COOLING WATER SYSTEM CHEMICAL TREATMENT

Water is used in cooling systems as a heat transfer medium and frequently also as the final point to reject heat into the atmosphere by evaporating inside cooling towers. Depending on the quality of available fresh water supply, waterside problems develop in cooling water systems from: Scaling Corrosion Dirt and dust accumulation Biological growth Any of these problems or more usually a combination of them result in costly unscheduled downtime, reduced capacity, increased water usage, high operation and maintenance costs, expensive parts replacements, and acid cleaning operations which reduce the life of the cooling system. Selection of water treatment program for a specific system depends on: 1. System design, including system capacity, cooling tower type, basin depth, materials of construction, flow rates, heat transfer rates, temperature drop and associated accessories. 2. Water, including make up water composition / quality, availability of pre-treatment and assumed cycle of concentration. 3. Contaminants, including process leaks and airborne debris. 4. Wastewater discharge restrictions. 5. Surrounding environment and air quality.

The critical parameters for cooling water are: conductivity, total dissolved solids (TDS), hardness, pH, alkalinity and saturation index.

Corrosion Problems Factors Many factors affect the corrosion rates in a given cooling water system. Few important factors are:

1. Dissolved Oxygen - Oxygen dissolved in water is essential for the cathodic reaction to take place.

2. Alkalinity & Acidity - Low alkalinity waters have little pH buffering capability. Consequently, this type of water can pick up acidic gases from the air and can dissolve metal and the protective oxide film on metal surfaces. More alkaline water favours the formation of the protective oxide layer.

3. Total Dissolved Solids - Water containing a high concentration of total dissolved solids has a high conductivity, which provides a considerable potential for galvanic attack. Dissolved chlorides and sulphates a particularly corrosive.

4. Microbial Growth - Deposition of matter, either organic or inorganic, can cause differential aeration pitting (particularly of austenitic stainless steel) and erosion/corrosion of some alloys because of increased local turbulence. Microbial growths promote the formation of corrosion cells in addition; the byproducts of some organisms, such as hydrogen sulphide from anaerobic corrosive bacteria are corrosive. 5. Water Velocity - High velocity water increases corrosion by transporting oxygen to the metal and carrying away the products of corrosion at a faster rate. When water velocity is low, deposition of suspended solids can establish localized corrosion cells, thereby increasing corrosion rates.

6. Temperature - Every 25-30F increase in temperature causes corrosion rates to double. Above 160F, additional temperature increases have relatively little effect on corrosion rates in cooling water system.

Some contaminants, such as hydrogen sulphide and ammonia, can produce corrosive waters even when total hardness and alkalinity are relatively high.

Treatment Methods Most corrosion control strategies involve coating the metal with thin films to prevent free oxygen and water from coming into close contact with the metal surface. This breaks the reaction cell, and reduces the corrosion rates. Several major chemical treatment methods can be used to minimize corrosion problems and to assure efficient and reliable operation of cooling water systems.

1. Anodic inhibitor 2. Cathodic inhibitor 3. Mixed inhibitor

Corrosion Inhibitors A corrosion inhibitor is any substance which effectively decreases the corrosion rate when added to an environment. An inhibitor can be identified most accurately in relation to its function: removal of the corrosive substance, passivation, precipitation, or adsorption. Deaeration (mechanical or chemical) removes the corrosive substance-oxygen. Passivating (anodic) inhibitors form a protective oxide film on the metal surface. They are the best inhibitors because they can be used in economical concentrations, and their protective films are tenacious and tend to be rapidly repaired if damaged. Precipitating (cathodic) inhibitors are simply chemicals which form insoluble precipitates that can coat and protect the surface. Precipitated films are not as tenacious as passive films and take longer to repair after a system upset.

Scaling Problems Factors

Typical scales that occur in cooling water systems are:

1. Calcium carbonate scale - Results primarily from localized heating of water containing calcium bicarbonate. Calcium carbonate scale formation can be controlled by pH adjustment and is frequently coupled with the judicious use of scale inhibiting chemicals.

2. Calcium sulfate scale - Usually forms as gypsum is more than 100 times as soluble as calcium carbonate at normal cooling water temperatures. It can usually be avoided by appropriate blowdown rates or chemical treatment.

3. Calcium and magnesium silicate scale - Both can form in cooling water systems. This scale formation can normally be avoided by limiting calcium, magnesium, and silica concentrations through chemical treatment or blowdown.

4. Calcium phosphate scale - Results from a reaction between calcium salts and orthophosphate, which may be introduced into the system via inadequately treated wastewater or inadvertent reversion of polyphosphate inhibitors present in recycled water.

The most common type of scaling is formed by carbonates and bicarbonates of calcium and magnesium, as well as iron salts in water. Calcium dominates in fresh water while magnesium dominates in seawater.

Control Scale can be controlled or eliminated by application of one or more proven techniques: 1. Water softening equipment Water softener, dealkalizer, ion exchange to remove scale forming minerals from make up water.

2. Adjusting pH to lower values - Scale forming potential is minimized in acidic environment i.e. lower pH.

3. Controlling cycles of concentration - Limit the concentration of scale forming minerals by controlling cycles of concentration. This is achieved by intermittent or continuous blowdown process, where a part of water is purposely drained off to prevent minerals built up.

4. Chemical dosage - Apply scale inhibitors and conditioners in circulating water. 5. Physical water treatment methods Filtration, magnetic and de-scaling devices

Control of scale with pH adjustment by acid addition is a simple and cost effective way to reduce the scaling potential. It functions via chemical conversion of the scale forming materials to more soluble forms - calcium carbonate is converted to calcium sulfate (using sulfuric acid), a material several times more soluble. Sulfuric acid (H2SO4) and hydrochloric acid (HCl) are the most common additives used for controlling the formation of calcium carbonate scale. The reaction of the acid with calcium bicarbonate is: H2SO4 + Ca (HCO3)2 = CaSO4 + 2H2O + 2CO2 2HCl + Ca (HCO3)2 = CaCl2 + 2H2O + 2CO2

Microbiological Growth Problems

Possible types of micro-organisms that exist in cooling water Micro-organisms Algae

Impact on cooling tower system

Provide a nutrient source for bacterial growth Deposit on surface contributes to localized corrosion process Loosened deposits can block and foul pipe work and other heat exchange surfaces

Fungi Proliferate to high number and foul heat exchanger surfaces

Bacteria Some types of pathogenic bacteria such as Legionella may cause health hazards Sulphate reducing bacteria can reduce sulphate to corrosive hydrogen sulphide Cathodic depolarization by removal of hydrogen from the cathodic portion of corrosion cell

Bacteria - A wide variety of bacteria can colonize cooling systems. Spherical, rod-shaped, spiral, and filamentous forms are common. Some produce spores to survive adverse environmental conditions such as dry periods or high temperatures. Both aerobic bacteria

(which thrive in oxygenated waters) and anaerobic bacteria (which are inhibited or killed by oxygen) can be found in cooling systems.

Fungi - Two forms of fungi commonly encountered are molds (filamentous forms) and yeasts (unicellular forms). Molds can be quite troublesome, causing white rot or brown rot of the cooling tower wood, depending on whether they are cellulolytic (attack cellulose) or lignin degrading. Yeasts are also cellulolytic. They can produce slime in abundant amounts and preferentially colonize wood surfaces.

Algae - Algae are photosynthetic organisms. Green and blue-green algae are very common in cooling systems. Various types of algae can be responsible for green growths which block screens and distribution decks. Severe algae fouling can ultimately lead to unbalanced water flow and reduced cooling tower efficiency. Diatoms (algae enclosed by a silicaceous cell wall) may also be present but generally do not play a significant role in cooling system problems.

Treatment Methods Chemical biocides are the most common products to control the growth of micro-organisms. Three general classes of chemicals are used in microbial control.

1) Oxidizing biocides 2) Non-oxidizing biocides 3) Bio-dispersants.

Oxidizing Biocide Oxidizing biocides are powerful chemical oxidants, which kill virtually all micro-organisms, including bacteria, algae, fungi and yeasts. Common oxidizers are chlorine, chlorine dioxide, and bromine, ozone, and organo-chlorine slow release compounds. Ozone is now days widely used to curb microbial growth. The most effective use of oxidizing biocides is to maintain a
constant level of residual in the system. Oxidizing biocides are usually maintained at a continuous level in the system.

Since oxidizing biocide may sometimes be corrosive, corrosion inhibitors shall be added and selected to ensure compatibility.

Non-oxidizing Biocide Non-oxidizing biocides are organic compounds, which kill micro-organism by targeting specific element of the cell structure or its metabolic or reproductive process. Non-oxidizing biocides are not consumed as fast as the oxidizing types and remain in the system for a significant period of time until they pass out with the blowdown. They often have the added advantage of breaking down into harmless, nontoxic chemicals after accomplishing their bacteria-killing purpose. They are effective where chlorine may not be adequate.

Chlorine Chlorine is the most widely adopted biocide for large circulating water systems. It provides a residual biocide in the treated water and can be readily checked. Its effectiveness increases when it is used with other non-oxidizing biocides and biological dispersants. Chlorine can be dosed in the form of sodium hypochlorite. A mixture of hypochlorous acid (HOCl), hypochlorite ion (OCl), and chloride ion (Cl) is formed when hypochlorite is added to water.

COOLING WATER TREATMENT IN F&N DAIRIES PRODUCT NAME NAME OF CHEMICAL (ACTIVE INGREDIENT) DIANODIC DN 2101 NICLON 70T CORRSHIELD NT 4201 SPECTRUS NX 1100 GENGARD GN 7002 CWT 3366 CWT 3050 CWT 3060 Potassium Hydroxide Calcium Hypochlorite Sodium Hydroxide Biocide Polymer Solution Phosphate Organic amines Halogen oxidizer

DIANODIC DN 2101

It is a corrosion inhibitor. It is an aqueous alkaline solution of inorganic salt, phosphonate, polymer and organic heterocyclic compound. Used in non-chromate cooling water treatment technology. It is a two component treatment program featuring a truly effective calcium phosphate inhibitor that permits higher phosphate concentrations necessary for proper mild steel corrosion protection.

The first component is the corrosion inhibitor-a blend of orthophosphate and polyphosphate for ferrous metal protection, phosphonate for calcium carbonate prevention and a copper corrosion inhibitor. The second component is the calcium orthophosphate inhibitor/dispersant.

NICLON 70T

Used for disinfection purpose. It is calcium hypochlorite granular. Disinfection and sanitization are achieved by dissolving calcium hypochlorite in water to produce a chlorine solution. Several grades, known collectively as Niclon-70, are typically used for sterilizing

and disinfecting swimming pools and drinking water, and is also used in sewage treatment systems.

CORRSHIELD NT 4201 It is a corrosion inhibitor. It is an aqueous alkaline solution of inorganic salts. CorrShield NT4201 cooling water treatment provides superior corrosion inhibition to multi-metal systems operating at high or low temperatures. It is normally used for diesel and other internal combustion engines, hot water heating systems, chilled water circuits and other closed systems containing ferrous and non-ferrous metals.

SPECTRUS NX 1100 Spectrus NX1100 is a proprietary blend of antimicrobial agents, specifically formulated for industrial water applications. It may be used in open or closed recirculating cooling water systems. Spectrus NX1100 is also approved for use in auxiliary water systems as well as wastewater and waste material disposal applications. Spectrus NX1100 is water-based to minimize impact on the environment. It contains no metal-based stabilizers, such as copper or iron.

Spectrus NX1100 has been formulated in a waterbased solvent system, eliminating BOD and COD associated with solvents, such as glycol and oils. A water-based formulation is also safer to store and handle than a solvent-based formulation.

GENGARD GN 7002

It is a deposit control agent. It is used for most advanced and effective water treatment technology for open re-circulating cooling systems. It can be applied across the entire pH spectrum from neutral to alkaline and ensure. GenGard GN7000 series of products are designed for cooling systems operating in the near neutral pH 6.8 - 7.8 range. They utilize high levels of inorganic phosphate to promote the formation of a thin, protective iron oxide film on steel surfaces. This protective oxide film is extremely tenacious and does not interfere with heat transfer.