MXPA97007182A - Improved air heating and air conditioning systems that incorporate solid-steam absorption reactors with reacc altitude capacity - Google Patents
Improved air heating and air conditioning systems that incorporate solid-steam absorption reactors with reacc altitude capacityInfo
- Publication number
- MXPA97007182A MXPA97007182A MXPA/A/1997/007182A MX9707182A MXPA97007182A MX PA97007182 A MXPA97007182 A MX PA97007182A MX 9707182 A MX9707182 A MX 9707182A MX PA97007182 A MXPA97007182 A MX PA97007182A
- Authority
- MX
- Mexico
- Prior art keywords
- complex compound
- gas
- reactors
- heating
- metal salt
- Prior art date
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 86
- 238000010521 absorption reaction Methods 0.000 title description 15
- 238000004378 air conditioning Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 145
- 238000006243 chemical reaction Methods 0.000 claims abstract description 132
- 150000003839 salts Chemical class 0.000 claims abstract description 75
- 239000011780 sodium chloride Substances 0.000 claims abstract description 75
- 238000009792 diffusion process Methods 0.000 claims abstract description 55
- 238000003795 desorption Methods 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000012530 fluid Substances 0.000 claims abstract description 29
- 238000004891 communication Methods 0.000 claims abstract description 7
- KGJZTOFHXCFQIV-UHFFFAOYSA-N Sodium tetrafluoroborate Chemical compound [Na+].F[B-](F)(F)F KGJZTOFHXCFQIV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003990 capacitor Substances 0.000 claims abstract description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K AlF3 Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract 2
- 150000004820 halides Chemical class 0.000 claims abstract 2
- 229910001509 metal bromide Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 130
- 239000003507 refrigerant Substances 0.000 claims description 63
- 238000001816 cooling Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 17
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 235000011148 calcium chloride Nutrition 0.000 claims description 9
- JHJLBTNAGRQEKS-UHFFFAOYSA-M Sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000567 combustion gas Substances 0.000 claims description 6
- WGEFECGEFUFIQW-UHFFFAOYSA-L Calcium bromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 5
- YJPVTCSBVRMESK-UHFFFAOYSA-L Strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 claims description 5
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 229910001625 strontium bromide Inorganic materials 0.000 claims description 5
- OTCKOJUMXQWKQG-UHFFFAOYSA-L Magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910002850 SnCl2 Inorganic materials 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L Tin(II) chloride Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 229910019131 CoBr2 Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L Iron(II) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L MANGANESE CHLORIDE Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021380 MnCl2 Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 108060007803 SPC25 Proteins 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L Barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims 1
- 101710030029 COLEC12 Proteins 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 229910001626 barium chloride Inorganic materials 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- BICAGYDGRXJYGD-UHFFFAOYSA-L bromide;chloride Chemical compound [Cl-].[Br-] BICAGYDGRXJYGD-UHFFFAOYSA-L 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 210000001736 Capillaries Anatomy 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003842 bromide salts Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052803 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001419 dependent Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000670 limiting Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reduced Effects 0.000 description 2
- 230000001429 stepping Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002459 sustained Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 101700013479 ASL Proteins 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910004682 ON-OFF Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N Rhenium Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001174 ascending Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning Effects 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 230000000051 modifying Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000036961 partial Effects 0.000 description 1
- 230000000737 periodic Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000135 prohibitive Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000002441 reversible Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004326 stimulated echo acquisition mode for imaging Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
Abstract
The present invention relates to a heating system comprising: a) one or more reactors or banks of reactors each containing a complex compound formed by the adsorption of a polar gas on a metal salt and in which the polar gas alternatively adsorbed and desorbed on the complex compound, the metal salt comprises a halide, nitrate, oxalate, perchlorate, sulfate or sulphite of an alkali metal, alkaline earth metal, transition metal, zinc, cadmium, tin or aluminum or sodium borofluoride or a double metal bromide chloride and wherein the complex compound in the one or more reactors is formed by restricting the volumetric expansion and controlling the density thereof, during the adsorption of the polar gas on the metal salt, by which the complex compound has a capacity of increased reaction rates in moles of polar gas adsorbed and / or desorbed per mole of the complex compound per hour at times of adsorption or desorption of less than 60 minutes respectively, compared to a complex compound formed without restricting the volumetric expansion and controlling the density thereof, the one or more reactors each having a heat transfer section for thermally exposing a fluid of heat transfer and / or polar gas condensed in heat exchange communication with the complex compound, b) capacitor means comprising at least one capacitor for condensing the polar gas and heat recovery means cooperating therewith to recover the heat generated in the condenser means, c) evaporator means comprising at least one evaporator for evaporating the condensed polar gas, d) a first conduit for directing the condensed polar gas from the condenser means to the evaporator means; e) one or more second conduits cooperating with the condenser means and the one or more reactors to direct the polar gas c condensed media from the condenser means to the heat transfer section of the reactor and to direct the vaporized polar gas therefrom to the condenser means; f) one or more third conduits to direct the polar gas from the evaporator means to the condensers; reactors and from the reactors to the condenser means, and g) heating means cooperating with the one or more reactors for heating the complex compound therein, the system being characterized in that one or more reactors have one or more reaction chambers in the same, which have a maximum average mass diffusion path length of less than about 15 millimeters and / or a maximum thermal diffusion path length of less than 1.5 millimeter
Description
IMPROVED AIR HEATING AND CONDITIONING SYSTEMS INCORPORATING SOLID-STEAM ABSORPTION REACTORS WITH HIGH REACTION SPEED CAPABILITIES BACKGROUND OF THE INVENTION US Pat. Nos. 5,298,231, 5,328,671, and 5,441,716 describe improved methods and apparatus for achieving high reaction rates of adsorption / desorption between polar gases and certain metal salts. These adsorption / desorption reactions, often referred to as "absorption" or "chemisorption" in the technical literature, produce complex compounds which are the basis for efficient cooling, thermal storage, heat pump systems and systems. of power that have high energy density. The methods described above result in increased or maximized reaction rates between the gas and the complex compound, that is, the time it takes to absorb or desorb a given amount of the ao gas from the complex compound to produce an increased or improved potency that can be supplying by the system, that is, more energy supplied, over a period of time, which translates into a greater cooling capacity of the apparatus In the aforementioned patents 5,298,231 and 5,328,671, complex compound reactors are described in which the absorbers of the complex compound are those created by optimizing the density of the complex compound by limiting its volumetric expansion formed during at least the initial absorption reaction between the metal salt and the polar gas. The resulting complex compounds are those in which the velocities of
REF: 25452 adsorption and desorption reaction are increased compared to the reaction rates using a complex compound formed without restricting the volumetric expansion and controlling the density during such reaction. The increase in reaction rates is expressed as an increase in the number of moles of polar gas adsorbed and / or desorbed per mole of the complex compound per hour at times of the adsorption or desorption cycle of less than 60 minutes. The description of such methods, reactors and complex compounds of the aforementioned patents and applications are incorporated herein by reference. US Patent 5,441,716 discloses further improved methods and apparatus for achieving improved reaction rates incorporating absorption reactors having thermal and mass diffusion path lengths within important defined limits. The reactors and the resulting reactions are capable of reaching a maximum power density per mass of absorber, maximum power density per reactor mass and maximum power density per desired or required reactor volume. US Pat. No. 5,477,706 discloses methods and apparatus for achieving improved heat rejection and an adsorption reactor in solid-vapor absorption systems. The systems include apparatuses in which the refrigerant of the system is used as the heat transfer fluid to cool an adsorption reactor, the activation of a heat rejection cycle to cool an adsorption reactor when using the displacement of transfer fluid of heat without requiring a thermostat or solenoid valve control of the cooling circuit and to transfer heat from a single heat source to either one or the other of two reactors to provide continuous cooling or cooling.
BRIEF DESCRIPTION OF THE INVENTION The present invention relates to heating and air conditioning apparatuses and systems that include furnaces and heat pumps incorporating reactors and methods described in the patents and incorporated applications mentioned above. Specific preferred appliances include single-stage and multi-stage ovens and air conditioning systems and heat pumps for residential and commercial use. The design and specific components of such an apparatus will be described in the detailed description hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a single-stage heating and oven system of the invention; Figure 2 schematically illustrates an example of a heat pump of two absorbent banks that includes an inversion valve for the selective heating and cooling operation; Figure 3 is a schematic illustration of a two-stage heat pump apparatus of the invention and Figure 4 schematically illustrates a 3-stage heat pump apparatus useful for heating and air conditioning.
Detailed description. The heating and air conditioning systems of the invention incorporate and utilize solid-vapor absorption reactors which contain a complex compound formed by the absorption of a polar gas on a metal salt and in which the absorption reaction has been carried out. by restricting the volumetric expansion of the complex compound formed. The polar or refrigerant gas used in the chemisorption reactions is capable of forming a coordinated covalent bond with the salt. The complex compounds are those described in U.S. Patent No. 4,848,994. The preferred reactive polar gases are ammonia, water, lower alkanols (C1-C5), alkylamines and polyamines. Sulfur dioxide, pyridine and phosphine can also be used. Preferred metal salts include nitrates, nitrites, perchlorates, oxalates, sulfates, sulphites and alloys, in particular chlorides, bromides and iodides of alkali metals, alkaline earth metals, transition metals, particularly chromium, manganese, iron, cobalt, nickel, copper, tantalum and rhenium, as well as zinc, cadmium, tin and aluminum. The double metal chloride or bromide salts in which at least one of the metals is an alkali metal or alkaline earth metal, aluminum, chromium, copper, zinc, tin, manganese, iron, nickel or cobalt are also useful. Another salt of special interest NaBF4. Other useful complex compounds are those described in U.S. Patent Nos. 5,186,020 and 5,263,330 and are incorporated herein by reference. The preferred complex compounds used in the reaction of the invention are as follows or comprise adsorption / desorption compositions containing at least one of the following as a component:
TABLE Complex compound Value X SfCL -? | NH3 | 0-1. 14 CaCL - x IML; 0-1. 12.24.4-8 ZnCL - X NHJ 0-1, 1-2, 24, 4-6 ZnBrt-X (NHV 0-1.12, 24.4-6 Zní-iMH,) 0-1. 1-2, 24, 16 C? • X (IÍHJ 0-T 12, 26
CdBr, -Xpttj oi, 1-2, 2-6 0-2.2-6 E C1- - X (HH,) 0-8 UBO, • X (MHj) D », T -2, 2-6 Mgßrz • X (NH,) 0-1, T-2.2-6 ttít, -xdírc 02, 2-6 FßCL. X (UK,) 0-1, 1-2.2-6 Fßrj-XflrV 0-1, 12.2-8 Filj- dtLJ 0-2, 24 «a, • x?» And 0-1, MM KBr2-X . { NH, l 0-1, 12.2-8 MI- - X (NrJ 0-2.2-6 Srí, 'X (NH 0-1, 1-2.2-6.
Srfc, • X IW CU, VZ 2-8 S * Z • X (KrUJ Q-2, 2.54, 4-9 SRSG3-X (Nig 0-1.1-2, 2-3.3-5, S Ba6r, -X | f »g 0-1.12,24,4-8 MiC ^ - ÍNH,) r1, U2-6 MftBf, INri 0-1.12.2-6 u * _ • x (my sz 24 Caí, • X IMH]) 0 -1.12.26, 68 UCI XfNH ^ »f.1Z2-3.34 IBlfltV 0-1.12.23.34 HA-XIW,) 05? NIBF, - x tug asís
N? F, • X INH.) 0 * 2.8 Nat * X. { NH,) 04.8 KjFtcij - x ?? ny os.5 * ß-p K.ZnCL - X (NHJ 048-12 MDÍCIQJ, «X WHJ 0-8 UiWO ^ -XWHJ 0X24. * SrtaO? XflH,) 04.8-7 CT? Tj XfHHJ I »Cria, • X INHJ 0-1»
W XWHJ 0-13-5,5-6,6,7,712 A «» 'X Wj) 8113, 3 * Sß.6-7, 7-14 CüSO.-XWiy Mp 1.2.24. ,5
Especially preferred are any of the complexes CaCl2X (NH3), SrCfe 1-8 (NH3), SrBr22-8 (NH3), CaBr2-2-6 (NH3), Cal2-2-6 (NH3), FeCI22-6 (NH3) ), Fel -2-6 (NH3), CoCl22-6 (NH3), CoBr22-6 (NH3), gCI22-6 (NH3), MgBr22-6 (NH3), MnCI22-6 (NH3) and MnBr2 2-6 (NH3), and mixtures thereof. According to the invention, the solid-gas adsorption reactions, that is, absorption and desorption of the gas on solid, are carried out under conditions and in a proposed apparatus to produce high power densities. Such reactions have the capacity of preference to reach a maximum power density per mass of absorbent, maximum power density per reactor mass and maximum power density per desired or required reactor volume. The half-cycle times, that is, absorption or desorption reaction times of the reactions having improved reaction rates according to the present invention are carried out, at least for one of the adsorption or desorption phases in less of 60 minutes, generally less than 30 minutes preferably in less than about 20 minutes and usually between about 3 and about 15 minutes. It will be understood that not all applications require identical times for adsorption and desorption and in some cases one or both reactions may be as short as approximately 2 minutes while in other cases, one of the reactions may extend a few minutes beyond 30 minutes. In addition, during partial load conditions, when the equipment is not expected to produce its full heating capacity, cooling, cooling or power, the reaction times can be extended in order to limit the inherent process cycles and avoid unnecessary thermal losses. It will be understood that full cycles or full cycle time periods also require a period of time to adjust or change the pressure between the half cycles of adsorption and desorption.
Thus, a period of complete cycle comprises the sum of the times of the half cycles plus two times of adjustment of the pressure-temperature, the latter are each usually from a few seconds to a few minutes. The optimal reaction rates are dependent on a variety of independent parameters, which include the density of the absorber, the length of the mass diffusion path, the length of the heat or thermal diffusion path, as well as the conditions of thermodynamic operations. The latter include the total conditions of the process, that is, the specific temperature and pressure conditions in which the process is carried out, the differential pressure or DELTAP that is, the difference between the operating pressure of the system and the pressure equilibrium of the complex compound and the temperature of the process or (T, which is usually greater than 8 ° K during at least one of the adsorption or desorption reactions.) Finally, the parameter of the specific salt and the complex compounds formed between the salt and a specific selected polar gas should be considered, it will be understood that the characteristics of such salts and the resulting complex compounds, which include the equilibrium pressures thereof, are important determinations for balancing the parameters mentioned above, to optimize the reaction conditions and reach a system that has maximized reaction rates. In the present, the term "optimized reaction product" or "optimized complex compound" is a complex compound in which the process of absorbing the polar gas on the metal salt is carried out under process conditions that result in a reaction product of the complex compound having the aforementioned characteristics which leads to an economic optimum. Each reaction chamber or reactor module has dimensions which provide a basis for measuring or determining the length of the thermal diffusion path (heat transfer) and the length of the mass diffusion path (mass transfer), respectively . The length of the thermal path is the distance from a highly thermally conductive surface to the center of the mass of a complex compound. A heat conducting fin is an example of such a thermally conductive surface. In this example the thermal diffusion in a given reactor is mainly a function of the fin count, that is, the number of fins per unit length (height of the reactor modules). The greater the number of fins per unit of reactor length, the better the thermal diffusion and the smaller the length of the thermal diffusion path. The thermal diffusion path is the path from the most distant particle of the complex compound to the nearest heat conducting surface. Thus, the length of the simplified thermal path is half the distance between two adjacent fins or plates. According to the invention, the length of the thermal diffusion path is less than 4.5 millimeters, preferably about 4 millimeters or less, and more preferably about 3.0 millimeters or less. When using a group of the preferred salts described herein, the most preferred thermal path length is between 0.6 and 3.2 rtriiipB rcs. This is also equivalent to a fin count of at least 4 fins per inch and preferably of about 9 to 25 fins per inch (1.4 to 0.5 millimeters of thermal path length), or greater if practical for manufacturing, for optimized power density requirements. The preferred thermal path length fluctuates for some specific salts, as described in the aforementioned U.S. Patent No. 5,441,716. It will be understood that such determination of the length of the simplified trajectory does not take into account the wall of the, although that surface also contributes to the thermal path. The normal practical appropriate fin thicknesses will vary from approximately 0.07 millimeters to approximately 2 millimeters. Where the lengths of the thermal diffusion path are relatively short, the smaller fin thicknesses are usually preferred. The fin thickness is normally set to give a small drop or rise in temperature in the fin, as compared to the temperature of the adsorption or desorption process. The determination or measurement of the length of the thermal path can be easily determined for any three-dimensional reaction chamber. The size and shape of the fins or heat exchanger or thermal conductive surfaces is based on the common heat transfer calculations comprised by those skilled in the art. For example, the reactor may incorporate a plurality of heat exchange surfaces, fins or plates extending vertically radially along a conduit of the heat exchange fluid. Reactors of this type are illustrated in the aforementioned patents 5,298,231 and 5,441,716. In this example, the distance between the fins or plates varies, due to the wedge-like shape of the different reaction chambers between the adjacent plates which are not parallel. However, the average distance between two adjacent plates will be measured at a point halfway between the inner and outer edges of the respective plates. In the reactors of a design in which the height of the fin is quite low or small or in which the count of fins is under the proximity of a salt or complex compound molecule to a primary heat transfer surface such as Tubes or plates also becomes important in determining the length of the thermal path. The measurement and determination of the length of the thermal path can be done independently of the shape or size of the adjacent solid fin or wall surfaces of the reaction chamber that extend from and in thermal communication with the conduit or conduits of the reactor. heat exchange that extend through the reactor. Such heat exchange surfaces, walls, plates or fins also usually comprise the walls of the gas impermeable reactor module, which define or form the reaction chamber or reaction chambers within the reactor. The reactor core may also comprise a tube fin reactor that uses multiple tubes to direct the heat transfer fluids through the reactor in thermal contact with the adsorption layer confined between the plates or fins and a gas permeable wall. This and other reactor examples are shown and described in U.S. Patent No. 5,441,716. Although the length of the thermal diffusion path is a highly important parameter, as summarized above, the length of the mass diffusion path, ie, the length of the path of a refrigerant molecule to and from a particle or molecule of Adsorption is also quite critical in reactors or reaction chambers in which the density of the mass of the reaction product has been controlled by limiting the volumetric expansion, according to the present invention. In order to achieve the high reaction rates according to the present invention, a reactor or reaction apparatus must be designed for the ability to move a substantial amount of refrigerant within the adsorbent mass in a relatively short period of time. For this reason, the length of the mass diffusion path of the reactor is of relevant importance. The length of the mass diffusion path is determined by measuring the distance between the gas entry point or surface to the mass of adsorbent (chamber or reaction module) to the opposite end or wall of the chamber, which represents the greater distance that the gas must travel to and from the molecules or particles of the complex compound during the cycles of adsorption and desorption. This dimension is easily determined for any size or shape of reaction chamber. However, the important consideration in the determination of desirable preferred or optimized mass diffusion path lengths should take into account the entire mass of the adsorbent particles in relation to the gas distribution means, that is, gate, vent, etc., from which the gas is directed to and from the mass of adsorbent within the reaction chamber. It will also be understood that the flow of refrigerant through the adsorbent mass to and from the adsorption sites is not simply based on the permeability or penetration of the gas through a porous medium, nor is it based solely on the penetration of the gas through the gas. a dense product mass contained in a limited volume. Instead, in the present chemisorption reaction process, the absorber of the complex compound changes its properties throughout the process as it coordinates and absorbs the gas molecules. Since coordination is commonly a polar gas adsorbed on the complex compound in one or more coordination spheres, the absorption rates are impacted by the coverage of the coordination site and by the shield resulting from the accumulation of coordinated polar gas molecules. in front of incoming polar gas molecules during adsorption. Therefore, the length of the mass flow path or the average mass diffusion path becomes extremely important and critical to achieve high reaction rates and power density according to the invention. Thus, in any reactor, it is not only a maximum mass transfer distance to an adsorbent particle that will be considered, but also the average or average distance that the gas must travel to and from all the particles in the mass. As used herein, the term length or distance of the average mass diffusion path is defined as the arithmetic mean in all particles of the shortest distance from each particle to a gas permeable surface, which limits the compound, input of gas distribution, outlet or other means of gas distribution. Thus, the length of the average mass diffusion path is equal to:
where di = the shortest distance from the ith particle to a gas permeable surface and n is equal to the number of particles. According to the invention, for rapid adsorption and desorption reactions that absorb a substantial amount of coordination sphere of the available refrigerant theoretically in less than about 30 minutes and preferably less than 20 minutes, by at least one of the adsorption cycles or desorption, the length of the average mass diffusion path is less than 15 millimeters and preferably about 13 millimeters or less and more preferably less than 8 millimeters. In order to meet this critical requirement, the chamber or chambers of the reactor or reaction of the apparatus in which the adsorbent is present and the gas distribution components, ie, pipes, reactor walls, channels, inlets, gates, Vents, etc., are preferably designed in such a way that the average mass diffusion path as defined above in such a reactor is 15 millimeters or less. For the group of preferred salts described herein, the most preferred average mass path length is between 3 and 7 millimeters. It is also preferred in reactors or reaction chambers that at least 60% of the metal salt or complex compound, by weight, be within 25 millimeters or less of a gas distribution medium. The range of the length of the preferred average mass diffusion path specific for some specific salts is described in U.S. Patent No. 5,441,716. From the foregoing it will be apparent that the lengths of the thermal and mass diffusion path can be changed or varied by selecting or designing a reactor having reaction chambers (modules) of fin depth dimensions and chamber height. desirable reaction. An increase in fin counts or number of fins per unit length of the reactor will increase the thermal conductivity of the system and reduce the length of the thermal path. Also, the length of the mass diffusion path can be selected by selecting or designing a reactor having a greater or lesser distance between the gas permeable media through which the gaseous reactant passes during the adsorption reaction phases and Desorption alternatives and the opposite end of the reaction chamber. For example, additional slots, gas pipe or gas permeable materials such as refractory brick, porous cement, porous plastics, sintered metals or ceramics, wire mesh, etc. may be used in the design of the reactor assembly to increase the gas inlet and outlet exposure to reduce the lengths of the mass diffusion path. When designing or selecting reactors and reaction chamber configurations, these two independent parameters must be considered and selected to give a reactor that has the reaction chambers of the lengths of the mass diffusion path and thermal diffusion desired to give velocities of optimal or preferred reactions. Therefore, optimal reactors capable of achieving the desired reaction rates and the desired power density according to the invention will have thermal diffusion (heat) and mass path lengths as summarized above. When designing the reactor cores to optimize the dimensions of the reaction chamber or of the reactor module according to the invention, although the relatively short gas diffusion paths are desirable from a viewpoint of the reaction rate, the ratio by weight of the physical elements of the heat exchanger to the absorber can become prohibitive. In order to balance these characteristics, the following principles can be applied. The extension of the heat transfer surface can be made of a thermally conductive and gas permeable material, which has less resistance to gas flow than that found in the complex compound. For such advantage the fin plates of the reactor core by themselves can be designed to conduct the gas through the surface of the fin or plate directly to the layer of the adsorbent on each side of, or otherwise, in contact with the fin plate. Examples of the appropriate fin plate material include sintered or powdered metals, metal foams or highly conductive non-metallic ceramics or other porous materials. When using such fin plates for heat transfer and gas distribution, the mass transfer distance described above would no longer apply, since the distance between the adjacent fins or plates would become the distance of the heat transfer path and mass to be considered. Second, where the use of gas permeable reactor fin plates for heat and mass transport is undesirable, the gas permeable components or materials spaced between the fin plates of the reactor can be used. Such gas-permeable materials which are compatible with the solid reactant and the gaseous refrigerant offer low gas resistance and substantially improve and contribute to the increased gas distribution throughout the solid adsorbent. A third means for increasing the gas diffusion through the complex compound is to use a porous gas permeable material added to the salt, then the mixture is introduced to the reactor core. Of particular interest are the materials which can be mixed with the adsorbent salt and which have geometries that offer a directional flow for the gas through the mass of the salt and the complex compound. Reference is made herein to such materials as gas directional flow mixture components or gas distribution mixture compositions. These materials can be used to improve the total transport of the gas or refrigerant to and from the adsorption sites of the complex compounds or mixtures which contain complex compounds and comprise components having microporous, elongated or extended surfaces, such as microtubes or other appropriate geometries. of materials that are permeable to gas and have a transport resistance to gas less than the adsorbent of the complex compound by adsorption and / or desorption. A description and further explanation of such materials is described in U.S. Patent No. 5,441,716 and are incorporated herein by reference. Another parameter to be determined is the mass of salt per unit volume of reaction chamber cavity or charge density of the metal salt, in solid particles introduced to the reactor and the optimum density of the reaction product of the resulting complex compound to reach optimal or desired reaction rates or power densities to adsorb and desorb the gaseous reactant to and from the complex compound. In order to achieve the desired or optimum density of the complex compound between a reactor having a fixed volume, the quantity or volume of the unreacted salt introduced into the reaction chambers must be sufficient, so that when the Reaction mass structure of the complex compound during the reaction of the absorption process, the volumetric expansion results in each chamber or reaction module being filled with the structure composition of the newly formed complex compound having the desired density. Normally, the density of the complex compound formed will be lower than the density of the salt before the initial reaction, although the density of a fully adsorbed complex compound is often higher. The density of the complex compound will also vary depending on the operating conditions, that is, pressure and temperature. Each salt and complex compound will react somewhat differently at different temperatures and pressures. A) Yes, such operating conditions, also as the equilibrium pressure of the complex compound and the process pressure, should be considered. Therefore, the optimized density for each complex compound under such operating conditions must also be determined independently. According to the invention, the charge density of the adsorbent salts to react with ammonia in the cavity of the heat exchanger is preferably between about 0.2 and 1.0 g / cc and more preferably between 0.3 and 0.8 g / cc but for the salts having a high bulk density or flow density, the charge density must exceed 1 g / cc in particular for relatively high molecular weight absorbers. However, according to the invention, these density ranges must also take into account the heat and mass transfer parameters described above. Thus, the selection of a density of the salt, within the limits mentioned above, will be used in a reactor or reaction chamber having a path length of thermal diffusion and / or a path length of mass diffusion as it is summarized and described above in the present. The preferred charge density ranges, the lengths of the mass diffusion path and the lengths of the thermal diffusion path for certain specific salts used with ammonia refrigerants are shown in Table 1 of U.S. Patent No. 5,441,616 and the which information is incorporated herein by reference. Specific improvements in the reaction chambers by optimizing the lengths of the thermal diffusion and mass diffusion path and the density of the complex compound result in substantial improvements and increase in reactor economy. This improvement substantially impacts the efficiency of the complex compounds and concomitantly the amount of energy which can be provided by the system or apparatus in a given reaction cycle period. For example, in some equipment applications, reaction rates of approximately 10-15 mol / mol-hr, involve half cycle periods of approximately ten to twelve minutes, that is, a ten minute time required to adsorb or desorb the amount of the gaseous ligand of the compound compiejo. In comparison, reaction rates of 25 to 35 mol / mol-hr, involve half-cycle periods of approximately 5 to 7 minutes, to approximately double the energy available from such a system for a given period of time operation. The high reaction rates obtained by using the optimized reactors as described above are capable of being sustained not only for periods of a short cycle, but in periods of up to 20 minutes or more. Thus, reaction rates of more than 6 mol / mol-hr, normally 10 - 20 mol / mol-hr, can be sustained for at least 6 minutes, normally up to 12 - 15 minutes and for some reactions up to 20 - 30 minutes . The aforementioned reaction rate figures are averages, based on the average reaction rates at time when it is consummated or otherwise completed. The reactors of the invention, in which the volumetric expansion of the complex compounds is restricted during the reactions of the adsorption process are capable of absorbing, that is adsorbing and desorbing, at least 0.02 g (20 milligrams) of NH3 per minute and per ce of expanded adsorbent where the reaction times are 30 minutes or less.
Furthermore, where the reaction times are limited to 30 minutes or less, such reactors are capable of absorbing up to 0.01 g (10 milligrams) of NH3 per minute per ce of the total volume of the reactor envelope, that is, within the total volume of the pressurized reactor envelope, such process may be limited by the possible previous consummation of the adsorption if saturation is obtained in less than 30 minutes. The reaction rates are usually dependent on the degree of completion of the reaction. You can use equations of form:? N =? Nmax (1-elct) where:? N = extension of the reaction (moles / mol)? Nmax - extension of the maximum reaction (moles / mol) t = time (seconds ) k = value of the reaction kinetics (seconds -1) (k is called in the present reaction constant) can be used to describe the progress of the reaction with the passage of time.
The above equation is put into terminology and units useful for the complex-compound adsorption reactions of the present invention. The reaction constant k describes the dependence at the time of the progress of the reaction for any time. Reaction rates can be obtained from an expression that involves k and time.
N (1-e t) Velocity = =? Nmax (mol / mol-hr) (tx3600) (tx3600) with units again convenient for the absorption reactions as described herein. As an example of using these equations, SrCI2 NH3 can complex up to 7 moles of ammonia in stage 1 to 8, so that? Nmax is 7. For a time of 6 minutes (360 seconds) and a value of k of 0.0004 seconds-1,? N is 5.3 moles of ammonia per mole of salt. The reaction progress up to 6 minutes requires an average speed, during this period of 6 minutes, of 53 mol / mol-hr. A reaction constant of 0.0004 gives an? N of 0.94 in 6 minutes or an average reaction rate of 9.4 mol / mol-hr. Given a reaction constant (k) for any configuration of sorbent with any salt, the extent of the completion of the reaction and the reaction rates at any time are easily determined. The actual amount of the adsorbed refrigerant and the speeds depend on the size of the absorption stage,? Nma. The adsorption rates achievable by the present invention lead to the following minimum values for the reaction constant:? Nmax k up to 4.5 moles / mole 0.0004 between 4.5 and 5 moles / mole 0.0003 greater than 6 moles / mole 0.0002 Such reaction determinations are useful for periods of adsorption and / or desorption of less than about 30 minutes. The reactivity of the salts can be further improved by initially adsorbing a small amount of a gaseous ligand on the salt, which additive ligand is different from the gaseous reactant to be used in the complex compound. Any of the polar gaseous reagents mentioned above can be used and particularly preferred are ammonia, water, lower molecular weight aliphatic alcohols, amine or phosphine. The amount of the additive material is preferably between about 0.05% and about 10% by weight of the salt. The use of a hydrated salt containing a small but effective amount of water adsorbed on the salt may be satisfactory for that purpose. In FIG. 1, one embodiment of a single reactor heating system of the invention is shown schematically. In the one reactor system, the reactor 10 comprises one or more reaction chambers containing one or a mixture of the aforementioned complex compounds which have been formed according to the method described above to restrict the volumetric expansion and control the density of the complex compound formed during the adsorption of the polar gas on the metal salt. The construction of the reactor that includes the inner reaction chambers or cores, the positioning or relative location of the fins to achieve the desired thermal and mass diffusion path lengths, the thicknesses and shapes of the fins as well as the description of the means for directing the refrigerant gas to, through and from the reaction chambers are described in patents No. 5,328,671, 5,298,231 and 5,441,716 and are incorporated herein by reference . The reactor also contains a heat transfer section 11 whereby the heat transfer fluid and the heat transfer fluid or refrigerant are thermally exposed to the complex compound for heating and cooling thereof during desorption and adsorption respectively. The system shown also includes a burner 18 for directing the hot combustion gases to the boiler 16 to heat water or other heat transfer fluid to be directed via the conduit 28 to the heat transfer section of the reactor 10. The system also includes a condenser 12 and evaporator 14 for condensing and evaporating respectively the polar gas refrigerant. In the embodiment shown, the capacitor 12 is a condenser of the forced convection type, which cooperates with a fan 15 to provide space heating, typically for heating a room or rooms by forced heated air as it is directed over the transfer surfaces of the air. condenser heat. However, other capacitors may be used and combined with a hydronic circuit apparatus for hot water heaters, radiators, and other embodiments of heating apparatus as will be described hereinafter. Thus, the forced convection condenser 12 shown in the embodiment of Figure 1 is only an example of the use of heat from a system condenser and the invention is not limited to the example shown. The evaporator 14 is located outside to adsorb the thermal energy, where such energy is not to be used, where an evaporator cooling function is not used. The conduit 21 directs the condensed refrigerant via the thermostatic expansion valve 25 to the evaporator 14. The expansion valve can be replaced by using any other equivalent component, such as a throttle valve, capillary tube or other appropriate refrigerant expansion device. In addition to the examples described above, virtually all conventional refrigerant expansion devices can be used. Passive expansion devices such as capillaries or orifices are much more difficult to apply to very small ammonia systems and are increasingly difficult with periodic adsorption systems. In addition to the thermostatic expansion valves, constant pressure expansion valves and electronic expansion valves can be used. For electronic expansion valves (on-off) modulated by pulse width used in very small refrigeration systems, it is useful to include a flow restriction (orifice or capillary) downstream of the valve, with controlled volume between the valve and the valve. the restriction. When the valve is opened, this volume is filled and slowly vented to the evaporator. The minimum required pulse time of the valve is thus reduced. The conduits 26 and 23 direct the polar gas from the evaporator 14 to the reactor 10 via the unidirectional valve 29 and the conduit 13. The polar gas desorbed from the reactor 10 is redirected to the condenser 12 via the conduit 13, the unidirectional valve 27 and the conduit 24. The system shown also includes the conduit 22 and the solenoid valve 22 to selectively direct the condensed refrigerant from the condenser 12 to the heat transfer section 11 of the reactor 10 and the conduit 17 to direct the vaporized refrigerant from the heat transfer section back to the condenser 12 via the conduit 24. The container 61 resides and accumulates the condensed refrigerant of the condenser 12. A closing valve 63 optionally it can also be provided to selectively regulate the flow of refrigerant from the vessel to the evaporator. The condenser 12 can also be designed to incorporate a container function to accumulate the condensed refrigerant. Other means for heating the reactor to drive the desorption reaction in the reactor 10 may include heating the complex compound by direct heating of the adsorbent tubes or using heat from the hot combustion gases of a burner or the burner and the ke may be replace by heating elements by resistance. AlternativelyThermosiphon heating or heat pipes, well known to those skilled in the art, can be used to transfer heat to the adsorbent. Although one embodiment of a single reactor is illustrated, two or more reactors can be used and operated with a polar reactor gas cooler as the complex compound is heated, while the other reactor adsorbs the polar gas. The use of paired reactors operated in half cycles of opposite cycles will provide a continuous supply of gaseous refrigerant desorbed to the condenser to facilitate continuous heating operations, especially if the desorption periods are shorter than the adsorption periods. In the operation of the one reactor mode shown, during the heating phase, to supply the polar gas refrigerant desorbed to the condenser, the hot combustion gases from the burner 18 are directed to the boiler 16 to produce hot water, steam or other heated heat transfer fluid which is directed via line 28 to heat transfer section 11 of reactor 10. The heat transfer section of the reactor directs the heat to the complex compound which causes desorption of the polar gas which is directed via conduit 13, unidirectional valve 27 and conduit 24 to condenser 12, where it condenses, to produce the heat used for the heating purposes mentioned above for which the system is designed. When the complex compound in the reactor has been desorbed to the desired extent or for a desired time, the burner 18 is turned off and the adsorption phase is initiated. The adsorption of the polar gas refrigerant by the complex compound in the reactor begins when the complex compound is sufficiently cooled by the condensed refrigerant directed to the heat transfer section 11 of the reactor upon opening the valve 20 operated by solenoid. The gaseous refrigerant condensed in the heat transfer section of the reactor 10 is thermally exposed to the hot complex compound and thus vaporized, which cools the reactor. The vaporized refrigerant is directed from the reactor to the condenser via duct 17 and 24. Such cooling of the adsorption reactor may use components of the method and apparatus described in U.S. Patent Application Serial No. 08 / 327,150, the descriptions of which are incorporated herein by reference. Once the reactor is sufficiently cooled by the vaporizing refrigerant in the heat transfer section of the reactor, the reduced vapor pressure of the salt or the complex compound desorbed is sufficiently low to begin to remove the vapor from the evaporator coolant. as the exothermic adsorption is initiated and continues until the adsorption of the refrigerant gas on the adsorbent is substantially complete. The circulation of the refrigerant through the condenser and the heat exchange section of the reactor continues throughout the adsorption phase, thereby maintaining the reactor close to the temperature of the condenser. Then, with the reactor again near the condenser temperature, the solenoid valve 20 is closed, heat is supplied to the reactor via the burner 18 and the kettle 16 and the next desorption cycle begins. In the embodiment shown, a heat exchanger 19 in the form of a liquid subcooler is used to transfer heat between the vapor of the cold refrigerant passing from the evaporator 14 via the conduits 26 and 23 to the reactor 10 during the adsorption phase with the refrigerant hot condensate from the condenser 12 passing to the evaporator via conduit 21. The use of such a subcooler improves the efficiency of the system by cooling the hot condensed refrigerant against the cooler refrigerant vapor, whereby a smaller fraction of the liquid will be distilled instantaneously steam in an isenthalpica expansion, to increase the capacity of the system. In addition, such subcooler increases the energy provided in the vapor stream of the evaporator to the adsorption reactor, thereby finally decreasing the amount of raw energy necessary to drive the desorption reaction. Thus, the capacity and COP of the system are increased when using such a subcooler. As previously indicated, a plurality of reactors can be used in place of a single reactor, the operation proceeds substantially as described above, except that the two reactors will be operated in substantially opposite phases or half cycles. For continuous operation, it may also be desirable to operate a system of two or more reactors, in which desorption is carried out more rapidly than adsorption. Such an operation will result in the completion of the desorption phase prior to the consummation of the adsorption in an adsorption reactor, thereby providing a continuous adsorption suction on the evaporator. Such operation reduces or eliminates the DELTA T shutdown time, the time it takes for the evaporator to recover from the switching of the half cycles of the reactor. To obtain such an advantage, the desorption is preferably carried out at least 10% faster than the adsorption and more preferably 25% faster than the adsorption reaction time. The use of two condensers or two sections of the condenser may be advantageous to facilitate cooling of the second desorbed adsorbent, while the first adsorbent is still in the adsorption stage, although a condenser could serve both functions as well. The single stage thermal pump apparatus described above is suitable for providing domestic heating and / or cooling. The system has the ability to provide heat from the usable condenser at a temperature between approximately 32 ° C (90 ° F) and approximately 71 ° C (160 ° F) and most commonly 37.8 ° (100 ° F) and 65 ° C (150 ° F). Again such heat can be used for water heaters, also as for space heating, directly or indirectly. The system can also be used to provide cooling by inverting the function of the condenser and evaporator components previously described. For such a function, appropriate valves known to those led in the art (not shown in Figure 1), would be switched to direct the polar gas refrigerant desorbed from a reactor to the evaporator 14, which would function as a condenser, from the evaporator 14 to the evaporator 14. capacitor 12, which will function as an evaporator and to the reactor (or reactors) for adsorption. As adsorption occurs, the suction of the evaporator gas 12 in operation will provide cooling as the refrigerant evaporates. The switching of functions or works of the heat exchanger can also be achieved by external means, that is, a heat transfer circuit with valves that connects the internal and external coils with the evaporator and condenser as required by the cooling load / heating of the construction. Such a feature is of particular interest in dual utility applications such as summer cooling with simultaneous production of hot water using the heat from the condenser. Internal switching can also be used for dual duty applications that incorporate a heat transfer circuit to transport heat between the hot water and the heat exchanger which then acts as a condenser. It is also of particular advantage to use the superheat collected from the condenser or from a de-superheater (not shown) to heat water to obtain water hotter than would otherwise be possible by using only a phase change condensation. The use of combustion exhaust heat is also possible to reinforce the temperature of the hot water, especially if the use of such heat is not or is already a practical limit to provide preheating combustion air. The use of exhaust heat, overheating and sanitary facilities to provide space heating and / or water heating and space cooling and / or water heating or water heating is only known to those skilled in the art and is within range of the invention. It will be understood that the cooling or cooling efficiency of such a single stage system is somewhat limited. For the single-step apparatus described above, the most preferred complex compounds are: SrBr22-8 (NH3), CaBr22-6 (NH3), FeCI22-6 (NH3), CoCl22-6 (NH3), MnCI22-6 (NH3) ) and FeBr22-6 (NH3). Other useful compounds include SrCI21-8 (NH3), CaCl2
2-4 (NH3), LiCl 0-3 (NH3), NiCI22-6 (NH3), CoBr22-6 (NH3), MgCl2 2-6 (NH3),
MgBr2 2-6 (NH3), MnBr2 2-6 (NH3), Cal2 2-6 (NH3), Fel2 2-6 (NH3), CuSO4 2-4
(NH3), SnCl2 0-2.5 (NH3), NaBF4 0.5-2.5 (NH3), NaBr 0-5.25 (NH3), CaCl2 0-1
(NH3), CaCl? 1-2 (NH3) and mixtures thereof.
Figure 2 shows an example of a system that acts as a heat pump and incorporates two banks of reactors 66 and 68 that include a reversing valve 71 to select the function of the heat exchanger to provide heating and / or cooling. The respective reactor banks desorb and adsorb refrigerant in alternating and opposite cycles as described in the patents and patent applications mentioned above. A kettle 72 which can be heated by gas, oil or electric heats each of the reactor banks to drive the exothermic desorption of the refrigerant from the complex compounds in the adsorbents / reactors. The heat exchange sections of the absorbers are also cooled to initiate adsorption and during adsorption they use the condensed refrigerant from vessel 73 and by the selective operation of valves 75 and 77, each to direct the liquid refrigerant to a different bank of absorbents. The heat exchange coils 70 and 80 of the evaporator / condenser components are shown. The heat exchange coil 70 is located inside and the heat exchange coil 80 is located outside. The unidirectional valves, 78, 79, 63 and 64 direct the refrigerant to and from the reactor bank. Upon operation of the reversing valve 71, heating or cooling is selectively provided by the coil 70 of the indoor heat exchanger for heating or cooling of space or water. Thermostatic expansion valves 74 and 76 are also shown. Cycle inversion, that is, reversing the heating and cooling function of the system, requires a capability to control the flow of the refrigerant either to one or the other of the coils ( any coil that is functioning as the evaporator) while allowing the free return of the condensate to the other coil. There are several ways to accomplish this. For example, a second four-way valve could be used, which allows the condenser to drain into the container and which also directs the refrigerant from an expansion valve to the evaporator. Another method is to use flow meters (see components 65 and 67 in the system of Figure 3) which are unidirectional valves that have a hole in the valve plug. Such valves restrict flow in one direction and provide free flow in the opposite direction. Thus, the condensate flows freely from the condenser while the flow of the liquid refrigerant to the evaporator is controlled by a hole. Still another method comprises the use of two thermostatic expansion valves (TXV) as shown in Figure 2 which may be of an electrical or mechanical type. The condenser always has overheating at the input end where the TXV detector is attached whereby the TXV opens and allows free flow from the condenser to the vessel. The bulb on the opposite coil controls the overheating of the exit steam, as desired for the control of the flow of refrigerant to the evaporator. However, it will be understood that the invention is not limited to the above described examples of cycle reversal and refrigerant flow control devices and other suitable and equivalent means may be used. A subcooler of the type illustrated in Figure 1 can also be added, also as heat exchangers for pre-heating the combustion air. In Figure 3 a two-reactor embodiment of the invention is illustrated, which uses a two-stage constant pressure motor for greater efficiency. In the system shown schematically the first reactor 30 contains a first complex compound and the second reactor 40 contains a second complex compound different which results in differences of temperature of adsorption and desorption between the reactors. In such an apparatus, the different complex compounds of the two reactors are staggered by directing the adsorption heat of the second complex compound in the higher temperature adsorbent 40 to drive the desorption of the complex compound in the adsorbent 30 at the lower temperature. Such stepping of the constant pressure machine (CPES) is described in U.S. Patent Nos. 5,079,928 and 5,283,330, the disclosures of which are incorporated herein by reference. The different complex compounds are selected in such a way that the adsorption temperature of the lower stage, the vapor pressure compound decreases at the low reaction pressure (adsorption) in the reactor 40 is at least 8 ° C higher than the desorption temperature of the highest stage, the high pressure vapor compound at high reaction pressure (desorption) in the reactor 30. In the counter apparatus, the conduit 48 and the solenoid operated valve 20 direct a transfer fluid of heat different from the refrigerant, for the interstate heat transfer between the reactors. As in the embodiment described above, the low temperature adsorbent 30 is cooled during the adsorption with the condensed refrigerant. The system also includes a burner 18 and a boiler 16 for providing a heat transfer fluid such as steam, hot water, etc., via line 46 to heat and drive desorption in the highest temperature absorbent 40 with the fluid directed to section 41 of heat transfer thereof. Again, stepping is provided between the reactors by directing a heat transfer fluid from the higher temperature absorbent 40 via the pipe 48 during adsorption to provide heat to the lower temperature absorbent 30 to drive the desorption therein. . The apparatus also includes component 32 and 34 of the evaporator-condenser, each of which is capable of condensing the polar refrigerant gas to create heat, which can be used to heat a residential or commercial structure, water or the like and to evaporate condensed polar refrigerant to provide cooling to such structures or for any other proposed use. In the illustrated embodiment, a hydronic heating and cooling system is used to provide heating and / or cooling to a residence 58. The heat exchanger 45 is in heat transfer communication with the evaporator-condenser 32 to heat or cool the heat transfer fluid pumped via conduit 35 with pump 36 to heating and cooling apparatus 38 within residence 58 via heat exchanger 43. The evaporator-condenser 34 is positioned outside the structure to be heated and cooled to adsorb or reject the thermal energy. Such a system acts as a heat pump to selectively provide heating or cooling or cooling and heating of water when desired. The preferred apparatus also includes a subcooler 19 as previously described to increase the efficiency of the system to transfer heat between the cooler coolant vapor and the hotter condensed coolant. The four-way valve 44 directs the refrigerant gas from a desorption reactor to either of the components 32 or 34 of the evaporator-condenser. Where cooling is to be provided, component 32 acts as an evaporator to evaporate the refrigerant received from component 34, by operating as a condenser. The four-way valve 44 directs the refrigerant from a desorption reactor to the condenser 34 via the conduit 81. The condensed refrigerant is directed to the evaporator 32 via the flow meters 65 and 67, the conduit 33 and subcooler 19. With the solenoid valve 42 open, a portion of the condensed refrigerant is routed via the conduit 39 from the condenser 34 to the reactor 30 via the conduit 47 to cool the adsorbent 30 to initiate adsorption and to cool the reactor during adsorption, as the liquid refrigerant vaporizes in the heat transfer section 31 of the reactor. The vaporized refrigerant is directed back to the condenser 34 by means of the conduits 54, 52 and 31 via the valve 44. Concurrently, during the adsorption in the low temperature adsorbent 30, the higher temperature absorbent 40 is in one stage of desorption as heat is supplied to the heat transfer section 41 of the kettle reactor 16 via the conduit 46. The refrigerant desorbed from the reactor 40 is routed via the conduit 60, the unidirectional valve 59, the conduit 52 and the valve 44 of four directions to the condenser 34. The gaseous refrigerant of the evaporator 32 is directed to the adsorber reactor 30 via the valve 40 by means of the subcooler 19 and via the conduit 53 and the unidirectional valve 57. In the alternating half-cycle operation of the system, with the adsorbent 40 of higher temperature in adsorption, and the lower temperature adsorbent 30 in desorption, with the solenoid valve 20 open, the heat of the adsorption generated in the reactor 40 heats up a heat transfer fluid directed from the heat transfer section of the reactor 40 to the heat transfer section 31 of the reactor 30 via the line 48 to drive the desorption reaction. The refrigerant desorbed in the reactor 30 is directed via the conduit 56, the unidirectional valve 55, the conduit 52 and the four-way valve 44 to the condenser 34 in operation. Where the heat pump operates to supply heat to the residence 58, the four-way valve 44 is switched to reverse the functions of the evaporator-condenser 32 and 34 while the functions of adsorption and desorption of the reactors are carried out as described previously. Again, the switching of the heating and cooling functions may be by means of external fluid circuit fittings known to those skilled in the art. In applications where dual work, eg, water heating, and space cooling, is required, the condenser must have a heat transfer connection to the hot water with optional use of deheating and combustion gas heat exchange for heat recovery. The preferred high temperature low vapor pressure complex compounds are SrCl2-8 (NH3), 2.4 CaCl2 (NH3), LiCl 0.3 (NH3), SrBr2 2-8 (NH3), CaBr2 2-6 (NH3), FeCI2 2-6 (NH3), CoCl2 2-6 (NH3), FeBr2 2-6 (NH3), NiCI2 2-6 (NH3), CoBr2 2-6 (NH3), MgCI2 2- £ (NH3), MgBr2 2 -6 (NH3), MnCl2 2-6 (NH3), MnBr2 2-6 (NH3), CuS04 2-4 (NH3), SnCl2 0-2.5 (NH3), CaCl2 0-1 (NH3), CaCl2 1-2 (NH3) and mixtures thereof. The preferred high pressure vapor complex compounds are CaCfe 4-8 (NH3), CaC 2-4 (NH3) and mixtures thereof, SrCl2-8 (NH3), BaCI2 0-8 (NH3), LiCI 0- 3 (NH3), SrBr2 2.8 (NH3), CaBr2 2-6 (NH3), CuS04 2.4 (NH3), NaBF 0.5-2.5 (NH3) and NaBr "0.5-25 (NH3). multistage, stepped apparatus, include the identification of low and high pressure compound are described in the North American Reissue patents 34,259, 5,079,928 and 5,263,330.Figure 4 illustrates a residential 3-stage heat pump system. one of the reactors 30, 40 and 50 contains a different complex compound.The different complex compounds are selected to provide an ascending order of the vapor pressure of the gaseous reagent by which the adsorption temperature of a complex vapor pressure complex more low to a low reaction pressure (adsorption) is higher than the desorption temperature of the s The next highest vapor pressure complex composite successive to a high reaction pressure (desorption) as previously described with respect to the two stage system of Figure 3. The lowest temperature, highest temperature complex composite is located at the reactor 50, a complex intermediate temperature compound in reactor 40 and a high pressure, low temperature complex compound in reactor 30. Each of the reactors is provided with a heat exchange section and conduits extending therebetween to cooperate to direct the interstate heat transfer fluids to scale the reactions in the respective reactors. Burner 18, or other heat source, provides heat to desorb the complex compound in reactor 50. When reactor 50 is in the adsorption step, a heat transfer fluid heated by the exothermic adsorption reaction is directed from reactor 50 to reactor 40 to drive adsorption therein. When the reactor 40 is in the adsorption stage, due to its temperature differential with the complex compound in the reactor 30, a heat transfer fluid directs the heat from the adsorption reactor 40 to the desorption reactor 30. As previously described, when the low temperature adsorbent 30 is in adsorption, the condensed refrigerant from the evaporator-condenser 32 or evaporator-condenser 34 is directed to the heat transfer section of the reactor 30 to cool the reactor as previously described . The four-way valve 44 directs the refrigerant either to the 32 or 34 components of the evaporator-condenser, depending on the desired function of the heat pump to heat or cool the residence 58. An optional domestic hot water storage tank 49 it is shown in the hydronic circuit comprising the components illustrated in Figure 3. Further descriptions of such multi-phase CPES systems and operations are described in U.S. Patents 5,263,330 and 5,079,928 and are incorporated herein by reference. It will be understood that the description of the various apparatuses herein for heating or cooling a residence can be used for any other desired heating or cooling function, either heating or cooling of space, heating radiators and / or with components for the manipulation. of the heating of spaces or air conditioning, heating of hot water or the like. Although a burner is disclosed to provide the main heat to drive the desorption reactions in the high temperature reactors of Figures 3 and 4 or the reactors illustrated in Figures 1 and 2, other heat sources include solar heating apparatus, alone or in combination with electric heating elements, steam sources, gas heaters, combustion exhaust gas, petroleum or other fuels and the like may also be used and incorporated into such systems. These as well as other advantages of such systems will be apparent to those skilled in the art within the scope of the invention. It is noted that in relation to this date, the best method known by the applicant to carry out the invention citation is the conventional one for the manufacture of the objects to which it refers. Having described the invention as above, property is claimed as contained in the following
Claims (67)
- Claims 1. A heating system comprising: a) one or more reactors or reactor banks each containing a complex compound formed by the adsorption of a polar gas on a metal salt and in which the polar gas is adsorbed and alternatively desorbing on the complex compound, the metal salt comprises a halide, nitrate, nitrite, oxalate, perchlorate, sulfate or sulphite of an alkali metal, alkaline earth metal, transition metal, zinc, cadmium, tin or aluminum or sodium borofluoride or a double metal chloride or bromide and wherein the complex compound in the one or more reactors is formed by restricting the volumetric expansion and controlling the density thereof, during the adsorption of the polar gas on the metal salt, by which the complex compound has a capacity of reaction rates increased in moles of the polar gas adsorbed and / or desorbed per mole of the complex compound per hour at times of ad sorption or desorption of less than 60 minutes respectively, compared to a complex compound formed without restricting the volumetric expansion and controlling the density thereof, the one or more reactors each having a heat transfer section for thermally exposing a transfer fluid of heat and / or polar gas condensed in heat exchange communication with the complex compound; b) condenser means comprising at least one capacitor for condensing the polar gas and heat recovery means cooperating therewith to recover the heat generated in the condenser means; c) evaporator means comprising at least one evaporator for evaporating the condensed polar gas; d) a first conduit for directing the condensed polar gas from the condenser means to the evaporator means; e) one or more second conduits cooperating with the condenser means and the one or more reactors to direct the condensed polar gas from the condenser means to the heat transfer section of the reactor and to direct the vaporized polar gas therefrom to the condenser means; f) one or more third conduits for directing the polar gas from the evaporator means to the reactors and from the reactors to the condenser means; and g) heating means cooperating with the one or more reactors to heat the complex compound therein; the system is characterized in that one or more reactors have one or more reaction chambers therein, which have a maximum average mass diffusion path length of less than about 15 millimeters and / or a maximum thermal diffusion path length of less than 1.5 millimeters.
- 2. The system according to claim 1, characterized in that the one or more reactors comprise one or more reaction chambers having a maximum average mass diffusion path length of less than about 15 millimeters.
- 3. The system according to claim 2, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of between about 0.6 and about 3 millimeters, a maximum average mass diffusion path length of between about 2.5 and about 7 millimeters and wherein the salt or complex compound has a density of between about 0.2 and about 0.8 g / cc of the volume of the reaction chamber.
- 4. The system according to claim 2, characterized in that it includes a plurality of heat transfer fins that extend along the reactor and in heat transfer communication with the metal salt where the distance between the fins is 2.8 millimeters or less.
- 5. The system according to claim 2, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of less than about 4.5 millimeters.
- 6. The system according to claim 2, characterized in that the complex compound or the metal salt has a density in the reactor of between about 0.2 and about 1.0 g / cc of the volume of the reaction chamber.
- 7. The system according to claim 2, characterized in that it includes gas distribution means for directing the polar gas to and from the metal salt or the complex compound in the one or more reaction chambers and wherein at least 60% of the the metal salt or the complex compound by weight is within 25 millimeters or less of a gas distribution medium.
- 8. The system according to claim 2, characterized in that it includes one or more heat exchange surfaces in thermal contact with the metal salt and the complex compound and comprises a gas permeable material.
- 9. The system according to claim 2, characterized in that it includes one or more gas permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 10. The system according to claim 2, characterized in that the metal salt and the complex compound comprise a mixture thereof respectively, with a gas permeable mixture composition having a microporous surface to distribute the polar gas in the mixture.
- 11. A system according to claim 1, characterized in that the one or more reactors comprise one or more reaction chambers having a maximum thermal diffusion path length of less than 1.5 millimeters.
- 12. The system according to claim 11, characterized in that it includes gas distribution means for directing the polar gas to and from the metal salt or the complex compound in the reaction chambers and wherein at least 60% of the salt of metal or the complex compound, by weight, is within 25 millimeters or less of a gas distribution medium.
- 13. The system according to claim 11, characterized in that the one or more reaction chambers have a maximum average mass diffusion path length of less than about 15 millimeters.
- 14. The system according to claim 11, characterized in that it includes one or more heat exchange surfaces in thermal contact with the metal salt and the complex compound and consist of a gas permeable material.-
- 15. The system according to claim 11, characterized in that it includes one or more gas-permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 16. The system according to claim 11, characterized in that the metal salt and the complex compound comprise a mixture thereof, respectively, with a gas permeable mixture composition having a microporous surface to distribute the polar gas in the mixture.
- 17. The system according to claim 1, characterized in that the one or more reactors comprise one or more reaction chambers in which at least 60% of the metal salt or the complex compound, by weight, is within 25 millimeters or less than one means of gas distribution.
- 18. The system according to claim 17, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of less than 1.5 millimeters.
- 19. The system according to claim 17, characterized in that it includes one or more heat exchange surfaces in thermal contact with the metal salt and the complex compound and comprise a gas permeable material.
- 20. The system according to claim 17, characterized in that it includes one or more gas-permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 21. The system according to claim 1, characterized in that the heating means comprise heating means by electrical resistance.
- 22. The system according to claim 1, characterized in that the heating means comprise the direct heating or hot combustion gases for heating the complex compounds.
- 23. The system according to claim 1, characterized in that the heating means comprises a heat transfer fluid for heating the complex compounds.
- 24. The system according to claim 23, characterized in that it includes a burner for heating the heat transfer fluid.
- 25. The system according to claim 23, characterized in that it includes solar heating means for heating the heat transfer fluid.
- 26. The system according to claim 1, characterized in that the heating means comprise a hot tube or thermosiphon for heating the complex compounds.
- 27. The system according to claim 1, characterized in that the heat recovery means cooperating with the condenser includes a forced air convection apparatus.
- 28. The system according to claim 1, characterized in that the apparatus of the heat recovery means comprises a hydronic heating apparatus that includes space heating and / or hot water components.
- 29. The system according to claim 28, characterized in that the hydronic heating apparatus includes a pump and conduits that direct the hot water.
- 30. The system according to claim 1, characterized in that it includes a heat exchanger that cooperates with the first conduit that directs the polar gas condensed from the condenser to the evaporator and a second conduit that directs the polar gas from the evaporator to one or more reactors to transfer heat between them.
- 31. The system according to claim 1, characterized in that the complex compound comprises complexes of CaCl2 X (NH3), SrCI2-8 (NH3), SrBr2 2-8 (NH3), CaBr2 2-6 (NH3), Cal2 2- 6 (NH3), FeCl2 2-6 (NH3), FeBr2 2-6 (NH3), Fel2 2-6 (NH3), C0CI2 2-6 (NH3), CoBr2 2-6 (NH3), MgCI2 2-6 ( NH3), MgBr2 2-6 (NH3), MnCl2 2-6 (NH3), MnBr2 2-6 (NH3), NiCI2 (2-6 (NH3), LiCI 0-3 (NH3), CuS0 2-4 (NH3 ), SnCl2 0-2.5 (NH3), NaBF4 0.5-2.5 (NH3), NaBr 0-5.25 (NH3) or mixtures thereof.
- 32. The system according to claim 1, characterized in that it comprises one or more first reactors or reactor banks and one or more second reactors or reactor banks, the first reactors or reactor banks and the second reactors or reactor banks adsorb and desorben Polar gas in opposite cycles, respectively, the system includes control means cooperating with the conduits to reverse the heating and cooling function of the system and to control the flow of polar gas to the condenser means and the evaporator means.
- 33. The system according to claim 32, characterized in that the control means includes a pair of flow measuring valves in the first conduit.
- 34. A heating system according to claim 1, characterized in that it comprises a heat pump system having two or more reactors or banks of reactors each containing a different complex compound therein and wherein the different complex compounds each have a different polar steam vapor pressure and wherein the adsorption temperature of a vapor pressure compound lower than the adsorption pressure is at least 8 ° C higher than the desorption temperature of a compound of Higher vapor pressure at the desorption pressure, the two or more reactors or reactor banks each have a heat transfer section for thermally exposing a heat transfer fluid and / or polar gas condensed gas in heat exchange communication. heat with the complex compound; wherein the condenser means and the evaporator means comprise a first evaporator-condenser means for supplying heating and cooling and heat exchange means cooperating therewith to recover heating and cooling and second evaporator-condenser means and means of heat exchange that cooperate with them to reject the thermal energy of the same. a first conduit for directing the condensed polar refrigerant between the first and second evaporator-condenser means; one or more second conduits to direct the polarized gas condensed from an evaporator-condensing condenser medium to the heat transfer section of a reactor containing the highest vapor pressure complex compound and to direct the vaporized polar gas therein to evaporator-condensing condensing media; one or more third conduits for directing the polar gas from an evaporator-evaporation condenser means to the two or more reactors; and heating means cooperating with the two or more reactors to heat the complex compound therein.
- 35. The system according to claim 34, characterized in that the one or more reactors comprise one or more reaction chambers having a maximum average mass diffusion path length of less than about 15 millimeters.
- 36. The system according to claim 35, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of between about 0.6 and about 3 millimeters, a maximum average mass diffusion path length of between about 2.5 and about 7 millimeters and wherein the salt or complex compound has a density of between about 0.2 and about 0.8 g / cc of the volume of the reaction chamber.
- 37. The system according to claim 35, characterized in that it includes a plurality of heat transfer fins that extend along the reactor and in heat transfer communication with the metal salt where the distance between the fins is 2.8. millimeters or less.
- 38. The system according to claim 35, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of less than about 4.5 millimeters.
- 39. The system according to claim 35, characterized in that the complex compound or the metal salt has a density in the reactor of between about 0.2 and about 1.0 g / cc of the volume of the reaction chamber.
- 40. The system according to claim 35, characterized in that they include means for distributing gas to direct the polar gas to and from the metal salt or the complex compound, in the one or more reaction chambers and where at least 60% of the metal salt or the complex compound, by weight, is within 25 millimeters or less of a gas distribution medium.
- 41. The system according to claim 35, characterized in that it includes one or more heat exchange surface in thermal contact with the metal salt and the complex compound and comprises a gas permeable material.
- 42. The system according to claim 35, characterized in that it includes one or more gas permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 43. The system according to claim 35, characterized in that the metal salt and the complex compound comprise a mixture thereof, respectively, with a mixture composition, permeable to gas having a microporous surface to distribute the polar gas in the mixture. .
- 44. The system according to claim 34, characterized in that the one or more reactors comprise one or more reaction chambers having a maximum thermal diffusion path length of less than 1.5 millimeters.
- 45. The system according to claim 44, characterized in that it includes gas distribution means for directing the polar gas to and from the metal salt or the complex compound in the reaction chambers and wherein at least 60% of the salt of metal or the complex compound, by weight, is within 25 millimeters or less of a half gas distribution.
- 46. The system according to claim 44, characterized in that the one or more reaction chambers have a maximum average mass diffusion path length of less than about 15 millimeters.
- 47. The system according to claim 44, characterized in that it includes one or more heat exchange surfaces in thermal contact with the metal salt and the complex compound and comprises a gas permeable material.
- 48. The system according to claim 44, characterized in that it includes one or more gas permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 49. The system according to claim 44, characterized in that the metal salt and the complex compound comprise a mixture thereof, respectively, with a mixture composition, permeable to gas, having a microporous surface to distribute the polar gas in the mixture. .
- 50. The system according to claim 34, characterized in that the one or more reactors comprise one or more reaction chambers in which at least 60% of the metal salt or complex compound, by weight, is within 25 millimeters or less than one means of gas distribution.
- 51. The system according to claim 50, characterized in that the one or more reaction chambers have a maximum thermal diffusion path length of less than 1.5 millimeters.
- 52. The system according to claim 50, characterized in that it includes one or more heat exchange surfaces in thermal contact with the metal salt and the complex compound and comprise a gas permeable material.
- 53. The system according to claim 50, characterized in that it includes one or more gas permeable surfaces extending to the reaction chamber in contact with the metal salt and the complex compound along at least a portion of the surface permeable to gas.
- 54. The system according to claim 34, characterized in that the heating means comprise heating means by electrical resistance.
- 55. The system according to claim 34, characterized in that the heating means comprise hot combustion gases for heating the complex compounds.
- 56. The system according to claim 34, characterized in that the heating means comprises a heat transfer fluid for heating the complex compounds.
- 57. The system according to claim 56, characterized in that it includes a burner for heating the heat transfer fluid.
- 58. The system according to claim 56, characterized in that it includes solar energy heating means for heating the heat transfer fluid.
- 59. The system according to claim 33, characterized in that the heating means comprise a heat pipe or thermosiphon for heating the complex compounds.
- 60. The system according to claim 34, characterized in that the heat exchange means cooperate with the first evaporator-condenser means including a hydronic heating apparatus including space heating and / or hot water components.
- 61. The system according to claim 34, characterized in that the heat exchange means cooperating with the first evaporator-condenser means includes a forced air connection apparatus.
- 62. The system according to claim 60, characterized in that the heat exchange means cooperating with the first evaporator-condenser means includes a forced air convection apparatus.
- 63. The system according to claim 34, characterized in that it includes means for supplying a heat transfer fluid to and from the reactors and for directing the heat transfer fluid from an exothermic adsorption reaction to a reactor to drive an endothermic desorption reaction. .
- 64. The system according to claim 34, characterized in that a high vapor complex complex compound is selected from the group consisting of CaCl 2 (4-8 (NH 3), CaCl 2 (2-4 (NH 3) and mixtures thereof, SrCl 2 (1-8 (NH3), BaCl2 (0-8 (NH3), LiCI (0-3 (NH3), SrBr2 (2-8 (NH3), CaBr2 (2-6 (NH3), CuSO4 (2-4 ( NH3), NaBF4 (0.5-2.5 (NH3) and NaBr (0-5.25 (NH3), and mixtures thereof.
- 65. The system according to claim 34, characterized in that a complex compound of lower vapor pressure is selected from the group consisting of SrCI2-8 (NH3), CaCl2 2-4 (NH3), SrBr2 2-8 (NH3) , CaBr2 2-6 (NH3), FeCI2 2-6 (NH3), CoCl2 2-6 (NH3), FeBr2 2-6 (NH3), NiCI2 2-6 (NH3), CoBr2 2-6 (NH3), MgCl2 2S (NH3), MgBr2 2-6 (NH3), MnCl2 2-6 (NH3), MnBr2 • 2-6 (NH3), SnCl2 2-5 (NH3), CuSO4 2-4 (NH3) and CaCl2 0-1 (NH3), CaCl2 1-2 (NH3) and mixtures thereof.
- 66. The system according to claim 34, characterized in that it comprises one or more first reactors or banks of reactors and one or more second reactors or reactor banks, the first reactors or reactor banks and the second reactors or reactor banks adsorb and desorben the polar gas in opposite cycles, respectively, the system includes control means cooperating with the conduits to reverse the heating and cooling functions of the system and to control the polar gas flow to the condenser means and the evaporator means.
- 67. The system according to claim 66, characterized in that the control means includes a pair of flow measuring valves in the first conduit.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08412147 | 1995-03-28 | ||
US08/412,147 US5598721A (en) | 1989-03-08 | 1995-03-28 | Heating and air conditioning systems incorporating solid-vapor sorption reactors capable of high reaction rates |
PCT/US1996/001241 WO1996030706A1 (en) | 1995-03-28 | 1996-01-31 | Improved heating and air conditioning systems incorporating solid-vapor sorption reactors capable of high reaction rates |
Publications (2)
Publication Number | Publication Date |
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MX9707182A MX9707182A (en) | 1997-11-29 |
MXPA97007182A true MXPA97007182A (en) | 1998-07-03 |
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