SM

TECHNIFAX

Condensate system protection

source. Corrosion of the condensate system can result in increased maintenance and equipment replacement costs, energy loss through steam leaks and loss of process heat transfer efficiency.
TF-150

The prime considerations in the operation of boiler systems are maximizing energy efficiency and reliability, and eliminating unscheduled outages caused by water-related problems. One economically attractive method is increasing the amount of condensate return. Returned condensate, being condensed steam, is extremely pure and has a high heat content. Increased condensate return can improve boiler system economics through water and energy conservation. As more condensate is returned, less make-up water is required, saving on water and make-up water treatment costs. The high purity allows for greater boiler cycles of concentration, thus reducing water and energy losses to blowdown. The high heat content (148 Btu/lb at 180F) can provide substantial energy savings. Corrosion in condensate systems can limit the quality or quantity of returned condensate because of iron and copper corrosion products which can deposit on boiler heat transfer surfaces. This reduces heat transfer efficiency and could cause tube failure. Condensate corrosion control is required to protect process equipment, lines and tanks, as well as to maintain the condensate as a quality feedwater

1. 2NaHCO3 + H2O

heat Na2CO3 + CO2

heat 2. Na2CO3 + H2O 2NaOH + CO2 The first reaction proceeds 100% to completion. The second proceeds to approximately 80% completion. The liberated CO2 is carried with the steam into the condensate system. It becomes apparent that high alkalinity feedwater will produce extremely corrosive condensate.

CAUSES OF CONDENSATE SYSTEM CORROSION

Condensate corrosion is caused by gases in the steam that dissolve in the condensate to form a corrosive solution. Common gases found in condensate systems are oxygen, carbon dioxide and ammonia. Carbon dioxide and oxygen are most corrosive to ferrous metals, while oxygen and ammonia are extremely corrosive to copper and copper alloys. Either carbon dioxide or oxygen can cause corrosion; however, the presence of both accelerates the corrosion rate significantly (1040% faster than the sum of the corrosion rates occurring from either gas alone).

Reactions of Carbon Dioxide

Carbon dioxide is not harmful until it dissolves in condensate. As it dissolves, it forms carbonic acid: CO2 + H2O = H2CO3 = H+ + HCO3 Since condensate is extremely pure, even small quantities of carbonic acid can significantly lower condensate pH and increase its corrosivity. Corrosion rates increase with increasing temperatures. Since condensate is hot, this causes condensate to be even more aggressive to metal surfaces. Carbonic acid attack is characterized by a smooth overall loss of metal surfaces as shown in Figure 1. It can also cause channeling, worming or roughness on metal surfaces.

Sources of Carbon Dioxide

The major source of carbon dioxide in steam is the breakdown of feedwater bicarbonate and carbonate alkalinity in the boiler. At boiler temperatures and pressures, the following reactions occur:

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Sources of Oxygen
Oxygen is present in most makeup waters but is usually removed prior to entering the boiler by mechanical and chemical means. If oxygen is not removed, it will flash with the steam and enter the condensate system. However, the major source of oxygen is inleakage in the condensate system itself. The prime areas for air to enter a system are vented receiver tanks, packing glands of vacuum pumps, poorly maintained valves, units which operate under a vacuum or intermittently and pull a vacuum as the equipment cools. Oxygen and carbon dioxide entering a system in this manner can cause severe corrosion. Although chemical solutions to this problem exist, air in-leakage should be solved by making the required system repairs.

Figure 2 Corrosion resulting from presence of oxygen

Figure 1 Corrosion resulting from presence of carbon dioxide

Treatment for Oxygen Corrosion

When oxygen is present in condensate systems, the in-leakage source should be located and corrected. Filming amines are used to form a protective film on the metal surfaces but require strict pH and dosage control. Volatile oxygen scavengers/metal passivators can also be used; however, the pH must be maintained above 8.3 for passivation to occur.

Treatment for Carbon Dioxide

Carbon dioxide in the steam can be decreased by reduction of alkalinity in the feedwater. This can be accomplished by a well controlled lime softening program, dealkalization, demineralization, or degasification processes. Although alkalinity in the feedwater can be reduced, a certain amount is required to maintain proper boiler water alkalinity. Thus, CO2 will always be present in the steam. Neutralizing amines are fed to neutralize the carbonic acid and raise condensate pH. Filming amines can also be fed to form a protective film on metal surfaces. These applications will be discussed in more detail under chemical treatment programs.

Reactions of Oxygen
Similar to the preboiler system, oxygen in the condensate will react with the metal surface causing corrosion and forming deposits of FeO, Fe2O3 and Fe3O4. This corrosion will increase with increasing temperature. Normally, oxygen will be present with carbon dioxide. At pH levels below 6.0, the combined corrosion will appear as a general metal loss with rough surfaces and some pitting present. At higher pH, the characteristic pitting attack (see Figure 2) will be more noticeable.

Sources of Ammonia
Ammonia is present in some water sources, or may be generated by the breakdown of boiler water additives such as hydrazine.

Reactions of Ammonia
Ammonia, having a high volatility, will distribute unevenly across a condensate system, raising the condensate pH only at certain areas of the system. This can give a false sense of corrosion protection of the entire system if not enough sample points are monitored. Above a pH of 9.2, corrosion of copper and copper

alloys by ammonia becomes appreciable. The combination of ammonia and oxygen is extremely aggressive to copper. This corrosion is accelerated below pH 8.5 and above pH 9.2.

Table 1 V/L ratios Pressure, psig 0 50 150 600 900 Cyclohexylamine 2.7 3.0 4.0 10.0 6.6 Morpholine 0.4 0.4 0.5 1.2 1.2 Carbon Dioxide 3.0 4.8 8.5 15.8 >99.0

CHEMICAL TREATMENT PROGRAMS

Neutralizing amines are nitrogen containing compounds which are added to steam systems to neutralize carbonic acid and raise condensate pH. These amines offer no protection against oxygen attack and must be restricted to those systems where oxygen in-leakage is not a problem. Neutralizing amine programs are most effective when fed to maintain a pH of 8.5-9.0. This range will maximize corrosion protection since CO2 does not exist above pH 8.3. Maximum protection of copper and copper alloys is also maintained in this range. Neutralizing amines are added in direct proportion to the amount of carbon dioxide in the steam. Therefore in high alkalinity feedwater systems where CO2 generation is appreciable, excessive amounts of neutralizing amines may be required to neutralize the carbonic acid. (Filming amines should be considered in these instances.) Neutralizing amines are characterized by a specific volatility, acid neutralization ability, and basicity.

Volatility
Every gas in a condensate system has a specific volatility or vapor to liquid distribution ratio (V/L). The V/L distribution ratio is defined by: V = L (concentration in the liquid or condensate phase) (concentration in the vapor or steam phase)

It is important to realize that V/L ratios are significant when a phase separation occurs. For example, in a flash tank, condensate enters the vessel while both condensate and steam exit the vessel. Low volatility amines such as morpholine will dissolve in the condensate exiting the flash tank. High volatility cyclohexylamine will go with the steam, exiting the flash tank. V/L ratios are not significant when total condensation occurs. Total condensation occurs when all the carbon dioxide and amines in the steam entering a unit are dissolved into the condensate (no phase separation exists).

The V/L distribution ratio indicates whether the species would condense with the condensate or stay with the steam. To neutralize carbon dioxide, the amine must be in the condensate as the CO2 dissolves. For example, a V/L ratio of 4.0 indicates that 4.0 ppm of amine must be present in the steam to get 1.0 ppm in the condensate. The higher the V/L ratio, the more amine will be in the steam. V/L ratios vary with pressure, pH, temperature, and other operating conditions. Table 1 indicates the V/L ratio of two common neutralizing amines and carbon dioxide.

Acid Neutralizing Ability

In addition to V/L ratio, which determines the distribution of an amine in a system, another very important aspect of amine choice is its acid neutralizing ability. This is the amount of amine required on a weight basis to neutralize the carbonic acid present. The amine reacts with the carbonic acid in solution to form an amine bicarbonate: RNH2 + H+ + HCO3 ( RNH3+ + HCO3

This characteristic is primarily dependent upon the molecular weight of the amine. On a pound-for-pound basis, lower molecular weight amines will neutralize more carbonic acid than higher molecular weight amines.

Basicity
Once all the acid in the condensate system has been neutralized (at a pH of about 8.3), amine basicity becomes important. This is a measure of amine hydrolysis. Any additional amine added to the condensate system will hydrolyze, raising the condensate pH: RNH2 + H2O ( RNH3+ + OH Basicities of neutralizing amines also vary. For example, cyclohexylamine is a much stronger base than morpholine. Past a certain pH, additional quantities of the weaker neutralizing amines such as morpholine will do little to further increase pH. The V/L ratio, acid neutralizing ability, and the basicity of each amine must be considered when selecting a condensate corrosion inhibitor program. A filming amine program does not neutralize CO2 as do neutralizing programs. Filming amines form a non-wettable film on all metal surfaces in contact with the condensate (Figure 3). This film acts as a barrier between the metal surface and the corrosive condensate.

Figure 3 This section of condensate pipe, treated with a filming inhibitor, shows complete repellence to the three drops of water.

Octadecylamine and octadecylamine acetate are filming amines which can be used in FDA and USDA applications. The pH for successful application must be closely controlled between 7.0 and 7.5. At pH below 6.5, the film will strip off metal surfaces, causing sticky deposits. This can also happen at pH above 8.0. Filming amines have minimal neutralizing capacity. Therefore to maintain the correct pH control range, supplemental neutralizers or combination neutralizer/filmer programs are necessary.

Proprietary Filming Amines

Nalco markets a proprietary filming amine which has several advantages over octadecylamine. The amine film is stable over a pH range of 6.5-9.0. In complex systems where pH may very this widely, this amine offers a definite advantage. This amine is not applicable for use in FDA or USDA regulated plants. It is available as an easy-to-feed liquid program.

Filming amines protect against carbonic acid and oxygen attack. Therefore, filming amines should be used wherever there is a high probability of oxygen in-leakage. Filming amines can cause formation of a sticky wet deposit or gunk balls when overfed or if the pH is not maintained in a certain range. These deposits can cause pluggage in steam traps, pump strainers, control valves and low flow areas of a system. Care should be taken when starting up a filming program in a previously untreated system due to system clean-up and the possibility of overfeed. Always start at low dosages and increase feed slowly.

OXYGEN SCAVENGERS/ METAL PASSIVATORS

Oxygen scavengers are also used in condensate systems. These chemicals react directly with the oxygen present. Oxygen scavengers do not provide protection against CO2. Therefore to maintain the correct pH control range, neutralizing amines must also be fed.

Some oxygen scavengers enhance metal passivation. At condensate temperatures, metal passivation occurs preferentially over oxygen scavenging. However, the pH must be maintained above 8.3 for passivation to occur. Oxygen and carbon dioxide can be drawn into cyclically operating components of a steam system. For example, paper machine dryers or heat exchangers cool off as they are shut down. This cooling process creates a partial vacuum in the heat exchanger and draws air in to the system. Oxygen and carbon dioxide will dissolve in the condensate and produce corrosion. Volatile oxygen scavengers should be fed to the steam phase. Sulfite is not recommended for condensate systems.

Several condensate practices and equipment items require special attention. These include combined steam sources, heavy venting, steam traps, turbines, thermocompressors, flash tanks, and cascading systems. Combined steam can be of the same pressure but from different sources, such as turbine exhaust or extraction, flash tanks and reduced pressure steam. When predicting the pH of the resultant condensate, each steam source must be evaluated individually for pH and amine content. System venting - Units vented to the atmosphere disrupt condensate equilibrium, because some gases and neutralizing amine will be lost. Therefore, the pH of the condensate exiting a vented receiver will not be the same as that entering. Improperly vented equipment may allow air inleakage which increases system corrosion. Samples should be taken from the streams entering and exiting the receiver to properly evaluate oxygen inleakage and pH. Steam traps are used to remove accumulated condensate from steam lines. A routine steam trap maintenance program should be established. Steam traps that are stuck in the open position will result in significant energy losses and may allow air in-leakage. Turbines utilizing superheated steam require special consideration due to high temperatures. Under these conditions, amine decomposition could occur.

Overfeed of filming amines can cause deposition on turbines. Thermocompressors combine steam of varying pressures to produce an intermediate pressure steam. As with combined steam sources, each steam source must be evaluated separately. Flash tanks - When hot condensate under pressure is released to a lower pressure, flashing occurs. The resultant steam and condensate may not contain the proper amine levels, depending on the V/L ratio of the amine program. Cascading systems, employing multiple flash tanks, compound this problem. Both the condensate and the steam exiting a flash tank should be monitored. This low pressure flashed steam is a common area of treatment problems.

MONITORING AND CONTROL

The selection and application of a condensate treatment program will be most successful when all aspects of the system are considered. The treatment program, if improperly selected or incorrectly applied, will result in corrosion in certain areas of the system. If there is a deficit of sample points in the condensate system or if the samples are not representative, corrosion in the neglected areas of the system can occur. When setting up a monitoring program, sample point selection is extremely important. The first step is the development of a detailed system survey.

SAMPLING PROCEDURES
Technifax 141 covers physical condensate sampling techniques. The important points to remember include: 1. Samples should be cooled to less than 90F to prevent flashing of amine and/or carbon dioxide from the sample, which could cause erroneous results. 2. Throttling of sample flow through a sample cooler should be at the outlet of the cooler. Inlet throttling can create a partial vacuum which can draw in air.

3. Sampling metallurgy must be stainless steel to prevent erroneous test results. For the same reasons, samples should run continuously to assure representative test results. 4. Tests should be run as soon as possible after sampling; pH, oxygen and carbon dioxide should be run on site.

TESTING
The following tests should be run on condensate samples to locate problem areas: pH The pH will indicate whether the treatment program is in the correct control range. Total iron and copper These tests will indicate the presence of corrosion products in the system. If the condensate is returned to the boiler, these corrosion products can cause deposition on boiler heat transfer surfaces. Insoluble iron (Millipore) This test is an excellent way to visually verify iron levels present. This is only valid as a trend analysis. Dissolved carbon dioxide This test will measure actual CO2 in the sample. Dissolved oxygen This test will indicate an air in-leakage contamination problem. Total hardness This test will indicate a cooling water or service water contamination problem.

P and M alkalinity The reaction of amines with CO2 produces an amine bicarbonate or carbonate in solution. These species are titratable as P and M alkalinity. For example, if you have 10-20 ppm of CO2 in the steam, neutralization with an amine will produce 5-10 ppm of M alkalinity and a pH of 8.3. If alkalinity does not exist and the pH is low, then CO2 is the only species present. If alkalinity exists and the pH is low, an excess of CO2 is present in comparison to amine. Conductivity This test will indicate a boiler carryover problem or a contamination problem. Note: Conductivity can be present in the sample from amine bicarbonate and amine carbonate. Product residuals Filming amine residual and oxygen scavenger residual should be run where applicable to determine program control. Ammonia This test will tell you if you have a potential for copper corrosion problems.

The Mobile Condensate Center is on-line with the plant steam/ condensate system. It measures the combined effects of product blends, dosages, and system characteristics. A series of pressures are run to profile the condensate system and identify potentially overtreated, undertreated, or untreated areas. The N-Compas Condensate Computer Model helps determine the most cost-effective product and feed location for a plants specific steam/condensate system. After entering plant data for the system, the model screens hundreds of possible product formulations and determines the best options for providing optimum corrosion protection. Performance monitoring of condensate systems can be done using the Nalco Particle Monitor and Condensate Corrosion Sensor. The Particle Monitor measures particulate contamination levels present, typically iron and copper. It can be used to indicate when condensate can be reused as boiler feedwater or should be dumped to protect the boiler. The Condensate Corrosion Sensor provides continuous mpy corrosion readings which can be used to adjust condensate treatment levels in a corrosion preventive manner. Diagnostic evaluation of condensate flowrates, distribution, and percent return can be accomplished using TRASAR Technology to aid in optimization of energy efficiency. Contamination problems due to mechanical

MONITORING TOOLS
Monitoring tools include the Nalco Mobile Condensate Center (MCC), the N-Compas Condensate Computer Model, Particle Monitor, and Condensate Corrosion Sensor, diagnostic TRASAR Technology, and corrosion coupons.

carryover or cooling water inleakage can also be identified. Corrosion coupons can be used for trend analysis of corrosion of a given metal. The coupon can be installed in a condensate line with a rod style corrosion coupon holder. The coupon should not touch the metal pipe. A corrosion coupon rack can also be used. The rack should be constructed of stainless steel with a sample cooler at the outlet of the rack. Flow should be throttled with the valve at the outlet of the cooler. Always monitor corrosion of condensate, not steam.

FEED SYSTEMS
Condensate corrosion inhibitors should typically be fed neat (undiluted) to the steam header through a stainless steel retractable injector (Nalco part number P2434). The most common exception to this is treatment of boiler systems using demineralized makeup, where amines are commonly fed to the feedwater for alkalization. Feeding ahead of the deaerator, to the boiler feedwater or to the boiler steam drum will result in some product loss through the deaerator vent and/or through the boiler blowdown. The amount of a specific amine lost will vary according to its V/L ratio as well as boiler pressure, cycles of concentration and azeotrope formation. See Figure 4 for losses of some typical amines in the boiler blowdown at 10 cycles of concentration.

Figure 4 Percent amine lost in blowdown at 10 cycles

Most condensate products consist of blends of amines designed to protect entire condensate systems. When fed to the boiler feedwater, a greater percentage of the low volatility amines will be lost via blowdown. The higher V/L ratio amines which reach the condensate system will best protect the final condensation areas of the system. Corrosion may occur in the initial condensation areas. Thus, the total amine loss is not as important as the disproportionate loss of the individual amines in the product. Nalco CUSTAMINE products can be designed to minimize your overall corrosion rate even when boiler feedwater injection is necessary.

Retractable injectors are necessary to ensure mixing of the chemical with the steam. (See Figure 5.) Retractable injectors allow the installation and removal of the injector while the steam line is in service. The retractable injector is 18 inches long allowing adjustment of the depth of the injector into the pipe. Assure that the injector extends at least 4 inches beyond the pipe wall. In comparison, a quill cannot be replaced during service and it is only 3 inches long.

All condensate corrosion inhibitors must be fed on a continuous basis to prevent corrosion of the condensate system. Neat feed is required for several reasons. It allows accurate measurement of the exact amount of chemical being fed. Troubleshooting becomes extremely difficult when feeding diluted products. When feeding into steam lines, several problems with dilution water can occur. Oxygen, sodium, conductivity, silica, etc. can enter the steam system through the dilution water causing possible turbine deposition, oxygen corrosion, etc. Water entering a steam line can also cause steam hammer, erosion and possible line failure. If the dilution water is above 90F, high V/L ratio amines will flash from the dilution tank causing hazardous amine vapors and disproportionate amine feed.
Figure 5 Nalco Retractable Injector dimensions

All feedlines, pump heads, valves, etc. in the feed system must be of stainless steel because of product compatibility and feed system safety requirements. Bulk storage tanks must be of stainless steel or polyethylene construction.

CONCLUSION
Adequate corrosion protection of a condensate system can be obtained if the program is correctly selected, applied and monitored. The selection and application of a condensate treatment program will be most successful when all aspects of the condensate system are considered. This requires a detailed system survey, sufficient sample points and good monitoring techniques. A reliable feed system and the correct feedpoint will assure excellent program results.