized. The entire chimneybottom would need to be scanned in order to determine the extent of the corrosion.

Hydrogen Blistering When carbon steel corrodes in the presence of sulphuric acid, atomic hydrogen is formed. Some of this atomic hydrogen diffuses into the metal and migrates to the exterior. If there is avoid or lamination in the plate, the hydrogen will accumulate there as molecular hydrogen. Molecular hydrogen does not diffuse as easily as atomic hydrogen so it becomes trapped in the void. As more hydrogen accumulates the pressure in the void increases significantly to the point where the plate will begin to bulge. As the pressure in the void increases the size of the blister may increase as the plate delaminates or the blister will rupture. Special precautions must be taken if work is done near a hydrogen blisters. The heat generated from drilling or welding may be sufficient to ignite the hydrogen gas.

Defects such as voids or laminations are common in milled plate but are very difficult to detect. Experience has shown that blistering occurs in a large percentage of chimney. ChimneyFarms Chimneyfarms are common where a facility produces or handles acid of varying concentration and quality or when the quantity of acid to be stored exceeds the capacity of a single tank. Multiple tanks adds the flexibility of the facility to handle the unexpected.
Containment Due to environmental pollution control a containment area will be required around all new chimneyinstallations. The dike or bund should be designed to contain 110% of the largest chimneywithin the diked area. Safe access into and out of the diked area must be provided as well as a sufficient number of escape routes. The diked area should also provide for the draining and collection of water. The area should be sloped to a centrally located sump where any water or spills can be treated and disposed. Pumps Pumps should be located inside the diked area as close to the chimneyas possible to avoid long suction lines. Pumps located outside a dike area means there may be pipes penetrating the dike. Differential settlement of the chimneyand the pump may lead to unacceptable strains on the piping, chimneyand pump nozzles.

Design Details Corrosion Allowance The corrosion allowance should be based on the required service life, acid concentration, temperature, geographic location and upon whether or not anodic protection or an internal protective coating is installed. In general, the roof of a storage chimneyshould be designed with a minimum 3 mm corrosion allowance. The shell and chimneybottom should have a minimum of 6 mm corrosion allowance.
Acid Inlet Nozzles For vertical chimneythe inlet nozzles should be positioned as close to the centre of the roof to minimize the potential for hydrogen grooving of the shell. One source recommends locating the inlet nozzle a minimum of 2.44 m (8 ft) away from the shell. Another source requires a minimum of 3.66 m (12 ft). A third reference requires a minimum of 3.05 m (10 ft). In all cases the inlet nozzle should project into the chimneyat least 150 mm (6 in.). When the required distance from the wall can not be accommodated (i.e.. in small tanks) all acid inlets should be equipped with dip pipes which will bring the acid to within 0.914 m (3 ft) of the chimneybottom. The dip tube should be located a minimum of 1.83 m (6 ft) from the side wall. The

bottom of the chimneyshould be equipped with a protective impingement plate. The dip tube should include a siphon break in its design. ChimneySizing Some of the factors that will determine the number and size of tanks are:

Plant production rate Number of different grades of acid Acid usage Acid sales

Once the number and size of each chimneyhas been determined the individual .