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BOILER WATER TREATMENT

Presented by Adrian Estcourt AQUACARE

March 2009

SECTION 1 - PRINCIPLES OF WATER TREATMENT

1. Introduction A boiler in basic terms is nothing more than a container in which heat can be transferred from one media through the walls of the container to water. Because thermal energy transport is directly related to cross-sectional area, boilers are designed to contain the maximum amount of surface area to volume ratio which will enable structural rigidity and reasonably controllable operation. With the ever increasing cost of materials and fuel, design engineers are continuously challenged to produce higher efficiency boilers and optimise the materials of construction whilst maintaining structural rigidity. This trend in turn challenges the Water Treatment Company to provide chemical treatment programmes and technical back up service which will allow the boiler plant to operate at maximum efficiency while ensuring extended equipment operating life. 2. The Steam Circuit A typical steam circuit is described as follows. Water which enters the boiler is referred to as boiler feedwater. Boiler feedwater may be made up of make up water and one or more sources of return condensate. Make up water is raw water which may be pre-treated for use in the boiler to remove specific impurities. Examples of pre-treatment are softener, demineraliser, reverse osmosis and de-alkaliser plants. In most instances a softener unit is commissioned to remove hardness from the water. Due to the high capital cost, demineraliser and reverse osmosis plants are seldom used in low pressure industrial boiler plants. Return condensate is steam which has been condensed back to water through the process and is returned for further use in steam production. The impurities present in return condensate will differ from the make up water depending on factors such as the type of process involved and potential contaminants, plant operating conditions, materials in use etc. Boiler water refers to the water which is heated inside the boiler to produce steam. Due to the evaporation process and introduction of make up water, the level of impurities increases in the boiler water and these must be controlled at specified levels through boiler water blowdown. 3. Water Impurities Impurities may be classified into three types: Dissolved solids Dissolved gasses Suspended solids
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Pure water does not exist in nature and impurities vary widely. While one may consider rain water to be pure, before the water has reached the earth's surface it has absorbed pollutants, oxygen and carbon dioxide. Due to the high solvency of water, additional impurities are dissolved from the land surface. A few examples include: Calcium Carbonate (limestone) Magnesium Carbonate (dolomite) Calcium Sulphate (gypsum) Magnesium Sulphate (epsom salts) Silica (sand) Sodium Chloride (common salt) Iron If all waters carried the same impurities, treatment could zero in on a nearly standard programme for each use. This is however not the case and water quality varies across South Africa depending on the type of ground material. Chemical treatment must therefore be designed to handle specific conditions and potential problems. 4. Deposit Formation in Boilers Due to evaporation in the boiler, the concentration of dissolved impurities increases to the point where they precipitate out of solution and adhere to the heat transfer surfaces forming boiler scale. Certain minerals such as Calcium Carbonate experience inverse solubility, whereby the higher the temperature, the less soluble the material. For this reason these types of minerals will tend to exceed their solubility at the high temperature steel surfaces and form deposits while remaining soluble in the bulk water. The deposits typically found in boilers include: Calcium Carbonate Calcium Phosphate Silica Iron In most instances the ingression of hardness into the boiler is the major cause of scale formation and highlights the importance of efficient softener plant operation. Consider a boiler plant running continuously at 10 Tph with a feedwater hardness of 10ppm. If one allowed this hardness to deposit in the boiler then the scale build up would be almost one ton over a one year period. The energy implication of scale deposits is significant as shown in the example below.
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For example, a 1mm deposit consisting mainly of carbonate will result in a 1.8% increase in fuel consumption. Therefore a boiler plant running continuously at 10 Tph will consume an additional 130 tons of HFO per annum. Assuming HFO costs R 3 000-00 per ton, this equates to energy wastage of R 390 000-00 per annum. If the 1mm scale deposit consists mainly of iron/silica, then this increase in fuel costs escalates to R 1 300 000-00. Further problems caused by scale deposits are; Failure of boiler tubes due to overheating of the metal Corrosion of the metal surface under the deposit Increased boiler cleaning expenses to remove the deposit

5. Corrosion Corrosion is the loss of metal as it oxidises back to the ore form, for example iron reverts to iron oxide. The corrosion mechanisms involved are extremely complex electrochemical reactions and as such will not be dealt with in this paper. Of importance, however, is that corrosion can be uniform over the metal surface or localised, resulting in deep pits in the metal. Pitting corrosion caused mainly by dissolved oxygen is severe and can result in premature replacement of boiler tubes, feedwater lines and condensate return lines. Corrosion can be experienced in four areas: Feedwater System: Caused by low pH, dissolved oxygen and carbon dioxide. Caused by high or low alkalinity, dissolved oxygen and deposits in the boiler. The corrosion process is accelerated by high temperatures and stresses in the boiler. Corrosion of boilers during out of service periods can be severe when correct lay up procedures are not followed. The major causes of corrosion are oxygen pitting and low alkalinity. Caused by carbon dioxide / carbonic acid, oxygen and process contaminants.

Operating Boilers:

Standby Boilers:

Steam / Condensate System:

The cost of corrosion is immense, resulting in production downtime and high costs for equipment replacement. To retube a boiler can cost between R 300 000-00 and R 500 000-00. A further problem associated with corrosion is the deposition of corrosion products (iron, copper) on the boiler tubes which results in increased fuel costs and further underdeposit corrosion.
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The secret for preventing high corrosion rates in the boiler is through the formation and maintenance of a magnetite layer (Fe3O4) on the metal surface. The ability to use inexpensive carbon steel material for boiler construction, where the metal surface is in contact with water at high temperatures and pressures, is due to the reaction that takes place between iron an oxygen-free alkaline water to form magnetite. The maintenance of this corrosion resistant layer is the difference between success and failure. With this in mind, effective corrosion prevention can be achieved by: Removing dissolved oxygen from the feedwater Maintaining correct alkalinity levels in the boiler Keeping metal surfaces clean and deposit free Protecting boilers during standby periods Chemically treating corrosive gasses in the steam / condensate system. 6. Steam Quality Poor steam quality results from a combination of poor boiler water quality and poor boiler operation. The steam produced from the boiler should always be as dry as possible and contain minimal dissolved solids. Boiler water carryover results in poor quality steam and is caused through two problem areas: Foaming: Bubbles form on the boiler water surface and leave with the steam. Foaming is caused by high TDS, high suspended solids and contaminants such as oils, greases, fats and certain organics. Oil, in particular, can cause major problems due to the saponification process where it reacts with caustic in the boiler water to form soaps. This is a more severe form of carryover where a sudden surge of boiler water is drawn into the steam line. Priming can be caused by operating the boiler above its rating, sudden changes in steam demand and finally by operating the water level in the boiler too high.

Priming:

Carryover results in dissolved solids entering the steam / condensate system and forming deposits. The deposits will have a negative effect on heat transfer and will increase corrosion in the system. Where live steam is used, carryover will result in process contamination and production losses eg. food industry.

7. Chemical Treatment Programmes Having discussed the potential problems existing in the boiler plant we can now look at prevention of these problems through the application and control of a chemical treatment programme. It follows that the objectives of the programme would be to: Prevent scale deposits in the boiler system Minimise corrosion in the boiler system Assist in producing good quality steam In order to achieve these objectives, the composition of the chemical programme must be able to perform the functions listed below. React in some manner with the feedwater hardness and prevent it from forming scale in the boilers Disperse any suspended solids or sludge in the boiler and prevent deposits of this material Remove dissolved oxygen from the feedwater thereby preventing pitting corrosion Provide sufficient alkalinity to minimise boiler corrosion Provide antifoam to minimise boiler water carryover Protect the steam / condensate system against corrosion Boiler water treatment technology has advanced significantly over the past century. Antiscalants can be divided into two categories, namely stoichiometric reactants which chemically react with feedwater impurities to change their chemical structure and then nonstoichiometric reactions which alter the behaviour of impurities. Some examples are shown below: Stoichiometric Reactants Carbonate Phosphates Chelants Synthetic Polymers Nonstoichiometric Reactants Natural Organics Lignins - Tannins - Starches - Polyacrylates - Polymethacrylates - Styrene/Maleic Phosphonates

Phosphate based programmes are termed precipitating programmes whereby impurities such as calcium are brought out of solution to form a loose sludge in the boiler water. The ability to use this type of programme effectively is based on the addition of organic polymers in the treatment, which condition and disperse the suspended solids and allow them to be removed through blowdown without depositing on the boiler tubes. With correct application and control this programme is used with excellent results. Solubilising programmes include chelants (NTA, EDTA), polymers, metal dispersants and organic sludge conditioners. The use of chelants (NTA, EDTA) is often avoided because of the potential corrosiveness, particularly when they are incorrectly applied. Polymer type solubilising programmes prevent scale formation by distorting crystalline growth of the scale and dispersing the small particles as colloids. Chemicals used for oxygen scavenging are almost exclusively sulphite and hydrazine which can both be catalysed to increase their rate of oxygen removal. Each product has its merits and selection is generally based on boiler operating conditions and food grade approval. Some characteristics of the two products are shown below: Sulphite has food grade approval while hydrazine does not Both are catalysed, however sulphite will remove oxygen more rapidly at low temperatures Sulphite increases boiler water TDS while hydrazine does not Sulphite reacts with oxygen at an 8 : 1 ratio while hydrazine reacts at a 1 : 1 ratio. Generally, hydrazine is more cost effective Hydrazine will actively promote metal passivation while sulphite will not Hydrazine is volatile and will provide condensate line protection. Being non-volatile, sulphite does not provide this function Both products are suitable for offline lay-up of boilers Condensate line protection is achieved by using either neutralising amines, filming amines or a combination. Neutralising amines will neutralise carbonic acid formed in the steam / condensate system and raise the ph to non-corrosive levels. Filming amines coat the metal surfaces and provide a physical barrier against the corrosive condensate. This is particularly effective when oxygen corrosion is a problem.

SECTION 2 MANAGING YOUR WATER TREATMENT PROGRAMME

With the advanced technology available to the water treatment industry and the proven effectiveness of the products in use, one would expect to find deposit and corrosion free conditions existing in all boilers. This is however not the case as many boilers under treatment are opened for inspection and found to be either heavily scaled or severely corroded. The question is obviously raised at this point as to why poor results are being experienced. It must be understood that the chemicals being used are not magical and therefore cannot do the job alone. Achieving an excellent result is probably 30% due to product performance and 70% due to the application and the control of the programme and boiler operation. Poor results are therefore almost always due to poor management. When selecting the correct water treatment for a plant, there are basically three areas which the engineer must consider; Results Costs Service Engineers may vary in their opinion as to which factor is the most important to them. However, it has been proven over and over that all three areas are strongly interdependent and must be correctly managed to achieve effective results. Let us look at each aspect more closely. 1. Results The boiler water treatment programme used on the plant must able to produce the desired results in terms of a deposit free boiler, minimal corrosion and good steam quality. Without this prime objective in mind we are truly wasting our time and money. Results are directly dependent on the following basic factors; a. Select the right type of treatment for your plant. For example, dont use uncatalysed sulphite when your feedwater temperature is very low, dont select non food grade approved products if your factory requires this approval, dont use acidic products when your feed alkalinity is low etc. b. Dose the chemical treatment correctly. This is probably the most commonly found area of mismanagement and leads directly to poor results. The basic rules for dosing the treatment should be closely followed.
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Wherever possible avoid the dilution of the chemicals with water (apart from sulphite powder) Dose scale inhibitor and oxygen scavenger products separately Use sufficiently sized holding tanks Never hand dose the chemicals Inject the oxygen scavenger as far from the boiler as possible to allow reaction time Use a proportional to feed dosing system. This can be effected by an electrical interlock between the boiler feedwater pump and the chemical dosing pumps in situations where the boiler water level is controlled by on/off operation of the feedwater pump. A modulating feed valve system will not suit this arrangement. The most effective proportional system consists of a feedwater meter with pulse generator which drives the chemical dosing pumps. This system ensures the correct concentration of chemicals under all conditions of load, and will also give an indication of the boiler plant steaming rate. It also allows for dosing of more than one boiler and can be used to calculate your treatment cost per m3 feedwater. To ensure reliable and uninterrupted dosing, select good quality chemical pumps with readily available spares and back up service. c. Ensure continuous soft water supply. Softener operation is critical to achieve results. The majority of scale deposits found in boilers are directly connected to hard water entering the boiler. Some chemical treatment programmes are designed to handle intermittent hardness ingression but extended high levels of hardness will lead to scale deposition. Once again the basic rules must be followed to ensure soft water supply. Select the right size unit for your plant It is preferable to install a duplex system which will supply soft water at all times Make sure the regeneration is automated and set to the correct frequency Service and maintain the unit regularly Add the correct quantity of salt to the brine tank Test water at least once a day

d. Protect the standby boilers against corrosion. Corrosion in boilers is in most instances caused during offline or standby conditions. Oxygen pitting is most commonly found and results in devastating localised metal loss leading to costly re-tubing of the boiler. Correct treatment of standby boilers under wet conditions is therefore essential and the following guidelines should be followed. Boilers which are shut down for short periods (2 3 days) should have a sulphite residual control of 100ppm at all times. The slightly higher sulphite residual does not have a major impact on chemical costs For longer storage periods the boiler must be slug dosed with correct quantity of oxygen scavenger and alkalinity builder Ensure that the chemicals added are completely mixed in the boiler by either heating or recirculating the boiler water. Fill the boiler completely with water to protect the steam space. A small header drum can be connected to the top of the boiler. Sample and test the standby boiler regularly e. Monitor the conditions of your plant regularly. Your chemical supplier will offer an onsite service which will vary in frequency between once a month and once a week. Whatever the frequency, it is imperative that daily tests be conducted by either your laboratory or boiler house personnel. The purpose of regular testing is to identify problems before damage has taken place requiring expensive rectification. The testing methods can be simple and will take minimal time to complete. Softener: Feedwater: Condensate: Boiler: 2. Costs This aspect appears to be foremost on the minds of many engineers, and is often the deciding factor when selecting a water treatment programme. The "penny-wise pound foolish" principle can often apply in these cases with the cheapest option turning out to be the most costly. Treatment costs must therefore be carefully considered together with the factors of service and results. The simple part of the decision appears to be selecting the most cost
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TDS, Hardness TDS, Hardness, pH TDS, Hardness, pH TDS, OH Alkalinity, Sulphite

effective treatment for your plant, thereafter the hardest part is maintaining actual costs close to that predicted. Actual costs must be closely monitored on a regular basis as part of the management system and related back to the expected figures. Chemical treatment costs will depend on: Scale Inhibitor: Oxygen Scavenger: Condensate Treatment: Dosage rate and unit price. Dosage rate and unit price (feed temperature has a direct impact on dosage rate). Dosage rate and unit price

The most efficient method of evaluating cost is related to feedwater usage. And example would be as follows; Product Scale Inhibitor Oxygen Scavenger Condensate Treatment Total Treatment Cost Dosage on Feed 50ppm 80ppm 10ppm = R 2-90/m3 feed Unit Price R 20-00/kg R 20-00/kg R 30-00/kg Cost per m3 feed R 1-00 R 1-60 R 0-30

Therefore, a plant with an annual feedwater usage of 50 000m3 will expect to spend R 145 000-00 on water treatment. Underdosing the programme will give lower cost and poor results, while overdosing will not improve the result in proportion to cost and is therefore money wasted. Assuming no major changes in plant operating conditions, a well managed water treatment programme will give actual costs close to that expected.

3. Service Customers are strongly dependent on the technical service and expertise of their supplier. This service must go further than merely analysing boiler water samples once or twice a month and should consist of a package which is geared to complete management of the water treatment programme. The technical representative responsible for your account is therefore the most important person as he/she must ensure that all facets of the service package are in place. These services include; Ensuring correct treatment programme is used Ensuring correct dosing procedures and equipment are used
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Ensuring good softener operation Site visits, analysis and recommendations Establishing in-house monitoring with feedback system Training Monitoring of feedwater usage, softener usage and condensate return percentage Check consumption of products against that expected Calculate the cost per m3 feedwater and report back on a regular basis Carry out boiler inspections and keep photographic record Problem solving

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SECTION 3 OTHER ENERGY CONSIDERATIONS

1. Boiler Blowdown Boiler blowdown represents an area of energy loss in the boiler plant which can be optimised to ensure good control of impurities, steam quality and efficient boiler operation. Blowdown is generally controlled on the basis of boiler water TDS between the ranges of 2 000 3 500ppm for a 10 Bar boiler. A more applicable blowdown control in terms of energy is to consider the cycles of concentration in the boiler. If we consider the relationship between fuel required (kg/ton steam) and the boiler cycles of concentration, the optimum cost effective operation is reached in the range of 25 30 cycles. Increasing above this does not result in any significant fuel saving and could lead to poor quality steam due to the increased potential for boiler water carryover. In addition, operating the boiler at unnecessarily high cycles will concentrate any contaminants or suspended solids entering the boiler to problematic levels. For example, a boiler plant with a feedwater TDS of 200ppm operated at 10 cycles will result in a boiler water TDS of 2000ppm and a blowdown fuel requirement of 2.2kg HFO/ton steam. If this boiler were to operate at 15 cycles or a TDS of 3000ppm, then the blowdown fuel requirement would be 1.4kg HFO/ton steam. The fuel saving would then be 0.8kg HFO/ton steam. Once again using a 10Tph boiler in continuous operation, the fuel saving would be R 210 000-00 per annum. 2. Feedwater Temperature Increasing the feedwater temperature will reduce the chemical oxygen scavenger requirements and more significantly decrease the boiler plant fuel consumption. It must be noted, however, that increasing the feedwater temperature through deaerator operation or a silent steam heater in hotwell will not reduce overall fuel usage. In order to gain this saving, the feedwater temperature must be increased via some means of waste energy recovery such as: Economiser operation to recover flue gas waste heat Lagging of condensate return lines and hotwell Increasing the quantity of condensate return Heat recovery from the blowdown water If we consider the relationship between fuel required (kg/ton feedwater) and the feedwater temperature, the potential savings are significant. For example, raising
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the feedwater temperature from 400C to 600C for a boiler operating continuously at 10Tph, will result in a HFO saving of approximately R 630 000-00 per annum.

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