FREQUENTLY ASKED QUESTIONS ON COOLING WATER TREATMENT

INDEX

CHPATER NO CHAPTER 1 CHAPTER 2 CHAPTER 3 CHAPTER 4 CHAPTER 5 CHAPTER 6 CHAPTER 7 CHAPTER 8 CHAPTER 9

DESCRIPTION WATER CHEMISTRY COOLING WATER SYSTEMS TERMINOLOGY USED SCALING CORROSION MICROBIAL GROWTH

CHAPTER 2 : COOLING WATER SYSTEMS

Q 2.1 What are the Different Types of Cooling Water Systems ? There are Three Different Types of Cooling Water Systems : 1. ONCE THROUGH SYSTEM 2. OPEN RECIRCULATING SYSTEM 3. CLOSED RECIRCULATING SYSTEM 1. ONCE THROUGH SYSTEM In a ONCE THROUGH SYSTEM, water is passed through the Heat Exchange Equipment & the cooling water is then discharged directly without recirculation. This system is used where water is readily available in plenty & at low cost. The water source can be sea, river or lake. However the water does not concentrate. Both make up water & recirculating water have almost the same characteristics. Water supply 2. OPEN RECIRCULATING SYSTEM In an OPEN RECIRCULATING SYSTEM , water is passed through an Heat Exchanger & absorbs Heat. This heated water is cooled in a Cooling Tower by partial evaporation & releasing the latent heat of evaporation. In this way water is recirculated & reused using the pumps. The dissolved solids in the water become concentrated due to evaporation. Hence some quantity of recirculating water has to be blown from the system to control the concentration of dissolved salts.The system is prone to have more severe problmes of Scaling , Corrosion, Fouling & Biological Growth.

3. CLOSED RECIRCULATING SYSTEM In a closed recirculating system the water is cooled in a secondary cooler using air , sea water or the cooling water from open recirculating system. It is then recirculated & reused. This system does not employ open evaporation for cooling. Usually water losses are low & hardly exceed 0.5% of the recirculation rate. The Closed Recirculating Systems are used in Diesel Engines, Air Conditioners, Nuclear Reactor Auxiliary Cooler , Comfort Cooling etc.

CHAPTER : 5 CORROSION
Q 5 .1 What is Corrosion ? Corrosion is an electrochemical process by which a metal returns to its natural state. For corrosion to occur there must be an anode, a cathode, an electrolyte & a metallic path for the electrons generated (usually the metal itself). At the Anode, metal ion dissolves into the electrolyte (water) Fe Fe 2+ + 2 e Anodic Reaction

As metal ion goes into solution at Anode, electrons are released which migrate through the metal to the Cathodic area, where the cathodic reaction takes place ie the electrons are consumed. O2 + H2O + 2 e- 2 OHCathodic Reaction

Fe 2+ & OH ions react further to form ferrous hydroxide which is precipitated. Fe 2+ + 2 OH - Fe(OH) 2 Ferrous Hydroxide is rapidly oxidised to Ferric Hydroxide. Fe(OH)2 + O2 + H2O Fe(OH)3 Ferric Hydroxide sludge when dried ,dehydrates to form insoluble ferric oxide which is known as rust. 2 Fe(OH)3 Fe2O3 + 3 H2O Fe2O3, FeO,Fe(OH)2,& Fe(OH)3 are found as Corrosion products on the metal surface & equipments. In the absence of oxygen , Hydrogen ion H+ participates in the reaction at Cathode instead of oxygen & completes the electric circuit. 2H+ + 2e - H2 The electrochemical reactions occur due to potential difference between the anode( - ve potential) & the cathode(+ ve potential ) .Every metal surface is covered with innumerable small anodes & cathodes.

Q. 5.2

What are the factors influencing Corrosion ?

Some important factors influencing Corrosion in cooling water systems are as follows: a) pH Generally corrosion rate decreases with increase in pH. Corrosion is more severe in acidic pH as the protective oxide film is soluble in acidic water. Corrosion of steel is uniform at low pH .At higher pH ,unevenness & tuburculation occurs. b) Dissolved Gases i. CO2 in water forms carbonic acid & reduces the pH ii. O2 dissolved in water is necessary for the cathodic reaction to take place. Corrosion rate of steel increases with increase in dissolved oxygen in water. iii. Nitrogen aggravates cavitation Corrosion. iv. Ammonia is selectively corrosive to copper based metals. v. H2S tends to depolarise the anodic area. H2S is aggressive to iron. vi. Chlorine promotes acid attack & strips corrosion inhibitor film. c) Dissolved Solids The influence of dissolved solids on corrosivity is very complex. Chlorides, Sulfates penetrate passive oxide film & promote local attack resulting in pitting type of corrosion. Hardness salts & alkalinity retard corrosion by forming corrosion inhibiting films. ie DM water is more corrosive than soft water which in turn is more corrosive than hard water. c) Suspended Solids Mud, Sand, Silt, Dirt etc settle to form deposits promoting differential aeration cell corrosion. They can also cause erosion or barasion. d) Microorganisms Microorganisms lead to slime, tubercles. The bacteria proliferate under high pH, low velocity , high sulfates & non sterilised conditions. Even the by products of some organisms are corrosive. Corrosion caused by microbial attack is called as Microbial Induced Corrosion (MIC). e) Temperature In an open recirculatory system , the corrosion rate increases with increase in temperature due to diffusion of oxygen to the metal surface. Above 70 C, due to loss of dissolved oxygen the corrosion rate decreases. In a closed loop corrosion increases steadily as the temperature rises. f) Velocity High velocity promotes erosion corrosion & removes certain passivating film. Similarly low velocity can lead to deposition ,decreases amount of corrosion inhibitor reaching & passivating the metal surfaces causing localized corrosion cells.

g) Heat Transfer Heat Transfer surfaces are more susceptible to corrosion because of differential temperature conditions. h) Dissimilar Metals Direct contact of dissimilar metals results in corrosion f active metal causing galvanic corrosion. i) Metallurgy Metal surface flaws,cuts,nicks,scratches etc favour anodic site formation. Metal under tensile stresses may crack causing tensile stress corrosion cracking. Microstructure ie metal inclusions, precipitation at grain boundaries, differing adjacent grains etc promote galvanic cell formation. Q 5.3. What are the different types of Corrosion ? Different types of Corrosion are as follows : a) Uniform Attack Uniform Attack is a form of corrosion that occurs with equal intensity through the surface of the metal. At neutral pH & below , the corrosion of steel tends to be fairly uniform. b) Pitting It is a localised attack caused by formation of highly active local anodic sites. In Pitting , small pits are formed on the metal surface. These may result from unequal ionic concentration or oxygen differentials. Pitting is the most common cause of metal failure. c) Under Deposit Corrosion Deposits such as Corrosion products, scales, slime etc formed on the metal surface gives rise to differential concentration cell. This gives rise to Corrosion. Under Deposit Corrosion leads to deep pitting & perforation of metal surface. Low flow areas are prone for this type of corrosion. d) Crevice Corrosion This is another form of electrochemical corrosion. This form of corrosion occurs due to accumulation of aggressive ions & oxygen differentials inside the crevices. A water or liquid trapped between a pipe & a flange can lead to Crevice corrosion. A stagnant liquid in the crevice had a lower oxygen concentration & this leads to crevice corrosion. e) Selective Leaching Selective Leaching occurs when one metal or constituent of a metal selectively corrodes. The most common examples are Dezincification , Graphitication & Dealuminification. Dezincification of Brass occurs in cooling water systems with high chlorine levels. After leaching mechanical properties of the metal are impaired & the chance of metal cracking are more.

f) Erosion Erosion Corrosion is caused by high velocity & turbulence This is caused by the a combination of chemical attack as well as physical abrasion. Liquids with high suspended solids are prone for Erosion corrosion. g) Stress Corrosion Cracking Metals under tensile stress in a corrosive environment & temperature develop this type of corrosion. Cracking is more commonly observed with stainless steel &can be either Intergranular or Intragranular. Once a stress crack begins , it easily propagates throughout the metal . h) Waterline Attack If the heat exchanger system or the distribution system is not completely filled with water, then there is a region or area filled with air. This causes differential aeration cell corrosion. The corrosion takes place due to wetting & drying at water interface. Q.5.3 How do we Control Corrosion ? The most widely accepted methods for Corrosion Control in industrial cooling water system are as follows : a) Protective Coating / Lining b) Oxygen Scavenging c) Cathodic Protection d) Use of Sacrificial Anodes e) Adjustments to water chemistry eg pH , Conductivity , Bicarbonate equilibrium etc. f) Use of Corrosion Inhibitors The selection of the method depends upon :i) Techno Economic Consideration ii) Expected Life of an Equipment iii) Desired performance of Equipment iv) Corrosion Allowance & Expected Corrosion Rate v) Combination of Two or more Methods

Q.5.4 What are different types of Corrosion Inhibitors ? Corrosion Control in Cooling water systems is achieved by using Corrosion Inhibitors. Corrosion Inhibitors are normally classified based on their mode of action as follows : a) Anodic Corrosion Inhibitor b) Cathodic Corrosion Inhibitor c) Mixed Corrosion Inhibitor A) Anodic Corrosion Inhibitor These inhibitors function by blocking anodic corrosion sites through formation of a protective oxide/inhibitor film. To ensure complete protection all anodic sites must be filmed. That is why Anodic Inhibitors are generally applied at high dosages. Typical Anodic Inhibitors are i) Chromates ii) Molybdates iii) Ortho Phosphates iv) Nitrites v) Silicates B) Cathodic Corrosion Inhibitor Cathodic Corrosion Inhibitors form a visible film along the cathode surface which polarises the metal surface by restricting the access of dissolved oxygen to the metal substrate. The dosage required is less than the anodic corrosion inhibitor. Typical Cathodic Corrosion Inhibitors are j) Polyphosphates k) Zinc l) Calcium Carbonate C) Mixed Corrosion Inhibitors An inhibitor which has both cathodic as well as anodic mechanism is called as Mixed Corrosion Inhibitor. Organic Filming Amines, Phosphonates give corrosion inhibition by both anodic as well as cathodic mechanism. A) Synergistic Blend of Corrosion Inhibitors Practically , the use of only one corrosion inhibitor in open recirculating system is rare. Usually two or more corrosion inhibitors are blended to utilise the advantage of each & to minimise their respective limitations. A combination of cathodic and anodic corrosion inhibitors give a better corrosion control at economical use levels. eg A Zinc Chromate based Corrosion Inhibitor blend used at 40 50 ppm gives better corrosion control than 200 ppm or more of Chromate alone.

Most commonly used synergistic blends of Corrosion Inhibitors are :a) Zinc Chromate b) Zinc Polyphosphate c) Zinc Phosphonate d) Chromate Polyphosphate e) Chromate Orthophosphate f) Zinc- Polyphosphate- chromate g) Polyphosphate Silicate h) Molybdate- Zinc Azole i) Molybdate Nitrite Borate j) Nitrite- Borate silicates k) Molybdate - Phophonate- Dispersant l) Molybdate orthophosphate Dispersant Q.5.5 How Non Ferrous Metals are protected against corrosion ? Copper & its alloys such as Admiralty Brass, Cupro Nickel (90:10 ) are frequently used in cooling water heat exchangers. These are relatively resistant to corrosion. The chemical factors such as low pH, ammonia, cyanides, sulphides, excessive chlorine residuals cause corrosion of copper & its alloys. When corrosion occurs there is an increase in copper content of recirculating water. This copper will get deposited on steel surfaces & create galvanic cell action resulting in pitting corrosion of the steel. High velocity causes erosion of copper based materials. Azoles such as Mercaptobenzothaizole (MBT) , Benzotriazole (BT) , Tolytriazole (TT) are very effective in inhibiting corrosion of copper & copper based alloys. Recently Halogen Resistant Azole (HRA) is also used as copper corrosion inhibitor. This is effective even in the presence of high chlorine residuals in recirculation. Q.5.6 How do we measure Corrosion? Proper monitoring of Corrosion rates is very much essential for control of corrosion. Corrosion rates are normally determined by two techniques 1. Corrosion Meter 2. Corrosion Coupons Corrosion Meter works by measuring an electrical potential across electrodes made of the metal being evaluated. Corrosion Meter gives an instantaneous reading & indicates the corrosive tendency of water at the time of measurement. Corrosion Meter helps to monitor day to day water quality & corrective steps can be taken immediately. Probes of various metallurgy are used to determine corrosion rate. Corrosion coupons determine the long term effect of water & metal contact under fluctuating system conditions. Preweighed coupons are exposed in the water for a period of 30/60/90 days & thus it gives average corrosion rate for the period of exposure. The corrosion coupons give us an idea about both general & pitting corrosion as well as fouling conditions.

Besides these , regular analysis of a cooling water can give an indication of the corrosion in a system . The parameters monitored are normally associated with the material of construction. Q.5.7 What is MPY ? MPY means Mils Per Year. One Mil is 1/1000 inch. Corrosion rate is normally expressed as weight loss per unit area per unit time( weight loss/area/time). This weight loss can be expressed as mdd ie milligrams per square decimeter per day or mpy ie mils per year or mpd ie mils per day. Q5.8 How do we calculate Corrosion Rate ? The Corrosion rate is calculated using the following formula : Corrosion Rate (In mils per year mpy) = CxWxK AxT

where C = 18.2 W = Area of exposed coupon in cm2 K = Density Factor of metal T = no. of days coupon exposed K density factor for various metals are as follows : Sr No 1 2 3 4 5 6 Metal Carbon Steel Stainless Steel a) Types 201,302,304 b) Types 309,310,316,316L Copper Admiralty Brass 687 Admiralty Brass 442,443 Copper K Factor 1.000 0.990 0.985 0.879 0.944 0.923 0.879 Density g/cm2 7.86 7.94 7.96 8.94 8.33 8.52 8.94

The Area of a coupon is calculated as follows : Area of Coupon = { 2 LW + 2 LT + 2 WT } -- 2 D2 + D T 4 where L W T D = = = = = Length of the coupon Width of the coupon Thickness of the coupon Diameter of the hole 22 / 7 = 3.1428

Q.5.9

What is the accepted standard corrosion rate ?

Based on the exposure time of 30 days for coupons the corrosion rate is rated as follows: a) Less Than 2 mpy : Excellent Corrosion Protection b) 2 5 mpy : Good Corrosion Protection c) 5 10 mpy : Moderate or doubtful Protection d) More than 10 mpy : Poor or no Protection These Corrosion rates are for Mild Steel or carbon Steel. For Copper & Copper based alloys like Admiralty Brass , Cupro Nickel (90:10) & Stainless Steel the corrosion rate of 0.5 mpy is considered to be good.

CHAPTER 6 : MICROBIAL GROWTH

Q.6.1 What are the different types of organisms found in recirculating water systems ? The recirculating water system provides a unique environment for the rapid growth of microorganisms. Algae , Fungi & Bacteria are the types of organisms which grow & proliferate in cooling water systems. They may be airborne, entrained during the construction, or can come through raw water make up. The temperature condition of the recirculating water system is usually suitable for their growth. ALGAE Algae requires air, water & sunlight for its growth. They carry out photosynthesis with sunlight . They manufacture their own food by fixation of carbon dioxide using water , inorganic salts & water. The distribution decks, & the side walls of a cooling tower are ideal locations for the growth of an algae. They are introduced into the cooling water system through air borne dust & make up water. If not treated, very often mats of algae are seen on cooling tower decks. Normally algae have very little direct effect on the heat exchangers , However dislodged algae may interfere with the proper water distribution on the tower deck & thereby reduce the heat transfer. Algae biomass can become nutrient source for bacteria. If attached to & / or deposited on metal surface it can contribute for localised corrosion viz. Micribiologically Induced Corrosion (MIC). FUNGI Fungi are non photosynthetic organisms. They are either unicellular , colonial or filamentous.Fungi are plants without chlorophyll. They live on dead organic matter.They utilise wooden structure of the cooling towers as a source of nutrient & thus destroy wood lumber. The excessive fungal growth on the wood is called as Woodrot Fungi are classified as Yeast & Molds. Mold forming or spore forming fungi ,which are found in circulating water , remain dormant for a long period under unfavourable conditions. This dormant condition makes them relatively harmless. The circulating wtaer pH & temperature conditions are favourable for the growth of fungi. BACTERIA Many types of bacteria are found in cooling water system. Based on the shape of the bacteria are classified as Rods(rod shaped), Cocci(spherical shaped) & spirals (spirally shaped). Bacteria exist as Unicelluar or Multicellular. Autotrophic bacteria manufacture their own food by oxidation of inorganic material. eg Sulphate Reducing Bacteria (SRB), Iron consuming Bacteria. Heterotrophic bacteria derive their food from both organic & inorganic material eg Slime forming bacteria.

Bacteria can be also described as Aerobic or Anaerobic depending upon whether they flourish in oxygenated environment or environment void of oxygen. Q.6.2 What is Slime ? Slime is an extra cellular gelatinous secretion of varying consistency. Slime formation depends on the environmental conditions such as temperature , availability of nutrients etc. Suspended matter, air borne dust, mud, silt, etc becomes entrapped the slime mass .They deposit on metal surface . They reduce the heat exchanger efficiency & also create differential aeration cells resulting in high localised corrosion rates. Q.6.3 What are the factors influencing Microbiological Growth ? Cooling water systems provide ideal environment for the growth of microorganisms. Following physical & chemical factors affect the microbiological growth : a) Ambient & system temperature b) Roughness of solid surface c) pH of water d) Particulate Matter in the water e) Sunlight Cooling water system offers plenty of water, good aeration & a continuous supply of nutrients, Process contamination, Oil ingress is another major source of nutrient supply to microorganisms. Increased use of phosphate based chemicals & rising use of nutrient containing waste water such as treated sewage water as make water are ideal sources for the microorganisms to flourish. Q.6.4 How Microbiological growth is controlled ? Neither physical nor chemical conditions can be changed ina practical way to control microbiological growth. Hence only way to control it is to add certain chemicals in cooling water system. These chemicals are termed as BIOCIDES. Biocides kill the microorganisms. It is very difficult to kill all the microorganisms in a cooling water system. What is best achieved is the maximum killing & control of growth. The efficacy of biocide depends upon the operating pH of the cooling water system, temperature, nature & amount of pollutants such as Hydrocarbons, process contaminants eg Ammonia, other nutrients such as ortho phosphate present. Q.6.5 What are the different types of Biocides used in cooling water system ? Biocides are usually classified as BIOCIDES. OXIDISING BIOCIDES & NON OXIDISING

Oxidising Biocides are capable of undergoing oxidative reactions with organic molecules. Oxidising Biocides ,notably forms of Chlorine & Bromine are the primary biocide used in cooling water systems. They are more widely used because they are effective & less expensive. Non oxidising biocides are more effective than oxidising biocides. There are variety of Non oxidising biocides available. The selection of proper biocide or combination of biocides depends on the type of organisms present , type of cooling water system, water characteristics, plant past history & environmental limitations. & restrictions. Q.6.6 What are the different types of Oxidising Biocides ? Different types of Oxidising Biocides used in Cooling water systems areas follows : 1. Chlorine Compounds Chlorine compounds such as Chlorine gas, Sodium Hypochlorite , Bleaching Powder , Chlorinated isocyanuartes are typical examples of this class. They are different in their functional mechanism but are different in their form. These chlorine compounds dissociate in water to produce Hypochlorous acid (HOCl). Cl2 + H2O HOCl + HCl .. (1)

Ca(OCl)2 + H2O

Ca(OH)2 + 2 HOCl .. (2) NaOH + HOCl . (3)

NaOCl + H2O

HOCl further dissociates to form Hypochlorite ion( OCL -) & hydrogen ion (H+) HOCl H+ + OCl . (4)

B) Chlorine Release Compounds These are the compounds such as Chloroisocyanurates & Chlorohydantoins which generate hypochlorite & Hypochlorous ions when dissolved in water. These stabilised forms of chlorine are easier or safer to feed than gaseous or liquid chlorine. These organochlorine compounds vary markedly in stability, product form , cost & chlorine release mechanism. Free Residual Chlorine of 0.2 to 0.5 should be maintained in cooling water return to cooling tower. Process contamination, oil ingress , ammonia contamination result in high chlorine demand. The biocidal activity of Chlorine is very sensitive to pH & decreases rapidly above 7 pH. Recently chlorine use is dropping because of its reduced effectiveness in high pH water & in reclaimed water containing ammonia. 3. BROMINE COMPOUNDS An alternate to chlorine is becoming very popular.. it is generated by action of bromide salts with chlorine gas, hypochlorite liquid producing hypobromous acid or sodium

hypobromite.Bromine is more biologically active & cost effective than chlorine at pH above 7.5 & in the presence of ammonia. 4. CHLORINE DIOXIDE Chlorine dioxide is becoming popular because of its effectiveness at high pH levels(pH above 7.5) & non reaction with ammonia. It must be generated on site. Its production requires handling of several liquids. Unlike Chlorine it does not react with water to form hypochlorous acid & hydrochloric acid. It is less corrosive than chlorine. 5. OZONE Ozone is an allotropic form of oxygen. Ozone is a powerful & naturally unstable oxidising gas. Ozone is prepared by reformation of oxygen molecule s using high voltage , high frequency electric field. Ozone enriched gas is then bubbled through cooling water & the residual is maintained at 0.01 to 0.1 ppm. It is affected by temperature , pH , organics , contamination etc. Q.6.7 What are the different types of Non Oxidising Biocides used in Cooling Water Systems ? Different types of Non Oxidising Biocides used in Cooling Water Systems are as follows: A) Chlorinated Phenols They were most commonly used non oxidising biocid. They control most organisms except aerobic slime forming bacteria. Sodium PentaChloroPhenate ( SPCP) was the most widely used . However due to toxicity to aquatic life the use of SPCP is dropping. B) Quaternary Ammonium Compounds ( QUATs) Quats are cationic surface active quaternary nitrogen compounds.They are effective against algae & bacteria especially at neutral & alkaline pH range. Their mode of activity is attributed to cationic charge which forms an electrostatic bond with the negatively charged microoragnism cell wall. They cause cel death through protein denaturation by distorting the permeability of the cell wall. The activity of quats is reduced by high chloride concentration , organic contamination, heavily fouled system with dirt & debris. Overfeed of Quats can cause foaming problem. Quats can react with anionic dispersants to cancel the effectiveness of both. C) Organic Sulfur Compounds The most commonly used Organo sulfur based non oxidising biocide is MBT ie Methylene Bis Thiocyanate. It is effective against Sulfate Reducing Bacteria.MBT hydrolyses rapidly at pH above 8. Besides MBT , various carbamates are also widely used as Non Oxidising Biocides.

D) Glutaraldehyde Biocide formulations based on Glutaraldehyde are gaining more acceptance. They are effective against trouble some bacteria. They have however limited effectiveness against algae & fungi. E) Dichlorophene It is a non oxidising phenolic based biocide effective against bacteria & algae. It is more effective under alkaline pH Range. F) Dodecyl Guanidine Hydrochloride It is a broad spectrum non oxidising biocide. It functions like a cationic surfactant by disruption of extra cellular enzyme reactions. High dosages of this biocide can lead to foam problem. G) Isothiazolines Blends of two or more Isothiazoline compounds are used as a broad spectrum biocide. They are particularly effective against bacteria & are active over a wide pH range. They are effective at low use concentration. H) Organobromine Compounds Compounds such as Dibromo nitrilopropionamide (DBNPA) , Bromonitro propanediol (BNPD) are effective broad spectrum , organobromine based Non oxidising biocides. They are effective in controlling bacterial growth. They are used in systems with relatively high levels of biomass & organic contaminants. Q.6.8 What is Biodipersant ? Biodispersants are the chemicals whih hav little or no biocidal activity. They loosen microbiological deposits which can then be flushed away. They prevent microorganism attachment or reomve attached biofilm. They also expose new layers of microbial slime or algae to the attack of biocide thereby enhancing the effectiveness of the biocide. The biodispersants also act as Deposit Penetrants . They are dosed either continuously or as needed before or during biocide addition. Organic accumulations caused by oil leakages & greases are penetrated & dispersed by them. They also fluidise deposit forming silts & clay which can foul heat tranfer surfaces & restrict flow. Q.6.9 What are the acceptable norms for Microbiological Control in recirculating water systems ? The acceptable level of organisms present in the recirculating water systems will vary form plant to plant. The following data indicates particular values that provide a basis for assessing the effectiveness of a microbiological control program. i) Total Bacterial Count (TBC) ii) Sulfate Reducing Bacteria : Not more than 500000 organisms per ml : 100 organisms per 100 ml

Q.6.10 How do we select a Biocide ? The selection of a Biocide is based on number of variables which include the type of microbial growth, water chemistry, system design , & retention time, compatibilty with other products , cost considerations, safety in handling & government regulations. Following points should be kept in mind while selecting a biocide program : i) Chlorine & Chlorine releasing biocide should be avoided in systems with high chlorine demand. ii) Based on the retention time , biocide should be selected eg for systems with low retention time, a fast reacting biocide should be selected. iii) The compatibility of biocide with other chemicals added in the system should be known prior to dosing of biocide. iv) The past plant history should be known before biocide selection eg if certain species have developed immunity towards a specific biocide, it should be known before. v) Local restrictions governing discharge of the blow down water form cooling system must be considered. Q.6.11 What should be the dosage of Biocide & what should be the frequency of Biocide Dosing ? Since variety of microorganisms are flourishing at different locations in the recirculatory cooling water system , it is practically impossible to design a universal biocide program. Higher dosages are recommended for heavily biofouled systems. Initially a high dose of biocide is added to control existing microorganisms. After biocide addition it is desirable to shut off blow down & allow a retention time of minimum 4 8 hours & thereafter give heavy blowdown. Once the system is brought under control , it is necessary to inhibit further growth & proliferation of microorganisms. This subsequent dose is usually lower than the initial dose. The frequency of dosage depends upon the retention time within the system, temperature, sunlight, process contamination etc. As microorganisms are prone to develop immunity towards biocide, it is desirable to recommend two or more biocides to be dosed alternately. Biocides are usually slug fed to a system. This gives a rapid & effective reduction in the number of microorganisms. Typically two biocides are dosed to a system alternately. This avoids the problem of immunity developed by the microorganisms. Biocide dose is based on the system hold up . Chlorine is injected into the system using chlorination equipment . Chlorine can be dosed continuously or intermittently depending upon the requirement.

CHAPTER 4 : SCALING
Q.4.1 What is a Scaling ? Scaling is the formation of insoluble particles in the bulk water & then the subsequent adherence of these particles to metal surface. The formation of these insoluble particles takes place only when the solubility of the salt in the cooling water is exceeded. Q.4.2 What are the factors affecting Scaling ? The factors affecting scaling are as follows: A) Water Temperature Many Scale Forming salts exhibit Inverse Temperature Solubility ie the solubility of these species decreases with an increase in temperature. eg Calcium Carbonate , calcium Phosphate . Generally these salts precipitate at high skin temperature area B) System pH or Alkalinity The scaling potential of scales such as Calcium Carbonate , Calcium Phosphate, Zinc Phosphate , Zinc Hydroxide etc increases with increase in pH . Low pH accelerates corrosion potential thereby providing nucleation sites for scaling. Also low pH increases potential for Silica scaling. C) Water Flow Velocity As the water flow rate increases the scaling rate decreases. As a thumb rule , the scaling rate at a flow rate of 0.6 m/sec is @ 1/5 th of that at a flow rate of 0.2 m/sec. Low flow velocity can allow time for nucleation for scale formation, crystal growth & also will lead to a formation of dense , adherent scales. D)Amount of scale forming salts present A number of mineral salts may lead to deposition of insoluble products in cooling water systems . The principal anions are Bicarbonates, Carbonates, Hydroxides, Phosphates, Sulphates & Silicates. The principal cations are Calcium, Magnesium, Aluminium, Iron, Zinc . Certain ions form a soluble ion pairs that decrease the deposition potential of scale forming salts. eg Mg will form Magnesium sulfate thereby decreasing the scaling potential of calcium sulphate. 6. Influence of Dissolved Solids & Suspended Solids High Dissolved Solids caused due to presence of highly soluble salts can extend the solubility of some scale forming salts eg Calcium Sulphate in presence of high Sodium . High Suspended Solids can provide nucleation sites there by increasing scale potential.

Q.4.3 What are the different types of Scales commonly encountered in Cooling Water Systems ? Common scales encountered in Cooling Water Systems are as follows : A) Calcium Carbonate Calcium Carbonate is the most common component of scale found in cooling water systems especially in hard water . It has an inverse solubility ie as the temperature increases the solubility decreases. It is formed by the decomposition of Calcium bicarbonate which is present in water . B) Calcium Sulphate Calcium Sulphate is relatively more soluble than Calcium carbonate. It will pose a problem if its solubility limits are exceeded. Use of sulphuric acid for pH Control will increase the sulphate ions in cooling water systems. C) Calcium Phosphate Calcium Phosphate also exhibits inverse solubility like calcium carbonate. The combination of calcium , Orthophosphates, high pH & high temperature is conducive for the precipitation of calcium phosphate. It precipitates as amorphous form , tricalcium phosphate , octacalcium phosphate & hydroxyapatite. D) Calcium Fluoride Calcium Fluoirde scales are observed in systems using municipal waste water as a make up water . These scales are tightly adherent & are difficult to remove with chemical treatment. These scales are also found in gas scubbers in smelting & coking operations where Feldspar is used as a raw material on the process side. E) Silicates Silicate Scales are very hard , tenacious & difficult to remove. Higher operating cycles & Increased use of reclaimed waste water accounts to high silica levels. Magnesium silicate scale precipitation is influenced by pH , Mg & Silica levels. To prevent magnesium Silicate deposition, the a mgnesium & silica concentrations are controlled . The solubility product of Magnesium as calcium carbonate & Silica as Silica should not exceed 35000 limit. F) Silica Pure Silica scales are usually not found in cooling water systems.Silica scales can be prevented by limiting the silica concentration in circulating water systems upto 160 ppm. The solubility of silica increases with pH. & also temperature. G) Iron Salts Iron in the ferrous form is soluble. This soluble iron is present in many make up waters. This soluble iron gets converted into insoluble ferric form by either aeration or by oxidising material. & thus gets precipitated as Fe2O3 or Fe(OH)3. Iron Phosphate is a yellowish white precipitate found when make up water contains high levels of iron. High Temperature , Low Flow , high phosphates lead to iron phosphate precipitation.

H) Zinc Salts Zinc Phosphate scales result from high operating pH ( pH > 7.5) or overfeed of Chromate zinc-phosphate or zinc phosphate chemicals. It precipitates in low flow heat transfer areas. This scales also lead to under deposit corrosion. Q.4.4 What are the different methods of Scale Prevention & Control ? Scale prevention & control is achieved using following methods : A) Pretreatment of Water The most obvious method of scale prevention is to remove the scale forming constituents from the make up water. This can be achieved by removal of either hardness salts & making water soft or by removing all salts & making water demineralised. The use of Demineralised water is an effective scale prevention method however such water will be corrosive & expensive . B) pH Control A typical method of scale control in cooling water systems is by use of Acid Dosing for pH Control. The solubility of scale forming salts is usually increased as pH is lowered. The pH control can be achieved by acid dosing usually sulphuric acid. This reduces bicarbonate hardness by chemical reaction ,forming Calcium & Magnesium Sulphate. These are more soluble than carbonates. C) Limit the concentration of Scale forming salts The scale forming salts in the cooling water systems can also be maintained by limiting the cycles of concentration via blowdown. This will reduce the build up of concentration of scale forming ions . D) Alter System Design or Operation The scaling rate is influenced by water flow rate, water temperature, heat flux,& skin temperature, etc. Scale control can also be achieved by making mechanical changes in the system to reduce the chances of scale formation. Some of the mechanical method s of scale control are as follows : i)Increase in the water flow rate from 0.2 to 0.6 m/sec lowers the scaling rate to @ 1/5th . ii) modify the exchanger design by reducing the number of passes. iii) Air rumble on a periodic basis to dislodge & remove scales . Loosely adherent scales will get easily removed. iv) Use of sponge balls for on line cleaning v) Change the system metallurgy of the heat transfer surface eg Mild steel heat transfer surfaces will scale under conditions where copper & other alloys will not. vi) Reduce the heat flux by reducing the process load This will reduce the metal temperature & scaling potential. E) Use of Scale Control / Scale Inhibiting Chemicals

Q.4.5. Explain various terms associated with Scale Prevention & Control ? Various terms associated with Scale Prevention & Control are as follows : a) Sequestering Agents ( Or Chelating Agents) They react with scale forming ions to form water soluble complex . This complex viz Chelate prevents the precipitation of scale containing sequestered or chelated ions. Polyphosphates & anionic polymeric dispersants are used as sequestering agenst. They sequester ions such as Ca2+, Fe2+, Mn2+ Other chelating agents eg EDTA, NTA also react with ions to form soluble complex or chelate . b) Scale Conditioners Scale Conditioners chemically modify the crystal structureof a scale . They are included in the crystal lattice to form bulky, loosely adherent deposits instead of hard scales. Typical examples are Lignins, Tannins, Polycarylates. c) Threshold Inhibitors These chemicals inhibit the precipitation of scale forming ins at dosages fat below the stoichiometric quantities required for sequestrationor chelation. They function by adsorption mechanism. They delay or retard the rate of precipitation . They cause crystal lattice distortion so that scales formed are loose & can be easily removed from the system by blowdown. Typical Threshold Inhibitors are Low Molecular Polyacrylates , Organophosphonates such as Hydroxy Ethylidine Di Phosphonic Acid (HEDP), Amino Tri Methylene Phosphonic Acid(ATMP) , 2 Phosphono Butane-1, 2,4 TriCarboxylic Acid (PBTC) d) Crystal Modifiers The Crystal Modifier distorts the crystal lattice structure of scale so that the scales are not adherent . It is also a form of Threshold Inhibitor, which is used at a substoichiometric amount .Typical examples are organophophonates, polymeric dispersants based on polyacrylates.