Drew Marine Division

Control of Oxygen Corrosion in Marine Steam Generating Systems

Dissolved oxygen corrosion is seen as pitting in the pre-boiler, boiler, and after-boiler sections of the steam generation process. The effect of pits on metal surfaces is the same as that of general corrosion, but at a localized and more rapid rate of metal loss. Pitting may occur in the pre-boiler section due to the transport of water containing dissolved oxygen. Once oxygenated water enters into the boiler, the oxygen will be liberated in the higher temperatures and pose potential problems in the boiler and in the after-boiler sections. Generally, oxygen pitting will occur near or above the waterline of the steam drum in an operating boiler or very close to the point of feedwater entering the boiler. Pitting of metal surfaces below the waterline is virtually nonexistent in operating boilers. Some of the oxygen will pass through the upper portion of the steam space and may lead to pitting on the upper boiler surfaces. Pitting may occur at any point in the steam or condensate systems. Reducing the dissolved oxygen content in the makeup water through mechanical, thermal or chemical means controls corrosion caused by oxygen. Mechanical Deaeration (Atomization of the makeup into a steam or elevated temperature area) Efficient operation of vented deaerating heaters is essential to good boiler operation. Deaerating heaters as contrasted to closed, non-vented stage heaters serve three purposes in a steam generating system. They are: Removal of non-condensable gases such as oxygen and ammonia Increase feedwater temperature Storage of boiler feedwater

A properly functioning vented deaerator normally removes dissolved oxygen in the makeup water to less than 0.007 ppm (7 ppb). The remaining oxygen can be removed by adding a chemical oxygen scavenger to the storage section of the deaerator.

Thermal Deaeration (Temperature Elevation) Increasing the temperature of water reduces the solubility of gases such as oxygen as seen in Figure 1. When mechanical deaeration (atomization) is not possible, it is recommended to heat the feedwater to 90C or as high a temperature as practical followed by the addition of an oxygen scavenger to the feedwater.

Figure 1 12 8 ml/L Oxygen 4 Content 0 -1 21 43 66 88 110 Degrees Centigrade

Chemical Deaeration (Scavenging) Although mechanical and thermal deaeration removes most of the dissolved oxygen in water, chemical oxygen scavengers are used to scavenge remaining oxygen. Chemical oxygen scavengers differ in their ability to remove oxygen, the amount required for the chemical reaction, under various conditions of temperature and pH, to passivate metal surfaces, their volatility (distribution ratio), thermal stability and toxicity. The remainder of this paper will discuss the differences between the primary oxygen scavengers used in marine steam generating systems. The discussion of each oxygen scavenger includes six categories; reaction with oxygen, passivation, decomposition, volatility or distribution ratio, dissolved solids and health hazard data. An Oxygen Scavenger Summary Chart is attached and offered as a quick reference guide.

SODIUM SULFITE Reaction with Oxygen Sodium sulfite was the first widely used oxygen scavenger in marine boiler water treatment. It reacts readily with oxygen to form sodium sulfate by the following reaction: 2Na2SO3 sodium sulfite + O2 oxygen 2Na2SO4 sodium sulfate

The stoichiometry (the quantity of one substance to react with another substance) of this reaction reveals that 8 parts of sodium sulfite are required to react with one part of dissolved oxygen. The rate of reaction of sodium sulfite with oxygen increases with increased temperature, increased solution pH and the presence of a catalyst as in Drew Marines CATALYZED SULFITE corrosion inhibitor. Passivation While sodium sulfite is an excellent oxygen scavenger, it does not have any passivation property. Therefore, it does not produce a barrier on the metal surface to provide additional corrosion protection. Sodium sulfite and the sodium sulfate formed in the reaction with oxygen are nonvolatile and will remain in the water phase, thereby adding to the dissolved solids content of the boiler water. The increased level of dissolved solids necessitates the need for additional boiler blowdown. The additional dissolved solids also increase the potential for carryover. Sulfites only provide protection against oxygen from the point of feed, up to and including the boiler. They do not protect the after-boiler section due to the fact that they are non-volatile. Decomposition At high pressures (above 600 psig or 42 bar) sulfite can decompose into sulfur (gas) and sulfur dioxide. When sulfur dioxide dissolves in the condensate, sulfuric acid forms. The acid condensate can then cause corrosion in the after-boiler section. Therefore, the use especially of sulfite above 600 psig (42 bar) is not the preferred oxygen scavenger. Na2SO3 + sodium sulfite H2O water + heat 2NaOH sodium hydroxide + SO2 sulfur dioxide

4Na2SO3 + sodium sulfite

2H2O water

heat

3Na2SO4 + sodium sulfate

2NaOH sodium hydroxide

H2S hydrogen sulfide

Volatility Sodium sulfite provides protection against oxygen from the point of feed, up to and including the boiler. Sodium sulfite does not protect the steam and after-boiler section from oxygen corrosion due to the fact that it is non-volatile. Dissolved Solids Since sodium sulfite and the sodium sulfate formed in the reaction with oxygen are non-volatile and will remain in the water phase, they add to the dissolved solids content of the boiler water. The increased level of dissolved solids necessitates the need for additional boiler blowdown. The additional dissolved solids, unless controlled, increases the potential for carryover. Health Hazard Data The following toxicity data is from the RTECS (Registry of Toxic Effects of Chemical Substances) compiled by the National Institute for Occupational Safety and Health of the U.S. Department of Health and Human Services. Mouse LD50 Route: Oral; Dose: 820 mg/kg

HYDRAZINE Reaction with Oxygen Hydrazine was first introduced as an oxygen scavenger for boiler water treatment in the 1950s and has been a standard treatment for high pressure systems since the 1960s. Hydrazine reacts with oxygen to form water and inert nitrogen gas. N2H4 + O2 2H2O + N2 hydrazine oxygen water nitrogen The stoichiometry of this reaction (the theoretical requirement of the amount of chemical to react with oxygen) is one part of hydrazine reacts with one part of dissolved oxygen. This reaction shows that much less hydrazine is required to react with oxygen than sodium sulfite. The rate of reaction of hydrazine with oxygen increases with increased temperature, increased solution pH and the presence of a catalyst as in Drew Marines AMERZINE corrosion inhibitor. Passivation In boiler systems passivation is attributed to the formation of a thin adherent oxide film on metal surfaces. The oxide film provides a barrier between the metal and the water, thereby minimizing corrosion attack. Hydrazine is an excellent passivator, producing magnetite (Fe3O4), which is a passivated oxide state of iron with a very compact and adherent crystalline structure. N2H4 + hydrazine 6Fe2O3 ferric oxide (hematite) 4Fe3O4 + ferrous oxide (magnetite) 2H2O water + N2 nitrogen

Decomposition Hydrazine begins to decompose at 235 psig (16 bar) to form ammonia and nitrogen. 3N2H4 + hydrazine heat 4NH3 ammonia + N2 nitrogen

A significant amount of ammonia can be formed due to the decomposition of hydrazine. The ammonia can, in the presence of oxygen, attack copper and copper alloys in the condensate and feedwater systems. Keeping the excess hydrazine level low and the systems tight with minimal air inleakage can avoid this. Volatility Although hydrazine is volatile and does not add dissolved solids to the boiler water, its volatility is limited. Volatility of an amine is classified by its vapor liquid distribution ratio. The vapor liquid distribution ratio of hydrazine is reported as 0.08. This means that at any point in the system there should be 0.08 ppm of hydrazine in the steam or vapor phase for every 1 ppm of hydrazine in the water phase. The low distribution ratio of hydrazine means that it does not travel far into the after-boiler section and the majority of any unreacted hydrazine stays in the boiler. As a comparison, the distribution ratio for ammonia is noted as approximately 10.0 meaning that there will be 10 ppm of ammonia in the vapor phase for every 1 ppm of ammonia in the liquid phase. It is known that ammonia travels far into the after-boiler sections and can return to the boiler where it can be recycled.

Dissolved Solids Hydrazine and the reaction products of hydrazine do not add any dissolved solids to the boiler water. Health Hazard Data The following toxicity data is from the RTECS (Registry of Toxic Effects of Chemical Substances) compiled by the National Institute for Occupational Safety and Health of the U.S. Department of Health and Human Services. Rat LD50 Route: Oral; Dose: 60 mg/kg

According to the NTP (National Toxicology Program), hydrazine has been categorized a Group 2 agent, a substance which may reasonably be anticipated to be a carcinogen. There is sufficient evidence of carcinogenicity in experimental animals, but inadequate evidence in humans. According to the IARC (International Agency for Research on Cancer, hydrazine is categorized as a Group 2B agent, a substance that is possibly carcinogenic to humans. The exposure circumstance entails exposures that are possibly carcinogenic to humans. It was found that evidence in humans was inadequate and evidence in animals was sufficient.

DEHA (Diethylhydroxylamine) Reaction with Oxygen DEHA was introduced commercially in 1981 as an oxygen scavenger for treating boiler systems. The reaction of DEHA with oxygen is a complex process involving several reactions. The overall reaction of DEHA with oxygen can be summarized as: 4(C2H5)2 NOH DEHA + 9O2 oxygen 8CH3COOH acetic acid + 2N2 + nitrogen 6H2O water

When sodium hydroxide is present in the boiler water, the acetic acid is neutralized and removed by blowdown as sodium acetate. The stoichiometry of this reaction (the theoretical requirement of the amount of chemical to react with oxygen) is 1.24 parts of DEHA reacts with one part of dissolved oxygen. The rate of reaction of DEHA with oxygen increases with increased temperature, increased solution pH and the presence of a catalyst as in Drew Marines DREWPLEX OX corrosion inhibitor. Passivation DEHA has been shown to be a good metal passivator by forming magnetite oxide film on metal surfaces. 2(C2H5)NOH DEHA + 6Fe2O3 ferric oxide (hematite) 4Fe3O4 + ferrous oxide (magnetite) 4CH3COOH acetic acid + 3H2O water

Decomposition DEHA is thermally stable up to 300 psig (21 bar). The major thermal decomposition products are two main dialkylamines; diethylamine and ethylmethylamine. These dialkylamines are volatile and contribute to elevating condensate pH, thereby reducing the requirement for a separate primary neutralizing amine such as morpholine in higher pressure systems. DEHA also decomposes to ammonia but to a lesser extent than hydrazine. Volatility Like many other amines, DEHA is very volatile. Its vapor liquid distribution ratio is 1.26. This means that there will be approximately 1.26 ppm of DEHA in the vapor phase of the system for every 1 ppm of DEHA in the liquid phase. Therefore, DEHA will be distributed through the afterboiler section of the system providing protection against dissolved oxygen corrosion. With a vapor liquid distribution ratio of 1.26 versus that of hydrazine at 0.08, there will be approximately 16 times more DEHA than hydrazine in the vapor phase. This results in a much better passivation of the after-boiler section with the use of DEHA than hydrazine. Because of the high volatility of DEHA it is important to sufficiently vent the mechanical/thermal deaerator to remove any non-condensable gases that may have formed. Venting of the deaerator directly to the atmosphere is an important practice that allows the escape of noncondensable gases such as oxygen, ammonia and amines that otherwise would return to the boiler. In marine systems the deaerator may be vented to the gland exhaust condenser rather than to the atmosphere. The vent line to the gland exhaust condenser may or may not have an orifice plate. In cases where the vent line to the gland exhaust condenser does have an orifice plate, the size of the orifice may need to be increased to permit effective removal of gases such as oxygen, ammonia and amines.

Below are suggestions for evaluating deaerator venting process efficiency. It is essential to check the accuracy of the gauges used for measuring temperature and pressure before making an evaluation. 1. Difference in temperature between the water space and the steam space in the deaerator should be a maximum of 1C or 2F. 2. A convenient rule of thumb is that the saturation temperature increases by 3F (or 1.6C) per psig between 0 and 10 psig (0 and 0.7 bar). Therefore a deaerator operating at 3 psig (0.2 bar) should maintain a temperature of 221F (105C). 3. An alternate method is to check the saturated steam tables to obtain the corresponding temperature and pressure figures. Dissolved Solids DEHA and its reaction products do not add dissolved solids to the boiler water. Health Hazard Data The following toxicity data is from the RTECS (Registry of Toxic Effects of Chemical Substances) compiled by the National Institute for Occupational Safety and Health of the U.S. Department of Health and Human Services. Mouse LD80 Route: Oral; Dose: 2150 mg/kg

Oxygen Scavenger Summary Chart

Chemical

Reaction with Oxygen Stoichiometry

Metal Passivation

Volatility Distribution Ratio

Thermal Decomposition Above 600 psig (42 bar) can decompose to sulfur gas and sulfur dioxide

Sodium Sulfite

8:1 Reacts with oxygen to form sodium sulfate. Increases dissolved solids level in the boiler.

None

N/A

Hydrazine

1:1 Reacts with oxygen to form water and nitrogen. Does not add dissolved solids to the boiler water.

Good passivation in pre-boiler and boiler sections.

0.08

Begins at 235 psig (16 bar) to form ammonia and nitrogen.

DEHA

1.24 Reacts with oxygen to form acetic acid, nitrogen and water. Acetic acid is neutralized by hydrate alkalinity in the boiler water forming sodium acetate that is then removed by boiler blowdown. DEHA does not add dissolved solids to the boiler water.

Good passivation throughout the boiler system.

1.26 Good distribution through the afterboiler section.

Over 300 psig (21 bar) to form volatile diethylamine and ethylmethylamine which contribute to condensate pH neutralization.

All statements, information and data presented herein are believed to be accurate and reliable but are not to be taken as a guarantee, express warranty or implied warranty of merchantability or fitness for a particular purpose, or representation, express or implied, for which seller assumes legal responsibility, and they are offered solely for your consideration, investigation and verification. Statements or suggestions concerning possible use of this product are made without representation or warranty that any such use is free of patent infringement and are not recommendations to infringe on any patent. 2002 Ashland, Inc. Registered trademark, Trademark of Ashland Inc. Printed in U.S.A. *Responsible Care and the Responsible Care logo are registered service marks of the American Chemistry Council in the U.S., of the Canadian Chemical Producers Association in Canada and of different entities in other countries.

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