Comparative study of brine management technologies for desalination plants

Depósi o de In es igación de la Uni e sidad de Se illa h ps://idus.us.es/ This is an Accep ed Manusc ip o an a icle published by Else ie in Desalina ion, Vol. 336, on Ma ch 2014, a ailable a : h ps://doi.o g/10.1016/j.desal.2013.12.038 © 2014 Else ie . En idUS Licencia C ea i e Commons CC BY-NC-ND Compa a i e s udy o b ine managemen echnologies o desalina ion plan s José Mo illo1, José Use o1, Daniel Rosado1, Hicham El Bakou i2*, Abel Riaza2, F ancisco- Ja ie Be naola2 1. Depa men o Chemical and En i onmen al Enginee ing, Uni e si y o Se ille, 41092 Se ille, Spain 2. Abengoa Wa e S.L.U, Resea ch De elopmen Cen e , P olongación c/ Don Remondo s/n, Ba iada Fuen e del Rey, 41703 Dos He manas, Spain. HIGHLIGHTS:  B ine managemen sys ems o desalina ion plan s  Technologies o educing he olume o he gene a ed b ines  Technologies o sal s eco e y o m b ines  B ine condi ioning o o he p ocesses CORRESPONDING AUTHOR: * R&D Cen e o Abengoa Wa e , P olongación c/ Don Remondo s/n, Ba iada Fuen e del Rey, 41703 Dos He manas, Spain. Tel.: 0034 955404963; E-mail add ess: hicham.elbakou [email p o ec ed]bengoa.com (H. El Bakou i). Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 1 Abs ac In ecen yea s, e e se osmosis (RO) has g own as an al e na i e o adi ional po able wa e sou ces. A majo disad an age o he RO p ocess is he huge amoun o b ine and i s nega i e impac as a esul o i s high salini y. This b ine is usually discha ged o inland wa e bodies o o he sea and cons i u es a h ea o ecosys ems and species, such as Posidonia oceanica in he Medi e anean Sea; hus, u he esea ch is needed o in oducing en i onmen ally iendly and economically iable managemen op ions o RO b ines. This pape gi es an o e iew o ecen esea ch as well as di e en echnologies a ailable a se e al scales o o e come he en i onmen al p oblems and e alua e p o i abili y ela ed o discha ge o RO concen a es. The ea men op ions ha e been classi ied in o ou di e en g oups acco ding o hei inal pu pose: 1) echnologies o educing and elimina ing b ine disposal, 2) echnologies o comme cial sal eco e y, 3) b ine adap a ion o indus ial uses and 4) me al eco e y. Sola e apo a ion, wo-s age e e se osmosis, elec odialysis, in eg a ed p ocesses and b ine adap a ion o he chlo -alkali indus y a e some o he opics ha his pape deals wi h. In he conclusion sec ion, all o he echnologies a e compa ed emphasizing all hei ad an ages and d awbacks, easibili y and de elopmen s age in o de o p o ide a decision ool o selec he bes echnology o each si ua ion. Keywo ds Seawa e desalina ion, Re e se osmosis, B ine ea men , Wa e eco e y, Sal eco e y. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 2 1 In oduc ion Po able wa e p oduc ion has become a wo ldwide conce n; o many communi ies, p ojec ed popula ion g ow h and associa ed demand exceed con en ional a ailable wa e esou ces. O e 1 billion people ha e no access o clean d inking wa e and app oxima ely 2.3 billion people (41% o he wo ld popula ion) li e in egions wi h wa e sho ages [1]. The sho age o wa e supplies o d inking and i iga ion pu poses is al eady a e y se ious p oblem o he No h A ican coun ies, he Middle Eas and se e al coun ies in Sou heas Asia and La in Ame ica. I no hing is done, acu e wa e sho ages will also occu in many coun ies o he Eu opean Union and he no he n Medi e anean by 2020, such as G eece, I aly (sou he n egions and islands), Po ugal (Alen ejo and Alga e egions and islands such as Po o San o, Co o, e c.) and Spain (sou he n and eas e n egions). Fo he en i e Medi e anean egion, conse a i e es ima es indica e a wa e sho age o abou 10 million m3/day by he yea 2020 [2]. Desalina ion has become an impo an sou ce o d inking wa e p oduc ion, wi h he mal desalina ion p ocesses de eloping o e he pas 60 yea s and memb ane p ocesses de eloping o e he pas 40 yea s [3]. Today, e e se osmosis (RO) is he leading echnology o new desalina ion ins alla ions, wi h a 44% sha e in wo ld desal ing p oduc ion capaci y and an 80% sha e in he o e 15,000 desalina ion plan s ins alled wo ldwide [4]. The Middle Eas has o ged ahead as he leade in la ge-scale seawa e desalina ion. Wi h only 2.9% o he wo ld’s popula ion, i holds app oxima ely 50% o he wo ld’s p oduc ion capaci y. In 2005, Is ael opened he wo ld’s la ges seawa e RO desalina ion plan , wi h a p oduc ion capaci y o 330,000 m3/day, o 100 million m3/yea [4]. The use o memb ane desalina ion has inc eased as ma e ials ha e imp o ed and cos s ha e been educed [3]. Bu he main eason why RO desalina ion has succeeded is because i equi es less ene gy han he mal desalina ion — only 1.5-2.5 kWh/m3 o RO e sus 15-25 kWh/m3 o e apo a ion [1]. Fu he mo e, imp o emen s in memb anes and ene gy eco e y ha e signi ican ly lowe ed he cos o RO desalina ion. As a esul o inc eased in e es in RO desalina ion, he conce n abou po en ial en i onmen al p oblems has g own. RO desalina ion plan s ex ac la ge olumes o wa e and discha ge a dense b ine concen a e back in o he en i onmen [5]. I is widely sugges ed ha desalina ion plan b ines ha e a s ong po en ial o de imen ally impac bo h physicochemical and ecological a ibu es o ecei ing en i onmen s [6]. The e has been wo y in Medi e anean coun ies abou Posidonia oceanica o he las ew yea s. P. oceanica is he mos abundan sea Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 3 g ass species in he Medi e anean, whe e i co e s abou 40,000 km2 o he sea loo [7] and o ms la ge meadows om he su ace o 40 m dep hs. In addi ion, i is conside ed a e y impo an ecosys em and is ecognized by he Eu opean Habi a s Di ec i e [8] as a habi a o p io i y in e es . Ne e heless, meadows o P. oceanica ha e unde gone eg ession in se e al coas al a eas [9] and unde ield condi ions, P. oceanica is e y sensi i e o b ine discha ges om desalina ion plan s [10]. Many solu ions ha e been de eloped o p o ec his plan , mainly based on dilu ing b ine be o e disposal. B ine disposal cos s a e high oday, be ween 5 and 33% o o al desalina ion cos [11], complica ing implemen a ion. This cos depends on he quali y o he concen a e, ea men le el be o e disposal, disposal me hod and he olume o quan i y o concen a e [12]. Disposal cos s o inland desalina ion plan s a e e en highe han hose o plan s discha ging b ine in o he sea [12]. Some o he op ions o b ine disposal om inland desalina ion plan s a e deep well injec ion, e apo a ion ponds, discha ge in o su ace wa e bodies, disposal o municipal sewe s, concen a ion in o solid sal s and i iga ion o plan s ole an o high salini y [12,13]. Due o he en i onmen al p oblems ha b ine disposal can cause and high disposal cos , many echnologies ha e been de eloped o eco e y. Examples a e enewable ene gy gene a ion [14] and use in e apo a ion ponds o p oduce sal o chemicals o indus y. Ne e heless, mo e in es iga ion is needed o educe b ine quan i y and o allow eco e y and euse o b ine. In his e iew, cu en and eme ging echnologies a e analyzed acco ding o hei o igin, he ma u i y o he echnologies and hei inal goal. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 4 2 Technologies o educing and elimina ing b ine disposal 2.1 Sola e apo a ion Sola e apo a ion consis s o lea ing b ine in shallow e apo a ion ponds, whe e wa e e apo a es na u ally hanks o he sun’s ene gy. Sal is le in he e apo a ion ponds o is aken ou o disposal [15]. E apo a ion ponds a e ela i ely easy o cons uc , while equi ing low main enance and li le ope a o a en ion compa ed o mechanical sys ems. In addi ion, no mechanical equipmen is equi ed, excep o he pump ha con eys he was ewa e o he pond [16]. Ne e heless, e apo a ion ponds o disposal o concen a e om desalina ion plan s need o be cons uc ed as pe he design and main ained and ope a ed p ope ly so as no o c ea e any en i onmen al p oblem, especially wi h ega ds o g oundwa e pollu ion [16]. Sola e apo a ion is a sui able echnology o be used in a id egions whe e land is a ailable [17]. Land is c ucial because shallow ponds ( anging om 25-45 cm) a e op imal o maximizing he a e o e apo a ion [16]. Howe e , due o he quan i y o e ain needed, e apo a ion ponds ha e limi ed use, especially in we a eas. Fo ins ance, only 6% o he ins alla ions in he US used his me hod o concen a e disposal up o 1993 and only 2% a e 1993, always o small plan s [18]. Wind aided in ensi ied e apo a ion echnology (WAIV) was pa en ed as an al e na i e o na u al e apo a ion. This me hod educes b ine quan i y hanks o na u al d yness. B ine eci cula es and alls, c ea ing a hin liquid laye on e ical su aces pa allel o wind di ec ion. Gil on e al. [17] ca ied ou expe imen s in a pilo plan and demons a ed ha he e apo a ion a io (L/(m2∙d)) can be imp o ed be ween 50% and 90% compa ed o e apo a ions ponds. Ka zi e al. [15] es ima ed ha using WAIV echnology inc eases he e apo a ion a e 10- old o e na u al e apo a ion, which allows e apo a ion ponds o be 10 imes smalle . They also s udied WAIV echnology possibili ies o eco e y o sal s and hei use as aw ma e ials. Fo his pu pose, RO and elec odialysis concen a es om b ackish g oundwa e we e used as eedwa e . Al hough WAIV echnology has ad an ages compa ed o e apo a ion ponds, expe imen s a indus ial scale a e needed in o de o p o e easibili y o la ge lows o b ine. 2.2 E apo a ion and c ys alliza ion sys ems Many au ho s ha e s udied e apo a ion and c ys alliza ion sys ems in o de o e alua e echnical and economic easibili y. Za zo e al. [19] published an a icle abou he esea ch Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 5 done by he companies o Sady and Sc inse (bo h in he Spanish Sacy -Vallehe moso g oup) and Ecoagua. Tha esea ch aimed a he emo al o sal s om desalina ion plan b ines o educe he impac o he discha ges and o ob ain sal s o by-p oduc s. This p ojec s udied Ze o Liquid Discha ge (ZLD) sys ems based on e apo a ion-c ys alliza ion echnologies. Two pilo plan s we e ins alled: one a labo a o y scale a he Complu ense Uni e si y o Mad id and he o he a he Cue as de Almanzo a desalina ion plan (25,000 m3/d o b ackish wa e ea ed wi h RO). The Complu ense Uni e si y plan had an e apo a ion capaci y o 7 L/h. I wo ked in con inuous mode unde acuum condi ions. The ene gy consump ion was e y high, abou 0.9 kWh/kg, wi h an es ima ed inal cos o €0.095/kg o b ine e apo a ed. The pilo plan a he Cue as de Almanzo a desalina ion plan was an e apo a ion-c ys alliza ion plan wi h a lash e apo a o ope a ing unde acuum condi ions and con inuous eed. The plan capaci y was 100 L/h, al hough expe imen s wo ked wi h a low a e o app oxima ely 70 L/h. The Cue as de Almanzo a desalina ion plan was mo e ene gy e icien han con en ional e apo a ion- c ys alliza ion because i u ilized he apo gene a ed in e apo a ion o hea he eedwa e en e ing he e apo a o . The au ho s concluded ha e apo a ion-c ys alliza ion echnology appea s o be economically iable only i i is associa ed wi h a sys em o eco e esidual hea o s eam as he p ocess has high ene gy consump ion. Mickley e al. [20] did esea ch on high eco e y and ze o liquid discha ge echnologies. They sugges ed many al e na i es o di e en eedwa e composi ions. Those al e na i es a e based on combina ions o RO, lime so ening (LS), he mal b ine concen a o (BC), he mal c ys allize (CRYST), sp ay d ye (SD), e apo a ion ponds (EP) and land ill (LF) o ea b ackish wa e wi h eco e ies o e 96%. The s udy concluded ha he yield o he p ocess depends basically on salini y and wa e composi ion. They eached he same conclusion o capi al and ope a ing cos s, speci ying ha e apo a ion ponds and land ills a e he bigges cos s. In addi ion, he pape emphasizes la ge sys ems equi ing mul iple equipmen modules, hus minimizing he economy o scale. 2.3 Memb ane dis illa ion sys ems Memb ane Dis illa ion (MD) is a non-iso he mal e apo a i e echnology ha uses a hyd ophobic mic opo ous memb ane being he d i ing o ce he apo p essu e di e ence be ween bo h memb ane sides. Ex ended in o ma ion on MD may be ound in Khaye and Ma suu a [21]. MD can be applied o he ea men o saline solu ions wi h high Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 6 concen a ions. Vacuum memb ane dis illa ion (VMD) is a a ian o MD, in which low p essu e o acuum is applied on he pe mea e side o he memb ane module, o example by means o acuum pump(s). The applied pe mea e p essu e mus be lowe han he sa u a ion p essu e o ola ile molecules o be sepa a ed om he eed solu ion and condensa ion akes place ou side he memb ane module a empe a u es lowe han he ambien empe a u e. Me icq e al. [22] applied VMD con igu a ion o he ea men o RO b ines (Figu e1). Simula ions we e pe o med o op imize he VMD ope a ing condi ions and hen hey we e comple ed by bench-scale expe imen s using syn he ic RO b ines con aining only he mine al pa o seawa e wi h o al sal concen a ions up o 300 g/L. High pe mea e luxes we e ob ained e en o he highes sal concen a ions. Howe e , he pe mea e lux was limi ed a high sal concen a ions by scaling, mainly due o calcium p ecipi a ion. Despi e his incon enience, scaling had only a pa ial impac on he pe mea e lux (i.e. 24% dec ease o 43 L/(h∙m2) pe mea e wi h he highes sal concen a ion). Calcium ca bona e (CaCO3) and calcium sul a e (CaSO4) p ecipi a ed i s due o hei low solubili y and o med mixed c ys al deposi s on he memb ane su ace. These phenomena only occu ed on he memb ane su ace and did no o ally co e he memb ane po es. The c ys als we e easily emo ed simply by washing he memb ane wi h wa e . Simula ions we e pe o med o s udy he yield o he p ocess wi h 40,000 m3/day o 38.9 g/L seawa e , achie ing a eco e y o 40% o VMD i sel and up o 89% o o e all eco e y by coupling RO and VMD. Resul s also showed ha concen a e quan i y can be educed by a ac o o 5:5, making i possible o double o e all wa e p oduc ion. Figu e 1. Schema ic o seawa e desalina ion by RO and acuum memb ane dis illa ion (VMD) in eg a ed p ocess [22]. Ji e al. [23] in es iga ed he pe o mance o memb ane dis illa ion c ys alliza ion (MDC) bench-scale plan in e ms o wa e eco e y and NaCl c ys alliza ion kine ics. The ex ensi e Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 7 con ac a ea p o ided by hollow ibe memb anes made i possible o achie e eliable pe mea e luxes a mode a e empe a u es (40-50 oC) wi h ene gy consump ion anging om 15-20 kWh/m3, which is lowe han ha o con en ional e apo a i e sys ems o NaCl c ys alliza ion ha ing a speci ic ene gy consump ion o 30 kWh/m3. Expe imen al es s ca ied ou on a i icial RO concen a es esul ed in 21 kg/m3 p oduc ion o NaCl c ys als and he inal wa e eco e y ac o inc eased up o 90%. Analogous in es iga ions ca ied ou on RO b ines om na u al seawa e we e a ec ed by he p esence o dissol ed o ganic ma e , showing 20% educ ion in he amoun o sal c ys allized and 8% dec ease o he pe mea e lux. The e o e, adequa e p e ea men be o e he RO s age is needed o educe he nega i e e ec o dissol ed o ganic ma e on he MDC pe o mance. This s udy con i ms he abili y o MDC o concen a e RO b ines. In p inciple, he indus ial scale-up o he MDC p ocess in ol ing la ge olumes o b ines do no show any echnical complexi y. Howe e , his echnology is no a ailable a a comme cial scale and u he in es iga ions a e needed on he en i onmen al impac s and economics. Ma ine i e al. [24] s udied acuum-enhanced di ec con ac memb ane dis illa ion (VEDCMD) o inc ease wa e eco e y du ing desalina ion o b ackish wa e (Figu e 2). In hei es s, wo RO b ine s eams we e used as eed o he VEDCMD sys em, wi h o al dissol ed solid concen a ions anging be ween 7,500 and 17,500 mg/L. A eco e y ac o up o 81% was achie ed. Howe e , eco e y ac o s we e always limi ed by he p ecipi a ion o ino ganic sal s on he memb ane su ace. Ma ine i e al. [24] also showed also ha cleaning echniques we e able o emo e he scaling laye om he memb ane su aced es o ing he wa e pe mea e lux o almos i s ini ial le el. The au ho s also claimed ha he addi ion o scale inhibi o s du ing he p ocess was e ec i e in main aining high wa e pe mea e lux du ing an ex ended VEDCMD ope a ing ime. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 14 highly concen a ed d aw solu ion [37]. Since he d aw solu ion is he d i ing o ce behind he FO p ocess, he solu e wi hin he d aw solu ion mus mee se e al c i e ia in o de o be sui able o he FO p ocess. High osmo ic e iciency is equi ed, and he d aw solu e mus be highly soluble in wa e and, a he same ime, o low molecula weigh , easily and economically sepa a ed and ecycled, non- oxic and chemically compa ible wi h he memb ane being used [37]. McGinnis [38] and McCu cheon e al. [39] p oposed d aw solu es ha me all he equi emen s. Howe e , s udy esul s e ealed ha RO memb anes a e no sui able o he FO p ocess because o ela i ely low pe meabili y a ibu ed o se e e in e nal concen a ion pola iza ion in he po ous suppo and ab ic laye s o he RO memb ane. McCu cheon e al. [39] p esen ed a FO p ocess using an ammonium bica bona e ((NH4)HCO3) d aw solu ion o ex ac wa e om saline eedwa e ac oss a semi-pe meable polyme ic memb ane. The sys em yields high wa e luxes and can esul in e y high eedwa e eco e ies. Upon mode a e hea ing, (NH4)HCO3 decomposes in o ammonia (NH3) and CO2 gases ha can be sepa a ed and ecycled as d aw solu es, lea ing he esh p oduc wa e . Expe imen s wi h a labo a o y-scale FO uni using a la shee cellulose i-ace a e memb ane demons a ed high p oduc wa e lux and ela i ely high sal ejec ion. Tang and Ng [40] in es iga ed FO using a labo a o y-scale uni . These expe imen s achie ed 38.5% eco e y using a eed s eam simila o RO concen a es (1-2 M NaCl, 58.5-117 g/L) and 5 M uc ose as d aw solu ion (900 g/L). Assuming a RO-FO p ocess o seawa e wi h 45% eco e y o RO [3], an o e all eco e y a e anging om 66 o 76% could be achie ed wi h he eco e y a es o FO es ima ed by Tang & Ng [40]. Ca h e al. [35] s a ed ha sal ejec ion in FO is o e 97%. McCu cheon e al. [41] indica ed 95-99% and con i m Ca h e al. [35], wi h g ea e ejec a highe wa e low a es. Ene gy equi emen s we e less o FO han o o he desalina ion echnologies. McGinnis e al. [42] poin ed ou ha he FO p ocess p oposed by McCu cheon e al. [39,41] can achie e ene gy sa ings o 72% compa ed o RO and 85% compa ed o mul i-s age lash dis illa ion. Wa e low o a eed solu ion o 0.5 M NaCl (29.5 g/L NaCl), simila o seawa e , anged om 3.2 o 23 L/(m2h) a osmo ic p essu e di e en ials be ween 22 and 217 ba [41]. Howe e , o FO i anged om 4 o 7.2 L/m2 wi h 2 M NaCl (117 g/L NaCl) eed solu ion and p essu e di e en ials om 80 o 127 ba . Ano he al e na i e o ake in o conside a ion is FO as a s age Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 15 p io o RO. Ca h e al. [36,43] achie ed eco e y a es o e 95% in esea ch done wi h sewage. Ca h e al. [44] did a s udy on combining FO and RO o ob ain esh wa e om pollu ed wa e by using seawa e as d aw solu ion. Wi h his hyb id p ocess, seawa e is dilu ed be o e desalina ion, dec easing ene gy cos s and educing he quan i y o pollu ed wa e . Ma ine i e al. [24] in es iga ed FO o wa e eco e y enhancemen in desalina ion o b ackish wa e (Figu e 9). In he cu en s udy, wo RO b ine s eams wi h o al dissol ed solid concen a ions a e aging 7,500 and 17,500 mg/L we e u he desalina ed by FO wi h a cons an -concen a ion d aw solu ion o 50 g/L NaCl. FO achie ed wa e eco e ies up o 90% om he b ines, limi ed by sal p ecipi a ion on memb anes. Figu e 9. Schema ic d awing o FO sys em p oposed by Ma ine i e al. [24]. 2.6 Elec odialysis Elec odialysis (ED), unde he in luence o an elec ic ield, enables he sepa a ion o dissol ed ions in wa e h ough selec i e ion exchange memb anes. Ko ngold e al. [45] applied ED o concen a ed b ine solu ions simila o e luen s om he desalina ion o b ackish and indus ial wa e . Resul s showed ha ED can be used o inc ease he concen a ion o a b ine solu ion om 0.2-2% o 12-20% wi h ene gy consump ion in he ange o 1.5-7.1 kWh/m3, in con as o app oxima ely 25 kWh/m3 by he mal e apo a ion. Howe e , elec ical e iciency dec eases when he b ine concen a ion is signi ican ly inc eased and CaSO4 p ecipi a es on he memb anes. Ne e heless, p ecipi a ion on memb anes can be a oided by p e ea men . Ko ngold e al. [46] buil an ED pilo plan ed wi h b ackish wa e in which b ine ci cula ing h ough he ED cells passed h ough a sepa a e CaSO4 p ecipi a o con aining gypsum seeds. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 16 ED p o ed o be usable o inc easing he concen a ion o RO b ine solu ion om 1.5% o 10% a an ene gy equi emen o 7.0-8.0 kWh/m3. O en e al. [47] es ed a hyb id p ocess combining RO and ED, which was shown o be e ec i e in eco e ing 97-98% o b ackish wa e as p oduc wa e wi h chlo ide le els o 200 mg/L o less. Po en ial o scaling on he b ine side o he ED uni was p e en ed by acidi ica ion, ope a ing he ED in e e sal mode, called elec odialysis e e sal (EDR), and a side loop c ys allize which p e en ed buildup o scaling componen s. This p ocess was demons a ed in a se ies o mo e han eigh y ba ch expe imen s o 1.5 o 1.8 m3 o RO concen a e o aw b ackish g oundwa e om he Nege Highland in Is ael. The eedwa e was concen a ed om 0.3% o o e 10% TDS supe concen a e while p oducing wa e ha could be ecycled o he RO pe mea e. This supe concen a e om he EDR uni was u he concen a ed in a wind-powe ed WAIV uni ha b ough inal b ine TDS o o e 30%. Ini ial economic es ima es showed ha his hyb id p ocess is compe i i e wi h con en ional RO and o he enhanced eco e y p ocesses o inland desalina ion equi ing use o e apo a ion ponds. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 17 3 Technologies o comme cial sal eco e y 3.1 SAL-PROC p ocess SAL-PROC is an in eg a ed p ocess o sequen ial ex ac ion o dissol ed elemen s om ino ganic saline wa e s in he o m o aluable chemical p oduc s in c ys alline, slu y and liquid o ms. An analysis indica ed ha a ious ypes o sal s, including gypsum, NaCl, Mg(OH)2, calcium chlo ide (CaCl2), CaCO3 and sodium sul a e (Na2SO4), can be p oduced om he ejec b ine o desalina ion plan s. This p ocess is pa icula ly ecommended o inland b ines wi h high concen a ions o sul a e, po assium and magnesium. Figu e 10 shows a simpli ied diag am o he p ocess. F om an economic poin o iew, i was es ima ed ha by p ocessing 405,000 m3 o ejec b ine pe yea , comme cial sal s wo h $895,000 could be p oduced [48]. Al hough he economic bene i will p obably be lowe , he comme cializa ion po en ial o sal s is an op ion o imp o e p o i abili y o desalina ion p ocesses. Figu e 10. Simpli ied diag am o SAL-PROC p ocess [48]. A akel e al. [49] used SAL-PROC o p ocess b ackish wa e om Tu chewop Lake (Vic o ia, Aus alia). This lake ecei es a discha ge o app oxima ely 64,000 /yea o sal . The p ocess made i possible o eco e high quali y Mg(OH)2, NaCl, a mix u e o gypsum and Mg(OH)2 and a highly concen a ed solu ion o CaCl2. The SAL-PROC ou e used in his case is desc ibed in de ail in Figu e 11. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 18 Figu e 11. SAL-PROC p ocess used in he ea men o b ackish wa e om Tu chewop Lake [49]. A akel e al. [49] combined RO and SAL-PROC in a p ocess known as ROSP. This p ocess was used o ea ing RO b ine wi h a high bica bona e concen a ion in he e luen coming om coal-based me hane ex ac ion (CBM ex ac ion) in Queensland, Aus alia (Figu e 12). The ROSP p ocess p oduces CaCO3, Na2SO4 and NaCl. Figu e 12. ROSP p ocess o ea men o wa e coming om coal-based me hane ex ac ion (CBM) gas ield [49]. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 19 3.2 Ze o Discha ge Desalina ion Pa en o Uni e si y o Sou h Ca olina The Uni e si y o Sou h Ca olina [50] de eloped a echnology called ze o discha ge desalina ion (ZDD) o he ea men o seawa e RO b ines (PCT pa en PCT/US03/24250). The p ocess ocuses on p oducing esh wa e and aluable sal s: NaCl, Mg(OH)2 and b omine (B 2). The p ocess has di e en con igu a ions, all based on ED. In he basic con igu a ion (Figu e 13) NaCl is eco e ed as a d y sal and he was e s eams o Mg(OH)2 and B 2 a e e u ned o he sea. In he second con igu a ion, pu e NaCl is eco e ed by adding a c ys allize , and he was e s eams ha e u n o sea in he i s case a e ea ed by e apo a ion o d ying and p oduc ion o oad sal (Figu e 14). Figu e 13. P ocess schema ic o ze o discha ge desalina ion wi h op ional seawa e discha ge [50]. Expe imen s ca ied ou a labo a o y scale showed ha abou 75% o NaCl in he b ine was eco e ed as high-pu i y NaCl c ys als in he e apo a ion-c ys alliza ion s age. Because o ED concen a es NaCl up o 20%, NaCl can be c ys allized wi h only one- hi d o he he mal ene gy ha would be equi ed i he o al amoun o wa e in he RO ejec we e o be e apo a ed. Figu e 14. P ocess schema ic o ze o discha ge desalina ion [50]. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 20 These expe imen s poin ed ou ha Mg(OH)2 p oduc ion o g ea e han 99% pu i y was achie ed by p e ea men wi h Na2CO3 o emo e calcium. Howe e , using Na2CO3 also p ecipi a es magnesium and a ec s p ocess yield. B 2 p oduc ion was es ima ed by a ma hema ical model de eloped o his pu pose. Simula ions showed ha abou 0.38 ons o b omine ion would be eco e ed in he ED b ine associa ed wi h 3.79 million m3 o seawa e RO pe mea e, and essen ially all o ha could be eco e ed as B 2 by con en ional echniques. ZDD scale-up could be easily achie ed because all he sepa a ion p ocesses in ol ed a e a ailable on a comme cial scale. The Uni e si y o Sou h Ca olina assessed ZDD p o i abili y. The capi al cos s o he analysis we e based on epo ed cos s o he indi idual p ocesses. Ope a ing cos s we e based on da a om he p ocess model. The es ima ed alues o eco e ed sal and wa e p oduc s we e $0.60/m3 o wa e , $60/ o NaCl, $673/ o Mg(OH)2 as Mg and $900/ o B 2. Resul s indica ed ha he eco e ed p oduc s can be sold o p ices ha will co e he cos o hei eco e y. The main bene i o eco e ing NaCl om RO concen a e is he ene gy sa ings because he s a ing sal concen a ion is wice ha o seawa e . Tanaka e al. [51] indica ed ha he ene gy consump ion in a sal manu ac u ing p ocess using RO b ine is 80% o he ene gy consump ion in he p ocess using seawa e . Bu p oducing sal om seawa e is also p o i able. Japan has used ED o eco e NaCl om seawa e and p oduce edible sal on a la ge scale o abou 40 yea s. In ecen yea s, ED plan s ha e been ins alled by Japanese companies in Kuwai and Sou h Ko ea o eco e NaCl om seawa e o use in chlo -alkali plan s. 3.3 In eg a ed p ocesses Tu ek [52] in es iga ed ED o seawa e in a wo-s ep s and wi h an ED-Mul i-s age Flash (MSF)-C ys alliza ion sys em (Figu e 15). Figu e 15. Schema ic o desalina ion in ED-MSF-c ys alliza ion sys em [52]. ED ollowed by EDR in coun e cu en low mode (Figu e 16) was p oposed o seawa e desalina ion. In he i s s ep, mono alen ions we e emo ed, p oducing a pe mea e wi h a o al Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 21 dissol ed solid concen a ion a ound 10 g/L (0.38 g/L calcium, 1.26 g/L magnesium, 4.08 g/L chlo ide and 2.78 g/L sul a e). EDR elimina ed mos o he ions, achie ing a pe mea e eady o human consump ion. A single-pass low esidence ime mode o ope a ion was applied o a oid gypsum c ys alliza ion in he EDR concen a e. ED wa e eco e y was 73.8% while he EDR eco e y was 90%, yielding 66.4% o al ED(R) s age eco e y. Figu e 16. Schema ic o seawa e desalina ion by elec odialysis in ED-MSF- c ys alliza ion sys em [52]. This in es iga ion included a cos es ima e o ED(R) s age seawa e desalina ion. The cos was calcula ed o an indus ial ED uni wi h 80% e ec i e memb ane su ace. The ene gy cos was assumed as $0.06/kWh, he e iciency o pumps as 0.85 and he memb anes’ li e as 10 yea s. The o al in es men cos s we e assumed as $320/m2 o memb ane and main enance cos s as 25% o in es men cos s. Cos s we e also es ima ed o 1 m3 o wa e . I was assumed ha he MSF uni cos was equal o $1.0/m3. The cos s o u he e apo a ion accompanied by sal c ys alliza ion we e es ima ed based on he s udy o he cons uc ion o he plan and we e assumed o be $8/ o sal ob ained. The alue o sal ob ained was $30/ while he sal eco e y was 80%. The au ho s poin ed ou ha wi h his p ocess he po able wa e cos is es ima ed o be only $0.44/m3 and sal p oduc ion is 23.7 kg/m3 o po able wa e . Tu ek [53] also in es iga ed wo a angemen s: ul a il a ion (UF)-nano il a ion (NF)-MSF-c ys alliza ion (Figu e 17) and UF-NF-RO-MSF-c ys alliza ion (Figu e 18) o p oducing sal and esh wa e . Seawa e was assumed o be he inpu and NF eco e y o 70% was ob ained. Fu he mo e, he ejec ion coe icien o he NF memb ane was assumed o be 0.83 o calcium, 0.87 o magnesium, 0.93 o sul a e and 0.1 o NaCl. The NaCl concen a ion in NF pe mea e is 28.70 g/L. I 85% NaCl eco e y is assumed, hen 17.07 kg o NaCl pe 1 m3 o UF pe mea e is ob ained. The cos es ima ion o 1 m3 o UF pe mea e is p esen ed in Table 2. A alue as low as $0.18/m3 in he NF p ocess was assumed because he p e ea men cos was conside ed Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 22 sepa a ely as UF cos . The cos s o u he e apo a ion accompanied by sal c ys alliza ion we e es ima ed based on he s udy o he cons uc ion o he plan and we e assumed o be $8/ o sal ob ained. The alue o sal ob ained was $30/ and he cos o desalina ed wa e was $0.71/m3. Since concen a ing by RO is cheape han by MSF in he ange o ela i ely low sal concen a ions, hen p e-concen a ing by RO may be assumed o dec ease he cos o he desalina ion-sal p oduc ion p ocess. The cos es ima e o his p ocess is p esen ed in Table 3. I was assumed ha RO eco e y was 65% while i s cos was $0.63/m3 and he alue o sal ob ained was also $30/ . The cos o desalina ed wa e was hen $0.43/m3. Figu e 17. Schema ic o desalina ion in UF-NF-MSF-c ys alliza ion sys em [53]. Figu e 18. Schema ic o desalina ion in UF-NF-RO-MSF-c ys alliza ion sys em [53]. Table 2. Cos o desalina ion and sal p oduc ion in UF-NF-MSF-c ys alliza ion sys em pe 1 m3 o UF pe mea e [53]. Cos , $ Uni cos Pe 1 m 3 o UF pe mea e UF 0 . 07 /m 3 0 . 070 /m 3 NF 0 . 18/ m 3 0 . 126/m 3 MSF 1 . 0 0 / m 3 0 . 613/m 3 C ys alliza ion 8 . 00 / 0 . 137/m 3 To al 0 . 946/m 3 Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 23 Table 3. Cos o desalina ion and sal p oduc ion in UF-NF-RO-MSF- c ys alliza ion sys em pe 1 m3 o UF pe mea e [53]. Cos , $ Uni cos Pe 1 m 3 o UF pe mea e UF 0 . 07 /m 3 0 . 070/m 3 NF 0 . 18/m 3 0 . 126/m 3 RO 0 . 63/m 3 0 . 287/m 3 MSF 1 . 0 0 /m 3 0 . 158/m 3 C ys alliza ion 8 . 00 / 0 . 137/m 3 To al 0 . 778/m 3 Nano il a ion is a p essu e-d i en p ocess be ween RO and ul a il a ion. I s main ad an ages a e lowe wo king p essu e and g ea e ejec ion as di alen ca ions han mono alen s. Nano il a ion can be used combined wi h o he echnologies o seawa e ea men . D ioli e al. [54] de eloped an in eg a ed memb ane sys em in o de o eco e CaCO3, NaCl and magnesium sul a e hep ahyd a e (MgSO4·7H2O) om seawa e nano il a ion e en a e. The diag am is shown in Figu e 19. In his wo k, nano il a ion e en a e calcium ions we e p ecipi a ed as ca bona es by eac ion wi h sodium bica bona e (NaHCO3) and Na2CO3 solu ions. These solu ions we e p e iously p oduced by eac i e ans e o CO2 in o NaOH solu ions in a hollow ibe memb ane con ac o (3.85 cm x 12.32 cm LiquiCel-Celga d) wi h 1.4 m2 o con ac a ea. The alkaline solu ion was ed in con inuous mode on he shell side in coun e cu en o he gaseous CO2 s eam lowing h ough he ibe s. The amoun o CO2 ans e ed om he gas phase o he liquid phase was calcula ed using he mass balance o he gas s eam. The low diag am was comple ed wi h a c ys alliza ion sys em based on a memb ane p ocess ha allows supe sa u a ion. In all es s, he solu ion was ed in o he c ys allize and eci cula ed h ough he memb ane ibe s wi h a low a e o 120 L/h. Tempe a u es measu ed a he module inle on e en a e and dis illa e sides we e 35 and 15 oC, espec i ely. The pH o he c ys allizing solu ion was adjus ed o 5 by hyd ochlo ic acid (HCl) addi ion in o de o p e en Mg(OH)2 p ecipi a ion, which a oids he o ma ion o magnesium sul a e c ys als. Highe emo als we e also ob ained a highe pH alues due o he eac ion o CO2 wi h hyd oxide ions o gi e bica bona e and ca bona e. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 30 con igu a ion ollowing a e e se osmosis p ocess could inc ease wa e eco e y be ween 19 and 29%. Fu he mo e, he ene gy cos o di ec osmosis is lowe han ha o o he desalina ion echnologies, al hough i is closely ela ed o he ca yo e o solu es (osmo ic solu ions) wi h sui able cha ac e is ics. Technologies o ien ed owa d ob aining comme cial sal s show g ea e po en ial han hose whose main pu pose is o elimina e e luen s. I is undeniable ha he po en ial o comme cializing sal s is a key op ion o imp o e he cos -e ec i eness a io o desalina ion p ocesses. These echnologies combine di e en ypes o p ocesses depending on he objec i e sough . The aim o he SAL-PROC pa en is o eco e p oduc s con ained in he b ine: a mix u e o gypsum and magnesium hyd oxide, magnesium hyd oxide, sodium chlo ide, calcium ca bona e, sodium sul a e and calcium chlo ide. The p ocess is pa icula ly app op ia e o b ine wi h high le els o dissol ed sul a e, po assium and magnesium sal s. Theo e ical s udies highligh he economic easibili y o his echnology; al hough he da a should be aken wi h ce ain ese a ions since he e a e cu en ly no seawa e desalina ion plan s wi h his echnology ins alled (i has been es ed only wi h b ackish wa e ). The Uni e si y o Sou h Ca olina’s ZDD pa en was de eloped explici ly o seawa e . The p ocess is o ien ed o he p oduc ion o esh wa e and aluable sal s om e e se osmosis ejec in seawa e ea men : sodium chlo ide, magnesium hyd oxide and b omine. Theo e ical s udies ca ied ou by he Uni e si y o Sou h Ca olina show he economic easibili y o he p ocesses de eloped. I is he e o e a echnology well wo h bea ing in mind, al hough i is no cu en ly in ope a ion. The e a e o he ele an echnologies o he p oduc ion o esh wa e and sal s om seawa e , such as ul a il a ion and nano il a ion, al hough hey a e likewise no cu en ly ope a ing on an indus ial scale. One o he al e na i es wi h po en ial o applica ion is he ea men o b ine o use in he chlo -alkali indus y. This equi es p ocesses o concen a e he b ine, among which elec odialysis is one o he mos a ac i e. I is also necessa y o elimina e he di alen ca ions in b ine because hey exceed he speci ica ions o memb ane elec olysis. These ea men s in ol e high cos s, which can be o se by he p oduc s ob ained om elec olysis. I is ad isable o ins all he elec olysis plan as an annex o he desalina ion plan . The eco e y o me als om seawa e o b ine is ano he p omising al e na i e, conside ing he me als ha can po en ially be ob ained om seawa e and hei economic alue. Resea ch is Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 31 needed in his ield o de elop selec i e ex ac ion p ocesses o he desi ed elemen s ound in seawa e and b ine. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 32 Table 5. Compa ison o me hods. Pa 1. Technology De elopmen s a us Technical obse a ions Economic obse a ions E apo a ion ponds Indus ial scale La ge ex en s o land. Simple ope a ion. Possible con amina ion o g oundwa e . Possibili y o sal s eco e y. Low economic cos . WAIV echnology Pilo plan scale La ge ex en s o land. Possible con amina ion o g oundwa e . 50 o 90% highe e apo a ion a e han e apo a ion ponds. Possibili y o sal s eco e y. Low economic cos . E apo a o - C ys allize Indus ial scale Technology a ailable. Mo e de elopmen needed o educe ene gy use. High economic cos . No aluable chemicals eco e y . Memb ane dis illa ion Pilo plan scale F om 81 o 90% wa e ecycled when coupled wi h e e se osmosis sys ems. Technically easible o ea ing la ge amoun s o wa e in seawa e desalina ion plan s. Possible p oblems wi h dec eased low caused by p ecipi a ion o sal s on memb anes. Ve y high ene gy use (15 o 20 kWh/m3) ela i e o ene gy use o e e se osmosis, bu less han adi ional e apo a ion and c ys alliza ion sys ems. Two-s age e e se osmosis Indus ial scale Technology a ailable. Can inc ease ecycled wa e o 60%. The ene gy cos is a o dable wi h ene gy eco e y sys ems. Chemical p ecipi a ion p ocesses Well known echnology. No es ed wi h seawa e b ine. Technology a ailable. No s udies done wi h seawa e b ine. Can inc ease ecycled wa e om 60 o 90%. High eagen dosage ha conside ably inc eases p ocess cos . Fo wa d osmosis Pilo plan scale. Ex ensi e esea ch expe ience Simple echnology. Recycles 76% o wa e when coupled wi h e e se osmosis sys ems. P ecipi a ion o sal s on memb anes diminishes low. Mo e de elopmen needed in memb ane echnology. Low ene gy equi emen s as compa ed o o he echnologies. Elec odialysis Indus ial scale P oblems wi h p ecipi a ion on he elec odialysis memb ane. Inc ease om 1.5 o 10% achie ed in b ine concen a ion. Elec ic ene gy use is 7-8 kWh/m3 o concen a ed b ine om RO. Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 33 Table 6. Compa ison o me hods. Pa 2. Technology De elopmen s a us Technical obse a ions Economic obse a ions SAL-PROC p ocess Pa en ed. No es ed wi h seawa e b ine Simple echnology based on chemical p ecipi a ion eac ions. Reco e s comme cial sal s. S udies show i is economically easible o b ackish inland wa e s. ZDD echnology Pa en ed o seawa e All he p ocesses included in he echnology a e cu en ly a ailable. S udies based on ma hema ical models and es s asse 76 o 100% wa e eco e y . S udies indica e i is economically easible. Reco e s comme cial sal s. In eg a ed p ocesses Pilo plan scale o seawa e Combine a ious a ailable echnologies. 90% wa e eco e y. Sal p oduc ion o 23.7 kg/m3 om desalina ed wa e . Asse s p oduc ion o desalina ed wa e wi h cos s be ween 0.43 and 0.71 USD/m3. In eg a ed sys em o eco e y o CaCO3, NaCl and MgSO 4 •7H 2 O Pilo plan scale o seawa e A ailable echnology based on nano il a ion combined wi h p ecipi a ion and c ys alliza ion. Up o 95% wa e eco e y. 78% o dissol ed NaCl eco e ed. P oduc ion o 8.4 kg MgSO4·7H2O pe m3 o ejec om he nano il a ion uni . B ine condi ioning o he chlo -alkali indus y Indus ial scale Simple, a ailable echnology. Need o concen a e and elimina e di alen ions. Po en ial bene i o he chlo -alkali indus y. Me al s eco e y Be n ch scale Requi es use o selec i e ex ac ion me hods. Elemen s like Rb, Cs and U a e a po en ially impo an bene i . Compa a i e s udy o b ine managemen echnologies o desalina ion plan s 34 7 Re e ences [1] R.F. 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