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Concept of adsorbent optimal for adsorptive
Article in Applied Thermal Engineering · November 2014
DOI: 10.1016/j.applthermaleng.2014.04.077





1 author:
Yuri I. Aristov
Boreskov Institute of Catalysis

Available from: Yuri I. Aristov
Retrieved on: 08 October 2016

the Dubinin adsorption potential being used as a universal measure of the affinity between the adsorbent and the adsorptive.applthermaleng. Pirogova str. small capacity http://dx. 5.and mass-transfer Nano-tailoring Database of adsorbent properties Sigmoid isobar shape Limiting efficiency and power 1. Concept of adsorbent optimal for adsorptive cooling/heating.2]. Russia Novosibirsk State University.  Modification of aluminophosphates. 2.1016/j.04.  Harmony of the optimal adsorbent with other components. cycle boundary conditions. Moreover. and some of them have passed over from the prototype stage to small serial production (SorTech.3 Zeolites 3 0. New efficient adsorbents harmonized with particular ACH cycles are a prerequisite to achieving a major breakthrough in ACH. InvenSor) [5].org/10. 5. Novosibirsk 630090. creation of database of their properties as well as harmonization of the adsorbent and other components of ACH unit.doi.077 1359-4311/© 2014 Elsevier Ltd. Nishiyodo Kuchouki Co. Introduction Adsorptive cooling and heating (ACH) is an emerging technology that offers both economic and ecological advantages [1. Russia h i g h l i g h t s  Concept of the adsorbent optimal for specific adsorptive cooling/heating (ACH) cycle.elsevier.1 0. Lavrentiev Av. Novosibirsk 630090. All rights reserved. are pivotal for this challenging application. cycle boundaries and duration. therefore. and therefore. Aristov. adsorptive chillers appeared on the market as early as in 1986 from two Japanese companies.: þ7 3833309673. © 2014 Elsevier Ltd.0 0 5 10 15 20 25 Adsorption potential.2014. and cycle management strategy are briefly discussed.2 4 0. we consider the role of adsorbents in adsorptive cooling/heating (ACH) and analyse which are optimal for specific ACH cycles. greenhouse gases.doi. indirect emissions [1]. Russia. The conclusions are formulated in terms of the optimum isobar shape. Applied Thermal Engineering (2014).com/locate/apthermeng Concept of adsorbent optimal for adsorptive cooling/heating Yuri Aristov a.Applied Thermal Engineering xxx (2014) 1e10 Contents lists available at ScienceDirect Applied Thermal Engineering journal homepage: www. quite large (50e1000 kW). Selection/tailoring of the optimum adsorbents.applthermaleng.1016/j. http://dx.077 .2014. The ACH development was initiated by the 1973 oil crises. Keywords: Adsorption cooling/heating Optimal adsorbent Adsorption dynamics Heat. Lavrentiev Av. g/g a 2 0.04. E-mail address: aristov@catalysis. waste heat can be utilised to drive the process reducing the consumption of fossil fuel It uses benign working fluids which reduce the direct emissions of * Boreskov Institute of Also. Novosibirsk 630090. Various small adsorption chillers (5e22 kW) were developed in the 21st century.  Testing of known adsorbents and tailoring of new adsorbents for various ACH cycles. Please cite this article in press as: Y. All rights reserved. metal-organic frameworks and composites. b. Tel. and Mycom [4]. g r a p h i c a l a b s t r a c t 1 Water uptake. Ltd [3]. * b Boreskov Institute of Catalysis. and the first. kJ/mol a r t i c l e i n f o a b s t r a c t Article history: Received 2 December 2013 Received in revised form 16 April 2014 Accepted 22 April 2014 Available online xxx In this paper.

and external heat source Tg) uniquely define the cycle. and deep freezing (DF1. condenser Tc ¼ T1. 6. and discuss which COP and SCHP can be obtained if they are limited only by properties of the adsorbent. further R&D is necessary to realize the potential economic and ecological advantages of ACH technology [8].2 Y.doi. 1b). We have added one more air-conditioning cycle with Te ¼ 15  C (AC1) that is also commonly in demand. (1) can be solved graphically to get Tmin(Te. 2. Fortunately. Those bound more strongly remain adsorbed and are not involved in the heat transformation cycle. Fig. Here. for classical zeolites. and Tg ¼ 60. Five basic applications. The DFmaxevalues associated with the regeneration conditions (Pc. HP2). such as air-conditioning (AC2).g.applthermaleng. 1. (1) depend on the adsorbate nature. Two options were suggested for the external cooling: Tc ¼ 40  C for water-cooled units and Tc ¼ 50  C for aircooled units (55  C for heat pumping) [12]. so that there is still a big room for its improvement [7]. analyse which adsorbent is optimal for a specific ACH cycle. We offer here two realistic changes in those boundary conditions: Te ¼ 5  C instead of 3  C for AC2. Presentations of ACH cycle A three temperature (3T) ACH cycle consists of two isosters and two isobars and is commonly presented on the Clapeyron diagram ln(P) vs. http://dx. Te ¼ (Tc)2/Tg that can be reached in the evaporator if the adsorbent was regenerated at temperature Tg and pressure Pc ¼ Po(Tc). the cycle cannot be realized at all. and 56  C for the weakest one. regardless of the nature of adsorbate (Table 3). we mainly consider the ACH cycle on the diagram w(DF) that is rarely used yet [9].04. Point A in Fig. (1/T) (Fig.077 . DF2). adsorbents promising for AC should have a moderate affinity to a working fluid lying between these limits. This potential depends on the adsorptive nature as seen from Table 1 that displays the DFmin-values for several ACH cycles selected as reference cycles in the key review [12]. Aristov / Applied Thermal Engineering xxx (2014) 1e10 (up to 15 kW) gas fired adsorption heat pumps have recently been developed by Vaillant and Viessmann [6]. the minimal desorption temperature does not (Table 3). and Tc ¼ 35  C instead of 40  C for water-cooled units. Other usable ways to present this cycle are w(T) and T(S) diagrams. which is typical e. the minimal regeneration temperature is determined as Tmin ¼ 102  C. 1a) and corresponds to the adsorption potential DFmax ¼ RT3 ln[Pc/Po(T3)] that is defined by the conditions of heat rejection (Tc) and adsorbent regeneration (Tg). These upper and lower boundary adsorbents are quite different. 1a). Point B in Fig. there is a one-to-one correspondence between the equilibrium uptake w and the DF-value [11]. 80. 1a). 1b represents the boundary conditions at the end of the desorption stage (point 3. for the majority of adsorbents that are promising for ACH. For the strongest adsorbent. and all others adsorbents suitable for AC should lie between these two. if the temperature of the external heat source Tg is lower than Tmin. heat pumping (HP1. Thus. Tmin ¼ ðTc Þ2 Te (2) within an accuracy of ±1  C [11].66. If the two boundary temperatures Te and Tc are fixed. 2. Common Clapeyron diagram of 3T AHT cycle (left) and the same cycle presented in the w vs. Evidently. In particular. The easiest conditions for air conditioning are Te ¼ 15  C and Tc ¼ 35  C which corresponds to DFmin ¼ 3. A large temperature lift . a strong affinity to adsorptive. two different curves describe the ad/desorption runs. Tc). the minimal desorption temperature Tmin can be estimated by equating the DF-values for the rich and weak isosters RTc ln½Pe =Po ðTc Þ ¼ RTmin ln½Pc =Po ðTmin Þ: (1) Eq. and 1. it must be in harmony with all other elements and the cycle strategy. Please cite this article in press as: Y. where S is the entropy change. DF co-ordinates (right). Eq. this value is equal to that calculated by simple Trutoun's rule [13. and 3.14] . Despite significant progress. i h    ðTc  Te Þ ¼ Tc eðTc Þ2 Tg ¼ Tc 1eTc Tg (3) can be obtained only if the adsorbent has high regeneration temperature Tg and.2014. Aristov.21. The Dubinin adsorption potential DF ¼ RT ln(P/Po) was introduced as a universal measure of the adsorbent affinity to the adsorptive [10] (here Po is the saturated vapour pressure at temperature T). Similar analysis can be done for heat pumping and deep freezing. the ACH technology as yet remains unfinished and expensive. The most severe AC conditions are Te ¼ 5  C and Tc ¼ 50  C which corresponds to DFmin ¼ 7.70 kJ/mol (Table 1). respectively. Although both right and left parts of Eq.58 kJ/mol for water. In this paper we consider the role of adsorbent in ACH technology.10. 100  C in Table 2. Applied Thermal Engineering (2014). Adsorbate molecules that are bound to the adsorbent with an affinity lower than DFmax ¼ RTg ln[Pc/Po(Tg)] can be desorbed during the regeneration stage 2e3.1016/j. methanol and ammonia. 1b represents the boundary conditions at the end of the adsorption stage (point 1 on Fig. Tg) are collected for Tc ¼ 35 and 50  C. It corresponds to the adsorption potential DFmin ¼ RT1 ln[Pe/Po(T1)] that characterizes the minimal adsorbent affinity necessary to bind an adsorptive at temperature T1 ¼ Tc and pressure P(Te). If hysteresis is present. which is briefly considered as constituent of real ACH unit. Interestingly. The ACH cycle in the w(DF) presentation is very simple: it is just one line which represents both isobaric adsorption and desorption stages of a 3T ACH cycle (Fig. hence. Concept of adsorbent optimal for adsorptive cooling/heating. Fig. it is valid for adsorbenteadsorbate pairs described by the DubininAstakhov or DubinineRadushkevich equations. although important. were suggested. Therefore. Three temperatures (those of evaporator Te. (2) also defines the minimal temperature. Since the adsorbent is just one.

methanol and ammonia that should be in the range 3.4 8.2e0.50 3.05e5. At larger (7) HP 2 DF 2 4 DF 1 3 2 1 Table 2 DFmax-value for the reference boundary conditions and selected values of Tg. kJ/mol Tc.  C Tc. 1a).doi. respectively (see Table 1).92 1. and the COP-value is also dependent on the adsorbate mass Dw exchanged in the cycle  eQc =Т с þ Qe =Т e þ Qd Т g eQa =Т a ¼ DS  0:    COPc ðDwÞ ¼ Qe Dw Qd Dw þ C Tg  Tc ¼ 6 ¼ COPid c ½Dw=ðDw þ BÞ. To increase the first law efficiency. the cooling COPc can not exceed 0. They require an adsorbent with affinity to water. 3.077 .7e0. (4) should be supplemented with the entropy balance (the second law) and given as.45 2. b) for any cooling application.65e0. respectively. It is important to highlight that: a) searching for adsorbents with very large Dw values (>0.9) for “single effect” AC cycles.2).09e10. Classification of methanol adsorbents: the affinity at adsorption stage for various ACH applications. Applied Thermal Engineering (2014).76e7. is significantly lower than predicted for a reversible Carnot cycle with the same boundary temperatures [17] (Table 3 and Section 3.2014. DFmin.75 3.30 4. The latter is calculated for the reference cycles assuming that Tg ¼ Tmin þ 20 K.32 1.05 1. therefore.8 1.  C Tmin.75.90e10. that have lower affinity for water vapour. 2 and HP1 cycles.43e6. http://dx.76e7. The same is true for HP2 and DF1 but at higher affinity level than for AC.2e17. heating of inert masses is also important.90 7.64 4.3 15.  C 35 Tg . Well enough adsorbents of water. (see definition of heats on Fig. (5) for cooling and heating.46e4.58e2. Such an adsorbent may be considered as harmonized with a particular cycle. Aristov / Applied Thermal Engineering xxx (2014) 1e10 Table 1 DFmin-value for the reference ACH cycles.85 9.46e3.93 e Dw. For silica gels. Adsorbents for DF2 application require much greater affinity than those for the other applications.applthermaleng.06 2.16].0e7.9.10 4.9.12 6.28 1. The first law efficiency For an ideal 3T cycle (with zero thermal masses) the energy balance is given as Qc eQe eQd þ Qa ¼ 0 (4) Cycle Te. 2.70 2.74e6.90 4.15 0.55 0 50 0 5 10 15 20 Free adsorption energy.66e4.21 4.15e6.1.53e10.5 Table 1 and Fig. E. For real systems.3) g/g for exchange of water and methanol (ammonia).4 9.15e6. The answer evidently depends on how one evaluates the cycle efficiency.1e0.3 18. (6) AC 1 AC 2 Methanol HP 1 5 where B ¼ C(TgTc)/Qd which is the ratio of the sensible heat of all inert masses to the latent heat necessary for desorption.  C 15 5 5 15 18 50 Table 3 Minimal desorption temperature Tmin and the Carnot efficiency COPCarnot.07e1.Y. methanol and ammonia adequately satisfy this condition for AC1.2. the energy balance (the first law) of Eq. the first law efficiency attains the maximum value (Qe/Qd) for “single effect” AC cycles and is no longer dependant on Dw. the COP approaches its maximum value (Qe/Qd) already at Dw  (0. kJ/mol Fig.47 5.9. Concept of the optimum adsorbent Here we analyse which adsorbent is optimum for a particular ACH cycle.83 1.6e21.50 3. the COPc can reach z0.5 g/g) is the ultimate priority for heat storage rather than for cooling/ heating.g.04e0. Hence. the exchanged mass Dw ¼ wmaxwmin ¼ w(DFmin)w(DFmax) must be g/g and (0.20 4. Aristov.78 2.10 4.04. 1.6 2.95 3.71 3. 3.85 6.  C 60 80 100 60 80 100 Water Methanol Ammonia 3.37e1. Concept of adsorbent optimal for adsorptive cooling/heating. The second law efficiency COPid c ¼ Qe =Qd COPid h ¼ ðQc þ Qa Þ=Qd ¼ 1 þ COPc For an ideal 3T system. c) the maximum COPc (0. The first law efficiency or the Coefficient Of Performance (COP) is then defined as 3. for small-pore aluminophosphates the heat of water desorption is Qd ¼ 55e60 kJ/mol [15.1016/j. 2 show that various ACH applications need quite different adsorbents.  C 35e50 35e50 35e55 35e55 35e50 35e50 3 H2O CH3OH NH3 3.25 5. 2 and HP1 are the most commonly used ACH applications.35 8.37e2.12 8. Tc.73e12. AC2 asks for a moderate affinity and requires adsorbents very similar to HP1. respectively. Cycle AC1 AC2 HP1 HP2 DF1 DF2 Te.  C COPCarnot AC 1 AC 2 HP 1 HP 2 DF 1 DF 2 15 5 5 15 18 50 35e50 35e50 35e55 35e55 35e50 35e50 56e89 68e102 68e112 95e144 99e136 152e195 1. Please cite this article in press as: Y. the efficiency increases at lower heats of desorption. For well-designed ACH units.5e4.1 kJ/mol.02e12. to achieve the maximum first law efficiency it is sufficient to use an adsorbent that exchanges the mentioned amount of a working fluid (or more) between the rich and weak isosters.12 2.73e1.90 7.6e6. AC1. 2.

but sophisticated methods of heat recovery in multi-bed [20] and thermal wave [21] systems.13].applthermaleng. d) and S-shaped (c) isobars of adsorption (at P ¼ Pe) and desorption (at P ¼ Pc) optimum from the thermodynamic (b. or “multi-effect” cycles in which waste heat from an upper cycle is used to drive a lower cycle [2. Concept of adsorbent optimal for adsorptive cooling/heating. the adsorbent optimum for ACH should have a step-wise adsorption isobar. If the adsorbent is not optimal so that the adsorbate is removed at Tg > Tmin. It is also often valid for water adsorption [23]. Aristov.61]. no entropy is generated. in theory. This imposes an appropriate requirement on the shape of the sorption isobar for an optimum adsorbent: the rich and weak isosters must coincide. A key difference is found for AC1 at the boundary con C.90 ¼ 0.2014. respectively [11]. (10) where m is the adsorbent mass and t is the cycle time. 3b). c (8)    COPCarnot ¼ 1=Te e1 Tg =ð1=Te e1=Tc Þ: h (9) If the heat for regeneration is supplied directly at the minimal desorption temperature (Tg ¼ Tmin). the COP-values calculated from the first and second laws are equal. The Carnot values calculated for the reference cycles at a moderate coupling of 20 K are displayed in Table 3. For loose grains configuration. Its Volumetric version (VLTJ) was suggested to study ad/desorption dynamics under conditions that are close to those at isobaric stages of ACH cycles [22]: ad/ desorption are initiated by a large drop/jump of temperature of HEx wall that is in thermal contact with the The final aim of the dynamic analysis is to maximize the specific ACH power which can be defined for cooling as SCP ¼ Qe =ðm tÞ.  C): ditions (Te.  C.3. Tg) ¼ (15 35 76 COPCarnotCOPc ¼ 1. efficiency of heat supply/rejection. so that the maximum (Carnot) efficiency is reached [19]. etc. so that the cycle becomes degenerated. Such adsorption equilibrium corresponds to isotherms of types V and VI in the IUPAC classification. 3.04. pressure and temperature levels. Hence.1016/j. This difference rapidly increases at larger DT therefore to enhance the second law efficiency the thermal coupling should be minimized. the dynamic harmonization means that the most advantageous adsorption isobar is step-like Please cite this article in press as: Y. 1a) occur immediately and completely at the temperatures Tc and Tg (Fig. the entropy generation is equal to zero (DS ¼ 0). A Large Temperature Jump (LTJ) method appears to be very useful for making the dynamic analysis. Fig.73e0. 3.077 . The dynamic analysis may be simplified if the adsorption rate is controlled by the heat transfer between the adsorbent and the HEx fin. c) and dynamic (d) points of view [8. Among these are the design of the “adsorber e heat exchanger”. The adsorbent has to sorb a large amount of adsorbate in a stepwise manner directly at Tc and Pe and completely desorb it at Tg and Pc (Fig. Under the heat transfer control. Degenerated AHT cycle characterized by a single ad-/desorption isoster (a). and the Carnot COP can be calculated for cooling and heating [13. 3a).doi. 3b). As a result. display S-shaped adsorption isobars (Fig. corresponding step-like (b.4 Y. 3c) instead of strictly step-wise ones. The second law harmonization of the adsorbent and the cycle means that the position of the step must coincide with the boundary temperatures Tc ¼ T4 at P ¼ Pe and T2 ¼ Tg at P ¼ Pc as shown in Fig. The dynamic efficiency As opposed to the thermodynamic efficiencies considered above. This suggests that a high second law efficiency may be attained by a proper choice of adsorbent without using efficient.1e10 bar. and the isobaric adsorption 4e1 and desorption 2e3 (Fig. it is a case for methanol and ammonia adsorption [23] because it occurs at a relatively high pressure of 0. http://dx. however. Aristov / Applied Thermal Engineering xxx (2014) 1e10 If all the processes are completely reversible.83. Applied Thermal Engineering (2014).18]    COPCarnot ¼ 1=Tc e1 Tg =ð1=Te e1=Tc Þ. the efficiency becomes lower than the Carnot efficiency due to the thermal entropy production caused by the external thermal coupling DT ¼ TgTmin [17]. Tc. The degenerated cycle can be realized only with an adsorbent characterized by a mono-variant equilibrium. Real adsorbents. the adsorbent dynamic efficiency depends less on adsorbent inherent properties and more on a number of external factors [8].

This is because the RD silica gels are commercially available. b) The temperature lift is typically low.doi. etc) e can not be used for ACH as they adsorb water and methanol at P/Po too high (or DF too low) for ACH applications [24]. type A). the more hydrophilic the zeolite structure (e. and relatively high cost. 4. http://dx. 0. pellets and paper-like foil glued to a HEx surface. respectively (Fig.077 . a zeolite DDZ-70 was developed by UOP.4. SWS1L. 4.05e0. aerogels. c) Despite these obstacles.35 g/g) at large DF-values (see the data for zeolites 13X and 4A in Figs. can be used for AC1. ads/des ( ). ads/des ( ) [74].03e0.4].16]) and moderate pore volume (0. 4). MCM.g. 4. Thus. thus.2. They can be regenerated with very low temperature heat (down to 45e50  C) [14]. and they reach maximum adsorption uptake (c. A survey of the main classes of adsorbents and their feasibility for ACH cycles can be found in very recent reviews [24. The reported findings on the boundary DFminvalues. des (C) [32]. ads/des ( ) [60]. a linear increase of the adsorbed amount of water with the Mg ion exchange degree is found for zeolite NaA (from 0.12 g/g within a typical ACH cycle [9. because the majority of water is removed at 50e70  C.34 to 0.3. If both parameters are important. [24]. 5) or “double effect” ACH cycles rather than for “single effect” ones. minimal desorption temperature Tmin and optimal isobar shape may significantly simplify a practical selection of adsorbent for a particular ACH cycle. a reasonable compromise must be reached by intelligent design of Ad-HEx unit (see Section 7). Aristov. 4. Applied Thermal Engineering (2014). It is a high silica content Y zeolite (Si/Al > 10) that is exchanged with cerium as described in Ref. b) For zeolites with low (Si/Al) ratio. In the following sections data relating to the main adsorbent classes for ACH are analysed taking into account their affinity to water in terms of the adsorption potential DF.24e26]: e.35 cm3/g) (both may restrict the cooling COPc).29].g. Silica gel Grace 127B has been applied in a small commercial adsorption chiller [27]. 5) and. The heat of water adsorption on DDZ-70 is 2335 J/g [30] which is advantageous for adsorptive cooling.36 g/g) and NaX (from 0. Concept of adsorbent optimal for adsorptive cooling/heating.25]. Screening of adsorbents developed for other applications To reduce the affinity for water and better fit with ACH demands. Thus. 3d). Characteristic curves for water sorption on zeolite 13. The Mitsubishi Chemical Ltd. ordered mesoporous silicates (SBA.applthermaleng.26. the Si/Al ratio [28]: the lower the ratio of Si to Al.Y.a. FAM-Z02. the affinity for water is very high. stable and cheap. big ACH units. Fig.1016/j. ads (o). The temperature lift using classical zeolites can exceed 50e70  C. These materials could be mainly interesting for deep freezing (Fig. They are likely to be used in small adsorption chillers recently appeared in the market [5]. The selected areas represent DFmin-windows for typical AC1 (1). Preliminary selection In Section 3 we considered which adsorbent is optimal for a particular ACH cycle. Classical zeolites Application of classical zeolites (aluminosilicates) for ACH can be summarized as follows [24]: a) Water adsorption properties of classical zeolites can be adjusted by changing the framework composition. Fuji silica RD. a Fuji silica RD exchanges 0. FAM-Z01. The dynamic requirement to maximize the average temperature difference between the adsorbent and the fin is in direct contradiction with the thermodynamic requirement to minimize this difference [11. This high affinity is profitable for gas drying or deep freezing but not for AC and HP because of too high temperature required for regeneration. FAM-Z02.41 g/ g) [29]. This results in large silica mass required and thus. It has been concluded that among new materials pure and substituted aluminophosphates and metalorganic frameworks can be considered as potentially interesting for ACH application.17].04. and here we just briefly summarize their main features for ACH: a) RD silica gels exchange just Dw ¼ 0.16. 6). possible ad/desorption hysteresis (see FAM-Z02 on Fig. proper choice of the isobar step position greatly depends on which output parameter is to be maximized e COP or SCP. Similar Dw-values were reported for an RD silica gel Grace 127B [26]. The main AP disadvantages are high heat of desorption (55e60 kJ/mol [15. step-like (sigmoid) adsorption isobars are advantageous from both thermodynamic and dynamic points of view. It is available as a fine powder.11 g/g and 0. Z02. developed three AP based adsorbents specialized for ACH. Aluminophosphates Pure and substituted aluminophosphates (APs) are found to be promising for ACH applications because they have quite steep and properly positioned adsorption isobars and relatively low desorption temperature (60e90  C) [15.32]. namely. 15e25  C. This material adsorbs water at lower DF-values (Fig. Other porous silicates e LD silica gels.31].1.2014. A vast number of new adsorbents with diverse structures and properties are synthesized every year.25e0. 2 and HP1. Aristov / Applied Thermal Engineering xxx (2014) 1e10 5 with the largest possible DT between the step temperature and the HEx fin temperature (Fig. [30]. 4.g.07 g/g in typical AC1 and AC2 All are commercially available from the Mitsubishi Plastics Ltd. Zeolites 4A. and Z05 [16. c) Post synthetic ion exchange presents another tool for tuning zeolite sorption properties: e. Please cite this article in press as: Y. 4. RD silica gels are the only adsorbents currently used in large commercial adsorptive chillers [3. 13X and particularly DDZ-70 can thus be considered as water adsorbents suitable for ACH [12.24. Silica gels Silica gels were considered in detail in Ref. 4 and 5). (AC2/HP1) (2) and HP2 (3) cycles. as coated heat exchangers.28 to 0.

MIL100 has larger affinity to water vapour probably because of its smaller cages (2. HP2/DF1 e 3. Cr) [38.15 or DF ¼ 4. The preparation method of APO-Tric shows the importance of the fluoride route for AP synthesis. will be tested for ACH field. Water uptake. The authors of [42] analysed the performance of 26 “ACeammonia” pairs under typical conditions of three ACH cycles: Te ¼ 5  C and Tc ¼ 35  C (ice making).) have been evaluated with promising results [15. kJ/mol Fig. etc. Therefore. The influence of the carbons physical characteristics on the ACH performance was theoretically studied in Ref. Substituted aluminophosphates Efficient tuning of the AP pore structure and adsorption properties can be made by isomorphous substitution of various metals Please cite this article in press as: Y.26]. ads( ) [15]. the potential of MOFs for ACH has not been fully unveiled. http://dx. cloth. APOTric. however. granular. and UiO-66 [40].5. ads( ) [32]. there is an AC optimal to obtain the best cycle performance. various pure ACFs were comprehensively tested for ACH cycles as adsorbents of methanol [48. Numerous experiments and results on the application of ACFs in ACH are summarized in Ref. MIL-53(Cr) [37]. After this. 4A. 6) that makes this material challenging for AC2/HP1. compacted cloth and powder). Characteristic curves for water adsorption on zeolite NaX. These AC absorbents were mainly coconut shell and coal based types in various shapes and sizes (monolithic.g.6. MIL-100 (Fe) displays no reduction in adsorption capacity after 2000 ad/desorption tests [38]. ACs are available and relatively cheap. Several other materials from this class (AlPO-5. Nanotailoring and intent modifying 5.39 g/g) and AC Maxsorb III (0. Aristov / Applied Thermal Engineering xxx (2014) 1e10 MIL-100 (Fe. [46.25 g/g.41e43] among which the most tested was AC-35 [44]. the affinity to water is hardly sufficient even for the AC1 cycle. It was assumed that the frameworks containing double-six or double-four rings would provide steep isobars because Al in this case can readily change its coordination between 4 and 6 [15. ads ( ) [15]. Only a small reduction in its adsorption capacity was detected after 50 ad/desorption cycles. Practical shortcomings due to the low density and thermal conductivity of ACFs are also addressed [51]. and Te ¼ 5  C and Tc ¼ 40  C (HP1). Fe) [26. Metal-organic frameworks Metal organic frameworks (MOFs) present a new family of supra-molecular materials potentially interesting for ACH [34. Since ACs are microporous and have large affinity to methanol and ammonia. AlPO-11. The APO-Tric material synthesized in a fluoride containing medium was discussed in Ref. compacted granular. Characteristic curves for water sorption on FAM-Z02. Commonly. Further progress may be expected if new AP. The ACF type A-20 was concluded to be the best adsorbent due to its large surface area and pore volume.25 g H2O/g in an extremely narrow range of the relative pressure P/Po ¼ 0. ads( )/des( ) [32].35]. DFmin e windows for AC1 e 1. UiO-65. 0. MIL-101 (Cr. Other obstacles to using MOF's are significant ad/desorption hysteresis and low hydrothermal stability.8e1.0 0 2 4 6 8 10 12 Adsorption potential.077 . A comprehensive thermophysical characterisation of 6 commercial ACs with particular focus on ACH applications was reported in Ref. g/g 0. 6.36]. DF2 e 4. ads/des ( ) [75]. iron or nickel phosphates. E. FAM-Z05. and it is quite possible that a target-oriented modification/ screening of MOFs may reveal novel highly efficient working pairs. Porous carbons Many Activated Carbons (ACs) were suggested and analysed as adsorbents of methanol and ammonia in ACH systems [12. fibre.2014. 4. a high regeneration temperature is necessary. chemical modification to enhance the MOFs affinity to water is strictly necessary (see Section 5. Applied Thermal Engineering (2014). On the whole.3 3 0. The main advantages of MOFs are steep adsorption isobars and large capacity. compacted fibre. Many MOFs exhibit S-shaped isotherms of water sorption that are “true” for ACH: DUT-4. [51]. 5. [15] for use in solar energy storage. including zinc. ads/des ( ) [74]. HKUST-1 (Cu-BTC) [36]. [43]. Much larger exchange was found for Tsurumi activated charcoal (0. 5. kJ/mol Fig. 4.1016/j. (AC2/HP1) e 2.4 nm). ethanol and ammonia remain very attractive for ACH applications driven by heat with a temperature potential higher than 100e150  C.47].doi.51 kJ/ mol (Fig. The authors showed that. High attraction for ACH has Activated Carbon Fibres (ACFs). An ACF Busofit. ads(O)/des(C) [32]. Aristov. FAM-Z01.g.2 g H2O/g for MIL-100 and MIL-101. Quite good performance was found at Tg ¼ 200  C.33]. Al.3 1 2 0. was first applied for ACH in Refs.12-0. whereas the maximal one reaches 0. 1 2 Water uptake.04.38 g/g.1 0.93e5.1. Te ¼ 10  C and Tc ¼ 35  C (between AC1 and 2). and DDZ70 ads/des ( ). AlPO-17. g/g 0. AlPO-18.49] and ethanol [50]. AC2/HP1 e 2. because of the huge variety of porous carbons and their excellent adsorption characteristics these adsorbents of methanol.1.2 0. the latter corresponds to a specific cooling enthalpy of 244 kJ/kg. It exchanges z0. MIL-125 (Ti) [40]. In general.applthermaleng. e.1 etc.0 0 5 10 15 20 25 Adsorption potential. The typical methanol exchange was 0. for given cycle boundary temperatures.3).2 4 0.5 nm) in comparison with those for MIL-101 (3. Concept of adsorbent optimal for adsorptive cooling/heating. Thus. [41].6 Y.39]. HKUST-1 and DUT-4 are not enough stable towards water. APOTric. AlPO-18.65 g/g) at Tg ¼ 90  C [45]. DFmin-windows for AC1 . pure and impregnated with metal chlorides.

and the cycle management strategy.61]. every property that is essential for analysing or modelling ACH cycles has to be tabulated in the database.applthermaleng. i. Conformity with the heat exchanger Two-component composites “salt in porous matrix” (CSPMs) offer wide opportunities for nanotailoring their sorption properties by varying the salt chemical nature and content. CSPMs have been tested for various applications. especially at low regeneration temperatures (70e90  C) [29.. binary salt systems [64] and modern physical methods [65] are considered in Ref. The authors assumed that this can be attributed to appropriate variation in the hydration energy of these counter anions. 5. the adsorbent properties which should be collected therein and a tentative list of adsorbents to be included were discussed in Ref.04. porous structure of the host matrix and synthesis conditions [55]. both FAM-Z01 and Z02 have high durability of 200.000 cycles. for NH2-MIL-125 a steep uptake rise was observed at 0. Modified MOFs Chemical modification aiming to enhance MOFs affinity to water can be performed by changing MOF structural components such as organic ligands. which can cause corrosion of metal parts of the ACH unit and emission of noncondensable gas. [61]. All the materials displayed equal adsorption increases at P/Po < 0.25 (up to 0.Y. such as gas drying [56].g. The adsorption of water vapour on three MIL-100s with Cr3þ. and counter anions. there is still much scope for further optimization and development of CSPMs with pre-requested properties. The most famous family of substituted APs is presented by SAPO materials (Si inserted instead of P): e.6 g/g within a temperature range of just 2e3  C [62]. c) covering the external surface of the CSPM grains with a hydrophobic coating. The principles of creating such a database. [66]. Another important progress may be by increasing the total micropore volume of both pure and substituted APs. Solution leakage can also be avoided by proper organization of the ACH hardware. the pressure of water adsorption was found to depend on the anion nature: for SO2 4 both adsorption steps moved to lower P/Po-values.3. New trends in developing and studying CSPMs such as using of mono-sized host matrices [63]. [38. Composites “salt in porous matrix” 7.1. The current state of the art and new trends in developing efficient CSPMs for various ACH cycles are surveyed in Ref. Conformity of the optimum adsorbent with the ACH unit/ cycle The adsorbent is an important part of any ACH unit. caused by consecutive capillary condensation in the mesoporous cages of 2. eNO2. Finally. Three MIL-100(Cr) adsorbents are synthesized using different types of counter anions (F. 7. Comprehensive CSPM examination has revealed many potential obstacles that could impede the introduction of these composites in practice.8e0.What are the optimum size of adsorbent grains and the bed thickness? Please cite this article in press as: Y.9 g/g). theoretical analysis and modelling of ACH cycle performance. b) an anchoring the salt cations to the matrix surface.g.1 < P/ P0 < 0. the effect of the functional group in the organic ligand of MIL-101(Cr) on water adsorption was evaluated by varying different substituents (eH. which has to be in harmony with all other components. The most worrying could be a leakage of the salt solution formed during sorption from the matrix pores. Aristov. metal cations. eNH2. while for (Cl) shifted to higher P/Po. Applying isomorphous substitution for synthesizing novel MAPOs which have S-shaped isotherms of methanol and ammonia sorption could be important for ACH applications.54]. metal cations. respectively [32]. extraction of water from the atmosphere [57].What is the optimum adsorbent mass per 1 m2 of a HEx? . and counter anions.000 and 60. as revealed for MAPO-5.65 g/g) and MIL-100(Cr or Fe) (0. The isotherms of MIL-101-NH2 and MIL-101-SO3H moved to lower P/Po as compared to that of common MIL-101 due to a high hydrophilicity of these functional groups. Several ways to avoid or at least to reduce this risk are considered in Ref. These can lead to the development of new MOFs adapted for ACH cycles. MAPO-11 and APO-31 [52]. a composite sorbent of methanol LiCl/silica exchanges 0. http://dx. and adsorptive cooling/heating [60]. The step positions for all the adsorbents are only slightly shifted.2014. Two adsorption steps are then observed. E. Thus. The shape was shown to be controlled mainly by the amount of the substituted metal rather than the type of the metal. This database would play an important role in the unification and comparison of adsorbent properties. FAM-Z02 is a kind of SAPO-34.doi. This would greatly assist in implementation of advantages that the optimum adsorbent promises. 7 in ventilation systems [58]. eSO3H) [53. The ACH performance essentially depends on both thermodynamic and dynamic properties of the working pair “adsorptive e adsorbent”. Applied Thermal Engineering (2014).2 [40]. Aristov / Applied Thermal Engineering xxx (2014) 1e10 into the AP framework [52]. 6.39]. Concept of adsorbent optimal for adsorptive cooling/heating. The step position for MIL-101-NO2 was almost the same as for MIL-101. despite the significant progress in CSPMs synthesis and application in various ACH cycles. regeneration of heat and moisture For Ad-HEx harmonization one has to understand: .e.g. the MOF adsorption properties can be intentionally tuned by changing organic ligands. Despite expectation that displacement of substituting cations from the framework sites may result in the structural degradation in ad/desorption cycles. Database of promising adsorbents for ACH Developing a database of adsorbents that are promising for ACH is very timely [66]. The amino-modified UiO-66 and MIL-125 exhibit very promising water adsorption isotherms: e. the cycle boundary conditions.9 nm. The substitution approach still has great potential as the isotherm shape is very sensitive to such substitution. [61]. however significant difference in the final water uptake was observed between MIL-100(Al) (0. Thus. CO2 abatement [59]. Several CSPMs have been tested for ACH and demonstrated promising performance. Fe3þ and Al3þ as metal cations was studied in Refs. To summarise.077 . the amount of adsorptive in an evaporator should be restricted in such a way that the outflow is not possible even if the whole of fluid from the evaporator is sorbed on CSPM. 5.1016/j. Cl. SO2 4 ) for better adaptation to ACH cycles [38]. [61]: a) proper selection of the salt content in the CSPM.15 g/g) that is due to water adsorption on the active metal sites.5 nm and 2. FAM-Z01 and -Z05 also belong to substituted aluminophosphates (FAPO-5 and FAPO-34) with Fe instead of Al and P.20-0.2.

3. For a well-designed Ad-HEx (e.5 2. both the COP and the cooling power may significantly increase as compared with the common case tdes ¼ tads. Heifets. and b) tailoring of new adsorbents adapted to a variety of ACH cycles.N.Y.25 ( ).5 3. the Dubinin adsorption potential being used as a universal measure of the affinity between the adsorbent and the adsorptive. I. L.0 1. and 2 layers of 0. namely.5 0. Acknowledgements The author thanks Drs. 7. with S/ m ¼ 4 m2/kg).5 0.000 0. Two complementary lines to select the optimum adsorbent are considered: a) testing of adsorbents initially developed for applications different from ACH. 8. and proper reallocation is necessary to allow more time for adsorption at the expense of desorption time reducing [72e74]. A. etc. http://dx. The dynamic study of water. the Russian Please cite this article in press as: Y. the size of adsorbent grains. F.0 0. For all these configurations S/m ¼ const ¼ 1. This ratio is naturally limited from the upper side as the thermal mass of the metal should not be too large with respect to that of the adsorbent.003 3. Dr.g. Although the above examples concern adsorbents of water.2 0.9 ( ) and 1. Conclusions New materials are a prerequisite for major breakthrough applications influencing our daily life. Results obtained by the LTJ method have suggested that the equal duration of adsorption and desorption phases is hardly an optimal case. Bonaccorsi and R.56 m2/kg and the grain size 0. carbon dioxide [77].2 0. Conformity with the durations of the cycle isobaric stages Proper cycle management strategy may also help in realizing advantages which the optimum adsorbent offers.5e2.1 ( ) mm. Despite significant progress achieved.1016/j. 2. Aristov. For the optimum ratio f ¼ tads/tdes.D. L. 7a)) [23. methanol and ammonia this approach can be also applied for sorbents of hydrogen [75].1 [69]: a .0e1. Methanol adsorption on AC-35. In this review. m /kg b) 1.5 1. L.0 0. the DTav-value of 2e3  C results in the cycle-averaged power Wav ¼ ADTav (S/m) ¼ 0.6 q W0.68]. is presented. M. Applied Thermal Engineering (2014).8e0.8 0.applthermaleng. The optimal S/m ratio is expected to be between 2 and 5 m2/kg which gives an estimation of the optimum adsorbent mass. Profs. more R&D is still necessary to push the ACH technology to be competitive with the current state of the art. b e kinetic curves at (S/m) ¼ 1.4 0. Grekova and Mr.6e1.8 ( ). The latter was also revealed by mathematical modelling of AC performance with zeolite 13X [69] and SWS-1L [70] as water sorbents. it must guarantee the “grain size insensitive” regime.1e0. Okunev for modelling of coupled heat and mass transfer. Veselovskaya.9 mm grains (Fig.04.005 5. Tokarev.M. and the cycle management strategy. to maximize the SCP it is necessary to use Ad-Hex’s with high S/m ratios. An overview of original and collected data on several classes of materials which are potentially promising for ACH application.4 0.002 2.67.8 ( ). Glaznev.2 kW/kg. Freni. Reasonable compromise is possible if one properly chooses a shape of the adsorption isobar which affects the cycleaveraged temperature difference DTav between the adsorbent and the HEx fin [71]. metalorganic frameworks. Conformity with the cycle boundary temperatures As demonstrated in 3. Critoph for useful discussions.3 0. D ¼ 0. Girnik for their experimental contributions. however.0e4. ethanol [76].0 3.5e2. We hope that this review will provide a new impetus to targetoriented research on the novel adsorbents for AHT and may also prove beneficial for further consolidating international activities in materials science and heat transformation applications. it is thermodynamically profitable to supply heat right at the minimal desorption temperature (Tg ¼ T2).5 times that offers essential dynamics improvement [23].8e1.6e1. and 4.0 0.5e3.I.V. porous carbons and composites “salt in porous matrix”. Concept of adsorbent optimal for adsorptive cooling/heating. 7.2 and 3. Hence. Surprisingly that the methanol adsorption dynamics is the same for 1 layer of 1.8 mm carbon grains.doi. Possible power enhancement due to optimizing the isobar shape may reach 1. I.004 4. 7.G.077 . Recommendations on how to choose the HEx design. methanol and ammonia adsorption on loose grains of various adsorbents has revealed that commonly the sorption rate is proportional to the ratio (S/m) of the area of heat transfer surface S between the adsorbent bed and the HEx fins to the adsorbent mass m (Fig.S.006 a) 6.56 m2/kg. B. whereas good dynamics asks for maximizing the difference (Tg e T2). A. 1. For practice. bed thickness and so on are made. we have considered the role of adsorbents in adsorptive cooling/heating (ACH) and analysed which adsorbents are optimal for specific ACH cycles. Meunier. This reallocation realized in a single bed adsorption chiller [73] confirmed that the optimum desorption duration should indeed be 1. the cycle boundary conditions. s 400 600 Fig.4 kW/kg). aluminophosphates. Aristov / Applied Thermal Engineering xxx (2014) 1e10 0.2. Gordeeva.001 1. This is much larger than for common ACH units which use loose adsorbent grains (0. The conclusions are formulated in terms of the optimum isobar shape.2014.the initial rate as function of the ratio S/m.8e0.0 2.8 (:). 1. classical zeolites. We briefly consider several issues of harmonizing the optimal adsorbent with other components of ACH unit. J.0 2 S/m. and therefore new efficient adsorbents are pivotal for the adsorption heat transformation. thus giving a decent compromise option. silica gels.5 0. 7b)). it means that it is not strictly necessary to precisely select the adsorbent grain size.9 ( ).8e0.3. kW/kg R0.6e1.5 times shorter that the adsorption one. kg/(kg s) 8 0 200 t.S.

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