Module 8 Boiler Feed-water Conditioning

Course Contents
1. Water - The universal solvent - Remarkable properties of water Effect of water impurities on boiler operations Water chemistry Water treatment - External water treatment - Basic types of demineralizers and resins used - Internal water treatment

2. 3. 4.

Water
Water - The universal solvent Water is a poor conductor of electricity As more ions dissolve, water becomes a better conductor As the conductivity of water increases, the potential for corrosion and scale formation increases The polar charges on the water molecule make it an exceptional solvent

Water
Water - The universal solvent (cont) Water contains various types of impurities 1. Dissolved solids magnesium, calcium, iron, silica 2. Dissolved gases oxygen, carbon dioxide/monoxide, ammonia 3. Suspended solids silts, clay, sand

Water
Remarkable Properties of Water 1. Water vapor (steam has a high energy content and is an effective medium for transferring energy in industrial plant operations, buildings, and homes 2. Great heat capacity than many substances, so it is an effective heat transfer medium. For each incremental change in temperature, water absorbs or release more heat. 3. Water also releases more heat upon freezing than do other compounds. It is the only chemical compound that is present in the natural environment in all 3 states of matter. 4. High surface tension this causes water to rise in a capillary tube. This physical property (capillarity) is partly responsible for the system of circulation developed by living plants through their roots and tissue system.
5

Water
Remarkable Properties of Water (cont) 5. High dielectric constant water molecules in contact with a crystal orient themselves to neutralize the attractive forces between the ions in the crystal structure. The liberated ions are then hydrated by these water molecules. This keep ions from recombining and thus precipitating from solution. 6. Osmotic pressure This important phenomenon occurring in water solutions related to dissolved matter (solutes), rather than to water (solvent) is osmotic pressure. If 2 aqueous solutions are separated by a membrane, water will pass from the more dilute into the more concentrated one. This important process controls the performance of all living cells.

Water
Remarkable Properties of Water (cont) The formula for water (H2O) by its self tells us only its composition and molecular weight. It does nothing to explain the remarkable properties. The remarkable properties of water are the result of its unique molecular arrangement.

105o

Water
Remarkable properties of water (cont) Two hydrogen atoms are located 105O apart, adjacent to the oxygen atom, so that the molecule is asymmetrical, positively charged on the hydrogen side and negatively charged on the oxygen side. For this reason water is said to be dipolar. This causes the molecules to agglomerate, the hydrogen of one molecule attracting the oxygen of a neighboring molecule. The linking of molecules resulting from this attraction force is called hydrogen bonding. One of the consequence of hydrogen bonding is that molecules cannot leave surface readily Hydrogen bonding produces crystal arrangement that causes ice to expand beyond its original liquid volume.

Effect of Water Impurities on Boiler Operation

Certain impurities have harmful effects on effective and economical boiler operation when they are present in feedwater.

Scale forming impurities 1. Dissolved calcium carbonates, calcium sulphate, magnesium carbonate, magnesium chloride, magnesium sulfate and silica. 2. Some suspended solids particularly salts of a wide variety of chemical make up coming from industrial wastes which abound in the waters from rivers.
Corrosion 1. Corrosion results from dissolved carbon dioxide and oxygen. 2. Grease and oil from animal or vegetable sources in feedwater has a specific ultimate corrosive effect. 3. Much of the organic and sewage content of impure water also tends to increase corrosion.
9

How Scale is Formed

The basic types of scales encountered in the steam boiler are salts of calcium and magnesium. The troublesome scales are usually carbonate and sulfates. Silicate scale will develop in high pressure operations where there is appreciable clay or source of alumina. Scale can be form either by physical attachment to the metal of precipitated calcium or magnesium salts or by crystallization on the metal direct from the boiler water.

10

Scale Control

Scale control are generally concerned with the control of carbonate or salts of calcium and magnesium. External treatment of the feedwater can reduce sources of scales to such low level that subsequent treatment is reduced to minimum.

11

Water Chemistry
Water Chemistry and Interpretation of Water Analysis Common denominator of majority of water problems is hardness Tradition defines hardness as the soap-consuming capacity of water. For practical purposes, it is the calcium and magnesium content of water Hardness is usually expressed in terms of calcium carbonate (CaCO3)

12

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) Alkalinity and Acidity H2O H+ + OHK = [H+] x [OH-] = 10-14

pH Notation pH = log 1/[H+] = -log [H+]

13

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) The importance of CO2 The atmosphere is a mixture of gases containing 79% N2 and 21 O2 by volume. However, it also includes 0.04 % CO2. - Plants containing chlorophyll utilize carbon dioxide in building cellular material such as carbohydrates (photosynthesis) - 6CO2 + 6H2O C6H12O6 (glucose) + 6O2 chlorophyll catalyzes reaction - When CO2 dissolves in water, it reacts with water to form carbonic acid, which dissociates into the hydrogen ion and the bicarbonate ion according to the reaction CO2 + H2O H2CO3 H+ HCO3-

14

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) Source of Alkalinity The alkalinity of most natural water supplies is caused by dissolved bicarbonate (HCO3-) Water containing CO2 dissolves magnesium and calcium from a dolomite (CaCO3 . MgCO3), to produce hardness and alkalinity in ground water. H2O + CO2 + MgCO3 Mg(HCO3)2 Mg2+ + 2(HCO3-) H2O + CO2 + CaCO3 Ca(HCO3)2 Ca2+ + 2(HCO3-) In the pH range of 4.4 to 8.2, there remains a balance between excess CO2 and bicarbonate ions.

15

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) CO32-/HCO3- Distribution Most natural waters contain bicarbonate alkalinity and are at a pH less than about 8.2 to 8.4. Above this pH, CO2 ceases to exist in measurable quantities and the carbonate ion begins to make itself known. The equilibrium reaction is: HCO3- CO32- + H+

In the range of pH 8.2 to 9.6, the bicarbonate and carbonate ions exist together in the absence of measurable carbon dioxide or hydroxyl ions.
Distribution between the carbonate and bicarbonate ions can be determine as follows: CO3 = 2 x P HCO3 = M - CO3 = M - 2P
16

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) CO32-/HCO3- Distribution Distribution between the carbonate and hydroxyl can be determine as follows: CO3 = 2(M P) OH- = 2P - M HCO3 = 0

17

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont)
Neutrality H+ = OHM end point P end point

CO2 escapes quickly

Free CO2 gas

Hydroxyl Alkalinity

Bicarbonate Alkalinity Free Mineral Acid Carbonate Alkalinity

________________________________________________ 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

18

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) Pointers 1. Methyl orange alkalinity (M alkalinity) blue color on the alkaline side and red on the acid side, with gray at the end point. 2. M alkalinity exists above the approximate pH of 4.2 to 4.4. 3. pH of water at about 9.6 to 9.8 hydroxyl ions begins to appear. 4. In water chemistry, the dividing point between acidity and alkalinity is not pH 7, but rather the M alkalinity endpoint, corresponding to a pH of about 4.4. 5. Above 9.6, hydroxyl alkalinity becomes measurable.

19

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) Langelier Index Langelier developed a method for predicting the saturation pH (called pHs) of any water. Parameters involved are: - raw water hardness (mg/l as CaCO3) - Alkalinity (mg/l) - pH - temperature - Chart (pHs) Langelier index = pH - pHs
20

Water Chemistry

Langelier Index (cont) If the actual pH of the water is below pHs, water has a negative Langelier and will dissolve CaCO3. Water is corrosive If measured pH exceeds pHs, Langelier index is positive, and being saturated with CaCO3, water is likely to form scale. Useful in bulk system (low velocity flow) such as lime softener, filters, or reservoirs.

21

Water Chemistry
Water Chemistry and Interpretation of Water Analysis (cont) Ryznar index or stability index Stability index applied only to flowing system, where the environment at the pipe wall is quite different from that of the bulk water. Useful in flowing system where velocity is greater that about 2 ft/sec. Stability index (SI) = 2pHs pH. Water is considered corrosive when SI exceeds approximately 6 and scale forming when the index is less than 6.

22

Water Treatment

Objective The objective of water treatment is to eliminate internal water conditions that lead to scale formation, corrosion, embrittlement and carryover. The prevention of scale formation becomes a problem of putting these salts into such a condition that they cannot or will not deposit in either way. The best answer therefore, lies in treatment of the boiler water in accordance with its content of scale forming salts or solids. One treatment is based on the fact that it is possible to precipitate calcium and magnesium salts in a form that will no longer crystallize on the boiler metal to form scale.

23

Water Treatment

Generally water treatment is approached two ways 1. External water treatment 2. Internal treatment

24

Water Treatment
Summary of most common problems arising from the presence of major impurities such as hardness, iron and microorganisms. Substance in Water Process used for removal Hardness Precipitation Ion exchange Alkalinity Precipitation Ion exchange Neutralization Precipitation Ion exchange Chemical used lime, soda ash, caustic, phosphate salt, acid lime, gypsum acid, salt acid Lime caustic
25

Carbon dioxide

Water Treatment
Summary (cont) Substance in Water Process used for removal Carbon dioxide (cont) Dissolved solids Neutralization Degasification Chemical used lime, caustic none

Reverse osmosis none Reduction by removal of separate components adding to dissolved solids Coagulation, flocculation, sedimentation Alum, aluminates, coagulant aids
26

Suspended solids

Water Treatment
Summary (cont) Substance in Water Process used for removal Iron and manganese Oxidation and Filtration Precipitation Ion exchange Precipitation Ion exchange Clarification Oxidation Adsorption Chemical used chlorine, lime lime, chlorine, air Salt, acid iron, salt, magnesia caustic alum, aluminates chlorine Activated carbon
27

Silica Organic matter

Water Treatment
Summary (cont) Substance in Water Process used for removal Oxygen Micro-organisms Degasification Reduction Clarification Sterilization Chemical used none sulfite, hydrazine various coagulants chlorine, sterilants, heat

28

Water Treatment

External water treatment process 1. Clarification suspended solid removal - Coagulation - Flocculation - Sedimentation - Filtration 2. Softening hardness removal - Precipitation - Ion exchange - Demineralizer

29

External Water Treatment

1. Clarification Turbid raw water contains suspended matter - both settleable solids (particles large enough to settle quiescently) and dispersed solids (particles which will nor readily settle). A significant portion of these nonsettleable solids may be colloidal. Each particle is stabilized by negative electric charges on its surface, causing it to repel neighboring particles just as magnetic poles repel each other. Above prevents these charged particles from colliding to form larger masses, they do not settle.

30

External Water Treatment

Coagulation Colloidal species encountered in raw water include clay, silica, iron and other heavy metals, color and organic solids. The destabilization (charge neutralization) of the colloidal particles in the water caused by the addition of the coagulant which neutralizes the electrical charges of the particles. Colloids are categorized as hydrophobic (water hating) or hydrophilic (water loving). Hydrophobic colloids do not react with water. Most natural clay are hydrophobic. Hydrophilic colloids react with water. The organics causing color are hydrophilic. Aluminum salts, iron salts, or polyelectrolytes are the chemical coagulants usually used. Coagulant used here ferric chloride
31

External Water Treatment

Coagulation (cont) Colloids always require coagulation to achieve an effective size and settling rate Mixing is required to supplement coagulant addition to destroy stability in the colloidal system. Zeta potential is the measurement of colloidal particle charge strength. For natural water in a ph range of 5 to 8, the zeta potential is generally -14 to -30 mv. The more negative the number, the stronger the particle charge.

32

External Water Treatment

Flocculation The coagulated particles formed by the agglomeration of several colloids may not be large enough to settle or dewater at the desired rate. A flocculant gathers together these particles in a net, bridging from one surface to another and binding the individual particles into large agglomerates (grouping and compacting of coagulated particles into larger assemblages called floc) Alum, iron salts, and high molecular weight polymers are common flocculants Flocculant used here sodium aluminate

33

External Water Treatment

Flocculation (cont) Polyelectrolytes - Polyelectrolytes are large water soluble organic molecules made up of small building blocks called monomers, repeated in a long chain. - Structure contain an ion exchange sites which give the molecule an ionic charge. - Cationic positive charge, Anionic negative charge - They react with colloidal material in the water by neutralizing charge or by bridging (tying together) individual particles to form a visible, insoluble precipitate or floc. - Polyelectrolytes used here 34

External Water Treatment

Sedimentation

Removal of suspended solids from water by gravitational settling. The velocity of the water must be reduced to a point where solids will settle by gravity if the detention time in the sedimentation vessel is great enough. Settling rate of particles is affected by their size, shape, and density as well by the liquid they are settling through As a particle settles, it accelerates until the frictional drag of its surface against the liquid equals the weight of the paticle in the suspending liquid.

35

External Water Treatment

Sedimentation (cont)

Steps in settling of particulates in water 1. Particles at first fall freely through the water. 2. As they come closer together, their rate of sedimentation is restricted, and settled sludge volume increases. In the final stages, compaction or compression becomes very slow. - Hindered settling is reached as particulates become so close to each other that the passages between them restrict the ability of water to escape from the sludge - Compaction occurs naturally, but slowly, by gravity and by dehydration of the particulates

36

External Water Treatment

Filtration - Water is filtered by passing it through fine strainers or other porous media to remove suspended solids mechanically 1. Granular Media Filtration Generally applicable for removal of suspended solids in the 5 to 50 mg/l range where an effluent of less than 1 JTU Medium normally silica sand or crushed anthracite Backwashing water or water & air Bed coarse to fine grain medium 2. Multimedia Filter Beds Two layers (Dual media) Provide coarse to fine filtration in a down flow pattern Medium Anthracite grains and silica sand Different grain size and specific gravity
37

External Water Treatment

Filtration (cont) 3. Septum Filters Often referred to as DE (diatomaceous earth) filter Above is used as a filter precoat Applied as slurry to a porous septum to produce a filtering surface

38

External Water Treatment

Tests Test Used to Select Best Chemical and Dosage Level for Clarification 1. Jar test (Used for stream with <5000 mg/l suspended solids) 2. Cylinder test (Used for stream with >5000 mg/l suspended solids) Jar Test 1. Measured coagulant is measured into a sample of turbid water with a high degree of mixing [to disperse it in the water and promote increased frequency of collisions. The duration may be short, less than 1 min. The actual mixing time is refined as the test regimen proceed (in essence, defining the optimum G factor. 2. Particle growth starts to occur because of charge neutralization. 3. Additional coagulant or flocculant is added during the last few seconds of rapid mix if required
39

External Water Treatment

Jar Test (cont) 4. In the slow mix period which follows, floc building proceeds until the floc becomes so big that shear forces finally overcome the bridging forces, breaking the floc apart, limiting floc size 5. After slow mixing for optimum period of time, found only by repeated test (usually 5 to 20 mins), the jars are allowed to settle for 5 to 10 mins.

40

External Water Treatment

Cylinder Test Designed to indicate how fast the suspended solids will settle 1. The slurry sample is placed in a cylinder, chemical is added and cylinder is stoppered 2. Cylinder is gently inverted several times to mix 3. After mixing cylinder is set upright and the interface between the water and the settling solids observed. 4. Time and solids level are recorded 5. Data are plotted on a graph.

Note: On both tests different chemicals [and at different dosages] are run side by side to determine most effective products.

41

External Water Treatment

2. Water Softening Hardness removal used to remove both carbonate and noncarbonated hardness Softening process 1. Precipitation 2. Ion Exchange

42

External Water Treatment

Precipitation Stability Index roughly predict whether a particular water will tend to corrode metal or form a CaCO3 scale Precipitation process makes use of the solubility product of a compound containing an ion or radical that is considered detrimental, and that should be removed before water is put to use. Key variable in precipitation 1. solubility 2. particle size 3. temperature 4. time

43

External Water Treatment

Hardness Removal by Precipitation - Treatment chemicals are generally used to lower solubility of scale forming impurities and to precipitate them as sludge. - Either lime or caustic soda gives hydroxide for precipitation of magnesium hydroxide. - Carbonate to precipitate calcium is usually added as soda ash. - Some carbonate is available when natural bicarbonate is converted to carbonate form by use of lime or caustic soda. - When raw water does not contain enough magnesium to reduce silica content, it is added as magnesium oxide or a component of dolomitic lime.

44

External Water Treatment Hardness removal by Precipitation (cont) Lime and Soda Ash Reaction

1. Lime removes carbonate hardness as insoluble calcium carbonate Ca (HCO3)2 + Ca (OH)2 2CaCO3 + 2H2O calcium bicarbonate calcium hydroxide calcium carbonate water
2. Soda-ash is the second step in removing noncarbonated hardness CaSO4 + Na2CO3 CaCO3 + Na2SO4 calcium sulfate sodium carbonate calcium carbonate sodium sulfate

45

External Water Treatment

Lime and Soda Ash Reaction (cont)

3. Soda ash (sodium carbonate) also reacts with calcium chloride to form calcium carbonate CaCl2 + Na2CO3 CaCO3 + 2NaCl calcium chloride sodium carbonate calcium carbonate sodium chloride
Cold process softening is the term used when these reactions are carried out at room temperature. When water is heated above room temperature, it is called hot process softening. Usually, above 212oF

46

External Water Treatment

Hot process softening operation Hot process softening are used for boiler feed water treatment. Units operate at 2120F or higher. The heat source is steam. A hot process softener mixes steam, raw water and chemicals in the upper zone. The water then flows to bottom, rises through sludge blanket and discharges to anthracite filters. Cold water enters unit through a float-controlled regulating valve in response to water-level changes in the sedimentation tank. Water is heated by spraying it into the upper steam space. Inlet flow actuates a proportioning device to control amount of lime and soda ash fed to the heating and mixing zone. Chemical reactions, already described, take place almost instantly. Sedimentation proceeds at a rapid pace because of the elevated temperature. A sludge collecting cone at the bottom receives the precipitates and discharges them to the sewer periodically. Clarified water leaves the settling tank and is fed to the anthracite filters for polishing.

47

External Water Treatment Hot process softening operation (cont) Hot-process equipment is capable of treating large flows in relatively small units. Chemical dosages are much lower than required by cold-process units. Job handled by the hot-lime softener include: 1. Softening by removing calcium and magnesium, 2. Silica removal with magnesium salts, 3. Oxygen removal and 4. Turbidity removal.

48

External Water Treatment Hot process softening operation (cont) Lime and soda ash are among the most commonly employed chemicals for external water softening, with or without a coagulant to insure the formation of a suitable floc for speedy precipitation (see figure 7). Other chemicals are also used including caustic soda and barium salts, alone or in combination with lime, etc. It must be remembered that the efficiency of water softening is dependent on the controls employed in operating the system. A water softening system is an invaluable aid in economical and efficient boiler operation. Used as the only treatment of boiler water, such a system can give a false sense of security and lead to considerable operating troubles. In general practice, where external water softening system is used, it is possible to recommend the internal treatment required to insure safe and efficient operation of the boiler using the feedwater. Routine tests of the boiler water will then insure a smooth-running and trouble-free system. Heat losses caused by blowdown can be kept at a minimum and the overall quantity of treating chemicals kept low.
49

External Water Treatment

Ion exchange - Removes unwanted ions from a raw water by transferring them to a solid material, called an ion exchanger, which accepts them while giving back an equivalent number of a desirable species stored on the ion exchanger skeleton. - Ion exchangers sodium alumino silicates, zeolite (greensand), synthetic organic ion exchangers. - Ion exchangers used in water conditioning are skeleton like structure having many ion exchange sites. - This insoluble plastic skeleton is an enormously large ion that is electrically charged to hold ions of opposite charge - Types of ion exchangers cation and anion exchangers

50

External Water Treatment

Ion exchange (cont) 1. Exchangers with negatively charged sites are cation exchangers because they take up positively charged ions - Two types of operations 1. Sodium cycle regenerated by sodium salt (ie NaCl) 2. Hydrogen cycle regenerated by Acid (ie H2SO4) 2. Anion exchangers have positively charged sites and take up negative ions. - Two general varieties weak base and strong base exchangers - Anion exchangers are regenerated using alkali (i.e. NaOH, NaCl) - Plastic structure is porous and permeable, so entire ion exchange particle participates in the process.
51

External Water Treatment

Cation Exchanger
Softening Assume a unit, filled with styrene base resins, and start running water through it. Calcium and magnesium ions in the water are replaced with sodium ions from the resin. This is called sodium cycle operation. If hydrogen cycle is used, the calcium, magnesium, and sodium ions in the water would be traded for hydrogen ions. On both cases, the trading or exchange of ions continues until the resin run out of ions to exchange. This is called breakthrough point and when it occurs the exchanger is taken out of service.
52

External Water Treatment

Cation Exchanger (cont) Regeneration The first step in regeneration of the resins is backwashing. Whereas the normal flow is downward, this initial backwash of the resin is upward. This up flow lifts the resin and scrubs off dirt and debris. When the up flow is stopped the resin settles into a uniform bed, decreasing the possibility of direct water flow through the bed (channeling). Next the regenerant chemical is added to the resin bed. Sodium cycle units use salt at a concentration of 10 to 12 as regenerant. Various acids are used for hydrogen cycle regeneration with sulfuric and hydrochloric acid being the most common. Acid concentration is low at first with 2 % being maximum. Further into the process it may reach 6 %.

53

External Water Treatment

Regeneration (cont): The amount of regenerant is calculated to provide the greatest exchange capacity for the amount of chemical added Once the regenerant has been added, the resin is rinsed, usually in two stages to wash away excess regenerant. Now the resin is ready for service and the cycle begins again. A common method used in treatment today is stream softening where the outlets of hydrogen and sodium cycle are combined. Reason is to use the alkalinity in sodium cycle water to neutralize the slight acidity in the hydogen cycle effluent.

54

External Water Treatment

Sodium cycle (Zeolite Softening) Impurities that dissolve in water dissociate to form positively and negatively charged particles known as ions. These impurities or compounds are called electrolytes. 1. The positive ions are called cations because they migrate to the negative electrode (cathode) in an electrolytic cell. 2. Negative particles are then anions since they are attracted to the anode. 3. These ions exist throughout the solution and act almost independently. For example, magnesium sulfate (MgSO4) dissociates in solution to form positive magnesium ions and negative sulfate ions. .

55

External Water Treatment

Sodium cycle - Zeolite Softening (cont) 4. Generally, all natural waters contain electrolytes in varying concentration. 5. Ion exchange material has the ability to exchange one ion for another, hold it temporary in chemical combination, and give it up to a strong regenerating solution. 6. Since sodium zeolite method works by replacing calcium and magnesium in the raw water with sodium, there is no precipitation of solids from the water. The actual content of dissolved solids in the water is increased. 7. The treated water will contain sodium carbonate and bicarbonate from the carbonate hardness And sodium sulfate, sodium chloride and sodium nitrate from noncarbonate hardness.

56

External water treatment

Sodium cycle - Zeolite Softening (cont) Chemical Reactions 1. Softening (exhaustion) Sodium cation exchangers swap sodium ions for other metal ions Ca2+ + Na2X CaX + 2Na+ Mg2+ + Na2X MgX + 2Na+

57

External Water Treatment

Chemical Reactions (cont) 2. Regeneration (brining) Regeneration restores exchanger capacity by replacing calcium ions with sodium 2NaCl + CaX Na2X + CaCl2 2NaCl + MgX Na2X + MgCl2

58

External Water Treatment

59
Sodium cycle

External Water Treatment

Sodium cycle

60

External Water Treatment

Hydrogen cycle The development of ion exchange that could be regenerated with acid to exchange hydrogen ions for cations in water provided the first practical chemical process for removal of sodium, potassium, and ammonia, all of whose salts are extremely soluble Chemical Reactions 1. Softening (exhaustion) Hydro cation exchangers swap hydrogen ions for metal cations Ca2+ + H2X CaX + 2H+

61

External Water Treatment

Hydrogen cycle (cont) Chemical Reactions 1. Softening (exhaustion) Mg2+ MgX Fe2+ FeX 2Na+ Na2X 2NH4+ (NH4)2X Ca(HCO3)2 CaSO4 + H2X CaX + 2H2O + + H2X CaX + H2SO4 2CO2

62

External Water Treatment

Chemical Reactions (cont) 2. Regeneration Regeneration with acid restores hydrogen exchange capacity H2SO4 + CaX H2X + CaSO4 X cation exchanger

63

External Water Treatment

Hydrogen cycle

64

External Water Treatment

Sodium and Hydrogen cycle in series

65

External Water Treatment

Anion Exchanger Anion exchange fall into 2 general categories weak base and strong base. Strongly basic exchange material picks up acid radicals and silica from a hydrogen unit, leaving essentially pure water 1. Weak Base Resins Weak base exchangers dont take out carbon dioxide and silica. They remove strong acids by a process thats more like absorption than it is ion exchange. However the end result is the same, and efficiency of strong acid removal is far superior to that of a strong base material doing the same job.

So weak base units are very useful when water is high in sulfates and chlorides. In these cases they precede a strong base unit. If silica isnt an objection, they handle the complete job of demineralizing alone.
66

External Water Treatment

Anion Exchanger (cont) 2. Strong Base Resins Strong base resins are available as either type I or type II. Type II resins capacity and efficiency is somewhat higher than type I. But type I is commonly used because of 2 main reasons: 1. Type I exchangers are usually more stable 2. They reduce silica to lower residual in range of 0.02 ppm.

67

External Water Treatment

Anion Exchanger (cont) Chemical Reaction 1 Softening (exhaustion) Anion exchanger takes on sulfate anion, gives up hydroxide to form water H2SO4 + X(OH)2 XSO4 + 2H2O Strong base anion exchanger takes on silica ion, gives up hydroxide to form water 2H2SiO3 + X(OH)2 X(HSiO3)2 + 2H2O 2. Regeneration Regeneration with caustic restores capacity for hydroxide exchange XSO4 + 2NaOH X(OH)2 + Na2SO4

68

External Water Treatment

Demineralization - Generally refer to external treatment scheme where relatively pure water is desired - Conventional demineralization unit cation (hydrogen form) exchanger follows by anion (strong base) exchanger - In this process, the anions in the cation effluent are exchanged for hydroxide. - If there are cations present, such as sodium, the effluent will contain sodium hydroxide and this is the most prominent factor affecting the quality of finished demineralized water.

69

External Water Treatment

Demineralization (cont)

Following are the basic types of demins and resins used.

70

Basic Types of Demins & Resin Used

Scheme
1.

Removal Cations Strong Anions Weak Anions

Two Bed

SCR

WBR

By SCR

By WBR

None

2.

Two Bed

SCR or WCR

SBR or MB

1. By SCR 2. By WCR + SCR in MB

By SBR By SBR in MB

71

Basic Types of Demins & Resin Used

Scheme
3.. Mixed Bed

Removal Cations Strong Anions Weak Anions

MB

By SCR

By SBR

4.

Three Bed

By SCR

By WBR

By SBR

SCR

WBR

SBR

72

Basic Types of Demins & Resin Used

Scheme
5. Three Bed

Removal Cations Strong Anions Weak Anions By WCR + By WBR By SBR in MB SCR in MB

WCR

WBR

MB

6. Two Bed with DG

SCR or WCR

DG

SBR or MB

1.By SCR By SBR By DG + SBR 2.By WCR + By SBR By DG + SBR SCR in MB in MB in MB

73

Basic Types of Demins & Resin Used

Scheme
7.

Removal Cations Strong Anions Weak Anions 1.By SCR By WBR By DG + SBR 2. By WCR + By WBR By DG + SCR in MB SBR in MB

SCR or WCR

DG

WBR

SBR or MB

SCR Strong Cation resin WCR Weak cation resin SBR Strong base resin WBR Weak base resin DG Degasifier MB Mixed Bed

74

External Water Treatment

Demineralizer

75

External Water Treatment

76

External Water Treatment

Hydrogen exchanger combined with an acid-adsorber unit (anion exchanger) that removed acids from its effluent and degasifier, producing demineralized water

77

External Water Treatment

Deaeration Dissolved oxygen in the feedwater is one major source of corrosion in a steam boiler. Oxygen is a dissolved gas that does not react chemically with water and become less and less soluble as water temperature increases. Oxygen can be removed by bringing water to the boiling point corresponding to its operating pressure.

78

External Water Treatment

Deaeration (cont) Steam deaerator break up water into a spray or film and then sweep the steam across and through it to force out dissolved gases like oxygen or carbon dioxide. A typical deaerator has a heating and deaerating section plus storage for hot deaerated water. Sometimes a separate tank is provided alongside or underneath unit to hold 10 minutes storage at rated capacity. Steam deaerators fall into 2 broad types. 1. Spray 2. tray 3. combination of both.

79

Internal Water Treatment

Scale prevention Phosphates Phosphates are known to be effective precipitating agents. When used, the calcium and magnesium salts causing scale formation are precipitated in such form that there is negligible tendency to form adherent deposits. Advantages: Precipitate calcium and magnesium as insoluble phosphate salts which has no marked scale forming tendencies. When used in conjunction with suitable dispersants, the precipitated phosphates become integrated parts of the sludge formed. Requires relatively lower concentration.
80

Internal Water Treatment

Chelants Chelants are also used to minimize scale formation in boilers. They are the prime additives in solubilizing boiler water treatment program. Advantages Ability to complex with, and prevent the deposition of many cations (hardness and heavy metals) under boiler water conditions by locking the metal into a soluble organic ring structure. Boilers with higher evaporation rates create conditions suitable for iron oxide deposition. Chelants have the ability to complex iron deposits. Forgiving type ability to remove deposits that may form when feedwater quality or treatment control deviates

81

Internal water Treatment

Dispersant Boiler water dispersants are used in conjunction with precipitating (phosphate) or solubilizing (chelant) internal treatment programs. Dispersants prevent deposition of solid particles and precipitates on heat transfer surfaces. Rather, a fluid sludge forms which collects in the boiler mud drum and exits via blowdown. Solid particles in boiler water can be carryover from raw water filters, clarifiers, or lime softeners, corrosion products from condensate returns, or calcium and magnesium precipitates resulting from hardness in feedwater.

82

Internal Water treatment

Alkalinity Control Another effect of high temperature which accompanies increased operating pressure is the greatly narrowed limits within which protection from corrosion is assured by maintenance of alkalinity in the boiler water. Range is usually between a ph of 9.6 and 10.6.

The possibility of dangerous excess alkalinity is inherent when using strong alkali as caustic soda.
A disastrous problem caused by caustic is caustic embrittlement which is intergranular cracking of steel.

83

Internal Water Treatment

Condensate treatment Corrosion in condensate return lines presents 2 problems: 1. Equipment damage and frequent replacement of steam traps and condensate lines 2. Corrosion products are frequently carried back into steam generating equipment and can result in increased internal deposition and tube failure within the boiler.

84

Internal Water Treatment

Condensate Treatment The major causes of condensate corrosion are dissolved oxygen and carbon dioxide. Dissolved oxygen attack is characterized by tuberculation, pitting, and iron oxide buildup. Dissolved oxygen can enter the condensate system with boiler feedwater or by direct infiltration. Carbon dioxide corrosion is characterized by a general thinning or grooving attack, normally resulting from carbonate and bicarbonate alkalinity decomposition in the boiler which liberates CO2. Carbon dioxide in the presence of water, forms carbonic acid which can cause acidic attack.

85

Internal Water Treatment

Condensate Treatment (cont) Condensate corrosion can be controlled by: neutralizing amines filming amines combination of both

86

Internal Water Treatment

Condensate Treatment (cont) 1. Neutralizing amines directly react with dissolved carbon dioxide, thereby raising ph and eliminating acidic attack. It will not prevent attack by dissolved oxygen 2. Filming amines function by placing a protective barrier film between the metal and corrosive environment Combination treatment jointly employ neutralizing and filming amines. The neutralizer functions to distribute the filmer to insure against an over buildup and to promote the detergency of the filming amine.

3.

87

Internal Water Treatment

Condensate treatment (cont) Control 1. Ph effect of neutralization can be seen directly 2. Iron/copper values indicate any increase or decrease in corrosion 3. Corrosion coupon this are preweighed test specimens which are inserted into condensate bypass piping. Periodically removed and reweighed.

88