Abstract:
A stabilized absorption composition comprising (a) a halogenated hydrocarbon refrigerant, (b) a liquid absorbent of a polyethylene glycol methyl ether and (c) at least one stabilizer selected from phosphite esters, epoxy compounds and organotin compounds is excellent in stability and can be used for an absorption type refrigerator for a long period of time without causing corrosion.

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to a stabilized absoption composition including a novel liquid absorbent for absorption type refrigerators, which absorbent is stable against the halogenated hydrocarbon type refrigerants in the absorption type refrigerators and also little corrosive on metals. 
     The mechanical compression type refrigerators have gained ground and spread widely since the 1940&#39;s with the improvement of working precision of the machines. Recently, however, in order to meet the growing request for utilization of solar heat or waste heat, attention is again being given to the absorption type refrigerators using a halogenated hydrocarbon type refrigerant. 
     Generally, in the absorption type refrigerators, a closed circuit containing an absorbent is adopted and a liquid halogenated hydrocarbon type refrigerant evaporates in an evaporator constituting a part of said circuit to drive out heat from the surrounding to thereby effect cooling. The vapor of said halogenated hydrocarbon type refrigerant contacts with and is absorbed into the low-concentration liquid absorbent in an absorber and the resultantly formed high-concentration absorbent is sent into a generator where said absorbent is heated by an external heat source to release vapor of the halogenated hydrocarbon type refrigerant. This vapor is condensed by a condenser and again flows into the evaporator. On the other hand, the low-concentration absorbent formed by releasing vapor of the halogenated hydrocarbon refrigerant again returns into the absorber and absorbs vapor of the halogenated hydrocarbon type refrigerant. 
     In such absorption type refrigerators where a halogenated hydrocarbon is used as refrigerant, use of a furan compound as an absorbent is proposed (U.S. Pat. No. 4,072,027). But the furan compounds are not suited for practical use as they are expensive and hardly available commercially. It is also proposed to use as absorbent a polyethylene glycol methyl ether type compound which has a very high absorbing capacity (Japanese Patent Appln. Kokai (Laid-Open) Nos. 55849/79 and 152257/79). However, when such polyethylene glycol methyl ether type compound is used as absorbent, there arises a problem of poor stability of the system wherein the halogenated hydrocarbon type refrigerant, a metal which forms a refrigerator and said absorbent coexist, and also a metal corroding reaction may occur as said absorbent contracts with Fe 2  O 3  formed on the surface of the surrounding iron type metal material during operation of the refrigerator. For example, when monochlorodifluoromethane is used as the halogenated hydrocarbon type refrigerant, the following reaction takes place: 
     
         6CHClF.sub.2 +Fe.sub.2 O.sub.3 →3CHF.sub.3 +3CO+FeF.sub.3 +3HCl 
    
     As a result, iron halide is produced on the metal surface. There is also produced hydrogen chloride which is a corrosive element on the metal surface also promotes deterioration of the absorbent itself. This reaction is accelerated in the presence of water, and such a reaction also occurs when using other halogenated hydrocarbon type refrigerants. As for stabilizers for improving such metal corrosion, no report on studies has been made at present. Although the use of phosphite esters is disclosed in the above-mentioned U.S. Pat. No. 4,072,027 but said U.S. patent is quite silent on and gives no suggestion whether the phosphite esters are effective for a composition including a halogenated hydrocarbon as a refrigerant and an ethylene glycol series absorbent. The halogenated hydrocarbon type refrigerant to be used in this invention is of the type which has a boiling point of from -40° to +25° C., but when the absorption type refrigerator is operated by using as absorbent a polyethylene glycol methyl ether type compound of the general formula: CH 3  --O--C 2  H 4  --O) n  R (I) (wherein n is an integer of 1 to 6, and R is H, CH 3  -- or CH 3  CO--), remarkable corrosion occurs on the metal surface of the generator. Therefore, establishment of certain anticorrosive means is essential for the practical use of said absorption type refrigerator for a long period of time. 
     SUMMARY OF THE INVENTION 
     As a result of extensive studies, the present inventors found that said corrosion of metal can be prevented by adding a specific stabilizer to the absorbent composed of a polyethylene glycol methyl ether type compound of the following general formula: 
     
         CH.sub.3 --O--C.sub.2 H.sub.4 --O).sub.n R                 (I) 
    
     wherein n is an integer of 1 to 6, and R is H, CH 3  -- or CH 3  CO--, and attained the present invention. 
     Thus, an object of this invention is to provide a stabilized absorption composition including a liquid absorbent for absorption type refrigerators, which absorbent is stable against the halogenated hydrocarbon type refrigerant used in the refrigerator and also little corrosive on metals. 
     This invention provides a stabilized absorption composition comprising 
     (a) halogenated hydrocarbon as a refrigerant, 
     (b) a polyethylene glycol methyl ether type compound represented by the general formula: 
     
         CH.sub.3 --O--C.sub.2 H.sub.4 --O).sub.n R                 (I) 
    
     wherein n is an integer of 1 to 6, and R is H, CH 3  -- or CH 3  CO--, as absorbent, and 
     (c) at least one stabilizer selected from the group consisting of phosphite esters, epoxy compounds and organotin compounds. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The polyethylene glycol methyl ethers of the formula (I) are usable as absorbent in this invention, but among these compounds, those of the formula (I) wherein n is 2 to 5 and R is CH 3  are preferred. As typical examples of such polyethylene glycol methyl ethers, the following may be cited: diethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, pentaethylene glycol dimethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether and pentaethylene glycol monomethyl ether. These ethers may be used either singly or as a mixture thereof. 
     Aliphatic phosphite esters may be used as stabilizer in this invention, and as examples of such aliphatic phosphite esters, one may cite the following: trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, trilauryl phosphite, trimyristyl phosphite, tricetyl phosphite, tristearyl phosphite, trioleyl phosphite, distearylpentaerythritol diphosphite, diisodecylhydrogen phosphite, dilaurylhydrogen phosphite, dioleylhydrogen phosphite, diisodecylpentaerythritol diphosphite, etc. 
     Aromatic phosphite esters may be also used as stabilizer in this invention. Examples of such aromatic phosphite esters are diphenylisodecyl phosphite, triphenyl phosphite, tris(4-phenylphenol) phosphite, tris(nonylphenyl) phosphite, diphenyl(tridecyl) phosphite, tricresyl phosphite, phenyldiisooctyl phosphite, diphenylnonylphenyl phosphite, phenylisodecyl phosphite, trixylenyl phosphite, phenyldiisodecyl phosphite, tris(cyclohexylphenyl) phosphite, diphenyl phosphite, diphenylnonyl phosphite, di(nonylphenyl)nonyl phosphite, tetraphenyldipropylene glycol diphosphite, etc. 
     These phosphite esters may be used either singly or as a mixture thereof. 
     As the epoxy compounds also usable as stabilizer in this invention, there may be cited, for example, bis(2,3-epoxycyclopentyl) ether, 2,2-bis(3,4-epoxycyclohexyl)propane, 1-phenoxy-2,3-epoxypropane, 1,2,5,6-diepoxy-4,7-hexahydromethanoindane, 2-(3,4-epoxy)cyclohenxyl-5,5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, 1,2-bis[5-(1,2-epoxy)-4,7-hexahydromethaneoxyl]ethane, 1,2-bis[5-(1,2-epoxy)-4,7-hexahydromethanoindaneoxyl]methane, 3,4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexyanecarboxylate, 3,4-epoxycyclohexamethyl-(3,4-epoxy)cyclohexane carboxylate, phenylglycidyl ether, 1,4-butanediolglycidyl ether, allylglycidyl ether, p-t-butylenyl-2,3-epoxypropyl ether, 2,3-epoxypropyl-p-methoxyphenyl ether, butylene oxide, 1-epoxyethyl-3,4-epoxycyclohexane, and the like. These epoxy compounds can be used alone or as a mixture thereof. Among these epoxy compounds, those having a glycidyl ether group and butylene oxide are more preferred. 
     Organotin compounds are further usable as stabilizer in this invention, and the examples of such organotin compounds include tetraethyltin, tetrabutyltin, tertraphenyltin, dibutyldisalicyltin, di-n-octyltin malate, di-n-octyltin laurate, di-n-octyltin dilaurate, di-n-octyltinbis(2-ethylhexyl) malate, dibutyltin malate, dibutyltin laurate, dibutyltin dilaurate epoxy, dibutyltin diacetate, dibutyltindiisooctyl malate, dibutyltin dilaurate, etc. These organotin compounds can be used alone or as a mixture thereof. 
     The above-said three types of stabilizer compounds may be used as a mixture thereof. 
     Said stabilizer is preferably added in an amount of 0.1 to 5% by weight based on the total weight of the absorbent and the stabilizer. If the amount of the stabilizer is too small, for example less than 0.1% by weight, there is provided no satisfactory chlorine capturing capacity, while if said amount is too large, for example greater than 5% by weight, such stabilizer may be reacted with the absorbent (halogenated hydrocarbons) to lose its stabilizing effect. 
     As mentioned above, the refrigerant to be used in this invention is selected from the halogenated hydrocarbons having a boiling point of from -40° to +25° C., and as such halogenated hydrocarbons, the following may be named; trichloromonofluoromethane, dichlorodifluoromethane, 1,1,1,2-tetrafluoroethane, monochlorodifluoromethane, dichloromonofluoromethane, monochloromonofluoromethane, monochloromethane, 1,1-difluoromethane, 1,2-dichlorotetrafluoroethane, 1,1-dichlorotetrafluoroethane, monochloroethane, monochloropentafluoroethane, hexafluoropropane, octafluorocyclobutane, 1-chloro-1,1,2,2-tetrafluoroethane, hexafluorocyclobutane, etc. 
     The invention is further described hereinbelow by way of Examples, but it is to be understood that the scope of the invention is not restricted in any way by these Examples. Stability of the absorbent against the halogenated hydrocarbon type refrigerants and metal corrosiveness were evaluated by using the sealed tube testing method which is a standard method of this type of evaluation. The test was conducted as follows. 0.5 Ml of a liquid absorbent and 0.5 ml of a halogenated hydrocarbon refrigerant were put into a glass tube of 6 mm in inner diameter and 3 mm in thickness, and as the metal test material, an iron sheet (SM 41, measuring 40 mm in length, 1 mm in thickness and 4 mm in width) was placed in said tube. After sealing the tube, it was heated at 180° C. for 500 hours, and coloration of the absorbent and the corroded condition of the iron sheet were examined and also the amount of Cl - , which is the decomposition product of the halogenated hydrocarbon refrigerant, was measured. The measurement of the amount of Cl -   was made according to &#34;Determination of inorganic chlorides in oil&#34; prescribed in JIS-C-2321, involving titration with an AgNO 3  solution. 
    
    
     EXAMPLE 1 
     An iron sheet was placed in each of mixed solutions of tetraethylene glycol dimethyl ether (absorbent) and monochlorodifluoromethane (refrigerant) added with 0.5% by weight of various types of phosphite ester (stabilizer), and said solution was heated in a sealed tube at 180° C. for 500 hours and the resulting discoloration of the absorbent, amount of Cl -   produced and discoloration of the iron sheet were examined. The results are shown in Table 1. 
     
                                           TABLE 1__________________________________________________________________________             Absorbent (tetraethylene glycol             dimethyl ether) after test                     Amount of C1.sup.-                     produced                             DiscolorationStabilizer        Discoloration                     (× 10.sup.-3 mg)                             of iron sheet__________________________________________________________________________Distearylpentaerythritol diphosphite             Light yellow                     7       No change                             of colorTrihexyl phosphite             &#34;       5       No change                             of colorTriisooctyl phosphite             &#34;       4       No change                             of colorTridecyl phosphite             &#34;       8       No change                             of colorTrilauryl phosphite             &#34;       4       No change                             of colorTris(4-phenylphenol) phosphite             &#34;       6       No change                             of colorTris(nonylphenyl) phosphite             &#34;       5       No change                             of colorDiphenylnonylphenyl phosphite             &#34;       3       No change                             of colorTetraphenyldipropylene glycol             &#34;       7       No changediphosphite                       of colorDi(nonylphenyl)nonyl phosphite             &#34;       5       No change                             of colorNone              Brown   1,358   Blackened__________________________________________________________________________ 
    
     As seen from Table 1, the absorbents added with a phosphite ester suffered little discoloration and were also very limited in generation of Cl - . Further, the metal surface remained unchanged in color and was almost free of corrosion. 
     EXAMPLE 2 
     An iron sheet was placed in each of the mixed solutions of tetraethylene glycol dimethyl ether (absorbent) and monochlorodifluoromethane (refrigerant) added with 0.5% by weight of various types of epoxy compound (stabilizer), and each said solution was heated in a sealed tube at 180° C. for 500 hours and the discoloration of the absorbent, amount of Cl -   generated and color change of the iron sheet was examined. The results are shown in Table 2. 
     
                                           TABLE 2__________________________________________________________________________             Absorbent (tetraethylene glycol             dimethyl ether) after test                     Amount of C1.sup.-                     generated                             DiscolorationStabilizer        Discoloration                     (× 10.sup.-3 mg)                             of iron sheet__________________________________________________________________________Bis(2,3-epoxycyclopentyl) ether             Light yellow                     45      Partly discol-                             ored to brown2,2-Bis(3,4-epoxycyclohexyl)propane             &#34;       23      Partly discol-                             ored to brown1,2-Bis[5-(1,2-epoxy)-4,7-hexahydro-             &#34;       20      Partly discol-methanoinoxyl]methane             ored to brown1-Epoxyethyl-3,4-epoxycyclohexane             &#34;       29      Partly discol-                             ored to brownPhenylglycidyl ether             &#34;        4      No change of                             color1,4-Butanediolglycidyl ether             &#34;        3      No change of                             colorAllylglycidyl ether             &#34;        5      No change of                             colorButylene oxide    &#34;        2      No change of                             color__________________________________________________________________________ 
    
     As is clear from Table 2, the discoloration of the absorbent, generation of Cl -   and color change of the iron sheet are all very limited or null in case of adding an epoxy compound, too, thus showing the effect of the epoxy compounds as stabilizer in the composition of this invention. 
     EXAMPLE 3 
     An iron sheet was placed in each of mixed solutions of tetraethylene glycol dimethyl ether (absorbent) and monochlorodifluoromethane (refrigerant) added with 0.5% by weight of various types of organotin compounds (stabilizer), and each said solution was heated in a sealed tube at 180° C. for 500 hours and the resulting discoloration of the absorbent, amount of Cl -   generated and color change of the iron sheet were examined, obtaining the results shown in Table 3. 
     
                       TABLE 3______________________________________     Absorbent (tetraethylene     glycol dimethyl ether)     after test                Amount of C1.sup.-       Discolor-                generated   DiscolorationStabilizer  ation    (× 10.sup.-3 mg)                            of iron sheet______________________________________Dibutyltin diacetate       Light    85          Slightly dis-       yellow               colored to grayTetrabutyltin       Light    11          No change of       yellow               colorDibutyldisalicyltin       Light     9          No change of       yellow               colorTetraphenyltin       Light     9          No change of       yellow               colorDibutyltin laurate       Light    21          No change of       yellow               colorDibutyltin dilaurate       Light    27          No change of       yellow               colorNone        Brown    1,358       Blackened______________________________________ 
    
     As noted from Table 3, all of the absorbents added with an organotin compound showed little discoloration, were limited in generation of Cl -   and caused no or only a slight discoloration of the metal surface. These attest the effect of the organotin compounds as stabilizer in the composition of this invention. 
     EXAMPLE 4 
     An iron sheet was placed in each of the mixed solutions of difluoromonochloromethane (refrigerant) and six types of compounds (absorbent) represented by the general formula: CH 3  --O--CH 2  CH 2  --O) n  X (wherein n is a number of 3 or greater, and X is hydrogen atom or a methyl group) added with 0.5% by weight of tris(nonylphenyl) phosphite (stabilizer), and each said solution was heated in a sealed tube at 180° C. for 500 hours and the resulting discoloration of the absorbent, amount of Cl -   generated and discoloration of the iron sheet were examined. The results are shown in Table 4. 
     
                                           TABLE 4__________________________________________________________________________             Absorbent after test                    Amount of C1.sup.-                    generated                            DiscolorationAbsorbent         Discoloration                    (× 10.sup.-3 mg)                            of iron sheet__________________________________________________________________________Triethylene glycol dimethyl ether             Light yellow                    4       No dis-                            colorationTetraethylene glycol dimethyl ether             &#34;      5       No dis-                            colorationPentaethylene glycol dimethyl ether             &#34;      5       No dis-                            colorationTriethylene glycol monomethyl ether             &#34;      10      No dis-                            colorationTetraethylene glycol monomethyl             &#34;      11      No dis-ether                            colorationPentaethylene glycol monomethyl             &#34;      9       No dis-ether                            coloration__________________________________________________________________________ 
    
     As seen from Table 4, in case tris(nonylphenyl) phosphite is added in said various types of absorbents, each of the absorbents is limited in discoloration and generation of Cl -   and also each mixed solution causes no discoloration of the metal surface, which indicates the effect of said stabilizer in the composition of this invention. 
     EXAMPLE 5 
     An iron sheet was placed in each of the three types of mixed solutions consisting of tetraethylene glycol dimethyl ether (absorbent) added with 1.0% by weight of tris(nonylphenyl) phosphite (stabilizer) and difluorodichloromethane, monofluorodichloromethane or monofluorotrichloromethane (refrigerant), and each said mixed solution was heated in a sealed tube at 180° C. for 500 hours and the resulting discoloration of the absorbent, amount of Cl -   generated and discoloration of the iron sheet were examined. The results are shown in Table 5. 
     
                       TABLE 5______________________________________      Absorbent after test                 Amount of C1.sup.-        Discolor-                 generated   DiscolorationRefrigerant  ation    (× 10.sup.-3 mg)                             of iron sheet______________________________________Difluorodichloro-        Light    12          No dis-methane      yellow               colorationMonofluorodichloro-        Light     8          No dis-methane      yellow               colorationMonofluorotrichloro-        Light    14          No dis-methane      yellow               coloration______________________________________ 
    
     As is clear from Table 5, in case tris(nonylphenyl) phosphite is added in the absorbent, the solution causes no corrosion nor discoloration of the metal surface regardless of the type of the refrigerant blended. From this, the effect of addition of the stabilizer is clear. 
     EXAMPLE 6 
     Tetraethylene glycol dimethyl ether was used as absorbent, and to this absorbent was added 0.5% by weight of tris(nonylphenyl) phosphite as stabilizer. Also, monochlorodifluoromethane was used as halogenated hydrocarbon type refrigerant. The effect of the stabilizer in case of using this mixed absorbent solution in an absorption type refrigerator was compared with that of a similar absorbent solution not added with tris(nonylphenyl) phosphite. The absorption type refrigerator (with a capacity of 10 tons of refrigeration) used was operated under the following conditions. These conditions are merely intended to be illustrative and not restrictive to the present invention. 
     Said absorption type refrigerator was operated by controlling the refrigerant vapor temperature in this evaporator at 5° C., the absorbent temperature in the absorber at 45° C., the absorbent temperature in the generator at 130° C. and the liquid refrigerant temperature in the condenser at 45° C. The pressure on the side of the generator and condenser under said temperature conditions was 18 kg/cm 2  and the pressure on the side of the evaporator and absorber was 5 kg/cm 2 . When said refrigerator was operated under these conditions continuously for 500 hours, in case of using the liquid absorbent added with 0.5% by weight of tris(nonylphenyl) phosphite, the iron type wall surface in the generator remained free of any corrosion and the amount of Cl -   generated was as small as 0.01×10 -3  mg, but in case of using the absorbent solution not added with tris(nonylphenyl) phosphite, the iron type wall surface in the absorption type refrigerator discolored to liver brown and also Cl -   was generated in an amount as large as 0.023×10 -3  mg. These results show the inhibitory effect of the liquid absorbent of this invention against metallic corrosion even when said liquid absorbent is used in an absorption type refrigerator. 
     As described above, the liquid absorbent for absorption type refrigerator according to this invention is stable and highly effective for arresting metal corrosion, and thus it is useful as absorbent for the absorption type refrigerators where a halogenated hydrocarbon is used as refrigerant.