Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems

Definitions

• the present invention relates to a composition for an absorption refrigerator comprising a refrigerant and an absorbent.
• compositions are generally of high viscosity, are metal corrosive and crystallizable.
• the condenser and the absorber need to be cooled by water.
• Ammonia-water system is also used.
• Halogenated methane-dimethylformamide system is also used
• C OP grade of performance
• At least one refrigerant of a hydrogenated alcohol which has 2 to 10 carbon atoms is a liquid at ordinary pressure, and can be a vapor at normal pressure or decompression when heated.
• a composition for an absorption refrigerator having at least one of a species and an atmospheric pressure higher than that of the refrigerant and having at least one type of an absorbent capable of absorbing the refrigerant.
• fluorinated alcohol in the composition of the present invention examples include fluorinated ⁇ , second and third alcohols represented by the following general formulas (i), ( ⁇ ) and ( ⁇ ).
• Group, H 2 , R 5 and E 6 are halogen (nitrogen or fluorine and chlorine) substituted or unsubstituted hydrocarbon groups.
• Unsubstituted hydrocarbon groups include alkyl groups (methinole, tyl, or iso-propynole, n-, iso-, sec- or tert-butyl, Bentyl, hexinole, heptyl, octyl-.norre group, etc.); cycloanole quinole group (cyclohexyl group, etc.); aryl group (phenyl, tolyl group, etc.); aralkyl group (pentyl, phenethyl) Group)
• fluorinated second alcohol represented by the formula (If) include the following. 4,4,3,3,1,1,1 -Heavy Fluoro -Z-Butanol, 1,1,1 -Trifluoro mouth -2 -Octanocre, 1,1,1 -Trif noreo mouth-2-Nonano nore, 6, 6, 5, 5, 4, 4, 3, 3, 2, 2-Deca nore mouth-1-Methynole-1 ⁇ , 6, 6, 5, 5, 4, 4, 3, 3, 3,
• fluorinated tertiary alcohol represented by the formula ( ⁇ ) include the following: 7, 7, 7, 6, 6, 5, 5, 4, 4, 3, 3, 2, 2-Tridecafolo mouth-1, 1-Dimethinolle-1-Hebutanore, 2, 2, 3, 3-Tetrafunoreole-1, 1-Dimethinole-1-Broha Nonole , 1, 1, 1-Trif nore Mouth-2-Feninole-2-Professional nore, 1, 1, 1, 1, 3, 3, 3 Hexaph norero-2-Bueninore- 2-Brono * Norre and 1, 1, 1, 3, 3, 3 ⁇ Kisafnorrero--( ⁇ -Trinore)-2-Broha 'Norore.
• fluorinated low-aliphatic alcohols having a normal pressure bay point of 120 X or less are preferred. These can operate the refrigerator with a low heat source and have good thermal efficiency.
• fluorinated low-Sai aliphatic aliphatic alcohols are S, 2- trifluorene mouth, 1-ethanol ethanol, 2,2-diphenyl alcohol, and 1-ethanol alcohol.
• a compound having an electron donating property can be used basically because the alcohol exhibits an electron withdrawing property. That is, a skyscraper compound containing an electron-donating atom such as an unpaired electron
• the organic compound capable of absorbing the refrigerant is capable of forming a complex with the refrigerant of the refrigerant.
• the absorption coefficient of the present invention is higher than the atmospheric pressure boiling point of the refrigerant (preferably at least 50 mm, more preferably
• the material has a boiling point at normal pressure and has low viscosity and does not cause solidification or crystallization when mixed with a refrigerant.
• the boiling point of the absorbent at normal pressure is usually ⁇ or more, preferably 1 to 5 to S00X.
• absorption takes place in a mixture with refrigerant (
• the material give a high viscosity.
• absorbents include ethers, polyols, and esters.
• the ethers, grayed Li co over ethers, for example volume Li c 2 ⁇ , mono of alkylene Nguri co Lumpur - or di - include alkyl ethers and cyclic form ethers.
• the polyalkylene glycol monoalkyl ether has the formula (F):
• E 7 is an alkyl group having 1 to 4 carbon atoms; 11 is a polyethylene glycol / lemono anoalkyl ether represented by an integer of J 2 to 5.
• diethyl glycol monomono Methyl ether, polyethylene glycol monoethylene, polyethylene glycol, etc. • Vinyl monolithic mouth; vinylothene, triethylene glycol monolithic methylone, polyethylene glycol, polyethylene glycol, etc.
• Tere and tetraethylene glycol alcohol monobrovir ether i
• polyalkylene glycol alcohol dialkyl ethers examples include those represented by the formula
• R S is an alkyl group having 1 to 4 carbon atoms. More specifically, diethylene glycol dimethyl alcohol, diethylene glycol cornole genie terre, geilelen liqueur konorejibuchi vinoreete tenore, triety lendari konoreresin chinoreete tere, and triethylene glycol delecetate Tenoré, Tri
• Cyclic ethers include furan derivatives, for example, US Pat.
• Polyols include glycols, poly C 2-3 alkylene
• n 2-5 integer
• n 2-5 integer
• n 2-5 integer
• n 2-5 integer
• n 2-5 integer
• Examples of the trivalent or more Borioru acids For instance glycerin Li down, the Application Benefits methylol Ruburopan, hexane Application Benefits All such and these C 2 ⁇ 3 alkyl Les Noki shea de adduct into (e.g. addition mol teaching 1-12 Mol).
• Esthenores include estenolle canoleponate, estenolate phosphate, and borate.
• aliphatic, alicyclic or aromatic mono- or polycarboxylic acids specifically acetic acid, brobionic acid, oxalic acid, oxalic acid, malonic acid, adibic acid, tetrahydrophthalic acid And phthalic acid.
• the Ci ⁇ 8 C However Okishikarubon acids :) excluding carbon atoms of the carboxyl groups, specifically
• .. to i- Examples include glycolic acid, lactic acid, citric acid, tartaric acid and the like.
• Hydroxy group-containing compounds constituting these carboxylic acids and esters include: aliphatic, alicyclic or aromatic alcohols of Ci to e ; specifically, methanol, ethanol, propanol, and the like. Or the like, or the above-mentioned glycol monoalkyl ethers or the above-mentioned polyols.
• esters of these carboxylic acids and hydroxy compounds include lower alcohol esters of dicarponic acid such as dimethinolate malonate and dimethyl oxalate; and 'monocarboxylic acid' such as diamine acid and butinole brobionate.
• Examples of the phosphoric acid ester include an ester of the above-mentioned hydroxy group-containing compound or phenol and a phosphorus-containing acid such as phosphoric acid or polyphosphoric acid, for example, trietinolephosphate, Libutinorephosphate, triphenylphosphate, tricresinolephosphate, etc .; phosphoric acid or poly (ethylene oxide) adduct (for example, 3 to 12 mol) Is raised.
• phosphoric acid or poly (ethylene oxide) adduct for example, 3 to 12 mol
• boron ester examples include a borate ester of the above-mentioned hydroxy group-containing compound, for example, a boric acid triester, specifically, a glycol'ether ether triborate ester.
• amides the formula (3 ⁇ 4):
• R 9, R w and E 11 is hydrogen atom or a ⁇ ⁇ 10 alkyl group, amino de compound represented by the full E double les group :
• dimethyl Chiruhorumuami de, - dimethicone Rease preparative A mi de GETS Chino Les phosphono REM a mi de, Ho REM a mi de, ⁇ Se Toami de, Asetayuri Sat; cyclic ⁇ Mi de example C S or ⁇ Ma properly ⁇ lactams ⁇ , pyromellitic Li Dong specifically Lactam, turnip lactam, cabrilactam, laurolactam, etc .; Ci-4 alkyl substitutions of these lactams, specifically N-methyl- 2 -vinylidone, N-ethyl-2-vinylidone. And the lactam
• amines more than c e, preferably c 7 to are aliphatic monoamines such as primary amines such as hebutylamine, secondary amines such as dihexylamine, and trioctylamine Tertiary amines such as amines; aliphatic boronides such as alkylenediamines, specifically trimethylenediamine, hexamethylenediamine, etc .; polyalkylenediamines , Such as triethylenetetramine of polyethylenepolyamine having a degree of polymerization of 2 to 6; cyclohexylamine, dicyclohexylamine, isophoronemine Alicyclic amines, such as mine and dicyclohexyl oletandiamine; aromatic amines, such as penzylamine, dibenzylamine, xylendiamine; morpholines, a Chaniazoru such, Lee Mi Dazonore such, Biperi gin acids, pyrazo
• Ketones include cyclohexanone, inholonacetyl acetate, and acetonitrile acetate; aldehydes include
• C 5 ⁇ is as a two-door Li le system '! Two to two torr, for example, Paleronitrile, etc., respectively.
• ethers suitable for use in the present invention are ethers, particularly glycol ethers and cyclic amides. Preferred among the Dali-cold ethers is
• Preferred among the cyclic amides are N-alkyl- 2- pyrrolidone, especially N-methyl-2-pyrrolidone.
• the fluorinated alcohol In the composition of the present invention, the fluorinated alcohol and absorption of the refrigerant
• the content of the agent can be varied over a wide range, not particularly. That is, based on the weight of the composition, the refrigerant is usually 5-60%, preferably 10-50% by weight, and the absorbent is usually 40-95%, preferably 50-90% by weight. A composition is used.
• agent especially ethers, polyols
• an organic amine is added to the agent to obtain a corrosion inhibiting effect on metals (irons).
• metals irons
• this amine is mixed into the fluorinated alcohol evaporated from the generator, and the metal of the equipment from the generator to the evaporator is also removed. A corrosion inhibiting effect is obtained.
• the addition of this amine alleviates the air condition, and can improve the disadvantages that the vapor pressure changes remarkably in a state where the degassing is insufficient, making it difficult to operate as a refrigerator.
• organic amine to be used in combination those having a boiling point of 150 I or less, especially 50 to 1150 C are preferable.
• Such amines include amines used as the absorbing agent (amines having a boiling point higher than the boiling point of the refrigerant by 50 X or more), and those having a boiling point of 150 C or lower, and those having a boiling point lower than that. Includes point amines.
• suitable amines include aliphatic amine granules such as ⁇ ⁇ ⁇ aliphatic primary amides (methicreamin, ethinoreamin, propinoleamin, butyramine, aminoleamine, etc.).
• the amount of the organic amine used depends on its boiling point, but is usually 0.05 to 10%, preferably 0.1 to 5% by weight based on the weight of the absorbent. Good with a small amount when low boiling amines (e.g. Chimaki point 100 C or less) (for example 0.0 5 to 1 by weight), but in a high-boiling ones (e.g. boiling point 100 ⁇ 150 ⁇ ) relatively large amount (e.g. 1-5. It is preferable to use it for heavy halo). When amine is used as the absorbent, it can be used in a larger amount (5 to 100% by weight) than the above.
• water can be added to the composition of the present invention.
• the addition of water is effective in preventing corrosion of carbon dioxide, and the amount of addition is preferably about 0.08 to 0.5% by weight based on the weight of the composition.
• the composition of the present invention may contain an additive such as a stabilizing agent or an anti-corrosive agent to improve heat stability and anti-corrosion properties.
• additives include benzotriabul, benzonitria triazonole, hindered phenol (2,6-di; -t-butynophenol, etc.).
• the amount of these additives is usually less than 5 weight, preferably 0.01 to 2 weight, based on the weight of the composition.
• the present invention provides a volatile refrigerant and an absorbent.
• At least one fluorinated alcohol refrigerant having 2 to 10 carbon atoms which is liquid at normal temperature, and which becomes a vapor at normal pressure or decompression when heated, and the refrigerant It is an object of the present invention to provide an absorption refrigeration system having a higher normal pressure boiling point and using at least one kind of absorption that absorbs the refrigerant.
• absorption chiller used for refrigeration using the composition ⁇ ! of the present invention a conventional absorption chiller can be used.
• Fig. 1 is a block diagram showing the basic cycle of a general absorption refrigerator
• Fig. 2 is a 2,2-trifluo port-1-petano-nore (hereinafter referred to as TFE) as a refrigerant.
• TFE 2,2-trifluo port-1-petano-nore
• DME ethylene glycol monomethyl ether
• TFE as the refrigerant
• N-methyl as the absorption layer in FIG.
• FIG. 4 shows a cross-sectional view of a tube made of a pressure-resistant glass for a heat resistance and a vapor pressure measurement test used in Example 6, which will be described later in Example 6, respectively.
• An absorption refrigerator generally has a basic circuit configuration as shown in Fig. 1, and (1) is composed of an absorption liquid diluted by absorbing a refrigerant (a composition formed by absorption of a refrigerant by absorption :).
• a generator that heats and separates the refrigerant
• a decompressor that reduces the liquid refrigerant of the condenser
• An evaporator that achieves the desired cooling function by evaporating by depressurizing in (4) and spraying under low pressure conditions, and (5) by absorbing the refrigerant vaporized in evaporator C3) with an absorbing liquid.
• Absorber which allows intermittent cooling movement in evaporation ⁇ CS), (6) is the absorber in which the refrigerant is separated in generator (1) and sent to absorber C5). Liquid) and absorber C5) to generator (1).
• An analyzer and rectifier that separates the refrigerant and the absorbent when
• the refrigerating cycle in the absorption refrigerator using the fluorinated alcohol as the refrigerant is performed by diluting liquid (generating refrigerant vapor from the absorption liquid having a low absorption concentration, condensing refrigerant vapor into liquid, depressurizing the refrigerant). This is achieved by repeating the process of evaporating the liquefied refrigerant (evaporation :) and absorbing the refrigerant vapor into the liquid (absorbing liquid having a high concentration :).
• the concentration of the concentrated liquid and the diluted liquid depends on the type of absorption used.
• the conversion conditions that is, the heating temperature of the diluted liquid (temperature of the generator), the evaporation temperature of the refrigerant liquid ( It is set arbitrarily according to the temperature inside the evaporator) and the absorption temperature of the refrigerant (humidity inside the absorber).
• composition for an absorption refrigerator As described above, the use of the composition for an absorption refrigerator according to the present invention has the following five advantages as described in detail in Examples described later.
• composition does not azeotrope and the absorbent used is a refrigerant having a normal pressure point of 50 TC or more, the analyzer and the rectifier are not used in the absorption refrigerator.
• composition does not have crystallinity, the circulation power is reduced and the transmission resistance is reduced. It can also be used in cold climates.
• the carrier is less corrosive to irons.
• the composition is toxic.
• fluorinated alcohol especially fluorinated alcohol having a boiling point of 130 C or less
• the temperature at which the refrigerant is separated from the CD carrier is not very high.
• the temperature at which the refrigerant is condensed is not very low40. Air cooling is sufficient for cooling in the condenser and absorber.
• the heating temperature in the generator 1) is not so high that it is absorbed.
• the cooling medium is separated from the collected liquid, and the cooling temperature in the condenser ( 2 ) is
• the refrigerant can be condensed and liquefied at least at a very low temperature. For example, if the heating temperature required at the generator CD is 80-200 C
• the refrigerant can be liquefied at 40 to 60X ;, even an air-cooled condenser functions sufficiently as a condenser, and this liquefied refrigerant is absorbed at 40 to 60 60 in the absorber, so that An air-cooled cooling device is also sufficient.
• the refrigerant vaporization temperature must be 5
• the refrigerant has a large latent heat of vaporization and low toxicity.
• the use range of the air-cooled absorption refrigerator can be significantly increased.
• composition for an absorption refrigerator of the present invention can be applied to an air-cooling type or a water-cooling type, and a refrigeration system using the composition can be used for various purposes such as home use, cooling systems for factories and factories, and air conditioners. Can be used.
• Figure 2 line (A) is a saturated vapor pressure for each temperature T FE, also line (Bi) (B 2) ( B s) is TFE; DME weight Jfc respectively 30 ⁇ 0, 25/75 ' The boiling point of TFE is '75 TC as shown in the figure, and the boiling point of DME is about 196 ° C. Was also confirmed.
• TFE flows into the generator (1) (point a in Fig. 2).
• Low absorption liquid absorption ⁇ of the weight ratio of DME is 2 7 73 (diluted solution) live This is added to about 117 TC, and ⁇ is vaporized (point b in Fig. 2) and sent to the condenser.
• the absorption concentration is increased to approximately 81 weight, and the absorbent concentration is high.
• the absorption liquid (concentrated liquid) is cooled through the heat exchanger ( 6 ) and flows into the absorber (5; (point c in Fig. 2).
• the TFE that flows into the condenser (2) is approximately 50 X: It is cooled and liquefied, and is supplied to the evaporator (3) at a pressure of about 19 ⁇ ⁇ ⁇ ⁇ through a decompression device (4), where it is sprayed. The object is cooled to about 51 C. Since the vaporized TFE is absorbed by the concentrated liquid sprayed in the absorber (5), the inside of the evaporator (3) is kept at approximately 19 jm, and the gas of ⁇ is absorbed. has been (FIG. 2 point d) generated diluted solution is absorber in ripe exchanger (6) (5): entering the dark liquid heat exchanger and the temperature was raised was then again generator (1) flowing into the ( Figure 2, point a).
• the boiling point of ⁇ is as follows: Since there is a difference between the boiling point of DME and the boiling point of about ISO C as described above, azeotropy does not occur. There is no need to add (S) or a rectifier (9), and the equipment configuration can be simplified.
• the present invention is characterized in that the operating pressure of the absorption refrigerator is about 250 araH on the high pressure side where the generator (1) is located, and about 20 on the low pressure side where the evaporator (3) is located.
• the operating pressure is lower than the atmospheric pressure, and the operating pressure is 10 to 20 K / on the high pressure side, like the conventional ammonia-water system and the fluoro-tetraethylene glycol dimer ether system, and even on the low pressure side. 5
• There is no danger of leakage of liquid or gas from the absorption chiller by using ILg / cjH and the refrigerant system operated under high pressure conditions, and also reduce the strength of the components of the chiller and facilitate maintenance.
• a vapor pressure temperature diagram substantially the same as that of FIG. 2 was obtained for a composition comprising 26.8% by weight of TFE, 72.562% by weight of DME, 0.299% by weight of water, and 0.30% by weight of benzotriazole. Matape Nzoto Riazor amount of. Was found to be 5 wt 0.5 0.03 weight is effective.
• Example 5
• FIG. 3 shows the vapor pressure temperature diagram when TFE was used as the refrigerant and ⁇ -methyl-2- vilolidone was used at various concentrations as the absorption 3 ⁇ 4.
• FIG (Alpha) shows the saturated vapor pressure for each temperature of TFE, ⁇ ( ⁇ ( ⁇ 2) ( ⁇ 3) is TFEZN -. Methyl - 2 - Biro weight ratio of Li Don it it 50Z . 5 0, there is shown based on the value obtained by measuring the steam for each temperature of the composition of 40/60 and 3 Q 7 0 boiling is shown in FIG Although T FE is 75 X: It was also confirmed that the boiling point of N-methinole-2-viridone was 2021C.
• the concentrated liquid having an N-methinole-J2-pyrrolidone concentration of about 60 weight is cooled through the heat exchanger ( 6 ) and supplied to the absorber (5) (point c in Fig. 3).
• the TFE that has flowed into the condenser (2) is cooled to about 50 TC, liquefied, passed through the evaporator ( 3 ) at about the pressure through the decompression device, and sprayed alongside.
• the object around the evaporator ( 3 ) is cooled down to about 5 ⁇ . Since the vaporized TFE is absorbed by the concentrated liquid sprayed in the absorber (5;), the inside of the evaporator (3) is maintained at approximately 19 vH, and the TFE gas is generated by absorbing the TFE gas (third part). (Point d in Figure 3) '' The diluted liquid exchanges heat with the concentrated liquid flowing into the absorber ( 5 ) in the heat exchanger ( 6 ), heats it, and then flows into the regenerator (1) again (point in Figure 3 at point a :).
• the boiling point of TFE and the boiling point of N-methyl-2-pyrrolidone have a boiling point difference of about 130 C, as described above, so that azeotropy does not occur.
• an analyzer (8) 'or a rectifier (9) to the configuration of the absorption refrigerator, and the device configuration can be simplified.
• the operating pressure of the very characteristic of the absorption refrigerating model in apply in this invention from about 25 0 in the high-pressure side with a generator (1) Simplified H?
• the difference of about 20 from the atmospheric pressure is lower than the atmospheric pressure. Is 10 to 20 g ed at high pressure
• the composition of the Kome Example did not crystallize in the absorption liquid under ordinary cultivation conditions of the absorption refrigerator and did not significantly increase the viscosity, so that operation in a cold region was not disabled.
• the condenser (and the absorber) can be air-cooled, there is no need for a water-cooling mechanism or cooling tower as in conventional water-lithium bromide systems, and absorption cooling in areas with poor water conditions. The operation of the freezer is also possible.
• a pressure-resistant glass tube with a breakable seal (10: breakable seal; 11: sample injection and tube seal; 153: connection to vapor pressure measuring device)
• amides with a boiling point of 150 TC or less are also contained in the TFE fraction. Therefore, corrosion of metals (particularly irons) in equipment from the generator to the evaporator is suppressed.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Combustion & Propulsion (AREA)
• Thermal Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Sorption Type Refrigeration Machines (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1980
  • 1980-02-12 JP JP55016315A patent/JPS592477B2/ja not_active Expired
• 1981
  • 1981-02-09 US US06/314,083 patent/US4455247A/en not_active Expired - Lifetime
  • 1981-02-09 GB GB8129893A patent/GB2080821B/en not_active Expired
  • 1981-02-09 WO PCT/JP1981/000026 patent/WO1981002301A1/ja not_active Ceased
  • 1981-02-09 DE DE813134448T patent/DE3134448T1/de active Granted
  • 1981-02-09 EP EP81900418A patent/EP0048281B1/en not_active Expired
  • 1981-10-12 SE SE8106031A patent/SE442999B/sv not_active IP Right Cessation

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