nergy Conversion and Management 19 (2018) 111960 Contents lists available a ScienceDirect Energy Conversion and Management ELSEVIER Journal homepage: www-lsevier.comMlocate/enconman Contribution of Metal-Organic-Heat Carrier nanoparticles in a R245falow- @ grade heat recovery Organic Rankine Cycle ear G. Cavazzini*”, S. Bari", P. McGrail’, V. Benedetti‘, G. Pavesi*, G. Ardizzon® se nae gent ay Pb ly pace ere Nato Labrty, ed State “re vey of Bore, aly ARTICLEINFO AmSTRACT eyor This pape presens an in-depth investigation ofthe applications ofan innovative nanotud suspensions of aoe nanoparticles ina base din the ORC field, Dated on a nev clas of nanoparciles ~ terme Metal Organic Wate eae Heat Cariers (OHCs) ~moledlary engineered to reversibly uptake and release the working fd molecules in oe ‘which they ae suspended. Unike anced nanoparticles (i. AlsO Al), these MOHCs make i porsble to ‘xtrataddvonal eat rom the encothermie enthalpy of sorption which canbe ae mth ae twice the level of the iatenthest of vaporization of the pe fie phate lone. The pperiarate te development ofa ni merical mode! for atesng the MOFIC-based nanafisd gin in ORC systems. More specially, the posse ‘onder. To propery model the reversible advorpton/gerorption proces, experimental analy were ear fut to racy the uptake ofthe R245f in MILIOL at efferent operating conditions and geparting fom the war optimized in arr to matimize the aeado-power ati, Promising rents were achieved inter fst 1. Introduction However, to exploit the demonstrated large potential by OR modiles the main issues that need solving are: Industri processes account for about a third of the total energy consumed in a country [1.2] and are characterized by poor efficiency ‘with 25% up to 55% of energy losses inthe form of medium and low ‘The lack of a commercial product characterized by & good com: promise between performance and costs temperature Waste Heat (WH) due to the absence of internal heat de ‘mand (3) low efficiency values in power recovery from low and ultralow- grade heat sources are actually present in state-of-the-art systems. As regards Organie Rankine Cycles (ORC), the few available market solu tions focused their attention on the maximization of nominal efficiency values, forcing costs into the background, The result are ORC modules With efficiencies sul stacked between 5% and 9% ((4,5)), but with accompanying prohibitive costs (51000 to 81000 €/KW (6,72) whieh annul their economic sustainability in real industeial applications be cause of pay-back times exceeding 10 years, Nevertheless, one ofthe most promising options for recovering en: ergy from low and ultralow-grade heat sources (< 150°C) is un 0, Which could contribute to the increase ofthe enthalpy drop, or by an absorption process (Myjain Mjars) <0, ‘which could reduce the increase of the enthalpy drop in comparison with the pure uid 4A, Numerical model forthe nanefluld ‘To verify the impact of the considered nanofluid MIL01/R245fa on Bog amet and Manage 199 2018) 111960 the performance of an ORC system, a proper numerieal model was developed “The development of a numerical model for similating the nanofluié performance in an ORC system present some issues, mainly related to the fact cht it is not possible to acquire the nanofluid properties by means of standard software (i.e. CoolProp) as is the case for pure fluids fang mixtures. “To overcome this setback, experimental analyses were needed to etermine the enthalpy of absorption/desorption (Section 42.1), as well as an equation to determine the absorbed/desorbed mass a8 4 fnetion of pressure and temperature (Section 4.22. Nonetheless, © model the nanofluid behavior in an ORG, {€ was necessary to make some simplilying hypotheses anyway: ‘The contribution ofthe nanofluid was not taken into account during the pumping phase, neglecting the influence of the nanoflud ad: sorption process ‘© To appreciate the influence of adsorption/desorption processes on the ORC performance, the nanofid was assumed to be used in the ‘ORC optimized forthe pure Nuid R245Fa. Therefore, some operating conditions such a evaporating and condensing pressures were equal {noth cases ‘© The nanoparticle mass fraction loading in the pure Mud (5) was assumed constant and equal to 0.79 This value was chosen on the basis of the experimental analyses (both capillary tube and heat exchangers tests), where it allowed to achieve promising results in 2645-107 +458 8 Baap 2645-10" 14506: 10 yn, P73 «Dray hae = [to we ane =1)] ac Bhan Oh +o ~1)# — Thay = FPeee ha) aM tg Ma Sint] ves Toa Bl ig 9, erative procedure for determining the temperature Ty and enthalpy iy ofthe nano atthe owe of the evaporter in the numeral model6 conn Bog amet and erage 199 2018) 111960 INPUT DATA Tym oTe Tosa 24S opr conditions (Oe aga Th Tr eT 8p) I NUMERICAL MODEL for the NANOFLUID erative procedure | —e Tang i Bhzser tay = Bayt hy (ten gy* Tam Tr Sap =F (Perp Tag) = SPen Sop) ba = Bag ~ (hay ~ Ba) ep T= f@onuho) erative procedure > Tags Aya ns Te + (Oya angi Mg = Pan, Ty PEAOEAD, Tag = yy Pella) haTe = S(Pemarte=Di Ter ayer) im, = utend elie Fa Toa Pouny = Mag (fa —hy):—ap = Mar Rant ~ he) Pap ~ Fm conor Varn = (CSTs) "Pons taacon = ToT apr HEMT, Ay = Et Boaponate Yeray = F(8Tap) snap? Oy) cpap? ™aPevas) celia UnpBtnteney Awe Swrerhewter Uae = I (en) u(y eee) jon Usesup = FBT) na TOP) cgua? a Peond) = Fig. 10, Numerical model fr determining the performance of an ORC operating with «nano6. Coan terms of particles suspension stability [39,72] + The nanoflld specific hea can be determined by assuming thermal equilibrium between the nanoparticles and the base fluid phase (7 (= Pearsons + PPvonety He oo Pe op Eq, (28) can be simplified inthe following equation (75-78) Spat = (1 ~ #)epar + 6am eo Because of the low nanoparticle mas oa faction (@ = 0,790) and Decause ofthe specific heat ofthe nanoparticle zane = 2122) lower ‘than that ofthe pure lull during the evaporation process, the nanofluld specific heat ffers less than 0,446 from the base uid specific hat, For this reason, it was assumed to be equal tothe base fluid one: Staring from this hypothesis, the end point ofthe heat transfer from the heat source in the nanoflid numerical mode is expected to belong to the same isobar asthe pure working id + The enthalpy gain due to the nanoflud (Eq, (25)) depends on the evaporation pressure (via mits = f Goa Ty) ~EQS. (30) ane (31)) and on the temperature of the nanoflid at the outlet of the heat ‘exchangers (Ty). To determine this, an iterative procedure was applied (ig. 9) += The enthalpy drop relating tothe nanoflid expansion process in the expander (Fg. (52)) depends on the evaporation and condensing pressure (Egs. (30) and (1) and on the temperature of the nano- ‘uid at the init and outlet of the heat exchangers (yy and Ty) ‘Once the nanofluid thermodynamie condition atthe outlet of the evaporator (Tyr, 5, hy) i determined, those atthe outlet of the evaporator (Ty, hes) were calculated by applying the same itera tive procedure of Fig. 8. Starting from these hypotheses, the numerical model for de termining the ORC performance was developed, as summarized in the flow chart of Fig. 10. [AS regards the calculations of the globel heat transfer, since MIL101/8245(a is a novel ful and its properties are not avallable in the literature, it cannot beset a8 the working fluid in the commeretal software wsed for U ealelations (Section 22). Therefore, the look-up tables were built for the manoflig, starting from those of the pure 'R24Sfa fluid, The presence ofthe MIL1O1 nanoparticles was considered by changing the profile temperature distribution ofthe nanofluid and ‘comparing that of the pure fluid in each heat exchangers section ac «cording to the modeled behavior of the 8245fa/MILI01 nanofluid 5, Results ‘able 4 presets the results achieved by the five pure organic fluids ‘under consideration. Their cycle parameters were optimized to min ‘mize the total heat exchanger area per net power output and by the ‘R24Sfa/MILIO1 nanofluid according to the numerical model defined in Bog Comers an erage 199 2018) 111960 ski Fig. 1. Cyels ofthe pure Nui R245 (ue ine) an ofthe R245f4/MILIO1 ‘anos (pink line in he Ts dagram fra het source temperature of 100°C. Section 43. ‘Among the pure organie fluids, dhe Aud R134a isthe best in terms ‘of objective fanetion and in its ability to achleve the greatest net power output (12.86KW) with an average total heat exchangers area (9.841 m), As for the remaining fuids, R24Sfa is the best one in terms fof total area Ay, Being 1m lower thas that of the R134 ‘The introduction ofthe MIL101 nanoparticles in the pure R24Sfe sakes itpossible to achieve a further gain in terms of total area per unit ‘of power output, since the enhanced heat transfer capacity of the na ‘ofluid leads to slight reduction ofthe total heat exchanger areas in ‘comparison with the pure Ould (8.873 m* vs, 8:997 n°), The fact that the gain is mainly related to the heat exchanger size is confirmed in Fig 11. where the Ts diagram ceports the resulting cycles of the pure ‘uid (bla line and ofthe nanofluid (pink line) for the considered heat source temperature Ty of 100°C. ‘The two cycles almost superimpose one another, with a negligible variation in the maximum cycle temperature TS (75.0°C for the [R24Sfa/MILLOI vs. 75°C for the pure R24Sfe). The reason for this re sult has to be located inthe behaviour of the MOCH-based nanoflug ‘whose contribution is strictly related to the desorption process in the ‘evaporator. Iti lear from Eq, (25) that i the desorbed organic Auld ‘mass Army is smaller than the nanoparticles mass dispersed in the ‘working fluid mann, the enthalpy gain related to the sensible heat of ‘the nanoparticles and tothe desorption process could even be canceled Jn Table 9, i clear thatthe desorbed mass is much smaller than the nanofluid mass maze and the fist term of Ba. (25) Aw! ip + (Stee 2) fren 4 Bhoge + Aha] aura ‘is much smaller than the enthalpy gain ah,,of the pure R245 ‘Table a Resale of the optimization ofthe ORC for five pe organ fu and rel of the nsmerial mode! adapted fr the nanoisd R2¢Sfa + MILLOI for heat souree temperate Tai 0 100°C ud Or Po wl Gide Cpt ARE Pow WT Pa EHAWT masa = nn 20.00 nes an msunmor 35 8 20.00 Mee ns6. Coan Bog Comers an erage 199 2018) 111960 ‘ables [R24Sfa mases vs, MILLOI forthe ORG optimized for a het source emperatue of 100°C ~ evaporator. wl) malt maaan) reneatile) er) (212 9413/49) ‘To better highlight the sensitivity of the desorption process on the Conversely, this reduction is not compensated by the sensible heat thermodynamic conitions, a parametric analysis hae been caried out ‘of the nanoparticles or by the heat of desorption, represented by the on the enthalpy gain in the evaporator (Eq. (25) at different values of Stsond em of B28) Bho? Srporaon ere a “hepa id wos considered as operating int opinined cond ah = 9 [Sst m+ sna ak ike tions at each heat source temperature. Starting from the optimized cycle of the R24Sf4, the variation in percentage enthalpy gain In the expander, the nanofluid faces an adsorption process °] was determined as » function ofthe evaporation pres on Sa lati nieces aMase soc Sanlaeosencenigc onan leat Shiga! of Bq. (32) ‘optimized values. sit [+ a( tae) anna sf cst Soe nt ty epee None ‘sure, ranging from + 6% even to ~ 8%. sos nente comin oe cee aonen ones ew pie me ng ture values forthe nanofiid in order to fairly evaluate the potential contribution ofthe nanofluid in ORC applications as, it must be pointed out thatthe nanofluid contribution is also y affected by the value ofthe mass fraction losding g which was (| 22h] = ~0.09kT/Rg) Cale 6), which concurs in an higher cehalpy atthe expander outet, However, hanks to the positive con tebution of the sensible heat ofthe nanoparles, the Second (er hy gi of Ea, (32) “ ero ae saa antegrade 1 must be pointed out thatthe simplifications adopted in the de- _dothermic enthalpy of desorption. This can be as much as twice as high velopment ofthe numerical model (mean MOHC heat capacity, mean as the latent heat of vaporization of the pure fuid phase alone. ‘enthalpy of adsorption, ete.) introduced uncertainties in the final re In order to assess the potential benefits of the adoption of this, sults and these uncertainties coulé affect the significance of the gain paticular type of nanoparticles in ORGS for waste heat recovery ap- (1.4%) achieved by the nanofluid at 100°C. However, at higher heat plications, a numerical analysis has been carried out and, more speci source temperatures (Table 7, the nanoflukdcontsibution significantly fleally, the posible combination of the base fluid R245fa with the na Inereased up =18.9% and it is clear that the nanofid enhances its nopartcle MILIO1, a cobust Metal Organic Heat Carrer, was performance asthe heat source temperature increases, behaving better considered, ‘than the pure fvid forall the considered heat source temperatures, with ‘To properly model the reversible adsorption/desorption process, performance increasing with increasing heat source temperature ‘experimental analyses were carried out for studying the uptake ofthe However, a closer look at the results shows thatthe main benefit of R24Sfa in MILIOI at different operating conditions and, starting from ‘the adoption of the R24Sfe/MILI01 nanofuid is related tothe redue- the experimental results, proper semi-empirical correlations were de- tion ofthe heat exchanger areas, since the net power output is almost fined. ‘equal among the pure R245fe and R245fa/MILIOI results. However, Subsequently, these correlations were properly adopted in a nu: since the working Muid uptake is strictly related to pressure and tem. mereal model specifically developed for assessing the nanofluld gain in perature (Eg. (30), Its elear thatthe evaporation pressure Peep And texms of atea fo net poster ratio in comparison with the pure fluid the inlet temperature Ta ofthe pure fluid R245fo, adopted forthe na- _R2ASfo, whose cycle was optimized by an optimization algorithm. In nofluid according to the numerical model (Section $3), are not opt- order to quantitatively appreciate the diferent behaviour between pure mized for the MOHChased nanoflid. Tai has a significant influence R245(a and R245fa/MILIOL, the performance achievable with other ‘on the positive contribution ofthe desorption process, since the mass for pure organic flids, whose cycle was also optimized in order to uptake varies sigificandly with pressure and temperature values minimize the Area to power ratio, have heen determined ig. 7. ‘The result ofthe comparison highlighted a significant influence of Table 6 DA5ta masses vs MILIOI forthe ORC optimized ors eat source temperature of 100°C ~ expander nase US) men 81 maseneaes B/)— mcnte A) Smads] Se! Ag) Bho Hg) AA Dah ab OM6. conn t 7 Bog amet and erage 199 2018) 111960 Comparison between the pure ongaie fs R24Sfa andthe nanofisid R24Sf/MILLOI at dteent hes source trperares, ranging fom 100°C ta 150°C. BO Ae te Ba Toa Teas Omens mene me Aa reat rare iow rar tet a Enthalpy eitference at evaporator = R248t¥IL101 Influence the work reported in this paper. SNe References 7 Leta (0 ni a ay Tee nape “Aon z ime 2s A ta Fhe. Rd Maes rma ntl wae a ie Ap Bory ants a38 Iso a toy Tasty, su, An vee of omega a a ‘Sey prt pcan of nteped ytem hae on ot ~*~, (5) Phat I ean, Ning Experinestl sy ofthe oii nine s 16) Turgut MS, Turgut OF. Mutiabjcive optimization ofthe bale and sngletans 9 on 909 a0 |] aa «=«=«*TY:‘Toel Pa, Pesci, anche Bl see Orne Rankine Cyce Pay (KPa {8} Tehanche BF, tambrinos , Prangoudahis A, Papadais GLawegrade heat conver Fig. 12. Influence ofthe evaporation pressure on the percentage enthalpy gain Jaw tun meg he mies ee {a} Soy the byt a cay ota nla tua) Cao Yang Wang ang X. Gon Hear Anas a rpc Rkine the operating eyele conditions on the enthalpy gin related to the (noe und Ra sing Fars Deneon Poet ‘adoption ofthe nanofiid Interestingly, the main Benefit ofthe adop lp Apps abieac a “ tio ofthe R24Sf/MIL1O1 nanfluid wast reduce he heat exchanger! Li Bane Vein al lope atom a Tm areas, since the net power output was slmost equal for all the heat (12) hin un) yeoman sal of ean Race ye ns ee oe source temperaures considered. This result is malnly de tothe eva ire ppl bry ont 2061807466 poration pressUre Pop andthe inlet temperature Ts of the pure Mud {18 ess ink tne abs icc ad pial poms -R245fa, which were optimized for the pure Aud, but not forthe MONG: sbinsoayanese based nanofuid. Since the working fd uptake is strictly related ¢o {141 Sch Yorba, Wendad Fiche J. Woking Mids fw epee Dresrre and temperature, the contribution ofthe desorption procest jug) Cn dorani OY Scanlan fh ven of hrmadrani cer nd tured out to be negatively affected by the high value ofthe evapore- treihing forthe eanserson af pad eat Rene Sula Ey ev tion pressure presen ‘sensitivity analysis, carieé out to analyze the influence ofthe {261 ICG <4 soy eine pap of wig il sal ae ‘evaporation pressure on the nanofiuid performance, demonstrated the 17) Su vu cot empwntie esng or seein of wring a abe Posty of increasing by up to 69% the enthalpy gain athe evaporator ‘hic rere Gran Rankine es Baers 214 7HOV TIS. fon reducing the evaporation presute. Further benefits are also ex: 081 LX Zhe La FZ @ wong did scan Psd oo ie pee pected by optimizing the mass fraction loading This dearly high So ue vee teen Rakn eee Sel Cn Teco Set lights the need to optimize operating conditions and nanofuid prop- U9} Cas © ois Ma Arey © Ams SO-baedlnt e ccs in onder to fairy evaleate the potenal contibution of the Ssh epee ariel Ons Rane Se hey ‘anofiid in ORC applications. (20) Cho S08, Postman JA akacing hema conc fs 0, the optimization of the manofluid properties and operating parce ASE rato cane Eo conditions eould give the possiblity to signfeantly increase cyle ef be feiencies for low-grade heat source temperatures and to reduce the 2) 0. SS. ar re Ss heat exchanger areas, with Benefits inthe application elds suffering of 22) buansurse wal Atensaheapon tie dssnelecnacac a tagte 2 severe size lms (or ex. automotive fel). Non Page aout omen tay hf ene, adn dl EA. eas hl on Declaration of Competing Interest Seonraczases vanes wit (ot) iets nas 0 cha Spgs eran hing ‘The authors declare that they have no known competing financial interests or personal relationships that could have appeared to (251 Cadun Rae 2 Mob al 9, Woogie. Enhancmet af et ater og6 cara ea tes) er) ves) 9) (30) 21 bo) ba bs be bn bs 1 0) wa a 8) ts ts) 6) te 8) 1 130 sa stain oven Re Sun Eergy Re 2010140 62-4. 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Aaa Asta Choecan 8, Naja GBelorE. es of ead Nisin ye egy conver Manag 209 1¢2becobee 218} a90 Dor Piva © Pane naa a option oa Orga Raine {jet with mee bed npr eagles Rene Eee Bone Tid C Opinion of solar wgeeates item Wi tof pbb Uough coc Eanes 2017100 Scot, Tolapay Banca), Nabe Sk eas bang LX Maar foc hn cra ets Rane Egy 18a) 38, Fy eta A hvu wept bse so nth asl lee pote ‘olume and ari aren Sec (00) S003 somone) 2090-2 et Sen i a mr so Dal ¥ Wang J, Gat. Parametrie eptinization and eampuratve sey of organic unin cy ORC) tom res are at never. Ens) Coes Nakeg {eu Bl Foss Tadeo easy dy fhe nerton of 4 (Store satcde ORS teal se ay, Eegy Cones Maney ‘Avadbanula VK, Lin 5. 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