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Hardness

Water is referred to as being either 'hard' or 'soft'. Hard water contains scale-forming impurities while soft water contains little or none. The difference can easily be recognised by the effect of water on soap. Much more soap is required to make a lather with hard water than with soft water. Hardness is caused by the presence of the mineral salts of calcium and magnesium and it is these same minerals that encourage the formation of scale. There are two common classifications of hardness:

Alkaline hardness (also known as temporary hardness) - Calcium and magnesium bicarbonates are responsible for alkaline hardness. The salts dissolve in water to form an alkaline solution. When heat is applied, they decompose to release carbon dioxide and soft scale or sludge. The term 'temporary hardness' is sometimes used, because the hardness is removed by boiling. This effect can often be seen as scale on the inside of an electric kettle. See Figures 3.9.3 and 3.9.4 - the latter representing the situation within the boiler.

Fig. 3.9.3 Alkaline or temporary hardness

Fig. 3.9.4 Non-alkaline or permanent hardness (scale + carbonic acid)

Non-alkaline hardness and carbonates (also known as permanent hardness) - This is also due to the presence of the salts of calcium and magnesium but in the form of sulphates and chlorides. These precipitate out of solution, due to their reduced solubility as the temperature rises, and form hard scale, which is difficult to remove. In addition, the presence of silica in boiler water can also lead to hard scale, which can react with calcium

and magnesium salts to form silicates which can severely inhibit heat transfer across the fire tubes and cause them to overheat.

Total hardness
Total hardness is not to be classified as a type of hardness, but as the sum of concentrations of calcium and magnesium ions present when these are both expressed as CaCO 3. If the water is alkaline, a proportion of this hardness, equal in magnitude to the total alkalinity and also expressed as CaCO 3, is considered as alkaline hardness, and the remainder as non-alkaline hardness. (See Figure 3.9.5)

Fig. 3.9.5 Total hardness Top

Non-scale forming salts


Non-hardness salts, such as sodium salts are also present, and are far more soluble than the salts of calcium or magnesium and will not generally form scale on the surfaces of a boiler, as shown in Figure 3.9.6.

Fig. 3.9.6 The effects of heat

Comparative units
When salts dissolve in water they form electrically charged particles called ions. The metallic parts (calcium, sodium, magnesium) can be identified as cations because they are attracted to the cathode and carry positive electrical charges. Anions are non-metallic and carry negative charges - bicarbonates, carbonate, chloride, sulphate, are attracted to the anode. Each impurity is generally expressed as a chemically equivalent amount of calcium carbonate, which has a molecular weight of 100.

pH value
Another term to be considered is the pH value; this is not an impurity or constituent but merely a numerical value representing the potential hydrogen content of water - which is a measure of the acidic or alkaline nature of the water. + Water, H2O, has two types of ions - hydrogen ions (H ) and hydroxyl ions (OH ). If the hydrogen ions are predominant, the solution will be acidic with a pH value between 0 and 6. If the hydroxyl ions

are predominant, the solution will be alkaline, with a pH value between 8 and 14. If there are an equal number of both hydroxyl and hydrogen ions, then the solution will be neutral, with a pH value of 7. Acids and alkalis have the effect of increasing the conductivity of water above that of a neutral sample. For example, a sample of water with a pH value of 12 will have a higher conductivity than a sample that has a pH value of 7. Table 3.9.3 shows the pH chart and Figure 3.9.7 illustrates the pH values already mentioned both numerically and in relation to everyday substances.

Table 3.9.3 The pH scale

DM Plant Commissioning
We are commissioning a D.M. Plant which consists of S.A.C -- D.G.-- W.B.A -- S.B.A -- M.B. The plant designed capacity is 21 cum/hr. The required output between regeneration is 320 cum. The individual vessel sizes and the process flow rates are as follows S.A.C : mode of regeneration : counter current ,service from top to bottom, regeneration from bottom to top with 5% HCl resin quantity : 4400 ltr (Henkel C-20 RESIN) regeneration flow rate : 5.0 cum/hr regeneration and 2.0 cum/hr ceiling water time :45 min HCl quantity : 850 kg 33% vessel dimensions : 1520 dia x 3500 mm Ht pipe line size : 65 nb linear velocity in the vessel : 15 m/hr D.G. Air blower capacity : 540 cum/hr @100 mm WATER COLUMN D.G Tower Dimensions : 700 Dia x 2800 mm Ht. W.B.A mode of regeneration : co current ,with 2.5% NaOH thoroughfare from S.B.A regeneration flow rate : 6.5 cum/hr regeneration time :45 min vessel dimensions : 1500 Dia x 3500 mm Ht pipe line size : 65 nb linear velocity in the vessel : 15 m/hr resin quantity : 2900 lt (Henkel A368) SB.A. mode of regeneration : co current ,with 5% NaOH regeneration flow rate : 2.5 cum/hr regeneration time :45 min

quantity : 400 kg (50% NaOH) vessel dimensions : 800 Dia x 3500 mm Ht pipe line size : 65 nb linear velocity in the vessel ; 42 m/hr resin quantity : 800 lt (Henkel A-113 D)

THE RAW WATER ANALYSIS IS AS FOLLOWS pH : 5.72 T.D.S : 640 ppm as caco3 Total alkalinity : 90 ppm as caco3 P alkalinity : 0 ppm as caco3 Non carbonate hardness: 150 ppm as caco3 calcium :180 ppm as caco3 magnesium : 60 ppm as caco3 sodium :120 as sodium potassium : 9 as k chloride :215 as chloride sulphate : 110 as sulphate nitrate :6 as nitrate fluoride : 0.15 as f silica : 33 ppm as silica

Demineralisation
A Demineralisation Plant consists of two pressure vessels containing cation and anion exchange resins. Various types of ion exchange resins can be used for both the cation and the anion process, depending on the type of impurities in the water and what the final water is used for. Typically, the cation resin operates in the hydrogen cycle. The cations in the water (i.e. calcium, magnesium and sodium) pass through the cation exchange resin where they are chemically exchanged for hydrogen ions. The water then passes through the anion exchange resin where the anions (i.e. chloride, sulphate, nitrate and bicarbonate) are chemically exchanged for hydroxide ions. The final water from this process consists essentially of hydrogen ions and hydroxide ions, which is the chemical composition of pure water. The simplified demineralisation plant consists of: Composite resin vessels with charge of strong cation and anion resin; control-panel encompassing a conductivity measurement and alarms, etc; acid and caustic injection facility from bulk, semi-bulk or carboy containers. What is demineralised water used for? The high-purity water from a demineralised plant is typically used for high pressure boiler feed, wash water for computer chip manufacture, pharmaceutical process water, micro-electronics and any process where high-purity water is a requirement. Why are there numerous types of resins used in demineralisation plants? The type of resins employed and selected depends on numerous factors:

Treated water quality required

Input water quality Presence of organic foulants Water temperatures Flow through plant required Regeneration method - either counter-current or co-current regeneration

There is a vast range of resins to select from, e.g. purafine resins, enhanced capacity resins, gel polystyrene resins, potable clear gel resins, resins for water containing organic matter, resins to achieve low silica levels. What is co-current flow regeneration? The resin contained in the pressure vessel has about 50% free space above the resin (known as resin-free board). This free space allows backwashing, removal of any entrained solids, re-classification of the resin bed and it relieves bed compaction. Water and acid/caustic regeneration is carried out in a down-flow direction. What is counter-current flow regeneration? With counter-flow regeneration, the regenerant acid and caustic passes in the opposite direction to the service flow water. With counter-flow regeneration, the regenerant passes through the resin near to the outlet of the unit and, hence, counter-current flow regeneration has lower leakage to service than the co-current method. How do you regenerate a demineralisation plant? demineralisation plants regenerate automatically according to conductivity. The regenerant for the cation column is 28% hydrochloric acid and 30% caustic soda for the anion column. What is mixed-bed demineralisation? Polishing mixed beds come after the cation and anion standard vessels and, as the name implies, they are there to polish the water. The bed is an intimate mix of anion and cation resins. These resins are not regenerated at a pre-set time according to conductivity and are not operated to exhaustion but are regenerated on time and volume. What is the quality of the treated water from a demineralisation plant? The quality of the water depends on the type of scheme used: Cation-Anion-Polishing Mixed Bed With this configuration, this type of plant should produce water of the following quality: - Conductivity 0.1 S/cm at 25C - Sodium 0.01 mg/l - Reactive silica 0.02 mg/l Cation-Anion (Counter-Current Regeneration) With typical counter-flow regeneration, the average water quality is: - Conductivity 0.5 to 1.0 S/cm at 25C - Sodium 0.05 to 0.1 mg/l

- Reactive silica 0.025 mg/l Cation-Anion (Co-Current Regeneration) With typical co-current regeneration, the outlet quality will depend on the regenerant applied, resin employed and raw water quality. - Conductivity 5 to 30 S/cm at 25 C - Sodium 0.5 to 3 mg/l - Silica 0.1 to 0.3 mg/l How do I size a demineralisation plant? For the sizing of a demineralisation plant, a good in-depth water analysis is normally required which gives the breakdown of total anions and total cations and any potential organic foulants. The final required quality water specification is required, as well as flow rate and water used per day.