Development of two adsorption heat pump / air conditioning systems Dr. Robert E. Critoph, M.Inst.

E University of Warwick, Coventry CV4 7AL, UK Summary There are two projects underway at the University of Warwick that could be used for heat driven air conditioning. They both use active carbon ammonia adsorption cycles. The convective thermal wave cycle has high efficiency and a 10kW version is under development in a project funded by industry ond government. The newer modular regenerative system is best suited to lower powers but is also highly efficient and potentially lower cost. Introduction Adsorption cycles can be used in heat-driven refrigerators, air conditioners or heat pumps in which the energy source is a burning fuel or waste heat. The conventional vapour compression cycle demands a mechanical work input, which is normally provided by an electric motor. The benefits of high efficiency adsorption machines include reduced running costs and, in general, a reduction in the use of primary energy needed for cooling or heating and the associated reduction in CO2 emissions. [These reductions are largest when considering waste heat or CHP (Combined Heat and Power) driven applications, and significant in gas fired heat pumps. Savings are can also be made in gas-fired cooling, but depend on the precise application.] Technical background Adsorption refrigeration and heat pump cycles rely on the adsorption of a refrigerant gas into an adsorbent at low pressure and subsequent desorption by heating. The adsorbent acts as a chemical compressor driven by heat. In its simplest form an adsorption refrigerator consists of two linked vessels, one of which contains adsorbent and both of which contain refrigerant as shown in Fig. 1. Our preferred adsorbent and refrigerant are active carbon and ammonia. Ammonia is a low cost, environmentally friendly refrigerant. Although toxic if inhaled, if it is released to the environment it is quickly absorbed and neutralised without harm. It has zero ozone depletion potential and zero greenhouse warming effect and is still the refrigerant of choice in many industrial applications.

Figure 1 Basic adsorption cycle Initially the whole assembly is at low pressure and temperature, the adsorbent contains a large concentration of refrigerant within it and the other vessel contains refrigerant gas (a). The adsorbent vessel (generator) is then heated, driving out the refrigerant and raising the system pressure. The desorbed refrigerant condenses as a liquid in the second vessel, rejecting heat (b). This is part of the useful heat output of a heat pump. Finally the generator is cooled back to ambient temperature, readsorbing the refrigerant and reducing the pressure. The reduced pressure above the liquid in the second vessel causes it to boil, absorbing heat and producing the refrigeration effect. The heat rejected by the generator forms the other part of the useful heat output of the heat pump. The cycle is discontinuous since useful cooling only occurs for one half of the cycle. Two such systems can be operated out of phase to provide continuous cooling. Such an arrangement has a comparatively low Coefficient of Performance (Refrigeration COP = Cooling / Heat Input and Heat pump COP = Heat

Output / Heat Input). Also, since the thermal conductivity of the bed is generally poor, the time taken for a cycle could be an hour or more and the cooling power per mass of adsorbent could be less than 100 W/kg. Greatly improved heat transfer is required to reduce the cycle time to a few minutes and thereby increase the power density of the adsorbent to the order of 1 kW/kg. It can also improve the COP by maximising the quantity of heat regenerated. The heat rejected by one bed when adsorbing can provide a large part of the heat required for desorption in other bed. The convective thermal wave cycle The need for good heat transfer is not just to reduce the size and cost of the machine but to allow effective transfer of heat between the beds in a high COP regenerative cycle. Our patented Convective thermal wave cycle (1) being developed at Warwick uses two carbon and two inert beds in a similarly highly regenerative cycle but without the need for special heat exchangers. A schematic of the test rig is shown in Figures 2a and 2b and a photograph in Figure 3. Detailed results of the work are given by Critoph (2). The operation is as follows:

Figure 2a Figure 2b In the desorption phase (Figure 2a) the bed of activated carbon is heated by the stream of hot ammonia refrigerant blown through it in the direction shown. The flow rates and thermal capacities are such that a temperature front or thermal wave (ideally square) travels down the bed. The time taken for the wave to travel the length of the bed is typically three minutes. The exit gas emerges cold until the thermal wave starts to break through. As the mean temperature of the bed rises, ammonia refrigerant is desorbed at a rate typically 10% of the mass flow rate of the circulating gas. This desorbed gas condenses in the coldest part of the system, the condenser, which rejects heat to ambient. The cold gas leaving the active bed passes through the pump to the cold end of the inert bed which is a packed bed regenerator of steel balls. This inert bed has been charged with heat in the previous adsorption phase and now the stored heat is used to preheat the circulating gas. A cold thermal wave passes from the bottom to the top of the inert bed and the exit gas emerges pre-heated. It is brought to full temperature (150 - 250C depending on the application) in the heat exchanger which transfers heat from the energy source (gas flame, solar heat, waste heat, etc.). At the end of the desorption phase the active bed has been heated, the inert bed has been cooled and a quantity of ammonia has been condensed. The refrigerant circulating pump direction is reversed and adsorption commences. In the adsorption phase (Figure 2b) the processes are reversed. The ammonia entering the bottom of the active bed has been cooled close to ambient and creates a cold wave travelling up the bed. The cooling causes the carbon to adsorb ammonia leading to a drop in pressure and the boiling of the ammonia liquid in the evaporator. This is the useful cooling effect. The heat of adsorption produced in the active bed is removed by the circulating gas. The gas emerging from the top of the active bed is hot and passes to the inert bed where it is stored. In the storage process a hot thermal wave passes down the inert bed, but the exit gas remains comparatively cold until breakthrough occurs and the cycle is once more reversed.

The test rig is shown in Fig. 3. Note that since there is one inert and one active bed, cooling is intermittent. A system having continuous cooling needs two pairs of beds operated out of phase.

Figure 3 Convective wave test rig Figure 4. Impression of production machine The storage and subsequent reuse of the heat of adsorption from the adsorbing bed, which would otherwise be rejected, leads to high COPs. Computer simulation, based on heat and mass transfer data suggests a cooling COP of 0.95 under ARI conditions. At the time of writing a figure of 0.85 has been achieved. New research on the convective thermal wave cycle We believe that a novel reconfiguration, still covered by our patent, can lead to a cost effective product. There is a good solution to the problem of a low cost circulating pump that we are investigating. The configuration of the new demonstration machine that are building and testing is shown in Figure 4 The work is supported by the UK government and a consortium of companiies consisting of Thermomax, Searle, Britannia, Hymatic, Calor and Advantica. The schematic shows a system capable of providing continuous cooling. Each of the two hermetically sealed steel pressure vessels (approx. 1m high, 0.25m diameter) contains ammonia, an active bed and an inert bed. When one vessel is in the desorbing phase the other is in the adsorbing phase. No ammonia enters or leaves either vessel but heat is transferred in or out by the use of fluid loops or heat pipes.. With the exception of the gas circulator all of the components are standard items and readily obtainable. The circulator (a centrifugal fan with reversing valves) is under construction at the time of writing. The modular regenerative cycle This study examines the possibility of using many simple modular beds in an arrangement that allows effective heat transfer between them. The cycle is patented (3) and described more fully in Critoph (4). A single module is shown schematically in Figure 5. It is a tube having a sorption generator at one end and a combined evaporator and condenser at the other. The first such module that we have made has a stainless steel tube 12.7 mm in diameter and 500 mm long containing the generator. It is lined with a 3 mm layer of monolithic carbon. The carbon shape is formed within the tube and so the heat transfer between steel and carbon is very high. The other end of the module is a receiver for the liquid adsorbate; ammonia in our work. The adiabatic section separates the generator and receiver, reducing longitudinal conduction between them. Heat may be transferred to or from the generator and receiver by passing air or any other fluid across them. Fins can enhance this if necessary. In desorption, the generator is heated and desorbed refrigerant condenses in the receiver, which is cooled. In adsorption the generator is cooled and heat is provided to boil the

refrigerant in the receiver. The whole module is the very simplest type of adsorption refrigerator or heat pump.

Figure 5: Sorption Module It is possible to combine many such modules in an assembly that allows regenerative heating between them. Figures 6 and 7 show one possible way of doing this in schematic form. In this example the machine is an air-to-air heat pump or air conditioner. 16 modules are shown, arranged in a cylindrical shell. All rotate about the central axis (X in Figure 6) typically completing one revolution in ten minutes. Air is blown over the tubes, counterflow to their direction of motion and exchanging heat with them. Seals prevent the air from travelling directly between the adsorbing and desorbing zones but allow the tubes to pass through when necessary. Consider the path of a single tube beginning at position 1 in Figure 3. The carbon is at its coldest, perhaps 50C and has maximum concentration. As it moves clockwise through the annular duct it is heated by air flowing in the opposite direction. If the 'thermal mass flow rate' of the generator is approximately the same as that of the air, then the desorption section acts like a counterflow heat exchanger with capacity ratio close to unity. In reality, the effective specific heat of the carbon varies during a cycle but it is still possible to balance the flow rates quite well. The result is that by the time the module reaches the end of the desorption section it is perhaps at 200C. Whilst the carbon is heated it desorbs ammonia which condenses in the receiver section of the module. In an air conditioning application, a stream of ambient temperature air cools the receiver section. A similar process occurs in the adsorbing section, but with evaporation occurring in the receiver, which cools the airstream passing over it. In the course of cooling down, the generator tubes heat the stream of ambient air induced at position 2. This pre-heated air is removed from the annular duct at position 3 and heated by an external high grade heat source before being re-introduced to the duct at position 4. The greater the number of modules, the better the approximation to a continuous process with counterflow regeneration of heat. The advantages of the system are the absence of refrigerant valves and complex or expensive heat exchangers. Potential problems might include the sealing mechanism to direct the air flows and possible degradation of the carbon due to thermal shock. Figure 6: Schematic air to air heat pump / chiller Figure 7: Section through the generators Initial experimentation

Figure 6: Schematic air to air heat pump/chiller

Figure 7: Section through the generators

Previous experience with monolithic carbon (5) suggested that monolithic carbon should be proof against the thermal cycling and could be made to adhere strongly to the tube wall. A manufacturing technique was devised and a 500 mm length of 12.7 mm outside diameter 0.9 mm wall thickness stainless steel tube was lined with 3 mm of active carbon, as shown in Figure 8. A simple test rig was built which subjected the generator to alternating flows of hot (150C) and ambient air whist the receiver was kept in a flow of ambient air. An optional glass receiver allowed observation of the quantity of liquid ammonia building up or boiling. Repeated heating and cooling for tens of cycles showed no tendency for the carbon to break up and drop into the receiver. This was encouraging, but obviously in a real system there will be many thousands of cycles and further testing is necessary. There are over one hundred parameters input to the simulation but the effect of two are illustrated in Figures 9 Figure 8: Generator Section and 10. The variation in COP and SCP with the heater exit temperature is shown in Figure 9. The values of other parameters is not optinised and so the absolute values of COP are comparatively low. It is noticeable that the COP is comparatively insensitive to heater temperature in the range chosen, although it does have a peak at around 175C. At higher temperatures, although a little more ammonia can be desorbed, not all of the sensible heat load can be regenerated and COP drops.However, the cooling power rises with increasing heater temperature in a linear fashion. The minimum mean concentration for a heater temperature of 250C is 3% whereas for 150C it is 10%. The variation in COP and SCP with the number of tube modules is non-linear over the range chosen. In the limit of one tube there is no regeneration and for an infinite number of tubes there will be maximum regeneration. Assuming the mass flow rate of modules to be constant the SCP will decrease with an increasing number of tubes. Figure 10 shows the variation for 24 to 64 tubes. The improvement in COP at high module numbers is due mainly to the improved regeneration, but also to the reduced temperature lift resulting from the reduced evaporator and condenser load. In reality the modules will be finned and the optimised results of COP and SCP as a function of fin area are shown in Figure 11. It can be seen that a COP (based on fuel input) of 0.85 is quite achievable. A full system is under construction at present. Since it is more readily adapted to handling air and combustion gas streams which must be in close proximity, small unitary air conditioner / heat pumps seem an ideal
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Figure 11: Performance v. Fin area with optimal flow rates REFERENCES 1. PCT/GB95/02251 Sec. 371 Date May 9,1997 Sec. 102(e) Date May 9,1997 PCT Filed Sep. 22, 1995 PCT Pub. No. WO96/09504 Pub. Date Mar. 28, 1996. 'Thermal compressive device', R.E. CRITOPH, R.N. Thorpe. 2. Critoph R.E, Forced convection adsorption cycle with packed bed heat regeneration, Int. J. Refrigeration, 22, 38-46, 1999 3. Critoph R.E, UK Patent Application 9922339.8, filed 21 Sep. 1999, 'Thermal regenerative compressive device'. 4. Critoph R.E, Continuous multiple-bed regenerative adsorption cycle refrigerator / heat pump, 4th Int. Seminar Series Heat Pipes, Heat Pumps, Refrigerators, Minsk, 2000. 5. Critoph, R.E., Tamainot-Telto Z., and Davies, G.N.L. Adsorption refrigerator using a monolithic carbon-aluminium laminate adsorbent and ammonia refrigerant. Proceedings of the Int. Sorption Heat Pump Conf., Munich, March 1999: 349-353.