ABSTRACT

The main purpose of this report is to provide essential understandings of the waste heat adsorption cooling systems. Adsorption cooling technology can meet the needs for cooling requirements such as air-conditioning, food and vaccines transportation, comfort cooling, cold storage applications, supermarket display and retails. They almost no moving parts and environmentally friendly for these reasons there is an growing interest in the development and use of adsorption cooling technology owing to their various environmental benefits. The adsorption cooling technology utilise the physical adsorption process where the molecules of the water vapour or gas are bound to the surface of the porous adsorbent by Van-der-Waals forces. These adsorbent are porous materials like silica-gel, zeolite and activated carbons. The main structural feature of the porous adsorbent and refrigerant pair is the amount of adsorbed fluid per unit of dry porous adsorbent Industrial design and development of adsorption cooling systems started in the 1920s by using silica gel and sulphur dioxide. However, this technology was not as popular as the mechanical vapour compression driven cooling system in the 1970s. Two design and development companies, Tchernev and Meunier started work on adsorption working pairs to be used in adsorption cooling systems. This was used for the cooling of vaccines in developing countries. However, because of this development the interest in this type of technology started to grew rapidly in the 1980s with many cooling system researchers worldwide working on a variety of adsorption cooling system. A company called Nishiyodo Kuchou Manufacturing Company (Japan) in 1986, designed and manufactured the first industrial adsorption cooling system. Since then, the adsorption chillers has been used and closely evaluated in a wide area of applications in Japan, Europe and USA with high initial acceptance.

INTRODUCTION The interest in adsorption systems started to increase, firstly due to the oil crisis in the 1970s that lead to a concern about the energy shortage, and then later, in the 1990s, because of ecological problems related to the use of CFCs and HCFCs as refrigerants. Such refrigerants, when released into the atmosphere, deplete the ozone layer and contribute to the Greenhouse effect. Furthermore, with the increase of the energy consumption worldwide, it is becoming even more urgent to find ways of using the energy resources as efficiently as possible. Thus, machines that can recover waste heat at low temperature levels, such as adsorption machines, can be an interesting alternative for a wiser energy management. The conventional adsorption cycle has been presented extensively in the literature and it mainly includes two phases: 1) Adsorbent cooling with adsorption process, which results in refrigerant evaporation inside the evaporator and, thus, in the desired refrigeration effect. At this phase, the sensible heat and the adsorption heat are consumed by a cooling medium, which is usually water or air. 2) Adsorbent heating with desorption process, also called generation, which results in refrigerant condensation at the condenser and heat release into the environment. The heat necessary for the generation process can be supplied by a low-grade heat source, such as solar energy, waste heat, etc. In comparison with mechanical vapour compression systems, adsorption systems have the benefits of energy saving if powered by waste heat or solar energy, simpler control, no vibration and lower operation costs. In comparison with liquid absorption systems, adsorption ones present the advantage of being able to be powered by a large range of heat source temperatures, starting at 50C and going up to 500 C. Moreover, the latter kind of system does not need a liquid pump or rectifier for the refrigerant, does not present corrosion problems due to the working pairs normally used, and it is also less sensitive to shocks and to the installation position. These last two features make it suitable for applications in locomotives, busses, boats and spacecrafts. Although adsorption systems present all the benefits listed above, they usually also have the drawbacks of low COP and low specific cooling power (SCP). However, these inconveniences can be overcome by the intensification of the heat and mass transfer properties in the adsorber, by increasing the adsorption properties of the working pairs and by a better heat management during the adsorption cycle. Thus, most research on this kind of system is related to the evaluation of the adsorption and physical-chemical properties of the working pairs, to the development of predictive models of their behaviour in different working conditions and to the study of the different kinds of cycles

HISTORICAL OVERVIEW OF ADSORPTION/DESORPTION The phenomenon of adsorption/desorption was discovered over two centuries ago by C. W. Scheele in 1773 and by the F. Fontana in 1777. In 1785, they found that when they heated charcoal contained in a test tube it desorbed gases. The gases then adsorbed back when the charcoal was cooled. The nature of adsorption/desorption has always been a controversial one throughout the nineteenth century. In a paper Faraday (1834) discussed the possibility that gases are held onto the surface by an electrical force and suggested that gases could react more easily once they were in the adsorbed state. However, Berzelius (1836) noted that the best adsorbent was highly porous materials. Therefore, Berzelius proposed that adsorption was a process where surface tension or some other force caused gas to be condensed into the pores of a porous media. The idea that most adsorption/desorption processes were really just pore condensations was actively debated in the literature in the 1850s to 1920s. Magnus (1825, 1853) and Magnus [1929] showed that pore condensation does occur. However, other investigators found there was some data that were not in accord with the idea that pore condensation alone explained adsorption/desorption.

TYPES OF ADSORPTION
Types of adsorption will depend upon the vacuum pressure present between vapour or gas molecules and porous adsorbent, adsorption are classified into two types:

1. Physical adsorption (Physisorption): If a force of attraction existing between

adsorbate and porous material surface this is the Vander Waals forces, the adsorption is physical adsorption. In physical adsorption the attraction between the vapour or gas and porous material surface are weak, hence this type of adsorption can be easily reversed by heating. 2. Chemical adsorption (Chemisorption): If the force of attraction existing between vapour or gas and porous material surface are the same strength as chemical bonds, this type of adsorption is named chemical adsorption. In chemisorption the force of attraction is strong therefore chemisorption adsorption cannot be easily reversed. WHAT IS ADSORPTION AND DESORPTION PHENOMENON? The adsorption phase: During the refrigeration phase (or adsorption) the zeolite attracts water vapour and incorporates it in its crystal while releasing heat at the same time. The internal pressure drops and the remaining water cools down and freezes immediately. This allows us to use it for cooling purposes. The desorption phase (regeneration):During the regeneration phase (or desorption), we heat the zeolite, the water molecules inside the zeolite leave the crystal as vapour, and liquefy, bringing the system back to the starting point.

Figure. Adsorption and Desorption phenomenon

ADSORPTION CYCLE DESCRIPTION

Adsorption Cycle: A basic adsorption cycle consists of four steps as shown in figure: 1) Heating and Pressurization, 2) Desorption and Condensation, 3) Cooling and Depressurization, 4) And adsorption and Evaporation. 1) Heating and Pressurization: In the first step, the adsorber is heated by a heat source at a temperature of TH. The pressure of the adsorber increases from the evaporating pressure up to the condensing pressure while the adsorber temperature increases. This step is equivalent to the compression in the vapour-compression cycle. 2) Desorption and Condensation: In the second step, the adsorber continues receiving heat and its temperature keeps increasing, which results in the desorption (or generation) of refrigerant vapour from adsorbent in the adsorber. This desorbed vapour is liquefied in the condenser and the condensing heat is released to the first heat sink at a temperature of TC. This step is equivalent to condensation in the vapour-compression cycle. 3) Cooling and Depressurization: At the beginning of the third step, the adsorber is disconnected from the condenser. Then, it is cooled by heat transfer fluid at the second heat sink temperature of TM. The pressure of the adsorber decreases from the condensing pressure down to the evaporating pressure due to the decrease in the adsorber temperature. This step is equivalent to the expansion in the vapour-compression cycle. 4) And adsorption and Evaporation: In the last step, the adsorber keeps releasing heat while being connected to the evaporator. The adsorber temperature continues decreasing, which results in the adsorption of refrigerant vapour from the evaporator by adsorbent, producing the desired refrigeration effect. This step is equivalent to the evaporation in the vapour-compression cycle. The basic adsorption refrigeration cycle is an intermittent system and the cooling output is not continuous. A minimum of two adsorber are required to obtain a continuous cooling effect (when the first adsorber is in the adsorption phase, the second adsorber is in desorption phase). These adsorber will sequentially execute the adsorption-desorption process.

Figure: Adsorption Cycle

Advantages of adsorption cooling system over absorption cooling system

These systems are attracting increasing attention because they can be activated by low-grade thermal energy and use refrigerants having zero ozone depletion potential and low global warming potential. The adsorption refrigeration system has several advantages compared to the absorption refrigeration system. 1) Wide range of operating temperatures Adsorption systems can be activated by a heat source with a temperature as low as 50C (122F), while the heat source temperature for an absorption system should be at least 90C (194F). 2)No corrosion also adsorption systems have less corrosion issues for the adsorbentrefrigerant working pairs when they incorporate high temperature heat sources compared to an absorption system, while severe corrosion might occur in absorption systems when the regeneration temperature is greater than 200C (392F). 3) No crystallization issue. In the lithium bromide (LiBr)/water absorption system, there is a specific minimum solution temperature for any given LiBr solution concentration below which the salt begins to crystallize out of the solution.2 Crystallization results in interruption of machine operation and possible damage to the unit. By contrast, in adsorption systems the adsorbent remains in a solid state, which means no crystallization issues. 4)Suitability for application where serious vibration occurs Absorption systems cannot operate normally under conditions where serious vibration occurs, such as in fishing boats and locomotives, because the absorbent in these systems, which is in a liquid state, may flow from the generator to the condenser or from the absorber to the evaporator. Adsorption systems are suitable for such applications, because their adsorbents stay in a solid state. ADVANCED ADSORPTION CYCLE Since the efficiency of the basic adsorption refrigeration cycle is low, and the cooling output is not continuous, many advanced adsorption refrigeration cycles have been developed to improve efficiency and practicability.

The mass recovery cycle:

The mass recovery cycle uses refrigerant mass recovery between two adsorbers to effectively increase cooling output and COP of the system. In the end of the desorptionadsorption phase, the high-pressure adsorber is connected to the low-pressure adsorber in a closed loop. The refrigerant in the high-pressure adsorber will be re-adsorbed by the adsorbent in the low-pressure adsorber due to the pressure difference between the two adsorbers. In a mass recovery process, the adsorption quantity of adsorbent is increased, which causes the cooling capacity and COP to increase. The experimental results showed the mass recovery cycle may help obtain a COP increase of more than 10%.21

Figure. The mass recovery cycle

The heat recovery cycle:

The heat recovery cycle is an advanced adsorption cycle used in a system with two or more adsorbers. After the adsorption phase and desorption phase are finished in the adsorbers, the heat from the hot adsorber is transferred to the cold adsorber by circulating heat transfer fluid between them in a closed loop. The experimental results show that the COP of the system will increase by up to 25% with the heat recovery cycle. and only limited thermal energy is required from the heat source since about 65% of the total energy received by each adsorber can be internally recovered

Figure. The heat recovery cycle

Porous Adsorbents Materials

Almost all porous adsorbents materials have the capacity to adsorb water vapour and gases by physical and or chemical forces. The porous media materials used on adsorb purpose are called the adsorbents. The moisture or gases adsorbed can be driven out from the adsorbent by heating, and the cooled 'dry' adsorbents can adsorb moisture or gases again. The popular adsorbents are silica-gel, zeolite, and activated carbon

Figure. Porous Adsorbents Materials

Silica gel:
Silica gels have been the object of many studies in adsorption cooling in recent years. This is due to the adsorption capability of water vapour because of the physical porous structure of silica gel and large surface area. It has the adsorption capability to adsorb 50% of its mass of vapour without changing its mass. The adsorption ability of silica gel increases when the polarity increases. One hydroxyl can adsorb one molecule of water. Each kind of silica gel has only one type of pore, which usually is confined in narrow channels. The pore diameters of common silica gel are 2, 3 nm (A type) and 0.7 nm (B type), and the specific surface area is about 1001000 m2/g. Type A- silica gel is a fine pore silica gel it has a large internal surface area. Having a high moisture-adsorbing capacity at low humidity and is used as an adsorbent in adsorption cooling system. Type B contains large pores so type B adsorbs water vapour at low heat and releases it at high heat so this type of silica gel would be more practical for system design to desorbs water vapour at high humidity and at adsorbs at low humidity. Type C silica gel is also fine pore silica gel. It is known as macro pored silica gel available in spherical this type will also work as a good adsorbent in adsorption cooling system.

Zeolite:
Zeolite is a highly porous adsorbent material, which belongs to the class of aluminasilicates. These adsorbent are characterised by a three-dimensional pore structure. The corresponding crystallographic structure is formed by crystal of (AlO4) and (SiO4). These crystals are the fundamental construction for various zeolite such as zeolite A and X, the common adsorbents used in the application of adsorption cooling system. The porosity of the zeolite is between 0.2 and 0.5. There are about 40 types of natural zeolite.13X zeolite adsorbent are the main types used for adsorption cooling system. The adsorption and desorption heat of zeolite pairs are high, and the desorption temperature of these pairs is also high, and about 250300C. The zeolites are usually employed in adsorption cooling system that has a heat source between 200 and 300C.

Activated carbon:
Activated carbon has been a key adsorbent material in adsorption cooling technology for many years due to their porous surface. The specific area of activated carbon is between 500 and 1500 m2/g. The net structure of activated carbon pores is composed of irregular channels, which have larger pore area at the surface of the grain, and narrow pore area within the grain. The difference between activated carbon and other types of adsorbent is the surface feature. The whole surface of activated carbon is covered by an oxide matrix and by some inorganic materials, and therefore, it is non-polar or has a weak polarity. The adsorption heat of activated carbon pairs is lower than that of other types of physical adsorbent pairs. Pores in Activated Carbon is classified into three types: Micropores (pore diameter less than 20 nm), Mesopores (pore diameter 20-200 nm) and Macropores (200 nm & above).

Types of working Adsorbate and Adsorbent Pairs

At present, three types of working adsorbate and adsorbent, respectively, are favoured for pairing for use in adsorption refrigeration technology: ammonia, methanol and water for adsorbate and activated carbon, silica-gel and zeolite for adsorbent.

The selection of any pair of adsorbent/adsorbate depends on certain desirable characteristics these are listed below: 1. Evaporation 2. Small size of molecules such that it can easily be adsorbed into the adsorbent. 3. Microspores of diameter less than 20 A. 4. High latent heat of vaporization and low specific volume. 5. Thermally stable with the adsorbent at the cycle operating temperature ranges. 6. Non-toxic, non-corrosive and non-flammable. 7. Low saturation pressures (above atmospheric) at normal operating temperature. MAIN ADVANTAGES OF ADSORPTION COOLING TECHNOLOGY 1. Can be operated with low-grade thermal energy such as solar, geothermal and waste heat 2. Thermal energy storage possible 3. It is a robust technology. 4. The materials used today (zeolite, silica gel) are environmentally friendly 5. Very low electricity consumption. Electricity is only required for the switching valves and the control unit. 6. Very little moving parts with the potential of low maintenance effort and costs.

MAIN DISADVANTAGES OF ADSORPTION COOLING TECHNOLOGY 1. High requirements to the vacuum tightness of the container. 2. Lower COP than for comparable absorption technology. 3. Commercially available machines are expensive and only some suppliers are on the market. 4. Larger volume and weight.

APPLICATION
Applications of adsorption cooling systems are refrigeration, air conditioning, water chiller. Following table shows the performance of adsorption cooling system for different application and experiment conducted by Oak Ridge National Laboratory UK.

Transport box for chilled and frozen goods

Initially researchers implemented the functional principle in a transport box having a useful volume of 50 liters, which has now been developed to production ready status. Insulated with 80 mm polyurethane foam, five walls of mobile freezer are actively cooled by in wall evaporator filled with one liter of water. A built in cooler contains 13.5 kg of zeolite for the sorption process. Around half an hour after cooling commences, the inside temperature of box reaches -18C. At an ambient temperature of 30C this can be maintained for around 24 hours. A 1350 watt electrical heating element is provided for regeneration, which takes about two hours. Then the valve between the cooler and the evaporator is closed and box is ready for use the zeolite needs to be left to cool down for about five hours. Afterwards the cool box is ready for use again. It can be stored indefinitely before being cooled down again when the valve is opened.

Figure. Researchers at Zeo-Tech GmbH in Germany have developed freezer boxes.

Mini fridge
It is same as above cooling box but with modification, to maintain a low temperature during desorption, the evaporator is located at top inside the cooling chamber. Warmer air around the evaporator stays in this upper region. The air only cools down in the cooling phase, when it falls to the bottom of the cooling chamber. A well insulated mobile fridge with a 40 liter capacity requires a continuous cooling capacity of around 8-9 W to ensure an internal temperature of 5-8 C at 25C ambient temperature. If the fridge is designed for a 24 hours cycle time, approximately 690 KJ of cooling energy needs to be generated per cycle. This is equivalent to the evaporation of approx. 300g of water and requires a mass of zeolite of approx. 2 Kg for the water adsorption.

Figure. Researchers at Zeo-Tech GmbH in Germany have and mini refrigerators

Advanced Portable Air Conditioning System

A man mounted micro-climatization system (MiCS) The technology has been successfully used by US Navy. Air supply, to be distributed to the system's interior climatization zones by means of an air blower. Depending on the prevailing environmental conditions, the air flow has to be conditioned for cooling and heating -which transforms the blower into a Climatization System. System description Provide approx. 250 l/min of air at least 2 hours: Cool ambient air of 35 C (95F) at relative humidity below 50 % by approx. 8 1 C for a minimum time period of 2 hours. Total weight of the system < 6 kg For regeneration/desorbs (regenerate) the zeolite, heat gun is used the heat gun is operated electrically (AC 110V/220V). The regeneration process will take about 2.5 hours at a temperature of 350 C (662 F) for complete regeneration (drying) of the zeolite.

Figure. A man mounted micro-climatization system (MiCS) WATER CHILLER

CONCLUSION
From this literature review it can be concluded that the prospect of using adsorption cooling technology is an alternative to mechanical vapour refrigeration system. The adsorption cooling system compared to the mechanical system has low maintenance and the absence of moving components is also a very important feature that makes this type of system suitable for numerous other applications such as air-conditioning and cooling food storage units. The environmental benefits are also impressive, when compared to conventional compressor cooling technology. The absence of harmful or hazardous products such as CFCs, together with a substantial reduction of CO2 emissions due to very low consumption of electricity, creates an environmentally safe technology. Low-temperature waste heat or solar energy can be used. Although adsorption systems present all the benefits listed above, they usually also have the drawbacks of low COP and low specific cooling power (SCP). However, these inconveniences can be overcome by the intensification of the heat and mass transfer properties in the adsorber, by increasing the adsorption properties of the working pairs and by a better heat management during the adsorption cycle.