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A Review of Working Fluid and Expander Selections for Organic Rankine Cycle

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  A review of working  󿬂 uid and expander selections for organic Rankine cycle  Junjiang Bao, Li Zhao n Key Laboratory of Ef   󿬁 cient Utilization of Low and Medium Grade Energy, MOE, Tianjin University, No. 92 Weijin Road, Tianjin 300072, People '   Republic of China a r t i c l e i n f o  Article history: Received 23 October 2012Received in revised form5 March 2013Accepted 15 March 2013Available online 18 April 2013 Keywords: Organic Rankine cycleOrganic working  󿬂 uidsExpandersMixed working  󿬂 uids a b s t r a c t How to effectively utilize low and medium temperature energy is one of the solutions to alleviate theenergy shortage and environmental pollution problems. In the past twenty years, because of itsfeasibility and reliability, organic Rankine cycle has received widespread attentions and researches. Inthis paper, it reviews the selections of working  󿬂 uids and expanders for organic Rankine cycle, includingan analysis of the in 󿬂 uence of working  󿬂 uids '  category and their thermodynamic and physical propertieson the organic Rankine cycle ' s performance, a summary of pure and mixed working  󿬂 uids '  screeningresearches for organic Rankine cycle, a comparison of pure and mixture working  󿬂 uids '  applications anda discussion of all types of expansion machines '  operating characteristics, which would be bene 󿬁 cial toselect the optimal working  󿬂 uid and suitable expansion machine for an effective organic Rankine cyclesystem. &  2013 Elsevier Ltd. All rights reserved. Contents 1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3262. Working  󿬂 uid selection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3262.1. Working  󿬂 uids '  category and their thermodynamic and physical properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3272.1.1. Working  󿬂 uids '  category . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3272.1.2. The thermodynamic and physical properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3282.2. Review of pure working  󿬂 uids '  screening. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3312.3. Review of mixed working  󿬂 uids '  screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3332.4. Limitation of working  󿬂 uid selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3342.4.1. Limitation of evaporation and condensing pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3342.4.2. Limitation of the highest decomposition temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3352.4.3. Limitation of expansion machines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3352.4.4. Limitation of environment and safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3353. Expansion machines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3363.1. Turbine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3363.2. Scroll expander . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3373.3. Screw expander. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3373.4. Reciprocating piston expander . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3383.5. Rotary vane expander . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3383.6. Various expanders '  comparison and selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3394. The knowledge gaps and development directions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3395. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340 Contents lists available at SciVerse ScienceDirect journal homepage: www.elsevier.com/locate/rser Renewable and Sustainable Energy Reviews 1364-0321/$-see front matter  &  2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.rser.2013.03.040 n Corresponding author. Tel.: + 86 22 27890051; fax: + 86 22 27404188. E-mail address:  jons@tju.edu.cn (L. Zhao).Renewable and Sustainable Energy Reviews 24 (2013) 325 – 342  1. Introduction The invention of the electric power is the core impetus of thesecond industrial revolution, and steam Rankine cycle driven byfossil fuels is still the dominant power supply method. As is knownto all, the accelerated consumption of fossil fuels has caused manyserious environmental problems such as air pollution, globalwarming, ozone layer depletion and acid rain [1]. How to effec-tively utilize low and medium temperature energy which is vastbut undeveloped is one of the solutions to alleviate the energyshortage and environmental pollution problems. However, manyproblems are encountered when using water as working  󿬂 uid forsteam Rankine cycle [2]:   need of superheating to prevent condensation during expansion   risk of erosion of turbine blades   excess pressure in the evaporator   complex and expensive turbinesVarious thermodynamic cycles such as the organic Rankine cycle,supercritical Rankine cycle, Kalina cycle and trilateral 󿬂 ash cycle havebeen proposed and studied for the conversion of low-grade heatsources into electricity [3]. Compared with the Kalina cycle ' s complexsystem structure, trilateral  󿬂 ash cycle ' s dif  󿬁 cult two-phase expansionand supercritical Rankine cycle ' s high operating pressure, organicRankine cycle has the characteristics of simple structure, highreliability and easy maintenance. Organic Rankine cycle, which hasthe same system con 󿬁 guration as steam Rankine cycle but usesorganic substances with low boiling points as working 󿬂 uids, can usevarious types of heat source, including industrial waste heat [4,5], solar energy [6,7], geothermal energy [8,9], biomass energy [10,11] and ocean energy [12] etc. Meanwhile, in order to improve energyutilization, it can be easily combined with other thermodynamiccycles, such as the thermoelectric generator [13,14], fuel cell [15], internal combustion engine [16 – 19], micro turbine [20], seawater desalination system [21 – 23], Brayton cycle [24,25] and gas turbine- modular helium reactor (GT – MHR) [26,27]. Furthermore, it also can be used as prime movers of combined cooling and power system[28,29], CHP [10,30,31] and CCHP [32,33] systems. Chen et al. [3] summarized pure working  󿬂 uids which weresuitable to subcritical and supercritical organic Rankine cycle, butmixed working  󿬂 uids were not included, and furthermore, thecomprehensive pure working  󿬂 uid candidates and the optimal onesare not reviewed; Tchanche et al. [2] and Fredy et al. [81] made comprehensive reviews of organic Rankine cycle for all kinds of applications;Qiu et al. [82] reviewed various expansionmachines, butthe main purpose of their study was to select a expander applied inmicro CHP systems and the large numbers of experiments andcomparisons among differenttypes of expanders are also not covered.Because the rapid development in the researches of organic Rankinecycle ' s working 󿬂 uid and expansion machine and their selections playa key role in organic Rankine cycle performance and economy, thispaper has done a comprehensive review about them. As to working 󿬂 uids,  󿬁 rst of all, the in 󿬂 uences of the working  󿬂 uids '  types andthermalphysical properties onorganicRankine cycle performance arediscussed; secondly, the researches of pure and mixed working  󿬂 uidsare summarized, including the discussion of the working  󿬂 uids ' screening results, the comparison of the pure and mixed working 󿬂 uids and the clari 󿬁 cation of mixture ORC advantages and disadvan-tages;  󿬁 nally, some limitations in the process of the working  󿬂 uids ' screeningarediscussed.Regarding totheexpansionmachines, 󿬁 rstalltypes of expansion machines '  operating characteristics are analyzed;second various types of expansionmachine prototypes '  researches aresummarized;  󿬁 nally, the applicable scopes of different types of expansion machine are compared, which is bene 󿬁 cial to ORC expan-sion machine selection during the design process. 2. Working   󿬂 uid selection Because affecting the ef  󿬁 ciency of system, the sizes of thesystem components, the design of expansion machine, the systemstability and safety and environmental concerns, the selection of working  󿬂 uids is very important for the ORC system performance    T  e  m  p  e  r  a  u   t  r  e ,   T   T  e  m  p  e  r  a  u   t  r  e ,   T Specific Entropy,sT  1 T  2 1  P  1  P  2 2 0< dT ds SubcooledLiquid Vapour+LiquidSuperheatedVapourSaturetedVapourSaturetedLiquid Specific Entropy,sT  1 T  2 1  P  1  P  2 2 SubcooledLiquidVapour+LiquidSuperheatedVapourSuperheatedVapourSaturetedVapourSaturetedLiquid0 dT ds    T  e  m  p  e  r  a  u   t  r  e ,   T Specific Entropy,sT  1 T  2 1  P  1   P  2 2 SubcooledLiquidVapour+LiquidSaturetedVapourSaturetedLiquid0 dT ds => Fig. 1.  Diagram  T  – s  for  󿬂 uids (a) wet, (b) isentropic and (c) dry [38].  J. Bao, L. Zhao / Renewable and Sustainable Energy Reviews 24 (2013) 325 –  342 326  and economy [34 – 36]. Different from the characteristics of otherthermodynamic cycles, such as compression refrigeration cycle(working conditions are determined) and Kalina cycle (working 󿬂 uid composition is set although mass fractions vary), working 󿬂 uid selection of ORC system is a more complicated task owing tothe following two reasons basically:1. The working conditions and heat source types of ORC varywidely: from low-temperature heat source of 80  1 C (e.g.geothermal, plate type solar collector) to high- temperatureof 500  1 C heat source (e.g. biomass).2. Except for some substances whose critical temperatures are toolowor too high, hundreds of substances can be used as working 󿬂 uid candidates of ORC, including hydrocarbons, aromatichydrocarbons, ethers, per 󿬂 uorocarbons, CFCs, alcohols, silox-anes and inorganics (which should not inherently not be anORC but due to the similarity with ORC so that included) etc.  2.1. Working   󿬂 uids '   category and their thermodynamic and physical properties 2.1.1. Working   󿬂 uids '   category Except for the structural point of view and type of atoms in the 󿬂 uid molecule, the working  󿬂 uids could be categorized according tothe saturation vapor curve, which is one of the most crucialcharacteristics of the working  󿬂 uids in an ORC [4]. This characteristicaffects the  󿬂 uid applicability, cycle ef  󿬁 ciency, and arrangement of associated equipment in a power generation system [37]. As shownin Fig. 1 [38], there are generally three types of vapor saturationcurves in the temperature-entropy ( T  – s ) diagram: a dry  󿬂 uid withpositive slopes, a wet  󿬂 uid with negative slopes, and an isentropic 󿬂 uid with nearly in 󿬁 nitely large slopes. The examples of wet  󿬂 uidsare water and ammonia. It is observed from the  T  – s  diagram that asuperheater is employed to superheat the vapor. The saturated vaporphase of a dry  󿬂 uid becomes superheated after isentropic expansion.An isentropic  󿬂 uid has a nearly vertical vapor saturation curve, e.g.R11 and  󿬂 uorinal 85. Since the vapor expands along a vertical line onthe  T  – s  diagram, vapor saturated at the turbine inlet will remainsaturated throughout the turbine exhaust without condensation. Thefeatures of persistent saturation throughout expansion and the factthat there is no need for installing a regenerator makes isentropic 󿬂 uids become ideal working  󿬂 uids for ORCs [4,37]. Due to the negative slope of the saturation vapor curve for awet  󿬂 uid, outlet stream of the turbine typically contains lot of saturated liquid. Presence of liquid inside turbine may damageturbine blades and it also reduces the isentropic ef  󿬁 ciency of theturbine. Typically, the minimum dryness fraction at the outlet of aturbine is kept above 85%. To satisfy the minimum dryness fractionat the outlet of the turbine, wet  󿬂 uid at the inlet of the turbineshould be superheated [39]. Due to reduction in heat transfercoef  󿬁 cient in the vapor phase, heat transfer area requirement andhence, the cost of the superheater goes up signi 󿬁 cantly. There areother operational issues related to the superheater as well. While “ isentropic ”  and  “ dry ”  󿬂 uids do not need superheating, therebyeliminating the concerns of impingement of liquid droplets on theexpander blades. Moreover, the superheated apparatus is notneeded. Therefore, the working  󿬂 uids of   “ dry ”  or  “ isentropic ”  typeare more adequate for ORC systems [39,40]. If the  󿬂 uid is  “ too dry, ” the expanded vapor will leave the turbine with substantial  “ super-heat ” , which is a waste and adds to the cooling load in thecondenser [3]. Usually a regenerator is used to reclaim theseexhaust vapor to increase the cycle ef  󿬁 ciency; however, it wouldincrease the system ' s initial investment and complexity, whichexists trade-off. Therefore, Hung et al. [4] thought that isentropic 󿬂 uids are most suitable for recovering low-temperature wasteheat. In their latter research [41] about the in 󿬂 uence of types of the saturation vapor curve for a  󿬂 uid on system ef  󿬁 ciency andirreversibility, results indicated that wet  󿬂 uids with very steepsaturated vapor curves in  T  – s  diagram have a better overall perfor-mance in energy conversion ef  󿬁 ciencies than dry  󿬂 uids and isen-tropic  󿬂 uids. They are not always suitable for ORC systems whenother thermo physical properties are taken into consideration.With respect to the overheating, Hung et al. [4] found foroperation between two isobaric curves, the system ef  󿬁 ciencyincreases and decreases for wet and dry  󿬂 uids, respectively, andthe isentropic  󿬂 uid achieves an approximately constant value forhigh turbine inlet temperatures. For dry working  󿬂 uids, when thepressure is high, overheating can increase system ef  󿬁 ciency bysmall degree. Hung et al. [41] argued the property of dry orisentropic  󿬂 uids would reduce the area of net work in the  T  – s diagram. The second law ef  󿬁 ciency would decrease with turbineinlet temperature due to the increased irreversibility [4,42]. As it was found the cycle thermal ef  󿬁 ciency is a weak function of theturbine inlet temperature, it was recommended it is not necessaryfor organic  󿬂 uids to be superheated [4,5,42,43]. Consequently, the 300180425100%0255075100200300400T ° CT ° C    E  x  a  u  s  t   G  a  s    W  a  t  e  r Vaporizing    P  r  e   h  e  a  t   i  n  g       S    u    p     e    r     h   e   a     t     i    n   g   33090425100%0255075100200300400    E  x  a  u  s  t   G  a  s  O  r  g   a  n   i  c    F   l  u   i  d Vaporizing    P  r  e   h  e  a  t   i  n  g    S  u  p   e  r   h  e  a  t   i  n  g  ∆ T =30 ° C ∆ T =30 ° C Fig. 2.  The effects of vaporization latent heat on the irreversibility in the heat transfer process [48].  J. Bao, L. Zhao / Renewable and Sustainable Energy Reviews 24 (2013) 325 –  342  327  optimum ef  󿬁 ciency of ORC working with a dry  󿬂 uid could beachieved when the  󿬂 uid operates along the saturation curvewithout being superheated [42,44,45].  2.1.2. The thermodynamic and physical properties The performance of ORC systems strongly depends on working 󿬂 uids '  properties, which affects system ef  󿬁 ciency, operating con-ditions, environmental impact and economic viability [3,46]. The relationships between working  󿬂 uid properties and the ORCcommon economic and thermodynamic performance criteria froma theoretical and analytical point of view are discussed as follows:  2.1.2.1. Vaporization latent heat.  The thermal ef  󿬁 ciency of an ORCsystem can be written as [4,8] η  Ι   ¼  W  net Q  in ð 1 Þ where  W  net  is the net output work and  Q  in  is the input heat of theORC system.A study presented in [47] notes that high vaporization latentheat enables most of the available heat to be added during thephase change operation, hence avoiding the need to regulate thesuperheating and expansion of the vapor through regenerativefeed heating in order to enable higher ef  󿬁 ciency. From the point of view of output work, Chen et al. [3] found that  󿬂 uids with higherlatent heat produce larger unit work output when the tempera-tures and other parameters are de 󿬁 ned. However, when the heatsource is the waste heat, organic  󿬂 uids with lower speci 󿬁 cvaporization heat are preferred. Lower vaporization heat of theworking  󿬂 uid causes the heat transfer process in the evaporator tooccur mostly at variable temperature. Therefore the temperaturepro 󿬁 le of the working  󿬂 uid in the evaporator better follows thetemperature pro 󿬁 le of heating  󿬂 uid in the heat source [48]. Thismeans that the temperature difference between  󿬂 uids in the heatexchanger is reduced as illustrated in Fig. 2, hence the irreversi-bility in the heat transfer process is decreased. In a word, for wasteheat or geothermal binary plants, suitable but not large vaporiza-tion latent heat would result in better overall performance of ORCplants.Regarding to vaporization latent heat, the ratio of vaporizationlatent heat and sensible heat in 󿬂 uences the thermal ef  󿬁 ciency andexergyef  󿬁 ciency of ORC extremely. From literature [49], it could befound that both high evaporation temperature and vaporizationenthalpy ratio (the ratio of vaporization latent heat and sensibleheat) would result in a high ORC ef  󿬁 ciency. Through the thermo-dynamic derivation, Mikielewicz et al. [50] recommended athermodynamic index, in which a Jacob number was de 󿬁 ned. Infact, this Jacob number is very close to the ratio of vaporizationlatent heat and sensible heat. Moreover, Kuo et al. [51] recom-mended a  󿬁 gure of merit de 󿬁 ned as:Figure _ of  _ merit ð FOM  Þ ¼  Ja 0 : 1  T  cond T  evap   0 : 8 ð 2 Þ which combining the Jakob number, condensing temperature andevaporation temperature. Here, different from [50], this Jakobnumber was de 󿬁 ned as  Ja ¼ Cp n dT  / Hv , where  Cp n dT   is the vapor-ization sensible heat and  Hv  is vaporization latent heat, that is thereciprocal of the ratio of vaporization latent heat and sensible heat.Their results showed that the smaller  󿬁 gure of merit that is alarger ratio of vaporization latent heat and sensible heat is, thelarger thermal ef  󿬁 ciency is, which explained the results of litera-ture [49].From the point of view of exergy ef  󿬁 ciency which is de 󿬁 ned as[8,52] η  Π   ¼  W  net E  in ð 3 Þ where  W  net  is the net output work and  Q  in  is the input exergy of the ORC system, it could be seen from the analysis of Stijepovicet al. [46] that smaller the ratio of vaporization latent heat andsensible heat is, the larger exergy ef  󿬁 ciency is, and therefore, thereare trade-offs when the ratio of vaporization latent heat andsensible heat is regarded as the optimum indicator for bestworking  󿬂 uids. It should be pointed out that the thermal ef  󿬁 ciencyis more appropriate as the performance index for solar energy andbiofuel [7,49], while the net work is more suitable as the performance index for waste heat and geothermal applications[53,54]. Then, exergy ef  󿬁 ciency is a useful tool to account for theenergy quality, which could be applied in every renewableapplications for analyzing the system irreversibility.  2.1.2.2. Density.  High vapor density is of key importance,especially for  󿬂 uids showing a very low condensing pressure (e.g. silicon oils). A low density leads to a higher volume  󿬂 ow rate:the pressure drops in the heat exchangers are increased, and thesize of the expander must be increased. This has a non-negligibleimpact on the cost of the system [3,55]. Under the assumption of neglecting any in 󿬂 uence of Reynoldsnumber, the isentropic ef  󿬁 ciency can be expressed as a function of two parameters only [56]:the size parameter SP   ¼  ffiffiffiffiffiffiffiffiffi _ V  out  p  ffiffiffiffiffiffiffiffiffiffi Δ H  is 4 p   ¼  ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi _ m out  =  ρ out  p  ffiffiffiffiffiffiffiffiffiffi Δ H  is 4 p   ð 4 Þ which accounts for the actual turbine dimensions and the isen-tropic volume  󿬂 ow ratio VFR ¼ _ V  out  _ V  in ¼  ρ in  ρ out  ð 5 Þ de 󿬁 ned as the speci 󿬁 c volume variation across the turbine in anisentropic process, which accounts for the effect of the compres-sibility through the expansion.According to Macchi and Perdichizzi [56], a higher value of SPresults in larger turbine size. From Eq. (4) it appears that a higherdensity at turbine outlet has a negative impact on SP and thereforeturbine size will be smaller. Also based on Macchi and Perdichizzi  Table 1 Listing of speci 󿬁 c work, total work of pump and liquid speci 󿬁 c heat for selectedworking  󿬂 uids [60]( T  e ¼ 80  1 C and  T  c  ¼ 30  1 C).Working  󿬂 uids  w  p  [kJ/kg]  W   p  [kW]  C   pl  [kj/kg/k]Propylene 5.24 95.29 2.73Propane 5.2 88.41 2.78R1234yf 2.25 86.2 1.42R227ea 1.37 62.13 1.20R134a 1.91 59.59 1.45R1234ze 1.78 54.18 1.40RC318 0.96 43.37 1.13R152a 1.96 39.74 1.83R600a 2.47 34.82 2.46R236fa 0.99 31.79 1.28R236ea 0.76 22.07 1.27R245fa 0.69 16.25 1.33R245ca 0.47 10.32 1.34MM 0.1 1.81 1.92Cyclohexane 0.14 1.54 1.85Benzene 0.11 1.22 1.75Toluene 0.06 0.59 1.72MDM 0.01 0.29 1.83  J. Bao, L. Zhao / Renewable and Sustainable Energy Reviews 24 (2013) 325 –  342 328

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