Product Notes

Removal of oxygen using commercial sodium sulfite and a catalyzed sodium sulfite makes great difference. After 25 seconds of contact, catalyzed sodium sulfite removed the oxygen completely. Uncatalyzed sodium sulfite removed less than 50% of the oxygen in this same time period. In a boiler feedwater system, this could result in severe corrosive attack.

The following operational conditions necessitate the use of catalyzed sodium sulfite:

• low feedwater temperature
• incomplete mechanical deaeration
• rapid reaction required to prevent pitting in the system
• short residence time
• use of economizers

High feedwater sulfite residuals and pH values above 8.5 should be maintained in the feedwater to help protect the economizer from oxygen attack.

Some natural waters contain materials that can inhibit the oxygen/sulfite reaction. For example, trace organic materials in a surface supply used for makeup water can reduce speed of scavenger/oxygen reaction time. The same problem can occur where contaminated condensate is used as a portion of the boiler feedwater. The organic materials complex metals (natural or formulated catalysts) and prevent them from increasing the rate of reaction.

Sodium sulfite must be fed where it will not contaminate feedwater to be used for attemporation or desuperheating. This prevents the addition of solids to the steam.

At operating pressures of 1,000 psig and higher, hydrazine or organic oxygen scavengers are normally used in place of sulfite. In these applications, the increased dissolved solids contributed by sodium sulfate (the product of the sodium sulfite-oxygen reaction) can become a significant problem. Also, sulfite decomposes in high-pressure boilers to form sulfur dioxide (SO2) and hydrogen sulfide (H2S). Both of these gases can cause corrosion in the return condensate system and have been reported to contribute to stress corrosion cracking in turbines. Hydrazine has been used for years as an oxygen scavenger in high-pressure systems and other systems in which sulfite materials cannot be used. Hydrazine is a reducing agent that removes dissolved oxygen by the following reaction:

Because the products of this reaction are water and nitrogen, the reaction adds no solids to the boiler water. The decomposition products of hydrazine are ammonia and nitrogen. Decomposition begins at approximately 400°F and is rapid at 600°F. The alkaline ammonia does not attack steel. However, if enough ammonia and oxygen are present together, copper alloy corrosion increases. Close control of the hydrazine feed rate can limit the concentration of ammonia in the steam and minimize the danger of attack on copper-bearing alloys. The ammonia also neutralizes carbon dioxide and reduces the return line corrosion caused by carbon dioxide.

Hydrazine is a toxic material and must be handled with extreme care. Because the material is a suspected carcinogen, federally published guidelines must be followed for handling and reporting. Because pure hydrazine has a low flash point, a 35% solution with a flash point of greater than 200°F is usually used. Theoretically, 1.0 ppm of hydrazine is required to react with 1.0 ppm of dissolved oxygen. However, in practice 1.5-2.0 parts of hydrazine are required per part of oxygen.

The factors that influence the reaction time of sodium sulfite also apply to other oxygen scavengers.  Rate of reaction as a function of temperature and hydrazine concentration. The reaction is also dependent upon pH (the optimum pH range is 9.0-10.0)