January, 2001

Technical Bulletin

Importance of Good Boiler Feedwater Treatment

Attention: Re: Question: HRSG End Users Understanding Boiler Feedwater Water Issues Why should we be concerned about boiler feedwater?

Maintaining good feedwater is an important and fundamental aspect of any steam turbine power plant. A plant that maintains good feedwater achieves the following three benefits: 1. 2. 3. Help to ensure maximum life out of its boilers, steam turbines, condensers, and pumps. Reduce maintenance expenses. Maintain optimal thermal performance

The purpose of this newsletter is to provide a summary of power plant feedwater quality issues so that designers and operators can be better informed. Results of Poor Water Treatment In the ideal situation, water would be feed to a boiler free of any impurities. Unfortunately, this is not the case. Water clean up is always required. The following items are the most problematic to boilers and steam turbines: Calcium (Ca) scale Calcium forms with sulfates (SO4 ) and other compounds to form calcium sulfate, calcium bicarbonate, calcium carbonate, calcium chloride, and calcium nitrate. During evaporation, these chemicals adhere to boiler tube walls forming scale. Its formation increases with the rate of evaporation so these deposits will be heaviest where the gas temperatures are highest. Scale is a nonconductor of heat which leads to a decreased heat transfer of the boiler tubes, and can result in tube failure due to higher tube metal temperatures. Buildup of scale also clogs piping systems and can cause control valves and safety valves to stick. Magnesium (Mg) scale Same issues as with calcium. Silica (SiO2) Silica can form scale at pressures below 600 psig. Above 600 psig, silica starts to volatize, passing over with steam to potentially form deposits on the steam turbine diaphragms and blades. These deposits change the steam path components profiles resulting in energy losses. The degree of loss depends upon the amount of the deposits, their thickness and their degree of roughness. For example, if the nozzle area of the first stage flow path was reduced by 10%, the output of the steam turbine would be approximately 3% less. A similar loss could occur if the gas turbine received steam for power augmentation purposes. Sodium (Na) Sodium can combine with hydroxide ions creating sodium hydroxide (caustic). Highly stressed areas of boiler piping and steam turbines can be attacked by sodium hydroxide and cause stress-corrosion cracks to occur. This was a problem in older boiler with riveted drums because of stresses and crevices in the areas of rivets and seams. While less prevalent today, rolled tube ends are still vulnerable areas of attack as well as welded connections. Chloride (Cl) Chlorides of calcium, magnesium, and sodium, and other metals are normally found in natural water supplies. All of these chlorides are very soluble in water and therefore, can carry over with steam to the steam turbine. Chlorides are frequently found in turbine deposits and will cause corrosion of austenitic (300 series) stainless steel and pitting of 12 Cr steel. Corrosion resistant materials protect themselves by forming a protective oxide layer on their surface. These oxides are better known by their generic name ceramic. All ceramics will pit if exposed to chlorides. If the metal piece is under tensile stress either because of operation or Vogt Power International Inc. 1 of 5

4000 Dupont Circle, Suite 400 Louisville, Kentucky 40207 502/899-4500 Fax: 502/899-4690 Sapulpa Manufacturing Operations: 2110 N. Industrial Drive Sapulpa, Oklahoma 74066 918/227-4202 Fax: 918/227-4207

January, 2001

Technical Bulletin
residual stress left during manufacturing, the pits formed by chlorides attacking the passivated layer will deepen even more. Since the piece is under tensile stress, cracking will occur in the stressed portions. Usually there will be more than one crack present causing the pattern to resemble a spiders web. The most common source of chloride contamination is from condenser leakage. Iron (Fe) High iron is not found in raw water but high concentrations can come from rusted piping and exfoliation of boiler tubes. Iron is found in condensate return in a particle form as it does not dissolve in water. The detrimental aspect of iron is called steam turbine solid particle erosion, which causes significant erosion of steam turbine steam path components. Oil Oil is an excellent heat insulator, and adherence of oil on tube surfaces exposed to high temperatures can cause overheating and tube damage. Oxygen (O2) Oxygen is found in feedwater and its partial pressure is relatively high so it will requires a near saturation temperature to disassociate itself from water. Oxygen in combination with water will attack iron and cause corrosion. The reaction occurs in two steps: Fe++ Ferrous ion then 4Fe(OH)2 + Soluble Ferrous Hydroxide O2 Dissolved oxygen + 2H2O Water
=

2OHHydroxyl ion

Fe(OH)2 Ferrous hydroxide

4Fe(OH)3 Insoluble ferric hydroxide

The ferric hydroxide is highly insoluble and precipitates on heated surfaces. The precipitate is called magnetite or rust. The closer the water is to the saturation temperature, the more corrosion will occur. Carbon Dioxide (CO2) Carbon dioxide can react with water to form carbonic acid (H2CO3). Carbonic acid will cause corrosion in team and return lines. Carbon dioxide can originate from condenser air leakage or bicarbonate (HCO3) alkalinity in the feedwater. pH The pH value of water is a measure of its alkalinity or acidity and has a direct bearing on the corrosive properties. All water contains alkaline (hydroxyl, OH) ions and hydrogen (H) ions. The product of the concentrations is always approximately 10-14. The pH value of the water is the log of the reciprocal of the H ion value. If the water is neutral, the OH and H ion concentrations are each 10-7. A pH below 7 indicates acidity; over 7 designates an alkaline condition. Low pH in local areas is the second most common cause of corrosion in mild steel boilers Above roughly 400, mild steel corrosion results in the formation of magnetite, a tight adherent that acts as a barrier between boiler water and steel. The corrosion reaction stops after a uniform magnetite layer is formed . Rapid general corrosion can ensue if this protective film is disrupted, so water chemistry must be carefully controlled to maintain the film. An acidic condition can destroy the magnetite film; therefore, boiler water is maintained in the alkaline range of a pH of 9.0 to 10.5. Foaming Foaming is the formation of bubbles or froth on the water surface. It is caused by a high amount of total and suspended solids. Foam will fill the free surface area of a separating device increasing local velocities and promoting a serious carryover of boiler water. Priming Priming is a violent and spasmodic discharge of water with steam into the steam space. Slugs of water are thrown over with the steam causing damage to the steam turbine.

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4000 Dupont Circle, Suite 400 Louisville, Kentucky 40207 502/899-4500 Fax: 502/899-4690 Sapulpa Manufacturing Operations: 2110 N. Industrial Drive Sapulpa, Oklahoma 74066 918/227-4202 Fax: 918/227-4207

January, 2001

Technical Bulletin
Carryover When boiler water solids are carried over into the moisture mixed with steam even though there is no indication of foaming or priming, this is considered as carryover. Carryover can be the result of high steam flow which overloads the dryers (separators). The dryers work by sudden changes in stem velocity so that foreign particles are thrown out by centrifugal force. Raw Water Cleaning Raw water can come from a variety of sources, lakes, rivers, and wells for example. Each source of water will have its own constituents and therefore, its own requirements for cleanup. These cleanup requirements should be specified by experts in this field of work. Raw water from reservoirs, lakes, rivers, and wells can have varying characteristics as provided below: Silica (SiO2) Iron (Fe) Calcium (Ca) Magnesium (Mg) Sodium (Na) Potassium (K) Carbonate (CO3) Bicarbonate (HCO3) Sulfate (SO4) Chloride (Cl) Fluoride (F) Nitrate (NO3) Dissolved solids Total hardness as CaCO3 Non carbonate hardness Specific conductance Color pH 0.4 to 39 ppm 0.0 to 2.1 ppm 1.7 to 79 ppm 0.4 to 33 ppm 1.4 to 147 ppm 0.4 to 4 ppm 1 to 4 ppm 10 to 328 ppm 0.8 to 560 ppm 2.6 to 195 ppm 0.0 to 2.5 ppm 0.0 to 4.0 ppm 23 to 1380 ppm 6 to 316 ppm 0 to 197 ppm 29.5 to 1040 micromhos at 25 C 0 to 15 5.8 to 8.4

In general, raw water is cleaned via four processes. They are summarized below: 1. Aerification This process removes undesirable gases such as carbon dioxide and hydrogen sulfide by mixing water with air. The mixing adds oxygen to the water while removing the carbon dioxide and hydrogen sulfide. Increasing the temperature, the areation time and the surface area of water improves the removal of gases. Coagulation This is the process of adding chemicals to reduce coarse suspended solids, silt, turbidity, and colloids in a clarifier. The impurities will settle out of solution with the added chemicals. Some chemicals used for coagulation are filter alum, sodium aluminate, copperas, ferrisul, activated silica, and various organic compounds. Filtration Filters remove coarse suspended matter and removes floc or sludge from coagulation or process softening systems. Beds of gravel or coarse anthracite are common materials used for the filter beds. Specially made precoated filters can be used to remove oil and reduce color. Softening There are several methods to remove calcium, magnesium, silica, and silt (softening). They are summarized as follows: Lime soda softening Calcium carbonate (lime) is added to feedwater to precipitate the calcium bicarbonate to calcium carbonate and magnesium salts to magnesium hydroxide. Sodium carbonate (soda ash) is added to reach Vogt Power International Inc. 3 of 5

2.

3.

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4000 Dupont Circle, Suite 400 Louisville, Kentucky 40207 502/899-4500 Fax: 502/899-4690 Sapulpa Manufacturing Operations: 2110 N. Industrial Drive Sapulpa, Oklahoma 74066 918/227-4202 Fax: 918/227-4207

January, 2001

Technical Bulletin
with calcium chloride and calcium sulfate to corm calcium carbonate. This process is more efficient at hot temperatures. After the lime-soda process, the residual hardness will be approximately 17 to 25 ppm. Hot-process phosphate softening Phosphate is added to remove calcium and magnesium. This process results in precipitated tricalcium phosphate and magnesium hydroxide. The chemical reactions occur above 212 F and will reduce hardness to nearly zero. Zeolite softening Zeolites are any in a group of crystalline mineral compounds whose framework of atoms forms microscopic tunnels and rooms. The internal structure of zeolites makes them useful as filters and catalysts. In water softening processes, zeolites are used to exchange calcium and magnesium ions with sodium in the zeolite. The calcium and magnesium are passed to waste and the zeolite is regenerated by passing a sodium chloride (salt) solution through the softner. Demineralization Demineralizers are used to remove ionized mineral salts. Calcium, magnesium, and sodium cations are removed in a hydrogen cation exchanger by sulfonic, carboxylic, and phenolic hydroxyl compounds. Anions of bicarbonates, sulfates, chloride, and soluble silica are removed by amino or quaternary nitrogen. Reverse Osmosis - Reverse osmosis is defined as the passage of water from a more concentrated solution to a less concentrated solution through a semipermeable membrane under pressure. The pressure is required to reverse the natural process of osmosis by overcoming the osmotic pressure. Simply, osmotic pressure can be looked at as being directly related to concentration so the higher the salt concentration in the feed, the higher the osmotic pressure. This osmotic pressure is real. For example, seawater, which contains approximately 3.5%, or 35,000 mg/l salt, the majority of which is sodium chloride (NaCl), has an osmotic pressure of 410 psi (28.3 bar). Before desalting can occur, an RO system must be pressurized to a minimum of 410 psi (28.3 bar) to overcome the osmotic pressure inherent in the solution. Two-stage RO is defined as running two RO systems in series with the product (permeate) of the first acting as the feed to the second RO. Staged or series operation is typically done when a single-stage RO system does not produce the required quality of product water. Another justification for two-stage RO is where the additional expenses of operating the second RO system is lower than alternative forms of polishing the first-stage RO permeate to reach a higher quality of final product water. Boiler Water Control Items to control in the boiler water are oxygen and dissolved solids. Each of these are controlled in the following manner:

Oxygen Oxygen will be found in steam condenser condensate as well has in makeup water. It is most commonly removed via one of two system arrangements. A common method is the use of a vacuum condenser. A vacuum is created in the condenser by steam jet air ejectors pumps prevents the water from absorbing oxygen because the vacuum is lower that the oxygens partial pressure in water. The other method is to use an integral deaerator arrangement. For this arrangement a deaerator is located atop the low pressure drum and water from the HRSG feedwater heater is sent to the integral deaerator where it mixes with saturated steam from the low pressure drum thereby removing the oxygen. Dissolved Solids During the evaporation process, most solids stay in the water section of the drum while steam is sent to the superheater. As the solids increase in water, they are removed by sending a small portion (typically 1 to 2% of the feedwater flow rate) though a drum blowdown pipe to the blowdown tank. This water is most often released to a drain. The separation ratio of solids in steam vs. drum water depend upon pressure. Separation values provided by the ABMA are listed as follows:

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4000 Dupont Circle, Suite 400 Louisville, Kentucky 40207 502/899-4500 Fax: 502/899-4690 Sapulpa Manufacturing Operations: 2110 N. Industrial Drive Sapulpa, Oklahoma 74066 918/227-4202 Fax: 918/227-4207

January, 2001

Technical Bulletin
DRUM MAXIMUM STEAM TDS MAXIMUM PRESSURE, BOILER WATER CORRESPONDING TOTAL psig SOLIDS, ppm TO MAX. BW TDS, ALKALINITY, ppm ppm as CaCO3 0 - 300 3500 1.0 (1) 301 - 450 3000 1.0 (1) 451 - 600 2500 1.0 (1) 601 - 750 1000 0.5 (1) 751 - 900 750 0.5 (1) 901 - 1000 625 0.5 (1) 1001 - 1800 100 0.1 (2) 1801 2350 50 0.1 (2) 2351 2600 25 0.05 (2) 2601 - 2900 15 0.05 (2) NOTES: (1) (2) (3) (4) 20% of Actual Boiler Water Solids For TDS < 100 ppm, the total alkalinity is dictated by the boiler water treatment Does not include vaporous silica carryover The ABMA defines FCO as Fractional Carryover. MAXIMUM SUSPENDED SOLIDS, ppm 15 10 8 3 2 1 1 1 1 1 MAXIMUM FCO, FRACTIONAL CARRYOVER (3) 0.0003 0.0003 0.0004 0.0005 0.0006 0.0007 0.001 0.002 0.002 0.003

AndyRagland Marketing Manager Email: Sales@vogtpower.com

Jeff Daiber Director of Aftermarket Aftermarket@vogtpower.com

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4000 Dupont Circle, Suite 400 Louisville, Kentucky 40207 502/899-4500 Fax: 502/899-4690 Sapulpa Manufacturing Operations: 2110 N. Industrial Drive Sapulpa, Oklahoma 74066 918/227-4202 Fax: 918/227-4207