CN105505324A - Refrigerant and preparation method and application thereof - Google Patents
Refrigerant and preparation method and application thereof Download PDFInfo
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- CN105505324A CN105505324A CN201510940092.6A CN201510940092A CN105505324A CN 105505324 A CN105505324 A CN 105505324A CN 201510940092 A CN201510940092 A CN 201510940092A CN 105505324 A CN105505324 A CN 105505324A
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 70
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000001294 propane Substances 0.000 claims abstract description 31
- 239000001282 iso-butane Substances 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 29
- 229940126062 Compound A Drugs 0.000 claims abstract description 23
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 23
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 31
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical group CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims description 18
- 229940051271 1,1-difluoroethane Drugs 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- -1 ethane halogen Chemical class 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000460 chlorine Substances 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 235000013847 iso-butane Nutrition 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 1
- 238000005057 refrigeration Methods 0.000 description 51
- 239000007789 gas Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 24
- 230000008859 change Effects 0.000 description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
- 238000009835 boiling Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005437 stratosphere Substances 0.000 description 2
- 239000005436 troposphere Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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
- C09K5/041—Materials 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
- C09K5/044—Materials 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
- C09K5/045—Materials 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 containing only fluorine as halogen
-
- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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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)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses refrigerant and a preparation method and application thereof. The refrigerant comprises a compound A, a compound B, ethane, propane, iso-butane and propylene; the structure of the compound A is as indicated in the formula (I), and the structure of the compound B is as indicated in the formula (II), wherein R, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine. According to the design, an ethane halogen derivative which does not contain chlorine is used as the main raw material for preparing the refrigerant, a certain proportion of ethane, propane, iso-butane and propylene are added therein, and through the matching, the compression system construction effects that flammability is low, ODP is zero, the GWP value is extremely low, safe use can be guaranteed, and meanwhile freon refrigerant which is used at present is not changed are achieved.
Description
Technical Field
The invention relates to the field of refrigerant materials and production and preparation, in particular to a refrigerant and a preparation method and application thereof.
Background
Up to now, the refrigerant types are roughly classified into four types in consideration of thermodynamic conditions such as refrigerant type, evaporation temperature, condensation temperature, and pressure, and the use place of the refrigeration equipment: i.e., inorganic compounds, freons, hydrocarbons, and azeotropic solutions.
Inorganic compound refrigerants are relatively simple and include ammonia, water, carbon dioxide, and the like.
Freon is the refrigerant which is the most widely used and has the best effect at present, because freon is stable in chemical property, non-inflammable, non-toxic, low in dielectric constant, high in critical temperature, easy to liquefy and the like, the freon is widely used as the refrigerant of refrigeration equipment and air conditioning equipment, originates from the thirties of the nineteenth century and is about 60 years later than ammonia, and is a general term of halogen (fluorine, chlorine and bromine) derivatives of saturated hydrocarbon or consists of fluorine, chlorine and hydrocarbon. Freon is the original cause of ozone depletion, has stable chemical property and no flammability and toxicity, is widely used as a foaming agent and a cleaning agent besides being used as a refrigerant, and is widely used in the fields of household appliances, foamed plastics, daily chemicals, automobiles, fire-fighting equipment and the like. In the later period of the 80's of the 20 th century, the production of Freon reaches the peak and the yield reaches 144 ten thousand tons. The worldwide release of freon into the atmosphere has reached 2000 million tons before control of freon is exercised. Since their average life in the atmosphere is hundreds of years, most of the emissions remain in the atmosphere, most of which remain in the troposphere and a small portion rises into the stratosphere. After the freon with quite stable troposphere rises to enter the stratosphere, the freon can be decomposed under the action of strong ultraviolet rays under certain meteorological conditions, and chlorine atoms released by decomposition and ozone can generate chain reaction, thereby continuously destroying ozone molecules. Scientists estimate that one chlorine atom can destroy tens of thousands of ozone molecules.
Hydrocarbon refrigerants are a refrigerant developed in later stages, and are composed of ethane, propylene, and the like. Because the ozone depletion potential value ODP and the global warming potential value GWP value are zero, the environment influence is small, but because the flammability, the irritation and the toxicity have many problems, the ozone depletion potential value ODP and the global warming potential value GWP value are limited by the use of many countries and regions, and the market consumption is small.
The azeotropic solution is a mixture of more than two refrigerants, and the evaporation and condensation processes are not separated, just like one refrigerant. Currently, R500, R502, and the like are practical. Compared with R22, the pressure is slightly higher, and the refrigerating capacity is improved by about 13% at lower temperature. Also at the same evaporation temperature and condensation temperature. The discharge temperature of the compressor is low. The service temperature range of the single-group compressor can be enlarged, so the development prospect is good.
Regarding the pollution problem of the refrigerant to the atmospheric environment, the pollution problem is a big concern about human health and survival, and is a common concern. Many experts have conducted intensive research for this purpose for many years, and it is hoped that a new CFC type freon substitute refrigerant is developed, so that the refrigerant not only has zero potential for atmospheric ozone depletion, but also has to meet the requirement in terms of global warming potential which directly affects greenhouse effect after being discharged into the atmosphere. The destruction of the ozone layer has become an environmental focus of global general attention, and international society has established the "vienna convention for the protection of the ozone layer" and the "montreal protocol for the depletion of ozone layer substances" in 1985 and 1987, respectively, and has added the international convention organization of the montreal protocol in 1991 and promises the control schedule of the depletion of ozone layer substances, i.e., the complete elimination time of R12 and R22 in 2010 and 2030, respectively. Therefore, it is urgent to provide a new environment-friendly refrigerant.
Therefore, it is an urgent need to provide a refrigerant and a method for preparing the same, which has low flammability, zero ODP, and extremely low GWP, and can be safely used without changing the structure of the conventional compression system using a freon refrigerant.
Disclosure of Invention
In view of the above prior art, the present invention aims to overcome the problems of the refrigerant in the prior art, such as environmental protection, flammability, irritation, toxicity, etc., causing great impact on the environment and further damaging the living environment, and thus provides a refrigerant which has low flammability, zero ODP, and extremely low GWP value, can be safely used without changing the structure of the existing compression system using freon refrigerant, and a preparation method thereof.
In order to achieve the above object, the present invention provides a refrigerant, wherein the refrigerant comprises a compound a, a compound B, ethane, propane, isobutane and propylene, wherein the compound a has a structure represented by formula (I), and the compound B has a structure represented by formula (II):
a compound of the formula (I),
formula (II); wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
The invention also provides a preparation method of the refrigerant, wherein the preparation method comprises the following steps: adding first ethane, a first compound A, propane, isobutane, a second compound A, a compound B, second ethane and ethylene into a container in sequence, and mixing to prepare a refrigerant; wherein,
the structure of the compound A is shown as a formula (I), and the structure of the compound B is shown as a formula (II):
a compound of the formula (I),
formula (II); wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
The invention also provides an application of the refrigerant or the refrigerant prepared by the preparation method.
According to the technical scheme, the halogen derivative of ethane is used as the main raw material, and a small amount of ethane, propane and propylene with lower boiling points and isobutane with a higher boiling point are added into the main raw material, so that compared with a simple main raw material, the prepared mixed refrigerant is added into the main raw material with a high boiling point due to the fact that a small amount of low-boiling-point components are added, the refrigeration coefficient of the prepared refrigerant is improved, and energy consumption is reduced; meanwhile, a small amount of high-boiling point components are added into the main raw material with a lower boiling point, so that the suction specific volume is reduced, the refrigerating capacity of the refrigerant is increased, and a lower evaporation temperature is obtained. Meanwhile, the refrigerant can play the environmental protection characteristic of hydrocarbon refrigerant, can reduce the inflammability of the refrigerant, increases the stability of the refrigerant, improves the use efficiency, achieves the energy-saving effect, and does not change the effect of the compressor system of the conventional air-conditioning refrigerator at present.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph showing the variation of the refrigeration coefficient with the amounts of 1,1,1, 2-tetrafluoroethane and ethane in examples 1 to 13 according to the present invention;
FIG. 2 is a graph showing the variation of the refrigeration coefficient with the amount of isobutane and propane used in examples 1 to 13 according to the present invention;
FIG. 3 is a graph showing the variation of the refrigeration factor with the amount of ethane and 1, 1-difluoroethane used in examples 1-13 provided by the present invention;
FIG. 4 is a graph showing the change of the refrigeration coefficient with the amounts of 1,1,1, 2-tetrafluoroethane and propylene in examples 1 to 13 according to the present invention.
Description of the reference numerals
1-M1 refrigeration factor 2-M2 refrigeration factor
3-M3 refrigeration factor 4-M4 refrigeration factor
5-M5 refrigeration coefficient 6-M6 refrigeration coefficient
7-M7 refrigeration coefficient 8-M8 refrigeration coefficient
9-M9 refrigeration factor 10-M10 refrigeration factor
Refrigeration coefficient of 11-M11 and refrigeration coefficient of 12-M12
13-M13 refrigeration factor.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a refrigerant, wherein the refrigerant comprises a compound A, a compound B, ethane, propane, isobutane and propylene, wherein the structure of the compound A is shown as a formula (I), and the structure of the compound B is shown as a formula (II):
a compound of the formula (I),
formula (II); wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
According to the design, halogen derivatives of ethane are used as main raw materials, and a small amount of ethane, propane and propylene with lower boiling points and isobutane with a higher boiling point are added into the main raw materials, so that compared with a simple main raw material, the prepared mixed refrigerant is added into the main raw material with a high boiling point due to the fact that a small amount of low-boiling point components are added, the refrigeration coefficient of the prepared refrigerant is improved, and energy consumption is reduced; meanwhile, a small amount of high-boiling point components are added into the main raw material with a lower boiling point, so that the suction specific volume is reduced, the refrigerating capacity of the refrigerant is increased, and a lower evaporation temperature is obtained. Meanwhile, the refrigerant can play the environmental protection characteristic of hydrocarbon refrigerant, can reduce the inflammability of the refrigerant, increases the stability of the refrigerant, improves the use efficiency, achieves the energy-saving effect, and does not change the effect of the compressor system of the conventional air-conditioning refrigerator at present.
Of course, the content of each substance can be adjusted according to actual needs, for example, in a preferred embodiment of the present invention, in order to further improve the refrigeration coefficient of the refrigerant obtained and greatly improve the flame retardancy, the content of the compound a is 5 to 10 vol%, the content of the compound B is 30 to 70 vol%, the content of ethane is 1 to 5 vol%, the content of propane is 1 to 5 vol%, the content of isobutane is 1 to 10 vol%, and the balance is propylene, based on the total volume of the refrigerant. Of course, the conditions for measuring the volume of each gas are not limited to the above, and it is needless to say that the volume is measured under the conditions of the temperature 293.15K (20 ℃) and the pressure 101.325KPa, which are prescribed in Standard orifice plate calculation method for Natural gas flow in China, in consideration of the accuracy of actual operation.
In a more preferred embodiment of the present invention, in order to obtain a refrigerant having a higher refrigeration coefficient, the compound a may be further selected to be 1,1,1, 2-tetrafluoroethane, and the compound B may be further selected to be 1, 1-difluoroethane. Of course, other halogen derivatives of ethane may be used herein as long as they satisfy the structures described by the formulas (I) and (II), and the present invention is not limited to the combined use of the above two substances.
The invention also provides a preparation method of the refrigerant, wherein the preparation method comprises the following steps: adding first ethane, a first compound A, propane, isobutane, a second compound A, a compound B, second ethane and ethylene into a container in sequence, and mixing to prepare a refrigerant; wherein,
the structure of the compound A is shown as a formula (I), and the structure of the compound B is shown as a formula (II):
a compound of the formula (I),
formula (II); wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
Of course, the content of each substance can be adjusted according to actual needs, for example, in a preferred embodiment of the present invention, in order to further improve the refrigeration coefficient of the refrigerant obtained and greatly improve the flame retardancy, the amount of the compound a is 5 to 10 vol%, the amount of the compound B is 30 to 70 vol%, the amount of the ethane is 1 to 5 vol%, the amount of the propane is 1 to 5 vol%, the amount of the isobutane is 1 to 10 vol%, and the balance is propylene; and the ethane is composed of a first ethane and a second ethane, and the compound A is composed of a first compound A and a second compound A. The gas volume measurement is as described above and will not be described in detail here. Of course, the order of addition of the gases is required to be in the order mentioned above, and the ethane and the first compound A are added in two portions, and the amount of the two portions can be adjusted according to the actual situation.
For example, in a preferred embodiment of the present invention, in order to make the first and second additions of ethane and the first compound a to further increase the refrigeration coefficient of the finally produced refrigerant, the amount of the first ethane may be further selected to be 40 to 60 vol% based on the amount of the ethane, and the balance of the ethane may be added as the second ethane; the amount of the first compound a may further be selected to be 40-60 vol% based on the amount of the compound a, and the balance of the compound a is added as the second compound a.
Of course, in order to minimize the effect of other gases on the refrigerant effect, in a preferred embodiment of the invention, the process may further comprise first evacuating the vessel before adding the first ethane.
Of course, in order to further reduce the influence of impurity gas on the preparation of the refrigerant, in a more preferred embodiment of the present invention, the preparation method may further include injecting ethane gas after the first vacuuming, and performing second vacuuming after injecting ethane gas.
Of course, the evacuation operation may be performed according to an operation manner conventionally adopted in the art, and the conditions in the evacuated container may not be limited, for example, in a preferred embodiment of the present invention, in order to minimize the influence of impurity gases in the evacuated container, the first evacuation and the second evacuation are performed by evacuating the container to a pressure of not more than 0.2 Pa.
The mixing process is a conventional manner in the art, for example, the above gas may be left to stand to mix it, and in order to make the mixing effect more uniform, in a preferred embodiment of the present invention, the mixing process may be left to stand in a container for 1.5 to 2 hours.
In order to make the use of the prepared refrigerant more convenient, in a preferred embodiment of the present invention, the preparation method may further include performing a pressure liquefaction operation after the mixing.
The invention also provides an application of the refrigerant or the refrigerant prepared by the preparation method.
The present invention will be described in detail below by way of examples. In the following examples, the 1,1,1, 2-tetrafluoroethane, the 1, 1-difluoroethane, the ethane, the propane, the isobutane and the propylene were conventionally commercially available. The volumes were, of course, determined at a temperature of 293.15K (20 ℃) and a pressure of 101.325 KPa. The refrigeration coefficients of the following refrigerants were measured in accordance with GB/T5773-2004.
Example 1
Vacuumizing a steel storage tank to a pressure of not more than 0.2Pa, cleaning the steel cylinder, filling excessive ethane into the cleaned steel cylinder through a gas blender, vacuumizing for the second time to a pressure of not more than 0.2Pa, sequentially adding 1.66 parts by volume of ethane, 2.49 parts by volume of 1,1,1, 2-tetrafluoroethane, 3.65 parts by volume of propane, 7.80 parts by volume of isobutane, 2.49 parts by volume of 1,1,1, 2-tetrafluoroethane, 47.03 parts by volume of 1, 1-difluoroethane, 1.66 parts by volume of ethane and 33.22 parts by volume of propylene through the gas blender, standing for 1.5h, and pressurizing and liquefying to obtain the refrigerant M1. (in conjunction with the change law between the substances in FIGS. 1 to 4, for example, as can be seen in FIG. 1, 4.98% by volume of 1,1, 2-tetrafluoroethane, 3.32% by volume of ethane, and 7.8% by volume of isobutane, and 3.65% by volume of propane, for the refrigeration index M1, and 3.32% by volume of ethane, and 47.03% by volume of 1, 1-difluoroethane, for the refrigeration index M1, for the refrigeration index M363, and 3.98% by volume of propane, for the refrigeration index M1, and 33.22% by volume of propylene, for the refrigeration coefficients of M1 in FIGS. 1 to 4, respectively, in FIG. 4, 1,1, 2-tetrafluoroethane, and 33.22% by volume of propylene, for the refrigeration index M1, which is obtained by combining the contents of the substances described above in example 1, can be determined to be 3.10, in conjunction with FIGS. 1 to 4, and the refrigeration index of the refrigerant in the following examples can be similarly obtained by combining FIGS. 1 to 4, the specific reference numerals are given to the respective refrigeration coefficients in FIGS. 1 to 4, and the following embodiments are not specifically described in conjunction with the drawings
Example 2
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 0.835 parts by volume of ethane, 2.70 parts by volume of 1,1,1, 2-tetrafluoroethane, 2.35 parts by volume of propane, 5.47 parts by volume of isobutane, 2.70 parts by volume of 1,1,1, 2-tetrafluoroethane, 66.44 parts by volume of 1, 1-difluoroethane, 0.835 parts by volume of ethane and 18.67 parts by volume of propylene, to obtain refrigerant M2. (the refrigeration coefficient of refrigerant M2 was measured to be 4.23 according to the change law between substances in FIGS. 1-4.)
Example 3
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 2.18 parts by volume of ethane, 2.94 parts by volume of 1,1,1, 2-tetrafluoroethane, 0.96 parts by volume of propane, 3.24 parts by volume of isobutane, 2.94 parts by volume of 1,1,1, 2-tetrafluoroethane, 43.30 parts by volume of 1, 1-difluoroethane, 2.18 parts by volume of ethane and 42.26 parts by volume of propylene, to produce refrigerant M3. (the refrigeration coefficient of refrigerant M3 was measured to be 3.15 according to the change law between substances in FIGS. 1-4.)
Example 4
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 1.34 parts by volume of ethane, 3.11 parts by volume of 1,1,1, 2-tetrafluoroethane, 1.99 parts by volume of propane, 0.95 parts by volume of isobutane, 3.11 parts by volume of 1,1,1, 2-tetrafluoroethane, 63.95 parts by volume of 1, 1-difluoroethane, 1.34 parts by volume of ethane and 22.22 parts by volume of propylene, to obtain refrigerant M4. (the refrigeration coefficient of refrigerant M4 was measured to be 4.45 according to the change law between substances in FIGS. 1-4.)
Example 5
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 0.50 parts by volume of ethane, 3.325 parts by volume of 1,1,1, 2-tetrafluoroethane, 2.68 parts by volume of propane, 8.49 parts by volume of isobutane, 3.325 parts by volume of 1,1,1, 2-tetrafluoroethane, 40.29 parts by volume of 1, 1-difluoroethane, 0.50 parts by volume of ethane and 40.89 parts by volume of propylene, to produce refrigerant M5. (the refrigeration coefficient of refrigerant M5 was measured to be 2.68 in conjunction with the law of change between the substances in FIGS. 1-4)
Example 6
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 1.84 parts by volume of ethane, 3.54 parts by volume of 1,1,1, 2-tetrafluoroethane, 1.34 parts by volume of propane, 6.22 parts by volume of isobutane, 3.54 parts by volume of 1,1,1, 2-tetrafluoroethane, 59.94 parts by volume of 1, 1-difluoroethane, 1.84 parts by volume of ethane and 21.75 parts by volume of propylene, to produce refrigerant M6. (the refrigeration coefficient of refrigerant M6 was measured to be 4.2 according to the change law between substances in FIGS. 1-4.)
Example 7
The preparation was carried out according to the preparation method of example 1, except that the gases added in sequence were: 1.005 parts by volume of ethane, 3.735 parts by volume of 1,1,1, 2-tetrafluoroethane, 4.31 parts by volume of propane, 4.03 parts by volume of isobutane, 3.735 parts by volume of 1,1,1, 2-tetrafluoroethane, 36.63 parts by volume of 1, 1-difluoroethane, 1.005 parts by volume of ethane and 45.55 parts by volume of propylene, and a standing time of 2 hours, to obtain the refrigerant M7. (the refrigeration coefficient of refrigerant M7 was measured to be 2.34 according to the change law between substances in FIGS. 1-4.)
Example 8
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 2.53 parts by volume of ethane, 3.935 parts by volume of 1,1,1, 2-tetrafluoroethane, 3.01 parts by volume of propane, 1.75 parts by volume of isobutane, 3.935 parts by volume of 1,1,1, 2-tetrafluoroethane, 56.58 parts by volume of 1, 1-difluoroethane, 2.53 parts by volume of ethane and 25.75 parts by volume of propylene, to produce refrigerant M8. (the refrigeration coefficient of refrigerant M8 was measured to be 4.10 according to the change law between substances in FIGS. 1-4.)
Example 9
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 1.51 parts by volume of ethane, 4.16 parts by volume of 1,1,1, 2-tetrafluoroethane, 1.66 parts by volume of propane, 10.60 parts by volume of isobutane, 4.16 parts by volume of 1,1,1, 2-tetrafluoroethane, 33.60 parts by volume of 1, 1-difluoroethane, 1.51 parts by volume of ethane and 42.80 parts by volume of propylene, to produce refrigerant M9. (the refrigeration coefficient of refrigerant M9 was measured to be 2.78 according to the change law between substances in FIGS. 1-4.)
Example 10
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 0.665 parts by volume of ethane, 4.365 parts by volume of 1,1,1, 2-tetrafluoroethane, 5.05 parts by volume of propane, 6.98 parts by volume of isobutane, 4.365 parts by volume of 1,1,1, 2-tetrafluoroethane, 53.13 parts by volume of 1, 1-difluoroethane, 0.665 parts by volume of ethane, and 24.78 parts by volume of propylene, to produce refrigerant M10. (the refrigeration coefficient of refrigerant M10 was measured to be 3.85 according to the change law between substances in FIGS. 1-4.)
Example 11
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 2.01 parts by volume of ethane, 4.625 parts by volume of 1,1,1, 2-tetrafluoroethane, 3.32 parts by volume of propane, 4.73 parts by volume of isobutane, 4.625 parts by volume of 1,1,1, 2-tetrafluoroethane, 29.50 parts by volume of 1, 1-difluoroethane, 2.01 parts by volume of ethane and 49.19 parts by volume of propylene, to produce refrigerant M11. (the refrigeration coefficient of refrigerant M11 was measured to be 2.25 according to the change law between substances in FIGS. 1-4.)
Example 12
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 1.17 parts by volume of ethane, 4.82 parts by volume of 1,1,1, 2-tetrafluoroethane, 2.01 parts by volume of propane, 2.51 parts by volume of isobutane, 4.82 parts by volume of 1,1,1, 2-tetrafluoroethane, 50.43 parts by volume of 1, 1-difluoroethane, 1.17 parts by volume of ethane and 33.07 parts by volume of propylene, to produce refrigerant M12. (the refrigeration coefficient of refrigerant M12 was measured to be 3.65 according to the change law between substances in FIGS. 1-4.)
Example 13
The preparation was carried out according to the preparation method of example 7, except that the gases added in sequence were: 2.34 parts by volume of ethane, 5.00 parts by volume of 1,1,1, 2-tetrafluoroethane, 4.64 parts by volume of propane, 9.33 parts by volume of isobutane, 5.00 parts by volume of 1,1,1, 2-tetrafluoroethane, 70.00 parts by volume of 1, 1-difluoroethane, 2.34 parts by volume of ethane and 1.35 parts by volume of propylene, to produce refrigerant M13. (the refrigeration coefficient of refrigerant M13 was measured to be 4.56 according to the change law between substances in FIGS. 1-4.)
The refrigeration coefficient of the conventional refrigerant is usually 1.40-2.20, for example, the related records in the Master's academic paper entitled "ternary working medium used for air source heat pump capacity regulation theory and experimental research" published by the students in Liu east of the university of Zhejiang, etc. in 3 months of 2010 are clearly shown, and the conventional experimental value of the refrigeration coefficient is 1.40-2.20, so that, through the above examples 1-13, the refrigeration coefficient of the refrigerant prepared by the invention is still good, the refrigeration coefficient is higher than 2.20, and reaches about 70% of the total data of more than 3.0, and reaches about 40% of the total data of more than 4.0, therefore, the refrigeration coefficient is obviously better than the conventional value, and because no chlorine is contained therein, and the ozone layer destruction potential values (ODP) in the above substances are all 0, and the greenhouse effect potential value (GWP) is also lower, therefore, the damage to the environment is greatly reduced, the damage to the ozone layer is greatly avoided, and meanwhile, the refrigerant can be used after being pressurized and liquefied, so that the refrigerant can be completely adapted to the existing refrigerating machine without replacing the structure of the refrigerating machine, and meanwhile, the gases are non-flammable substances and the combination of the gases greatly reduces the flammability.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The refrigerant is characterized by comprising a compound A, a compound B, ethane, propane, isobutane and propylene, wherein the structure of the compound A is shown as a formula (I), and the structure of the compound B is shown as a formula (II):
wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
2. The refrigerant according to claim 1, wherein the content of the compound a is 5 to 10 vol%, the content of the compound B is 30 to 70 vol%, the content of ethane is 1 to 5 vol%, the content of propane is 1 to 5 vol%, the content of isobutane is 1 to 10 vol%, and the balance is propylene, based on the total volume of the refrigerant.
3. The refrigerant according to claim 1 or 2, wherein the compound a is 1,1,1, 2-tetrafluoroethane and the compound B is 1, 1-difluoroethane.
4. A method for producing a refrigerant, comprising: adding first ethane, a first compound A, propane, isobutane, a second compound A, a compound B, second ethane and ethylene into a container in sequence, and mixing to prepare a refrigerant; wherein,
the structure of the compound A is shown as a formula (I), and the structure of the compound B is shown as a formula (II):
wherein,
r1, R2, R3, R4, R5 and R6 are each selected from fluorine, bromine or iodine.
5. The production method according to claim 4, wherein the compound A is used in an amount of 5 to 10 vol%, the compound B is used in an amount of 30 to 70 vol%, the ethane is used in an amount of 1 to 5 vol%, the propane is used in an amount of 1 to 5 vol%, the isobutane is used in an amount of 1 to 10 vol%, and the balance is propylene, based on the total volume of the refrigerant; and the ethane is composed of a first ethane and a second ethane, and the compound A is composed of a first compound A and a second compound A.
6. The production method according to claim 5, wherein the first ethane is used in an amount of 40 to 60% by volume based on the amount of the ethane; the amount of the first compound a is 40 to 60 vol% based on the amount of the compound a.
7. The production method according to any one of claims 4 to 6, further comprising first evacuating the vessel before adding the first ethane;
preferably, the preparation method further comprises injecting ethane gas after the first vacuum pumping, and performing second vacuum pumping after injecting ethane gas.
8. The production method according to claim 7, wherein the first evacuation and the second evacuation are carried out by evacuating the container to a pressure of not more than 0.2 Pa.
9. The preparation method according to any one of claims 4 to 6, wherein the mixing process is standing in a container for 1.5 to 2 hours;
preferably, the preparation method further comprises performing a pressurized liquefaction operation after the mixing.
10. Use of a refrigerant according to any one of claims 1 to 3 or a refrigerant produced by the method according to any one of claims 4 to 9.
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| CN107513372A (en) * | 2017-02-22 | 2017-12-26 | 唐建 | A kind of ternary mixed refrigerant |
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