Recent updates on the adsorption capacities of adsorbent-adsorbate pairs for heat transformation applications

Renewable and Sustainable Energy Reviews 119 (2020) 109630

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Recent updates on the adsorption capacities of adsorbent-adsorbate pairs for heat transformation applications Faizan Shabir a, b, Muhammad Sultan, Dr.Eng. a, *, Takahiko Miyazaki c, d, Bidyut B. Saha d, e, Ahmed Askalany f, Imran Ali g, Yuguang Zhou h, i, Riaz Ahmad h, Redmond R. Shamshiri j a

Department of Agricultural Engineering, Bahauddin Zakariya University, Bosan Road, Multan, 60800, Pakistan Department of Agricultural Engineering, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan Faculty of Engineering Sciences, Kyushu University, Kasuga-koen 6-1, Kasuga-shi, Fukuoka, 816-8580, Japan d International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan e Mechanical Engineering Science, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka-shi, Fukuoka, 819-0395, Japan f Institute of Materials and Processes, School of Engineering, The University of Edinburgh, Mayfield Road, EH9 3BF, Edinburgh, Scotland, UK g College of Environmental Science and Engineering, Ocean University of China, Qingdao, 266100, China h Bioenergy and Environment Science & Technology Laboratory, College of Engineering, China Agricultural University, Beijing, 100083, China i National Center for International Research of BioEnergy Science and Technology, Ministry of Science and Technology, Beijing, 100083, China j Leibniz Institute for Agricultural Engineering and Bioeconomy, Max-Eyth-Allee 100, 14469, Potsdam, Bornim, Germany b c

A R T I C L E I N F O

A B S T R A C T

Keywords: Adsorption equilibrium Heat transformation Adsorption cooling Adsorbent Adsorbate Comparative analysis Review

Adsorption cooling is getting huge attention from last few years due to environment-friendly and thermallydriven technology. Many systems designs based on various adsorbent-adsorbate pairs are investigated world­ wide to develop a cost-effective and high-performance system. Until now, performance of the systems is lower as compared to conventional compressor-based systems. Performance of the adsorption systems mainly depends on adsorption equilibrium, adsorption kinetics, isosteric heat of adsorption, and thermo-physical/chemical prop­ erties of assorted adsorbent-refrigerant pairs. Thereby, the present study aims to review and compare the physical properties (surface area, pore volume/size etc.) of adsorbents and adsorption equilibrium (adsorption isotherm) by various types of adsorbent-adsorbate pairs available in the literature. Amount of adsorbate adsorbed per unit mass of adsorbent has been critically reviewed and compared accordingly. Highest adsorption uptake was attributed in case of R-32 adsorption onto phenol resin-based activated carbon i.e. 2.23 kg/kg (excess adsorption) and 2.34 kg/kg (absolute adsorption) at 30 � C and 1670 kPa. Activated carbon of type Maxsorb-III being highly microporous possesses high surface area and shows good adsorption uptakes for most of the ad­ sorbates including ethanol, methanol R-134a, CO2, R-507A and n-butane. In addition, fundamentals, principle and features of adsorption cooling systems are discussed. Adsorption equilibrium models used to express the adsorption mechanics of adsorbent-adsorbate pairs are explored, and the models’ parameters are collectively listed and discussed. The review is useful to prioritize available adsorbent-adsorbate pairs for adsorption based heat transformation applications. The study is useful for researchers working for the development of adsorbent materials for various applications and conditions.

1. Introduction Primary energy consumption is predominantly involved in heating, cooling, humidification, dehumidification, ventilation and/or airconditioning (HVAC) systems. It is because of the higher living stan­ dards and unfavorable outdoor conditions in urban areas. About 15% of global energy is consumed by HVAC systems only [1]. It has a key

concern with the conventional refrigeration systems which employs the vapor compression technology. Such systems not only consume a huge amount of electrical energy but also pose threats to the environment like ozone depletion and global warming. Therefore, utilization of thermal energy, i.e. solar energy, for air-conditioning and refrigeration has gained much attention of scientists working in the field [2,3]. In this regard, adsorption cooling systems appear to be a suitable substitute for conventional refrigeration technologies. These systems are driven by

* Corresponding author. Department of Agricultural Engineering, Bahauddin Zakariya University, Bosan Road, Multan, 60800, Pakistan. E-mail address: [email protected] (M. Sultan). https://doi.org/10.1016/j.rser.2019.109630 Received 20 May 2019; Received in revised form 16 October 2019; Accepted 25 November 2019 Available online 9 December 2019 1364-0321/© 2019 Elsevier Ltd. All rights reserved.

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

List of abbreviations A a AC ai A(Ts) b bo B(Ts) COP D E HVAC k Ki Koi MOF n P Ps

[kPa] saturated pressure at silica gel temperature [kPa] saturated pressure at water vapor temperature [kPa] isosteric heat of adsorption [kJ/kmol] absolute adsorption capacity [mol/kg] maximum amount adsorbed of component ‘i’ [mol/kg] isosteric heat of adsorption [kJ/mol] gas constant.[kJ/(kg.K)] specific cooling power [m3/ton/day] specific cooling effect [kJ/kg] scanning electron microscopy system heterogeneity parameter [ ] adsorption temperature [� C] adsorbent temperature [� C] reference temperature [K] saturated temperature [� C] equilibrium adsorption uptake [kg/kg] monolayer adsorption uptake [kg/kg] Co, Ko GAB model adjustable constant for temperature effect Wo maximum adsorption uptake [kg/kg] Ws saturated adsorption capacity [kg/kg] ΔHc, ΔHk functions related to water sorption heat [kJ/kg] ΔHi isosteric heat of adsorption of component ‘i’ at zero coverage [J/mol] �th model [ ] ϕ constant temperature parameter of To

Ps(Ts) Ps(Tw) Q qi qi, max Qst R SCP SCE SEM t T, Ta Tads To Ts W Wm Wmo, qm,

adsorption potential [kJ/kg] parameter related to b and the saturation capacity [mol/ kg.kPa] activated-carbon number of neighboring sites occupied by adsorbate molecule ‘i’ [ ] adjusted parameter replaceable to Wo adsorption affinity constant [kPa 1] affinity at the reference temperature [kPa 1] adjusted parameter replaceable to 1/n coefficient of performance [ ] exponential constant of D-R and D-A equations [ ] characteristic energy [J/mol] heating, cooling, de/humidification, ventilation and/or air-conditioning characteristic constant of modified D-A equation [ ], constant for pseudo saturated vapor pressure equation [ ], exponential constant of D-R equation [(mol/J)2] adsorption constant of Multisite Langmuir Model [kPa 1] adsorption constant of component ‘i’ at the limit of T→∞ [kPa 1] metal organic framework structural heterogenity parameter [ ] equilibrium pressure [kPa] saturated pressure of refrigerant for given temperature

thermal energy sources e.g. solar energy and low-grade waste heat from various sources. Correspondingly, they are environment-friendly and possess zero global warmings and ozone depletion potentials [4]. Together with adsorption cooling, adsorption has its widespread appli­ cations, i.e. ice-making [5–9], gas storage [10–13], CO2 capturing [14–17] and automobile air-conditioning [18–20]. Likewise, desiccant air-conditioning is adsorption based system. It works in an open cycle utilizing the same adsorption phenomenon with water as adsorbate for

the dehumidification process [21,22]. The adsorption cooling systems may couple with other cooling technologies to develop a more efficient hybrid cooling system [23–25]. Adsorption cooling system though utilized low-grade waste heat and natural refrigerants. But it still has not been commercialized due to its low thermodynamic performances in term of the coefficient of perfor­ mance (COP) and specific cooling power (SCP), as compared to vaporcompression technology. Researchers have investigated various

Fig. 1. Studied adsorption cooling pairs for the development of the adsorption cooling system. 2

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Fig. 2. Adsorption mechanism of adsorbate molecules onto heterogeneous porous adsorbent [42].

strategies to increase the thermodynamic performance of adsorption cooling systems. Some of them are (i) different scheme of adsorption beds i.e. double beds [26,27], three beds [28–31], four beds [32,33] and multi-stage & multiple beds [34,35], (ii) Heat and mass recovery schemes [36,37] (iii) improving heat exchanger design [38,39] (iv) optimized operating conditions [26,40,41]. However, the system per­ formance can be improved by utilizing such adsorbents that could have the ability to adsorb a larger amount of adsorbate. Therefore, the adsorption behavior of various adsorbent-adsorbate working pair is broadly studied by the researchers in the literature. Thus, this study aims to gather the adsorption uptakes data of hundreds of adsorbent-adsorbate pairs in order to propose the optimum adsorbent-adsorbate pair for the adsorption cooling system. Adsorbents like activated carbon, zeolite, silica gel, composite and metal organic framework (MOF) are studied in this study, as shown in Fig. 1. Adsorption equilibrium models are also discussed for each working pair along with the optimized parameters as reported in the literature. This is useful for the material scientists to develop the appropriate working pair for adsorption systems. Adsorption phenomena occur due to interaction between molecules of adsorbate and surface of the adsorbent. Adsorption uptake by the adsorbent largely depends on its surface characteristics, i.e. pore vol­ ume/size and surface area. During the adsorption process, the adsorbate molecules surround the adsorption sites of porous adsorbents having a specified level of energies. These energy sites of the adsorbent are divided into three categories of pores sizes which are classified in accordance IUPAC i.e. micro-pores (<2 nm), meso-pores (2–50 nm) and macro-pores (>50 nm), as presented in Fig. 2. The optimal range of pore size is from micropores to mesopores, for which the higher adsorption capacity exhibited. Thereby, the present study aims to review and compare the physical properties (surface area, pore volume/size etc.) of various adsorbents.

2. Principle and features of adsorption cooling system A typical close cycle adsorption cooling system consists of an evap­ orator, adsorption/desorption bed, condenser and expansion valve as illustrated in Fig. 3. In this cycle, refrigerant moves toward adsorption bed and gets adsorbed onto the adsorbent surface at evaporator pres­ sure. The heat of adsorption is released during this process due to its exothermic nature. Adsorption temperature is thus maintained by using cooling water cycle. When the adsorbent becomes fully saturated with the adsorbate, it subsequently put into a desorption mode by heating bed through the hot water cycle. Desorption of adsorbent causes an increase in adsorbate pressure up to condenser pressure. While reaching the condenser adsorbate will become condense by rejecting the heat through heat exchanger. This high-pressure refrigerant is then passing through an expansion valve which causes a drop in adsorbate pressure. Due to which boiling point of adsorbate comes down, and it starts evaporating. The heat required for evaporation is extracted from the surrounding space which in turn give the required cooling effect. Pressure-Temperature-Concentration (P-T-W) diagram of ideal adsorption cooling cycle is shown in Fig. 4. The adsorption cooling cycle consists of four following processes: A-B (pre-heating), B-C (desorption), C-D (pre-cooling), and D-A (adsorption). Process (A-B) involves heating of adsorbent. There is no change in concentration of refrigerant within the adsorbent during this process (i.e. isosteric heating process) while triggering the adsorbate to increase its pressure up to condensation pressure. The process (B-C) is an isobaric heating process in which heat given to the adsorbent is utilized in desorption of adsorbate. It further condensed into a liquid at condensation pressure. During the process (CD) the pressure drops to evaporator pressure accompanied by a decrease in temperature. Lastly, the adsorption process (D-A), in which adsorber is connected to the evaporator to initiate the adsorption process. The cooling effect is produced by the evaporation of refrigerant by extracting heat from the evaporator. 3

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Fig. 3. Schematic diagram of a typical adsorption cooling system.

[49], Maxsorb-III was treated with KOH-H2 and H2 which yielded ethanol adsorption uptakes of 1.01 kg/kg and 1.23 kg/kg, respectively, at adsorption temperature of 30 � C. This indicates the slight improve­ ment in ethanol adsorption uptake due to surface functionalities. In other studies [100–102], the effect of oxygen content and surface functionalities of parent Maxsorb-III was also investigated which shows a good agreement in results by El-Sharkawy et al. [49]. Two synthetic ACs were prepared from waste palm trunk (WPT-AC) and mangrove (M-AC) using chemical activation of KOH [85]. WPT-AC and M-AC showed ethanol uptake of 1.90 kg/kg and 1.65 kg/kg, respectively, at saturation conditions and 30 � C adsorption temperature. Ethanol adsorption uptakes by these both ACs adsorbents are up to 35% higher than Maxsorb-III. Fiber based AC (ACF) of type A-20 and A-15 have been experimen­ tally studied for ethanol adsorption [50]. A-20 and A-15 showed ethanol uptake of 0.797 kg/kg and 0.570 kg/kg, respectively, at saturation conditions of 30 � C adsorption temperature. In addition, the perfor­ mance of A-20/ethanol adsorption cooling system was investigated by Saha et al. [103,104]. The system achieved a COP of 0.64 for the heat source temperature of 85 � C. Commercial ACs were prepared in the shapes of grain, pellets and fibers from the raw materials like coconut shell and coal [51]. The ad­ sorbents were named as SRD 1352/3, FR20, AP4 -60, ATO and COC-L1200. They have been studied to compare their adsorption cool­ ing potential for refrigeration and air-conditioning applications. Among these adsorbents, SRD 1352/3 have shown maximum ethanol adsorp­ tion uptake, i.e. 0.82 cm3/g (~0.64 kg/kg) at saturation conditions and 30 � C adsorption temperature. Ethanol adsorption uptake by each studied AC has been compared in Fig. 5. The highest ethanol adsorption uptake by AC available in the literature is attributed to phenol resin-based spherical AC (SAC) treated with KOH6-PR (2.00 kg/kg) [47] followed by WPT-AC (1.90 kg/kg) [85] and M-AC (1.65 kg/kg) [85], at saturation conditions and adsorption temperature of 30 � C. It is important to mention that the SAC treated with KOH4-PR do not provide good results as compared to KOH6-PR. While at low adsorption temperatures, KOH4-PR/ethanol pair shows fast kinetics as compared to KOH6-PR/ethanol pair. Different kinds of activation and treatments change the physical properties of parent adsorbent. For example, surface area and pore volume of SAC treated with KOH6-PR and KOH4-PR are found 3060 m2/g, 1.90 cm3/g and 2910 m2/g, 2.53 cm3/g respectively. Similarly, a study determines the effect of pellet dimension of AC adsorbent (Norit RX3) on adsorption performance [105]. Results showed that the adsorption rate decreases with the increase in pellet dimension while adsorption uptakes decrease

Fig. 4. Pressure-Temperature-Concentration (P-T-W) diagram of ideal adsorp­ tion cooling cycle.

3. Activated-carbon (AC) based adsorption cooling Activated-carbons (ACs) are extensively studied adsorbents in the literature due to high microporous structure and good adsorption properties. ACs are usually prepared by carbonization and activation of raw materials like wood, coal, coconut shell etc. Activation of raw ma­ terials is usually done at high temperature to obtain designed porous structure [96]. In the literature, ACs have been extensively considered for the development of adsorption cooling systems, and thereby adsorption uptakes of various refrigerants have been reported accord­ ingly. The coming headings will briefly review the studies of adsorption of various refrigerants onto different kinds of ACs. In this regard, Table 1 presents the fundamental equation of adsorption models and their generalized suitability for various adsorbent-refrigerant pairs. 3.1. AC/ethanol Adsorption of ethanol onto various kinds of ACs have been studied in the literature for the development of energy-efficient adsorption cooling systems [97–99]. Maxsorb-III has been considered as one of the efficient AC for ethanol adsorption. It showed adsorption uptake of 1.20 kg/kg at saturation conditions and 30 � C adsorption temperature [48]. In a study 4

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Table 1 Adsorption isotherm models used for the presentation of adsorption equilibrium data. Adsorption model D-A

Modified D-A D-R

Governing Equations � � � � �n � A Ps ; A ¼ RT ln W ¼ Wo exp E P OR � �n � � �n � Ps R ; D ¼ W ¼ Wo exp D T ln E P

Multisite Langmuir Langmuir-Freundlich Freundlich Modified Freundlich (S-B-K equation) T� oth

AC-CO2 [43–46] AC-Ethanol [47–51] AC-n–butane [52] AC-Methanol [53–56] AC-R134a [57–60] AC-R507a [61,62] Silica gel-H2O [63] Zeolite-H2O [64,65] Composite-H2O [66,67] Composite-Ethanol [51,68,69] MOF-Ethanol [70] MOF-H2O [71] Zeolite-H2O [72]

� �n T k AÞ; A ¼ 1 Ts � � � �2 � A Ps ; A ¼ RT ln E P

W ¼ Wo expð � W ¼ Wo exp OR

Langmuir

Adsorbent-Refrigerant Pairs

AC-Ethanol [47,49–51] AC-Methanol [73] Composite-H2O [68]

� �2 � � � Ps 2 R ; D ¼ D T ln E P� � W bP Qst ; b ¼ bo exp ¼ Wo 1 þ bP RT � W ¼ Wo exp

qi

!

"

qi

¼ Ki P 1

!#ai

� Ki ¼ Koi exp

ΔHi RT

�

qi;ma qi;max W bPt ¼ t Wo 1 þ ðbPÞ � �1=n W P ¼ Wo Ps � � Ps ðTwÞ BðTs Þ W ¼ AðTs Þ AðTs Þ ¼ A0 þ A1 ðTs Þ þ A2 ðTs Þ2 þ A3 ðTs Þ2 BðTs Þ ¼ B0 þ B1 ðTs Þ þ B2 ðTs Þ2 þ B3 ðTs Þ2 Ps ðTsÞ � � � � W bP Qst ¼ ; b ¼ bo exp Wo RT t 1t ð1 þ ðbPÞ Þ OR � �� � � � bP Q Q T Ws ¼ Wo exp ϕ 1 ; b ¼ bo exp W ¼ Ws 1 RT RTo To ð1 þ ðbPÞt Þ t aP W ¼ ; b ¼ bo expðE =TÞa ¼ ao expðE =TÞ; t ¼ to þ ðc =TÞ 1 ð1 þ ðbPÞt Þ t 1=t W ðbPÞ ¼ Wo 1 þ ðbPÞ1=t � � � � �q � Wm C KðP=Ps Þ ΔHc ΔHk m W ¼ Wm ¼ Wmo exp ; C ¼ Co exp K ¼ Ko exp ð1 KðP=Ps ÞÞð1 KðP=Ps Þ þ CKðP=Ps ÞÞ RT RT RT W ¼ KP =

=

Multi-temperature T� oth model

=

Sips Guggenheim-Anderson-De Boer (GAB) Henry Law

AC-Methanol [74] AC-n-butane [75,76] Zeolite-CO2 [77] MOF-CO2 [78] AC-CO2 [79,80] AC-CO2 [81] Zeolite-CO2 [82] Silica gel-H2O [83] Silica gel-H2O [34] AC-CO2 [84] AC-Ethanol [85] Silica gel-H2O [86] Zeolite-CO2 [87–89] Composite-H2O [90] MOF-Ethanol [91] Silica gel-H2O [92] Zeolite-H2O [92] AC-CO2 [84] Silica gel-H2O [93] Polymer-H2O [94] Zeolite-CO2 [95]

as adsorption temperature increases. Physical properties of the adsorbents play a significant role in the adsorbent/adsorbate interactions and finally adsorption properties. Thus, this study provides a detailed comparison of the physical prop­ erties of studied adsorbent as shown in Table 2. The optimized param­ eters of correlated adsorption isotherm models are also furnished in Table 2 which are useful by the researchers working in the field for the simulation and analyses. 3.2. AC/methanol Adsorption of methanol onto various kinds of ACs have been studied in the literature for the development of energy-efficient adsorption cooling system [106–108]. Maxsorb-III is considered one of the most promising adsorbents for methanol adsorption uptake. It possesses the highest adsorption uptake, i.e. 1.24 kg/kg at saturation conditions and 30 � C adsorption temperature. It showed the highest specific cooling energy (SCE) of 721 kJ/kg in comparison with the studied adsorbents at a regeneration temperature of 90 � C [73]. It is highly microporous adsorbent and thereby possesses surface area and micropore volume of 3045 m2/g and 1.7 cm3/g, respectively. In contrast, other ACs adsor­ bents have shown a relatively lower amount of methanol adsorption uptakes as compared to Maxsorb-III [53–56]. Six kinds of ACs derived from coconut shell, peat and stone coal was

Fig. 5. Adsorption isotherms of ethanol on to different activated carbons at 30 � C: Maxsorb-III [48], KOH-H2 treated Maxsorb-III [49], H2 treated Maxsorb-III [49], ACF(AC-15) [50], ♠ ACF(AC-20) [50], WPT-AC [85], ■ M-AC [85], SRD 1352/3 [51], FR 20 [51], AP4-60 [51], ♣ ATO [51], COC-L1200 [51], ○ KOH6-PR [47], KOH4-PR [47]. Norit RX3 [105] (25 � C). 5

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Table 2 Adsorption properties and adsorption isotherm parameters for different activated carbons-ethanol cooling systems. Activated Carbon

Surface Area [m2/g]

Pore Volume [cm3/g]

3045

1.70 (MI)

KOH-H2 treated Maxsorb-III

2992

1.65 (MI)

Adsorption Equilibrium Models

References

Model

Parameter

value

D-A

Wo [kg/kg] n[ ] E [J/mol]

1.2 1.75 5538

[48]

D-A

Wo [kg/kg] n[ ] E [kJ/kg]

1.0 1.9 152

[49]

6

Maxsorb-III

SEM Images

[100]

(continued on next page)

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[100]

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Table 2 (continued ) Activated Carbon

Surface Area [m2/g]

Pore Volume [cm3/g]

3029

1.73 (MI)

ACF(A-20)

1930

1.028

Adsorption Equilibrium Models

References

Model

Parameter

value

D-R

Wo [kg/kg] n[ ] E [kJ/kg]

1.23 2 138

D-R

Wo [kg/kg] D [K 2]

0.797 1.716 � 10

7

H2 treated Maxsorb-III

SEM Images

[100]

6

[50]

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(continued on next page)

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Table 2 (continued ) Activated Carbon

Surface Area [m2/g]

Pore Volume [cm3/g]

SEM Images

Adsorption Equilibrium Models

References

Model

Parameter

value

1400

0.765

D-R

Wo [kg/kg] D [K 2]

0.570 1.067 � 10

WPT-AC

2927

2.51

T� oth

Wo [kg/kg] Qst [kJ/mol] t[ ] bo [ ]

1.9 44.23 3.88 4.09 � 10

6

8

ACF(A-15)

[85] 6

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(continued on next page)

Activated Carbon M-AC

Surface Area [m2/g] 2924

Pore Volume [cm3/g]

SEM Images

2.18

Adsorption Equilibrium Models

References

Model

Parameter

value

T� oth

Wo [kg/kg] Qst [kJ/mol] t[ ] bo [ ]

1.65 46.30 3.42 2.37 � 10

Langmuir

Wo [kg/kg] b[ ]

0.3354 47.96

[105]

Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ]

0.82 8.78 1.5 0.75 13.5 2 0.45 10.6 2 0.61 11.2 1.7

[51]

NA

NA

SRD 1352/3

2613

0.65

NA

D-A

FR 20

2180

0.75

NA

D-R

AP4-60

1428

0.47

NA

D-R

ATO

1745

0.64

NA

D-A

6

9

Norit RX3

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Table 2 (continued )

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(continued on next page)

Activated Carbon

Surface Area [m2/g]

Pore Volume [cm3/g]

SEM Images NA

Adsorption Equilibrium Models

References

Model

Parameter

value

D-R

Wo [cm3/g] E [kJ/mol] n[ ] Wo [kg/kg] E [kJ/kg] n[ ]

0.44 13.3 2 1.43 128 2

Wo [kg/kg] E [kJ/kg] n[ ]

1.98 90 1.5

1412

0.49

KOH4-PR

3060

1.90

D-R

KOH6-PR

2910

2.53

D-A

[47]

10

COC-L1200

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Table 2 (continued )

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Key: NA: not available. MI: micropores volume.

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1.0217 and k ¼ 3.65. Maxsorb-III and A-20 showed the R-32 adsorption uptake as high as 1.44 kg/kg and 0.94 kg/kg, respectively, for 30 � C adsorption temperature and pressure up to 1400 kPa. The D-A adsorp­ tion isotherm model gave good fitting for both adsorbents with opti­ mized parameters of Wo ¼ 4.05 cm3/g, E ¼ 3939 J/mol & n ¼ 1.15 for Maxsorb-III, and Wo ¼ 4.58 cm3/g, E ¼ 4098 J/mol & n ¼ 1.09 for A-20. 3.4. AC/R-134a Adsorption of R-134a onto many ACs have been reported in the literature for the development of a thermally driven adsorption cooling system [114–116]. The corresponding adsorption isotherms of the studied ACs are presented in Fig. 8. Maxsorb-III was found one of the most promising adsorbents as far as adsorption equilibrium is a concern. It yielded the highest adsorption equilibrium uptake of 2.10 kg/kg at 30 � C of saturation conditions [57]. The D-A model has successfully pre­ sented the adsorption data, and the optimized parameters of the model are Wo ¼ 2.1 kg/kg, E ¼ 8460 J/mol and n ¼ 1.30. R-134a adsorption uptake by Chemviron and Fluka typed ACs were 0.369 kg/kg and 0.584 kg/kg, at 30 � C saturation conditions, respectively [60]. The optimized correlated D-A isotherm model parameters for Chemviron are Wo ¼ 0.000279 m3/kg, E ¼ 14.87 kJ/mol and n ¼ 1.60 whereas it is Wo ¼ 0.000449 m3/kg, E ¼ 8.90 kJ/mol and n ¼ 0.95 for Fluka. The adsorption uptake of R-134a by granular activated carbon (GAC) typed AC was measured [58]. The adsorbent has a surface area of 900 m2/g and a total pore volume of 0.88 cm3/g. The equilibrium adsorption uptake is 1.64 kg/kg at 30 � C saturation conditions. The D-A model was correlated, and the optimized parameters are Wo ¼ 1.68 kg/kg, E ¼ 9575 J/mol and n ¼ 1.83. The ACF of type (A-20) and GAC of type (SRD-1352/3) were experimentally evaluated for R-134a adsorption [59]. The adsorption uptake by A-20 and SRD-1352/3 at 550 kPa are 1.20 kg/kg and 0.95 kg/kg at adsorption temperatures of 30 � C and 26.8 � C, respectively. The D-A model fitted the data precisely and the optimized parameters for A-20 are Wo ¼ 1.256 kg/kg, D ¼ 7 � 10 5 J/mol and n ¼ 1.4, whereas, it is Wo ¼ 0.926 kg/kg, D ¼ 3 � 10 6 J/mol and n ¼ 1.8 for SRD 1352/3. The A-20 AC based adsorption cooling system showed better COP and SCE as compared to SRD 1352/3.

Fig. 6. Adsorption isotherms of methanol on to different activated carbons at 30 � C: ♠ Maxsorb-III [73], Tsurumi Coal HC-20C [73], ○ FX-400 [74], ⋄ KF-1000 [74], 207EA [53], WS-480 [53], ♣ 207C [53], Carbo Tech A35/1 [54], G32-H [54], NORIT R1-Extra [54], NORIT RX3-Extra [54], ▾ CarboTech C40/1 [54], RÜTGERS CG1-3 [54], LH [55], DEG [55], PKST [55], □ Chinese (LSZ30) [56], Thai (MD6070) [56].

studied by Henninger et al. [54]. Thermo-physical properties of each adsorbent were experimentally determined. Maximum adsorption up­ take by one of the AC (Carbo Tech A35/1) was recorded as high as 0.58 kg/kg at saturation conditions and 30 � C adsorption temperature. In a study, Two ACFs of type FX-400 and KF-1000 have been experimentally investigated for methanol adsorption, and FX-400 showed 30% higher methanol uptake than KF-1000 [74,109]. The adsorption uptake by FX-400 and KF-1000 are 0.434 kg/kg and 0.307 kg/kg, respectively, at 30 � C adsorption temperature and relative pressure of 0.90. Similarly, three ACs namely LH, PKST and DEG were experimentally evaluated for methanol adsorption equilibrium [55]. The LH had shown methanol uptake of 0.64 kg/kg at saturation conditions and 30 � C adsorption temperature. Methanol adsorption uptake by two ACs named as Chinese: LSZ30 and Thai: MD6070 was measured as 0.32 kg/kg and 0.78 kg/kg, recorded at saturation conditions and 30 � C adsorption temperature, respectively [56]. Methanol adsorption uptake by the studied ACs is compared in Fig. 6. It is important to mention that methanol adsorption by phenol resinbased spherical ACs is not measured in the literature until now. They could be higher adsorption uptake as compared to Maxsorb-III just like in case of ethanol. Physical properties for all the studied pairs and the optimized parameters of the correlated adsorption isotherm models are furnished in Table 3. Most of the AC/methanol pairs are of Type-I iso­ therms according to IUPAC classification, which reflects the monolayer adsorption behavior and correlated by the D-A model [110].

3.5. AC/R-507A R-507A adsorption uptake has been measured in the literature by two kinds of ACs named as Maxsorb-III and ACF of type A-20 [61,62]. The corresponding adsorption isotherms are presented in Fig. 9. Maxsorb-III and A-20 have shown the adsorption uptake of 2.05 kg/kg and 1.19 kg/kg, respectively at 25 � C and 1100 kPa. Experimental adsorption isotherm data was successfully correlated in literature by D-A model and the optimized parameters are Wo ¼ 2.05 kg/kg, E ¼ 7547.24 J/mol & n ¼ 1.34 for Maxsorb-III, and Wo ¼ 1.19 kg/kg, E ¼ 8100.78 J/mol & n ¼ 1.45 for A-20. Adsorption uptake by Maxsorb-III/R-507A pair measured by Saha et al. [62] and Loh et al. [61] are not similar due to the difference in methods of adsorption measurement.

3.3. AC/R-32

3.6. AC/n-butane

R-32 adsorption uptake has been measured in the literature by three kinds of ACs named as ACF of type A-20, Maxsorb-III, and phenol resinbased spherical AC of type SAC-2 [111,112]. The R-32 adsorption iso­ therms by each adsorbent are shown in Fig. 7. The SAC-2 possessed maximum R-32 adsorption uptake which is 2.23 kg/kg (excess adsorp­ tion) and 2.34 kg/kg (absolute adsorption) at 30 � C and 1670 kPa. The SAC-2 belongs to the SAC adsorbent series [47,113] and holds high surface area of 2992 m2/g and pore volume of 2.52 cm3/g. As far as our understanding is a concern, this is the highest R-32 adsorption uptake by any adsorbent available in the literature. The D-A model was best fitted with experimental isotherms data. Its adsorption isotherm parameters for SAC-2/R-32 pair are Wo ¼ 3.1344 cm3/g, E ¼ 3.4981 kJ/mol, n ¼

Adsorption of n-Butane onto various ACs and their corresponding adsorption isotherms of the studied pairs are presented in Fig. 10. Maxsorb-III possesses the highest adsorption uptake, i.e. 0.8 kg/kg at adsorption temperature of 25 � C pressure of 230 kPa [52]. The D-A was model successfully correlated with the experimental data. The opti­ mized parameters of the model are Wo ¼ 0.8 kg/kg, E ¼ 300 kJ/kg, n ¼ 1.05. The adsorption uptake by Maxsorb-III is found relatively higher as compared to the rest of ACs. Adsorption of n-butane over GAC was studied [75]. The adsorbent has BET surface area and pore volume of 1600 m2/g and 1.15 cm3/g, respectively. GAC/n-butane pair has adsorption uptake of 0.34 kg/kg at 25 � C adsorption temperature 11

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Table 3 Adsorption properties and adsorption isotherm parameters for different activated carbons-methanol cooling systems. Activated Carbon

Surface Area [m2/g]

Pore Volume [cm3/g]

Maxsorb-III Tsurumi activate charcoal (HC-20C)

3045 [41] NA

1.70 (MI) [41] NA

D-R

FX-400

1458

0.683

Langmuir

KF-1000

1227

0.648

Langmuir

207EA

NA

NA

D-A

207C

NA

NA

D-A

WS-480

NA

NA

D-A

Carbo Tech A35/1

1414

0.786 (MI)

D-A

G32-H

921

0.482 (MI)

D-A

NORIT R1-Extra

1045

0.519 (MI)

D-A

NORIT RX3-Extra

1111

0.551 (MI)

D-A

CarboTech C40/1

1288

0.633 (MI)

D-A

RÜTGERS CG1-3

1009

0.535 (MI)

D-A

LH

NA

NA

D-A

DEG

NA

NA

D-A

PKST

NA

NA

D-A

Chinese (LSZ30)

NA

NA

D-A

Thai MD6070

NA

NA

D-A

Adsorption Equilibrium Models

References

Model

Parameter

value

D-R

Wo [kg/kg] D [K 2] Wo [kg/kg] D [K 2] Wo [kg/kg] b[ ] Wo [kg/kg] b[ ] Wo [kg/kg] D[ ] n[ ] Wo [kg/kg] D[ ] n[ ] Wo [kg/kg] D[ ] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [l/kg] D[ ] n[ ] Wo [l/kg] D[ ] n[ ] Wo [l/kg] D[ ] n[ ] Wo [l/kg] D[ ] n[ ] Wo [l/kg] D[ ] n[ ]

1.24 4.022 � 10 6 0.705 3.012 � 10 6 0.434 12.06 0.307 36.98 0.28 8.45 � 10 7 2.08 0.15 9.67 � 10 6 1.72 0.27 9.08 � 10 6 1.78 0.786 11.72 1.76 0.482 19.22 2.59 0.519 17.38 2.27 0.551 16.89 2.06 0.633 12.46 1.85 0.535 14.26 1.8 0.86 2.574 � 10 4 1.321 0.534 1.96 � 10 4 1.31 0.258 9.656 � 10 7 2 0.405 31.97 � 10 5 1.26 0.988 88.98 � 10 5 1.12

[73]

[74]

[53]

[54]

[55]

[56]

Key: NA: not available. MI: micropores volume.

relative pressure of 0.9. Langmuir model (see Table 1) successfully predict the experimental data of adsorption equilibrium. The optimized parameters of the model are Wo ¼ 0.389 kg/kg and b ¼ 5.72, at adsorption temperature of 25 � C. Kureha type AC was experimentally analyzed for adsorption of n-Butane [117]. It exhibits a BET surface area of 1300 m2/g and total micropore volume of 0.56 cm3/g. Adsorption uptake of 0.29 kg/kg was measured at 25 � C and pressure of 50 kPa. The �th model (see Table 1) and the optimized data was correlated by To parameters at 25 � C are Wo ¼ 6.19 mol/kg, bo ¼ 56.61/kPa, t ¼ 0.333. Adsorption uptake by AC of type Ajax:976 is 0.29 kg/kg at 25 � C and 80 kPa [76]. The experimental data was successfully correlated with the Langmuir model and the optimized parameters at 20 � C are Wo ¼ 4.80 � 103 mol/cm3and b ¼ 10.5 � 10 5 cm3/mol. Adsorption of n-butane onto AC prepared from the Brazilian coconut shell was of 0.523 kg/kg at 25 � C and 70 kPa [118].

3.7. AC/CO2 Adsorption of CO2 onto many ACs has been studied in the literature for various applications, i.e. adsorption cooling [119,120] and carbon capturing [121,122]. The corresponding adsorption isotherms are pre­ sented and compared in Fig. 11. Maxsorb-III shows the highest adsorp­ tion uptake of 1.44 kg/kg at 30 � C and 6800 kPa [43]. CO2 adsorption onto ACF of type A-20 was experimentally measured, i.e. 0.935 kg/kg at 30 � C and 7040 kPa [44]. Adsorption uptake by Maxsorb-III is 1.70 times higher than A-20. CO2 adsorption has been studied for a few ACs namely Norit R1 extra, BPL, Maxsorb, A-10 and type-A [45]. The corresponding adsorp­ tion isotherms are shown in Fig. 11. Similarly, commercially available ACs of type Norit RB3 and Norit Darco were studied for adsorption of CO2 [46]. The adsorption uptake by Norit RB3 and Norit Darco are 0.97 kg/kg and 0.81 kg/kg, respectively, at 25 � C saturation conditions. CO2 adsorption can be enhanced by nitrogen treatments on ACs and 12

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Fig. 7. Adsorption isotherms of R-32 on to different activated carbons SAC-2 (30 � C) [112], ACF (A-20) (24.8 � C) [111], ● Maxsorb-III (24.8 � C) [111].

Fig. 10. Adsorption isotherms of n-butane on to different activated carbons: ■ Maxsorb-III (25 � C) [52], Brazilian Coconut (25 � C) [118], Granular Activated Carbon (25 � C) [75], Kureha (25 � C) [117], Ajax (30 � C) [76].

Fig. 8. Adsorption isotherms of R-134a on to different activated carbons: ■ Maxsorb-III (30 � C) [57], ACF (A-20) (30.2 � C) [59], GAC (25 � C) [58], Chemviron (20 � C) [60], Fluka (20 � C) [60].

Fig. 11. Adsorption isotherms of CO2 on to different activated carbons: Maxsorb-III (30 � C) [43], ▴ ACF-A20 (30 � C) [44], BPL (25 � C) [45], Norit R1 Extra (25 � C) [45], ACF-A10 (25 � C) [45], ♠ Honey comb Monolith (25 � C) [80], Norit Darco (25 � C) [46], Norit RB3 (25 � C) [46], þ AC Beads (25 � C) [79], OXA-GAC (30 � C) [84], ♣ GAC (30 � C) [84], Norit (25 � C) [120], CP-2-600 (25 � C) [123], □ AC/MEA (25 � C) [81], AC/TEA (25 � C) [81].

performance is based on the nature of nitrogen sources and type of activation. Such as N-dope sample of AC namely CP-2-600 has a sharp rise in adsorption uptake up to 0.14 kg/kg in the low-pressure range of 100 kPa [123] as shown in Fig. 11. The CO2 adsorption equilibrium by parent GAC and ammonia-modified GAC (i.e. OXA-GAC) was investi­ gated [84]. Nitrogen functional group block the micro-pores of OXA-GAC due to ammonia modification. Thereby, the adsorption equilibrium is increased by 30% as compared to parent GAC. Adsorption equilibrium and kinetics of CO2 for pitch based AC beads have been investigated which shows adsorption uptake of 1.918 mmol/g at 30 � C and 100 kPa [79]. SEM image of the adsorbent shows a narrow range of particles with average macropores diameter of 0.40 μm (Table 4). It has a large number of micropore which contributes toward the larger sur­ face area, i.e. 845.87 m2/g. Similarly, adsorption of CO2 onto AC of type honeycomb monolith was experimentally measured which results in adsorption uptake of 4 mol/kg (0.176 kg/kg) at 26 � C and 580 kPa [80]. Physical properties for all studied AC/CO2 pairs and the optimized

Fig. 9. Adsorption isotherms of R507A on to different activated carbons at 25 � C: Maxsorb-III [61], ACF (A-20) [61].

13

2000

3045 [48]

Maxsorb-III

ACF (A-20)

Surface Area [m2/g]

Activated Carbon

1.03 (MI)

1.7 (MI) [48]

Pore Volume [cm3/g]

14 [120]

[100]

SEM Images

Table 4 Adsorption properties and adsorption isotherm parameters for different activated carbons-CO2 cooling systems.

D-A

D-A

Model

[44]

[43]

References

(continued on next page)

1.002 4468.22 2 1.14

1.540 5254.7 4.504 1.326

Wo [cm3/g] E [J/mol] k[ ] n[ ]

Wo [cm3/g] E [J/mol] k[ ] n[ ]

Value

Parameter

Adsorption Equilibrium Models

F. Shabir et al.

Renewable and Sustainable Energy Reviews 119 (2020) 109630

15

483

Honey comb Monolith

1450

Norit R1 Extra

1200

1150

BPL

ACF-A10

Surface Area [m2/g]

Activated Carbon

Table 4 (continued )

0.5

0.53

0.47

0.43

Pore Volume [cm3/g]

NA

[120] NA

SEM Images

MultisiteLangmuir

D-A

D-A

D-A

Model

ΔHi [kJ/mol] qi,max [mol/kg] ai [ ]

25.76 7.21 2.01

7

[80]

[45]

References

(continued on next page)

0.67 6300 2 1.43 0.54 7370 2 1.66 3.27 � 10

0.51 6510 2 1.38

Wo [cm3/g] E [J/mol] k[ ] n[ ]

Wo [cm3/g] E [J/mol] k[ ] n[ ] Wo [cm3/g] E [J/mol] k[ ] n[ ] Koi [kPa 1]

Value

Parameter

Adsorption Equilibrium Models

F. Shabir et al.

Renewable and Sustainable Energy Reviews 119 (2020) 109630

876.45

978.04

Norit RB3

Norit Darco

Surface Area [m2/g]

Activated Carbon

Table 4 (continued )

0.73

0.51

Pore Volume [cm3/g]

SEM Images

D-A

D-A

Model

16

4

3

[46]

References

(continued on next page)

8.98 � 10 5569.79 1.40 2

1.09 � 10 4957.91 1.24 2

Wo [m3/g] E [J/mol] n[ ] k[ ]

Wo [m3/g] E [J/mol] n[ ] k[ ]

Value

Parameter

Adsorption Equilibrium Models

F. Shabir et al.

Renewable and Sustainable Energy Reviews 119 (2020) 109630

Surface Area [m2/g]

845.87

768 734

1700

Activated Carbon

AC Beads

GAC OXA-GAC

CP-2–600

Table 4 (continued )

17 0.88

0.387 0.381

NA

Pore Volume [cm3/g]

NA NA

SEM Images

EO

EO T� oth

MultisiteLangmuir

Model 1

]

EDU Wo [mol/kg] bo [atm 1] t[ ] Qst [kJ/mol] EDU

ΔHi [kJ/mol] qi,max [mol/kg] ai [ ]

Koi [kPa

Parameter

Adsorption Equilibrium Models

3.57 0.66 0.65 22.23

23.16 17.66 2.90

8

[123]

[84]

[79]

References

(continued on next page)

6.06 � 10

Value

F. Shabir et al.

Renewable and Sustainable Energy Reviews 119 (2020) 109630

Renewable and Sustainable Energy Reviews 119 (2020) 109630

LangmuirFreundlich

Wo [mg/g] b [bar 1] t[ ] Wo [mg/g] b [bar 1] t[ ] LangmuirFreundlich

470 0.09 0.81 552 0.10 0.82

Parameter Model

Adsorption Equilibrium Models

Value

[81]

References

F. Shabir et al.

Fig. 12. Adsorption isotherms of H2O on to different silica gels: Type A (30 � C) [86], ♣ Type A (31 � C) [83], RD-Type (30 � C) [93], RD-Type (31 � C) [86], ■ Silica gel (Grade 40) (25 � C) [92], Type Aþþ (25 � C) [63], Type-A5BW (25 � C) [63], Type-RD 2560 (25 � C) [63], Type 3A (30 � C) [126].

parameters of the correlated adsorption isotherm models are furnished in Fig. 11.

Silica gel is porous, non-hazardous and high thermally stable adsorbent having a high water vapor adsorption af­ finity of approximately 40% by its weight. Subsequently, its regeneration can easily be done up to 150 � C. It is princi­ pally prepared by the polymerization of a colloidal mixture of sodium silicate and silicic acid [96]. Water adsorption onto many silica gels has been re­ ported in the literature to develop a thermally driven adsorption system for various applications [124,125]. The corresponding adsorption isotherms are presented and compared in Fig. 12. RD-Type silica gel possesses the highest uptake of 0.4465 kg/kg at 31 � C and 4.43 kPa [86]. While Type A has adsorption uptake of 0.4014 kg/kg at 31 � C and �th isotherm model was 5.22 kPa, as shown in Fig. 12. To successful with experimental data of both adsorbents, and the optimized parameters are presented in Table 5. How­ ever, in other studies, water adsorption uptakes by Type A [83] and RD-Type [93] are less than that reported by Chua et al. [86]. In another study, a silica gel RD-Type/water based dual-mode adsorption chiller was designed for uti­ lizing low regeneration temperature [34]. A modified Freundlich model or K-S-B equation (see Table 1) was correlated with the adsorption data and its optimized pa­ rameters are placed in Table 5. Water adsorption behavior of silica gel Type 3A was investigated by Ng et al. [126]. It shows the adsorption uptake of 0.3 kg/kg at 30 � C and 2.47 kPa. In another study, water adsorption uptake by silica gel typed Grade 40 is 18.9 mol/kg (0.304 kg/kg) at 25 � C and 2.43 kPa [92]. The measured adsorption data was success­ �th model, and its fully correlated with multitemperature To optimized parameters are presented in Table 5. Silica gels of types Type Aþþ, Type-RD 2560 and TypeA5BW were studied to analyze the water adsorption ca­ pacities for adsorption desalination application [63]. Type Aþþ has maximum water adsorption uptake of 537 cm3/g (0.432 kg/kg) at 25 � C of saturation condition. Adsorption

Key: NA: not available. EO: experiments only. EDU: Experimental data used. MI: micropores volume.

NA 1749 AC/MEA

1.181

NA 8 AC/TEA

0.018

Surface Area [m2/g] Activated Carbon

Table 4 (continued )

Pore Volume [cm3/g]

SEM Images

4. Silica-gel/H2O adsorption cooling

18

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Table 5 Adsorption properties and adsorption isotherm parameters for different silica gel-water cooling systems. Silica Gel Type A

RD-Type

Surface Area [m2/g]

Pore Volume [m3/g]

Adsorption Equilibrium Models

References

Model

Parameter

Value

Wo [kg/kg] n[ ] Wo [kg/kg] bo [kPa 1] Qst [kJ/kg] t[ ] A0 A1 A2 A3 B0 B1 B2 B3 Wmo [kg/kg] qm [kJ/kg] Co Ko ΔHc [kJ/kg] ΔHk [kJ/kg] Wo[kg/kg] bo [kPa 1] Qst [kJ/kg] t[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] Wo [cm3/g] E [kJ/mol] n[ ] ao [mol/(kg‧kPa)] bo [kPa 1] E [K] to [ ] C [K]

0.346 1.6 0.4 4.65 � 10 10 2.71 � 103 10 6.5314 0.072452 0.23951 � 10 0.25493 � 10 3 15.587 0.15915 0.50612 � 10 0.5329 � 10 6 0.121 190.458 0.164 1.966 464.225 250.363 0.45 7.30 � 10 10 2.693 � 103 12 0.489 3.804 1.35 0.455 3.585 1.25 0.327 4.384 1.35 1.767 � 102 2.787 � 10 5 1.093 � 103 1.190 � 10 3 2.213 � 101

650 [86]

0.36 [86]

Freundlich

720 [86]

0.4 [86]

Modified Freundlich (S-B-K equation)

T� oth

GAB

T� oth

Type Aþþ

863.6

0.476

D-A

Type-A5BW

769.1

0.446

D-A

Type-RD 2560

636.4

0.314

D-A

Silica gel (Grade 40).

NA

NA

Multitemperature T� oth

[83] [86]

[34] 3

3

[93]

[86]

[63]

[92]

Key: NA: not available.

isotherms of the assorted pairs are correlated with D-A model, and the optimized parameters of the model are presented in Table 5. Physical properties of assorted adsorbents are given in Table 5. Thus, it indicates the highest surface area of 863.6 m2/g is possessed by the Type Aþþ. 5. Zeolite based adsorption cooling Zeolites are three-dimensional microporous solid adsorbents, which consist of aluminosilicates crystalline tetrahedral structures that are coordinated with each other by an oxygen atom in a regular framework. Thus, they possess uniformity in their pores sizes as compared to other adsorbents. Furthermore, the surface properties of zeolite can be controlled by the aluminium and silicon ratio and by the number of cations (of group I or II). 5.1. Zeolite/H2O Adsorption of water onto various kinds of zeolites have been studied in the literature for the development of energy-efficient adsorption cooling system [127–129]. The corresponding adsorption isotherms are presented and compared in Fig. 13. Binderless zeolite 13X shows the highest water adsorption uptake of 0.341 kg/kg at 30 � C of saturation conditions [64]. Similarly, water adsorption by zeolite 13X beads and zeolite 5A was measured by the volumetric method [92]. They have shown the adsorption uptake of 14.2 mol/kg and 13.8 mol/kg for the pressure of 1.83 kPa and 1.58 kPa, respectively at 25 � C. In a study, the

Fig. 13. Adsorption isotherms of H2O on to different zeolites: AQSOA-Z01 (25 � C) [65], AQSOA-Z02 (25 � C) [65], AQSOA-Z05 (25 � C) [65], ■ � � Binderless 13X (30 C) [64], □ FAM Z01 (25 C) [130], 5A (25 � C) [92], 13 x (25 � C) [92], NaZSM-5 (25 � C) [131], HZSM-5 (25 � C) [131].

19

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Table 6 Adsorption properties and adsorption isotherm parameters for different zeolite-water cooling systems. Zeolite

Surface Area [m2/g]

Pore Volume [cm3/g]

Adsorption Equilibrium Models

References

Model

Parameter

Value

Wo [ml/g] E [kJ/mol] n[ ] Wo [kg/kg] k[ ] n[ ] ao [mol/(kg‧kPa)] bo [kPa 1] E [K] to [ ] C [K] ao [mol/(kg‧kPa)] bo [kPa 1] E [K] to [ ] C [K] Wo [kg/kg] E [kJ/mol] n[ ] Wo [kg/kg] E [kJ/mol] n[ ] Wo [kg/kg] E [kJ/mol] n[ ]

341.03 1192.3 1.55 0.1219 5.052 1.4 3.634 � 10 6 2.408 � 10 7 6.852 � 103 3.974 � 10 1 4.199 1.106 � 10 8 4.714 � 10 10 9.955 � 103 3.548 � 10 1 5.114 � 101 0.21 4000 5 0.285 7600 2.9 0.22 2700 6

Binderless 13X

NA

NA

D-A

Natural zeolite

NA

NA

Modified D-A

13X

NA

NA

Multi temperatureT� oth

5A

NA

NA

Multi temperatureT� oth

AQSOA-Z01

189.6

0.071

D-A

AQSOA-Z02

717.8

0.27

D-A

AQSOA-Z05

187.1

0.07

D-A

[64] [72] [92]

[65]

Key: NA: not available.

water adsorption equilibrium uptakes by zeolites of type AQSOA-Z01, AQSOA-Z02 and AQSOA-Z05 were 0.21 kg/kg, 0.29 kg/kg and 0.22 kg/kg, respectively, at 25 � C of saturation conditions [65]. Physical properties for all the studied pairs and the optimized parameters of the correlated adsorption isotherm models are furnished in Table 6. AQSOA-Z02 owing to have good adsorption equilibrium uptake possess the surface area and pore volume of 717.8 m2/g and 0.27 cm3/g. Adsorption chiller employing zeolite of type FAM-Z01 was analyzed

to check its performance at low regeneration temperature [130]. It shows the adsorption uptake of 0.20 kg/kg at 25 � C and relative pressure of 0.40. Similarly, a natural zeolite shows the average adsorption ca­ pacity of 0.12 kg/kg [72]. In a study, water adsorption on to Naþ and Hþ cations based zeolites, i.e. NaZSM-5 and HZSM-5 have been studied [131]. Isotherm profile of these adsorbent shows a rapid increase in adsorption uptake initially, and it turns into smooth as pressure in­ creases. Thus, exhibit strong attraction of water at low pressure. How­ ever, they own relatively lower adsorption uptakes as compare to other studied adsorbents. 5.2. Zeolite/CO2 CO2 adsorption on to zeolite adsorbents has been studied in various studies for several adsorption based applications, i.e. CO2 capture, sep­ aration and purification [132–134]. The corresponding adsorption iso­ therms are presented and compared in Fig. 14. Zeolite 13X adsorbent shows the highest adsorption uptake of 0.324 kg/kg at 25 � C and 3200 kPa [135]. Similarly, CO2 adsorption by zeolite 13X from palm oil mill fly ash (POMFA) was investigated [136]. Adsorption uptake possessed by acid-activated POMFA-zeolite 13X (6M HCl/4 h) is 0.282 kg/kg at 32 � C and 403 kPa, which is 22% higher than its un-activated sample. In addition, it shows good adsorption uptake than zeolite 13X in the low-pressure range up to 500 kPa. In another study, synthesized zeolite 13X from natural clays (i.e. kaolin, bentonite and feldspath) have been studied [77]. Natural kaolin-based zeolite (13X-K) shows maximum adsorption uptake of 0.31 kg/kg at 25 � C and 2000 kPa among other synthesized zeolites 13X. Langmuir-Freundlich model (see Table 1) give the good fit for adsorption data of assorted adsorbents, whose parame­ ters are listed in Table 7. CO2 adsorption on to zeolite adsorbents from silica origin named as BEA, FER, CHA, MFI, STT, AEI and RRO has been experimentally measured [95,137]. Among these zeolites, STT gives good adsorption uptake of 2.00 mol/kg (0.088 kg/kg) at 30 � C and 101.3 kPa. But in low-pressure range, FER performs better. Adsorption characteristics of binderless 5A zeolite for the application of CO2 separation from flue gases were analyzed [87]. Adsorption up­ take by binderless 5A zeolite is 0.220 kg/kg at 32 � C and 500 kPa. In

Fig. 14. Adsorption isotherms of CO2 on to different zeolites: 13X (25 � C) [135], POMFA-zeolite 13X (32 � C) [136], ■ Acid-activated POMFA-zeolite 13X (6M HCl/4 h) (32 � C) [136], 13X-K (25 � C) [77], 13X-C (25 � C) [77], 13X-B (25 � C) [77], 13X-F (25 � C) [77], T Type (T1) (25 � C) [82], Binderless 5A (32 � C) [87], ♠ Chabazite (32 � C) [88], BEA (30 � C) [95], CHA (30 � C) [95], MFI (30 � C) [95], FER (30 � C) [95], STT (30 � C) [95], □ AEI (30 � C) [137], ♧ RRO (30 � C) [137], NaX (25 � C) [89], NaY (25 � C) [89], KX (25 � C) [89], ✕ KY (25 � C) [89], ☆ RbX (25 � C) [89], RbY (25 � C) [89], CsX (25 � C) [89], ✹ CsY (25 � C) [89]. 20

F. Shabir et al.

Table 7 Adsorption properties and adsorption isotherm parameters for different zeolite-CO2 cooling systems. Surface Area [m2/g]

Pore Volume [cm3/g]

13X

NA

POMFA-zeolite 13X

405.2

Zeolites

SEM Images

Adsorption Equilibrium Models

References

Model

Parameter

Value

NA

MultisiteLangmuir

Wo [mol/kg] ΔHi [kJ/mol] bo [MPa 1] ai [ ]

17.901 3.20 � 10 54.729 13.120

0.294

EO

EDU

8

[135]

[136]

21 Renewable and Sustainable Energy Reviews 119 (2020) 109630

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Table 7 (continued ) Zeolites Acid-activated POMFA-zeolite 13X (6M HCl/4 h)

Surface Area [m2/g]

Pore Volume [cm3/g]

369.4

0.920

SEM Images

Adsorption Equilibrium Models Parameter

EO

EDU

Langmuir

Wo [mmol/g] b[ ]

References Value

22

Model

13X-K.

591

0.250 (MI)

2.70 6.90 � 10

5

[77]

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Table 7 (continued ) Zeolites 13X-B

Surface Area [m2/g]

Pore Volume [cm3/g]

505

0.160 (MI)

SEM Images

Adsorption Equilibrium Models Parameter

EO

EDU

EO

EDU

References Value

23

Model

13X-F

72

0.140 (MI)

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Table 7 (continued ) Zeolites

Pore Volume [cm3/g]

SEM Images

13X-C

588

NA

T Type (T1)

425.41

0.240 (MI) 0.17 (MI)

Binderless 5A

526

Adsorption Equilibrium Models

References

Model

Parameter

Value

EO

EDU

LangmuirFreundlich

Wo [mmol/g] b [kPa 1] t[ ]

3.94 8.11 1.47

T� oth

Wo [mmol/kg] bo [1/bar] t[ ] Qst [kJ/mol]

5.11 2.1 � 10 0.61 38.1

[82]

24

Surface Area [m2/g]

0.25 (MI)

5

[87]

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(continued on next page)

Surface Area [m2/g]

Pore Volume [cm3/g]

SEM Images

Chabazite

415

0.348

NA

AEI

613

0.27 (MI)

RRO

452

0.19 (MI)

Adsorption Equilibrium Models

References

Model

Parameter

Value

T� oth

EO

Wo [mol/kg] bo [kPa 1] t[ ] Qst [kJ/mol] EDU

4.27 0.035 � 106 0.46 44.9

EO

EDU

[88]

[137]

25

Zeolites

F. Shabir et al.

Table 7 (continued )

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Table 7 (continued ) Zeolites

Surface Area [m2/g]

Pore Volume [cm3/g]

CHA

572

STT

411

SEM Images

Adsorption Equilibrium Models

References

Parameter

Value

0.27 (MI)

Henry law

K [mol/(kg‧ atm)] at T ¼ 303K

2.72

0.19 (MI)

Henry law

K [mol/(kg‧ atm)] at T ¼ 303K

2.87

[95]

26

Model

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F. Shabir et al.

Table 7 (continued ) Surface Area [m2/g]

Pore Volume [cm3/g]

BEA

395

FER

282

Zeolites

SEM Images

Adsorption Equilibrium Models

References

Parameter

Value

0.21 (MI)

Henry law

K [mol/(kg‧ atm)] at T ¼ 303K

1.38

0.13 (MI)

Henry law

K [mol/(kg‧ atm)] at T ¼ 303K

4.35

27

Model

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(continued on next page)

Zeolites

28

Surface Area [m2/g]

Pore Volume [cm3/g]

MFI

312

0.14 (MI)

LiX

NA

NA

LiY

NA

NaX

SEM Images

Adsorption Equilibrium Models

References

Parameter

Value

Henry law

K [mol/(kg‧ atm)] at T ¼ 303K

2.83

NA

T� oth

NA

NA

T� oth

NA

NA

NA

T� oth

NaY

NA

NA

NA

T� oth

KX

NA

NA

NA

T� oth

KY

NA

NA

NA

T� oth

RbX

NA

NA

NA

T� oth

RbY

NA

NA

NA

T� oth

CsX

NA

NA

NA

T� oth

CsY

NA

NA

NA

T� oth

Wo [mol/kg] b [kPa] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ] Wo [mol/kg] b [kPa 1] t[ ]

10.51 0.747 0.336 7.89 0.028 0.834 6.83 0.190 0.557 6.09 0.035 1.206 5.42 0.329 0.593 4.8 0.100 1.025 5.63 8.00 0.327 5.1 0.263 0.711 4.33 1.61 0.387 3.46 0.161 0.591

Key: NA: not available. EO: experiments only. EDU: Experimental data used. MI: micropores volume.

[89]

Renewable and Sustainable Energy Reviews 119 (2020) 109630

Model

F. Shabir et al.

Table 7 (continued )

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Fig. 16. Adsorption isotherms of ethanol on to different composites at 30 � C: Maxsorb-III (50%)-EG (40%)-Binder (10%) [68], Maxsorb-III (70%)-EG (20%)-Binder (10%) [68], SG/LiBr [51], ■ Maxsorb-III (90%)-Poly IL [VBTMA][Ala] (10%) [69].

Fig. 15. Adsorption isotherms of H2O on to different composites: CaCl2/silica gel (SWS-1L) (31 � C) [90], Alumina/Zeolite 13X (30 � C) [67], þ LiCl2/silica gel (35 � C) [66], CaCl2/MWCNT (37 � C) [142], ● AC (33%wt)/silica gel (3% wt)/CaCl2 (64%wt) (27 � C) [140], SGB/LiCl (20 � C) [141], SGC/LiCl (20 � C) [141], SAPO-34_97 (25 � C) [144], ○ Zeo-Y_97 (25 � C) [144], S2 (25 � C) [145], CaCl2-FeKIL2 (5.60 kPa) [143].

parameters of the correlated adsorption isotherm models are furnished in Table 7. SEM image of binderless 13X shows very narrow crystal size distribution. Similarly, the morphology of AEI, RRO, CHA and STT by SEM images show well-defined cuboid shape, uniform prismatic plate, a pseudo-cubic shape and aggregates of plate-like crystals, respectively.

another study, the adsorption capacities of pure gases and their mixtures by zeolite, i.e. natural chabazite were measured [88]. The maximum CO2 adsorption uptake by natural chabazite zeolite was 0.224 kg/kg at 32 � C and 3000 kPa. CO2 adsorption on to T-type zeolite nanoparticles was investigated [82]. T-type zeolite nanoparticles show the adsorption uptake of 0.176 kg/kg at 25 � C and 100 kPa, which is about 30% greater than T-type zeolite micro level particles. In another study, the effect of ion-exchanged cations (Kþ, Liþ, Rbþ, and Csþ) for X and Y zeolites on the CO2 adsorption was studied [89]. Adsorption at 25 � C and 1 atm show higher adsorption capacity of lithium cations among these cations. It has smaller cation size which holds higher ion-quadrupole interaction than other Alkali metal cations. Physical properties for all the studied pairs and the optimized

6. Composite adsorbent based adsorption cooling 6.1. Composite adsorbent/H2O Adsorption of water onto various kinds of Composite adsorbent has been studied in the literature for air-conditioning and refrigeration [138]. The corresponding adsorption isotherms are presented and compared in Fig. 15. SWS-1L is the composite adsorbent obtained by confining inorganic salt CaCl2 (33.7 wt %) in to the porous host matrix of KSKG silica gel [139]. A double bed adsorption chiller of SWS-1L/water pair was modelled by Saha et al. [90]. The studied pair gave adsorption

Table 8 Adsorption properties and adsorption isotherm parameters for different composites-ethanol and composites-water cooling systems. Composite Adsorbent

Refrigerant

Surface Area [m2/g]

Pore Volume [cm3/g]

Adsorption Equilibrium Models Model

Parameter

Value

Wo [kg/kg] E [(kJ/kg] n[ ] Wo [kg/kg] E [(kJ/kg] n[ ] Wo [cm3/kg] E [kJ/mol] n[ ] Wo [kg/kg] E [kJ/kg] n[ ] Wo [kg/kg] Qst [kJ/kg] t[ ] bo [1/Pa] Wo [mol/kg] E [J/mol] n[ ] Wo [kg/kg] k[ ] n[ ]

0.61 125 2 0.89 119 1.8 0.68 6.9 1.8 1.12 126 1.86 0.8 2760 1.1 2 � 10 35 1355 0.2811 0.489 0.342 1.604

Maxsorb-III (50%), EG (40%) Binder (10%)

Ethanol

1420 � 30

0.787

D-R

Maxsorb-III (70%), EG (20%) Binder (10%)

Ethanol

2000 � 34

1.094

D-A

SG/LiBr

Ethanol

181

0.73

D-A

Maxsorb-III (90%) Poly IL [VBTMA][Ala] (10%)

Ethanol

3040

1.59

D-A

CaCl2/silica gel (SWS-1L)

H2O

350

1

T� oth

Alumina/Zeolite 13X

H2O

455

0.161 (MI)

D-A

LiCl2/silica gel

H2O

350.424

0.613

D-A

Key: NA: not available. MI: micropores volume. 29

References [68]

[51] [69] [90] 12

[67] [66]

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

Ethanol uptake [kg/kg]

1.2 1 0.8 0.6 0.4 0.2 0 0

2

4

6 Pressure [kPa]

8

10

Fig. 17. Adsorption isotherms of Ethanol on to different MOFs:, MIL-101Cr MIL-101-3 (25 � C) [150], ■ MIL-101Cr (25 � C) [70], □ (30 � C) [91], Cu-BTC (25 � C) [70], Fe-BTC (25 � C) [70], MIL-53 Cr (25 � C) [70], MIL-100Cr (25 � C) [70], CPO-27 Ni (25 � C) [70].

Fig. 19. Adsorption isotherms of H2O on to different MOFs at 25 � C: aluminium fumarate [71], CPO-27(Ni) [71], MIL-101(Cr) [166], HKUST-1 [164], ♣ ZIF-8 [161], MIL-100(Fe) [161], ■ MIL-101 [161], ☆ Uio-66 [165], MOF-801-P [165], ♠ MOF-801-SC [165], MOF-802 [165], þ PIZOF-2 [165], ○ DUT-67 [165], MOF-808 [165], MOF-841 [165], ⋄ CAU-10-H [173], Basolite™ A100 [171], Basolite™ F300 [171], MIL-100 MIL-100 Al [168], μp-AF [163], ♤ MIL-100 Cr [169], Fe [168], MIL-101Cr [160].

uptake of 0.5 kg/kg at 31 � C and 2 kPa. Similarly, composite adsorbent LiCl2/silica gel featuring hygroscopic salt lithium chloride confined to silica gel porous host matrix was investigated [66]. It possessed the adsorption uptake of 0.39 kg/kg at 35 � C and 2.62 kPa. In another study, activated carbon, silica-gel and CaCl2 were amalgamated to produces a composite adsorbent [140]. Thirteen different samples were prepared by varying composition of AC, Silica gel and CaCl2. A sample having a composition of AC (33%wt), Silica gel (3%wt), and CaCl2 (64%wt) gives the highest difference in equilibrium water uptake of about 0.805 kg/kg between 25 � C and 115 � C. It shows an improvement of 324% as compared to parent AC. Composites adsorbents were prepared by mixing three different sil­ ica gels (Microporous, Type B and mesoporous) with different salts (CaCl2, LiCl, and LiBr) [141]. After impregnation surface area and pore volume of all samples become smaller than parent silica gel. As a matrix host, microporous silica gel is not a good choice for water adsorption.

Whereas, Type B and mesoporous silica gel gave good results. LiCl shows a good impact on water adsorption all silica gel as compared to other hygroscopic salts. Water adsorption of SGB/LiCl and SGC/LiCl shows adsorption uptake of 0.936 g/g and 0.9 g/g, respectively, at 20 � C and relative pressure up to 0.9. Water vapor adsorption on to the Alumina/Zeolite 13X composite was studied [67]. It has shown the adsorption uptake of 0.359 kg/kg at 30 � C of saturation condition. In another study, composite adsorbents have been prepared by the impregnation of multi-wall carbon nanotubes (MWCNT) with salts, i.e. CaCl2, LiCl, and LiBr [142]. CaCl2/MWCNT composite adsorbent shows the highest water adsorption uptake of 0.97 Fig. 18. Adsorption isotherms of CO2 on to different MOFs: ■ MOF-200 (25 � C) [152], MOF-210 (25 � C) [152], MOF-205 (25 � C) [152], MOF-5 (25 � C) [152], MOF-177(25 � C) [152], IRMOF-1 (25 � C) [153], ⋄ IRMOF-6 (25 � C) [153], IRMOF-3 (25 � C) [153], □ IRMOF-11 (25 � C) [153], CU3(BTC)2 (25 � C) [153], MOF-74 (25 � C) [153], MOF-505 (25 � C) [153], MOF-2 (25 � C) [153], ♣ HKUST-1(30 � C) [154], ♠ MIL-101(Cr) (30 � C) [154], ☆ MIL-96 (23 � C) [155], ▾ MIL-53 (23 � C) [155], aluminum fumarate (30 � C) [78], ◂ UiO-66(Zr)_(COOH)2 (30 � C) [156].

30

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Renewable and Sustainable Energy Reviews 119 (2020) 109630

kg/kg at 37 � C and 3.4 kPa. Physical properties for all the studied pairs and the optimized parameters of the correlated adsorption isotherm models are furnished in Table 8. In another study, a composite CaCl2-­ FeKIL2 was prepared in order to investigate the water adsorption characteristics for energy storage application [143]. The host matrix FeKIL2 possess the surface area of 712 m2/g which after impregnation with CaCl2 get lower to 418 m2/g. However, the water adsorption ca­ pacity of the composite will become three times higher than the host matrix probably due to the presence of the salt in it. The composite possesses the adsorption uptake of 0.58 kg/kg at 30 � C and relative pressure up to 0.73. Kummer et al. [144] prepared the two sets of composite materials by successfully combining (i) silica-aluminophosphate (SAPO-34) and (ii) zeolite Y with the aluminum-plates (AlMg3-alloy) by using silicone resin binder (MP50E). Four composite samples of each adsorbent were pre­ pared with a different binder to adsorbent mass ratios. The adsorption isotherms of adsorbents i.e. SAPO-34_97 and zeo-Y_97 having the 2.5 wt % of binder contents are presented in Fig. 15. The results show no sig­ nificant improvement on the maximum adsorption capacity over pure adsorbents by the use of a binder. Similarly, in another study, new composite materials were prepared by coating zeolite A on copper and fibrous stainless steel plates for the application in the heat pump system [145,146]. The adsorption isotherms of zeolite coatings on copper and fibrous stainless steel plates were quite typical of type I just like powdered zeolite NaA. However, with the addition of polymer into the zeolite coatings on fibrous stainless steel (namely S2) changed the isotherm to type II as shown in Fig. 15.

coordination of organic linkers and the inorganic metal ions to form an open crystalline structure. The most common organic linkers are organic carboxylates, while the inorganic part is the metal-containing unit which is known as secondary building unit. 7.1. MOF/ethanol Adsorption of ethanol onto various kinds of MOF has been studied in the literature for adsorption cooling and heating applications [149]. The corresponding adsorption isotherms are presented and compared in Fig. 17. MOF of type MIL-101Cr gives highest ethanol uptake of 1.1 kg/kg at 30 � C and relative pressure up to 0.9 [91]. MIL-101Cr has gained much importance due to its high surface area of 4100 m2/g and �th isotherm model was found to be suitable pore volume of 2 cm3/g. To for theoretical investigation of adsorption behavior of MIL-101Cr/ethanol pair. The optimized parameters of the model are Wo (kg/kg) ¼ 1.150, bo (1/kPa) ¼ 0.342, t ( ) ¼ 2.193, Q/RTo ¼ 17.845, ϕ ¼ 0.358. Adsorption and desorption performances of Shaped MIL-101 (MIL-101-3)/ethanol pair for adsorption refrigeration were investi­ gated [150]. MIL-101-3 is derived from powder MIL-101. It shows ethanol adsorption uptake of 0.74 kg/kg at 25 � C and 6.05 kPa. Its adsorption isotherms were found to be a complex shape of type I and VI isotherms collectively. Ethanol adsorption of some MOFs i.e.MIL-101Cr, MIL-100, MIL-53Cr, CPO-27Ni, Fe-BTC and Cu-BTC) were measured [70]. MIL-101Cr owns higher ethanol uptake of 1.2 kg/kg at 25 � C of saturation condition. D-A model was successfully correlated with the experimental data, and the optimized parameters of the model are given as Wo ¼ 1.1005 kg/kg, E ¼ 6527.4 J/mol, n ¼ 2.6033.

6.2. Composite adsorbent/ethanol

7.2. MOF/CO2

Adsorption of ethanol onto various kinds of Composite adsorbent has been studied in the literature for adsorption cooling application [51, 147]. The corresponding adsorption isotherms are presented and compared in Fig. 16. Consolidated AC composite adsorbents prepared by the mixture of AC Maxsorb-III and polymerized ionic liquid (vinylbenzyl trimethyl ammonium alanate) as a binder were investigated [69]. Its sample with composition Maxsorb-III (90%) and Polymerized IL [VBTMA][Ala] (10%) possess the surface area 3040 m2/g and pore volume of 1.59 cm3/g. It shows the highest ethanol adsorption uptake of 1.11 kg/kg at 30 � C of saturation conditions. The adsorption data was successfully correlated with D-A isotherm model the optimized param­ eters of the model are given in Table 8. Similarly, the adsorption ca­ pacity of ethanol on consolidated composite adsorbents have been studied by El-Sharkawy et al. [68]. The adsorbents were prepared by the mixture of AC Maxsorb-III, expanded graphite (EG) and binder. The composite adsorbent (Maxsorb-III (70%), EG (20%), Binder (10%)) gave the adsorption uptake of 0.89 kg/kg, while the other composite (Max­ sorb-III (50%), EG (40%), Binder (10%)) have shown adsorption uptake of 0.61 kg/kg at 30 � C of saturation conditions. The D-R and D-A models have been used to fit adsorption data, and the optimized parameters of the models are furnished in Table 8. Adsorption potential of composite adsorbent of lithium bromide and silica gel (SG/LiBr) for the refrigeration and air conditioning applica­ tions was investigated [51]. It has shown that the adsorption uptake of 0.53 kg/kg at 30 � C of saturation conditions. The composite SG/LiBr have a low surface area of 181 m2/g but exhibit high pore width of 17.2 nm. D-A model well fitted with experimental data and the optimized parameters are presented in Table 8.

Adsorption of CO2 onto various kinds of MOF has been studied in the literature for various adsorption based applications i.e. [16,134,151]. The corresponding adsorption isotherms are presented and compared in Fig. 18. MOF-200 and MOF-210 possess the highest CO2 adsorption uptake of 2.40 kg/kg at 25 � C and 5000 kPa [152]. MOFs namely MOF-5, MOF-177, MOF-200, MOF-205, and MOF-210 were prepared by linking zinc acetate Zn4O(CO2)6 unit to the different organic carboxylate or benzoate linkages. They possess high BET surface area as follow MOF-200 (4530 m2/g), MOF-205 (4460 m2/g) and MOF-210 (6240 m2/g). In another study, nine different kinds of MOFs, i.e. lMOF-2, MOF-505, Cu3(BTC)2, MOF-74, MOF-177, IRMOF-1, IRMOF-3, IRMOF-6 and IRMOF-11 were studied for CO2 storage [153]. MOF-177 shows maximum CO2 adsorption uptake of 1.47 kg/kg at ambient air temperature and 4200 kPa. IRMOFs shows better adsorption uptakes

7. Metal organic frameworks (MOF) based adsorption cooling Metal organic frameworks (MOFs) are well-known for their ultrahigh porosity, higher surface areas and flexibility in their internal geometry. The porosity of MOFs is typically greater than 50% of its volume and possess high surface area (i.e. 1000-10,000 m2/g), which is far more than any available adsorbents [148]. MOFs are formed by the

Fig. 20. Adsorption isotherms of H2O on to different polymers: [94], PS II (25 � C) [94]. 31

PS I (25 � C)

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than other assorted MOFs. While MOF-2, MOF-505, MOF-74, and Cu3(BTC)2 shows the sharp rise in adsorption uptake at low pressure range. Volumetric adsorption of CO2 on to HKUST-1 and MIL-101(Cr) was simulated by grand canonical Monte Carlo simulation model [154]. The pore volume and BET surface area for HKUST-1 are 0.78 cm3/g and 1850 m2/g, respectively. While, MIL-101(Cr) possesses a BET surface of 3302 m2/g and a total pore volume of 1.54 cm3/g at P/Po ¼ 0.98. The HKUST-1 and MIL-101(Cr) resulted in CO2 adsorption capacities of 0.356 kg/kg and 0.316 kg/kg, respectively, at 30 � C and 1000 kPa. Three different types of MOF i.e. MIL-53, MIL-96, and amino-MIL-53 for CO2 adsorption under static and dynamic conditions were analyzed [155]. These adsorbents exhibit BET surface area of 1519 m2/g, 687 m2/g, and 262 m2/g respectively. CO2 adsorption uptake by MIL-53, MIL-96 and amino-MIL-53 are 64 cm3/g, 124 cm3/g and 48 cm3/g, respectively at 0 � C and 100 kPa. CO2 adsorption on to the aluminum fumarate was investigated for the carbon capturing application [78]. The CO2 isotherms of aluminum fumarate at 30 � C and the pressure of 800 kPa adsorption uptake of 0.22 kg/kg. The isotherms were correlated with Langmuir adsorption isotherm model presented the following model parameters: W0 ¼ 5.90 (mmol/g), b0 ¼ 1.35 � 10 4 (bar 1), Qst ¼ 20928 (J/mol). Similarly, MOF of type UiO-66(Zr)_(COOH)2 for the CO2 adsorption was investi­ gated by Moreira et al. [156]. The adsorbent is acid-functionalized UiO-66(Zr) MOF possess the surface area and pore volume of 568 m2/g and 0.727 cm3/g, respectively. CO2 adsorption measurements at 30 and 600 kPa reveals that it have maximum adsorption capacity of 0.32 kg/kg.

analyzed for the application of locomotive air-conditioning and de­ humidifiers [165]. The investigated MOF includes six types of self-prepared zirconium-based MOFs (841, 812, 808, 806, 805, and 802), five types of zirconium MOFs (PIZOF-2, DUT-67, UiO-66, MOF-801 and MOF-804) and some other porous solids. The water vapor adsorption on these adsorbents showed maximum uptake by MOF-801-P and MOF-841 of 22.5 wt% and 44 wt% at a relative pressure of 0.1 and 0.3 respectively, for 25 � C. MIL-101 (Cr) was doped with alkali metal ions (Liþ, Naþ, Kþ) to analyzed their effect on the water vapor adsorption and adsorption rate as compared to parent MIL-101 (Cr) [166]. After doping, the surface area and pore volume of doped become less than parent adsorbent. Adsorption isotherm data found to be of S-type isotherms. The parent MIL-101 (Cr) give the higher water adsorption uptake of 1 kg/kg at 25 � C of saturation condition. Hydrophobic length of parent MIL-101 (Cr) was found to be higher at lower pressure range up to 0.35 P/Po, and it shows higher water uptakes than doped MIL-101 (Cr) at high pressure. While in another study, the post-synthetic modification of MIL-101Cr was made with the amino and nitro functionalities in order to increase its water adsorption capacity [167]. As compared to non-modified MIL-101Cr, the amino-functionalized MIL-101Cr-NH2 possess good water uptake of 1.06 kg/kg and nitro-functionalized MIL-101 Cr-NO2 show less water uptake of 0.44 kg/kg at 20 � C and relative pressure up to 1. The difference in adsorption capacities of both functionalized MIL-101Cr is due to the large variation in their BET surface area and pore volume i.e. MIL-101Cr-NH2 and MIL-101 Cr-NO2 possess surface area and pore volume of 2690 m2/g, 1.44 cm3/g and 1245 m2/g, 0.58 cm3/g respectively. MIL-100(Al, Fe) MOFs were investigated for heat transformation application [168]. MIL-100 (Fe) and MIL-100 (Al) possess surface area and pore volume of 1917 m2/g, 1.00 cm3/g and 1814 m2/g, 1.14 cm3/g respectively. Water adsorption uptake by the MIL-100 (Fe) (0.77 kg/kg) is higher than the MIL-100 (Al) (0.51 kg/kg) for 25 � C and relative pressure up to 1 as shown in Fig. 19. The water adsorption isotherms of MIL-100(Fe), is in very good agreement as reported by Küsgens et al. [161]. Similarly, these MOFs are also studied by Kim et al. [169] and found the same isotherms of type IV with two steps, as shown in Fig. 19. Results show that water adsorption does not significantly affect by the type of unsaturated metals (Fe, Al and Cr) in MIL-100 (M). In another study by Wickenheisser et al. [170], MIL-100(Cr) is grafted with ethylene glycol (EG) and diethylene glycol (DEG) shows a slight improvement in the water adsorption uptake while having 50% less BET surface area, as compared to non-modified MIL-100(Cr). This is prob­ ably due to the increase in hydrophilicity of material after modification. Water adsorption by MOF of type Basolite™ A100 and Basolite™ F300 was measured for the adsorption heat pump processes by Hen­ ninger et al. [171]. Basolite™ A100 have BET surface area of 1300–1600 m2g–1 while Basolite™ F300 structure is unknown. Basolite™ F300 and Basolite™ A100 give the water adsorption uptake of 0.34 kg/kg and 0.37 kg/kg, respectively, at 25 � C and relative pressure of 0.9. Similarly, MOF of type CAU-10-H was studied for the investigation of its water adsorption behavior [172,173]. CAU-10-H give adsorption isotherm of s-shape with a steep increase in adsorption uptake up to 0.3 kg/kg at a low relative pressure range of 0.15–0.25.

7.3. MOF/H2O Adsorption of H2O onto various kinds of MOF has been studied in the literature for adsorption cooling and heating applications [157–159]. The corresponding adsorption isotherms are presented and compared in Fig. 19. The highest water adsorption uptake was attributed to MOF MIL-101Cr of 1.43 kg/kg at 25 � C and relative pressure up to 0.9 [160]. In a study by Küsgens et al. [161], the studied MOFs exhibit BET surface area of MIL-101 (3017 m2/g), HKUST-1 (1340 m2/g), ZIF-8 (1255 m2/g), MIL-100(Fe) (1549 m2/g) and DUT-4 (1360 m2/g) [161]. They show thermal stability toward the water and are hydrophilic in nature. In addition, HKUST-1 and DUT-4 possess instability toward the water, but the former is highly hydrophilic while later shows hydrophobic characteristics. Among the studied MOFs MIL-101 give higher water adsorption of 1664 cm3/g (1.34 kg/kg) at 25 � C and relative pressure up to 1 [161]. In another study by Ehrenmann et al. [162], the MOF adsorbent MIL-101 give a lower water adsorption uptake of 1.01 kg/kg at 25 � C as compared to that reported by Küsgens et al. [161]. MOFs of type CPO-27(Ni) and aluminium fumarate was studied for water vapor sorption, which shows higher adsorption uptake by aluminum fumarate of 0.53 kg/kg as compared to CPO-27(Ni) of 0.47 kg/kg, at 25 � C and relative pressure of 0.9 [71]. They showed type I and type IV isotherms respectively. BET surface area of aluminum fumarate is 893.965 m2/g which is higher than CPO-27(Ni) of 469.777 m2/g. The water adsorption isotherms of aluminum fumarate are in good agree­ ment as reported by Jeremias et al. [163]. Therefore, give the same type IV isotherms with a steep increase in a narrow relative pressure range of 0.2–0.3. However, microporous aluminum fumarate (μp-AF) have slightly lower maximum water adsorption of 0.48 kg/kg, at 25 � C and relative pressure of 0.9, as compared to that reported by Elsayed et al. [71]. HKUST-1 for the adsorption of water vapor was investigated [164]. Water adsorption shows type-IV isotherms that give two rises in the adsorption isotherms. It showed adsorption uptakes of 31 mmol/g (0.546 kg/kg) at 25 � C and to 3.05 kPa. Dual Site Langmuir-Freundlich model well predict water isotherms of HKUST-1. Similarly, water vapor adsorption of twenty different MOFs was

7.4. Polymeric adsorbent/H2O The water vapor adsorption isotherms and kinetics on to Polymeric adsorbents i.e. PS-I and PS-II were experimentally measured [94,174]. Adsorption experiment was done by the magnetic suspension adsorption unit for the temperature range of 20–80 � C. The water adsorption uptake by PS-I and PS-II are 0.648 kg/kg and 0.88 kg/kg, respectively, at 30 � C of saturation conditions as presented in Fig. 20. GAB model (see Table 1) well predicts the adsorption data for fitting range of (0.01–0.9) P/Po at selected temperatures. The model parameters for PS-I/water pair are Mmo (kg/kg) ¼ 0.058, Co ( ) ¼ 0.256, Ko ( ) ¼ 1.155, qm (kJ/kg) ¼ 32

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202.378, ΔHc (kJ/kg) ¼ 433.408 and ΔHk (kJ/kg) ¼ 60.48. and for PS-II/water pair are Mmo (kg/kg) ¼ 0.0418, Co ( ) ¼ 0.143, Ko ( ) ¼ 1.7944, qm (kJ/kg) ¼ 308.528, ΔHc (kJ/kg) ¼ 489.02 and ΔHk (kJ/kg) ¼ 129.89. But at lower relative pressure adsorption data is not consistent with the fitted values of GAB model. On contrary the BET model does well in lower relative pressure range of 0.05–0.35.

various applications. There is a believe among the researchers that these systems could have bright future in terms of environmental impact. Consequently, researches have been conducted in several directions to develop these systems and to avoid their shortcomings, which is sum­ marized in low efficiency. The researches pursued several ways including trying to raise the system efficiency by providing sophisticated designs and materials with minimum energy loss. One of the methods is to find new material(s) that could have the ability to adsorb larger amount of adsorbate for wide range of system applications. Therefore, this review is mainly focused on the adsorption equilibrium amount by various adsorbent-adsorbate pairs. It is evident that the research is well underway in desperate attempts to develop energy-efficient systems and to commercialize them accordingly, in order to replace the traditional technology. Researchers adopted multi-bed and/or multi-stage strate­ gies with novel adsorbent-adsorbate pairs to enhance the system per­ formance. The efficiency of these system has relatively improved e.g. the SCP was used to less than 100 m3/ton/day, however, some recent re­ searches showed that it can be reached to 400 m3/ton/day. It indicates that the adsorption cooling systems are coming strongly to the com­ mercial market and we may soon see one of these systems sold commercially.

8. Comparative summary A comparative adsorption uptake of various adsorbates onto different kinds of ACs show the highest adsorption uptake was attributed in case of R-32 adsorption onto phenol resin-based AC i.e. 2.23 kg/kg (excess adsorption) and 2.34 kg/kg (absolute adsorption) at 30 � C and 1670 kPa. Maxsorb-III being highly microporous possess higher surface area and shows good adsorption uptakes for most of the adsorbate. The adsorption uptake of R-134a pair by Maxsorb-III was found 2.10 kg/kg at 30 � C of saturation conditions. Similarly, Maxsorb-III shows the promising results for the adsorption of CO2, R507A and n-butane. In addition, Maxsorb-III-methanol pair have high SCE of 731 kJ/kg for desorption, adsorption and evaporator temperatures of 90 � C, 30 � C and 7 � C, respectively. The adsorption uptakes of silica gel-water pairs are relatively lower as compared to ACs. RD-type silica gel shows water adsorption uptake of 0.4465 kg/kg at 31 � C and 4.43 kPa. However, type Aþþ silica gel though possesses maximum surface area of 863.6 m2/g and gave the adsorption uptake of 0.432 kg/kg at 25 � C of saturation condition. H2O and CO2 adsorption uptakes by zeolite adsorbents are even lower than silica gel adsorbents. Zeolite binderless 13X gives the maximum water adsorption of 0.341 kg/kg at 30 � C of saturation con­ ditions. While zeolite 13X adsorbent exhibit the maximum CO2 adsorption uptake of 0.324 kg/kg at 25 � C and 3200 kPa. In some cases, zeolite-water pairs show the adsorption isotherm of S-type or type V, i.e. AQSOA-Z01 AQSOA-Z02 and AQSOA-Z05. Thus, it indicates the pore filling phenomena that enable higher adsorption uptake for a narrow range of pressure. In addition, natural zeolite though has low water uptake but have a low dependency on condenser and evaporator temperature. A comparative H2O and ethanol adsorption uptake by various com­ posite adsorbents showed that the CaCl2/MWCNT composite adsorbent exhibit highest water adsorption uptake of 0.97 kg/kg at 37 � C and 3.4 kPa. In case of ethanol, adsorption uptake by the consolidated com­ posites (Maxsorb-III (70%)-EG (20%)-Binder (10%)), (Maxsorb-III (50%)-EG (40%)-Binder (10%)) and (Maxsorb-III (90%)-Poly IL [VBTMA][Ala] (10%)) are lower than parent Maxsorb III. However, the thermal conductivity of the composites is far better than the parent Maxsorb-III. MOF of type MIL-200 and MOF-210 showed highest CO2 adsorption uptakes, i.e. 2.40 kg/kg. However, the highest water adsorption uptake is belonging to MIL-101Cr, i.e. The highest water adsorption uptake was attributed to MOF MIL-101Cr of 1.43 kg/kg at 25 � C and relative pres­ sure up to 0.90 [173]. It exhibits large step rises in adsorption uptake for a high relative pressure range of 0.40–0.50. Similarly, the water adsorption uptake by polymeric adsorbents, i.e. PS-I and PS-II are 0.648 kg/kg and 0.88 kg/kg, respectively, at 30 � C of saturation conditions. More detailed research is still required to develop/find out the optimum adsorption working pair for various applications.

10. Conclusions Hundreds of studies have been reported in the literature for the development of energy-efficient thermally-driven adsorption cooling systems. It is always challenging to find optimum adsorbent-adsorbate pair for a typical application of the adsorption cooling system. Perfor­ mance of a working pair is mainly related to the physical structure of the adsorbent, adsorption equilibrium and adsorbent-adsorbate in­ teractions. Therefore, this study aims to provide a comprehensive review and comparison accordingly using several kinds of adsorbent-adsorbate pairs. Adsorption uptake data are classified and compared accordingly by means of adsorption isotherms. The parameters of adsorption iso­ therms models are collectively listed and reviewed accordingly. The study covers a various class of adsorbents like activated-carbons (ACs), silica gel, zeolites, composites and metal organic frameworks (MOFs). Among the studied ACs, the maximum adsorption uptake was attributed in case of R-32 adsorption onto phenol resin-based AC, i.e. 2.23 kg/kg (excess adsorption) and 2.34 kg/kg (absolute adsorption) at 30 � C and 1670 kPa. In addition, adsorption uptake of R-134a pair by AC of type Maxsorb-III was found 2.10 kg/kg at 30 � C saturation conditions. Similarly, Maxsorb-III is found promising adsorbent for adsorption of CO2, R507A and n-butane. In case of water adsorption by silica-gel, zeolite and polymeric adsorbents the promising adsorbents are RDType Binderless 13X and PS-II, respectively. The adsorbents MIL-200 and MOF-210 from the studied MOFs pairs possessed maximum CO2 adsorption uptakes as high as 2.40 kg/kg at 25 � C and 5000 kPa. Pre­ dominantly, Maxsorb-III have the most promising surface area and pore volume of 3045 m2/g and 1.70 cm3/g, respectively. However, its surface treated sample (KOH6-PR) possess even higher surface area of 3060 m2/ g and pore volume of 1.90 cm3/g. The study is useful for selecting the appropriate adsorbent-adsorbate pair for typical adsorption cooling application. The presented review is useful for the material scientists to develop the appropriate working pair for adsorption systems. Declarations of interest

9. Future of adsorption cooling and limitation for commercialization

There are no interests to declare.

Adsorption phenomenon was discovered a long time ago, however, its measurement and use did not occur until the late eighteenth century. Scientific use of adsorption concept in cooling application was started at twentieth century, when it emerged the need to find alternatives of compression cooling. From that moment, many scientists are interested in the development of energy-efficient adsorption cooling systems for

Acknowledgements This study is financially supported by Bahauddin Zakariya Univer­ sity, Multan under research promotion grant titled “Investigation of agriculture based low-cost ad/sorbents for desiccant air conditioning applications”. The necessary copyright permissions are ensured 33

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accordingly for all copyrighted graphics, images, tables and figures.

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