WO2014082420A1

WO2014082420A1 - Working substance pair for absorptive heat circulation system with heat source temperature between 60°c and 130°c

Info

Publication number: WO2014082420A1
Application number: PCT/CN2013/074671
Authority: WO
Inventors: 程寒松; 韩超群; 郑敏; 张大鹏
Original assignee: 中国地质大学（武汉）
Priority date: 2012-11-30
Filing date: 2013-04-25
Publication date: 2014-06-05
Also published as: CN102965082A; CN102965082B

Abstract

Provided is a working substance pair for an absorptive heat circulation system with a heat source temperature between 60°C and 130°C. The working substance pair consists of a working substance and an absorbing substance. The working substance is selected from one or a mixture of more than two of fluoroalkanes, fluoro-olefins, fluoroethers, non-substituted alkanes, or olefins. The absorbing substance is a liquid mixture composed of an ionic liquid of 1%-50% by mass and an organic liquid of 50%-99% by mass. The working substance is miscible with the absorbing substance at a temperature of 20°C to 80°C. The working substance pair overcomes some defects of a conventional working substance pair and has the features of being non-toxic, safe, environmentally friendly and so on.

Description

Working substance pair for an absorption thermal cycle system with a heat source temperature between 60 ° C and 130 ° C

[0001] The present invention belongs to the field of utilization of new energy technologies, and more particularly to a working substance pair for an absorption thermal cycle system having a heat source temperature between 60 ° C and 130 ° C.

Background technique

[0002] The absorption type thermal cycle system includes an absorption heat pump, an absorption type refrigerator, and an absorption type heat exchanger, etc., and is a circulation system that uses a low-grade heat source to pump heat from a low-temperature heat source to a high-temperature heat source. It mainly uses natural gas, solar energy, geothermal energy, industrial waste heat and waste heat as the driving force. It only needs a small amount of electric energy to achieve the purpose of cooling or heating. It is an effective device for recycling low-temperature heat energy and saves energy. And the dual role of protecting the environment.

[0003] At present, this technology is still not the most widely used, the main reason is the failure to find a safe, efficient and reasonable working substance pair. The main systems currently used are lithium bromide/water systems and ammonia/water systems, but these two systems have serious drawbacks. Lithium bromide/water system may precipitate during the low temperature, and block the pipelines, valves, etc., which may cause damage to the equipment and decrease the efficiency. The concentration of lithium bromide can only be kept within a certain range, the degassing range is reduced, and the lithium bromide aqueous solution is applied to the system. Corrosive; ammonia/water system Because the vapor pressure of the absorbent water is high, the separation of the working object and the absorbent must be carried out, resulting in a decrease in the overall efficiency, and at the same time ammonia is toxic, and the ammonia water is corrosive to the equipment.

[0004] The working substance pairs studied so far have the following disadvantages: 1) the solubility of the working substance in the absorbent is too low; 2) the vapor pressure of the absorbent is too high and volatile; 3) the entire temperature range of the study Inside, the viscosity of the absorbent is too large or crystallized, which affects the circulation of the system; 4) Corrosion to the equipment.

[0005] Some high-boiling, low-saturation vapor pressure, low-viscosity organic liquids are generally non-corrosive to equipment when used as an absorbent for an absorption thermal cycle system, but organic liquids will still be used when the absorption heat cycle system is operated at a higher temperature. There is a problem of separation of work and absorbent. Ionic liquids have unique physicochemical properties: almost no vapor pressure (thus not forming azeotrope), non-flammability, high thermal stability (not decomposed at 300 ° C or even 40 CTC), wide liquid phase range (-60 °C to 400 ° C for the liquid phase), good solubility for certain work. However, due to the strong hydrogen bonds and van der Waals forces between the anions and cations, the viscosity of the ionic liquid at normal temperature is usually relatively large, which means higher mass transfer resistance and transport power consumption.

[0006] Therefore, the comprehensive use of the special properties of the above two types of liquid substances is likely to be applied to the design and development of absorbents for new absorption thermal cycle systems.

Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an absorption for a heat source temperature between 60 ° C and 130 ° C. The working substance pair of the thermal cycle system, the absorbent of the working substance pair has good solubility to the working object, the absorbent is not volatile, the viscosity of the absorbent is small, and the device is non-corrosive and non-toxic.

[0008] The technical solution adopted by the present invention to solve the above technical problem is:

A working substance pair for an absorption type thermal cycle system having a heat source temperature of between 60 ° C and 130 ° C, wherein the working substance pair is composed of a work substance and an absorbent, and the work substance is selected from the group consisting of fluorine a mixture of one or more of an alkane, a fluoroolefin, a fluoroether, an unsubstituted alkane, or an olefin; the absorbent is from 1% to 50% by mass of ionic liquid and from 50% to 99% A mixed liquid composed of an organic liquid, the work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0009] In the above scheme, the fluoroalkane is monofluoromethane, difluoromethane, trifluoromethane, tetrafluoromethane, monofluoroethane, 1,1-difluoroethane, 1,1,1-three. Fluorine, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane, or perfluoroethane; the fluoroolefin is monofluoroethylene 1,1-difluoroethylene, 1,2-difluoroethylene, trifluoroethylene, tetrafluoroethylene, monofluoropropene, 1,3-difluoropropene, 1,1-difluoropropene, 3,3-di Fluoropropene, 1,1,3-trifluoropropene, 1,2,3-trifluoropropene, 1,3,3-trifluoropropene, 1,1,2-trifluoropropene, 2,3,3-three Fluoropropene, 3,3,3-trifluoropropene, 1,2,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,1,2,3-tetrafluoropropene, 1 ,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,2,3,3-pentafluoropropene, 1,1,3,3,3-pentafluoropropene , 1,2,3,3,3-pentafluoropropene, or hexafluoropropylene; the fluoroether is monofluoro-methoxymethane, 1,1-difluoromethyl ether, 1,2-difluoromethyl Ether, 1,1,1-trifluoromethyl ether, 1,1,2-trifluoromethyl ether, 1,1,3,3-tetrafluoromethyl ether, 1,1,1,3-tetrafluoromethyl ether, 1,1,1,3,3-pentafluoromethyl ether, hexafluoromethyl Ether, monofluoro-ethoxymethane, 1-fluorosuccinylethane, 1-fluoro-2-methoxyethane, difluoromethoxyethane, 2,2-difluoroethylmethyl Ether, 2,2,2-trifluoroethyl methyl ether, trifluoromethoxyethane, pentafluoroethoxymethane, trifluoromethyl-trifluoromethoxymethane, or perfluoromethyl ether; The non-substituted alkane is methane, ethane, propane, n-butane, or isobutane; the olefin is ethylene, propylene, isobutylene, or n-butene.

[0010] In the above solution, the absorbent satisfies the following conditions, wherein 25 ° C, a saturated vapor pressure of 100 Pa at a standard atmospheric pressure, preferably a saturated vapor pressure of 50 Pa, particularly preferably a saturated vapor pressure of 30 Pa; 20 ° C, a standard atmospheric pressure The lower viscosity is 300 mPa · s, preferably the viscosity is 200 mPa · s, particularly preferably the viscosity is 100 mPa · s; both at a standard atmospheric pressure and at a temperature ranging from 20 ° C to 150 ° C, preferably at a temperature of from 0 ° C to 18 ° C. The range is all liquid, and it is particularly preferable to be in a liquid state in a temperature range of -20 ° C to 20 CTC.

[0011] In the above aspect, the ionic liquid is a salt satisfying the following formula: ! or !0:

[C] _n +[A] ⁿ - (I )

[Ci] ⁺ [C ₂ ] ⁺ [C ₃ ] ⁺ [A] ³ - (lib)

[Ci] ⁺ [C ₂ ] ⁺ [C ₃ ] ⁺ [C ₄ ] ⁺ [A] ⁴ - (li e) [Ci] ⁺ [C ₂ ] ⁺ [C ₃ ] ⁺ [M!] ⁺ [A] ⁴ - ( Ili a)

[Ci] ⁺ [C ₂ ] ⁺ [M!] ⁺ [M ₂ ] ⁺ [A] ⁴ - (Illb)

[Ci] ⁺ [M!] ⁺ [M ₂ ] ⁺ [M ₃ ] ⁺ [A] ⁴ - ( OI c)

[Ci] ⁺ [C ₂ ] ⁺ [M!] ⁺ [A] ³ - (Hi d)

[Ci] ⁺ [M!] ⁺ [M ₂ ] ⁺ [A] ³ - (Ill e)

[Ci] +[C ₂ ]+[M ₄ ] ²⁺ [A] ⁴ - ( H g)

[Ci] ⁺ [M!] ⁺ [M ₄ ] ²⁺ [A] ⁴ - (IHh)

Wherein [C] +, [d]\ [C ₂ ]+, [C ₃ ] ⁺ or [C ₄ ] ⁺ are quaternary ammonium salt cations, quaternary salt cations, imidazolium cations, pyridinium cations, pyrrolidine cations, morpholines a cation, or a piperidine cation; [A] ⁿ - is a monovalent to tetravalent anion, [Μ^Γ [M ₂ ] ⁺ , [M ₃ ] ⁺ is a monovalent metal cation, [M ₄ ] ²⁺ is two a valence metal cation, [M ₅ ] ³⁺ is a trivalent metal cation, n is 1, 2, 3 or 4; for the metal ion described in the above formula (III) [MJ^ [M ₂ ] [M ₃ ] [ M ₄ ] ²⁺ , [M ₅ ] ^{3+ are} preferred elements of the IA, II A group of the periodic table and Cr ³⁺ , Fe ³⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Ag ⁺ , Zn ²⁺ , or Al ³⁺ .

[0012] In the above aspect, the cation [C] ⁺ , [d] ⁺ , [C ₂ ]+, [C ₃ ]+, or [C ₄ ]+ of the ionic liquid is the following structure and low in the structure Polymer:

Quaternary ammonium salt cations:

12

R3

Seasonal salt cations:

Pyrrolidine cation:

Morpholine cations:

Structural formula (1) to (7) is a group R is C _r C ₂₅ linear, branched, or cyclic saturated hydrocarbon groups and unsaturated hydrocarbon, and can be inserted into or substituted by a hetero atom or a functional group a hydrocarbon group, wherein the hetero atom is all atoms which can be inserted or substituted in principle, preferably nitrogen, oxygen, sulfur, phosphorus, silicon; the functional group is all functional groups which can be attached to a carbon atom or a hetero atom;

Except that R is directly bonded to the same N or P atom at the same time as R ₃ cannot be hydrogen, and R ₇ may independently be hydrogen, dC ₂₅ linear, branched, or cyclic saturated hydrocarbon and unsaturated. a hydrocarbon group, and may be a hydrocarbon group inserted or substituted by a hetero atom or a functional group, wherein the hetero atom is all atoms which can be inserted or substituted in principle, preferably nitrogen, oxygen, sulfur, phosphorus, silicon; It can be attached to all functional groups on a carbon atom or a hetero atom.

[0013] In the above scheme, the quaternary ammonium salt cation is tetramethylammonium, butyltrimethylammonium, benzyltrimethylammonium, and the third Hydroxyethyl ammonium, dodecyl trimethyl ammonium, cetyl trimethyl ammonium, octadecyl trimethyl ammonium, triethyl ammonium, benzyl triethyl ammonium, tetraethyl ammonium, Tetrapropylammonium, tetrabutylammonium, tetraoctylammonium, trioctylmethylammonium, or tetramethylphosphonium; the quaternary salt cation is tributylmethyl scale, tributylethyl scale, tetrabutyl Keel, tributylhexyl scale, tributyl octyl scale, tributyl fluorenyl scale, tributyl lauryl scale, tributyl tetradecyl scale, tributyl octadecyl scale, Or tetraphenyl scales;

The imidazolium cation is 1-methylimidazole key, 1-ethylimidazole key, 1-butylimidazolium salt, 1-octyl imidazole key, 1-dodecyl imidazole key, 1-tetradecylimidazole key , 1-hexadecyl imidazolium, 1,3-dimethylimidazole, 1-ethyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-butyl-3-methyl Imidazolium, 1-pentyl-3-methylimidazole, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazole, 1-octyl-3-methylimidazole , 1-mercapto-3-methylimidazolium, 1-dodecyl-3-methylimidazolium, 1-tetradecyl-3-methylimidazole, 1-hexadecyl-3- Methyl imidazole, 1-vinyl-3-methylimidazole, 1-propyl-3-ethylimidazole, 1-butyl-3-ethylimidazole, 1-pentyl-3-ethyl Imidazole, 1-hexyl-3-ethylimidazolium, 1-heptyl-3-ethylimidazole, 1-octyl-3-ethylimidazole, 1-mercapto-3-ethylimidazole, 1-dodecyl-3-ethylimidazole, 1-tetradecyl-3-ethylimidazole, 1-hexadecyl-3-ethylimidazole, 1-vinyl-3-B Imidazolium, 1-dodecyl-3-butyl Imidazole, 1-tetradecyl-3-butylimidazolium, 1-hexadecyl-3-butylimidazole, 1-vinyl-3-butylimidazole, 1-dodecyl- 3-octyl imidazole, 1-tetradecyl-3-octyl imidazole, 1-hexadecyl-3-octyl imidazole, 1-vinyl-3-octyl imidazole, 1, 2 , 3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazole, 1-butyl-2,3-dimethylimidazole, 1-hexyl-2,3-dimethyl Imidazole, 1-octyl-2,3-dimethylimidazole, 1-dodecyl-2,3-dimethylimidazole, 1-tetradecyl-2,3-dimethylimidazole Key, 1-hexadecyl-2,3-dimethylimidazolium, or 1-butyl-3-methylbenzimidazole key;

The pyridinium cation is 1-methylpyridine, 1-ethylpyridinium, 1-butylpyridyl, 1-octylpyridine, 1-dodecylpyridine, 1-tetradecylpyridine , 1-hexadecylpyridine, 1,2-dimethylpyridine, 1-hexyl-2-methylpyridine, 1-octyl-2-methylpyridine, 1-dodecyl-2 -methylpyridine, 1-tetradecyl-2-methylpyridinium, 1-hexadecyl-2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1, 2-di Ethylpyridinium, 1-butyl-2-ethylpyridinium, 1-hexyl-2-ethylpyridinium, 1-dodecyl-2-ethylpyridinium, 1-tetradecyl-2 -ethylpyridinium, 1-hexadecyl-2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1-butyl-2-methyl-3-ethylpyridinium, 1-hexyl-2-methyl-3-ethylpyridinium, 1-butyl-4-methylpyridinium, 1-hexyl-4- Methylpyridinium, 1-octyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-hexyl-3-methylpyridinium, or 1-octyl-3-methyl Pyridine key; the pyrrolidine cation is 1,1-dimethylpyrrolidine, 1,1-butyl-methylpyrrolidine, 1,1-propyl-methylpyrrolidine, or 1,1-ethyl-methylpyrrolidine ;

The morpholine cation is 1,1-dimethylmorpholine, 1,1-methyl-ethylmorpholine, 1,1-methyl-propylmorpholine, or 1,1-methyl-butylmorpholine;

The piperidine cation is 1,1-dimethylpiperidinyl, 1,1-methyl-ethylpiperidinyl, 1, 1-methyl-propylpiperidinyl, or 1,1-methyl - butyl piperidine;

The anions are PF ₆ —, BF ₄ —, CF ₃ S0 ₃ , (CF ₃ S0 ₃ ) ₂ N— , CH ₃ C0 ₂ , HC0 ₃ , S0 ₄ ² —, N0 ₃ , N0 ₂ , S0 ₄ ² , B0 ₃ ³ , Mn0 ₄ , HB0 ₃ ² , H ₂ B0 ₃ , Si0 ₄ ⁴ , CN, SCN, HS0 ₄ , HS0 ₃ , P0 ₄ ³ , HP0 ₄ ² -, H ₂ P0 ₄ -, CH ₃ OS0 ₃ - , C ₂ H ₅ OS0 ₃ -, CuCl ₂ -, CI", Br-, S ² -, HS -, Γ , F - , A1C1 ₄ -, SbF ₆ ", HCF2CF2SO3, CF3CHFCF2SO3, HCCIFCF2SO3, (CF ₃ S0 ₂ ₂ N—, (CF ₃ S0 ₂ ) ₃ C—, CF ₃ C0 ₂ —, A1 ₂ C1 ₇ —, or BC1 ₄ —.

[0014] In the above solution, the organic liquid satisfies the following conditions: a saturated vapor pressure of 150 ° C at 150 ° C, preferably a saturated vapor pressure of 100 Pa; a viscosity of 20 ° C and a standard atmospheric pressure of 100 mPa · s, preferably a viscosity of 50 mPa · s; It is liquid at a standard atmospheric pressure and at a temperature ranging from 20 ° C to 150 ° C, preferably at a standard atmospheric pressure and at a temperature ranging from -20 ° C to 200 ° C.

[0015] In the above scheme, hydrocarbons, halogenated hydrocarbons, alcohols and ethers, nitros and amines, phenols and anthracenes, ketones and aldehydes, and acids having good solubility to a working substance Esters, heterocyclics and derivatives thereof can be used as organic liquids in the absorbent. The organic liquid is preferably one of a glycol ether-based organic liquid, an alcohol-based organic liquid, a pyrrolidone-based organic liquid, an ester-based organic liquid, or an amine-based organic liquid, or a mixture of two or more thereof.

[0016] In the above solution, the glycol ether organic liquid includes diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethyl Glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol single Propyl ether, tetraethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, Triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol One or a mixture of two or more of dibutyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, ethylene glycol dibutyl ether, or propylene glycol phenyl ether;

The alcoholic organic liquid includes diethylene glycol, triethylene glycol, benzyl alcohol, 2-ethylhexanol, decyl alcohol, diacetone alcohol, methyl hexanol, glycerol, 1,3-propanediol, 1, a mixture of one or more of 2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-pentanediol, or benzyl alcohol;

The pyrrolidone organic liquid includes 1,3-dimethyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N -propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2 - One or a mixture of two or more of pyrrolidone or N-vinylpyrrolidone; The ester organic liquid includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisopropyl phthalate, dibutyl phthalate, ortho Diisobutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl adipate, dimethyl glutarate, dimethyl succinate, ethyl lactate, benzoic acid Ethyl ester, diethyl oxalate, 2-butoxyethyl acetate, ethyl salicylate, ethyl acetoacetate, methoxydiethylene glycol acetate, ethylene glycol diacetate, diethyl Glycol diacetate, triethylene glycol diacetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexyl acetate , 2-ethylbutyl acetate, decyl acetate, γ-butyrolactone, tributyl citrate, propylene carbonate, amyl lactate, butylene carbonate, diisobutyl adipate, succinic acid Diisobutyl acrylate, isooctyl acetate, isopropyl benzoate, tributyl phosphate, dibutyl oxalate, diamyl oxalate, n-butyl lactate, benzyl acetate acetate Cyclohexyl acrylate, isobutyl or butyl acetate or as a mixture of two or more;

The amine organic liquid includes aniline, hydrazine, hydrazine-dimethylaniline, octylamine, ethanolamine, diethanolamine, hydrazine-methyldiethanolamine, hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-dimethyl methacrylate. a mixture of one or more of amide, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-diethylformamide, hydrazine-methylcaprolactam, or hydroxyethylethylenediamine;

The organic liquid may also be 1,3-dimethyl-2-imidazolidinone, oxime-acetyl-2-imidazolidinone, ethyltetrahydrofuran ether, methyltetrahydrofuran ether, propyl tetrahydrogenation. Furan ether, or butyl tetrahydrofuran ether.

[0017] In the above aspect, the absorption type thermal cycle system includes an absorption heat pump, an absorption refrigeration system, or an absorption heat exchanger.

[0018] The principle of the present invention is as follows: The working material of the working medium does not use a conventional refrigerant such as Freon which is destructive to the ozone layer, but selects a kind of refrigeration working material which also has a high vaporization enthalpy. . For absorbents, we want to find a balance between boiling point, saturated vapor pressure, and viscosity. Some organic liquids have good absorption and low viscosity for the work, but because of their high saturated vapor pressure, they cannot meet the requirements of the absorbent. We can mix the organic liquid with the ionic liquid in an appropriate ratio. The purpose of reducing the saturated vapor pressure of the absorbent is achieved; for some ionic liquids, because the melting point is too high or the viscosity is too large in the operating temperature range, the requirement as an absorbent can be achieved by mixing with the organic liquid. In short, through the above operations, we can broaden our horizons to find the most perfect absorbent material, and then find the most reasonable working material pair. The choice of anion [Α] ^η - for the ionic liquid may be all anions capable of binding to the cation to produce an ionic liquid. Viscosity and melting point are important indicators for us to choose suitable ionic liquids. Because the interaction between cation and cation of ionic liquid is usually much stronger than the van der Waals force between common organic solvent molecules, the viscosity of ionic liquid at normal temperature is very high. Preferably, when combined with a cation, the ionic liquid can have an anion having a low melting point and a low viscosity.

[0019] Compared with the prior art, the beneficial effects obtained by the present invention are:

Mixing an ionic liquid and an organic liquid as an absorbent in a pair of working fluids in an absorption thermal cycle system, compared with conventional absorbents A big advantage.

[0020] First, the mixed absorbent is composed of an organic liquid and an ionic liquid, both of which can be synthesized by chemical means, and can design an absorbent molecule having a higher solubility to the working object for the characteristics of different refrigeration working objects. Therefore, the absorbent can have a higher solubility for the work.

[0021] Secondly, the ionic liquid has a vapor pressure of almost zero due to its unique properties. Mixing the ionic liquid with a low vapor pressure organic liquid further reduces the saturated vapor pressure of the mixture according to Raoult's Law. Therefore, the absorbent can have a very low saturated vapor pressure.

[0022] Again, organic liquid absorbents generally have a very low viscosity, and even when mixed with a higher viscosity ionic liquid, the mixed absorbent still has a very low viscosity coefficient. Therefore, the absorbent has a very low viscosity coefficient compared to the lithium bromide solution in the existing lithium bromide-water system.

[0023] Finally, the work materials and absorbent materials are selected to be low-toxic, safe, non-flammable, and environmentally friendly, and there is no corrosion to materials such as copper and iron.

[0024] Therefore, based on the above characteristics, the patent of the present invention has a greater advantage than the working substance pair of the existing absorption type thermal cycle system, and is a new type of practical working pair.

detailed description

The invention is further described in the following examples, and the following examples are not to be construed as limiting the invention.

Embodiment 1:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is R134a (C ₂ H ₂ F ₄ ), and the absorbent is a mixed liquid composed of 40% by mass of an ionic liquid and 60% of an organic liquid. The ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and the organic liquid is N-methyl-2-pyrrolidone. The work and absorbent are miscible at a temperature of 20 to 80 °.

[0027] The solubility of the working substance pair was measured using a Hyde/IGA-100 from the UK Hyde Company. The measurement results showed that the solubility of the working substance R134a in the absorbent at 35 ° C, 4 bar was 54 wt%.

[0028] The viscosity at 20 ° C was measured using a SNB-1 digital viscometer, and the viscosity of the absorbent was 15.7 mPa · s.

[0029] The saturated vapor pressure of N-methylpyrrolidone was measured by a vapor pressure meter to be 46 Pa (25 ° C). Because the saturated vapor pressure of the ionic liquid is negligible, it can be regarded as a non-volatile solute. Therefore, according to Ur's Law (Raoult's Law is Ρ=Ρ* · Χ, Ρ is the partial pressure of the solvent in the solution, Ρ* is the saturated vapor pressure of the pure solvent, X is the amount of the solvent substance), and it is known that the absorbent is at 25 ° C. The vapor pressure is 40.0 Pa. [0030] Example 2:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is R134a (1,1,1,2-tetrafluoroethane), and the absorbent is a mixed liquid composed of 40% by mass of an ionic liquid and 60% of an organic liquid. The ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and the organic liquid is tetraethylene glycol dimethyl ether. The work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0031] Solubility (35 ° C, 4 bar) and viscosity (20 °) of the mixed absorbent according to the same method as in Example 1.

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 56 wt%, 17.3 mPa - s, < 1.2 Pa.

Example 3:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is R134a (1,1,1,2-tetrafluoroethane), and the absorbent is a mixed liquid composed of 30% by mass of an ionic liquid and 70% of an organic liquid. The ionic liquid is tetramethylammonium bistrifluoromethanesulfonimide salt, and the organic liquid is ethanolamine. The work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0034] The solubility of the mixed absorbent (35 ° C, 4 bar), viscosity (20) in the same manner as in Example 1.

°C), saturated vapor pressure (25 ° C) for measurement.

[0035] The results were: 34 wt%, 28.0 mPa.s, 33.0 Pa.

[0036] Example 4:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is R134a (1,1,1,2-tetrafluoroethane), and the absorbent is a mixed liquid composed of 20% by mass of an ionic liquid and 80% of an organic liquid. The ionic liquid is tributylmethylscale bistrifluoromethanesulfonimide salt, and the organic liquid is diisobutyl succinate. The work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0037] The solubility of the mixed absorbent (35 ° C, 4 bar) and viscosity according to the same method as in Example 1 (20)

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 17 wt%, 26.3 mPa - s, 2.1 Pa.

Example 5:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work is R134a (1,1,1,2-tetrafluoroethane), and the absorbent is A mixed liquid consisting of 10% by mass of ionic liquid and 90% of organic liquid. The ionic liquid is 1,2-dimethylpyridine hydrochloride, and the organic liquid is N-methyl-2-pyrrolidone. The work and absorbent are miscible at a temperature of 20 to 80 °C.

[0040] The solubility of the mixed absorbent (35 ° C, 4 bar ) and viscosity according to the same method as in Example 1 (20)

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 54 wt%, 13.4 mPa * s, 41.0 Pa.

Example 6:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is R134a (1,1,1,2-tetrafluoroethane), and the absorbent is a mixed liquid composed of 10% by mass of an ionic liquid and 90% of an organic liquid. The ionic liquid is 1,1-butyl-methylpyrrolidine tetrafluoroborate, and the organic liquid is ethanolamine. The work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0043] The solubility of the mixed absorbent (35 ° C, 4 bar ) and viscosity according to the same method as in Example 1 (20)

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 14 wt%, 25.3 mPa - s, 34.1 Pa.

[0045] Example ⁷ :

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The working substance is HFE-134a (1,1,1-trifluoromethyl ether, CF ₃ -0-CH ₃ ), and the absorbent is composed of 49% by mass of ionic liquid and 51% of organic liquid. Mix the liquid. The ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and the organic liquid is N-methyl-2-pyrrolidone. The work and absorbent are miscible at a temperature of 20 to 80 °C.

[0046] The solubility of the mixed absorbent (35 ° C, 4 bar ) and viscosity according to the same method as in Example 1 (20)

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 53 wt%, 29 mPa - s, 43.0 Pa.

Example 8:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work material is tetrafluoroethylene (C ₂ F ₄ ), and the absorbent is a mixed liquid composed of 40% by mass of an ionic liquid and 60% of an organic liquid. The ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and the organic liquid is N-methyl-2-pyrrolidone. The work and absorbent are miscible at a temperature of 20 to 80 °. [0049] The solubility of the mixed absorbent (35 ° C, 4 bar ), viscosity (20) in the same manner as in Example 1.

°C), saturated vapor pressure (25 ° C) for measurement.

The results were: 13 wt%, 15.7 mPa - s, 40.0 Pa.

Example 9:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The work was isobutane (C ₄ H ₈ ), which was a mixed liquid composed of 40% by mass of an ionic liquid and 60% of an organic liquid. The ionic liquid is 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and the organic liquid is N-methyl-2-pyrrolidone. The work and the absorbent are miscible at a temperature of 20 to 80 °C.

[0052] Solubility (35 ° C, 4 bar ) and viscosity (20 °) of the mixed absorbent according to the same method as in Example 1.

°C), saturated vapor pressure (25 ° C) for measurement.

[0053] The results are: l l wt%, 15.7 mPa - s, 40.0 Pa.

Example 10:

This embodiment provides a working substance pair for an absorption type thermal cycle system having a heat source temperature between 60 ° C and 130 ° C, the working substance pair being composed of a work substance and an absorbent. The working substance is HFE-134a (1,1,1-trifluoromethyl ether, CF ₃ -0-CH ₃ ), and the absorbent is composed of 40% by mass of ionic liquid and 60% of organic liquid. Mix the liquid. The ionic liquid is 1,1-methyl-ethylmorpholine bistrifluoromethanesulfonimide salt, and the organic liquid is tetraethylene glycol dimethyl ether. The work and absorbent are miscible at a temperature of 20 to 80 °C.

[0055] Solubility (35 ° C, 4 bar ) and viscosity (20 °) of the mixed absorbent according to the same method as in Example 1.

°C), saturated vapor pressure (25 ° C) for measurement.

[0056] The results were: 47 wt%, 16.9 mPa. s, < 1.2 Pa.

Example 11:

The working substance pair used in this embodiment is composed of R134a (1, 1, 1, 2-tetrafluoroethane) as a working substance, ionic liquid 1-ethyl-3-methylimidazolium acetate and organic liquid tetraethylene glycol. a mixed liquid of dimethyl ether as an absorbent, an absorbent solution of 1-ethyl-3-methylimidazolium acetate and tetraethylene glycol dimethyl ether in the absorber and an absorbent solution formed by the working substance R134a is passed through a liquid pump Pressurization (pressure rises from 0.5MPa to l.lMPa), enters the generator; the mixed liquid in the generator is heated to 80 °C by the hot water produced by the solar water heater, due to the increase in temperature R134a in 1-ethyl-3 - The solubility of the methyl imidazolium acetate and the tetraethylene glycol dimethyl ether in the absorbent liquid is reduced, part of R134a is separated from the absorbent solution, and the high pressure R134a gas passes through the gas-liquid separation device and enters the condenser, and the remaining The absorbent solution is depressurized back to the absorber through the flow control valve; the high pressure R134a is lowered to 25 ° C in the condenser, and the throttle valve is decompressed and expanded, the temperature is lowered to 5 ° C, and R134a becomes Low-temperature gas-liquid two-phase mixture, the low-temperature R134a gas in the evaporator is exchanged for cooling through the cooling medium, and the low-temperature R134a gas rises to the absorber and is dissolved in 1-ethyl-3-methyl. A mixed liquid of imidazole acetate and tetraethylene glycol dimethyl ether.

[0058] The new working substance pair can realize the refrigeration cycle in the conventional absorption heat pump system, and the working object and the absorbent can be completely separated, and no pipe blockage occurs.

[0059] The mixed liquid of the absorbent 1-ethyl-3-methylimidazolium acetate and tetraethylene glycol dimethyl ether has a low vapor pressure, a small viscosity, a wide liquid range, and good solubility to R134a, The system is non-corrosive; the work R134a is non-toxic, non-explosive and environmentally friendly.

[0060] It is to be understood that those skilled in the art should understand that the invention may be modified or equivalently substituted without departing from the spirit and scope of the present invention. Within the scope of the request.

Claims

WO 2014/082420 Right and j request PCT/CN2013/074671

A working substance pair for an absorption heat cycle system having a heat source temperature of between 60 ° C and 130 ° C, wherein the working substance pair is composed of a work substance and an absorbent material, and the work substance is selected from the group consisting of a mixture of one or more of a fluoroalkane, a fluoroolefin, a fluoroether, an unsubstituted alkane, or an olefin; the absorbent is from 1% to 50% by mass of an ionic liquid and 50% - A mixed liquid composed of 99% organic liquid, the work substance and the absorbent are miscible at a temperature of 20 to 80 °C.

2. The working substance pair according to claim 1, wherein the fluoroalkane is monofluoromethane, difluoromethane, trifluoromethane, tetrafluoromethane, monofluoroethane, 1,1-difluorocarbon. Ethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroacetamidine, pentafluoroethane, or perfluoroethane The fluoroolefin is monofluoroethylene, 1,1-difluoroethylene, 1,2-difluoroethylene, trifluoroethylene, tetrafluoroethylene, monofluoropropene, 1,3-difluoropropene, 1,1 -difluoropropene, 3,3-difluoropropene, 1,1,3-trifluoropropene, 1,2,3-trifluoropropene, 1,3,3-trifluoropropene, 1,1,2-three Fluoropropene, 2,3,3-trifluoropropene, 3,3,3-trifluoropropene, 1,2,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,1 , 2,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,2,3,3-pentafluoropropene, 1,1 , 3,3,3-pentafluoropropene, 1,2,3,3,3-pentafluoropropene, or hexafluoropropylene; the fluoroether is monofluoro-methoxymethane, 1,1-difluoro Methyl ether, 1,2-difluoromethyl ether, 1,1,1-trifluoromethyl ether, 1,1,2-trifluoromethyl ether, 1,1,3,3-tetrafluoromethyl ether, 1,1 , 1,3-tetrafluoromethyl 1,1,1,3,3-pentafluoromethyl ether, hexafluoromethyl ether, monofluoro-ethoxymethane, 1-fluorosuccinylethane, 1-fluoro-2-methoxyethane , difluoromethoxyethane, 2,2-difluoroethyl methyl ether, 2,2,2-trifluoroethyl methyl ether, trifluoromethoxyethane, pentafluoroethoxymethane, Trifluoromethyl-trifluoromethoxymethane, or perfluoromethylether; the unsubstituted alkane is methane, ethane, propane, n-butane, or isobutane; the olefin is ethylene, propylene, isobutylene, Or n-butene.

The working substance pair according to any one of claims 1 to 3, wherein the absorbent satisfies the following conditions, wherein 25 V, a saturated vapor pressure of 100 Pa at a standard atmospheric pressure; 20 ° C, at a standard atmospheric pressure Viscosity

300mPa · s _; in a standard atmospheric pressure and in the temperature range of 20 ° C to 150 ° C are liquid.

The working substance pair according to any one of claims 1 to 3, wherein the ionic liquid is a salt satisfying the following formula ¹¹ or ¹¹¹ :

[C] _n +[A] ⁿ — C ¹ )

[Ci] ⁺ [C ₂ ] ⁺ [C ₃ ] ⁺ [A] ³ - ( ^Il b)

[Ci] ⁺ [C ₂ ] ⁺ [C ₃ ] ⁺ [C ₄ ] ⁺ [A] ⁴ - ( c)

[Ci] ⁺ [C ₂ ] ⁺ [M!] ⁺ [M ₂ ] ⁺ [A] ⁴ - ( ^m b) ( ^1JI c )

( ^II! d)

( ^I!I e)

( ^]II f)

( ^II5 g )

( ^m h)

Wherein [C] +, [d]\ [C ₂ ]+, [C ₃ ]+ or [C ₄ ]+ are quaternary ammonium salt cations, quaternary phosphonium cations, imidazolium cations, pyridinium cations, pyrrolidine cations, morpholines a cation, or a piperidine cation; [A] ⁿ - is a monovalent to tetravalent anion, [M^ [M ₂ ] ⁺ , [M ₃ ] ⁺ is a monovalent metal cation, [M ₄ ] ²⁺ is a divalent The metal cation, [M ₅ ] ³⁺ is a trivalent metal cation, and n is 1, 2, 3 or 4.

The working substance pair according to claim 4, wherein the ionic liquid has a cation [C] ⁺ , [ ] ⁺ , [C ₂ ] ⁺ , [C ₃ ] ⁺ , or [C ₄ ]+ The following structures and oligomers containing these structures:

Quaternary ammonium salt cations:

Seasonal salt cations:

(2) Imidazolium cation

Morpholine cations: Piperidine cation:

(7);

The group R in the structural formulae (1) to (7) is a dC ₂₅ linear, branched, or cyclic saturated hydrocarbon and an unsaturated hydrocarbon group, and may be a hydrocarbon inserted or substituted by a hetero atom or a functional group. a group, wherein the hetero atom is all atoms that can be inserted or substituted in principle; a functional group is all functional groups that can be attached to a carbon atom or a hetero atom;

Except that R is directly bonded to the same N or P atom at the same time as R ₃ cannot be hydrogen, and R ₇ may independently be hydrogen, dC ₂₅ linear, branched, or cyclic saturated hydrocarbon and unsaturated. a hydrocarbon group, and may be a hydrocarbon group inserted or substituted by a hetero atom or a functional group, wherein the hetero atom is all atoms which can be inserted or substituted in principle; the functional group is all functional groups which can be attached to a carbon atom or a hetero atom .

6. The working substance pair according to claim 4 or 5, characterized in that:

The quaternary ammonium salt cation is tetramethylammonium, butyltrimethylammonium, benzyltrimethylammonium, trimethylhydroxyethylammonium, dodecyltrimethylammonium, cetyltrimethyl Ammonium, octadecyltrimethylammonium, triethylammonium, benzyltriethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium, trioctylmethylammonium, Or a tetramethyl sulfonium key;

The quaternary salt cations are tributylmethyl scale, tributyl ethyl scale, tetrabutyl scale, tributylhexyl scale, tributyl octyl scale, tributyl sulfhydryl scale, tributyl dodecane Ketone, tributyltetradecyl scale, tributyl octadecyl scale, or tetraphenyl scale;

The imidazolium cation is 1-methylimidazole key, 1-ethylimidazole key, 1-butylimidazolium salt, 1-octyl imidazole key, 1-dodecyl imidazole key, 1-tetradecylimidazole key , 1-hexadecyl imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazole Key, 1-propyl-3methylimidazole, 1-butyl-3-methylimidazole, 1-pentyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1- Heptyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, 1-mercapto-3-methylimidazolium, 1-dodecyl-3-methylimidazole, 1- Tetradecyl-3-methylimidazole, 1-hexadecyl-3-methylimidazole, 1-vinyl-3-methylimidazole, 1-propyl-3-ethylimidazole, 1-butyl-3-ethylimidazolium, 1-pentyl-3-ethylimidazole, 1-hexyl-3-ethylimidazole, 1-heptyl-3-ethylimidazole, 1-octyl 3-ethylimidazolium, 1-mercapto-3-ethylimidazolium, 1-dodecyl-3-ethylimidazole, 1-tetradecyl-3-ethylimidazole, 1 -hexadecyl-3-ethylimidazolium, 1-vinyl-3-ethylimidazolium, 1-dodecyl-3-butylimidazole, 1-tetradecyl-3-butyl Imidazole, 1-hexadecyl-3-butylimidazolium, 1-vinyl-3-butylimidazolium, 1-dodecyl-3-octyl imidazole, 1-tetradecyl- 3-octyl imidazole, 1-hexadecyl-3-octyl imidazole, 1-vinyl-3-octyl imidazole, 1,2,3-three Methyl imidazole, 1-ethyl-2,3-dimethylimidazole, 1-butyl-2,3-dimethylimidazole, 1-hexyl-2,3-dimethylimidazole, 1 -octyl-2,3-dimethylimidazole, 1-dodecyl-2,3-dimethylimidazole, 1-tetradecyl-2,3-dimethylimidazole, 1- Cetyl-2,3-dimethylimidazolium, or 1-butyl-3-methylbenzimidazole key;

The pyridinium cation is 1-methylpyridine, 1-ethylpyridinium, 1-butylpyridyl, 1-octylpyridine, 1-dodecylpyridine, 1-tetradecylpyridine , 1-hexadecylpyridine, 1,2-dimethylpyridine, 1-hexyl-2-methylpyridinium, 1-octyl-2-methylpyridinium, 1-dodecyl-2 -methylpyridine, 1-tetradecyl-2-methylpyridinium, 1-hexadecyl-2-methylpyridinium, 1-methyl-2ethylpyridinium, 1, 2-di Ethylpyridinium, 1-butyl-2-ethylpyridinium, 1-hexyl-2-ethylpyridinium, 1-dodecyl-2-ethylpyridinium, 1-tetradecyl-2 -ethylpyridinium, 1-hexadecyl-2-ethylpyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1-butyl-2-methyl-3ethylpyridinium, 1-hexyl-2-methyl-3-ethylpyridinium, 1-butyl-4-methylpyridinium, 1-hexyl-4- Methylpyridinium, 1-octyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-hexyl-3-methylpyridinium, or 1-octyl-3-methyl Pyridine key; the pyrrolidine cation is 1, 1-dimethylpyrrolidine, 1,1-butyl-methylpyrrolidine, 1,1-propyl-methylpyrrolidine, or 1,1-ethyl-methylpyrrolidine;

The morpholine cation is 1,1-dimethylmorpholine, 1,1-methyl-ethylmorpholine, 1,1-methyl-propylmorpholine, or 1,1-A Base-butyl morpholine key;

The anions are PF ₆ , BF ₄ -, CF ₃ S0 ₃ —, (CF ₃ S0 ₃ ) ₂ N— , CH ₃ C0 ₂ —, HC0 ₃ —, S0 ₄ ² —, N0 ₃ —, N0 ₂ , S0 _{^{_{^{4 2, B0 3 3, Mn0}}}} 4, HB0 3 2, H 2 B0 3, Si0 4 4, CN, SCN, HS0 4, HS0 3, P0 4 3, HP0 4 2 -, H 2 P0 4, CH 3 OS0 ₃ -, C ₂ H ₅ OS0 ₃ -, CuCl ₂ -, CI", Br-, S ² -, HS -, Γ, F - , A1C1 ₄ -, SbF ₆ —, HCF ₂ CF ₂ S0 ₃ —, CF ₃ CHFCF ₂ S0 ₃ —, HCC1FCF ₂ S0 ₃ (CF ₃ S0 ₂ ) ₂ N―, (CF ₃ S0 ₂ ) ₃ C―, CF ₃ C0 ₂ —, A1 ₂ C1 ₇ —, or BC1 ₄ —.

The working substance pair according to any one of claims 1 to 5, wherein the organic liquid satisfies the following conditions: a saturated vapor pressure of 150 Pa at 25 ° C; a viscosity of 100 mPa at 20 ° C and a standard atmospheric pressure; · s; is liquid at a standard atmospheric pressure and in the temperature range of 20 ° C to 150 ° C.

The working substance pair according to claim 7, wherein the organic liquid is a glycol ether organic liquid, an alcohol organic liquid, a pyrrolidone organic liquid, an ester organic liquid, or an amine organic liquid. One or a mixture of two or more.

9. The working substance pair according to claim 8, wherein

The glycol ether organic liquid includes diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, alcohol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol. Monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, alcohol monomethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, diethyl Diol dimethyl ether, alcohol monoethyl ether, monoethyl alcohol monopropyl ether, decyl alcohol monobutyl ether, mono/ol monomethyl ether, monoethyl alcohol monoethyl ether, alcohol dipropyl ether, triethylene glycol dibutyl ether, four Ethylene glycol dipropyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, dibutyl ether, ethylene glycol monobutyl ether, ethylene glycol phenyl ether, ethylene glycol dibutyl ether, or propylene glycol benzene One or a mixture of two or more of ethers;

The pyrrolidone organic liquid includes 1,3-dimethyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N -propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, 1^-octyl-2 4 one or a mixture of two or more of a pyrrolidone or an N-vinylpyrrolidone;

The ester organic liquid includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisopropyl phthalate, dibutyl phthalate, ortho Diisobutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl adipate, dimethyl glutarate, dimethyl succinate, ethyl lactate, benzoic acid Ethyl ester, diethyl oxalate, 2-butoxyethyl acetate, ethyl salicylate, ethyl acetoacetate, methoxydiethylene glycol acetate, ethylene glycol diacetate, diethyl Glycol diacetate, triethylene glycol diacetate, diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexyl acetate , 2-ethylbutyl acetate, decyl acetate, Y-butyrolactone, tributyl citrate, propylene carbonate, amyl lactate, butylene carbonate, diisobutyl adipate, succinic acid Diisobutyl acrylate, isooctyl acetate, isopropyl benzoate, tributyl phosphate, dibutyl oxalate, diamyl oxalate, n-butyl lactate, benzyl acetate One or a mixture of two or more of ester methyl acetate, or isobutyl acetate;

10. The working substance pair according to claim 1, wherein the absorption type thermal cycle system comprises an absorption heat pump, an absorption refrigeration system, or an absorption heat exchanger.