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

Claim 2

.[.In a.]. .Iadd.A .Iaddend.heat exchange system containing a .Iadd.liquid and a complex compound for being mixed therewith and comprising a heat exchange surface exposed to said liquid and/or said mixture, said .Iaddend.complex compound consisting of a metal salt and ammonia for being alternately heated and cooled to alternately desorb and adsorb, respectively, at least a portion of said ammonia, .[.the improvement comprising.]. said metal salt being selected from the group consisting of (a) an alkaline earth metal chloride, bromide or chlorate salt, (b) a metal chloride, bromide or .[.chloride.]. .Iadd.chlorate .Iaddend.salt in which the metal is chromium, manganese, iron, cobalt, nickel, cadmium, tantalum.Iadd., .Iaddend..[.or.]. rhenium .Iadd.or tin.Iaddend., (c) a double chloride salt selected from NH 4 AlCl 4 , NaAlCl 4 , KAlCl 4 , (NH 4 ) 2 ZnCl 4 , (NH 4 ) 3 ZnCl 5 , K 2 ZnCl 4 , CsCuCl 3 , and K 2 FeCl 5 , and (d) sodium bromide or ammonium chloride.[...]. .Iadd., and said liquid selected from the group consisting of alcohols, alcohol-ethers, glycol-ethers, esters, ketones and pyridines. .Iaddend.

Claim 3

The system of claim 1 wherein said complex compound is selected from the group consisting of the following complex compounds and wherein said complex compound is alternately heated and cooled to alternately desorb and adsorb, respectively, at least a portion of the ammonia moiety thereof between numerical limits and cause refrigerating .[.desorption and.]. ligand evaporation in the temperature range as follows: BeCl 2 ·X(NH 3 ), wherein X is between 2 and 4 and said temperature range is between -10 and -65° C., MgCl 2 ·X(NH 3 ) wherein X is between 2 and 6 and said temperature range is between 0 and -60° C., MgBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -65° C., Mg(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 0 and -6 and said temperature range is between 0 and -65° C., CaCl 2 ·X(NH 3 ), wherein X is between 2 and 4 and said temperature range is between 0 and -30° C., CaCl 2 ·X(NH 3 ), wherein X is between 4 and 8 and said temperature range is between 10 and -20° C., CaBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -40° C., Ca(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -45° C., SrCl 2 ·X(NH 3 ), wherein X is between 1 and 8 and said temperature range is between 10 and -30° C., SrBr 2 ·X(NH 3 ), wherein X is between 2 and 8 and said temperature range is between 0 and -40° C., Sr(ClO 2 )·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -40° C., BaBr 2 ·X(NH 3 ), wherein X is between 4 and 8 and said temperature range is between 10 and -30° C., BaCl 2 ·X(NH 3 ), wherein X is between 0 and 8 and said temperature range is between 10 and -25° C., MnCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -40° C., MnBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -50° C., FeCl 2 ·X(NH 3 ), wherein X is between 3 and 6 and said temperature range is between 0 and -45° C., FeBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -50° C., CoCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -60° C., CoBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -60° C., NiCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -65° C., NiBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -65° C., Ni(ClO 3 ) 2 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -40° C., CrCl 2 ·X(NH 3 ), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0 and -60° C., CdBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0 and -40° C., TaCl 3 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 10 and -30° C., ReCl 3 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 5 and -40° C., ReBr 3 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 5 and -40° C., SnCl 2 ·X(NH 3 ), wherein X is between 0 and 2.5 and said temperature range is between 0 and -60° C., NH 4 AlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -65° C., NaAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -65° C., KAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -65° C., (NH 4 ) 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 4 and said temperature range is between 0 and -60° C., (NH 4 ) 3 ZnCl 5 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0 and -45° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 5 and said temperature range is between 0 and -40° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 5 and 12 and said temperature range is between 0 and -35° C., CsCuCl 3 ·X(MH 3 ), wherein X is between 2 and 5 and said temperature range is between 0 and -55° C., K 2 FeCl 5 ·X(NH 3 ), wherein X is between 2 and 5 and said temperature range is between 0 and -55° C., NH 4 Cl·X(NH 3 ), wherein X is between 0 and 3 and said temperature range is between 15 and -20° C., and NaBr·X(NH 3 ), wherein X is between 0 and 5.25 and said temperature range is between 15 and -15° C.

Claim 4

The system of claim 2 .[.including a liquid therein in which.]. wherein said complex compound is disbursed.[.,.]. .Iadd.in .Iaddend.said liquid .[.selected from the group consisting of alcohols, alcohol-ethers, glycol-ethyers, esters, ketones and pyridines.]..

Claim 6

The system of claim 2, wherein said liquid is selected from the group consisting of 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, .[.butyroloctone.]. .Iadd.butyrolactone .Iaddend.and collidine.

Claim 11

The method of claim 7 wherein said heating and cooling is carried out in a heat exchange vessel.

Claim 12

The method of claim 8 comprising alternately directing said ammonia between the heat exchange vessel and an ammonia storage vessel.

Claim 13

The method of claim 7 comprising introducing a different one of said metal salts into different heat exchange vessels, respectively, alternately adsorbing and desorbing said ammonia from said different metal salts, and directing said ammonia between said heat exchange vessels. .[.11. The method of claim 7 comprising disbursing said complex compound in a liquid selected from the group consisting of alcohols, alcohol-ethers, glycol-ethers, esters, ketones and pyridines..]. .Iadd.12. A compressor charged thermal energy storage system containing a complex compound consisting of a metal salt and ammonia, wherein said complex compound is selected from the group consisting of the following complex compounds, wherein a compressor is used to draw ammonia from said complex compound and to compress the ammonia for condensation, and wherein said complex compound is alternately heated and cooled to alternately desorb and adsorb, respectively, at least a portion of the ammonia moiety thereof between numerical limits to recover thermal energy in the temperature range as follows: BeCl 2 ·X(NH 3 ), wherein X is between 2 and 4 and said temperature range is between -10° and -65° C., MgCl 2 ·X(NH 3 ) wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., MgBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -65° C., Mg(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 0 and -6 and said temperature range is between 0° and -65° C., CaCl 2 ·X(NH 3 ), wherein X is between 2 and 4 and said temperature range is between 0° and -30° C., CaCl 2 ·X(NH 3 ), wherein X is between 4 and 8 and said temperature range is between 10° and -20° C., CaBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -40° C., Ca(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -45° C., SrCl 2 ·X(NH 3 ), wherein X is between 1 and 8 and said temperature range is between 10° and -30° C., SrBr 2 ·X(NH 3 ), wherein X is between 2 and 8 and said temperature range is between 0° and -40° C., Sr(ClO 2 )·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -40° C., BaBr 2 ·X(NH 3 ), wherein X is between 4 and 8 and said temperature range is between 10° and -30° C., BaCl 2 ·X(NH 3 ), wherein X is between 0 and 8 and said temperature range is between 10° and -25° C., MnCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -40 ° C., MnBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -50° C., FeCl 2 ·X(NH 3 ), wherein X is between 3 and 6 and said temperature range is between 0° and -45° C., FeBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -50° C., CoCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., CoBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., NiCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -65° C., NiBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -65° C., Ni(ClO 3 ) 2 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -40° C., CrCl 2 ·X(NH 3 ), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0° and -60° C., CdBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -40° C., TaCl 5 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 10° and -30° C., ReCl 3 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 5° and -40° C., ReBr 3 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 5° and -40° C., SnCl 2 ·X(NH 3 ), wherein X is between 0 and 2.5 and said temperature range is between 0° and -60° C., NH 4 AlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., NaAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., KAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., (NH 4 ) 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 4 and said temperature range is between 0° and -60° C., (NH 4 ) 3 ZnCl 5 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -45° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 5 and said temperature range is between 0° and -40° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 5 and 12 and said temperature range is between 0° and -35° C., CsCuCl 3 ·X(NH 3 ), wherein X is between 2 and 5 and said temperature range is between 0° and -55° C., K 2 FeCl 5 ·X(NH 3 ), wherein X is between 2 and 5 and said temperature range is between 0° and -55° C., NH 4 Cl·X(NH 3 ), wherein X is between 0 and 3 and said temperature range is between 15° and -20° C., and NaBr·X(NH 3 ), wherein X is between 0 and 5.25 and said temperature range is between 15° and -15° C. .Iaddend.

Claim 14

.Iadd.3. A method for storage and recovery of thermal energy using a system of claim 12 comprising charging said system using said compressor and drawing said ammonia from said complex compound and compressing said ammonia with said compressor. .Iaddend. .Iadd.14. A heat exchange system comprising a heat exchanger and a vessel containing a complex compound selected from the following complex compounds and wherein said complex compound is alternately heated and cooled to alternately desorb and adsorb, respectively, at least a portion of the ammonia moiety thereof between numerical limits and cause refrigerating ligand evaporation in the temperature range as follows: BeCl 2 19 X(NH 3 ), wherein X is between 2 and 4 and said temperature range is between -10° and -65° C., MgCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., MgBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -65° C., Mg(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 0 and -6 and said temperature range is between 0° and -65° C., Ca(ClO 4 ) 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -45° C., SrCl 2 ·X(NH 3 ), wherein X is between 1 and 8 and said temperature range is between 10° and -30° C., Sr(ClO 2 )·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -40° C., BaBr 2 ·X(NH 3 ), wherein X is between 4 and 8 and said temperature range is between 10° and -30° C., MnBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -50° C., FeBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -50° C., CoCl 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., CoBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -60° C., NiBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -65° C., Ni(ClO 3 ) 2 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -40° C., CrCl 2 ·X(NH 3 ), wherein X is between 0 and 3 and between 3 and 6 and said temperature range is between 0° and -60° C., CdBr 2 ·X(NH 3 ), wherein X is between 2 and 6 and said temperature range is between 0° and -40° C., TaCl 5 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 10° and -30° C., ReCl 3 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 5° and -40° C., ReBr 3 ·X(NH 3 ), wherein X is between 0 and 7 and said temperature range is between 5° and -40° C., SnCl 2 ·X(NH 3 ), wherein X is between 0 and 2.5 and said temperature range is between 0° and -60° C., NH 4 AlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., NaAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., KAlCl 4 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -65° C., (NH 4 ) 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 4 and said temperature range is between 0° and -60° C., (NH 4 ) 3 ZnCl 5 ·X(NH 3 ), wherein X is between 0 and 6 and said temperature range is between 0° and -45° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 0 and 5 and said temperature range is between 0° and -40° C., K 2 ZnCl 4 ·X(NH 3 ), wherein X is between 5 and 12 and said temperature range is between 0° and -35° C., CsCuCl 3 ·X(NH 3 ), wherein X is between 2 and 5 and said temperature range is between 0° and -55° C., K 2 FeCl 5 ·X(NH 3 ), wherein X is between 2 and 5 and said temperature range is between 0° and -55° C., NH 4 Cl·X(NH 3 ), wherein X is between 0 and 3 and said temperature range is between 15° and -20° C., and NaBr·X(NH 3 ), wherein X is between 0 and 5.25 and said temperature range is between 15° and -15° C. .Iaddend. .Iadd.15. The system of claim 14 wherein said complex compound is SrCl 2 ·XNH 3 wherein X is between 1 and 8. .Iaddend. .Iadd.16. The system of claim 14 wherein said complex compound is SnCl 2 ·XNH 3 wherein X is between 0 and 2.5. .Iaddend. .Iadd.17. The system of claim 14 wherein said complex compound is CoCl 2 ·XNH 3 wherein X is between 2 and 6. .Iaddend.