Utilities in Process Plants 1 Chapter 1 UTILITIES IN PROCESS PLANTS 11. RELATION OF CHEMICAL ENGINEERING TO BASIC SCIENCES Chemical Engineering is concerned with commercial scale production of chemicals. The study of chemical engineering requires sound knowledge of basic sciences such as physical chemistry, physics, organic chemistry, inorganic chemistry and electrical sciences. It is so because commercial production of chemicals is much more complicated than laboratory methods; and too many constraints and limitations have to be met. Consider an example of manufacture of phenol from cumene. The relation can be : expressed by following block diagram. 50°C, pH 85-105 55-6500 Aqueous oa Cumene—] peupification |? Hvar —| — Phenol + Acetone mixture Peroxide 1 cc aq. H;SO, Ae (10-25%) Phycial Properties of Reactants and Products ‘Camene Phenol ‘Acetone MW. 120 or j 38 aE Sp. Density 086 1.07 1 079 MP. 97°C 42°C 95°C BP. L 152°C I 181°C l 56°C, ‘Chemical reactions are: CH, CH, aac sls cH, iG e O— OH CH @ eae eos ‘Cumene Hydro peroxide EmulsionProcess Plant Utilities (b) Hydrolysis: OH Cumene hydro peroxide + aq. H,S0,—> + (CH), CO Acetone Phenol For the laboratory manufacture, the whole process appears to be very simple. However, in order to produce 50-100 Tons/day of phenol, a medium scale complex chemical plant will be wveded with an investment of the order of Rs. 300 crores or more. Why is it so that for large scale, the production processes become very complicated? The limitations come from many aspects which are not considered important in laboratory process. For example: (1) Space for carrying out reaction. (2) Raw materials handling and transport. @) Raw materials purity: Raw materials obtained for industrial use will never be very pure, hence side reactions will also take place. Hence the impurities should be so converted as to avoid any effect on progress of reaction or final product. For example, in this process, impurities such as unsaturated parts and a-methyl styrene are hydrogenated over nickel catalyst at 100°C in order to avoid undesirable decomposition of peroxide during oxidation. (4) Method of producing uniform aqueous emulsion. {6) Separation of H,S0, (aqueous phase) from phenol-acetone mixture (organic phase). (©) Separation of acetone from phenol. (7) Storage and packaging of phenol. ‘The above aspects are only feasibility aspects, i. they are required in order to make the process feasible. This is the first step of the process design. However all feasible manufacturing processes may not be legally allowed or economically viable. Moreover, safety and hazard analysis of process is also required. ‘The design of various equipments used in above process e.g. pumps, storage tanks, agitators, crystallizers etc. will require knowledge of physics and fluid mechanics. The most qesourable conditions for carrying out reactions will be known from the knowledge of chemistzy- Knowledge of other disciplines will also be required at different stages. “The safety aspect is nowadays becoming more important. The golden rule is that safety and hazard analysis of the process should be done prior to the design of various equipments, ‘rather than evaluating safety as a modification /improvement of the process. Every process should be made pollution-controlled so that it becomes legally acceptable. There is a terimum tolerance limit of various pollutants which can be discarded into the atmosphere. These limits are set by pollution control boards. If these limits are exceeded, the pollution control boards can charge a penalty, or even order closure of the plant. 1.2 VARIOUS UNITS OF A MODERN CHEMICAL PLANT AND THEIR IMPORTANCE In the layout of a chemical plant, the various areas are planned and various piece of equipments put according to their use and importance. The area where main Processing takes place is called ISBL (In Side Battery Limits). By main processing, we mean various reactions,= Utilities in Process Plants 3 ‘mixing and /or separation processes. This is the most vital area of a chemical plant. This area may contain various equipments such as reactors, mixing tanks, distillation columns ete. Some of these equipments may be very costly eg, distillation columns. While some other may contain hazardous /inflammable liquids or gases, possibly at a high temperature and pressure. That is why this area is one of the most heavily instrumented area containing hundreds of temperature and pressure indicators and controllers, safety valves and other safety devices. ” Nowadays, almost all plants have automatic/computerized control systems. All the instructions /adjustment for control of process is done from a building called control room. The control room may contain hundreds of panels where detailed record of all the temperature /pressure variations of all the units of plants are maintained. ‘Another area of a plant is storage tank area. The storage tanks area may contain feed tanks as well product tanks, This area is connected to battery limits by large pipe lines (called headers). Though in this area, apparently the activity is less, a mistake done by an operator in any valve operation can force the plant shut or may even put the whole plant in danger. Moreover, storage tank is the area which is the source of various fires and accidents. Any chemical plant requires raw materials in order to produce final product. It also requires various other services called utilities for smoothly carrying out the process. Utility is neither a product not a reactant. But utilities are required for maintaining adequate conditions of a manufacturing unit. Utility area is also an important area of a chemical plant, This may house various boilers, large compressors, refrigeration systems, air conditioning systems, water treatment plants, cooling towers etc. Uiilities also include electric power so power plants are also considered as a part of utilities. The lines which carry process fluids inside them are called process lines while those carrying utility fluids are called utility lines. Inside Battery limits, there is a complex internesting of process and utility lines. 1.3 IMPORTANCE OF UTILITIES That the utilities are situated outside battery limits should not give any wrong impression that utilities are any less important than the main process, because it is the efficient management of utilities that generates profits. On the other hand bad management of utilities can make even the most efficient processes unprofitable. Thus we can distinguish between two kinds of fluids in a chemical plant as follows: Utility Fluid Gervice) Process Fluid (@ Water, steam, air, etc. () Raw material and products. (2) Generally reusable. (2) Generally not reusable. 3) usually of low unit value. Q) Usually of high unit value. (4) Can't be stocked, therefore regular (4) Can be stocked. supply is extremely crucial. (5) Composition change is not severe. (5) Severe composition changes. (6) Source of some utilities like water (6) We can have very huge source of ‘are practically limited. Raw materials. (7) Long design modification period (7) Short design modification period (30-50 years) (10-15 years). However, there will be many instances when the distinction between utility fluids and process fluids will be blurred. ~ The utilities help to maintain proper process conditions, (mainly pressure and temperature), without which it will be impossible to carry out the process.: = Process Plant Utilities Most of the modern engineering practices are aimed at reducing the consumption of utilities. The production of utilities, be it compressed air, steam or water, requires energy; and energy is becoming costlier day by day. ‘Wifitiont utility thanapenonk Ades not and at ost culling. If ubllites supply is nok proper, the equipments of the battery limits may not last their full life. For example, if the steam higher than desired temperature enters heat-exchangers, the exchangers may get damaged. ‘One more important area of a chemical plant is effluent treatment plant (ETP). The ETP treats the effluent and reduces the concentration of effluent below required limits as suggested by environmental norms. Not only this, the proper analysis of effluent can suggest that from which equipment, loss of material is happening. Thus it should be well understood that utilities are as important as process streams and any negligence on part of quality of utilities should not be ignored. Air, water and steam are the common utilities. However, when air, water and steam come into direct contact of process fluids, they play the role of process fluids. Water may be a process fluid when it is used for washing purpose (However many will disagree). For example washing of textiles, washing of yarn etc. Water required by pharmaceutical and electronic indiistry should be ultra pure. It is a process water. Air becomes a process fluid when it takes part in reactions, The amount of air required forcertain reactions could be enormous. For example to produce 1 ton H,SO, from sulfur, 2.8 tons of air is required. To oxidize ammonia to produce 1 ton of HNO3, 5.3 tons of air is required. Steam can also be used as process fluid or as a utility fluid. However the futility of dispute over whether to consider a particular stream as process stream or utility stream should be well understood. The aim of an engineer should be to provide air, water, steam and other services in required quantity and of quality as required by end users.Water: 2A1 2A.2 2A.3 2A4 2A.5 24.6 2A.7 2A.8 24.9 2A.10 An Important Utility 5 Chapter 2 WATER: AN IMPORTANT UTILITY 2A WATER QUALITY INDICATORS’ H,0: ONE MOLECULE: MANY ASPECTS. SOURCES OF WATER. WATER RESOURCES: INDUSTRIAL PERSPECTIVE. GENERAL WATER RESOURCE DEVELOPMENT AND MANAGEMENT SCHEME. EFFECT OF SEASONAL CHANGES ON WATER RESOURCES. IMPURITIES PRESENT IN WATER. PARAMETERS OF QUALITY OF WATER. DIFFERENT ASPECTS OF WATER CHEMISTRY. MAJOR IMPURITIES AND THEIR EFFECT. ESTIMATION OF HARDNESS BY EDTA METHOD. 2B PROCESS OF COAGULATION AND FLOCCULATION THE PROCESS OF COAGULATION. THE PROCESS OF FLOCCULATION. PLANT DESIGN OF FLOCCULATION/COAGULATION SYSTEM. SEDIMENTATION PROCESS. FILTRATION.Pz 6 2C.1 20.2 20.3 2C.4 2C.5 20.6 2C.7 20.8 2c.9 2C.10 2C.11 2C.12 20.13 2C.14 2C.15: 2C.16 2C.17 2C.18 2C.19 2C.20 2C.21 2D.1 2D.2 2D.3 2D4 Process Plant Utilities 2C REMOVAL OF DISSOLVED IMPURITIES PRECIPITATION. LIME SOFTENING. MORE COMPLETE SOFTENING AT HIGH TEMPERATURE. SILICA REMOVAL. HEAVY METALS REMOVAL. MANGANESE REMOVAL. ORGANIC Mn/Fe REMOVAL. EMULSION BREAKING. ION EXCHANGE METHODS. ION EXCHANGE RESINS METHOD. PRACTICES ABOUT ION EXCHANGE. SODIUM EXCHANGE CYCLE (ZEOLITE SOFTENING). PROBLEMS ASSOCIATED WITH ACID REGENERATION. SOME CORRECTIVE ACTIONS FOR FOULED RESINS. PROCESS OF LEAKAGE. DAMAGES CAUSED TO RESINS. PROBLEMS AND PERFORMANCE EVALUATION. NON-CONVENTIONAL RESIN BED OPERATIONS. OTHER USES OF ION EXCHANGE RESINS. DEAERATION AND DEGASIFICATION. CHEMICAL OXYGEN REMOVAL. 2D MEMBRANES - A NOVEL WATER PURIFICATION METHOD MEMBRANE SEPARATION MEMBRANE TERMINOLOGY COMPARISON OF VARIOUS DRIVING FORCES USED IN MEMBRANE PROCESSES BRIEF DISCUSSION OF VARIOUS MEMBRANE PROCESSEStant Utility, 2A - WATER QUALITY INDICATORS HzO : ONE MOLECULE : MANY ASPECTS The importance of water for flora and’ fauna is paramount. It is one of the most vital ents of the ecosystem. However for human and industrial consumption, sea water, which ts for 97% of the water resources of the earth, is almost useless. The other sources are er uniformly distributed nor have waiform quality which leads to geological water e. Hence industrial agglomerations tend to sprout around easily available water es. Industrial growth leads to population accumulation which in turn leads to more ial growth thus straining the demand-over loaded water resources. A need for judicious and minimizing the wastages is nowadays increasingly felt, for two reasons, (a) conservation of water. (b) maintaining quality of water resources by controlling pollutant entry. Water from natural resources is almost never a pure molecule H,O and contains mpurities in form of various dissolved and suspended mineral salts, organic impurities and iotic matter like algae, micro-organisms etc. A need for purification is always present even for ‘ordinary washing and drinking purpose. Moreover various kinds of industries require differently processed waters for different purposes. For example, fibre industry requires water with less calcium content for washings, food processing industry requires micro-organism free water and power plants require highly deionized water to prevent any corrosion and scaling of . As the purity demand goes up, cost of purifying also increases and wasting of such purified water is highly unjustified. ‘According to GEO-1 (Global Environmental Outlook 1) report, the world is leading towards a water crisis hence, it is extremely important that use of water should be done judiciously. Many modern methods of reducing water consumption are being thought. One such technique is to reduce the size of effluent stream by finding the minimum theoretical fresh ‘water required by ‘pinch calculations’. The pinch calculations (or pinch technology) originated in the field of heat transfer. By applying this technology, many industries found (to their surprise) that the LP exhaust ‘steam/condensate which was being thrown away earlier could be employed to do useful ‘heating in some other exchanger equipment or plant. They were able to detect this because they first carried out an overall heat balance of the plant and then they determined the mum theoretical heat required. The pinch coordinates are the heat content (enthalpy) of the and the temperature. In case of water also many mills follow wasteful and unjudicious planning. They empt to lower fresh water demand and waste water generation with a single treatment plant. e plant takes the effluent from all the parts of a mill, mixes it, cleans it and recycles most of it. itis not an efficient process. The outlet from one unit may be contaminated, yet it may be quite an’ to serve as inlet of another process. Hence the emphasis in pinch technology is on al recycles and multiple use of water with little or no treatment The pinch technology uses water flow rate and purity as pinch coordinates and tries to ‘ne ‘pinch’ i.e. minimum fresh water demand.8 Process Plant Utilities 2A.2 SOURCES OF WATER (1) Rain Water: It is a result of evaporation cycle, and should be considered as least contaminated. However as it comes in contact with atmosphere, gases do get dissolved. in it, especially CO,, It may also entrap suspended dust particles. (2) River Water: On land, the drainage essentially goes to rivers. During their course of flow, rivers dissolve minerals of rocks. The larger the distance travelled, the more minerals will be dissolved. Apart from that, rivers also have suspended silica and bio-mass. In India, rivers have specific importance as many textile processing units, one of the largest consumers of water, are situated close to them. The minerals contained in river water are generally Cr, SO; and HCO} of Na’, Ca", Mg", Fe** and Fe***, River water also contains organic matter. The hardness of river water is normally high. The dissolved CO, may become acidic by formation of carbonic acid which is corrosive to mild steel, the material of construction of most of the equipments. (3) Lake Water: The lakes have lesser concentrations of dissolved solids because they are non-flow water reservoirs. However, they are less exposed to oxygen hence contain high unoxidized organic matter and hence have a large BOD. (4) Sea Water: The largest reservoir of water is most impure too resulting into limitation of water supply. It is misfit not only for human use but also for any major industrial consumption due to its high salt content which causes fouling, corrosion and erosion of industrial units. 2A.3. WATER RESOURCES: INDUSTRIAL PERSPECTIVE Most of the industries like fiber, textile, sugar, food processing, paper etc. are very much dependent on bulk supply of water. They need to manage their water consumption in order to reduce load on primary water source, to cut down water processing costs and to control the quality as well as quantity of effluent/waste water in order to be in permissible pollution emission limits. Contrary to the general impression, in many cases, industries require water of very high purity. In general, we can make following classification: (1) Bulk Requirement: Industries which require huge amount of water but purity is not of prime concern. eg. fibre, textile, pulp and paper etc. (2) Specially processed water requirement: e.g. Boiler feed water (low pressures), wash waters for finished textiles, etc. (3) Very pure water: For pharmaceutical, electronics industries, very high pressure boiler feed water etc. 2A.4 GENERAL WATER RESOURCE DEVELOPMENT AND MANAGEMENT SCHEME ‘Though it is not an specialization of Chemical or Process Engineer, he has to actively liasion with other specialists in this regard. The following scheme is suggested. 2A.4.1 Estimation of Raw Water Consumption: (a) Process consumption in chemical reactions. (b) Raw materials products washing purposes. (0) Effluent discharge. (d) Losses from units such as boilers, cooling towers etc. (e) human consumption.Recycle Water 1. Teatile Units 2. Pulp & Paper Units 3. Rood Processing Units 4, Chemical Units Separate Toxics and sludge for dumping ‘Raw Water From Lake, River ete. Controlled ee WIP wwrP ETP WaterTreatment Plant Waste Water Treatment Plant Effluent Treatment Plant Fig. 241 - Water Consumption Planning 2A.4.2 Source Identification The water source has to identified in view of its capacity (or source life - i. Jong it can fulfil requirements), hydrologic data, seasonal data of reservoir etc. 24.4.3 Source Development Huge Civil Engineering activities and large investment is required in this stage because foundations for pumps, suction pipe lines and other auxiliary facilities are constructed in this stage. 2A.4.4 Pipeline system design Water from the reservoir has to reach different points of consumption. So pipelines have to be designed. Usually the quality of water required for different applications will also ‘be different, so a whole system of water lines may be required. The major parameters in pipe line design are: ~ capacity, — operating pressure and pressure drop ~ MOC and cost. Ps While deciding the operating pressure, one has to pay attention to internal pressure, water hammer pressure, change in direction and resulting stresses thereby, and also to the thermal stresses. ‘Material of construction (MOC) will depend upon operating pressure, corrosion, cost and durability. The most common MOC are: (Iron - Cast Iron - Now its use is rather obsolete. Ductile Iron: Now in use due to being light and less brittle because it has P and S content and a magnesium alloy is added to it. Sometimes to fight corrosion, the pipe is cement lined, or it may be lined with some bituminous material. Lining is slightly tapered at the ends to facilitate easy fitting. (2) Steel pipe: Used for larger diameters and higher pressures. It is cheaper than iron . for how. pipe. (3) Concrete pipe Very common for buried pipe line system carrying (4) Asbestos cement pipe sewage water /corrosive waste etc. (5) Plastic pipe: Lighter and cheaper than Iron/Steel,used especially for distribution10 Process Plant Utilities 2A.4.5 Distribution and Storage Systems Three kind of systems are possible: (a) Gravity distribution, (b) Pumping without storage, (©) Pumping with storage. Normally a water system will use all the above three methods in judicious combination depending upon criticality of the processes. Storage of water may sometimes be necessary to equalize pumping rates. Mostly the storages will be at elevation and may be of either concrete or steel. 24.5 EFFECT OF SEASONAL CHANGES ON WATER RESOURCES (1) Sudden rainfall: Sudden dilution of rainfall can be very disruptive for a water treatment plant. The location of river intake should be carefully chosen to counter this problem. To avoid this, usually suction is not direct but through a jack well. Tides also affect the water in take of WTPs because they tend to reverse the normal river flow. To even out variations between high tide and low tide, many times reservoirs are provided to collect water at low tide when river flow is not disturbed and hence quality of water is also superior. During high tide, salinity and turbidity of river water may deteriorate. Seasonal temperature changes also affect water quality. Low temperatures hamper coagulation process, increase solubility of gases and’ increase water viscosity thereby creating larger AP in the filter beds. (2) Underground Water: This has the largest supply of fresh water for human use. The composition of underground water is more or less constant. As it has passed through hundreds of meters of porous rocks, much of the impurities are held back in rocks and the water is very clear. The composition of underground water also depends upon local geology. The water produced along with oil production (oil field brine) has a very high salinity (© 100,000 mg/L), usually more than sea water. Its handing creates special problems due to its scale forming/corrosive properties. (3) Protection of International water resources: The pollution and contamination of international waters is realized among four major environmental problems of the 21st century, along with global warming, ozone depletion and declining bio-diversity. The contamination patterns are likely to give rise to new materials and processes. The sources/causes of water pollution are vehicular pollution which leads to acid rains, over use of chemical fertilizers, dumping of nuclear and hazardous wastes under sea-beds which eventually disturb aquatic life. The lakes which are already low in natural alkalinity due to absence of calcium rocks are especially hit by acid rains. Many times the high acidity may have to be externally neutralized. The ground water, especially near the coastal region is being affected due to unmindful dumping of hazardous waste and garbage. Many times, such garbage is used as landfill. One of the common practices is to pack the waste in drums and then dump these drums. Leakage occurring from these drums is also responsible for ground water contamination. 2A.6 IMPURITIES PRESENT IN WATER (1) Suspended Impurities: These are dispersion of solid particles that are large enough to be removed by filtration or sedimentation. Suspended impurities include: (a) Clay or silt: These cause turbidity. (b) Bacteria: may be pathogenic. (©) Algae, protozoa: may cause odour, colour and turbidity. However, some of the algae may be helpful because they are able to produce oxygen by photo-synthesis.Water: An Important Utility 1 (2) Colloidal impurities: These are usually finely divided clay particles, silica, alumina, ferric hydroxide, organic waste products, etc. (3) Dissolved Impurities: These are (a) Calcium, Magnesium - cause alkalinity and hardness. (©) Sodium - Causes salinity. (c) Metal and Metal Oxides: () Manganese - produces black /brownish color. (ii) Iron Oxide - Causes red colour. (ii) lead and arsenic - can cause toxicity. (d) Gases: (i) Oxygen - corrodes the metals, especially at higher temperatures. (i) H,S - causes odour, corrosion. Typically raw water contains about 1000 ppm solids dissolved. Thus raw water is 99.9% pure. But this is a very poor quality water. 24.7 PARAMETERS OF QUALITY OF WATER How can one define the quality of water? Well, the quality of water can be defined using a set of parameters, some quantifiable, others just desirable. A set of parameters may be: (1) Colour (2) Taste and odour (3) Turbidity. (4) Microorganisms (6) Dissolved mineral matter - hardness, alkalinity, total solids. (6) Dissolved gases. (7) Silica content. (8) Oxidability - BOD, COD. The most important indication of water quality is hardness. Hardness is the concentration of calcium and magnesium ions in the water, irrespective of nature of anions present. It is usually expressed as calcium carbonate. CaCO, is chosen as basis only for the convenience (MW = 100, EW = 50) and not due to any of the physical properties of CaCO,. Thus instead of reporting concentrations of variety of ions present, the CaCO, Equivalent is the simple identification of hardness. e.g. MWof Alumina AJ,O, Valency of Al*** ion 102 3 Total valencies = 3x2=6 _ 102 Equivalent Wt. ee Chemical are equated on equivalent wt. Hence 1 Eq Alumina = 1 Eq. of CaCO; Hence 17 gm Alumina 50 gm CaCO; {Chemical Equality] 50 Hence 1 gm Alumina or [1gm Alumina = 2.94 gm CaCO; For reporting the analysis of water normally three methods are used: () Ionic Method: In this method, anions and cations are reported as mg/L, both individually as well as total anions and cations. The water being electrically neutral, the total anions should be equal to total cations. However, many times, some slight discrepancy may be there because some minor constituents (e.g. NH,*, a cation) may not be reported. aProcess Plant Utilities Silica, Iron and Manganese are reported as SiO,, Fe and Mn. (2) Equivalent per million: In this analysis, the concentration of each anion and cation is. first calculated as part per million and then converted to equivalent per million (EPM) by diving ppatby equivalent wt. () CaCO, (mg/L): here each anion/cation is converted to as CaCO; and reported as “mg/Las CaCO;”. eg. MWofCa™ = 40 EW of Ca’ = 20 Then, if in an analysis of water, 44 mg/L of Ca‘* are present, then its CaCO, equivalent 100) will be rn mg/Lx Soy = 110mg/L In other words, [ 44mg/L Ca** = 110 mg/L of CaCO, 24.8 DIFFERENT ASPECTS OF WATER CHEMISTRY 2A.81 Concept of pH (Alkalinity/Acidity) It is related to dissociation constant of water, and to hydrogen ion concentration. ak Hp: = HO K, dissociation constant = [H"] x [OH] = 10 pH =-log [1] Because K of water is very small, only 10", the concentration of hydrogen ion will be very small, eg,, for neutral water it will be only 0.001 mg/L - an inconvenient choice, so that is why, pH is used as a convenient unit. The pH of neutral water will be 7.0 while that of acidic ‘water will be less than 7. , When pH drops close to 5, the H” concentration becomes high enough to be determined accurately by titration using an organic dye indicator. ‘The earlier dye used was methyl orange whose color change HH orange (alkaline side) —————> ink (acidic side) about 4.2-4.4 was not easily visible. Hence new indicators have been developed but the chemists still define alkalinity as Methyl Orange Alkalinity (‘M’ alkalinity) which exists above pH range of 4.2-4.4. ALKALINITY RELATIONSHIPS 7 T Condition | OH- is HCO, P=0 0 0 | M. P<05M 0 2P | M-2P P=05M | 0 2P | 0 P>05M 2P-M. | 2(M-P) 0 P=M M | 0 0 P=P-alkalinity All units as ppm CaCO3 M-=Mealkalinity Fig. 24.2indicator is phenol phthalein which changes color from colourless (acidic) fred (alkaline). s is divided into as carbonate (temporary) hardness which is equivalent to P ity and non carbonate hardness which is in excess to P alkalinity. If both P ity are known, it is possible to calculate CO;?, HCO;-and OH- ion dation and Reduction ‘Oxidation number of elements affect their solubility. e.g, FeO (Oxidation number of Fe 4 soluble while Fe,O, (Oxidation number of Fe = +3) is not. Similarly, an effective inhibitor, chromate, becomes a heavy metal ion with no useful properties when it tates as Cr (OH), to produce suspended matter. ‘The source of alkalinity in water The most common cause is dissolved bicarbonate (HCO;) salts. A common mineral, ‘ite (CaCO; . MgCO;) reacts with atmospheric CO; to produce hardness and alkalinity in //river water because Mg (HCO,) is water soluble. MgCO, + H,O + CO, ——> Mg (HCO), ===> Mg” + 2 HCO,- CaCO, + H,0 + CO, ——+ Ca (HCO,), ===> Ca++ + 2HCOS 8.4 Prediction of solubilities using solubility product This concept simply means that concentration of a cation multiplied by concentration of is constant at a constant temperature. e.g., for calcium carbonate: [Ca] (CO;"]=K, F The plot of [Ca*] vs. [CO;*] will, then be a hyperbola, at constant temperature, in a saturated CaCO, solution: 100 Ca, mg/L as CaCO, 100 0 Carbonate, mg/L as CaCO; Fig. 2A.3 ~ Solubility Curve of CaCO, The higher the solubility product, the higher the solubility of a compound. e.g. MgC, [K, = 1x 10°] CaCO; [K, = 5x 10°] more soluble less soluble as at 25° C a“Process Plant Utilities Note that solubility products are a function of temperature, the correlation is not always positive. Foreign ions interference reduce the value of solubility product concept. The ions present in a typical water sample are of large variety. So it is highly unlikely that a pure precipitate such as CaCO, will be formed. The presence of foreign ions will increase [while that of common ion will decrease] solubility of CaCO,. Even if pure CaCO; precipitates, it may form two kind of crystals, calcite and aragonite (less stable). "another factor affecting solubilities is presence of organic matter dissolved in water. It is found that residual calcium from lime — softening of sewage is 2 to 3 times the solubility in fresh water, presumably due to organic complexes. However, the same effect is not observed with magnesium. ‘Another example of complexities is precipitation of Alum [Al; (SO,)s- 14H,0] when dissolved in water. The expected reaction would be: Al, (SO,) + 6H,0 —— 2l (OH), | + 3H,SO, But in the lattice of precipitate, we will find that some SO,” ions have replaced OH” ns. 2A.8.5 Concept of Equilibrium ae ———— AB+ C [AB] x [C] Then equilibrium constant K = ea 24.8.6 Concept of Chelation A chelating agent is a molecule, usually organic, which is soluble in water and can undergo reactions with metal ions to hold them in solution. So chelation is analogous to ion exchange - the only difference being in solubility of the exchanger. In case of ion exchange resins, these are solids and not soluble in water. A common chelant Na, EDTA will take part in the ion exchange like this: Cat* +Nay EDTA ——> CaNa, EDTA + 2Na* Thus, this chelant will absorb calcium, will keep it afloat in the solution and will prevent it from depositing on boiler heat transfer surface. A number of natural organic materials such as humic acid and lignin have chelating properties. 2A.8.7 Sequestration (Threshold Treatment) This is also a concept related to chelation. While chelation helps to keep Ca?* afloat, some compounds especially polyphosphates prevent deposition of iron, Mn and also of CaCO, Polyphosphates are like long chain polymer compounds, with unit block consisting of P-O-P chain. The most common polyphosphate is hexa meta phosphate (NaPO;),. Water with high concentration of Ca*", if treated with only 0.5 mg/L of (NaPO;),, will not form CaCOs deposit. ‘The amount of polyphosphate is much less than required for softening on a stoichiometric basis, hence the name threshold treatment. Polyphosphate can also hold Fe and Mn in solution when they would otherwise precipitate, e.g, in a environment of pH over 8 with presence of oxygen/ chlorine. Such value of polyphosphate is destroyed when they revert to original orthophosphate (from which they are synthesized). ‘Solutions of glassy polyphosphate remain stable for months, but in water systems, they may be reverted to polyphosphate by low pH, high temperature, and by the presence of heavy metals especially iron.Important Utility 15 CO;*/HCO; distribution ‘Most natural waters contain HCO; alkalinity and are at a pH about 8. Above pH of 82 8.4, the carbonate alkalinity becomes more predominant. The equilibrium reaction is: HCO;+ === co,++H* Many times, treated waters have P alkalanity above 9.6. In the range of 8.2 - 9.6, CO3*-/HCOs coexist. The CO;?-/HCO> can be determined after measuring P and M alkalinities as follows: CO, = 2xP HCO, = M-CO; = M-2P As pH rises above 9.6, the OH’ alkalinity also becomes measurable. These approximations are subject to various interferences, by some compounds like ammonia and by alkaline ions other than bicarbonate, such as sulfide, phosphate, silicate and borate. However, we still continue to use traditionally collected data which results into above listed convenient relationships. Examination of acidity - alkalinity relationship reveals that solubility of such materials as CaCO; and Mg (OH); is more complicated than predicated by solubility products. For these reasons, water scientists prefer to relay upon experimental data rather than solubility product, to predict precipitation reaction. The presence of HCO;/CO;*- acts as a powerful buffering system, so that natural water alkalinity almost always falls in a fairly neutral pH range of 5 - 9. Solid matter turbidity: Solid matter occurs as suspended solids and colloidal matter. The concentration of suspended solids can be obtained by filtration. Suspended solids which are large and heavy are called settlable solids. The supernatant liquid above is called turbidity. Turbidity is measured by opaqueness of the water against light. light-interference analytical methods are called nephelometric, and turbidity measurement is done by using Nephelometric Turbidity Units (NTU). The original method uses a standardized candle, developed by Jackson and is called Jackson Turbidity Unit (TU). JTU is measured by transmitted light beams while NTU relies on scattering of light. The two units are not easily interconvertible. 3 Colloidal matter is some times beneficial and sometimes not. Beneficial colloids provide a dispersive effect e.g. sodium silicate in colloidal form, lignin and tannin (which occur in mostly colored waters). Note that silica as itself can be very harmful because it forms very hard- to-remove scales. 24.9 MAJOR IMPURITIES AND THEIR EFFECT Bicarbonate: It is the principal alkaline constituent, ranges to 5 - 500 mg/L as CaCO. Control of alkalinity is important in many industrial applications because of its effect on CaCO; stability index. Alkalinity control is very important for boiler water and cooling water applications. Alkalinity has to be reduced either by lime-softening or by direct acid addition. Alkalinity is objectionable in beverage industry because it interferes with fruit acids and also in textile operations, where it interferes with acid dyeing. Calcium: Major cause of hardness, usually in the range of 5 - 500 mg/L (as CaCO,). ‘Must be removed from water systems during softening operations. Its removal is required in ‘many industrial operations particularly in boiler makeup, textile finishing, cleaning and rinsing ‘operations in metal finishing. Hardness can be reduced to above 35 mg/L by cold lime soda process and to 25 mg/L hhot lime soda process. It can be reduced to 1 mg/L by cation exchange methods. In textil16 Process Plant Utilities finishing, deposits of calcium/magnesium soap scum adhere to the yarn. Such scum creates problem in dyeing because it does not produce exact shade of colour and may produce spots. in sugar industry, hardness interferes with crystallization. Chloride: Almost all chloride salts are highly soluble in water, therefore Cl concentration in freshwater will range from 10 - 100 mg/L. Seawater may contain about 30 g/L of CI as NaCl and underground brine wails may actually be saturated containing 25% NaCl. ‘Anion exchange is only process which can remove CI’ ions. Physical processes like evaporation and reverse osmosis can separate the feed water in two streams, one of high and other of low NaCl concentration. The recommended upper limit for NaCl in drinking water is 250 mg/L based entirely on taste. Magnesium: The Mg” hardness is about 1/3 of total hardness, the remaining being due to Ca**. Typical range is 10 to 50 mg/L (equivalent to 40 - 200 mg/L CaCO). In seawater, Mg concentration is about 5 times that of calcium on equivalent besis. The production of Mg (OH), is the starting point for manufacture of Mg from sea water. Mg is also abundant in many rocks. MgCO, is more soluble than CaCO,, hence MgCO, does not scale much except in seawater evaporators. However for producing soft/DM water-for boiler feed, it must be removed alongwith Ca’. ‘Removal limits of various processes (as CaCO,): upto 30 - 50 mg/L cold lime soda process 1-2 mg/L hot lime soda process <1 mg/L ion exchange process Organic Matter: They may be of innumerable variety, essentially containing carbon. They are sometimes responsible for giving color to water. Sometimes they may work as a chelant to entrap heavy metal ions among them. Their presence is objectionable because: (1) In drinking water - due to aesthetic/hygiene factor. (2) In feedwater for DM plant - they may foul/clog the resins. Silica (SiO,) - Almost all the silica is present in colloidal form, though part of it may be converted to soluble bisilicate (HSiO,). There exists some kind of loose equilibrium between Si0,/HSiIOs~. Presence of silica in high concentrations is undesirable in evaporative cooling water systems due to its unsure solubility. In boiler feedwater, it may form very hard deposits on turbine blades as weil as tubes. Silica must be brought down to a very low level especially in high pressure boilers because it vaporizes at high temperatures and thus will go and deposit on turbines blades. Sodium Ions (Na*): Usually present as NaCl. The only process for removal is hydrogen-cycle-based ion exchange. Evaporation/R.O. can at the best produce two streams of differing concentrations. ‘Sulphate (SO,*)- It dissolves in water from certain rocks, especially from gypsum. Typical range is 5 - 200 mg/L. Sulphates are also objectionable in evaporative systems. Total dissolved solids (TDS) - It is sum of all the dissolved solids and usual range is 25 - 500 mg/L. Alkaline hardness: Hardness due to bicarbonates, carbonates and hydroxides of hardness producing metals. (Also called carbonate hardness). Measurement of Alkalinity: M Alkalinity = HCOy + CO? + OH IfM Alkalinity < Total Hardness then Alkaline Hardness = M Alkalinity Non-alkaline Hardness = Total Hardness - M Alkalinity= Water: An Important Utility Ww 2A.10 ESTIMATION OF HARDNESS BY EDTA METHOD EDTA will make complexes with Ca’’/Mg™, as well as with many other metal cations. The hardness can be determined by using Eriochrome Black T indicator (blue colour in free state, red when it reacts with metal) using NH,OH buffer at pH ~ 10. Reactions: Titration => between = MgD- + H,Y? > MgY*- + HD? + H+ thesetwo — NajxY ——+ 2Na*+H.Y* Mg? +HD? ——> Mgb-+H* s (Blue) (red) EDTA complex (Blue) Y = EDTA D = Indicator Dye Effect of CO,: CO; content may greatly vary from 0.5 ppm in fresh rain water to 50 ppm in highly organic matter laiden rivers. Effect of CO, on pH values: When CO; dissolves in water, it forms weakly dissociated carbonic acid H,CO, to some extent. If the water is free from all traces of alkali and is saturated with CO; (about 1450 ppm at 77° F) then the pH will be about 3.8. However such low pH is not found in natural waters (except those which contain free mineral acids) because of the presence of some bicarbonate alkalinity. Thus the pH of water is a function of CO; content as well as bicarbonate alkalinity. Dissolved CO, present in boiler feed water produces an acidic corrosive effect. Further, CO» is an accelerating factor in dissolved oxygen corrosion, especially at low pH values.18 Process Plant Utilities ‘Constitutent | Chemical formula Difficulties Caused ‘Means of treatment ‘Turbidity | None-expressed in | Imparts unsightly appearance to water. | Coagulation, settling and saa analysis as units. Deposits in water lines, process equipment | filtration, etc, Interferes with most process uses. Colof see | None-expressed in | May cause foaming in boilers, Hinders | Coagulation and _filteration, analysis as units. precipitation methods such as iron removal | Chlorination. Absorption by and softening, Can stain product in process | activated carbon. Hardness | Calcium and Chief source of scale in heat-exhchange | Softening, Demineralization, ‘magnesium salts equipment, boilers, pipelines, etc. Forms | Internal-boiler-water treatment. expressed as CaCO3. | curds wth Soap, interferes with dyeing, ete. | Surface-active agents Alkalinity Carbone dioxide — pH. Sulfate Chlorie Nitrate ‘Silica . ‘Manganese Oxygen Hydrogen sulfide Ammonia Dissolved solids Suspended solids Total solids. Biabonaie HCO carbonate (CO, shad ydrte (SH) expressed as CaCO3. H,S0,, HCI, etc expressed as CaCO Op ‘Hydrogen ion concentration defined as:pH =log[ 1 aL] ae Nox SiO Fet* (ferrous) Fet* (ferric) None None Foaming and carryover of solids with steam. Embrittlement of boiler steel, Bicarbonate and carbonate produce COz in steam, a source of corrosion in condensate lines. Corrosion. Corrosion in water lines and particularly steam and condensate lines. pH varies according to acidic ot alkaline solids in water. Most natural waters have a pH of 60-80. ‘Adds to solids content of water but in itself not usually significant. Combines with calcium to form calcium sufate scale. Adds to solids content and increases corrosive character of water. ‘Adds to solids content but is not usually significant industrially. Useful for control of boiler-metal embrittlement. Scale in bilers and cooling water systems. Insoluble turbine blade deposits due to silica vaporization. Discolors water on precipitation. Source of deposists in water lines, boilers, etc Interferes with dyeing, tanning, paper- making ete. Same as iron. Corrosion of water lines, heatexchange equipment, boilers, return lines, ee. Cause of "rotten egg” odor. Corrosion. Corrosion of copper and zine alloys by’ formation of complex souble on. “Dissolved soilds” is measure of total amount of dissolved matter, determined by evaporation. High concentrations of dissolved solids are objectionable because ‘of process interference and as a cause of foaming in boilers. “Suspended solids” is the measure of undis- solved matter determined gravimetrically. Suspended solids cause deposists in heat texhcange equipment, boilers, water lines etc. “Total solids” is the sum of dissolved & sus pended solids, determined gravimetrically Lime and lime-soda softening, Acid treatment. Hydrogen zeolite softening, Demineralization, De- alkalization by anion exchange, Neutralization with alkalies. Aeration, Deaecation, Neutralization with alkalies. pH can be increased by alkalies and decreased by acids. Demineralization. Demineralization Demineratization. Hot-process removal with magneisum salts. Adsorption by highly basic anion-exchange resins, in conjunction with demineralization. Aeration, Coagulation & filtration. Lime softening. Cation exchange. Contact filteration. Surface-active ‘agents for iron retention. ‘Same as iron. Deaeration, Sodium sulfite, Corrosion inhibitors Aeration, Chlorination. Highly basic anion exchange. Cation exchange with hydrogen zeolite Various softening processes, such as lime softening and cation exchange by hydrogen zeolite, will reduce dissolved solids. Demineralization. Subsidence, Filtration, usually preceded by coagulation and setting. See “Dissolved solids” and “Suspended solids”. Fig. 2A.4— Common Impurities in Fresh Water.n Important Utility 19 Ch. 2(B) PROCESS OF COAGULATION AND FLOCCULATION These two stand for two different processes which enhance the settling properties of turbid waters. Though generally these two are used interchangeably, however the differences between two can provide useful insight. Colloidal Matter in Water: The raw water as well as waste water may contain many colloidal species e.g. clay, silica, organic mater, iron and other heavy metals, oil etc. In a water sample, there will usually be size distribution of colloidal particles, the small sizes taking much longer time for settling down. Colloids are of two types - hydrophobic and hydrophilic. Most natural clays are hydrophobic. Hydrophilic colloids cause maximum difficulty because these react chemically with the coagulant used, so these require larger dosage of coagulant. The cause of stability of colloidal suspension, is the negative charge which colloidal particles acquire outside their surface. Due to electrostatic repulsion, the particles are always held in suspension and do not settle unless the charge distribution is changed /disturbed some how. The smaller the particle, the larger will be the specific surface area and hence larger the charge outside and larger the stability of colloid. Not that the overall charge on a colloid particle is zero e.g. in a SiO, particle, the particle is electrically neutral. It is only the external surface that acquires a negative charge. 2B.1 THE PROCESS OF COAGULATION Coagulation is carried out by adding certain coagulants to the water. Coagulants are such chemicals which will usually provide positive charges so that negative charges of the colloid may be partially (but seldom completely) neutralized. Coagulation usually occurs when there is still some -ve charge on the surface. If too much coagulant is added, the surface charge may become positive and particles may again get redispersed. Many times, coagulant dosage may be required for even those turbid systems which are not truely colloidal (and particles may settle down if given enough time) to increase the settling rates. Coagulants may be required in high pH water treatment systems such as lime softening because CaCO; particles carry a negative surface charge and cationic coagulants may be required for reducing colloidal residual hardness. On the other hand, Mg (OH), is having a positive charge, so in a system where both CaCO; and Mg (OH)2 are present, they tend to co- precipitate. Coagulation process requires mixing to destroy stability of colloidal systems because coagulation process requires frequent collision between particles. That is why, for coagulation of low turbidity waters, sometimes recycle of previously settled solid proves beneficial because it increases number /frequency of collisions. 2B.2 THE PROCESS OF FLOCCULATION Flocculation is gathering of solid particles together in some kind of internetting whereby a large number of particles may stick together and thus become heavy enough for settling down by forming larger agglomerates. Alum, iron salts and high molecular weight polymers are common flocculants. In contrast with coagulation, flocculation is promoted by slow mixing which brings flocs gently together but not by severe mixing which tends to break away flocs.20 Process Plant Utilities Coagulation (2) Nature of solids (2) Types of chemicals used Numerous, fine particles Low molecular weight charge neutralizer (3) Mixing (4) Velocity gradient 6) Time inprocess Differences between Coagulation and Flocculation Flocculation Scattered, large flocs High molecular weight particle binder Slow stirring Low Minutes Chemicals used in Coagulations/Flocculation: Earlier, alum and iron salts were used for these coagulants and flocculants. The reactions are as follow: es | eee ot Al; (6O4)3 + 6H,0. FeCl; + 3H,0 processes. They worked both as 2Al (OH); 1 +3H,S0, Fe (OH); 1 + 3HCI Al and Fe hydroxide being heavy precipitates are able to bind together the flocs. But they have one drawback that they produce acid thereby bringing down alkalinity. Toneutralize these acids, if bases are added, they will increase TDS of water. Sometimes these acids will react with alkalinity and thereby produce CO; which again interferes with floc-formation. To solve these problems, another chemical, Poly Aluminium Chloride (PAC), is used which does not react with alkalinity. The floc formed incorporates chloride ions also in it so it is not available for reducing pH and producing CO;, Another advantage is that these are not sensitive to pH. Modern water treatment uses many modified flocculants called poly electrolytes. Modifications are basically done in molecular weight and ion exchange capacity. These materials can also be produced without an ionic charge, Then they are called non-ionic polymers. Cationic poly electrolytes are basically polyamines or quaternary amines. In wat these will hydrolyze as follows: R>NH+H,O ——> > NH- HY +08 It is quite obvious that at high pH values these polyelectrolytes will not ionize and will remain non-ionic, which means a loss in ion-exchange capacity as pH increases: Coagulation a Macrotioc Destabilized colloid Microfioc Flocculation +2\~ “agora Polymer“ Macrotloe Fig. 2B.2 - How polyelectrolytes help in coagulationWater: An Important Utility a Apart from ionic nature, other factors which affect poly electrolytes are polar nature of non-ionic bonds in the molecules, molecular size and geometry. Similarly anionic poly electrolytes will tend to produce H’ ions and hence they will work well at high pH. The steps in settling of particulates in water: Particles at first fall freely through the water. As they come closer together, their raté of sedimentation is restricted, and settled sludge volume increases. In the final stages, compaction or compression becomes very slow. Activated silica is another coagulant which is non-ionic in nature. It is also a very effective coagulant especially for colour removal. ‘A simple and common test to check efficiency of a coagulant is by sedimentation. TIME “S—FREE SETTLING>-®—HINDERED SETTLING —-*=COMPRESSION =P TIME Fig, 2B.3 - Steps in sedimentation (settling) process. The rates of settling decrease with time. In the final stage, compaction (dewatering) of sludge takes place ‘Sample Without Treatment - 28.4 — Effect of Chemical Treatment on Settling Process ‘A coagulant is usually chosen depending upon property of water to be treated. The quality of clear liquid desired and obtained will indicate the choice. 2B.3 PLANT DESIGN OF FLOCCULATION/COAGULATION-SYSTEM Generally the lower the suspended solids in the process stream or the desired effluent purity, the more critical is the mixing. ‘Mixing can be achieved by (1) Hydraulic jumps in open channels. (2) Venturi flurnes. G) Pipelines with tortuous baffles.22 Process Plant Utilities Solid liquid separation is required for removal of solids by sedimentation, straining, floating and filtration and also by thickening /dewatering by gravity. 2B.3.1 Selection of Process for Separation It will depend upon size and character of solids, their distribution and concentration and required quality ie. purity, colour, etc. e.g. For very large solids (pebbles) - wire mesh strainer, Fine solids - may require both sedimentation and filtration. In many cases, instead of granular filtration, micro straining is used. The micro strainer usually consists of a rotating drum with fine wire mesh bound on it. 28.3.2. How Coagulants help in Settling? Action of coagulants in a complex process may help in setting in following ways: (1) Dissolution of salts ~ Disturbs the charge distribution on colloidal particles. (2) Formation of complex hydroxy oxides of metals which may be highly charged. (3) Entrapment of individual particles in the precipitate formed. (1) Dissolution step: Al, (SO,)3 ——> 2Al (H,0) + 380," (2) Hydrolysis: Al (H,0) + Hy0 —— Al (H,0)s OH'? + H* so on. (3) Polymerization: OH H,0 | ON S| Ae et eb a OH ino Overall Simplified Reaction: Al; (S04); + 640 ——> 2Al (OH)s +3H,S0, This acid formation results in drop of alkalinity therefore an alkaline salt must be added to increase the buffer capacity of the solution. 2B.4 SEDIMENTATION PROCESS Sedimentation is removal of large suspended solids by settling. Definition of suspended solids: Solids which can be captured by 0.45 um filter membrane. Solid which pass thorough this are called colloidal or dissolved Theoretical design of sedimentation tank is based on concept of ideal settling basin. An ideal settling basin assumes that: (i) The particles entering the basin will have a horizontal velocity equal to fluid velocity. (ii) Steady state = Input of water = output of water23 —Po Sludge Zone Fig. 2B.5 ~ Ideal Settling Basin @ Minimum settling velocity = terminal velocity = ® = gz (@ .—@ Mf? for proper setting, time to settle < residence time L Vv = Le ® = minimum posible length of setting tank Problems in sedimentatio: (1) Short circuiting, h hence, % $ (1) Changes in inlet composition. (2) Changes in flow rate. (3) Changes in specific gravity and temperature. (4) Changes in localized sludge deposits. To produce sedimentation the flow (Horizontal) velocity of water should be quite small that particles may settle by gravity. Hence the rate of overflow should be kept small. The ‘of sedimentation depends upon particle shape, size as well as buoyancy. Initially at the top, is little mutual interaction between solids followed by hindered settling and compression. The major objective of sedimentation is to produce a clear liquid effluent, rather than a low sludge. SEDIENTED RAW WATER BL WATER OUTLET INLET JF CHANNEL ‘CHANNEL [ 3 P BAFFLE WALLS by pce seomenten (Dp See SWUDGE A Sedmentation Basin with Baffles provides Larger Retention Time - Baffles also ensure horizontal flow24 Process Plant Utilities Clarifying basins (clarifiers) are used for sedimentation purpose. These are basically of three types. (1) Plane sedimentation basins: Normally by clarifiers we mean plane sedimentation basins. They are of various kind depending upon feed conditions: = central feed - most common ~ rectangular - ~ peripheral feed (2) Solid contact unit. @) inclined plane settler. 28.4.1 Central Feed Clarifier Lets describe central feed clarifier in detail: Ithas four distinct sections, each with its own function: (1) The inlet (feed water) section: It allows a smooth transition from high feed velocities to lower velocities required for settling because higher velocities may disturb settling process by short circuiting, channelling and carry over. The turbulence is detrimental to the settling process. 2) Quiescent (silent) settling zone: This should be large enough to reduce upward velocity of water to a value less than settling velocity of turbid solids. (3) Overflow zone: The overflow zone is such designed so as to provide a transition from low velocities to relatively high velocities so that there is sufficient output from clariflocculator. The design usually consists of a weir. (4) Sludge zone: This zone located at the centre should provide a very effective settling and compression of sludge so as to reduce the volume of sludge to be disposed /handled. The settling rate of sludge should be effective and appropriate so that the solids settling above this zone are not disturbed. The clarifiers, for effective sludge collectioh are provided with a 5° - 8° slope towards the centre. The sludge is moved towards the centre with help of a rake. Rake usually moves at a very slow velocity so that sludge does not come back to the surface of water. The other type of clarifiers are rectangular clarifier, peripheral (rim) feed clarifier, sludge blanket clarifier, slurry recirculation clarifier etc. The details can be seen in any water treatment book. 28.4.2 How to Choose a Correct Clarifier? Clarifiers are used both by water treatment plant and effluent treatment plant. The governing factors are: (1) Size: Size being the most single important factor especially if one is installing a second unit/modification. (2) Capacity of water required. (3) Quality of feed water. (4) Cost. 28.4.3 Chemicals Used in Clarification (@) Alum Aly (60,); H;0 is added at a concentration of 30 ~ 100 ppm at 5.5 to 7.5 pH. (2) Ferric sulfate Fe, (SQ,)s is added at 20 ~ 60 ppm at 7.5 - 10.5 pH. (3) Ferrous sulfate FeSO, is also added at 20 - 60 ppm at 7.5 - 10.5 pH. It is oxidized in solution by dissolved O;/Cl, to ferric sulfate Fe, (S0,)5. 2B.4.4 Coagulant aids which are added during clarification ‘These are activated silica and poly electrolytes. Several hundred poly electrolytes are available, characterized by average M.W. (or chain length), charge type and charge density. They have proved to be very useful in coagulation process.25 Slud outer, <— Fig. 2B.7 - A Central Feed Clarifier with Various Zones Shown CENTRAL SHAFTS: => WATER OUTLET PADDLES: INLET CO-AGULANTS. ‘SOLUTION RAW WATER INLET FLOOR WITH SLOPE 1 IN 50 Fig. 2B.8 - A Rectangular Clarifier 28.5 FILTRATION : S After Coagulation - Flocculation - Clarification, the logical step will be to filter the water. Process of clarification by passing the water through a porous material which is capable of retaining coarse impurity on its surface is called filtration. Theoretically speaking, one can remove most of the turbid impurities by sedimentation and clari-flocculation processes but the cost of doing so will be prohibitive because of amount of chemicals required and the investment required in designing very large settling basins. It should be well understood by young engineers that in a process plant, floor area is at a premium and should be used in best possible manner. Hence filtration is the most obvious choice. The purpose of providing clariflocculators before filters is to produce water of ‘filterable” quality. By filterable quality, we mean that (1) The turbid content of water is considerably reduced so that filter will not choke much often and frequent back wash will not be required.26 Process Plant Utilities (2) The amount of sludge (cake) formed in filters is not excessive because its handling may be a problem. In fact, where the raw water is relatively less turbid, the common practice is to avoid clari-flocculator steps and to feed raw water directly to the filter. There will be only slightly more frequent backwashes but that is justified because no investment in clariflocculators is required. ‘One more advantage of filtration is that by using pressure filters (as against gravity filters) one can get a high output of considerable quality without sacrificing floor area. The only added cost is of pumping the water. Filter media: (1) Quartz and (2) Porous clay are the two most common filter media. Filtration is used for removal of suspended solids in the range of 5 - 50 mg/L. Sand filters provide about 90% removal. Very low turbidity waters are directly sand filtered without any chemical treatment. Filtration mechanism: (1) Adsorption - Surface exposed for adsorption - 5000 ft?/ft° of media. (2) Straining - Cake formation at the top of filter surface. It increases AP (head loss). Depending upon the filtration rate, following classification is done of the filtration process. (1) Slow sand filtration: large filter area. = not capable of removing colloidal impurities. = not capable of removing gelatinous substances. (2) Rapid sand filtration: Multiple media, large bed depth. (8) Rapid pressure filtration: = no need to break the hydraulic head. = no need to build up the AP again and again. Filtration could be of many types on basis of media used. (1) Granular media filtration: A packed bed of sand and pebbles work as a filter media. (2) Membrane filtration: A membrane acts as a filter media which allows passage of small particles but prevents big particles. Normal working level e ‘Operating 7 li Wash trough ~ HCO; cay OH- +HCO; ——> H,0+CO; +) CO} +Ca** ——> caco,t As regarding Mg**, MgCl, + Ca(OH); ——> CaCl; + Mg (OH), (1)Water: An Important Utility 3 For softening, other compounds can also be used, (NaOH, KOH) but these cannot compete with low cost of lime which is easily available as CaO. Most of the softening reactions occur at about 10 pH. At this pH, CaCO, usually carries a negative charge, and Mg (OH); a positive charge. So these precipitates will not settle smoothly unless these charges are neutralized. Cationic coagulants are required for CaCO, precipitation while anionic ones are used for Mg (OH). There are two lime processes, cold lime and hot lime. They owe their origin to negative solubility curve of CaCO, by which we mean that solubility of CaCO, is more in cold water compared to hot water. Cold process is carried out in 4 - 32° C range while hot process with 102 - 110°C range. Hot processes differ from cold processes in that (1) different equipment is used. (2) precipitated CaCO, and Mg (OH); have lower solubilities at higher temperatures. (3) coagulants are usually not required. (4) CO, is vented to atmosphere by heat, so no lime is required to neutralize CO, 2C.2.1 Partial lime softening The most common hardness reduction is precipitation as CaCO, Since Ca hardness is usually present in bicarbonate (HCO, ) form and CO; is usually present in dissolved state, usually the equations discussed in previous section apply. The process of precipitation of CaCO} does not depend upon a single factor/reaction and is interfered by stabilization of colloidal CaCO; (which prevents CaCO, precipitation). the theoretical solubllity curve is of little practical value. The actual amount of lime wequized. can. be delermined reventaly oily by wordiueting & bench/pilot plant test. The proper lime feed can be determined by measuring both the Palakalnity and M (or total) alkalinity. 2C.2.2 Complete lime softening Sometimes the partial lime softening may not be able to remove all the hardness. This will happen when amount of HCO; present in the original water is not significant. Thus on addition of lime, less CO; will be available and hence Ca** precipitation will be less. The added 2 soda ash serves as source of CO; . So additional calcium reduction is achieved by addition of soda ash. This process is also called soda-ash process. The reaction proceeds as follows: Ca*+ + Na,CO, ——> CaCO; | + 2Na* (Soda Ash) ‘The amount of soda ash can be calculated by stoichiometric reaction. The excess amount of soda ash does not serve any purpose. If the Mg'* hardness reduction is also required, appropriate excess should be added. At one time, lime-soda process was common process for treating water for steam locomotives. Low hardness levels were achieved due to long retention time. Soda ash is never used when ever alkalinity exceeds hardness. If the carbonate alkali is too high, it can be reduced by addition of gypsum, CaSO, according to the following reaction CO} +CaSO, ——> CaCO, 1 +S0F34 Process Plant Utilities 2C.3 MORE COMPLETE SOFTENING ATHIGH TEMPERATURE Solubility of both Ca**/Mg"* is lower at higher temperatures, hence the rate of reaction is considerably increased. Moreover the precipitate settles at faster rates in hot water due to decreased viscosity. Hot processes can be of also two types - lime soda and lime zeolite. The amount of lime required is less because usually none is required for CO, reaction because most of the CO) is evaporated due to heating. The CO; solubility is more at low temperatures. The Mg (OH), precipitate is also able to adsorb some of silica. The processes can be carried out in either batch or continuous manner. 2C.4 SILICA REMOVAL Though it is possible to remove silica by adsorption on iron floc in the coagulation process, the settling rates are quite low. Hence when ever silica is to be removed, the hot/ warm process is used and silica is usually entrapped by Mg (OH), precipitate which is either formed by lime-softening reaction or added by using dolamitic lime (which have MgO content between. 28 - 35%) as the water softening reagent. Some times MgO is added when silica reduction is not sufficient due to low amounts of Mg (OH), precipitated. Silica removal is apparently multi-step process, involving adsorption of SiO, on Mg (OH), - followed by chemical combination between adsorbent [(Mg (OH)a] and SiO;. When MgO is used, time is required for hydration before it begins adsorbing SiO>. (This time is obtained by recycling the sludge back into the inlet water). In almost all the cases, water treated with lime /lime-soda is scale forming. To bring the water into chemical balance, 10 to 20 ppm of acid (as CaCOs) is added. Skipping this adjustment may result in precipitation of CaCOs in filters, zeolite softners, piping etc. ‘Comparison between lime/lime - soda process and zeolite/Ion exchange process Lime/Lime Soda Process Zeolite/lon Exchange Process @ Compete utilization of lime and (i) Only 60% of the salt used for soda-ash used. zeolite regeneration. (2) Waste product of the lime system (2) Ibis very difficult to compact brine (sludge CaCO,) is less voluminous then is the | solution. salt, and generally less objectionable. Sludge can be compacted. (3) Some’ silica reduction can be (3) No silica reduction is achieved. achieved by cold lime process, and fairly ‘good reduction with hot-lime process. (4) Overall solids reduction is (4) In zeolite softening, one ion is generally achieved in lime-softening. simply replaced by other (Ca‘* and Mg* is replaced by sodium). (8) Soluble iron can be precipitated (8) Zeolites can remove iron, but not and removed with sludge without a serious loss in efficiency due to fouling, (6) Lime handling is quite difficult. The lime is generally dusty and clogs the feed system 5 (7) Sludge handling is a nuisance but with proper disposal area and dewatering (compacting equipment) or both, the problems are minimal.Water: An Important Utility 35 2C.5 HEAVY METALS REMOVAL Heavy metals are usually removed by precipitation. The hydroxides of heavy metals are usually insoluble, so lime is usually used for precipitating them. However, sometimes the carbonates, phosphates or sulphides are less soluble than hydroxide, so sometimes, precipitation in these forms should also be considered. hence sometimes precipation with sulfide and phosphate is also considered as a secondary treatment. Solubility depends on many factors such as temperature, valance state of metal and surface charge on heavy metal colloidal precipitate. The surface charge should be properly neutralized for proper flocculation. Similarly the solubility of metal depends upon its oxidation state. e.g. Ferrous ion (Fe**) is more soluble then Fe? (Ferric) ion. That is why iron/Mn will usually not be present in well aerated water. It will be found usually in acidic and deep well waters. The removal processes involve oxidation and pH clevation. On more difficulty in heavy metal precipation is formation of complex metal ions which is very common with waters containing organic compounds, especially ammonia or cyanide e.g. iron forms ferrocyanide ions which are generally soluble and will remain so unless broken by chemical treatment. Iron is removed by precipitation by oxidizing its reduced form to yield insoluble ferric hydroxide. The oxidation is usually carried out with oxygen derived from air, chlorine or potassium permangate. The reactions are: 4Fe (HCO;). +0, +2H,;O ——> 4Fe (OH); + 8CO, 2Fe (HCO,); + Ch + 2H, ——> 2Fe (OH); + 2HC1 3Fe (HCO,)2 + KMnO, +2H,0 ——> MnO; + KOH + 3Fe (OH)s It is obvious that oxygen is most effective. However, due to air’s low oxidation potential, the oxidation is relatively slow at low pH. Chlorine required for the same oxidation will be more but chlorine oxidizes iron more rapidly at lower pH than does air. The oxgyen will take 15 minutes while chlorine will do the job in 3 - 4 minutes. In most cases, the chlorine is fed into the line carrying the raw water upstream of a filter. 3 - 4 minutes contact is sufficient to oxidize and precipate iron. ‘The precipated iron particles may be too small and may pass through the filter. A small amount of coagulant (e.g. alum) is used to increase the size of particles. Treatment with KMn0Q, is similar: KMnO, can also precipitate iron but it has a big disadvantage that feed must be accurately controlled since excess of it will result in pink colur water containing manganese. Permanganate is used more frequently in conjunction with manganese zeolite. The zeolite bed oxidizes the iron to the more insoluble Fe (OH)3 and also retains it due to its filter like action. Excess permanganate is taken up by zeolite, which is being regenerated. When zeolite’s oxidizing effect is depleted, it is restored by the permanganate. 2C.6 MANGANESE REMOVAL The manganous (Mn2*) manganese at higher pH also creates problem especially in fibre - industries. The method of Fe removal can also be used for removing Mn, but at a higher pH, (mainly when chlorine air is used for Mn’ oxidation). A pH of about 10 is needed for effective manganese removal. The chemical requirements for oxidzing manganese are double those of iron. Reactions are: 2Mn** +0, +2H,0 ——> 2MnO, + 4H* Mn*+ + Cl +2H,O ——> MnO, +2Cl +4H* 3Mn** + 2MnO, ——> 5MnO; + 4H*36 Process Plant Utilities 2C.7 ORGANIC Mn/Fe REMOVAL Water from wells /swampy areas may contain Fe/Mn in organic (chelate) form. Organic forms of Fe and Mn do not respond to air oxidation, and quite often do not respond to oxidation by chlorine at the usual pH of 7 fo 8. But they can be removed in lime-softening operation. The most common means of removing organic Fe and Mn is by coagulation with a material such as alum, followed by settling and filteration. 2C.8. EMULSION BREAKING ‘An emulsion is an intimate mixture of two liquid phases such as oil and water. Of course, oil and water are immiscible into the other but when they are intimately mixed, one phase may get dispersed into other. Oil in water (O/W emulsions) stands for oily, water with a little oil content while water in oil (W/O emulsion) means waste oil emulsions with a little water. O/W and W/O emulsions can be physically differentiated. ‘O/W > appears like just oily, dirty water, a drop of emulsion added to water mixes rapidly with water. W/O — usually thick and viscous. A drop of emulsion added to water maintains its entity. ‘ ‘O/W emulsions: Apart from oil, it may also contain many other impurities such as solid silt, metal particles, emulsifiers, cleaners, soaps, solvents and other residues. The types of oil will normally depend upon industry and may include fats, lubricants, cutting fluids, heavy hydrocarbon etc. One source of oil in otherwise naive water supplies can be pump lubrication. These oils can be extracted from water by hexane, CCl, CHCl; or fluorocarbons. O/W emulsions owe their stability to surface charge present in colloid. The surface charge may increase by addition of surface active agents. These surfactants usually carry an electronic charge. The enhanced stability is also due to their bifuntional nature. One end of surfactant molecule is soluble in water while the other end is soluble in hydrocarbon. This provides a bridging action at water-oil interface and stabilizes the emulsion. Many times, some process may require presence of emulsified water and to achieve this, emulsifiers are added. An emulsifier is a complex molecule having hydrophilic group at one end and hydrophobic at the other end. Process of Emulsion Breaking: Emulsion breakers are used for this purpose. The accumulated electric charges on the emulsified droplet are neutralized by introducing a charge opposite to that of the droplet. Chemical emulsion breakers work by providing the opposite charge. Emulsions usually carry negative charges. Therefore, to destabilize the emulsions, positive emulsion breakers are required. When emulsion is broken, ideally speaking we should get one oil rich layer and one water rich layer. But usually a third unclear layer is also.formed in which all the solids and emulsifier get collected. The emulsion breaking process may consist of two steps - coagulation (destruction of emulsifying properties) and flocculation (agglomeration of neutralized droplets). Traditionally, sulfuric acid has been used as the first step in emulsion breaking. Chemical coagulating agents such as salts of iron or aluminium may also be used instead of acids but sludges formed by these hydroxides are different to dewater. Acids have better emulsion breaking properties but the water must be adequately neturalized. 2C.9 ION EXCHANGE METHODS Ton exchange methods include zeolite (permutit) method and ion exchange resin ‘method. These methods are used to produce soft and DM (demineralized) water. Zeolites: Zeolites are crystalline alumino silicates of Group IA and IIA such as Na, K, Mg and Ca. These are complex crystalline inorganic polymers based on an extended network= SS Water: An Important Utility 37 by AlO, and SiQ, tetrahedrons. These tetrahedra are interlinked by sharing of O? ions. The empirical formulas is M; [(AlO3), (6i0,)y] - Z H;0 The network of zeolite contains channels/inter connected voids that are occupied by. cations and water molecules. Cations are mobile and are readily ionexchanged. Due to cations mobility, ion exchange and dehydration are quite reversible. ‘The structure of zeolite can be shown as built up of silica and alumina tetrahedra. In other words, these tetrahedra are building blocks of zeolite. Their structure is: < —» < Silica Tetrahedron Mumia retaheddn: ‘As alumina tetrahedron is not neutral, it requires a cation [M*] which is usually Nat. Na‘ can be easily replaced (by other cations) thus making ion exchange easy. Moreover, zeoiltes have large surface area. Due to open framework of zeolites, the surface area is true surface area and not just termination point, In the water softening calculations, zeolite is represented by Z and exhausted bed can be regenerated by treatment with HCl or NaC MgCl +NajZ ——> MgZ+2NaCl _Exhausion Equation ‘MgZ +2NaCl ——> Na,Z+MgCh _Regernation Equation, the soluble MgClz sit* has to be rinsed The advantages /disadvantages of zeolite process are compared below: ‘Advantages Disadvantages @) hardness completely (@) Cannot handle highly turbid water because it} _ removed. will block zeoilte pores. (2) Can work under (2) pH should be about’ 7.0 to protect zeoilte pressure. structure. " (3) No sludge (3) Fe?* and Mn?* in-feed water will change NapZ to formation. FeZ and MnZ, which can't be easily regenerated. (4) Cannot handle hot water. @) Acid radicals are not removed by this process. Therefore this process cannot be used for producing DM water. If used in-boilers, it may cause caustic embrittlement as equation below: NaHCO; —+ NaOH + CO; . Castic Acidic embrittlement corrosion (© Sometimes, the large amount of brine generated in regeneration may be more objectionable compared to sludge formation.38 Process Plant Utilities 2C.10 ION EXCHANGE RESINS METHOD In the ion exchange method, the undesired ions from water are removed and transferred to a solid (called ion exchanger) which accepts them while returning an equivalent number of desired ions. {Hence the name ion-exchange]. The ion exchanger has only limited number of such desired ions, so after certain duration, its ion-exchange capacity decreases and eventually gets exhausted and the ion- exchanger becomes useless. However it can again be put to use by a process called regeneration whereby the ion-exchange resin is washed with a solution containing the desirable ions. After regeneration, the ion-exchange resin works like a fresh one. Thus the ion exchange resin operation is a cyclic process and the same resin can be used for many cycles before finally discarding it. The ion exchange resin material is essentially related to the poly electrolytes used for coagulation /flocculation, but,deliberately made so high in molecular weight so as to be essentially insoluble, ; There are two kind of ion’ exchange resins - cation exchange resins take up and give back (exchange) cations ey Cate ——— Nat (Water) (Resin) while anion exchange ones exchange anions. Typical resins are glassy looking small beads (size 20 - 50 mesh i.e 0.8 to 0.3 mm), The exchange-capacity of resins can be expressed in terms of normality of desirable ion concentration if one considers resins as solid solution. Thus 1 N resin means that it has 1 gm. Equivalent of desirable ions per 1 litre (true volume) of resin. (The ion exchange resins are essentially non- porous). One can convert, by knowing the resin density, the ion exchange capacity, on unit weight basis of resin. A typical (fresh) cation exchange resin has normality of 2 while that of anion exchange resin could be about 1.3. Using normality notation, one can express the exchange capacity as follows: WAN] where Vx = Volume of exchange resin N, = Normality of resin Vy = Water processed per cycle (volume) Nw = Normality of exchangeable ions with water. In above notation, x stands for exchange resin while w stands for water. In Ny, we will include only those ionic species which will actually take part in ion exchange. For example with a Na cycle cation exchange resins, Nw will stand for all cations present in water except Na* and H*. Of course, anions will not be included for cation exchange resin calculations. [It is another matter-that water being electrically neutral, the number of equivalent of cations and anions present should be same]. Most of the exchangers, as told earlier, look like glassy beads and are synthetic plastic materials such as co-polymers of styrene and divinyl benzene. The solubility and water penetrability will depend upon’ cross linking. A loosely cross linked polymer will be having high water penetrability thus giving free access to water but at the same time may be slightlyWater: ‘An Important Utility 39. ‘other hand, a very tightly crossed linked polymer resin may be insoluble but it ‘useless because it may not allow entry of water and regenerating chemicals. hhas to be maintained regarding amount of cross-linking, In practice, water ‘are essentially non-soluble and may last for 5 - 10 years, if premature fouling ion Exchange Resins: To produce it, the plastics (polymer) are reacted with The sulphonic (SOsH-) groups get attached to the skeleton of plastic and are active Obviously this resin will work as a Hydrogen cycle resin because R SO3H will RSO; species and the reaction will proceed as: Ca** + 2RSOjH ——> (RSO;) Ca + 2H” hardness Influent hardness Resin ee in resin In the above reaction, R stands for plastic skeleton group to which sulphonic group is The above resin will also be able to remove sodium ions from water as per following Nat + 2RSO;H ——> (RSOs) Na+ Ht The above equation can also be written as (Ca +HjX ——> CaX+2H* —_(X stands for exchanger; hydrogen cycle) cat + HyZ ——> CaZ + 2H" (Z stands for zeoilte; Hydrogen cycle) In the above notation, use of X or Z is due to historical usage where X or Z stands for 2 In contrast to hydrogen cycle, the equation for sodium exchange cycle can be written as: Catt +Na,Z ——> CaZ + 2Na* (Na-cycle-zeolite process) The sodium cycle cannot replace Na* ions, hehce it can’t completely demineralize water ‘will produce only soft water. After exhaustion, the resins have to be regenerated with HCl cycle operation) or with NaCl (sodium cycle operation) as 2HCL + CaX ——> HX + CaCl, 2HCI + NajX —— HX +2NaCl 2NaCl + CaZ ——> NayZ + CaCl, } ‘The resins discussed above are strong cation resns which can exhcange all cations weak or strong). There is another kind of resins called Weak Cation Resins (WCR). Use of Weak Cation Resins (WCR): WCR have Carboxyl group as active agent. The is R- COOH (with H* exchangeable) WCR will react with only strong cations. Hence practice is to put a SCR (Strong Cation Resins) after WCR. The SCR will nullify shardness. Such WCR resins are also used as polishers. (b) Anion Exchange Resins: They are also produced from resinous plastic type polymers ling some styrene - divinyl benzene copolymers). In cation exchange resins, the active ‘are acidic or cation (Na* or H*) while in case of anion exchange resins, the active group ‘basic or anionic. } Hydrogen Cycle Regeneration Sodium Cycle Regeneration40 Process Plant Utilities In the water treatment process, water is first fed to cation excharige resins which ‘takes up objectionable cations but it also makes water acidic (in hydrogen cycle). The anion exchange resin should be basic enough to.neutralize acidity and also to take up undesirable anions. Hence, the active group in anion exchange resins is amine (the organic equivalent of ammonia). ‘Types of anion exchange resions are: (i) Weak anion resins (also called Weak Base Resins, WBR) which can exchange only strong acids or anions. or (2) Strong base Resins (SBR)| R — N* — R" |havea quarternary amine which 7 * Ng al se can exchange all anions. For WBR, the overalll reaction can be shown as an adsorption reaction (rather than ion- exchange reaction). HCl+WBR ——> WBR- HCl Such exhausted WBR can be easily regenerated by alkali. Strong Base Resins (SBR) are true ion - exchange materials. They can be of many forms eg = ‘ | Bicarbonate and HCO t (SBR) Ch ——> SBR (HCO3); + 2Cr ential SO; + (SBR) Clr > SBR «SO, + 2Cr with Cl-form SBR But the most common SBR will be of OH" form SBR and will be able to react with acid produced in cation exchange. 2Cl- + SBR (OH), ——> SBR Cl, + 20H- Such OH" form SBR can be regenerated with NaOH. e.g. 2NaOH-+ SBR Cl; ——> SBR (OH); + 2NaCl (©) Production of Resins from styrene and divinyl benzene: CH;= CH, CH,= CH, Styrene (vinyl benzene) (VB) Divinyl benzene (DVB) CH,= CH, — CH, — CH, — CH, — CH; — CH, — Polymerisation of styrene to polystyrene (PS)Water: An Important Utility 41 Copolymerization of DVB and PS CH, — CH, — [Ps] — | [Ps]. — CH, CH, CH, | CH, CH; ee - eeu a a DVB is able to produce cross linking (@) Forms of resins: Gel and MR-form: The polymer phases for ion-exchange resins are classified as gelular or macro reticular (MR). Gel: Gelular resins are made of a single, continuous polymer phase. This gel phase has microporosity which can be manipulated by controlling the resins’ degree of cross-linking with divinyl benzene. Most cationic/anionic inorganic ions and organic species of roughly MW < 200 can easily diffuse into and out of gelular structure, MR: These beads have a continuous discrete pore phase dispersed through a continuous gel phase. MR resins are available as ion-exchange resins and as polymer absorbers having high surface area (©) Hydrogen cycle exhaustion and regeneration steps: 0% TOP Ht ANg/ (ona i. i) (2) (3) (4) FRESH aT AFTER AFTER EXHAUSTION BACKWASH REGENERATION WITH ACID Fig, 2C.1 - Changes in ionic distribution of a cation exchange (Hydrogen cycle) bed - Cocurrent operation - both service and regeneration downward2 Process Plant Utilities The reaction for a hydrogen exchange cycle will be as follows: Ca CaX Mg? Mgx Be +H;X—— FexX +2H* 2Nat 2NaX 2 (NH) (NH4):X Order of appearance of IONS in the effluent The first ions to appear in effluent will be NH,* and Na* if the exhausted bed is analyzed. For anion exchange resins, the ion distribution during demineralization for cocurrent regeneration will be as follows: woe MOLE MOL WoL : oH , oti sorron (1) (2) (3) (4) New n ATER ATER ‘OksFORW —EXHAUTION BACKWASH add 5 euvTion Fig. 2C.2 - Changes in ionic distribution of an anion exchange resin bed - both service and regeneration downward 2C.11_ PRACTICES ABOUT ION EXCHANGE Ina practical ion-exchange situation, there are some useful practices: (1) Most ion exchange units are simple vessels containing a bed of resins which are operated as follows: (a) down flow before exhaustion (service, usually 5 — 10 gpm/ft?) (b) upflow cleaning (back wash 5-7 gpm/ft?) (c) downflow regeneration (say 10% soln. at 1 gpm/ft? of resin for approx 20 min.) (4) upflow rinsing. Because both water and regenerating chemicals flow in the same direction, after regeneration, when the bed is started, the water leaving the bed has the highest concentration of contaminants and hence of worst quality. Of course, some relief is achieved by upflow regeneration. (2) The resin is never fully regenerated because it will require long time. Hence the bed has usually more than minimum required capacity. 3) Because of cyclic operation with cocurrent flow of water and regenerant, the chemical utilization is very poor. (4) The ion exchange beads are of 20 - 50 mesh size, so it has its advantages and disadvantages. The advantages include good filtering ability. But this filtering ability also leads to fouling /coating of resins with unwanted foulants.Water: An Important Utility 43 (6) Bed dimensions are usually 1-7 ft dia. and 4 - 12 ft height. Depth of resin bed is minimum 2 feet. The large diameter, shallow bed design requires very efficient distributor systems. : (6) The rinse flow rate should be 1 gpm/ft? of resin for approximately 1 hour to remove excess regenerant. A faster rinse of 1.5 gpm/ft® for 10 - 15 minutes saves time as well as resin loss. (7) Strong oxidants such as chlorine degrade most resins. (8) Higher temperatures increase the rate of reactions, which is especially significant for WBR and WCR. The temperature also changes flow properties of water. (9) Iron salts can be very damaging, especially if they are oxidized from ferrous to ferric state after being adsorbed. This may crack the resins. 2C.12 SODIUM EXCHANGE CYCLE (ZEOLITE SOFTENING) As discussed earlier: (1) Many zeoilte softeners are designed to run at higher temperature service. Such softeners are installed in line with hot lime softenters and filter system. The zeolite used should be able to withstand high temperature and its matrix should not collapse. (2) The regeneration of zeoilte softener is by NaCl and this process is called brining. The higher the brine concentration, the better will be a regeneration. But at the same time, higher - salt (NaCl) amount will be required. As the large amount of spent brine to be handled will create disposal problems, hence an optimum regeneration should be chosen. (3) In the water treatment reaction Ca?*/Mg** + NazZ ——> CaZ/MgZ + 2Na* The zeoilte has more selectivity towards Ca‘* compared to Mg®*. Hence at break through (near exhaustion), Mg** hardness will predominate. (4) Split stream softening is one of the most common designs where a part of stream is treated with zeoilte and remaining with Hydrogen cycle exchanger. 2C.13_ PROBLEMS ASSOCIATED WITH ACID REGENERATION In case of hydrogen cycle exchanger (cation resins), poor regeneration is achieved with acid regeneration. This is due to (1) Cocurrent regeneration. (2) Need to keep H;SO, concentration low because at higher concentrations, CaSO, will precipitate on resins and will provide a coating which will render resins useless. (3) Also the spent acid disposal is a problem because it contains a good part of unused acid plus CaSO,. Of course, these problems will not occur if HCI is used for regeneration but it will be costlier in comparison to H;SO,. HCI also requires special material of construction and its vapours should also be effectively vented. 2C.14_ SOME CORRECTIVE ACTIONS FOR FOULED RESINS (1) CaSO, fouling: Acidize with HCl. Modify regeneration using a low concentration H,S0, initially, followed by higher concentration. (2) Silica: Remove with a caustic wash of 2 - 4%. NaOH at 40 - 50°C. (8) Iron: Acidize with HCI, or treat with reducing agent plus Chelants. (4) Organic fouling: Treat with brine, brine - caustic mixture or detergent.44 Process Plant Utilities Ton exchange is an evolving science. New designs are capable to work at reduced chemical dosage. These improved performances are achieved by: RAW WATER UPPER DISTRIBUTOR LOWER DISTRIBUTOR Fig. 2C.3—A bed design for service downflow and regeneration upflow (counter current). ‘During regeneration, downward water flow prevents bed from excessive expansion (1) Countercurrent regeneration techniques. (2) Multiple stages of water treatment. (3) Multiple stages of regeneration. (4) Use of weak resins wherever possible. (6) Pretreatment of water to-reduce load (e.g. by partial/complete lime softening, RO techniques). (6) Pretreatment of water to reduce fouling ete. 2C.15 PROCESS.OF LEAKAGE Leakage means slipping of undesirable ions into the effluent. Leakage may occur due to: (@) Short circuiting/channelling of water - when a part of water flows down without coming into contact with resins. To prevent this, the packed bed design should be proper. Q) Due to improper regeneration, the concentration of undesirable ions may be high in the resin. The optimum regeneration should be achieved. ) Silica is most loosely held anion (in HSiO3 form) while Na* is most loosely held cation, hence their leakage is most expected. 2C.16 DAMAGES CAUSED TO RESINS ‘These include physical ones like particle size reduction (fines), fractured resins, debris accumulated in the resin bed, coating of resin particles with undesirable organic/inorganic materials which restrict water entry, accumulation of metal oxides on cation resins, and of organic materials in the pores of anion resins: Or these may include chemical changes like destruction of resin structure by foulants present in the water, especially by oxidising agents. Tf any of these problems are doubted, the resin first of all should be examined by a magnifying glass artd compared with fresh resin. If visual examination does not provide any _ clue , then a partial or complete analysis must be done.Water: An Important Utility 45 If the visual examination shows loose precipitate accumulation, it means improper backwash. Sometimes precipitate may find way inside the resins resulting into cracks. If the sieve analysis gives too much of fines, it will give too much of pressure drop thus resulting into poor performance. The excessive fines indicate that hydraulic design of bed is not proper. An increased water retention to 60 - 70% compared to fresh resin value of about 50% indicates that too much water has gone into resin resulting into cracks/swelling of resin. Such swollen resin should be better replaced. One reason due to which cross-linking of resins may get damaged is due to dissolved oxygen. * The anion-exchange resins are too sensitive towards fouling due to organic material. Too much silica and iron in water can also damage resins. Hence their removal upstream of exchanger system should be sought. 2C.17_ PROBLEMS AND PERFORMANCE EVALUATION (1) A single unit operating even with constant quality feed water will show variation in output in range of + 5 - 10% because the flow distribution may not be constant. Flow of water should be evenly distributed. (2) Mostly the problem is of dirty resins due to improper backwash. Many times corrosion may destroy the nozzles of distributors. (3) The regeneration should be proper. The regeneration curve i.e. the regenerant salinity vs. time curve should be of bell-shape with a flat maximum rather than a sharply peaked one. In other words, the salt concentration in the spent regenerant should exceed about 8% for a period of atleast about 30 min. 5 14 *B'Good elution 727 plug flow "A*Poor olution, due to dilution or. channeling 0 10 2p, age aoe eno 70) Minutes afte start of brining Fig. 2C.4 - The ideal regeneration outlet curve should be bell shaped rather than sharply peaked one (4) There should be no by passing or channelling of water. (6) The resins should not get damaged. (6) One problem is that of limited solubility of the product or waste. (e.g. calcium precipitation occurs when regenerating a cation exchanger in the calcium form with sulfuric acid). (7) Osmotic shock on the resin, causes high breakdown and loss. (8) Use of regenerants /Chelating agents that have oxidizing potential (e.g. peroxides, potassium permanganate, nitric acid etc.). (9) Dilution of the concentrated regenerant by water in the resin bed, which may result into heat of dilistion raising temperature above those recommended for the resi46 Process Plant Utilities Generally a 10% concentration of acids/bases is the practical upper limit in most ion exchange operations. However, in some cases, where less waste handling is desired, a concentration of 20% may be tolerable. (10) Unwanted flotation: Special care must be taken since ion-exchange resins may float in higher density solutions. (11) Resins used for condensate polishing should have high attrition resistance because condensate usually is very corrosive and it picks up lot of corrosion debris along with it. This debris is likely to rub resins as condensate passes through the bed. = 2C.18 NON-CONVENTIONAL RESIN BED OPERATIONS Layered Bed Operation: When resins of different kinds are put as layers in the same bed, some economies results in equipment cost. e.g. a WCR can be put in the same vessel as SCR and the bed functions in two separate layers. Continuous system of operation: This keeps removing and regenerating a small portion of resin bed. These systems have some advantage in efficiency but require more careful operation than conventional design. Mixed Bed Operation: In order to enhance efficiency, instead of using two beds, only cone bed is used in which cation and anion exchange resins are intimately mixed. The net effect fe that of hundreds of stages of demineralization. Mixed bed offers significant advantages over single bed system. They have a higher degree of ion-removal in ‘addition to maintaining controlled pH. To enhance efficiency, counter-current operation may also be opted for (service flow downward, regeneration upward). To prevent the bed from expanding during regeneration, a Counter flow (downward) of water may be required to maintain balance of pressure. Such Vessels are also higher because head room (unfilled space) is to be provided (above resin packed height) for back washing. Units of this kind are used for polishing the water as the final Perit either for Boiler Feed Water (BFW) or for condensate polishing: These units operate at very high flow rates because water fed to the bed is almost pure. “The backwash separates two resins, anion resins being lighter collect in the top half portion of bed. The resins are than taken out and regenerated. The mixed bed resins should have good attrition resistance too. ‘There are some resins where both anion and cation exchange sites are transplanted on same polymeric skeleton. These sites are weak, so they can be simultaneously regenerated with help of hot water. The typical formula and exchange of NaCl may be as follows: NH; NH,Cl 1 ii } R—-R—R—R |+Nacl———» R—R=R—R | Step 1 cooH cOoNa NHicl Ni Re c ee ee es Re eel | Step \ COONa coon This process finds an application of low temperature energy (which is otherwise wasted in process plants).suopesad ped Paxtn ~ $97 BH aauno pan SHNOH BNO4 OL OM 3AVL NYO SSBOOUd SHILNA alvaul SNISSU NOILVO ALISNAO HOIH = 30VHS UVC SISSY NOINY ALISN3G MO = 30VHS LHOM SOIAUSS NI HOVE LINN ONILLNd 6s ASNIy 40 ONS 5-2 NOILVH3dO NIS3Y (BN) G38 GaXIW NI Sd3LS 000-0 0.0.00 mes oo mae ae espa NON wounamisia —— ‘8 o3KN (i) on Sonsstt09 OvAURINI =) uaoNvH0x3 NoINy—e-] Moa ouusnv9) 2 5 ;| pa vamores tage wos TOO UaLYM SYM | é 1 1 ates “5 for ive oe Es 5 : aaa uly =Process Plant Utilities Demineralizaer System ‘Applicat “Typical Effluent ‘Advantages and Disadvantag, = Silica and CO are not] Specific conductivity 10] Low equipment and cal objectionable. to 30 micromhos /em?. | regenerant costs. Silica unchanged. {is not objectionable | Specific conductivity 10] Low regenerant cests, but but CO2 removal is] to 20 micromhos /cm?. | requires repumping. sa] val > required. Silica unchanged, Low alkalinity raw water, | Specific conductivity 5to| Low equipment costs, silica removal required. | 10 micromhos/em?.Silica| repumping not required, , 0.020 0.10 ppm. high chemical costs High alkalinity, raw water, | Specific conductivity 5 to] Low chemical costs, silica removal required. | 15 micromhos/om® Silica | repumping is required. 0.0210 0.0 ppm. High alkalinity, sulfate and | Specific conductvity 5 to | Low chemical costs, high some chloride raw water, | 15 micromhos/em?.Silica|equipment costs, silica removal required. | 0.020010 ppm. ‘ | repumping required. High hardness, alkalinity, | Specific conductivity 5] Lowest chemical cost, high sulfate and chloride raw] to 15 micromhos/em?. | equipment cost, repumping. water, silica removal] Silica 0.02100.10 ppm. | required. required, High alkalinity, high sodium | Spcific conductivity 1 to] Low chemical costs, high raw water, high purity] 5 micromhos/em?.Silica] equipment costs, treated water required. | 0.01 10.005 ppm. repumping requited. Low solids, aw water, high] Specific conductivity is| High chemical costs, ow purity treated water|less than 1 equipment costs. required. micromho/cm’. Silica {101 to 005 ppm. High alkalinity _and| Specific conductivity is | Lower chemical cost, high dissolved solids raw water,| ess than 1/ equipment cost, requires high purity treated water| micromho/cm’, Silica | rempumping. requited 01 0 005 ppm. Key: Suongly Weakly Gq). acc adic weak [gg]. strong [] Desasifiter Mixed PA] nydrogen hydrogen basearion [8 Jase anton orvacunes bed ‘cation ‘cation a “Lmho =1 siemens Fig. 2C.6 - Demineralization arrangements for various applications Septum Filters: These filters use mixture of powdered anion and cation resins deposited ‘on a membrane. The volume handled in quite less. Ultrapure water: It is required in such applications like transistor manufacture. The resins come in use and dispose type cartridges.SSS Water: An Important Utility 49 RF operation of Resin Beds: CR (Cocurrent Regeneration, both service and regeneration downflow) and CCR (Counter Current Regeneration, service downflow and regeneration upflow) have disadvantage that nearly one half of the vessel is to be kept empty at the top to allow for resin expansion during backwash. In RF (Reverse flow, service up flow and regeneration downflow), however, the whole bed is filled with resin. RF, back washable, packed-bed resin systems are most modern, simple to operate and economical systems. They give at reasonable cost, high purity water and generate less waste compared to CR/CCR systems. 2C.19 OTHER USES OF ION EXCHANGE RESINS Apart from water treatment, these versatile materials perform a wide range of tasks in both aquous and non-aquous environment. Some of the diverse applications are: - Acid /base catalysis. ~ Manufacture of high purity solvents and reagent chemicals. Separation of by-products of fermentation processes. — Deacidifiation of organic solvents. High purity water production for semiconductor manufacture. — Recovery of valuable waste from dilute process effluents. — Controlled release of pharmaceutical products. — Chromatography, both on analytical and industrial scale. The key to understand the potential of ion - exchange resins is to look beyond their ion- exchange and adsorptive characteristics and see their fundamental nature. 2C.20 DEAERATION AND DEGASIFICATION In water there may be a variety of gases in dissolved forms, especially CO; and air (=O, +N,). However there is a difference between CO; and other dissolved gases that CO, gets ionized as CO; + H,O [===> HCO, ===> 2H* + CO}. Hence the only unreacted part of CO, can exert gas pressure. At the pH below about 4.5, all of CO; is present as a gas. Above 8.5 all of it is ionized. Other gases which ionize in water are H,S, HCN and NH. One more aspect is that CO,/O; ratio is dependent upon active biological metabolism. Algae and other green vegetation may consume CO, while bacteria and other microbes may produce CO,. ‘The solubility of gases in water is governed by classical Henry's Law. The solubility is a strong negative function of temperature because increased temperature results into increasing water vapour pressure itself which pushes out gas molecules. Another related factor is diffusion of gas molecules through water. The diffusion rate increases with increasing temperature because kinetic energy of gas molecules increases and viscosity of water decreases. The rate of gas transfer to water can be empirically given Q = Ka ap Q = rate of gas transfer a = exposed contact area AP = log mean pressure difference (driving force) K = Gas transfer coefficient is a function of gases being transferred and the geometry of system. These principles are used in designing degasification towers as well as gas-liquid contact towers. Degasification tower designs: (1) Packed Stripping Tower: It contains most usually random packings. The water flow is downward, and is counter current of upward flow of gases (usually air) other than the gases being removed. The stripping gas is usually air to remove dissolved gases such as CO;, NHy, H,S or CH,50 Process Plant Utilities (2) LD. Degasifier: In this design, water is sprayed at top through various nozzles. As the water is atomized, its surface area becomes high and it itself gets degasified. The LD. fan above the inlet makes easy removal of gases possible. Packed stripping tower is most commonly used in refineries/paper mills for steam stripping of sour condensates. Unfortunately, NH; is best removed at pH above 10, and HS and HCN are best removed at pH below 6. In pH range 7-8, these gases are in ionized form and hence, their removal is not easy. Therefore, sometimes two-stage degasification may be more practical idea. To enhance degasification, sometimes, water may have to be heated because as discussed earlier, the degasification efficiency increases at higher temperatures. (3)Vacuum deaeration: This is especially used for Boiler Feed Water because the oxygen can be highly corrosive at high temperatures and high velocities. The vacuum is usually created by using steam jet ejectors. To optimise steam consumption, usually two stage ejector degasifier systems are used. The packings used are usually Raschig Rings. (4) Deaerating Heaters: Tray type deaerating heaters are the oldest of such devices. The packings used are SS/CI slotted trays and steam is used both as stripping /heating media. This design is still very popular in boiler plants because of its higher thermal efficiencies compared to atomizing type deaerators. 2C.21 CHEMICAL OXYGEN REMOVAL The spray type and thermal type deaerators discussed above have disadvantages in that they require large equipments, LD. fans, pumps and large H.P. steam consumption. One more disadvantage is that deaeration in them is never complete. To avoid problems, chemical ‘oxygen removal methods are resorted to. Two most common chemicals are sodium sulfite (NaSO;) and Hydrazine (N;H,). These chemicals react with any of the residual oxygen. 2Na,SO3 + 0; ——> 2Na,S0, NH, + 0) ——> 2H,0 +Nz Oxygen at high temperatures can be highly corrosive to steel. Hence, oxgyen destruction should be quite fast. ‘CO; removal is also sometimes desirable. The free form can be stripped and the ionic form can be neutralized by the application of lime, caustic or sodium carbonate. 2D - MEMBRANES ~ A NOVEL WATER PURIFICATION METHOD 2D.1 MEMBRANE SEPARATION Membrane separation for water purification is a modern application. Semipermeable membranes can be natural as well synthetic. Note that it is not justified to call all membranes as permeable. By such membranes, we mean membranes which allow for selective passage of certain material. Synthetic membrane processes are used for both water purification purpose and for separation of mixture of various compounds. The latter being a special field in itself, we will restrict ourselves only to former. When membrane separation is used for purification, water passes through the membrane leaving behind some of the original impurities as concentrate. The amount and type of impurities removed depend upon the type of membrane used, the type of driving forces applied and the quality of feed water. The quality of membrane separation tends to deteriorate with time due to various factors including fouling and clogging. Hence, the rejection factor of a certain species decreases and passage factor increases with time. It is also to be noted that rejection factor may differ for different species.Water: An Important Utility 51 ‘Membrane separation processes differ from ordinary processes in following manners: (1) Membrane processes prevent intermingling of feed and outlet stream hence the chances of accidental surge of impurities are low unless membrane rupture occurs. (2) Membranes prevent ordinary hydrodynamic flow of material. (3) Movement of substance through membranes is by diffusion. (4) Membranes can selectively control the passage of material, i.e. they may allow certain materials to pass while at the same time, they may prevent certain others materials from passing. ‘Membranes may be of two types - microporous and permeable. Microporous membranes contain small pores. Passage of materials through these membranes is by diffusion. Rate of diffusion is proportional to ia . These membranes are capable of separating a particular gas from gas mixtures. Permeable membranes are selectively soluble membranes. These membrane contain no pores. The substance first dissolves in the membrane and then diffuses through it, the rate of separation depending upon differences in solubility. Some examples of permeable separation are: (1) Helium from natural gas by Fluorocarbon polymer membrane (Gas - Gas separation) (2) Purification of Alcohol + Water liquid solution. Alcohol preferentially dissolves into membrane and after passage through membrane, vaporizes on the other side (Gas - liquid separation). The membrane separation process could be of many types like osmosis, Reverse Osmosis (RO), Dialysis, Electrodylasis (ED) etc., the main difference being the type of driving force applied to achieve separation. 2D.2. MEMBRANE TERMINOLOGY In membrane process terminology, the common terms are: Solution = Solute + Solvent Solute = It usually means impurity (which may be solid colloidal, dissolved ions or liquid) which is present in small quality in the solution. Solvent = It means liquid (which is water in case of water purification process). The aim of the process is to increase the purity of solvent. Percentage Rejection = It stands for how much purification of a certain compound has been achieved. For example 80% rejection of chloride ions means that out of every 1 litre solution passing through membrane, 80% of chloride ions are prevented from passing to the product side (permeate) and only 20% of ions pass through membrane (called passage factor) Feed = The solution to be purified, Permeate = The product achieved after purification. Concentration Polarization: As the impurities are not able to pass through the membrane, their concentration starts increasing on the feed side of membrane. This effect is called concentration polarization.Process Plant Utilities p— Permeate Concentation Polarization ™ Concentration of Impurity Feed Side 4 Permeate Side Membrane Fig. 2D.1 - Concentration Polarization affects % Rejection Bleed: As the concentration polarization can be harmful for membrane and ifit increases beyond a certain limit, breakthrough passage of impurities can occur thereby spoiling the permeate quality, hence, all efforts should be done to decrease concentration polarization. Hence a part of concentrated impure liquid is continuously withdrawn. This stream is called bleed. Recycle: Many times, to prevent membrane from fouling, the flow across the membrane is not perpendicular to the membrane. Rather the flow is kept parallel to the membrane. This high velocity flow keeps on washing away the impurities and does not allow concentration build-up. But membrane processes are inherently very slow and they cannot process very high feed rates. Hence, usually the feed intake is kept small and incoming feed is mixed with recycle stream. : The whole scheme of material balance is as follows: Feed (F) at Ce - Permeate (P) at Cp Recycle loop (R) at Cp a Bleed (B) at Cp Fig. 2D.2 - Mass Balance of Membrane SystemWater: An Important Utility 53, (1) For complete rejection: CR (concentration ratio) = G = Recovery Rate (2) For partial rejection: CR = € Ex rejection factor 2D.3. COMPARISON OF VARIOUS DRIVING FORCES USED IN MEMBRANE PROCESSES Osmosis: It is a naturally occurring process. When on one side of membrane, solution is kept and on the other side of membrane, solvent is kept, the solvent will have a tendency to go towards the solution side and thereby diluting the original solution. As the membrane is permeable only to solvent, the pressure of water on the diluted solution side will rise. This pressure is called osmotic pressure (OP). The driving force for process is concentration difference. Reverse osmosis: Reverse osmosis is not a naturally occurring process: Rather we have to apply pressure energy greater than OP on the solution side. This applied pressure makes the solution more concentrated. Thus in RO, the solution is really squeezed so that water from the solution goes to the other side while the concentrated solution remains on one side, The driving force for the process is pressure difference ie. (Applied pressure - AP) 2 GAUGE CYLINDER, 4 LEVEL PISTON IN. B : | _||__ MEMBRANE | CLOSED STRONG VESSEL~.,| SOLUTION STRONG SOLUTION osmosis Reverse Osmosis requires (Naturally Occuring) external pressure Fig. 2D.3 Dialysis: It is process in which colloidat impurities can be removed. The membrane is permeable to solvent and dissolved ions but colloidal impurities can not pass through itProcess Plant Utilities Electrodiolysis: In this process, (1) Ion selective membranes are used which allow passage of either cations (cation selective membrane) or anions (anion selective membrane). (2) Electric force ie. external voltage is applied across membranes to enhance mobility of ions. Thus electric potential is the driving force. SEA SEA SEA WATER WATER WATER E 9 CATHODE ANDOE POSITIVE IONS, MEMBRANE MEMBRANE CONCENTRATED PURE CONCENTRATED BHINE: WATER BRINE Fig. 2D.4 — In ED, Ions movement is governed by potential applied BRIEF DISCUSSION OF VARIOUS MEMBRANE PROCESSES (1) Microfilteration: Membrane acts as a porous barrier. The pores are quite large, in the range of 0.1 - 20 u. The number of pores per unit surface area and their shape and configuration can vary greatly depending upon the membrane type which in turn influences production rates and quality. The common membranes are cellulose acetate and polyamides. The membrane action is not simply sieve type but many physio-chemical changes also’take place like swelling of membrane and chemical /electrochemical interaction between membrane and solute. ‘The major problem of these membranes is clogging: Such clogging cannot be removed by flushing/back washing; changing the membrane is the only solution. The pressure applied is < 20 psi. (2) Ultrafilteration: If the pore size of membrane become < 0.1 ym, the AP required becomes substantially higher than 20 psi to produce acceptable flow rates. This process is called ultrafilteration. The purpose of using smaller pores is to remove fine colloids and high molecular weight organic materials. The major problems of these membranes are: (1) Due to smaller pores, the clogging is more severe. (2) Concentration polarization which decreases rejection and flow rate through membrane. (3) Rerverse osmosis (RO, also called hyper filtration or super filtration: In this process, external pressure must exceed osmotic pressure. Therefore, transmembrane pressure of about 300 psi must be maintained. If pressure is decreased, two things will happen: (i) Flow rate of water will decrease. i) Rejection of salt/ impurities may decrease.AP in RO process means that a substantial cost is that of pumping energy. The other major cost factors are disposal of reject stream and membrane replacement. To optimise cost factors, most RO units are made two stages. Transport of water through membrane is not the result of flow through pores but it is due fo diffusion, one molecule at a time, through vacancies of the molecular structure of the membrane material. The vacancies in such membrane structure are in a state of flux, ie. are not fixed, RO membranes are usually made of amorphous polymers e.g. cellulose acetate, triacetate and polyamide polymers. ‘Operating temperatures must be carefully monitored. because it is the major cause of membrane failure. Polysulfone membranes can be used at high temperature. For wider pH operations, polyethylenimine and polyfurane membranes may be used. There is usually an aging effect which results in surface compaction and decrease in flow area, That is why aging factor must be considered in design stage itself to allow longer membrane life. ‘The process of RO can remove even low molecular weight solutes but flow rates are quite small. (4) Dialysis: Dialysis, though seldom used for water purification, is an important membrane process. This process can be used to remove colloidal impurities from ionic solutions e.g. Cu particles from H,SO, solutions. Ions of large ionic radius diffuse more slowly compared to ions of small radius, hence a separation of ionic species may also sometimes be possible. The most ‘common material for membrane is hydrated cellophane. Selectively of a given membrane is largely related to pore size. (5) Electrodialysis (B.D): The driving force is electrical. Semipermeable ion selective cation and anion membranes are alternately stacked in a chamber with narrow channels between them, Stacking i.e. use of number of narrow compartments increases the peiformance because, (a) Current consumption is minimized because ions have to move only a short distance. (b) Excessive ion deposits at cathodes and anodes is minimized because, with number of membranes, neutralization takes place also betweert Al Brind C interface (A = Anion selective membrane, C = Cation selective membrane). Therefore scale formation is minimized. ‘The current required is dependent upon electrical conductivity of water, and hence the salt concentration of water. As the concentration of salt between the stacks decreases, the electrical conductivity decreases and hence current requirements increase. This means that for removal of additional salt, large amount of extra electrical energy is required.—— = = — | 56 Process Plant Utilities SEA WATER FEED ANION SELECTIVE MEMBRANE CATION SELECTIVE MEMBRANE oO D o CATHODE, > ‘ANODE pune ouner= CONCENTRATED: ‘SEAWATER Fig, 2D.5 - Use of Ion Selective Membranes enhances efficiency of ED process The amount of salt removed depends upon the number of stacks used, electric potential and current applied and the width (narrowness) of channels, Too high current should not be applied because it may result into electrolysis (water - splitting). Concentration Polarization is a very severe problem with ED. Due to this, a membrane potential opposite to applied potential develops which reduces % rejection and causes scale formation. Scale formation occurs because concentration of Ca** ions in the brine channels exceeds the solubility of CaCO or CaSO. Concentration polarizationjand walter spitting increase the tendency for scale formation as concentrations of calcium in brine channels exceed the solubility of CaCO; and/or CaSOj. Such scales are most likely to form at anion exchange membrane ~ concentrate interface due to higher pH (due to OH ions.) “The scale formation affects membrane in many ways. It causes fouling of membrane quite similar to pitting. It reduces transmembrane ion mobility and increases current requirements. ‘One method to solve concentration polarization is polarity reversal where polarity is reversed every 20 - 25 min. and also the direction of flows of feed and brine. Improvement in membrane and stacks design have helped to minimize the effects of concentration polarization. Methods for reducing scale forming tendency (scale stabilization) and cleaning of stacks during run time have been developed which has helped to avoid frequent shutdowns, increasing reliability, decreasing shutdown frequencies due to concentration polarization membrane fouling and membrane rupture, and decreasing both equipment cost and energy costs are the major objectives of designs of modern E.D. systems.Cooling Water Systems 31 me 6) 34 a5 3.6 3.7 3.8 3.9 3.10 Sih 3.12 3.13 3.14 Chapter 3 COOLING WATER SYSTEMS COOLING WATER SYSTEMS: TYPES. SALIENT FEATURES. PROCEDURES USED FOR COOLING WATER TREATMENT. IMPORTANT COOLING WATER VARIABLES AND THEIR EFFECTS/IMPORTANCE. GENERAL CORROSION INHIBITORS. FOULING CONTROL. MICROBIAL CONTROL. BASIC PRACTICE OF COOLING WATER TREATMENT. SEA WATER FOR COOLING AND CONDENSING. ‘CaCO, STABILITY INDEXES. COOLING TOWERS. CONSTRUCTION AND OPERATION OF COOLING TOWERS. TYPES OF COOLING TOWERS. FIRE AND FIRE WATER SYSTEM.