Use of nanofiltration membrane technology for ceramic industry wastewater treatment

103 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 BOLETIN DE LA SOCIEDAD ESPAÑOLA DE ARTICULO Ce ámica y Vid io Use o nano il a ion memb ane echnology o ce amic indus y was ewa e ea men R. MOLINER-SaLVaDOR (1), a. DERaTaNI (2), J. PaLMERI (3), E. SáNCHEz (1) (1) Ins i u o de Tecnología Ce ámica. Asociación de In es igación de las Indus ias Ce ámicas. Uni e si a Jaume I. Cas ellón. Spain (2) Ins i u Eu opéen des Memb anes, UMR CNRS-ENSCM-Uni e si é Mon pellie 2, 34095 Mon pellie , F ance (3) Labo a oi e de Physique Theo ique, UMR CNRS-Uni e si é Paul Saba ie , 31062 Toulouse, F ance A s udy has been unde aken o an ad anced was ewa e ea men app oach using polyme nano il a ion memb anes, in an a emp o ob ain wa e o su icien quali y o allow i o be eused in he same p oduc ion p ocess o , al e na i ely, o be discha ged wi hou any p oblems. The s udy has ini ially ocused on he emo al o o ganic ma e ( educ ion o COD) and he mos ep esen a i e ions p esen in he was ewa e , such as Na + , Mg 2+ , Cl - , and SO 4 2- . In a i s pa o he s udy, wi h a iew o op imising he expe imen al phase, a simula ion has been pe o med o he nano il a ion p ocess using he NanoFlux so wa e. Among o he hings, he simula ion allows he mos sui able memb anes o be selec ed as a unc ion o he pe mea e low a e and desi ed le el o e en ion in he subs ances o be emo ed. The subsequen expe imen a ion was ca ied ou in a labo a o y angen ial il a ion sys em ha wo ks wi h la memb anes. I was ound ha e en ion alues o abou 90% we e ob ained o he s udied subs ances, wi h a good pe mea e low a e, using low ope a ing p essu es. These esul s demons a e he easibili y o he s udied echnology and i s po en ial as a ea men o imp o ing ce amic indus y was ewa e quali y. Key wo ds: Nano il a ion, Memb ane, Was ewa e , Ce amic Tiles Indus y, Red/Whi e Ce amics Uso de la ecnología de nano il ación a a és de memb anas pa a el a amien o de aguas esiduales de la indus ia ce ámica Es e es udio ha sido emp endido con el in de ace ca la nano il ación a a és de memb anas polimé icas al a amien o de las aguas esiduales indus iales de la indus ia ce ámica, espe ando ob ene un agua con la su icien e calidad como pa a se eu ilizada en el p opio p oceso p oduc i o o, al e na i amen e, pode e e la. El es udio se ha cen ado en la eliminación de ma e ia o gánica ( educción de D.Q.O) y algunos iones p esen es en las aguas esiduales, ales como Na + , Mg 2+ , Cl - y SO 4 2- . En p ime luga , se ha ealizado una simulación del p oceso de nano il ación usando el so wa e NanoFlux. En e o as cosas, la simulación pe mi e selecciona las memb anas más ap opiadas en unción del caudal de pe meado ob enido y en unción del ni el de e ención de la sus ancia que se desea elimina . En una segunda pa e, se ealiza on los ensayos expe imen ales en un sis ema de labo a o io de il ación angencial que abaja con memb anas planas. La e ención ob enida pa a las sus ancias es udiadas es de ap oximadamen e el 90%. Todo ello, con un buen caudal de pe meado y usando bajas p esiones de abajo. Es os esul ados demues an la iabilidad de la ecnología y su po encial como a amien o pa a mejo a la calidad de las aguas esiduales de es a indus ia. Palab as Cla e: Nano il ación, Memb ana, Aguas Residuales, Baldosas Ce ámicas, Ce ámica Roja/Blanca. 1. INTRODUCTION Wa e managemen has become an inc easingly c i ical issue in mos adi ional indus ial sec o s, owing o he la ge quan i ies o was ewa e hey p oduce. In he case o he ce amic ile indus y, mos o he was ewa e a ises in he washing ope a ions o he acili ies used o he p epa a ion and applica ion o glazes and o he coa ings. In addi ion, a conside able amoun o g oundwa e is used as he esh wa e sou ce o glaze and o he coa ings p epa a ion. Howe e as he g oundwa e esou ce becomes mo e and mo e limi ed, ce amic indus y has o ind solu ion o lowe i s g oundwa e bole ín de la Sociedad Española de Ce ámica y Vid io Vol 51, 2, 103-110, Ma zo-ab il 2012 ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 consump ion. One possibili y is, o ins ance, o use ecycled wa e in glazing ope a ions. The composi ion o hese ce amic indus y was ewa e s a ies widely and may include suspended solids and elec oly es o e y di e en na u e, as well as o ganic subs ances ha mos ly come om he addi i es used in deco a ing he iles. Howe e , he ea men echniques ha a e cu en ly used (gene ally physico-chemical ea men s) a e no en i ely e ec i e, in pa icula wi h ega d o non- biodeg adable o ganic compounds ha inc ease he wa e Es e abajo ha sido p esen ado como comunicación o al, as su e aluación po el Comi é Cien í ico, en el XII Fo o Global del Recub imien o Ce ámico. QUALICER (13 y 14 eb e o 2012. Cas ellón. España). 104 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 R. MOLINER-SALVADOR, A. DERATANI, J. PALMERI, E. SÁNCHEz COD, ce ain ions such as alkaline and alkaline-ea h ca ions, bo on compounds, chlo ides, sulpha es, e c. This inadequa e was ewa e ea men makes i impossible o euse his wa e in he same p oduc ion p ocess and may e en impede wa e discha ge. As a esul , his wa e needs ex e nal handling o addi ional ea men , en ailing high economic cos s and/o en i onmen al impac . Memb ane echnology is an ad anced me hod o wa e ea men . I has been demons a ed ha ions and molecules can be selec i ely emo ed om pollu ed wa e s using memb ane p ocesses. Selec ion o he app op ia e memb ane sui able o add ess he desi ed sepa a ion is de e mined by he eed composi ion o wa e o be ea ed and he objec i e o pu i ica ion o be eached, as well. Nano il a ion (NF), which has ecen ly been de eloped, p esen s signi ican ad an ages on compa ing wi h o he memb ane p ocesses. NF p ocess allows an almos comple e emo al o mul i alen ions and o ela i ely small o ganic compounds, and a good ejec ion o mono alen ions depending on he memb ane and he ope a ing condi ions while i equi es lowe ope a ing p essu e han e e se osmosis (RO). In his wo k i is p oposed o make a p elimina y e alua ion o he applica ion o nano il a ion echnique o was ewa e s om he ce amic ile indus y wi h a iew o emo ing o ganic ma e ( educing COD) as well as dissol ed sal s in o de o enhance he euse o ea ed wa e in he ce amic indus y. Bo on compounds we e no included in he s udy because he was ewa e con aining hese needs o unde go a p e- ea men . E icien pu i ica ion has o dec ease he o ganic pollu ion and he o al dissol ed sal s (TDS) unde a ce ain limi ha can be es ima ed o he mos commonly cleaning uses o be abou 50 mg O2/l o COD and 500 mg/l o TDS. This objec i e can be, in p inciple, eadily ob ained using a NF s age. 2. METHODOLOGY 2.1 Memb ane p ocesses in wa e ea men Pu i ica ion o wa e by ea men s using memb ane ma e ials began o be impo an in 60’s because o he good pe o mances ha o e ed syn he ic memb anes. Memb ane sepa a ion p ocess has he ollowing ad an ages: cos ly e icien , en i onmen ally benign and clean echnology since no addi ional chemicals a e needed, easy o ope a e and no much sensi i e o composi ion a iabili y, allowing he p oduc ion o high quali y wa e . Ne e heless, i has been in he las yea s when he memb ane ea men has begun o be applied in he was ewa e pu i ica ion. The de elopmen o memb ane echnology o new applica ions has been he esul o nume ous ad ances in he ield o memb anes elabo a ion. A memb ane can be de ined as a selec i e ba ie ha sepa a es wo phases. F om his de ini ion i appea s ha anspo o species om ups eam o downs eam is es ic ed in a selec i e manne due o di e ences in physical and/o chemical p ope ies be ween he memb ane and he pe mea ing species (1). Dissol ed solids and compounds in he eed phase can hen be o ally o pa ially e ained in e en a e, whe eas pe mea e will be ee o compounds ejec ed by he memb ane. Shape, size and cha ge a e he main cha ac e is ics ha de e mine memb ane ejec ion. Di e en d i ing o ces such as p essu e, elec ical ield, and concen a ion g adien can o igina e he anspo h ough he memb anes, he p essu e d i en p ocesses being he mos de eloped in he case o wa e memb ane ea men . The ollowing sec ion will desc ibe he di e en ypes o p essu e d i en memb ane p ocesses commonly used in wa e ea men . 2.1.1 CLASSIFICATION OF MEMBRANE PROCESSES IN WATER TREATMENT As p e iously ou lined, memb ane can ac as a sie ing ba ie . The selec i e anspo ac oss he memb ane is hen mainly go e ned om he a io be ween he size o dissol ed species and ha o he memb ane po es. The ollowing classi ica ion in memb ane p ocesses can a ise depending on he memb ane po e adius size ( p): mic o il a ion, ul a il a ion, nano il a ion and e e se osmosis. (Fig 1) Mic o il a ion (MF) memb anes ha e he p anging om 0.1 o 10 µm and he la ges memb ane pe meabili y. In MF p ocess he applied p essu e is low ( om 0.2 o 1 ba ) and he componen s a e e ained by a sie ing mechanism. Consequen ly only componen s wi h a size highe han he memb ane po e size a e e ained. MF memb anes ypically ejec suspended solids, la ge pa icles, colloids and some mic o o ganisms as bac e ia. MF memb anes a e he a mos widely used memb ane p ocess wi h he main applica ions o cla i ica ion, disin ec ion and as an e icien p e- ea men o u he memb ane ea men s eps. Ul a il a ion (UF) memb anes ha e smalle p ( om 2 o 100 nm) and lowe pe meabili y han MF memb anes. This ea u e implies ha UF p ocess equi es highe ope a ing p essu es ( om 0.5 o 5 ba ) han MF p ocess. In his case, sie ing mechanisms a e also mainly in ol ed o ejec ing he eed componen s. These memb anes can e ain small bac e ia, i uses and soluble mac omolecules such as p o eins. NF p ocess (NF) is an in e media e echnique be ween UF and e e se osmosis (RO) ha has been mo e ecen ly de eloped. NF memb anes ha e p smalle han 2 nm. In his case in e ac ions in addi ion o s e ic hind ance ake place due o he small size o memb ane po es. Thus he anspo mechanism is mainly desc ibed by sie ing and elec ic (Donnan exclusion) e ec s among o he s. The e is equilib ium be ween he cha ged memb ane and he solu ion. Fo his eason a lo o ionic species a e ejec ed, e en species wi h size smalle han ha o memb ane p. Finally, he RO memb anes consis in a dense ba ie wi hou p ede ined po es. The anspo mechanism is he e o e comple ely di e en and is belie ed o occu acco ding o a solu ion-di usion mechanism (2-3). I esul s ha pe meabili y is much lowe in his case han o he abo e men ioned memb anes. On he o he hand, ejec ion o he cha ged solu es con ained in he eed solu ion is almos comple e. I should be no ed ha RO usually equi es high p essu es (up o 120 ba ) depending o he osmo ic p essu e o he eed solu ion ha makes his echnique qui e ene gy consuming. 2.1.2 NANOFILTRATION As seen in Fig. 1, NF is a echnique o sepa a ion by memb anes loca ed be ween RO and UF. Ini ially i was included wi h RO bu oday i is ega ded as a di e en 105 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 USE OF NANOFILTRATION MEMBRANE TECHNOLOGY FOR CERAMIC INDUSTRY WASTEWATER TREATMENT echnique conside ing ha he anspo in ol es an ac ually di e en mechanism as ou lined be o e. NF is mainly cha ac e ized by a anspo mechanism based no only on s e ic hind ance bu also acco ding o he solu e cha ge wi h he ollowing implica ions: • Neu al solu es a e ejec ed acco ding o he sie ing e ec due o he memb ane po e size • A selec i e sepa a ion akes place be ween eadily ejec ed mul i alen ions and pa ially ejec ed mono alen ions • A pa o cha ged species a e anspo ed ac oss he memb ane dec easing he osmo ic p essu e. • The ope a ing p essu es a e lowe (3 o 20 ba s) han hose used in RO and highe pe mea e a e a e ob ained wi h his echnique leading o a mo e ene gy e iciency compa ed o RO. This echnique can be applied in a lo o sec o s such as bio echnology and ood indus y o ex ac ion and pu i ica ion o aluable low molecula weigh compounds, wa e and was ewa e ea men o he d inking wa e p oduc ion and he en i onmen al p o ec ion (4). 2.2 NanoFlux NanoFlux (5,6) is a compu e simula ion p og am de eloped in he Eu opean Ins i u e o Memb anes in Mon pellie (F ance) o model solu e anspo in he NF ange (and in some cases, loose RO and igh UF). I can be used o cha ac e ize NF memb anes and also p edic hei pe o mance is-à- is complex mix u es o neu al molecules and ions. This p og am allows one o calcula e, s a ing om s anda d eed inpu da a, all he necessa y NF p ocess ou pu (ionic and molecula ejec ion, o passages, luxes,…) om he le el o a single memb ane elemen up o ha o mul i-module/ mul i-s age plan s. I is possible o ob ain quick and eliable simula ion esul s hanks o bo h he powe ul and obus compu a ional algo i hms inco po a ed in o he p og am and he in e nal NanoFlux da abase ha con ains he p incipal comme cial memb anes. NanoFlux is also easy o use, hanks o i s e gonomic g aphical use in e ace and has been es ed and alida ed using eal case s udies (5-7). Pe iodic addi ions a e made and up-da es o he NanoFlux da abase pe o med in o de o ollow echnical and ma ke e olu ions. This modeling p og am is hus a powe ul aid in decision-making and inno a ion, when i comes o economically choosing he igh memb ane and op imizing nano il a ion p ocesses. I can also be used o minimize signi ican ly di icul and cos ly pilo s udies, he eby educing he o al cos and ime needed o choose he app op ia e memb ane and o scale-up and ope a e NF plan s. The modeling me hod used in NanoFlux consis s in i s es ima ing he po e size om he ejec ion o model neu al solu es (5,6). A memb ane-sal cha ac e iza ion s ep by s udying he ejec ion o a limi ed numbe o simple sal s (NaCl, MgSO4, Na2SO4, CaCl2) is o be subsequen ly ca ied ou . The expe imen al esul s o hese 1:1, 2:2, 1:2, 2:1 ( ) sal s a e analyzed using NanoFlux ia a nume ical i ing p ocedu e in o de o de e mine he op imal alues o he wo pa ame e s (e ec i e memb ane cha ge densi y and hickness) ha cha ac e ize he memb ane/ sal pai . Theo e ical ion ejec ion p edic ions o elec oly e solu ions a e ob ained by sol ing nume ically he “Hinde ed T anspo ” Ex ended Ne ns -Planck ion lux equa ions. The bes i pa ame e alues, which minimize he di e ence be ween he expe imen al and heo e ical ejec ions, a y as a unc ion o he sal concen a ion and pH o he eed. This analysis allows us o c ea e he in e nal NanoFlux da abase. The e ec i e memb ane cha ge and e ec i e hickness o ion mix u es a e hen de e mined as a unc ion o eed solu ion pH, ionic s eng h and composi ion using he single sal da abase combined wi h an in e pola ion and weigh ing Fig. 1 Classi ica ion o memb ane ea men s 106 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 R. MOLINER-SALVADOR, A. DERATANI, J. PALMERI, E. SÁNCHEz scheme. The ejec ion and solu ion lux o complex mul i- elec oly e mix u es can be well p edic ed using he in e nal single sal da abase (5,6). NanoFlux can he e o e be a he basis o a combined expe imen al and heo e ical me hod o cha ac e izing, simula ing, and op imizing he pe o mance o cha ged nano il e s. NanoFlux a emp s o ill in a gap in me hods o p edic ing and op imizing NF pe o mance ha has a isen due o he complexi y o he undamen al ion anspo p ocesses and has mos likely slowed he widesp ead indus ial de elopmen o NF. 2.3 Me hod 2.3.1. APPARATUS The il a ion pilo plan (Fig. 2) used o NF expe imen s consis s o a Sepa CF II labscale 316 SS cell sys em [10], a eed ank [3] wi h a s ainless s eel imme sed coil [5] and a olume ic pump [8] (ca pump 231, cons an low 9 L/min). The closed loop o he eed solu ion is made o esis ing ubing o high empe a u e (up o 60°C) and p essu e (up o 20 ba ). The eed solu ion is hea ed o cooled in he 30 li es eed ank by a ci cula ing he mal ba h [1] (F igi he m-10 P- Selec a) by means o he imme ged coil. The empe a u e eed ank is measu ed and con olled by an ex e nal PT100 P osenso p obe [4] imme ged in he eed solu ion. The e en a e empe a u e when i ci cula es back o he eed ank is also measu ed. The p essu e o he eed solu ion and he e en a e, modi ied by he al e [11], a e gi en by p essu e gauges [9]. The pe mea e mass is measu ed by a balance [12] (Sa o ius CP323S) a s eady s a e and he mass lux calcula ed is egis e ed in a compu e [13] ia an RS232 ou pu . 2.3.2. MEMBRANES In his s udy DOW FILMTEC memb anes ha e been used. These memb anes a e la and ha e an e ec i e su ace a ea o 133 cm2. NanoFlux p edic ion and p elimina y es s showed ha he NF-90 memb ane was he mos sui able o ou applica ion. The ob ained da a we e hen compa ed o hose ob ained o ano he memb ane NF-200. Speci ica ions gi en by he manu ac u e o hese wo memb anes a e ga he ed in he able I. 1- Ci cula ing he mal ba h, 2- Bill-pos e empe a u e, 3- Feed ank, 4- Tempe a u e p obe, 5- Coil, 6- Pu ge, 7- Th ee-way al e, 8- High-p essu e pump, 9- Manome e , 10- Sepa CF II Cell (Osmonics), 11- P essu e Con ol Val e, 12- Balance, 13- Pe sonal compu e Fig. 2. Schema ic diag am o he NF pilo . Table I. speCI ICaTIons o The n memb anes gI en by The manu aCTu e Memb ane Pe mea e Flow Ra e (L/(h m2 ba ) S abilized Sal Rejec ion (%) NF-90 8,68 > 97 NF-200 5,99 97 No e: Pe mea e low and sal ejec ion based on he ollowing es condi ions: 2000 ppm MgSO4, 25°C and 15 % eco e y. Pe mea e lows o indi idual elemen s may a y by -15 %/+50 % 2.3.3 EXPERIMENTAL PROCEDURE The app oach used consis s o wo s ages: • P edic ion o he memb ane pe o mances o NF o he s udied was ewa e (simpli ied composi ion) using NanoFlux. This s age allowed us o selec he mo e app op ia e memb ane and ope a ing condi ions o he second s age. 107 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 USE OF NANOFILTRATION MEMBRANE TECHNOLOGY FOR CERAMIC INDUSTRY WASTEWATER TREATMENT • Expe imen al alida ion using he selec ed memb ane and ope a ing condi ions o he ea men o eal was ewa e s. The expe imen al p ocedu e ollowed du ing he es o he memb anes included he ollowing s eps: • Memb ane condi ioning: be o e using new memb anes a condi ioning s ep mus be made o elimina e p ese a ion p oduc s and o compac he memb ane. Memb ane is placed in he memb ane cell and pu e wa e is ci cula ed h ough he memb ane o 1 hou . Applied empe a u e and p essu e (30 ºC and 17.5 ba ) we e highe han hose in he no mal ope a ing condi ions. This s ep was only ca ied ou once when he memb ane is new. • Pu e wa e pe meabili y: a e he condi ioning s ep and a e e e y es , pu e wa e pe meabili y was de e mined o ensu e abou he memb ane s abili y and in eg i y. These measu emen s we e pe o med using demine alised wa e . • Flow and ejec ion measu emen s o se e al eed was ewa e s ( ixed ope a ing condi ions): when he desi ed empe a u e was eached, he eed was ci cula ed and he p essu e inc eased s ep by s ep ill he desi ed p essu e was eached. The eed solu ion ci cula es a cons an angen ial eloci y (1,23 m/s), which allows o neglec concen a ion pola iza ion e ec s in memb ane su ace. A e a ound 5 min o ci cula ion, i was assumed ha he s eady s a e was eached. The pe mea e ac ion was e-ci cula ed in o he eed o keep he solu ion concen a ion cons an . The pe mea e lux was de e mined om mass measu emen s. A sample was hen collec ed o calcula e ejec ion. • Rejec ion calcula ion: collec ed samples in he p e ious s ep we e analysed and esul s we e compa ed wi h he eed samples analyses. Then ejec ion (%) we e calcula ed acco ding o he ollowing equa ion: whe e and a e he concen a ion o pe mea e and eed espec i ely. 2.3.4 ANALYSES Conduc i i y and pH o solu ions we e de e mined using a conduc ime e JF 340 WTW and a pHme e PHN 81 Tacussel, espec i ely. Me hods and equipmen used o analyze he di e en pa ame e s and species in he was ewa e s a e lis ed in able II: 3. RESULTS AND DISCUSSION 3.1 Ce amic indus y was ewa e composi ion Was ewa e s can be analysed using di e en pa ame e s like pH, conduc i i y and chemical oxygen demand (COD), hese wo pa ame e s being indica i e o o al dissol ed sal s (TDS) and o he o ganic pollu ion, espec i ely. The hand ope a ed cleaning usually made in ce amic indus y and he la ge ange o p oduc s en ail a wide a iabili y in composi ion. Table III shows he mean a e age alues o he pa ame e s desc ibing he was ewa e composi ion (8): pH, conduc i i y, he mo e abundan ions and TDS and COD. Table II. meThods and equIpmenT o wasTewaTe analysIs Pa ame e Me hod Equipmen COD UNE 77-004/89 - B Azome ine-H me hod by UV-VIS spec opho ome y UV-160A Shimadzu SO4 2- and Cl-Ionic ch oma og aphy ICS-100 Dionex Na+, K+, Mg2+ and Ca2+ A omic abso p ion spec opho ome y UNE 77-056 1100B Pe kin Elme Table III. Ce amIC IndusT y wasTewaTe ComposITIon Pa ame e Va ia ion in e al pH 7-9 Conduc i i y (µS/cm) 2000-5000 Chlo ides (mg /L) 100-1100 Sulpha es (mg /L) 100-1000 Calcium (mg /L) 50-500 Magnesium (mg /L) 10-100 Sodium (mg /L) 50-750 Bo on (mg /L) 1-75 TDS (mg/L) 300-3700 COD (mg O2/L) 100-1300 3.2 NanoFlux p edic ion As abo e-men ioned NanoFlux compu e simula ion p og amme allows us o p edic he pe o mances o NF memb anes o pe mea ion o neu al and cha ged species. Model solu ions con aining wo neu al solu es o di e en molecula size we e chosen o mimicking he emo al o o ganic ma e om he was ewa e s. As an example, Table IV gi es he p edic ed ejec ion da a o pe mea ion o wo neu al species (e hyl alcohol and poly(e hyleneglycol), PEG- 400) using wo NF memb anes (NF-90 and NF-200). I should be no ed ha PEG- de i a i es a e compounds o in e es in he ce amic indus y since hey a e used in he deco a ion s age o he ile manu ac u ing p ocess. As i can be seen 108 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 R. MOLINER-SALVADOR, A. DERATANI, J. PALMERI, E. SÁNCHEz NanoFlux p edic s ha PEG 400 is 100 % ejec ed by bo h memb anes whe eas a small molecule as e hyl alcohol is mo e signi ican ly ejec ed by he NF-90 memb ane In he same way, p edic ion o memb ane pe o mances can be ob ained o pe mea ion o cha ged species. F om he able III, i appea s ha a mix u e o he anions Cl- and SO4 2- and he ca ions Na+ and Mg2+ can gi e a good model solu ion o he s udied was ewa e s. Table V p esen s simula ion da a ob ained o he wo same memb anes (NF-90 and NF-200) o a solu ion con aining an equimola mix u e o NaCl and MgSO4 wi h a o al sal concen a ion o 0.03M (2.69 g/l). Table I . nano lux p edICTIon o pe meaTIon o Two neuT al speCIes (eThyl alCohol and peg-400) on n -90 and n -200 memb anes. Memb ane P essu e (ba ) Flux (L/h·m2)Rejec ed species Mola mass (g/mol) Rejec ion (%) NF-90 < 5 - PEG-400 400 100 5 23 E hyl alcohol 46 80 NF-200 < 5 - PEG-400 400 100 5 25 E hyl alcohol 46 62 Table V. NaNo lux p edicTioN o aN equimola mixTu e o NaCl aNd MgSO4 wiTh a ToTal salT coNceNT aTioN o 0.03m (2,69 g/L) Memb ane P essu e (ba ) Flux (L/h·m2)Ions Rejec ion (%) NF-90 5 23 Na+90 Cl-87 Mg2+ 97 SO4 2- 100 11 60 Na+90 Cl-90 Mg2+ 100 SO4 2- 100 NF-200 5 27 Na+47 Cl-60 Mg2+ 85 SO4 2- 98 11 75 Na+72 Cl-65 Mg2+ 94 SO4 2- 100 Again he memb ane NF-90 shows he be e pe o mances in ejec ing he conside ed ions e en a ela i ely low ope a ing p essu e (5 ba ) and wi h simila pe mea e lux. I was hen decided o alida e he simula ion by pe o ming pe mea ion o eal was ewa e s on NF-90. 3.3 Resul s wi h eal was ewa e s o he ce amic indus y The NF ea men was ca ied ou a low p essu e wi h was ewa e samples collec ed in wo di e en companies a e he physico-chemical ea men s age. The ope a ing condi ions o bo h samples a e summa ized in able VI. (*) 109 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 USE OF NANOFILTRATION MEMBRANE TECHNOLOGY FOR CERAMIC INDUSTRY WASTEWATER TREATMENT Table VII ga he s he pa ame e da a ob ained o he wo samples be o e and a e he NF pu i ica ion on NF-90 memb ane. These esul s show a educ ion o mo e han 90 % o he o al dissol ed sal s (TDS). As expec ed, mul i alen ions (SO4 2-, Mg2+ and Ca2+) a e almos o ally ejec ed du ing he NF pe mea ion. On he o he hand, he mono alen ones (Cl-, Na+ and K+) a e abou 90 % ejec ed by he NF-90 memb ane as p edic ed by he NanoFlux simula ion so wa e. When conside ing he COD pa ame e , i appea s ha he NF pe mea ion pe mi s an e icien emo al o he o ganic pollu ion since his pa ame e gi es alues lowe han 50 mg O2/l. This e ec is pa icula ly s iking in he case o he highe loaded solu ion (was ewa e 1) wi h a COD educ ion o mo e han 90%. Finally, i has o be no ed ha hese esul s we e ob ained only by using NanoFlux p edic ion and wi hou any expe imen al op imisa ion o he p ocess. 4. CONCLUSIONS Ad anced p ocess based on memb ane sepa a ion echnique may be use ul o ce amic indus y o imp o e managemen o hei was ewa e s. This imp o emen can allow o companies a g ea e eusabili y o ea ed was ewa e s gi ing ise o impo an economic sa ings and educing he en i onmen al impac . Expe imen al indings ob ained in his s udy show ha NF can be a good echnique o pu i ica ion o ce amic indus y was ewa e s because a e y signi ican o al dissol ed sal s (TDS) and COD educ ion ( e en ion alues o abou 90%) is achie ed. On he o he hand, hese esul s also p o e ha NanoFlux is a good ool o p edic ion ha can sa e ime and money in expe imen al s udies, because p edic ions done by he p og am a e qui e nex o he esul s ob ained expe imen ally. ACkNOWLEDGMENTS The au ho s wish o hank he Valencian Ins i u e o Small and Medium-Sized En e p ises (IMPIVA) in Comunidad Valenciana (Spain) and Eu eka P og am o i s inancial help (IMAETA/2005/11,IMIDIE/2009/3and∑!4121). Table II. pu I ICaTIon daTa o wasTewaTe s usIng nano IlT aTIon on n -90 memb ane Analysed pa ame e s Was ewa e 1 Was ewa e 2 A e physico- chemical ea men A e NF ea men wi h NF90/5 ba A e physico- chemical ea men A e NF ea men wi h NF90/4 ba Analyses Analyses Rejec ion Analyses Analyses Rejec ion pH 8,35 7,44 - 7,95 7,03 - Conduc i i y (mS/cm) 3,5 0,16 95% 2,33 0,17 93% B (mg/L) 5,9 3,9 34% 3,6 2,8 22% SO4 2- (mg/L) 258 < 10 >96% 304 <10 >97% Cl- (mg/L) 932 36 96% 619 41 93% Na+ (mg/L) 555 28,4 95% 304 30,4 90% k+ (mg/L) 16,8 0,9 95% 18,8 2,1 89% Mg2+ (mg/L) 28 0,3 99% 24,8 0,3 99% Ca2+ (mg/L) 75 <0.1 >99% 101 <0.1 >99% COD (mg/L) 1156 44 96% 129 < 30 > 77% Table I. ope aTIng CondITIons used In TesTs wITh wasTewaTe samples Sample P essu e (ba ) Tempe a u e (°C) Flux (L/(h m2 ba )) was ewa e 1 5 25 2,27 was ewa e 2 4 25 3,45 110 Bol. Soc. Esp. Ce am. Vid . Vol 51. 2, 103-110, Ma zo-Ab il 2012. ISSN 0366-3175. eISSN 2173-0431. doi: 10.3989/cy .152012 R. MOLINER-SALVADOR, A. DERATANI, J. PALMERI, E. SÁNCHEz REFERENCES (1) MULDER, M. Basic p inciples o memb ana echnology, 2nd Do d ech : Kluwe Academic Publishe s, 1996 (2) Van de BRUGGEN, B.; VANDECASTEELE, C.; Van GESTEL, T.; DOYEN,W. ; R. LEYSEN, R. A e iew o p essu e-d i en memb ana p ocesses in was e wa e ea men and d inking wa e p oduc ion, En i on.P og., 22(1), 46-56, 2003. (3) BAKER, R. W. Memb ana echnology and applica ions, 2nd. Chiches e : John Wiley & Sons, L d. 2004. (4) GUIZARD, C. Guide de la Nano il a ion. Mon pellie : Club F ançais des Memb anes, 2000. (5) PALMERI, J.; SANDEAUX, J.; SANDEAUX, R. e al. Modeling o mul i- elec oly e anspo in cha ged ce amic and o ganic nano il e s using he compu e simula ion p og am NANOFLUX. Desalina ion, 147, 231- 236, 2002. (6) LEFEBVRE, X.; PALMERI, J.; SANDEAUX, J., e al. 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