BOILER WATER CHEMISTRY/ ANALYSIS

Knowledge Requirement
1. Why the measurement of dissolved Oxygen is so important for boiler feed water?
Dissolved Oxygen (Free) can and will corrode feed lines, economizers, steam drum(s) and downcomers. The corrosion can be general but is more likely evident as pitting of internal surfaces. Idle boilers, not properly stored will corrode until either the oxygen has been used or the boiler returned to service. In any case the boiler life will be shortened. Thats why the measurement of dissolve oxygen is so important for boiler and feed water.

2. Describe the working principle of the dissolved Oxygen analyzer..?

The measurement of dissolved oxygen is based on the well-known Clark cell principle. An oxygen-permeable membrane isolates the electrodes from sample water, thus obviating the need for sample conditioning. Other reducible or oxidizable ions do not interfere, because they cannot pass through the gas permeable membrane. A constant voltage supply powers two electrodes, maintaining each at a constant potential. A gold working electrode (cathode) reduces the dissolved oxygen to hydroxyl ions. O2 +2H2O + 4e- = 4OHA large silver counter electrode (anode) provides the oxidizing reaction which occurs at its surface. 4Ag+ + 4Br+ = 4AgBr + 4eThe reduction of oxygen is the current limiting reaction, thus making the cell current linearly proportional to the dissolved oxygen concentration. Electrochemical reactions and diffusion rates are temperature-sensitive. The measuring cell, therefore, is equipped with a temperature sensor which allows automatic temperature compensation.

3. What types of chemicals are dosed in feed water system, what is the function of each chemical? chemical?
The following chemicals are dosed in the feed water/condensate systems:

Phosphate Hydrazine or Carbohydrazine Amine.

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PHOSPHATE: Phosphate is dosed directly into the IP and HP Steam/Water Drums to reduce scale formation and to control drum water pH. Hydrazine or Carbohydrazine: As oxygen scavenger is dosed directly into the CEP discharge. Oxygen reacts with iron and other metals to form a metal oxide. Oxygen dissolved in boiler water having traces of chlorides or solids can cause pitting corrosion of metal surfaces. The resulting condition may be severe, even at low pressure. Oxygen and other gases are removed from the feed water before they can enter the boiler both mechanically within the de aerating condenser and chemically Oxygen scavenger into the condensate dosing with Hydrazine or Carbohydrazine also promotes the formation of a magnetite layer and decomposes to form ammonia, which combines with condensate in the condenser to form NaOH and assists in pH control. Amine: Amine is dosed directly into the CEP discharge to maintain pH in the condensate system. Low pH is one of the most common causes of localized corrosion. Corrosion in steam and condensate return lines may be caused by a low pH induced by carbonic acid resulting from the association of CO2 coming from the boiler with water. The CO2 itself may originate from air leakage into the condenser or bicarbonate alkalinity in the feed water. A buildup of acid reduces condensate pH leading to loss of metal and grooving of the condensate piping (General Corrosion). The affect is accelerated in the presence of O2. Hydrogen can evolve in a low pH environment and can have the following effects: It can diffuse into the boiler metal React with ferrous carbide to produce methane

4. Why Sodium measurement plays a specific role compared to pH, Conductivity and silica traces..?
Sodium measurement can indicate if there is Sodium slippage from the Ion Exchanger.

5. Why sample conditioning is necessary in Sodium analysis..?

Providing the dematerialized water is of good quality and the dematerializing train is not experiencing sodium slip, the saturated steam sodium analyzer should give the first indication of a condenser tube leak.

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6. Explain about CoCo-ordinate ordinate Phosphate control program and what what is phosphate range for HP and IP drum?
High pressure boilers using demineralized make up water generally have a large percentage of condensate returns and high heat transfer areas. These conditions, more than the operating pressure, make high pressure boilers prone to caustic attack, requiring special treatment. Because high pressure boiler make up is generally free of hardness, hardness deposits are not often found in the boiler. However iron and copper deposits are common and can lead to severe problems. Porous iron or copper oxide deposits on the radiant wall tubes or high heat transfer areas, act like miniature boilers. Boiler water is drawn into the deposit and steam or pure water leaves the deposit; solids in the water remain under the deposit. Extremely high levels of hydroxide or caustic can form beneath the deposit. The protective magnetic layer and even the parent metal can suffer caustic attack. A treatment approach known as Coordinated Phosphate Treatment was developed to limit the localized concentration of caustic. Excess caustic combines with phosphate and effectively buffers the pH. Proper PO4 levels ensure the absence of free hydroxide or caustic. For the program to work, it is essential to have sufficient phosphate available to combine with free caustic. Coordinated phosphate treatment was simple process to monitor and control. To prevent the formation of free NaOH, the operator had to keep below the upper line in the plot of pH vs. phosphate concentration plot shown in Figure 1. That line corresponds to three sodium for each phosphate, i.e. the Na/PO4 ratio of 3.0 found in pure tri sodium phosphate.

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Different form of phosphate consume or add caustic as the phosphate shifts to the proper form; addition to monosodium phosphate consumes caustic as it reacts with caustic to form disodium phosphate in the boiler water: NaH2PO4 + NaOH Na2HPO4 + H2O

Addition to tri sodium phosphate adds caustic, increase boiler pH; Na3PO4 + H2O Na2HPO4 + NaOH

Control is achieved through feed of proper type of phosphate to either raise or lower pH while maintaining proper phosphate level. HP DRUM PHOSPHATE (PO4) range is 2 ~5 ppm, and IP DRUM PHOSPHATE (PO4) range is 3 ~ 15 ppm.

7. What is the physical significance of PH..?

pH is short from for Power (p) of Hydrogen (H). pH is defined as the negative log of the Hydrogen Ion activity, a H+ or the effective Hydrogen Ion concentration. pH is a unit of measure that describes the degree of acidity or alkalinity of a solution. Acidity is defined as the concentration of Hydrogen Ions [H+] in solution and alkalinity as the concentration of Hydroxyl Ions [OH-] in solution. As seen above the actual theoretical definition of pH is -Log110 a H+. But, since the activity coefficient (a) for Hydrogen (H+) is 1 the practical definition for pH can then be defined as Log10 [H+].

8. How the pH meter / analyzer do works..?

There are two ways of measuring pH. The first is a Colorimetric Method, which uses color indicators to indicate the pH of the sample. There limitations to this measurement technique. A more effective way to measure pH in an industrial setting is the potentiometric method of pH analysis. The potentiometric method allows continuous, on-line measurement and is not subject to operator bias. Potentiometric analysis has four parts: 1) sample, 2) pH sensing electrode, 3) reference electrode and 4) signal amplifier / readout. pH Sensing Electrode: The pH sensing electrode acts as one half of a battery whose potential varies with the hydrogen ion concentration in solution. The Standard Glass Electrode is commonly used in industrial application because of its ruggedness and versatility. The glass electrode basically consists of four major components: 1) The Glass Membrane, 2) The Internal Buffer Solution, 3) The Reference Wire and 4) The Glass Stem. The glass electrode is primarily composed of Alkali Silicates that are comprised of Sodium, Potassium, Lithium, Silica, Oxygen and Hydrogen. All of these components are combined to form a Hydrogen Ion specific sensing glass: the amount of each constituent in the glass determining its pH sensing properties.

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When the glass is put into solution it undergoes a chemical reaction, which forms a leached layer. This layer is the area at the surface of the glass where an ion exchange reaction takes place. In this surface layer Hydrogen Ions migrate in and replace other positively charged ions such as Sodium or Potassium. This causes a Silica-Oxygen-Hydrogen bond to be set up which is essential for sensing Hydrogen Ion in solution. The pH glass electrode actually works on a two-reference electrode basis, a reference inside the glass and a reference that is in contact with the externals of the glass. pH measurement requires measurement of the potential difference in the pH electrode system. The formation of a leached layer actually occurs on both sides of the glass membrane. The difference in potential between the two layers is called the Phase Boundary Potential, and is the potential difference that gives the pH signal. In the pH glass there must also be a charge transport mechanism so that a millivolt potential will be seen. In between the two leached layers there remains a glass membrane layer that does not undergo the ion exchange that occurs at the surface. In this membrane layer Potassium and Sodium, major constituents of the glass, act as the charge carriers. For best results a Symmetrical Cell is set up on both sides of the glass membrane. To set up the Symmetrical Cell, the internal fill solution in the glass and the reference fill solution are similar in their makeup. The symmetry is important so that the temperature curves for the two solutions are as close as possible and minimizes the temperature effect. For Symmetry purposes the internal buffer is made of KCI (Potassium Chloride) solution that is the same as the reference solution.

9. What do you know about phosphate hideout phenomenon?

Phosphate Hideout: When the concentration of phosphate in the boiler water is too high, phosphate will react with boiler scale forming iron and iron sodium phosphates or precipitate to form a solid phase on the hot boiler tube surfaces and elsewhere. This phenomenon is called phosphate hideout and it can result in changes of pH, as well as the concentrations of phosphate and other chemical species in the boiler water. Hideout usually first occurs in boiler tubes with the highest heat flux and low mass flow, where departure from nucleate boiling (DNB) or under deposit concentration occur. Surprisingly, hideout and boiler tube corrosion can also occur in HRSGs where the heat flux is much lower than in coal- or oilfired units. This is because there may be accumulation of corrosion products or inadequate mass flow through some generating tubes; particularly during duct burner firing. Because the solubility of phosphate decreases as boiler pressure increases, hideout is typically only noticed during load changes. Elevated temperatures at the boiler tube wall or deposits can result in some precipitation of phosphate which usually occurs when load increases. When the load reduced, phosphate reappears.

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10. What is the PH and conductivity limits in condenser Water, feed water, drum water and steam?

pH and conductivity Range

pH Range 1 2 3 4 5 6 7 Condensate LP Drum IP Drum HP Drum LPSH IPSH HPSH 9.3 10.0 9.3 9.7 9.3 - 10.0 9.0 - 10.0 9.0 10.0 9.0 10.0 9.0 10.0 Conductivity Range 6-20 S/cm 6-15 S/cm <100 S/cm < 40 S/cm 10-25 S/cm 10-25 S/cm 10-25 S/cm

11. Why temperature measurement and compensation is required required in PH and Conductivity analysis..?
Temperature plays an important role in the characteristics of a solution. With the variation of temperature the ionization rate of the solution varies. When we go for measuring pH, we are indirectly measure the total Hydrogen ion in the solution. The more temperature of a solution the more H+ ion in it and pH of the solution is the less and vice versa. Due to increasing of ionization with temperature the charge carrying capacity of the solution increases which means increase in conductivity. Since temperature has a direct effect in the measurement of pH & conductivity it needs to be measured and compensated during the measurement of pH & conductivity

12. What are recommended silica limit in make up water, condenser Water, Water, drum and main steam?
Silica range Make up water Condenser water HP drum water IP drum water HP, IP & LP steam : : : : : <0.02ppm < 0.02ppm < 2ppm < 40ppm < 0.02ppm

13. What you will do if HP super heater silica goes to 50 ppb? 6

Open HP drum CBD to reduce silica concentration. Check make-up water silica. Reduce ST load.
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14. If HP drum Water is in Free Caustic zone , what action you will take..?
Open CBD more Stop phosphate pump.

15. What will be your action if PH falls with dosing pumps still running? running?

Check the running pump is pumping properly, if the running pump is not pumping properly; change over to the stand by dosing pump. Check running pump stroke position, if the pump stroke minimum; increase the pump stroke. Check the dosing tank solution concentration and if less concentration solution, add some Na3PO4 in the dosing tank. Check HP drum blow down condition.

16. What is the different chemistry parameters measured online?

Online Parameters
# 1 2 3 4 5 6 7 8 9 10 11 Condensate LP Drum IP Drum HP Drum LP Steam IP Steam HP Steam LP Economizer LP Saturated Steam IP Saturated Steam HP Saturated Steam Parameters pH, conductivity, Cation Conductivity pH, conductivity, Silica pH, conductivity, Silica pH, conductivity, Silica pH, conductivity pH, conductivity pH, conductivity pH, conductivity pH, Cation Conductivity, Sodium pH, Cation Conductivity, Sodium pH, Cation Conductivity, Sodium

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17. What is the purpose of the Spectrophotometer..? Spectrophotometer..? Please explain its working working principle.
Accurate, easy to use, and affordable! By design the spectrophotometer is ideally suited for both routine testing and demanding analysis in water treatment, industrial processes, surface finishing, food and beverage processing, pharmaceutical production, and chemical synthesis. The DR/4000 Spectrophotometer provides digital readouts in direct concentration units, absorbance, or percent transmittance. When a user generated or HACH programmed method is selected, the on-screen menus and prompts direct the user through the test. This menu system also can be used to generate reports, statistical evaluations of generated calibration curves, and to report instrument diagnostic checks.

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