What are Zeolites ?

Zeolites are microporous crystalline solids with well-defined structures. Generally they contain silicon, aluminium and oxygen in their framework and cations, water and/or other molecules wthin their pores. Many occur naturally as minerals, and are extensively mined in many parts of the world. Others are synthetic, and are made commercially for specific uses, or produced y research scientists trying to understand more a out their chemistry. !ecause of their uni"ue porous properties, #eolites are used in a variety of applications with a glo al market of several milliion tonnes per annum. $n the western world, ma%or uses are in petrochemical cracking, ion-exchange &water softening and purification', and in the separation and removal of gases and solvents. Other applications are in agriculture, animal hus andry and construction. (hey are often also referred to as molecular sieves.

Framework Structure
) defining feature of #eolites is that their frameworks are made up of *-connected networks of atoms. One way of thinking a out this is in terms of tetrahedra, with a silicon atom in the middle and oxygen atoms at the corners. (hese tetrahedra can then link together y their corners &see illustration' to from a rich variety of eautiful structures. (he framework structure may contain linked cages, cavities or channels, which are of the right si#e to allow small molecules to enter - i.e. the limiting pore si#es are roughly etween + and ,- . in diameter. $n all, over ,+- different framework structures are now known. $n addition to having silicon or aluminium as the tetrahedral atom, other compositions have also een synthesised, including the growing category of microporous aluminophosphates, known as )/0Os.

Catalysis
Zeolites have the a ility to act as catalysts for chemical reactions which take place within the internal cavities. )n important class of reactions is that catalysed y hydrogen-exchanged #eolites, whose framework- ound protons give rise to very high acidity. (his is exploited in many organic reactions, including crude oil cracking, isomerisation and fuel synthesis. Zeolites can also serve as oxidation or reduction catalysts, often after metals have een introduced into the framework. 1xamples are the use of titanium Z2M-3 in the production of caprolactam, and copper #eolites in 4Ox decomposition. 5nderpinning all these types of reaction is the uni"ue microporous nature of #eolites, where the shape and si#e of a particular pore system exerts a steric influence on the reaction, controlling the access of reactants and products. (hus #eolites are often said to act as shape-selective catalysts. $ncreasingly,

attention has focused on fine-tuning the properties of #eolite catalysts in order to carry out very specific syntheses of high-value chemicals e.g. pharmaceuticals and cosmetics.

Adsorption and Separation

(he shape-selective properties of #eolites are also the asis for their use in molecular adsorption. (he a ility preferentially to adsor certain molecules, while excluding others, has opened up a wide range of molecular sieving applications. 2ometimes it is simply a matter of the si#e and shape of pores controlling access into the #eolite. $n other cases different types of molecule enter the #eolite, ut some diffuse through the channels more "uickly, leaving others stuck ehind, as in the purification of para-xylene y silicalite. 6ation-containing #eolites are extensively used as desiccants due to their high affinity for water, and also find application in gas separation, where molecules are differentiated on the asis of their electrostatic interactions with the metal ions. 6onversely, hydropho ic silica #eolites preferentially a sor organic solvents.Zeolites can thus separate molecules ased on differences of si#e, shape and polarity.
(he shape of para-xylene means that it can diffuse freely in the channels of silicalite

Ion Exchange
(he loosely- ound nature of extra-framework metal ions &such as in #eolite 4a), right' means that they are often readily exchanged for other types of 2odium Zeolite ), used as a water metal when in a"ueous solution. (his is exploited in a ma%or way in water softener in detergent powder softening, where alkali metals such as sodium or potassium prefer to exchange out of the #eolite, eing replaced y the 7hard7 calcium and magnesium ions from the water. Many commercial washing powders thus contain su stantial amounts of #eolite. 6ommercial waste water containing heavy metals, and nuclear effluents containing radioactive isotopes can also e cleaned up using such #eolites.

Zeolites and the Environment

Zeolites contri ute to a cleaner, safer environment in a great num er of ways. $n fact nearly every application of #eolites has een driven y environmental concerns, or plays a significant role in reducing toxic waste and energy consumption. $n powder detergents, #eolites replaced harmful phosphate uilders, now anned in many parts of the world ecause of water pollution risks. 6atalysts, y definition, make a chemical process more efficient, thus saving energy and indirectly reducing pollution. Moreover, processes can e carried out in fewer steps, miminising unecessary waste and y-products. )s solid acids, #eolites reduce the need for corrosive li"uid acids, and as redox catalysts and sor ents, they can remove atmospheric pollutants, such as engine exahust gases and o#one-depleting 686s. Zeolites can also e used to separate harmful organics from water, and in removing heavy metal ions, including those produced y nuclear

fission, from water.

Zeolites in the

Zeolite science and technology has traditionally een very strong in the 59. 0artly this has een due to the scientific legacy of the late 0rofessor :ichard !arrer, the 7father of #eolite science7 who, during a career of over 3- years in various !ritish universities, laid the foundations for the study of #eolites and discovered many of their important properties. (he prominence of the 59 has also een associated with the strength of its chemical industry, particularly in areas where #eolites have applications, such as petrochemicals, detergents, fine chemical synthesis and nuclear processing. Many !ritish companiescontinue to have ma%or :;< pro%ects in these areas. R.G. Bell, May 2001

Zeolites
In recent years, zeolites have been mentioned in the conservation literature, but information on what they are and how they work has been scarce. (A recent paper on passive conservation techniques was given by Yvonne hashoua of the !ritish "useum at the resins conference in Aberdeen, eptember #$%#&, #''(. he compared the performance of gaseous )*l absorbers and found that the best absorber was zeolite.+ The PQ Corporation's Zeolites and Catalysts Division has given permission to reprint parts of their brochure, "Zeolites and the Environment The !ear "###," $hich should fill part of that need% &or more information, call the company at '()##*+,-(.)). or fa/ them at "'0*"+,(.0'#%

What is Zeolite?
Composition The term 1eolite $as originally coined in the ')th century by a 2$edish mineralogist named Cronstedt $ho observed, upon rapidly heating a natural 1eolite, that the stones began to dance about as the $ater evaporated% 3sing the 4ree5 $ords $hich mean "stone that boils," he called this material 1eolite% 6 commonly used description of a 1eolite is a crystalline aluminosilicate $ith a cage structure% Technically, $e spea5 of a 1eolite as a crystalline hydrated aluminosilicate $hose frame$or5 structure encloses cavities 7or pores8 occupied by cations and $ater molecules, both of $hich have considerable freedom of movement, permitting ion e/change and reversible dehydration%

This definition places it in the class of materials 5no$n as "molecular sieves%" 9The pores in dehydrated 1eolite are : ;ngstroms in si1e, $hile those of a typical silica gel average about 0# ;, and activated carbon averages '#0 ;%< =ore than '0# 1eolite types have been synthesi1ed and -# naturally occurring 1eolites are 5no$n% 9The formula of one of the better 5no$n 1eolites is sho$n belo$%< %%% Zeolites occur as hydrates, and all members of the family contain at least one silicon atom per aluminum atom% >a(6 >a"? @ 6l"?, @ "2i?" @ -%0 A"? Natural and Synthetic Formation Zeolites form in nature as a result of the chemical reaction bet$een volcanic glass and saline $ater% Temperatures favoring the natural reaction range from ".BC to 00BC, and the pA is typically bet$een + and '#% >ature reCuires 0# to 0#,### years to complete the reaction% >aturally occurring 1eolites are rarely phase(pure and are contaminated to varying degrees by other minerals 9e%g% &eDD, 2?-(, Cuart1, other 1eolites, and amorphous glass<% &or this reason, naturally occurring 1eolites are e/cluded from many important commercial applications $here uniformity and purity are essential% 2ynthetic 1eolites hold some 5ey advantages over their natural analogs% The synthetics can, of course, be manufactured in a uniform, phase(pure state% Et is also possible to manufacture desirable 1eolite structures $hich do not appear in nature% Zeolite 6 is a $ell(5no$n e/ample% 2ince the principal ra$ materials used to manufacture 1eolites are silica and alumina, $hich are among the most abundant mineral components on earth, the potential to supply 1eolites is virtually unlimited% &inally, 1eolite manufacturing processes engineered by man reCuire significantly less time than the 0# to 0#,### years prescribed by nature%

Commercially Important Physical/Chemical Properties of Zeolite

6ll commercially useful 1eolites o$e their value to one or more of three properties adsorption, ion e/change, and catalysis% Adsorption

The most fundamental consideration regarding the adsorption of chemical species by 1eolites is molecular sieving% 2pecies $ith a 5inetic diameter $hich ma5es them too large to pass through a 1eolite pore are effectively "sieved%" This "sieve" effect can be utili1ed to produce sharp separations of molecules by si1e and shape% The particular affinity a species has for an internal 1eolite cavity depends on electronic considerations% The strong electrostatic field $ithin a 1eolite cavity results in very strong interaction $ith polar molecules such as $ater% >on(polar molecules are also strongly adsorbed due to the polari1ing po$er of these electric fields% Thus, e/cellent separations can be achieved by 1eolites even $hen no steric hindrance occurs% 6dsorption based on molecular sieving, electrostatic fields, and polari1ability are al$ays reversible in theory and usually reversible in practice% This allo$s the 1eolite to be reused many times, cycling bet$een adsorption and desorption% This accounts for the considerable economic value of 1eolite in adsorptive applications% Ion Exchan e Fecause cations are free to migrate in and out of 1eolite structures, 1eolites are often used to e/change their cations for those of surrounding fluids% The preference of a given 1eolite among available cations can be due to ion sieving or due to a competition bet$een the 1eolite phase and aCueous phase for the cations that are present% %%% 2odium 1eolite 6 is among the $orld's most efficient removers of $ater hardness ions% This is its principal function as a detergent builder% Catalysis Zeolites ma5e e/tremely active catalysts%%%% 2teric phenomena are very important in 1eolite catalysis, and a ne$ term, "shape selective catalysis," $as coined to describe these effects% E/tremely selective reactions can be made to occur over 1eolites 9$hen certain products, reactants or transition states are 5ept from forming $ithin the pores because of si1e or shape<%

!eter ent Zeolite "ealth and Safety

&ar and a$ay, the largest outlet for 1eolite volume is the global laundry detergent mar5et% Fy the end of '++" 9it $as e/pected that the $orld $ould< be consuming detergent 1eolite 71eolite 68 at the rate of '%-- million anhydrous metric tons per year% 3nli5e phosphates, 1eolite 6 cannot contribute to the eutrophication of la5es, streams or bays%%%% ?ther 6pplications Gefrigeration The heat of $ater adsorption for 1eolites is high% They also possess high adsorption capacity, undergo reversible adsorption*desorption, and are structurally stable% These properties enable 1eolite to be used in solar(po$ered refrigerators and to store energy during off(pea5 periods and release it during pea5 periods% Zeolites can also be used in refrigeration and air cooling systems to reduce $ater in the air to very lo$ concentrations, allo$ing very effective evaporative cooling to occur%

Natural Zeolites
Consumption Zeolites are found in abundance throughout the $orldH% Ao$ever, the value of the synthetic 1eolites sold is far higherH% =any of the uses for natural 1eolites are environmentally related%

En#ironmentally !ri#en $ar%et Applications

&adioacti#e Waste 'reatment >atural 1eolites are being used to treat lo$ and intermediate aCueous $aste% Current users are Fritish >uclear &uels in 4reat Fritain, Iest Jalley >uclear and Date Gidge >ational Kaboratory% >atural 1eolite has been used in the clean(up at Three =ile Esland and Chernobyl% $unicipal Waste Water 'reatment Certain natural 1eolites have a high affinity for ammonium ions and are being used in a tertiary $ater treatment system at Truc5ee, California% =unicipal effluent is treated by passing it through columns pac5ed $ith a natural 1eolite clinoptilolite to reduce the ammonium ion concentration to less than " ppm%

Pet (itter and )dor Control >atural 1eolites are uniCuely effective in adsorbing ammonia and also adsorb hydrogen sulfide% These properties ma5e natural 1eolites ideal for use in pet litter to prevent emanation of irritating odors% &or similar reasons, natural 1eolites can be used for effective control of irritating gases in horse stalls, barns, 5ennels, etc% 3GK http **cool%conservation(us%org*byorg*abbey*an*an"#*an"#(.*an"#( .#"%html Timestamp 2unday, #)(=ay("#'' '0 ,: ', PDT Getrieved &riday, #+(=ar("#'" '- 00 -. 4=T
All natural waters contain, in various concentrations, dissolved salts which dissociate in water to form charged ions. Positively charged ions are called cations; negatively charged ions are called anions. Ionic impurities can seriously affect the reliability and operating efficiency of a boiler or process system. Overheating caused by the buildup of scale or deposits formed by these impurities can lead to catastrophic tube failures, costly production losses, and unscheduled downtime. Hardness ions, such as calcium and magnesium, must be removed from the water supply before it can be used as boiler feedwater. For high pressure boiler feedwater systems and many process systems, nearly complete removal of all ions, including carbon dio!ide and silica, is re"uired. Ion e!change systems are used for efficient removal of dissolved ions from water. Ion e!changers e!change one ion for another, hold it temporarily, and then release it to a regenerant solution. In an ion e!change system, undesirable ions in the water supply are replaced with more acceptable ions. For e!ample, in a sodium #eolite softener, scale forming calcium and magnesium ions are replaced with sodium ions. HISTORY In $%&', (ans, a (erman chemist, used synthetic aluminosilicate materials )nown as #eolites in the first ion e!change water softeners. Although aluminosilicate materials are rarely used today, the term *#eolite softener* is commonly used to describe any cation e!change process. +he synthetic #eolite e!change material was soon replaced by a naturally occurring material called (reensand. (reensand had a lower e!change capacity than the synthetic material, but its greater physical stability made it more suitable for industrial applications. ,apacity is defined as the amount of e!changeable ions a unit "uantity of resin will remove from a solution. It is usually e!pressed in )ilograins per cubic foot as calcium carbonate. Figure - $. .icroscopic view of cellular resin beads /0& '& mesh1 of a sulfonated styrene divinylben#ene strong acid cation e!hcanger. /,ourtesy of 2ohm and Haas ,ompany.1

+he development of a sulfonated coal cation e!change medium, referred to as carbonaceous #eolite, e!tended the application of ion e!change to hydrogen cycle operation, allowing for the reduction of al)alinity as well as hardness. 3oon, an anion e!change resin /a condensation product of polyamines and formaldehyde1 was developed. +he new anion resin was used with the hydrogen cycle cation resin in an

attempt to deminerali#e /remove all dissolved salts from1 water. However, early anion e!changers were unstable and could not remove such wea)ly ioni#ed acids as silicic and carbonic acid. In the middle $%4&5s, ion e!change resins were developed based on the copolymeri#ation of styrene cross lin)ed with divinylben#ene. +hese resins were very stable and had much greater e!change capacities than their predecessors. +he polystyrene divinylben#ene based anion e!chan ger could remove all anions, including silicic and carbonic acids. +his innovation made the complete deminerali#ation of water possible. Polystyrene divinylben#ene resins are still used in the ma6ority of ion e!change applications. Although the basic resin components are the same, the resins have been modified in many ways to meet the re"uirements of specific applications and provide a longer resin life. One of the most significant changes has been the development of the macroreticular, or macroporous, resin structure. 3tandard gelular resins, such as those shown in Figure - $, have a permeable membrane structure. +his structure meets the chemical and physical re"uirements of most applications. However, in some applications the physical strength and chemical resistance re"uired of the resin structure is beyond the capabilities of the typical gel structure. .acroreticular resins feature discrete pores within a highly cross lin)ed polystyrene divinylben#ene matri!. +hese resins possess a higher physical strength than gels, as well as a greater resistance to thermal degradation and o!idi#ing agents. .acroreticular anion resins /Figure - 01 are also more resistant to organic fouling due to their more porous structure. In addition to polystyrene divinylben#ene resins /Figure - 71, there are newer resins with an acrylic structure, which increases their resistance to organic fouling. In addition to a plastic matri!, ion e!change resin contains ioni#able functional groups. +hese functional groups consist of both positively charged cation elements and negatively charged anion elements. However, only one of the ionic species is mobile. +he other ionic group is attached to the bead structure. Figure - 4 is a schematic illustration of a strong acid cation e!change resin bead, which has ionic sites consisting of immobile anionic /3O781 radicals and mobile sodium cations /9a:1. Ion e!change occurs when raw water ions diffuse into the bead structure and e!change for the mobile portion of the functional group. Ions displaced from the bead diffuse bac) into the water solution. CLASSIFICATIONS OF ION EXCHANGE RESINS Ioni#able groups attached to the resin bead determine the functional capability of the resin. Industrial water treatment resins are classified into four basic categories;

3trong Acid ,ation /3A,1 <ea) Acid ,ation /<A,1 3trong =ase Anion /3=A1 <ea) =ase Anion /<=A1

3A, resins can neutrali#e strong bases and convert neutral salts into their corresponding acids. 3=A resins can neutrali#e strong acids and convert neutral salts into their corresponding bases. +hese resins are utili#ed in most softening and full deminerali#ation applications. <A, and <=A resins are able to neutrali#e strong bases and acids, respectively. +hese resins are used for deal)ali#ation, partial deminerali#ation, or /in combination with strong resins1 full deminerali#ation. 3A, resins derive their functionality from sulfonic acid groups /H3O781. <hen used in deminerali#ation, 3A, resins remove nearly all raw water cations, replacing them with hydrogen ions, as shown below;

+he e!change reaction is reversible. <hen its capacity is e!hausted, the resin can be regenerated with an e!cess of mineral acid. 3trong acid cation e!changers function well at all pH ranges. +hese resins have found a wide range of applications. For e!ample, they are used in the sodium cycle /sodium as the mobile ion1 for softening and in the hydrogen cycle for decationi#ation. <ea) acid cation e!change resins derive their e!change activity from a carbo!ylic group / ,OOH1. <hen operated in the hydrogen form, <A, resins remove cations that are associated with al)alinity, producing carbonic acid as shown;

+hese reactions are also reversible and permit the return of the e!hausted <A, resin to the regenerated form. <A, resins are not able to remove all of the cations in most water supplies. +heir primary asset is their high regeneration efficiency in comparison with 3A, resins. +his high efficiency reduces the amount of acid re"uired to regenerate the resin, thereby reducing the waste acid and minimi#ing disposal problems. <ea) acid cation resins are used primarily for softening and deal)ali#ation of high hardness, high al)alinity waters, fre"uently in con6unction with 3A, sodium cycle polishing systems. In full deminerali#ation systems, the use of <A, and 3A, resins in combination provides the economy of the more efficient <A, resin along with the full e!change capabilities of the 3A, resin. 3=A resins derive their functionality from "uaternary ammonium functional groups. +wo types of "uaternary ammonium groups, referred to as +ype I and +ype II, are used. +ype I sites have three methyl groups;

In a +ype II resin one of the methyl groups is replaced with an ethanol group. +he +ype I resin has a greater stability than the +ype II resin and is able to remove more of the wea)ly ioni#ed acids. +ype II resins provide a greater regeneration efficiency and a greater capacity for the same amount of regenerant chemical used. <hen in the hydro!ide form, 3=A resins remove all commonly encountered anions as shown below;

As with the cation resins, these reactions are reversible, allowing for the regeneration of the resin with a

strong al)ali, such as caustic soda, to return the resin to the hydro!ide form. <ea) base resin functionality originates in primary /2 9H01, secondary /2 9H251, or tertiary /2 92501 amine groups. <=A resins readily re move sulfuric, nitric, and hydrochloric acids, as represented by the following reaction;

SODIUM ZEOLITE SOFTENING

3odium #eolite softening is the most widely applied use of ion e!change. In #eolite softening, water containing scale forming ions, such as calcium and magnesium, passes through a resin bed containing 3A, resin in the sodium form. In the resin, the hardness ions are e!changed with the sodium, and the sodium diffuses into the bul) water solution. +he hardness free water, termed soft water, can then be used for low to medium pressure boiler feedwater, reverse osmosis system ma)eup, some chemical processes, and commercial applications, such as laundries. Principles of Zeoli e Sof enin! +he removal of hardness from water by a #eolite softening process is described by the following reaction;

<ater from a properly operated #eolite softener is nearly free from detectable hardness. How ever, some small amounts of hardness, )nown as lea)age, are present in the treated water. +he level of hardness lea)age is dependent on the hardness and sodium level in the influent water and the amount of salt used for regeneration. Figure - ' is a typical profile of effluent hardness from a #eolite softener during a service cycle. After final rinse, the softener produces a low, nearly constant level of hardness until the ion e!change resin nears e!haustion. At e!haustion, the effluent hardness increases sharply, and regeneration is re"uired. As illustrated by the softening reactions, 3A, resin readily accepts calcium and magnesium ions in e!change for sodium ions. <hen e!hausted resin is regenerated, a high concentration of sodium ions is applied to the resin to replace calcium and magnesium. +he resin is treated with a $&> sodium chloride solution, and regeneration proceeds according to the following e"uation;

?uring regeneration, a large e!cess of regenerant /appro!imately 7 times the amount of calcium and magnesium in the resin1 is used. +he eluted hardness is removed from the softening unit in the waste brine and by rinsing. After regeneration, small residual amounts of hardness remain in the resin. If resin is allowed to sit in a

stagnant vessel of water, some hardness will diffuse into the bul) water. +herefore, at the initiation of flow, the water effluent from a #eolite softener can contain hardness even if it has been regenerated recently. After a few minutes of flow, the hardness is rinsed from the softener, and the treated water is soft. +he duration of a service cycle depends on the rate of softener flow, the hardness level in the water, and the amount of salt used for regeneration. +able - $ shows the effect of regenerant level on the softening capacity of a gelular strong cation resin. 9ote that the capacity of the resin increases as the regenerant dosage increases, but the increase is not proportional. +he regeneration is less efficient at the higher regenerant levels. +herefore, softener operating costs increase as the regenerant level increases. As shown by the data in +able - $, a $'&> increase in regenerant salt provides only a @A> increase in operating capacity. +able - $. Bffect of regenerant salt level on strong acid cation resin softening capacity. Table 8-1. Bffect of regenerant salt level on strong acid cation resin softening capacity. S"l #l$%f &' @ $& $' C"p"ci ( #!r%f &' $-,&&& 0&,&&& 04,&&& 7&,&&&

E)*ip+en +he e"uipment used for sodium #eolite softening consists of a softener e!change vessel, control valves and piping, and a system for brining, or regenerating, the resin. Csually, the softener tan) is a vertical steel pressure vessel with dished heads as shown in Figure - @. .a6or features of the softening vessel include an inlet distribution system, free board space, a regenerant distribution system, ion e!change resin, and a resin retaining underdrain collection system. +he inlet distribution system is usually located at the top of the tan). +he inlet system provides even distribution of influent water. +his prevents the water from hollowing out flow channels in the resin bed, which would reduce system capacity and effluent "uality. +he inlet system also acts as a collector for bac)wash water. +he inlet distributor consists of a central headerDhub with distributing lateralsDradials or simple baffle plates, which direct the flow of water evenly over the resin bed. If water is not prevented from flowing directly onto the bed or tan) walls, channeling will result. +he volume between the inlet distributor and the top of the resin bed is called the free board space. +he free board allows for the e!pansion of the resin during the bac)wash portion of the regeneration without loss of resin. It should be a minimum of '&> of the resin volume /-&> preferred1. +he regenerant distributor is usually a header lateral system that evenly distributes the regenerant brine during regeneration. +he location of the distributor, @ in. above the top of the resin bed, prevents the dilution of regenerant by water in the free board space. It also reduces water and time re"uirements for displacement and fast rinse. +he regenerant distributor should be secured to the tan) structure to prevent brea)age and subse"uent channeling of the regenerant. <ater is softened by the bed of strong acid cation e!change resin in the sodium form. +he "uantity of resin

re"uired depends on the water flow, total hardness, and time desired between regeneration cycles. A minimum bed depth of 04 in. is recommended for all systems. +he underdrain system, located at the bottom of the vessel, retains ion e!change resin in the tan), evenly collects the service flow, and evenly distributes the bac)wash flow. Cneven collection of water in service or uneven distribution of the bac)wash water can result in channeling, resin fouling, or resin loss. Although several underdrain designs are used, there are two primary typesEsubfill and resin retaining. A subfill system consists of multiple layers of support media /such as graded gravel or anthracite1 which support the resin, and a collection system incorporating drilled pipes or subfill strainers. As long as the support layers remain intact, the resin will remain in place. If the supporting media becomes disturbed, usually due to improper bac)wash, the resin can move through the disrupted layers and e!it the vessel. A resin retaining collector, such as a screened lateral or profile wire strainer, is more e!pensive than a subfill system but protects against resin loss. +he main valve and piping system directs the flow of water and regenerant to the proper locations. +he valve system consists of a valve nest or a single multiport valve. A valve nest includes si! main valves; service inlet and outlet, bac)wash inlet and outlet, regenerant inlet, and regenerantDrinse drain. +he valves may be operated manually, or automatically controlled by air, electrical impulse, or water pressure. In some systems, a single multiport valve is used in place of the valve nest. As the valve rotates through a series of fi!ed positions, ports in the valve direct flow in the same manner as a valve nest. .ultiport valves can eliminate operational errors caused by opening of the incorrect valve but must be properly maintained to avoid lea)s through the port seals. +he brining system consists of salt dissolvingDbrine measuring e"uipment, and dilution control e"uipment to provide the desired regenerant strength. +he dissolvingDmeasuring e"uipment is designed to provide the correct amount of concentrated brine /appro!imately 0@> 9a,l1 for each regeneration, without allowing any undissolved salt into the resin. .ost systems use a float operated valve to control the fill and draw down of the supply tan), thereby controlling the amount of salt used in the regeneration. Csually, the concentrated brine is removed from the tan) by means of an eductor system, which also dilutes the brine to the optimum regenerant strength /- $&> 9a,l1. +he brine can also be pumped from the concentrated salt tan) and mi!ed with dilution water to provide the desired regenerant strength. Sof ener Oper" ion A sodium #eolite softener operates through two basic cycles; the service cycle, which produces soft water for use, and the regeneration cycle, which restores resin capacity at e!haustion. In the service cycle, water enters the softener through the inlet distribution system and flows through the bed. +he hardness ions diffuse into the resin and e!change with sodium ions, which return to the bul) water. 3oft water is collected in the underdrain system and discharged. 3ervice water flow to the softener should be as constant as possible to prevent sudden surges and fre"uent on off operation. ?ue to resin re"uirements and vessel designs, the softening operation is most efficient when a service flow rate between @ and $0 gpm per s"uare foot of resin surface area is maintained. .ost e"uipment is designed to operate in this range, but some special designs utili#e a deep resin bed to permit operation at $' 0& gpmDftF. ,ontinuous operation above the manufacturer5s suggested limits can lead to bed compaction, channeling, premature hardness brea)through, and hardness lea)age. Operating well below the manufacturer5s recommended flow rates can also negatively affect softener performance. At low flow rates, the water is not sufficiently distributed, and the optimum resin water contact cannot ta)e place.

<hen a softener is e!hausted, the resin must be regenerated. .onitoring of the effluent hardness reveals resin e!haustion. <hen hardness increases, the unit is e!hausted. Automatic monitors pro vide a more constant indication of the condition of the softener than periodic operator sampling and testing, but re"uire fre"uent maintenance to ensure accuracy. .any facilities regenerate softeners before e!haustion, based on a predetermined time period or number of gallons processed. .ost softening systems consist of more than one softener. +hey are often operated so that one softener is in regeneration or standby while the other units are in service. +his ensures an uninterrupted flow of soft water. Prior to placing a standby softener into service, the unit should be rinsed to remove any hardness that has entered the water during the standing time. Sof ener Re!ener" ion +he regeneration cycle of a sodium #eolite softener consists of four steps; bac)wash, regeneration /brining1, displacement /slow rinse1, and fast rinse. =ac)wash. ?uring the service cycle, the downward flow of water causes suspended material to accumulate on the resin bed. 2esin is an e!cellent filter and can trap particulate matter that has passed through upstream filtration e"uipment. +he bac)wash step removes accumulated material and reclassifies the resin bed. In the bac)wash step, water flows from the underdrain distributor up through the resin bed and out the service distributor to waste. +he upward flow lifts and e!pands the resin, allowing for removal of particulate material and resin fines and the classification of the resin. 2esin classification brings the smaller beads to the top of the unit while the larger beads settle to the bottom. +his enhances the distribution of the regenerant chemical and service water. =ac)washing should continue for a minimum of $& min or until effluent from the bac)wash outlet is clear. +he bac)wash flow should be sufficient to e!pand the resin bed volume by '&> or more, depending on the available free board. Insufficient bac)wash can lead to bed fouling and channeling. B!cessive bac)wash flow rates result in the loss of resin. =ac)wash flow rates usually vary between 4 - /ambient temperature1 and $0 $' /hot service1 gpm per s"uare foot of bed area, but each manufacturer5s recommendation should be followed. +he ability of water to e!pand the resin is greatly affected by temperature. Gess flow is re"uired to e!pand the bed with cold water than with warm water. 2esin bed e!pansion should be chec)ed regularly and the flow rate ad6usted as needed to maintain proper bed e!pansion. Csually, the bac)wash water is filtered raw water. <ater leaving the bac)wash outlet is unchanged in chemistry but can contain suspended solids. In order to conserve water, the bac)wash effluent can be returned to the clarifier or filter influent for treatment. 2egeneration /=rining1. After bac)wash, regenerant brine is applied. +he brine stream enters the unit through the regenerant distributor and flows down through the resin bed at a slow rate /usually between &.' and $ gpm per s"uare foot of resin1. =rine flow is collected through the underdrain and sent to waste. +he slow flow rate increases contact between the brine and resin. +o achieve optimum efficiency from the brine, the solution strength should be $&> during brine introduction. ?isplacement /3low 2inse1. Following the introduction of regenerant brine, a slow flow of water continues through the regenerant distribution system. +his water flow displaces the regenerant through the bed at the desired flow rate. +he displacement step completes the regeneration of the resin by ensuring proper contact of the regenerant with the bottom of the resin bed. +he flow rate for the displacement water is usually the same rate used for the dilution of the concentrated brine. +he duration of the displacement step should be sufficient to allow for appro!imately one resin bed volume of water to pass through the unit. +his provides a

*plug* of displacement water which gradually moves the brine completely through the bed. Fast 2inse. After completion of the displacement rinse, water is introduced through the inlet distributor at a high flow rate. +his rinse water removes the remaining brine as well as any residual hardness from the resin bed. +he fast rinse flow rate is normally between $.' and 0 gpm per s"uare foot of resin. 3ometimes it is deter mined by the service rate for the softener. Initially, the rinse effluent contains large amounts of hardness and sodium chloride. Csually, hardness is rinsed from the softener before e!cess sodium chloride. In many operations, the softener can be returned to service as soon as the hardness reaches a predetermined level, but some uses re"uire rinsing until the effluent chlorides or conductivity are near influent levels. An effective fast rinse is important to ensure high effluent "uality during the service run. If the softener has been in standby following a regeneration, a second fast rinse, )nown as a service rinse, can be used to remove any hardness that has entered the water during standby. HOT ZEOLITE SOFTENING Heolite softeners can be used to remove residual hardness in the effluent from a hot process lime or lime soda softener. +he hot process effluent flows through filters and then through a bed of strong acid cation resin in the sodium form /Figure - A1. +he e"uipment and operation of a hot #eolite softener is identical to that of an ambient temperature softener, e!cept that the valves, piping, controllers, and instrumentation must be suitable for the high temperature /00& 0'&IF1. 3tandard strong cation resin can be used at temperatures of up to 0A&IF, but for a longer service life a premium gel or macroreticular resin is recommended. <hen operating a #eolite system following a hot process softener, it is important to design the system to eliminate flow surges in the hot lime unit. ,ommon designs include the use of bac)wash water storage tan)s in the hot lime unit and e!tended slow rinses for the #eolite in lieu of a standard fast rinse. Applic" ions "n, A,-"n "!es 3cale and deposit buildup in boilers and the formation of insoluble soap curds in washing operations have created a large demand for softened water. =ecause sodium #eolite softeners are able to satisfy this demand economically, they are widely used in the preparation of water for low and medium pressure boilers, laundries, and chemical processes. 3odium #eolite softening also offers the following advantages over other softening methods;

treated water has a very low scaling tendency because #eolite softening reduces the hardness level of most water supplies to less than 0 ppm operation is simple and reliable; automatic and semiautomatic regeneration controls are available at a reasonable cost salt is ine!pensive and easy to handle no waste sludge is produced; usually, waste disposal is not a problem within certain limits, variations in water flow rate have little effect on treated water "uality because efficient operation can be obtained in units of almost any si#e, sodium #eolite softeners are suitable for both large and small installations

Li+i " ions Although sodium #eolite softeners efficiently re duce the amount of dissolved hardness in a water supply, the total solids content, al)alinity, and silica in the water remain unaffected. A sodium #eolite softener is not a direct replacement for a hot lime soda softener. Plants that have replaced their hot process softeners with

only #eolite softeners have e!perienced problems with silica and al)alinity levels in their boilers. =ecause the resin is such an efficient filter, sodium #eolite softeners do not function efficiently on turbid waters. ,ontinued operation with an influent turbidity in e!cess of $.& J+C causes bed fouling, short service runs, and poor effluent "uality. .ost city and well waters are suitable, but many surface supplies must be clarified and filtered before use. +he resin can be fouled by heavy metal contaminants, such as iron and aluminum, which are not removed during the course of a normal regeneration. If e!cess iron or manganese is present in the water supply, the resin must be cleaned periodically. <henever aluminum coagulants are used ahead of #eolite softeners, proper e"uipment operation and close control of clarifier pH are essential to good softener performance. 3trong o!idi#ing agents in the raw water attac) and degrade the resin. ,hlorine, present in most municipal supplies, is a strong o!idant and should be removed prior to #eolite softening by activated carbon filtration or reaction with sodium sulfite. DEMINERALIZATION 3oftening alone is insufficient for most high pressure boiler feedwaters and for many process streams, especially those used in the manufacture of electronics e"uipment. In addition to the removal of hardness, these processes re"uire removal of all dissolved solids, such as sodium, silica, al)alinity, and the mineral anions /,l8, 3O4F8, 9O781. ?eminerali#ation of water is the removal of essentially all inorganic salts by ion e!change. In this process, strong acid cation resin in the hydrogen form converts dissolved salts into their corresponding acids, and strong base anion resin in the hydro!ide form removes these acids. ?eminerali#ation produces water similar in "uality to distillation at a lower cost for most fresh waters. Principles of De+iner"li." ion A deminerali#er system consists of one or more ion e!change resin columns, which include a strong acid cation unit and a strong base anion unit. +he cation resin e!changes hydrogen for the raw water cations as shown by the following reactions;

A measure of the total concentration of the strong acids in the cation effluent is the free mineral acidity /F.A1. In a typical service run, the F.A content is stable most of the time, as shown in Figure - -. If cation e!change were $&&> efficient, the F.A from the e!changer would be e"ual to the theoretical mineral acidity /+.A1 of the water. +he F.A is usually slightly lower than the +.A because a small amount of sodium lea)s through the cation e!changer. +he amount of sodium lea)age depends on the regenerant level, the flow rate, and the proportion of sodium to the other cations in the raw water. In general, sodium lea)age increases as the ratio of sodium to total cations increases. As a cation e!change unit nears e!haustion, F.A in the effluent drops sharply, indicating that the e!changer should be removed from service. At this time the resin should be regenerated with an acid solution, which returns the e!change sites to the hydrogen form. 3ulfuric acid is normally used due to its affordable cost and its availability. However, improper use of sulfuric acid can cause irreversible fouling of the resin with calcium

sulfate. +o prevent this occurrence, the sulfuric acid is usually applied at a high flow rate /$ gpm per s"uare foot of resin1 and an initial concentration of 0> or less. +he acid concentration is gradually increased to @ -> to complete regeneration. 3ome installations use hydrochloric acid for regeneration. +his necessitates the use of special materials of construction in the regenerant system. As with a sodium #eolite unit, an e!cess of regenerant /sulfuric or hydrochloric acid1 is re"uired up to three times the theoretical dose. +o complete the deminerali#ation process, water from the cation unit is passed through a strong base anion e!change resin in the hydro!ide form. +he resin e!changes hydrogen ions for both highly ioni#ed mineral ions and the more wea)ly ioni#ed carbonic and silicic acids, as shown below;

+he above reactions indicate that deminerali#ation completely removes the cations and anions from the water. In reality, because ion e!change reactions are e"uilibrium reactions, some lea)age occurs. .ost lea)age from cation units is sodium. +his sodium lea)age is converted to sodium hydro!ide in the anion units. +here fore, the effluent pH of a two bed cation anion deminerali#er system is slightly al)aline. +he caustic produced in the anions causes a small amount of silica lea)age. +he e!tent of lea)age from the anions depends on the chemistry of the water being processed and the regenerant dosage being used. ?eminerali#ation using strong anion resins removes silica as well as other dissolved solids. Bffluent silica and conductivity are important parameters to monitor during a deminerali#er service run. =oth silica and conductivity are low at the end of the fast rinse, as shown in Figure - %. <hen silica brea)through occurs at the end of a service run, the treated water silica level increases sharply. Often, the conductivity of the water decreases momentarily, then rises rapidly. +his temporary drop in conductivity is easily e!plained. ?uring the normal service run, most of the effluent conductivity is attributed to the small level of sodium hydro!ide produced in the anion e!changer. <hen silica brea)through occurs, the hydro!ide is no longer available, and the sodium from the cation e!changer is converted to sodium silicate, which is much less conductive than sodium hydro!ide. As anion resin e!haustion progresses, the more conductive mineral ions brea) through, causing a subse"uent increase in conductivity. <hen the end of a deminerali#er run is detected, the unit must be removed from service immediately. If the deminerali#er is allowed to remain in service past the brea)point, the level of silica in the treated water can rise above that of the influent water, due to the concentrating of silica that ta)es place in the anion resin during the service run. 3trong base anion e!changers are regenerated with a 4> sodium hydro!ide solution. As with cation regeneration, the relatively high concentration of hydro!ide drives the regeneration reaction. +o improve the removal of silica from the resin bed, the regenerant caustic is usually heated to $0&IF or to the temperature specified by the resin manufacturer. 3ilica removal is also enhanced by a resin bed preheat step before the introduction of warm caustic.

E)*ip+en "n, Oper" ion +he e"uipment used for cation anion deminerali#ation is similar to that used in #eolite softening. +he primary difference is that the vessels, valves, and piping must be made of /or lined with1 corrosion resistant materials. 2ubber and polyvinyl chloride /PK,1 are commonly used for ion e!change vessel linings. +he controls and regenerant systems for deminerali#ers are more comple!, to allow for such enhancements as stepwise acid and warm caustic regenerations. ?eminerali#ers are similar in operation to #eolite softeners. +he service flow rate guidelines for a deminerali#er range from @ to $& gpm per s"uare foot of resin. Flow rates of over $& gpm per s"uare foot of resin cause increased sodium and silica lea)age with certain waters. Anion resin is much lighter than cation resin. +herefore, the bac)wash flow rates for anion e!change resins are much lower than those for cation resins, and anion resin e!pansion is affected by the temperature of the water more than cation resin e!pansion. +he water used for each step of anion resin regeneration should be free from hardness, to prevent precipitation of hardness salts in the al)aline anion resin bed. ,ontinuous conductivity instruments and silica analy#ers are commonly used to monitor anion effluent water "uality and detect the need for regeneration. In some instances, conductivity probes are placed in the resin bed above the underdrain collectors to detect resin e!haustion before silica brea)through into the treated water occurs. A,-"n "!es "n, Li+i " ions ?eminerali#ers can produce high purity water for nearly every use. ?eminerali#ed water is widely used for high pressure boiler feedwater and for many process waters. +he "uality of water produced is comparable to distilled water, usually at a fraction of the cost. ?eminerali#ers come in a wide variety of si#es. 3ystems range from laboratory columns that produce only a few gallons per hour to systems that produce thousands of gallons per minute. Gi)e other ion e!change systems, deminerali#ers re"uire filtered water in order to function efficiently. 2esin foulants and degrading agents, such as iron and chlorine, should be avoided or removed prior to deminerali#ation. Anion resins are very susceptible to fouling and attac) from the organic materials present in many surface water supplies. 3ome forms of silica, )nown as colloidal, or non reactive, are not removed by a deminerali#er. Hot, al)aline boiler water dissolves the colloidal material, forming simple silicates that are similar to those that enter the boiler in a soluble form. As such, they can form deposits on tube surfaces and volatili#e into the steam. DEAL/ALIZATION Often, boiler or process operating conditions re"uire the removal of hardness and the reduction of al)alinity but not the removal of the other solids. Heolite softening does not reduce al)alinity, and deminerali#ation is too costly. For these situations, a deal)ali#ation process is used. 3odium #eoliteDhydrogen #eolite /split stream1 deal)ali#ation, chloride anion deal)ali#ation, and wea) acid cation deal)ali#ation are the most fre"uently used processes. So,i*+ Zeoli e%H(,ro!en Zeoli e #Spli S re"+' De"l0"li." ion In a split stream deal)ali#er, a portion of the raw water flows through a sodium #eolite softener. +he remainder flows through a hydrogen form strong acid cation unit /hydrogen #eolite1. +he effluent from the sodium #eolite is combined with the hydrogen #eolite effluent. +he effluent from the hydrogen #eolite unit contains carbonic acid, produced from the raw water al)alinity, and free mineral acids. <hen the two streams are combined, free mineral acidity in the hydrogen #eolite effluent converts sodium carbonate and

bicarbonate al)alinity in the sodium #eolite effluent to carbonic acid as shown below;

,arbonic acid is unstable in water. It forms carbon dio!ide gas and water. +he blended effluents are sent to a decarbonator or degasser, where the carbon dio!ide is stripped from the water by a countercurrent stream of air. Figure - $& shows a typical split stream deal)ali#ation system. +he desired level of blended water al)alinity can be maintained through control of the percentage of sodium #eolite and hydrogen #eolite water in the mi!ture. A higher percentage of sodium #eolite water results in higher al)alinity, and an increased percentage of hydrogen #eolite water reduces al)alinity. In addition to reducing al)alinity, a split stream deal)ali#er reduces the total dissolved solids of the water. +his is important in high al)alinity waters, because the conductivity of these waters affects the process and can limit boiler cycles of concentration. So,i*+ Zeoli e%C1lori,e Anion De"l0"li." ion 3trong base anion resin in the chloride form can be used to reduce the al)alinity of a water. <ater flows through a #eolite softener and then an anion unit, which replaces the carbonate, bicarbonate, sulfate, and nitrate ions with chloride ions as shown in these reactions;

+he chloride anion deal)ali#er reduces al)alinity by appro!imately %&> but does not reduce total solids. <hen the resin nears e!haustion, treated water al)alinity increases rapidly, signaling the need for regeneration. +he #eolite softener is regenerated as previously described. In addition, the anion resin is also regenerated with a sodium chloride brine that returns the resin to the chloride form. Fre"uently, a small amount of caustic soda is added to the regenerant brine to enhance al)alinity removal. 2e"0 Aci, C" ion De"l0"li." ion Another method of deal)ali#ation uses wea) acid cation resins. <ea) acid resins are similar in operation to strong acid cation resins, but only e!change for cations that are associated with al)alinity, as shown by these reactions;

where H represents the resin. +he carbonic acid /H0,O71 formed is removed by a decarbonator or degasser as in a split stream system. +he ideal influent for a wea) acid cation system has a hardness level e"ual to the al)alinity /both e!pressed

in ppm as ,a,O71. In waters that are higher in al)alinity than hardness, the al)alinity is not removed to its lowest level. In waters containing more hardness than al)alinity, some hardness remains after treatment. Csually, these waters must be polished by a sodium #eolite softener to remove hardness. ?uring the initial portion of a wea) acid cation service run /the first 4& @&>1 some cations associated with mineral anions e!change, producing small amounts of mineral acids in the effluent. As the service cycle progresses, al)alinity appears in the effluent. <hen the al)alinity in the effluent e!ceeds $&> of the influent al)alinity, the unit is removed from service and regenerated with a &.'> sulfuric acid solution. +he concentration of regenerant acid should be )ept below &.' &.A>, to prevent calcium sulfate precipitation in the resin. <ea) acid cation resin e!change is very efficient. +herefore, the amount of acid re"uired is virtually e"ual /chemically1 to the amount of cations removed during the service cycle. If the materials of construction for the down stream e"uipment or overall process cannot tolerate the mineral acidity present during the initial portions of the service cycle, a brine solution is passed through the regenerated wea) acid resin prior to the final rinse. +his solution removes the mineral acidity without a significant impact on the "uality or length of the subse"uent run. B"uipment used for a wea) acid cation deal)ali#er is similar to that used for a strong acid cation e!changer, with the e!ception of the resin. One variation of the standard design uses a layer of wea) acid resin on top of strong acid cation resin. =ecause it is lighter, the wea) acid resin remains on top. +he layered resin system is regenerated with sulfuric acid and then with sodium chloride brine. +he brine solution converts the strong acid resin to the sodium form. +his resin then acts as a polishing softener. Direc Aci, In3ec ion In the process of direct acid in6ection and decarbonation, acid is used to convert al)alinity to carbonic acid. +he carbonic acid dissociates to form carbon dio!ide and water and the carbon dio!ide is removed in a decarbonator. +he use of an acid in6ection system should be approached with caution, because an acid overfeed or a brea)down in the pH control system can produce acidic feedwater, which corrodes the iron surfaces of feedwater systems and boilers. Proper pH monitoring and controlled caustic feed after decarbonation are re"uired. A,-"n "!es "n, Li+i " ions of De"l0"li." ion S(s e+s Ion e!change deal)ali#ation systems produce hardness free, low al)alinity water at a reasonable cost, and with a high degree of reliability. +hey are well suited for processing feedwater for medium pressure boilers, and for process water for the beverage industry. 3plit stream and wea) acid cation systems also reduce the total dissolved solids. In addition to these advantages, the following disadvantages must be considered;

deal)ali#ers do not remove all of the al)alinity and do not affect the silica content of a water deal)ali#ers re"uire the same influent purity as other ion e!change processes; filtered water that is low in potential foulants must be used the water produced by a deal)ali#ation system using a forced draft decarbonator becomes saturated with o!ygen, so it is potentially corrosive

COUNTERFLO2 AND MIXED 4ED DEIONIZATION ?ue to increasing boiler operating pressures and the manufacture of products re"uiring contaminant free water, there is a growing need for higher water "uality than cation anion deminerali#ers can produce. +herefore, it has become necessary to modify the standard deminerali#ation process to increase the purity of the treated water. +he most significant improvements in deminerali#ed water purity have been produced

by counterflow cation e!changers and mi!ed bed e!changers. Co*n erflo5 C" ion E6c1"n!ers In a conventional deminerali#er system, regenerant flow is in the same direction as the service flow, down through the resin bed. +his scheme is )nown as co current operation and is the basis for most ion e!change system designs. ?uring the regeneration of a co current unit, the contaminants are displaced through the resin bed during the regeneration. At the end of the regeneration, some ions, predominately sodium ions, remain in the bottom of the resin bed. =ecause the upper portion of the bed has been e!posed to fresh regenerant, it is highly regenerated. As the water flows through the resin during service, cations are e!changed in the upper portion of the bed first, and then move down through the resin as the bed becomes e!hausted. 3odium ions that remained in the bed during regeneration diffuse into the decationi#ed water before it leaves the vessel. +his sodium lea)age enters the anion unit where anion e!change produces caustic, raising the pH and conductivity of the deminerali#ed water. In a counterflow regenerated cation e!changer, the regenerant flows in the opposite direction of the service flow. For e!ample, if the service flow is downward through the bed, the regenerant acid flow is up through the bed. As a result, the most highly regenerated resin is located where the service water leaves the vessel. +he highly regenerated resin removes the low level of contaminants that have escaped removal in the top of the bed. +his results in higher water purity than co current designs can produce. +o ma!imi#e contact between the acid and resin and to )eep the most highly regenerated resin from mi!ing with the rest of the bed, the resin bed must stay compressed during the regenerant introduction. +his compression is usually achieved in one of two ways;

a bloc)ing flow of water or air is used the acid flow is split, and acid is introduced at both the top and the bottom of the resin bed /Figure - $$1

Mi6e, 4e, E6c1"n!ers A mi!ed bed e!changer has both cation and anion resin mi!ed together in a single vessel. As water flows through the resin bed, the ion e!change process is repeated many times, *polishing* the water to a very high purity. ?uring regeneration, the resin is separated into distinct cation and anion fractions as shown in Figure - $0. +he resin is separated by bac)washing, with the lighter anion resin settling on top of the cation resin. 2egenerant acid is introduced through the bottom distributor, and caustic is introduced through distributors above the resin bed. +he regenerant streams meet at the boundary between the cation and anion resin and discharge through a collector located at the resin interface. Following regenerant introduction and displacement rinse, air and water are used to mi! the resins. +hen the resins are rinsed, and the unit is ready for service. ,ounterflow and mi!ed bed systems produce a purer water than conventional cation anion deminerali#ers, but re"uire more sophisticated e"uipment and have a higher initial cost. +he more complicated regeneration se"uences re"uire closer operator attention than standard systems. +his is especially true for a mi!ed bed unit. OTHER DEMINERALIZATION PROCESSES +he standard cation anion process has been modified in many systems to reduce the use of costly regenerants and the production of waste. .odifications include the use of decarbonators and degassers, wea) acid and wea) base resins, strong base anion caustic waste /to regenerate wea) base anion

e!changers1, and reclamation of a portion of spent caustic for subse"uent regeneration cycles. 3everal different approaches to deminerali#ation using these processes are shown in Figure - $7. Dec"r$on" ors "n, De!"ssers ?ecarbonators and degassers are economically beneficial to many deminerali#ation systems, because they reduce the amount of caustic re"uired for regeneration. <ater from a cation e!changer is bro)en into small droplets by sprays and trays or pac)ing in a decarbonator. +he water then flows through a stream of air flowing in the opposite direction. ,arbonic acid present in the cation effluent dissociates into carbon dio!ide and water. +he carbon dio!ide is stripped from the water by the air, reducing the load to the anion e!changers. +ypical forced draft decarbonators are capable of removing carbon dio!ide down to $& $' ppm. However, water effluent from a decarbonator is saturated with o!ygen. In a vacuum degasser, water droplets are introduced into a pac)ed column that is operated under a vacuum. ,arbon dio!ide is removed from the water due to its decreased partial pressure in a vacuum. A vacuum degasser usually reduces carbon dio!ide to less than 0 ppm and also removes most of the o!ygen from the water. However, vacuum degassers are more e!pensive to purchase and operate than forced draft decarbonators. 2e"0 Aci, "n, 2e"0 4"se Resins <ea) functionality resins have a much higher regeneration efficiency than their strong function ality counterparts. <ea) acid cation resins, as described in the deal)ali#ation section, e!change with cations associated with al)alinity. <ea) base resins e!change with the mineral acid anions /3O4F8, ,l8, 9O781 in a strong acid solution. +he regeneration efficiency of wea) resins is virtually stoichiometric, the removal of $ )gr of ions /as ,a,O71 re"uires only slightly more than $ )gr of the regenerant ion /as ,a,O71. 3trong resins re"uire three to four times the regenerant for the same contaminant removal. <ea) base resins are so efficient that it is common practice to regenerate a wea) base e!changer with a portion of the *spent* caustic from regeneration of the strong base anion resin. +he first fraction of the caustic from the strong base unit is sent to waste to prevent silica fouling of the wea) base resin. +he remaining caustic is used to regenerate the wea) base resin. An additional feature of wea) base resins is their ability to hold natural organic materials that foul strong base resins and release them during the regeneration cycle. ?ue to this ability, wea) base resins are commonly used to protect strong base resins from harmful organic fouling. Re!ener"n Re*se ?ue to the high cost of caustic soda and the increasing problems of waste disposal, many deminerali#ation systems are now e"uipped with a caustic reclaim feature. +he reclaim system uses a portion of the spent caustic from the previous regeneration at the beginning of the ne!t regeneration cycle. +he reused caustic is followed by fresh caustic to complete the regeneration. +he new caustic is then reclaimed for use in the ne!t regeneration. +ypically, sulfuric acid is not reclaimed, because it is lower in cost and calcium sulfate precipitation is a potential problem. CONDENSATE POLISHING Ion e!change uses are not limited to process and boiler water ma)eup. Ion e!change can be used to purify, or polish, returned condensate, removing corrosion products that could cause harmful deposits in boilers. +ypically, the contaminants in the condensate system are particulate iron and copper. Gow levels of other contaminants may enter the system through condenser and pump seal lea)s or carry over of boiler water

into the steam. ,ondensate polishers filter out the particulates and remove soluble contaminants by ion e!change. .ost paper mill condensate polishers operate at temperatures approaching 0&&IF, precluding the use of anion resin. ,ation resin, which is stable up to temperatures of over 0A&IF, is used for deep bed condensate polishing in these applications. +he resin is regenerated with sodium chloride brine, as in a #eolite softener. In situations where sodium lea)age from the polisher adversely affects the boiler water internal chemical program or steam attemperating water purity, the resin can be regenerated with an ioni#ed amine solution to prevent these problems. +he service flow rate for a deep bed polisher /0& '& gpm per s"uare foot of resin surface area1 is very high compared to that of a conventional softener. High flow rates are permissible because the level of soluble ions in the condensate can be usually very low. Particulate iron and copper are removed by filtration, while dissolved contaminants are reduced by e!change for the sodium or amine in the resin. +he deep bed cation resin condensate polisher is regenerated with $' lb of sodium chloride per cubic foot of resin, in a manner similar to that used for conventional sodium #eolite regeneration. A solubili#ing or reducing agent is often used to assist in the removal of iron. 3ometimes, a supplemental bac)wash header is located 6ust below the surface of the resin bed. +his subsurface distributor, used prior to bac)washing, introduces water to brea) up the crust that forms on the resin surface between regenerations. An important consideration is the selection of a resin for condensate polishing. =ecause high pressure drops are generated by the high service flow rates and particulate loadings, and because many systems operate at high temperatures, considerable stress is imposed on the structure of the resin. A premium grade gelular or macroreticular resin should be used in deep bed condensate polishing applications. In systems re"uiring total dissolved solids and particulate removal, a mi!ed bed condensate polisher may be used. +he temperature of the condensate should be below $4&IF, which is the ma!imum continuous operating temperature for the anion resin. Additionally, the flow through the unit is generally reduced to appro!imately 0& gpmDftF. Ion e!change resins are also used as part of a precoat filtration system, as shown in Figure - $4, for polishing condensate. +he resin is crushed and mi!ed into a slurry, which is used to coat individual septums in a filter vessel. +he powdered resin is a very fine filtering medium that traps particulate matter and removes some soluble contaminants by ion e!change. <hen the filter media becomes clogged, the precoat material is disposed of, and the septums are coated with a fresh slurry of powdered resin. COMMON ION EXCHANGE SYSTEM PRO4LEMS As in any dynamic operating system incorporating electrical and mechanical e"uipment and chemical operations, problems do occur in ion e!change systems. +he problems usually result in poor effluent "uality, decreased service run lengths, or increased consumption of regenerant. +o )eep the ion e!change system operating efficiently and reliably, changes in water "uality, run lengths, or regenerant consumption should be considered whenever problems are detected. +he cause effect diagrams for short runs /Figure - $'1 and poor "uality effluent /Figure - $@1 show that there are many possible causes for reduced performance of a deminerali#ation system. 3ome of the more common problems are discussed below. Oper" ion"l Pro$le+s ,hanges in raw water "uality have a significant impact on both the run length and the effluent "uality produced by an ion e!change unit. Although most well waters have a consistent "uality, most surface water

compositions vary widely over time. A $&> increase in the hardness of the water to a sodium #eolite softener causes a $&> decrease in the service run length. An increase in the ratio of sodium to total cations causes increased sodium lea)age from a deminerali#er system. 2egular chemical analysis of the influent water to ion e!changers should be performed to reveal such variations. Other causes of ion e!change operational problems include;

Improper regenerations, caused by incorrect regenerant flows, times, or concentrations. .anufacturer5s recommendations should be followed when regenerating ion e!change resins. ,hanneling, resulting from either high or low flow rates, increased suspended solids loading or poor bac)washing. +his causes premature e!haustion even when much of the bed is in a regenerated state. 2esin fouling or degradation, caused by poor "uality regenerant. Failure to remove silica from the resin, which can result from low regenerant caustic temperature. +his can lead to increased silica lea)age and short service runs. B!cess contaminants in the resin, due to previous operation past e!haustion loads. =ecause the resin becomes loaded with more contaminants than a normal regeneration is designed to remove, a double regeneration is re"uired following an e!tended service run.

Mec1"nic"l Pro$le+s +ypical mechanical problems associated with ion e!change systems include;

Gea)ing valves, which cause poor "uality effluent and prolonged rinses. =ro)en or clogged distributor, which leads to channeling. 2esin loss, due to e!cessive bac)washing or failure in the underdrain screening or support media. ,ation resin in the anion unit, causing e!tended rinse times and sodium lea)age into the deminerali#ed water. Instrumentation problems, such as faulty totali#ers or conductivity meters, which may indicate a problem when none e!ists, or may introduce poor "uality water to service. Instrumentation in the deminerali#er area should be chec)ed regularly.

RESIN FOULING AND DEGRADATION 2esin can become fouled with contaminants that hinder the e!change process.Figure - $A shows a resin fouled with iron. +he resin can also be attac)ed by chemicals that cause irreversible destruction. 3ome materials, such as natural organics /Figure - $-1, foul resins at first and then degrade the resin as time passes. +his is the most common cause of fouling and degradation in ion e!change systems, and is discussed under *Organic Fouling,* later in this chapter. C"*ses of Resin Fo*lin! Iron "n, M"n!"nese. Iron may e!ist in water as a ferrous or ferric inorganic salt or as a se"uestered organic comple!. Ferrous iron e!changes in resin, but ferric iron is insoluble and does not. Ferric iron coats cation resin, preventing e!change. An acid or a strong reducing agent must be used to remove this iron. Organically bound iron passes through a cation unit and fouls the anion resin. It must be removed along with the organic material. .anganese, present in some well waters, fouls a resin in the same manner as iron. Al*+in*+. Aluminum is usually present as aluminum hydro!ide, resulting from alum or sodium aluminate use in clarification or precipitation softening. Aluminum floc, if carried through filters, coats the resin in a

sodium #eolite softener. It is removed by cleaning with either acid or caustic. Csually, aluminum is not a foulant in a deminerali#er system, because it is removed from the resin during a normal regeneration. H"r,ness Precipi " es. Hardness precipitates carry through a filter from a precipitation softener or form after filtration by post precipitation. +hese precipitates foul resins used for sodium #eolite softening. +hey are removed with acid. 3ulfate Precipitation. ,alcium sulfate precipitation can occur in a strong acid cation unit operated in the hydrogen cycle. At the end of a service cycle, the top of the resin bed is rich in calcium. If sulfuric acid is used as the regenerant, and it is introduced at too high a concentration or too low a flow rate, precipitation of calcium sulfate occurs, fouling the resin. After calcium sulfate has formed, it is very difficult to redissolve; therefore, resin fouled by calcium sulfate is usually discarded. .ild cases of calcium sulfate fouling may be reversed with a prolonged soa) in hydrochloric acid. =arium sulfate is even less soluble than calcium sulfate. If a water source contains measurable amounts of barium, hydrochloric acid regeneration should be considered. Oil Fo*lin!. Oil coats resin, bloc)ing the passage of ions to and from e!change sites. A surfactant can be used to remove oil. ,are must be e!ercised to select a surfactant that does not foul resin. Oil fouled anion resins should be cleaned with nonionic surfactants only. .icrobiological Fouling. .icrobiological fouling can occur in resin beds, especially beds that are allowed to sit without service flow. .icrobiological fouling can lead to severe plugging of the resin bed, and even mechanical damage due to an e!cessive pressure drop across the fouled resin. If microbiological fouling in standby units is a problem, a constant flow of recirculating water should be used to minimi#e the problem. 3evere conditions may re"uire the application of suitable sterili#ation agents and surfactants. Silic" Fo*lin!. 3ilica fouling can occur in strong base anion resins if the regenerant temperature is too low, or in wea) base resins if the effluent caustic from the 3=A unit used to regenerate the wea) base unit contains too much silica. At low pH levels, polymeri#ation of the silica can occur in a wea) base resin. It can also be a problem in an e!hausted strong base anion resin. 3ilica fouling is removed by a prolonged soa) in warm /$0&IF1 caustic soda. C"*ses of Irre-ersi$le Resin De!r"," ion O6i," ion. O!idi#ing agents, such as chlorine, degrade both cation and anion resins. O!idants attac) the divinylben#ene cross lin)s in a cation resin, reducing the overall strength of the resin bead. As the attac) continues, the cation resin begins to lose its spherical shape and rigidity, causing it to compact during service. +his compaction increases the pressure drop across the resin bed and leads to channeling, which reduces the effective capacity of the unit. In the case of raw water chlorine, the anion resin is not directly affected, because the chlorine is consumed by the cation resin. However, downstream strong base anion resins are fouled by certain degradation products from o!idi#ed cation resin. If chlorine is present in raw water, it should be removed prior to ion e!change with activated carbon filtration or sodium sulfite. Appro!imately $.- ppm of sodium sulfite is re"uired to consume $ ppm of chlorine. O!ygen saturated water, such as that found following forced draft decarbonation, accelerates the destruction of strong base e!change sites that occurs naturally over time. It also accelerates degradation due to organic fouling. T1er+"l De!r"," ion. +hermal degradation occurs if the anion resin becomes overheated during the

service or regeneration cycle. +his is especially true for acrylic resins, which have temperature limitations as low as $&&IF, and +ype II strong base anion resins, which have a temperature limit of $&'IF when in the hydro!ide form. Or!"nic Fo*lin! Organic fouling is the most common and e!pensive form of resin fouling and degradation. Csually, only low levels of organic materials are found in well waters. However, surface waters can contain hundreds of parts per million of natural and man made organic matter. 9atural organics are derived from decaying vegetation. +hey are aromatic and acidic in nature, and can comple! heavy metals, such as iron. +hese contaminants include tannins, tannic acid, humic acid, and fulvic acid. Initially, organics bloc) the strong base sites on a resin. +his bloc)age causes long final rinses and reduces salt splitting capacity. As the foulant continues to remain on the resin, it begins to degrade the strong base sites, reducing the salt splitting capacity of the resin. +he functionality of the site changes from strong base to wea) base, and finally to a nonactive site. +hus, a resin in the early stages of degradation e!hibits high total capacity, but reduced salt splitting capacity. At this stage, cleaning of the resin can still return some, but not all, of the lost operating capacity. A loss in salt splitting capacity reduces the ability of the resin to remove silica and carbonic acid. Organic fouling of anion resin is evidenced by the color of the effluent from the anion unit dur ing regeneration, which ranges from tea colored to dar) brown. ?uring operation, the treated water has higher conductivity and a lower pH. Pre-en ion. +he following methods are used, either alone or in combination, to reduce organic fouling;

Prechlorination and clarification. <ater is prechlorinated at the source, and then clarified with an organic removal aid. Filtration through activated carbon. It should be noted that a carbon filter has a finite capacity for removal of organic material and that the removal performance of the carbon should be monitored fre"uently. .acroporous and wea) base resin ahead of strong base resin. +he wea) base or macroporous resin absorbs the organic material and is eluted during regeneration. 3pecialty resins. Acrylic and other specialty resins that are less susceptible to organic fouling have been developed.

Inspec ion "n, Cle"nin!. In addition to these preventive procedures, a program of regular inspection and cleaning of the ion e!change system helps to preserve the life of anion resin. .ost cleaning procedures use one of the following;

<arm /$0&IF1 brine and caustic. .ild o!idants or solubili#ing agents can be added to improve the cleaning. Hydrochloric acid. <hen resins are also fouled with significant amounts of iron, hydrochloric acids are used. 3olutions of &.0' &.'> sodium hypochlorite. +his procedure destroys the organic material but also significantly degrades the resin. Hypochlorite cleaning is considered a last resort.

It is important to clean an organically fouled resin before e!cessive permanent degradation of the strong base sites occurs. ,leaning after permanent degradation has occurred removes significant amounts of

organic material but does not improve unit performance. +he condition of the resin should be closely monitored to identify the optimum schedule for cleaning. RESIN TESTING AND ANALYSIS +o trac) the condition of ion e!change resin and determine the best time for cleaning it, the resin should be periodically sampled and analy#ed for physical stability, foulant levels, and the ability to perform the re"uired ion e!change. 3amples should be representative of the entire resin bed. +herefore, samples should be collected at different levels within the bed, or a grain thief or hollow pipe should be used to obtain a *core* sample. ?uring sampling, the inlet and regenerant distributor should be e!amined, and the condition of the top of the resin bed should be noted. B!cessive hills or valleys in the resin bed are an indication of flow distribution problems. +he resin sample should be e!amined microscopically for signs of fouling and crac)ed or bro)en beads.It should also be tested for physical properties, such as density and moisture content /Figure - $%1. +he level of organic and inorganic foulants in the resin should be determined and compared to )nown standards and the previous condition of the resin. Finally, the salt splitting and total capacity should be measured on anion resin samples to evaluate the rate of degradation or organic fouling.