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JMST Advances

, Volume 1, Issue 1–2, pp 161–180 | Cite as

Emerging sorption pairs for heat pump applications: an overview

  • Bidyut Baran SahaEmail author
  • Kutub Uddin
  • Animesh Pal
  • Kyaw Thu
Review

Abstract

The research efforts to find an alternative system for the cooling/heating application have been intensified worldwide since the imposition of international restrictions on production and use of refrigerants accountable for ODP and GWP. Nowadays, the demand for the cooling/heating system is increased also due to safeguarding the adverse environmental effect which results in additional consumption of electrical energy and ecological problem. The use of adsorption system is considering as a promising alternative for the last few decades. The low heat and mass transfer coefficient of the adsorbent material is the main bottleneck of the adsorption cooling/heating system and resulting in large size and low performance. To make the system commercially competitive with the conventional system, high-performance refrigerant/adsorbent pairs are required. In this review, the favorable achievement in adsorbent development in terms of porous properties and their interaction with natural refrigerants is focused. Current application of different working pairs and their future prospect with special reference to their utilization are studied. Future research direction of adsorption working pairs is also analyzed.

Keywords

Adsorbent Coefficient of performance Heat pump Synthesis 

Nomenclature

A0 ~ A3

Adjustable parameter (−)

B0 ~ B3

Adjustable parameter (−)

\( b_{0} \)

Equilibrium constant (kPa−1 or MPa−1)

\( c_{{{\text{p}},{\text{Ad}}}} \)

Specific heat capacity of adsorbent (J g−1 K−1)

\( c_{{{\text{p}},{\text{ref}}}} \)

Specific heat capacity of refrigerant (J g−1 K−1)

\( E \)

Adsorption characteristic energy (kJ mol−1)

\( t \)

Heterogeneity constant in Tóth equation (–)

hf

Fluid enthalpy (kJ kg−1)

\( h_{\text{fg}} \)

Latent heat of vaporization (kJ kg−1)

\( k \)

Freundlich constant (–)

\( n \)

Exponent of D-A equation (–)

\( P \)

Pressure (kPa or MPa)

\( P_{\text{c}} \)

Pressure at critical point (kPa or MPa)

\( P_{\text{s}} \)

Saturation pressure (kPa or MPa)

\( Q \)

Heat energy (J)

Qst

Isosteric heat of adsorption (kJ kg−1)

\( q \)

Volumetric adsorption uptake (cm3 g−1)

\( q_{0} \)

Maximum volumetric adsorption capacity (cm3 g−1)

\( R \)

Gas constant (J mol−1 K−1)

\( T \)

Temperature (°C or K)

\( T_{\text{C}} \)

Temperature at critical point (°C or K)

TPh

Preheating temperature (°C)

\( V_{\text{m}} \)

Molar volume (cm3 g−1)

vm

Pore volume of the adsorbent (cm3 g−1)

Vt

Specific volume of liquid carbon dioxide (cm3 g−1)

\( W \)

Equilibrium uptake (kg kg−1)

\( W_{0} \)

Maximum equilibrium uptake (kg kg−1)

z

Constant for pseudo saturated vapor pressure (−)

Greek symbols

\( \alpha \)

Thermal diffusivity (m2 s−1)

\( \alpha^{*} \)

Thermal expansion of the adsorbed gas (K−1)

\( \rho \)

Density (kg m−3)

\( \Delta W \)

Effective uptake (–)

Subscripts

Ad

Adsorbent

Ads

Adsorption

Cond

Condenser

Des

Desorption

Eq

Equilibrium

Evap

Evaporator

Lat

Latent heat

max

Maximum

min

Minimum

ref

Refrigerant

s

Saturation

sat

Saturation

Sen

Sensible

th

Theoretical

Tot

Total

1 Introduction

Research on alternative cooling/heat pump technology got momentum after noticing the worldwide energy crisis in 1970 [1]. Due to the increasing trend of global energy consumption, it is urgent to find ways to use energy resources efficiently. According to global energy sources, 15% of the total energy is consumed by air conditioning and refrigeration technologies [2]. For a residential building, almost half of the primary energy is consumed by the cooling/heating technology [3]. The main reason behind the consumption of a high amount of energy is the usage of the mechanical compressor in the conventional heat pump system.

Adsorption cooling/heat pump system does not use a mechanical compressor for continuous operation; instead, it uses a thermal compressor. This compressor relies on natural adsorption and desorption phenomenon. The adsorption happens at low temperature and pressure, whereas desorption happens at high temperature and pressure. This system has many advantages over the vapor-compression system, which includes, almost no use of primary energy, use natural refrigerant, vibration, noise free, etc. [4]. Low-grade thermal energy can easily drive the system which is abundant in the present world.

The history of working on the adsorption cooling system is not new. Before the 1970s, the studies of adsorption process extensively considered for gas separation [5, 6, 7], purification [8, 9], and catalysis [10, 11]. A few studies found where the adsorption processes were tried to use for cooling or heating system. The earliest record was the ammonia adsorption onto AgCl, found by Faraday in 1848, to produce cooling effect. In the 1920s, Hulse [12] suggested a refrigerator to store food on cargo wagon that utilized silica gel-SO2 as the working pair and reached the evaporation temperature of about − 12 °C. Plank and Kuprianoff [13] developed an activated carbon–methanol adsorption refrigeration system in 1929. An adsorption refrigerator was used on the train from London to Liverpool in 1940–1945, with CaCl2-NH3 as adsorption working pair and water vapor at 100 °C as the heat source [14].

However, due to the availability of electrical power and development of CFC refrigerants, vapor-compression cycle became the dominant refrigeration cycle and the sorption technology did not lead to vast commercialization until the 1970s. In the 80’s, environmentalist raises their voices against the emission of CFCs which is identified as the major contributor to deplete the ozone layer around the globe and adds to the greenhouse effect. It is expected that the global energy demand and CO2 emission will increase almost 60% by 2030 compared to the beginning of this century [15]. Consequently, Montreal Protocol on substances that deplete the ozone layer (1987) and Kyoto Protocol on greenhouse gas emission (1997) were signed to stop the production and utilization of environmentally unfriendly gases [16, 17, 18, 19]. Considering these aspects, research interest on environment-friendly adsorption cooling/heating system got momentum. The modern revival of this technology started after the 1970s when Meunier (1978) and Tchernev (1979) began to work on adsorption pairs suitable for use as solar refrigerators. Nowadays, this study is undertaken with the objective of the rational use of primary energy, using solar energy or low-grade waste heat to run the system along with the use of totally environment-friendly refrigerants [20, 21, 22, 23, 24, 25, 26]. Adsorption systems are also used for desalination and cooling. These systems can be operated using low-temperature waste heat and can produce potable water together with the cooling [27, 28, 29].

Figure 1 illustrates the general layout of heat-driven systems. The performance of the adsorption cooling/heat pump and desalination system mostly depends on the porous properties of the adsorbent together with the selection of refrigerants. A significant achievement is observed recently to develop highly porous adsorbing materials varying activation procedure of precursor materials. The different synthesis process is applied to confirm the stability and repeatability of the material after improving its porous properties. Table 1 represents the porous properties of some commonly used adsorbent found in the open literature. On the other hand, selection of refrigerants depends on its adsorption capacity at a certain temperature and pressure as well as its environmental impact. Many type adsorbent/refrigerant pairs have been studied in the last few decades considering its application area and thermophysical properties [30, 31, 32, 33]. The performance of different working pairs is related to the adsorbed amount, the adsorption heat, the adaptability to the driving temperature and to the desired application area [4].
Fig. 1

Application of adsorption–desorption phenomenon for thermal comfort

Table 1

Porous properties of popular adsorbents

Adsorbent

Surface area (m2 g−1)

Pore volume (cm3 g−1)

Pore size (nm)

References

Silica gel A

716

0.28

0.8–5

[137]

Silica gel RD

838

0.37

0.8–7.5

[137]

Silica gel 3A

606

0.45

3.0

[138]

AQSOA Z01

132

0.081

0.74

[79]

AQSOA Z02

590

0.2769

0.37

[79]

LiBr/silica

181

0.73

15

[139]

SRD 1352/3

2613

0.65

0.56

[132]

WPT-AC

2927

2.51

1.68

[140]

Maxsorb III

3045

1.7

1.12

[141]

H2-Maxsorb III

3029

1.73

1.15

[141]

KOH-H2-Maxsorb III

2992

1.65

1.11

[141]

KOH4-PR

3060

1.9

1.25

[93]

KOH6-PR

2910

2.53

1.78

[93]

M-AC

2924

2.18

1.47

[140]

AC-35.4

1200

0.69

2.3

[142]

ACF

2200

1.0

2

[143]

AX21

3106

1.29

[144]

BPL

1150

0.43

[145]

Norit R1 Extra

1450

0.47

[145]

Activated carbon A

1207

0.54

[145]

ACF (A-20)

1900

1.028

2.16

[146]

ACF (A-15)

1400

0.765

2.175

[146]

GAC (AquaSorb 2000)

1050

1.04

280

[147]

AC-WS-480

1231.3 ± 1.5

0.663 ± 0.005

Microporous

[148]

AC-207EA

951.0 ± 20

0.464 ± 0.005

Microporous

[148]

CSAC

804.02

0.43

1.76

[149]

Norit RB3 (steam-activated rod)

978.04

0.51

2.10

[150]

Norit Darco (ND) (100 mesh size)

876.45

0.73

3.33

[150]

ND (12 × 20 US mesh size)

462.67

0.50

4.28

[150]

FR20

2180

0.75

0.59

[132]

F30/470

993.5

0.497

[135]

AP4-60

1428

0.47

0.64

[132]

ATO

1745

0.64

0.59

[132]

COC-L1200

1412

0.49

0.59

[132]

AQSOA-Z01

189.6

0.071

1.178

[151]

AQSOA-Z02

717.8

0.27

1.184

[151]

AQSOA-Z05

187.1

0.07

1.176

[151]

Zeolite 13X

643

0.33

0.605

[152]

AlFum MOF

821

0.44

1.1  and 1.6 

[134]

AlFum MOF (DMF based)

792

0.48

[134]

MIL-101(Cr) MOF

2235

1.22

[153]

MIL-101

3402.69

1.59

1.8469 and 2.3129

[154]

Li-MIL-101

2054.03

0.94

1.8469 and 2.3129

[154]

Na-MIL-101

2000.66

0.91

1.8469 and 2.3129

[154]

CAU-10

553.32

0.25

0.5996, and 1.1258

[154]

HKUST-1

1850

0.78

2.64

[89]

MOF-177

3275

1.69

2.65

[155]

MAX-MIL composite

2670

1.27

1.9 and 2.4

[153]

Table 3 furnishes equilibrium adsorption parameters of several widely used adsorbent/refrigerant pairs which are studied experimentally. Based on the application area, these pairs are categorized into cooling, refrigeration, heat pump, and cooling cum desalination. The drawbacks of this environment-friendly system are the low coefficient of performance (COP) and large geometry which hinders commercially dissemination. To improve the performance of the thermal compressor, the design of the bed and its arrangement in the system are important together with the utilization of minimum heat source temperature and heat recovery scheme. The intensification of specific cooling power is urgent to reduce the size of the system for its widespread commercialization. Saha et al. [34, 35] studied single-stage, two-bed silica gel/water adsorption chiller which can be operated by the heat source of temperature below 100 °C. In another endeavor, authors have investigated the three-bed, four-bed, or even multi-bed adsorption chillers from the perspectives of increasing efficiency and smoothen the delivered chilled water temperature [36, 37, 38]. To use heat source temperature below 70 °C, multi-stage and multi-bed approaches were taken by many authors [39, 40, 41, 42, 43]. The adsorption–desalination system is also considered as an emerging process of thermal desalination cum refrigeration and capable of utilizing low-grade heat source [44, 45, 46, 47].

In this review, the development of state-of-the-art adsorbents is reported, and their ethanol and CO2 adsorption capacities are compared with commercial adsorbents. The performance of some widely used refrigerant/adsorbent pairs is calculated using time-independent thermodynamic analysis. Application of different working pairs and their future prospect are focused. The available scope for future research considering different working pairs is also investigated.

2 Adsorbent and refrigerant

Adsorbent and refrigerant are the key components to design an adsorption system. The commonly used adsorbents are the porous material with higher adsorption affinity towards adsorbate molecules. Followings are the important parameters to select the adsorbent and the refrigerant for sorption application. Some commonly used highly porous adsorbent material are presented in Table 1.

2.1 Choice of adsorbent

  • Adsorption of a large amount of the adsorbate under low-temperature conditions to yield a good coefficient of performance (COP).

  • Desorption of most of the adsorbate when exposed to low-grade thermal energy.

  • Wide concentration changes in a small change of temperature.

  • Reversibility of adsorption process for many cycles.

  • Possession of high latent heat of adsorption compared to sensible heat.

  • High packing density and thermal conductivity.

  • Non-toxic and non-corrosive.

  • Low cost and widely available.

2.2 Choice of refrigerant

  • The refrigerant latent heat should be high, so the circulation rate of the refrigerant and amount of adsorbent can be minimized.

  • Smaller molecular size to enable it to be adsorbed onto the adsorbent surface.

  • The refrigerant should be much more volatile than the adsorbent so that the two can be separated easily without the need for a rectifier.

  • The absorbent should have a strong affinity for the refrigerant under the condition in which adsorption takes place.

  • Moderate operating pressure is required to adjust the size of the system for reducing pressure drop in the vapor path.

  • Thermally stable with the adsorbent.

  • Non-toxic, non-corrosive, and non-flammable

Moreover, the refrigerants are selected considering the application area and environmental friendliness [4]. Unfortunately, no refrigerants possess all the above characteristics. For example, water has been using as the most common working fluid in adsorption cooling application for its high evaporation enthalpy and environment friendliness, but it cannot operate below 0 °C due to the freezing effect. Ammonia and methanol can overcome this freezing problem, but these two are toxic. Ethanol is not toxic, but its performance is lower than ammonia and methanol. Many refrigerant/adsorbent pairs have been studied so far; few of them are shown based on the application area.

3 Adsorbent material synthesis and characterization

The porous properties of the adsorbent material, for instance: surface area, pore size, pore volume, etc., influence the adsorption capacity and cycle time, the two important parameters for designing adsorption refrigeration, heat pump, and desalination system. Over time, there is a constant demand for larger pores with well-defined pore structures to confine the larger number of guest molecules. The powder form of adsorbent ensures the maximum value of all the properties except thermal conductivity. There are different synthesis techniques to develop suitable adsorbent materials for engineering application. Sometimes, adsorbent surface is treated by chemicals to modify the adsorption isotherm shape and adsorption kinetics.

3.1 Synthesis of adsorbent

To design an adsorption system, the properties of the adsorbent materials and its interaction with adsorbate play an important role. Naturally found adsorbent also requires activation to increase its surface area and pore volume, and clears its pore aperture. Several techniques are used to synthesize adsorbent materials considering the origin of the precursor. Some widely used adsorbents and their synthesis processes are briefly discussed in the following subsections.

3.1.1 Activated carbon (AC)

Activated carbon is a versatile adsorbent for its excellent adsorption properties and its ability for coexistence under different forms, e.g., powder, fiber, and composite, etc. Several methods are found in the open literature to synthesize porous carbon materials from a variety of precursors [48, 49, 50, 51]. Among the processes, physical and chemical activation are popular to prepare highly porous carbon materials. In physical activation, carbonaceous precursor first carbonizes at high temperature to form a char which is then activated with the presence of activating agents like steam and carbon dioxide. For the chemical activation process, carbonization of the precursors happens in the presence of chemical agents. Chemical agents are usually hydrating agents which influence pyrolytic decomposition and prevent the formation of tar [52, 53]. The physiochemical process, which is a combination of the physical and chemical process, is also an effective process to prepare porous activated carbon. Carbonization and activation temperature along with activation time are critical parameters for these processes for the structural evolution of the resultant carbon char [54, 55]. Otowa et al. [56] prepared highly porous activated carbon, namely Maxsorb from crushed petroleum coke. The dried coke was dehydrated at 400 °C for 2 h followed by activation at 600-900 °C under the inert atmosphere. Figure 2 shows the flow of the synthesis process of activated carbon by physical and chemical activation.
Fig. 2

Flow diagram to prepare highly porous AC [70, 71]

3.1.2 Silica gel

The porous silica gels are made from silicon alkoxides or organic salts after sequentially undergoing the process of hydrolysis and condensation, aging, and finally drying and calculations [57, 58, 59]. Natural silica particles contain different metal impurities which diminish the porous properties like surface area and pore volume, also responsible for blockage of pores aperture. Different methods of synthesis of silica nanoparticles and nanocomposites were reviewed by Rahman and Padavettan [58]. Synthesis process focused on the enhancement of adsorption sites and its stability to use as adsorbent materials in engineering applications [22, 58, 60, 61, 62]. Mesoporous silicates based on mobile crystalline material (MCM) were obtained by hydrothermal synthesis and liquid templating mechanism [63, 64, 65, 66, 67, 68]. Nakamura and Matsui [69] prepared silica gel nanotubes from TEOS (tetraethyl-orthosilicate) with the addition of ammonium hydroxide at room temperature. Figure 3 shows the structure of commonly used adsorbents.
Fig. 3

Structure of commonly used adsorbents

3.1.3 Zeolite

Microporous zeolites are inorganic crystalline aluminosilicates with a network of pores of the molecular dimension (pore size: 0.3–2 nm). It is derived from natural or synthetic origins, with structures characterized by a framework of SiO4 and AlO4 tetrahedron primary building units connected with corner sharing of oxygen atoms that enclose pores [72]. Zeolites are found in a meta-stable state through a kinetically controlled hydrothermal crystallization process [73, 74]. Finally, the crystallized zeolites are removed from the synthesis mixture. By varying the synthesis composition and the cation (inorganic and/or organic), a wide variety of zeolites structures can be synthesized [59]. The water sorption properties of the aluminosilicates zeolite can be adjusted by adjusting the composition of Si and Al in the framework composition. Post-synthetic ion exchange presents another tool for tuning zeolite sorption properties [75]. Mesoporous zeolite also synthesized to improve the diffusion limitation imposed by microporous zeolite and to increase the external surface area [76]. Mitsubishi Plastics developed a new aluminophosphate-based zeolite AQSOA-Z01, Z02, and Z05 to use in adsorption chiller and desiccant wheels. The attractive feature of these materials is an ‘S’-shaped isotherm which follows a Type IV or V adsorption behavior that consists of a monolayer–multi-layer adsorption stage at low partial pressure followed by micropore filling at higher partial pressure [77, 78, 79]. This S-shape isotherm leads to an extremely sharp rise in equilibrium moisture content over a narrow range of relative humidity. Figure 4 shows the s-shape water adsorption isotherm data of newly developed zeolite (AQSOA).
Fig. 4

Water adsorption isotherm of zeolite (AQSOA) at three different temperatures [79]

3.1.4 MOFs

Metal–organic Frameworks (MOFs) are a new class of microporous material which has been drawn attention in the last decade. These are composed of an organic linker, dicarboxylic acid, and transition metal. The preparation process of MOFs is conventionally achieved using the so-called modular synthesis method, wherein metal ions and organic ligands are combined to afford a crystalline, porous network. Fine tuning of the parameters like temperature, solvent compositions, reagent ratios, and concentrations and reaction time is important to prepare desired MOFs [80, 81, 82, 83]. The key features of these well-defined structured MOFs are high micropore volume, uniform pore size and enormous surface area, and crystallinity with high metal content which offers potential sorption sites [84, 85, 86, 87, 88]. Figure 3 shows the structure of Cr-soc-MOF which was synthesized for water adsorption. There has been a rapid development in the past decade considering its application area in gas separation, storage and adsorption cooling and desalination, etc. [89]. Millward and Yaghi [90] found very high CO2 uptake onto MOF-177 which was 33.5 mmol g−1 at 35 bar followed by Maxsorb III (25.0 mmol g−1 at 35 bar) and zeolite (7.4 mmol g−1 at 32 bar). For methane adsorption, Mu et al. [85] found that the highest uptake in UMCM-1 was 8.0 mmol g−1 at 24.2 bar. Figure 5 shows the SEM pictures of high-performance adsorbents which are used for water, ethanol, and pressurized gas adsorption.
Fig. 5

SEM pictures of the studied adsorbents: a mesoporous silica gel [91], b AQSOA-Z02 zeolite powders [79], c AC fiber (A-20) [92], d phenol resin-derived AC [93], e waste palm trunk-derived AC [94], and f metal–organic framework (MIL-101Cr) [95]

3.1.5 Composite adsorbent

The low density of powder adsorbent increases the geometry of the adsorption cooling system. It also leads to poor heat transfer inside the bed [96]. Research work to increase the thermal conductivity of the porous adsorbents started in the late 80’s without changing its permeability [97]. Composite adsorbents are synthesized by simple mixture, impregnation, or consolidation [98, 99, 100]. The approach is to make composite adsorbent to increase the heat and mass transfer within the bed using binder together with the thermal conductivity enhancer [101, 102, 103, 104]. Silica gel composites were developed by impregnating hygroscopic salts and found higher uptake and lower regeneration temperature than parent silica gel [105, 106, 107, 108, 109, 110]. A significant improvement was achieved for activated carbon composite using expanded graphite + CaCl2 [111, 112], CaCl2 [99, 113], EG + PVA [114], etc. Figure 6 shows the conventional techniques to prepare consolidated composites.
Fig. 6

Consolidated composite preparation processes [112, 119]

3.1.6 Coated adsorbent

A good coating on the adsorber bed wall increased the overall heat transfer coefficient between the heat transfer medium to the adsorbent [115, 116, 117, 118]. Initial idea was to enhance the poor heat transfer properties of an adsorber by developing consolidated adsorbent bed. Later, coating is considered as a possible solution to achieve high heat and mass transfer efficiency through the adsorber. Coating ensures perfect interaction between the heat exchanger surface and porous adsorbents [26, 120, 121, 122]. Usually, coating can be done by gluing the adsorbent grains on the metal surface or by immersing metal substrate into a liquid solution made of binders [123, 124, 125]. The excess solvent was removed by the heat treatment. The change of adsorption kinetics with the variation of coating thickness was studied by many authors [116, 126, 127, 128]. The extent of the cycle duration depended on the thickness of the zeolite coating and an optimum thickness value maximizing the useful effect obtained from the heat pump existed in the range 50–150 μm for the cases investigated [129]. Bonaccorsi et al. [130] studied a direct synthesis of zeolite coating on metal surfaces for the preparation of coated adsorbent beds for heat pump applications. Figure 7a, b shows the SEM images of zeolite coating on stainless steel and aluminum, respectively.
Fig. 7

Zeolite SAP coating on a stainless steel and b aluminum [130]

3.2 Characterization of adsorbent

After synthesizing the adsorbent materials, characterization is performed by many experimental or theoretical methods. The following subsections describe few but necessary techniques to characterize the adsorbent materials.

3.2.1 Porous properties

High porous properties such as surface area, pore volume, and desired pore size can be attributed to a good adsorbent for gas adsorption in various applications. Higher surface area and pore volume generally mean higher affinity to the adsorbate molecules. Usually, metal–organic frameworks (MOFs) and activated carbon (AC)-based adsorbents possess high surface area and pore volume followed by silica gel and zeolite. However, there is no simple quantitative theory for predicting porous properties without studying gas adsorption isotherm. From the very beginning, N2, He, and Ar gas adsorption experiment have been used for calculating porous properties. However, nitrogen (N2) adsorption is very popular and standard procedures to determine the porous structure of adsorbents. Currently, N2 adsorption/desorption isotherm is measured to understand the porous properties and hysteresis behavior of the adsorbent material [91, 114, 131, 132]. N2 adsorption isotherms were measured at 77 K using volumetric method [91, 94, 119, 132]. The isotherm data were then analyzed by many methods; BET (Brunauer–Emmett–Teller) method was used to determine the specific surface area [94, 114, 119, 133, 134]; t plot was for micropore analysis [91, 135]; alpha-s plot was for external surface area and micropore volume [94]; D–A (Dubinin–Astakhov) was for specific surface area and micropore volume [131], whilst Horvath–Kawazoe [132, 136], NLDFT (Non-Local Density Functional Theory) [114, 119, 134], and BJH (Barrett–Joyner–Halenda) [132] were employed to estimate the pore volume and size. Among the methods, BET and NLDFT, are well-accepted methods in the adsorption science community to determine the specific surface area, pore size, and pore volume. In Fig. 8, the primary axis shows the N2 adsorption–desorption isotherm for activated carbon, whereas the secondary axis shows the N2 adsorption–desorption isotherms for silica gel and zeolite adsorbents. N2 adsorption for AC at lower relative pressure is significantly higher than the silica and zeolite which confirm the microporous property of AC. Figure 9 shows the pore size distribution of high-performance adsorbents where the pore size varies up to 4 nm depending on the adsorbents. Figure 10 presents the maximum equilibrium uptake of ethanol onto various adsorbents with different pore volume. It is found that the ethanol uptake linearly increases with the size of pore volume. The highest pore volume of KOH6-PR and WPT-AC achieve maximum ethanol uptake about 2 kg per kg of adsorbents. Table 1 shows the surface area, pore volume, and pore size of promising adsorbents used for refrigerant adsorption in various applications.
Fig. 8

N2 adsorption/desorption isotherms of various adsorbents

Fig. 9

Pore size distribution of various adsorbents

Fig. 10

Equilibrium ethanol uptake onto various adsorbents with different pore size

3.2.2 Isotherm

Adsorption isotherm is crucial for designing the adsorption system. It presents the maximum amount of refrigerant adsorbed at constant pressure and temperature. The behavior of equilibrium adsorption uptake of a particular pair entirely depends on adsorbent properties and its interaction with the adsorbate molecules. There are two common methods are used to measure the isotherm of various types of pairs used in adsorption cooling/heat pump application, gravimetric, and volumetric [4, 141, 156].

Gravimetric method deals with the direct measurement of the adsorbed amount by weighting the adsorbent at certain equilibrium condition of pressure and temperature [93, 157]. In constant volume variable pressure method (CVVP), the mass of adsorbed refrigerant is basically estimated by measuring the pressure change in a vessel with known volume and temperature [138, 145, 158]. Figures 11 and 12 show the equilibrium uptake data measured by the gravimetric method. It can be seen from the figures that the equilibrium uptake increases significantly with the development of new adsorbents.
Fig. 11

Equilibrium ethanol uptake of newly developed adsorbents

Fig. 12

Equilibrium CO2 uptake of newly developed adsorbents

To describe the isotherm data, there are a good number of fundamental and semi-empirical equations used with success. The adsorption isotherm models namely Freundlich, Langmuir, Tóth, and S–B–K are widely used to describe the water–silica gel pair [34, 159, 160]. Dubinin–Astakhov (D–A) and Dubinin–Radushkevich (D–R) models have been widely used for working pairs operate at pressurized and partial vacuum conditions [161]. Following Eqs. (1)–(8) represent the simplified mathematical formula for the different models:

Freundlich model:
$$ \frac{W}{{W_{0} }} = \left( {\frac{P}{{P_{\text{s}} }}} \right)^{{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 k}}\right.\kern-0pt} \!\lower0.7ex\hbox{$k$}}}} . $$
(1)
Langmuir model:
$$ \frac{W}{{W_{0} }} = \frac{bP}{1 + bP}. $$
(2)
Tóth model:
$$ \frac{W}{{W_{0} }} = \frac{bP}{{\left( {1 + \left( P \right)^{t} } \right)^{{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 t}}\right.\kern-0pt} \!\lower0.7ex\hbox{$t$}}}} }}. $$
(3)
The b and t in Eqs. (2 and 3) can be written as follows:
$$ b = b_{0} \exp \left[ {\frac{{Q_{\text{st}} }}{RT}\left( {\frac{{T_{0} }}{T} - 1} \right)} \right] $$
(4)
$$ t = t_{0} + \alpha \left( {1 - \frac{{T_{0} }}{T}} \right). $$
The temperature dependent Qst in Eq. (4) can be written as follows:
$$ Q_{\text{st}} = Q - \frac{1}{t}\left( {\alpha RT_{0} } \right)\left\{ {\ln \left( {bP} \right) - \left[ {1 + \left( {bP} \right)^{t} } \right]\ln \left[ {\frac{bP}{{\left( {1 + \left( P \right)^{t} } \right)^{{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 t}}\right.\kern-0pt} \!\lower0.7ex\hbox{$t$}}}} }}} \right]} \right\}. $$
S–B–K model:
$$ W = A\left( T \right)\left[ {\frac{{P_{\text{s}} \left( {T_{\text{Eq}} } \right)}}{{P_{\text{s}} \left( T \right)}}} \right]^{B\left( T \right)} , $$
(5)
where A(T) and B(T) can be written as follows:
$$ \begin{aligned} A\left( T \right) = A_{0} + A_{1} T + A_{2} T^{2} + A_{3} T^{3} \hfill \\ B\left( T \right) = B_{0} + B_{1} T + B_{2} T^{2} + B_{3} T^{3} . \hfill \\ \end{aligned} $$
Dubinin–Astakhov (D–A) model:
$$ W = W_{0} \exp \left[ { - \left( {\frac{RT}{E}\ln \left( {\frac{{P_{\text{s}} }}{P}} \right)} \right)^{n} } \right]. $$
(6)
Dubinin–Radushkevich (D-R) model:
$$ W = W_{0} \exp \left[ { - \left( {\frac{{R T}}{E}\ln \left( {\frac{{P_{\text{s}} }}{P}} \right)} \right)^{2} } \right]. $$
(7)
Modified Dubinin–Astakhov (D-A) model:
$$ q = q_{0} \exp \left[ { - \left( {\frac{RT}{E}\ln \left( {\frac{{P_{\text{s}} }}{P}} \right)} \right)^{n} } \right]. $$
(8)
The q in Eq. (8) can be written as follows:
$$ q = WV_{\text{m}} . $$
(9)
The molar volume Vm of adsorbed phase can be calculated using the following equation:
$$ V_{\text{m}} = V_{t} \exp \;\left( {\alpha^{*} \;\left( {T - T_{t} } \right)} \right). $$
(10)
At triple point, the value of parameter Vt of liquid carbon dioxide is 0.84858 cm3 g−1. The thermal expansion α* of the adsorbed gas is 0.0025 K−1 as suggested by Saha et al. [162], and Himeno et al. [145]. Amankwah et al. [163] proposed a modified D-A model for estimating pseudo-vapor pressures that are given by the Eq. (8). This methodology introduces a parameter, z, which accounts for interactions in the adsorbate–adsorbent systems. It is a fitting parameter and can be obtained from experimental adsorption isotherm data:
$$ P_{\text{s}} = \left( {\frac{T}{{T_{\text{C}} }}} \right)^{z} P_{\text{C}} . $$
(11)

3.2.3 Thermal conductivity

Adsorbents employed for adsorption cooling/heat pump systems are mainly powder and granular form. Adsorbent particles are loosely packed in bed due to its highly porous properties. Consequently, their thermal conductivity is very low which hinders the widespread use of adsorption technologies. Table 2 represents the thermal conductivity of some commonly used adsorbents reported in the literature. Their thermal conductivity varies between 0.044 and 0.198 W m−1 K−1 as can be seen from the table. Therefore, it is urgent to enhance heat and mass transfer properties of adsorbents to increase the specific cooling power of the system. The heat transfer in the adsorber bed could be intensified by making consolidated composite adsorbents employing various additives and binders. Synthesis of composites and improvement of thermal conductivity have been studied extensively in the last few years. It was reported that, after making consolidated composites, thermal conductivity increased to a very large value compared to parent adsorbent; for instances 5.8 times [164]; 7 times [103]; 11 times [114]; 150 times [165]; 172% [113, 166]; 78.6% [167]. Thermal conductivity values of recently developed activated carbon-based, silica gel-based, and zeolite-based composite are furnished in Table 2. Figure 13 depicts the improvement of thermal conductivity when composites are synthesized employing binders and additives. It is found that the thermal conductivity increases with the increase of additive in the composites.
Table 2

Thermal conductivity of some commonly used adsorbents reported in the literature

Sample

Thermal conductivity [W m−1 K−1]

References

Parent adsorbent (powder or granular) form

 Silica gel type A

0.174

[138]

 Silica gel type RD

0.198

[138]

 Silica gel type 3A

0.174

[138]

 Silica gel (100–200 mesh)

0.07

[104]

 Maxsorb III (AC)

0.066

[114]

 Granular AC from Chemviron (80–100) mesh)

0.23

[112]

 Coconut shell-AC (type XY-20)

0.36

[103]

 WPT-AC

0.044

[140]

 M-AC

0.052

[140]

 Natural zeolite

0.155

[168]

Composite adsorbents

 Maxsorb III (90 wt%) + PVA (10 wt %)

0.099

[119]

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

0.122

[119]

 80% Maxsorb III, 10% EG, 10% binder

0.140

[114]

 70% Maxsorb III, 20% EG, 10% binder

0.247

[114]

 60% Maxsorb III, 30% EG, 10% binder

0.435

[114]

 50% Maxsorb III, 40% EG, 10% binder

0.605

[114]

 33% AC + 67% ENG-TSA (serial no. 1)

34.2

[112]

 50% Silica gel + 50% ENG-TSA (sample no. S448-0.5)

19.1

[104]

 AC + ENG composite (1:1.5)

2.61

[103]

 Silica gel + PVP composite

0.24–0.28

[167]

 EG (20–30%)-silica gel

10–20

[169, 170]

Fig. 13

Thermal conductivity improvement with the increase of additive in the composite

3.2.4 Surface functional group

To understand the function and usefulness of adsorbent materials, the surface chemistry of the adsorbent is very important [171]. During activation, there is a chance to form functional groups on the surface of adsorbing materials as the activation occurred at very high temperature with the presence of some chemical agents. It is found that the adsorption capacity and kinetics is strongly depended on oxygen or hydrogen-containing functional groups, it can either enhance or decrease the adsorption capacity [172]. During ethanol adsorption, the influence of oxygen functionalities on activated carbon surface increases the adsorption energy by the electrostatic interactions between adsorbate molecules and functional groups formed on the surface [173]. The influence of surface oxygen groups on SO2 physisorption on activated carbons was studied by Furmaniak et al. [174]. Authors found the rise in oxygen contents increase the number of carbonyl groups which causes the sharper isotherms at low coverage, but at high coverage uptake depends only on the total coverage [175]. Kil et al. [176] studied the influence of surface functionality of adsorption behavior, especially when ethanol adsorbed on activated carbon micropores. Authors found the AC which contained an increased amount of surface functional groups, ethanol uptake curve showed a significant decrease in the adsorption amounts, but shortened equilibrium times compared to those with less surface functional groups throughout the entire relative pressure region. The surface functionalization of mesoporous silica gel with organic or inorganic functional groups provides new physical and chemical properties for different applications [177, 178, 179, 180, 181]. The microporous zeolites neither have large external surface nor surface Si–OH groups; that is why, it is difficult to functionalize microporous zeolite which limits its wider applications [73, 182].

Solid-state nuclear magnetic resonance (NMR) has been used to investigate the influence of surface functionalities on adsorption characteristics, such as adsorption amounts and kinetics. The adsorption states of the ethanol molecules in carbon micropores were studied by Kil et al. [176]. Figure 14 shows CH3CH2-OD-adsorbed NMR spectra for three samples reported in [141, 176] where the ACs with higher oxygen functionality yielded broader spectra. The authors concluded that ethanol molecules in micropores of ACs strongly interacted with the surface functionalities and were in oriented adsorption states with the hydroxyl group facing the oxygen-containing surface functional groups.
Fig. 14

H2-NMR spectra of the CH3CH2-OD-adsorbed Maxsorb III series for a narrow chemical shift range

4 Refrigerant/adsorbent pairs

The refrigerant/adsorbent pair is the main part of an adsorption cooling/heat pump system. The pair is selected depending on certain desirable properties which are: application area of the system, adsorption–desorption properties, cost, and availability [30, 33]. Table 3 shows the state of the art of refrigerant/adsorbent pairs experimentally studied around the world. There are many new pairs which could be used in the system to investigate its performance. Performance of some promising pairs listed in the table is compared with commercial adsorbent in terms of effective uptake, specific cooling effect (SCE), and coefficient of performance (COP).
Table 3

Refrigerant/adsorbent pairs for cooling, heat pump, and desalination applications

Application

Pair

Isotherm model

Fitting parameters

Accuracy (%) or R2

References

Refrigeration

Ethanol/KOH4-PR

D-R

W0 = 1.43 kg kg−1; E = 128 kJ kg−1; n = 2

 

[93]

Ethanol/KOH6-PR

D-A

W0 = 1.98 kg kg−1; E = 90 kJ kg−1; n = 1.5

 

[93]

Ethanol/Maxsorb III

D-A

W0 = 1.2 kg kg−1; E = 139.5 kJ kg−1; n = 1.8

 

[141]

Ethanol/H2-Maxsorb III

D-A

W0 = 1.23 kg kg−1; E = 138 kJ kg−1; n = 2

 

[141]

Ethanol/MOF

D-A

W0 = 1.1005 kg kg−1; E = 6527.4 J mol−1; n = 2.6003

± 4.0

[188]

Ethanol/ACF-A20

D-R

W0 = 0.797 kg kg−1; D = 1.716 × 10−6; n = 2.0

 

[146]

Ethanol/ACF-A15

D-R

W0 = 0.57 kg kg−1; D = 1.067 × 10−6; n = 2.0

 

[146]

Ethanol/SG-LiBr

D-A

W0 = 0.68 cm3 g−1; E = 6.9 kJ mol−1; n = 1.8

 

[132]

Ethanol/SRD135-3

D-A

W0 = 0.82 cm3 g−1; E = 8.78 kJ mol−1; n = 1.5

 

[132]

Ethanol/WPT-AC

D-A

W0 = 1.9 kg kg−1; E = 91.55 kJ kg−1; n = 1.43

5.43

[140]

Ethanol/M-AC

D-A

W0 = 1.65 kg kg−1; E = 105.91 kJ kg−1; n = 1.62

3.40

[140]

Ethanol/MIL-101Cr

Tóth

W0 = 1.15 kg kg−1; b0 = 0.342 kPa−1; t = 2.193; Q/RT0 = 17.845; φ = 0.358

 

[95]

Ethanol/Zeolite

D-A

a0 = 1.126 mmol g−1; E = 10,000 J mol−1; n = 2

0.9913

[189]

Methanol/A35-1

D-A

W0 = 0.786 cm3 g−1; E = 11.72 kJ mol−1; n = 1.76

 

[190]

Methanol/AC-207EA

D-A

W0 = 0.33 kg kg−1; D = 1.6 × 10−5; n = 1.655

0.9815

[148]

Methanol/AC-WS 480

D-A

W0 = 0.49 kg kg−1; D = 2.8 × 10−5; n = 1.65

0.9963

[148]

R134a/AC

D-A

W0 = 0.767 cm3 g−1; D = 5 × 10−6 J mol−1; n = 1.7

1.07

[191]

R134a/ACF

D-A

W0 = 1.01 cm3 g−1; D = 3 × 10−5 J mol−1; n = 1.5

1.34

[191]

HFC-152a/Maxsorb III

D-A

W0 = 3.438 cm3 g−1; E = 90.05 kJ kg−1; n = 1.3

 

[192]

HFC-152a/Maxsorb III

Tóth

C0 = 3.4 cm3 g−1; b0 = 1.02 × 10−6 kJ kg−1; t = 0.57; Hst = 324.01 kJ kg−1

 

[192]

R32/Maxsorb III

D-A

W0 = 4.05 cm3 g−1; E = 3939 J mol−1; n = 1.15

0.03

[143]

R32/ACF (A-20)

D-A

W0 = 4.58 cm3 g−1; E = 4098 J mol−1; n = 1.09

0.005

[143]

HFC410A/AC

D-A

W0 = 5.96 cm3 g−1; E = 59.6 kJ kg−1; n = 1.17

 

[193]

HFC410A/ACF (A-20)

D-A

W0 = 3.25 cm3 g−1; E = 72.5 kJ kg−1; n = 1.43

 

[193]

HFC410A/ACF (A-20)

Tóth

W0 = 1.68 kg kg−1; b0 = 1.84 × 10−6 kPa−1; z = 0.83; Hst = 249 kJ kg−1

 

[193]

HFC-404A/GAC (AquaSorb 2000)

D-A

W0 = 1.035 cm3 g−1; E = 98.14 kJ kg−1; n = 1.03

 

[147]

HFC-407C/GAC (AquaSorb 2000)

D-A

W0 = 1.139 cm3 g−1; E = 6885.8 kJ kg−1; n = 1.36

 

[194]

Heat pump

CO2/ACF-A20

Tóth

C0 = 1.56 kg kg−1; b0 = 2.55 × 10−4 MPa−1; t = 0.696; Q = 19.23 kJ mol−1

3.40

[162]

CO2/Maxsorb III

Tóth

q0 = 2.3601 g g−1; b0 = 1.842 × 10−7 kPa−1; t = 0.799; Q = 19296.56 J mol−1

1.716

[195]

CO2/CSAC

Modified D-A

W0 = 5.99 × 10−7 m3 g−1; k = 2.88; E = 9109.96 J mol−1; n = 1.39

0.99

[149]

CO2/AC1

D-A

W0 = 1.09 × 10−3 m3 g−1; E = 4957.91 J mol−1; n = 1.24

0.97

[150]

CO2/AC2

D-A

W0 = 8.98 × 10−4 m3 g−1; E = 5569.79 J mol−1; n = 1.40

0.98

[150]

CO2/AC3

D-A

W0 = 6.20 × 10−4 m3 g−1; E = 5550.04 J mol−1; n = 0.91

0.97

[150]

CO2/AC composite

Modified D-A

W0 = 1.109 cm3 g−1; k = 4.844; E = 5.42 kJ mol−1; n = 1.29

 

[196]

Cooling cum Desalination

Water/SG-A

Tóth

W0 = 0.4 kg kg−1; K0 = (4.65 ± 9) × 10−10 kg kg−1 kPa−1; ΔH = (2.71 ± 0.1) × 103 kJ kg−1; t = 10

 

[137]

Water/SG-RD

Tóth

W0 = 0.45 kg kg−1; K0 = (7.3 ± 2) × 10−10 kg kg−1 kPa−1; ΔH = (2.693 ± 0.1) × 103 kJ kg−1; t = 12

 

[137]

Water/SG-3A

Henry’s law

K 0 1  = 5.2 × 10−12 Pa−1; Qst = 2.38 × 103 kJ kg−1

 

[138]

Water/SG-RD

Henry’s law

K 0 1  = 5.5 × 10−12 Pa−1; Qst = 2.37 × 103 kJ kg−1

 

[138]

Water/zeolite AQSOA Z01

D-A

x0 = 0.21 kg kg−1; E = 4000 J mol−1; n = 5

 

[79]

Water/zeolite AQSOA Z02

D-A

x0 = 0.31 kg kg−1; E = 7000 J mol−1; n = 3

 

[79]

Here, meaning of symbol and its unit are kept as like of reference article

5 Thermodynamic analysis

Thermodynamic analysis helps to predict the system performance using equilibrium isotherm data after fitted with isotherm model [150, 156, 183]. In this section, the effective uptake of some new generation adsorbents is compared with commercial activated carbon, Maxsorb III considering similar operating condition. Effective uptake (ΔW) is the difference between the equilibrium uptakes at adsorption state and desorption state. Figure 15 shows that the ΔW for ethanol/KOH6-PR is 48% higher than ethanol/Maxsorb III pair, considering that evaporator, adsorption, and desorption temperatures are 10, 30, and 85 °C, respectively. Similarly, ethanol/WPT-AC shows 38% higher ΔW than ethanol/Maxsorb III (see Fig. 16). Figure 17 presents the comparison of the volumetric capacity of ethanol/AC composite with ethanol/AC powder and found 22% higher ΔW. Above pairs seem very promising to developed adsorption cooling/refrigeration system. The equilibrium cycle performance analysis is done using isotherm parameters for a particular adsorbent + adsorbate pair [156, 183, 184].
Fig. 15

Comparison between adsorption uptake difference of adsorption cooling cycles using ethanol/KOH6-PR (dashed line) and ethanol/Maxsorb III (solid line) pairs at evaporator, adsorption, and desorption temperatures of 10, 30, and 85 °C, respectively

Fig. 16

Comparison between adsorption uptake difference of adsorption cooling cycles using ethanol/WPT-AC (dashed line) and ethanol/Maxsorb III (solid line) pairs at evaporator, adsorption, and desorption temperatures of 10, 30 and 85 °C, respectively

Fig. 17

Comparison between volumetric uptake difference of adsorption cooling cycles employing ethanol/PIL binder-based composite (solid line) and ethanol/Maxsorb III (dashed line) pairs at evaporator, adsorption, and desorption temperatures of 10, 30, and 85 °C, respectively

In this case, the effects of adsorption kinetics, heat, or mass recovery scheme are not considered. The performance of a thermally driven system might differ with equilibrium performance due to their operating conditions, design, multi-bed, multi-stage scheme, etc. [185, 186].

The specific cooling effect (SCE) is written as follows:
$$ SCE = \left( {W_{\hbox{max} } - W_{\hbox{min} } } \right)\left\{ {h_{\text{fg}} \left( {T_{\text{Evap}} } \right) + \int_{\text{Cond}}^{\text{Evap}} {dh_{\text{f}} } } \right\}. $$
(12)
The coefficient of performance (COP) of the cycle is given as follows:
$$ {\text{COP}}_{\text{Eq}} = \frac{\text{SCE}}{{q_{\text{Tot}} }}. $$
(13)
Here, specific heat input, \( q_{\text{Tot}} \) is the sum of latent heat and sensible heat components as follows:
$$ q_{\text{Tot}} = q_{\text{Lat}} + q_{\text{Sen}} $$
(14)
$$ q_{\text{Lat}} = \int_{{T_{\text{Ph}} ,P_{Cond} }}^{{T_{\text{Des}} ,P_{\text{Cond}} }} {Q_{st} \left( {T,P} \right) \times W\left( {T,P} \right) \times {\text{d}}W} $$
(15)
$$ \begin{aligned} q_{\text{Sen}} &= \int_{{T_{\text{Ads}} }}^{{T_{\text{Des}} }} {c_{{{\text{p}},{\text{Ad}}}} \times dT} + W_{\rm{max} } \times \int_{{T_{\text{Ads}} ,P_{\text{Evap}} }}^{{T_{\text{Ph}} ,P_{\text{Cond}} }} {c_{{{\text{p}},{\text{ref}}}} \left( {T,P} \right) \times {\text{d}}T} + \\ &\quad \int_{{T_{\text{Ph}} ,P_{\text{Cond}} }}^{{T_{\text{Des}} ,P_{\text{Cond}} }} {W\left( {T,P} \right) \times c_{{{\text{p}},{\text{ref}}}} \left( {T,P} \right) \times {\text{d}}T} . \\ \end{aligned} $$
(16)

The adsorbed phase-specific heat capacity is assumed to be equivalent to the heat capacity of the refrigerant at a particular temperature and pressure.

In adsorption cycle for refrigeration/cooling applications, the cooling load is estimated by the latent heat of evaporation of refrigerant, whilst the isosteric heat of adsorption is considered as the minimum heat input to run the cycle. Invoking the conservation of mass for the cycle, the theoretical COP of the adsorption cycle for various surface loadings is written as follows:
$$ {\text{COP}}_{\text{th}} = \frac{{h_{\text{fg}} \left( {T_{\text{Evap}} } \right)}}{{Q_{\text{st}} \left( {T_{\text{Des}} ,P_{\text{Cond}} } \right)}}. $$
(17)

During calculation, the preheating temperature (TPh) and the precooling temperature (TPc) are determined using the shooting method in place of the graphical method to eliminate the uncertainties associating with graphical technique. The heat input component is calculated assuming a linear temperature rise in the adsorbent from adsorption temperature to the desorption temperature. The thermodynamic properties of the refrigerants are taken from CoolProp library functions, whilst the calculations are performed using Mathematica v10.3 [187].

The specific cooling effect (SCE) and coefficient of performance (COP) for an adsorption cooling cycle are calculated based on isothermal parameters of different refrigerant/adsorbent pairs presented in Table 3. The operating temperatures for evaporation, adsorption, and desorption are assumed 7, 25, and 80 °C, respectively. Figure 18 shows the SCE of different pairs which are able to work for refrigeration, cooling/desalination system. It can be seen from the figure that the ethanol pairs show higher SCE than methanol and water pairs. Higher SCE of ethanol pairs coincides with its higher adsorption capacity (see Table 3). Especially, the newly developed adsorbents KOH6-PR, WPT-AC, and M-AC show SCE are 887.2, 824.6, and 809.3 kJ kg−1, respectively. The SCE for ethanol/Maxsorb III is found 592.9 kJ kg−1 considering the same operating condition. Though the adsorption capacity of water is lower than ethanol, its large amount of evaporation enthalpy influences the SCE. Water has another advantage as it can be used in a desalination system to produce potable water together with cooling. The adsorbents zeolite AQSOA and silica gel RD are found promising for water adsorption.
Fig. 18

SCE of different sub-atmospheric refrigerant/adsorbent pairs

For the pressurized refrigerant/adsorbent pairs, Fig. 19 shows R410/ACP achieved highest SCE (79.5 kJ kg−1) followed by CO2/Maxsorb III (60.6 kJ kg−1) and CO2/composite (45.7 kJ kg−1). The refrigerant R410 is facing strong criticism due to its higher GWP (= 1900). Figure 20 plots the equilibrium COP and theoretical COP to visualize the gap between these two COPs. Some pairs work at lower operating pressure show the COPEq is closer to COPth whereas the pressurized working pairs show significantly lower COPEq than COPth. It can be seen that there are a lot of scopes to work on CO2-based system to boost its COPEq.
Fig. 19

SCE for different pressurized refrigerant/adsorbent pairs

Fig. 20

Comparison of COP (equilibrium and theoretical) for different refrigerant/adsorbent pairs

6 Scope of future study

In the most of the cases, the maximum adsorption happens at the low relative pressure which is the key problem of adsorbents for cooling applications. It means that the effective working capacity over the cooling cycle is only a small part of the total adsorption capacity of the adsorbent. There is a chance to modify the isotherm shape by adjusting pore size, framework structure, and composition.

The consolidated adsorbent composite improved the thermal conductivity considerably. It can be seen in Fig. 21 that the thermal conductivity increases when the ratio of binder and additives in the composite increases, whereas the amount of parent AC decreases in the composite which results in lower adsorption uptake. The packing density is another factor which influences the thermal conductivity. Though some development is observed recently to optimize the mixing ratio, but still the performance of the composite is far below the expected line which indicates the scope of the future study. R&D is required to develop adsorbent, binder, and additive to reach closer to the target level.
Fig. 21

Adsorption uptake and thermal conductivity of consolidated activated carbons composite as a function of adding binder and additives

According to the result of the thermodynamic analysis performed in this study, the theoretical COPth is much higher than that of equilibrium COPEq especially for pressurized pairs. The performance gap can be reduced by improving COPEq in a system.

7 Conclusions

Adsorption cooling/heat pump systems are considering as a promising alternative to the mechanical system not only to serve the need for cooling/heating but also to meet the demand for energy conservation. The environmental benefit of these thermally driven technologies is also impressive. Difficulties to improve its performance are overcoming day by day with the development of innovative adsorbents and system design.

It is exciting that some authors reported the finding of new adsorbent materials with excellent thermophysical properties compared to commercial adsorbents. These are named as KOH6-PR, WPT-AC, M-AC, MOFs, and zeolite AQSOA having higher specific cooling effect (SCE) which can lead to reducing the sizes of the chillers. Synthesis of composite adsorbents helps to improve the heat transfer properties of the system. However, those new synthesized materials still need further study for the practical utilization in the system by means of a low-grade heat source.

Notes

Acknowledgements

Authors acknowledge the International Institute for Carbon–Neutral Energy Research (WPI-I2CNER), Kyushu University, Japan for the support.

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Copyright information

© The Korean Society of Mechanical Engineers 2019

Authors and Affiliations

  • Bidyut Baran Saha
    • 1
    • 2
    Email author
  • Kutub Uddin
    • 1
    • 3
  • Animesh Pal
    • 1
    • 4
  • Kyaw Thu
    • 1
    • 4
  1. 1.International Institute for Carbon–Neutral Energy Research (WPI-I2CNER)Kyushu UniversityNishi-kuJapan
  2. 2.Mechanical Engineering DepartmentKyushu UniversityNishi-kuJapan
  3. 3.Faculty of PhysicsJagannath UniversityDhakaBangladesh
  4. 4.Kyushu University Program for Leading Graduate School, Green Asia Education Center, Interdisciplinary Graduate School of Engineering SciencesKyushu UniversityKasuga-shiJapan

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