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    Marta Herrero-Gonzalez

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    Asad Saeed
    Electromembrane technologies, such as electrodialysis with bipolar membranes (EDBM) have been widely proposed for the treatment and valorization of seawater reverse osmosis (SWRO) concentrated streams

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    Marta Herrero-Gonzalez

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    Asad Saeed
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    Electromembrane technologies, such as electrodialysis with bipolar membranes (EDBM) have been widely proposed for the treatment and valorization of seawater reverse osmosis (SWRO) concentrated streams

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    Electromembrane technologies, such as electrodialysis with bipolar membranes (EDBM) have been widely proposed for the treatment and valorization of seawater reverse osmosis (SWRO) concentrated streams

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    © All Rights Reserved
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    8 views11 pages

    Marta Herrero-Gonzalez

    Uploaded by

    Asad Saeed
    Electromembrane technologies, such as electrodialysis with bipolar membranes (EDBM) have been widely proposed for the treatment and valorization of seawater reverse osmosis (SWRO) concentrated streams

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    © All Rights Reserved
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    Separation and Purification Technology 242 (2020) 116785 Contents lists available a ScienceDirect Separation and Purification Technology ELSEVIER journal homepage: www. lsevier.com/locatelsenpur Highly concentrated HCl and NaOH from brines using electrodialysis with bipolar membranes ® aE Marta Herrero-Gonzalez, Pedro Diaz-Guridi, Antonio Dominguez-Ramos’, Angel Irabien, Raquel Ibafez Departmen de ngniras Qube y ume, Ue de Casts Avene das Cars /m, 3905 Snead, Coss Spin Eeromembrane tehneloges, such ar electrodialysis with bipolar membranes (EDBM) have Been wide propored forthe treatment and valorization of reatatercevese xmas (SWRO) concentrated streams. The EBM technology applieg to brine progsces ei (Cl and bares (NaOH with as to inp eecse energy brine producing commercial HCl at 35 wed by meane ofthe integration of EDBM teclogy under constant (Galvanotate,equvalent to the use of eleteal energy fom the ged mi) and variable current intensity (equivalent othe use of PV solar energy) sid atetrpicdstilation. Caneetratons af HCl and NaOH vp to “33 moll.~ snd 16 molt ae abained respessly, whieh are los 50% higher than any ater reported ln the lterture so far using this technology. The apeiieenery eostumplion ofthe EDBM unt asi the age ff 21.8 kWhg-" of Hl and 42.3 kWh of ICL, beng dependant onthe average sppled current dens ‘These HCI concentrations, although belng acceptable for internal we in the SWRO plant, didnot reach com serial levels (35 wh of HCD, a frbereopeetzation stage using dstilaon has been evaluated trough Simulation Snimum values of he overall BDBM plus esllaton process specie energy consumption (SEC) twas between ~40 KWhkg™* and ~50 hWhkg™* of HCL Moreover, che environmental burdens asoeated with the energy consumption ae quantified in terms of the carbon forint (1. Although the SECow is slightly higher, the ws of PV soar energy instead ofthe gid mi let the proces to provide a beter environmental performance The renewable alternative provides values between 161 kg CO,eq kg"! of HCl Gull PV soar energy) and 697 kg Org kg” of HCl PV solar energy and teas) 1, Introduetion availabilty. In this sense, it can be estimated that SWRO plants ‘worldwide spend 815 million €year™" on reagent purchase, assuming 2 In recent years, desalination sechnologies have gained noticeable global average dosages of HCl of ~73 mgL.~' of freshwater and of attention ae a critical altemative to adérese water searcity istues that ‘exist in regions all over the world. Seawater reverse osmosis (SWRO) i the most widespread technology, aceounting for 348 of the global Aesalination capacity, Le. 32:4 milion may" [1]. One of the key drawbacks of the SWRO technology Is the highspeciic energy re ‘quirement per uni of freshwater produced, which i in the range from 2.5 kWhm™* to 6,0 kWhm*, this sharing most of the operation cost of the desalination plan, contributing up to 40% in the water cost of seawater desalination [2.3]. Apart ftom specific locations/aclites, reagent consumption is also a drawback, due to both cost and “Corresponding thor ‘mall adres a:oniodominguenunian es (A. Domlnguen Ras). naps: //do org/101018/)seppu 2020116785 Received 12 November 2018; Received in revised form 6 February 2020 Acepted Available online 02 March 2020 1385-5866/ © 2020 Eeevier BV, Al sights reserve, NaOH of ~60 mgi.~! of freshwater [4). Recent personal communica tions with a desalination plant located in the Mediterranean area con Firm the requirements of HCl from 0.2 gin of freshwater 00.5 gin" of freshwater and of NaOH from 30 gm" of freshwater to 60 gm" of freshwater, which ate emplayed at commercial concenteations from 31 WO% to 35 WEA CIOL molt 11.4 moll") and 50 wae (18.9 molt", respectively, being able to employ lower concentrations {incurring in greater pumping requirements Hlectromembrane technologies, such as electrodialysis (ED) and lectrodialysis with bipolar membranes (EDEM) have been widely March 2020| proposed for the treatment and valorization of SWRO concentrated sreams, the so-called brines, which features NaCl at high concentra tion, thus they ean be considered as hypersaline steams. Available literature mainly approaches these processes from a zero ligud dis ‘charge (ZLD) point of view (5,6). This ZLD approach pursues the almost total recovery of products from the SWRO brine thus no real liquid ‘effluent can escape the facility as a waste: thsi equivalent to an almost 100% recovery ofthe involved species. However, other approaches are also useful not entailing the efforts derived from a 100% recovery. In this work itis envisaged the brine asa source to create added value by means of the generation of acd and bases using EDBM. Therefore, the brine is used partially rather than totally as under a ZLD approach, The EDBM technology applied to brines produces acids (HCD) and bases (a0H) with jst two inputs: electric energy and brine, Thos, reagents seltsupply could be achieved (4,7), which definitively Sts the princ ples ofthe Circular Economy [5). The arising question is related tothe technical specifications of the obtained products, mainly ite con centration, as very diluted stream would demand too much pumping ‘as previously mentioned. A high concentration of HCl and NaOH is therefore expected. Low concentration ofthe products neither is tech nically interesting due extra energy for pumping nor from a storage point of view due to the potential large occupied volumes. Table | summarizes the maximum concentrations of HC! and NaOH obtained using EDBM technology according to previously published works. The concentrations of obtained products neither did exceed in any ofthe reported studies ~2.0 mol~ for the acd, nor ~2.5 moll.~” for the base. Therefore, the concentrations of HCl and NaOH with this EDBM technology reported in the literature did not reach the specified commercial ones, 35 we% (114 molL™) for HCl and 50 wea (18.9 molt.~}) forthe NaOH, requiring potential further concentration stages. Of course, this situation may hamper the economic and en: Viconmeatal competitiveness ofthis selCsupply strategy, making it lest atwactive, Additionally, iti noteworthy that all previous studies in "le 1 are complete at Ib-scale, Te Iterature reviewed also reports ‘operating times usually below 30 h and the bipolar membrane area does also below 3040 em. Qualitativaly, it ean be stated thatthe vo lume and the intial concentration ofthe feed tothe EDBM process baz fan inflence inthe final concentration of the products obtained. Inthe reported literature, the NaCl feed tends tobe depleted with time, thus not allowing the achievement of higher concentrations levels. On the ‘other hand, the use of the EDBM would represent additional energy burdens for the already energy intensive SWRO facility. In order alleviate enviconmental buedens such as carbon footpent derived for this extra energy use, the integration of photovoltaic solar (PV) energy is proposed, Indeed, the technical feasibility of HCl and NaOH pro duction by means of EDBM using both constant (grid mix energy) and vatiable (PV solar energy) current intensity has been previously re ported by the authors (9-11) In the light of recent peblications focused inthe recovery of NaOH ‘by means of EDBM and additonal puifcation steps, it is clear thatthe target is to reach commercial concentration (25). Therefore, the aim of the present work is to demonstrate the viability of a new strategy to valorise SWRO brine producing commercial HCl at 35% we, by means of the integration of (1) an eletromembrane technology (EDBMD snd constant (galvanostatic, equivalent to the wse of electical energy from the grid mix) and variable current intensity (equivalent tothe wse of PV soler energy targeting concentration values higher than those pre viously reported in the EDBM unit (~20 molL~* for HCl and -25 moll? for NaOH), and (2) an azeotropic distillation. A simpli ‘hed model syathetie solution, which replicate the TDS contribution from Na" and Cl” ions coming from a rea brine, 25) has been used the HCI stream after the EDBM unit is expected to be further con centrated using distillation inorder to reach the aforementioned com mercial concentration suitable for the self-supply strategy within 'SWRO facility exemplified here as 11.4 moll"! of HCI of 35 wt.% of HD, Additionally, i is of interest to evalsate the specific energy ‘consumption ofthe produced HCl to benchmarking it aginst existing references. The overall specific energy consumption of a process in ‘hich the EDBM HCl output stream is sent to a distillation unit is in cluded in order to analyse the potential synergistic effects of such in tegration. Moreover, the environmental burdens associated tothe en ergy consumption are quantified in terms of carbon footprint (CP), 2. Experimental methodology 2.1, Lab scale experimental setup All the experiments in this work were performed in a modified PCCell (Germany) bench scale laboratory ED system, composed of dif ferent elements as shown in Fig. 1. A proper description of the ex perimental set-up is given in previous works 9). 21.1. Membrane and cel stack configuration EDBM is an electromembrane process requiring a cll in which the Aiferent required membranes are configured. In the experimental set ‘up employed, 2 commercial cleerodialyss cell Glektolyse Project, Netherlands) composed of two electrodes made of titanium and coated ‘with ruthenium exide, with an effective area of 100 em (square, 10 em ‘each side) was assembled. Na,SO, has been selected a electrolyte ‘based on previous works (9). Commercia heterogeneous polyethylene bated anion (AM-PP RALEX) and cation (CM-PP RALEX) exchanges membranes from Mega (Czech Republic) were selected. In adltion, the Dipolar membranes (Fumasep FEM) were provided by Pumatech (Ger. many). The unit cell configuration is AEM/BM/CEM, so the stack config: uration follows the next sequence CEM/AEM/BM/CEM/CEM (or ab broviated as -CABCC configuration). Once all the experiments were completed, we did not observed any macroscopic damage in the ‘membranes atthe operating pH values, thus confirming the expected ‘004 performance 2.2. Power supply and solar array stmltor Constant current intensity is provided thanks to @ power supply (Statron, Germany) which is integrated into the modified bench seale system. Variable current intensity is provided by means ofa PV solar array simulator (Chroma, Netherlands). This power supply is able to simulate the electreal output of a PV solar array, by defining a set of parameters and a given solar irradiation profile. The software is able to provide the current intensty-voltage (LU) and powersvoltage (P-U) ‘operation curves through two Inputs: the panel parameters and the i radiation and temperatures curves chosen by the operator. The current intensity (D and the voltage (U) relaion is determined by the total ‘ohmic resistance between the electrodes ofthe stack, which s obviously ‘ot fixed by the simulator. Therefore, the behaviour ofthe simulator is ‘the same as areal PV solar array. The selected parameters for this case study, based ona eal PV panel parameter are shown in previous works (927), 24.3. Solutions prepared for the experiments The brine tank wa intially loaded with 20 L of 1.0 motL~? Nacl (Acs grade, Scharlau, Spain), which represents a simplified synthetic model SWRO brine (5-11. The use of Na* and CI” synthetic model solutions avoids the problems derived from divalent ions in real brins. [As a result, i helps at the acessment ofthe system feasibility under favorable operating conditions. Asin previous works [10), the initial acid and base concentrations were set up at 0.1 molL—? HCL (1 L) and. (0.1 mol.~* NaOH (11) instead of 0.0 moll." for both species to avoie| the excessive Inerease inthe sick resistance. Both acid and base were [ACS grade and purchased from Panzese (Spain). A 0.5 mall Na,SOx (ACS grade, Scharlau, Spain) solution was employed as electrolyte ‘Mil-g water was used to prepare the solutions Me ter Gnses, Serato an etn Teg 242 (2020) 16785. ‘Tablet ‘Summary of maximum concenttations of products Hl and NaOH obtained using EDBM, ode of operon Intl eed Tpsheseobace Cave Wolage Mae HCL ‘Max OKC fet tenet fennty ——(eonmant)_—enteaton—_concannaton (econo) ont he ot el Tew ot ch Neciimiae se - as ans ss boar ae Nac” 190 espa BP asco on 1 : to) ‘miennuons Many Nos 07 and Rematch bo = 0 1 oo nl contin oe Nec 100 Fumase (Fumaeeh) 220, - ome 16s 7 ve Min Nuc 902 toosto = 02 moa - het Toss 20gi- Fastech 1000 = ios 10 Fassoo Us) Minty Na-"016 ane Robe * isos : te el eh Muny Ne045.079 Neavepla BPI and POM 100, - oso ous rez sedi" 048078 ame ice enor ewe cel) - ‘ a a a st aes craw aa, Pe - as as nas os foo) sof: 003 (Paymerthense Ne oae mee Me" 00055 aes estas FEA Perchemie = 6 a a - wa ae sob-astoa2 Fe came) a ae aa ss ea} eae Ie = eth Nesey BFL mow ost - Tee feet ates His04 + Fs04 Nesey BP socio = oe - nas pa {Referred 0 NaOH (hig of NAD. » expressed has nommality. Valence of ionic species i 1, so normality and molarity are equal

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