April 1997 Ref : 02005Ren9775

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Wastewater effluents Technology

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Thermal Generation Study Committee

20.04 THERCHIM 20.05 THERRES
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Thermal Generation Study Committee Groups of Experts: Thermal Power Plant Chemistry Mangement and Thermal Power Plant Residue Management ..................................................................................................................................... Wastewater Effluents Technology ..................................................................................................................................... Paper prepared by: Roger ROOFTHOOFT (LABORELEC, Belgium); William S. KYTE (POWERGEN, United Kingdom); Eric SMITSHUYSEN (VESTKRAFT, Denmark); Antonio TOSI (ENEL, Italy); Gianmaria GUARDIANI (ENEL, Italy); Stefano CONCARI (ENEL, Italy)

CONTENT

1. INTRODUCTION AND OBJECTIVES OF THE REPORT

1.1. GENERAL INTRODUCTION

1.2. OBJECTIVES OF WATER EFFLUENT TREATMENT TECHNOLOGY REPORT

2. WATERS USED IN POWER PLANTS

2.1. CONTINUOUS OR REGULAR USED WATER 2.1.1. COOLING WATER 2.1.2. BOILER MAKEUP WATER 2.1.3. SLAG FLUSH, COOLING WATER, ASH TRANSPORT WATER 2.1.4. DESULPHURISATION PLANT MAKE UP WATER 2.1.5. FLUSH AND DRAIN WATER 2.1.6. LABORATORY WATER 2.1.7. SANITARY WATER 2.2. PERIODICALLY OR SELDOM USED WATER 2.2.1. WASHING OF BOILERS, AIR PREHEATERS AND ASH PRECIPITATORS 2.2.2. BOILER ACID CLEANING AND CONDENSER ACID CLEANING

2 2 2 3 3 3 4 4 4 4 4

3. OVERVIEW OF WASTEWATER TREATMENT TECHNOLOGY

3.1. INTRODUCTION 3.1.1. BASIC PRINCIPLES 3.1.2. THE BASIC TECHNOLOGICAL PRINCIPLES 3.2. TECHNOLOGIES 3.2.1. OILY WASTEWATER 3.2.2. SANITARY WATER 3.2.3. SUSPENDED SOLIDS 3.2.4. INORGANIC POLLUTANTS 3.2.5. SPECIFIC INORGANIC POLLUTANTS

5 5 6 8 8 19 22 27 36

3.2.6. FINAL TREATMENT

40

4. SURVEY OF THE SITUATION IN UNIPEDE COUNTRIES

43

5. CONCLUSIONS AND RECOMMENDATIONS

56

5.1. CONCLUSIONS

56

5.2. RECOMMENDATIONS

57

EXECUTIVE SUMMARY

In the past, the subject of waste water from power plants has received little attention and was not considered as a high priority topic. Increasing focus on water quality in recent years however resulted in more severe restrictions on discharges. Therres and Therchim, two Unipede Expert Groups, recognised the need for a report in this area and agreed that a joint study had to be undertaken. Four major topics were identified. This report focuses on Water effluent treatment technology. It gives an overview of available technologies and effluents of thermal power plants. This overview is the result of an inquiry performed in Unipede member countries. The different flows are identified in nature and flow rates or annual volumes (chapter 4). Continuous waste streams are mainly cooling water, slag flush and ash transport water, FGD-effluents, drains, laboratory water and sanitary water (chapter 2). Discontinuous or periodic waste effluents are generated by acid cleanings and washing waters from boilers, air preheaters and ash precipitators. Specific technologies are available for oily waste water, sanitary water, suspended solids removal, heavy metals and specific inorganic pollutants (mainly nitrogen compounds). These are described in chapter 3. Possibilities and limits of the processes are given as well as small comparison tables taking economic evaluations into account. The report shows that : many technologies, simple and advanced, are available for solving almost every problem of pollution however good knowledge of the different steams and an appropriate design are necessary as well as a good process control and appropriate supervision and maintenance approaches vary from country to country in function of national or local regulations and depending on age and design of the power plants economic considerations can be of prime importance almost all countries use technologies to reduce heavy metals and oils in water water re-use and integrated water management get more attention. It is recommended that integrated water and waste management should receive a high priority. The power industry must keep a continuing awareness of developments in water treatment technology. Exchange of information in this area should continue within the Unipede countries.

1.

INTRODUCTION AND OBJECTIVES OF THE REPORT

1.1.

GENERAL INTRODUCTION The subject of waste water from power stations has received little attention in the past and has

not in general been regarded as a high priority issue. However increasing focus in recent years on water quality has resulted in ever tightening restrictions on the discharge of FGD and other emission control technologies has greatly increased the number of chemical species that have to be considered. These developments have meant that the complexity of waste water treatment has increased as well as the risk of exceeding consent limits. Recognising this the two UNIPEDE Groups THERRES and THERCHIM, independently decided that there was a need for a UNIPEDE report in this area. At the initiative of the two chairmen the Thermal Generation Study Committee (THER) agreed that a joint study should be undertaken in order to take advantage of the combined resources and expertise. Accordingly a series of joint studies has been initiated under the generic title "Waste Water and Water Residues Management. Four reports will be produced: Waste Water and Water Residue Management Regulations Water effluent treatment technology Utilisation and disposal Monitoring and analysis (THERRES) (THERCHIM/THERRES) (THERRES/THERCHIM) (THERCHIM)

1.2.

OBJECTIVES REPORT

OF

WATER

EFFLUENT

TREATMENT

TECHNOLOGY

The objectives of this report on Water effluents treatment technology are: a) to give a general overview of the waters used and the technologies available for waste water treatment in thermal power plants; b) to survey the situation in thermal power plants in UNIPEDE member Countries: c) to compare the treatment technologies used and to comment on their applicability with respect to specific situations; d) to make appropriate recommendations.

2.

WATERS USED IN POWER PLANTS Beside the fuels, water is the most used chemical substance in the energy producing industry.

This section gives an overview of the water consumption on a power station and the waste water caused by this consumption. The quality of the water used varies from station to station depending on the resources accessible that often depend on the geographical location. The water qualities/sources can be classified as: clean water (e.g. municipal water, well water, etc.), low salinity water (e.g. river water, lake water, etc.), brackish water, seawater.

At the power station these water qualities are processed/cleaned to meet the quality demands. 2.1. 2.1.1. CONTINUOUS OR REGULAR USED WATER COOLING WATER Cooling water causes the steam from the turbines to condense in a large heat exchanger (condenser). The demand for cooling water depends on the operation mode of the power station (back pressure or condensing mode). When operating at condensing mode, a large amount of cooling water at lowest possible temperature is required. Depending on the geographical location, cooling water is supplied from a closed circuit or from an open circuit. A cooling tower is necessary in a closed circuit. When flood or sea water is used, the circuit has to be constructed in a way to avoid corrosion. When a closed circuit with a cooling tower is used, make up water has to be processed to avoid scaling and corrosion in the system. The effluent stream can contain small amounts of corrosion products from the condenser, bio and corrosion inhibitors like biocides, chlorine, iron sulphate, etc. The temperature increase of the cooling water may also cause problems, especially from systems without cooling towers. 2.1.2. BOILER MAKEUP WATER The water/steam system at the power plant contains high purity water. The water is evaporated in the boiler to high pressure and high temperature steam. The steam is expanded through the turbine and condensed in the condenser. The condensate is returned through the feed water tank to the boiler. To avoid corrosion and depositions in the water/steam system there are very high demands for the purity of boiler make up water. The conductivity of make up water is typically below 0.2 S/cm. The acid conductivity of the steam is normally held well below 0.2 S/cm. Waste water from the boiler (blow down) is normally very clean only containing small amounts of for example ammonia and/or sodium hydroxide/phospates. This type of waste water seldom causes treatment problems and the water is often reused for other purposes.

To achieve this high purity water the available raw water has to be processed. The traditional way of producing high purity water is to demineralise water in an ion exchange plant, after a pretreatment if necessary. Other technologies like reverse osmosis, electrodialysis and distillation have been developed and together with pretreatments like oxidation, flocculation, filtration, etc. give the possibility to use a very wide range of water qualities in the production of boiler make up water. The waste water from an ion exchange plant contains the concentrated impurities from the raw water as well as salts from the regeneration chemicals (hydrochloric acid or sulphuric acid and sodium hydroxide). Usually the ion exchange process is the most efficient water process ( 10 % wastewater) and reverse osmosis is the less efficient process (25 - 30 % wastewater). The other processes are intermediate. The ion exchange process is the most chemical demanding process. To maintain the very high purity in the water/steam system it is possible to clean the condensate; this is done by ion exchange technology (condensate polishing) and/or filtration. Waste water from the condensate polishing plant contains ammonia and salts from regeneration chemicals. Waste water from filters is flush water containing solids (corrosion products and precoats products, if any). Some steam can be extracted from the main thermal cycle to preheat heavy fuel oil. The condensate could be polluted by fuel oil itself. 2.1.3. SLAG FLUSH, COOLING WATER, ASH TRANSPORT WATER The cooling and transportation of slag from the boiler to the storage can be performed by means of water. All types of water can be used. Restrictions can occur to avoid corrosion. Slag cooling and transport water will contain suspended matter, dissolved salts, trace metals and may also have an elevated pH. When wet transportation of fly ash is used, demands and problems are similar. 2.1.4. DESULPHURISATION PLANT MAKE UP WATER The quantities of water used in flue gas cleaning plants depend on the technology used, for example dry, semidry, wet absorption and the absorption chemicals used. Most water qualities can be used. At plants with a wet process often the make up water quality (salinity) sets the demands on the system bleed off. Only wet processes produce waste water. This waste water will typically contain chloride, sulphate, nitrate, suspended matter and heavy metal salts. 2.1.5. FLUSH AND DRAIN WATER Water is also used for all round cleaning purposes at the power station. Large areas and a great part of machinery are flushed with water. The quality of flushing water normally depends on its use so no damage is done to the flushed item. Water that has been used for flushing/cleaning outdoors as well as indoors typically contains cleaning chemicals, waste oil, coal and ash as well as desulphurisation and regeneration chemicals.

2.1.6.

LABORATORY WATER In the laboratory there is normally a demand of two qualities of water: service water and high

purity water. Waste water from laboratories can be characterised as either sanitary waste water or chemical waste, (often a combination depending on the organisation of the laboratory, the discipline concerning the use of waste receptacles and so on). The amount of laboratory waste water is extremely limited compared with other waste water streams. 2.1.7. SANITARY WATER Water for "human" use is usually well water or municipal water. Sanitary wastewater from for example kitchens, bathing facilities, etc., will contain organic matter, detergents and bacteria. 2.2. 2.2.1. PERIODICALLY OR SELDOM USED WATER WASHING OF BOILERS, AIR PREHEATERS AND ASH PRECIPITATORS Power stations have different traditions in terms of washing the boiler and the flue gas path. The boilers are typically flushed prior to the maintenance work on them. Washing is carried out to improve the working environment and also to facilitate inspection of the boiler. Most types of water can be used but low salinity water is preferred. Used wash water contains solid combustion residues as well as dissolved salts and trace metals produced by the combustion process. Depending on the type of fuel used the flush water may contain considerable amounts of sulphuric acid or alkalising agents used to neutralise acid during operation. 2.2.2. BOILER ACID CLEANING AND CONDENSER ACID CLEANING The purpose of the acid cleaning of the boiler is to dissolve and remove oxide film on the inner walls of the boiler tubes. This is performed immediately before commissioning a new boiler or if the amount of deposits on the inner tube surface gives rise to problems. Water quality requirements are normally the same as for boiler make up water. The contents of the waste water are dependent on the cleaning chemicals used. The typical contents are hydrofluoric acid, hydrochloric acid, organic acids, ammonia, organic inhibitors, suspended matter and salt. Condenser acid cleaning is by analogy with boiler acid cleaning but the water quality demands are less strict and the acid used depends on the materials used for the construction of the condenser.

3.

OVERVIEW OF WASTEWATER TREATMENT TECHNOLOGY

3.1.

INTRODUCTION Superficially the treatment of wastewater from thermal power plants would appear to be a

very simple operation. Historically this has been the case and in many old power plants little or no treatment was required. The presence of large quantities of cooling water meant that very often simple treatments together with dilution were sufficient. However, a number of developments have meant that the treatment of wastewater can now be quite complicated, even sometimes approaching that on a chemical plant. The main developments have been: 1. 2. 3. increasingly stringent environmental constraints more chemical processes, for example FGD integrated plant water management

The use of dilution to achieve concentration constraints is no longer an option. These developments mean that increasing amounts of water have to be treated with ever increasing complexity. 3.1.1. BASIC PRINCIPLES The wastewater treatment technologies that are used on power plants are not significantly different from those that are used in other industries. Complications can arise because many of the streams that need to be treated are intermittent or of high volume. A further complication is often that waste streams have been added during the lifetime of the plant so that water treatment may not be integrated but built up on a piecemeal basis. This often means that technologies of different generations are utilised on the same plant. Another distinction that can make a significant difference is whether the power station is completely selfcontained or whether it is connected to an external sewage system, either domestic or industrial. In many cases, power stations have been built in rural areas and have therefore had to be completely self-sufficient and have their own domestic sewage system. In some cases the power plant has the benefit of being connected to either or both domestic and industrial sewage systems. In these cases the treatment, on plant, is very much simplified, though treatment may still be carried out in order to minimise sewage charges. Water management, both on the process and wastewater side, is an exiting new concept that is being taken up on many power plants. This management is usually restricted to the power plant site but can in some s circumstances be extended to outside sources and sinks. Power stations are well used to integrating their sources of fuel and uses of by-products with outside industries but the integration of water resources is a much more novel concept. This can have very significant advantages for the environment. The concept is however not completely new as, in many cases, advantage has always been taken of mutual properties of waste streams. Thus on probably every power plant the neutralisation of acid waste streams with alkaline waste streams (as for example with regeneration waste streams of ion exchange) has been practised for many years. It is now realised that there are many more opportunities for minimising the use of process

water and the discharge of wastewater, by careful examination of the properties of the waters required and of the wastewater produced. The introduction of new technologies, such as FGD, has greatly accelerated this tendency. The minimisation of the use of water has become of increasing importance as it has become more difficult to use clean sources. Hence it is necessary for a rigid prioritisation of the use of water with the cleanest waters being preserved for those processes which absolutely need them, and thus in many cases there can be a cascading of waters down through the processes so that the waste from one process can become the input to another process. This not only minimises the use of clean waters but also minimises the amount of wastewater produced. The price that has to be paid is an increasing complexity of water management, of treatment processes and of the interdependence of processes on each other. It also leads to a fundamental debate of whether there should be distributed wastewater treatment or whether wastewater is best treated in a single dedicated plant. At the present time this debate has not been resolved and both systems are in common use. There is still much room for development and increasing attention is being paid to what once was a very neglected area. 3.1.2. THE BASIC TECHNOLOGICAL PRINCIPLES Wastewater treatment systems are based upon physical, chemical, physico-chemical and biological processes. These types of processes are used both independently and in series depending upon the wastewater that needs to be treated. 3.1.2.1. PHYSICAL TREATMENT SYSTEMS Physical treatment systems are used on every power plant. These include screening, sedimentation, filtration (including centrifuges), decanting and other such simple physical separation processes. They rely on the physical principle of separation through a membrane in such as screening and filtration, or by using differential gravity processes such as sedimentation or decanting. Evaporation/crystallisation is the only technology that can be used when zero liquid discharge is required. This can also be accomplished by injection into the flue gas upstream of the ESP 3.1.2.2. CHEMICAL PROCESSES Simple chemical treatment processes have been used on power stations for many years. The simplest chemical process is that of neutralisation or pH control to produce a wastewater within acceptable limits. In some cases, oxidation to remove Chemical Oxygen Demand has been used. There is now an increasing focus on the presence of trace metals, particularly from ash effluents or the effluent from FGD, and these are being treated by chemical means. The usual method is by precipitation using lime and/or sulphides to produce the insoluble hydroxides and sulphides of toxic metals. These are then removed by sedimentation or filtration. 3.1.2.3. PHYSICO-CHEMICAL PROCESSES Physico-chemical processes that are used for wastewater treatment include ion-exchange, absorption and membrane separation methods. All these technologies tend to be relatively expensive and

are therefore usually used for polishing streams or when a particular compound or element must be removed. Membrane processes are occasionally used when wastewater is purified for recycling

3.1.2.4.

BIOLOGICAL PROCESSES Many power plants have conventional sewage treatment processes for domestic wastes.

However some power plants, particularly those fitted with advanced NOx controls, may have biological processes to remove nitrogen compounds such as ammonia or nitrates. In a few cases bacteria are being used to metabolise organic matters such as oil and resins.

3.2. 3.2.1.

TECHNOLOGIES OILY WASTEWATER Water polluted by oil is mainly treated by gravity separation. This technology takes advantage

of the natural insolubility of most hydrocarbons present in the oils and of the consequential natural separation of organic and aqueous layers based on the different densities. A complete separation of the layers can not however be always ensured only by the different densities of immiscible oil and water, thus often a complementary treatment (for example filtration) can be very helpful to obtain a higher efficiency in oil removal. In some particular cases it is possible that organic and aqueous phases create an emulsion or that the densities of the different phases are very similar. This can lead to the application of specific treatments that enhance the separation of organic compounds from the water phase before gravity separation is applied (for example flotation, coalescing filtration). The concentration of organic compounds in wastewater can also be reduced by the application of nonspecific processes such as the combination of coagulation, flocculation and sedimentation that are usually applied for the removal of suspended solids and inorganic pollutants. The treatment applied for the removal of oil from wastewater offers also partial removal of suspended solids. Thus some considerations reported here are relevant to this subject that is presented in the following section with more details. 3.2.1.1. GRAVITY OIL SEPARATION The process relies on the different densities of immiscible oil and water for successful operation. The organic substances present in the oil can be lighter or heavier than water and thus in general two immiscible organic phases separate from water. One (mainly composed by light oils) floats at the top due to its density lower than water, and the other (mainly composed by tar and pitch and including often also suspended solids) settles to the bottom. The wastewater stream is generally fed to a basin designed to provide a quiescent zone of sufficient retention time to allow the various phases to separate. The best efficiency in separation is obtained when the density differences among the various phases are large. Gravity separation is generally used as an initial treatment step for oil polluted wastewater if no emulsions are present. Typically oil/water gravity separators are of two different types: those designed in accordance with guidelines established by the American Petroleum Institute (API), those made with corrugated plate interceptors (CPI). API separators This kind of separator is one of the most widely used in wastewater treatments.

3.2.1.1.1.

As can be seen from the scheme presented in figure 1, a typical API oil/water separator resembles a rectangular primary clarifier in construction, though specific sizing and design details differ in order to better suit the purpose of oil removal rather than solids removal. Figure 1 - API Separator schematic
Recovered oil pump to tank Decanted water Decant tank Chain drive Adjustable slotted pipe oil skimmer Flight scraper Wastewater feed Baffle Skimming pump

Treated wastewater to thickening and disposal Sludge hopper Sludge pump

The wastewater firstly passes through an inlet section (pre-separator flume, trash rack, oil skimmer and forebay) and after enters into the tank, where a velocity diffusion device (vertical slot baffle or reaction jet inlet) is positioned immediately downstream of the influent entrance. The function of this diffusion device is to reduce flow turbulence and to distribute the flow equally over the cross sectional area of the channel. Removal of settled sludge and floating oil is usually accomplished with a chain drive mechanism. Attached between a pair of endless chains are crosspieces or "flights", extending the full width of the tank and spaced at about 3 m intervals. Settled sludge is dragged to a sludge hopper (there can be more than one) at one end of the basin where it is pumped out for further processing. Floating materials are usually skimmed to the effluent end of the basin by the "flights" returning at the liquid surface. The floating material may then be manually scraped up an inclined apron or removed hydraulically or mechanically. Rotating discs and oleodynamic "ropes" are often used devices to mechanically remove oil from the liquid surface and collect it separately from water for recovery. Typical process sizing and design criteria for API separators are given in table I.

Table I - API design criteria and process sizing Horizontal velocity Maximum = 0.9 m/min (or 15 times the rate of rise of an oil globule, whichever is smaller) 0.9 - 2.4 m 1.8 - 6 m max. 90 m 0.3 - 0.5 3 - 6 m/min 1 - 2 min

Depth Width Length Depth to width ratio Velocity in the pre-separator section Retention time in pre separator section

3.2.1.1.2.

Corrugated Plate Interceptors CPI are typically vendor supplied and are based on proprietary designs. A CPI consists

however in general of a tank containing a number of parallel corrugated plates mounted from 2 to 4 cm apart and inclined at a certain angle. Wastewater flows upwards between the plates, whit the oil droplets floating upward and collecting on the underside of adjacent plates where they coalesce. The coalesced oil droplets move up the plates to form a floating layer that is skimmed from the surface of the process tank. Skimming of oil can be helped mechanically or hydraulically in the same way as for the API process. The solids and the oil fraction with densities higher than water settle from the wastewater stream and collect on the top of the adjacent plates; they then move down the plates and drop off into the bottom of the CPI vessel. Laminar flow in the zone between the plates enhances the separation efficiency of oil from water. A typical CPI separator is presented in figure 2. Typical process sizing and design criteria for CPI separators are proprietary information. 3.2.1.1.3. API and CPI comparison The two types of gravity separators described above can produce about the same effluent quality. CPI are in general smaller and easier to cover (for control of atmospheric emissions). However the smaller size is at the same time a disadvantage since it may not provide sufficient volume to accommodate slugs of oil, and may not provide sufficient retention time for breaking emulsions.

Figure 2 - CPI Separator schematic

Recovered oil pump to tank Treated wastewater

Decant tank

Skimming pump

Wastewater feed

Sludge pump

to thickening and disposal

In general API separators may be preferred because of their simplicity and lack of internals subjected to fouling and plugging. The best application for a CPI separator in fact is for the wastewater streams that do not contain significant solids or heavy oil that would foul the unit. In both types of separator chemicals, such as iron and aluminium salts, and polymers, are sometimes added to the wastewater to improve the efficiency of gravity separation. These chemicals help in the destabilisation of colloidal particles and the enhancement of the agglomeration of fine particles to promote settling at a faster rate. Particle growth is often improved by gentle mechanical mixing. Higher removal efficiency achieved by chemical addition can also increase the hydraulic throughput rate. Both types of gravity separators have an oil removal efficiency that can vary from 66 to 99 % and at the same time give a suspended solid removal efficiency in the range 10 to 50 %. The actual removal efficiency depends on many factors, including the relative densities of the oil and aqueous phases, the configuration of the separator, the retention time, and the size of the oil and tar droplets. In addition to those mentioned above, other parameters such as temperature, pH or the type of solids present in the wastewater can also affect the separation efficiency. In both types of separator the by-products obtained from wastewater purification are the skimmings and the settled solids and heavy oil. The skimmings may have enough oil content to justify recovery and reuse of the oil. The settled solids and heavy oil are typically dewatered prior to final disposal. The possibility to reuse this solid residue for energy recovery should however be evaluated case by case in relation to its calorific value and to the legal requirements. Final treatment either for the reutilisation of wastewater or to meet very severe limitations on discharge are often used on the effluent from both types of gravity separator.

3.2.1.2.

FLOTATION Flotation is used to remove oil from industrial wastewater, especially in the case where the

more simple treatment by gravity separation could not ensure the required oil removal efficiency. The main application of flotation is related to oil polluted wastewater streams where difficult to break emulsions are present. In the flotation process, small gas bubbles rising through the wastewater adhere to solid particles or oil globules, decreasing the density (prior to flotation, oil has density very similar to that of water) of the particle-bubble combination to less than that of water. As a result of this density decrease, the particles rise to the water surface where they can be skimmed off. The bubbles may be added to the wastewater by entraining a gas in the liquid by mechanical or diffused aeration, or they can be induced by a sudden pressure reduction of a supersaturated portion of the wastewater stream, causing the excess gas to come out of solution as bubbles. The gas used in closed flotation units is generally nitrogen, especially in the petroleum industries, in order to reduce the possibility of fires. Air flotation units represent however the majority of flotation units currently in service. The two types of flotation most commonly used in wastewater treatment are: dissolved air flotation (DAF) induced air flotation (IAF). Dissolved air flotation In this type of flotation units, three different variations are currently being used: full flow pressurisation consists of saturating all of the wastewater stream with air under pressure and releasing the pressure at the inlet to the flotation chamber, split-flow pressurisation consists of isolating a portion of the treated stream and saturating it with air under pressure before combining it again with the remainder portion in the flotation chamber, recycle pressurisation consists of saturating a portion of the clarified effluent stream with air under pressure and combining this stream with the raw influent in the flotation chamber. The air is generally added under a pressure of 200 - 500 KPa. The pressurised flow is held in a retention tank for at least 1 - 3 minutes, to allow air dissolution. On reducing the pressure of the saturated wastewater stream, dissolved air in excess of saturation at atmospheric pressure is released in extremely small bubbles. The air solubility in wastewater is lower than the air solubility in clean water and in full scale systems the ratio between the two solubilties is normally between 0.5 and 0.8. Because of this, in general the preferred DAF system is recycle pressurisation, a scheme of this kind of plant is presented in figure 3. The main advantages of this type of DAF system are the minimisation of emulsion formation by pressurising treated effluent rather than oil containing influent, reducing at the same time the cost of the pressurising system. Usually flotation tanks are available in circular (diameter ranging from 3 to 30 m) and rectangular (width as great as 6 m and lengths as great as 24 m) units with a wastewater depth varying from about 0.9 to 3 m.

3.2.1.2.1.

Figure 3 - Dissolved air flotation with recycle pressurisation schematic recycle pump

air pressure retention tank

treated wastewater skimmed float wastewater feed flotation tank settled solids to thickening and disposal float/bottoms pump

chemical feed system

Typical process sizing and design criteria for DAF systems are given in table II. Table II - DAF systems design criteria and process sizing Recycle pressure Air solubility correction factor Air to solids ratio (w/w) Hydraulic retention time Surface loading Recycle rate Pressure tank retention time 200 -500 KPa 0.5 - 0.8 0.01 - 0.1 20 - 60 min. 0.02 - 0.14 m/min 5 - 100 % 1 - 3 min

3.2.1.2.2.

Induced air flotation Induced air flotation systems can be of two types:

mechanically induced IAF, hydraulically induced IAF.

In both cases the air dissolution at elevated pressure is not required, although they operate on the same principle as pressurised air DAF as far as bubble oil interaction. Mechanically induced IAF In this case the air is self-induced by a rotor-disperser mechanism. The rotor is submerged in the liquid and forces the liquid through the disperser openings, thereby creating a subatmospheric pressure. The air is pulled downward into the liquid promoting the air-liquid contact. The liquid normally moves through a

series of four cells, each one with a retention time of about one minute. The float skimmings overflow weirs on each side of the unit. Hydraulically induced IAF In this case, to create the induction of air, liquid is recirculated from the outlet chamber, by a centrifugal pump, through a delivery tube to each cell. The delivery tube extends down into the cell through a standpipe or draft tube. Liquid flowing through the delivery tube and induction nozzle creates a Venturi effect, evacuating liquid from the standpipe and inducing the air into the water. Typical process sizing and design criteria for IAF systems are given in table III. Table III - IAF systems design criteria and process sizing Air to liquid ratio (v/v) Hydraulic retention time Surface hydraulic loading rate Recycle rate 6 4 min 0.4 - 0.6 m/min 25 - 50 % for hydraulic IAF

3.2.1.2.3.

Comparison of IAF and DAF systems IAF typically generates greater volumes of float than DAF. Typical hydraulic loading rates for

IAF are greater than for DAF while IAF retention times are significantly lower than those for DAF. IAF is more sensitive than DAF to proper chemical addition (higher dosages are however required with IAF) and to upsets from large slugs. Both DAF and IAF are often used in conjunction with flocculation. The chemicals (for example alum, demulsifiers, polyelectrolytes and acids) are usually added prior to flotation and can significantly improve the removal efficiency. Laboratory specific tests with wastewater are usually performed to determine if chemical addition is required. Pilot or bench-scale tests are conducted to define the chemicals required and the optimal dosages. Removal efficiencies of about 60 - 80 % for oil and of about 40 - 65 % for suspended solids are normally achieved without chemical addition in both types of flotation devices. With adequate chemical addition the removal efficiencies can be improved to 85 - 89 % for oil and grease and to 80 - 93 % for suspended solids. Process sizing and design criteria (reported separately above for DAF and IAF systems) are normally based on the oil and total suspended solid concentration in the wastewater to be treated. One of the limitations of the DAF process is the reduced effectiveness for treating wastewater at elevated temperatures due to the decreased solubility of air in water (especially important for temperatures > 65 C). In flotation systems the by-products obtained from wastewater treatment are the froth layer skimmed off the top of the unit and the settled sludge. Typically these two by-products are dewatered together prior to final disposal.

3.2.1.3.

FILTRATION Filtration is one of the most widely used processes employed for the removal of suspended

solid and can be helpful also for the removal of moderate concentrations of oil and grease from wastewater. Many systems of filtration can be used depending on the filtering media and on the configuration of the filter. Filtration in most wastewater treatments is inserted as the final or polishing step, to reduce suspended solid and/or oil and grease to relatively low levels. If the suspended solid concentration in the influent stream is greater than 100 mg/l, or if immiscible oils are present in concentrations greater than 25 mg/l, pretreatment facilities (for example sedimentation, flotation, etc.) should be inserted prior to filtration. Filtration can be carried out through membranes, cartridges, precoat filters, granular media, etc. For the removal of suspended solid and oil from wastewater and for the pretreatment of fresh water withdrawn from natural sources, the most applied filters are those that use granular media. For the removal of suspended solid typical industrial processes are: single media filtration (usually sand whose particle size can vary depending on the quality of the water to be treated), dual media filtration (typically sand and anthracite) multi media (for example garnet, sand and anthracite).

For the removal of oil, especially as the final step after gravity separation or other oil removal treatment, granular oleophilic media such as activated carbon are applied. Sometimes activated carbon can be also combined with conventional granular materials in a single vessel. More widespread is the application of granular oleophilic media in a treatment configuration after a separate granular material filter (typically sand) to remove suspended solids. Granular media filters can be of the gravity or pressure type and the flow of liquid stream through the bed can be downflow or upflow. Conventional filtration units are operated in either filtration or backwash modes. During backwashing the filter is taken out of service and due to this, filter systems often consist of two or more units to allow off-line cleaning. Oleophilic media, that are more commonly applied in pressure filters, usually swell when oil is absorbed, and in some cases backwashing is not recommended. In the case the media is spent, the unit is taken out of service and reloaded with new or regenerated media (typically thermal regeneration). The efficiency of oil and solid removal can vary greatly depending on the type of granular media filter used, the nature and fluctuations in wastewater solid content and on the specific operation of the filter. Granular media filtration units may require doses of fungicides or microbiocides from time to time to remove biological slime layers that can accumulate on the media. If the oleophilic media is activated carbon, the presence of oxidative compounds (for example residual chorine from biofouling treatment) in the water to be treated can cause partial consumption of the media and, after regeneration, it is more frequently necessary to add new material.

Some polymers such as flocculant aids are sometimes used immediately prior to the filter units to increase the strength and size of particles entering the filter. Polymer dosage is usually in the range 0.01 to 0.1 mg/l. By-products coming from filtration systems are backwash and/or regeneration effluents, and spent filter media. A typical downflow gravity filter generally consists of a granular media layer of 0.3 to 0.6 m. Hydraulic loading is typically 0.08 to 0.24 m/min. Pressure filters that are similar to gravity filters in most respects can have higher hydraulic loading (0.20 to 0.40 m/min) than gravity filters. Backwashing or regenerating cycles can be controlled on a time schedule or more commonly by pressure drop across the filter. Oil removal efficiencies from 50 to 85 % can be obtained in granular media filtration following oil/water gravity separation. Oil and grease concentrations below 1 mg/l have been registered in granular media filtration after secondary clarification. 3.2.1.4. COALESCING FILTERS This process is a variation on multimedia filtration and is particularly used for the removal of free and emulsified oils ensuring a good removal of suspended solids. Coalescing filters work by promoting collisions of small dispersed oil droplets so that they can coalesce to form larger oil droplets that can be more easily separated from the water phase. The surface of the coalescing media can be wetted by oil and enhances the oil droplets to collide and to form a film. The larger oil particles are then shed from the surface with the assistance of gravity and/or viscous forces caused by fluid flow. Three different types of coalescing filters are available: loose filter media separators (the most widely used), fixed media coalescers (involving foam materials or cylindrical cartridges) parallel plate separators (corresponding to CPI as described in the gravity separation chapter).

Coalescing filters can be of the upflow or downflow type but the most interesting are upflow coalescing filters. These filters collect droplets of oil that break free from the coalescing surfaces during normal filter operation. Because of the upward flow configuration, gravity and viscous forces work in combination to release droplets of coalesced oil. As with granular media filtration systems, coalescing filters also find application mainly as the final polishing step at the end of oil and solid removal processes. They are particularly efficient in the treatment of low to intermediate concentrations of finely divided oil droplets with low specific gravity (0.85 kg/l). Removal efficiency tends to decrease slightly with increasing specific gravity of the oil, and in these cases coalescing filters might be preceded by flotation and gravity separation. The coalesced droplets migrate upward through the media and are released into a gravity separation section at the top of the vessel where the oil collects in a layer and is periodically removed. The outlet for treated water in the separation section is located in the lower part of this section. Solid and heavy oil, if any, are trapped in the media as in conventional filtration. The build-up of solid in the media contributes to increased pressure drop and requires the filter to be taken out of service for

backwashing. In order to obtain good removal of solids included in the filter media, backwashing should be done in different steps: upward flow with strong agitation, simultaneous water backwashing and high rate gas flow. Backwashing normally occurs at scheduled time intervals (for example once a day) or when the pressure drop reaches a preset limit (typically 135 to 170 kPa). Polymers are often added upstream of the filter to assist in coalescing fine oil droplets by reducing the surface charges on oil droplets that result in repulsive forces preventing collisions and coalescence. Surfactant chemicals, added to backwash water or steam, are sometimes used to help remove the oil film from sand grains. The oil removal efficiency of coalescing filters is mainly affected by the stability of oil in water emulsions in the feedwater. In fairly difficult heavy oil applications, with feed wastewater oil concentrations from 30 to 100 mg/l, treated wastewater with 3 to 10 mg/l is typical. Solid concentration in the feed wastewater must be kept below 100 mg/l to keep the backwashing frequency within a reasonable range. Typical process sizing and design criteria for coalescing filters are given in table IV. Table IV - Coalescing filters design criteria and process sizing Surface loading rate Backwash flow Backwash duration Gas scour rate Gas scour duration Media depth Vessel diameter 0.16 to 0.24 m/min 1 m/min 10 to 20 min. 0.9 to 1.8 m/min 5 to 20 min 1.5 to 3.5 m 1.2 to 4.2 m

The by-products produced by this process are dirty backwash water, oily sludge, coalesced oil and spent media. Dirty backwash can be settled and further retreated in coalescing filters. Oily sludge and exhausted media should be dewatered and disposed of or incinerated. Coalesced oil can be recovered and reutilised in the same manner as the surface oil from gravity separation process. 3.2.1.5. EVALUATION OF THE TECHNOLOGIES FOR THE TREATMENT OF OILY WASTE WATER Table V presents a comparative evaluation of the technologies that can be applied to treat oily waste water. This evaluation is a very general one and must be read keeping in mind that the techologies discussed are not completely interchangeable.

Table V - Oily water treatment technologies

Technology Performance Economic factors installation costs API L L operation costs L Technical factors complexity environmental impact M not very efficient for heavy oil removal not very efficient for heavy oil removal Comments

CPI

Flotation Filtration

H H

H M

H H

H M

H L effective only final treatment as

Coalescing filters

General graduation: Higher, Medium, Lower and Equal

Equal is used if there is less than 10-15 % between highest and lowest values Two levels Higher and Lower are used if there is more than 15 % an less than 50 % between highest and lowest values Three levels Higher, Medium and Lower can be used if there is more than 50 % between highest and lowest values

ITEMS Performance: The possibility of the technology to achieve the goal. H = best, L = worst. the meaning of L is only in comparison with other technologies in the table. A technology with the mark L can still have high performance. Economic factors: Installation costs and operating costs. H = high costs, L = low costs. Technical factors, complexity: H = high complexity, L = low complexity Technical factors, environmental impact: An overall impact on the environment. In consideration is taken performance, energy consumption, toxicity of residues, handling problems of residues, etc. H = worst, L = best

Technologies are only compared inside the single table and there can not be made comparison between different tables. Besides the economical factors the comparisons are widely based on author evaluation.

3.2.2.

SANITARY WATER Sanitary water is often sent to municipal sewage duct and treated outside of the power station.

In the power station where sanitary wastewater treatment plants are installed, they are only of the aerobic biological oxidation (activated sludge) kind. The other type of plants that can be utilised to treat sanitary wastewater are only briefly described in this section. 3.2.2.1. ACTIVATED SLUDGE (BIOLOGICAL AEROBIC OXIDATION WITH NITRIFICATION) Activated sludge is an aerobic biological wastewater treatment process that oxidises organic matter and, in some cases, ammonia contained in a wastewater by using microorganisms living in the presence of oxygen. Biological oxidation processes remove the organic compounds and, in some cases, ammonia from the wastewater through the production of new bacterial cells. Because dissolved oxygen is necessary for aerobic bacterial metabolism, it must be available continuously to ensure proper functioning of the process. The production of the bacteria also requires a source of carbon, phosphorous, nitrogen, and other nutrients. The degree and rate of organics and ammonia removal are dependent on the biodegradability of the particular waste, on the temperature, on the presence of inhibitory compounds, and on the process design sizing, as well as on adequate operation of the plant. The activated sludge process consists of two primary components: an aeration basin and a clarifier. A schematic of the activated sludge process is shown in figure 4. In the aeration basin the influent wastewater contacts biological organisms in the presence of air or oxygen. The suspension of organisms is known as mixed-liquor suspended solids. The main parameter that affects the sizing of this basin is the solid retention time, which is the average retention time of solids in the activated sludge system. Figure 4 - Activated sludge process

ir Influent Wastewater

Aeration blowers Treated effluent

Aeration tank Return activated sludge

Clarifier Waste activated sludge To solids handling

The mixed-liquor flows from the aeration basin to the clarifier, where the suspended solids are separated from the waste stream. Most of these settled biological solids are returned to the aeration basin (return activated sludge).

The biological oxidation of organics and ammonia usually results in a net production of biological solids. These excess solids must be removed from the system (waste activated sludge). The activated sludge process can also be designed to achieve ammonia conversion to nitrate (commonly termed nitrification) either in the same system with organics removal, or in a separate system, following organics removal. An activated sludge system designed for nitrification generally requires a larger aeration volume, longer residence time of solids, and greater aeration capacity than in a system designed for organics removal alone. Several aeration basin configurations are commonly used for the activated sludge process. The conventional system uses long rectangular aeration basins with aeration being provided uniformly along the basin length. A significant recent improvement in aeration basin designs is the use of biological selectors. The selector is a short retention time oxic, anoxic or anaerobic basin upstream of the aeration tank. The purpose of the selector is to promote conditions for development of good settling and flocculated bacteria, and to discourage the growth of poor settling filamentous bacteria. Anoxic selectors also provide denitrification and the associated return of some alkalinity destroyed by nitrification. Aeration basins are typically constructed of concrete or steel in either square, rectangular, or circular configuration. The vessels usually are constructed at depths of 3 m to 6 m, although depths as high as 18 m have been used. Air is introduced to the wastewater using diffused aeration equipment located on the reactor bottom or by floating surface aerators. The aeration system serves the dual purpose of wastewater oxygenation and reactor mixing to maintain the biological solids in suspension. Variations of the activated sludge process include the use of pure oxygen instead of air and the addition of powdered activated carbon to enhance removal of absorbable pollutants. Organic removal as measured by BOD5 should exceed 90 to 95 % with activated sludge. Because of the presence of bioresistant organics in the wastewater the COD removal can be sometimes lower The expected performance values for activated sludge are summarised in table VI. Table VI - Expected performance values for activated sludge process Parameter Expected effluent concentration or percent removal BOD5 COD TSS 94 to 98 % 60 to 75 % 30 mg/l

As already said, the most important process performance variable of the activated sludge process is the solid retention time or mean cell residence time. To ensure adequate treatment, activated sludge systems are generally designed for a solid retention time of 4 to 30 days. With warm (> 20 C) wastewater a solid retention time above 8 to 15 days, nitrification can be expected to occur simultaneously with organics removal. Conservative sizing for an activated sludge system with nitrification would be a design for a 20 day solid retention time.

3.2.2.2.

BIOLOGICAL NITRIFICATION AND DENITRIFICATION Biological nitrification is the conversion of ammonia to nitrate which occurs under aerobic

conditions. The conversion of ammonia to nitrogen is a two step process involving two different classes of bacteria. Biological denitrification is the conversion of the produced nitrate to gaseous nitrogen. The conversion of nitrate to nitrogen occurs under anoxic conditions by means of microorganisms Biological nitrification and denitrification plants, at present, have not found application in power plants to treat sanitary water. Considering however that this process can be applied to remove ammonia, nitrite and nitrate in the treatment of other wastewater streams, biological nitrification and denitrification process is described in detail in the following section 3.2.5 relevant to the treatment of wastewater containing specific inorganic pollutants. 3.2.2.3. ANAEROBIC PROCESSES This kind of alternative process to reduce/remove organics from wastewater, at present has not found application in power stations in Europe and thus only a short presentation of the basic principle is included in this report. Anaerobic biological treatment is an alternative to more commonly applied aerobic wastewater treatment processes used to remove organic constituents from a waste stream. Anaerobic degradation is a multi step biological process involving two basic groups of bacteria. One group (acid formers) consists of bacteria that hydrolyse and ferment complex organic compounds into simple organic acids. The other group (methane formers) converts the organic acids produced by the acid formers into methane gas and carbon dioxide gas (the combination of which is termed biogas). Both groups of organism live in the absence of oxygen and thus are classified as anaerobic. The two groups of bacteria can co-exist and their metabolic reactions can take place simultaneously. From a microbiological standpoint, all anaerobic process configurations are similar. However, different reactor configurations have been developed for the different process variations.

3.2.3.

SUSPENDED SOLIDS Often the presence of suspended solids in wastewater is tied to the presence of other pollutants

that can be dissolved in the water phase or to organic immiscible compounds. Because of this the suspended solid removal is often performed by one or more treatment steps included in a more or less complex treatment that removes most pollutants from wastewater. Coagulation and flocculation followed by sedimentation represent however the typical treatment that leads to the removal of the suspended solids from wastewater. While precipitation is used to remove dissolved wastewater pollutants, coagulation/flocculation followed by sedimentation represents the specific treatment for the removal of colloidal and finely divided solids. In general the most common wastewater treatment plants of various industries use coagulation and precipitation reactions at the same time and in the same reaction vessels, since precipitation of dissolved constituents aids in the coagulation of colloidal solids. Suspended solids can also be removed from wastewater by filtration processes whose principles of operation have already been described. In the following presentation only additional aspects relevant to filtration of suspended solid are reported. 3.2.3.1. 3.2.3.1.1. COAGULATION/FLOCCULATION/SEDIMENTATION Coagulation Colloidal solids in an aqueous phase typically carry an electrical charge and since most particles have the same charge, they tend to repel each other, thereby impeding sedimentation. In the coagulation process the mechanism of removal is twofold: destabilisation of the repellent electrical charges on the colloidal particles formation of a "blanket" of chemical precipitate that enmeshes suspended particles as it settles and thus sweeps them from suspension. The neutralisation of particle charges and the precipitate formation are promoted by coagulant chemicals that are added to the water to be treated. Aluminium (sulphate or alum) and iron (ferric chloride) salts, polymers and lime are commonly used coagulants, that are added in a small rapid-mix vessel in order to be rapidly dispersed and to let the initial coagulation reaction take place essentially instantaneously. Bench scale tests are normally performed for coagulant selection and dosage optimisation. 3.2.3.1.2. Flocculation Flocculation consists of the agglomeration of individual destabilised particles to form larger and heavier solid masses (flocs) which can be more readily settled. The flocculation is the result of chemical addition and/or special mixing techniques. Flocculated solids are commonly removed by sedimentation and/or filtration. Polyelectrolytes (cationic, anionic or non-ionic organic polymers) are added to the water stream as a flocculation aid. The addition of polyelectrolytes is often made directly following the rapid-mix coagulation or in later stages, and no vigorous mixing is required. As with coagulants the polyelectrolyte selection and dosage optimisation must be determined by scale bench testing. The floc formed during flocculation can

help to trap additional colloidal and larger suspended solids; attention should be paid to not overdosing polyelectrolyte because restabilisation of colloidal particles can be caused. There are many types of flocculators, including hydraulic, air mechanical and turbine mixing units. Multiple basins of reduced size are preferable to one large basin of equal total size. A progressively reduced mixing action can be helpful to promote floc formation and to prevent shear force action. The retention time required depends largely on the wastewater characteristics and generally is inversely proportional to the concentration of destabilised colloidal solids; in this case combined

coagulation/flocculation/sedimentation units may be more appropriate. Combined units offer cost and space savings, and because of their increased solids contact they promote the formation of floc, thereby affording a reduction in overall hydraulic retention time. 3.2.3.1.3. Sedimentation Sedimentation is used to separate flocculated solids from the wastewater. The sizing and the performance of sedimentation units are thus strongly influenced by the degree of particulate and flocculant settling and by the degree of solid compaction achieved, and thus also strongly dependent on any previous coagulation and flocculation treatment steps. The tests on bench or pilot scale, performed for evaluating best chemicals for coagulation and flocculation steps, should thus also consider the impact on the sedimentation efficiency. Sedimentation is due to gravity separation to the bottom of chemically flocculated sludge. This can happen in three different types of clarifiers: horizontal flow basins, upflow basins, and solid contact basins. Horizontal flow basins are usually employed for the process where separated tanks are provided for coagulation, flocculation and sedimentation. The other two types of clarifier, combine the coagulation, flocculation and sedimentation steps in one integral unit. In all three types of clarifiers, a blanket of settled sludge is maintained as aid to thickening sludge and to promote floc formation. Sludge may be withdrawn continuously or intermittently and sent to thickening and dewatering units. Performance obtained by the combination of coagulation, flocculation and sedimentation in wastewater treatment ensure an effluent suspended solid concentration below 100 mg/l also at high suspended solid concentration of the influent stream. Generally removal of total suspended solids varying from 55 to 70 %, of colloidal solids from 25 to 75 %, of total solids from 25 to greater than 75 %, of turbidity from 50 to 90 % and of oil and grease from 75 to 85 % can be expected from a properly designed coagulation, flocculation sedimentation facility treating concentrated wastewater. Conventional design criteria for separated steps of coagulation, flocculation and sedimentation are given in table VII. Conventional design criteria for a combined coagulation/flocculation/sedimentation unit are given in table VIII.

Table VII - Conventional design criteria for separated coagulation, flocculation and sedimentation Coagulation Rapid mixing retention time 1 second - 2 minutes

Flocculation Retention time Power input 20 - 30 min 3.95 W/m3

Sedimentation Overflow rate Retention time Clarifier depth Weir overflow rate 0.015 - 0.03 m/min 1-4 h 2-4m 0.07 -0.43 m3/min/m

Table VIII - Conventional design criteria for combined coagulation/flocculation/sedimentation Hydraulic retention time Mixing zone Flocculation zone Sedimentation zone Sedimentation zone Rise rate Average liquid depth 3.2.3.2. FILTRATION Filtration has already been considered for the removal of oil from wastewater (see chapter 3.2.1). If the concentration of suspended solid is greater than 100 mg/l, pretreatment facilities (for example coagulation, flocculation, sedimentation) should be considered prior to filtration. In many wastewater treatment plants, filtration is applied as final treatment for the removal of suspended solids not eliminated in previous treatments. The granular media usually applied for suspended solids filtration are sand, anthracite and garnet that can be in single media, dual media or multi media filter, as described in the previous chapter. 0.02 - 0.04 m/min 3-6m 2 - 5 min 10 - 25 min 2 - 3h

In case of utilisation of dual media or multi media filters, often a train configuration, with a sand filter as protection of the more expensive media, is designed. In multi media filters the media are usually graded with granule size increasing and granule density decreasing from the bottom to the top. After backwashes, density differences between the filter media allow the layers to settle out in the proper order. The advantage in using dual or multi media filters versus single media is that in this case the entire depth of the bed is used to remove solids, rather than just the media surface. In downflow multimedia filters larger solids are removed by the top coarser layer saving the capacity of the sand and garnet layers for increasingly finer solids. Dual media and multi media filters can increase filter run times (time between backwashes) by 200 to 300 % compared to single media sand filters. As far as chemical addition, typical sizing and design criteria, and removal efficiency are concerned the same consideration already reported for oil polluted wastewater has to be considered. 3.2.3.3. EVALUATION OF THE TECHNOLOGIES FOR THE REMOVAL OF SUSPENDED SOLIDS Table IX briefly presents a comparative evaluation of the treatment processes that can be applied to remove suspended solids from wastewater. This evaluation is a very general one and must be examined bearing in mind that the techologies are not completely interchangeable; in particular filtration can be effectively utilised only for low suspended solid waters and/or as a final treatment.

TABLE IX - Wastewater with suspended solids treatment technologies

Technology Performance Economic factors installation costs Coagulation + Flocculation + Sedimentation Filtration L H operation costs H Technical factors complexity environmental impact E Comments

It needs a low TSS influent.

General graduation: Higher, Medium, Lower and Equal

Equal is used if there is less than 10-15 % between highest and lowest values Two levels Higher and Lower are used if there is more than 15 % an less than 50 % between highest and lowest values Three levels Higher, Medium and Lower can be used if there is more than 50 % between highest and lowest values

ITEMS Performance: The possibility of the technology to achieve the goal. H = best, L = worst. the meaning of L is only in comparison with other technologies in the table. A technology with the mark L can still have high performance. Economic factors: Installation costs and operating costs. H = high costs, L = low costs. Technical factors, complexity: H = high complexity, L = low complexity Technical factors, environmental impact: An overall impact on the environment. In consideration is taken performance, energy consumption, toxicity of residues, handling problems of residues, etc. H = worst, L = best

Technologies are only compared inside the single table and there can not be made comparison between different tables. Besides the economical factors the comparisons are widely based on author evaluation.

3.2.4.

INORGANIC POLLUTANTS The inorganic pollutants dealt with in this paragraph are ionic substances dissolved in water.

This includes in general metal (salts), acids, bases and in particular ammonia, nitrate and nitrite. In general the removal of inorganic pollutants is based on precipitation. Dissolved inorganic pollutants are treated by changing pH and/or adding chemical substances whereby the dissolved pollutants precipitate and become removable from the waste water by sedimentation. This kind of treatment is primarily aimed at the removal of heavy metals but other components that coprecipitate with metal hydroxides can be removed. The actions (number of steps in the chemical treatment) necessary to remove pollutants are dependant on the amount (flow) of waste water, the load (concentrations) of the pollutants and the final destination. 3.2.4.1.
PH INCREASE

By increasing pH a broad range of heavy metals precipitates as metal hydroxides. The concentrations of dissolved heavy metals that can be achieved in the waste water are given by the solubility products KSP [table X] for the reaction

Me a + + aOH Me( OH ) a a+ a a and K SP [ Me ] [OH ] Me OH

Table X - Solubility products of hydroxides Component Ca(OH)2 Mg(OH)2 Cd(OH)2 Fe(OH)2 Zn(OH)2 Ni(OH)2 Hg(OH)2 Pb(OH)2 Fe(OH)3 KSP 7,610-5 1,910-10 4,210-13 1,110-14 1,810-14 2,710-14 10-25 1,410-20 2,810 -36

With a pH range of 8.5 to 9, low concentrations of dissolved heavy metals can be achieved, even if the i differ from 1 due to high salinity. However it will be the capability to remove the insoluble particles of metal hydroxides (normally by sedimentation) from the waste water that give the achievable total concentration of remaining heavy metals. The increase in pH is achieved by adding chemicals such as limestone, quicklime, slaked lime or sodium hydroxide. The choice of chemical depends on the amount and the composition of the waste water.

3.2.4.1.1.

Limestone Limestone (CaCO3) is only used for pre-treatment when the waste water has a very low pH

(< 1) or for neutralisation of a single batch of waste water. Limestone is added to the wasterwater either as a powder or as a slurry. The advantage is a very low price. The disadvantages are: the handling of the powder, the need of large quantities, the release of CO2. 3.2.4.1.2. Quicklime/Lime Quicklime (CaO) can be used as an alternative to limestone or lime. The advantages are: smaller quantities, no release of CO2, faster reaction. The disadvantages are: the handling of the alkaline and hygroscopic powder, very large heat production. 3.2.4.1.3. Slaked lime Slaked lime (Ca(OH)2) is commonly used in the waste water treatment at power stations. Slaked lime is added to the waste water either as a powder or as a slurry (milk of lime). When used in pretreatment or in the first step (in two steps pH increment) slaked lime can be added as powder, but normally slaked lime is added as a slurry. The advantage is a low price. The disadvantage is the handling of the powder. Advantages and disadvantages in comparison with sodium hydroxide are summarised in table XI. 3.2.4.1.4. Sodium hydroxide Sodium hydroxide (NaOH) is also commonly used but not as frequent as slaked lime. Sodium hydroxide is always added to the waste water as a solution. Advantages and disadvantages in comparison with slaked lime are shown in table XI. Table XI - Advantages and disadvantages in the use of sodium hydroxide and slaked lime Sodium Hydroxide, NaOH Slaked lime, hydrated hydroxide, Ca(OH)2 Delivery and storage By road tanker or in pallet tanks. By road tanker or in sacks. lime, calcium

When used at high concentrations (46%), Silos for storage have to be insulated to care should be taken to prevent temperatures prevent condensation and subsequent below 15 C because of freezing. formation of lumps. Storage volume need 1 kg 100% NaOH is equivalent to 25 moles 1 kg Ca(OH)2 is equivalent to 27 moles of of divalent heavy metal (e.g. 5,0 kg of Hg) divalent heavy metal (e.g. 5,4 kg of Hg) Normally delivered in concentrations of 32 to Normally delivered as a powder with a bulk 3 46 %. density of 600 kg/m . A 20 % suspension (slurry) has to be prepared before use.

Preparation None A 5-20 % suspension (slurry) has to be prepared before use. When used in two stage neutralisation, powder can be used in the first step. Dosage Dosage is done by pump with variable length Slurry has to be pumped continuously of stroke and/or variable speed through pipes and be recycled to prevent precipitation. Dosage from pipes by using valves Reaction/Regulation Added sodium hydroxide solution will be mixed quickly in the reaction tank. This gives a fast regulation of pH with a minimum risk of unacceptable pH variation Because the slaked lime is dosed as a slurry or a powder, it has to be dissolved and mixed before reaction. This gives a slow regulation of pH with the risk of unacceptable pH variation. To minimise this pH variation neutralisation can be done in two steps (or a large reaction tank can be used)

General problems Risk of scaling Health and safety Cauterising fluid Cauterising powder

Closed pipe and tank systems. Possible to Closed pipe and silo systems. Cleaning before clean by flushing before maintenance. Risks maintenance is necessary. Contact with are well known at power stations due to powder is difficult to avoid experience from water treatment. Price A NaOH mole equivalent costs 4 times the price of a Ca(OH)2 mole equivalent. Price based on road (Denmark, July 1994) 3.2.4.1.5. pH reduction High pH is seldom a problem but, if necessary, hydrochloric or sulphuric acid at a convenient concentration can be used. tanker delivery

3.2.4.2.

TREATMENT WITH SULPHIDE Environmental demands can seldom be met by pH increment only. By adding sulphide or

complexing agents, the solubility of the heavy metal can be further lowered. The concentrations of dissolved heavy metals that can be achieved in the waste water are given by the solubility products KSP [table XII] for the reaction

xMe a + + yS 2 Mex S y
and K SP Me Me [
x a+ y ]x [S 2 ] y S

Table XII - Solubility products of sulphides Component FeS ZnS NiS PbS CdS HgS Fe2S3 KSP 9,610-16 1,210-23 1,410-24 3,410-28 3,610-29 10-52 1,410-86

The treatment with sulphide is achieved by adding sodium sulphide, trimercapto-s-triazin (TMT-15) or similar. The choice of chemical is depending on the treatment plant construction, environment demands and the composition of the waste water. Advantages and disadvantages in the use of sulphide and trimercapto-s-triazin are compared in table XIII. 3.2.4.3. ADDITIONAL CHEMICALS To optimise the precipitation of the heavy metals additional chemicals can be added to the treated (pH and sulphide) waste water. The chemicals to be added are coagulants, flocculants and polyelectrolytes. 3.2.4.3.1. Coagulants To ensure the formation of flocks a coagulant can be added. The coagulant is normally a non toxic metal that precipitates with increasing pH: iron or aluminium as iron sulphate/chloride or aluminium sulphate. When coagulants typically iron sulphate/chloride is added to the waste water in large quantities, it will precipitate in large flocks and secure that smaller particles are adsorbed to the surface of the hydroxide floc. Addition of iron sulphate/chloride is necessary to neutralise sulphide or similar added in a previous step of the process.

Table XIII - Advantages and disadvantages in the use of sulphide and TMT15 Sodium sulphide, Na2S TMT15, trimercapto-s-triazin, C3N3S3Na3 Delivery and storage In 33 kg bags on pallets. In 25 L cans on pallets. Delivered in 15 % concentration. Preparation Flake or powder has to be dissolved in water. None Dosage Dosage is done by pump with variable length Dosage is done by pump with variable length of stroke and/or variable speed of stroke and/or variable speed Reaction Sodium sulphide reacts very effectively with TMT15 reacts primarily with divalent heavy all heavy metals that precipitate with metals that precipitate with sulphide. sulphide. Remaining TMT15 has to be neutralised. Iron sulphate/chloride has to be added afterwards in sufficient amounts to neutralise the remaining sulphide Health and safety Poisonous and cauterising fluid/powder Bags with flakes or powder have to be handled. Closed pipe and tank systems. Possible to clean by flushing before maintenance. It produces poisonous gas (H2S) when in contact with acid. Price The use of TMT15 is 40 to 50 times more expensive than the use of sodium sulphide 3.2.4.3.2. Flocculants Flocculants are organic polymers based on acrylamid, neutral or weak basic, that help to increase the size of flocs and optimises sedimentation. 3.2.4.3.3. Polyelectrolytes Polyelectrolytes are organic polymers, neutral or weak acid, that optimise the water release from the sludge when de-watered in the filter press. 3.2.4.4. TYPICAL FLOW SHEETS Some typical waste water treatment plants flow sheets are described in this section. The flow sheets show only principles, for example mixing can be achieved in several ways, here shown as mechanical steering but recirculation with pumps, steering by compressed air, etc. will serve the same purpose. The Non toxic

choice of the steering principle depends on the amounts of waste water, batch/continuous treatment, plant construction, economics, etc. The particle removal function is shown as a clarifier in all figures but a lamella precipitator, a clarification basin, etc. will have the same purpose. The pH increment is shown (figures 6 10) as addition of slaked lime, milk of lime or sodium hydroxide but any of the in paragraph 3.2.4.1 mentioned chemicals can be used. Figure 5 and 6 show the most simple waste water treatments. The removal of solids is the only treatment taking place in figure 5. This simple treatment is only used for the batch treatment of waste water and only when the demands are low or when treated waste water can be reused. This kind of treatment is commonly used for waste water coming from boiler rinse, air preheater rinse, ash precipitator rinse, flush water from mechanical filters, flush water, floor drains, etc. When there is a need for pH adjustment, or if there are some demands for removal of heavy metals this can be done with the treatment shown in figure 6. The treatment is used for the waste water streams mentioned in figure 5 and for example: slag flush water, slag cooling water, ash transport water, waste water from acid cleaning, regeneration waste water, etc. Figure 5 and figure 6

Lime

Influent

Effuent

Influent

Effuent

Sludge

Sludge

High pH waste water coming from slag flushing or regeneration can be dealt with or whitout pH adjustment over a wide range. The amounts of slag flushing water are normally small in comparison with other waste water streams. Slag flush water (with a high pH) can be used to increase pH in other waste water streams or just be diluted into those streams. Regeneration waste water with high pH can be avoided by regenerating anions and cations simultaneously and with balanced amounts of acid and base. Both figures 7 and 8 show flow sheets of waste water cleaning plants with full treatment for removal of heavy metals. The two flow sheets differ in the pH increasing (neutralisation) step. The two step neutralisation will be necessary in a system with a high flow rate and slaked lime neutralisation to ensure correct pH. When sodium hydroxide is used for neutralisation two steps can be avoided. If pH in the waste water is very low, two step neutralisation can be necessary. When the waste water contains a large amount of solids, the first step in a two step neutralisation can be used to remove coarse sludge from the waste water and thereby reduce the load on the clarifier. Recycling some percentage of the sludge will optimise the

building of flocs and reduce chemical consumption. This kind of system is normally used for the treatment of regeneration waste water or waste water from small flue gas cleaning plants. Figure 7

Lime

Na2S

FeCl3

Poly

Water

Influent Effluent

Sludge

Figure 8

Lime

Na2S

FeCl3

Poly

Water

Influent Effluent

Sludge

Figure 9 and figure 10 show flow sheets of waste water cleaning plant commonly used with wet gypsum desulphurisation plants. The first removal of solids and supersaturated calcium sulphate is necessary to avoid scaling in the remaining system. The major difference is the sludge management system (gypsum and fly ash removal). By not increasing pH in the first step in figure 9 the amount of heavy metals in the sludge

from this step is minimised and the amount of heavy metal sludge from the following treatment is reduced. When the first step is running completely without chemicals (no use of flocculants) the sludge from this step can be recycled to the absorber slurry in the desulphurisation plant. The system in figure 10 combines the removal of solids and supersaturated calcium sulphate and the necessity of two step neutralisation when using slaked lime. Figure 9
Poly NaOH Na2S FeCl3 Poly

Influent Effuent

Sludge

Figure 10
FeCl3
Lime

Poly

Na2S

FeCl 3

NaOH

Poly

Influent Effuent

Sludge

3.2.4.5.

EVALUATION OF TREATMENT FOR REMOVAL OF INORGANIC POLLUTANTS Table XIV briefly presents the comparative evaluation of different technologies that can be

applied to wastewater streams to remove inorganic pollutants.

TABLE XIV - Wastewater containang inorganic pollutants treatment technologies

Technology Performance Economic factors installation costs pH adjustment (fig. 5 and 6) 1 step neutralisation 1 step precipitation (fig 7) 2 step neutralisation 1 step precipitation (fig. 8) 2 step neutralisation 2 step precipitation (fig. 9 and 10) L L operation costs L Technical factors complexity environmental impact H Comments

Only necessary when wastewater contains large quantities of suspended matter

General graduation: Higher, Medium, Lower and Equal

Equal is used if there is less than 10-15 % between highest and lowest values Two levels Higher and Lower are used if there is more than 15 % an less than 50 % between highest and lowest values Three levels Higher, Medium and Lower can be used if there is more than 50 % between highest and lowest values

ITEMS Performance: The possibility of the technology to achieve the goal. H = best, L = worst. the meaning of L is only in comparison with other technologies in the table. A technology with the mark L can still have high performance. Economic factors: Installation costs and operating costs. H = high costs, L = low costs. Technical factors, complexity: H = high complexity, L = low complexity Technical factors, environmental impact: An overall impact on the environment. In consideration is taken performance, energy consumption, toxicity of residues, handling problems of residues, etc. H = worst, L = best

Technologies are only compared inside the single table and there can not be made comparison between different tables. Besides the economical factors the comparisons are widely based on author evaluation.

3.2.5.

SPECIFIC INORGANIC POLLUTANTS The inorganic pollutants that cannot be removed from the waste water by precipitation are

primarly ammonia and nitrate. Efforts have to be made to remove them from the waste water by specific reactions. Ammonia can be removed by stripping (distillation) or by converting ammonia into nitrate. Nitrate can be converted into nitrogen by biological processes. Methods to convert nitrate catalytically to nitrogen or ammonia are still at a development stage for power plants. Removal of ammonia and nitrate is often done by diversion to municipal wastewater cleaning plants. Often the biological removal of nitrate is inhibited by high salinity in the waste water from a power station. This is avoided by dilution with other municipal waste water streams. The choice of principle depends of the amounts of wastewater and the concentrations of pollutants as well as geographical location. At the power station the conditioning of the water/steam cycle is the largest ammonia contributor through the regeneration of the condensate polishing plant. Waste water from a desulphuriastion plant in combination with high dust DeNOx will also contribute ammonia. The regeneration waste water from the makeup water plant will contribute the major part of nitrate but waste water from desulphurisation plants will also contain nitrate. 3.2.5.1. AMMONIA STRIPPING Figure 11 shows an ammonia stripping column. Wastewater pH is increased with sodium hydroxide to convert ammonium to ammonia. The ammonia is stripped from the water phase by the steam. Concentrated ammonia is removed from the column top through a cooler and a part of the ammonia is refluxed into the column to optimise the process. Treated water is taken out at the bottom of the column. The major disadvantages of the stripping process are: large energy consumption, solids in the wastewater have to be removed before the process and treated water has to be neutralised (pH decreased). Figure 11
Effluent Cooling water Concentrate
NaOH

Influent

Steam

3.2.5.2.

BIOLOGICAL NITRATE REMOVAL Figure 12 shows a biological nitrate treatment plant. The flow sheet only shows principles, the

reaction tank containing the biological active sludge can be constructed in several ways. The sludge can be in a reaction tank as shown, the reaction tank can be a fluid bed reactor with the sludge particles attached to sand, sludge can be attached to a support media, etc. When a support media is used there is no need for the clarifier or precipitator, instead the support media have to be cleaned periodically. This technology is well known but has previously only be used at municipal waste water treatment plants. Power station wastewater does not contain sufficient amounts of organic carbon and phosphate for the biomass to live on. In a first step carbon and phosphate are added to feed the biomass. The second step is a reaction tank where anoxic bacteria reduce nitrate to nitrogen. The third step is a coagulation and flocculation step followed by a clarifier. Besides the lack of organic carbon and phosphate the salinity is the major problem in power station wastewater. Especially wastewater from desulphurisation plants can contain more than 30 g/kg chloride. It is possible to run denitrification at high salinity levels but the bacteria culture is very sensitive to changes in salinity. Figure 12
H3PO4
C3H7OH

FeCl3

Poly

Influent Effluent

Sludge

3.2.5.3.

BIOLOGICAL AMMONIA, NITRITE AND NITRATE REMOVAL Figure 13 shows a flow sheet of a biological waste water plant for removal of ammonia, nitrite

and nitrate. The waste water is pre-treated in a reaction tank with aerobic bacteria that oxidise ammonia and nitrite to nitrate.

Figure 13
HCO4 Buffer H3PO4
C3H7OH

FeCl3

Poly

Influent Effluent Air

Sludge

3.2.5.4.

CATALYTIC NITRATE REMOVAL Resins loaded with for example copper and palladium can be used as catalyst to reduce nitrate

to nitrogen with hydrogen. This technology is used by the drinking water suppliers. Because nitrate concentrations are very high in power station wastewater compared with drinking water, the process has not yet been used successfully because nitrate has been reduced to ammonia. The advantage of this process is its insensitivity to the fluctuations in the concentrations of other components in the waste water. The major disadvantage is the high operating cost. 3.2.5.5. EVALUATION OF TREATMENT FOR REMOVAL OF SPECIFIC INORGANIC POLLUTANTS Table XV briefly presents the evaluation of different technologies that can be applied in order to remove from wastewater streams some specific inorganic pollutants that are not removed by typical treatment technologies described above for inorganic pollutants. This evaluation is a very general one and must be read keeping in mind that the techologies discussed are not completely interchangeable.

TABLE XV - Wastewater containing ammonia treatment technologies

Technology Performance Economic factors installation costs Ammonia stripping (fig. 11) Biological ammonia, nitrite and nitrate removal (fig. 12) Biological nitrate removal (fig 13) E M operation costs H Technical factors complexity environmental impact H Removes only NH3 Operating problems

Sensitive salinity

to

high

Sensitive salinity

to

high

General graduation: Higher, Medium, Lower and Equal

Equal is used if there is less than 10-15 % between highest and lowest values Two levels Higher and Lower are used if there is more than 15 % an less than 50 % between highest and lowest values Three levels Higher, Medium and Lower can be used if there is more than 50 % between highest and lowest values

ITEMS Performance: The possibility of the technology to achieve the goal. H = best, L = worst. the meaning of L is only in comparison with other technologies in the table. A technology with the mark L can still have high performance. Economic factors: Installation costs and operating costs. H = high costs, L = low costs. Technical factors, complexity: H = high complexity, L = low complexity Technical factors, environmental impact: An overall impact on the environment. In consideration is taken performance, energy consumption, toxicity of residues, handling problems of residues, etc. H = worst, L = best

Technologies are only compared inside the single table and there can not be made comparison between different tables. Besides the economical factors the comparisons are widely based on author evaluation.

3.2.6.

FINAL TREATMENT The requirements for power plants concerning the treatment of wastewater before discharge

are now increasing for environmental protection. The treatments described in sections from 3.2.1 to 3.2.5, cannot in several cases meet the demands. Because of these increasing demands, an additional final treatment of the wastewater is required. The possible treatments cover a wide field from simple filtration through active systems as ion exchange to the extreme of zero discharge by evaporation. Another alternative is diversion to a municipal system for further treatment. 3.2.6.1. SAND FILTERS Sand filters ensure that sludge escaping from the clarifier or precipitator is retained. The precipitation of heavy metals ensures a very low concentration of dissolved heavy metals but the particle size and the efficiency of the sedimentation step limit the absolute concentrations that can be achieved. Sand filters will remove small particles not retained in the clarifier or precipitator. 3.2.6.2. ACTIVATED CARBON FILTERS Activated carbon filters are used after sand filters when heavy metals, for example Hg and Cd, are required to be reduced to concentrations as low as 3 to 5 g/kg. This level can be reached by the use of final treatment with sand filters only but to ensure low levels in a critical situation activated carbon filters may be necessary. Activated carbons also adsorb very fine particles that are not retained in the sand filters. 3.2.6.3. SELECTIVE ION EXCHANGE RESIN FILTERS Ion exchange resin filters can be an alternative or a supplement to the use of activated carbon filters to achieve a very low level of heavy metal concentrations in the water effluent. Ion exchange technology is well known at power stations but is seldom used in wastewater treatment. There are some ion exchange resin products on the market which are specific for the removal of heavy metals. For example a resin used for general removal of heavy metals (except Hg) which can be regenerated, or a resin used for specific Hg removal that cannot be regenerated. New resins are being developed using chelating effects. These are loaded with ammonia. The heavy metal forms a chelate with the ammonia on the resin. Because the chelate is a very strong/stable complex, the heavy metal complexes with, for example chloride in the waste water are broken and the heavy metal absorbed. 3.2.6.4. EVAPORATION If the environment is sensitive even to the salinity in the waste water, evaporation is the only possibility to achieve zero discharge. The main problem with evaporation is the energy demand and the production of a brine which cannot be disposed of in a normally protected waste disposal site. A less energy demanding alternative to evaporation is to spray the waste water into the flue gas. This however gives some problems about fly ash disposal and flue gas emissions.

Reuse of the salts dissolved in the treated waste water can be achieved by crystallisation. By evaporating the treated waste water stepwise the dissolved salts will crystallise in pure form when their solubility products are exceeded. 3.2.6.5. FINAL SLUDGE TREATMENT. Nearly all waste water treatments produce some kind of residual besides the treated waste water. Residuals can either be recycled to the boiler or be discharged to a disposal site. Sludge normally has a solid content of about 3 to 8 % on leaving the clarifier or the precipitator. This concentration is too low for disposal. A stable sludge suitable for disposal can be produced by draining the sludge and/or adding fly ash and/or cement to the sludge. Dewatering is mainly achieved by a centrifuge or a filterpress. With a centrifuge water can be removed and give a fat high viscosity sludge with 20 to 40 % solids. This sludge can not be discharged without adding fly ash or cement to get a stable sludge suitable for disposal. With a filterpress 50 - 85 % solids content can be reached depending on the filter system. Even with sludge at a high solid content it can be necessary to add fly ash or cement because of chemical instability. 3.2.6.6. EVALUATION OF FINAL TREATMENTS Table XVI briefly presents the different technologies that can be applied to wastewater streams as final step for polishing before discharge or reutilisation.

TABLE XVI - Final treatment for treated wastewater

Technology Performance Economic factors installation costs Sand filter Activated carbon L(1) M(1) L L operation costs L H Technical factors complexity environmental impact E E Very few experiences. Very few experiences. Removes only a small range of ions Comments

L L

Selective ion exchange resin

H (1)

(1)

Technology only usable in combination with the first four technologies in table XIV

General graduation: Higher, Medium, Lower and Equal

Equal is used if there is less than 10-15 % between highest and lowest values Two levels Higher and Lower are used if there is more than 15 % an less than 50 % between highest and lowest values Three levels Higher, Medium and Lower can be used if there is more than 50 % between highest and lowest values

ITEMS Performance: The possibility of the technology to achieve the goal. H = best, L = worst. the meaning of L is only in comparison with other technologies in the table. A technology with the mark L can still have high performance. Economic factors: Installation costs and operating costs. H = high costs, L = low costs. Technical factors, complexity: H = high complexity, L = low complexity Technical factors, environmental impact: An overall impact on the environment. In consideration is taken performance, energy consumption, toxicity of residues, handling problems of residues, etc. H = worst, L = best

Technologies are only compared inside the single table and there can not be made comparison between different tables. Besides the economical factors the comparisons are widely based on author evaluation.

4.

SURVEY OF THE SITUATION IN UNIPEDE COUNTRIES In this chapter a brief overview of the wastewater treatment technologies applied in the

UNIPEDE Countries is presented. In order to collect the necessary information ENEL, as leader of the working group Wastewater Effluent "Technology", prepared a questionnaire (see enclosure) oriented to evaluate: all the wastewater streams that can be present in a Power Station; the flowrate and the main characterisation of these streams; the pollutant removal technologies applied for every individual stream or for more similar streams collected in a unique treatment line. The questionnaire form was transmitted to all Therchim and some Therres members with the suggestion that information relevant to the most representative case(s) was supplied. The list of the members who returned the forms are shown in table XVII. From the data received it has been possible to partially fill the table XVIII which presents a summary of most important wastewater streams produced and treated in Power Stations in these countries. Table XIX summarises the information presented in tables XX XXVIII, identifying for every stream the main (mostly applied) technology. Tables XX XXVIII present for each effluent or group of similar effluents the flowrate (or monthly/yearly total volume for discontinuous streams), the main characteristics and the treatment applied with the related removal efficiency in the most representative cases where similar streams have been identified.

Table XVII - Overview of answers to questionnaire

Country Austria

Number of questionnaire 11 (2) (1) (2) (2) (4)

Companies OKA, Wienstrom, EVN and VKG, Linzer Elektrizitats, Steweag Electrabel CEZ

Power (MWe)

Fuel

Desox

Denox

Wide range of electrical Coal power and heat capacity Natural gas and fuel oil Natural gas and coal Natural gas Coal, fuel oil and natural gas 6 units 900 total 5 units 1000 total Lignite coal

several

several

Belgium Czech Republic Denmark

1 1

no in construction yes yes yes

no no

(1) (1) (1)

SK Power, Vestkraft, Midkraft Studstrupvaerket IVO EDF VKR Hungarian Power Companies

600 375 + heat 4 units 1125

Coal Coal Coal and fuel oil

no no no

Finland France Germany Hungary

Brochure on environment 1 1 2

5 units 3200 total 880 (th.) 5 units 2600 total 15 units 2150 total 3 units 915 total 4 units 2640 total 4 units 1256 total

Coal and oil Coal Lignite Oil and natural gas Coal Coal, fuel oil and natural gas (multifuel units)

no yes no no no yes

no yes no no no yes

Ireland Italy Portugal

1 1 Additional data to draft resuming tables 2

ESB ENEL CPPE

Spain

Iberdrola

2 units 1084 total 2 units 505 total 4 units 2000 total

Coal and fuel oil

no

no

United Kingdom

Powergen

Coal

yes

no

- 44 -

Table XVIII - Summary of produced and treated wastewater streams

Country Wastewater streams

Polluted by oil Sanitary Demineralisation plant regenerations CP deep bed regenerations CP filtration regenerations Boiler blowdown Chemical cleaning with inorganic acids sol. Chemical cleaning with organic acids sol. De-copperizing cleaning solutions Cleaning with complexing agents solutions Fire side boiler washing solutions Air preheater washing solutions Electrostatic precipitator washing solutions Stack washing solutions Boiler conservations solutions Bottom ash circuit blowdown Fly ash handling solutions Car/truck washing solutions Meteoric water from solid waste storage Clean meteoric water (roofs, parking etc.) Coal pile run-off FGD pre-scrubber blowdown FGD scrubber blowdown FGD components washing solutions
t u a p u* = treated

t t/u* t/u t t/u u a a a a t t t t t t/u a t/u a t/u t/u t t t

t t

t t

a a

t t u t a a t a a a a a a a t u u t a u a a a a

t t/u* t t t/u u t a t/u p t t t a p t t t/u u** t/u t a t t

t t t t t t a t t a t t t a u t t t t a a a

a u* u u a a p p a p a p a a a t a a a u t t a a

t t t t a t a a a a t t a a a a t t a t/u a a a a

a t t t p a t a

t a u t t a a a

t t t t t a a t a a t t t t t a a t t u t t t t

t t t a a t t t a a

t a p t t t

t t/u* t t t t/u t t t t t t t t t t a t t t t a a a

the washing solutions can be polluted by ammonia in presence of high dust SCR Denox

= untreated (this can also mean untreated within plant limits but collected by an e xternal company for treatment) = absent = present but not declared if treated or not = untreated into the power station and usually treated in municipal plant

u** = untreated but sent to FGD

- 45 -

Table XIX - Summary of produced and treated wastewater streams

Treatment technology Wastewater streams

Polluted by oil Sanitary Demineralisation plant regenerations main
added to main added to main added to main added to main in some in one country in some in one country countries countries alternative in one country

main

added to main in one country

added to main added to main added to main in one country in one country in one country alternative in added to main added to main some or alternative or to countries in some alternative in countries some countries

main

added to main in one country

CP deep bed regenerations CP precoat filtration regenerations Boiler blowdown Chemical cleaning with inorganic acids solutions Chemical cleaning with organic acids solutions De-copperizing cleaning solutions Cleaning with complexing agents solutions Fireside boiler washing solutions Air preheater washing solutions Electrostatic precipitator washing solutions Stack washing solutions Boiler conservations solutions Bottom ash circuit blowdown Fly ash handling solutions Car/truck washing solutions Meteoric water from solid waste storage Clean meteoric water (roofs, parking etc.) ** Coal pile run-off FGD pre-scrubber blowdown FGD scrubber blowdown FGD components washing solutions * **

main main main main main main main main main main main main

main main main main main main main main main main main main

main main main main main main main main

and added to alternative in one country

alternative in some countries

added to main added to main added to main in one country in one country in some countries

alternative in some countries alternative in one country

added to main in one country added to main in one country added to main in one country

added to main in one country alternative in ome country

added to main added to main added to main in one country in one country in some countries added to main in some countries added to mian in one country added to main in one country added to main in one country

main
and added to alternative in one country

alternative in one country

adde to main added to main in one in one country * country * added to main added to main in one in one country * country *

main main main main main main main

in one country alternative in some countries added to main in one country added to main in one country

added to main added to main in some in one country countries

added to main added to main added to main in one country in one country in some countries added to main one country

added or alternative to main in some countries in some countries

added to main in one case

added to main added to main in one country in one country added to main added to main in some in some countries countries

added to main in one country alternative in added to main added to main added to main one country in one country in some in one country countries

added in one case added to main in one case

added to main in one country

added to main added to main in one country in one case added to main added to main in one country in one case

added to main in one case

main main main

main main main

main main main main

main main main

added to main in one country added to main in one country added to main in one country added to main in one country

main main main

added to main in some cases added to main in some cases

added to main in one case added to main in one case

For ammoniated solution due to the presence of high dust SCR Denox Mainly untreated

- 46 -

Table XX - Main reference cases of wastewater treatment Wastewater polluted by oil

Country Composition
N. units considered Total Load capacity (MW) Flowrate (m3/h) (if continuous) Volume (m3/month) TDS(mg/l) Oil cont. (mg/l) TREATMENT TECHNOLOGY

Austria --Wienstrom

Czech Republic --CEZ

Denmark --SK Power

Denmark --Vestkraft

France --EDF

Hungary --Hungarian Power Companies 13 + 2 g.t. 2150 3.5 - 4.5

Hungary --Hungarian Power Companies 5 2600 variable

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain

Iberdrola

combined cycle 464 30

5 1000

5 1500 (th)

1 375 only small amounts

5 3200 1 -2*

3 915 not present

4 2640 30 -100**

4 1256

505

50000 550 > 10 Gravity separation and mechanical skimming 1.5 Gravity separation and sorbents

10000-20000

500*

11700 450 variable

20000 < 500 < 50 All meteoric water passed through oil interceptors Gravity separation, skimming systems, sand and activated carbon filtration. Reutilised as service water Gravity separation and mechanical skimming < 750

200

Meteoric water Fired with coal by gravity separation; reutilised for FGD. High salinity wastewater by gravity separation and activated carbon filtration; reutilised for coal pile wetting. The recovered oil is fired.

Gravity separation

Gravity separation

Gravity separation

Gravity sepa ration

Capacity (m3/h)

100

2500

35 m3 (total volume of hte basins) > 99 %

150

150

100

Oil removal efficiency or effluent concentration * ** Meteoric water not included Depending on meteoric water

98 %

90 %

90 %

> 96 %

< 10 mg/l

- 47 -

Table XXI - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Sanitary wastewater

Country Composition
N. units considered Total load capacity (MW) Flowrate (m3/h) (if continuous) Volume (m3/month) BOD5 (mg/l) COD (mg/l) NO3 (mg/l) NH3 (mg/l) Total N (mg/l) TREATMENT TECHNOLOGY

Austria --EVN and VKG

Belgium --Electrabel

Czech Republic --CEZ

Denmark --SK Power

France --EDF

Germany --VKR

Hungary --Hungarian Power Companies

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain --Iberdrola

United Kingdom --Powergen

2 755

6 900

5 1000 10

5 1500 (th)

5 3200 3

1 800 (th)

5 2600 60

3 915

4 2640 5 3000

4 1256

2 1084

4 2000 15

600

1000 40 - 75 60 4.4

7200 5.5 15

3000

2100 5.3 26 2.6 1.5

300

3200 8.8 5.6 < 20

2000

300 350

10000 5

100 - 200 200 - 1000

10

<1

10 Aerobic biological oxidation Aerobic biological oxidation Aerobic biological oxidation Activated sludge biological oxidation aerated by stirring Aerobic biological oxidation Untreated Aerobic biological oxidation, settlement, UV disinfection. The effluent further treated by alkalisation, flocculation, settlement and pH correction. 100
BOD5 80-90 % BOD5 < 40 mg/l COD < 60 mg/l

Preliminary screening, activated sludge biological oxidation with extended aeration

Aerobic biological oxidation

Preliminary screening, primary settlement, activated sludge aeration and final settlement

Capacity (m3/h) Removal efficiency or effluent concentration

BOD5 < 50 mg/l COD < 150 mg/l

15
BOD5 60-90 %

100
Total N < 10 mg/l

160

15

- 48 -

Table XXII - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Demineralisation plant regeneration wastewaters

Country Composition
N. units considered Total load capacity (MW) Volume (m3/month) TDS (mg/l)

Austria --EVN and VKG

Belgium --Electrabel

Czech Republic --CEZ

Denmark --SK Power

Denmark --Vestkraft

France --EDF

Hungary --Hungarian Power Companies

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain --Iberdrola

United Kingdom --Powergen

2 755 300 - 900

6 900 3400 13000

5 1000 70000

5 1500 (th.) 15000

1 375 200

5 3200 12000

5 2600 4000 4500

3 915 1600 2000 (max)

4 2640 360 10000

4 1256 5000

2 505 2200 Cond. 16000 S/cm

4 2000 variable variable

TSS (mg/l) SO4 (mg/l) TREATMENT TECHNOLOGY Flocculation and settlement (with iron hydroxide) Untreated Neutralisation Clarification (with soda)

10 4.8 Neutralisation Neutralisation and reutilisation in ash handling system Neutralisation High salinity solution treated by alkalisation, flocculation and heavy metals precipitation, settlement, coagulation flocculation and neutralisation, lamella separation. Low salinity solutions treated by alkalisation, flocculation, settlement, pH correction and sand and activated carbon filtration

< 2000

Neutralisation. Homogeneisation with other wastewaters, coagulation, flocculation, settlement and final pH correction

Neutralisation, homogeneisation with other wastewaters, settlement and final pH correction

Dilution prior to discharge

- 49 -

Table XXIII - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Condensate polishing wastewater, boiler blowdown and boiler conservation

Country Composition
N. units considered Total load capacity (MW) Deep bed regeneration Volume (m3/month) pH TDS (mg/l) NH3 (mg/l) Precoat filtration regeneration Volume (m3/month) TSS (mg/l) Boiler blowdown Volume (m3/month) NH3 (mg/l) PO4 (mg/l) NaOH (mg/l) Boiler conservation Volume (m3) and frequency NH3 (mg/l) N2H4 (mg/l) TREATMENT TECHNOLOGY

Austria --Wienstrom

Austria --EVN and VKG

Czech Republic --CEZ

Denmark --SK Power

Denmark --Vestkraft

France --EDF

Germany --VKR

Hungary --Hungarian Power Companies 5 2600

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain Iberdrola

Spain --Iberdrola

combined cycle 464 85 6.5 - 9.5 > 100 130

2 755

5 1000

5 1500

1 375

5 3200

1 880 (th)

3 915

4 2640

4 1256

2 1084

2 505

120 1 1000 125

20000 9 0.01 0.01 not present

1350 0 - 13 3000 not measured

500

800 5.5 - 8.5

200 - 400 6.5 - 9.5 150 - 500

160 7.5 - 9

200 6-9 500

200 - 400 variable 10000 1000 240 - 1200 2000 - 2500 not present

not present

660 - 1320 2 - 12

not present

not present 100 m3 only during start 1 0 0 not measured

not present

not present

not measured

not present

not present

105 10000 600 - 900 0.3 8 - 15 400 - 500 1 - 2 a year 10 100 Precoat filtration collected with other wastewater into sludge thickener, thickener effluent treated for pH correction. Boiler blowdown sent to cooling closed circuit.

not present

not present

not present

not measured

260 ?

not present

1500

not present

not measured 0.3

900 0.1 3-6 300 1 - 2 a year 10 100 Homogeneisation with other wastewaters, neutralisation, air agitation pool, neutralisation, floccula-tion, settlement and final pH correction

700 once a year

400 1 every 4 years 1250 Flocculation and settlement (with iron hydroxide)

not present

900 30 a year

not present

not present

30 -100 variable 10 - 50 10 - 300 Deep bed regenerations treated by neutralisation Conservation solution diluted by cooling water

400 4 - 6 a year 200 500 Deep bed regeneration and boiler conservation with ammonia treated by alkalisation, flocculation, settlement, hardness removal with sodium carbonate, settlement, alkalisation with soda and am-monia strip-ping. Precoat filtration wastewater treated by alkalisation, flocculation, settlement, pH correction and sand and activated carbon filtration. 40 ammoniated 300 others TSS > 95 % NH3 > 99 %

225 4 - 8 a year 10 100 Homogeneisation with other wastewaters, coagulation, flocculation, settlement and final pH correction

Ammoniated wastewater treated with FGD wastewater by oxidation, alkalisation, thickening, ammonia stripping, flocculation, neutralisa-tion, lamella settlement, hypochlorite oxidation, gravel and activated carbon filtration

Ammoniated wastewater reduced by adopting CWT conditioning. Rege-neration waste-waters reutili-sed in FGD after neutralisa-tion

Clarification

Neutralisation

Untreated

Deep bed regeneration treated by neutralisa-tion and reutili-sed in ash handling sy-stem. Boiler blowdown treated with other technological wastewater in gravity separation.

Untreate

Capacity (m3/h)

10.5 ammoniated TSS < 30 mg/l NH3 99 % TSS < 20 mg/l NH3 < 120 mg/l

150 sedimentation

200

100

300

Removal efficiency or effluent concentration

TSS 98 %

TSS 99 %

- 50 -

Table XXIV - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Chemical cleaning solutions

Country Composition
N. units considered Total load capacity (MW) Cleaning with inorganic acids Volume (m3) Frequency (n/year) pH Cu (mg/l) Fe (mg/l) HCl (mg/l) HF (mg/l) Cleaning with organic acids Volume (m3) Frequency (n/year) pH NH3 (mg/l) Organic acids (mg/l) Fe (mg/l) De-copperizing cleaning Volume (m3) Frequency (n/year) pH (mg/l) Cu (mg/l) Cleaning with complexing agents Volume (m3) Frequency (n/year) pH (mg/l) Cu (mg/l) TREATMENT TECHNOLOGY

Czech Republic --CEZ

Denmark --SK Power

France --EDF

Germany --VKR

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain --Iberdrola

United Kingdom --Powergen

5 1000 400 0.25 2 10000 10000 not present

5 1500 (th) 200 5 2 100 100 100 not present 2

5 3200 not present

1 880 (th) once since 1975

1 270 134 7 - 10

4 2640 not present

4 1256 225 4 1 8000 50000 1000

2 1084 300 0.4

4 2000 not present

60000 70000 500 - 1000 5 - 25 17000 22000 not present 1500 1 3-4 200 5000 - 6000 1000 not present

4000 45000

225 4 8-9 5000 1000 not present 300 0.4

1000 1 4.5 - 5 30000 5000 450 1

not present

200 5 2 100

included in cleaning with organic acids

not present

500 not present 800 0.1 not present included in cleaning with organic acids not present not present

not present

200 5

500 - 1000 Flocculation, settlement and pH correction Cleaning with inorganic acids neutralised with lime prior to discharge Cleaning solution with organic acids treated by alkalisation, flocculation and heavy metal precipitation, settlement, coagulation, flocculation and neutralisation, lamella separation pH correction, air agitation, coagulation, flocculation, settlement and final pH correction Homogeneisation with other wastewaters, neutralisation, air agitation pool, pH correction, flocculation, settlement and final pH correction

- 51 -

Table XXV - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Fireside washing wastewaters

Country Composition
N. units considered Total load capacity (MW) Combustion chamber Volume (m3/year) pH TSS (g/l) SO4 (mg/l) Air preheater Volume (m3/year) pH TSS (mg/l) SO4 (mg/l) NH3 (mg/l)* Electrostatic precipitator Volume (m3/year) pH TSS (mg/l) SO4 (mg/l) NH3 (mg/l)* Stack Volume (m3/ year) pH SO4 (mg/l) TREATMENT TECHNOLOGY

Austria --EVN and VKG 2 755 not present

Belgium --Electrabel 6 900 9000

Denmark --SK Power 5 1500 (th) 100000 acid

France --EDF 5 3200 2000 - 4000 5.7 5900

Hungary --Humgarian Power Companies 13 + 2 g.y. 2150 260 2 - 2.5 50

Italy --ENEL 4 2640 3500(1) - 7000(2) variable(1) - acid(2) 1000(1) - 10000(2)

Spain Iberdrola 2 1084 400 - 800 3-5 10 - 100

United Kingdom --Powergen 4 2000

no data available

1000 5-9

included in combustion chamber cleaning

50000 acid

10000 - 20000 8.5 70 28000

300 - 2000 2.5 - 3.5 5-6

5000(1) - 7200(2) variable(1) - acid(2) 500 10000(1) - 30000(2) (1) 100 - 1000(2) 1500 variable(1) - acid(2) 2500(1) - 25000(2) 10(1) - 150(2)

1500 - 3000 9 - 10 200 - 10000

no data available

not present

50000

3000 - 6000 9 10.4 1.2

not present

not present

no data available

not present

not present

not present

not present

Flocculation and settle- Settlement ment (with iron hydroxide)

Flocculation, settlement and pH correction. Reutilised in FGD

Alkalisation with lime to Neutralisation and pH 8.5. settlement

200 variable(1) - acid(2) 1000(1) - 25000(2) Ammoniated wastewaters treated by alkalisation, flocculation, settle-ment, hardness remo-val with sodium carbo-nate, settlement, alkali-sation with soda and ammonia stripping. Non ammoniated wastewaters treated by alkalisation, flocculation and heavy metal precipitation, settlement, coagulation, flocculation and neutralisation, lamella separation

not present

Homogeneisation with other wastewaters, neutralisation, flocculation and settlement, final pH correction

Untreated

* due to the presence of high dust SCR Denox

(1)

With reference to units firing coal With reference to units firing heavy oil

(2)

- 52 -

Table XXVI - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Wastewater from ash handling systems and car/trucks washings

Country Composition
N. units considered Total load capacity (MW) Bottom ash handling Volume (m3/h) pH TSS (mg/l) Metals

Austria --OKA

Czech Republic --CEZ

Denmark --SK Power

France --EDF

Germany --VKR

Hungary --Hungarian Power Companies 5 2600 not present

Ireland --ESB

Portugal --CPPE

Spain --Iberdrola

United Kingdo --Powergen

5 1000 10 8 - 8.5 20 - 400 50 7.3 16

5 1500 (th) 1000 8.5 15 Pb, Hg, Cd, Cr, Cu, As, Ni, at very low level 66

5 3200 120 9 1000 Fe 20 mg/l, Cu, Ni, Zn, Cr lower than 1 mg/l

1 880 (th) not measured 8-9 50 - 250

3 915 not present

4 1256 closed circuit

2 505 overflow from closed circuit

4 2000 720 7 25

no data availa

Fly ash handling (ash pond) Volume (m3/h) pH TSS (mg/l) Metals Car/truck washing Volume (m3/d) pH TSS (mg/l) Metals TREATMENT TECHNOLOGY

not present

inlcuded in bottom ash handling system

not present 8.5 as for bottom ash

670 10 - 11 Pb, Fe, Mn, Zn and Cd

not measured

6000

10

10

not present

15

ash pond runoff 6 -9 < 30 trace elements at very low level included in station drain with meteoric water

not present

not presen

not measured

10

not measure

Alkalisation, flocculation, settlement and pH correction

Wastewater from Settlement bottom and fly ash handling system untreated. Car/truck washing are recirculated

Settlement

Clarification, decarbonisation and reutilised as cooling tower water

Settlement

Homogeneisation with other wastewaters, neutralisation, settlement and pH correction

Untreated

- 53 -

Table XXVII - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Meteoric wastewater

Country Composition
N. units considered Total load capacity (MW) Solid waste storage Volume (m3/year) pH TSS (mg/l) Metals

Austria --OKA

Austria --Wienstrom

Czech Republic --CEZ

Denmark --SK Power

France --EDF

Germany --VKR

Hungary --Hungarian Power Companies

Hungary --Hungarian Power Companies

Ireland --ESB

Italy --ENEL

Portugal --CPPE

Spain --Iberdrola

Kingdom

Powerge

combined cycle 464 not present not present

5 1000 not present

5 1500 (th) not measured

5 3200 1500 7 21 Zn, Mn, Ni, Cu, Cr at very low level

1 880 (th) not present

5 2600 not present

13 + 2 t.g. 2150 not present

3 915

4 2640 some thousands 2 - 10 100 - 200 Fe, Ni, V, Al, Zn, Mn, Cu, Cr ranging from 1 to 10 mg/l

4 1256 not measured 8.6 40 Al, As Cd, Pb, Cu, Cr, Fe, Mn, Hg, Ni, Ti, Zn at very low level V up to 23 mg/l not measured

2 505 60500 12.5 10 - 15 Al 3-4 mg/l, Cr, Cu, Hg, Zn, Cd at very low level

not measu

Clean meteoric Volume (m3/year) pH TSS (mg/l) Coal pile run-off Volume (m3/year) pH TSS (mg/l) Metals

not measured

160000

50000

50000

not measured

500000

not measured

not measured 6-9 < 30 mg/l

100000 6

not measured

not measu

2500 7.5 - 8.5 < 0.3 (20 max.)

not present

1000

78000 6.9 7

not measured

not present

not present

150000 5-7 < 100 Mn, Al, Fe, Zn, V, Ni from 0.1 to 2 mg/l All meteoric water collected by the power station drain and treated on oil interceptors Wastewater from solid waste storage treated by alkalisation, flocculation and heavy metal precipitation, settlement, coagulation, flocculation and neutralisation, lamella separation. Clean meteoric wastewater untreated Coal pile runoff treated by settlement and partially reutilised for wetting the coal pile

not measured 7.5 - 8.5 < 30 Al, As, Cd, Pb, Cu, Cr, Fe, Mn, Hg, Ni, Ti, V, Zn at very low level Wastewater from solid waste storage recirculated, and overflow treated by homogeneisation with other wastewaters, co-agulation, floc-culation, settle-ment and final pH correction. Coal pile runoff treated by preliminary screening and settlement followed by the same treat-ment of overflow from solid waste storage. Clean meteoric wastewater trea-ted by screening and settlement.

38500 7.8 500 - 1000

not measu

Fe up to 1 m Zn up to 0

TREATMENT TECHNOLOGY

Clean meteoric water untreated

Partially (about 32000 m3/y) treated with a heavy oil separation system

Clean meteoric wastewater untreated

All meteoric wa- Settlement stewater treated by oil separation, settlement and pH correction. If reutilised in FDG a further treatment of floc-culation and sand filtration

Clean meteoric wastewater untreated. Coal pile runoff treated in a 3 chamber clarifier

Clean meteoric wastewater trea-ted with other wastewaters by gravity separation

Clean meteoric wastewater untreated

Wastewater from solid waste storage areas treated by neutralisation Clean meteoric wastewater and coal pile runoff treated by settle-ment

Untreated

- 54 -

Table XXVIII - MAIN REFERENCE CASES OF WASTEWATER TREATMENT Wastewater from FGD plants

Country Composition
N. units considered Total load capacity (MW) Prescrubber blowdown (mc/h) Scrubber blowdwon (mc/h) pH TSS (mg/l) TDS (mg/l) COD (mg/l) SO3 (mg/l) NO3 (mg/l) NH3 (mg/l) Cl (mg/l) F (mg/l) Metals

Austria --OKA

Austria --Wienstrom combined cycle 464 not present 10 6.2

Austria --Linzer Elektrizitats 9 80 + 220 (heat) not present 5000 4.2 - 5

Denmark --SK Power 5 1500 not present 15

Denmark --Vestkraft 1 290 not present 10 - 16.5 4.8 - 5.6 22300

Germany --VKR 1 880 (th) 10 - 20 not present <1 500 - 2000

Italy --ENEL 4 2640 130 10 1-2 1000 -10000 80000 200 max 10 - 300 < 50 40000 100 Ba, Sn, As, Hg, Cd, Se, Cr, Zn, Cu, Mn, Ni, Pb lower than 1 mg/l 3000 - 6000 acid Alkalisation with lime, flocculation and hea-vy metal precipitation, settlement, coagulation, flocculation and neutralisation, lamella separation

United Kingdo --Powergen

7 not present 0.5 - 2 1000 100 - 200 <1 300 - 600 10 1000 - 2000 100 - 500

4 2000 not present 100 6

up to 10000

> 25 > 150 >5 50 - 100 V, Ni, Fe, Al 1000 300 20 26500 < 50 Cd, Hg, NI, Se lower than 1 mg/l < 10 800 - 900 1 - 10 15000 - 20000 5000 - 7000

< 25 < 700 <1 30000 - 4000

Components washing Volume (m3/year) pH Metals TREATMENT TECHNOLOGY

not present

Gypsum precipitation, fluorine precipitation, heavy metal precipitation, thickening

750 1.5 V and Ni Oxidation, alkalisation, thickening, ammonia stripping, flocculation, neutralisation, lamella settlement, hypochlorite oxidation, gravel and activated carbon filtration 15 TSS 30 mg/l Al, F, NH4 10 mg/l Zn 3 mg/l Fe, Co, Ni 2 mg/l Pb, Cu 1 mg/l Cr 0.5 mg/l As, Cd 0.1 mg/l Hg 0.01 mg/l

not present

300 acid Heavy metal precipitation with Na2S, sand filtration and pH correction. The effluent treated on municipal biological plant

not measured

not present

not present

Oxidation with air, alkalisation, settlement, neutralisation, flocculation and final settlement

Removal of gypsum and ash by settlement, neutralisation with soda, heavy metal precipitation with Na2S, neutralisation and flocculation, settlement, sand and activated carbon filtration TSS < 10 mg/l NO3- N 145 mg/l NH3 < 5 mg/l Ni 0.035 mg/l As, Se < 0.02 mg/l Zn 0.015 mg/l Cu < 0.004 mg/l Cr, Pb < 0.002 mg/l Cd 0.001 mg/l Hg < 0.0002 mg/l

Two step neutralisation, flocculation and heavy metal precipitation with TMT 15, settlemment

pH correction wit me, flocculation, tlement, sulphide dition, flocculatio and settlement, l mella separation

Capacity (mc/h) Removal efficiency or effluent concentration

5 F 8.1 mg/l Pb, Zn 0.11 mg/l Cr, Ni < 0.1 mg/l Cu < 0.05 mg/l Cr(VI) 0.04 mg/l Cd, CN < 0.01 mg/l As, Hg < 0.005 mg/l

42 Mn 4 mg/l NH3 2.5 mg/l Fe, Se 0.1 mg/l Al 0.05 mg/l Ni, Cu 0.01 mg/l V < 0.005 mg/l Pb < 0.003 mg/l Cr 0.002 mg/l As < 0.001 mg/l Cd 0.0005 mg/l Hg 0.0003 mg/l

30 500 F 10 - 15 mg/l TSS > 95 % Cd, Hg, Zn < 0.01 mg/l Al, Ba, Cr, Fe, Hg, Ni, Cr, Pb, Cu < 0.05 mg/l Pb, Zn > 99 % As, Cu, Mn, Se > 93 % Cd 70 - 90 % SO3 > 99 % F > 90 %

220 Majority of metal trace elements 95 - 99 % Sb ca. 65 %

- 55 -

5.
5.1.

CONCLUSIONS AND RECOMMENDATIONS

CONCLUSIONS Increasing stringent environmental regulations and the more and more elevated cost of the

supply of water are focusing attention on water treatment technology. This study has highlighted the following: 1) Many technologies, simple and advanced, are available on the market for solving almost every problem of pollution removal from wastewaters. 2) Reliable operation of wastewater treatment plants requires a good knowledge of the wastewater streams and an appropriate design to cope with all operational conditions. It needs also a good process control and an appropriate supervision and maintenance. 3) Power companies, in the UNIPEDE countries, use a variety of different technologies. 4) The choice in individual countries is determined by a number of factors including: a) national or local regulations b) age / design of power plant c) economic factors 5) In almost all countries technologies are used to reduce (see table XIX) a) heavy metals b) oils in water 6) Older plants tend to use disaggregated water systems 7) There are discernable trends to a) reutilise water and b) integrate water streams treatment to optimise overall water management.

5.2.

RECOMMENDATIONS

1) For new plants or when substantial alterations are made to existing plants, integrated water and related waste management should be given a high priority. 2) In order to comply with increasingly stringent regulations the power generation industry must keep a continuing awareness of developments in water treatment technology. 3) It is recommended that this report is used as a screening tool to find the technologies that can be used for a particular stream. The user can then identify those technologies that might be more appropriate but the final choice can only be made on a case-by-case basis taking account of all the specific local circumstances. 4) Members of UNIPEDE should continue to exchange information in this area.

wastew.doc

Enclosure Questionnaire form

ENEL SpA DCO - Central Laboratory Unit Piacenza

Contribution to UNIPEDE Therchim

WATER EFFLUENTS TREATMENT Streams Definition - Technologies - Utilization/Disposal QUESTIONNAIRE

COUNTRY

.................................................................................................

COMPANY

.................................................................................................

Reference year

.............

1.

POWER STATION/S Please describe the Power Station/s to which the water effluents treatment refers. Select the most complete case/cases (including FGD, DeNOx, ESP, if any)

.................................................................................... ................................................. ..................................................................................................................................... ...................................................................... ............................................................... ..................................................................................................................................... ........................................................ ............................................................................. ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ......................................................................................................................... ............ .....................................................................................................................................

........................................................................................................... .......................... 2. STREAMS DEFINITION present yes no 2.1 WATER POLLUTED BY OIL Stream sources (e.g. meteoric water, fuel oil heating condensate) ............................................................................................................... .......................................................................................................... ..... ............................................................................................................... ............................................................................................................... Flow rate (if continuous) Volume Oil concentration TDS mc/h mc/month mg/l mg/l ............... ............... ............... ............... treated yes no

2.2

SANITARY WATER Stream sources (e.g. toilet, showers, canteens): ............................................................................................................... ................................................................................... ............................ ............................................................................................................... ............................................................................................................... Flow rate (if continuous) Volume BOD5 COD NO3 NH3 mc/h mc/month mg/l mg/l mg/l mg/l ............... ............... ............... ............... ............... ...............

2.3

DEMINERALISATION PLANT REGENERATION SOLUTION Volume Frequency pH TDS mg/l mc n./month ............... ............... ............... ...............

3
present yes no 2.4 CONDENSATE POLISHING REGENERATION SOLUTION treated yes no

2.4.1 Deep bed demineralisation

q
mc n./month ............... ............... ............... mg/l mg/l ............... ...............

Volume Frequency pH TDS NH3 2.4.2 Precoat filtration

q
mc n./month mg/l ............... ............... ...............

Volume Frequency TSS

2.5

BOILER BLOW-DOWN

q
mc/h mc/day mg/l mg/l mg/l mg/l ............... ............... ............... ............... ............... ...............

Flow rate (if continuous) Volume TDS NH3 PO4 NaOH

2.6

CHEMICAL CLEANING SOLUTIONS:

cleaning with inorganic acid cleaning with organic acid Volume Frequency Rough composition: .......................................................................................................... .......................................................................................................... mc ............... ...............

q q

q q

q q

q q

4
present yes no de-copperizing cleaning Volume Frequency Rough composition: .......................................................................................................... .......................................................................................................... cleaning with complexing agents Volume Frequency Rough composition: ............................................................................................... ........... .......................................................................................................... boiling-out solution Volume Rough composition: .......................................................................................................... .................................................................................................. ........ others: ......................................................................................................... ......................................................................................................... mc ............... mc ............... ............... mc ............... ............... treated yes no

2.7

FIRE SIDE WASHING SOLUTION:

Boiler Volume Frequency Rough composition: .......................................................................................................... .............................................................................. ............................ Air preheater Volume Frequency Rough composition: .......................................................................................................... .......................................................................................................... mc ............... ............... mc ............... ...............

5
present yes no Electrostatic Precipitato r Volume Frequency Rough composition: .............................................................. ............................................ .......................................................................................................... Stack Volume Frequency Rough composition: .......................................................................................................... .................................................... ...................................................... mc ............... ............... mc ............... ............... treated yes no

2.8

BOILER CONSERVATION SOLUTION

q
............... ............... ............... ...............

Volume Frequency NH3 N2H4 Others:

mc n./year mg/l mg/l

.......................................................................................................... ......................................................................... .................................

2.9

WATER FROM FLY AND BOTTOM ASH HANDLING

2.9.1 Effluent from wet circuit for bottom ash handling

Flow rate pH TSS Metals:

mc/h

............... ...............

mg/l

...............

.......................................................................................................... ............................................................... ...........................................

6
present yes no 2.9.2 Effluent from wet circuit for fly ash handling (ash pond) treated yes no

Flow rate pH TSS Metals:

mc/h

............... ...............

mg/l

...............

.......................................................................................................... ...................................................... ....................................................

2.9.3 WASTEWATER FROM CAR/TRUCK WASHINGS

Volume TSS

mc/d mg/l

............... ...............

2.10

METEORIC WATER

2.10.1 Water from solid waste storage and leaching from landfills

Volume pH TSS Metals:

mc/year

............... ...............

mg/l

...............

.......................................................................................................... ................................................................................................... .......

2.10.2 Clean meteoric effluents (from roofs, parkings, clean yards)

Volume Rough composition

mc/year

...............

.......................................................................................................... ..........................................................................................................

7
present yes no 2.11 COAL PILE RUN-OFF treated yes no

q
mc/year ............... ............... mg/l ...............

Volume pH TSS Metals:

.......................................................................................................... ..........................................................................................................

2.12

DeSOx PLANT:

2.12.1 Pre-scrubber blow-down Scrubber blow-down Flow rate pH TDS TSS COD SO3 NO3 NH3 Cl F: Others: .......................................................................................................... .......................................................................................................... Metals and trace elements: .......................................................................................................... .......................................................................................................... ....................................................................... ................................... .......................................................................................................... mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mc/h ............... ............... ............... ............... ............... ............... ............... ............... ............... ...............

q q

q q

q q

q q

8
present yes no 2.12.2 Discontinuous streams from components washings (e.g. Gavo, demisters) treated yes no

Volume Frequency Rough composition:

mc n./year

............... ...............

..................................................... ..................................................... .......................................................................................................... ............................................................................................. .............

2.12.3 Condensate from cold stack

q
mc/h ............... ............... mg/l ...............

Flow rate pH TDS Rough composition:

.......................................................................................................... .......................................................................................................... ..........................................................................................................

2.13

DeNOx SCR OR SNCR SYSTEM:

2.13.1 Ammoniated water from fire side washings

Air preheater NH3 E.S.P. NH3 2... OTHERS mg/l ...............

q q
mg/l ...............

q q

q q

q q

..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... .....................................................................................................................................

2.14

WATER STREAMS REDUCTION OR AVOIDANCE Please describe if some of the previously described waste water stream is directly treated to decrease its flow rate or avoided by some specific technology (e.g. demineralisation waste water by the use of membrane technique) ..................................................................................................................................... ............................................................................................................. ........................ ..................................................................................................................................... ............................................................................................... ...................................... ..................................................................................................................................... ................................................................................. .................................................... ..................................................................................................................................... ................................................................... .................................................................. ..................................................................................................................................... ..................................................... ................................................................................ ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... .....................................................................................................................................

10

3.

TREATMENT PLANTS Please add a flow-sheet of the whole treatment system, describe how the various water streams indicated in point #2 are collected and mixed before the treatment in drains, holding tanks and reservoirs, and how the treated streams are mixed before the discharge.

yes 3.1 DISOLEATION PLANT

no

Exhaustive description of the plant and process/ess: ..................................................................................................................................... ............................................................................................ ......................................... ..................................................................................................................................... .............................................................................. ....................................................... ..................................................................................................................................... ................................................................ ..................................................................... ..................................................................................................................................... capacity oil removal efficiency mc/h % ............... ...............

3.2

SANITARY PLANT

Exhaustive description of the plant and process/ess: ................................................................................................. .................................... ..................................................................................................................................... ................................................................................... .................................................. ..................................................................................................................................... ..................................................................... ................................................................ ..................................................................................................................................... ....................................................... .............................................................................. Chemicals used/annual quantity: ..................................................................................................................................... ..................................................................................................................................... ................................................................................................................................. .... ..................................................................................................................................... Capacity BOD5 removal efficiency mc/h % ............... ...............

11

yes 3.3 PHYSICO-CHEMICAL TREATMENT PLANT

no

Treated streams: ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... Exhaustive description of the plant and process/ess: ..................................................................................................................................... ....................................................................................... .............................................. ..................................................................................................................................... ......................................................................... ............................................................ ..................................................................................................................................... ........................................................... .......................................................................... ..................................................................................................................................... Chemicals used/annual quantity: ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ....................................................................................................................... .............. Capacity mc/h ...............

Plant removal efficiency for the most important parameters (e.g. TSS, Metals): ............................................................................................................................... ...... ..................................................................................................................................... ................................................................................................................. .................... ..................................................................................................................................... ................................................................................................... ..................................

3.4

DeSOX WASTE WATER TREATMENT PLANT

Exhaustive description of the plant and process/ess: .................................................................. ................................................................... ..................................................................................................................................... .................................................... ................................................................................. ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... .....................................................................................................................................

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Chemicals used/annual quantity: ............................................................................................................... ...................... ..................................................................................................................................... ................................................................................................. .................................... Capacity mc/h ...............

Plant removal efficiency for metals, trace elements, SO 3 - NH3 - F: .................................................................................................................... ................. ..................................................................................................................................... ...................................................................................................... ............................... ..................................................................................................................................... ........................................................................................ .............................................

yes 3.5 AMMONIATED WATER TREATMENT PLANT

no

Exhaustive description of the plant and process/ess: ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... ..................................................................................................................................... Chemicals used/annual quantity: ............................................................................................. ........................................ ..................................................................................................................................... ............................................................................... ...................................................... Capacity NH3 removal efficiency 3..... OTHERS .............................................................................................................. ....................... ..................................................................................................................................... ................................................................................................ ..................................... ..................................................................................................................................... .................................................................................. ................................................... ..................................................................................................................................... mc/h % ............... ...............

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4.

TREATED WATER EFFLUENTS RE-USE Please refer to the most complete case/cases: ..................................................................................................................................... ........................................................................................................... .......................... .....................................................................................................................................

4.1

RE-USED STREAMS yes no

4.1.1 Disoleation plant effluent Use of effluents - Industrial water (raw water) - Service water (low salinity water) - Demi water production Recovery of treated effluent % ...............

q q q q

q q q q

4.1.2 Sanitary plant effluent Use of effluents - Industrial water (raw water) - Service water (low salinity water) Recovery of treated effluent % ...............

q q q

q q q

4.1.3 Physico-chemical plant effluent Use of effluents - Industrial water (raw water) - Service water (low salinity water) Recovery of treated effluent % ...............

q q q

q q q

4.1.4 DeSOX waste water treatment effluent Use of effluents - Industrial water (raw water) - Service water (low salinity water) Recovery of treated effluent % ...............

q q q

q q q

4.1.5 Ammoniated water treatment effluent Use of effluents - Industrial water (raw water) - Service water (low salinity water) Recovery of treated effluent % ...............

q q q

q q q

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4.1.6 Others ..................................................................................................................................... ................................................................................................ ..................................... ..................................................................................................................................... .................................................................................. ................................................... .....................................................................................................................................

4.2

POSSIBLE PROBLEMS CONNECTED WITH THE EFFLUENTS REUSE ..................................................................................................................................... .................................................................................................................................. ... ..................................................................................................................................... .................................................................................................................... ................. ..................................................................................................................................... ...................................................................................................... ............................... ..................................................................................................................................... ........................................................................................ .............................................

Piacenza, May 1995

A:ENCLOS1.DOC

Publications Order Form Name:............................................................................................................................................... Position:............................................................................................................................................ Undertaking:..................................................................................................................................... Address:............................................................................................................................................ Town: .......................................................Country:.......................................................................... (with postal code) Telephone:.......................................................Fax:.......................................................................... (with regional code) E-mail: UNIPEDE-EURELECTRIC member: Title1 p Yes p No (Tick the appropriate box)

Reference No.

Quantity

To be returned to: Concetta PALERMO UNIPEDE-EURELECTRIC Documentation 66, Boulevard de l Impratrice BE-1000 Brussels Tel.: Fax: + 32 2 515 10 00 + 32 2 515 10 10 E:mail: cpalermo@unipede.org or cpalermo@eurelectric.org Web: http://www.unipede.org http://www.eurelectric.org

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