zie INTRODUCTION i Water is the most important compound for the of human beings, animals and plants. About 80% of the cart surface is occupied by water. The main sources of water 27¢ 1. rain, 2. rivers and lakes (surface water), 3. wells and springs (underground water). 4. sea water. Among the above sources of water, rain water is the purest form of water but it is very difficult to collect whereas sea water is the most impure form. So, surface and underground water are normally used for domestic and industrial purposes. Such water must be free from undesirable impurities. The process of removing all types of impurities from water and making it fit for domestic or industrial purposes is called water technology (or) water treatment. Before treating the water, we should know the nature as well as the amount of impurities. zize HARD WATER AND SOFT WATER 1. Hard water Water, which does not produce lather with soap solution, but produces white precipitate (scum) is called hard water. This is due to the presence of dissolved Ca and Mg salts.Chsrsies . = (Cp Ny CON Ca be ang, IC yg HagPOONa 4 Ca" harttneee eosin cea onisind (water oluble)] | jon | (scr) tewater i 2. Soft water Water, which produces lather readily with soap colutinn is called soft water. This is duc to the absence of Ca and Mg salts grse HARDNESS OF WATER Hardness is the property or characteristics of water, which does not produce lather with soap. How to detect hardness? Hardness of water can be detected in two ways. 1. When the water is treated with soap solution, if it prevents lathering and forms white scum, the water contains hardn 2C}7HysCOONa + CaCly —>(C}7H35COO), Ca + 2NaCl hardness hard soap causing substance soap 2. Water containing hardness, gives wine red colour with Eriochrome Black-T indicator at pH 9-10. 1.3.1 Types of hardness Depending upon the types of dissolved salts present in Water, hardness of water can be classified into two types. 1. Temporary hardness. 2. Permanent hardness, nananWater JONI ssc ene 1. Temporary hardness (or) Carbonate hardness (CH) (or) Alkaline hardness This is due to the presence of bicarbonates of calcium and magnesium, It ean be removed by (i) boiling the water (ii) adding lime to the water. The above two. proces: convert the bicarbonates into insoluble carbonates and hydroxides, which can be removed by filtering. A Ca(HCO3), —>CaCO,l + H,0 + CO Mg(HCO;), + 2Ca(OH), ->Mg(OH)>! + 2CaCO31 + 2HO (lime) 2. Permanent hardness (or) Non-carbonate hardness (NCH) (or) Non-alkaline hardness This is due to the presence of chlorides and sulphates of calcium and magnesium. It cannot be removed by boiling the water. But, it can be removed by (i) Lime-soda process (i) Zeolite process. CaCl, + NayCO3; —>CaCO31 + 2NaCl (soda) CaSO, + Na)Ze —>CaZe + Na,SO, (sod. zeolite) Total hardness The sum of temporary hardness and permanent hardness. BOILER FEED WATER The water fed into the boiler for the production of steam is called boiler feed water. Boiler feed water should be free from turbidity, oil, dissolved gases, alkali and hardness causing substances. If hard water obtained from natural sources is fed directly into the boilers, the following troubles may arise.td a : ng a —Lngineering Chen = St Roiler troubles (or) disadvantages of using hardwater i 1. Formation of deposits (Seales and shu te in boiler, ges) in boiler Priming and foaming (carry over y over) 3, Cause embrittlement. 4, Boiler corrosion. 1.4.7 Formation of deposits (Scales and sludges) in boilers and heat exchanges When water changers, the concentration of dissolved progressively. When the concentration of 1 uration point, they are thrown out in th ithe inner walls of the boilers or heat recipitated first. is continuously converted into steam 1 in poilers or heat ex jn water increases Its reaches their sat recipitates 0! t soluble one gets Pp sal form of Pp exchangers. The leas Loose precipitate ; suspended in water Hard adhering precipitate on (sludge) Boller: ee yee walls of boiler (scale) @) Fig 1.1 (a) Sludge in boiler (b) Scale in boiler 1. Sludge (Loose deposit) If the precipitate is loos Sludges are formed by the sul MgSO, and CaCl). They have greater solu than cold water. and slimy it is called sludge. stances like MgCl2. MgCO3. bilities in hot waterWater Technology 15 2, Seale (Hard deposit) OW the other hand, if the precipitate forms hard and adherent coating on the inner walls of the boiler, it is called geale. Seales are formed by CaSOq and Mg(ON); Table 1.1°Comparison of substances like Ca(HCOs)o. Scales and Sludges 2 Scale’ a loose, slimy non-adherent and precipitate. Scale is a hard, adherent coating. iy The main sludge forming substances are MgCO3, MgCl), MgSO, ( and CaCl, ete,. The main scale forming substances are Ca(HCO3)>. CaSOs, Mg(OH)>. Disadvantages: Sludges are poor conductors of heat. Excess of sludge formation decreases the efficiency of boiler. Disadvantages: Scales act as thermal insulators. It decreases the efficiency of boiler. Any developed on the leads to explosion. crack scale, Prevention (i) Sludge formation can be prevented ~~ by using softened water. Prevention @ Scale formation can be prevented by dissolving using acids like HCl, H5SO,. (ii) Sludges can also be removed by |; -, blow-down operation”. (ii) Scale formation can’ be removed by (a) External treatment. (b) Internal treatment.(iii) Blow-down op is a proces: removing a portion thermal shock, ri Scrapers, wire by fresh water ete, ie brush, frequently from the boiler during steam production. of concentrated water Disadvantages of Scale Formation 1. Wastage of fuels Scales have low thermal conductivity, so the heat transfer from: boiler to inside water is not efficient. In order to provide steady- supply of heat to water, overheating is done and this causes wastage of fuel. The wastage of fuel depends on the thickness and nature of the scale, which is shown in the table. Thickness of scale (mm) | 0.325 | 0.625 | 1.25] 2.5 | 12 Wastage of fuel sg 10% | 15% | 50% | 80% | 150% 2. Decrease in efficiency Scales sometimes deposit in the valves and condensers of the boiler and choke. This results in decrease efficiency of the boiler. 3. Boiler explosion Sometimes due to over heating the thick scales may crack and causes sudden contact of high heated boiler material with water. This causes formation of a large amount of steam and high pressure is developed which may lead to explosion. Prevention of scale formation 1 At the initial stage, scales can be removed using Scraper, wire brush etc.,Water Technology If scales are brittle, they can be removed by thert shocks, wR 3° By using suitable chemicals like dil. acids (for CaCO; scale), EDTA (for CaSO4 scale) with which they form suitable complexes. 4 If the scales are loosely adhering, they can be removed by frequent blow down operation. 1.4.2 Priming and Foaming (carry over) During the production of steam in the boiler, due to rapid boiling, some droplets of liquid water are carried along with steam. Steam containing droplets of liquid water is called wet steam. These droplets of liquid water carry with them some dissolved salts and suspended impurities. This phenomenon is called carry over. It occurs due to priming and foaming. 1. Priming Priming is the process of production of wet steam. Priming is caused by (i) High steam velocity. (ii) Very high water level in the boiler. (iii) Sudden boiling of water. (iv) Very poor boiler design. Prevention Priming can be controlled by (i) Controlling the velocity of steam. (ii) Keeping the water level lower. (iii) Good boiler design. (iv) Using treated water.18 ____— Ini On CEH ai nistry 2. Foaming aa The formation of stable bubbles called foaming. These bubbles eY t water IS 3 ‘ Aa Strface steam leading 0 excessive priming, MC cartieg Oven i s i Foaming is caused by the (i) presence of oil, and grease. (ii) presence of finely divided Particles Prevention Foaming can be prevented by (i) adding coagulants like sodium 4), - aluminium hydroxide, aluminate, (ii) adding anti-foaming agents _ ike synthetic polyamides. 1.4.3. Caustic Embrittlement (Intercrystalline Cracking) “Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler water usually contains a small proportion of Na CO3. In high pressure boilers this NayCO3 undergoes decomposition to give NaOH. NayCO; + H)O0 —>2NaOH + CO, This NaOH flows into the minute hair cracks and crevices, usually present on the boiler material, by capillary action and dissolves the surrounding area of iron as sodium ferroate. Fe + 2NaOQH—>Na,FeO, +H? This causes brittlement of boiler parts, particularly stressed parts like bends, joints, rivets, etc., causing even failure of the boiler.\ater_Techpology prevention Caustic embrittlement can be prevented by 4) ustiy sodium phosphate as softening agent instead of sodium carbonate, Gi) by adding tannin, lignin to the boiler water, which blocks the hair cracks. \ 4.4.4 Boiler corrosion Corrosion in boilers is due to the presence of 1. dissolved oxygen. 2. dissolved carbon dioxide. 3. dissolved salts. 1. Dissolved oxygen Dissolved oxygen in water is mainly responsible for the corrosion of boiler. The dissolved oxygen in water attacks the poiler material at higher temperature. . 4Fe + 6H,0 + 30) —>-4Fe(OH); 4 Removal of dissolved oxygen ‘ Dissolved oxygen can be removed by chemical or mechanical methods. (a) Chemical method Sodium sulphite, hydrazine are some of the chemicals used for removing dissolved oxygen. 2Na,SO3 + 0, —>2NaySOq NjHy + 0) —>Np + 2H,0 Hydrazine is found to be an jdeal compound for removing dissolved oxygen in the water, since the products are water and inert Np gas.1.10 Engineerin Chemist "5 (b)) Mechanical de-aeration Dissolved oxygen can also be remov cca ed from wa mechanical deaeration (Fig. 1.2), ™ water by Water sn _<— Cita -—— Vacuum pump ee fe) fa O\*— Heater WH Oo Tower | Deaerated water Fig. 1.2 Mechanical deaeration of water In this process, water is allowed to fall slowly on the perforated plates fitted inside the tower. The sides of the tower are heated, and a vacuum pump is also attached to it. The high temperature and low pressure produced inside the tower reduce the dissolved oxygen content of the water. 2. Dissolved carbon dioxide Dissolved carbon dioxide in water produces carbonic acid, which is acidic and corrosive in nature CO, +H,0 —>H,CO; ii the Carbon dioxide gas is also produced from decomposition of bicarbonate salts present in water. A Ca(HCO3)) —>CaCO, | + H,0 +CO2TvA 1a \ Keealtcunay tag) Water Technology Ay at Removal of dissolved Carbon dioxide a) Ca ioxi (Carbon dioxide can be removed from water by adding a calculated amount of NH,OH into water. 2NHJOH + CO, —>(NHy)3CO3 + 120 (b) Carbon dioxide along with oxygen can also be removed mechanically by de-aeration method. - 3, Dissolved MgCl, | Acids, produced from salts dissolved in water. are also mainly responsible for the corrosion of boilers. Salts like MgCly, CaCl, etc, undergo hydrolysis at higher temperature to give HCl, which corrodes the boiler. MgCl, + 2H,0 —>Mg(OH),1 + 2HCI Fe + 2HC1 —>FeCh + Hy? FeCl, + 2H,O —>Fe(OH)2 + 2HCl Removal of acids by neutralisation Corrosion by acids can be avoided by the addition of alkali to the boiler water. HC] + NaOH —>NaCl + H,O 1.4.5 Requirements of Boiler Feed Water Any natural source ‘of water does not supply a perfectly suitable boiler feed water. The boiler feed water must have the following requirements. Hardness Soda alkalinity 0.15-1.0 ppm Caustic alkalinity 0.15-0.45_ ppm. Excess soda_ash 0.3-0.55_ ppm Dissolved gases like O2, CO, |0 ppmfeed water should have zero hardness, ales ad sludges yan iced, Which pyr be efficient heat transfer pre 2 {lt must be free from dissolved — gases like 0>, CO). It leads Corrosion. 3. {lt should be free from| Produces Wet steam suspended impurities. . 4. [It should be free from Produces caug dissolved salts and embrittlement, whisk alkalinity. causes —_brittlement of (OH, COZ” & HCO3), | boiler parts. 5, {It should be free from oil Produces Priming ang and turbidity. foaming, 6. [It should be free from] Produces Priming ang total dissolved solids. foaming, caustic aise SOFTENING or CONDI embrittlement etc., TIONING METHODS Water used for industrial Purposes should be free from hardness producing substances, suspended impurities and dissolved gases etc. “The process of removing hardness Producing salts from water is known as_ softenin: conditioning of water, gor) Softening of water can be done in two methods 1 2. External conditioning. Internal conditioning.Water Technolo, chnology nia Tee EXTERNAL CONDITIONING ae Tt involves the removal of hardness producing he Water before feeding: into the boiler. ‘The external treatrnent can be done by two process 1. Demineralisation or lon-exchange process 5 Zeolite pro 1.6.1 lon Exchange (or) Demineralisation process This process removes almost all the ions (both anions and cations) present in hard water. RCa+ 2HCI RH) + MgSO, —>RMg + H)SO4 RH + NaCl —>RNa + HCl The cation free water is then passed through a anion exchange column, which absorbs all the anions like cr, soy, HCO;, etc., present in the water. R‘(OH), + 2HC1 —>R’ Ch + 2H,0 R’(OH), + HySO, —>R’SO, + 2H,0Acid for: = . " Alkali for se een It 9 jeeseeaes EEN seyeneration exchanger t exchanger a + Deionised water Fig. 1.3. Demineralisation process The water coming out of the anion exchanger is completely free from cations and anions. This water is known as demineralised water or deionised water. Regeneration When the cation exchange resin is exhausted, it can be regenerated by passing a solution of dil HCl or dil H2SO4. RCa + 2HCI —>RH) + CaCly . RNa + HCl-—>RH + NaCl Similarly, when the anion exchange resin is exhausted, it can be regenerated by passing a solution of dil NaOH. R’Cl, + 2NaOH —>R(OH), + 2NaCl. Advantages of ion-exchange process (i) Highly acidic or alkaline water can be treated by this process.d by this process ys s (nearly 2 ppm), Will have very Disadvantages of ion-exchange process (i) Water containing turbidity, Fe and M treated, because turbidity ‘redy Fe, Mn form stable compoun (ii) The equipment is cost} chemicals are needed. 1 cannot b, : e Tete Output and with the resin, 'Y and more expensive 1.6.2 Zeolite (or) Permutit Process Zeolites are naturally Occurring hydrated , aluminosilicate, 1s general formula is NaO. ALO, ea “Met 2. _yHyO.(x=2-10,y=2—6) . Natural zeolites are green sand and non-porous. The synthetic form of zeolite is known as permutit, which is porous and possess gel like structure, hence it is generally used for water softening. , Synthetic zeolite is represented by NaZe. The sodium ions which are loosely held in NayZe are replaced by Ca’* andMg"* ions present in the water. Process When hard water is passed through a bed of sodium zeolite (NayZe), kept in a cylinder (Fig. 1.4), it exchanges its sodium ions with Ca?* andMg** ions present in the hard water to form calcium and magnesium zeolites. The various reactions taking place during softening process are Ca(HCO;), + NayZe —>CaZe + 2NaHCO Mg(HCO;), + NapZe —>MgZe + 2NaHCO; CaSO, + Na,Ze —>CaZe + NapSO4 MgSO, + Na,Ze —>MgZe + NazSO4A water Technology _ Nac ¥ ye ant water a Hard water |-<— Sodium zeolite Soft water Fig. 1.4. Zeolite Process CaCl, + NayZe —>CaZe + 2NaCl MgCl, + NajZe —>MgZe + 2NaCl The softened water is enriched with large amount of sodium salts, which do not cause any hardness, but cannot be used in boilers. Regeneration oe ‘After some time zeolite gets exhausted. The exhausted zeolite is again regenerated by treating with 10% solution of NaCl. CaZe + 2NaCI—SNayZe + CaCl, MgZe + 2NaCl —>NajZe + MgCl, Advantages of Zeolite process (i) Water obtained by this process will have only hardness of 1-2 ppm. (ii) This method is cheap, because the regenerated zeolite can be used again. (iii) No sludge is formed during this process. (iv) The equipment used is compact and occupies a small space.Ysera (vy Its operation is casy Disadvantages of Zeolite process Purbid water cannot be treated, pores of the zeolite bed. because it blocks the a Acidic water cannot be treated, because it decomposes the structure of zeolite. (ii) The sofiened water contains more: dissolved sodi like NaHCO 3, NajCO3, in boilers, CO, and NaOH is produced resulting in boiler Git) UM salts etc. When such water js boiled corrosion and caustic embrittlement. Water containing Fe, Mn cannot be treated, because regeneration is very difficult. This process cannot be used for softening brackish water, é : + i because brackish water contains Na* ions. So the ion exchange reaction will not occur. Table 1.2 Differences between Zeolite and Demineralisation process It exchanges only cations. s well as anions. 2. [Acidic water cannot be| Acidic water can be treated because _acid| treated. decomposes the zeolite. 3. |The treated water|The treated water does contains relatively large amount of dissolved salts, which leads to priming, foaming and caustic embrittlement in boiler: not contain any dissolved salts. Hence there is no priming and foaming.Water Teohnotopy 19 water tmibidity, He, Ma eannotfeontaining turbidity, Vey be treated Mu cannot be treated 1.7£ INTERNAL CONDITIONING or INTERNAL TREATMENT or BOILER COMPOUNDS It involves the removal of scale forming substance, which were not completely removed in the external treatment, by adding chemicals directly into the boiler, ‘This chemicals are also called boiler compounds. 1, Carbonate conditioning 2°) Scale formation can be avoided by adding Ni the boiler water. It is used only in low pressure boilers. The scale forming salt like CaSO, is converted into CaCO3, which can be removed easily. CaSOy + NagCO, —> CaCO; b+ NaySOy.) 5, 2. Phosphate conditioning Scale formation can be avoided by adding sodium phosphate. It is used in high pressure boilers, The phosphate + reacts with Ca?* and Mg? salts to give soft sludges of calcium and magnesium phosphates... 3 CaSO, + 2 NazPOy —> Caz(PO4)2 + 3NagSOq Generally 3 types of phosphates are employed. (a) Trisodium phosphate - NaxPO4 (Too alkaline) - used for too acidic water. (b) Disodium hydrogen phosphate - NajHPO4 (weakly alkaline) - used for weakly acidic water.420 Enginoortng Chemisty ly 4 (c) Sodium dihydrogen phosphate ~ Nall,PO, (acidic) ~ sey for alkaline water. 3. Calgon conditioning Calgon is. sodium) hexa meta : Phosphate [Nay(POsol. This. substance inte ce swith calcium ions forming a highly soluble complex and thus Prevents ‘th precipitation of scale forming salt, 2 CaSO, + Nag{Nay(PO3)6] ——> Nag[Cay(PO3)6] +2 NaySO,, The complex Nay [Ca(POs)g] is soluble in water ang there is no problem of sludge disposal. So calgon conditioning is better than phosphate conditioning. 4, Colloidal conditioning Scale formation can be avoided by adding colloidal conditioning agents like kerosene, agar-agar, gelatin, etc., It is used in low pressure boilers. These colloidal substances get coated over the scale forming particles and convert them into non-adherent, loose precipitate called sludge, which can be removed by blow down operation. DESALINATION OF BRACKISH WATER The process of removing common salt (sodium chloride) from the water is known as desalination. The water containing dissolved salts with a peculiar salty or brackish taste is called brackish water. Depending upon the quantity of dissolved solids, water 1s graded as I. Fresh water - Contains < 1000 ppm of dissolved solids. 2. Brackish water - Contains > 1000 but < 35,000 Ppm of dissolved solids. éwater Technology a 3. Sea water - Contains > 35,000 ppm of dissolved solids, Sea water atid brackish water can be made available as drinking Water through desalination process. Desalination. is carried out cither by reverse osmosis or electrodialysis. 1.8.1 Reverse Osmosis (RO) When two solutions of different concentrations ate sepprated by a semi-permeable membrane... solvent (water) flows from a region of lower’ concentration to” higher concéfifration. This process is called osmosis. The driving force _in this phenomenon is called osmotic pressure. If a hydrostatic pressure in excess of osmotic pressure ‘is applied on the: higher concentration side, the solvent flow is reversed i.c., solvent flows from higher concentration to ‘lower concentration. This process is called reverse osmosis | Fig. 1.5). Thus, in the process of reverse osmosis pure water is separated from salt water) This process is also known as super-filtration, The membranes used are cellulose acetate, cellulose butyrate, etc: a . Direction of —Saline water _/reverse osmosis, ‘— Fresh water - membrane —_Direction of osmosis Fig. 1:5 Reverse Osmosis1.22 Enginoorin, Chomisy (i) The life time of the membrane is | be replaced within few minutes, high, and it ¢, z (i) It removes ionic as well as Non-ionic, coftg: “impurities. * Salloig (iii) Due to low capital cost, simplicity, this process is used for converting drinking water. low peratin Sea water jn, ANNA UNIVERSITY QUESTIONS 1. What is meant by carbonate and non-carbonate hardney of water? Explain with examples [Nov. 0 2. What are boiler troubles? How are they caused? Sugges steps to minimize the boiler troubles. [Dec 9 3. Discuss in detail the problems caused due to the Usag, of hard water in boilers. (June 06 4, What are boiler troubles? How they are caused? How the; are minimized by colloidal conditioning, phosphat conditioning and calgon conditioning. (May 2007 5. Discuss the disadvantages of using hard water in boilen (Chen A.U. Dec 2006)(TNV. AU. Jan 2003 6. What are scales and sludges. Describe the disadvantage of scale and sludge formation: (June 05 A.U.TNV A.U. Jan 2016 7. What is caustic embrittlement: How can it be pera (June 0: 8. Discuss the causes and prevention of priming ” foaming. (June 9. What are the problems one would face when hard wat Make 59 (Dec. 0: is used in boiler industriWater Technoingy ony ew CHEING 1.23 10. Explain the following boiler troubles suggesting the 19. 20. remedical methods: (i) Sludge and scale formation Gi) Caustic embrittlement (CBE. U. Jan 2009) (AU Jan 2013) How will you protect boiler from corrosion. (Dec. 96) Describe _de-mineralisation process of water softening. Explain the reactions involved. [Dec-2002, May 2007, May 2008] How is the exhausted resin regenerated in an ion-exchanger? What are the merits and demerits of ion-exchange method? (AU. Model Q.P) With a neat diagram describe the ionization process of water softening. (TNV. AU. May 2009) Explain how demineralization of water is done in water technology? (CBE. A.U. Jan 2009) Explain the softening of water by deionization process. (TNV A.U. Jan 2009)(Chen. A.U. Jan 2009) Explain the demineralization of water by ion-exchange process. How are exhausted cation and anion exchange resins regenerated? (TNV A.U. Jan 2010) How is the softening of water carried out using the zeolite process? (TCY A.U. Jan 2010) Describe the principle and procedure involved in the zeolite process for water treatment. (A.U Jan 2013) What are ion exchange resins? How are they useful in removing hardness of water. (Chen A.U. Jan 2010) How is internal treatment of boiler water carried out using phosphate and calgon. - (AU. June 06) Explain the Phosphate conditioning. (A.U. Dec. 05) Explain phosphate and carbonate methods of internal treatment of boiler feed water. (A.U. Dec. 06 (TCY A.U. Jan >#19))‘atm, (AU, Dec 2006, Jan 201 Of boiler 3YTI a HEY. 80 .Hhan 20%, 25. Describe briefly the various methods of : conditioning of boiler feed water, (ChenA.y, A Mer, PAU. Jun ‘ : : e 20) 26. What is calgon? Why is calgon conditioning ie | Ma phosphate conditioning? (TN ‘ater, 27. Define the term desalination with a neat diagram, q, desalination by reverse osmosis method. Leoscth (Dec 2003; May 2003, May 4 28. Describe the Reverse Osmosis method for de: Salination , water. (Chen A.U. June 2009)(TNV. AU. May 209 29. What is meant by reverse osmosis? Explain 4 purification of water by reverse osmosis, (Chen. A.U. Jan 2009, May 20 30. What is reverse osmosis? How will you purify the s water by reverse osmosis? Mention’ its advantages, (INV A.U. Jan 201 31. What is. desalination? Explain any one method desalination. (Coim A.U. Jan 2010) (AU Jan 20) 32. What is desalination? With a neat diagram, describe | ‘reverse osmosis’ method for the desalination of brack water. (Chen A.U. Jan 20.