Dealkalization

DEALKALIZATION

Often, boiler or process operating conditions require the removal of hardness and the reduction of alkalinity but not the removal of the other solids. Zeolite softening does not reduce alkalinity, and demineralization is too costly. For these situations, a dealkalization process is used. Sodium zeolite/hydrogen zeolite (split stream) dealkalization, chloride-anion dealkalization, and weak acid cation dealkalization are the most frequently used processes.

Sodium Zeolite/Hydrogen Zeolite (Split Stream) Dealkalization

In a split stream dealkalizer, a portion of the raw water flows through a sodium zeolite softener. The remainder flows through a hydrogen-form strong acid cation unit (hydrogen zeolite). The effluent from the sodium zeolite is combined with the hydrogen zeolite effluent. The effluent from the hydrogen zeolite unit contains carbonic acid, produced from the raw water alkalinity, and free mineral acids. When the two streams are combined, free mineral acidity in the hydrogen zeolite effluent converts sodium carbonate and bicarbonate alkalinity in the sodium zeolite effluent to carbonic acid as shown below:

Carbonic acid is unstable in water. It forms carbon dioxide gas and water. The blended effluents are sent to a decarbonator or degasser, where the carbon dioxide is stripped from the water by a countercurrent stream of air.

The desired level of blended water alkalinity can be maintained through control of the percentage of sodium zeolite and hydrogen zeolite water in the mixture. A higher percentage of sodium zeolite water results in higher alkalinity, and an increased percentage of hydrogen zeolite water reduces alkalinity.

In addition to reducing alkalinity, a split stream dealkalizer reduces the total dissolved solids of the water. This is important in high alkalinity waters, because the conductivity of these waters affects the process and can limit boiler cycles of concentration.

Sodium Zeolite/Chloride Anion Dealkalization

Strong base anion resin in the chloride form can be used to reduce the alkalinity of a water. Water flows through a zeolite softener and then an anion unit, which replaces the carbonate, bicarbonate, sulfate, and nitrate ions with chloride ions as shown in these reactions:

The chloride anion dealkalizer reduces alkalinity by approximately 90% but does not reduce total solids. When the resin nears exhaustion, treated water alkalinity increases rapidly, signaling the need for regeneration.

The zeolite softener is regenerated as previously described. In addition, the anion resin is also regenerated with a sodium chloride brine that returns the resin to the chloride form. Frequently, a small amount of caustic soda is added to the regenerant brine to enhance alkalinity removal.

Weak Acid Cation Dealkalization

Another method of dealkalization uses weak acid cation resins. Weak acid resins are similar in operation to strong acid cation resins, but only exchange for cations that are associated with alkalinity, as shown by these reactions:

where Z represents the resin. The carbonic acid (H₂CO₃) formed is removed by a decarbonator or degasser as in a split stream system.

The ideal influent for a weak acid cation system has a hardness level equal to the alkalinity (both expressed in ppm as CaCO₃). In waters that are higher in alkalinity than hardness, the alkalinity is not removed to its lowest level. In waters containing more hardness than alkalinity, some hardness remains after treatment. Usually, these waters must be polished by a sodium zeolite softener to remove hardness. During the initial portion of a weak acid cation service run (the first 40-60%) some cations associated with mineral anions exchange, producing small amounts of mineral acids in the effluent. As the service cycle progresses, alkalinity appears in the effluent. When the alkalinity in the effluent exceeds 10% of the influent alkalinity, the unit is removed from service and regenerated with a 0.5% sulfuric acid solution. The concentration of regenerant acid should be kept below 0.5-0.7%, to prevent calcium sulfate precipitation in the resin. Weak acid cation resin exchange is very efficient. Therefore, the amount of acid required is virtually equal (chemically) to the amount of cations removed during the service cycle.

If the materials of construction for the down-stream equipment or overall process cannot tolerate the mineral acidity present during the initial portions of the service cycle, a brine solution is passed through the regenerated weak acid resin prior to the final rinse. This solution removes the mineral acidity without a significant impact on the quality or length of the subsequent run.

Equipment used for a weak acid cation dealkalizer is similar to that used for a strong acid cation exchanger, with the exception of the resin. One variation of the standard design uses a layer of weak acid resin on top of strong acid cation resin. Because it is lighter, the weak acid resin remains on top. The layered resin system is regenerated with sulfuric acid and then with sodium chloride brine. The brine solution converts the strong acid resin to the sodium form. This resin then acts as a polishing softener.

Direct Acid Injection

In the process of direct acid injection and decarbonation, acid is used to convert alkalinity to carbonic acid. The carbonic acid dissociates to form carbon dioxide and water and the carbon dioxide is removed in a decarbonator. The use of an acid injection system should be approached with caution, because an acid overfeed or a breakdown in the pH control system can produce acidic feedwater, which corrodes the iron surfaces of feedwater systems and boilers. Proper pH monitoring and controlled caustic feed after decarbonation are required.

Advantages and Limitations of Dealkalization Systems

Ion exchange dealkalization systems produce hardness-free, low-alkalinity water at a reasonable cost, and with a high degree of reliability. They are well suited for processing feedwater for medium-pressure boilers, and for process water for the beverage industry. Split stream and weak acid cation systems also reduce the total dissolved solids. In addition to these advantages, the following disadvantages must be considered:

·     dealkalizers do not remove all of the alkalinity and do not affect the silica content of a water

·     dealkalizers require the same influent purity as other ion exchange processes; filtered water that is low in potential foulants must be used

·     the water produced by a dealkalization system using a forced draft decarbonator becomes saturated with oxygen, so it is potentially corrosive