System for low temperature refrigeration and chill storage using ammoniated complex compounds

Abstract: An improved heat exchange system incorporates the cooling created by using a metal salt/ammonia ligand complex compound which is alternately heated and cooled to alternately desorb and adsorb, respectively, the ammonia creating useful cooling or refrigeration in the temperature range of between -65°C to 15°C.

Description: SUMMARY OF THE INVENTION According to the present invention, it has been found that specific ammoniated complex compounds are ideal for energy storage and refrigeration in the temperature ranges of between about -65°C and 15°C. It is to the use of complex ammoniated salts for chill storage and refrigeration at temperatures below about 15°C that the present invention is directed. The complexes are used in systems in which the salt alternately adsorbs and desorbs the ammonia ligand to alternately reject or store heat, respectively. In such a system, a single complex may be alone, or, combinations of different salt complexes may be used. The complex compounds may be used in a dry system, or, in another embodiment, combined with selected liquids having a boiling point above about 60°C and a melting point below about +5°C. According to the present invention and complementary to the teaching of FR-A 683767, the complexes may be used in the dry form in systems with compressors or for the purpose of storage and recovery of thermal energy by refrigeration or elshow with a liquid in several types of refrigeration systems. DETAILED DESCRIPTION OF THE INVENTION The specific ammoniated complex compounds of the invention are selected from the following groups of salts: (1) an alkaline earth metal chloride, bromide or chlorate salt, (2) a metal chloride, bromide or chlorate salt in which the metal is chromium, manganese, iron, cobalt, nickel, cadmium, tantalum or rhenium, (3) a double chloride salt selected from NH₄AlCl₄, NaAlCl₄, KAlCl₄, (NH₄)₂ZnCl₄, (NH₄)₃ ZnCl₅, K₂ZnCl₄, CsCuCl₃, K₂FeCl₅, and (4) sodium bromide or ammonium chloride. Within each of these groups of salts, the ammoniated complex is one in which ammonia is present between specific lower and upper limits. At any given time during the reaction process, the amount of ligand present in the complex will depend on the state of adsorption or desorption. Each complex will be used to store energy and refrigerate in a specific temperature range determined by the vapor pressure equilibria of the adsorbing complex and the ammonia vapor pressure (where a single complex is used) or the corresponding desorbing complex. Within each group, the preferred specific salts, the limits of the ligand in the complex and the temperature ranges in which each complex is used for thermal energy storage and refrigeration,according to the invention, are given in the following table in which X is zero or a positive number, including a fraction, between the limits set forth: When alternately heated and cooled, portions of the ammonia ligand moiety are desorbed and adsorbed, respectively, within the aforesaid limits of X for the respective complex compounds. The cold temperature range described above, in which each individual complex compound is most effective is different with each range being a function of the chemisorption characteristics of the respective complex. Thus, the rates of adsorption and desorption will vary, depending on the specific temperature and pressure in which the system is operated. It is to be understood that the aforesaid temperature limits are the temperatures created by desorption of ammonia in a corresponding complex or by evaporation of free ammonia. The salts themselves are subjected to heat rejection temperatures in the usual range of between about 20° and about 50°C to force the cooling or refrigeration in the aforesaid ranges. Normally, in the use of such complex compounds for thermal energy storage and refrigeration, pressures between about 0.001 and about 50 atmospheres are used, and the most effective pressures will be selected by those skilled in the art. When the complex compounds are used for thermal energy storage or refrigeration in the dry state, dry bed configurations incorporate a layer of desired thickness, for example, between about 1 and about 40mm for refrigeration systems and between about 2 and about 60mm for thermal storage systems, with the bed in a suitable vessel provided with heat exchange components as well as means for heating and cooling the complex compounds therein and for recovering energy and particularly cooling which occurs during the adsorption phase of the reaction by means of ligand evaporation or by desorption of the corresponding complex. In the desorption phase, the complex compounds are heated and ammonia ligand is released. During the adsorption phase, heat is rejected, and the thermal energy differential is recovered by suitable heat exchangers present. Various heat exchange means may be used for alternately heating or cooling the compounds or in recovering the thermal energy transferred by the respective reactions, for example by providing heat pump evaporator or condenser coils or tubing to the environment created by the respective reactions. Thus, such a process is particularly valuable for refrigeration systems and for cold or chill storage apparatus. The heat generated in the exothermic phase of the reaction, may also be used for heat pump systems, or it may be recovered and used for any heating requirement, or it may be simply used as waste heat or dumped to atmosphere. In an alternative embodiment, instead of using the complex compounds in the dry state as previously described, they may be incorporated in a liquid system. The specific liquid used is one which does not significantly dissolve the complex and does not chemically react with the adsorbent. The purpose of the liquid is to function as a holding medium to provide a greatly extended surface for the adsorbent, with the small crystalline particles of the complex compound disbursed therein. Thus, the liquid actually acts as a catalyst, by reducing the activation energy barrier thereby minimizing the pressure differential required to drive the adsorption and desorption reactions. The preferred groups of organic liquids comprise alcohols, alcohol-ethers, glycol-ethers, esters, ketones and pyridines. Since these liquids are to operate in the temperature ranges designed for ammonia evaporation and condensation, between about -45°. and about 50°C, the liquid has a boiling point above about 60°C and a melting point below about 5°C. Preferred liquids are aliphatic alcohols between about 4 and about 12 carbon atoms, lower alkyl acetates, lower alkyl acetoacetates, polyalkylene glycol alkyl ether acetates, polyalkylene glycol dialkyl ethers, butyroloctone and collidine and mixtures of these liquids with water. Of the alcohols, the lower alcohols within the aforesaid range are least preferred, with those having six or more carbon atoms being more preferred because the salt of the complex compounds tends to be less soluble although this solubility will vary with different ones of the aforesaid complexes of the invention. The specifically preferred liquids within the aforesaid groups include n-heptanol, octanol, isopropyl acetate, ethyl acetoacetate, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether as well as butyroloctone and collidine. Other liquids known to those skilled in the art may also be used. Specific storage systems used to take advantage of chemisorption reactions of the aforesaid complexes include stand-alone chill storage systems designed as indirect coupled heat actuated chiller/storage systems, or a compressor may be used to compress the ammonia ligand which is in direct contact with the complex. In such a system, the liquid ammonia ligand is expanded in an expansion valve and evaporates in the evaporator to yield the cooling effect. This operating mode allows for a direct contact integration of the storage system into an ammonia refrigeration plant. At the same time, the vapor pressure of the ammonia at the low evaporator temperature is still higher than the complex compound vapor pressure at the high heat rejection temperature maintained by an evaporative condenser. As a result, ammonia leaves the ligand storage tank, evaporates, and undergoes an exothermic adsorption with the complex compound. In charging such a system, ammonia gas flow is reversed by raising the ammonia pressure sufficiently high to condense and ultimately directing the liquid back into the ligand storage tank. If a compressor is used to charge the system, ammonia is drawn out of the complex and compressed to a pressure adequate for ammonia condensation in a condenser. The complex compound may be heated with a chiller reject heat thereby maintaining small compression ratios and the condenser may be maintained a low temperature by means of the chiller evaporator. The complex vapor pressure may also be raised by applying waste or prime heat, if available whereby the condenser temperature of the storage system can be easily maintained by the chiller thus embodying a heat-activated chiller. Other suitable systems include an integrated indirect contact chill storage system, for example, using an indirect coupled chiller activated complex compound of the chilled storage system in which the charging process is performed by the chiller. Condenser heat of the chiller maintains a high complex temperature and the chiller evaporator is coupled with the storage system condenser to maintain a low ligand condensation temperature. In yet other systems, combinations of the various complex salt/ligand compounds may be used, with a different salt/ammonia complex in different vessels, which are sequentially heated and cooled, with the gaseous ligand selectively directed between the vessels to take advantage of the thermal energy transfer between the adsorption and desorption reactions. The system may also be operated as a chiller such that the ammonia ligand is desorbed from the complex by means of prime or waste heat. Such chillers can be designed as single stage configurations using one complex compound and ammonia condensation/evaporation, or using two paired complex compounds in corresponding adsorption/desorption reactions, and in Double Effect and Generator Absorber Heat Exchange (GAX) versions known in the art. Such systems as well as others utilizing the complex compounds of the invention to achieve the desired storage and heat exchange effects will be evident to those skilled in the art.

Claims: A composition for use in a heat exchange system, characterized in that the composition comprises a liquid and a complex compound, the complex compound comprising a metal salt and ammonia for being heated and cooled alternately to desorb and adsorb at least a portion of the ammonia; wherein the metal salt is selected from the group comprising: an alkaline earth metal chloride, bromide, or chlorate salt; a metal chloride, bromide or chlorate salt in which the metal is chromium, manganese, iron, cobalt, nickel, cadmium, tantalum, rhenium or tin; a double chloride salt selected from NH₄AlCl₄, NaAlCl₄ , KAlCl₄, (NH₄)₂ ZnCl₄, (NH₄)₃ ZnCl₅, K₂ZnCl₄, CsCuCl₃, K₂FeCl₅;and sodium bromide or ammonium chloride; and wherein said liquid is selected from the group comprising alcohols, alcohol-ethers, glycol-ethers, esters, ketones and pyridines. A composition as claimed in Claim 1 wherein said liquid is selected from the group comprising aliphatic alcohols having between about 4 and about 12 carbon atoms, lower alkyl acetates, lower alkyl acetoacetates, alkylene glycols, polyalkylene glycol alkyl ether acetates, alkylene glycol ethers, polyalkylene glycol dialkyl ether, dialkyl sebecates, dialkyl phthalates, butorolactone and collidine, said liquid having a boiling point at about 60°C and a melting point below about 5°C. A composition as claimed in Claim 1 or 2 wherein said liquid is selected from the group comprising n-heptanol, octanol, isopropyl acetate, ethyl acetoacetate, ethylene glycol, diethylene glycol, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, butyrolactone and collidine. A composition as claimed in any preceding Claim whrein the complex compound is selected from the group comprising: BeCl₂ · X(NH₃), wherein X is between 2 and 4, MgCl₂ · X(NH₃) wherein X is between 2 and 6, MgBr₂ · X(NH₃), wherein X is between 2 and 6, Mg(ClO₄)₂ · X(NH₃), wherein X is between 0 and - 6, CaCl₂ · X(NH₃), wherein X is between 2 and 4, CaCl₂ · X (NH₃), wherein X is between 4 and 8, CaBr₂ · X(NH₃), wherein X is between 2 and 6, Ca(ClO₄)₂ · X(NH₃), wherein X is between 2 and 6, SrCl₂ · X(NH₃), wherein X is between 1 and 8, SrBr₂ · X(NH₃), wherein X is between 2 and 8, Sr(ClO₂) · X(NH₃), wherein X is between 0 and 6, BaBr₂ · X(NH₃), wherein X is between 4 and 8, BaCl₂ · X(NH₃), wherein X is between 0 and 8, MnCl₂ · X(NH₃), wherein X is between 2 and 6, MnBr₂ · X(NH₃), wherein X is between 2 and 6, FeCl₂ · X(NH₃), wherein X is between 3 and 6, FeBr₂ · X(NH₃), wherein X is between 2 and 6, CoCl₂ · X(NH₃), wherein X is between 2 and 6, CoBr₂ · X(NH₃), wherein X is between 2 and 6, NiCl₂ · X(NH₃), wherein X is between 2 and 6, NiBr₂ · X(NH₃), wherein X is between 2 and 6, Ni(ClO₃)₂ · X(NH₃), wherein X is between 0 and 6, CrCl₂ · X(NH₃), wherein X is between 0 and 3 and between 3 and 6, CdBr₂ · X(NH₃), wherein X is between 2 and 6, TaCl₃ · X(NH₃), wherein X is between 0 and 7, ReCl₅ · X(NH₃), wherein X is between 0 and 6, ReBr₃ · X(NH₃), wherein X is between 0 and 7, SnCl₂ · X(NH₃), wherein X is between 0 and 2.5, NH₄AlCl₄ · X(NH₃), wherein X is between 0 and 6, NaAlCl₄ · X(NH₃), wherein X is between 0 and 6, KAlCl₄ · X(NH₃), wherein X is between 0 and 6, (NH₄)₂ZnCl₄ · X(NH₃), wherein X is between 0 and 4, (NH₄)₃ZnCl₅ · X(NH₃), wherein X is between 0 and 6, K₂ZnCl₄ · X(NH₃), wherein X is between 0 and 5, K₂ZnCl₄ · X(NH₃), wherein X is between 5 and 12, CsCuCl₃ · X(NH₃), wherein X is between 2 and 5, K₂FeCl₅ · X(NH₃), wherein X is between 2 and 5, NH₄Cl · X(NH₃), wherein X is between 0 and 3, and NaBr · X(NH₃), wherein X is between 0 and 5.25. A method of heat exchange using the composition of any preceding Claim in a heat exchange system wherein the complex compound is heated and cooled alternately to desorb and adsorb at least a portion of the ammonia moiety thereof. A method of heat exchange using the composition of Claims 1, 2 or 3 in a heat exchange system wherein the complex compound is heated and cooled alternately to desorb and adsorb at least a portion of the ammonia moiety thereof between numerical limits and cause refrigerating ligand evaporation in the following temperature range according to the complex compound selected: BeCl₂ · X(NH₃), wherein X is between 2 and 4 and said temperature range is between - 10 and - 65°C., MgCl₂ · X(NH₃) wherein X is between 2 and 6 and said temperature range is between 0 and - 60°C., MgBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 65°C., Mg(ClO₄)₂ · X(NH₃), wherein X is between 0 and - 6 and said temperature range is between 0 and - 65°C CaCl₂ · X(NH₃), wherein X is between 2 and 4 and said temperature range is between 0 and - 30°C., CaCl₂ · X (NH₃), wherein X is between 4 and 8 and said temperature range is between 10 and - 20°C., CaBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 40°C., Ca(ClO₄)₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 45°C., SrCl₂ · X(NH₃), wherein X is between 1 and 8 and said temperature range is between 10 and - 30°C., SrBr₂ · X(NH₃), wherein X is between 2 and 8 and said temperature range is between 0 and - 40°C., Sr(ClO₂) · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C., BaBr₂ · X(NH₃), wherein X is between 4 and 8 and said temperature range is between 10 and -30°C., BaCl₂ · X(NH₃), wherein X is between 0 and 8 and said temperature range is between 10 and -25°C., MnCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -40°C., MnBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C., FeCl₂ · X(NH₃), wherein X is between 3 and 6 and said temperature range is between 0 and -45°C., FeBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C., CoCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C., CoBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C., NiCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C., NiBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C., Ni(ClO₃)₂ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C., CrCl₂ · X(NH₃), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0 and -60°C., CdBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -40°C., TaCl₅ · X(NH₃), wherein X is between 0 and 7 and said temperature range is between 10 and -30°C., ReCl₃ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 5 and -40°C., ReBr₃ · X(NH₃), wherein X is between 0 and 7 and said temperature range is between 5 and -40°C., SnCl₂ · X(NH₃), wherein X is between 0 and 2.5 and said temperature range is between 0 and -60°C., NH₄AlCl₄ · X(NH₃), wherein X in between 0 and 6 and said temperature range is between 0 and -65°C., NaAlCl₄ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C., KAlCl₄ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C., (NH₄)₂ZnCl₄ · X(NH₃), wherein X is between 0 and 4 and said temperature range is between 0 and -60°C., (NH₄)₃ZnCl₅ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -45°C., K₂ZnCl₄ · X(NH₃), wherein X is between 0 and 5 and said temperature range is between 0 and -40°C., K₂ZnCl₄ · X(NH₃), wherein X is between 5 and 12 and said temperature range is between 0 and -35°C., CsCuCl₃ · X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C., K₂FeCl₅ · X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C., NH₄Cl · X(NH₃), wherein X is between 0 and 3 and said temperature range is between 15 and -20°C., and NaBr · X(NH₃), wherein X is between 0 and 5.25 and said temperature range is between 15 and -15°C. A method of heat exchange as claimed in Claim 5 or 6 wherein a compressor is used for drawing ammonia from said complex compound and to compress ammonia for condensation. A method of heat exchange as claimed in Claim 7 in which a compressor is used to charge the heat exchange vessels. A heat exchange system comprising a vessel for storing a composition as claimed in any one of Claims 1-4 in communication with an ammonia storage vessel for receiving and discharging the ammonia alternately. A heat exchange system comprising two heat exchange vessels for storing the liquid and a different one of the complex compounds claimed in any one of Claims 1-4, the vessels being in communication with one another whereby ammonia vapour may be selectively transferred between the vessels. A heat exchange system as claimed in Claim 9 or 10 further comprising a compressor for drawing ammonia from the complex compound and compressing ammonia for condensation. A heat exchange system in which ammonia is alternately adsorbed and desorbed on a complex compound comprising a metal salt and ammonia, the system including a compressor for drawing ammonia from said complex compound and operable to compress ammonia for condensation, and a complex compound is selected from the following complex compounds. BeCl₂ · X(NH₃), wherein X is between 2 and 4, MgCl₂ · X(NH₃) wherein X is between 2 and 6, MgBr₂ · X(NH₃), wherein X is between 2 and 6, Mg(ClO₄)₂ · X(NH₃), wherein X is between 0 and - 6, CaCl₂ · X(NH₃), wherein X is between 2 and 4, CaCl₂ · X (NH₃), wherein X is between 4 and 8, CaBr₂ · X(NH₃), wherein X is between 2 and 6, Ca(ClO₄)₂ · X(NH₃), wherein X is between 2 and 6, SrCl₂ · X(NH₃), wherein X is between 1 and 8, SrBr₂ · X(NH₃), wherein X is between 2 and 8, Sr(ClO₂) · X(NH₃), wherein X is between 0 and 6, BaBr₂ · X(NH₃), wherein X is between 4 and 8, BaCl₂ · X(NH₃), wherein X is between 0 and 8, MnCl₂ · X(NH₃), wherein X is between 2 and 6, MnBr₂ · X(NH₃), wherein X is between 2 and 6, FeCl₂ · X(NH₃), wherein X is between 3 and 6, FeBr₂ · X(NH₃), wherein X is between 2 and 6, CoCl₂ · X(NH₃), wherein X is between 2 and 6, CoBr₂ · X(NH₃), wherein X is between 2 and 6, NiCl₂ · X(NH₃), wherein X is between 2 and 6, NiBr₂ · X(NH₃), wherein X is between 2 and 6, Ni(ClO₃)₂ · X(NH₃), wherein X is between 0 and 6, CrCl₂ · X(NH₃), wherein X is between 0 and 3 and between 3 and 6, CdBr₂ · X(NH₃), wherein X is between 2 and 6, TaCl₅ · X(NH₃), wherein X is between 0 and 7, ReCl₃ · X(NH₃), wherein X is between 0 and 6, ReBr₃ · X(NH₃), wherein X is between 0 and 7, SnCl₂ · X(NH₃), wherein X is between 0 and 2.5, NH₄AlCl₄ · X(NH₃), wherein X is between 0 and 6, NaAlCl₄ · X(NH₃), wherein X is between 0 and 6, KAlCl₄ · X(NH₃), wherein X is between 0 and 6, (NH₄)₂ZnCl₄ · X(NH₃), wherein X is between 0 and 4 , (NH₄)₃ZnCl₅ · X(NH₃), wherein X is between 0 and 6, K₂ZnCl₄ · X(NH₃), wherein X is between 0 and 5, K₂ZnCl₄ · X(NH₃), wherein X is between 5 and 12, CsCuCl₃ · X(NH₃), wherein X is between 2 and 5, K₂FeCl₅ · X(NH₃), wherein X is between 2 and 5, NH₄Cl · X(NH₃), wherein X is between 0 and 3, and NaBr · X(NH₃), wherein X is between 0 and 5.25. A method of operating the system of Claim 12 wherein said complex compound is alternately heated and cooled to respectively desorb and adsorb at least a portion of the ammonia moiety thereof between numerical limits and cause refrigerating ligand evaporation in the following temperature range according to the compound selected. BeCl₂ · X(NH₃), wherein X is between 2 and 4 and said temperature range is between - 10 and - 65°C., MgCl₂ · X(NH₃) wherein X is between 2 and 6 and said temperature range is between 0 and - 60°C., MgBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 65°C., Mg(ClO₄)₂ · X(NH₃), wherein X is between 0 and - 6 and said temperature range is between 0 and - 65°C CaCl₂ · X(NH₃), wherein X is between 2 and 4 and said temperature range is between 0 and - 30°C., CaCl₂ · X (NH₃), wherein X is between 4 and 8 and said temperature range is between 10 and - 20°C., CaBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 40°C., Ca(ClO₄)₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and - 45°C., SrCl₂ · X(NH₃), wherein X is between 1 and 8 and said temperature range is between 10 and - 30°C., SrBr₂ · X(NH₃), wherein X is between 2 and 8 and said temperature range is between 0 and - 40°C., Sr(ClO₂) · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C., BaBr₂ · X(NH₃), wherein X is between 4 and 8 and said temperature range is between 10 and -30°C., BaCl₂ · X(NH₃), wherein X is between 0 and 8 and said temperature range is between 10 and -25°C., MnCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -40°C., MnBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C., FeCl₂ · X(NH₃), wherein X is between 3 and 6 and said temperature range is between 0 and -45°C., FeBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C., CoCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C., CoBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C., NiCl₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C., NiBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C., Ni(ClO₃)₂ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C., CrCl₂ · X(NH₃), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0 and -60°C., CdBr₂ · X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -40°C., TaCl₅ · X(NH₃), wherein X is between 0 and 7 and said temperature range is between 10 and -30°C., ReCl₃ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 5 and -40°C., ReBr₃ · X(NH₃), wherein X is between 0 and 7 and said temperature range is between 5 and -40°C., SnCl₂ · X(NH₃), wherein X is between 0 and 2.5 and said temperature range is between 0 and -60°C., NH₄AlCl₄ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C., NaAlCl₄ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C., KAlCl₄ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C., (NH₄)₂ZnCl₄ · X(NH₃), wherein X is between 0 and 4 and said temperature range is between 0 and -60°C., (NH₄)₃ZnCl₅ · X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -45°C., K₂ZnCl₄ · X(NH₃), wherein X is between 0 and 5 and said temperature range is between 0 and -40°C., K₂ZnCl₄ · X(NH₃), wherein X is between 5 and 12 and said temperature range is between 0 and -35°C., CsCuCl₃ · X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C., K₂FeCl₅ · X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C., NH₄Cl · X(NH₃), wherein X is between 0 and 3 and said temperature range is between 15 and -20°C., and NaBr · X(NH₃), wherein X is between 0 and 5.25 and said temperature range is between 15 and -15°C. A method for storage and recovery of thermal energy by refrigeration at temperatures between about -65 and 15°C comprising alternately heating and cooling a complex compound consisting essentially of a metal salt and ammonia causing refrigerating ligand evaporation at temperatures between the following temperature limits, respectively to alternately desorb and adsorb, respectively at least a portion of the ammonia moiety thereof between the following numerical limits, said complex compound selected from: BeCl₂ . X(NH₃), wherein X is between 2 and 4 and said temperature range is between -10 and -65°C; MgCl₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C; MgBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C; Mg(ClO₄)₂ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C; Ca(Cl0₄)₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -45°C; Sr(Cl0₄)₂ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C; BaBr₂ . X(NH₃), wherein X is between 4 and 8 and said temperature range is between 10 and -30°C; MnBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C; FeBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -50°C; CoCl₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C; CoBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -60°C; NiBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -65°C; Ni(Cl0₃)₂ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -40°C; CrCl₂ . X(NH₃), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0 and -60°C; CdBr₂ . X(NH₃), wherein X is between 2 and 6 and said temperature range is between 0 and -40°C; TaCl₅ . X(NH₃), wherein X is between 0 and 7 and said temperature range is between 10 and -30°C; ReCl₃ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 5 and -40°C; SnCl₂ . X(NH₃), wherein X is between 0 and 2.5 and said temperature range is between 0 and -60°C; NH₄AlCl₄ . X(NH₃), wherein X is between O and 6 and said temperature range is between 0 and -65°C; NaAlCl₄ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C; KAlCl₄ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -65°C; (NH₄)₂ZnCl₄ . X(NH₃), wherein X is between 0 and 4 and said temperature range is between 0 and -60°C; (NH₄)₃ZnCl₅ . X(NH₃), wherein X is between 0 and 6 and said temperature range is between 0 and -45°C; K₂ZnCl₄ . X(NH₃), wherein X is between 0 and 5 and said temperature range is between 0 and -40°C; K₂ZnCl₄ . X(NH₃), wherein X is between 5 and 12 and said temperature range is between O and -35°C; CsCuCl₃ . X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C; K₂FeCl₅ . X(NH₃), wherein X is between 2 and 5 and said temperature range is between 0 and -55°C; NH₄Cl . X(NH₃), wherein X is between 0 and 3 and said temperature range is between 15 and -20°C; and NaBr . X(NH₃), wherein X is between 0 and 5.25 and said temperature range is between 15 and -15°C.

Inventors: ROCKENFELLER UWE, ROCKENFELLER, UWE
Applicants: ROCKY RESEARCH
Application year: 1989
Main classification: C09K5
IPC codes: B01J20, C09K5, F25B15, F25B17