Reading 2

EN3502/CV4551-Water Supply Engineering
Reading Materials-2
on Filtration Disinfection Taste, Odor and Algae Control Removal of Iron and Manganese Water Softening Membrane Technology
1. Reading Materials-2 is a compilation/extraction of information from various sources. All the copyrights remain with the original sources of information regardless of whether they are indicated. 2. It is only for the EN3502/CV4551 class and cannot be circulated/used for any commercial purposes.
EN3502-CV4551-Water Supply Engineering/Liu Yu
Table of Contents
Chapter 1 Conventional Filtration Technology 1.1. Introduction 1.2. Classification of filters 1.2.1 By filtration rate (a) Slow sand filter (b) Rapid sand filter 1.2.2 By types of medium (a) Single-medium filter (b) Dual-media filters (c) Multimedia filters 1.2.3 By driving forces 1.3. Mechanisms of particles removal by filtration 1.4 Gravity filters and accessories 1.5. Negative head and head loss 1.5.1. Negative head 1.5.2. The clean-water head loss through a granular porous medium (a) A general consideration: Bernoullis equation (b) Carmen-Kozeny equation (c) Rose equation 1.5.3. Head loss development 1.6. Filter backwash hydraulics 1.6.1. Backwash hydraulics 1.6.2. Working mechanisms of backwashing 1.7. Operation of granular medium filter 1.7.1. Constant head-variable flow 1.7.2. Constant flow-variable head 1.8. Design consideration for depth filter 1.8.1 Available filtration technologies 1.8.2. Evaluation of filter performance 1.8.2.1. Removal of turbidity 1.8.2.2. Removal of total suspended solids 1.8.2.3. Removal of particle size 1.8.3. Issues related to design and operation of filter system 1.8.3.1. Influent water characteristics 1.8.3.2. Selection of filtration technology 1.8.4. Principal variables in the design of granular medium filters 1.8.5. Typical design data for depth filters with mono medium. 1.8.6. Typical design data for dual- and multi-medium depth filters 1.8.7. Design criteria for rapid sand filters: an example
1.8.7.1. Filter bed 1.8.7.2. Backwashing system 1.8.7.3. Underdrains Chapter 2 Disinfection Technology 2.1. Characteristics of an ideal disinfectant 2.2. Disinfection methods 2.2.1. Disinfection by chemical agents 2.2.2. Disinfection by physical agents 2.2.3. Disinfection by radiation 2.3. Mechanisms of disinfection 2.4. Disinfection kinetics 2.5. Factors affecting disinfection process 2.5.1. Concentration of disinfectant and contact time 2.5.2. Intensity and nature of physical agent 2.5.3. Temperature 2.5.4. Types of organisms 2.6. Chlorination 2.6.1. Chlorination chemistry 2.6.2. Disinfection by chlorine 2.6.3. Chlorine reactions with ammonia 2.6.4. Breakpoint chlorination 2.6.5. Factors affecting disinfection by chlorine 2.6.6. Chlorination-associated undesirable byproducts 2.6.7. Practical methods of chlorination in Water Works 2.6.7.1. Prechlorination 2.6.7.2. Post-chlorination 2.6.7.3. Plain chlorination 2.6.7.4. Superchlorination 2.6.7.5. Hypo-chlorination 2.6.8. Minimum chlorine dosages 2.6.9. Dechlorination 2.6.9.1. Sulfur dioxide 2.6.9.2. Activated carbon 2.6.10. A simplified flowchart of Water Works 2.7. Ozonation 2.8. Chlorine dioxide 2.9. Other disinfectants Chapter 3 Taste, Odor and Algae Control 3.1. Source of taste and odors in water supplies 3.2. Groundwater
3.3. Surface water 3.4. Effects of microorganisms 3.5. Effects of inorganic and synthetic organics 3.6. Prevention and control of tastes and odors at source 3.6.1. Algicides 3.6.2. Reservoir Destratification 3.6.3. Biological Control 3.6.4. Watershed Management 3.7. Removal of tastes and odors in the water treatment plant 3.7.1. Oxidation 3.7.1.1. Chlorine 3.7.1.2. Permanganate 3.7.1.3. Ozone 3.7.1.4. Chlorine Dioxide 3.7.2. Activated Carbon Adsorption 3.7.3. Aeration 3.8. Algae control Chapter 4 Removal of Iron and Manganese 4.1. Chemistry of iron 4.2. Chemistry of manganese 4.3. Oxidation and removal 4.4. Design Considerations 4.5. Ion exchange 4.6. In-situ oxidation 4.7. Polyphosphate Chapter 5 Softening Technology 5. 1. Hardness 5.1.1. Total hardness (TH) 5.1.2. Carbonate hardness (CH) and noncarbonate hardness (NCH) 5.1.2.1. Carbonate hardness 5.1.2.2. Noncarbonate hardness 5.2. Bar chart of water composition 5. 3. Fundamentals of lime-soda softening 5.3.1. Working principle of lime-soda process 5.3.2. Softening chemistry 5.3.2.1. Source of hydroxide ions 5.3.2.2. Source of carbonate 5.3.3. Main softening reactions 5.3.4. Process limitations 5.3.5. Some empirical considerations
5.4. Softening operations 5.4.1. General view 5.4.2. Split treatment 5.4.3. Recarbonation 5.5. Ion exchange softening Chapter 6 Membrane Technology 6.1. Briefing of membrane 6.2. Classification of membrane 6.3. Osmosis 6.3.1 What is Osmosis? 6.3.2 What is a semipermeable membrane? 6.3.3 How to compute osmotic pressure ()? 6.4 Reverse Osmosis (RO) 6.5. Nanofiltration (NF) 6.6. Ultrafiltration (UF) 6.7. Microfiltration (MF) 6.8. Membrane element, module and bank 6.9. Mass transport and permeate flux 6.9.1. Resistance of membrane filtration 6.9.2 Transmembrane pressure 6.10 Membrane fouling 6.11 Applications of membrane in water supply 6.11.1 Process design: a briefing (i) Transmembrane pressure (ii) Production flow of a membrane system (iii) The conversion yield (iv) Feed and discharge pumps (v) Valve 6.11.2 Application of RO process 6.11.3. Application of NF 6.11.4. Application of UF 6.11.5. Application of MF References
Chapter 1 Conventional Filtration Technology
1.1. Introduction Filtration is a solid-liquid separation process in which the liquid containing suspended particles passes through a porous medium to remove much fine suspended solids as possible. As practiced in water treatment plants, filtration is a polishing step and is used to filter chemically coagulated and settled water to produce a high-quality drinking water. Although filtration removes many pathogenic organisms from water, filtration should not be relied upon for complete health protection. The filtration process may involve passing the water through a stationary bed of granular medium. Suspended solids in the water are retained by the filter medium. Several modes of operation are possible in granular medium filtration, including upflow, biflow, pressure and vacuum filtration, while the most common practice is gravity filtration in a downward mode, with the weight of the water column above the filter providing the driving force. 1.2. Classification of filters Filters may be classified according to filtration rate, the types of media used or driving force. 1.2.1 By filtration rate (a) Slow sand filter The first filters used on a widespread basis for water purification were slow sand filters. These filters were constructed of fine sand with an effective size of about 0.2 mm. The effective size is the size of the openings of the sieve that retains 10 percent of the medium. Such small size sands resulted in virtually all of the suspended material being removed at the filter surface. Additionally, a mat of biological organisms was allowed to develop at the water-sand interface, which aided in the filtration process. The resulting high head loss produced very low flow rates (0.12 to 0.32 m/h), necessitating the construction of very large filters. Cleaning was accomplished by periodically (usually no more frequently than once a month) draining the filters and mechanically removing the top few centimeters of sand, along with the accumulated solids and the biological mat.
Slow sand filters have large space requirement and are capital-intensive, while they do not function well with highly turbid water since the surface plugs quickly, requiring frequent cleaning. In this case, the rapid sand filter had been developed to alleviate these difficulties. (b) Rapid sand filter The rapid sand filter utilizes a bed of silica sand ranging from 0.6 to 0.75 m in depth. Sizes of silica sand may range from 0.35 to 1.0 mm or even larger, with effective sizes from 0.45 to 0.55 mm. These larger sizes, coupled with frequent cleaning and the absence of a biological mat, result in a rate of filtration an order of magnitude larger than that of the slow sand filter. The filtration rate in rapid sand filter falls into a range of 2.5 to 5.0 m/h. An important feature of the rapid sand filter is that it is cleaned by hydraulic backwashing with resulting stratification of the medium. Filtration of relatively clean water presents few problems. However, filtration of turbid water necessitates frequent backwashing. Coagulated water with large, strong flocs causes binding at the fine-grained surface and results in a rapid buildup of head loss, necessitating frequent cleaning. This situation could be alleviated if the gradation of the filter could be reserved so that larger grains were deposited on top with media of progressively decreasing size below, so that the smallest grains were on the bottom. Such an arrangement would mean the large pores on top would retain mostly large suspended material, while subsequently smaller pores would retain finer material. Thus, the entire depth of the filter would function efficiently, and larger volumes of suspended solids could be retained between backwashes. The overall result would be longer filter runs, less head loss, and greater filtering rates. By careful selection of medium with regard to size and density, it is possible to approximate this reverse gradation. Dual-media filters do this to some extent, and mixed-media filters essentially approximate reverse gradation. 1.2.2 By types of medium Under this category, filters may be classified as single-media, dual-media and multimedia filters. (a) Single-medium filter These filters have one type medium, usually sand or anthracite coal. (b) Dual-media filters
Dual-media filters are usually constructed of silica sand and anthracite coal. The depth of the sand may range from 0.15 to 0.4 m, with the coal depth ranging from 0.3 to 0.6 m. Size and uniformly coefficients of the two media can be selected to produce either a distinct separation or a given degree of mixing after backwashing, e.g. the following material would produce a filter 0.6 m deep with approximately 0.15 m of intermixing. The large pores in the anthracite layer remove large particles and flocs, while most of the smaller material penetrates to the sand layer before it is removed. Dual-media filters thus have the advantages of more effectively utilizing pore space for storage. This results in longer filter runs and greater filtration rates because of lower head losses. A disadvantage of dual-media filters is that the filtered material is held rather loosely in the anthracite layer. Any sudden increase in hydraulic loading dislodges the material and transports it to the surface of the sand filter, resulting in rapid binding at this level. Depth, m Specific gravity Effective size, mm Uniformity coefficient (c) Multimedia filters As noted earlier, the ideal filter would consist of a medium graded evenly from large at the top t small at the bottom. This can be accomplished by using three or more types of media with carefully selected size, density, and uniformity coefficients. A typical installation might consist of a 0.75-m bed with 60 percent anthracite, 30 percent silica sand, and 10 percent garnet sand, with specific gravities of 1.6, 2.6 and 4.2, respectively. Effective sizes ranging from a maximum of 1.0 mm for the anthracite to a minimum of 0.15 mm for the garnet, coupled with carefully selected uniformity coefficients, will produce intermixing and result in a pore-size gradation. Thus, the mixed-media filter (perhaps mixedup is a more descriptive term) approaches an ideal filter. Filtration rates range from10 to 20 m/h, considerably higher than rapid sand filters and about the same as for dual-media filters. The reverse gradation avoids the major problems of each of these media, however. Dual- and mixed-media filters make possible the direct filtration of water of low turbidity without settling operations. Coagulating chemicals are often added t the influent of the filter to produce small, strong flocs to enhance turbidity removal. Sand 0.3 2.65 0.5-0.55 <1.65 Coal 0.3 1.4-1.6 0.9-1.0 <1.8
1.2.3 By driving forces Water filtration through filter media can be driven by gravity, pressure and vacuum. In the family of conventional filters, there are major members, they gravity filter, pressure filter and vacuum filter. In water supply engineering, most of filters employed in full scale application are driven by gravity. In general, pressure and vacuum filters are often used in a relatively small scale. A special pressure driven filter is the diatomaceous filters Diatomaceous earth (D.E.) is a white, odorless porous silica powder with microscopic openings, when magnified, look like tiny sponges. Properly applied to the pressure side of filter elements, it forms a porous, relatively non-compressible coating through which water readily passes. Clear water can pass through these openings, but particles, as small as one to three microns, are trapped the first pass through the media. All D.E. filters (Fig. 1.1) have internal elements that become coated with D.E. It is this 'filter cake' that strains dirt, dust, algae and some forms of bacteria from the water. Similar to sand filters, when a D.E. filter becomes dirty, it is cleaned either by backwashing, or regenerating and draining, the clogged D.E. to the 'waste' line. To restore filtration, a fresh 'charge' of D.E. is added to the filter. Generally the slower the water is passed through the filter, the better the filtration performance. The rate of filtration depends upon the choice of filtration media, the type of water to be filtered, and the desired results that you wish to achieve. To form the coating on the filter element, D.E. powder is added to the water flowing through the filter tank, where it is rapped on the screen (grids or elements) as a uniform precoat about 1/16 to 1/8 inch thick on every part of each filter element. This coating of filter cake is the filtering surface that entraps suspended particles, holding them until the filter is backwashed. After backwashing, the filter cake is then discharged and replaced with fresh D.E.
Fig. 1.1 D.E. vacuum filter. 1.3. Mechanisms of particles removal by filtration The solid removal in granular-medium filters involves several complicated processes. . Large particles contained in suspension can be easily removed through the physical straining of particles by filter grains. . Small particles in settled water cannot be removed by simple straining. Removal of those small particles and flocs in the filter bed depends on mechanisms that transport the solids through the water to the surface of the filter grains as well as retention of the solids by the medium once contact has occurred. In general, transport mechanisms include settling (pore opening acts as miniature settling basins), inertial impaction, diffusion of colloids into areas of lower concentrations and/or lower hydraulic shear and so on. Retention of solids once contact has occurred can be attributed primarily to electrostatic forces, van der Waals force, and physical adsorption. With chemical preconditioning of the water, a well-designed and operated filter should remove virtually all solids down to the submicron size. Removal begins in the top portion of the filter. As pore openings are filled by the filtered material, increased hydraulic shear sweeps particles farther into the bed. When the storage capacity of bed has thus become exhausted, the filter must be cleaned. Modern practice is to clean the filter by hydraulic backwashing. Backwash water containing the accumulated solids is disposed of and the filter returned to service.
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Many variables influence the performance of granular media filters. An understanding of filter hydraulics, media characteristics, and operating procedures is necessary for the design of effective granular medium filters. 1.4 Gravity filters and accessories To date, rapid sand filers are still major filtration technology commonly used in water treatment practice, and they are usually of the gravity type and are housed in open concrete basins. Fig. 1.2 shows a perspective of a gravity sand filter system. In general, a gravity sand filter consists of following major components together with control and monitoring facilities: . Concrete box to house filter bed and piping lines; . Filter bed that may be sand, anthracite or other types of media; . Gravel layer to support fine filter media; . Influent feeding, effluent collecting and backwashing lines; . Wash trough system designed to collect used washwater; . Underdrains system to collect the treated water; . Clearwell to store the treated water.
Fig. 1.2 Overview of a gravity sand filter (Reynolds and Richards 1996).
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The functions of the above filter components can be easily understood except wash trough and underdrains. The wash troughs are channels design for collecting wash water during backwashing of the filter system. Detail design of the trough system will be presented later. When considering the collection of water, whether it be sewer systems over a hydrologic land area or underneath an over lying holding device, the collection system is often referred to as an underdrain. In the case of water treatment, underdrains are located beneath the filter media used to remove suspended solids from the water (Fig. 1.2). The underdrain serves a multifaceted purpose. First, it supports the filter media above it; second, it serves as a means of collecting the filtered water; third it provides a means of backwashing the filter media; and, finally, it acts as a barrier so that the filter media will not pass into the next stage of the treatment process (Reynolds and Richards 1996). 1.5. Negative head and head loss 1.5.1. Negative head When a filter is clean, there is some slight loss of head, 150 to 300 mm in the sand, gravel and underdrains. As clogging occurs, the friction losses increase greatly, mostly, however, in the top of water above the sand, the column of water below acts as a draft tube, and partial vacuum results. This condition is known as negative head, and when excessive, allows air to escape from solution in the water and lodge in the sand. This is known as air binding, and it may interfere considerably with filtration. At the beginning of the backwash, a mass of air may escape before the whole surface of the sand is broken. This will allow high local velocity of the washwater and may displace the gravel. An example is shown in Fig. 1.3 in which is assumed that c is 3 m below the water level of the filter and that the total loss of bead is 2.55 m. The three tubes with their water levels at A, B and C show the pressure heads at the water level, at b, which is 0.15 m, below the sand surface, and at c, which is in the effluent pipe, respectively. With the total friction loss 2.55 m, it is reasonable to assume that 2.25 m occurs in the top 150 mm of sand. By applying Bernoullis equation between A and b, with the datum at c, by equating pressure head and potential head at b plus friction head to the total head, neglecting velocity heads, then, Pb = 3 (3 1.4) 2.25 = -0.85 m Pb is the pressure at b in meters of water. Therefore, there is a partial vacuum or negative head of 0.85 m at b.
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Fig. 1.3 Diagram illustrating negative head. 1.5.2. The clean-water head loss through a granular porous medium Several equations have been developed to describe the flow of clear water through a porous medium. Some representative equation used to compute the clean water head loss through a granular porous medium is discussed here for reference. (a) A general consideration: Bernoullis equation When a clean filter is put into operation, the floc accumulation is in the top layers of the medium, while as the time operation increases, the floc accumulation extends deeper into the filter bed. The accumulated floc causes an increase in the hydraulic head loss. The magnitude of the head loss, hf can be described by the Bernoulis equation between the point 1 on the water surface in Fig. 1.4 and point 2 at the center of the effluent line. The resulting equation is
V12 p1 V2 p + + Z1 = 2 + 2 + Z 2 + h f 2g 2g
(1.1)
in which V1 and V2 are respective velocities, p1 and p2 are respective pressures, Z1 and Z2 are respective elevation heads, is specific gravity of water, g is acceleration constant and hf is head loss .
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Fig. 1.4 A filter in operation (Reynolds and Richards 1996).
If the relative pressure is used, p1 is equal to zero, V1 is zero, while if the datum is selected so that Z2=0. Thus, Eq. 1.1 reduces to
p2 V2 = Z1 2 h f 2g (1.2)
According to Reynolds and Richards (1996), a sand filter is normally operated in the way such that the filter has 1.22 m of water over the sand, 0.76 m of sand, 0.49 m of gravel, 0.3 m depth for the underdrains, while pipes are usually deigned for a water velocity about 1.22 m/s. In this case, Z1=1.22+0.76+0.49+0.3/2=2.62 m. hence, Eq. 1.2 becomes p2 1.22 2 = 2.62 h f = 2.54 m h f 2g (1.3)
In practice, when a clean filter is put in operation, the head loss is about 0.15 to 0.46 m. As the filter run progresses, the head loss increases. It appears from Eq. 1.3 that when the head loss is 2.54 m, the relative pressure at point 2 in Fig. 1.4 is zero. Any further increase in head loss will create a negative pressure at point 2, which is highly undesirable as discuss earlier. In practice, when the head loss reaches 1.8 to 2.4 m, the sand filter must be taken out of service and is backwashed. The amount of backwash water required is from 1 to 5% of the water filtered, a typical value is the range of 2 to 3% (Reynolds and Richards (1996).
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(b) Carmen-Kozeny equation

Filter hydraulics falls into two separate categories, the actual filtration process by which the water is cleaned and the backwashing operation by which the filter is cleaned. These operations are equally important in the overall filtration process. Flow through the packed bed can be analyzed by classic hydraulic theory. Carmen modified the Darcy-Wiesbach equations for head loss in a pipe to reflect conditions in a bed of porous media of uniform size. Development of this equation is presented in many textbooks, and will not be repeated here. The resulting equation, known as the Carmen-Kozeny equation, is
2 f ' 1 e L Vs hf = e3 d p g
(1.4)
in which hf = friction of loss through bed of particles of uniform size dp, m L = depth of the filter, m e = porosity of bed Vs = superficial filtration velocity, i.e., total flow Q to the filter divided by the area of the filter, m/s g = gravitational acceleration, m/s2 dp = diameter of filter media grains, m = particle shape factor (1.0 for spheres, 0.82 for rounded sand, 0.75 for average sand, 0.73 for crushed coal and angular sand) The remaining term f is a friction related to the coefficient of drag around the particles. In the range of filter velocities (laminar flow), this can be calculated by
f ' = 150
1 e + 1.75 Re
(1.5)
in which Re = Reynolds number = w Vs d p (1.6)
w and are the density and dynamic viscosity, respectively, of the water. The units of w are kilograms per cubic meter, and the units of are Newton seconds per square meter. The shape factor ranges from 0.75 to 0.85 for most filter material. It should be noted that Eq. 1.4 is applicable only to clean filter beds. The porosity of the bed changes with the accumulation of solids. As the porosity decreases, the head loss increases. The rate at which solids accumulate in the
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filter, and therefore the rate of head-loss change, is a function of the nature of the suspension, the characteristics of the media, and filter operation. In stratified beds, the Carmen-Kozeny equation becomes
2 L 1 e Vs p hf = f' 3 e g dg
(1.7)
in which p = fraction of particles (based on mass) within adjacent sieve size dg = geometric mean diameter between sieve sizes d1 and d2, d1d 2 , m Although attempts to formulate a mathematical expression of a general nature to quantify changes in head loss with solids removal have not been very successful, some general observations can be made. To maintain a constant filtering velocity Vs, an increment in driving force must be applied to match each increment in head loss resulting from decreased porosity. Conversely, if a constant driving force is applied, the filtering velocity will diminish as the porosity decreases. In filter operations, a run is terminated when sufficient solids have accumulated to (i) use up the available driving force; (ii) cause the filtering velocity t drop below a predetermined level; or (ii) exhaust the storage capacity of the bed so that solids begin to breakthrough into the effluent. At this point, the filter must be backwashed.
(c) Rose equation

On the basis of data obtained experimentally, Rose developed an expression to estimate the head loss through filter bed having uniform, spherical or nearly spherical particles, which is so-called Rose equation in filtration field. The Rose equation is similar to the Garmen-Kozeny equation and can be used directly to hydraulic calculations in rapid sand filter. In this derivation, the drag forces are applied to the conditions of flow in filtration where it will be equal to the difference in pressure (loss of head) between two horizontal planes. The final values obtained are as follows: For homogeneously packed, mixed beds
2 1.067 1 L Vs hf = Cd 4 e dp g
(1.8)
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For stratified beds

2 1.067 LVs p hf = Cd 4 e g dg
(1.9)
and
Cd =
24 Re 24 3 Cd = + + 0.34 Re Re
if Re<1 (laminar flow) if Re>1
(1.10a) (1.10b)
in which Cd = coefficient of drag dp = diameter of filter media grains, m dg = geometric mean diameter between sieve sizes d1 and d2, d1d 2 , m e = porosity of bed L = depth of the filter, m g = gravitational acceleration, 9.81 m/s2 p = fraction of particles (based on mass) within adjacent sieve size Vs = filtering velocity, m/s, as given in Eq. 1.4 = particle shape factor (1.0 for spheres, 0.82 for rounded sand, 0.75 for average sand, 0.73 for crushed coal and angular sand) Re = Reynolds number as defined by Eq. 1.6
1.5.3. Head loss development
During filtration in a conventional downflow filter containing suspended solids is applied to the top of the filter bed. As the water passes through the filter bed, suspended solids in the water is removed by variety of removal mechanisms. With the passage of time, as materials accumulate within the intersectices of the granular medium, the head loss through the filter starts to build up beyond the initial value, as shown in Fig. 1.5.
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Fig. 1.5 Length of filter run based on head loss and effluent turbidity (Metcalf and Eddy 2003). After some period of time, the operating head loss or effluent turbidity reaches a predetermined head loss or turbidity value, and the filter must be cleaned. Under ideal conditions, the time required for the head loss buildup to reach the preselected terminal value should correspond to the time when the suspended solids in the effluent reach the pre-selected terminal value for acceptable quality. The head loss through the filter is related to the suspended solids loading, as shown in Fig. 1.6. Head loss
Suspended solids loading Fig. 1.6 Head loss versus solids retention in a filter (Adapted from Eckenfelder 2003)
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An alternative approach used to determine head loss is to relate the development of head loss to the amount of materials removed by the filter. According to Metcalf and Eddy (2003), the head loss would be computed using the expression
H t = H o + (h i ) t
i =1 n
(1.11)
in which Ht is total head loss at time t (m), Ho is total initial clear water head loss (m), and (hi)t is head loss in ith layer of the filter at time t (m). For uniform sand and anthracite, the buildup of head loss in an individual layer of the filter was found to be related to the amount of solids captured within the layer, thus the head loss in the ith layer is
(h i ) t = a (Si ) b t
(1.12)
in which a and b are constants, (Si)t is solids deposited in the ith layer at time, t 3 (mg/cm ). For a given head loss, the filtration cycle depends on the influent suspended solids and the hydraulic flow rate. In practice, for raw water with constant quality, the build-up of head loss during filtration is also related to the filtration rate (Q). Theoretically, high filtration rate results in a high head loss of the filter. Figs. 1.7 and 1.8 show the shapes of the curves of the head loss versus filtrate volume obtained at different filtration rates. From these two figures, two types of filter action can be distinguished.
Qo Head loss
Volume of filtrate Fig. 1.7 Head loss curve for surface removal of compressible solids.
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Q2 Head loss Q1<Q2 Q1
Volume of filtrate Fig. 1.8 Head loss curve for depth removal of flocculated solids.
(i) If the filter action is by surface removal of compressible solids, the head loss curve will be exponential as shown in Fig. 1.7. This type of curve is normally associated with fine grained media and low filtration rates. In practice, the filter action by microscreens and diatomaceous earth filters is subject to surface removal mechanisms. (ii) If the filter action is depth removal of flocculated suspended solids, the head loss curve will be rather flat (Fig. 1.8). This type of curve is encountered with deep granular filters as relatively high filtration rates.
Qo Head loss
Q1
Q2 Qo<Q1<Q2
Volume of filtrate Fig. 1.9. Head loss curves for combined surface and depth removal of flocculated solids.
In addition, if the filter action is by a combined mechanism of surface removal and depth removal of flocculated suspended solids, the head loss curve will be shifted to Fig. 1.9, showing that at low filtration rates, surface removal is predominant and the curve is similar to that in Fig. 1.7. At higher filtration rates,
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the solids penetrate deep within the filter, in this case, the principal action is depth removal and the head loss curves are similar to those in Fig. 1.8. Finally, it should be stressed that in rapid sand filter at the usual filtration rates, depth removal is usually the main filter action and a flat head loss curve can be expected. Surface removal will result when the feed water contains large floc and high turbidity. The top pore spaces will rapidly become clogged, resulting in relatively short filter run, while depth removal will result when the feed water contains small floc and low turbidity, resulting in deeper penetration within the filter bed and relatively long filter runs. 1.6. Filter backwash hydraulics
During the operation of a sand filter, the head loss is building up gradually accompanied with an increased effluent turbidity as shown in Fig. 1.10. When the head loss or effluent turbidity reaches the maximum allowable values (Ha and Ca), the filter must be taken out of service at time ta and go to backwashing to clean filter media. In backwashing, clean water (normally filtrate) is introduced at the filter underdrains at such a velocity as to expand the bed. The expansion frees the sand from clogging materials by causing the grains to rub against each other dislodging any materials that has been clinging onto their surfaces. The dislodged materials are then discharged into washwater troughs. Effluent turbidity
Head loss
Ha Ca
Time
ta
Fig. 1.10 Head loss and effluent turbidity vs filter run time.
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1.6.1. Backwash hydraulics
Backwashing of granular-medium filters is accomplished by reversing the flow and forcing clean water upward through the media. To clean the interior of the bed, it is necessary to expand it so that the granules are no longer in contact with each other, thus exposing all surfaces for cleaning. To hydraulically expand a porous bed, the head loss must be at least equal to the buoyant weight of the particles in the fluid. For a unit area of filter this is expressed by w h fb = L(1 e) m w in which hfb = head loss required to initiate expansion, m L = bed dept, m 1-e = fraction of the packed bed composed of medium m = density of the medium, kg/m3 w = density of the water, kg/m3 The head loss through an expanded bed is essentially unchanged because the total buoyant weight of the bed is constant. Therefore, Weight of packed bed = weight of bed fluidized, that is,
w w L(1 e) m = L fb (1 e fb ) m w w or (1.14)
(1.13)
L fb = L
(1 e) (1 e fb )
(1.15)
in which Lfb = the depth of the fluidized bed; efb = the porosity of the fluidized bed. The quantity efb is a function of the terminal settling velocity (vt) of the particles and the backwash velocity. An increase in the backwash velocity will result in a greater expansion of the bed. The expression commonly used to relate the expansion to backwash velocity and particle settling velocity is:
VB e fb = v t
0.22
(1.16)
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in which VB is the backwash velocity (backwash flow Q divided by the total filter area). The depth of the fluidized bed and the backwash velocity for a given size medium (with known vt) can now be related as follows:
L fb = L(1 e)
0.22
VB 1 v t Total expanded depth should range from 120 to 155 percent of the unexpanded depth. It had been shown that optimum expansion for hydraulic backwashing occurs at expanded porosities of 0.65 to 0.70. The principal cleaning mechanism in backwashing filters is hydrodynamic shear, which tears adhered material away from medium grains. While increased backwash velocity might increase this shear, the resulting expansion could result in several undesirable effects. Jets of water aimed at the surface of the filter and/or mechanically powered rates are often employed to create turbulence in the expanded bed during backwash. In addition to increasing the shear forces without increasing backwash velocity, these operations also promote collisions of media grains, wit the inherent abrasion assisting in the cleaning process. Another technique, air scour, is also useful in increasing shear forces in backwashing filters. Air is introduced along with the backwash water and creates additional turbulence without substantially increasing expansion. Air scour at subfluidizing water flows may provide more effective cleaning of granularmedium filters.
(1.17)
1.6.2. Working mechanisms of backwashing

Fig. 1.11 is a schematic of a complete sand filter system. To wash a filter, the influent and effluent valves (valves 1, 3 and 4) are closed, and the washwater and waste washwater valves (valves 5 and 2) must be opened.
23
Fig. 1.11 A schematic of a complete sand filter system (Metcalf and Eddy 2003). When the backwash water valve is opened, the surface wash is started at a rate of about 1.22 m3/m2 h. After about 1 minutes of surface washing, the backwash flow is initiated by gradually opening the backwash water influent valve (valve 5), and the bed is allowed to expanded to the desired height that is above the wash trough. The backwash flow should be in the range of 36.7 m3/m2 h to 49 m3/m2 h, and the bed expansion should be from 20 to 50% to suspend the bottom sand grains. The backwashing is continued until the waste backwash water appears relatively clear, and the surface wash is terminated at 1 to 2 minutes prior to the end of the backwash. Usually 3 to 10 minutes of backwash flow is required for complete washing, and the total off-line time will be up to 20 minutes.
24
Fig. 1.12 Collection troughs during backwash of a sand filter (Gallagher 1996).
Fig. 1.13 Collection of waste backwash water (Gallagher 1996). It should be stressed that after the backwashing, the initial filtered water should be wasted through valve 3(see Fig. 1.11) until the effluent turbidity is acceptable. In practice, the volume of backwash water is about 1 to 5% of the water filtered, 2 to 3% being typical. Fig. 1.12 shows backwash water entering series of collection troughs, while Fig. 1.13 shows how the waste backwash water is collected by a main collection channel. How the collection troughs and main collection channel function during the backwashing is shown in Fig. 1.14.
25
Fig. 1.14 Backwashing of a typical sand filter (Reynolds and Richards 1996). 1.7. Operation of granular medium filter
The two basic modes of operating granular medium filters are (i) constant headvariable flow and (ii) constant flow-variable head. These two modes are often modified to obtain better results.
1.7.1. Constant head-variable flow

In the constant head-variable flow mode, the water level above the filter is kept at a preselected level. Since a clean filter bed presents limited head loss, the flow rate will be quite large. As the filter becomes clogged, the head loss increases and the flow rate diminishes. When the flow reaches the design minimums, the filter must be backwashed.
26
Because very rapid flow through a clean filter results in poor efficiency, throttling the flow from the filter with a flow-control valve may be necessary. This valve is designed to provide additional head loss in the underdrain system and decrease the flow rate to an acceptable level. When the filter medium is clean, the valve operates with a small opening to produce a large supplemental head loss. As the head loss increases due to medium plugging, the valve gradually opens to decrease supplemental head loss and to maintain a more or less constant head loss across the entire system. The result is essentially a constant head-constant flow filter.
1.7.2. Constant flow-variable head

If water is introduced into a clean filter at a constant rate, an equilibrium will be established between the height of the water column and the application rate. At first, the head will be low due to the minimal head loss in the medium. As the medium becomes plugged and greater head loss occurs, the height of the water column must increase to provide the needed driving force. When the water column reaches a predetermined level, the filter is backwashed and the cycle repeats itself. Filters that operate in this way must be designed t prevent dewatering of the bed during the initial filter cycle. A minimum depth of water above the bed can be assured by elevating the entrance t the clear well above the surface of the filter media. More recent design of larger filter plants usually makes use of a combination of the above modes of operation (Fig. 1.15). A constant flow is delivered to a bank of several filters through a common header and is allowed to distribute itself according to the operating rate of each individual filter. The height of the water column is the same above all the filter units, with the cleanest filter accepting the greatest flow. When the flow rate through any one unit decreases to a predetermined level, that filter is taken off-line and backwashed. Removal of one filter results in an increase in flow to the remaining filters, with a subsequent increase in head and flow rate through each filter. When backwashing is completed, the newly cleaned filter is returned to service and will accommodate a larger flow rate. Water level will therefore drop slightly in all the filters, resulting in a decrease in flow through each filter.
27
Centra-flotm Gravity Sand Filter

1. OverFlow 2. Filter Influent 3. Coarse Media 4. Fine Media 5. Filtrate Nozzles 6. Filtrate Chamber 7. Level Controller 8. Filter Reject 9. Washbox 10. Counter-Current Washer 11. Airlift 12. Central Feed Chamber 13. Actuated Valve
Fig. 1.15 Gravity sand filter. Regardless of the operating mode, a uniform flow rate is essential to the best performance of a granular-medium filter. Any increases in flow rate must occur gradually, or the quality of the effluent will deteriorate. Large changes occurring quickly produce the greatest degree of deterioration. When automatic control valves are used to regulate filter output, they must be maintained to ensure that they produce gradual changes in the orifice opening. Otherwise, a rapid change in flow rate will occur, with significant deterioration of the effluent quality. As noted earlier, fluctuation in filtering rates occur in variable-declining-rate filtration each time a filter is taken off-line for backwashing. The magnitude of the fluctuations increases as the number of filter units in the system decreases. To prevent significant disruption in filter quality, a minimum of four filters should be used in this mode of operation.
28
1.8. Design consideration for depth filter

The ability to select and design filter technologies relies on a number of issues as discussed below.
1.8.1 Available filtration technologies

Before going to filter design, engineer must have knowledge of the types of filters that are available. The filters can be classified according to a wide variety of criteria, such as media characteristics, operation mode and so on. To date, seven types of depth filters are commonly used fro water and wastewater filtration, they are: . Conventional downflow filters; . Deep-bed downflow filters; . Deep-bed upflow continuous-backwash filters; . The pulse-bed filter; . Traveling-bed filters; . Synthetic-medium filter; . Two-stage filter.
1.8.2. Evaluation of filter performance

The performance of a filter can be evaluated from a review of the turbidity, total suspended solids, and particle removal data for depth filters.
1.8.2.1. Removal of turbidity

Based on a series of tests conducted in seven types of filters as mentioned above, Metcalf and Eddy concluded that given a high-quality filter influent with a turbidity less than 5 to 7 NTU, all of the filters tested are capable of producing an effluent with an average turbidity of 2 NTU or less; when the influent turbidity is greater than 5 to 7 NTU, chemical addition will be required with all of the filters to achieve an effluent turbidity of 2 NTU or less.
1.8.2.2. Removal of total suspended solids

There are some empirical relationships between turbidity and suspended solids as given below. For settled secondary effluent: TSS (mg/L) = 2.0 to 2.4 turbidity in NTU (1.18)
29
For filter effluent: TSS (mg/L) = 1.3 to 1.5 turbidity in NTU (1.19)
1.8.2.3. Removal of particle size

Experimental evidence shows that the particle removal rate is essentially 2 independent of the filtration rate up to about 240 l/m min in settled wastewater. Most depth filters will pass some particles with diameters up to 20 m. It should be realized that particles in the size range from 10 to 20 m are of importance with respect to disinfection because they are of sufficient size to shield bacteria.
1.8.3. Issues related to design and operation of filter system

For design engineer, the critical question associated with the selection of any granular-medium depth filter is whether it will perform as anticipated.
1.8.3.1. Influent water characteristics

Design engineer need to account for the influent water characteristics, including suspended solid concentration, particle size and its distribution.
Suspended solid and turbidity The performance of filter is strongly related to the concentration of suspended solids in influent water. This is reflected in removal efficiency, backwash frequency. Since there are relationship between suspended solid concentration and turbidity as shown in section 6.2.2., turbidity is often used as a rapid means of monitoring the filtration process. Particle size and distribution The particle size may vary significantly in different water sources. The distribution of particle size is often subject to a bimodal curve. It seems reasonable to assume that the removal mechanisms for particles with a size below 1.0 m would be different from that for particles in the size range from 10 to 100 m.
30
1.8.3.2. Selection of filtration technology

When engineer selects a filtration technology for specific application, following issues must be taken into account properly. . .
Type of filter Selection or design of filter system must be based on basic design criteria and performance specifications. Filtration rate The filtration rate affects the real size of the filters that will be required. For a given filter application, the rate of filtration is dependent upon the strength of suspended solids and the size of the filter medium. On the other hand, filtration rate also affects the buildup of head loss and effluent quality attainable. The optimum filtration rate is defined as the filtration rate, which results in the maximum volume of filtrate per unit area while achieving an acceptable effluent quality. Filtration driving force In view of driving force, filtration system can be divided into two major categories: gravity filter and pressure or vacuum filter. Compared to the gravity filter, pressure filters normally are operated at higher terminal head loss, resulting in a longer filter runs and reduced backwash requirements. Number and size of filter units Based on the peak filtration and peak plant flow rates, the number and size of filter units must be determined in the design of a depth filtration system. The number of filtration units should be kept to as less as possible to reduce the cost of piping, construction and maintenance, but it should be sufficient to assure that backwash flow rates do not become excessively large, and when one filter unit is taken out of service for backwashing, the transient loading on the remaining units will not be so high that materials contained in the filters will be dislodged. To meet redundancy requirements, a minimum of two filters will generally be required. The size of the individual filter unit should be consistent with the size of equipment available for use as underdrains, washwater troughs and surface washers. Backwash water requirement According to the operation mode, depth filters can be classified as semi-continuous and continuous operation systems. In semicontinuous operation system, the filter is operated until the effluent quality starts to deteriorate or the head loss becomes excessive, at which point the filter must be backwashed to remove accumulate solids. In general, the backwash water is pumped from a filtered
31
water clear well or obtained by gravity from an elevated storage tank. However, in continuous operation system, the filtering and cleaning phases take place simultaneously. Filter-bed configuration Filter-bed configuration is one of the most important design parameters of filter system. According to the number of filtering mediums that are used, filter-bed configuration can be roughly classified as mono-medium, dual-medium and multi-medium beds. Selection of filter medium Once the type and configuration of filter to be used has been selected, the next step is to specify the characteristics of the filtering medium. When design engineer select filter medium, the following medium criteria should be taken into account: (a) size; (b) specific gravity; (c) solubility; (d) hardness and (e) depth of the various materials used in the filter bed. If more than one medium is used, the degree of intermixing in the dual-medium and multi-medium beds depends on the density and size difference of the various media. To avoid extensively intermixing the settling of the filter mediums comprising the dualand multi-medium filters must have essentially the same settling velocity. The following relationship can be used to establish the appropriate sizes (Kawamura, 2000): d1 2 w (1.20) = d2 1 w in which d1, d2 are effective size of filter mediums, 1, 2 are density of filter mediums and w is density of water.
0.667
Kawamura S. (2000) Integrated design and operation of water treatment facilities. John Wiley, New York.
32
1.8.4. Principal variables in the design of granular medium filters

Principal variables in the design of granular medium filters are summarized in the table below for reference only.
Variable 1. required effluent quality 2. Raw water characteristics a. Suspended solids concentration b. Floc or particle size and distribution c. Floc strength d. Floc or particle charge e. Fluid properties 3. Filter-medium characteristics a. Effective size b. Uniformity coefficient c. Type, grain shape, density and composition 4. Filter-bed characteristics a. Bed depth b. Stratification c. Degree of medium intermixing d. Porosity 5. Filtration rate
6. Chemical usage 7. Allowable headloss 8. backwash requirement
Metcalf and Eddy (2003).
Significance Usually fixed regulatory requirement Affect the removal characteristics of a given filter-bed configuration. To a limited extent the listed characteristics of raw water can be controlled by the designer
Affect particle removal efficiency and head loss buildup
Porosity affects the amount of solids that can be stored within the filter. Bed depth affects initial headloss, length of run. Degree of intermixing will affect performance of filter bed Used in conjunction with variables 2, 3 and 4 to compute clear water headloss Affect actual headloss Design parameter Affect the size of filter piping and pipe gallery
33
1.8.5. Typical design data for depth filters with mono medium.
From Metcalf and Eddy (2003).
34
1.8.6. Typical design data for dual- and multi-medium depth filters
From Metcalf and Eddy (2003).
35
1.8.7. Design criteria for rapid sand filters: an example

A rapid sand filter system mainly consists of three major components, filter bed, backwashing system and underdrains to collect filtered water.
1.8.7.1. Filter bed

a. The filtration area of the bed may range from 20 to 30 m , but not less than 10 2 m. b. The dimension of the filter bed may be in the range of 2.7 to 6 m. c. The ratio of length to breadth should fall into 1.25 to 1.33. d. As pointed out earlier, at least two filters must be provided. e. Total depth (gravel and sand) may vary from 1.0 to 1.2 m (the depth of sand layer: 0.40 to 0.60 cm). f. Free board is about 30 to 45 cm. g. Depth of water above the sand bed is 1.0 to 1.5 m. h. Height of under drainage system is 45 to 60 cm. 3 2 i. Rate of filtration may vary in between 4 to 5 m /m h, or sometimes can reach 3 2 4 to 6 m /m h.
2
1.8.7.2. Backwashing system

a. Backwashing time is above 3 minutes, usually 5 minutes is used in practice. 3 2 b. Rate of backwashing may vary in between 25 and 37 m /m h. 3 2 c. Compressed air for cleaning may be introduced in a rate of 1 to 1.5 m /m min. d. Pressure of backwashing may be in between 1 to 2 atmospheres.
1.8.7.3. Underdrains
a. b. c. d. e. f. g. h. Backwashing pressure at the laterals or strainers should not be more than 1 atmosphere. The velocity of flow inside laterals should not be more than 2m/s. The spacing of laterals should be 15 to 30 cm. Maximum length of the lateral should be 60 times of its diameter. The size of the openings in the laterals is about 6 to 12 mm. The spacing of openings is 7.5 cm for an opening with a diameter of 6 mm, and 20 cm for a 12 mm diameter opening. The total area of the opening should be about 0.3 to 0.5 percent of the surface area of the filter bed. The cross sectional area of the laterals ranges in between twice the area of the openings with a diameter of 12 mm, and four times the area of opening of 6mm diameters.
36
Chapter 2. Disinfection Technology

As practiced in water treatment, disinfection refers to operations aimed at killing or rendering harmless, pathogenic microorganisms. Sterilization, the complete destruction of all living matter, is not usually the objective of disinfection. Many water-treatment processes can assist in removing pathogens, e.g. over 90% of bacteria and virus should be removed by coagulation, settling and filtration, while excess-lime softening is an effective disinfectant due to the high pH involved. However, in order to meet the USEPAs standard of one coliform per 100 ml of water and to provide protection against regrowth or bacteria, additional disinfection must be practiced.
2.1. Characteristics of an ideal disinfectant

A good disinfectant must be toxic to microorganisms at concentration well below the toxic thresholds to humans and higher animals. Additionally, it should have a fast rate to kill and should be persistent enough to prevent regrowth of organisms in the water distribution system. The characteristics for an ideal disinfectant are summarized in Table 2.1. Table 2.1 Characteristics of an ideal disinfectant (Mecalft and Eddy 2003)
37
2.2. Disinfection methods

Disinfectants include chemical agents such as the halogen group, ozone, or silver; irradiation with gamma waves or ultraviolet light; and sonification, electrocution, heating, or other physical means. In America, disinfection and chlorination have become synonymous terms, while ozonation has been practiced more widely in Europe. It appears from the industrial disinfection practice that three kinds of disinfection techniques have been widely used, and they are (a) disinfection by chemical agents; (b) disinfection by physical agents; (c) disinfection by radiation.
2.2.1. Disinfection by chemical agents

Following chemical agents have been used as disinfectants in industrial practice: . Chlorine and its compounds; . Bromine; . Ozone; . Phenol and phenolic compounds; . Alcohols; . Heavy metals and related compounds; . Dyes; . Soaps and synthetic detergents; . Quaternary ammonium compounds; . Hydrogen peroxide; . Peracetic acid; . Various alkalies; . Various acids. In water supply industry, the most commonly used disinfectants are oxidizing chemicals, such as chlorine and ozone.
2.2.2. Disinfection by physical agents

In theory, physical disinfectants may include heat, light (UV) and sound waves.
2.2.3. Disinfection by radiation

The major types of radiation are electromagnetic, acoustic and particle. Gamma rays emitted from radioisotopes (e.g. cobalt-60) have been used to disinfect or sterilize both water and wastewater because of their penetration power.
38
2.3. Mechanisms of disinfection

To date, the following five principal mechanisms have bee proposed to explain how disinfectants act on microorganisms and further kill them: . . . . . Damage to the cell wall; Alteration of cell permeability; Alteration of the colloidal nature of protoplasm; Alteration of the organisms DNA or RAN; Inhibition of enzyme activity.
Table 2.2 lists the disinfection mechanisms of three disinfection methods using chlorine, ozone and UV as disinfectants. Table 2.2 Mechanisms of disinfection using chlorine, UV and ozone (Metcalf and Eddy 2003)
39
2.4. Disinfection kinetics

Experimental evidence shows that the disinfection process is subject to a firstorder kinetics such that
dN t = kN t dt
(2.1)
in which dNt/dt represents rate of change in the concentration of organisms with time, k is inactivation rate constant with a unit of time inverse, Nt is number of organisms at time t, and t is contact or reaction time. Integrating Eq. 2.1 yields N t = N o e kt (2.2)
in which No is the initial number of organisms, say at time zero. In fact, Eq. 2.2 shows the effect of contact time, t, on survival of organisms in disinfection process. The value of inactivation rate constant k can be obtained from the following linearization of Eq. 2.2: ln N t = ln N o kt (2.3)
It should be realized that Eq. 2.2 does not reveal how the concentration of disinfectant affects the efficiency of disinfection process. In fact, Watson (1908) showed that the inactivation rate constant k in Eq. 2.2 is a function of the concentration of disinfectant (C):
k = k' C n
(2.4)
in which k is die-off constant, and n is a coefficient of dilution. Substituting Eq. 2.4 into Eq. 2.1 gives the following expression:
dNt = k ' C n N t dt Upon integration of Eq. 2.5, we have

n Nt = e k'C t No
(2.5)
(2.6)
Eq. 2.6 can be rearranged to
40
ln
Nt = k ' C n t No
(2.7)
It appears from Eq. 2.7 that both the disinfectant concentration and contact time may influence the disinfection efficiency.
2.5. Factors affecting disinfection process
The efficiency of disinfection process is strongly related to a number of operating factors.

2.5.1. Concentration of disinfectant and contact time
The effect of concentration of disinfectant and contact time on the efficiency of disinfection process can be seen in Eq. 2.6. At a given disinfectant concentration, the disinfection efficiency increases with the increase of contact time, while at the same contact time, increased disinfectant concentration leads to a more efficient disinfection. Such effects are illustrated in Fig. 2.1. -lnNt/No 0 1 2 3 4 5
C1 C2 C3
6 0 0.5 1 2 Time Fig. 2.1 Schematic presentation of the effect of disinfectant concentration and contact time on the efficiency of disinfection process. C1>C2>C3. 3 4 5 6
41
2.5.2. Intensity and nature of physical agent
When physical agents are used for the purpose of disinfection, such as heat, light (UV). Experimental evidence shows that the effectiveness of those physical agents is s function of their intensity.
2.5.3. Temperature
The effect of temperature on the efficiency of chemical disinfection is subject to a form of the vant Hoff-Arrhenius relationship: t E (T2 T1 ) ln 1 = t2 RT1T2 (2.8)
in which t1, t2 = time for given percentage kill at temperature T1 and T2 (K), respectively, E = activation energy (J/mol) and R is gas constant, 8.314 J/mol-K. It can be seen in Eq. 2.8 that increasing temperature would result in a more rapid kill, and high disinfection efficiency. Some typical values for the activation energy for various chlorine compounds at different pH values are summarized in Table 2.3. Table 2.3 Activation energy for aqueous chlorine and chloramines at normal temperatures (around 20C) Compound pH E (kJ/mol) Aqueous chlorine 7.0 34.34 8.5 26.8 9.8 50.25 10.7 62.81 Chloramines 7.0 50.25 8.5 58.63 9.5 83.75
From Metcalf and Eddy (2003)
2.5.4. Types of organisms
The resistance of organisms to different disinfectants is related to the type, nature and condition of the organisms. Theoretically, dispersed, viable, growing bacteria are often killed more easily than older cells that developed a slime coating.
42
2.6. Chlorination 2.6.1. Chlorination chemistry
Chlorine may be applied to water in gaseous form (Cl2) or as an ionized product of solids [Ca(OCl)2, NaOCl]. The reactions in water are as follows: Cl 2 + H 2 O H + + HOCl (2.9) (2.10) (2.11)
Ca (OCl) 2 Ca 2+ + 2OCl
NaOCl Na + + OCl
The hypochlorous acid (HOCl) and the hypochlorite ion (OCl-) in the above equations are further related by
HOCl H + + OCl
(2.12)
A relationship is governed primarily by pH and temperature, as shown in Fig. 2.2. The sum of HOCl and OCl- is called the free residual and is the primary disinfectant employed. HOCl is the more effective disinfectant. As indicated in Eq. 2.9, HOCl is produced on a one-to-one basis by the addition of Cl2 gas, along with a reduction of pH which limits the conversion to OCl- (Eq. 2.12). Chlorine gas can be liquefied by compression and shipped to the site in compact containers. Because it can be regasified easily and has a solubility of approximately 700 mg/L in water at pH and temperature generally found in water purification plants, this form of chlorine is usually the preferred species. The application of the hypochlorites tends to raise the pH, thus driving the reaction more toward the less effective OCl-. Commercially available calcium hypochlorite contains approximately 70 to 80% available chlorite, while NaOCl contains only 3 to 15% available chlorite. Some practical difficulty is involved in dissolving Ca(OCl)2, and both hypochlorites are more expensive on an equivalence basis than liquefied Cl2.
43
HOCl (%)
OCl- (%)
Figure 2.2 Distribution of HOCl and OCl- as a function of solution pH. There are other concentrations, however, which sometimes dictate the use of hypochlorites. Chlorines gas is a very strong oxidant that is toxic to humans. Since it is heavier than air, it spreads slowly at ground level. Therefore, extreme care must be exercised in its manufacture, shipping, and use. Accounts of evaluations of populated areas because of rail or barge accidents involving chlorine gas have become common news items. The use of hypochlorites is often mandated where large quantities of chlorine are needed in treatment plants located in highly populated areas.
2.6.2. Disinfection by chlorine
At low concentrations, chlorine probably kills microorganisms by penetrating the cell and reacting with the enzymes and protoplasm. Hypochlorous acid is more effective than the hypochlorite ion by approximately two orders of magnitude. Because the free-chlorine species is related to pH, one would expect a relationship between efficiency and pH. Empirically, it has been found that chlorine dosages must be increased to compensate for higher pH. Chlorine concentration and contact time relationship is often expressed as
44
Cntp = k in which C = concentration of chlorine, mg/L tp = time required for given percent kill, min n, k = experimental derived constants for a given system
(2.13)
Provisions may be made for application of chlorine at several points within the water-treatment process. When treating raw water of good quality, no early applications may be necessary, yet it is advisable of design a plant to allow for easy application of early applications later, should future condition s require them. Chlorine may be added the incoming flow (prechlorination) to assist with the oxidation of inorganics or to arrest biological action that may produce undesirable gases in the sludge at the bottom of clarifiers. Chlorine is frequently added just prior to filtration to keep algae from growing at the medium surface and to prevent large populations of bacteria from developing within the filter medium. Safe and effective application of chlorine requires specialized equipment and considerable care and skill on the part of the plant operation. Liquefied chlorine is delivered to water-treatment plants in tanks containing anywhere from 75 to 1000 kg. Large plants may be designed to allow use of chlorine directly from a tank car. In such cases, designer should be aware of the Interstate Commerce Commission (ICC) and Occupational Health and Safety Agency (OHSA) regulations for shipping and handling chlorine. Mixing is one of the most important aspects of the chlorination process. A sufficient velocity gradient must be applied to ensure uniform concentration of chlorine throughout the water and to break up any remaining flocculent material that might shield microorganisms from contact with the chlorine. Any of the rapid-mixing devices discussed earlier may be used for this purpose. A contact chamber must be provided to ensure adequate kill time. In water-treatment plant operations, mixing and contact operations may be accomplished by sectioning off part of the clear well. Safety considerations mandate storing of chlorine tanks in a separate room. Storage and operating rooms should not be directly connected, nor should they be directly connected to other enclosed areas of the treatment plants. All doors to these facilities should be open to the outside, and windows should be provided for visual inspection from the outside. Safety equipment, including masks with air tanks, chlorine detection devices, and emergency repair equipment, should be provided in strategic locations. Given the problem associated with chlorination, it is surprising that a search for a substitute means of disinfection has been in progress for years. However, the list
45
of candidates for replacement remains quite small, with chlorine dioxide and ozone being the leading contenders. Although both of these are effective in destroying pathogens, ozone does not leave a disinfecting residual that can guard against pathogen regrowth in the distribution system, and both are more expensive than chlorine and have practical problems associated with their use.
2.6.3. Chlorine reactions with ammonia
Chloramines can be formed by first adding a small quantity of ammonia to the water, then adding chlorine. The reactions of chlorine with ammonia are as follows:
NH 3 + HOCl NH 2 Cl (monochlora min e) + H 2 O NH 2 Cl + HOCl NHCl 2 (dichloramine) + H 2 O
NHCl 2 + HOCl NCl 3 (nitrogen trichloride) + H 2 O
(2.14) (2.15)
(2.16)
These reactions are dependent on several factors, the most important of which are pH, temperature, and reactant quantities. At pH greater than 6.5 monochloramine will be the predominant species. Since combined residuals are less effective as a disinfectant, concentration of 2 to 3 mg/L with contact time in excess of 30 min is often required. Chloramines are persistent and provide continued protection against regrowth in the distribution system.
2.6.4. Breakpoint chlorination

Being a strong oxidant, chlorine will react with almost any material that is in a reduced state. In water, this usually consists of Fe2+, Mn2+, H2S and organics. Ammonia (NH3) is sometimes present in small quantities. These oxidizable materials will consume chlorine before it has a chance to act as a disinfectant. The amount of chlorine required for this purpose must be determined experimentally, since the exact nature and quantity of oxidizable material in water is seldom known. A typical titration curve is shown in Fig. 2.3.
46
Figure 2.3 Breakpoint chlorination curve.

Fig. 2.3 shows that as chlorine is added, readily oxidizable substances, such as Fe2+, Mn2+, H2S and organic matters, react with the chlorine and reduce most of it to the chloride ion (point A in Fig. 2.3). After meeting this immediate demand, the chlorine continues to react with the ammonia to form chloramines between point A and point B. For mole ratios of chlorine to ammonia less than one, monochloramine and dichloramine will be formed (see Eqs. 2.14 and 2.15). The distribution of these two forms is governed by their rates of formation, which are dependent upon the pH and temperature. Between point B and the breakpoint, some chloramines will be converted to nitrogen trichloride (see Eq. 2.16), the remaining chloramines will be oxidized to nitrous oxide (N2O) and nitrogen (N2), and the chlorine will be reduced to the chloride ion, such that
2 NH 2Cl + HOCl N 2 + H 2O + 3HCl
(2.17)
With continued addition of chlorine, most of the chloramines will be oxidized at the breakpoint. Theoretically, the weight ratio of chlorine to ammonia nitrogen at the breakpoint is 7.6:1. Continued addition of chlorine past the breakpoint will result in a directly proportional increase in the free available chlorine (unreacted hypochlorite). The advantages of breakpoint chlorination are as follows: . Effective removal of taste and odour;
47
. . .
Effective prevention of post-growth of bacteria in the water distribution networks; Removal of color; Effective and quick germicidal action.
2.6.5. Factors affecting disinfection by chlorine

At higher concentrations, oxidation of the cell wall will destroy the organisms. Factors affecting the process are i. ii. iii. iv. v. vi. Form of chlorine pH Chlorine concentration Contact time Type of organism Temperature
2.6.6. Chlorination-associated undesirable byproducts

The products of organics oxidized by chlorine are often undesirable. Organic acids (humic, fulvic) form chlorinated hydrocarbon compounds, such as trihalomethane (THM), that are suspected of being carcinogenic. Minute quantities of phenolic compounds react with chlorine to severe taste and odor problems. The original organics must be removed before chlorination, and undesirable compounds must be removed after chlorination, or the compounds must be prevented from forming. The compounds can be removed by adsorption onto activated carbon, or their formation can be prevented by the substitution of chloramines, which do not react with organics or phenols, for free chlorine.
2.6.7. Practical methods of chlorination in Water Works

The application of chlorine may be classified according to its point of application and the purpose of chlorination.
2.6.7.1. Prechlorination
When raw water is flowing into the water works, but before any other treatment, chlorine is added in the suction pipes of raw water pumps or to the water as it enters the mixing chamber for coagulation. Prechlorination has been proved to have the advantages such that (i) It may improve coagulation; (ii) It may reduce tastes and odours caused by microbe present in the primary sedimentation tank;
48
(iii)
It may reduce the growth of algae and other microbe, and avoid microbial clogging in the subsequent sand filter.
In water treatment practice, the dosage of chlorine in prechlorination step is often such that a combined residual of 0.1 to 0.5 mg/L goes to the filters. If raw water is microbiologically polluted, the combination of prechlorination and postchlorination is necessary in order to effectively reduce the bacterial load on the filters as well as in order to produce satisfactory finished water. Refer to Section 2.6.6, chlorine may react with organics present in raw water to form organic byproducts, such as THM. In water supply, the chloroform concentration, one of the THMs, should not excess 30 g/L according to the standard set by the US-EPA. In this case, for raw water having high organic contents, the practice of prechlorination is to be avoided or is not recommended.
2.6.7.2. Post-chlorination
After filtration treatment, the filtered water must be further disinfected by chlorine in order to meet the water standard in terms of number of coliform before distribution to final users. Another purpose of the post-chlorination is to maintain a certain chlorine concentration in the distributed water, this is necessary to reduce or minimize the potential post-growth of bacteria in the distribution network.
2.6.7.3. Plain chlorination

Plain chlorination is the simplest method and is applicable for water source that has a high quality and has been long stored. Chlorine may be added to the water in the pipe leading from an impounding reservoir to the city. The doses of chlorine or its equivalent are relatively small in a range of 0.2 to 0.5 mg/l, and sometimes rising up to 1 mg/L. Normally, a contact time of 30 minutes should be provided for efficient disinfection. It should be pointed out that the plain chlorination would become increasingly unreliable as the organic content of the water increases. This is simply due the fact that some organics may react with chlorine to produce phenolic compounds, which have strong taste and odour, and the formation of THMs is another problem to be considered.
2.6.7.4. Superchlorination
Super chlorination means large doses of chlorine for quick action. This method is particularly suitable for waters with fluctuating values of chlorine demand and bacterial content. At the large dose of chlorine, phenol present in the water may be destructed through chloroxidation to yield aliphatic acid that have no taste or odour problems, thus the superchlorination is a very effective method in
49
preventing taste and odour problems. Common superchlorination does can range from 1 to 10 mg/L as chlorine and contact time may be as long as two hours, but normally not less than 20 minutes. Free chlorine residual in superchlorination process is so large that dechlorination is strongly required before the water is delivered to the public water distribution system (see section 2.6.9).
2.6.7.5. Hypo-chlorination
Hypo-chlorination is indeed the oldest method of water chlorination. The principle of this method is that when chlorinated lime, such as calcium hypochlorite [Ca(OCl)2] or sodium hypochlorire (NaOCl) is in contact with water, free chlorine is released. The chlorinated lime may deteriorate along with storage and it is very difficult to handle the above chemical reaction in practice. To date, the hypo-chlorination is rarely used in water supply practice. However, it is still very useful in the following two cases: . . Chlorine gas or chlorinator are not available; Disinfection of reservoir and swimming pool water or algae control in reservoir.
2.6.8. Minimum chlorine dosages

As discussed earlier, the efficiency of chlorination is dependent upon a number of factors, it is impossible to come out a universal rule of application with regard to the chlorine dosages. As a guideline, the following values may be used as generally required for drinking water at 20C:
pH 6-7 7-8 8-9 9-10 10-11 Min. conc of residual Cl2 (mg/L) at a min. contact time of no less than 10 min 0.2 0.2 0.4 0.8 0.8 Min. conc of residual Cl2 (mg/L) at a min. contact time of no less than 60 min 1.0 1.5 1.8 >3.0 >3.0
As compared to water supply practice, the dosages of chlorine applied to wastewater are significantly higher than those reported in the above table. According to Metcalf and Eddy (2003), some typical dosages for various chlorination applications in wastewater collection, treatment and disposal is summarized in the table below for reference.
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Application Collection Corrosion control (H2S) Odour control Slime growth control Treatment BOD reduction Digester- and Imhoff tank-foaming control Digester supernatant oxidation Filter fly control Filter-ponding control Grease removal Sludge bulking control Disposal (disinfection) Untreated wastewater (prechlorination) Primary effluent Chemical precipitation effluent Trickling filter plant effluent Activated sludge plant effluent Filtered effluent after activated sludge treatment
Dosage range, mg/l as Cl2 2-9 2-9 1-10 0.5-2 2-15 20-140 0.1-0.5 1-10 2-10 1-10 6-25 5-20 2-6 3-15 2-8 1-5
2.6.9. Dechlorination
Dechlorination is the practice of removing the total combined chlorine residual that exists after chlorination to reduce the toxic effects of chlorinated water. As mentioned in the section 2.6.6, certain organic compounds in water interfere with the chlorination process, and many of them may react with the chlorine to form toxic compounds that can gave long-term adverse effects on the beneficial uses of the waters. To minimize the effects of these potentially toxic chlorine residuals on the users of the water, it has been found necessary to dechlorinate water, especially wastewater treated with chlorine. In the following sections, two commonly used dechlorination methods are briefed.
2.6.9.1. Sulfur dioxide

Sulfur dioxide (SO2) gas successively removes free chlorine, monochloamine, dichloramine, nitrogen trichloride, and poly-n-chlor compounds as shown as follows: Reaction with chlorine:
SO 2 + H 2O HSO3 + H+ + HOCl + HSO3 Cl + SO 2 4 + 2H ____________________________________
(2.18) (2.19)
Overall:
+ SO 2 + HOCl + H 2O Cl + SO 2 4 + 3H
(2.20)
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Eq. 2.20 shows that the stoichiometric weight ratio of sulfur dioxide to chlorine is 0.9:1. However, in practice, it has been found that about 1.0 mg/l of sulfur dioxide will be required for the dechlorination of 1.0 mg/l chlorine residue as Cl2. Reactions with chloramines:
SO 2 + H 2O HSO3 + H+ + + NH 2Cl + HSO3 + H 2O Cl +SO 2 4 + NH 4 + H ___________________________________________
(2.21) (2.22)
(2.23)
Overall:
Note:
+ + SO 2 + NH 2Cl + 2H 2O Cl + SO 2 4 + NH 4 + 2H
The reactions of sulfur dioxide with chlorine and chloramines are nearly instantaneous, thus contact time is not usually a factor and contact chambers are not used. However, rapid and positive mixing at the point of application is an absolute requirement.
2.6.9.2. Activated carbon

Carbon adsorption for dechlorination provides complete removal of both combined and free residual chlorine. When activated carbon is used for dechlorination, the following reactions may occur. Reactions with chlorine:
C + 2Cl 2 + 2H 2O 4HCl + CO 2
(2.24)
Reactions with chloramines:

+ C + 2 NH 2Cl + 2H 2O CO 2 + 2 NH 4 + 2Cl
(2.25) (2.26)
C + 4 NHCl2 + 2H 2O CO 2 + 2 N 2 + 8H + + 8Cl
Granular activated carbon (GAC) in column has proved to be very effective and reliable, thus water supply engineer may consider GAC adsorption where dechlorination is required, while the engineer should be aware that this method is quite expensive. It is often recommended that the primary application of GAC for dechlorination will be in situation where high levels of organic removal are also required.
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2.6.10. A simplified flowchart of Water Works

Fig. 2.4 shows a simplified flowchart of a typical water treatment plant, in which the location of chlorine dosing is indicated.
Prechlorination
Post-chlorination
Raw water
Coagulation
Filtration Finish water Sedimentation
Figure 2.4 A simplified flowchart of Water Treatment Plant.
2.7. Ozonation
Ozone, the allotropic form of oxygen, can be produced in a high-strength electrical field from oxygen in pure form or from the ionization of clean, dry air.
O 2 O + O
O + O2 O 3 (2.27)
high voltage
Ozone is a powerful oxidant which reacts with reduced inorganic compounds and with organic material. The difference, however, is that an oxygen atom, instead of a chloride atom, is added to the organics, the end result being an environmentally acceptable compound. Once this ozone demand has been met, the ozone reacts vigorously with bacteria and viruses. It is reported to be more effective than chlorine in inactivating resistant strains of bacteria and viruses. Because ozone is chemically unstable it must be produced on-site and used immediately. Typical dosages range from 1.0 to 5.3 kg/1000 m3, with power consumption of from 10 to 20 kW h/kg of ozone. Cost of ozonation is two to three times higher than the cost of chlorination. Since no residual remains, it will be necessary to use a small amount of chlorine after ozonation to provide continued protection against regrowth in the distribution system.
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Because ozone has a low solubility in water, it must be mixed thoroughly with the water to ensure adequate contact. This can be a problem when air is used as the oxygen source, since large volumes of nitrogen must also be handled. In spite of these problems, ozone is widely used in Europe for disinfecting water containing color and organic compounds. In the United States, ozonation has been limited, ozonation will no doubt come into wider use as a result of recently adopted standards on chlorinated hydrocarbon compounds. When raw water is known to contain precursors of haloform compounds, use of ozone should be seriously considered.
2.8. Chlorine dioxide

Chlorine dioxide (ClO2) has many of the same properties as ozone. A strong oxidant which forms neither chloroforms nor chloramines, it is particularly effective in oxidizing phenolic compounds. Although highly soluble, chlorine dioxide does not react chemically with water. Contact with the atmosphere will result in loss of ClO2 by gas transfer, and the presence of light results in photooxidation. Chlorine dioxide must therefore be generated on-site, in aqueous form, usually by the chlorination of sodium chlorite at low pH. The disinfectant properties of chlorine dioxide are similar to those of chlorine, and its use results in a measurable residual. Although its principal application has been in wastewater disinfection, chlorine dioxide has had limited use in potable water treatment for oxidizing iron and manganese and for removal of taste and odor compounds. Its possible reduction to chlorate, a substance which may be toxic to humans, makes questionable its use in potable water.
2.9. Other disinfectants

Irradiation with ultraviolet light is a promising method of disinfection. Although it provides no residual, this method is effective in inactivating both bacteria and viruses. Ultraviolet light spans the wavelengths of 2000 to 3900 angstrums. The most effective band for disinfection is in the shorter range of 2000 to 3000 . Light with this wavelength can be generated with low-pressure mercury vapor lamps. A power input of 30 W/cm2 applied to thin sheets of turbidity-free water should be sufficient. A means of keeping the glass surface clear of deposits must be provided. A variety of other disinfection methods may be used in special circumstances. These include other halogens (iodine, bromine), metals (copper, silver), other oxidants (KMnO4), solification, electrical current, and gamma-ray irradiation. It is unlikely, however, that any of these processes will find widespread use in disinfecting public water supplies in the foreseeable future. A technical paper on disinfection methods is enclosed herewith.
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Chapter 3. Taste, Odor and Algae Control

3.1. Source of taste and odors in water supplies
Tastes and odors in water supplies can generally be attributed to two different causative elements: the actions of human beings upon the aquatic environment and natural forces within the environment. But these sources of tastes and odors are not unrelated: for example, odors due to biological degradation of algae and their waste products may sometimes be traced to an upstream nutrient input of human origin. This section will examine the sources directly responsible for taste and odor production. The examination of these sources is essential when attempting to identify particular tastes and odors. Surface water supplies are more commonly linked to tastes and odors than groundwater supplies among large water utilities, both proportionally and quantitatively. A 1974 taste and odor survey of 120 large water purveyors in the United States and Canada showed that while only 40 percent of the utilities with only groundwater supplies had taste and odor problems, approximately 85 percent of the utilities using surface water had to deal with taste and odor problems. In addition, utilities with partial or total surface water supplies comprised five-sixths of all utilities surveyed. This combined impact of surface water supplies makes taste and odor a prevalent problem for water treatment plants in North America.
3.2. Groundwater
Most odors and tastes in groundwater supplies are natural in origin. They are caused by bacterial actions within the groundwater aquifers or the dissolution of salts and minerals as groundwater percolates and flows through geologic deposits. Intrusion of salt or mineral-bearing waters (such as seawater) may also result in taste and odor problems. Recently, tastes and odors in some groundwaters have been attributed to human sources, such as landfill leachate. One of the most common odor problems in groundwater supplies is hydrogen sulfide (H2S). It is frequently characterized as a rotten egg odor, but at low concentration it may also impart a swampy, musty odor. The odor threshold concentration of H2S in water is less than 100 ng/l (0.0001 mg/l) and odors from waters containing 0.1-0.5 mg/l or greater are offensive. Sulfides in groundwater result from anaerobic bacterial action on organic sulfur, elemental sulfur, sulfates, and sulfite. Reduced iron and manganese may also pose taste problems in groundwater. Although tastes due to dissolved iron or manganese are not particularly noxious, they can render water unpalatable and cause problems in pipelines, water services, laundry facilities, and so on.
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High salt content, as characterized by total dissolved solids (TDS) or conductivity, can result in taste problems but does not usually result in objectionable odors. Consumers generally prefer waters with lower TDS content, although this preference is not strong. The current revival of bottled mineralbearing waters, however, may indicate that other psychophysical effects may affect taste preference. Human-induced tastes and odors in groundwater occur as a result of chemical dumping, landfill disposal, mining and agricultural activities, or industrial waste disposal. A variety of synthetic organic chemicals have been identified in groundwater supplies. Examples include trichloroethylene (TCE), which has been at highly objectionable concentrations in wells throughout the country and numerous toxic substances.
3.3. Surface water

Taste and odor problems are proportionally more common in surface waters than in groundwater largely because of the presence of algae. In addition, direct organic inputs such as autumnal leaf fall, runoff, and agricultural drainage provide ample nutrients for microorganisms that can often generate taste- and odorproducing compounds. Decaying vegetation from leaf fall and other sources may result in brown-colored, sweet-smelling water. These effects are due to suspended and dissolved glucosides, such as tannin, which originate in vegetative matter. Other suspended particulates, such as colloidal silts and clays, may render a water unpalatable if not removal in treatment.
3.4. Effects of microorganisms

The most significant natural odor problems in domestic water supplies derive from the growth and decay of algae, actinomycetes, and other microorganisms. Blue-green algae, green algae, diatoms, and flagellates are the algae groups identified as the cause of various taste and odor problems. Within these groups, important genera are Anabaena and Oscillatoria, blue-green algae frequently responsible for odor, and Ulothrix and Scenedesmus, green algae that may produces sweet, grassy odors. Asterionella is a diatom responsible for taste problems at a number of locations. Odors from algae are a complex set of phenomena, resulting from the bacterial degradation of algae, algal waste products, or the algae themselves. Geosmin is the most well-known odor-producing metabolite. It is frequently responsible for musty, earthy odors in water supplies and gives soil its characteristic earthy odor. Geosmin was first identified as a product of actinomycete cultures but has since
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been noted as a product of various blue-green algae species. The aquatic conditions necessary to stimulate algal production of taste- and odor-causing metabolites are not clearly understood. Countless metabolites produced by many algal species may give rise to taste and odor problems. Thus, it is impossible to describe the specific cause-and-effect relationship in algal taste and odor incidents without familiarity with particular species and its prevalent conditions. Actinomycetes are described as moldlike bacteria due to their method of sporulation and mycelial (filamentous) development. They are primary decomposers of microbiota and have been observed to multiply greatly following blooms of various blue-green algae. The most common genus encountered in water supplies is Streptomyces, but Micromonospora and Nocardia may also be found. In a surface water, it is difficult to attribute tastes and odors to algal growth or biological degradation of that growth since a symbiotic relationship often exists between various organisms, such as algae and actinomycetes.
3.5. Effects of inorganic and synthetic organics

Certain naturally occurring inorganic compounds can also be responsible for tastes and odors in surface waters. For example, ferrous and manganous ions (Fe2+ and Mn2+) and sulfides appear in surface water for several reasons: thermal stratification and oxygen depletion in the benthic layer of lakes and reservoirs may trigger the reduction of insoluble iron and manganese deposits, and these substances are released when the lake or reservoir overturns and mixes. The specific compounds are determined by conditions such as pH and dissolved oxygen (DO) levels. Other metal and ions may also produce tastes when present in sufficient concentrations. Table 3.1 presents the thresholds of several metals and some inorganic and synthetic organic substances. Table 3.1 Taste thresholds for selected materials. Material Taste threshold (mg/l) 2+ Zn 4-9b Cu2+ 2-5b 2+ Fe 0.04-0.1b 2+ Mn 4-30b 2-chlorophenol 0.004 2,4-chlorophenol 0.008 Phenol 0.002 Fluoride > 1.0
a b
Created by the action of chlorine onphenol Threshold detected by 5 percent of panel
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Probably the most common cause of consumer complaints about human-origin tastes and odors is chlorination in the water treatment plant. Studies have shown that the taste threshold for chlorine in water at a neutral pH is about 0.2 mg/l. The threshold increases to about 0.5 mg/l at pH 9.0. The odor threshold for certain reaction products of chlorine (such as nitrogen trichloride, NCl3) are much lower. In studies of the taste of fluoridated water, it was found that the taste threshold of sodium fluoride is about 2.4 mg/l fluoride. Unless a particular taste is recognizable as an undesirable compound, however, the consumer may not necessarily reject the water supply even with concentrations of compounds above those taste thresholds. Phenolic odors are frequently encountered in waters from industrial rivers. These reported medicinal odors are often not really phenol but actually chlorinated compounds formed by chlorinating raw water, or other synthetic organics. In addition, pesticides and organic solvents from industrial installations may cause highly objectionable tastes and odors. These compounds have caused severe problems, but with increased governmental control, they may be effectively prevented from entering water supplies.
3.6. Prevention and control of tastes and odors at source

Taste and odor prevention and control may be accomplished at the source, in the treatment plant, and, to a certain extent, in the distribution system. Undoubtedly the most satisfactory site for control in surface supplies is at the source. This generally means controlling the growth of algae and related organisms. For groundwater supplies, source control must be accomplished through watershed management. For surface reservoirs, algicides, destratification/aeration, and watershed management are sued as control methods. Purveyors using continuous draft intakes with negligible raw water storage or detention most often address taste and odor problems in-plant rather than at the source.
3.6.1. Algicides
Although a number of other compounds can be used as algicides, copper sulfate almost exclusively dominates the field of potable water treatment. Presently, copper sulfate and chlorine are the only effective algicides that satisfy all necessary legal requirements. Most other synthetic algicides involve the use of mercury or tertiary and quaternary amines. Both copper sulfate and chlorine have been used as algicides for a number of decades. As most information available in the literature is based on batch-scale laboratory work or on unique field experience, a given purveyors own field experience is probably the best guide as to the dose necessary.
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Where copper is concerned, this experience generally indicates that maintaining a residual between 0.1 and 0.2mg/l for several hours is necessary. In order to maintain this residual, ordinarily a copper dose o about 0.5mg/l is required. One of the principal problems in copper sulfate treatment is very little of the copper added is present as free copper ion; the majority settles to the bottom as a precipitate. Microbiologists agree that copper and other heavy metals kill algae and bacteria by combining with the sulfhydryl (SH) groups of many enzymes that play an important role in catalysis and energy-yielding metabolism. In order to accomplish this, copper must diffuse through the cell wall. It is most likely that only the soluble Cu(II) species directly participate in this activity. Thus the efficiency of algal control through copper sulfate addition is limited since most of the copper added is lost through precipitation and sedimentation. The fact that most of the copper added is soon converted to particulate form in most water supplies has been recognized for some time, and various methods have been employed in attempts to circumvent the problem. One of the most common is to complex the copper added with citric acid. Normally, when citric acid is used to chelate copper ion for reservoir treatment, a mixture of 2:1 copper sulfate to citric acid by weight is used. One important shortcoming with any copper treatment is the association that has been postulated between the corrosion of new iron and galvanized pipe and the presence of significant amounts of copper in the water supply. In this regard, the use of citric acid probably has a detrimental effect. When copper sulfate is used alone, most of the copper is insoluble, and filtration will usually bring the level of Cu2+ to below 0.005 mg/l. When citric acid is used, either the ligand complex must be destroyed or the bulk of the copper must be removed by adsorption prior to the waters entrance to the distribution system and home plumbing unit. If this is not accomplished, the complexed copper will move through the water treatment plant, and accelerated pitting corrosion may occur in new galvanized surfaces. Because of this corrosion problem, copper algicides should be used with caution. Chlorine is also used for the control of algal growths in water storage reservoirs, particularly treated-water reservoirs. Its usefulness, however, is impaired by difficulty in maintaining adequate residuals. Residuals are difficult to maintain because the chlorine reacts rapidly with natural aquatic humus and spontaneously decomposes in the presence of light. Nevertheless, some agencies successfully employ chlorine as the principal means of algal control in large, open reservoirs.
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3.6.2. Reservoir Destratification

Thermal stratification is a phenomenon of lakes and reservoirs that may lead to taste and odor problems. Thermal stratification results when a warm water zone overlays a colder zone; temperature and density gradients form, and mixing is prevented. In the bottom layers, anaerobic conditions may prevail, producing reduced iron, manganese, and hydrogen sulfide at troublesome concentrations. At the surface, a stressed, warm water layer may also form, where taste- and odorproducing blue-green algae flourish. Destratification neutralizes these effects: it increases the dissolved oxygen throughout the water column so that anaerobic conditions do not prevail at the lower levels, and it eliminates or reduces the temperature gradient from surface to bottom so that the warm layer of surface water does not form. In temperate zones, natural destratification occurs in the fall and spring. If lake or reservoir intakes are located in the middle depths, and if the top and bottom layers are never mixed, tastes and odors may never pose a problem. However, layers frequently mix in the spring and fall, and tastes and odors often result from reduced metal compounds, algal blooms, or other sources. Destratification may be accomplished with mechanical mixing devices, such as pumps, or forced aeration through injection of compressed air. Although mechanical mixing and forced aeration are both effective, most U.S. water supplies who artificially destratify their reservoirs employ forced aeration systems. As a result of aeration or mixing, dissolved iron, manganese, and hydrogen sulfide in the raw water are eliminated. The oxidized iron and manganese materials are insoluble and settle out. However, the major reason to install destratification facilities is for the prevention of odors from algal growths. Indications are that mixing not only reduces the total production of algal biomass, but reduces blue-green algae more effectively than green algae or diatoms. This selectivity is probably due to the destruction of the very warm layer in the top few centimeters of the lake surface where most blue-greens flourish.
3.6.3. Biological Control

It had been found that some microbial species, such as Bacillus bacteria were apparently able to oxidize metabolites of Actinomycetes, which suggested that taste and odor problems in reservoirs or lakes that have experienced blue-green algal blooms may be circumvented by seeding with Bacillus cultures. This approach was field tested at a lake, in which. Bacillus cereus was applied to the surface after an algal bloom, with appurtenant taste and odor problems, had occurred. When concentrations reached a level of 105 bacteria per milliliter, odorcausing agents were greatly diminished within several days. To date, biological control of tastes and odors is not widely accepted. It is known that Bacillus species can form spores resistant to disinfection that may pass conventional water
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treatment measures. Once restored to their vegetative form, they can produce toxins in food stuff and stimulate the production of nitrites and nitrosamines.
3.6.4. Watershed Management

Control and management of watershed areas is an obvious yet often overlooked method of preventing the development of taste and odor problems. If possible, nutrient inputs should be limited to prevent abnormal algal growth. Municipal and industrial discharges should be regulated and monitored; drainage from septic tanks in the watershed should be minimized. It is impossible to accomplish all of these goals in urban areas or large river basins, but the potentially adverse effects of point and non-point pollution sources in a water supply basin should be minimized.
3.7. Removal of tastes and odors in the water treatment plant

Because of the various combinations of inorganic and organic compounds that cause tastes and odors in water supplies, a wide variety of treatment processes are employed. However, because most known taste and odor compounds are in reduced form, some form of oxidation is usually effective. Generally, no simple treatment process is cost effective for all taste and odors that may develop, and a case-by case analysis is recommended.
3.7.1. Oxidation
The compounds most commonly employed for removal of tastes and odors via oxidation are chlorine, permanganate, ozone, and chlorine dioxide.
3.7.1.1. Chlorine
Studies of taste and odor removal with chlorination have generally shown this oxidant to be very effective with low-level inorganic odors, such as hydrogen sulfide. However, when the hydrogen sulfide levels are too high, this technique becomes very complex. Chlorination must then be preceded by air stripping, or heavy chlorination must be used followed by complete dechlorination and subsequent rechlorination. Chlorination often increases odor problems when used for odors of industrial or certain algal origin. In this case, superchlorination to a free residual is necessary, usually followed by partial dechlorination. An example of this is the reaction of phenolic compounds from industrial sources with chlorine. When low dosages of chlorine are added to water that contains phenols, chlorophenol compounds are formed and impart and objectioanl medicinal taste to the water. The taste-
61
producing intensity of the water increases up to a maximum, after which increasing clorine doses reduce and finally eliminate chlorophenolic tastes. The cost of the process make this alternative less attractive today than it has been in the past. Chlorine is most effective with the organic sulfides, disulfides, and mercaptans, whereas low-level chlorinatin may only accentuate the odor of certain more complex algal products. This limitation may be the reason why chlorination is often unsuccessful for treating odors from actinomycete blooms. In any case, laboratory tests should be evaluated prior to full-scale chlorination for odor removal.
3.7.1.2. Permanganate
Unlike chlorination, potassium permanganate (KMnO4) treatment has been especially effective for certain industrial and algal odors as used by several utilities. Permanganate is more effective at alkaline rather than neutral or acid pHs and generally requires doses of 1 to 3 mg/ and a contact time of at least 1-2 hr. As exceptions, doses as high as 10 mg/l are used without adverse effects, and sometimes contact times of 10 to 15 min are adequate. To obtain longer contact times than would be available in the treatment plant basins, many utilities add KMnO4 to raw water pipelines at their sources. If excessive permanganate is used in the oxidation process, it will pass through the downstream filters and enter the distribution system. The soluble manganese will form manganese dioxide (MnO2) and blacken the water. In addition, manganese concentration in the final treated water will increase and may exceed the levels prescribed in the secondary regulation. Generally, overdosing is controlled by settling out the excess in the sedimentation basin noted by the disappearance of permanganates characteristic pink color. However, for plants without flocculation and sedimentation steps, such as in-line or direct filtration plants, special monitoring equipment must be used to prevent permanganate from passing through the filter. Excess permanganate residual can sometimes be removed through powdered activated carbon (PAC) addition. The PAC is added after the oxidation step to avoid reducing the permanganates efficiency. PAC may, however, pass through the filters and move into the distribution system.
3.7.1.3. Ozone
Ozone is widely known for its ability to oxidize tastes and odors. An allotrope of oxygen, ozone is the strongest oxidizing agent available for water treatment and the only effective oxidant that does not increase the TDS. Ozone must be generated on-site to meet demand and when introduced into solution it shortly dissipates. Generally, ozone doses of 0.5 to 5 mg/l have been required for effective odor control.
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3.7.1.4. Chlorine Dioxide

Although not as widely used as chlorine, permanganate or ozone, chlorine dioxide is also a strong oxidizing agent. Like ozone, it must be generated on-site. To accomplish this, most manufacturers take advantage of the reaction between chlorine gas and sodium chlorite to produce chlorine dioxide. A stable, aqueous form of chlorine dioxide is also available, which eliminates the need for on-site generation but, at present, it is too costly for regular use. Chlorine dioxide was being successfully used to control both algae and phenolic odors. Chlorine dioxide is especially effective for odors resulting from phenols and chlorinated phenols. Although chlorine dioxide can be used for control of algal odors, its cost is usually prohibitive.
3.7.2. Activated Carbon Adsorption

Activated carbon has long been viewed as a most reliable last recourse for removal of tastes and odors. Activated carbon can be used in either of two forms, powdered activated carbon (PAC) or granular activated carbon (GAC). In the past, powdered activated carbon was the most widely used in normal taste and odor applications, but tastes and odors from industrial sources are increasingly requiring the use of GAC. As currently used in conventional treatment plants, PAC works inefficiently in a co-current mode, with the most saturated carbon treating the cleanest water. PACs low capital cost can offset its low efficiency, and with infrequent use can bring the overall cost far below that of equivalent GAC treatment. Powered activated carbon, in slurry form, is usually added before coagulation or immediately before the filters. When relatively low doses are required (10 mg/l or less) and filter runs are long enough, PAC is best added immediately ahead of the filters. Experience has shown that a given amount of PAC is more effective when deposited in the filter. Care must be exercised to prevent PAC from passing the filter in this case. When relatively high doses of PAC are required, or when filter runs are already short, PAC is best added ahead of the coagulation-flocculation zone so that as much may be removed by sedimentation (if conventional treatment is employed) as possible. In normal practice, the doses of PAC required range from 3 to 15 mg/l; however, doses as high as 240 mg/l have been reported. For direct or in-line filtration plants, the PAC dose that can be effectively used is probably limited to between 10 and 15 mg/l. GAC is highly selective for some of the most troublesome odor compounds, even in the presence of substantial amounts of humic substances. As a result, GAC could be expected to have a very long life (approximately 2 years) where removal of these specific compounds is concerned. In general, GAC can be used for 2 to 3 years for odor removal in certain cases.
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3.7.3. Aeration
Aeration applied in water treatment practices is not useful for taste and odor control, except for the most easily removed substances, such as sulfides or volatile organics. Hydrogen sulfide may be effectively removed from a raw water through aeration, and both surface and groundwater supplies are frequently aerated for this purpose. Ferrous ion (Fe2+) at low concentrations may be oxidized to a ferric precipitate through aeration, but at high concentrations ferrous ion requires chemical oxidant addition or long detention times. Aeration does not effectively remove manganous ion (Mn2+) in normal detention times encountered in traditional water treatment plants. Consequently, aeration is not an effective method of oxidizing materials in a raw water but may be effective at removing dissolved, odor-causing and various volatile substances.
3.8. Algae control

Control of algae in small basins may be achieved by covering them to exclude sunlight. Many reservoirs and basins are so large that this is impractical, necessitating the use of chemicals. Copper sulfate is widely used for this purpose. The amounts necessary to kill various types of algae are shown Table 3.2. Some waterworks select a standard dose, such as 1 mg/l for all types. Smaller amounts are often successful as prophylactic doses to prevent trouble. Prevention is to be preferred since killing a heavy algae growth with copper sulfate is likely to be followed by a temporary intensification of tastes and odors. Care must also be taken to prevent overdosage in bodies of water that support fish life, or many will be killed. Table 3.3 shows the lethal doses of copper sulfate for various fish. In large reservoirs the copper sulfate is applied from boats by means of sacks or screened hoppers which contain the crystals and are dragged through the water. The boat systematically follows parallel paths some 5 m apart, and wave action is depended upon for further dispersion. The amount of chemical needed may be based upon a treatment of the top 2 m of the water, although some troublesome diatoms may flourish as low as 6 to 10 m below the surface. Another method of application consists of blowing the crystals onto the water surface from a boat, using material passing a 1-mm screen. The largest of such particles penetrated as far as 5 m before completely dissolving. In waters high in alkalinity copper may be precipitated as the carbonate. Addition of sodium citrate will complex the copper as the citrate which is soluble in waters of high alkalinity. Chlorine is also useful in controlling algae. Table 3.2 shows the amounts required by various organisms. If the trouble is occurring in a small collecting basin or reservoir, the water may be chlorinated before it enters. Prechlorination at rapid filter plants may be necessary from the standpoint of algae control in the plant. The entire contents of a reservoir may also be chlorinated using a portable gas chlorinator installed near the inlet. Combination
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of chlorination and dosing with copper sulfate has reportedly given excellent results. Table 3.2 Quality of copper sulfate and chlorine required for different organisms. Organisms Odor Copper sulfate, mg/l Chlorines, mg/l Chrysophyta Asterionella Aromatic, fishy, 0.10 0.5-1.0 geranium Melosira 0.30 2.0 Synedra Earthy 1.00 1.0 Navicula 0.07 Chlorophyta Conferva 1.00 Scenedesmus 0.30 Spirogyra 0.20 Ulothrix 0.20 Volyox Fishy 0.25 0.3-1.0 Xygnema 0.70 Coelastrum 0.30 Cyanophyta Anabaena Moldy, grassy, vile 0.10 0.5-1.0 Clathrocystis Grassy, vile 0.15 0.5-1.0 Oscillaria 0.20 1.1 Aphanizomenon Moldy, grassy, vile 0.15 0.5-1.0 Protozoa Euglena 0.50 Uroglena Fishy, oily 0.05 0.3-1.0 Peridinium Fishy 2.00 Chlamydomonas 0.50 Dinobryon Aromatic, violet, 0.30 0.3-1.0 fishy Synura Cucumber, fishy, 0.10 0.3-1.0 bitter Schizomycetes Beggiatoa Putrefactive 5.00 Crenothrix Putrefactive 0.30 0.5
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Table 3.3 Fish tolerance to copper sulfate. Fish Trout Carp Suckers Catfish Pickerel Goldfish Perch Sunfish Black bass
mg/L as CuSO4 0.14 0.30 0.30 0.40 0.40 0.50 0.75 1.20 2.10
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Chapter 4. Removal of Iron and Manganese

The basic principles of iron and manganese removal are similar. However, the widely varying chemistry of these compounds makes them difficult to discuss in parallel. For that reason the chemistry will be reviewed, first for iron and then for manganese.
4.1. Chemistry of iron

For instance, the fate of iron in oxidative environments is not clearly understood. It is normally assumed that a hydroxide precipitate is formed following of oxidation of iron. However, depending on the amount of carbonate alkalinity (> 250 mg/l as CaCO3) the chemistry may be such that ferric carbonate is formed rather than the hydroxide. The more rapidly the iron is oxidized, that is, through the use of strong oxidants such as permanganate, chlorine, or ozone, the more likely the end product will be hydroxide. However, when the oxidation is conducted more slowly through the use of aeration, it then appears that the most likely end product would be carbonate in a water having a high alkalinity. Further complicating the reaction system for iron is the impact of organic complexing agents. Various humics and similar materials can act to complex the iron and to slow down the kinetics of the oxidation. As a result, frequent reports in the literature will indicate that a particular approach, which has been effective in numerous locations, was not successful at that time. This is generally due to that inability to break the complex at a sufficiently rapid rate to allow the oxidation of the iron within the treatment system. The solution to problems of this nature is to more rapidly and completely oxidize the system to ensure that the system is kept at a very high state of Eh. In a highly oxidative state, the complex can be broken and the iron can be oxidized to ferric readily. In general, the use of aeration has been shown to be totally ineffective in complex waters of this nature. To ensure the complete and effective removal of iron, it is essential that the right combination of oxidizing agents be utilized in the right pH environment to produce total oxidation to the ferric state. In terms most commonly associated with chlorination, it is essential that a condition analogous to the breakpoint be reached during oxidation. That is, the concentration of the oxidant must exceed the demand, with a slight excess of oxidant remaining. The mechanisms for oxidizing iron will be discussed in the subsequent section.
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4.2. Chemistry of manganese

The chemistry of manganese is substantially more complex than that of iron, and only a limited understanding of manganese oxidation exists. The oxidation and control of manganese is complicated by factors that range from misunderstanding of the reaction chemistry to the relatively slow kinetics and the numerous oxidation states that result from this oxidation. Manganese precipitation is also affected by the formation of organic complexes. Prior to oxidation of the manganese, these complexes must be broken down in the same manner as discussed for iron. In general, the removal of manganese is enhanced by increased pH and by increasing the Eh. Manganese removal, although substantially more complex than that of iron, is less of a problem because the frequency of occurrence of manganese in water systems is less than that for iron.
4.3. Oxidation and removal

The basic approach utilized to remove iron and manganese involves oxidation and removal of the suspended material by either sedimentation or filtration. The single most important factor in the control of iron and manganese oxidation is that sufficient detention time to allow for complete and efficient removal. Without a doubt, this is the most significant problem in most iron and manganese removal system designs. In general, the designer has a vague understanding of the reaction chemistry of iron and manganese and, therefore, is subject to making errors with respect to judgment on the detention time required for the oxidative reaction of iron and manganese. Table 4.1 shows the relative oxidative requirements to achieve precipitation of iron and manganese. The most successful approach for removal of iron and manganese involves pH adjustment; chlorination; direct filtration on a sand or anthracite filter. Fig. 4.1 shows a typical iron and manganese removal system. This approach ensures that the reaction kinetics are taken into account and that proper filtration techniques are applied to remove the oxidized iron and manganese. Observing the discharge following the oxidation step indicates that even after 5 min of detention time, the water appears to be clear and still contains a substantial amount of microscopic colloidal iron and manganese. Frequently, no observed precipitation will occur until the solution reaches the filter bed, wherein previously precipitated iron and manganese act as a catalyst for precipitating the compounds on the media. During backwash, substantial quantities of dark red and black precipitates are observed, indicating that an efficient removal of iron and manganese has occurred. It is interesting that even though the reacting bed is required to complete
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this reaction, it does not appear to have excessive buildup of material on the media, which would eventually cause clogging and failure of the filter due to high head loss. Operation studies indicate that the filter can run at high rates in excess of 5 gpm/ft2 for extended periods without excessive head loss buildup when iron concentrations are less than 0.5 mg/l. Industrial practice showed that a water with 2.4 mg/L iron would have nearly 5 mg/L of suspended solids following oxidation. These levels of suspended solids are approaching the upper limit for direct filtration. As a result, it is clear that this is a viable approach and should be considered in all iron and manganese removal plants. Table 4.1 Iron and manganese chemistry. Element Precipitate Conditions 2+ Fe Fe(OH)2 In absence of O2, CO32(pH 10) 2+ Fe FeCO3 In absence of O2, S2(pH 8, alk > 10-2 eq/L) 1. 4 Fe 2+ + 2 H + + O2 Fe 2+ Fe 3+ Fe(OH)3 4 Fe 3+ + 2OH 2. 2 Fe 2+ + Cl 2 2 Fe 3+ + 2Cl 3Fe 3+ + MnO2 + 2 H 2 O 3. 3Fe 2+ + 4 H + + MnO4 1 Mn 4+ + H 2 O 1. Mn 2+ + 2 H + + O2 2 2. Mn 2+ + Cl 2 Mn 4+ + 2Cl 3. 3Mn 2+ + 2 Mn 7 + 5Mn 4+
Mn 2+ Mn 4+ MnO2
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Chemical injection Filter Raw water Finish water
Detention tank Recycled backwash water Sludge to be discharged
Backwashing water tank
Figure 4.1 Typical iron and manganese removal system.
4.4. Design Considerations

The selection of media for the filtration unit is important. The media should have a large effective size (>1.5 mm) to reduce head loss and should have a low uniformity coefficient, e.g. coal works well for this application because lower backwashing velocities can be utilized to clean the bed due to its low specific gravity. In general, the use of greensand, a natural zeolite which allows for more rapid oxidation and removal of iron and manganese, is not recommended because of the high head loss due to its small effective size. Sand or coal will generally acclimate within 3 weeks and produce high-quality water with low iron and manganese. The greensand media is generally not justified for large water treatment systems. In small systems, the use of the greensand has some significant advantages in that it can be precharged with permanganate on an intermittent basis. In this manner, it can be utilized without continuous chemical feed for periods of time. Thus, a small unit can be conveniently charged and left without attendance for a period of several weeks. The permanganate which is adsorbed on the media acts as an absorbent of iron and manganese. When permanganate is used as the oxidizing agent, it is essential that a media such as greensand be utilized which will absorb any excess permanganate during treatment. Otherwise, excess permanganate will bleed through as a pink color and will cause substantial consumer complaints in the water supply system. In the past, the use of permanganate was not justified because chlorine is a superior
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oxidizing agent and is more easily handled by the water treatment personnel. However, the formation of trihalomethanes with chlorine and the resulting use of alternative disinfectants may encourage the use of permanganate. Table 4.2 shows the design criteria recommended for iron and manganese control. These values are considered to be conservative and can be safely used in the design of iron and manganese removal systems. Table 4.2 Design criteria for iron and manganese control. Element Units 1. Detention time 5-30 min at average flow after chemical feed 1.5 mm effective size or greater anthracite 2. Filter media about 1.21.4 Uniformity coefficient 5 gpm/ft2 to 10 gpm/ft2 Q/A Backwash Q/A 15-25 gpm/ft2 3. Backwash tank size 20 min flow at 5 times normal Q/A Another significant consideration with respect to conventional iron and manganese removal systems is the recovery of the backwash water and the disposal of the sludge. Following backwash of the filtration system, the highquality water, which has been utilized for backwashing, can be collected and settled to remove the precipitated iron and manganese. Based on field experiences, approximately, three-quarters of the backwash water can be reclaimed with a very simple control system that consists of to pumps. One pump is located at approximately three-quarters of the depth of the holding tank for the backwash water and the other is located in the sump to pump the sludge. After approximately 2 hr of settling, the first pump can be initiated and the backwash water can be returned to the system for subsequent treatment. Following this period, the sludge is removed and pumped to an appropriate holding basin or to the domestic sewer for discharge. The discharge of these materials into the sewer is a viable alternative and will act to control sulfides to some extent if they are produced in the wastewater system. Backwash reclamation reduces the volume of wastewater that must be disposed and should be considered for all systems.
4.5. Ion exchange

The use of water softeners for iron and manganese removal is fairly common. Due to the divalent nature of these compounds, they are readily removed on ion exchange materials. One of the major difficulties involved in the control of iron and manganese with this method is that, if these materials are oxidized by the dissolved oxygen in water, the media can become coated and fouled. As a result, it is very important to control the levels of dissolved oxygen in ion exchange beds
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which are used on waters containing iron and manganese levels above the drinking water standards. It is possible to restore the original ion exchange capacity by dissolving the precipitated iron and manganese from the ion exchange materials with acid. However, this will reduce the useful life of the resin.
4.6. In-situ oxidation

In-situ oxidation for iron and manganese control involves a patented process called VYREDOX. In this process, oxygen, through the use of oxygenated water, is injected around the water supply well. The concept behind this treatment method is that the Eh is raised in the vicinity of the discharge of the well. Theoretically, a more oxidative environment will change the oxidation state of these materials and stop the dissolution of iron and manganese in the area of the well. Concerns with respect to the operation of this type of process involve the potential for contamination of the aquifer system, excessive bacterial growth in the area of the well, and subsequent clogging of the aquifer. Additional concerns include the impact of corrosion on the well screen and pumping system due to the introduction of oxygenated water into the aquifer. The basic operation of the process involves the intermittent injection of oxygenated water approximately every 2 weeks for a period of 20 hours as indicated by the vendor. It is difficult to assess the true feasibility of this process at this time. It has reportedly been used extensively in Europe; however, the number of installations in the United States is limited.
4.7. Polyphosphate
Another iron and manganese control alternative, considered to be adequate only in special cases, involves the use of polyphosphates. The polyphosphate reacts to complex the iron and manganese and hold it in solution so that the consumer is not aware of its presence. Polyphosphates are dosed at approximately two times the concentration of iron and manganese. However, polyphosphates will not be suitable when the total iron and manganese concentration exceeds 1 mg/L. Table 4.3 shows the relative cost of iron and manganese removal utilizing various treatment methods.
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Table 4.3 Chemical costs for iron and manganese control. Oxidant $/mil gala Cl2b 2.10 c KMnO4 5.75 Aeration 0.50 Chelation Polyphosphated 32.00 a Concentration of Fe = 1 mg/l; Mn = 0.5 mg/l. b $0.11/1b. c $0.55/1b. d $0.50/1b.
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Chapter 5. Softening Technology

The reduction of hardness, or softening, is a process commonly practiced in water treatment. Softening may be done by the water utility at the treatment plant or by the consumer at the point of use, depending on the economics of the situation and the public desire for soft water. Generally, softening of moderately hard water (50 to 150 mg/l CaCO3 hardness) is the best left to the consumer, while harder water should be softened at the water-treatment plant. Softening processes commonly used are chemical precipitation and ion exchange, either of which may be employed at the utility-owned treatment plant. Home-use softeners are almost exclusively ion-exchange units.
5. 1. Hardness
The term hardness is used to characterize a water that does not lather well, causes a scum in the bath tub, and leaves hard, white, crusty deposits (scale) on coffee pots, tea kettles and hot water heaters. The failure to lather well and the formation of scum on bath tub is the result of the reactions of calcium and magnesium with the soap as follows:
Ca 2+ + (Soap) Ca (Soap) 2 (precipitate)
(5.1)
Hardness is defined as the sum of all polyvalent cations (in consistent units). The common units of expression are mg/l or meq/l as CaCO3. The reduction of hardness, or softening, is a process commonly practiced in water treatment. Although all polyvalent cations contribute to hardness, the predominant contributors are calcium and magnesium. Thus, the following discussion will focus on the removal of calcium and magnesium. Table 5.1 shows a rough classification of hard water for reference only. Table 5.1 A rough classification of hard water Hardness range (mg/l CaCO3) 0 75 75 100 100 300 > 300 Description Soft Moderately hard Hard Very hard
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5.1.1. Total hardness (TH)

As pointed out earlier, calcium and magnesium are predominant species, it is often convenient in performing softening calculations to define the total hardness (TH) of a water as the sum of calcium and magnesium: TH = Ca 2 + + Mg 2 + (5.2)
In which the concentrations of each element are in consistent units (mg/l or meq/l as CaCO3).
5.1.2. Carbonate hardness (CH) and noncarbonate hardness (NCH)

In practice, total hardness is often broken down into tow components: . . That associated with the HCO3- anion, called carbonate hardness (CH); That associated with other anions, called noncarbonate hardness (NCH).
In this case, total harness can be expressed as follows:
TH = CH + NCH
5.1.2.1. Carbonate hardness
(5.3)
Carbonate hardness is defined as the amount of hardness equal to the total hardness or the total alkalinity, whichever is less. Carbonate hardness is often called temporary hardness because heating the water may remove it. When the pH is less than 8.3, HCO3- is the dominant form of alkalinity, and total alkalinity is nominally taken to be equal to the concentration of HCO3-.
5.1.2.2. Noncarbonate hardness

Noncarbonate hardness is defined as the total hardness in excess of the alkalinity. If the alkalinity is equal to or greater than the total hardness, then there is no noncarbonated hardness. Noncarbonate hardness is called permanent hardness because it is not removed when water is heated.
5.2. Bar chart of water composition

Bar charts of water composition are very useful in understanding the softening process. By convention, the bar chart is constructed with cations in the upper bar and anions in the lower bar.
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. .
Example:
In the upper bar, calcium is placed first and magnesium second. Other cations follow without any specified order. The lower bar is constructed with bicarbonate placed first. Other anions follow without any specified order. Given the following analysis of a groundwater, construct a bar chart of the constituents, expressed as CaCO3. Ion Ca2+ Mg2+ Na+ HCO3SO42Clmg/l as CaCO3 258 23 35 209 51 52
Solution:
According to the definition of bar chart, the results are plotted as: TH CH NCH 258
Ca2+ HCO3SO42-
281
Mg2+ ClNa+
316
0 209 CH 260 312
5. 3. Fundamentals of lime-soda softening

The different species of hardness have different solubility limits, as shown in Table 5.2. The least soluble forms calcium carbonate and magnesium hydroxide. Chemical precipitation is accomplished by converting calcium hardness to calcium carbonate and magnesium hardness to magnesium hydroxide. This can be accomplished by the lime-soda ash process or by the caustic soda process.
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Table 5.2 Equilibrium of solid and dissolved species of common ions Mineral Formula Solubility mg/l as CaCO3 at 0 o C Ca(HCO3)2 1,620 Calcium bicarbonate Calcium carbonate CaCO3 15 Calcium chloride CaCl2 336,600 Calcium sulfate CaSO4 1,290 Ca(OH)2 Calcium hydroxide 2,390 Magnesium bicarbonate Magnesium carbonate Magnesium chloride Magnesium hydroxide Magnesium sulfate Sodium bicarbonate Sodium carbonate Sodium chloride Sodium hydroxide Sodium sulfate Mg(HCO3)2 MgCO3 MgCl2 Mg(OH)2 MgSO4 NaHCO3 Na2CO3 NaCl NaOH Na2SO4 37,100 101 362,00 17 170,000 38,700 61,400 225,000 370,000 33,600
5.3.1. Working principle of lime-soda process

In lime-soda softening, it is possible to calculate the chemical doses necessary to remove hardness. Hardness precipitation is based on the following two solubility reactions: Ca 2 + + CO 3 2 CaCO 3 Mg 2 + + 2OH Mg (OH) 2 for calcium removal for magnesium removal (5.4) (5.5)
The symbol designates the solid form, and hence indicates that the substance has been removed from the water. The objective of the lime-soda softening is to precipitate the calcium as CaCO3 and the magnesium as Mg(OH)2, which have the least solubility (Table 5.2). The precipitation of CaCO3 and Mg(OH)2 is pH-dependent. The optimum pH for CaCO3 precipitation by lime addition is from 9 to 9.5, while effective precipitation of Mg(OH)2 under water-treatment plant conditions requires a pH of
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about 11.0. Since most natural waters have a pH considerably below these values, it is often necessary to artificially raise the pH. This can be accomplished by the addition of an excess amount of lime: CaO + H 2 O Ca 2 + + 2OH (5.6)
The addition of about 1.25 meq/L is sufficient to raise the pH to 11.0. If dissolved carbon dioxide is present in water it will also react with lime.
CO 2 + CaO CaCO 3
(5.7)
Although this reaction does not reduce hardness, it does consume lime. Removal of supersaturated CO2 by aeration is often practiced to reduce lime requirements. If CO2 exceeds 10 mg/l it may be economically advantageous to remove it prior to softening.
5.3.2. Softening chemistry

The chemical processes used to soften water are a direct application of the law of mass action. Refer to the following reactions, if we increase the concentration of carbonate and/or hydroxide ion by the addition of chemicals, the reactions will be driven to the right to for precipitates of CaCO3 and Mg(OH)2.
Ca 2 + + CO 3 2 CaCO 3
Mg 2 + + 2OH Mg (OH) 2
(5.8) (5.9)
5.3.2.1. Source of hydroxide ions

The common source of hydroxide ions is calcium hydroxide, Ca(OH)2. However, water treatment practice shows that using quicklime (CaO), so-called lime, is more economical than hydrated lime, Ca(OH)2. In fact, the quicklime can be easily converted to hydrated lime at the water treatment plant by mixing CaO and water to produce s slurry of hydrated lime, which is further fed to the water for softening. Such a conversion process is industrially called slaking:
CaO + H 2 O Ca (OH ) 2 + Heat
(5.10)
5.3.2.2. Source of carbonate

When carbonate ions need to be supplied to react with Ca2+, the most common chemical used in water treatment industry is sodium carbonate (Na2CO3). Sodium carbonate is often referred to as soda ash or soda.
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5.3.3. Main softening reactions

As discussed earlier, the softening reactions indeed are regulated by controlling the pH. Firstly, any free acids are neutralized, then pH is raised to precipitate the CaCO3; if necessary, the pH is raised further to remove Mg(OH)2. Finally, if necessary, CO32- is added to precipitate the noncarbonated hardness. An industrial softening process basically involves five important reactions. In each step reaction, the chemical that needs to be added is highlighted in bold type. It should be pointed out that the following reactions here are presented sequentially, but in reality they occur simultaneously.
(i)
Neutralization of carbonic acid (H2CO3)

In order to raise the pH, any free acids that may be present in the water must be neutralized first. In real water treatment plant, carbon dioxide is the principal acid present in unpolluted, naturally occurring water. CO 2 + Ca(OH) 2 CaCO 3 + H 2 O (5.11)
Note:
Although this reaction does not reduce hardness, it does consume lime. Removal of supersaturated CO2 by aeration is often practiced to reduce lime requirements. If CO2 exceeds 10 mg/l it may be economically advantageous to remove it prior to softening.
(ii)
Precipitation of carbonate hardness due to calcium

In order to precipitate carbonate hardness due to calcium, the water pH must be raised to about 10.3. To achieve this pH value, all the bicarbonate must be converted to carbonate. Then, the carbonate may serve as the common ion for the precipitation reaction as follows:
Ca 2 + + 2HCO 3 2 + Ca(OH) 2 2CaCO 3 +2H 2 O

(iii) Precipitation of carbonate hardness due to magnesium
(5.12)
If carbonate hardness related to the presence of magnesium must be removed, more lime needs to be supplied to further increase pH to a value of about 11.0. In this case, the reactions occur in two stages. The first stage occurs in a way similar to (ii).
Mg 2 + + 2HCO 3 2 + Ca(OH) 2 MgCO 3 + CaCO 3 +2H 2 O
(5.13)
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In the above stage, the water hardness does not change because MgCO3 is soluble. With the further addition of lime, the hardness-associated with magnesium is removed such that MgCO 3 + Ca(OH) 2 Mg (OH) 2 + CaCO 3 (5.14)
(iv)
Removal of noncarbonated hardness due to calcium

If one attempts to remove noncarbonated hardness due to calcium, no further increase in pH is required. Instead one must provide additional carbonate in the form of soda ash.
Ca 2 + + Na 2 CO 3 CaCO 3 +2 Na +
(v) Removal of noncarbonated hardness due to magnesium
(5.15)
If the noncarbonated hardness due to magnesium is removed, both lime and soda must be added. The lime provides the hydroxyl ion for precipitation of the magnesium. Mg 2 + + Ca(OH) 2 Mg (OH) 2 + Ca 2 + (5.16)
If we look at the above reaction equation, the magnesium is removed, but there is no change in the water hardness because the calcium is still in solution. In order for us to remove the calcium, soda must be added. Ca 2 + + Na 2 CO 3 CaCO 3 +2 Na + (5.17)
Note that this is the same reaction as the one to remove noncarbonated hardness due to calcium as shown in stage (iv). The sodium produced in stages (iv) and (v) is soluble and, unless excessive amounts are added, is permissible in potable water.
5.3.4. Process limitations

Water treatment engineer must be aware that lime-soda softening cannot produce a water completely free of hardness, this is simply because of the solubility of CaCO3 and Mg(OH)2, the physical limitations of mixing and contact as well as lack of sufficient time for the reactions to go to completion. It appears from real water softening practice that the minimum calcium hardness that can be achieved is about 30 mg/l as CaCO3, while the minimum magnesium hardness is around 10 mg/l as CaCO3.
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5.3.5. Some empirical considerations

(i) In order to achieve reasonable removal of hardness in a reasonable time period, an excess of Ca(OH)2 beyond the stoichiometric amount usually is added. Industrial practice recommend a minimum excessive addition of 20 mg/l of Ca(OH)2 expressed as CaCO3. (ii) Magnesium is more expensive to remove than calcium, so we leave as much as magnesium in the water as possible. In practice, magnesium in excess of about 40 mg/l as CaCO3 would form scales on heat exchange elements in hot water heaters. Taking into account of the cost of magnesium removal, normally only that magnesium which is in excess of 40 mg/l as CaCO3 will be removed. Some practical considerations are listed below with regard to the removal of magnesium: . . . For magnesium removal less than 20 mg/l as CaCO3, the basic excess of lime mentioned above, that is, 20 mg/l as CaCO3 is sufficient to ensure good results. For magnesium removals between 20 and 40 mg/l as CaCO3, an excess of lime equal to the magnesium to be removed must be added. For magnesium removals greater than 40 mg/l as CaCO3, the excess lime to be added is 40 mg/L as CaCO3.
Question: In the last case, why only 40 mg/l lime as CaCO3 is added? Hints:
Industrial practice shows that addition of excess lime in amounts greater than 40 mg/l as CaCO3 does not appreciably improve the reaction kinetics of magnesium removals. (iii) It is more expensive to remove noncarbonated hardness than carbonate hardness because another chemical (soda ash) must be added to provide CO32-. Therefore, in practice, we may wish to leave as much noncarbonated hardness in the water as possible. In order for environmental engineers to easily solve practical softening problems, a flow diagram including all operation steps and practical considerations is given in Fig. 5.1. (Note: all additions shown in the diagram are as CaCO3).
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Figure 5.1. A flow diagram for solving softening problem (Davis and Cornell 1998).
5.4. Softening operations 5.4.1. General view

Softening operations consist of several steps and may be carried out in one or two stages. The operations include mixing of the chemicals with the water, flocculation to aid in precipitate growth, settling of precipitate, and stabilization. These units operate in much the same manner as the systems for coagulating and removing turbidity as discussed in the first part of this course. Design criteria for softening process, however, are slightly different and are summarized in Table 5.3.
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Table 5.3 Typical design criteria for softening system

Parameter Detention time* Velocity gradient, s-1 Flow-through velocity, ft/s Overflow rate, gal/min/ft2 *: +: ++: Mixer 5 min 700 NA NA Flocculator 30-50 min 10-100 0.15-0.45 NA Settling basin 2-4 h NA 0.15-0.45 0.85-1.71 SolidsContact basin 1-4 h + NA 4.27++
This should be confirmed by pilot-plant analysis for each water. Velocity gradient in mixer and flocculator component should be approximately the same as in flow-through units. At slurry blanket-clarifier water interface.
5.4.2. Split treatment

Water with high magnesium hardness is often softened by a process called split treatment. This process bypasses the first-stage softening unit with a part of the incoming water (see Figure 5.2).
Flow=(1-X)Q Raw water Q
Recarbonation
Disinfection
Softening
Sedimentation
Filtration Finished water, Q
Bypass Fraction bypassed=fQ
Figure 5.2 Split-flow treatment scheme. Since no magnesium is removed in the bypassed water, the initial magnesium hardness and the allowable magnesium hardness in the finished water govern the quantity that may be bypassed: f = Mg f Mg l Mg r Mg l (5.18)
in which f= fraction of the total flow bypassed.
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Mgf = magnesium concentration in the finished water, 40 mg/l as CaCO3 usually acceptable. Mgl = magnesium concentration remaining in the fraction of the water receiving first-stage treatment. The value of Mg1 is commonly taken to be 10 mg/l as CaCO3, which is the practical limit of softening. Mgr = magnesium concentration in the raw water, mg/l as CaCO3.
5.4.3. Recarbonation
After softening, pH is still very high, and reducing pH is necessary. For this purpose, recarbonation is designed for pH reduction and stabilization (Fig. 5.3). In industrial practice, recarbonation normally takes place in a closed reactor. Carbon dioxide is added under pressure and dissolved according to gas-transfer principles. Fig. 5.3 shows a typical recarbonation reactor system.
Figure 5.3 A typical submerged burner for recarbonation.
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Typical recarbonation units consists of two chambers, one for mixing the CO2 and one in which the reactions occur. Detention time in the mixing chamber should be as short as 3 to 5 min, with a total detention time of at least 20 min. Where split treatment is employed it may be necessary to follow the recarbonation unit with a settling chamber if the influent to the units still contains an excess of lime. All recarbonation units should have provisions for periodic cleaning as some precipitate will accumulate. The source of CO2 may be the exhaust from combustion of natural gas ( CH 4 + 2O 2 CO 2 + H 2 O ) or CO2 which has been purified and shipped to the plant in containers. The stoichiometric quantity of CO2 required for recarbonation must be multiplied by a factor of 2 to compensate for inefficiency of CO2 transfer from the exhaust gases if submerged burners are used. Liquified CO2 that is essentially pure (99.5%) greatly enhances the efficiency of the recarbonation process. However, storage of liquid CO2 presents a problem since it gasifies at 31C, leading to in extremely high vapor pressure. The usual procedure is to store liquid CO2 at around -20C and 2000 kPa. This necessitates strong tanks and refrigeration equipment. Large water-treatment plants often find it economically advantageous to recalcify the CaCO3 sludge, recovering both lime and carbon dioxide. CaCO 3 CaO + CO 2
Heat
(5.19)
The precipitated sludges are essentially pure CaCO3, and recalcifying should produce an excess of both the lime and the CO2 requirements for the plant. Lime kilns represent a substantial investment in capital equipment and maintenance and operation costs and are usually justified only through economies of scale.
5.5. Ion exchange softening

A wide variety of dissolved solids, including hardness, can be efficiently removed by ion exchange. The discussion here will be limited to ion exchange for softening. As practiced in water softening, ion exchange involves replacing calcium and magnesium in the water with another, nonhardness cation, usually sodium. This exchange takes place at a solids interface. Although the solid material does not directly enter into the reaction, it is a necessary and important part of the ionexchange process. Early applications of ion exchange used zeolite, a naturally
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occurring sodium alumino-silicate material sometimes called greensand. Modern applications more often use a synthetic resin coated with the desirable exchange sites and are more easily regenerated. In equal quantities, calcium and magnesium are absorbed more strongly to the medium than is sodium. As the hard water is contacted with the medium, the following generalized reaction occurs. Ca Ca (5.20) + [anion] [ R] + 2 Na + [anion] Mg Mg The reaction is virtually instantaneous and complete as long as exchange sites are available. The process is depicted graphically in Fig. 5.4. When all of exchange sites have been utilized, hardness begins to appear in the effluent. Referred to as breakthrough, this necessitates the regeneration of the medium by contacting it with a strong sodium-chloride solution. The strength of the solution overrides the selectivity of the adsorption site, and calcium and magnesium are removed and replaced by the sodium. Ca Ca + 2 NaCl (excess) 2Cl + 2 Na[ R] Mg Mg The system can again function as a softener to Eq. 5.20. The capacity and efficiency of ion-exchange vary with many factors, including type of solid medium, type of exchange material used for coating, quantity of regeneration materials, and regeneration contact time. The overall quality of the water to be softened is also an important factor. Generally, the capacity of ionexchange materials ranges from 2-10 meq/g or about 15-100 kg/m3. Regeneration is accomplished using from 80 to 160 kg of sodium chloride per cubic meter of resin in 5 to 20% solution at a flow rate of about 40 l/min m2. The effluent from the regeneration cycle will contain the hardness accumulated during the softening cycle as well as excess sodium chloride. After regeneration, the medium should be flushed with softened water to remove the excess sodium chloride. These highly mineralized waters constitute a waste stream that must be disposed of properly. Ion-exchange operations are usually conducted in enclosed structures containing the medium. Water is forced through the material under pressure at up to 0.4 m3/minm2. Single r multiple units may be used and the medium may be contained in either a fixed or a moving bed. Where continuous operation is necessary, multiple units or moving beds are used. Single-stage fixed beds can be used when (5.21)
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the flow of treated water can be interrupted for regeneration. Most treatment-plant operations are of the continuous type, while some home softeners are serviced intermittently. Ion-exchange softening at water-treatment plants is becoming more commonplace as more efficient resins are developed and as the process is better understood by design engineers. Ion-exchange produces a softener water than chemical precipitation and avoids the large quantity of sludges encountered in the limesoda process. The physical and chemical apparatus is much smaller and simpler to operate. There are several disadvantages, however. The water must be essentially free of turbidity and particulate matter or the resin will function as a filter and become plugged. Surfaces of the medium may act as an adsorbent for organic molecules and become coated. Iron and manganese precipitates can also foul the surfaces if oxidation occurs in, or prior to, the ion-exchange unit. Softening of clear groundwater should be done immediately (before aeration occurs), while surface water should be receive all necessary treatment, including filtration, prior to softening by ion exchange. The water should not be chlorinated prior to-ionexchange softening.
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Figure 5.4 Ion-exchange process. Since the resin may remove virtually 100% of the hardness, it is necessary, in industrial practice, to bypass a portion of the water and then blend in order to obtain the desired final hardness. The percentage of bypass is often calculated as: % bypass = Hardness desired 100 Hardness initial (5.22)
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Chapter 6 Membrane Technology 6.1. Briefing of membrane

A membrane is a thin layer of material that is capable of separating materials as a function of their physical and chemical properties when a driving force is applied across the membrane. This means that membrane process is a physical or chemical separation process as Fig. 6.1 shows.
Feed
Retentate
Permeate
Fig. 6.1 A schematic of membrane filtration. Membrane separation can be realized according to the pore size of membrane. Fig. 6.2 shows that only those particles with size less than the pore size of membrane can pass through the surface of membrane under driving force, while the large size particles are retained.
Fig. 6.2 Working principle of membrane filtration.
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6.2. Classification of membrane

In water supply engineering, membrane may be classified by the range of materials separated, driving forces employed, membrane materials or membrane geometric configuration. According the pore size of membrane, membrane can be classified as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO). These membrane processes are driven by pressure to make transport of water across the membrane. Classification of MF, NF, UF and RO are based on the pore size of membrane employed (Fig. 6.3). MF, UF, NF and RO processes are driven by pressure as shown in Table 6.1.
Fig. 6.3a Particle size and membrane classification.
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Fig.6.3b Overview of treatment processes and solute/particle dimensions.
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It appears from Fig. 6.3 that the pore size of membrane on the order of RO<NF<UF<MF. Table 6.1 Main membrane operations in water treatment (Aptel and Buckley 1996) Membrane Driving force Mechanism of Membrane structure operation separation Microfiltration Pressure Sieve Macropores Ultrafiltration Nanofiltration Reverse osmosis Pressure Pressure Pressure Sieve Sieve+solution diffusion and exclusion Solution diffusion and exclusion Mesopores Micropores Dense
According to membrane materials, membrane commonly used can be divided into two major categories: . Organic membrane . Inorganic or ceramic membrane On the other hand, membranes can also be classified according to their geometric configuration as follows (Fig. 6.4): . Plate and frame membrane . Spiral wound modules . Hollow fibre membrane . Tubular membrane
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Fig. 6.4 Schematic representation of the four principal membrane modules: (a) plate and frame; (b) spiral module; (c) tubular module; (d) hollow fiber (Aptel and Buckley 1996)
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6.3. Osmosis
RO is a pressure-driven membrane operation in which the solvent of the solution is transferred through a dense membrane tailored to retain salts and lowmolecular-weight solutes. In order to understand reverse osmosis, we start from normal osmosis.
6.3.1 What is Osmosis?

Osmosis is the movement of a solvent (water) through a semipermeable membrane into a solution of higher solute concentration that tends to equalize the concentrations of solute on the two sides of the membrane. To understand what it means, Fig. 6.5 is helpful:
Fig. 6.5 Osmosis of water across semipermeable membrane On the left is a beaker filled with water, and a tube has been half-submerged in the water. As expected, the water level in the tube is the same as the water level in the beaker. In the middle figure, the end of the tube has been sealed with a semipermeable membrane and the tube has been half-filled with a salty solution and submerged. Initially, the level of the salt solution and the water are equal, but over time, the water in the tube actually rises. The rise is attributed to osmotic pressure. The pressure that stops the flow is called the osmotic pressure, (refer to Fig. 6.6).
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Fig. 6.6 A schematic presentation of osmotic pressure, .
6.3.2 What is a semipermeable membrane?

A semipermeable membrane is a membrane that will pass some atoms or molecules but not others. In Fig. 6.5, the membrane allows passage of water molecules but not salt molecules. One way to understand osmotic pressure would be to think of the water molecules on both sides of the membrane. They are in constant Brownian motion. On the salty side, some of the pores get plugged with salt atoms, but on the pure-water side that does not happen. Therefore, more water passes from the pure-water side to the salty side, as there are more pores on the pure-water side for the water molecules to pass through. The water on the salty side rises until one of two things occurs: . The salt concentration becomes the same on both sides of the membrane (which isn't going to happen in this case since there is pure water on one side and salty water on the other). . The water pressure rises as the height of the column of salty water rises, until it is equal to the osmotic pressure. At that point, osmosis will stop (Fig. 6.6).
6.3.3 How to compute osmotic pressure ()?

If there are solute molecules only in one side of the system, then the pressure that stops the flow is called the osmotic pressure (). Whenever a solute movement is blocked by a wall it will transfer momentum to it and, therefore, generate pressure
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on it. Since the velocity is the same as that of a free molecule, the pressure will be the same as the pressure of an ideal gas of the same molecular concentration. Hence, the osmotic pressure can be calculated by van't Hoff formula: (6.1) = CRT in which C is the molar concentration of the solutes, which equals the mass concentration divided by the molecular weight of the solutes, R is the gas constant (0.082 atm L/mol K), and T is the absolute temperature in K (273 + C). It should be pointed out that not all solutes in water exert high osmotic pressures. Higher-molecular-weigh solutes produce less osmotic pressure than do smallmolecular-weight compounds. At the extreme, colloidal particles may be considered as very large solutes with very high molecular weights. Osmotic pressure can be neglected in calculating the permeate flux of MF and UF membrane since the larger colloidal and macromolecular materials rejected by these membranes exert very little osmotic pressure and the smaller-molecular weight solutes pass through these membranes.
6.4 Reverse Osmosis (RO)

In reverse osmosis, the idea is to use the membrane to act like an extremely fine filter to create drinkable water from salty water. The salty water is put on one side of the membrane and pressure is applied to stop, and then reverse the osmotic process as shown in Fig. 6.7. If a concentrated saline solution is separated from pure water by a RO membrane, the difference in chemical potential tends to promote the diffusion of water from the diluted compartment to the concentrated compartment in order to equalize the concentrations. At equilibrium, the difference in the levels between the two compartments corresponds to the osmotic pressure of the saline solution as described above. To produce pure water from a saline solution, the osmotic pressure of the solution must be overcome by external pressure applied (P). When two water volumes are separated by a semi-permeable membrane, water will flow from the side of low solute concentration to the side of high solute concentration. The flow may be reversed by applying external pressure on the side of higher concentration (Fig. 6.7). This is called reverse osmosis. (RO) Based on the requirement of overcoming the osmotic pressure of the feedwater, the theoretical energy required to desalinate 1 m3 of seawater at 27C is on the order of 0.7 kWh. In practice, the applied pressure is 2 to 3 times the osmotic pressure. Assuming only 25% recovery and taking account of mechanical losses etc, the actual energy required to desalinate 1 m3 of seawater is approximately 10 times the theoretical value. Beware that this is still substantially less than the approximately 10 kWh/m3 required for competing distillation processes.
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P>
Osmotic pressure
Reverse osmosis
Fig. 6.7 Working principle of RO system.
6.5. Nanofiltration (NF)

NF often called low-pressure reverse osmosis or membrane softening, lies between RO and ultrafiltration in terms of selectivity of the membrane that is designed for removal of multivalent ions (calcium and magnesium) in softening operations. In NF, the monovalent ions are poorly rejected by the membrane. This explains why NF leads to an osmotic pressure that is much lower than that experienced with RO. As a consequence, the operating pressure used in NF is much lower than in OR, typically 0.5 to 1.5 MPa is commonly applied.
6.6. Ultrafiltration (UF)

In water treatment, UF membranes can be defined as a clarification and disinfection membrane operation. UF membranes are porous and allow only the coarsest solutes (macromolecules) to be rejected and nearly all types of microorganisms as virus and bacteria, or all types of particles. Since the lowmolecular-weight solutes are not retained by UF, the osmotic pressure is very low and in practice can be neglected. The operating pressure of UF is normally as low as 50 to 500 kPa. Full scale operation practice shows that almost all UF systems are operated in the mode of tangential or so-called cross flow. In UF module, the flow of the process solution is tangential to the membrane surface, minimizing concentration polarization. Tangential flow systems use a recirculating system to sweep retained materials back to the sample reservoir. The recirculation feature reduces solute adsorption by limiting the contact time between individual particles or molecules
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and the ultrafiltration membrane. The low fluid pressure associated with tangential flow systems enhances the recovery of sensitive substances.
6.7. Microfiltration (MF)

A major difference between MF and UF is membrane pore size; those of MF are 0.1 m or greater. Microfiltration is specifically the filtration of substances that range in size from 0.1 m to 10 m. Microfiltration is often used to refer to the removal of microbes, such as in cold sterilization since bacteria, fungal spores, yeast and some viruses fall into this size range. Filters with a 0.2 m or smaller pore size rating are frequently regarded as being able to sterilize solutions. Generally this is only approximately true and then only if the filter itself is sterilized before use. Filters with later pore size rating may be used to clarify samples without necessarily sterilizing them. The primary allocation for this operation is particulate removal (clarification). Applied pressures are similar to UF.
6.8. Membrane element, module and bank

The smallest operation unit in a membrane system is called membrane element that is a basic membrane unit for placement of defined surface of membrane and which is prepared for installation in the larger component of membrane system. A single membrane element consists of . membrane . construction element that holds pressure and ensures support of membrane . feed solution socket . concentrate outlet and permeate outlet According to geometry of membrane, the membrane element can be classified into four types as follows (Fig. 6.8): . plate element . tube element . element with hollow fibers . spiral-wound filtration element A membrane module consists of a number of membrane elements, while assembly of membrane modules is called as membrane bank as illustrated in Fig. 6.9. In practice, the number of membrane elements or modules can be increased or reduced easily according to the requirement of water production, thereby membrane technology is highly flexible process.
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Tube element
Spiral-wound element
Element with hollow fibers Fig. 6.8 Schematic of typical membrane elements.
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Bank of modules
Module
Membrane element
Membrane cartridge
Fig. 6.9 Membrane elements, modules and banks.
6.9. Mass transport and permeate flux

The capital and operating costs of membrane systems are directly as a function of the membrane permeate flux. Where it is possible to move more water across a unit area of membrane per unit time, less membrane area will be required to provide for the design flow. Thus, permeate flux and the factors influencing it are central considerations in determining membrane performance and cost.
6.9.1. Resistance of membrane filtration

Fig. 6.10 shows a schematic presentation of filtration resistance in a pressuredriven membrane system. (i) Polarization layer resistance (Rp) Polarization layer resistance is caused by concentration gradient from bulk to membrane surface.
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(ii) External fouling resistance (Ref) As the membrane filtration is proceeding, particulate materials will start to deposit on the surface of membrane. Consequently, a cake layer forms on the membrane surface. (iii) Internal resistance (Rif) Internal resistance is mainly due to materials absorbed into the membrane pores, and clogging of membrane pores will lead to a drop in filtration driving force. (iv) Intrinsic membrane resistance (Rm) Intrinsic membrane resistance is caused by the fabricating materials of membrane or so called, membrane back-bone materials. The sum of the above four resistances give the total resistance for membrane filtration, that is, R t = R p + R ef + R if + R m (6.2)
The respective Rt in RO, NF, UF and MF systems is about 1010, 108, 107 and 106 m-1, indicating that RO system has the highest filtration resistance.
6.9.2 Transmembrane pressure

The permeate flux J could be expressed as follows:
J=
P Rt
(6.3)
in which P is the pressure drop across the membrane (transmembrane pressure drop or TMP), and is viscosity of the permeate. In membrane operation, P is a key design and further operating parameter which acts as a driving force of membrane filtration as discussed earlier. Approximate values of P are 800 to 8000 kPa for RO, 350-1000 for NF, 50-700 for UF and 30-300 for MF.
6.10 Membrane fouling

The accumulation of materials in the membrane, e.g. by adsorption to pore walls, results in an increase in the resistance of the membrane over time. Consequently, permeate flux would decline significantly after membrane fouling occurs. Membrane fouling can be attributed to the following causes:
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. Precipitation of less soluble inorganic species (Scaling) . Adsorption of organic substances (Organic fouling) . Attachment and growth of microbe on membrane surface (Bio-fouling) Following strategies are helpful/useful in reducing or controlling membrane fouling: . Control of operation conditions: low pressure, high turbulence and intermittent filtration . Backwash with permeate, air or both . Chemical cleaning . Use membrane with improved surface properties: more hydrophilic, smooth surface or negatively charged or neutral membrane surface Biofouling is a very serous problem encountered in the membrane operation practice. Fig. 6.10 is SEM micrograph of biofilm developed on the surface of RO membrane. Control membrane biofouling is necessary not only during continuous plant operation, but also during extended periods of plant inactivity due to system repair or modifications. Especially, biofouling must be controlled when newly manufactured membrane modules are packaged and stored for long periods prior to shipping or installation. Some control and prevention strategies of membrane fouling are summarized in Table 6.2 for reference.
Fig. 6.10 SEM photo of biofilm development of the surface of RO membrane (Ridgway and Flemming 1996).
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Table 6.2 Potential points of intervention in the membrane biofouling process (Ridgeay and Flemming 1996). Intervention point or process Approach or strategy
Bacterial adhesion Addition to feed-water of biodispersants, surfactants, chaotropic agents, chelating agents, biocides and other chemical compounds or formulations that interfere with bacterial attachment and colonization processes Introduction of nonmetabolizable nutrient analogs, nutrient limitation (starvation), application of antimicrobial agents, biocides, electrical fields, or other conditions or substances that retard biofilm growth. Use of physicochemical processes such as continuous microfiltration, affinity columns, bioflocculants etc. that physically remove or precipitate bacteria from the feed-water. Treatment of biofilm with physicochemical cleaning agents, chelating agents, chaotropic agents, ultrasound, dispersants, electrical fields, air backwashes (in the case of MF), or other agents/conditions that tend to disrupt biofilm integrity. Addition of physicochemical agents/conditions or application of processes which enhance biofilm permeability to water and solute molecules; avoids need to remove biofilm. Design and synthesis of new membrane polymers with low affinity surfaces, surfaces that can be regenerated in situ, membranes with delayed-release antimetabolites or biocides incorporated, chlorine-resistant membrane etc.
Growth and cell division
Feed-water bacteria
Biofilm structure
Biofilm permeation
Membrane polymer
To date, biofouling control strategies fall into four general categories: . Selection and optimization of effective feed water pretreatment methods . Optimization of effective membrane cleaning methods . Optimization of system operating pressure and recovery . Use membrane with improved surface properties: more hydrophilic, smooth surface or negatively charged neutral membrane surface
. Use of antibiocides and antiscalants
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6.11 Applications of membrane in water supply

6.11.1 Process design: a briefing
(i) Transmembrane pressure a. RO module The transmembrane pressure (Ptm) is defined as the hydraulic pressure differential from the feed side to the permeate side. Fig. 6.11 shows a schematic of a typical RO module.
RO module
Feed
Pp, p Pf, f
Permeate
Valve
Concentrate
Fig. 6.11 Schematic of RO module.
The net pressure(Pfn) acting on the membrane in the feed side:

Pfn = Pf - f (6.4)
In which Pf is the pressure in the feed side provided by the feed pump and further adjusted by the valve set in the concentrate line (Fig. 6.11), and the osmotic pressure in the feed side is f.
The net pressure (Ppn) acting on the membrane in the permeate side:
Ppn=Pp- p (6.5)
in which Pp is pressure in the permeate side of membrane module and p the osmotic pressure in the permeate side. Thus, the transmembrane pressure P can be estimated as
104
P = Pfn - Ppn=(Pf f)-(Pp- p) b. NF or UF or MF module
(6.6)
The osmotic pressures are negligible in NF, UF and MF membrane systems (Fig. 6.12), thus Eq. 6.6 is reduced to P = Pfn - Ppn=Pf - Pp (6.7)
Feed
Pf
Pp
Permeate
Valve
Concentrate
Fig. 6.12 A schematic presentation of NF or UF or MF (ii) Production flow of a membrane system Application of transmembrane pressure produces a filtrate or permeate. The total production flow (Qp) of a membrane system can be calculated by Q p = J tm A (6.8)
in which Qp is system permeate flow rate, L/h, Jtm is transmembrane flux, L/h m2, and A is total effective membrane surface area, m2. In practice, the transmembrane flux is related to the pressures by Jtm = K P (6.9)
in which K is mass transfer coefficient for a unit area of membrane (L/m2-h-kPa). The transmembrane flux is a function of several variables specific to the membrane, quality of the feed water, and system operating parameters. For most
105
MF systems, transmembrane flux rates ranges from 80 to 200 L/m2 h. The total effective membrane surface area is calculated from the effective membrane area per module and the number of modules. The area for full-scale plant MF modules currently ranges from 1 to 15 m2. However, modules with membrane areas as high as 50 m2 are currently being considered by the MF manufacturing industry. (iii) The conversion yield The conversion yield is the ratio between the flow of permeate and the feed flow at the inlet of the membrane module:
Y=
Permeat flow Feed flow
(6.10)
For a given membrane module, it is advantageous to work at a high conversion yield, this indeed limits the capital cost for the pump and the pipes and also the energy consumed by the circulation of the concentrate. In the classical mode of operation of plate-and frame or tubular modules, pressure-driven membranes are operated under conditions of high cross-flow velocities to limit the polarization phenomena and/or thickness of the filtration cake. This leads to the choice of a low conversion in a single element and the necessity to combine several elements in series to obtain reasonable conversion at relatively low energy consumption. (iv) Feed and discharge pumps As shown in Figs. 6.11 and 6.12, a feed pump is designed to ensures pressurization of the feed and the circulation along the membrane, i.e. the feed pump offers major driving force for membrane filtration, while the discharge pump is used to draw off the permeate from the membrane module (refer to Figs. 6.11 and 6.12). (v) Valve A valve placed on the retentate (or concentrate) line can be used to maintain or adjust the pressure inside the membrane module.
6.11.2 Application of RO process

The RO system can be effectively used as water treatment option for following applications:

Boiler feed water Bottled water manufacturing
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Water for dilution in chemical process industry High purity water for manufacturing Water for dilution in food and beverage industry Drinking water production from ground and surface water Recovery of 2nd effluent from municipal wastewater treatment plant Seawater desalination
It should be realized that theoretically RO is not designed for solid particles removal, and he pretreatment is extremely important in RO system, i.e. the influent to a RO plant is already CLEAN. Thus, RO is used only to remove the ions, molecules and molecular aggregates.
6.11.3. Application of NF
Nanofiltration is ideal for removing hardness forming molecules, which are salts of Ca2+ and Mg2+ from water source. Compared to conventional softening processes, softening by NF has some advantages. Firstly, nanofiltration is a better method than conventional water softeners for producing purified soft water, as nanofiltration does not alter the composition of dissolved salts in water. Secondly, since no regeneration is required, nanofiltration is a clean and hassle free operation.
6.11.4. Application of UF
UF has been commonly used to produce ultrapure water for electronic industry or municipal drinking water. The UF process may have a number of advantages over conventional clarification and filtration operations, and new ground may be broken in the field of water purification, dominated until now by chemical coagulation and depth-filtration technology. The main advantages of low-pressure UF membrane processes when they are compared with conventional clarification and disinfection processes are as follows: . No need for chemicals (coagulants, flocculants, disinfectants, pH adjustment) . Size-exclusion filtration as opposed to media depth filtration . Good and constant quality of the treated water in terms of particle and microbial removal, regardless of the raw feed water quality . Process and plant compactness . Simple automation Many industries require ultra pure water for its manufacturing process, and UF can be used to produce ultrapure water for different industrial sectors, such as
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Pharmaceutical and Biotech Industry: for tissue culture buffer solution analytical solvents formulation aids, drugs and intravenous solutions for rinsing of equipment Fisheries: for removal of water borne microorganisms which adversly affect the fish during cultivation Power Generation: for colloidal silica removal. The colloidal silica form scaling on the turbine blades and in the pipelines which affects the overall efficiency of power generation. Polymer Industry: for removal of all suspended and colloidal matters that interfere with the polymerisation reaction. Semiconductors and Electronics Industry: for washing of the printed circuit boards (PCBs) and microchips.
Pretreatment process of water before RO is very important for membrane life and the economical operation of the RO plant. Conventional methods flowed by microfiltration are usually used to produce a feed water of very low turbidity. A number of cases are reported in which UF was used ahead of RO in the treatment of wastewater streams, and cases in which UF pretreatment was used before RO treatment of seawater. The replacement of RO membrane is prohibitively expensive, and the view is held that overdesign of the conventional stage of pretreatment is a better alternative to regular replacement of RO membranes. Pollutants in raw water include suspended solids (e.g. silt, clay, organic material, size range>1 m), microorganisms and marine organisms, soluble organic material (oil, fatty acids, polysaccharides, lipids), colloids (0.2 to 1. 0 m), and, sparingly, soluble inorganic matter, most of which can be ultrafiltered. The clarity of the feed water to the RO plant depends on the type of RO membrane and module used. Hollow fine-fiber module that produces permeate of the highest quality also require a high-quality feed water, whereas the quality requirements for feed to spiral-wrap modules are less stringent. The important features of UF pretreatment can be summarized as follows: . Continuous and easily automated operation . No breakthrough as occurs in granular media filtration
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. Good downstream protection of RO membranes . No addition of chemicals . Simple chemical shock disinfection treatment . Compact design of pretreatment equipment
6.11.5. Application of MF
The primary impetus for the more widespread use of MF has been the increasingly more stringent requirements for better removal of particles and microorganisms from drinking water supplies (Fig. 6.13a). Additionally, there is a growing emphasis on limiting the concentrations and number of chemicals that are applied during water treatment. In some MF applications for particle and microbial removal, no chemicals are added during the water production cycle of the process. In others, coagulation or adsorption processes are employed as pretreatment to MF. Because of many potential advantages of MF as compared to conventional water treatment, some full scale applications are in operation. A typical treatment train for this application consists simply of prescreening, MF and disinfection. Another application of MF process is for removal of natural or synthetic organic matter. In its normal operation, MF removes little or no organic matter, however, when pretreatment is applied, increased removals of organic matter as well as retardation of membrane fouling can be realized. A treatment train would consist of prescreening, pretreatment, MF and disinfection. The two most common pretreatments are metal coagulation and powered activated carbon (PAC) addition (Fig. 6.13b). Two other applications of MF are to use MF as a pretreatment to RO or NF (Figs. 6.13c and d). Both RO and NF have been traditionally employed on groundwaters for desalting or hardness removal. However, with the increasing emphasis on water conservation, RO is being used by an ever greater number of utilities to treat wastewater for reuse. Consequently, MF has been studied extensively as a pretreatment for RO for water reuse applications.
a:
Raw water
To distribute
Prescreen
MF
Clearwell
109
b:
Coagulant or PAC addition
Raw water
To distribute
Prescreen
MF
Clearwell
c:
Raw water
Prescreen
MF
RO
Clearwell
d:
Raw water
Prescreen
MF
NF
Clearwell
Fig. 6.13 Schematic of various applications of MF. a: MF for water treatment; b: organics removal by MF pretreatment with coagulation or PAC; c: MF as pretreatment to RO; d: MF as pretreatment to NF.
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Main Sources of Information:

Viessman W, Hammer MJ (2004) Water supply and pollution control. 7th edition, Addison-Wesley, California. Davis ML, Cornell DA (1998) Introduction to environmental engineering. McGraw-Hill, NY. Eckenfelder WW (2000) Industrial water pollution control. McGraw-Hill, NY. Metcalf and Eddy (2003) Wastewater treatment Engineering. 6th edition, McGraw-Hill, NY. Reynolds TD, Richards PA (1996) Unit operations and processes in environmental engineering. 2nd edition, PWS Publishing Company, New York. Sincero AP, Sincero GA (2000) Physico-chemical treatment of water and wastewater. CRC Press, New York Some information from internet is also included.
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EN3502/CV4551-Water Supply Engineering

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

Chapter 1 Conventional Filtration Technology

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

Fig. 1.4 A filter in operation (Reynolds and Richards 1996).

EN3502-CV4551-Water Supply Engineering/Liu Yu

(b) Carmen-Kozeny equation

in which Re = Reynolds number = w Vs d p (1.6)

EN3502-CV4551-Water Supply Engineering/Liu Yu

(c) Rose equation

EN3502-CV4551-Water Supply Engineering/Liu Yu

For stratified beds

if Re<1 (laminar flow) if Re>1

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

Q2 Head loss Q1<Q2 Q1

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.6.1. Backwash hydraulics

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.6.2. Working mechanisms of backwashing

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.7.1. Constant head-variable flow

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.7.2. Constant flow-variable head

EN3502-CV4551-Water Supply Engineering/Liu Yu

Centra-flotm Gravity Sand Filter

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1.8. Design consideration for depth filter

1.8.1 Available filtration technologies

1.8.2. Evaluation of filter performance

1.8.2.1. Removal of turbidity

1.8.2.2. Removal of total suspended solids

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.8.2.3. Removal of particle size

1.8.3. Issues related to design and operation of filter system

1.8.3.1. Influent water characteristics

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.8.3.2. Selection of filtration technology

EN3502-CV4551-Water Supply Engineering/Liu Yu

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.8.4. Principal variables in the design of granular medium filters

EN3502-CV4551-Water Supply Engineering/Liu Yu

From Metcalf and Eddy (2003).

EN3502-CV4551-Water Supply Engineering/Liu Yu

From Metcalf and Eddy (2003).

EN3502-CV4551-Water Supply Engineering/Liu Yu

1.8.7. Design criteria for rapid sand filters: an example

1.8.7.1. Filter bed

1.8.7.2. Backwashing system