US3505232A - Azeotropic mixture - Google Patents

Azeotropic mixture Download PDF

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US3505232A
US3505232A US607922A US3505232DA US3505232A US 3505232 A US3505232 A US 3505232A US 607922 A US607922 A US 607922A US 3505232D A US3505232D A US 3505232DA US 3505232 A US3505232 A US 3505232A
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mixtures
boiling
refrigerants
monochloromonouoromethane
refrigeration
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US607922A
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Kevin Paul Murphy
Sabatino R Orfeo
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Allied Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds

Definitions

  • a low boiling azeotropic composition consisting essentially of a mixture of monochloromonouoromethane and dichlorotetrafluoroethane, useful as a refrigerant, heat transfer medium, gaseous dielectric and as working fluid in a power cycle.
  • This invention relates to iiuorinated hydrocarbons, and more particularly to constant boiling iiuorocarbon mixtures, which comprise monochloromonofluoromethane and dichlorotetrajuoroethane and which are especially adapted for use as compression refrigerants particularly in system using centrifugal or rotary compressors.
  • the refrigerant capacity per volume pumped of a refrigerant is largely a function of boiling point, the lower boiling refrigerants generally offering the greater capacity at a given evaporator temperature. This factor to a great extent influences the design of refrigeration equipment and aiects capacity, power requirements, size and cost of the unit. Another important factor related to boiling point of the refrigerant is minimum cooling temperature desired during the refrigeration cycle, the lower boiling refrigerants being used to achieve the lower refrigeration temperatures. For these reasons a large number of refrigerants of different boiling temperature and capacity are required to permit flexibility of design and the art is continually faced with the problem of providing new refrigerants as the need arises for new capacities and types of installations.
  • the lower aliphatic hydrocarbons when substituted by uorine and chlorine are well-known to have potential as refrigerants. Many of these uoro-chloro hydrocarbons exhibit certain desired properties including lower toxicity and nonammability which have resulted in the extensive use of such components in a large number of refrigeration applications.
  • Trichloroiluoromethane (CClaF) and dichlorodiuoromethane (CCIZFZ) are two of the most commonly available chlorine-uorine hydrocarbon refrigerants available today.
  • -23.78 C. at atmospheric pressure, and the relatively low temperature of dichlorodiuoromethane, 29.8 C. at atmospheric pressure in order to have available refrigerants of good performance and varying capacities.
  • nuoro-chloro hydrocarbons have boiling points in this range but suffer from other deficiencies such as flammability, poor stability or poor thermodynamic performance.
  • Some examples of these types of refrigerants are tetrauorodichloroethane, uorodichloromethane, diuorochloroethane and uorochloromethane.
  • An object of the present invention is to provide new mixtures with a boiling point between that of trichlorouoromethane and dichlorodiuoroethane suitable for use as a refrigerant. More particularly it is an object of the present invention to provide a refrigerant system with a capacity between the refrigeration capacity of trichlorouoromethane and dichlorodiiluoroethane and which is useful as a compression refrigerant, particularly in systems using a centrifugal or rotary cornpressor.
  • Another object is to provide a new low boiling azeotropic mixtures which are useful in producing refrigeration in those systems in which cooling iS achieved by evaporation in the vicinity of the body to be cooled and in which because of the nature of the system, the problem of segregation is critical.
  • a further object is to provide low boiling azeotropic mixtures in which the ammability is reduced to substantially negligible proportions.
  • compositions consisting of dichlorotetra. uorocthane (C2Cl2F4) with approximately 30 Weight percent to weight percent monochloromonofluoromethane (CHZCIF) from azeotropic mixtures which have boiling points of about 12 C. at atmospheric pressure.
  • Monochloromonofluoromethane has a boiling point temperature of -9.6 C.
  • dichlorotetrauoroethane has a boiling point temperature of +3.6 C., at atmospheric pressure.
  • These monochloromonoiluoromethane and dchlorotetralluoroethane mixtures have a marked reduction in boiling point temperature as compared with the boiling temperature of the components. From the properties of the components alone the marked reduction in the boiling point temperature and the azeotropic characteristics of the mixtures are not expected.
  • the indicated monochlorornonofluoromethane and dichlorotetraliuoroethane mixtures provide substantial increased refrigeration capacity over the components and represent new refrigeration mixtures useful especially in systems using centrifugal and rotary compressors.
  • the use of the monochloromonouoromethane and dichlorotetrauoroethane mixtures eliminate the problem of segregation in handling and the operation of the system because azeotropic mixtures behave essentially as a single component as compared to simple mixtures.
  • flammability of monochloromonouoromethane is reduced by admixture with dichlorotetrafluoroethane such that all mixtures within the indicated range are substantially non-flammable.
  • Boiling points of monochloromonoiluoromethane and dichlorotetrauoroethane mixtures were determined using monochloromonoluoromethane and dichlorotetrafluoroethane compoents of better than 99.9% purity.
  • Monochloromonouoromethane and dichlorotetrailuoroethane mixtures of various compositions were prepared and boiling points were measured at about 45 p.s.i.a. by thermostatting the mixture and varying the temperature until the vapor pressure reached about 45 p.s.i.a. Temperatures were measured using a platinum resistance thermometer.
  • Table Il The data of Table Il is plotted in the drawing. This data shows that mixtures at 45 p.s.i.a. of about 30 to 80 weight percent monochloromonouoromethane have boiling points within about 1 C. and hence substantially similar vapor pressures. At 1 atmosphere the boiling points of these compositions are about 12 C. The compositions within the range of 45 to 65 weight percent monochloromonoluoromethane have boiling points within about 0.2" C. at 45 p.s.i.a. Because the temperature and hence the vapor pressures are so similar between the weight percent limits set forth in the last sentence, those weight percent limits are especially preferable.
  • the most preferable percentage by weight monochloromonouoromethane component in the monochloromonouoromethane-dichlorotetrailuoroethane azeotropic mixture is about 55 percent.
  • the monochloromonouoromethane-dichlorotetrauoroethane components employed should be substantially pure, preferably at least about 99.0% pure, and contain no substances deleteriously effecting the boiling characteristics of the mixture or use as refrigerante.
  • the mixtures of the invention exhibit desired refrigeration properties, include non-flammability, boiling point substantially lower than either component, compression ratio lower than either component, lack of the presence of wet compression, and superior H.P./ton value.
  • desired refrigeration properties include non-flammability, boiling point substantially lower than either component, compression ratio lower than either component, lack of the presence of wet compression, and superior H.P./ton value.
  • the mixtures disclosed herein may also be used for other purposes, including a heat transfer medium, gaseous dielectric, or as a working fluid in a power cycle.
  • a low boiling azeotropic composition consisting of a mixture of monochloromonouoromethane and dichlorotetraluoroethane in which the weight percent of monochloromonofluoromethane is within the range of about thirty to eighty.
  • a low boiling composition as recited in claim 1 said weight percent of monochloromonouoromethane being within the range of about forty-five to sixty-five.

Description

April 7, 1970 K, P, MURPHY ET AL 3,505,232
AZEOTROPIC MIXTURE Filed Jan.
Oo SHHLVHBdINEIJ.
INVENTORS KEVIN P. MURPHY SABATINO R.ORFEO )www Q Qwd;
A TTORNEY United States Patent O 3,505,232 AZEOTRUPIC MIXTURE Kevin Paul Murphy, Bernardsville, and Sabatino R. Orfeo,
Morris Plains, NJ., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York Filed Jan. 9, 1967, Ser. No. 607,922 Int. Cl. (109k 3/02 U.S. Cl. 252-67 6 Claims ABSTRACT F THE DISCLOSURE A low boiling azeotropic composition consisting essentially of a mixture of monochloromonouoromethane and dichlorotetrafluoroethane, useful as a refrigerant, heat transfer medium, gaseous dielectric and as working fluid in a power cycle.
This invention relates to iiuorinated hydrocarbons, and more particularly to constant boiling iiuorocarbon mixtures, which comprise monochloromonofluoromethane and dichlorotetrajuoroethane and which are especially adapted for use as compression refrigerants particularly in system using centrifugal or rotary compressors.
The refrigerant capacity per volume pumped of a refrigerant is largely a function of boiling point, the lower boiling refrigerants generally offering the greater capacity at a given evaporator temperature. This factor to a great extent influences the design of refrigeration equipment and aiects capacity, power requirements, size and cost of the unit. Another important factor related to boiling point of the refrigerant is minimum cooling temperature desired during the refrigeration cycle, the lower boiling refrigerants being used to achieve the lower refrigeration temperatures. For these reasons a large number of refrigerants of different boiling temperature and capacity are required to permit flexibility of design and the art is continually faced with the problem of providing new refrigerants as the need arises for new capacities and types of installations.
The lower aliphatic hydrocarbons when substituted by uorine and chlorine are well-known to have potential as refrigerants. Many of these uoro-chloro hydrocarbons exhibit certain desired properties including lower toxicity and nonammability which have resulted in the extensive use of such components in a large number of refrigeration applications. Trichloroiluoromethane (CClaF) and dichlorodiuoromethane (CCIZFZ) are two of the most commonly available chlorine-uorine hydrocarbon refrigerants available today. There is a recognized need for a refrigerant with a boiling point temperature between the relatively high temperature of trichlorouoromethane -|-23.78 C. at atmospheric pressure, and the relatively low temperature of dichlorodiuoromethane, 29.8 C. at atmospheric pressure, in order to have available refrigerants of good performance and varying capacities.
Several nuoro-chloro hydrocarbons have boiling points in this range but suffer from other deficiencies such as flammability, poor stability or poor thermodynamic performance. Some examples of these types of refrigerants are tetrauorodichloroethane, uorodichloromethane, diuorochloroethane and uorochloromethane.
It would also be possible to achieve the desired boiling point by mixing two refrigerants with boiling points above and below the desired one. In this case, for example, mixtures of trichlorofluoromethane and dichlorodiiluoromethane could be used. It is well known, however, that simple mixtures create problems in design and operation because of segregation of the components in the liquid ICC and vapor phases. This problem is particularly troublesome in systems using centrifugal compression because of the large quantities of liquid usually found in the evaporator.
An object of the present invention is to provide new mixtures with a boiling point between that of trichlorouoromethane and dichlorodiuoroethane suitable for use as a refrigerant. More particularly it is an object of the present invention to provide a refrigerant system with a capacity between the refrigeration capacity of trichlorouoromethane and dichlorodiiluoroethane and which is useful as a compression refrigerant, particularly in systems using a centrifugal or rotary cornpressor. Another object is to provide a new low boiling azeotropic mixtures which are useful in producing refrigeration in those systems in which cooling iS achieved by evaporation in the vicinity of the body to be cooled and in which because of the nature of the system, the problem of segregation is critical. A further object is to provide low boiling azeotropic mixtures in which the ammability is reduced to substantially negligible proportions.
The drawing shows boiling temperature of azeotropic mixtures according to the invention and will be discussed in more detail hereinafter.
In accordance with the invention it has been discovered that compositions consisting of dichlorotetra. uorocthane (C2Cl2F4) with approximately 30 Weight percent to weight percent monochloromonofluoromethane (CHZCIF) from azeotropic mixtures which have boiling points of about 12 C. at atmospheric pressure. Monochloromonofluoromethane has a boiling point temperature of -9.6 C. and dichlorotetrauoroethane has a boiling point temperature of +3.6 C., at atmospheric pressure. These monochloromonoiluoromethane and dchlorotetralluoroethane mixtures have a marked reduction in boiling point temperature as compared with the boiling temperature of the components. From the properties of the components alone the marked reduction in the boiling point temperature and the azeotropic characteristics of the mixtures are not expected.
The indicated monochlorornonofluoromethane and dichlorotetraliuoroethane mixtures provide substantial increased refrigeration capacity over the components and represent new refrigeration mixtures useful especially in systems using centrifugal and rotary compressors. The use of the monochloromonouoromethane and dichlorotetrauoroethane mixtures eliminate the problem of segregation in handling and the operation of the system because azeotropic mixtures behave essentially as a single component as compared to simple mixtures. Furthermore, flammability of monochloromonouoromethane is reduced by admixture with dichlorotetrafluoroethane such that all mixtures within the indicated range are substantially non-flammable.
An evaluation of the refrigeration properties of the monochloromonofluoromethane and dichlorotetrafluoroethane mixture and its components are shown in Table I, below.
It is particularly pointed out in relation to the data of Table I that (1) the compression ratio of the azeotrope is lower than either component, and this property allows more elicient compressor and design, and (2) the compressor displacement shows the displacement of azeotrope to be lower than either component, which is of obvious advantage in a compressor. In addition, its H.P./ton value is much superior to that of dichlorotetrauoroethane. When operated on similar cycles most refrigerants have very similar H.P./ ton requirements. In centrifugal systems even small differences in H.P. per ton are quite important because of the large quantities of energy involved. Power cost is a major item in the operating costs of such systems. A favorably low power requirement is thus of particular benefit in refrigerants for centrifugal service. Furthermore, the mixture does not have the problem of flammability associated with pure monochloromonofluoromethane.
In addition, it is known that in the case of some refrigerants, such as dichlorotetrauoroethane, on isentropic compression, such as occurs in the refrigeration cycle of a centrifugal or rotary compressor, the saturated vapor will partially condense. This is an undersirable situation as the liquid causes ineiciences and erosion in the compressor. To overcome this wet compression the gas must be somewhat superheated before compression which requires heat exchange equipment. On the other hand, some refrigerants have a tendency to heat excessively on isentropic compression. This results in undersirable high temperature in the system (monochloromonouoromethane and dichloromonofluoroethane are examples of this type of refrigerant). The monochloromonofluoromethanedichlorotetrafluoroethane mixtures, however, heat only slightly on compression and thus substantially avoid wet compression as well as excessive heat on compression and thus are particularly useful as refrigerant liquids.
Boiling points of monochloromonoiluoromethane and dichlorotetrauoroethane mixtures were determined using monochloromonoluoromethane and dichlorotetrafluoroethane compoents of better than 99.9% purity. Monochloromonouoromethane and dichlorotetrailuoroethane mixtures of various compositions were prepared and boiling points were measured at about 45 p.s.i.a. by thermostatting the mixture and varying the temperature until the vapor pressure reached about 45 p.s.i.a. Temperatures were measured using a platinum resistance thermometer.
TABLE 1I Boiling points of CH2ClF/C2C12F4 mixtures At about 45 p.s.i.a.
Weight percent CHZClF Boiling in solution: point C. 100.00 20.80 90.00 19.57 80.02 18.73 70.04 18.16 65.00 17.99 58.60 17.86 55.12 17.84 50.00 17.88 44.80 18.00 39.96 18.17 30.00 18.92 20.00 20.54
The data of Table Il is plotted in the drawing. This data shows that mixtures at 45 p.s.i.a. of about 30 to 80 weight percent monochloromonouoromethane have boiling points within about 1 C. and hence substantially similar vapor pressures. At 1 atmosphere the boiling points of these compositions are about 12 C. The compositions within the range of 45 to 65 weight percent monochloromonoluoromethane have boiling points within about 0.2" C. at 45 p.s.i.a. Because the temperature and hence the vapor pressures are so similar between the weight percent limits set forth in the last sentence, those weight percent limits are especially preferable.
As shown in the drawing, it has been found that the most preferable percentage by weight monochloromonouoromethane component in the monochloromonouoromethane-dichlorotetrailuoroethane azeotropic mixture is about 55 percent.
Makeup of the azeotropic mixture of the invention requires no special procedures. The monochloromonouoromethane-dichlorotetrauoroethane components employed should be substantially pure, preferably at least about 99.0% pure, and contain no substances deleteriously effecting the boiling characteristics of the mixture or use as refrigerante.
The mixtures of the invention exhibit desired refrigeration properties, include non-flammability, boiling point substantially lower than either component, compression ratio lower than either component, lack of the presence of wet compression, and superior H.P./ton value. In addition to being used as new refrigerants providing refrigeration, especially in systems using centrifugal or rotary compressors, it will be noted that the mixtures disclosed herein may also be used for other purposes, including a heat transfer medium, gaseous dielectric, or as a working fluid in a power cycle.
It is intended that applicants scope of protection only be limited by the claims that follow.
We claim:
1. A low boiling azeotropic composition consisting of a mixture of monochloromonouoromethane and dichlorotetraluoroethane in which the weight percent of monochloromonofluoromethane is within the range of about thirty to eighty.
2. A low boiling composition as recited in claim 1 said weight percent of monochloromonouoromethane being within the range of about forty-five to sixty-five.
3. A low boiling composition as recited in claim 2, said weight percent of monochloromonouoromethane being about ifty-ve.
4. The process of producing refrigeration which cornprises condensing an azeotropic mixture consisting of monochloromonouoromethane and dichlorotetrafluoroethane in which the Weight percent of monochloromonofluoromethane is within the range of thirty to eighty, and thereafter evaporating said mixture in the vicinity of a body to be cooled.
S. The process of producing refrigeration recited in claim 4, said weight percent of monochloromonouoromethane being within the range of forty-five to sixty-live.
6. The process of producing refrigeration recited in claim 5, said weight percent of monochloromonofluoromethane being about iifty-iive.
References Cited UNITED STATES PATENTS 3,047,506 7/ 1962 Broadley 252-67 FOREIGN PATENTS 529,031 11/ 1940 United Kingdom.
LEON D. ROSDOL, Primary Examiner S. D. SCHWARTZ, Assistant Examiner U.S. Cl. XR. 252-78; 62-112
US607922A 1967-01-09 1967-01-09 Azeotropic mixture Expired - Lifetime US3505232A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003215A (en) * 1974-06-24 1977-01-18 University Of Adelaide Absorption refrigeration system

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* Cited by examiner, † Cited by third party
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DE1097171B (en) * 1956-05-15 1961-01-12 Erich Zillmer Projector with built-in turbo fan
DE3105372C2 (en) * 1981-02-13 1985-04-04 Heinz Dipl.-Ing. 7951 Erlenmoos Gerbert Use of a non-azeotropic mixture of working fluids for heat pumps

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB529031A (en) * 1938-02-16 1940-11-13 Williams Oil O Matic Heating Improvements in or relating to working fluids and processes of producing cold by the absorption refrigerating principal
US3047506A (en) * 1957-12-13 1962-07-31 Allied Chem Refrigeration process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB529031A (en) * 1938-02-16 1940-11-13 Williams Oil O Matic Heating Improvements in or relating to working fluids and processes of producing cold by the absorption refrigerating principal
US3047506A (en) * 1957-12-13 1962-07-31 Allied Chem Refrigeration process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003215A (en) * 1974-06-24 1977-01-18 University Of Adelaide Absorption refrigeration system

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ES348998A1 (en) 1969-04-01
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FR1550737A (en) 1968-12-20
NL6800254A (en) 1968-07-10
GB1166791A (en) 1969-10-08
SE328551B (en) 1970-09-21

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