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Review

State-of-the-art review on crystallization control technologies for water/LiBr absorption heat pumps
Kai Wang*, Omar Abdelaziz, Padmaja Kisari, Edward A. Vineyard
Building Equipment Research Group, Energy & Transportation Science Division, Oak Ridge National Laboratory, One Bethel Valley Road, P.O. Box 2008, MS-6067, Oak Ridge, TN 37831-6067, USA

article info
Article history: Received 3 December 2010 Received in revised form 1 April 2011 Accepted 18 April 2011 Available online 1 May 2011 Keywords: Absorption system Heat pump Lithium bromide Crystallization Control

abstract
The key technical barrier to using water/lithium bromide (LiBr) as the working uid in aircooled absorption chillers and absorption heat-pump systems is the risk of crystallization when the absorber temperature rises at xed evaporating pressure. This article reviews various crystallization control technologies available to resolve this problem: chemical inhibitors, heat and mass transfer enhancement methods, thermodynamic cycle modications, and absorption system-control strategies. Other approaches, such as boosting absorber pressure and J-tube technology, are reviewed as well. This review can help guide future efforts to develop water/LiBr air-cooled absorption chillers and absorption heatpump systems. 2011 Elsevier Ltd and IIR. All rights reserved.

Etat de lart des technologies employees pour prevenir la ` ` cristallisation lors de lutilisation des pompes a chaleur a absorption au H2O/LiBr
s ` ` ` Mots cle : Systeme a absorption ; Pompe a chaleur ; Bromure de lithium ; Cristallisation ; Prevention

1.

Introduction

According to the 2009 Buildings Energy Data Book, space cooling and heating, and water heating consume 49.8% and 25.2% of primary energy consumed in U.S. residential

and commercial buildings (U. S. Department of Energy, 2009). Energy-efcient, environmentally friendly heat pumping technologies may be able to dramatically reduce this energy use, and ultimately substantially reduce emissions. Absorption heat pumps, rst developed in the nineteenth century

* Corresponding author. E-mail address: wangk@ornl.gov (K. Wang). 0140-7007/$ e see front matter 2011 Elsevier Ltd and IIR. All rights reserved. doi:10.1016/j.ijrefrig.2011.04.006

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Nomenclature AAC AHP CHP CNT Air-cooled absorption chillers Absorption heat pump Combined heat and power Carbon nanotube

COP LiBr LPA MPA VC

Coefcient of performance Lithium bromide Low-pressure absorber Medium-pressure absorber Vapor compression system

(Foley et al., 2000), have received growing attention in the last few decades. The increasing cost of fossil fuels and environmental concerns have made the particular features of the thermally activated heat-pump cycle attractive for residential, commercial, and industrial applications (Fiskum et al., 1996). The key market barrier to the application of water/LiBr absorption chiller technology in combined heat and power (CHP) systems is the need for a cooling tower to reject heat from the condenser and absorber to the ambient air (Zogg et al., 2005). The use of cooling towers in light-commercial absorption chiller systems is unpopular because they 1) provide a breeding ground for bacteria, 2) increase initial system costs, 3) require regular maintenance, and 4) require extra space for their installation (Zogg and Westphalen, 2006). The development of air-cooled water/LiBr absorption chiller technology could effectively eliminate these disadvantages. However, the key technology barrier in developing water/LiBr air-cooled absorption chillers is solution crystallization at high absorber temperatures for xed evaporating pressure (Foley et al., 2000; Kurosawa et al., 1988; Zogg et al., 2005). Water heating consumes 11% and 5.8% of primary energy consumption in U.S. residential and commercial buildings, respectively (U. S. Department of Energy, 2009). This reects a signicant market for energy-efcient heat-pump technologies for domestic and commercial heating applications. Among current heat-pump technologies, absorption heat pumps (AHPs) are attractive because of their high primary energy efciency compared to other technologies and their use of environmentally benign refrigerants. However, water/LiBr absorption heatpump systems are unable to operate at typical water heating temperatures because of crystallization limits of the mixture at high heat-rejection temperatures (Wang et al., 2011).

The single-effect water/LiBr absorption cycle, shown in Fig. 1, is composed of a condenser, an evaporator, an absorber, a solution heat exchanger, and a generator. The condenser and evaporator are identical in function to the corresponding components in a vapor compression (VC) refrigeration system. Refrigerant (water) is boiled off and pressurized in the generator (point 7 in Fig. 1), condensed to a liquid (point 8 in Fig. 1) in the condenser, then expanded using an expansion device and eventually evaporated in the evaporator to produce the cooling effect (point 10 in Fig. 1). The generator, absorber, and solution heat exchanger are used instead of the compressor of a VC refrigeration system and sometimes called a thermal compressor (Zaltash et al., 2007). Highpressure refrigerant water vapor (steam) is generated when heat is applied in the generator. The hot concentrated LiBr solution (points 4, 5, and 6) ows through the solution heat exchanger on its way to the absorber. The low-pressure water vapor (point 10) from the evaporator is absorbed into the concentrated LiBr solution in the absorber. As the vapor is absorbed, the LiBr mass fraction in solution is reduced to the level of the generator inlet and the low-concentration solution (points 1, 2, and 3) is pumped back to the generator, passing through the solution heat exchanger. The solution heat exchanger is used for internal heat recovery to preheat the solution leaving the absorber with the hot concentrated LiBr solution leaving the generator to improve system efciency. The crystallization line for water/LiBr is usually very close to the working concentrations needed for practical AAC and AHP systems operation. LiBr is a salt and has a crystalline structure in its solid state. There is a specic minimum solution temperature for any given LiBr salt concentration below which the salt begins to crystallize out of the solution.

Fig. 1 e Schematic diagram of single-effect water/LiBr absorption cycle.

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1.2. Excessively cold condenser water coupled with a high load condition (Florides et al., 2003)
Sudden cooling of the condenser water to below normal operating temperature results in lowering the temperature of the dilute absorbent solution leaving the absorber. This in turn lowers the temperature of the concentrated absorbent solution in the heat exchanger to below the crystallization point and will begin to block the heat exchanger.

1.3.

Over-ring the generator (Florides et al., 2003)

Fig. 2 e Duhring diagram of single-effect absorption system (see Fig. 1 for denition of state points).

Over-ring the generator, resulting in super-saturation of the absorbent solution, may also cause blockage of the heat exchanger passages by crystallization.

1.4.
For LiBr solution, LiBr begins to crystallize either when the concentration ratio is increased or when the solution temperature is reduced beyond the crystallization limit. Crystallization results in interruption of machine operation and possible damage to the unit. It is more prone to occur for the strong solution entering the absorber, which is point 6 in Fig. 1. Crystallization must be avoided because it may lead to the formation of slush in the piping network, which may result in complete ow blockage if the slush is solidied. If this occurs, the concentrated solution temperature needs to be raised signicantly above its saturation point in order to dissolve salt crystals within a reasonable time. Recovering absorber operation after crystallization is a labor-intensive and time consuming process. Fig. 2 compares the pressureetemperatureeconcentration (PeTeX) characteristics of a typical water-cooled water/LiBr absorption chiller to those for AAC and AHP systems in the Duhring diagram. The gure shows that the higher heat rejection temperatures associated with AAC or AHP systems bring the cycle closer to the crystallization curve, increasing the likelihood of crystallization. The following instances may trigger crystallization, either independently or in combination.

Electric power failure (Florides et al., 2003)

During normal shutdown, the machine undergoes a dilution cycle, which lowers the concentration of the solution throughout the system. In such cases, the machine may cool to ambient temperature without crystallization occurring in the solutions. Crystallization is most likely to occur when the machine is stopped while operating at full load, when highly concentrated solution is present in the solution heat exchanger. This article presents a state-of-art review of various crystallization control technologies available to resolve the LiBr crystallization problem using chemical inhibitors, heat and mass transfer enhancement methods, thermodynamic cycle modications, and absorption system-control strategies. Other approaches, such as boosting absorber pressure and J-tube technology, are reviewed as well. This review of relevant technologies can help the research and development community gain a better understanding of the crystallization issues, take corrective action, and pursue future efforts in developing water/LiBr AAC and AHP systems.

2.

Chemical crystallization inhibitors

1.1. Presence of non-condensable gases, such as air and hydrogen (Liao and Radermacher, 2007)
Since the absorption system operates under vacuum, outside air may leak into the system. The corrosion of metal in the absorption system will generate non-condensable gas (such as hydrogen), particularly at higher-temperature operation such as double-effect cycles, especially with direct-red generators. The presence of non-condensable gases decreases system capacity and COP, which causes the concentration of the concentrated absorbent solution to increase, depending on the amount of inert or non-condensable gases in the system. As the solution becomes more concentrated it tends toward saturation and may even become supersaturated to trigger crystallization. The onset of non-condensable gases could be controlled by designing the machine with routine purging systems.

Macriss (1968) and Macriss and Rush (1970) explored the performance of LiBreLiSCN (Lithium Thiocyanate)eH2O as a working uid in AACs, and its vapor pressure, crystallization, viscosity, and density data as a function of temperature and concentration. Compared with other working uids such as LiBreH2O, LiBrebutyrolactoneeH2O, and LiBreCsBreH2O, the solution of LiBreLiSCN was found to have desirable physical properties with good potential for air-cooled systems. Hence, the correlation equations of vapor pressure, heat of vaporization, and solution concentration were presented by Weil (1968), and were used for cycle analysis of LiSCNeLiBreH2O combinations in which the LiSCN/LiBr mole ratio is less than 4. A series of stability tests were conducted on LiBreLiSCN solutions with and without inhibitor (Li2CrO4) and with various construction materials (304 stainless steel, carbon steel, aluminum, and copper). The results show that 304 steel and aluminum appeared to promote decomposition. However, iron and copper, the most commonly used metals in

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absorption systems, have less effect on the stability of LiBreLiSCN solution (Rush, 1968). Biermann (1978) reviewed chemicals having the potential to sustain an air-cooled, solar-powered absorption refrigeration system. An aqueous chemical solution called Carrol was developed based on the review results (Reimann, 1981). It consists of LiBr, ethylene glycol, and 1-nonylamine (or phenylmethylcarbinol) as an absorbent mixture and water as the refrigerant. The ethylene glycol was used as a crystallization inhibitor, and originally the 1-nonylamine was used as an additive to enhance the heat and mass transfer but was replaced by phenylmethylcarbinol because of its side effect (when 1-nonylamine is heated in the presence of copper oxide, it forms chemically refractory copper soaps) (Lof, 1993; Zogg et al., 2005). The weight ratio of LiBr and ethylene glycol in Carrol is 4.5:1. The thermophysical properties (pressuree concentrationetemperature equilibrium properties, density, lm heat transfer coefcient, specic heat capacity, thermal conductivity, and viscosity, as well as crystallization curve) of Carrol had been documented by Reimann (1981). Fig. 3 shows the equilibrium diagram for aqueous solutions of Carrol and crystallization curves of LiBr and Carrol aqueous solution. The comparison between Carrol and LiBr aqueous solution crystallization curves shows that Carrol has a larger feasible area of operation than LiBr aqueous solution. Carrol had been tested extensively in solar-powered, water-cooled (Biermann and Reimann, 1981b), and air-cooled (Biermann and Reimann, 1981a) absorption applications both in the laboratory and in the eld. Since a traceable amount of ethylene glycol could possibly exist in the vaporized refrigerant in the generator, Inoue (1993) and Park et al. (1997) suggested utilizing a rectier in absorption systems that use Carrol as a working uid. Iyoki and Uemura (1981) also studied the feasibility of using LiBreethylene glycol aqueous solution as a working uid in solar-powered absorption refrigerating machines. The mole ratio of water and ethylene glycol is 10:1 in the aqueous solution. The specic gravity, solubility, vaporeliquid equilibrium, vapor pressure, and heat of mixing of the watere LiBreethylene glycol were measured experimentally. The

Fig. 3 e Equilibrium chart for aqueous solutions of Carrol, reproduced according to Reimann (1981).

enthalpyeconcentration chart was constructed from these results. The performance characteristics of single- and doubleeffect solar-powered absorption refrigerating machines were studied using this chart. Eisa et al. (1988) investigated the operational characteristics of an experimental absorption cooler using the same solution (water/ethylene glycol mole ratio 10). Kim et al. (1995) measured and compared the vapor pressure of LiBr ethylene glycol water (water/ ethylene glycol mole ratio 10) and LiBr LiCl ethylene glycol water (LiCl/LiBr mass ratio 1, water/ethylene glycol mole ratio 10). The physical and thermal properties of watereLiBre C4H6O2 (g-butyrolactone) solution were investigated to obtain its absorption refrigeration performance characteristics (Iyoki et al., 1984). The organic compound as a third component was added to improve system COP. It was envisioned that this additive might enlarge the difference in vapor pressure between refrigerant and absorbent solution and thus allow for an evaporating temperature near 0  C. The performance characteristics of this working uid were proven to be better than those of the watereLiBr solution. A new absorbenterefrigerant pair using water as the refrigerant and a 1:1 mixture of LiBr and zinc chloride (ZnCl2) by weight as absorbent was developed by Manago et al. (1984) and Ohuchi (1985). This new absorbent has been found to be a promising candidate for a heat pump and air-cooled cooling system to achieve superior performance. The simulation results show that the new absorbent solution gave a heating COP of 1.57 and a cooling COP of 1.00 for air-cooled, doubleeffect absorption cycles, with a boiler efciency of 80%. Modahl (2002) invented a new absorbenterefrigerant pair for the high-temperature loop of a dual loop triple effect absorption chiller system. The absorbent is zinc bromide (ZnBr2) and LiBr and the refrigerant is water. The mass ratio of ZnBr2 to LiBr is 1.75. The absorbent also contains 0.003 g of lithium hydroxide per gram of contained salt, and the concentration of solution is in the range of 80e91% (by weight). Park et al. (1997) carried out the experimental measurement of four physical properties (solubility, vapor pressure, density and viscosity) of LiBr 1,3-propanediol (b-propylene glycol) water solution (LiBr/1,3-propanediol mass ratio 3.5). The Duhring chart was generated using correlation results based on the experimental data and showed that the proposed solution could have a high absorber temperature, which is essential for the design of air-cooled absorption chillers. Park and Lee (2002) investigated the heat and mass transfer performance of water vapor absorption into the LiBr-based working uids (LiBr 1,3-propanediol water (LiBr/1,3propanediol mass ratio 3.5)), and LiBr LiI 1,3propanediol water solutions (LiBr/LiI 4 by mole ratio and (LiBr LiI)/1,3-propanediol 4 by mass ratio). The experimental results showed the heat and mass transfer characteristics of LiBr LiI 1,3-propanediol water solution were comparable with the LiBr water solution. Yoon and Kwon (1999) carried out the cycle analysis of an air-cooled, double-effect absorption chiller system using H2O/LiBr 1,3propanediol (HO(CH2)3OH) as a new working uid. The simulation results showed that the new working uid might provide an 8% higher crystallization limit than conventional

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water/LiBr solution. The authors noted that ambient air inlet temperature plays an important role in system performance and the corrosion problem. Kim et al. (1996a,b, 1997) and Young et al. (1997) measured the basic thermophysical properties for three solutions, LiBr H2N(CH2)2OH H2O, LiBr HO(CH2)3OH H2O, and LiBr (HOCH2CH2)2NH H2O (LiBr/H2N(CH2)2OH, LiBr/HO(CH2)3OH, and LiBr/(HOCH2CH2)2NH mass ratios are 3.5). These were selected as possible working uids for aircooled absorption chillers, and Kim et al. (1999) calculated the theoretical COPs at various operating conditions. They also checked the cooling capacity and crystallization problem for air-cooled cycle operation. Among these three working uids, LiBr H2N(CH2)2OH H2O was found to have the widest operating range. This advantage is mainly because of the enhanced solubility of the working uid. However, there are several issues, such as corrosion, heat and mass transfer performance deterioration, need for rectication, and higher viscosity, that need to be explored before using it in air-cooled absorption chillers. Ally (1988) presented simulation results aimed at comparing the potential performance of LiBr and ternary nitrate aqueous mixtures in high-temperature absorption heat-pump application. The ternary nitrate mixture is an aqueous solution of LiNO3, KNO3, and NaNO3 in mass ratio 53:28:19. The simulation results indicated that the ternary nitrate mixture may be operated at up to 260  C boost temperature, which is approximately 80  C higher than what has been demonstrated with LiBr. In lower-temperature lift regimes, the ternary nitrate mixtures are not competitive with LiBr. In higher-temperature regimes, the nitrates show the potential for 10% higher COPs and a marginally greater absorber capacity than LiBr. Herold et al. (1991) developed an aqueous ternary hydroxide working uid to replace LiBr aqueous solution. This aqueous ternary hydroxide sorbent consists of sodium, potassium, and cesium hydroxide in the proportions 40:36:24 (NaOH:KOH:CsOH). The crystallization characteristics of the salt solution can be avoided by mixing the three hydroxides with water over the full range of operating conditions expected in water heating applications. However, there are some corrosion problems in its application. Trace amounts of nitrogen (from minor air leakage into the system) will react with trace amounts of hydrogen (from the hydroxides) to form ammonia, which can attack the copper tubing used in water heaters (Zogg et al., 2005). De Lucas et al. (2003) measured the density, viscosity and vapor pressure of aqueous mixture of lithium bromide and potassium formate (CHO2K). The mass ratio of LiBr/CHO2K is 2. They (De Lucas et al., 2004) also theoretically investigated the performance of absorption refrigeration cycle utilizing this new absorbent. The results showed the efciency of the absorption cycle is improved. This new absorbent mixture requires a lower-temperature level (55  C) in the generator to activate the absorption cycle due to its low boiling point. The use of an aqueous mixture of LiBr and sodium formate (CHO2Na) was recently investigated (De Lucas et al., 2007). The new working uid composition maintains a ratio of LiBr/ CHO2Na of 2 by weight. This working uid was introduced as a potential competitor to aqueous LiBr solution for absorption

systems due to its higher water vapor absorption rates and lower required generation temperatures (De Lucas et al., 2004). Wang et al. (2010) conducted a systematic study to explore the crystallization temperature of LiBr/CHO2Na water solution and compared it against aqueous LiBr solutions. The results were then used to evaluate the feasibility of using this new working uid in heating applications. The aqueous solution of LiBr CHO2Na showed poor crystallization performance, which would limit its use in AAC and AHP system designs. Physical and thermal properties and corrosion characteristics of the H2O LiBr LiNO3 (Iyoki et al., 1993c), H2O LiBr LiI and H2O LiBr LiNO3 (Iyoki et al., 1993a,b), and H2O LiBr LiNO3 LiI LiCl (Koo et al., 1999) systems have been reported in the open literature. LiNO3 behaves as a crystallization inhibitor and corrosion inhibitor. LiI is also selected as a crystallization inhibitor, and LiCl serves as a vapor pressure suppression agent. A company in Japan (Iizuka et al., 1992; Tongu et al., 1993) patented a water LiBr LiCl LiI LiNO3 solution for an air-cooled, doubleeffect absorption chillereheater which increases allowable absorber and condenser operating temperatures to about 10  C and 4  C higher than for a water-cooled cycle. A new corrosion inhibitor was also developed so that the hightemperature generator could be operated at 175  C in an air-cooled absorption cycle. A comparative study based on thermodynamic simulation, numerical simulation of the absorption process in the vertical falling-lm absorber, and experimental tests of the absorption rate of working uid in a vertical tube absorber was performed by Bourouis et al. (2005) to evaluate the performance of air-cooled absorption air-conditioning systems working with a solution of water (LiBr LiCl LiI LiNO3) (5:2:1:1 molar ratio). The safety margin against crystallization of strong solution leaving solution heat exchanger is higher for water LiBr LiCl LiI LiNO3 solution than for LiBr aqueous solution. At the minimum generator temperature, the single-effect cycle with water (LiBr LiCl LiI LiNO3) solution shows a feasible temperature range in the absorber about 7  C wider than with LiBr aqueous solution. Ring et al. (2001) and Dirksen et al. (2001) tested the crystallization temperature of 27 crystallization inhibitors (at concentrations of 250e1500 ppm) within industrial LiBr solutions cooled at a rate of 20  C h1. Some of these additives (such as Methylene diphosphonic acid, Pyrophosphoric acid, Amino tri(methylene phosphonic acid), Diethylenetriamine pentamethylene phosphonic acid and 1-Hydroxyethylidene-1,1diphosphonic acid) further decreased the crystallization temperature by up to 13  C below the experimental crystallization temperature and up to 22  C below the equilibrium solubility of the same LiBr solution without additive. Nemoto et al. (2010) used H2OeLiBre1,4-dioxane as a new working uid for solar-powered absorption refrigeration system. The 1,4-dioxane is an organic substance whose azeotropic relationship with water lowers the boiling point of water. The pressureetemperatureeconcentration characteristics, evaporation characteristics, and solubility of this new working uid were experimentally examined. The results concluded that the absorption refrigerator can be expected to produce the chilled uid at 5  C with the hot-water temperature at 85  C from a solar collector.

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3.

Heat and mass transfer enhancement

The enhancement of heat and mass transfer performance of working uids and an absorber heat exchanger decreases the overall temperature lift, and lowers the risk of crystallization. The additional benets of this approach are reducing absorber size and initial system costs. Vertical falling-lm heat exchangers were used as absorbers (as shown in Fig. 4) by Reimann (1981) and Tongu et al. (1993). The solution and the refrigerant vapor ow down inside the tube while the outside of the tube is cooled by air. The authors have further used vertical in-tube condensation where condensed refrigerant ows down the tube forming a new continuous condensation surface to increase the heat transfer coefcient. Kiyota et al. (2003) carried out experimental and simulation studies for absorption inside aircooled vertical pipes. The results indicated that the heat transfer area of air-cooled absorber is about three times larger than that of a water-cooled absorber utilizing a vertical fallinglm conguration. Tsuda and Perez-Blanco (2001) employed a vertical vibrating screen to enhance the heat and mass transfer of working uid in the absorber. The experimental results covered a range of solution Reynolds numbers from 20 to 300, with mixing scales from 0.2 to 1 mm, and mixing frequencies from 20 to 100 Hz for solution ow over a vertical at plate. The analysis showed that this technology could signicantly increase the absorption rate. A comprehensive review of the mathematical model of the coupled heat and mass transfer phenomena that occur during falling-lm absorption is given in Killion and Garimella (2001). Miller and Keyhani (2001b) carried out mathematical and experimental analysis on the effect of roll waves (wavy-laminar ow) on the hydrodynamics of falling lms in vertical absorbers. Regression analysis showed that the Reynolds number (Re) and the Kapitza number (Ka) could describe the data trends in roll waves. The correlation could explain 96% of the total variation in the data and the deviation between experimental data and simulated data was within 4%. Miller and Keyhani (2001a) provided correlation equations for the coupled heat and mass transfer of aqueous LiBr solution in vertical column absorber without heat and mass transfer additive. Compared against experimental results (internally cooled smooth tube of

Fig. 4 e Air-cooled vertical falling-lm absorber (Zogg et al., 2005).

19.05 mm outside diameter and of 1.53 m length), the average absolute error in the Nusselt (Nu) correlation was 3.5%, and the average absolute error in the Sherwood (Sh) correlation was 5%. Warnakulasuriya (1999) and Warnakulasuriya and Worek (2006) investigated a spray absorber (as shown in Fig. 5), which utilizes pressure atomization of working uid to increase the heat and mass transfer rates due to increasing the area exposed to the brine solution compared to the fallinglm technique. A spray absorber was evaluated experimentally to investigate the effects of differential pressure across the nozzle and liquid absorbent ow rate on the absorption rate. A mathematical model was also developed to predict the mass transfer rate. Since the absorption process in this concept is adiabatic, the concentration of absorbent uid doesnt change signicantly. Hence, solution circulation rates through the absorber should be relatively high. This will increase the power consumption and decrease the efciency of the absorption system. In this design, absorbent solution is cooled by a separate process. Therefore, a rather large solution heat exchanger is necessary to accommodate the high solution circulation rates. Ryan et al. (1995) experimentally studied the absorption rate of water vapor into a spray of LiBr aqueous solution at sub-ambient pressure. Four kinds of sprays generated by four different nozzles were tested and compared. The test results showed that absorption rates are signicantly affected by any lamella produced by the spray before breaking up into drops. Orian et al. (2006) studied the performance of a special nozzle device and the inuence of nozzle geometry on spray characteristics, such as mean droplet diameter, size distribution and velocity, and spray cone angle and core length. The number of wings and spinner pitch angle were the dominant parameters affecting spray characteristics. Venegas et al. (2005) investigated the mass transfer coefcient of ammonia refrigerant vapor absorbed by lithium nitrateeammonia solutions in a spray absorber. The experimental analysis showed that the mass transferred reached a maximum (about 60% of the total) during the drop deceleration period. A time-average mass transfer coefcient equal to k 1.86 105 m s1 could be attained using the spray absorption method. Kang et al. (2000) carried out a parametric analysis to comparatively study two different absorption modes in ammoniaewater absorption heat-pump systems, namely, falling-lm mode and bubble mode (as shown in Fig. 6). A plate heat exchanger with an offset strip n in the coolant side was used to simulate the falling-lm absorber and the bubble absorber. The results indicated that the local absorption rate of the bubble mode is always higher than that of the fallinglm mode. The difference is due to the larger mass transfer area, better mixing, and higher heat transfer coefcients experienced in bubble mode. Furthermore, the size of bubble absorber heat exchanger is 48.7% less than that of falling-lm absorber. Merrill and Perez-Blanco (1997), Merrill (2000), and Castro et al. (2009) achieved similar conclusions. However, bubbling a vapor through a liquid solution will require higher energy compared to a falling-lm absorber (Garimella, 1999); consequently it will limit the efciency of this system. For this reason, a bubble absorber may not be appropriate for water/ LiBr systems (Palacios et al., 2009).

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Fig. 5 e Conventional absorber (above) and spray absorber with solution sub-cooler (below) (Warnakulasuriya and Worek, 2006).

Zaltash et al. (2007) carried out comprehensive experimental tests to evaluate the system performance of a 4.5 kW air-cooled water/LiBr hot-water-driven absorption chiller unit in a climate-controlled environment with rotating heat exchangers as absorbers and generators. The COP and cooling capacity of system were approximately 0.58 and 3.7 kW, respectively, at 35  C ambient temperature with 40  C cooling water temperature and 16.7  C chilled water temperature. Izquierdo et al. (2008) conducted the trial tests using the same type of absorption chiller in Madrid, Spain, in August 2005. The average COP for the test period as a whole was 0.49. When the electric power consumed by auxiliary equipment was counted into the calculation of COP, the COP decreased to 0.37. The heat exchangers of this unit are all enclosed in a hermetically sealed drum as shown in Fig. 7. The rotating speed of drum is about 300 revolutions per minute. This unit utilized rotational force to form thin lms in order to improve heat and mass transfer in the absorber and generator (Aoune and Ramshaw, 1999; Pravda, 1994; Ramshaw and Winnington, 1991; Winnington and Green, 2001; Winnington et al., 2001; Zogg et al., 2005). Theoretical investigation of an air-cooled micro-channel absorber performance in an absorption-based miniature

electronics cooling system (having cooling capacity of 100 W) was reported by Kim et al. (2008). As shown in Fig. 8, the water/ LiBr pair is used as the working uid and refrigerant vapor (water) ows counter-current against the LiBr aqueous solution. The heat released from the absorption process is rejected to the coolant in a liquid-cooled absorber or via the offsetstrip-n array in an air-cooled absorber. The simulation results showed that the air-cooled micro-channel absorber could have comparable performance to a liquid-cooled microchannel absorber. TeGrotenhuis et al. (2005) prototyped an ammoniaewater absorption heat pump, which utilized a micro-channel heat exchanger with thin-wick materials for absorber and used branching fractal structures for a generator. Fig. 9 is a schematic diagram of a thin-wick absorber. A planar wick (thickness varying from 0.1 to 0.5 mm) was put into a small channel with a plenum adjacent to the wick. High concentration ammonia solution ows through this wick from one end to the other, and the water vapor is absorbed by the uid in the wicks. Whenever the pressure of the ammonia solution in the wicks is lower than the water vapor plenum pressure, the capillarity will guide uid through the wicks, and vapor will ow through the adjacent plenum. The advantages of this

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Fig. 6 e Schematic diagram of plate heat exchanger with falling lm and bubble absorption modes (Kang et al., 2000).

concept are the ability to recover from process upsets as well as orientation-independence of the working uid. The design cooling capacity of this prototype machine is 250 W when the evaporating temperature and condensing temperature are 10  C and 49  C, respectively. The experimental results showed that the cooling capacity and COP of this system are 190 W and 0.39, respectively, at the aforementioned operating conditions. A chemical, 1-nonylamine, was used as an additive to enhance the heat and mass transfer of Carrol by Reimann (1981), but it was replaced by phenylmethylcarbinol due to a side effect of 1-nonylamine (Lof, 1993). The lm heat transfer coefcients of Carrol solution (70 wt%) with/without 1-nonylamine were measured as a function of absorber loading. Results showed that the addition of 1-nonylamine in Carrol would increase the lm heat transfer coefcient by at least 100% (Reimann, 1981). Kang et al. (2008) experimentally investigated the effect of nanoparticles of Fe and carbon nanotubes (CNT) on heat and mass transfer enhancement of the water/LiBr absorption process. It was found that mass transfer enhancement is much more signicant than heat transfer enhancement.

The mass transfer enhancement factors of CNT are 2.16 for 0.01 wt% and 2.48 for 0.1 wt% solutions. Comparatively, the mass transfer enhancement factors of Fe nanoparticles are 1.71 for 0.01 wt% and 1.90 for 0.1 wt%. These results show that CNT has superior performance to Fe nanoparticles and hence is a better candidate for LiBr aqueous solution mass transfer enhancement. Kim et al. (2007a) found that the size of the ammonia absorber can be reduced greatly by adding surfactants or nanoparticles, which is benecial to the miniaturization of absorption equipment. Kim et al. (2007b) further studied the use of Cu, CuO, and Al2O3 nanoparticles as additives to NH3/H2O solutions. They also investigated the use of 2-ethyl-1-hexanol, n-octanol, and 2-octanol as surfactants to improve heat and mass transfer coefcients. The results showed that the addition of surfactants and nanoparticles improved the absorption performance up to 5.32 times.

4.

Thermodynamic cycle modication

Kim and Infante Ferreira (2005) proposed half-effect, aircooled water/LiBr absorption cycles driven by hot water from

Fig. 7 e Rotating absorption chiller unit (Zaltash et al., 2007).

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Fig. 8 e Conceptual diagrams of (a) liquid-cooled and (b) air-cooled micro-channel absorber (Kim et al., 2008).

a solar collector. The half-effect absorption cycles can be categorized as single pump half-effect cycle and double pump half-effect cycle. Fig. 10 shows the Duhring chart of the single pump half-effect absorption cycle. Compared to the singleeffect absorption cycle, the half-effect cycle has one extra medium-pressure absorber (MPA). The heat released from the low-pressure absorber (LPA) is cooled by the evaporator. Hence the LPA could operate at lower temperature in a half-effect cycle than in a single-effect cycle, which decreases the risk of crystallization. A half-effect absorption prototype machine was built and tested in the laboratory by the same authors. The cooling capacity and COP of this unit are 4.36 kW and 0.25, which is lower than the design goals (10 kW and 0.38, respectively) due to system leakage and cavitation in the refrigerant gear pump. An air-cooled, heat-coupled, half-effect, parallelow, water/LiBr absorption cycle has been theoretically investigated for solar air conditioning in extremely hot climates (Kim and Infante Ferreira, 2009). Modeling results indicate that the chillers could produce chilled water at 7  C with a COP of 0.37 when the hot-water temperature and ambient air temperature are 90  C and 35  C, respectively. The cooling power would decrease by 64% when the ambient temperature

increases from 35 to 50 . A dilute LiBr aqueous solution was utilized as the working uid (concentrations varied from 44.5 to 57.4 wt%) so that the risk of crystallization is less than with other water-cooled absorption chiller systems. A comparative study of single-stage and double-stage absorption cycles has been performed to examine the crystallization limitation of air-cooled water/LiBr absorption systems using low-grade heat (Izquierdo et al., 2004). Simulation results show that the single-stage cycles could not operate due to crystallization when the condensing temperatures are higher than 40  C using the heat from solar panels. However, double-stage absorption cycles could avoid crystallization until condensing temperatures reach 53  C.

5.

Absorption system-control strategies

A self-decrystallization technique has been proposed and experimentally tested in a double-effect absorption air conditioner/heater prototype unit (De Vuono et al., 1992).

Fig. 9 e Schematic of a microwick absorber (TeGrotenhuis et al., 2005).

Fig. 10 e Duhring chart of half-effect absorption cycle d single pump cycle (Kim and Infante Ferreira, 2005).

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The ue gas from the burner is bypassed to heat the solution heat exchanger after the event of crystallization. The authors thought the solution heat exchanger was the most likely component prone to crystallization. Test results showed that it might require approximately 1.4 h to allow crystallized salt to dissolve and drain from the solution heat exchanger. Martini et al. (1998, 2004) developed and patented an overconcentration control system to prevent the crystallization of LiBr solution. They used an analog-type level switch that can respond to the changing refrigerant level in the evaporator, which is a direct indication of weak concentration in the solution leaving the absorber. Solution concentration and system temperatures were then used to theoretically evaluate the absorption cycle. The uid state closer to the crystallization curve was then monitored closely and compared to current operating conditions. Once the operating conditions approach crystallization concentrations, corrective action is taken to reduce the LiBr concentration and protect the chiller. Through the use of a microprocessor, the chiller can operate in a proactive way to prevent crystallization (Kalogirou, 2008). Liao and Radermacher (2007) proposed a new methodology to prevent crystallization by raising the chilled water temperature setting or reducing the exhaust inlet temperature according to the control strategy maps developed in their research. Wang et al. (2011) studied the impact of process water ow conguration on the performance of a single-effect AHP. Two ow congurations (the process water owing either from condenser to absorber or vice versa) have been simulated and investigated at typical single-effect AHP operating conditions using ABSIM (Grossman et al., 1987). It was shown that allowing the process water to ow rst through the absorber enables wider operating conditions. However, this ow conguration resulted in AHP performance degradation of 3.3% in efciency (COP) and 4% in heating capacity at design conditions due to higher condensing temperatures.

Fig. 11 e Boosting absorber pressure to avoid crystallization: (a) mechanical compression approach; (b) Duhring diagram of absorption cycle with boosted absorber pressure (Zogg et al., 2005).

6.

Other approaches

Zogg et al. (2005) discussed boosting the absorber pressure to avoid crystallization for air-cooled absorption chillers. Fig. 11 shows the schematic diagram of this concept accomplished through mechanical compression. As shown in Fig. 11 (b), the absorber would work further away from the crystallization curve if the pressure of absorber could be elevated. Mechanical compression devices such as axial-ow fans could be utilized to lift the pressure of the absorber. A preliminary analysis performed by the authors concluded that a pressure lift equating to an 8.34  C increase in absorber saturation temperature was desired. Several issues should be considered for this approach such as designing a practical and costeffective method to integrate mechanical compression devices to separate the absorber and evaporator and optimize the boosted pressure, and system cost to achieve the maximum benet for system operation. J-tube technology is considered to be another method to prevent LiBr solution crystallization in a solution heat exchanger. J-tube technology was developed and has been widely deployed in absorption refrigeration industry (Johnson Controls, 1997; Wang and Chua, 2009). As shown in Fig. 1,

crystallization is more prone to occur in a strong solution entering the absorber. When crystallization occurs, strong solution would be forced back up to the generator. When the salt solution level reaches a certain value in the generator, the hot, highly concentrated solution will bypass or overow into the absorber through the J-tube to immediately increase the temperature of the low-concentration solution. The heated low-concentration solution will warm the crystallized salt solution in the solution heat exchanger. This transfer of heat will increase the solubility of the salt solution and dissolve LiBr crystals into solution, consequently allowing the system to continue operation. Abu-Zour and Riffat (2010) proposed to exploit the exhaust air from buildings to cool down the absorber and condenser in the air-cooled absorption system. The exhaust air is cooler than the outdoor ambient air, and it will be mixed with the outdoor air then induced into the inlet passage of the absorber and condenser units to lower inlet air temperature in hot climates.

7.

Conclusions

In this review, we highlighted previous efforts to reduce or avoid crystallization problems in LiBr-based absorption systems. Most of these efforts were focused on air-cooled absorption chiller technology. Water/LiBr absorption heatpump systems also need to conquer the technical hurdle of limiting crystallization. Absorption heat-pump systems reach higher absorption temperatures than air-cooled absorption chillers, making these systems more vulnerable to crystallization problems. The article presented a detailed review of several crystallization control strategies such as chemical

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inhibitor additives, heat and mass transfer enhancements, thermodynamic cycle modications, system-control strategies, techniques to boost absorber pressure, and J-tube technology. This review of the relevant technologies can help guide future efforts to develop water/LiBr air-cooled absorption chillers and absorption heat-pump systems. One of the most effective crystallization control technologies is using crystallization inhibitors. The criteria for choosing a chemical crystallization inhibitor are 1) effectiveness in inhibiting the crystallization, 2) stability under systems highest temperature, 3) material compatibility, 4) heat and mass transfer performance, and 5) personal and environmental safety. The most successful chemical inhibitor used to date is ethylene glycol. The trade name Carrol (LiBr ethylene glycol phenylmethylcarbinol water) developed by a company in United States has been extensively tested both experimentally and in eld settings for solardriven, air-cooled absorption chiller application. The major drawback of this uid is the toxicity of ethylene glycol. Efforts are still being pursued to develop an ideal additive for LiBrbased absorption systems. Another promising technique is to enhance heat and mass transfer using chemical additives (such as 2-ethyl-1-hexanol with chromate or molybdate, and phenylmethylcarbinol with 1-nonylamine) and nanoparticles (such as iron nanoparticles and carbon nanotubes). Heat and mass transfer could also be improved using different heat exchanger designs such as the spray absorber, bubble absorber, rotating absorber, and micro-channel absorber. These heat exchanger designs have been shown to signicantly enhance system performance and have the potential to greatly reduce the size of absorption systems as well. Half-effect absorption cycles have been proposed as a viable option to avoid solution crystallization. In these cycles, part of the refrigerant is used to cool down the absorber and the rest of the refrigerant is used for cooling effect. Hence, the absorber operates at a lower temperature than in a single-effect cycle. This shifts the absorber operation away from the crystallization curve. The main drawback of such cycles is the lower COP and the design complexity. Finally, several systems-control strategies have been recommended in the open literature, such as selfdecrystallization, over-concentration control, evaporator pressure control, and process water ow direction. The selfdecrystallization control strategy only works after the event of crystallization, while the patented over-concentration control is a preventive technique and minimizes the incidence of crystallization. Evaporator pressure control, another preventive technique to control crystallization, might limit the systems ability to meet cooling load requirements. Process water ow direction control provides wider operating conditions to the absorption heat-pump cycle and allows the system to meet various load conditions. In conclusion, different crystallization control strategies need to be coordinated to reach optimum performance and allow air-cooled water/LiBr absorption chillers and absorption heat-pump systems to operate without onset of crystallization. This would allow engineers to use renewable and waste heat sources to cool buildings in arid regions and provide more efcient heating using absorption heat pumps.

Acknowledgment
The authors would like to acknowledge Dr. Abdolreza Zaltash and Dr. Moonis R. Ally of Oak Ridge National Laboratory for their support, enlightening discussions and insights. This work was performed with funding from the U.S. DOE Ofce of Energy Efciency and Renewable Energy, Building Technologies Program.

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