Corrosion--Corrosion, or a chemical action leading to the actual destruction of the boiler metal, is due to the solvent or oxidizing properties of the feed water. It results from the presence of acid, either free or developed[15] in the feed, the admixture of air with the feed water, or as a result of a galvanic action. In boilers it takes several forms:
1st. Pitting, which consists of isolated spots of active corrosion which does not attack the boiler as a whole.
2nd. General corrosion, produced by naturally acid waters and where the amount is so even and continuous that no accurate estimate of the metal eaten away may be made.
3rd. Grooving, which, while largely a mechanical action which may occur in neutral waters, is intensified by acidity.
Foaming--This phenomenon, which ordinarily occurs with waters contaminated with sewage or organic growths, is due to the fact that the suspended particles collect on the surface of the water in the boiler and render difficult the liberation of steam bubbles arising to that surface. It sometimes occurs with water containing carbonates in solution in which a light flocculent precipitate will be formed on the surface of the water. Again, it is the result of an excess of sodium carbonate used in treatment for some other difficulty where animal or vegetable oil finds its way into the boiler.
Priming--Priming, or the pa.s.sing off of steam from a boiler in belches, is caused by the concentration of sodium carbonate, sodium sulphate or sodium chloride in solution. Sodium sulphate is found in many southern waters and also where calcium or magnesium sulphate is precipitated with soda ash.
Treatment of Feed Water--For scale formation. The treatment of feed water, carrying scale-forming ingredients, is along two main lines: 1st, by chemical means by which such impurities as are carried by the water are caused to precipitate; and 2nd, by the means of heat, which results in the reduction of the power of water to hold certain salts in solution. The latter method alone is sufficient in the case of certain temporarily hard waters, but the heat treatment, in general, is used in connection with a chemical treatment to a.s.sist the latter.
Before going further into detail as to the treatment of water, it may be well to define certain terms used.
_Hardness_, which is the most widely known evidence of the presence in water of scale-forming matter, is that quality, the variation of which makes it more difficult to obtain a lather or suds from soap in one water than in another. This action is made use of in the soap test for hardness described later. Hardness is ordinarily cla.s.sed as either temporary or permanent. Temporarily hard waters are those containing carbonates of lime and magnesium, which may be precipitated by boiling at 212 degrees and which, if they contain no other scale-forming ingredients, become "soft" under such treatment. Permanently hard waters are those containing mainly calcium sulphate, which is only precipitated at the high temperatures found in the boiler itself, 300 degrees Fahrenheit or more. The scale of hardness is an arbitrary one, based on the number of grains of solids per gallon and waters may be cla.s.sed on such a basis as follows: 1-10 grain per gallon, soft water; 10-20 grain per gallon, moderately hard water; above 25 grains per gallon, very hard water.
_Alkalinity_ is a general term used for waters containing compounds with the power of neutralizing acids.
_Causticity_, as used in water treatment, is a term coined by A. McGill, indicating the presence of an excess of lime added during treatment.
Though such presence would also indicate alkalinity, the term is arbitrarily used to apply to those hydrates whose presence is indicated by phenolphthalein.
Of the chemical methods of water treatment, there are three general processes:
1st. Lime Process. The lime process is used for waters containing bicarbonates of lime and magnesia. Slacked lime in solution, as lime water, is the reagent used. This combines with the carbonic acid which is present, either free or as carbonates, to form an insoluble monocarbonate of lime. The soluble bicarbonates of lime and magnesia, losing their carbonic acid, thereby become insoluble and precipitate.
2nd. Soda Process. The soda process is used for waters containing sulphates of lime and magnesia. Carbonate of soda and hydrate of soda (caustic soda) are used either alone or together as the reagents.
Carbonate of soda, added to water containing little or no carbonic acid or bicarbonates, decomposes the sulphates to form insoluble carbonate of lime or magnesia which precipitate, the neutral soda remaining in solution. If free carbonic acid or bicarbonates are present, bicarbonate of lime is formed and remains in solution, though under the action of heat, the carbon dioxide will be driven off and insoluble monocarbonates will be formed. Caustic soda used in this process causes a more energetic action, it being presumed that the caustic soda absorbs the carbonic acid, becomes carbonate of soda and acts as above.
3rd. Lime and Soda Process. This process, which is the combination of the first two, is by far the most generally used in water purification.
Such a method is used where sulphates of lime and magnesia are contained in the water, together with such quant.i.ty of carbonic acid or bicarbonates as to impair the action of the soda. Sufficient soda is used to break down the sulphates of lime and magnesia and as much lime added as is required to absorb the carbonic acid not taken up in the soda reaction.
All of the apparatus for effecting such treatment of feed waters is approximately the same in its chemical action, the numerous systems differing in the methods of introduction and handling of the reagents.
The methods of testing water treated by an apparatus of this description follow.
When properly treated, alkalinity, hardness and causticity should be in the approximate relation of 6, 5 and 4. When too much lime is used in the treatment, the causticity in the purified water, as indicated by the acid test, will be nearly equal to the alkalinity. If too little lime is used, the causticity will fall to approximately half the alkalinity. The hardness should not be in excess of two points less than the alkalinity.
Where too great a quant.i.ty of soda is used, the hardness is lowered and the alkalinity raised. If too little soda, the hardness is raised and the alkalinity lowered.
Alkalinity and causticity are tested with a standard solution of sulphuric acid. A standard soap solution is used for testing for hardness and a silver nitrate solution may also be used for determining whether an excess of lime has been used in the treatment.
Alkalinity: To 50 cubic centimeters of treated water, to which there has been added sufficient methylorange to color it, add the acid solution, drop by drop, until the mixture is on the point of turning red. As the acid solution is first added, the red color, which shows quickly, disappears on shaking the mixture, and this color disappears more slowly as the critical point is approached. One-tenth cubic centimeter of the standard acid solution corresponds to one degree of alkalinity.
[Ill.u.s.tration: 2640 Horse-power Installation of Babc.o.c.k & Wilc.o.x Boilers at the Botany Worsted Mills, Pa.s.saic, N. J.]
Causticity: To 50 cubic centimeters of treated water, to which there has been added one drop of phenolphthalein dissolved in alcohol to give the water a pinkish color, add the acid solution, drop by drop, shaking after each addition, until the color entirely disappears. One-tenth cubic centimeter of acid solution corresponds to one degree of causticity.
The alkalinity may be determined from the same sample tested for causticity by the coloring with methylorange and adding the acid until the sample is on the point of turning red. The total acid added in determining both causticity and alkalinity in this case is the measure of the alkalinity.
Hardness: 100 cubic centimeters of the treated water is used for this test, one cubic centimeter of the soap solution corresponding to one degree of hardness. The soap solution is added a very little at a time and the whole violently shaken. Enough of the solution must be added to make a permanent lather or foam, that is, the soap bubbles must not disappear after the shaking is stopped.
Excess of lime as determined by nitrate of silver: If there is an excess of lime used in the treatment, a sample will become a dark brown by the addition of a small quant.i.ty of silver nitrate, otherwise a milky white solution will be formed.
Combined Heat and Chemical Treatment: Heat is used in many systems of feed treatment apparatus as an adjunct to the chemical process. Heat alone will remove temporary hardness by the precipitation of carbonates of lime and magnesia and, when used in connection with the chemical process, leaves only the permanent hardness or the sulphates of lime to be taken care of by chemical treatment.
TABLE 16
REAGENTS REQUIRED IN LIME AND SODA PROCESS FOR TREATING 1000 U. S. GALLONS OF WATER PER GRAIN PER GALLON OF CONTAINED IMPURITIES[16]
+-----------------------+-----------+-----------+ | | Lime[17] | Soda[18] | | | Pounds | Pounds | +-----------------------+-----------+-----------+ | Calcium Carbonate | 0.098 | ... | | Calcium Sulphate | ... | 0.124 | | Calcium Chloride | ... | 0.151 | | Calcium Nitrate | ... | 0.104 | | Magnesium Carbonate | 0.234 | ... | | Magnesium Sulphate | 0.079 | 0.141 | | Magnesium Chloride | 0.103 | 0.177 | | Magnesium Nitrate | 0.067 | 0.115 | | Ferrous Carbonate | 0.169 | ... | | Ferrous Sulphate | 0.070 | 0.110 | | Ferric Sulphate | 0.074 | 0.126 | | Aluminum Sulphate | 0.087 | 0.147 | | Free Sulphuric Acid | 0.100 | 0.171 | | Sodium Carbonate | 0.093 | ... | | Free Carbon Dioxide | 0.223 | ... | | Hydrogen Sulphite | 0.288 | ... | +-----------------------+-----------+-----------+
The chemicals used in the ordinary lime and soda process of feed water treatment are common lime and soda. The efficiency of such apparatus will depend wholly upon the amount and character of the impurities in the water to be treated. Table 16 gives the amount of lime and soda required per 1000 gallons for each grain per gallon of the various impurities found in the water. This table is based on lime containing 90 per cent calcium oxide and soda containing 58 per cent sodium oxide, which correspond to the commercial quality ordinarily purchasable. From this table and the cost of the lime and soda, the cost of treating any water per 1000 gallons may be readily computed.
Less Usual Reagents--Barium hydrate is sometimes used to reduce permanent hardness or the calcium sulphate component. Until recently, the high cost of barium hydrate has rendered its use prohibitive but at the present it is obtained as a by-product in cement manufacture and it may be purchased at a more reasonable figure than heretofore. It acts directly on the soluble sulphates to form barium sulphate which is insoluble and may be precipitated. Where this reagent is used, it is desirable that the reaction be allowed to take place outside of the boiler, though there are certain cases where its internal use is permissible.
Barium carbonate is sometimes used in removing calcium sulphate, the products of the reaction being barium sulphate and calcium carbonate, both of which are insoluble and may be precipitated. As barium carbonate in itself is insoluble, it cannot be added to water as a solution and its use should, therefore, be confined to treatment outside of the boiler.
Silicate of soda will precipitate calcium carbonate with the formation of a gelatinous silicate of lime and carbonate of soda. If calcium sulphate is also present, carbonate of soda is formed in the above reaction, which in turn will break down the sulphate.
Oxalate of soda is an expensive but efficient reagent which forms a precipitate of calcium oxalate of a particularly insoluble nature.
Alum and iron alum will act as efficient coagulents where organic matter is present in the water. Iron alum has not only this property but also that of reducing oil discharged from surface condensers to a condition in which it may be readily removed by filtration.
Corrosion--Where there is a corrosive action because of the presence of acid in the water or of oil containing fatty acids which will decompose and cause pitting wherever the sludge can find a resting place, it may be overcome by the neutralization of the water by carbonate of soda.
Such neutralization should be carried to the point where the water will just turn red litmus paper blue. As a preventative of such action arising from the presence of the oil, only the highest grades of hydrocarbon oils should be used.
Acidity will occur where sea water is present in a boiler. There is the possibility of such an occurrence in marine practice and in stationary plants using sea water for condensing, due to leaky condenser tubes, priming in the evaporators, etc. Such acidity is caused through the dissociation of magnesium chloride into hydrochloride acid and magnesia under high temperatures. The acid in contact with the metal forms an iron salt which immediately upon its formation is neutralized by the free magnesia in the water, thereby precipitating iron oxide and reforming magnesium chloride. The preventive for corrosion arising from such acidity is the keeping tight of the condenser. Where it is unavoidable that some sea water should find its way into a boiler, the acidity resulting should be neutralized by soda ash. This will convert the magnesium chloride into magnesium carbonate and sodium chloride, neither of which is corrosive but both of which are scale-forming.
The presence of air in the feed water which is sucked in by the feed pump is a well recognized cause of corrosion. Air bubbles form below the water line and attack the metal of the boiler, the oxygen of the air causing oxidization of the boiler metal and the formation of rust. The particle of rust thus formed is swept away by the circulation or is dislodged by expansion and the minute pit thus left forms an ideal resting place for other air bubbles and the continuation of the oxidization process. The prevention is, of course, the removing of the air from the feed water. In marine practice, where there has been experienced the most difficulty from this source, it has been found to be advantageous to pump the water from the hot well to a filter tank placed above the feed pump suction valves. In this way the air is liberated from the surface of the tank and a head is a.s.sured for the suction end of the pump. In this same cla.s.s of work, the corrosive action of air is reduced by introducing the feed through a spray nozzle into the steam s.p.a.ce above the water line.
Galvanic action, resulting in the eating away of the boiler metal through electrolysis was formerly considered practically the sole cause of corrosion. But little is known of such action aside from the fact that it does take place in certain instances. The means adopted as a remedy is usually the installation of zinc plates within the boiler, which must have positive metallic contact with the boiler metal. In this way, local electrolytic effects are overcome by a still greater electrolytic action at the expense of the more positive zinc. The positive contact necessary is difficult to maintain and it is questionable just what efficacy such plates have except for a short period after their installation when the contact is known to be positive. Aside from protection from such electrolytic action, however, the zinc plates have a distinct use where there is the liability of air in the feed, as they offer a substance much more readily oxidized by such air than the metal of the boiler.
Foaming--Where foaming is caused by organic matter in suspension, it may be largely overcome by filtration or by the use of a coagulent in connection with filtration, the latter combination having come recently into considerable favor. Alum, or potash alum, and iron alum, which in reality contains no alumina and should rather be called pota.s.sia-ferric, are the coagulents generally used in connection with filtration. Such matter as is not removed by filtration may, under certain conditions, be handled by surface blowing. In some instances, settling tanks are used for the removal of matter in suspension, but where large quant.i.ties of water are required, filtration is ordinarily subst.i.tuted on account of the time element and the large area necessary in settling tanks.
Where foaming occurs as the result of overtreatment of the feed water, the obvious remedy is a change in such treatment.
Priming--Where priming is caused by excessive concentration of salts within a boiler, it may be overcome largely by frequent blowing down.
The degree of concentration allowable before priming will take place varies widely with conditions of operation and may be definitely determined only by experience with each individual set of conditions. It is the presence of the salts that cause priming that may result in the absolute unfitness of water for boiler feed purposes. Where these salts exist in such quant.i.ties that the amount of blowing down necessary to keep the degree of concentration below the priming point results in excessive losses, the only remedy is the securing of another supply of feed, and the results will warrant the change almost regardless of the expense. In some few instances, the impurities may be taken care of by some method of water treatment but such water should be submitted to an authority on the subject before any treatment apparatus is installed.
[Ill.u.s.tration: 3000 Horse-power Installation of Cross Drum Babc.o.c.k & Wilc.o.x Boilers and Superheaters Equipped with Babc.o.c.k & Wilc.o.x Chain Grate Stokers at the Washington Terminal Co., Washington, D. C.]
Boiler Compounds--The method of treatment of feed water by far the most generally used is by the use of some of the so-called boiler compounds.
There are many reliable concerns handling such compounds who unquestionably secure the promised results, but there is a great tendency toward looking on the compound as a "cure all" for any water difficulties and care should be taken to deal only with reputable concerns.
The composition of these compounds is almost invariably based on soda with certain tannic substances and in some instances a gelatinous substance which is presumed to encircle scale particles and prevent their adhering to the boiler surfaces. The action of these compounds is ordinarily to reduce the calcium sulphate in the water by means of carbonate of soda and to precipitate it as a muddy form of calcium carbonate which may be blown off. The tannic compounds are used in connection with the soda with the idea of introducing organic matter into any scale already formed. When it has penetrated to the boiler metal, decomposition of the scale sets in, causing a disruptive effect which breaks the scale from the metal sometimes in large slabs. It is this effect of boiler compounds that is to be most carefully guarded against or inevitable trouble will result from the presence of loose scale with the consequent danger of tube losses through burning.
When proper care is taken to suit the compound to the water in use, the results secured are fairly effective. In general, however, the use of compounds may only be recommended for the prevention of scale rather than with the view to removing scale which has already formed, that is, the compounds should be introduced with the feed water only when the boiler has been thoroughly cleaned.