Soda ash is used primarily to reduce non-bicarbonate hard-ness (also called sulphate hardness or permanent hardness). It reacts as follows:
The calcium carbonate formed by the reaction tends to come out of solution as a sludge. The sodium sulphate and chloride formed are highly soluble and non-scale forming.
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What are the Various Methods of Lime-Soda Softening?
The two general types are intermittent (batch type) and continous. The older method of intermittent softening consists of mixing the chemicals with the water in a tank, allowing time for reaction and settling of the sludge, and drawing off the clear water. The more modern method of continous lime-soda softening involves the use of specially compartmented tanks with prvisions for
- proportioning chemicals continously to the incoming water
- retention time for chemical reactions and settling of sludge, and
- continous draw-off of softened water. Lime-soda softening may also be calssified as hot or cold, depending on the tempera-ture of the water. Hot process softeners increase the rate of chemical reactions and give better quality water.
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Why are Coagulants Used in the Lime-Soda Process?
Just as coagulants are used for removing suspended matter in clarification processes, they serve to clump togehter precipi-tates in the softening process. Coagulants can speed up settling of sludge as much as 25 - 50 per cent. Sodium aluminate has a special advantage as a coagulant in lime-soda softening since unlike most other coagulants it is alkaline and also contributes to the softening readtions, particularly in reducing magnesium.
Effective use of coagulants helps remove silica in hte softening process. Silica tends to be absorbed in the floc produced by coagulation of sludge.
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Under What Conditions Are Phosphate Softeners Use?
Sodium phosphates react readily with calcium and magnesium salts. Phosphate softeners are generally used only on naturally soft or presoftened waters, however, becauser relatively high amounts of magnesium in the water cause a very sticky precipitate in reacting with phosphate. Properly used, phosphate softeners can effectively reduce hardness to very low levels. Improved ion exchange softening methods have largely supplanted phosphate softners in new installations.
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What are the Disadvantages of Lime-Soda Softening?
The main disadvantage is that while hardness is reduced it is not completely removed. Wide variations in raw water composi-tion and flow rate also make control of this method difficult since this involves adjusting the amounts of lime and soda ash being fed.
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What are the Advantages of Lime-Soda Softening?
The main advantage is that in reducing hardness, alkalinity and silica can also be reduced. In addition, prior clarification of the water is not usually necessary since suspended matter and turbidity are also removed in the process. Another advantage is that with continous hot process softening some removal of oxygen and carcon dioxide can be achieved.
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What is Ion Exchange?
When minerals dissolve in water they form electrically charge particles called ions. Calcium carbonate, for example, forms a calcium ion with plus charges (a cation) and a carbonate ion with negative charges (an anion). Certain natural and synthetic materials have the ability to remove mineral ions from water in exchange for others. For exam-ple, in passing water through a simple cation excahnge softener all of calcium and magnesium ions are removed and replaced with sodium ions. Ion exchange materials usually are provided in the form of small beads or crystals which compose a bed several feet deep through which the water is passed.
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What are the Various Types of Ion Exchange Materials?
Ion exchange materials are basically of two types: cation and anion exchangers. Cation exchange materials react only with positively charged ions such as Ca++ and Mh++. Anion exchanger materials react only with the negatively charged ions such as carbonate (CO3-) and sulphate (SO4-).
Zeolite materials are cation exchangers composed chiefly of sodium, alumunium and silica. There are several other types of cation exchange materials of an organic or resinous nature. The anion materials are usually organic in nature and are of two
basic types: weak base and strong base types. Weak base exchagers don’t take out carbon dioxide or silica (actually carbonic acid and silica acid) but remove strong acid anions by a process that is more like adsorption than ion exchange. Strong base anion exchangers on the other hand can redce silica and carbon dioxide to very low values.
Cation exchangers usually opcles which settle out readily. In these cases clarifi-cation equipment merely involves the use of settling basins and/erate on either a sodium or hydrogen ‘cycleE That is, they may be designed to replace all cations in the water with either sodium or hydrogen. Strong base anion exchangers are generally operated on a hydroxideEweak base on a carbonate cycle. Chloride anion exchange is also used in some processe.
Why Water Treatment is Needed :
As feed-water enters a boiler the heat causes hardness (cal-cium and magnesium salts) to come out of solution. Untreated the hardness deposits on the hot boiler metal to from scale. As water evaporates in the boiler the feed-water impurities concentrate. Even small amounts ot iron, copper, and silica can accumulate in the boiler-water and cause serious deposit problems in higher pressure boilers. Since scale can cause overheating and failure of boiler metal, preventive water treatment is needed.
The corrosion of boiler system metal is a complex process and takes many forms: general attack, localized pitting, and various types of cracking in stressed metal. In general, the main factors causing corrosion are dissolved gases in the water (primarily oxygen) and acid conditions. High temper-atures speed up the corrosion process.Corrosion is damaging from several standpoints: it causes weakening and failure of metal and produces corrosion products which can cause boiler deposits.
High concentrations of dissolved and suspended matter in boiler-water can cause foaming of the water at the steam release surface. This produces carry-over of the water and its impurities into the steam.
Carry-over results in deposits and other problems in turbines, engines and other processes using steam. While mechanical and operational factors also cause carry-over, proper control of water conditions is important in producing pure steam.
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What is Boiler Water Carry-over?
Boiler water carry-over is the contamination of the steam with boiler-water solids. There are four common types of boiler-water carry-over. In one bubbles or froth actually build up on the surface of the boiler-water and pass out with the steam. This is called foaming and can be compared to the stable foam found on beer. In the second type small droplets of water in the form of spray or mist are thrown up into the steam space by the bursting of the rising steam bubbles at the steam release sur-face. This is sometimes called ‘aquaglobejectionEand is like ginger ale or champagne where no stable foam is formed but drop-lets of liquid are ejected from the liquid surface. The third condition of carry-over, called priming, is a sudden surge of boiler-water that carries over with the steam, similar to the effects produced in uncapping a bottle of charged water. stem contamination may also occur from leakage of water through im-properly designed or installed steam separating equipment in a boiler drum.
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What are the Disadvantages of Ion Exchange?
The main disadvantage with sodium cycle ion exchange soften-ing is that the total solids, alkalinity and silica contents of the raw water are not reduce. A problem encountered with cation exchange on the hydrogen cycle is corrrosion from acidity of the effluent. With demineralization the chief difficulties are with cost particularly on high solids raw waters, and the corrosive nature of the effluent water. In general, fouling of the ion exchange material with suspended or colliodal matter in the raw water can produce difficulties and some water impurities cause degradation of the material. In many cases, therefor, ion ex-change processes require paretreatment of the water supply.
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What are the Advantages of Ion Exchange?
The main advantage of zeolite softening is ease of control. Ordinary variations of hardness in the raw water or in flow rate do not affect completeness of softening. Also the system general-ly takes up less space than the lime-soda system and in most cases gives a softer water. The use of acid exchangers has advan-tages when a low alkalinity soft water is required. The main advantage of ion exchange demineralization is its ability to produce better quality water than can be obtained by any other method.
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How Does Oil Affect Carry-over?
Oil contamination in boiler feed-water, usually form recip-rocating engines, pumps, etc., can cause serious foaming. This is generally attributed to the formation of soaps in the boiler-water due to saponification of the oil by boiler-water alakalis.
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How Do Suspended Solids Affect Carry-over?
The theory advanced is that suspended solids collect in the surface film surrounding a steam bubble and make it tougher. The steam bubble therefore resists breaking and builds up a foam. It is believed that the finer the suspended particles the greater their collection in the bubble. Experience indicates, however, that many boilers operate with exceedingly high suspended solids without carry-over while others have carry-over with only a trace of suspended solids. This would seem to indicate that the type as well as the quantity of suspended solids has much to do with carry-over.
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What is Selective Silica Carry-over?
Silica can carry over into the steam in two ways. It can be present in the steam as the result of general boiler-water carry-over or it can go into steam in a volatile form. In the latter case silica acts much like a gas and is considered to be selec-tively carried over. As Pressures increase above 2760 kPa (400 p.s.i), there is an increased tendency for silica to be selectively carried into the steam in amounts proportionate to the amount of silica in the boiler-water.
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What Problems are Caused by Carry-over?
The disadvantages of wet steam include a general decrease in operating efficiency and erosion of turbines and engines. In addition any dissolved or suspended solids in the boiler-water tend to deposit out in the steam and condensate syste,. when the solids deposit in superheaters and turbine, overheating and failure of superheater tubes and reduction in turbine efficiency can result. Impurities carried over with the can cause difficul-ties in many processes for which the steam is used.
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What Measures are Usually Taken to Prevent Carry-over?
The most common measure is to maintain the concetratino of solids in the boiler water at reasonably low levels. Avoiding high water levels, excessive boiler loads, and sudden load chang-es also helps. Very often contaminated condensate returned to the boiler system causes carry-over problems. In these cases the condensate should be temporarily wasted until the source of contamination is found and eliminated. The use of chemical anti-foam agents can be very effective in preventing carry-over due to high concentrations of impurities in the boiler-water.
Removing Impurities from Water :
Coagulants are chemicals to enmesh fine particles of suspended matter in a water supply to form a floc which settles or can be filtered out. Adding softening chemicals
(lime, soda, ash, etc.) to a water causes some dissolved hardness salts to precipitate and the suspended matter can then be coagulated and filtered out. Precipitation processes
such as lime soda softening can effectively remove suspendedmatter, hardness and alkalinity and in some cases reduce the silica content of the water. When a salt dissolves in water it forms positive ions (cations) and negative ions (anions). For example, calcium carbonate (CaCO3) forms a calcium cation (Ca++) and a car-bonate anion (CO3=). The most common form of ion exchange involves passing water through material which substitutes sodium for calcium and magnesium cations. This is a typical softening treatment. Anions can also be removed from water by the use of special ion exchange resins. Demineralization or complete removal of dissolved minerals involves the use of both cation and anion exchange materials. In removing impurities from water htere are many possible combinations of coagulation, precipitation and ion exchange methods. Other methods of treatment include: deaeration (heating the water and venting the gases) for reduction of oxygen and carbon dioxide; and evaporation to produce distilled water.
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What is Coagulation?
Coagulation is the clumping together of finely divided and coloidal impurities in water into masses which will settle rapid-ly and/or can be filtered out of the water. Colloidal particles have large surface areas which keep them in suspension and in addition the particles have negative electrical charges which cause them to repel each other and resist adhering together. Coagulation, therefore, involves neutralizing the negative charg-es and providing a nucleus for the suspended particles to adhere to.
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What Various Types of Coagulants are Used?
The most common coagulants are iron and alumunium salts such as ferric sulphate, ferric chloride, alumunium sulphate (alum) and sodium aluminate. Ferric and alumina ions each have three positive charges and therefore their effectiveness is related their ability to react with the negatively charged colloidal particles. With proper use these coagulants form a floc in the water which serves as a kind of net for collecting suspended matter. In recent years synthetic materials called plyelectro-lytes have been developed for coagulation purposes. these consist of long chain like meolecules with positive charges. In some cases organic polymers and special types of clay are used in the coagulation in making the floc heavier, causing it to settle out more rapidly.
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What is Chemical Precipitation?
In precipitatino processes the chemicals added react with dissolved minerals in the water to produce a relatively insoluble reaction product. Precipitation methods are used in reducing dissolved hardness, alkalinity and in some silica. The most common example of chemical precipitation in water treatment is lime-soda softening.
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What is the Purpose of Deaeration?
Since dissolved oxygen in water is a big factor in corrosion in boiler systems it is desirable that this be removed before the water is put into a boiler. Feed-water deaeration is accomplished by intimately mixing the water and steam in a de-aerating heater. Part of the steam is vented, arrying with it the bulk of the dissolved oxygen from the water.
There are two basic types of steam de-aerators: the spray type and the tray type. In the spray de-aerator a jet of steam mixes intimately with the feed water being sprayed into the unit. In the tray type the incoming water is allowed to fall over a series of trays causing the water to be broken up into small droplets to permit intimate contact with incoming steam.
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How are Evaporators Employed?
Water is sometimes pretreated by evaporation to produce relatively pure vapour which is then condensed and used for boiler feed purposes. Evaporators are of several different types, the simplest being a tank of water through which steam coils are passed to heat the water to the boiling point. Sometimes to increase the efficiency the vapour from the first tank is passed through coils in a second tank of water to produce additional heating and evaporation. Other types of evaporation include a ‘flash typeEwhich operates under a partial vacuum causing a lowering of the voiling point of water and evaporation at lower temperatures.
Evaporators have advantages where steam as a sources of heat is readily available. They also have particular advantages over demineralization, for example, when the dissolved solids in the raw water are very high.
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What Combinations of External Treatment Methods are Generally Used?
As mentioned previously, water containing suspended solids,organics, and/or turbidity usually requires clarifications prior to ion exchange methods. Also, since simple cation exchange does not reduce the total solids of the water supply, it is sometimes used in conjunction with precipitation type softening. One of the most common and efficient combination treatments is the hot lime-zeolite precess. This involves pretreatment of the water with lime to reduce hardness, alkalinity and in some cases silica, and subsquent treatment with a cation exchange softener. This system of treatment accomplishes several functions: soften-ing, alkalinity and silica reduction, some oxygen reduction, and removal of suspended matter and turbidity.
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When is Internal Treatment of Boiler Feed-water Necessary?
Chemical treatment of water inside the boiler is usually essential whether or not the water has been pretreated. Internal treatment, therefor, complements external treatment by taking care of any impurities entering the boiler with the feed water (hardness, oxygen, silica, etc.) regardless of whether the quant-
ity is large or small. In many cases external treatment of the water supply is not necessary and the water can be treated by internal methods alone. Internal treatment can constitute the sole treatment when boileers operate at low or moderate pressure, when large amounts of condensed steam are used for feed water, or when the raw water available is of good quality.
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What Should a Good Internal Water Treatment Programme Accomplish?
The purpose of an internal treatment programme is fourfold: (1) react with any feed-water hardness and prevent it from pre-cipitating on the boiler metal as scale, (2) condition any sus-pended matter such as hardness sludge or iron oxide in the boiler and make it non-adherent to the boiler metal, (3) provide anti-foam protection to permit a reasonable concentration of dissolved and suspended solids in the boiler water without foam carry-over, and (4) eliminate oxygen from the water and provide enough alka-linity to prevent boiler corrosion. In addition, as supplementary measures an internal treatment should prevent corrosion and scaling of the feed-water system and protect againts corrosion in the steam-condensate systems.
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What chemicals are Used in Internal Treatment?
The softening chemicals used include soda ash, caustic and various sypes of sodium phosphates. These chemicals react with calcium and magnesium compounds in the feed water. At times sodium silicate is used to contributed alkalinity as well as react selectively with magnesium hardness. The materials used for conditioning sludge include various organic materials of the tannin, lignin or alginate classes. It is important that these organics are so selected and processed that they are voth effec-tive and stad stable at the boiler operating pressure. Certain synthetic organic materials are used as anti-foam agents. The chemicals used to scavenge oxygen include sodium sulphite and hydrazine. Various combinations of polyphosphates and organics are used for preventing scale and corrosion in feed-water sys-tems. Volatile neutralizing amines and filming inhibitors are used for preventing condensate corrosion.
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How are Carbonates Reacted on by INternal Treatment?
Calcium bicarbonate entering with the feed water is broken down at boiler temperatures or reacts with caustic soda to form calcium carbonate. Since calcium carbonate is relatively insolu-ble it tends to come out of solution. Sodium carbonate partially breaks down at high temperature to sodium hydroxide (caustic) and carbon dioxide. When phosphates are used in internal treatment they react with calcium carbonate to form calcium phosphate and sodium carbonate (soda ash). In the presence of sufficeint hy-droxide (caustic) alkalinity, mahnesium bicarbonate will pre-cipitate as magnesium hydroxide or will react with any silica present to form magnesium silicate. The minerals precipitated from solution (calcium carbonate, calcium phosphate, magnesium hydroxide, magnesium silicate, ect.) form sludge in the water
which must be conditioned to prevent its sticking to the metal. The conditioned sludge is removed from the boiler by blow-down.
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How are Sulphates Reacted on by Internal Treatment?
High temperatures in the boiler water reduce the solubility of calcium culphate and tend to make it precipitate out directly on the boiler metal as scale. Consequently calcium sulphate must be reacted upon chemically to cause a precipitate to form in the water where it can be conditioned and removed by blow-down. Calcium sulphate is reacted on either by sodium carbonate, sodium phophate or sodium silicate to form insoluble calcium carbonate, phosphate or silicate. Magnesium sulphate is reacted upon by caustic soda to form a precipitate of magnesium hydroxide. some magnesium may react with silica to form magnesium silicate. Sodium sulphate is highly soluble and remains in solution unless the water is evaporated almost to dryness.
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How is Silica Reacted upon by Internal Treatment?
In untreated waters silica tends to precipitate out directly as scale at hot spots on the boiler metal or it may combine with calcium to produce a hard calcium silicate scale.Treatment for silica involves keeping the boiler-water alkalinity high enough to hold silica in solution. Usually there is enough magnesium in the water to precipitate some of the silica as sludge. At times proper treatment with magnesium can tie up silica when it is a special problem. Some organic materials such as starches tend to prevent the adherence of silica to the boiler metal probably by a physical action.
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How is Sludge Conditioned in Internal Treatment?
There are two general approaches to conditioning sludge inside a boiler: by coagulation or dispersion. When the total amount of sludge is great (as the result of high feed-water hardness) it is practical to coagulate the sludge to form large flocculent particles. Thes flow readily with the boiler water and can be removed by blow-down. This can be accomplished by careful adjustment of the amounts of alkalis, phosphates and organics used for treatment, based on the fee-water analysis. When the amount of sludge is not great (low hardness feed-waters) it is more practical to use a higher percentage of phosphates in the treatment. Phosphates form finely divided sludge particles. A higher percentage of organic sludge dispersants is used in the treatment to keep the sludge particles dispersed throughout the boiler water.
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What Difficulties are Encountered in Internal Treatment?
The main difficulty is the presence of a large amount of sludge formed when feed-water hardness is high. This may increase the amount of blow-down required. When internal treatment is used alone (without pretreatment of the water by external means) there is more possibility for scale in the preboiler system and fee-water lines. it is important that someone experienced in the technology helps to set up an internal treatment programme which will minimize these difficulties.
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What are the Advantages of Internal Treatment?
The prime advantage is that in many instances internal treatment can eliminate the need for extensive external treatment equipment. This gives a definite economic advantage. In addition, the simplicity of an internal treatment programme offers a decid-ed savings in manpower for feeding and control. A qualified consultant can help decide what water quality is required for a specific boiler system, and choose the most economical means of obtaining the required quality.
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How are Internal Treatment Chemicals Fed?
Common feeding methods include the use of chemical solution tanks and proportioning pumps or special ball briquette chemical feeders. In general, softening chemical (phosphates, soda ash, causti, etc.) are added directly to the fee-water at a point near the entrance to the boiler drum. They may also be fed through a separate line discharging in the feed-water drum of the boiler. The chemicals should discharge in the fee-water section of the boiler so that reactions occur in the water before it enters thesteam generating areas. Softening chemicals may be added continously or intermittently depending on feed-water hardeness and other factors. Chemicals added to react with dissolved oxygen (sulphate, hydrazine, etc.) preferably should be fed continously as far back in the feed-water system as possible. Similarly, chemicals used to prevent scale and corrosion in the feed-water system (polyphosphates, organics, etc.) should be fed continous-ly. Chemicals used to prevent condensate system corrosion may be fed directly to the steam or into the feed-water system, depend-ing on the specific chemical used. continous feeding is preferred bu intermittent application will suffice in some cases.
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How are Chemical Dosages Controlled?
Chemical dosages are based primarily on the amount of impu-rities in the feed-water. For example, the amount of softening chemicals needed depends on fee-water hardness;the amount of sodium sulphate needed depends on the amount of dissolved oxygen in the feed-water. In addition, however, a set amount of extra chemical treatment is added to provide a residual is akind of insurance and serves as the basis for treatment control.
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What Boiler Water Tests are Used for Treatment Control?
Routinge control teste of the boiler water vary according to the type of chemical treatment used but they may include tests for: alkalinity,m phosphate, sulphate and organic color. Boiler water hardness tests are not often made because it is generally assumed that if there is enough alkalinity and/or phosphate present in the boiler-water, the hardness has reacted completely. In testing for sulphate it is assumed that if an adequate ridual is present, the feed-water oxygen has been removed;this may not always be true, especially if the sulphate feed is not continous and if ordinary uncatalyzed sodium sulphate is used. Generally antifoams are incorporated in organic treatments so testing for
organic color gives an indication both of sludge conditioner present as well as level of antifoam treatment.
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What Tests are Usually Made as a Check for Contaminants?
Here, again, the specific tests made vary with the type of contamination suspected. Some checks made fairly often, however, include teste for: iron, oil and silica. Usually the iron test serves as a check on corrosion products brought back with the condensate but may also be used when appreciable iron is present in the maka up water. Oil tests usually require laboratory facil-ities but visual inspection of samples can show up gross contami-nation. While silica is usually present to some extent in boiler waters, periodic checks are sometimes made to detect unusual contamination or to indicate when additional blow-down is needed to keep silica concentrations below a preset limit.
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What Units are Used in Expressing Water Analysis Results?
The most common unit is parts per million. One p.p.m. of a substance in a water sample represents one unit mass of the substance in each million unit mass of the water. For example, one p.p.m of salt (NaCl) means one kg of salt per million kg of water. There is still some die-hard use of the classic unit grains per gallon (g.p.g.) but this expected to disappear due to universal S.I. usage as will the unit equivalents per million (e.p.m). This mention is therefore made merely as a matter of record.
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Why are some Analysis Results Expresse ‘As CaCO2E
Water treatment reactions are based on the combining mass of the reacting substances. For example, 106 kilograms of soda ash (molecular mass 106) reacts with 136 kilograms of calcium sulphate (molecular weight 136). The molecular mass of calcium carbonate (CaCO3) is the round number 100. In order to simplify chemical dosage calculations all hardness and alkilinity results are usually based on the molecular mass of calsium carbonate and are expressed as ‘CaCO3E For example, using this system, one p.p.m of calcium culphate (expressed as CaCO3). This is the same as converting English pounds, German marks, or frech francs into a 100 cent dollar.
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What is Blow-down?
Blow-down is the removal from the boiler of water containing concetrated dissolved and suspended solids. As the blow-down water is replaced with lower solids feed water the boiler water is essentially being diluted. By regulating the amount of blow-down, therefore, the amount of solids in the boiler-water can be controlled.
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How much Blow-down is Needed?
This depends on how many concetrations of the various feed-water impurities a given boiler can tolerate;the more concentra-tions possible the less blow-down needed. For example, with 10 feedwater concentrations in a boiler, blow-down equal to 10 per cent of the feed-water flow rate is needed;with 20 concentrations
only 5 per cent blow-down is needed. To illustrate how blow-down requirements are calculated let us assume that the maximum amount of suspended solids (sludge) in the boiler water that a particu-lar boiler can tolerate is 500 p.p.m. If the fee-water contains 50 p.p.m. of hardness it can be concentrated only about 10 times (since feed water hardness is precipitated as suspended solids in the boiler water). This means that for every 50 kg of water fed to the boiler about 5 kh of boiler water must be blown down to keep the suspended solids from exceeding 500 p.p.m. Suspended solids, however, may not be the limiting factor in all cases; other factors which may limit feed-water concentrations include dissolved solids, alkalinity, silica or iron.
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What Tests are Made in Regulating Blow-down?
Since there are no simple test for routinely checking the amount of suspended solids in boiler-water, blow-down is usually controlled through use of a simple instrument which measures the electrical conductivity of the water. This test gives an estimate of the dissolved solids present in the boiler-water. Chloride tests are also used for blow-down control since chlorides are not reacted on by chemical treatment. By checking both the fee-water and boiler-water chlorides the number of feed-water concentra-tions can be calculated. In some higher pressure boilers, silica or iron tests may also be made to control blow-down.
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What is the Difference between Continous and ‘PuffEBlow-down?
All boilers have blow-down connections located at low points where sludge is likely to collect. Operning these blow-down valves periodically for shot intervals gives a ‘puffEor intermittent removal of sludge and conctrated solids. Many boil-ers also have vlow-down connections consisting of an offtake located just below the water level in the steam release area. A small amount of water is continously removed through these con-nections. The use of continous blow-down in addition to ‘puffEor bottom blow-down
kes it possible to maintain the solids and chemical residuals at more consistent levels in the boiler water. Continous blow-down also minimizes the amount of blo-down re-quired with resultant savings in heat and chemicals. Continous blow-down also causes less upset in boiler water circulation and operation.
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What Causes Corrosion in Steam Condensate Systems?
Most condensate system corrosion is caused by carbon dioxide and oxygen, arried into the system with the steam. Carbon diox-ide, dissolved in the pure condensed steam, form corrosive car-bonic acid. if oxygen is present with carbon dioxide, the corro-sion rate is much higher, and is likely to produce localised pitting. Ammonia, in combination with carbon dioxide or oxygen, attacks copper alloys.
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How is Steam Condensate Corrosion Prevented?
The general approach may involve removing oxygen from the feed-water mechanically and chemically, and providing
pretreatment of the make-up water to minimize potential carbon dioxide formation in the boiler. In addition, an effective chemi-cal treatment programme is required. This may consist of using volatile amines to neutralise carbon dioxide and/or a volatile filming inhibitor to form a barrier between the metal and the corrosive condensate. Mechanical conditions such as poor trapping and draining of lines, and air in-leakage may need to be correct-ed.
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How do Chemical Oxygen Scavengers Help Control Condensate System Corrosion?
As previously mentioned mechanical equipment (de-aerator) is often used to reduce feed-water oxygen. The best designed and operated de-aerators can reduce oxygen to as low as 0.007 parts per million or less. Most de-aerators or feed-water heaters are less effective. Since very samll amounts of oxygen, however, can cause boiler corrosion and corrosion in steam condensate system, chemical treatment is therefor, needed to assure complete oxygen removal. Sodium sulphate is the chemical most commonly used for this purpose. Greatly improved oxygen removal is obtained, hoev-er, when the sulphate is catalyzed. Catalyzed sodium sulphate can reduce oxygen content of water (at room temperature) from the saturation point to zero in less than 30 seconds. Without a catalyst it takes up to 10 minutes under the same conditionis to reduce the oxygen content by only about 30 per cent. Fast reac-tions are important since oxygen should be removed before the water enters the boiler. Otherwise some oxygen will escape form the boiling water into the steam lines and aggrave corrosion in the condensate system.
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What is the Basis for Choice between Neutralizing and Filming Inhibitors?
The proper choice of ingibitor depends on the boiler system, plant lay-out operating conditions and fee-water composition. In general, colatile amines are better with low make-up, low feed-water alkalinity, and good oxygen control. Filming inhibitors usually give more economical protection with high make-up, air in-leakage high feed-water alkalinity or where the system is operated interminently. In some cases a combination of treatments is needed.
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What Characteristics Should a Good Condensate Corrosion Inhibitor Have?
A goog volatile neutralizing amine should have a favourable distribution ratio in steam and condensate so that it protects the entire steam-condensate system. It should have no insoluble reaction products and should be stable at high temperatures and pressures. A goo filming inhibitor should be easy to disperse in water so that it can be fed uniformly. It should be stale under usage conditions and form a thin protective film without causing deposits in either the boiler or the steam-condensate system.
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How are Deposits and Corrosion Prevented in Feed-water Systems?
Deposits in feed-water systems are most frequently caused by hardness coming out of solution as the water goes through feed-
water heaters or as the feedlines enter the boiler. Deposits also can occur from premature reaction of treatment chemicals with hardness in the feed-water. Prevention involves the use of stabi-lizing chemicals fed continously to retard hardenss precipita-tion. Proper design of the chemical feed system can minimize premature chmical reactions.
Corrosion of feed-water system generally results from low alkalinity or dissolved oxygen in the water. Raising the pH of the water and the continous feed of catalyzed sodium sulphate will minimize this problem.
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What is the Wet Method of Boiler Lay-Up?
This is a method of storing boilers full of water so that they can be readily returned to service. it involves adding extra chemicals (usually caustic, organics, and sodium sulphite to the boiler-water.) The water level is raised in the idle boiler to eliminate air spaces and the boiler is kept completely full of treated water. Special considerations are needed for protecting superheaters.
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What is the Dry Method of Boiler Lay-Up?
This method of lay-up is usually for longer boiler outages. It involves draining, cleaning and drying out the boiler. a material which absorbs moisture such as hydrated lime or silica
gel is placed in trays inside the boiler. The boiler is then sealed carefully to prevent inleakage of air. Periodic inspection and replacement of the drying chemical is required during long storage periods.
DATA USED IN WATER CHEMISTRY
The chemicals listed in this section include those found as impurities in water and also those used as treaments. The chemical formulas, ion forms, and molecular and equivalent weights are given for each substance. Abbreviations and symbols are used extensively to simplify water analysis reports and calculations. This section explains the meanings of some common symbols and what they represent in water analyses. Very often the units used in water chemistry need to be converted back and forth for practical application. For example, parts permillion may be converted to grams per 1000 litres and vice versa. The conversion factors in this section simplify this type of calculation.
CATIONS |
Ion Formula |
Ionic Weight |
Equivalent Weight |
Alumunium |
A1+++ |
27.0 |
9.0 |
Ammonium |
NH4+ |
18.0 |
18.0 |
Calcium |
CA++ |
40.1 |
20.0 |
Hydrogen |
H+ |
1.0 |
1.0 |
Ferrous Iron |
Fe++ |
55.8 |
27.9 |
Magnesium |
Mg++ |
24.3 |
12.2 |
Manganese |
Mn++ |
54.9 |
27.5 |
Postassium |
K+ |
39.1 |
39.1 |
Sodium |
Na+ |
23.0 |
23.0 |
|
ANIONS |
|
Bicarbonate |
NCO3- |
61.0 |
61.0 |
Chloride |
CO3- |
60.0 |
60.0 |
Fluoride |
F- |
19.0 |
19.0 |
Nitrate |
NO3- |
62.0 |
62.0 |
Hydroxide |
OH- |
17.0 |
17.0 |
Phosphate (tribasic) |
PO4-- |
95.0 |
31.7 |
Phosphate (dibasic) |
HPO4-- |
96.0 |
48.0 |
Phosphate (monobasic) |
H2PO4- |
97.0 |
97.0 |
Sulphate |
SO4-- |
96.1 |
48.0 |
Sulphite |
SO3-- |
80.1 |
40.0 |
COMPOUNDS |
Formula |
Molecular Weight |
Equivalent Weight |
Alumunium hydroxide |
Al(OH)3 |
78.0 |
26.0 |
Alumunium sulphate |
Al2(SO4)3 |
342.0 |
57.0 |
Alumina |
Al2O3 |
102.0 |
17.0 |
Calcium bicarbonate |
Ca(HCO3)2 |
162.1 |
81.1 |
Calcium carbonate |
CaCO3 |
100.1 |
50.1 |
Calcium chloride |
CaCl2 |
111.0 |
55.5 |
Calcium hydroxide (pure) |
Ca(OH)2 |
74.1 |
37.1 |
Calcium hydroxide (90%) |
Ca(OH)2 |
-- |
41.1 |
Calcium sulphate (anhydrous) |
CaSO4 |
136.2 |
68.1 |
Calcium sulphate (gypsum) |
CaSO4.2H2O |
172.2 |
86.1 |
Calcium phosphate |
Ca3(PO4)2 |
310.3 |
51.7 |
Disodium phosphate |
Na2HPO4.12H2O |
358.2 |
119.4 |
Disodium phosphate (anhydrous) |
NaHPO4 |
142.0 |
47.3 |
Ferric oxide |
Fe2O3 |
159.6 |
26.6 |
Iron oxide (magnetic) |
Fe3O4 |
321.4 |
- |
Ferrous sulphate (copperas) |
FeSO4.7H2O |
278.0 |
139.0 |
Magnesium oxide |
MgO |
40.3 |
20.2 |
Magnesium bicarbonate |
Mg(HCO3)2 |
146.3 |
73.2 |
Magnesium carbonate |
MgCO3 |
84.3 |
42.2 |
Magnesium chloride |
MgCl2 |
95.2 |
47.6 |
Magnesium |
Mg(OH)2 |
58.3 |
29.2 |
Magnesium phosphate |
Mg3(PO4)2 |
263.0 |
43.8 |
Magnesium sulphate |
MgSO4 |
120.4 |
60.2 |
Monosodium phosphate |
NaH2PO4.H2O |
138.1 |
46.0 |
Monosodium phosphate (anhydrous) |
NaH2PO4 |
120.1 |
40.0 |
Metaphosphate |
NaPO3 |
102.0 |
34.0 |
Sodium aluminate |
Na2Al2O4 |
164.0 |
27.3 |
Sodium bicarbonate |
NaHCO3 |
84.0 |
84.0 |
Sodium carbonate |
Na2CO3 |
106.0 |
53.0 |
Sodium cholride |
NaCl |
58.5 |
58.5 |
Sodium hydroxide |
NaOH |
40.0 |
40.0 |
Sodium nitrate |
NaNO3 |
85.0 |
85.0 |
Sodium sulphate |
Na2SO4 |
142.0 |
71.0 |
Sodium sulphite |
Na2SO3 |
126.1 |
63.0 |
Trisodium phosphate |
Na3PO4.l2H2O |
380.2 |
126.7 |
Trisodium phosphate (anhydrous) |
Na3PO4 |
164.0 |
54.7 |
|
GASES |
|
Ammonia |
NH3 |
17 |
-- |
Carbon Dioxide |
CO2 |
44 |
-- |
Hydrogen |
H2 |
2 |
-- |
Oxygen |
O2 |
32 |
-- |
|
ACIDS |
|
Carbonic |
H2CO3 |
62.0 |
31.0 |
Hydrochloric |
HCl |
36.5 |
36.5 |
Phosphoric |
H3PO4 |
98.0 |
32.7 |
Sulphuric |
H2SO4 |
98.1 |
49.1 |