WORKING FLUID FOR HEAT PUMPS

Abstract: A process of adsorption or absorption is one wherein an azeotrope of n-propanol and water is absorbed by adsorbent e.g. a zeolite molecular sieve or absorbed by absorbent, e.g. aqueous lithium bromide, thereby evolving heat of adsorp­ tion or heat of absorption.

Description: Working fluid for heat pumps This invention relates to a process of using a working fluid in a heat pump. Water is a desirable working fluid for adsorption heat pumps because of its high latent heat of. vaporisation and because it is nontoxic. However it has two disadvantages, namely its relatively high freezing point and its low vapour pressure at desirable evaporation temperatures. It is not desirable to use inorganic freezing point depressants because they have the unfortunate property of lowering the vapour pressure of the water in solution still further. However surprisingly we have found that a certain organic freezing point depressant may be used which does not appreciably lower the partial pressure of water vapour above the solution and which will allow water to be used in conjunction with hydrophobic adsorbents such as activated charcoal. This organic depressant is n-propanol and it forms an azeotrope with water, the weight per cent of water varying from about 28 to 32 according to the temperature. According to this invention a process of sorption is one in which an azeotrope of n-propanol and water is sorbed by sorbent, thereby evolving heat of sorption. By the words "sorbate", "sorbent" and "sorption" we mean respectively "absorbate or adsorbate", "absorbent or adsorbent" and "absorption or adsorption The azeotrope of n-propanol and water has been found to have the following properties: Equilibrium vapour pressure mm Hg TOC Wt Z H20 in vapour 47 ¯ 31.8 200 56.68 29.6 400 71.92 29.0 600 81.68 28.5 740 87.0 28.3 1790 110.0 27.8 About 30 wt % water in the vapour amounts to 58.8Z by volume and partial pressure. Thus at a temperature of 56.680C pure water exerts a vapour pressure of approximately 128 mm Hg whereas the partial pressure of water vapour above the azeotrope at that temperature is approximately .59 x 200 mm Hg or approximately ll7 mm Hg. Thus it can be seen that the vapour pressure has not been appreciably lowered and at the same time the azeotrope will freeze at a temperature which is appreciably lower than OOC i.e. at -80C to 43 OC. This azeotrope can be used in adsorption or absorption processes. In the former the adsorbent will usually be a substance like a zeolite molecular sieve, e.g. the 4Aor Y type, activated charcoal and silica gel. When the adsorbate i.e. n-propanol-water azeotrope, is adsorbed by the adsorbent heat of adsorption will be evolved and this heat can be transfer elsewhere, for example to another partof a heat pump or for delivery to the load. This transfer is usually carried out by heat exchange, by the use for example of a heat exchanger, the coils of which are housed inside the adsorber and which are surrounded by adsorbent. After adsorption the azeotrope will have to be desorbed from the adsorbent if the process is to b2 cyclic. This is usually achieved by insertion of a heat exchanger in the adsorbent housed in the adsorber. Alternatively an electrical resistive heater can be located in the adsorbent housed in the adsorber. Systems employing an adsorber also make use of a heat of fusion heat store. In such systems the adsorbate vapour which is driven off from the adsorber is usually condensed in the heat of fusion heat store. In such heat stores there is a plurality of receptacles housing a substance with a relatively high melting point and a relatively high heat of fusion, for example stearic acid. The heat of condensation of the adsorbate as it condenses in the heat of fusion heat store is transmitted to this relatively low melting substance which then melts. In this way heat is stored in this substance housed in the receptacles. When heat is abstracted from this heat store the substance freezes, evolving latent heat of fusion. Processes and systems involving the adsorption of an adsorbate by an adsorbent and where -an n-propanol-azeotrope can be used as the adsorbate include those claimed in our prior patent applications GB8038283, (European 81305627;2), GB 8039157 and GB 8111392. The absorption process can be the conventional process of absorption wherein absorbate is driven off from a generator by heat supplied externally, vaporised absorbate is condensed in a condenser, rejecting heat of condensation, condensed absorbate afterbeing expanded is sent to an evaporator where it evaporates and from the evaporatcr vaporised absorbate is delivered to an absorber where the heat of absorption is rejected. Weak working -fluid (i.e. absorbate plus absorbent) is pumped from the absorber to the generator and strong working fluid is delivered from the generator to the absorber via an expansion valve. Such an absorption process can be used in conjunction with an adsorption process as described in our GB patent application 8039157 whereii the heat supplied to the generator is obtained from the latent heat of condensation of adsorbate vapour, said vapour being desorbed from adsorbent housed in an adsorber. Another such process is that described in oùrGB patent application 8017030 wherein the heat supplied to the generator is obtained from a solar panel or other source of -heat. Example A sorber was charged with a gel of lithium bromide and n-propanol water azeotrope supported in a porous matrix of coke breeze. The azeotrope was evaporated from an evaporator at a temperature of below OOC and sorbed by the sorbent. Heat of sorption was evolved at a temperature of above 600C and delivered to the load. Subsequently this azeotrope was desorbed by'thest from a resistive heat and then passed to a condenser and the azeotrope was then condensed in a heat of fusion heat store and returned to the evaporator. This cycle of sorption and desorption was then repeated indefinitely. GB.Aolication 8038283 claims a heating system wherein solar energy is used to supply heat to a heat of fusion heat store, adsorbate is stripped from adsorbent in an adsorber and thereafter condensed, the heat of condensation being delivered to the load, condensed adsorbate is sent to an evaporatoç adsorbate is vaporised in the evaporator and vaporised adsorbate is adsorbed in the adsorber, the heat of adsorption being delivered to the load. GB Application 8039157 claims a combined adsorption and absorption process in which an external source of heat is used to dex orb adsorbate from adsorbent housed in an adsorber. The adsorbate vapour is condensed and the latent heat of condensation used to remove absorbate from the working fluid in the generator of an absorption system. GB Application 8111392 claims a method of obtaining heat wherein adsorbate is evaporated from an evaporator and thereafter adsorbed by an adsorbent in an adsorber, the latent heat of adsorption providing heat to the load and thereafter the adsorbate is desorbed from the adsorbent and desorbed adsorbate condensed in a.heat of fusion heat store and the substance housed therein melting and thereafter solidifying, the latent heat of fusion providing heat to the load. When the azeotrope is used in absorption processes where it acts as an absorbate, the absorbent EMI5.1 for example an aqueous alkali metal halide, e.gOaqueous lithium bromide or lithium chloride.

Claims: Claims 1. A process of sorption wherein an azeotrope of water and n-propanol is sorbed by sorbent and heat of sorption is evolved. 2. A process according to claim 1 wherein the sorption is adsorption. 3. A process according to claim 2 wherein the adsorbent is a zeolite molecular sieve. 4. A process according to either of claims 1 and 2 wherein the heat of adsorption is delivered to the load. 5. A process according to any one of claims 2 to 4 wherein after adsorption by the adsorbent the azeotrope is desorbed from the adsorbent. 6. A process according to claim 5 wherein the desorbed azeotrope is condensed in'a heat of fusion heat store, the heat of condensation melting a relatively low melting and relatively high heat of fusion substance housed in receptacles housed in the heat store. 7. A process according to claim 1 wherein the sorption is absorption. 8., A process according to claim 7 wherein the absorbent is an aqueous alkali metal halide. 9. - A process according to either.. of claims 7 and 8 wherein the azeotrope is driven off from a generator by external heat, vaporised azeotrope is condensed in a condenser, condensed azeotrope after being expanded is sent to an evaporator and vaporised azeotrope is delivered from the evaporator tJ the absorber, absorbate plus absorbent as working fluid is pumped from the absorber to the generator and working fluid is delivered from the generator to the absorber via an expansion valve. 10. An azeotrope of water and n-propanol whenever sorbed by sorbent according to any one of th preceding claims. 11. The use of an azeotrope of water and n-propanol as a sorbate.

Inventors: MOSS, GERALD
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1982
Main classification: C09K5
IPC codes: C09K5, F25B29