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A typical concentration of NaCL (Table Salt) in raw might be only 0.003 parts per hundred, or 0.003%. In many cases, we use milligrams per liter (mg / 1) instead of ppm. Ppm and mg / l mean exactly the same thing in the very dilute solution.
A typical concentration of NaCL (Table Salt) in raw might be only 0.003 parts per hundred, or 0.003%. In many cases, we use milligrams per liter (mg / 1) instead of ppm. Ppm and mg / l mean exactly the same thing in the very dilute solution.
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A typical concentration of NaCL (Table Salt) in raw might be only 0.003 parts per hundred, or 0.003%. In many cases, we use milligrams per liter (mg / 1) instead of ppm. Ppm and mg / l mean exactly the same thing in the very dilute solution.
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Attribution Non-Commercial (BY-NC)
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SI. No. Subject Page No. 1. Fundamental Concepts 1 2. Raw Water and its Softening Process 21 3. Combating Corrosion 69 4. Boiler Water Treatment 81 5. Coal and its Analysis 98 6. Oil 145 A. Fuel Oils 145 B. Lubricating Oils 155 C. Insulating Oils 164 7. Hydraulic Fluids 166 8. Other Chemical Aspects of Power Plant 167 9. Model Session Plan 173
PMI, NTPC 1 1. Fundamental Concepts
Units of Measurement and Concepts
The term concentration refers to the amount of one thing dissolved in another. For example if we put pound of sugar in-to one gallon of water, the concentration of sugar in the water in one pound per gallon.
There are other ways to express concentration as well.
Probably the most familiar unit of measurement in Chemistry is percentage, which states the number of units (or parts) of a constituent in 100 units (or parts) of a solution. Thus, percent concentration could be thought of as parts per hundred.
A typical concentration of NaCL (Table Salt) in raw might be only 0.003 parts per hundred, or 0.003%. This number is so awkward that we use the smallest units: parts per million or parts per billion (ppb). These units mean weight per million units of weight of solution or weight per billion units.
In many cases, we use milligrams per liter (mg/1) instead of ppm. In the very dilute solution employed in water treatment chemistry, it is nearly always safe to assume that ppm and mg/l means exactly the same thing. This is because 1 liter of water weighs one million milligrams and so 1 mg/l is 1 ppm. Parts per billion (ppb) is used to express concentration less than 1 ppm.
The number of moles of a material is defined as the weight of material to be reacted divided by the molecular weight of that materials.
Elements combine to form compound in specific, whole number ratios according to the valency of the elements. Similarly, molecules compound react with each other in specific whole number ratios according to the weights of combining molecules. This ratio is determined from examination of the numbers preceding the molecular formula in the written equation for a chemical reaction. Lets examine reaction between Oxygen and Sodium sulphite to form Sodium Sulphate.
One molecule of Oxygen reacts with two molecules of Sodium Sulphite to form two molecules of Sodium Sulphate.
The Molecular Weight of Sodium Sulphite is 126 (2 Sodium atoms of 23 atomic Wt + 1 Sulphur atom of 32 atomic Wt + 3 Oxygen atoms of 16 atomic Wt each) thus
2 x 23 + 1 x 32 + 3 x 16 = 126
The weight of one atom (atomic weight) of oxygen is 16 (rounded off from 15.994 for convenient calculation). The weight of the oxygen molecule (molecular weight) is 32, then, since it contains two oxygen atoms.
PMI, NTPC 3 So, one oxygen molecule, weighing 32, reacts with two molecules of sodium sulphite, weighing 126 each a total of 252. Thus, we form two molecules of Sodium Sulphite, weighing 284 (the sum of 32 and 252).
This relationship can be conveniently displayed by writing the molecular weights above the components of the reaction in the equation.
2Na 2 SO 3 + O 2 ------- > 2Na 2 SO 4
252 32 284
It is now clear that it requires 252 parts (gm, pounds, tons, etc.) of sodium sulphite to react with 32 parts (grams, pounds, tons, etc) of oxygen to make desired sodium Sulphate.
If the molecular weight is expressed in grams, it is called molecular weight, or gram mole, for short. Thus, one gram mole of oxygen (32 grams) always reacts with two gram mole of sodium sulphite (252 gm). Some similar mole ratio is fixed and is always true for any reaction, so that it is possible to compute the amount of Chemicals required to participate in that reaction. This ability to compute chemical requirements and consumption is important to the power plant chemist.
It enables him to know how to compute the amount of chemicals to be added to a system.
PPM AS CaCO 3
In water chemistry, certain mineral constituents are nearly always present and are of particular interest due to their interaction with each other and due to their influence on corrosion and deposits problems. These constituents are the elements that cause hardness (Calcium or magnesium) and the radicals that PMI, NTPC 4 cause alkalinity (hydroxide, carbonate and bicarbonate). Because these minerals are involved in frequent chemical calculations, it is convenient to employ a common measurement unit for their concentration in water. In this way, one can compute their combinations without combining weight calculations & procedures.
We use for this purpose ppm as CaCo 3 , because CaCo 3 (Calcium Carbonate) includes both hardness (Ca) and alkalinity (CO 3 ) and because its molecular weight is the round number 100. Once the concentration of all minerals elements, compounds and radicals is expressed as ppm as CaCo 3 , the quantities can be added, subtracted and combined directly.
Solution Characteristics
A solution is a homogenous mixture of two or more substances, whose concentrations can vary continuously within certain limits (This variability distinguishes a solution from compound). Defining a solution as a homogenous (or uniform) mixture means that there are no distinguishable boundaries between any of the components. (This characteristic also distinguishes a solution, such as salt dissolved in water an example of heterogeneous mixture, is a combination of salt and pepper).
In a true solution, the individual particles of the components are no larger than molecules. Solution may be composed of gases, liquids and solids in any combination.
The following table gives the nine possible types of solutions and gives an example of each type:
PMI, NTPC 5 Stage Solution Example
Gaseous Gases in gases Oxygen in Nitrogen (Air) Liquid in gases Water in air Solids in gases Iodine in air
Liquid Gases in liquid Carbondioxide in water Liquids in liquids Alcohol in water Solids in liquids Salt in water
Solids Gases in solids Hydrogen in Steel Liquid in solids Mercury in silver (Amalgam)
Solids in solids Carbon in iron (Steel)
In water chemistry, the only types of solutions of major concern are solids in water, gases in water and solids in solids (alloy materials that may corrode in presence of water).
Solubility
The material that is dissolved is called the Solute, and the material in which it is dissolved is called solvent. When table salt is dissolved in water, the salt is the solute and the water is the solvent.
When a solute has been dissolved in a solvent to the extent that no more can be dissolved, the solution is said to be saturated. The saturation value for a specific solute in a solvent is called its solubility in that solvent. The solubility of any solute in water is usually depends on temperature. If the solute is a gas, it is PMI, NTPC 6 more soluble at low temp that an high temp. At higher pressure, it is more soluble than at low pressures.
Ionization
When compounds dissolve in water, they produce observable changes in some of the physical properties of the solution, such as increase in conductivity. The special effect of minerals dissolved in water is caused by the fact that, when minerals are dissolved in water, they break up partially into particles that are charged. In case of NaCl, for example the natural way for the compound to split up into sodium ion (one Na+) and one chlorine Ion (one CL - ). The minerals break up this way because the Sodium (Na) is only loosely attached to Chlorine (CL).
The charged particles formed are called ions. The positively charged ions are called cations. (One way to remember which is to spell Cation as Ca+ Ion, replacing the + with a + ). The negatively charged ions are called anions.
Ionization Constant
When compounds break up or ionize in solution, they do so only partially. Different compounds ionize to different degrees and it is important that we should note that water is slightly ionized. Most of the molecules in water remain as H 2 O and do not split or dissociate into cations and anions. We say, therefore that water has a low dissociation constant. Molecules of compounds which all split into cations and anions are said to have high dissociation constant.
Water itself is neutral, that is neither an acid nor alkali, because there is an equal number of hydrogen and hydroxyl ions, each hydrogen ion or acid ion is balanced or neutralized by the other half of the molecule, which is a hydroxyl ion or alkali ion.
PMI, NTPC 7 Acids
An acid is a substance that ionizes in water to release free hydrogen (H+) ions. The strength of an acid is determined by how many hydrogen ions it supplies (that is, its degree of ionization.)
(a) Strong Acids Typical examples of strong acids are hydrochloric acid (HCl). Sulphuric Acid (H 2 SO 4 ) and Nitric acid (HNO 3 ). In a solution, these acids ionize as follows:
HCl H + CL (92% ionized) H 2 SO 4 2H + S0 4 (60% ionized) HNO 3 H + + N0 - (92% ionized)
(b) Moderately Strong Acids
Phospheric acid (H 3 PO 4 )is only moderately strong and partially ionizes 1%
H 3 PO 4 H + H 2 PO - 4 (K 1 = 7.5x10 -3 )
Weak Acids
Carbonic acids (H 2 CO 3 ) is considered a weak acid. Its tendency to supply the hydrogen is very slight, far less than for acids such as HCL or H 2 SO 4 . Even moderately strong phosphoric acid has an ionization constant of 7.5 x 10 -3 , which is 25,000 times greater than the value for the hydrogen ion released from Carbonic Acid. PMI, NTPC 8 H 2 CO 3 H + + H 2 CO 3 (K = 3x10 -7 )
The ionization constant is then a measures of the degree of ionization of a compound in water. The larger the numbers the greater the degree of ionization. Generally speaking, the acids that readily ionize, HCL and H 2 SO 4 are more dangerous to handle than the weakly ionized acids, such as H 2 CO 3 , Carbonic acids.
Bases
A base, when dissolved and ionized in water, supplies free hydro xyl (OH - ) ions. As with acids, the strength of bases depends on their ionization constant.
(a) Strong Bases
Typical strong bases are the hydroxides, sodium hydroxide (NaOH), commonly called caustic soda; potassium hydroxide (KOH), commonly called potash; and calcium hydroxide [Ca(OH) 2 ], commonly called lime. The dissociation reactions and degree of ionization for these strong bases are as follows:
NaOH Na + + OH - (91% ionized)
KOH K + + OH - (91% ionized)
Ca(OH)2 Ca ++ + 20H - (90% ionized)
This degree of ionization determines the strength, or chemical reactivity, of that substance in water solution. The degree of ionization (also called dissociation) can be expressed numerically by a factor called the PMI, NTPC 9 ionization constant. For example, the ionization of a sodium chloride can be expressed by the following reaction:
NaCl ------------------ Na + Cl -
The ionization constant formula for this reaction can be written as follows:
K (NaCl) = ------------------ (Na+) (Cl - )
The symbol stands for the expression of solution concentration in moles per liter of the compound determines its strength or chemical reactivity, a highly reactive substance will be highly ionized. If it is highly ionized, the product of its ionic concentrations will be a large number.
If on the other hand, the dissolved compound is slightly reactive, the product of its ionic concentrations and its ionization constant will have a low value.
Useful Physical Chemical Properties
Water
Water is made up of hydrogen atom and oxygen atoms. A molecule of water is made up of two hydrogen atoms and one oxygen atom. Water itself is slightly ionized and the water molecule splits up into a cation (H + ) and an anion (OH - ).
HOH <==============> H + + OH -
The ion of water are called hydrogen ions (H + ) and hydroxyl ion and these ions are the basis of all acids (hydrogen ion) and alkali (hydroxyl ion). PMI, NTPC 10 (b) Weak Bases
A typical weak base is ammonium hydroxide (NH 4 OH):
NH 3 + H 2 O ---------------------------- NH - 4 + OH - (K 1 = 1.8x10 -5 )
Note that ammonia (NH 3 ) is a gas that dissolves in water to form NH 4 +
and OH - . In this case, you cannot say how much of the NH 3 has ionized. But as you can gather, the K 1 is quite small, indicating a low concentration of the ionized reaction products, NH 4 + and OH - .
Again, you most exercise caution when handling all strong bases.
Salts
Acids react with bases and neutralize one another. The reaction products are water and a compound called a salt. The salt is the compound formed by the cation (+ ion) of the base and the anion (-ion) of the acid. A typical neutralization reaction is the one between hydrochloric acid (HCL) and sodium hydroxide (NaOH) to form the salt, sodium chloride (NaCl). The reaction is written as follows:
HCL + NaOH ---------------------- Nacl + H 2 O Acids + base ----------------------- salt + water
The salt formed by the reaction between a strong base and a strong acid is said to be neutral. The cations balance the anions, and there is no residue of hydrogen or hydroxl ions to cause acidity basicity. Other examples of a neutral salt are potassium sulphate.
2 KOH + H 2 SO 4 --------------------- K 2 SO 4 + 2 H 2 O PMI, NTPC 11 and calcium nitrate,
Ca (OH) 2 + 2 HNO 3 ----------------- Ca (NO 3 ) 2 + H 2 O
The salts formed in these reactions are highly ionized, but not as much as the original acids and bases.
The reaction between a strong base and a weak acid or between a weak base and a strong acid forms a salt that is not neutral, but has acidic or basic properties like the stronger of its original components. For instance, the salt formed by a reaction between sodium hydroxide (strong base) and carbonic acid (weak acid) is basic. The large quantity of hydrogen from the strong base overwhelms the smaller quantity of hydrogen from the weaker acid to produce an excess of hydroxyl ion a basic condition.
Similarly, the salts known as ammonium sulphate (NH 4 ) 2 SO 4 , aluminum sulphate Al 2 (SO 4 ) 3 , and ferric chloride (FeCl 3 ) all have acidic properties, because they are formed from weak bases and strong acids. In other words, if any of these salts are dissolved in water, the resultant solution will be acidic.
In water chemistry, then, we must be alert to the possibility that some salt solutions may be either acidic or basic and must be properly treated before disposal.
1. pH 2. Alkalinity and Acidity
1. pH
a) Ionization of Water PMI, NTPC 12 Soluble acids, bases, and salts all ionize in water. Acids form free hydrogen ions (H + ) bases form free hydroxyl ions (OH - ) and salts produce either H + , or OH - unless they are completely neutral. When acids and bases react to form salts from the cation of the base and the anion of the acid, the other halves, H + and OH - , react to form water.
H + + OH - ---------------- H 2 O (or HOH)
Because water has a small ionization constant, however, the reaction is reversible to a slight degree. The ionization, or dissociation, constant for water is:
(H + ) (OH - ) K 1 = --------------------- = 1.8 x 10 -16
(H 2 O)
This small dissociation constant can also be expressed as an ion product:
K W = (H + ) (OH - )
In pure water, which is desirable in the power plant, (H + ) must equal or exactly balance (OH - ). It has been found that (H + ) and (OH - ) in pure water both have the value of 1.0 x 10-7 moles per liter. Therefore:
K W = (1.0 x 10 -7 ) (1.0 x 10 -7 ) = 1.0 x 10 -14
b) Definition of pH
Adding acids or bases to pure water changes the concentration of PMI, NTPC 13 H + and OH - ions. Acids increase (H + ) to a value greater than 1.0 x 10 -7 , and bases do the same for (OH - ). But, as long as the solution remains dilute K W is constant at 1.0 x 10 -14 of the (H + ) (OH - ) product. If this mathematical product is constant, any increase in either (H + ) or (OH - ) must be accompanied by a proportional decrease in the other. Therefore, as an aqueous solution becomes more acidic, (H + ) increases. As the solution becomes more basic, (H + ) decreases. This relationship is used to express relative degree of acidity or basicity in terms of the hydrogen ion concentration. This relationship has been given the name pH. It is defined mathematically in terms of the logarithm of the hydrogen ion concentration:
1 pH = log -------- H +
You do not need to remember this equation, but whenever you see log, you should think in terms of powers of ten. For simplicity the pH can be considered to be the power of the hydrogen ion. For example, a pH of 5 means a concentration of 1x10 -5 moles per liter of hydrogen ions. A pH of 6 means a concentration of 1x10 -6 moles per liter of hydrogen ions. Thus, a change from a pH of 5 to a pH of 6 is a decrease by a factor of 10 in the hydrogen ion concentration.
c) Range of pH Values - A neutral solution has a pH of 7. - An acid solution has a pH less than 7. - A basic solution has a pH greater than 7. (The term alkaline is frequently used in place of word basic)
PMI, NTPC 14 A change of one pH in either direction is a change by a factor of 10 in the H + concentration. A solution with a pH of 3, for example, has 10,000 times more (H + ) than a solution with a pH of 7. These concepts are demonstrated in Figure 4A and Table 1. Table 1 includes both the H + and OH - concentrations associated with specific pH values. Table 2 indicates the pH of some common materials and the pH of water in various plant systems. Remember that the pH scale is only an indicator of the balance between hydrogen and hydroxyl Ions. ------------------------------------------------------------------------------------------------------------ pH pH is an indication of the hydrogen ion concentration hydrogen ion concentration (Grams/Liter) ------------------------------------------------------------------------------------------------------------ 10 -0 10 -1 10 -2 10 -3 10 -4 10 -5 10 -6 10 -7 10 -8 10 -9 10 -10 10 -11 10 -12 10 -13
H + OR LIBERATING OR LIBERATING H + FROM WATER OH - FROM WATER
INCREASING H + ------------------------------------------------------------------------------------------------------------ THE PRODUCT OF H + & OH - CONCENTRATIONS IS A CONSTANT INCREASING OH - ------------------------------------------------------------------------------------------------------------ PMI, NTPC 15 d) Measurement of pH
The pH of a solution can be determine directly by measuring the voltage developed across a cell composed of two electrodes and the solution to be tested. The pH meter is a sensitive voltmeter whose output is calibrated in pH units. One of the two electrodes is a reference electrode, and the other is an electrode made of a pH -
sensitive glass. As the H + concentration of the solution changes, the voltage developed between the reference electrode and the glass electrode also changes. The pH meter measures the voltage developed in pH units.
Since the electrodes are sensitive to temperature, the temperature of the test solution must be measured, and a compensating dial on the pH meter must be adjusted. Some pH measuring systems measure the temperature and adjust the meter automatically. These automatic systems are generally used for the on-line pH meters that are installed in plants.
A pH meter is always calibrated with a solution of known pH to ensure that it operates properly. The solutions used are called Buffer Solutions, because they maintain constant pH over a range of concentrations and in the presence of small amounts of acidic or basic impurities.
Table 2 - PH OF SOME COMMON MATERIALS SOLUTION pH RANGE Beer 4.0 5.0 Blood 7.3 7.5 Cider 2.9 3.3 Maple Syrup 6.5 7.0 Milk 6.3 6.6 Orange Juice 3.0 4.0 Saliva 6.5 7.5 Soft Drinks 2.0 4.0 Water, Drinking 6.5 8.0 Wine 2.8 3.8
PH OF WATER IN VARIOUS PLANT SYSTEMS PH PLANT SYSTEM 7 Raw Water 7 Makeup Water 8.8 9.2 Feed Water 9.2 9.5 Boiler Water (phosphate)
PMI, NTPC 17 Alkalinity and Acidity
In all the previous discussion, the property of a solution that causes the presence of free hydroxyl ion has been referred to as basicity or alkalinity. But alkalinity has a specific meaning in water chemistry, the ability to neutralize acidity. Alkalinity is measured in some specific unit of concentration, commonly parts per million (ppm). Acidity is the ability to neutralize alkalinity and is also measured in ppm.
Alkalinity and acidity are invariably measured when characterizing the quality of a water. Knowing these properties helps to predict the behaviour of any water in service, practically whether it will form scale or be corrosive.
The alkalinity and acidity in natural waters always consists of free carbon dioxide, carbonate ions, bicarbonate ions, hydroxyl ions, or some combination of these components. In rare instances raw water will contain some other alkaline or acid ion as well, but this situation is so unusual that it is generally ignored.
a) Conductance of Solutions
A solution that conducts electricity is called an electrolyte. Electrolytes are water solutions of acids, bases, or salts. Electrolytes vary inability to conduct electricity. The ions in a solution actually carry the electricity through the solution and different ions have different carrying capacities or conductances. The hydrogen ion has the greatest conductance, the hydroxyl ion has about half the conductance of the hydrogen ion, and all other ions have considerably less conductance.
As the concentration of a solution increases, the conductance of the solution increases, since there are more ions to carry the electricity.
PMI, NTPC 18 Power Plant Chemistry is usually concerned with very dilute solutions in which there are few ions to carry electricity. Where there are few ions, it is easier to measure the resistance of solution to electricity. Because conductance is the ability to conduct an electric current, and resistance is the inability to conduct an electric current, these two concepts are related follows:
1 Conductance = ---------------- Resistance
Since resistance is commonly expressed in units called ohms, it was decided to use the unit mho (ohm spelled backwards) for conductance. In the very dilute solutions of interest in power plant water chemistry, conductance is so low that we employ units smaller than mhos. For instance, a common value for the conductance of high pressure boiler water might be 0.00005 mhos. For this reason, the common unit for conductance in water chemistry is the micromho, or one millionth of a mho (10 -6 mhos). This unit is abbreviated as mhos.
Conductance values are usually reported at the standard temperature of 25 O C. If they are measured at another temperature, it is necessary to convert our readings to the value in micromhos at 25 O C. There are accepted procedures for doing this.
b) Specific Conductance, or Conductivity
The conductance of a solution measured at 25 O C between two electrodes that are each 1 cm 2 in area and are spread 1 cm apart is called the specific conductance, or the conductivity of that solution. The units of conductivity are mohs/cm.
PMI, NTPC 19 c) Using Conductivity to Measure Concentrations
In the past, conductivity measurements were converted into ppm dissolved solids by using calibration curves developed for each conductivity measuring device. As a rule of thumb, dissolved solids can be related to conductivity as follows:
ppm of dissolved solids = 0.7 x conductivity in mhos/cm. This approximation holds true only for solutions of salts. For solutions of acids, bases, or salts that are strongly acidic or alkaline, the multiplier will be in the range of 0.5 to 0.6.
Conductivity measurements are important tools for monitoring quality of water in power plants because of their relationship to dissolved impurity concentration. As you know, it is important to know and control the relatively large amount of total dissolved matter in boiler water. It is also important to know and control the small dissolved contaminant concentration in water that must remain very pure (return condensate or demineralized water). The quantity of dissolved matter can be detected more simply and quickly by measuring conductivity than by evaporating a sample to dryness and weighing the residue.
d) Measurement of Conductivity
As we have seen, conductivity is defined as the conductance of solution measured at 25 O C between two electrodes that are each 1 cm 2 in area and spaced 1 cm apart. Since most conductivity cells in use do not have electrodes 1 cm 2 in area, and since the electrode are not spaced 1 cm apart, the cells are given a cell constant, or correction factor, by the manufacturer. The cell constant corrects the reading to what it would have been if the electrodes were 1 cm 2 and spaced 1 cm apart. The PMI, NTPC 20 conductivity, then, is equal to the conductance (measured at 25 O C) multiplied by the cell constant.
PMI, NTPC 21 2. Raw Water And Its Softening Process
Basic Water Chemistry
Water absolutely pure is not found in nature. As the water vapour condenses in Air and falls, it absorbs dust, dissolves Oxygen, Carbon dioxide and other gases. At the ground surface it takes up silt and other inorganic matter. A few bacteria will have entered the water also.
These impurities, whatever may be the source, always contains impurities either in solution or in suspension. The determination of these impurities make water treatment essential.
Sources
Various sources of water can be broadly classified as:
Rain Water
Surface waters (Rivers, Streams, Ponds, Lake and Reservoirs)
Ground water (Springs, Shallow wells & Deep wells)
Quality of Raw Water
The composition of water from different sources varies widely both in the amount of dissolved salts and in the dissolved gases which it contains. In addition, surface waters, that is water from rivers and lakes, etc., usually contain suspended matter and often contain organic matter in solution and in suspension, derived from either decayed plant material or sewage. PMI, NTPC 22
Most waters can be treated to make them suitable for cooling services, the purpose of any treatment employed being to minimize the risk of fouling or corrosion of the heat-exchanger surfaces, or corrosion of the associated plant through which the water passes.
Very pure water containing no more than a scarcely-measurable trace of dissolved salts is required for boiler feed make-up purposes.
Chemical Composition
The major constituents of all natural waters consist of the salts of sodium, potassium, calcium and magnesium, together with bicarbonate, carbonate, sulphate, chloride and nitrate ions. Other constituents present, usually in low concentrations but which may create special problems, are silica, hydrogen sulphate, ammonia, organic matter (particularly substances known as fulvic acids), detergents, phosphates, and dissolved gases. Silica occurs in water in several different forms some of which escape detection by the normal chemical test employed (non-reactive silicon), and phosphate can occur as complex phosphate which escapes detection by the normal test used for orthophosphates, but there is some evidence to suggest that it can interfere with water-softening reactions. Sea water contains traces of most of the soluble salts and small concentrations of nitrates. Ferrus iron and manganese are found in certain waters.
Calcium bicarbonate, usually included in the temporary hardness or alkaline hardness, is unstable and on heating breaks down depositing calcium carbonate. Some calcium and magnesium salts are sparingly soluable so that if the water is evaporated or concentrated they crystallize out as hard scale.
PMI, NTPC 23 The equivalent mineral acidity (E.M.A.) is a measure of the concentration of salts of strong acids (sulphuric, hydrochloric and nitric acids usually) present in the water.
Carbon dioxide in the form of carbonates and bicarbonate dissolved in the water and this is known as free carbon dioxide.
The other salts present in the water create no particular problem but since they are electrolytes they will, if present in sufficient concentration (for example sea water), allow galvanic action to take place between dissimilar metals, resulting in dissolution of the more anodic metals.
Reference has already been made to the fact that ultra-pure water is required for boiler feed water make-up in a modern generating station. A typical specification for a new high pressure station may call for the following guaranteed quality.
------------------------------------------------------------------------------------------------------------ Conductivity (before and after passage Not greater 0.10 micro mho/cm Through a cation-exchange column in the (corrected 20 O C) Hydrogen ------------------------------------------------------------------------------------------------------------ Sodium Not greater than 0.015 ppm. ------------------------------------------------------------------------------------------------------------ Silica (including non-reactive silicon) Not greater than 0.02 ppm with 95% condence limit ------------------------------------------------------------------------------------------------------------
The quality of the water required is almost that of absolutely pure water which has a conductivity of 0.056 micromho/cm at 25 O C and 0.038 at 18 O C and there is, therefore, little chance for improvement on the quality specified above. The PMI, NTPC 24 real problem to ensure that this quality is consistently maintained, with regard to silica.
Impurities
The major impurities of water can be classified in the following groups:
1. Non-ionic and Silt Mud and Undissolved Bacteria
2. Ionic and Dissolved Impurities-carbonate, bicarbonate, chloride and sulphate of Ca and Mg.
3. Gaseous-Oxygen and Carbon dioxide.
Non-ionic Impurities
They are mainly turbidity, silt, mud, dirt and other suspended matter; micro organism & other organic matter; oil and other corrosion products. It goes without saying that drinking water and most industrial water supplies should be clear and organics free.
Ionic and Dissolved Impurities
Any salt which dissolves in water splits into positively charged cations and negatively charged anion and since these permit the water to conduct electricity these salts are called electrolytes. Some of the most common cations in water are: Calcium, Magnesium, Sodium and iron rarely Ammonia and Manganese. These cations are associated with Anions like Bicarbonate, Carbonate Hydroxide, Sulphates & Chlorides. PMI, NTPC 25 The sum of Cations or total cations always equals the total of Anion. Quantitatively, these are expressed in parts per million or milligrams/litre. One part per million equals one ten thousands of one percent (0.0001%). One part per million means one part in a million parts, for example one ounce in a million ounces of water or one lb in a million lbs of water.
Dissolved silica is another troublesome impurity, especially in water fed to boilers at very high temperature & pressure.
Gaseous Impurities
Out of the atmospheric gases found in natural water only Carbon dioxide and oxygen are the main causes of many corrosion problems.
Various problems caused by the impurities
a) Scale Formation
The process of deposition of mineral constituents in boiler on metal surfaces is called scale formation. The primary cause of scale formation is the fact that the solubilities of scale forming salts decrease with increase in temp. Consequently, the higher the temp. and pressure of boiler operation, the more insoluble the encrusting salt become and may tend to form strong adherent scale on the evaporation surfaces. Amongst the natural substances found in water are salts of calcium and magnesium, which may give rise to scale formation. It is this particular salt which give water its Hardness.
Scale in boiler can be prevented by removing hardness salts from make up water, so that no calcium and magnesium enter the boiler from this PMI, NTPC 26 source and by internal chemical treatment of boiler water to deal with any trace which may enter the system.
Fig. No. 1 SCALING
Due to earlier mentioned salts in water they get deposited on the tube surfaces, when water is converted into steam.
This provides over-heating of tubes, less heat transfer and finally leads to tube leakages.
In modern boiler, all the impurities forming scale is removed before the water enters the boiler.
PMI, NTPC 27 b) Corrosion
Corrosion is the wasting away of metal in contact with water. Metallic iron in contact with water goes into solution as ferrous ions liberating negative charged electrons as per the following reaction:
M -------------- > M + + e .. (1)
The positively charged metallic ion react with negative (OH) - ions to form the hydroxide as below:
M + + OH - -----------------> MOH . (2)
The ferrous hydroxide formed is oxidized to ferric form by the oxygen present in water in the dissolved state.
The electrons released in the reaction (1) are neutralized by an equivalent amount of hydrogen ions from water to the neutral state as below:
e + H --------------------> H
The neutral H formed in the above reaction reacts with the dissolved oxygen present in water to form H 2 as per the reaction given below:
2H +1/2 O 2 ----------------H 2 0
Hence, for every hydrogen neutralized and converted to water a corresponding hydroxyl ion combines with the metal to form insoluable hydroxide ion and the corrosion process continues. It is quite evident that the oxygen present in water in the dissolved state has considerable effect in accelerating the rate of corrosion. PMI, NTPC 28 c) Carry Over
When steam leaves a boiler drum at rapid rate, tiny droplets of boiler water are carried upward with the steam as the droplets would become pure steam on further heating in super heaters, dissolved solids which also go along, are called Carry over. These solids may deposit in the super heater tubes or on the turbine lades, reducing the %. Silica is particular troublesome in this respect because it dissolves in high press steam and is transported through steam system.
As the Raw Water obtained from intake contains all the impurities mentioned earlier, it is unfit for is intended, before it can be supplied as make-up water to a boiler. The process commonly employed to remove impurities is shown in following block diagram:
PMI, NTPC 29
Raw water is fed to cascade aerator. Before aeration, through a mixing T, lime and chlorine (or Sodium sulphate) are injected to increase pH value and removal of bacterial infection any in the water. RAWWATER AERATION COAGULATION & CLARIFICATION ANTHRACITE FILTER ACTIVATED CARBON FILTER CATION EXCHANGER DEGASSER ANION EXCHANGER MIX BED EXCHANGER D.M. WATER PMI, NTPC 30
After aerator, water is dozed with the required amount of alum. Suspended particles present in water take a very long time to settle. It is therefore necessary to device a means to coagulate the very small particles in to bigger ones with higher settling values. It is achieved by adding certain chemical known as coagulant, the commonest is Aluminum Sulphate i.e. Alum.
The coagulant Alum is mixed in raw water in the Flash Mixer. Then it passes through a settling basin called Clariflocculator.
Water from the Flash Mixer enters into the flocculating zone of the clarifier through the R.C.C Central shaft opening. The clarifier is fitted with a rotating bridge driven by a electric motor. Here mechanical flocculation is done at the tip zone by the motor operated stirrer mounted on the bridge.
Preliminary settlement of flocs takes place in the bottom zone. Water then enters into the clarifying zone through bottom openings. The sludge in settling zone and other clarification zone is scrapped towards the central pit by means of scrappers linked with the rotating bridge. Sludge is then removed from this pit in the form of 10% slurry through sludge discharge pipe manually.
The object of water softening is to remove the calcium and magnesium salts causing scale deposition, particularly in evaporators.
Lime/Soda Softening
In lime soda softening, advantage is taken of the fact that calcium carbonate and magnesium hydroxide are sparingly soluble in water and can be precipitated from solution by the following reactions: PMI, NTPC 31 1. Ca(HCO 3 ) 2 + Ca (OH) 2 -----------------> 2Ca CO 3 + 2 H 2 O
2. Ca(SO 4 ) 2 + Na 2 C0 3 ---------------------> Ca CO 3 + Na 2 S0 4
It can be seen from the above reactions that the precipitating agents are calcium hydroxide (lime or more correctly hydrated lime, Ca (OH) 2 , and sodium carbonate (soda-ash or soda, Na 2 CO 3 ). These are the reagents normally used in water softening. But in fact any soluble carbonate or hydroxide could be used. However in removing temporary hardness, lime is a particularly suitable reagent since the only soluble product of the reactions (1) and (3) is water and this therefore results in a reduction of the T.D.S. of the water.
At 0 O C the solubility of calcium carbonate is 15 ppm and magnesium hydroxide 17 ppm. In the presence of a small excess of carbonate and hydroxide ions it is usually possible to reduce the combined residual hardness to below 20 ppm as CaCO 3 by cold lime-soda softening, the normal excess being:
20 ppm hydroxide alkalinity as ppm CaCO 3
40 to 60 ppm carbonate alkalinity as ppm CaCO 3
In considering the chemical reactions taking place in water softening, it is assumed that if the calcium and magnesium content is in excess of the bicarbonate concentration (bi-carbonate alkalinity) then all the bicarbonate alkinity is associated with calcium and magnesium and in this form is known as the temporary hardness. The excess of the calcium and PMI, NTPC 32 magnesium must then be associated with the chloride, sulphate and other anions present and this is known as the permanent hardness or non- alkaline hardness.
Calcium bicarbonate Ca (HCO 3 ) 2 Calcium nitrate Ca (NO 3 ) 2
Magnesium chloride MgCl 2
Magnesium bicarbonate Mg (HCO 3 ) 2
Magnesium Sulphate MgSO 4
Magnesium Nitrate Mg(NO 3 ) 2
Note
In water analysis it is normal to report all the main constituents in terms of the equivalent concentration of calcium carbonate (ppm CaCO 3 ).
At higher temperature the solubilities of both calcium carbonate and magnesium hydroxide are reduced and it is therefore possible to soften water to a lower residual hardness, using smaller excesses of hydroxide and carbonate alkalinities, if some form of heating is employed. As a corollary to this, poor water softening often occurs in period of low ambient temperature so that with softeners sited outdoors, improved performance can often be achieved if heat is available during the winter months.
PMI, NTPC 33 The reactions represented by equations (1) to (4) take place fairly rapidly since they are ionic reactions. However the particles of calcium carbonate and magnesium hydroxide first formed, will be of near colloidal dimensions and would pass through the various types of filter employed.
Over a period of time the precipitated material grows into larger crystal by a process of redissolving and recrystallisation and at normal ambient temperature in about 4-6 hours crystals of sufficient size and density will have formed and will sink to the bottom of the reaction vessel.
Use of Coagulants
If the small crystals formed in the early stages of the softening reaction can be induced to agglomerate into larger particles, the rate of sedimentation can be increased thus reducing the burden on the filter. This is achieved in water softening by adding small quantities (usually about 20 ppm) of the salts of relevant metals such as iron and aluminum. In the alkaline soft water these precipitate a bulky gelatinous floc of metal hydroxides which carry a small positive charge. These flocs agglomerated the calcium carbonate and magnesium hydroxide crystals, partly by pure physical entanglement and partly because the crystals carry a small negative charge.
Activated silica and starch are also used, often in conjunction with alum. Silica in the form of a gel has been found particularly useful on certain waters, notably those low in magnesium.
More recently organic chemicals having high molecular weights and with molecules having many ionisable groups, have been used successfully as coagulants. These chemicals are known as polyelectrolyte and many different types are available. They have the advantage of being effective PMI, NTPC 34 at a much lower concentration (usually 1 or 2 ppm) but at the present stage development they are very expensive and are not always as effective as the conventional coagulants.
To obtain the maximum effect, aluminum sulphate is added to the raw water after the softening chemicals. Alternatively sodium aluminate may be used and frequently this is premixed with the lime and soda as a combined softening charge.
(b) Effect of Nuclei
If suitable nuclei are present in the water the crystals of calcium carbonate and magnesium hydroxide will grow preferentially on them, resulting in more rapid growth of crystals large enough to settle.
Thus the time required for the softening reactions to be complete may be considerably reduced. The nuclei may be either added materials of suitable size such as sand, or alternatively the previously precipitated softening sludge may be recycled. This reduces the time required for softening to an hour or less, thus enabling the size of the reaction vessel for a given output to be reduced proportionately.
Types of Lime and Lime/Soda Softeners
To illustrate the various possibilities in greater detail, following three main types are more fully described:
A typical softener of this type is illustrated in Figure-3. In this case it consists of a tall cylindrical tank made of steel or concrete and a central cylindrical down comer which terminates at some distance above the bottom of the outer vessel. This serves as a mixing and reaction compartment. Raw water and softening chemicals enter at the top of this compartment and a coagulant, if added separately, enters a short way down. To ensure adequate mixing a stirrer is often included. The water flows downwards through the central chamber and then upward through the outer annular space. As it does so the precipated hardness falls into the dead space at the both concentrates into sludge and is drawn off either intermittent or continuously.
CONVENTIONAL LIME/SODA SOFTNER Fig No.: - 3
PMI, NTPC 36 In some of the earlier softeners (as illustrated) the upper part of the outer compartment contained a wood-wool filter through which the outgoing water passed. In other version filtration is done externally in pressure (sand or anthracite) filters. For either of these the aim is to produce clear water before it enters the filter in order to ensure long filter life.
This is achieved partly by the correct choice of coagulants and by designing the softener to ensure that the flow rate is sufficiently low and the retention time sufficiently long, so that even under conditions of low ambient temperature softening is complete.
Addition of softening chemicals: The solubilities of the two chemicals are very different, sodium carbonate (soda ash having solubility of about 17% at 20 O C whereas calcium hydroxide (lime) will only dissolve to the extent of less than 0.2% at 0 O C and also exhibits retrograde solubility. Therefore, if the chemicals are added separately, soda ash is added as solution and lime usually as a suspension. Only in some small softeners lime solution used and in this case a lime saturator is employed where part of the incoming raw water passes through a vessel containing powdered lime.
Where the composition of the raw water is fairly constant it is convenient to feed the two chemicals mixed together in suspension.
Control of the rate of addition of softening chemicals is effected by either volumetric apportioning gear regulated by the raw water flow or by using variable stroke metering pumps.
Sludge Blanket Softener
A softener of this type is illustrated diagrammatically in figure-4. It employs the principle referred to earlier of resuspending a proportion of the PMI, NTPC 37 precipitated sludge in the raw water, providing nuclei on which the freshly Precipitated hardness can crystalise.
Raw water is first mixed with the softening chemicals and some precipitated sludge, the mixing and re-entrainment of the sludge being assisted by the central stirrer. The mixture then flows upwards through the sludge zone into the central reaction chamber at a rate many times that employed in conventional softeners, usually about 20 ft/h and at this stage it is mixed with the added coagulant.
If the flow rate, the rate of addition of chemicals and the rate of sludge removal are correctly adjusted, the softening reactions should be completed within the sludge zone, and the precipitated material remains in this zone so that the sludge level is held constant and the water rising in the outer chamber is clear.
PMI, NTPC 38 The retention time in a sludge blanket softener is usually about l h and this is particularly useful where adjustment the rate of addition of chemicals have to be made, since control can be more easily effected and in a shorter time.
(c.) CATALYST Softener
The catalyst softener shown in figure-5 is used to remove calcium temporary harness, lime only being employed. It consists of a conical tank, which may if required be a completely closed pressurized vessel.
Raw water and lime enter tangentially at the bottom of the tank and in this way are induced to take a spiral path upward.
The catalyst is usually fine sand and is contained in the bottom part of the reactor. It is carried upwards by the flow of water and calcium carbonate grows on its surface. Gradually it increase in size until it can no longer be carried upward by the water. Periodically the reactor is blown down from the bottom to remove this grown sand and fresh sand is fed in at the top to make up for the loss.
PMI, NTPC 39
Ca (HCO) 2 + Ca (OH) 2 -------------------------- 2CaCO 3 + 2H 2 O . (5)
Mg (HCO 3 ) 2 + Ca (OH) 2 ----------------------- CaCO 3 + MgCO 3 + 2H 2 O (6)
Since magnesium hydroxide will not grow on sand it will be carried forward and overload the filter, if one is fitted.
In order to calculate the amount of lime required it is usually assumed that all the bicarbonates are associated with calcium, the magnesium with the sulphate and chloride etc. and in order to ensure that magnesium hydroxide is not precipitated, slightly less than the calculated amount of lime is used. Obviously in computing chemical reactions of this sort, success depends largely on the concentration of PMI, NTPC 40 the various constituents present. With a water having a high magnesium content (above about 40 ppm as CaCO 3 ) some precipitation of magnesium hydroxide is likely to occur and for this reason the catalyst softener is seldom used for these waters.
The advantages of the catalyst softeners are
1. Compact size.
2. It can be pressurized so that softened water can be fed direct to a filter without additional pumps.
3. The precipitated hardness is in a granular form having a low moisture content (that is, little water is wasted) and which can be easily disposed of.
The disadvantages are
1. Normally only calcium temporary harness is removed, although it is also possible to add soda and remove calcium permanent hardness.
2. Under low-temperature conditions sand growth is very slow with the result that filters become overloaded by the quantity of calcium carbonate carried forward to them.
3. With some water supplies, certain seasonal variations in water composition adversely affect the performance of the softener. The most troublesome period occurs in the late Autumn and Winter and it is believed that the problem is associated with the presence of increased concentration of organic matter and phosphates in the raw water at these times of the year. Where this problem has arisen it has often been found PMI, NTPC 41 that some improvement in performance has resulted from the addition of about 5 ppm of ferrous sulphate to the raw water.
Demineralization
Using synthetic ion-exchange resins similar to those described earlier, it is possible to remove all of the ionsable salts in a fresh supply and produce a water at least as pure as that obtained by softening and distillation.
The strongly acidic cation-exchange resins, similar to the synthetic base- exchange resins but in hydrogen form, will exchange hydrogen ions for other cations. The result is that neutral salts are converted to their corresponding acids, a process known as salt splitting.
Thus :
PMI, NTPC 42 The strongly basic anion-exchange resins, when they are regenerated with strong bases, such as sodium hydroxide (NaOH), will exchange other anions for hydroxyl ions (OH) -
If, therefore, the water after treatment in a cation exchanger is further treated in an anion exchanger, the salts originally present will be converted to water. Thus:
Synthetic Ion-Exchange Resins
These are organic substances of higher molecular weight made by either condensing together or polymerizing certain simple molecules. Chemically, the basic material is similar to many of the so-called plastics in common use today but it is treated during manufacture to confer ion-Exchange properties.
a) Cation-Exchange Resins
The first synthetic cation-exchange resins were formed by condensing tannins or phenols with formaldehyde and sulphonation of (reacting with sulphuric acid) the resulting resin. It was produced in large masses which were crushed and screened to yield a granular material of the required particle size, and materials of this type are still in use.
PMI, NTPC 43 Later methods of manufacturing cation-exchange resins which have improved stability. Particularly towards oxidizing agents involved the sulphonation of a polymer of styrene known as Polystyrene*, thus:
* Polystyrene is an example of a linear polymer since the basic structure of its molecule is a long chain of carbon atoms linked together.
If a small amount of divinyl benzene is included in the reaction mixture, a cross-linked co-polymer is formed which can again be sulphonated to yield a cation-exchange resin. Thus:
By varying the amount of divinyl benzene, the degree of cross-linking can be controlled and thus the pore size and the stability of the resins, the more highly cross-linked resins having similar pore size and being more resistant to temperature above ambient. PMI, NTPC 44 This copolymerization can be conveniently carried out by suspending the mixed liquid monomers in water and as they solidify, hard transparent spherical beads of predetermined sizes are formed which required no further crushing and screening.
Although the degree of cross-linking can be controlled, the actual sizes of cross- linking will occur in random fashion throughout the polymer chain so that we can only refer to the average pore size of the resin. By causing the linear polystyrene type of polymer to undergo self cross-linking, it is claimed that it is possible to produce a cross-linked polymer having sensibly constant pore size.
The sulphonated resins formed in this way are strongly acidic cation exchangers, that is they are capable of salt splitting. Weakly acidic cation-exchange resins can be produced by introducing a carboxylic group (---CO 2 H) in place of the sulphonic group (----SO3H), but they are produced more easily by copolymerizing methacrylic acid with divinyl benzene directly:
The product is an active ion-exchange material, without further treatment.
PMI, NTPC 45 b) Anion-Exchange Resins
If basic groups are introduced into the polystyrene resins instead of the acidic groups, anion-exchange properties are conferred on the resins. The basic group may be derived from ammonia or an amine, and in order to facilitate the introduction of the basic group into the polymer, the later may first be produced to contain, for example, chloro-methyl groups,
---------------- C ------------- CH 2 CL. Then, on reaction with ammonia or an amine,
basic groups are built into the resin structure, and the following summary of such reactions, the symbols R, R 1 and R 2 may be chosen from several subsidiary simple organic group.
(a) With ammonia, NH 3 : primary amine basic groups
---------------- C ------------- CH 2 ---N. are produced.
(b) With a primary amine, R ----- NH 2 ; secondary amine basic group
N ----------------- C ----------CH 2 are produced H
PMI, NTPC 46 R c) With a secondary amine NH territory amine groups,
R1
R --------------- C ----------CH 2 -------N are produced. R1
d) With a tertiary amine, R NR 2 , quaternary ammonium salt R1
The resins containing primary, secondary and tertiary amine groups behave as weak alkalis and will only exchange, or (more correctly) form, acid salts, with strong acids, The strong acids. (quaternary ammonium groups are strongly basic, similar in strength to strong alkalis and will exchange even weak acid such as carbonic acid and silicic acid or, in effect, carbon dioxide and silica in water.)
PMI, NTPC 47 Anion exchange materials are regenerated with alkalis. The weakly basic resins are usually regenerated with sodium carbonate (soda ash or soda) but almost any alkali will serve. The regeneration reaction is represented by the following equation:
2R.HCL + Na 2 CO 2 ----------------- 2R + 2 NaCL + H 2 O+CO 2
Resin acid complex Free base (exhausted resin) resin
The strongly basic resins require a strong alkali, such as sodium hydroxide (caustic soda) for regeneration, since the process involves the exchange of anions for hydroxyl ions, thus:
R.CL + NaOH ---------------- R.OH + NaCL Exhausted resin Regenerated resin in In chloride form hydroxyl form
In demineralization plants, the cation and anion exchange resins are often contained in separate to columns or units and the design of these ion- exchange units is similar to that of the base-exchanger unit. The complete demineralization plant contains one or more of each of the two types of units, the water passing through them in series.
c) Mixed Bed Exchange Units
The mixed bed unit is single column or unit containing both cation and anion exchange resins intimately mixed together. When water is passed through such as unit it comes into contact alternately with grains of cation PMI, NTPC 48 and anion resin, so that the water is subject to an almost infinite number of demineralization stages. In operation it behaves like a large number of two-stage demineralisers in series, with the result that it will produce a final water which is neutral and has a very low residual dissolved solids content. The conditions existing inside the mixed bed unit at different stages of operation and regeneration are illustrated in figure-6. During normal service, its mode of operation is similar to other ion-exchange units, in that water enters the top of the unit and leaves at the bottom.
MIXED BED ION EXCHANGE UNIT OPERATION & REGENERATION
Fig. No. 6
In order to regenerate the two different resins, it is necessary to have a more complex pipe-work and internals arrangement than for the single resin units.
PMI, NTPC 49 d) Strong and Weak Resins
A brief description of the chemical structure of ion-exchange resins has been given and some of the basic aspects of the use in the demineralization of water have been mentioned.
It is clear from the discussion so far that there is a wide variety of resins having different chemical structures, but in practice only a relatively small number find use in water treatment. The four major groups of resins, strong cation, weak cation, strong anion and weak anion exchange resins fairly clearly defined by their different ion-exchange properties but within each group, suitable changes in chemical and physical characteristics can yield a resin tailor-made for a particular ion-exchange application.
Weak resins have only a limited capability for ion exchange since strong resins will perform all of the functions of weak resins, there would appear to be little point in using them. However, in commercial operation it is possible to reduce the cost of demineralising water by employing a combination of two types of resin. In general it may be said that weak resin have a higher exchange capacity than strong resins and hence for a fixed output of treated water between regenerations, smaller volume of weak resin will be required; also weak resins can be regenerated with a smaller excess of chemicals. The higher exchange capacity helps to reduce the capital cost of the demineralization plant and the better regeneration efficiency helps to minimize running costs, so that by employing combinations of weak and strong resin-exchange units (a multi- stage plant) the overall cost is kept to a minimum using the strong resin units to perform only those functions which can not be performed by weak resin units.
PMI, NTPC 50 The data given in Table illustrates these differences in exchange capacity and regeneration efficiency.
Resin Exchange Capacity and Regeneration Efficiency
Type of resin Approximate Regeneration efficiency % Approximate Exchange capacity Kgr CaCO 3 /ft 3
Weak resins are regenerated with more dilute regenerates than are strong resins, thus in a multi stage demineralization plant the spent regenerate from the strong exchange resin unit can often be used to regenerate the weak resin unit; this is an additional way of reducing operation costs and is known as series regeneration. For example, cost of the strong resin unit is regenerated with 2% sulphuric acid, the spent regenerate leaving the unit will still contain about 1% sulphuric acid. Weak cation resins are usually regenerated with 0.8% to 1% acid so that the spent regenerate from the strong resion can be diluted slightly and used to regenerate a weak cation resin, if one is used.
Within the broad classification of strong and weak resins, the strong anion- exchange resins are further sub-divided into two types, known as Type-I and Type-II. Both have quaternary ammonium active groups, but in Type-I the groups (C n H 2r+1 ) such as methyl (-----CH 3 ) and ethyl (------C 2 H 5 ), whereas in the type-II resins one of type groups is an alcohol group such as ethanol (-----C 2 H 4 OH).
PMI, NTPC 51
Type- I Type II CH 3 CH 3
----- N ----------- CH 3 ------N --------------CH 3
CH 3 CH 3
Both are strongly basic resins, that is they are capable of salt splitting neutral salts, but Type-II is slightly less basic and has a higher regeneration efficiency than Type-I. Type II resins are not as efficient at removing silica from water and suffer more degradation at higher temperatures than Type-I, but where silica removal and temperature are not a problem, it is more efficient to use Type-II.
Regeneration
The process of regeneration for all ion-exchange units is similar and follows the description given for base-exchange softners. The resin is first back flushed, which removes any suspended matter filtered out of the raw water during operation, and also causes the resin to increase in appear volume.
Next the regenerant is admitted above the resin and flows downward through the bed. Finally the bed is rinsed again by downward flow to remove excess regnerant, the rinse water being run to waste until the quality is satisfactory unit to be returned to service.
PMI, NTPC 52 a) Cation Units
Sulphuric acid is usually used to regenerate cation-exchange resins as it is the cheapest acid commercially available. Since calcium sulphate, which may be formed as the resin is regenerated has a low solubility (about 0.2%) and may otherwise be precipitated on the resin, it is usually necessary to keep the strength of the sulphuric acid below 2%. For raw waters with very low calcium content, sulphuric acid strength up to 5% may be used. Table gives the maximum concentration of sulphuric acid recommended for the regeneration of the strong cation-exchange resin, Zeo-Karb 225.
In demineralization plants, the strong cation-exchange resins are normally regenerated with about 2% sulphuric acid but with weak resins a high level of regeneration can be achieved with more dilute acid and strengths of 0.8% to 1% are frequently used for these resins.
Hydrochloric acid may be used at almost any strength because there is no risk of precipitation. Strengths of up to 15% have been employed, but 2% to 4% is most common.
b) Anion Units
Weak basic anion-exchange resins can be regenerated with weak alkalis such as sodium carbonate. The regeneration process is in essence the neutralization of an acid and not true ion exchange, since it involves the conversion of the resin-acid complex to the free-base resin. Other alkalis which are used include sodium hydroxide and ammonia solution. Sodium PMI, NTPC 53 carbonate and sodium hydroxide are usually used as 4% solutions, but satisfactory regeneration can be achieved with more dilute solutions. If sodium hydroxide is used as the regenerant, the same solution can be employed to regenerate a strongly basic resin and a weak basic resin in series.
Table Maximum Strength of Sulphuric Acid for Regeneration
Strongly basic anion-exchange resins require a strong alkali to regenerate them to the hydroxyl (OH - ) form and 4% sodium hydroxide solution is normally used.
T o t a l
h a r d n e s s
%
o f
t o t a l
PMI, NTPC 54 c) Mixed Bed Units
In regenerating the mixed bed, the first state is to separate the two resins into two discrete zones. Fortunately the resins employed have different densities, so that the initial backwashing causes the resins to separate into two layers, the lighter anion resin being at the top.
To facilitate regeneration of the resins a central combined collector and distributor is provided at the interface of the two layers. Caustic soda is introduced at the top and the spent regenerant runs to waste from the central collector. The rinse water follows the same path.
Acid is then introduced at the central distributor, passes down through the cation resin and is run to waste from the bottom of the unit. This is followed by rinsing as for the anion resin. Finally the two resins are again intimately mixed by passing low-pressure air upwards through the unit and after a final rinse it is again ready for service.
The efficiency of regeneration in a mixed bed is never as high as in separate units, since separation of the two resins is never quite complete and there will always be some interference at the interface. For this reason a mixed bed unit requires more resin than two separate units and the running cost is higher but as mentioned earlier it can produce almost complete de-ionisation of the input water.
d) Resin Transport Regeneration
In water treatment demineralization plants, the water flow rate through the resin bed, the depth of resin and the size of the resin granules employed, are mainly determined by the kinetics of the ion-exchange reactions. The design parameter chosen ensure that, with a raw water having a T.D.S. of PMI, NTPC 55 perhaps several hundred ppm, virtually complete demineralization results. A water treatment plant for a 2000 MW station will have a through put of about 45,000 gal/h and units to handle this through-put with perhaps two complete demineralization streams operating in parallel can be designed to acceptable dimensions.
Mixed bed units, or sometimes cation-exchange units are also used to remove traces of contaminants (metal corrosion products silica and cooling water leaks) from feed water particularly in feed systems associated with once-through boilers. This is one method of condensate polishing. The condensate polishing ion-exchange units form an integral part of the feed system and may have to handle from 25% to 100% of the full feed water flow.
Fig No.: 7 PERMIT MIXED BED.
PMI, NTPC 56 For a 500 MW unit this will mean treating between 80,000 and 320,000 gal/h and with the flow rates normally used in ion exchange, would require a number of ion-exchange units operating in parallel:
These condensate polishing units have only to remove traces (less than 1 ppm) of contaminants from the feed water and reduce the concentration of these contaminants to an acceptable level. From this aspect, therefore, much higher water flow rates through the resin bed are acceptable and hence fewer units are required. With normally designed units, particularly with mixed beds, the laterals and distributors necessary for regeneration of the resin impose a serious resistance to water flow, but they must be sufficiently robust to withstand the pressure acting on them. These engineering considerations impose an upper limit on flow rate which is below that imposed by ion-exchange kinetics.
To achieve even higher flow rates, it has been necessary to simplify the internal design of the units so as to minimize resistance to water flow and with these simplified units regeneration in situ is no longer possible.
Regeneration of the exhausted resin is therefore carried out in a separate unit of normal design, to which the resin is transferred hydraulically. This process is known as resin transport regeneration.
The water flow rates acceptable for a mixed bed unit with different methods of regeneration are given in Table.
PMI, NTPC 57 Acceptable Water flow Rate for A Mixed Bed Unit with Differing Methods of Regeneration
------------------------------------------------------------------------------------------------------------ Mixed Bed Units Flow Rate gal/F ------------------------------------------------------------------------------------------------------------ 1. Make up water treatment plant 4 to 7
2. Condensate polishing with in situ regeneration upto 25
3. Condensate polishing with External regeneration upto 60 ------------------------------------------------------------------------------------------------------------
The use of resin transport regeneration in condensate polishing units has an additional advantage in that there is no longer a risk of strong regeneration accidentally contaminating the feed system.
e) Regeneration Equipment
The principal reagents used for regeneration ion-exchange resins are sodium hydroxide, sulphuric acid and sometime hydrochloric acid. Caustic soda used in other kinds of water treatment is normally purchased in solid form (anhydrous flakes) but for the large quantities used in demineralization plants it is usually more convenient to purchase it as a 46% solution liquid caustic soda.
Sulphuric acid is purchased as a 96% solution and at this strength it can be safely stored in mild steel vessels.
Hydrochloric acid is supplied as a 28% to 32% solution the lower strength being normally supplied during summer months in order to reduce the PMI, NTPC 58 nuisance due to hydrochloric acid vapour. It is very corrosive towards mild steel and all steel surfaces must be protected with a suitable lining as rubber.
The storage tanks are surrounded by bund walls, which is formed in collecting tank sized to contain the whole contents of the storage vessel, in the event of a major leak developing. Storage tanks are lagged proved with means of heating to ensure that the chemicals do not freeze during periods of low ambient temperature. Of the three principal regenerants mentioned, only liquid caustic soda and sulphuric acid are at all likely to give trouble by freezing at winter temperatures, and figures show freezing points at various concentrations of these chemicals.
PMI, NTPC 59 Using these liquid regenerants, the regeneration equipment employed is illustrated in figure-9. It consists of a closed measuring tank into which the concentrated regenerant is drawn from the bulk storage tank by suction. The measured quantity of regenerant is then run into tank to obtain a suitable strength. Finally the regenerant is further continuously diluted to the required strength and introduced into the unit to be regenerated by means of water ejectors. Whenever possible, the use of pumps to handle regnerant chemicals is avoided, because it is considered safer to avoid the pressurization of these potentially dangerous liquids.
Demineralisation Processes
The type of demineralization process chosen for a power station will depend on four main factors:
(a) The quality of the raw water PMI, NTPC 60 (b) The degree of de-ionisation required, that is, the quality of the final feed water.
(c) The capital cost
(d) The running cost
Although a large number of different processes is possible, the nine schemes illustrated in Figure represent some that are commonly in use in power stations. Schemes 1 to 4 will produce demineralised water suitable for low-or medium pressure plant (up to say 600/in 2 ) and will have low dissolved solids content, low carbon dioxide and silica less than 0.1 ppm. At the level of regeneration normally employed, up to 2 ppm of salts, particularly sodium salts may pass completely through the cation units without being exchanged. In the strongly basic anion-exchange units the PMI, NTPC 61 anions will be exchanged for hydroxyl ions so that the final treated water will contain a few ppm of sodium hydroxide and will therefore be alkaline.
Schemes 5 to 9 are used, where virtually de-ionised water is required, that is water having the following characteristics:
T.D.S. less than 0.5 ppm. Conductivity less than 0.5 micromho/cm. Silica less than 0.05 ppm. For modern high-pressure stations, a plant based on scheme 6 will commonly be used.
PMI, NTPC 62 Back Washing
Usually done after every service cycle, is one of the most important operations. Although feed water pre-treatment is designed to remove vast majority of suspended solids and colloids, trace quantities invariably pass into the ion exchange units. Resin fines and fragments also require removal suspended and colloidal matter are likely to accumulate at the beds upper surface, and possible on the bed surfaces throughout the bed. Film of this type will lead to channeling at points of flow break-through, poor kinetics and large pressure drops.
Proper back washing involves expansion of the bed, so each resin article is in the motion. Sufficient flow rate must be available for this purpose.
Typical Back Wash Flow Rates
2-4 gpm/ft 2 - For anions 5-10 gpm/ft 2 - For cations Duration - Usually 10 minutes
PMI, NTPC 63 Cation
Back Wash flow rate - 40M 3 /hr (1/2 of the normal flow rate). Duration - 5 Minutes Type of Water - Filtered Water
Anion
Back Wash flow rate - 20M 3 /hr (1/3 of the normal flow rate). Duration - 5 Minutes Type of Water - Filtered Water
Mixed Bed
Mixed bed differs from that of the single resin bed primarily with regard to the regeneration step. The key to the process is back wash, which serves to classing the two resin components the lighter anion resin forming at the top, the heavier cation resins remains at the bottom; when done properly, a clear and level interfacing is formed between two layers. An interface collector is incorporated at this point.
Back Wash flow rate - 18M 3 /hr Duration - 3 Minutes Type of Water - D.M. Water
2. Setting
Before regenerating, the bed is allowed to settle to its original volume to provide compactness necessary for proper chemical contacting.
PMI, NTPC 64 3. Regeneration
Dilute acid is applied to Cation exchangers and caustic to the anion exchangers. HCl is the usual acid choice, with concentration ranging from 2-10% Resin quantity 7400 Lit/Unit.
4. Cation
Type of Resin - 10 NAC C242 Capacity per regent - 1080 M 3
Period between regeneration - 18 Hrs. Regenerant Qty - 1931 Kg. (30% HCl) Final Con - 5% W/V
Anion
For regenerating anion exchange resin, caustic usually is applied as 5% solution.
Resin - IONAC A 440 Qty of Resin - 6630 Lit/Unit Reagent - NaOH 100% NaOH reqd./regeneration - 465 Kg. Final Conc. Of NaOH - 5%
5. Rinsing
Rinse water of likely quality is used to remove regenerant when process is completed-first at slow rate and then at fast rate.
PMI, NTPC 65 Volume used
For cation - 30-40 gallon/ft 3
For anion - 40-400 gallon/ft 3
Cation
Type of water - Filtered Water Slow rinse rate - 19.5 M 3 /m. Duration - 15 mts. Fast rinse rate - 65 M 3 /hr. Duration - 35 mts.
Anion
Type of water - Degassed Water Slow rinse rate - 15 M 3 /hr. Duration - 20 mts. Fast rinse rate - 65 M 3 /hr. Duration - 50 mts. Final value after rinsing silica - 0.5 ppm. Conductivity - Less than 20 mho/Cm
Mixed Bed
Regeneration quantity - 1050 lit. Anion - 1050 lit. Capacity per regeneration - 7560 M 3
Period between regeneration - 126 hrs. Qty. for regenerant
PMI, NTPC 66 HCl - 145 Kg. 30% HCl NaOH - 128 Kg. (100%)
Final Conc. - 16 Kg. 100% NaOH Dilution Tank - Final conc.
Hcl - 30% - 5% NaOH - 48% - 6%
Regeneration steps for cation, Anion & Mixed bed exchangers are shown below with the help of following schematic diagrams.
PMI, NTPC 67 Mixed Bed Blower (Plant Technical Data)
------------------------------------------------------------------------------------------------------------ Nos. off -2 Suction capacity 228M 3 /hr. Nos. operating 1 Discharge pressure 0.5 Kg/CM 2 . ------------------------------------------------------------------------------------------------------------ Blower Details Motor Details ------------------------------------------------------------------------------------------------------------ Type/Stage Single KP/KW - 10/75
Construction ---------------- RPM - 1500 Syn.
Material - C.I. IS219 Gr. Construction - Hor. Foot 20 Alloy Steel mounted
Make - Kay Engg. Works Frame size - 132 M
Model - 65 Make - Siemens ------------------------------------------------------------------------------------------------------------ ------------------------------------------------------------------------------------------------------------ Accessories Instruments Pressure Gauge ------------------------------------------------------------------------------------------------------------ 1) Suction strainer Type Burdon
2) Silencer Location Delivery
Nos. (Tag) 1047: 1048
Range 0-1 Kg/CM 2 ------------------------------------------------------------------------------------------------------------ PMI, NTPC 68
PMI, NTPC 69 3. Combating Corrosion
Introduction
The trend in India is now for higher pressure and higher capacity boiler in power Generation. Number of 200 & 500 MW units have been commissioned in India and very soon 660 MW units are going to be commissioned.
The operation of these units under such high pressure and temperature demands much higher standards of steam and feed water purity. The problem of maintaining the quality of feed and Boiler water can be well understood by the following example:
If one ppm of dissolved solids enters in each 1,000,000 lb. of feed water, one pound of dissolved material enters the boiler each hour. Since 999,000 of that water is removed as steam (pure water vapour), one pound of solids is left behind in the boiler in each hour of operation.
Obviously, if we continue to operate in this way, the solid content of the boiler water would keep on increasing. PMI, NTPC 70
Let us study steam-water cycle. The feed water is made up of condensate and make up water. It is essential to have good water treatment plant. Consumption of make up water used per unit generated is a good index of the state of maintainability of plant and should be closely monitored:
Various constituents in water in accordance with the trouble, they create are classified as:
In past, the water chemistry was not given due consideration. Higher operation reliability and hence maximum availability can be achieved by close and regular monitoring of water/steam circuit. Two possibilities to be considered are:
A. The penetration of unwanted substances into steam/water circuit. PMI, NTPC 71 B. The formation of unwanted substances within the circuit. The unwanted substances depend partly on the type of the boiler.
Main Aims of Monitoring the Steam/Water Ckt.
- To keep track of the performance of individual part of the plant and hence the plant as a whole in order to verify that specified values are maintained.
- Prevention of failure by early diagnosis.
- To achieve a high standard of reliability and maximum plant availability.
- In the event of a failure, to ascertain the cause after the event with the help of recorded data.
Plant availability is the function of the quality of working medium viz. Water/Steam. The analysis of water/steam is of importance due to following reasons:
- Inhibitation of corrosion.
- Prevention of deposits on boiler tubes, superheater tubes and turbine blade.
- Ability of condenser material.
The choice of parameters to be monitored, depends on the ground of operation safety and plant reliability.
PMI, NTPC 72 Importance of Individual Parameter: (Dissolved oxygen & Hydrazine measurement in feed water).
Corrosive substances are in the form of dissolved gases such as carbon dioxide and oxygen are dissolved in the feed water by operation and unavoidable contact with atmosphere.
Solubility of oxygen decreases with an increase in water temperature, the most common method of removal is the deaeration of water.
Dissolved oxygen hastens corrosion by a number of reactions depending on conditions.
The following is a typical type presentation of an important phase of iron-water corrosion accelerated by oxygen under alkaline or neutral conditions. Iron in contact with water exerts a certain solution pressure and sets up the anodic half reaction.
Fe ----------------- Fe 2 2C
This ceases after a certain potential is reached. However oxygen can react with water to give OH ion at the cathode.
O 2 + 2H 2 O + 4e ------------------ 4 OH
The Fe -2 + OH ---------------- Fe (OH) 2
The initial reaction then proceeds further. The electro chemical reaction can be summarised.
2Fe + O 2 + H 2 O ----------------- Fe (OH) 2
PMI, NTPC 73 Corrosion can be stopped by the removal of dissolved oxygen.
Deaeration in the condenser
Steam entering the condenser contains air and incondensable gases mainly due to in-leakage at parts of the system operating below atmospheric pressure. Make-up water, vents and drains to the condenser are other sources of incondensable gases which must be removed for the condenser to function.
The primary duty of the condenser is to condense the exhaust steam leaving the LP turbine, by passing it over the condenser tubes which are cooled by CW. As the steam is condensed it undergoes a massive reduction in specific volume and a vacuum is created. In condensing the steam the condenser also acts as a deaerator liberating incondensable gases. Unless these gases are removed they will blanket the condenser tubes and progressively impede the heat transfer process, which in turn will result in a deteriorating vacuum.
Air extraction equipment is installed to continuously remove these gases. Make- up water, in the form of a spray, is fed into the condenser steam space above the water level and the fine droplets expose a greater surface area to the vaccum resulting in more efficient deaeration. With good condenser deaeration the condensate will have dissolved oxygen content of less than 0.015 mg Kg -1
If any air leaks are present in the condensate pipe work or at the extraction pump glands, the dissolved oxygen content will increase and it is important that this part of the system is also maintained in an airtight condition.
Deaeraton in the Deaerator and LP Direct contact Heaters
Oxygen is least soluble in water at boiling point and the function of the deaerator and LP Direct contact Heaters is to raise the feed water temperature by mixing PMI, NTPC 74 with bled steam.
The feed water is finely divided by sprays and readily releases its oxygen which, together with other non-condensible gases, are vented to atmosphere or to the condenser. An efficient Deaerator can reduce the concentration of dissolved oxygen in the feed water to less than 0.005 mg kg -1 .
Operation Aspects
Mechanical deaeration alone cannot maintain the oxygen or carbon dioxide concentrations at acceptable levels in the feed water of a modern plant. Generating units which operate on a two shift basis are very prone to corrosion from dissolved oxygen and carbon dioxide. When the unit is offload, the water in the system cools down and tends to absorb air. Also, air fills the steam spaces as the vacuum is broken and contaminates the water.
As a result, when the unit is started-up, the feed water reserve in the system has a high concentration of dissolved oxygen and carbon dioxide making ideal conditions for corrosion. This can be minimized by keeping the deaerator water at boiling temperature using the off-load deaerator heaters.
Feed heaters with 70/80 cupro/nickel tubes suffer particularly from corrosion due to oxygen with regular two shift operation of the unit. This is known as exfoliation because the corrosion products on the tubes form as thin layers of oxide which flake off as the temperature changes. Exfoliation is much less pronounced when 90/10 cupro/nickel tubes are installed in the system.
Filling the system with nitrogen, to keep the air out, as the vacuum is broken has also been used with varying success. However, the difficulty of excluding all the oxygen from such large space and the cost of nitrogen, has led some power PMI, NTPC 75 stations to seal only their high pressure heaters where the corrosion is most serious.
Chemical Removal of Oxygen
Corrosion by oxygen and carbon dioxide in the feed lines and economizer can cause small amounts of corrosion debris to be carried into the boiler and be deposited on the tube surfaces. These deposits than act as potential areas for further corrosion. In the control of corrosion certain chemicals are added to the feed water to remove or neutralize gases that have entered the system and escaped mechanical deaeration.
Originally oxygen was removed from feed and boiler waters by adding sodium Sulphite (Na 2 SO 3 ) in the form of white crystals or Powder. This chemical has now been superceded because, whilst removing oxygen, it increases the total dissolved solids in the water.
2Na 2 SO 3 + 0 2 ------------------------- > 2 Na 2 SO 4
SODIUM OXYGEN SODIUM SULPHATE SULPHITE
Modern practice is to use hydrazine (N 2 H 4 ) and it reacts as follows:
N 2 H 4 + O 2 ------------------------ > N 2 + 2H 2 O HYDRAZINE OXYGEN NITROGEN WATER (Liquid) (gas) (Gas) (Liquid)
From the above chemical equation we can see that no solids are produced, in fact the product nitrogen and water are completely harmless. Hydrazine, therefore, is the ideal chemical for removing oxygen and its only disadvantage is PMI, NTPC 76 that it is expensive. Hydrazine, is a toxic substance and the approved protective clothing must be worn when it is handled.
Any surplus hydrazine that remains after removing the oxygen will decompose to give ammonia (an alkaline gas) and nitrogen.
3N 2 H 4 ----------------------- > 4NH 3 + N 2
HYDRAZINE AMMONIA NITROGEN (Liquid) (gas) (gas)
The significance of the ammonia and the fact that it is alkaline will be shown when the neutralization of carbon dioxide is studied. GOM72* recommends that for trouble free running the maximum concentrations of dissolved oxygen in water are as follows:
Extraction pump discharge 0.015 mgkg -1
Economizer inlet 0.005 mgkg -1
Neutralization of carbon dioxide
When acids and alkalis were discussed earlier in the lesson, we noted that carbon dioxide was an acidic gas and could form carbonic acid with water. We also saw that acids could be neutralized by alkalis.
Carbon dioxide is an acidic impurity in feed water, and its corrosive nature can be minimized by neutralizing it with an alkali such as ammonia.
2NH 3 + CO 2 + H 2 O ---------------- >(NH 4 ) 2 CO 3
AMMONIA CARBON WATER AMMONIUM CARBONATE DIOXIDE (Neutral) (Acidic) PMI, NTPC 77 Compounds called amines which decompose to give ammonia can also be used to neutralize carbon dioxide. They are known as neutralizing amines and can, under certain circumstances be more efficient than ammonia.
Cyclohexvlamine and morpholin are examples of neutralizing amines but are now rarely used because in most cases there is no advantage compared to ammonia and they are more expensive.
To summarise, feed water is dosed with sufficient hydrazine remove oxygen, any surplus will also produce ammonia and neutralize the carbon dioxide present. If the ammonia is insufficient then additional ammonia is introduced to maintaining pH of between 8.8 and 9.2 in the feed water.
Monitoring and Analysis of Feed Water
We have so far examined the preparation of purified and conditioned water acceptable as boiler feed. However contamination can still occur through system defects. Thus an essential part of the control of corrosion and scale formate is continuous monitoring of the quality of the condensate, feed water and boiler water, to ensure the water throughout the system contains the correct amount of treatment chemical and the minimum of corrosive impurities.
The important instruments include, dissolved oxygen recorder on-line pH meters, ammonia analysers, conductivity meters and sodium monitors. Concentrations of elements such as iron, copper and nickel (often referred to as crude) are also measured in modern plant to indicate the rate of corrosion of the system. These instruments are often on-line and known as auto-analysers.
If hydrazine is added to feed water primarily to remove oxygen it is possible that enough will remain to neutralize the carbon di-oxide also present in water. If the PMI, NTPC 78 hydrazine does not provide enough ammonia, more is added by chemist, after water has been analysed by the chemist.
It is a very important point to remember that feed water should be dozed with hydrazine (if necessary ammonia as well) to prevent any attack by acidic carbon dioxide & others.
In most boiler systems, the pH is maintained on the alkaline side, by adding chemicals, at about 8.8 to 9.5, this prevents acidic attack on the system tubes and pipes, so that pH measurement is very critical.
It is normal practice to use copper alloy tubes in the condenser and L.P. Heaters and Carbon steel in H.P. Heaters. The carbon steel required a mildly alkaline pH of about 9.5 while non-ferrous materials last longer between pH of about 8.8 9.0. Thus for system with both ferrous and non-ferrous materials, a compromise pH of 9.2 is usually recommended. A close control of pH is essential to avoid acidic attack on ferrous components or alkaline attack on non-ferrous components. However, if stainless steel (rather than carbon steel) tubes are used in Feed water Heaters, as experience has shown operation can be at pH compatible with copper base alloys.
Following table gives the relationship of NH 3 content water and its corresponding pH.
PMI, NTPC 79 7 Ammonia and 2 Hydrazine are mixed with water in two solution preparation cum feed tanks. Weak ammonia hydrazine solution are pumped to feed water suction line through hydrazine dosing pump (2 Nos.) These Candy K pumps are metering pumps of an accurate variable strokes positive displacement type which are capable of meeting a wide variety of pumping requirements.
Rotation of the stoke adjusting but varies the delivery setting of pump and this can be carried out with pump operating or at rest.
Hydrazine dosing is required to be done continuously. Quantity is to be adjusted as advised by the chemist. pH meter installed at various places, give indication a steady predetermined value, the chemist is assured that the correct amount of chemicals are added to the system to maintain optimum alkali condition.
By measuring the concentration of metals in water such as iron, copper and nickel, an indication is contained of corresponding products coming from plant manufacturers from these metals.
Filling amines are sometimes used in feed water treatment. They are octadecylamine and other decylamines. When added to feed water, form a thin protective skin on the metal surfaces of feed waters. The metal is then protected from attack, not only from carbon dioxide, but from all corrosive gases; because the film is very thin, it does not have an adverse effect on heat transfer. Filming amines are therefore very useful in the protection of feed system, although they nothing to remove corrosive gases from water.
The following are the recommended feed water quality for H.P. Drum type boilers.
PMI, NTPC 80 Recommended Feed Water Limits
Drum pressure kg/CM 2 (g) 61-100 101 & above Hardness Nil Nil pH at 20 O C (Copper Alloy 8.8-9.2 8.8-9.2 preboiler system) PH at 25 O C (*) 9.0-9.4 0.0-9.4 Oxygen max mm ppm 0.007 0.007 Total iron maximum ppm 0.01 0.01 Total copper maximum ppm 0.01 0.005 Total CO 2 Nil Nil Total silica 0.02 0.02 Hydrazine residual ppm 0.01-0.02 0.01-0.02 Oil Nil Nil
* (Not copper alloy preboiler system).
PMI, NTPC 81 4. Boiler Water Treatment
The solid impurities that are likely to enter a boiler can originate from one or more different sources.
1. Condenser leak 2. Faulty demineralization 3. Corrosion products from an improperly treated feed system
In all cases the solid impurities that enter the boilers water probably contain calcium and magnesium hardness salt. Chlorides and another compound, silica or silicon dioxide (SiO 2 ) which we have not yet mentioned.
Condenser leaks Evaporator Carry-over Faulty demineralization Contamination of the clean drains Recovery system Corrosion products from the feed system
In all cases, except the latter, the impurities that enter the boiler water probably contain calcium and magnesium hardness salts, chlorides and silica.
When discussing the hardness of water earlier, we mentioned that scale on a boiler tube would seriously affect the heat transfer properties and possibly lead to failure by over-heating. The impurities mentioned above will have detrimental effects other than scale formation and these are:
On load corrosion Carry over causing superheater and turbine deposits PMI, NTPC 82 The chloride impurities and in particular magnesium chloride chemically react with the water, in a process called hydrolysis to form hydrochloric acid.
MgCl 2 + H 2 O ------------------ >2 HCl + MgO Magnesium Water Hydrochloric Magnesium Chloride Acid Oxide
Acids are undesirable in boiler water because they attack the metal surfaces. This attack is known as acidic chloride corrosion. To combat this acid attack the boiler water is kept in a slightly alkaline condition (pH of 9-10) by dosing with sodium hydroxide (NaOH). This alkali will neutralize any acid produced by hydrolysis of chlorides. In recent years it has been found that sodium hydroxide itself can concentrate in the boiler and cause caustic corrosion. A fine balance is therefore necessary to prevent on the one hand acidic corrosion and on the other caustic corrosion.
Acidic chloride corrosion is often accompanied by hydrogen embrittlement. When an acid attacks metal hydrogen gas is produced and in a boiler the hydrogen reacts with the carbon in the boiler steel weakening the structure and producing methane as a by-product.
2H 2 + C < ================== > CH 4
Hydrogen Carbon Methane In steel
Eventually the hydrogen diffuses through the steel below the corrosion pit and a brittle fracture occurs.
Acidic chloride and caustic corrosion are usually referred to as on load corrosion because the very dilute solutions of chemicals and impurities in boiler waters can reach dangerously high concentrations whilst on load. This effect usually takes PMI, NTPC 83 place in areas of high heat transfer which are subject to poor circulation in the water circuit. Such areas are usually found at horizontal or inclined surfaces or at flow disturbances such as bends or welds. In these areas are usually found at horizontal or inclined surfaces or at flow disturbance such as bends or welds. In these areas, the tube surface is folded by porous deposits of iron and copper oxides carried forward from the feed system. These deposits prevent mixing and wick boiling takes place because the liquid is felt to the surface through the small pores in the deposit similar in action to a wick. Steam escapes through their larger lose leaving the salts behind enabling them to concentrate.
A similar effect occurs at boiling surfaces containing a narrow crevices in which the solution can concentrate. Crevices may be found at poor welds or at tube/tube plate joints. Although the addition of chemicals can neutralize the effects of impurities it is not necessarily the complete answer. For example, should a condenser leak occur there will be a massive rise in impurities in the boiler feed water. Adding chemicals will help to alleviate the condition but it must be accompanied by blow down to prevent an increase in dissolved salts in the boiler water which would cause carry over. When these measures can no longer contain the concentrations within the limits given in GOM 72 for the particular plant then the defective condenser must be isolated (or the unit taken out of service) and repairs carried out.
Control of carry-over to superheater and turbine deposits
When water is converted to steam in a boiler, a small proportion of any impurities in the water will be carried forward with the steam and deposited in the superheater or on the turbine blades by one of two mechanisms. These are:
a) Physical carry-over whereby small droplets of impure water escape through the steam scrubbers.
PMI, NTPC 84 b) Some impurities become more soluble and are carried forward as the saturation temperature of the steam increase with pressure.
Therefore on modern high pressure plant even with well designed drum internals and good operation it is imperative that the dissolved solids content of the water is as low as possible. Even very small deposits of sodium hydroxide and sodium chloride cause stress corrosion in austenitic steels in superheater and may lead to failure off the tubes.
Silica Control
One of the soluble impurities carried forward in the steam is silica (SiO 2 ). Silica is more soluble in steam than other impurities and when it deposits on turbine blades it is extremely difficult to remove. This effect is so pronounced that special precautions have to be taken. Fig. shows these plotted against different boiler pressures. These limits are controlled (a) by preventing dust particularly pfa, entering parts of the unit when opened up during survey or inspection and (b) monitoring and controlling silica at the outlet from the demineralization plant. Should the silica limits to reach they must be reduced by lowering the boiler pressure and blowing down.
PMI, NTPC 85
Austenitic (stainless) steels contain a higher percentage of chromium (ie., about 18%) than ferritic steels used elsewhere in the boiler. They are used in the high temperature zones because they have a longer life.
Tri Sodium Phosphate Treatment
Tri Sodium phosphate (Na 3 PO 4 ) often called TSP, is added to the water of many boilers, mainly low pressure below 62 bar (900lb/in) to combat the effects of scale forming calcium or magnesium salts, although most calcium and magnesium salt form hard scales. Therefore by the addition of TSP the salts are converted into calcium and magnesium phosphates and soft sludges are produced which can be removed by blow down.
3CaSO 4 + 2NA 3 PO 4 ---------------- > Ca 3 (PO) 3 + Na 3 SO 4
Hardness Trisodium Phosphate Soft Sludge Sodium Sulphate PMI, NTPC 86 Another useful property of trisodium phosphate is that it produces small quantities of sodium hydroxide (NaOH) which helps to control the alkalinity of the boiler water. Also disodium phosphate is formed and is available to produce phosphate sludge.
Na 3 PO 4 + H 2 O =========== > NaOH + Na 2 HpO 4 Trisodium water Sodium disodium phosphate Hydroxide
Therefore the alkalinity mentioned under sodium hydroxide treatment above, can be achieved and maintained by using trisodium phosphate. This is the reason that many countries use TSP in higher pressure boilers. It acts as a reserve to correct a rise in acidity without the necessity to add sodium hydroxide with the associated dangers of caustic corrosion. The main drawback of TSP is its comparatively low solubility which means it is much more prone to concentration effects than sodium hydroxide a term used to describe the phenomenon whereby the TSP disappears from the water whilst the boiler is steaming, only to re- PMI, NTPC 87 appear as the load is reduced. This is attributed to the fact that the TSP concentrates in various sites on the inside surfaces of the tubes and solid deposits form. Eventually all the TSP is deposited. As the rate of evaporation is reduced during de-loading the TSP redissolves in the water.
Recommended Boiler Water Limits ------------------------------------------------------------------------------------------------------------ Drum Pressure Kg/cm 2 (g) 61-100 100-above ------------------------------------------------------------------------------------------------------------ 1. Total dissolved solids Not more than 100 Not more than 100 ------------------------------------------------------------------------------------------------------------ 2. Phosphate residual ppm 15-20 5-10 ppm ------------------------------------------------------------------------------------------------------------ 3. pH 9.8-10.2 9.4-9.7 ------------------------------------------------------------------------------------------------------------ 4. Silica-To be controlled on the basis of silica in steam in the range of 0.02 pm leaving the drum.
Treatment for Once-through and Supercritical Boilers
The requirements for boiler water quality control differ in these boiler compared to drum type boilers and includes:
1) In a drum boiler the quality of the water can be monitored and the concentrations of impurities can be controlled by adding chemicals and blowing down to waste. Once-through and supercritical boilers do not have a drum, so boiler water sampling and control is not possible and the only option is to analyse and control the feed water at the boiler inlet.
2) In drum boilers the tube wall surfaces are usually wet. If dry spots occur then high concentrations of salts will form at the periphery. In a once PMI, NTPC 88 through boiler there will be regions where dry and wet walls exist by design. Thus the feed water to such boilers must be of exceptionally high quality.
3) Concentrations of normally safe materials in sub-critical boilers must be eliminated in the once through boiler with no blow down everything entering will either deposit or pass out with the steam to the turbine.
In case of the supercritical boiler, the problems of feed water treatment are accentuated by the fact that at critical pressure the solubility of dissolved salts is the same in the steam as in the water. There is no physical separation and impurities in the water may again pass through with the steam to be deposited in the superheater and on the turbine blades.
If deposition occurs, it can result in an increased pressure drop across the boiler. This will reduce output efficiency and affect heat transfer necessitating shut down to chemically clean the plant.
Also solutions of other, possibly corrosive, materials will concentrate and corrode the boiler. If these are carried forward to the turbine they can deposit and lead to loss of efficiency or possibly cause cracking of the special alloy steels used in turbine rotors.
For once-through boilers only volatile additives can be used for feed water dosing. These are normally ammonia and hydrazine. This is known as zero solids treatment or all volatile treatments (AVT). In order to achieve the high quality feed water required for once through boilers, it is necessary to polish the whole of the condensate continuously. This is particularly important at sea water stations where the ingress of salt from condenser leakage would cause rapid boiler corrosion.
PMI, NTPC 89 Condensate polishing
Unit make up water is typically between 1 and 3% of the maximum boiler evaporation capacity. The feed and condensate systems contain such a vast quantity of water that if contamination occurred the make-up water would do little to correct the impurity of the feed water.
When a turbine is started up, contamination of the feed water can occur if corrosion products are carried forward. The contaminant can be both suspended and soluble. To remove contaminants during start up, a method adopted to dump the condensate after the extraction pump. The disadvantages of this method are the waste of condensate and the time limit imposed by the amount of clean water reserve available in the de-aerator. Once the de-aerator water is used, dumping has to cease although there may still be some impurities in the condensate system.
Some of the earlier condensate polishing units incorporated a filter to remove crud but the filter proved to be unnecessary since the mixed bed resin was equally capable of performing this duty. The filter was omitted on subsequent polishing units which were therefore called naked mixed beds.
Condenser Leak Detection If a leakage of CW into the condensate occurs it is essential that an immediate indication is given so that the necessary action is taken to limit the unwanted impurities entering feed system.
The normal method of detecting condenser leaks is to monitor the conductivity of the condensate.
PMI, NTPC 90 Conductivity as a measurement is proportional to resistance equivalent to reciprocal megohms/cm or dionic units and the units are expressed in microsiemens/cm.
Pure water has a low conductivity because only a few of the H 2 molecules of water dissociate into cations and anions. Condensate should give an indication of less than 0.3 microsiemens/cm. On the other hand salt water will give a conductivity indication of about 50000 microsiemens/cm.
The conductivity cell used to measure water purity consists of two electrodes immersed in the water. The standard cell electrodes are each 1 cm square placed 1 cm apart to give conductivity units in mocrosiemen/cm. The current is conducted between the electrodes by the ions of the salts in the water. The more ions that are present the higher the conductivity indication.
The cell normally contains three ring-like electrodes equally spaced within an epoxy resin moulding which is accurately made so that the conductivity of a precise volume of solution is measured. Condition through the solution takes place between the central electrode and the two outer electrodes which are connected in parallel and act as one.
Conductivity is increased not only by unwanted impurities but also by dosing chemicals and a false reading of the level of contamination would be given if the conductivity cell was used alone. Thus the cation exchange resin column as well as amplifying the conductivity indication is essential to remove dosing chemicals such as ammonia and hydrazine allowing the true level of contamination to be measured.
The most recent method of condenser leak detection is to measure the concentration of sodium in the condensate which is as much as 100 times more PMI, NTPC 91 sensitive than conductivity test. Sodium can be detected and measured at much lower levels than would be indicated by a conductivity meter.
Recommended Limits for Water Steam and Super Heated Steam for 200/210 MW Sets of N.T.P.C.
Suppliers: B.H.E.L. and Bredo Thermo Meccanica (ANSALDO)
S.H. Steam 540 535 535 540 540 540 Temp. ( O C) -----------------------------------------------------------------------------------------------------------
PMI, NTPC 92 (A) Feed Water (Sample from Economiser Inlet) ----------------------------------------------------------------------------------------------------------- S.No. Characteristic Limit Freq. of Remarks Test ---------------------------------------------------------------------------------------------------------- 1 2 3 4 5 ----------------------------------------------------------------------------------------------------------- 1. pH at 25 O C i. 8.8-9.0 once/ i. If F.W. Heaters ii. 9.0-9.2 shift are of copper based alloy (See note 1) ii. If heater are of steel 2. Specific conductivity 0.3 once/ at 25 O C in s/cm) shift after passing through cation exchange in H +
form. 3. Total Hardness B.D.L. once/ B.D.L.Below Detect- (ppm as CaCO 3 ) shift able Limit 4. Dissolved Oxygen 0.007 once/ If in line instrument ppm (see note 2) day is not available Once/ If in-line instrument Week is available. Checkt he Instrument Calibration in mid Week. 5. Residual Hydrazine 0.02 Once/ (ppm) shift 6. Silica (ppm) 0.02 Once max. shift 7. Chloride (ppm) B.D.L. Once/ shift 8. Total Iron (ppm) 0.01 Once/week 9. Oil (ppm) B.D.L. Once/week 10. Copper (ppm) 0.005 Once/week ------------------------------------------------------------------------------------------------------------ PMI, NTPC 93
(B) Boiler Water (Sample from C.B.D. Line) ----------------------------------------------------------------------------------------------------------- S.No. Characteristic Limit Freq. of Remarks Test ----------------------------------------------------------------------------------------------------------- 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 9.0-9.5 Once/ shift 2. Specific conductivity 25 Once at 25 O C ( s/cm) shift 3. Total Dissolved solution 5 Once (ppm) shift 4. Phosphate (as ppm PO 4 3- 2-4 Once/ Any or mixture of shift tri, di or Mono sodium phosphate sodium Hexa- phosphate can be used. pH control by concurrent Tech.) 5. Total hardness B.D.L. Once/ (as ppm CaCO 3 ) shift 6. Free hydroxide B.D.L. Once (as ppm CaCO 3 ) shift by stremtium chloride method 7. Silica (ppm SiO 2 ) 0.4 (BTPS) Once/ shift 0.4 (SSTPP) Once shift 0.25 (KSTPP RSTPP) Once/ Shift 8. Chloride (ppm) B.D.L. Once/ shift 9. Sodium (ppm) Correspond Once/day ing to Na 3 PO 4
etc. addition
PMI, NTPC 94 (C) Steam & S.H. Steam (Samples from drum outlet & main steam line respectively) ------------------------------------------------------------------------------------------------------------ 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 9.0-9.2 Once/ shift 2. Specific Conductivity 0.3 Once/ Once/day if in-line at 25 O C (us/cm) shift instrument is available. (after passing through cation exchange in H + form) 3. Silica (ppm) 0.02 (Max.) Once/ shift 4. Total Iron (ppm) 0.01 Once/week 5. Copper (ppm) 0.001 Once/week 6. Sodium (ppm) 0.015 Max. Once/day 7. Ammonia (ppm) 0.5 Once/ shift ------------------------------------------------------------------------------------------------------------
PMI, NTPC 95 (D) Return Condensate (Sample from Condensate Extraction pump discharge) ------------------------------------------------------------------------------------------------------------ 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 9.0-9.2 Once/ shift 2. Specific conductivity 0.3 Once/ at 25 O C ( s/cm) shift (After passing through cation Exchanger in H + form) 3. Dissolved Oxygen 0.02 Once/day (ppm) 4. Silica (ppm SiO 2 ) 0.02 Max. Once/day 5. Total Hardness B.D.L. Once/day (ppm CaCO 3 ) 6. Free Ammonia (ppm) 0.5 Once/day 7. Chloride (ppm) B.D.L. Once/day 8. Total Iron (ppm) 0.01 Once/week 9. Copper (ppm) 0.001 Once/week 10. Sodium (ppm) 0.015 Continuous (Max.) ------------------------------------------------------------------------------------------------------------ PMI, NTPC 96 (E) Ejector Drip ------------------------------------------------------------------------------------------------------------ 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 9.5-10 Once/day If pH is more than 10 or if Ammonia is more than 10 ppm then reject the ejector drip. Ammonia (ppm) 10 Total Hardness (ppm CaCO 3 ) B.D.L. ------------------------------------------------------------------------------------------------------------ (F) Make Up Water: ------------------------------------------------------------------------------------------------------------ 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 6.8-7.2 Testing frequency to 2. Specific conductivity 0.2 be for WTP of at 25 O C (us/cm) 0.1 for KSTPP as KSTPP per operational Requirement of W.T.P. 3. Silica (ppm SiO 2 ) 0.02 It is design fig. for WTP of KSTPP 4. Sodium 0.005 5. Total Hardness B.D.L. (ppm CaCO 3 ) ------------------------------------------------------------------------------------------------------------
PMI, NTPC 97 (G) Generator Stator Cooling Water: ------------------------------------------------------------------------------------------------------------ 1 2 3 4 5 ------------------------------------------------------------------------------------------------------------ 1. pH at 25 O C 7.0-7.2 Once/day 2. Specific Conductivity 1.0 Max. Once/day This value S.O. at 25 O C (us/cm) (stator polise unit in service S.P.U. 3. Copper (ppm) 0.005 Once/week should always be in service. Lime Conductivity Monitor must be Installed. It should Be after passing Through cation column. ------------------------------------------------------------------------------------------------------------ Notes: 1. To raise pH from the pH brought about by Hydrazine to the desired value, use Morpholine, Cyclophexylamine or Ammonia. Thumb rule is: Use Morpholine for low make-up rate (2%) Use Cyclohexymine for medium make up rate (2-5%) Use Ammonia for high make up rate (75%).
2. If unit has tripped, open deaerator vent to the maximum opening. After the temperature and pressure of the unit have stabilized, check D.O. and then get the deaerator vent adjusted, till the designed value of D.O. from Deaerator outlet is obtained. Thumb rule is that if height of steam jet from Deaerator vent is 1 feet then it should be possible to adjust this.
PMI, NTPC 98 5. Coal And Its Analysis
What is Coal
Coal may be defined as that part of the earths crust which has been formed as a result of the accumulation of decayed plant remains million of years ago, and its subsequent consolidation over the years by a complex series of chemical and physical changes.
Today Coal is known to be a complex mixture of the degradation products of these plant remains and their associated mineral matter, and its properties vary considerably according to location, geological, bacterial, heat and pressure influences and chemical change. As these parameters all vary in their intensities, the final coal substances consequently also varies, to produce a large range of coals of differing characteristics. The term coal covers a wide variety of materials ranging from Lignite on one hand to Anthracite on the other.
Formation Theories
There are two main theories by which vegetable matter for the formation of Coal was accumulated. The first one considers that the deposits accumulated through the vegetable matter of the swamps, falling where it grew and is called In-Situ Theory. While second is Drift or transportation theory considers down streams and deposited in large shallow lakes or hug delta at the river mouth.
Indian Coals including Coals from Singrauli Coal field, have formulation on Drift theory.
The great of seams of presence of dirt bands in many seams are attributed to formation of Indian Coals by Drift Theory. PMI, NTPC 99
Coal Resources & Demand Pattern
Coal Production is expected to go up to about 400 mte by 2000-2001 AD. The total reserves as assessed by GSI in 1978 are about 85,000 mts (upto 600 mtrs depth) of which share of non cooking Coal is about 68,000 mte. Coal is npm renewable source of energy which not only has to be conserved but utilized properly.
Coal is perhaps the most versatile fuel. Power, Steel & Railways are the bulk consumers and consume about 60% of the total production and such a trend is expected to remain till turn of the century.
The Table -I gives the consumption pattern (actual) for 1977-78 and forecast for 1982-83, 1992-93, and for 2000-2001. the balance 40% of Coal production is utilized by very large number of small consumers such as cement, paper, fertilizer, textiles, brick burnings etc.
Analysis of Coal demand pattern as indicated in Table-I shows the major single consumer with the rapid rate of demand would be the power section. With this identification of Coal demand pattern to avoid vagaries of rail transportation from different sources., the concept of pit head thermal power plant was mooted.
For this purpose, Singrauli Coal field has been identified as the most potential area where Coal and Water is available up to the generation capacity of 20,000 MW within the region.
PMI, NTPC 100 Classification of Coal
Dr. Seylers Classification
In an attempt to predict the properties of Coals, from analytical data, Seyler, using dry mineral matter-free percentage of carbon and hydrogen as the main parameters, plotted the positions of all known Coals in a graphical form.
Seyler gave each class of Coal a distinctive name based on its rank (the rank of Coal being a function of its Carbon content calculated on the pure Coal basis) and named five main classes.
Seylers Coal Classification ------------------------------------------------------------------------------------------------------------ Sl. No. Class % Carbon in Coal ------------------------------------------------------------------------------------------------------------ 1. Lignitour 75 84 2. Bituminour 84 91 3. Carbonaeous & Semi-Anthracite 91 92.5 4. Anthracite over 92.5 ------------------------------------------------------------------------------------------------------------
Dr. Seylers Fuels Chart
Seylers Fuels Chart may be used to calculate any two unknown of the quantities Carbons, hydrogen, volatile matter & calorific value when the other two are known.
PMI, NTPC 101
THE SEYLER CLASSIFICATION OF COAL MAIN FEATURES DMMF BASIS
For example, if the calorific value and volatile matter are known, the carbon and hydrogen contents can be read off the charts at the intersection of the appropriate calorific value line (isocal) and volatile matter line (isoval) provided the coal falls within the coal band. For dull coals or coals outside the band, a correction is made to the volatile matter figure which is reduced by 0.5% for every 10% of durian (the dark grey, hard fraction of coal which contains much of inorganic matter) estimated to be present.
PMI, NTPC 102 The intersection of the corrected isovol with the isolcal is then found. Seylers chart can be used for checking boiler efficiency, but this is outside the scope of this manual.
Coal Sampling
Any Management requires to know for its power stations the quality:
a. of coal paid for when delivered. b. of coal consumed during a given period.
Any Generating Unit is paying for cost and transportation of coal, it is important, therefore, to monitor the quality of deliveries to ensure that value for money is obtained. In addition, knowledge of the quality of coals enables fuel supply officer to plan the supply of coal to individual station in accordance with their technical needs in the most economical way.
Secondly the performance of plant is frequently measured using coal test results so that any deviation from standard may be detected and steps taken to restore efficiency.
Since it is not possible to check every piece of coal in a consignment, laboratory tests are carried out on a sample which is taken crushed and reduced to represent the bulk of coal from which it was drawn.
These processes are scientifically specified and must be rightly observed in practice, for the final test sample to be dependably representative of the consignment. If the sample does not represent the bulk accurately, no reliable test results can be obtained.
PMI, NTPC 103 The most satisfactory way of obtaining a representative sample is from a falling stream of coal as near as possible to the station reception point. This can be taken as the coal leaves the reception hopper or as it falls from the first conveyor. Even sampling from a conveyor is difficult because, as the belt travels along, the vibration tends to move the bigger pieces of coal towards the edges. Big piece of coal often have a different ash content than smaller fine coal. Therefore, to obtain representative sample the increments must be taken from all parts across the width of the coal stream.
By sampling in correct manner the result obtained will very close to the average for the whole train. Few stations have automatic coal sampling equipment fitted at reception hoppers and conveyor belts. An automatic sampler obtains and increment coal at regular time interval from the coal stream and passes it to a crusher where the larger pieces are reduced in size. All the increments are collected together to form the gross sample.
Treatment of gross sample-
A correctly taken gross sample contains the same proportion of big pieces, small pieces, shale, slate, dirt, and poor coal as there was in the original delivery. This gross sample is too big to be analysed, so it is reduced to a few gms. These few gms, however, must still contain the same proportion of all the different constituents as the gross sample and to achieve this it is further crushed and reduced.
Analysis and Testing of Coal
Proximate Analysis
This is defined as the analysis of coal expressed in terms of moisture in the analysis sample volatile matter, ash and fixed carbon. Ash is the residue PMI, NTPC 104 remaining when coal is incinerated to constant weight under standard condition. Volatile matter is the loss of weight (other than that due to moisture) that occurs when coal is carbonized to a coke under standard condition. The test is an arbitrary one: if conditions are changed the result will be different. Volatile matter is not, therefore, an entry contained in the coal which can be extracted and measured like water and in consequence it is not strictly correct to speak of volatile mater content. Fixed carbon is a calculated figure.
Fixed carbon = 100-(moisture + volatile + ash) all expressed as per cent on the same basis. Its purpose is to measure the coke residue (except ash) from the volatile matter determination; like volatile matter it is not a substance contained in coal. Since the two figures are the expressions of one determination, chemists are tending to omit reporting fixed carbon.
Moisture Content
Moisture exists in all coals in three forms:
a) Free moisture: Surface moisture, also present on apparently dry coals, which is dried off when coal is exposed to the air without heating.
b) Inherent moisture: the moisture retained in the pores of the coal substances when free moisture has evaporated.
c) Water of hydration: This is the water of constitution chemically bound to the shales. Such water is driven off by heating to 105-110 O C as are free moisture and inherent moisture.
PMI, NTPC 105 Air dry moisture is a term used to describe that part of the total moisture retained in the 72 mesh analysis sample, after it has been exposed to the laboratory atmosphere and has attained approximate equilibrium with it.
This is necessary so that there should be no change in the condition of the sample either during weighing of a portion for test or whilst the sample is standing between the tests. It is not possible to handle the sample in the bone dry condition because finely ground coal will pick up moisture rapidly; on the other hand the presence of free during weighing but during preparation of the sample. In amount, the air dry moisture is similar to the inherent moisture.
Total moisture is the sum of free and inherent moisture. It is an inert constituent of coal and it reduces the calorific value it costs as much as coal to transport and its latent heat of evaporation is burned, contributes to flue gas losses.
Free Moisture
All coals contain some free moisture. Its origin may be underground mine water, water infused into coal seams and sprays used for dust suppression, washing process or exposure to rain. Free moisture is the proportion which is evaporated on bringing a sample into equilibrium with the ambient air. Free moisture is determined, as percentage from the loss in weight of a 10-30 lb. sample after exposure to freely circulating air at not more than 15 O C above ambient temperature for 16-24 hours. The sample is spread out into trays about 1 deep and if very wet the drying time may be extended beyond 24 hrs.
Inherent Moisture
When total moisture is determined on coal, the water in a 2 lb. sample is distilled off with toluene (6 pt 110 O C) and the amount of condensed water collected in the receiver during 6-8 hrs is noted. An alternative method suitable PMI, NTPC 106 for high rank coal only is to measure the loss in weight when a 2 lb. sample is heated in an oven at 105-110 O for 5-6 hours in a slow air current.
Mineral Matter and Ash
Mineral matter may occur either intimately mixed with the coal substances or as bands between coal seams. In the latter case partial separation of the mineral matter and coal occurs on taking and much of the impurity may be removed by dry or wet cleaning processes. Mineral mater once burnt becomes the ash. Ash is of three types:
i) Inherent ash that ash content which cannot be reduced by any method of cleaning. It may be thought of as the mineral constituents of the vegetable matter from which the coal was derived plus the silt on which it grew. Inherent ash is usually constant for a given coal seam and range from % to nearly 20%.
ii) Associated ash present in the coal seam as bands, lenticles and parting. One form of middling consist of such minerals matter, which has not been split off the coal lumps during mining.
iii) Adventitious Ash not present in the seam, but introduced from floor and roof during cutting, as a result of deliberate policy. Or because geological weaknesses dictate its removal to ensure a safe working roof. Adventitious ash may be fire clay or carbonaceous shallow from the clay deposited in shallow water when coal was laid down.
The determination of ash has, to a lesser degree, the empirical nature of determination of volatile matter and has to be carried out under standard conditions if reproducible and comparable results are to be obtained. Two methods are described. In the first a single muffle furnace is used: a known PMI, NTPC 107 weight of coal (1-2 g) is heated in air to 500 O C in 30 min; the temperature is then raised to 815 O C in a further 60-90 min. The sample is heated to constant weight. In the second two muffle furnaces are required. The sample is heated in one kept at 500 O C for 30 min.; the dish is then transformed to the other kept at 815 O C and is heated to constant weight. The second is preferable in laboratories which are required to test a large number of samples. In each case the furnace must be well ventilated to minimize the fixation of oxides of sulphur. Following table shows the most common constituents of ash.
Table
------------------------------------------------------------------------------------------------------------ Element Mixture of compound in Amount of compound Which element appears present in ash ------------------------------------------------------------------------------------------------------------ Silicon Silica or Silicates 50-90%
Aluminum In combination with Silicon
Iron Pyrites or marcasite (in combination with silicon) 0.20%
PMI, NTPC 108 Traces of other elements such as titanium, manganese, sulphur, phosphorus, chlorine, germanium, and nickel also occur.
Volatile Matter
Volatile matter is defined as the percentage loss in weight when 1 gm. of coal is heated under controlled conditions for seven minutes at 925 O C in a crucible from which air is excluded. An allowance is made for any moisture in the coal which would also be driven off at this temperature. The loss in weight is caused by distillation of gas. The percentage of volatile matter on the probable behaviour of a coal properties and characteristics such as flame length, rate of combustion, ignitability (the ease with which a coal will ignite) and calorific value can be calculated Bituminous coals have a volatile content of between 20% to 30% whilst anthracites have less than 20%.
Calorific Value
The calorific value is the basic standard of any fuel; it is a measure of its heating power and is the primary factor in coal pricing.
Calorific Value is the number heat unit liberated per unit weight of fuel when completely burned in oxygen. In Britain and the U.S., it is measured in British Thermal Units per pound (Btu/lb); the metric equivalent may be calories per gm. (Cal/GM or Kilo calories per kilogram these are numerically equivalent. The relationship between these two systems is simple:
Cal/gm x 1.8 = Btu/lb.
It is worth noting here that the calorific value of liquid fuels is occasionally stated in Btu per gallon; for gaseous fuels the unit is usually Byu per cubic foot.
PMI, NTPC 109 It is necessary to distinguish between four calorific values viz:
1. Gross calorific value at constant volume. 2. Net calorific value at constant volume. 3. Gross calorific value at constant pressure. 4. Net calorific value at constant pressure.
The laboratory bomb calorimeter determination is the first of these gross at constant volume the others may be calculated from it if the composition of the fuel is known. The word gross signifies that the latent heat of evaporation of the water present in the fuel plus that formed during combustion, is recovered by condensing the products, net signifies that the latent heat is lost, the water being discharged as vapour. For a typical coal (low rank, having 10% moisture and 4% hydrogen) with gross calorific value 10.500 Btu/lb the net calorific value will be 10,050 Btu/lb.
It will be realized that this latent heat of evaporation is not recoverable under the boiler operating conditions and this has led to the practice of continental manufacturers report that boiler efficiencies are based on the lower or net calorific value.
The efficiencies are some higher than the figures based on the higher or gross calorific value, which is normal for British and American installations, and this should be borne in mind when comparing reported performance.
Combustion of Coal in open space differ from that in a boiler; the first is the content volume, the other at nearly constant pressure.
When the products of combustion are allowed to expand at constant pressure, work is done and the gross calorific value at constant pressure is higher than the bomb determined calorific value, by the heat equivalent of this work. The PMI, NTPC 110 correction on this account is about 12 Btu/lb for coal and, being less than the uncertainty of sampling and analysis normally neglected.
There are a number of formulae whereby the calorific value be calculated to a fairly close approximation. It is necessary to know the ultimate analysis but as this is rarely available, it is simpler and more reliable to carry out where a direct determination, can not be made.
The calorific value of the pure coal substance (that is dry and free from all mineral matter) is virtually constant for the coal from any given seam in one locality. Once its value has been established, it may be used with the total moisture and ash content, to calculate the calorific value of any consignment from the same seam.
This approach has some advantage for the routine monitoring coal deliveries. The time and money employed in carrying a number of determinations of moisture and ash contents and calculating the calorific value, provides much more useful information about trends and average quality in the long run, than the same effort devoted to fewer direct determinations of calorific value in a bomb calorimeter.
In the short term, and for checking, there is no alternative to the standard procedure of bomb calorimetry.
A small quantity of the sample is burnt in compressed oxygen inside a stainless steel cylinder, or bomb which is immersed in water contained in a cylindrical calorimeter vessel. This vessel with its contents is situated inside a larger vessel of which the hollow cylindrical walls are filled with water to form the jacket and which has the purpose of minimizing the heat liberated on igniting the same by an electrical fuse, is calculated form the temperature of the calorimeter water which is accurately measured before, PMI, NTPC 111
during and after the rise in temperature resulting from combustion. The heat liberated is of course, essentially equal to the temperature rise multiplied by the effective heat capacity of water equivalent of the instrument.
Procedure
1 gm of the sample ground to pass a 72-mesh-sieve, is accurately weighed into the crucible which is then placed in the ring support attached to one of the electrodes, and a length of 44. s.w.g. platinum wire is fastened to the electrodes, just above the top of the crucible, so that the wire is taut. A short piece of sowing cotton is tied to the centre of the wire and positioned so that a part of the cotton measured into the lower part of the bomb which is then assembled with the cap carrying the electrodes and sample and the whole is charged slowly with pure oxygen to a pressure 30 atm (4401 lb/in 2 ). It is important that the original air in the bomb is not displaced when charging with oxygen. The trace of nitrogen is PMI, NTPC 112 required as a catalyst to promote oxidation of sulphite (SO 3 -----) to sulphite (SO 4 - -----).
Next the calorimeter vessel is partially filled with a measured quantity of water (preferable distilled), sufficient to cover the upper surface of the bomb cap, and the vessel is then located centrally inside the water jacket. The bomb is placed inside the calorimeter vessel, electrical connections to the electrode terminals are made and the stirrer, calorimeter thermometer, and covers are placed in position. The temperature of the water in the calorimeter vessel is adjusted at the commencement of the procedure so that, when assembly is complete, it is about 1.5 O C below that of the jacket.
The calorimeter thermometer conforming to B.S. 791 is of mercury-in-glass, graduated in 0.01 O C and is read with the aid of a magnifying viewer to 0.001 O C.
The stirrer is operated throughout the determination and after 10 min of stirring, the calorimeter thermometer is read at intervals of 1 min for 5 min, during which time there should be a uniform gentle rise in temperature. The charge is then ignited by momentarily connecting the electrode leads to a 6 to 12 V source of about 50W rating. Readings are continued without interruption at 1 min intervals, as the calorimeter water temperature rises to a maximum at 1 min intervals, as the calorimeter water temperature rises to a maximum which usually occurs 5 to 7 min after ignition, having risen by approximately 2.5 O C. Readings are ended after a further five or six observations during which a uniform fall in temperature should occur.
The bomb is then removed from the calorimeter. Pressure is released slowly and the bomb is dismantled. It can then be inspected for any sooty deposits on the internal parts and in the absence of such deposits, combustion is regarded as having been satisfactory. The inner surfaces of the bomb and the internal fittings are carefully washed with distilled water into a beaker, for the subsequent PMI, NTPC 113 determination of the corrections for nitric and sulphuric acids as mentioned below.
As a safety precaution the firing key should be operated from a position at some distance away from the calorimeter.
Corrections
A number of corrections must be applied for arriving at the calorific value, as follows:
Temperature corrections A cooling correction is calculated as shown in B.5/1016: part 5, to allow for heat transfer between calorimeter vessel and its environment during the rise in temperature, and a further correction is made for errors in the thermometer. Calorimeter thermometers should be sent for test at the National Physical Laboratory regularlyat 3-5 year interval usuallyand the thermometer correction is obtained from the test certificate which at the point of calibration by the N.P.L. is accurate to +200.002 O C.
Fixed corrections These are necessitated by heat released by the fuse wire and combustion of cotton, and are kept to a constant amount, about 20 cal., for every determination.
Nitric acid and sulphuric acid corrections Some of the nitrogen in the sample and air enclosed in the bomb is oxidized to nitric acid with the evolution of heat (about 10 cal) whereas this reaction does not occur perceptibly in boiler furnaces. Additionally, sulphur in the sample is oxidized to sulphiric acid in the bomb liberating more heat than it would be in a boiler where practically all the sulphur is converted to PMI, NTPC 114 sulphur dioxide. The correction here is usually between 15 to 60 cal/gm of coal depending on its sulphur content, and is either calculated (together with the nitric acid) from analysis of the bomb washings, or from the sulphur content of the sample, where this has been separately determined.
Mean effective heat capacity of the instrument
In order to complete the calculation of the calorific value, it is necessary to know what weight of water and metal (in terms of an equivalent weight of water) has absorbed the heat evolved during combustion in the bomb. This is obtained periodically as the mean of five determinations carried out as has been described but substituting 1.2 gm of dry benzoic acid in place of the sample. The benzoic acid, which is a crystalline organic substance containing only carbon, hydrogen and oxygen is specially purified for this purpose and is obtainable as thermo chemical standard having a calorific value certified by the N.P.L. which value is close to 6319 cal/gm or 11,374 Btu/lb.
Calculation of the result
To summarise the calculation, we have
(Tc x H) Cf-Cs-Cn CV = ----------------------------- g
where CV is the calorific value in calories per gram. Tc the temperature rise in degrees C of calorimeter water corrected for colling and thermometer errors.
H the mean effective heat capacity in calories per degree C, Cf the correction in calories, Cs the correction for sulphuric acid in calories, PMI, NTPC 115 Cn the correction for nitric acid in calories, g the weight of sample in grams.
When determining the effective heat capacity the certified calorific value of benzoic acid is taken as a standard, the temperature rise and corrections are calculated and a measured weight of benzoic acid is used; the effective heat capacity can thus be evaluated from the formula:
(CV X g) + Cf + Cn H = ---------------------------- Tc
Having determined the mean effective heat capacity, the calorific value of coal or other fuel can be calculated and the final result cal/gm, is converted to Btu/lb on multiplying by the factor 1.8. the difference between duplicates determined in one laboratory should not exceed 50 Btu/lb and the difference between the means of duplicate determinations from different laboratories should not exceed 120 Btu/lb. An experienced operator usually expects to obtain duplicate results within 20 Btu/lb.
Adiabatic Bomb Calorimeter
In the determination of calorific value using the static calorimeter, the magnitude and accuracy of the cooling correct depend on the temperature difference between the calorimeter water and the jacket, and it is not always convenient to compute this so as to produce small cooling correction particular when several determinations are to be made in one day. Further the calculation of the cooling correction takes time as does the need to read temperatures carefully at 1 min intervals during 15 to 20 min. For these reasons the adiabatic bomb calorimeter which eliminates the cooling correction, was developed commercially 12 to 15 years ago and has replaced static type ring in modern stations.
PMI, NTPC 116 The innovations of the adiabatic calorimeter are in the provision of the means to change the jacket temperature rapidly particularly to increase it, and this is done by installing electric heaters in the jacket through which the water is circulated. The uppermost cover of the calorimeter is also made in hollow form and the jacket water is passed through this in turn. Sensitive thermometers are placed, one in the calorimeter water and one in the jacket and these control the jacket heaters via a bridge circuit and relay so that as the calorimeter water temperature rises the jacket water is heated rapidly to the same temperature.
In this way there is a negligible heat transfer between the calorimeter and the jacket and it is only necessary to read the temperature accurately just before firing (when initial equilibrium has been reached) and again at a convenient time calculation of the result is the same as has just been described modified only by deleting the cooling correction.
Although at present the accuracy of an adiabatic calorimeter is not significantly greater than that of a properly controlled static instrument, it takes less time and is potentially simpler to operate. For these reasons although they are costlier and more complex instruments, adiabatic calorimeters have been widely adopted.
Sulphur
The determination of sulphur is part of the ultimate analysis of coal (g.v.) but is discussed separately because of its special importance in pricing, as well as technically, sulphur in coal is found in three combinations:
PMI, NTPC 117 Organic sulphur tends to be relatively constant but pyritic sulphur varies widely.
Sulphate sulphur exists as small quantities of ferrous sulphur (FeSO 4 . 2 H 2 O). They are found as thin plates in partings of the coal where the solution has evaporated.
Organic sulphur is combined with the carbon and nitrogen to form the coal substance. In consequence it is not removable by cleaning.
Pyrities (also known as marcasite) is ferrous sulphide (FeS). It occurs as massive nodules and lenticles, as brassy bands and as finely dispersed particles. The first form is easily removed by the various coal cleaning methods. Pyrities more closely associated with the coal is removable only with considerable loss of saleable carbonaceous material or vend.
Methods are available for assessing the amount of each of the forms of sulphur but usually they are not important for power station purposes. Total sulphur may be determined in the bomb-washings from the determination of calorific value; this is a simple procedure and is usually adopted since the result is required for the calorific value calculation. If total sulphur has to be determined, and the number of samples is not large, the Eschka or bomb method is used: large numbers of determinations are more conveniently carried out by the high temperature (tube) method.
In the Eschka method 1 gm coal is burned by heating in a crucible with a mixture of magnesium oxide and sodium carbonate. This alkaline mixture retains all the sulphur as soluble sulphates which are determined by the standard chemical method of precipitation as barium sulphate which is finally dried and weighed.
The high-temperature (tube) method requires costly equipment which can be made largely automatic and needs little special training to operate. The PMI, NTPC 118 justification for its use depends on the number of sulphur determinations to be carried out, or on results being required more rapidly than can be provided by the other methods. The coal sample (0.5 gm mixed with alumina) in a small refractory beat is pushed into a tube kept at 1350 O C through which passes a rapid current of oxygen. The sulphur oxides formed are absorbed as the oxygen from the tube is bubbled through hydrogen perioxide, which converts them wholly to sulphuric acid. The acid is measured by titration with standard alkali solution, a correction being applied for chlorine carried forward by the oxygen. (This is also a method for the estimation of chlorine (g.v.)
Mention should also be made that sulphur can be determined by the oxygen flask technique. In this method, 1/30 gm of coal wrapped in paper is burned in a glass flask filled with oxygen at atmospheric pressure. The flask contains hydrogen peroxide solution to dissolve and oxidize the sulphur gases to sulphuric acid. This is estimated by titration with standard barium per chlorate solution with a special indicator. Research at March wood Engineering Laboratories has shown that the accuracy of the method is almost as good as the classical methods and because of its simplicity it may usefully be applied to the routine determination of sulphur in coal.
Chlorine
Chlorine has been regarded as a significant constituent of coal since about 1939 when a correlation between chlorine content of the coal and the degree of gas- side boiler fouling resulting was observed. This aspect is discussed, with ash and sulphur contents, in a later section.
Chlorine occurs almost entirely as sodium chloride and potassium chloride. These salts drive from the shallow seas which covered the coal measures in a later geological period. Although the chlorides can in part be dissolved out by repeated water washing, some will always remain in the coal. In practice the PMI, NTPC 119 washing processes used in coal preparation do not significantly reduce the chloride content, partly because of insufficient residence time, but also because the washery water is largely recycled and tends to reach a state of equilibrium, where the wash clean water to rinse the washed coal or to dilute the wash water and in any case surplus washery water must be expensively cleaned to a rigid standard before disposal.
The methods available for estimation resemble those described for sulphur namely the Eschka and high temperature methods and for routine analyses the oxygen flask method has much to recommend it. The finish in all cases is by a volumetric titration.
The Ultimate Analysis of Coal
Strictly the ultimate analysis of coal is the determination of the elements of which its molecules are compounded and as such would include elements like chlorine, phosphorous, etc; for fuel technology purposes the term is defined as the analysis of coal in terms of its carbon, hydrogen, nitrogen and sulphur contents. Oxygen is usually taken as being 100 minus the sum of the former constituents, expressed as percentages. As such it includes the errors of estimation of the other elements and a direct method is being developed. The ultimate analysis is of great scientific interest and has important practical application in combustion calculations and heat balances as already stated, the C.V. can be calculated to a fairly close approximation from the ultimate analysis. Until recently elemental analysis by the classical Liebig method required high skill and experience and it was time-consuming. Accordingly for heat balance purposes, the ultimate analysis was frequently calculated from analyses which are on record for the particular seam or coal rank. More recently the high- temperature tube method, cutting down the combustion time from 2h to 9 min PMI, NTPC 120 and introducing other time saving modifications has been developed. In spite of those improvements the determination of carbon and hydrogen is not a simple operation and there is an intensive search for a rapid method based on instruments which will always yield reliable results so far none proposed has been found wholly acceptable. Carbon and Hydrogen
Two standard method are available for combustion at 800 O C (classical Liebig) and at 1350 O C (Sheffield high temperature). In both methods the calculated result is total carbon that is it includes carbon from coal as well as from any carbonates present and a correction is needed at a later stage. In each the hydrogen is converted to water which is absorbed and weighed together with the water present, as moisture in the coal and as water of hydrogen in the associated mineral matter. In this case corrections have to be applied for these interfering factors.
(a) In the low-temperature method. 3 gm of coal is burned in a slow stream of oxygen in a heated tube 50 in long. Capable of close temperature control in zones. The tube is packed so that the products of combustion pass through a plug of copper oxide 18 in long kept at 800 O C and then successively over a lead chromate plug (4 in long) and then a 1-in roll of silver gauze, both kept at 600 O C. the copper oxide ensures that all the carbon is converted to carbon dioxide and all the hydrogen to water. Oxide of sulphur are removed by the lead chromate and chlorine by the silver gauze.
The products of combustion carried by the stream of oxygen pass through in absorption train consisting of tubes which are packed with an absorbing substance.
PMI, NTPC 121 Water is first removed by magnesium perchlorite and measured by the increase in weight. Traces of nitrogen dioxide which would lead to erroneous results for carbon are then removed by manganese dioxide. Finally carbon dioxide is absorbed by soda-asbestos; again the increase in weight of the absorption tube measures the carbon dioxide evolved.
(b) The high-temperature method differs from the Liebig methods in having a shorter unpacked tube (only 26 in long) using a rapid stream of oxygen and operating at 1350 O C. At this temperature both sulphur and chlorine are trapped by a roll of silver gauze; nitrogen dioxide is not formed under these conditions and no special precautions are therefore necessary. The assessments of water and carbon dioxide produced can be as in the low temperature method or can be attempted by automatic instruments if speed is a necessary factor.
Nitrogen
Nitrogen in coal is an inert substance which takes n part in combustion processes. It may be estimated by the Kjeldahl method of heating the coal with concentrated sulphuric acid to destroy the organic material; the presence of a catalyst (selenium mercuric sulphate vanadium pentaoxide) ensures that all the nitrogen is rapidly converted to ammonium sulphate. When cool excess sodium hydroxide is added to free the ammonia which may then be steam distilled and collected for estimation in the condensate by titration with standard acid solution.
The estimation may be carried out with appropriate difference in detail 1 gm (macro method) or 0.1 gm (semi-micro method) of coal. In practice because of the shorter times of digestion (1/2h as against 2 h) and the smaller scale of the apparatus nearly all laboratories use the semi-micro method.
PMI, NTPC 122 Moisture
Moisture estimation has not been attended by the same degree of success as the estimation of mineral matter; however a brief description of some of the methods tried is given in the following paragraphs.
Moisture in cereals may be indicated satisfactorily by the change in capacitance of two plates when grain with a varying moisture flows between them but the difference in particle behavior between grain and coal introduces uncertainties greater than, are acceptable.
Attempts have been made to produce on automatic chemist which would take a known weight of coal dry it rapidly by flash-evaporation under low pressure whilst it is exposed to high energy infrared heating and then reweigh it.
A more successful methods is to measure the attenuation of a microwave radio signal when it is transmitted through the coal sample. The weakening depends on the hydrogen-oxygen bonds in the molecule of water but since there are a number of other bonds of a similar nature in the coal the response is not as clear as could be wished.
However more recently reports have been received of an instrument for which an accuracy of + 1% for total moisture contents in the range 3-25% has been claimed for all ranks of coal and a wide range of mineral matter. This instrument uses nuclear magnetic response (NMP) to estimate the hydrogen in coal substance).
NMR depends on the absorption of energy by the nucleus of an atom, when it is subjected to electromagnetic radiation whose frequency is related to the nuclear structure and to a strong magnetic field the strength of which can be varied PMI, NTPC 123 slowly. A recorder plots a derivative of the absorption and field strength so that water content may be read off directly.
As with other instrumental techniques there are the plant scale problems of taking and handling a representative coal sample.
Other Tests on Coal
Bulk Density
The measurement of the bulk density of coal in small heaps and in wagons in a fairely simple matter. It is much more difficult when the coal is a large stock-pile of compacted coal
Bulk density of coal in a wagon is the ratio of net weight to the volume calculated from the wagons dimensions and the level coal surface.
The same principles apply when using a special bin or box. It must be noted, however, that when dealing with smaller volume the effect of voids between the walls and coal lumps introduce error, the smaller the box the large the error.
It is not possible to measure the bulk density of coal in stock piles by these methods, since the sample when extracted has a large volume than the coal in situ. Accordingly the technique is reversed. A coal sample is dug out and weighed: the volume it occupied is assessed by lining the hole with polythene sheeting and measuring the volume of sand or water needed to fill it.
A further difficulty has to be considered. It is argued that surface results are not typical of the density at lower levels. To avoid this, it has been proposed that an auger be used to extract a coal sample which can be weighed; the volume it PMI, NTPC 124 occur is calculated from the cylinder that is represented by the inserted length of the auger.
In the last two or three years attempts have been made to adapt the Gamma ray back scatter method to this determination. A tube is driven into the pile and an emitter and detector are lowered to various depths at which readings on an indicator are taken. The method is not only subject to instrument error as in the ash determination but there is the practical difficulty of driving a tube into compacted coal, without bending ita bend can prevent the instrument from reaching the required depth. Claimed to have an accuracy of + 5% when used with care, and +3% after experience has been gained with particular coals packed by particular methods.
Grindability
75% of coal consumed in our boilers is pulverized for firing. It is desirable to know how the properties of the coal and mineral matter effect the grinding process, how easily the fuel can be reduced to the required fineness and what power is needed to do this. A variety of tests have been proposed; each has its merits and defects and an international group is now studying them.
The best tester for grindability is the hardgrove machine which is a miniature ring-ball type pulveriser. The grindability index from this machine was originally based on the increase in surface area produced on the coal particles but because its measurement was tedious a simplified procedure was introduced.
A 50-gm sample passing a No. 16 U.S. sieve and retained on a No. 30 U.s. sieve (0.0469 in and 0.0232 in respectively) is ground for 60 revolutions with 64 lb loading on the ball ring. The amount of coal now passing No. 200 U.s. sieve (0.0029) is weighed (W). Although this can be used directly as a measure of the ease with which the coal was ground in order to retain comparability with the PMI, NTPC 125 original Index based on surface area. It is transformed by the formula Hardgrove Index = 13+6.9 W.
The Hardgrove Index so calculated can range from over 100 for easily ground coals down to rather less than 50 for coals which are more difficult. This broad relationship also holds for other properties associated with rank, such as volatile matter carbon, etc.
This particular method of test has been criticized because (a) during preparation for the test some 50% of the sample is sieved out leaving a test portion which may not be properly representative (b) only part of the sample is taken to the final ground state and (c) the fines are not removed as they are produced.
Ash From Coal
The colour of coal ash varies from almost pure white to a dark chocolate colour depending mainly on the iron content. Its fusibility varies widely according to its chemical composition. Ash containing much iron from a highly pyretic coal, forms the readily fusible ferrous silicate which is a common source of clinker in furnaces.
The simplest coal ash consist of the refractory clay kaolin, composed only of alumina and silica to which may be added as the composition increases in complexity lime and oxides of iron in varying preparations. With increase of lime and iron contents the fusion point of ash falls significantly.
Quality Parameters: Singrauli Coals
There are three major coal seams in this coalfield i.e. Purewa, Tura and Kota. Purewa seam is split into two parts in kanor areas of the coalfield. The bottom most kota seam is thin and is not being envisaged to be mined at this stage. The PMI, NTPC 126 coalfield is divided into 11 blocks. Table enclosed gives in general the quality parameters and thinness of various seams in Jhingurda, Bina, Dudhichua, Jayant, Nigahi, Almori and Mohar blocks.
In this coalfield the quality of coal seams is varying both vertically and horizontally, as consequence of this, there is general improvement in coal quality from East to West Composite Tura seam coal with characteristics can be used mainly for power generation. Purewa seam in the entire coalfield is only suitable for power generations. Since large scale open cast mines are being contemplated in this coalfield selective mining would also be mined out. The combined coal quality parameters for each of the mining blocks make the coal suitable mainly for power generation only.
Since the quality of coal supplied to the power stations has direct bearing on the performance and availability of equipment in the thermal power station this aspect has to be gone into more details, before design. Inferior and inconsistent quality of coal creates a number of problems in design, operation and maintenance of thermal power station compared to better and consistent coal quality. The coal quality can be improved or consistent coal supplies can be ensured by resorting the coal beneficiation experience as beneficiation of non- coking coals in India is limited. The wet beneficiation or coal washing as it is normally called is very costly. In addition to cost of washing which itself is quite high, the moisture contents in washed coal are increased substantially. Also for the present there is no utility of rejects coming after such coal washing. These rejects are likely to catch fire. In addition to wastage of this energy, it would also create an environmental problems. The studies are being conducted for finding a suitable method of coal beneficiation in totality wherein the so called rejects also find a favourable use and the whole process of beneficiation becomes techno- economically viable.
PMI, NTPC 127 However, till the time a suitable solution is available power houses would have to tolerate fluctuations in coal qualities which are more or less inherent in the mining system.
Quality parameters of Jayant Mine linked to Singrauli STPP:
The coal quality parameters of Jayant mine linked to Singrauli STPP are indicated in Table enclosed.
As regards coal supplies from Jayant mine linked to Singrauli STPP is concerned NTPC is better placed compared to other power houses as coal for the first 10 to 12 years would be only supplied from Turra seam of Jayant project. The quality parameters of the same as indicated by CCL are given here.
Coal Characteristics of Singrauli Coalfield Proximate Analysis on 60% RH at 40 O C ------------------------------------------------------------------------------------------------------------ Excluding Dirt bands Included Dirt bands SEAM -------------------------------------------- ------------------------------ Moisture Ash V.M. Ash% GCV Kcal/Kg % % % ------------------------------------------------------------------------------------------------------------ Turra 7 15 25.4 18 5050 10-24.5 to to to to to 9 23.7 31 39.9 5810 ------------------------------------------------------------------------------------------------------------ Purewa Top 7.5 22.3 28 39.1 4760 5.04 to 10.93 to to to to to 8.7 25 30 49 5045
------------------------------------------------------------------------------------------------------------ Purewa Bottom6.2 19.8 28.6 26.5 4950 7.69 to 12.7 to to to to to 8.2 24.3 31.5 40 5275 ------------------------------------------------------------------------------------------------------------ Kota 7.4 19 29 26 5035 5 m to to to to 23 30 35 5380 PMI, NTPC 128 ------------------------------------------------------------------------------------------------------------ Jhingurda 8 25 28.3 33 4185 To to to to to 9 30.5 29.0 46.4 4500
Hard grove index 45 to 50 Initial Deformation 1180 to 1200 Temp. O Hemi Spherical over 1400 point O Flow temp. O over 1400
Proximate Analysis on 60% RH and 40 O C ------------------------------------------------------------------------------------------------------------
------------------------------------------------------------------------------------------------------------ Ash Characteristics Unit Purewa Purewa Bottom Turra Top seam seam seam ------------------------------------------------------------------------------------------------------------ Silica (SiO 2 ) % 60.9 64.6 56.66 Alumina (Al 2 O 3 ) % 24.8 24.8 27.46 Iron Oxide (Fe 2 O 3 ) % 7.7 5.1 6.40 Titania (TiO 2 ) 1.9 1.5 1.95 Phospheric (P 2 O 5 ) % 0.5 0.5 1.10 Anhydride Lime (CaO) % 0.9 0.9 1.81 PMI, NTPC 130 Magnesia (MgO) % 1.0 0.8 0.95 Sulphuric Anhydride % 0.2 0.1 0.27 (SO 2 ) Alkalis % 2.1 1.7 3.40 (By difference) ------------------------------------------------------------------------------------------------------------ Hard Grove Index 50-64 Initial Deformation 1190-1400 Temp O C Hemishpherical Over 1400 Point O C Flow Temperature O C Over 1400
Seam Thikcness On 60% RH basis Excluding Including In mts. Dirt. Direct Bands ------------------------------------------------------------------------------------------------------------ Turra 14-21 7-9 17-24-5700- 0.2-0.5 20-3 4400-4900
Combustion
Combustion can be defined as that rapid chemical union with oxygen of an element whose exothermic heat of reaction is sufficiently great and whose rate of reaction is sufficiently fast that useful quantities of heat are liberated at elevated temperature.
For thermal power generation in India, two types of fuels i.e. Coal & Fuel oils are being used and therefore, our discussion would be limited to combustion of coal & fuel oil in Boilers.
PMI, NTPC 131 Coal is proximately analysed into the following:
a) Moisture b) Volatile Matter c) Fixed carbon d) Ash
Quality wise gradation of coal is done on the basis of Moisture + ash content. The more they are, inferior the coal will be and lesser will be its calorific value and so the price. Fixed carbon & volatiles are the combustible portion of coal and give out heat when they combine with oxygen. Before combination can take place the atoms of oxygen & fuel must mix well together, and be in a highly agitated state in an atmosphere higher than the ignition temperature.
Therefore to obtain good & efficient combustion following conditions must be fulfilled.
1. Thorough mixing of fuel and air in proportions which will ensure complete combustion i.e. there should be turbulence in furnace. 2. Exposure of fuel particles to oxygen throughout a period time sufficient for their combustion i.e. certain time is required for complete combustion. 3. Combustion zone should maintain temperature above ignition temperature i.e. sufficient temperature is required for combustion to take place.
Thus there are three Ts which are essential requisites for efficient combustion and therefore fuel combustion equipments & furnaces are designed to ensure these conditions.
PMI, NTPC 132
When a coal is subjected to combustion conditions it first absorbs heat necessary for volatilization of the hydrocarbons. This includes both sensible heat & latent heat necessary to vaporize any moisture in the coal. After the distillation of volatiles is complete the remainder is coke a mixture of fixed carbon and ash. It is the hydrocarbons which must be carefully handled to obtain freedom from smoke and incomplete combustion. Hence a major function of any furnace or burner installation is the proper mixing of air with this distilled volatile matter and holding it at ignition temperature sufficiently long to obtain complete combustion.
The fixed carbon burns in a somewhat complicated way, the nature of which may be expressed most simply by saying that the manner of carbon combustion is an incomplete oxidation to carbon monoxide which itself is a fuel. The carbon monoxide will then be oxidized to carbondioxide provided enough oxygen is mixed with it, and it remains hot enough to continue combustion. During combustion each small piece of incandescent carbon becomes blanketed with either carbon dioxide or carbon monoxide and unless this gas blank can be continuously scrubbed off so as to expose a fresh surface the combustion will stop. Continuous combustion is accomplished in stokers and on grates by moving the air past a fuel bed at high velocity by draft pressure.
The process of Combustion
The combustion is a chemical process which takes place in accordance with natural law. By applying these laws the theoretical quantities of air required to burn a given fuel can be determined when the fuel analysis is known. The air quantity used in a furnace, expressed as percentage of excess above theoretical requirement, can be determined from the flue gas analysis.
When oxygen and the combustible elements or compound in a fuel are mixed in definite proportions at an eleouted temperature under ideal conditions, they will PMI, NTPC 133 combine completely. This shows that a given combustible element or compound requires a definite amount of oxygen for complete combustion. If additional oxygen is supplied the excess will not enter into the reaction but will pass through furnace, unchanged. On the other hand, if there is deficiency of oxygen, the combustible material will remain unburned. Briefly, the law of combining weight tells us that the elements and compounds combine in definite proportions which are in simple ratio to their atomic or molecular weights. In practice the oxygen supplied for combustion is obtained from the atmosphere. The atmospheric air is a mechanical mixture of gases which for practical purpose may be considered as being composed of the following:
Only the oxygen enters into chemical combination with the fuel. The Nitrogen passes through the combustion chamber and reduces the maximum temperature attained by the products of combustion.
In order to supply 1 lb. of oxygen to a furnace it is necessary to introduce:
1 ---------------- = 4.32 lb. of air 0.2315
Since one lb. of carbon requires 2.67 lb. of oxygen one must supply.
4.32 x 2.67 = 11.53 lb. of air/lb of carbon.
The burning of carbon in oxygen to form carbondioxide can be represented by the chemical equation. PMI, NTPC 134 C + O 2 = CO 2
12 + 32 = 44 or molecular weight = 12 + 32 = 44
By referring to the above equation we find that 1 lb. of carbon produces 3.67 lbs of carbon dioxide. Therefore, the total products of combustion formed by burning 1 lbs. of carbon with amount of air are 8.86 lbs. of Nitrogen and 3.67 lbs of carbon dioxide.
In a similar manner, it can be shown that 1 lb. of Hydrogen requires 34.56 lb. of air for complete combustion. The resulting products of combustion are 9 lbs. of water and 26.65 lbs. of Nitrogen, for 1 lb of sulphur 4.32 lbs. of air will be required with evolution of 3.32 lbs. of nitrogen and 2 lbs. of sulphur dioxide. This can be given in a tabular form.
Theoretical quantities Involved in Combustion of Fuel all Expressed in Lb/Lb of Fuel
Constituents Required Resulting Quantities O 2 Air CO 2 N 2 H 2 O SO 2
When quantities expressed in percentage by weight of carbon, hydrogen, sulphur and oxygen in a fuel are known the theoretical quantities of air can be determined by the following formula.
Lb of air required/Lb of fuel = 11.53C + 34.56 (H - 1/8 0) + 4.325 S
PMI, NTPC 135 In practice it is necessary and economical to supply more air than the theoretical amount in order to obtain complete combustion. The air supplied to a combustion process in an amount above the theoretical values is known as excess air. To exercise control over combustion it is necessary to determine the amount of excess air. This may be accomplished by chemical analysis of flue gas. The flue gas analysis is effective in determining the amount of air supplied for combustion as indicated in the above table. This table shows how the amount of excess air used in the combustion process indicated either by the percentage of carbon dioxide or oxygen in the flue gases. When a single fuel is burned the carbondioxide content of flue gas provides a satisfactory index of excess air being used. This can be explained by the fact that with the combustion of 1 lb. of carbon 3.67 lb. of carbondioxide is product.
When a relatively large amount of air is used, the fixed amount of CO 2 will be diluted and the percentage correspondingly lowered. Conversely if only a small amount of excess air is used, their will be less dilution and the percentage of CO 2
will be relatively high. For a given percentage of excess air fuels with higher carbon hydrogen ratio will have a higher percentage of CO 2 in the flue gas than fuels with lower percentage of excess air, the flue gas from a coal fired furnace will have a higher percentage of carbon dioxide than when fuel oil is burned. The percentage of oxygen provided an adequate measurement of excess air when either single or multiple fuels are being used. The oxygen in flue gas represents that portion which entered but did not combine with the combustible elements in the fuel. This oxygen in the flue gas and the Nitrogen with which it was mixed are the excess air. The theoretical oxygen and air requirement are approximately proportional to the heat content of the fuel even with variation into the Carbon-Hydrogen ratio. For a given percentage of oxygen the excess air is approximately the same for either coal or fuel oil.
Table for the corresponding percentage of excess air, carbon dioxide and oxygen for Bituminous coal and fuel oil is as follows: PMI, NTPC 136
Kind of fuel Ingradient % excess air O 20 40 Bituminous CO 2 18.6 15.5 13.2 O 2 0 3.5 6.0
Fuel Oil CO 2 15.5 12.6 10.6 O 2 0 3.7 6.4
The excess air in percentage of the theoretical requirements can be calculated by the following formula
O 2 - CO Percentage of excess air - ----------------------- X 100 0.263N 2 + CO-O 2
However when there is no carbon monoxide present the formula become.
O 2
Percentage of excess air - ----------------------- X 100 0.263N 2 - O 2
General specification For Coal and Fuel Oil to be Used Coal Indian Bituminous Fixed carbon 28% Volatile 30% Moisture 12% Ash 30% Grindability 55 HGI Heating Valve 4500 Kcal/Kg. Size of Coal 25 mm
PMI, NTPC 137 Performance Data For a proper combustion control the recommended O 2 % (Dry Volume) CO 2 % (Dry Volume) and excess air are as follows:
MCR NCR 200 MW a) Oxygen in gas at economiser 3.84 3.84 outlet (by dry volume%) b) Carbondioxide in gas at economiser 15.77 15.77 outlet (dry volme) % c) Excess air in gas at economiser outlet % 22.0 22.0
General Layout Furnace with No. Types of Burners FF Flame Detector Coal F EF Flame Detector Oil E DE Flame Detector Coal E CD Flame Detector Oil C BC Flame Detector Oil B AB Flame Detector Oil A AA Flame Detector Coal
1. Coal burners A, B, C, D, E & F 6 nos. X 4 = 24 Nos. 2 Oil burners AB, CD, EF 3 Nos. x 4 = 12 Nos. 3. Auxiliary air dampers AA, BC, DE, & EF 4 Nos. x 4= 16 Nos. 4. Flame Detector Oil 3 x 4 = 12 Nos. 5. Flame Detector Coal 4 x 4 = 16 Nos. PMI, NTPC 138 6. IFM Ignitor (by BHEL) 3 x 4 = 12 Nos. 7. HFA Ignitor 3 x 4 = 12 Nos.
Therefore four sets of 13 elevations at four corners of furnace, each set consists of 6 Nos. of coal burners, 3 Nos. oil-burners four nos. of auxiliary air dampers, 3 nos. of flue detector oil, four nos. of flame detector coal and 3 nos. of ignitors.
Hot flue gas from the furnace passes through platen super heater and economizer to two nos. of Air heaters A and B. From air heater it goes to electrostatic precipitator where dust is arrested. From ESP the flue gas goes to the chimney through ID fans.
On Line Recorder for %O 2 in Flue Gas
There are provisions for analysis of %O 2 in flue gas probe type oxygen analyzer. Two such on line analyses are there before airpreheater A and B. Model 218 probe type oxygen analyzer are used to measure the net concentrator of oxygen in the process. Oxygen remaining after oil and fuel are oxidized. This performs the task without the use of sampling system.
Cross Check of Flue Gas Quantity by Laboratory
In order to cross check the oxygen and carbon dioxide percentage in flue gas, there are sample pockets before the air heaters. Sampling of flue gas is done by sucking the gas either by sunction pump of suction bellows after proper filteration of dust particles. Flue gas after collection can be analysed by the following methods:
PMI, NTPC 139 i) Lloyd Gas Analysers
This is a portable precision apparatus for the determination of oxygen and carbon dioxide in flue gas. It is self compensating for temperature and pressure changes and results are obtained directly from the 10 ml burette. The main part of the apparatus is in one piece of glass and has a special five way stop cock through which the samples are introduced passed to the absorbents and finally expelled. The containing liquid is mercury.
ii) Orsat Gas Analyser
This apparatus consists of a graduated burette of 10 ml capacity one end of which is connected to a reservoir containing acidified brine solution with few drops of methyloxange. The other end is connected to the sample and absorption pipettes by means of a three way stop cock. The absorption pipettes contain the absorbents for oxygen and carbon dioxide. A known volume of sample is drawn from a bladder to the burette through the three way stop cock and the sample is first passed into one absorption pipette containing 40% KOH by raising the reservoir and again taken back to the burette by lowering the reservoir. In the process CO 2 is absorbed and the volume of the gas is noted down difference between the initial volume and final volume of the gas is noted down difference between the initial volume and final volume gives CO 2 %. For the determination of O 2 % residual sample is passed into another pipettle containing alkaline pyro gallol when O 2 is absorbed. The difference in the volumes of sample after absorbing CO 2 and the volume absorbing O 2 gives the % of O 2 in the sample.
Regents a) Potassium Hydroxide solution for CO 2 . Dissolve 40 gms of KOH in 100 ml of distilled water.
PMI, NTPC 140 b) Alkaline pyrogallon solution for O 2 . Dissolve 15 grams of pyrogallon in 25 ml of water and add the solution to 15 ml of 30% KOH solution.
Determination of Carbon Monoxide Sometimes it may be required to know the percentage of carbon monoxide in the flue gas. For this purpose one more absorption pipettes for oxygen and carbon dioxide, containing Ammonical Cuprous Chloride solution as an absorbent.
Preparation of Ammonical Cuprous Chloride Solution Add 75 gms of white cuprous chloride to 15 grams of ammonium chloride in 80 ml of water and then add sufficient concentrated. Ammonium Hydroxide solution until the solution is complete. A large excess of Ammonia is avoided. This solution should be kept in contact with copper gauge.
Effect of Fuel Quality on Combustion
Moisture
If the moisture content in coal is high, trouble starts right from mill. Hot primary air supplied to mills has two purposes. First to dry up the coal so that grinding is proper and second to carry coal dust to burners. If coal is not dry higher particles will be formed by sticking together of finer particles and air will not be able to carry them freely and efficiently. As a result of this mill will start getting over- loaded and consequently milling capacity will be reduced and so the load on the boiler will be reduced. Also fuel/air mixture temperature will be low and so the evolution of volatiles. They will retard the combustion process. If efforts are made to take the same output from mills, more hot air has to be supplied to dry up the coal sufficiently and to carry the coal to burners. This will cause excess air to PMI, NTPC 141 boiler and will lengthen the flame and affect the combustion. Also there will be heat loss due to excess air.
In stoker fired boilers, if the moisture of coal is very high, it will become difficult to maintain position of ignition line and grate spead will have to be reduced to maintain its position and so the output. But some amount of moisture should be maintained in coal for stoker fired boiler. This moisture is entrapped in the pores of coal and when gets heated up, becomes steam and cracks the coal lumps and thus helps in achieving better air fuel contact and so the combustion.
Volatiles
After removed of moisture from coal, distillation process takes place commencing from about 325 O C and completing at 965 O C in which hydrocarbons are released. These hydrocarbons, being in gaseous form get readily ignited and supply instant heat for further combustion of coke.
Since in P.F. Boilers, coal in powder form gets ignited readily, volatiles do not have as important part to play as in case of stoker fired boilers. If coal is low in volatile content, bright and steady flame is not obtained in P.F. boilers. On the contrary, high volatile coals produce bright and consistent flame.
In stoker fired boilers, since coal is in lump form, it does not get ignited easily and here volatiles play an important role in combustion. The Hydrocarbons evolved from coal are burnt above the grate near from arch with the help of secondary air. Heat provided by combustion of volatiles promotes combustion of coke laying on grate.
PMI, NTPC 142 Ash
Although ash has nothing to do with the combustion directly but on the whole it affects performance of the boiler very much. Moisture Ash content forms the basis of gradation of coal i.e. higher ash means reduction in combustible percentage and so lower the calorific value. High ash content coal causes increased wear and tear of mills, piping and ducts. If the boiler has been designed for high ash coals, it will take care of the poor quality of coal while maintaining furnace stability and load. But if a boiler has been designed for superior coal low in ash content, feeding of inferior coal will definitely affect the furnace stability and rate of heat release may not be sufficient to complete the combustion with the furnace. It may either cause after fires in super heater zone or wastage of combustibles.
Coal Fineness
Furnace is always designed for burning a particular size of coal so that its combustion may be complete by the time it leaves furnace. Therefore, if coarser coal dust is fed, combustion will not be complete in furnace and after fires may take place. This will also reduce the output and efficiency of the boiler. Coarse particles may also fall down to the lower zones of the furnace and may get entrapped in the slag resulting in loss of combustibles. If coal fineness is increased by changing classifier vane position, even the particle of correct size may not pass through classifier and come back to mill for further grinding thus reducing the milling capacity.
Coal Sizing
While coal fineness affect the performance of P.F. Boilers, so the coal sizing affects performance of stoker fire boilers. If the coal size is more, surface contact of air and combustibles will be less and so combustion will not be quick. This PMI, NTPC 143 may result in passing of unburnt coal into ash hopper and will go as waste. On the other hand if more fine size are fed, they may not only obstruct the small gaps in the grate which allow air to come into furnace but fuel bed itself become so uniform (not porous) that it may offer great resistance to flow of air, through it. Consequently, insufficient air will be available for combustion and combustibles may go as a waste in ash hopper.
Some Important Points of Combustion Control
i) A 20 O C rise in flue gas exit temp. results in 1% boiler efficiency down which costs approximately Rs. 6 lakh in additional coal cost for a 120 MW set.
ii) 1%O 2 variation in flue gas causes 0.25% variation boiler efficiency.
iii) High excess air operations, furnace slagging or inadvertent up tilt of burners can result in high steam temp. at different stages. Continued operations under these conditions are conductive to tube failure. Analysis and comparison of data with normal operating condition may help solving these problems.
iv) High input of fuel and consequently air with some streaming conditions raises outlet steam temp. particularly in the conductive zones. Super heater outlet steam temp. therefore needs to be closely watched to ensure that the metal temp. does not exceed the allowable limit. Limiting the load on this basis will mitigate problems of tube failure.
v) Unduly high steam side pressure drop, denotes blacking of few coils or deposition in the super heat tubes.
PMI, NTPC 144 vi) An increase in the radiant super heater outlet temp. for the same steaming conditions indicates slagging of the furnace. The soot blowing regime should then the suitably attended.
vii) Air leakage in the system may result into high O 2 content and high ID amperage.
viii) Burner tips wearing will lead to oil pressure drop, poor atomisation and soot formation on air heater.
PMI, NTPC 145 6. Oils
(A) Fuel Oil
In India fuel oil fired boilers are not being used because of acute shortage of oil and for being very expensive. Totally oil fired boilers are generally employed where oil is available in abundance or if power station is located near refinery. Here oil is being used in boilers only at the time of starting or for stabilizing flame if the combustion of coal is not proper due to its bad quality or very high moisture content. Therefore, our subject of discussion will not concern totally oil fired boilers, but will be limited to coal fired boilers in which oil is used for starting/flame stabilization purpose.
Oils used in power plant generation are nearly always by products of petroleum. Crude petroleum oil contains mainly carbon and hydrogen alongwith some small amounts of oxygen, Nitrogen and Sulphur. This crude oil is seldom used in original form. Approximate chemical composition of petroleum and its derivatives is carbon 85% & Hydrogen 15%. Many fuels are produced from crude oil by distillation and cracking, which is decomposition under condition of high temperature and pressure.
In power station following fuel oils are being used:
a) Light diesel oil (LDO), b) High Speed Diesel Oil (HSD) c) Furnace Oil (FO, & d) Low Sulphur Heavy Stock (LSHS)
PMI, NTPC 146 LDO and HSD are low viscosity and low flash point oils and can flow easily even at low temperatures. These oils are comparatively costly and have other important applications, such as HSD is used in automobiles and diesel locomotives etc. Both these oils can be used without heating and can be automotives etc. Both these oils can be used without heating and can be atomized by compressed air or by mechanical means i.e. passing it through spray/nozzle at high pressure. Their calorific value is near about 10720 KC al/kg. These oils are, therefore, ideal for starting the boiler from cold when no other source of steam is available for atomization.
Furnace oil, as its name suggests, is the most commonly used oil for limited power generation purpose as mentioned above. Furnace oils are available as low viscosity, medium viscosity and high viscosity types. These oils have definitely much higher viscosity than LDO or HSD. Although they are in fluid state even in winters but cannot easily be handled or used at that temperature. Particularly medium and high viscosity F.Os required heating at the time of unloading and pumping. Even while using, oil has to be preheated to about 110 O C to make it free flowing. Due to low viscosity, it can be atomized by compressed air or mechanically. But better atomization is obtained with steam.
Since generally steam is used for its atomization, F.O. can not be used when boiler is cold and no other source of steam is available. It is comparatively cheapter than HSD/LDO but not very cheap. Its calorific value is approximate 10270 kcals/kg.
LSHS is very thick constituent of petroleum. It is highly viscous. It has to be intensively heated even for unloading from tankers. It is so viscous that it almost solidifies in winters and becomes coal tar like substance. It is, of course, cheapter than F.O.
PMI, NTPC 147 Oil Combustion Equipment i.e. Oil Burners or Guns
The main purpose of oil gun is to atomize oil in very fine droplets (almost like a gas). As mentioned above there are three methods of oil atomization viz (a) by compressed air (b) by mechanical means (c) by steam. Accordingly, basically three types of guns are used although different manufacturers have designed them differently. Now a days oil guns are located in the centre of coal burners and can either be fitted manually when required or can be made to remain permanently in position with compressed air operated retract mechanism. Air for oil combustion is supplied through a concentric (to oil gun) pipe from the secondary air system.
At the tip of this pipe, vanes are provided, which give the air rotary turbulent motion which helps in proper mixing of air and atomized oil. In older P.F. boilers with long flame burners, steam atomization oil guns were provided from side walls i.e. at right angle to burner flame.
Compressed air atomization
Oil is brought to the oil gun tip from central portion and compressed air is supplied through the annular space of the gun. At the tip, gun assembly is comprised of an eddy plant or mixing plate having small holes in the central portion for oil and several holes near the periphery of mixing plate i.e. facing the annular space, for air. Some of the outer holes are connected to inner holes with slots for allowing mixing of compressed air with oil. Over this plate comes the spray plate which is dome shaped and is provided with holes. Both mixing plate and spray plate are tightened together to oil gun with the help of nozzle cap.
Oil is supplied at a pressure higher than air pressure by about 1-1.5 kg/cm 2 . Maintenance of this pressure differential is most essential for proper atomization. PMI, NTPC 148 If the air pressure is less than oil pressure, oil will enter into air passage. Air atomization is done generally in light oils.
Steam atomization
The arrangement of steam atomization guns is exactly same except steam is used in place of air and size of holes in mixing plate and spray plate are large to allow more quantity of oils to be burnt. Steam atomization is used in furnace oil or still heavier oils. Due to heat of the steam oil viscosity is reduced and oil becomes free flowing. Since even in coal fired boilers about 20% of initial load is taken with oil firing, arrangement is provided for controlling the pressure and quantity of oil flowing through the burner to control boiler output. Due to variable oil pressure, atomizing steam has also to be supplied at variable pressure so that steam pressure is maintained about 1-1.5 Kg/cm 2 lesser than oil pressure. Steam consumption is very small (of the order of 1% of boiler output).
Mechanical Atomization
Mechanical atomization is achieved by forcing the oil under pressure through a sprayer plate and orifice. The oil flows at high pressure in the central tube of oil gun and is discharged through tangential slots in the spray plate swirling chamber. This gives jet a swirling motion. Now oil passes through an orifice to create a hollow conical shaped spray. In this system oil pressure has to be maintained high about 16 kg/cm 2 -20 Kg/cm 2 .
Note
If atomization is not proper, droplets can be carried over under the suction of ID fan and can deposit on air heater tubes or plates. This deposit can catch fire if air heaters are not regularly soot blown.
PMI, NTPC 149 Further oil has high sulphur content, which on combustion turns into SO 2 & SO 3 . SO 3 raises the due point of flue gases and condensation may take place even at higher temperature in economizer and in heater zones.
Due to condensation of SO 3 and moisture formed because of combustion of Hydrogen of coal, Sulphuric acid is formed. This acid attacks economizer tubes and air heaters heating surfaces and corrodes them.
Fuel Oil
Following typical Heavy Fuel Oil has been specified for the use in our boilers-
1. Standard : IS 1593/1971 Grades LV -MV HV 2. Flash Point : 66 O C (Minimum) 3. Viscosity (Max.) : 80-120-370 CST at 50 O C 4. Gross Heating Value : 10270 Kcal/kg. (Typical) 5. Total Sulphur (Max.) : 3.5-4-4.5% by weight 6. A.P.I. gravity : 12 Sp. Gravity 0.986 at 15 O C
A coal fired unit contains oil burners having capacity of 15 to 20%.
The functions are: a) to provide necessary ignition energy to light off coal burners. b) to stabilize the coal flame at low boiler/burner loads. c) as a safe and reliable heat input source during light up of boiler.
Following characteristics of fuel oil is considered while selecting-
PMI, NTPC 150 Specific Gravity
Ratio of weights of equal volumes of oil and water at 60 O F.
In other words specific gravity tells us nothing more than what would be the weight of given volume of oil.
Viscosity
This is one of the most important factor while selecting oil for burning in boiler. Viscosity is measured in terms of time in seconds taken for a standard volume of oil to flow through a standard orifice at specified pressure and temperature.
This is measured in centistokes (CST), Redwood No. 1, say bolt Universal, Engler cct. Usually all these units are convertible.
Calorific Value
These are heat content of measured quantity of oil. These are expressed in Kcal/kg or B.T.U./lb.
Flash Point
This is the temperature at which when tested under specified conditions, oil gives out vapour which will just ignite if comes into contact with a flame. This determines the storage conditions of oil.
Pour Point
This is the temperature to which when cooled, the oil stops flowing.
PMI, NTPC 151 This may be due to crystallization of wax or due to increase in viscosity. The pour point determines the handling methods of oil.
Sulphur Content
High sulphur content in oil causes low temperature corrosion of AH elements.
At high temperature it burns as
S + O 2 ----------- > SO 2
With water at lower temperature zones like AH and sometimes economizers it forms sulphurous acid
H 2 O + SO ------------ > H 2 SO 2
This acid is highly corrosive to the metal over which it is deposited.
Methods of Fuel Oil & Lube Oil Analysis
Water % by Dean & Stark (for Petroleum and its product) IS: P-40 ZP-74.
Apparatus
Burner graduated glass trap; suitable condenser (straight condenser with a length 400 mm and suitable joint) Round bottom flask with suitable joint (250 mm).
PMI, NTPC 152 Solvent
The oil sample is thoroughly mixed. Weight 10 gm material directly into the round bottom flask and add 100 ml solvent. Assemble the components of the apparatus. Circulate cold water through the jacket of the condenser.
Apply heat to the round bottom flask, adjusting the rate of boiling so that condensed distillate discharges from the condenser at the rate of 2 to 3 drops per second. Continue distillation until no water is visible in any part of apparatus constant for 5 minutes.
When the evolution of water is complete, allow the trap and contents to cool to room temperature, dislodge any drops of water adhering to the side of the trap with a glass rod or other suitable means and transfer them to the water layer. Read the volume of the water in trap.
Calculation Volume of water in trap X 100 Water Percentage = ---------------------------------------- Mass (or volume) of sample
VISCOSITY INDEX D2270/P56 --------------------------- -----------------
It is the variation of viscosity with temperature, it determines whether the oil changes its viscosity with temperature or not and if it changes, then the extent to which it changes is the rate of change of viscosity with temperature. Viscosity index also measures the paraffinity of an oil as the paraffins have lower rate of change of viscosity with temperature. This is determined by determining viscosity at different temperatures.
PMI, NTPC 153 L - U L - U V.I. = ---------------------- X 100 (a) V.I. = ----------------------- X 100 L - H D
L = Kinematic Viscosity @ 37.8 O C of an oil of O viscosity index having the same viscosity @98.9 O C as the oil whose viscosity index is to be calculated. U = Kin viscosity A 37.8 O C of the oil whose viscosity index is to be calculated. H = Kin. Viscosity A 37.8 O C of an oil of 100 viscosity index having the same viscosity A98.9 O C as the oil whose viscosity index is to be calculated. D = L - H
Calculation
1. Determine the viscosity in centistokes of the oil A37.8 O C and 98.9 O C.
2. With the help of Lable obtain the value of L and D.
Example Given Kin. Viscosity A 37.8 O C = 82.50 C.St. Given Kin. Viscosity A 98.9 O C = 9.100 C.St From table L = 138.18 From table D = 60.44 Substituting in equation (2) = 138.18 82.5 X 100 ---------------------------- 60.44
V.I. = 92.1
3. Viscosity Index Book by ASTM: Sec. chart viscosity A 37.8 O C and 98.9
O C. PMI, NTPC 154 Oxidation Characteristics of Inhibited Steam Turbine Oil
In this method the oil sample is reacted with Oxygen in presence of water and an iron copper catalyst at 95 O C. Test continues until the measured total acid number of the oil is 2.0 mg/KOH or above. The number of test hours required for oil to reach 2.0 mg/KOH is the oxidation life time.
PMI, NTPC 155 (B) Lubricating Oils
If surface are separated by a fluid, the friction between them is considerably reduced and lubricating oil is normally used for this purpose. Good lubrication aims at retaining the oil film between the moving surfaces. Friction produces heat and so a lubricating oil is not only required to prevent the surfaces from coming into direct contact, but also to dissipate the heat from the parts being lubricated. In the case of turbine plant the heat transmitted along the shafts from the steam cylinders also has to be removed and this is another requirement of the lubricating oil.
Before mineral oils were developed in the middle of the last century lubricants were mostly fats such as tallow, castor oil and olive oil obtained from animals, fish and plants.
The fatty materials, although reducing friction initially, formed gums and sticky deposits. As machinery developed, these lubricants were gradually replaced by mineral oils obtained from petroleum. It is essential that a lubricating oil allows trouble free operation of the plant in which it is used. Deterioration of the oil inhibitors may cause rusting in oilways with debris being carried forward into journals and bearings. Shafts can be attacked by acids formed in the oil, or the lubricating properties of the oil can be impaired by emulsification which may result in damage to shafts and bearings. Regular examination of an oil can indicate its rate of deterioration. Thus the sampling and analysis of lubricating oils ensures that they are satisfactory for continued service. If an oil beings to deteriorate, it can be either changed or reconditioned (sometime at site) at a time suited to the operation of the plant, rather than waiting until deterioration makes the oil change essential at an inconvenient time.
PMI, NTPC 156 Lubricating Oil Requirements for Turbine and Large Rotating Plant
Turbine oil maintenance and examination is covered by generation operation under 84 (CP) which lays down the recommended tests to be carried out and the intervals between testing. This applies to all oxidation and rust inhibited oils in recirculation lubricating system of large plant e.g. feed pumps, gas turbine generators. The oil supplier is chosen from a limited number of oil companies which have been approved of both the CE GB and the plant manufacturer. Changes to the specification of the oil are first examined by the Central Electricity Research Laboratories (CERL) and these must comply with British Standard BS 489 and also with the CEGS standard 20722.
Sampling of Lubricating Oils
Lubricating oils are delivered to CEGB power stations by tanker or in 205 liter (45 gallon) steel drums. The weighted sampling bottle (Fig. 11.2) is used to sample the lubricating oil in tankers and storage tanks. Oil contained in a steel drum is sampled by using a clean, dry, tube, called a thief. The tube is dipped into the oil and by placing a finger or thumb over the open end a sample is withdrawn and put into a sample bottle.
Properties of Lubrication Oils
The increase in the size of turbines and generators has resulted in higher loadings of bearings and higher peripheral speeds of journals and the duty the oil is required to perform has become increasingly arduous. It has to withstand continuous thermal cycling and possible contamination by solid particles, sludge, water hydrogen and air.
PMI, NTPC 157 It is expected to readily release such contaminants and retain its lubricating and other properties over very long periods. New oils are expected to last 20 to 30 years.
A lubricating oil may deteriorate for several reasons. It can: 1. Increase or decrease in viscosity 2. Oxidise 3. Become contaminated with water 4. Lose its rust inhibitor 5. Foam 6. Emulisity 7. Become Acidic 8. Become contaminated by dirt or metallic particles
Any of the above may cause damage to any lubricated part of the plant. The tests carried out are designed to pinpoint the type of deterioration and cause so that remedial action can be taken. In a nuclear station lubricating oils used in gas circulators and drives in the vicinity of a reactor can become irradiated and so deteriorate. Lubricating oils are manufactured specifically for these applications and only oils resistant to damage by radiation, should be used.
1. Viscosity
If the viscosity decreases the oil film between the moving surfaces could become so thin that the surfaces actually touch each other. A shaft would then rub directly on its bearing causing damage from abrasion and overheating. If the oil viscosity increases, the thickening oil makes it more difficult for a shaft to revolve in a bearing i.e. the friction is increased. Thus it is important that lubricating oil is kept within its design temperatures. PMI, NTPC 158 Variations in viscosity can occur by thickening of the oil with age or by mixing with an oil of different viscosity. Therefore viscosity measurement is most important
The viscosity of a lubricating oil can be measured in a Redwood viscometer or more usually in a U tube viscometer immersed in a bath at a constant temperature.
The U tube viscometer is filled to the mark A with the oil under test. The tube is placed in the water bath which is at 40 O C until the oil and tube have reached that temperature. Oil is then drawn up into the right hand leg above mark B by applying suction to the open end E. the suction is removed and the oil allowed to fall through the capillary F. A stopwatch is used to record the time taken for the oil to drop from mark B to mark C.
The viscosity of the oil is calculated from the time recorded and expressed in centistokes (CST) as the kinematic viscosity at 40 O C. Some figures for viscosities of lubricating oils are given in table.
These are taken from British Standard 489 which the CEGB uses for all mineral oil lubricants.
Table Lubricating oil viscosities --------------------------------------------------------------------------------------------------- Grade Grade Number Viscosity in centistokes at 40 O C --------------------------------------------------------------------------------------------------- Minimum Maximum -------------- ---------------- Light 32 28.8 35.2 Medium 46 41.4 50.6 Heavy 68 61.2 74.8 Extra 100 90.0 110.0 ---------------------------------------------------------------------------------------------------
PMI, NTPC 159 The viscosity of all oils does not alter by the same amounts for the equivalent temperature change. If the viscosity of an oil remains fairly constant when its temperature is altered it is said to have a high viscosity index. On the other hand the viscosity of an oil within low viscosity index changes appreciably as the temperature is altered. It is desirable to use an oil with a high viscosity index in a pump or motor that is used only now and again i.e. it is subject to temperature changes between running and stopping periods. However, a pump or motor that runs continuously and so remains at a rarely steady temperature, can be lubricated with an oil having a low viscosity index.
2. Oxidation Stability
An oil becomes oxidised when the various compounds which make up the oil combine with oxygen. The compound formed as a result of this oxidation are usually fairly thick and sludge-like in quality. As well as increasing the viscosity of an oil sludges can block small bore pipes and orifices in a lubricating system and so their formation should be avoided. If metal or rust particles occur in an oil the rate of oxidation is increased. Additives called oxidation inhibitors are added to lubricating oils to stabilize them against oxidation. These inhibitors passivate any metals present in the oil and so make them ineffective. As an oil becomes oxidised its acidity increases. It is better to anticipate any oxidation that might occur rather than wait until the acidity has increased or sludges have formed. Oxidation stability tests are carried out on CEGB steam turbine oils at six monthly intervals to provide advance warning of this type of deterioration.
PMI, NTPC 160 3. Water Contamination
Water in steam turbine oils usually comes from the turbine glands, although it could come from a leak in an oil cooler. Sea or river water is often used for lubricating oil cooling. An oil cooler leak may result in the sea or river water entering the oil system which can cause the oil to deteriorate by forming rust and other corrosion products, by forming emulsions with the oil, and by forming other chemical compounds which cause sediments in the oil. A steam turbine oil in good condition will contain between 100 and 200 mg. of water and will appear clear. If the oil appears cloudy, the level of water contamination should be measured by boiling a known volume of the oil with a solvent in a flask known as the Dean and Stark apparatus. Droplets of condensed water vapour fall into the graduated tube and the volume of water is read directly as a percentage.
4. Rust Inhibition
Many oils have inhibitors added to prevent rust formation. Rust can block pipes, choke filters and score bearings. An anti-rust test is applied to an oil to determine its ability to resist the formation of rust. The results of the test are reported as absent, light, moderate or severe. An oil which has produced rusting, even if only light, fails the test. If this occurs further rust inhibitors are added, usually supplied by the oil company.
5. Emulsions
When water is churned up with an oil, initially it turns cloudy and then begins to cream forming an emulsion. If the oil does not demulsify, i.e. the emulsion persists and the water and oil do not separate, it is said to have poor demulsification characteristics. Good oils, however, do demulsify, PMI, NTPC 161 and the speed with which an emulsion breaks up is known as the demulsification number.
An oxidized oil forms emulsions much more easily than a new oil. Rust, metallic particles and dirt not only accelerate oxidation but also accelerate the formation of emulsions. Lubricating properties of an oil can be impaired by emulsions rupturing the bearing oil film and blocking small passages in the lubricating system.
6. Foams
Foams are produced by large amounts of air becoming constrained in an oil. Additives and inhibitors added to the oil to suppress other effects may cause foam formation to increase. Anti-foam agents are added to lubricating oils, although it is critical to limit these to a maximum 0.003% otherwise foaming may be increased.
7. Acidity
After a lubricating oil has been in service for sometime it tends to oxidize into acids. Acids are obviously undesirable because they cause corrosion of metals in the pipework, bearing and other parts of the lubricating system. The oxidation stability test gives advance warning of this type of deterioration, nevertheless lubricating oil acidities are measured since small amounts of acid can be tolerated.
Oil acidities are measured at monthly intervals whilst oxidation stability is measured only every six months because the acidity test takes less time to perform. In pumps and motors where small volumes of lubricating oil PMI, NTPC 162 are involved, it is often more economical to determine acidity in preference to oxidation stability.
Oil acidities are measured by neutralizing the acidity with an alkali, usually potassium hydroxide, in a known weight of oil. The acidity is then expressed as milligrams of potassium hydroxide per gram of oil (mg KOH/g oil).
8. Contamination by Dirt and Metallic Particles
These insoluble contaminants cause rust, accelerate oxidation, increase the acidity and increase the formation of emulsions. The contaminants should be removed by the filters, centrifuges or oil purifiers in the turbine lubrication system. In other large rotating plants such as pumps and motors similar safeguards may not be installed so the contaminants remain in the oil and can cause deterioration.
The test carried out measures the total amount of insoluble organic or inorganic material in oil. The organic material is generally caused by degradation of the oil and the inorganic material comes from wearing or corrosion of the metal parts of the lubrication system.
100 gm of the oil to be tested is diluted with 300 cm 3 of reptane solvent and left for two hours. The mixture is filtered through a fine glass mesh which is weighed before and after the filtration.
The filtrate, the liquid which passes through the filter, is rejected. The residue, the material which remains on the filter, consists of organic and inorganic material. Chloroform acetone and alcohol are then poured successively over the residue, to dissolve all the organic materials. The glass filter is weighed again and the amount of inorganic material can be PMI, NTPC 163 determined. The organic and inorganic material in the oil is then expressed as a percentage.
Other Properties
Lubricating oils are also analysed for various other properties to check their quality. These are mentioned briefly.
Appearance
A great deal of information on the quality of an oil can be obtained by visual inspection. For example, the British Standard 489 states that steam turbine oils shall be clean and free from water, suspended material, dirt, sediment and other impurities. If an oil sample in a clear glass bottle is held up to the light, all these impurities can be seen. Even small traces of water will make the oil appear cloudy.
Flash Point
This is determined on a lubricating oil in exactly the same way as we described earlier for a fuel oil. The minimum accented flash point, determined on a pansky- martins apparatus, for a steam turbine oil is 166 O C and any value lower than this indicates contamination.
PMI, NTPC 164 (C) Insulating Oils
Oil is a better insulator of electricity than air. Switchgear, circuit breakers and transformers operating at high voltages can be made more compact if filled with oil, rather than relaying on an air gap to prevent arcing or flash-over between contacts. Oil in transformers is also used as a coolant to transmit heat from the windings to the cooling surfaces where it is dissipated. In this aspect insulating oil is similar to lubricating oil, which is used as a coolant as well as a lubricant. Oil used as an insulator has to be very pure; impurities in oil act as a conductors (in the same way as impurities in water) and the chemist often has to test the oil and analyse any impurities to discover from where they are coming, what is causing them and how to cure the problem.
Insulating oils are very vulnerable to oxidation because of the heat and electric arcing that is liable to occur in transformers and switchgear. As we saw with lubricating oils, oxidation is accompanied by an increase in acidity, corrosion products and sedimentation. These impurities and water which may leak into an insulating oil or be formed by condensation, are the main causes of oils losing their insulating properties.
The voltage at which an insulating oil causes to act as in insulator (its breakdown voltage) is called the dielectric strength of the oil. This is sometimes measured by the chemist in his laboratory but in many power stations this test is carried out by the Electrical Department personnel. The other analysis that a chemist performs on insulating oils are flash point, acidity, viscosity (which are determined as for lubricating oils) and moisture content. The minimum flash point for an insulating oil should be 146.1 O C if British Standard BS 184 used by CEGB is to be adhered to. A lower flash point can indicate that combustible gases formed by severe electric arcing and oil decomposition in a transformer, have dissolved in the oil. PMI, NTPC 165 These gases include hydrogen, acetylene, and methane. In some power stations the individual gases are tested for, by using a gas chromatograph as already described under natural gas analysis. Acidity should be below 0.2 mg/KOH/g oil as in the case of lubricating oils.
The viscosity of an insulating oil should be below 37 centistokes at 21 O C so that the oil can move freely within a transformer. Convection currents will then be able to carry the hot oil from the core to the cooling surfaces. This test is not performed regularly, as viscosity is very rarely a cause of insulating oils becoming ineffective.
The presence of moisture in an insulating oil is indicated by the simple but sensitive crackle test. To carry out the test about 30mm (1 in) oil are poured into a clean dry test tube. The tube is then heated until the oil boils. If the oil contains any moisture an unmistakable cracking occurs. A similar sound is heard when damp chipped potatoes are thrown into boiling fact in a chip pan. Amounts of water as low as 30 ppm can be detected by the crackle test.
Moisture and other impurities such as dirt, sediment and corrosion products can be removed from an insulating oil by filtering the oil in a special filter press. The press is connected to the transformer and the oil circulated through the filter until all the impurities have been removed. The advantage of this method is that the oil does not have to be withdrawn from the transformer and later filtered in a separate operation.
PMI, NTPC 166 7. Hydraulic Fluids
Mineral Oil Hydraulic Fluids
These fluids, in being of mineral origin, are similar to the oils used for lubrication or insulation. They are soluble in water, forming emulsions and are used where not many moving parts are involved. Mineral oil hydraulic fluids are cheap, but if leaks occur in the hydraulic system, these fluids present a definite fire hazard, particularly at elevated temperature.
Water/Glycol hydraulic fluids
These fluids are better than mineral oils where greater oiliness is required. As they contain water, they are also reasonable fire resistant. At elevated temperatures, however, the water tends to evaporate and the fluids become thicker and sticky. A check on the viscosity of a water/glycol hydraulic fluid will show if the quality has deteriorated and if necessary, water can be added to restore the fluid to its original consistency. These fluids are more expensive than the soluble mineral hydraulic oils.
Synthetic Hydraulic Fluids
Included in these man-made products are hydraulic fluids with chemical names such as chlorinated hydrocarbons and phosphate esters. These have a high resistance to fire and so are used in boiler dampers and other systems where high temperatures are encountered.
Unfortunately, synthetic hydraulic fluid cost about eight times as much as mineral oil hydraulic fluids and the synthetic fluids also tend to attack sea or other similar parts in a hydraulic system. PMI, NTPC 167 8. Other Chemical Aspect Of Power Plant
The chemist in a power station is responsible for certain items of plant and the qualities of materials in addition to these which we have mentioned in the preceding sections of this lesion. We shall only outline these now, because they are mentioned in greater detail elsewhere in the course.
Stator Coolant
Certain designs of generator stators employ water as a coolant. We have already explained that water with dissolved impurities is a good conductor of electricity. Impure water, therefore, could not be used with any degree of safety to cool a stator and so stator coolant water is demineralized. The demineralization process is exactly the same as described earlier in the lesson and the chemist must ensure that the water is always the best possible quality.
Circulating Water
The water used to cool condensers in both conventional and nuclear power stations is usually drawn from a river, an estuary or the sea. Cooling towers may be installed if the volume of available flowing water is inadequate to supply the cooling needs of the power station.
The circulating water from any of the three sources mentioned above will contain certain organism (pieces of plant or animal matter) which could adhere to the insides of tubes in condensers, oil coolers and other heat exchangers in a power station. Much of this matter is removed mechanically by screens fitted into the circulating water system but the tiny organisms pass through the screens. Once inside the system the organisms could grow in the warm temperatures of the heat exchangers and this could seriously affect the efficiency of the cooling. PMI, NTPC 168
The chemist takes many samples of the cooling water in the early stages of the running of a power station and decides on the best method of dealing with the organisms in the water. Chlorine is usually added to the cooling water to kill the organisms, and the chemist will decide how much and how often the chlorine should be added.
He regularly samples and tests the cooling water of an operating power station to ensure that sufficient, but not too much, chlorine is being added to maintain the system in a clean condition.
In estuarine power stations mud or sand may tend to build up in cooling systems. The mud may contain organisms. Corrosion can occur under mud or other deposits and erosion (wearing away by rubbing) can be caused by sand. Mechanical aids are commonly installed to remove these deposits, but at some power stations the chemist is responsible for removing the mud by chemical means. A predetermined amount of a chemical compound called a polyelectrolyte is added to the circulating water.
Polyelectrolytes do not split up to give equal number of cations and anions as do salts which undergo normal ionization. A polyelectrolyte is charged either entirely positively or entirely negatively. Mud particles are usually charged negatively and, as they all have the same charge, they repel each other and settle slowly as very many fine particles which eventually build up into heavy deposits. The addition of a polyelectrolyte (in this case a positively charged polyelectrolyte) attracts the mud and neutralizes the mud particles. The mud particles, which are now neutral and no longer repel each other, come together and form flocculent masses. These remain in suspension and travel with the cooling water, instead of precipitating in the cooling water system. The chemical treatment using a polyelectrolyte is expensive and has met with varying success.
PMI, NTPC 169 Condenser Scaling
Another problem encountered by stations using river water particularly with cooling tower has been scaling of the condenser tubes.
Previously some stations suffered from calcium carbonate scaling which was easily controlled. In recent years however, the picture has changed and many stations are suffering from calcium phosphate scaling.
The change in composition of the scale is due entirely to a change in the river composition.
A number of potential remedies are being explored. These include the use of proprietary chemical additives, pH control, ultrasonic, mechanical solutions e.g. Taprogge and chemical cleaning. At present most stations are carrying out chemical cleaning as necessary and some stations use pH control by adding concentrated sulphuric acid to the circulating water.
Flue Gas Analysis
Most conventional power stations have automatic analysers installed in the boiler flue gas outlets to measure the concentration of carbon dioxide or carbon monoxide or oxygen, so that the efficiency of combustion in the furnace can be assessed. From time to time these automatic analysers are checked either by the efficiency of engineer or the chemist. The concentration of these gases can be measured either on a gas chromatograph (as explained in the natural gas section) or by using a cheaper portable piece of equipment called an orsat Apparatus.
PMI, NTPC 170 The concentration of sulphur dioxide in the flue gas can also be measured automatically and most oil-fired stations have sulphur dioxide meters installed in the outlets from their furnaces.
Stator Polishing Unit
Introduction
Stator winding cooling is carried out by passing DM Water from expansion tank. This tank is kept at a vacuum of 250-300 mm of Mercury. Due to low pressure existing, the DM water is stripped of dissolved oxygen and CO 2 . These dissolved gases are highly corrosive and objectionable to the conductor metal.
Stator Water cooling is a closed loop system designed to maintain a constant flow of cooling water to the Stator Winding at a specified range of inlet temperatures with the aid of pump and coolers.
Description of the Unit
1. Stator polishing unit is a conventional mixed bed exchangers using strongly acidic cation and strongly basic anion exchange resins. These are cylindrical, vertical MS shall rubber lined from inside and containing equal volume of cation and anion resins. Functionally these polishing units remove ionic impurities & also act as filters to remove any particulate matter. At the end of the service run which is indicated by high conductivity or increase in copper content of effluent water, resin bed is regenerated by using hydrochloric acid and sodium hydroxide, for easy mobility. The unit is trolley mounted so that regeneration is carried out in WTP building. This is done to avoid handling of acids and alkalis in turbine hall.
PMI, NTPC 171 Associated Equipments
The DM Water from DM Plant is pumped directly in a hermetically sealed tank where vacuum of 250-300 is maintained. The vacuum is maintained by connecting the tank to the outlet of water box of condenser cooling water. An additional ejector is also provided to the tank. The material of construction of the tank and associated pipelines is stainless steel.
Water Coolers
The Stator cooling water coming out from the winding has a high temperature. The water is cooled by two 100% duty water coolers. The stator water passes through the outer surface and the secondary cooling water (it may be DM Water, or clarified water) passes through the tubes. The entire system includes other equipments such as circulating Pump, Strainers, magnetic filters etc.
Instrumentation
i) Flow Indicators & Recorders Flow measuring instruments are provided. At specified low flow the unit trips.
ii) Specific Resistively Instruments The purity of stator cooling water is monitored by these instruments and at low resistively the unit trips.
iii) Temperature Measuring Instruments The temperature of the inlet water to the stator winding and that of the outlet water from the windings is monitored.
PMI, NTPC 172 TYPICAL DATA OF SPU (Figures given are nominal)
1. D.M. Water required for cooling 25 M 3 /hr
2. Pressure at inlet to winding 4.0 kg/cm 2
3. Quantity of water per coolers 110 25 M 3 /hr
4. Pressure drop of water through coolers 0.8 kg/cm 2
5. Cooling Water inlet temperature to winding 40 O C 45 O C
6. Specific Resistivity 200 K. ohm/cm
7. pH of inlet water to stator winding 6.5 7.5
8. Dissolved Carbon dioxide Nil
9. Dissolved Oxygen less than 0.2 ppm
10. Total Iron content 0.02 ppm max
11. Chlorides Nil
12. Copper content 0.02 ppm max.
PMI, NTPC 173 9. Model Session Plan
POWER PLANT CHEMISTRY DURATION : WEEK
DAY SESSION I & II SESSION III & IV 1. Various impurities in water & need for Water treatment. Water treatment process & Regeneration of ion exchange beds. 2. Boiler water treatment for conventional & once thro boilers. Sampling and analysis of coal, ash, fuel oil, lub. Oil, Hydraulic fluids and flue gas. 3. Mechanical and Chemical treatment for deaeration & combating corrosion Condenser Leak detection and chemical treatment. Sampling & analysis of H 2 & its purity control.