CN115340848A - Hydrocarbon refrigerant with warning effect and application thereof - Google Patents

Hydrocarbon refrigerant with warning effect and application thereof Download PDF

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CN115340848A
CN115340848A CN202210888888.1A CN202210888888A CN115340848A CN 115340848 A CN115340848 A CN 115340848A CN 202210888888 A CN202210888888 A CN 202210888888A CN 115340848 A CN115340848 A CN 115340848A
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mass
parts
hydrocarbon refrigerant
warning
refrigerant
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CN115340848B (en
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何国庚
刘菁菁
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Hubei Huahui Supportan Energy Management Co
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Hubei Huahui Supportan Energy Management Co
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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Abstract

The invention relates to a hydrocarbon refrigerant with a warning effect, and relates to the field of energy-saving and environment-friendly refrigerants, wherein the hydrocarbon refrigerant with the warning effect comprises 10-250 ppm of the hydrocarbon refrigerant and a warning agent, and each 100 parts by mass of the warning agent comprises 50-100 parts by mass of ethyl acrylate, 0-45 parts by mass of methyl acrylate and 0-5 parts by mass of 3-ethyl-2-methylpyrazine. Compared with the prior art, the warning agent is applied to hydrocarbon refrigerants for the first time, and has the advantages of high olfactory resolution, high stability, good safety, good compatibility with materials, low consumption of the warning agent, wide raw material source, low cost, economy and practicability.

Description

Hydrocarbon refrigerant with warning effect and application thereof
Technical Field
The invention relates to the field of energy-saving and environment-friendly refrigerants, in particular to a hydrocarbon refrigerant with a warning function and application thereof.
Background
Since scientists discovered ozone depletion, international society has become increasingly concerned with controlling the production of substances that are severely damaging to ozone. For this reason, the montreal protocol and its amendments accelerated the elimination of Hydrochlorofluorocarbons (HCFCs), a commonly used refrigerant, and stipulated that developed countries are totally banned from use in 2020, while developing countries may postpone the elimination period by 10 years, and decided that the trade of HCFCs of contracting parties and non-contracting parties was banned since 2004. At the same time, HFCs, once considered as a replacement for HCFCs, were found to have high greenhouse effect values (GWP), e.g., 1430 for R134a and 2010 for R410A, which are listed as the list of greenhouse-producing substances to be cut down in the kyoto protocol in 1997 and in the paris agreement in 2015. In particular, the capital and welfare amendment of Montreal protocol passed in 2016 clearly determines the cutting progress of HFCs, the developed countries must cut 85% by 2036 years, the developing countries must cut 80% by 2045 years, and HFCs refrigerants can only be used as transition refrigerants but cannot be finally replaced. Hydrocarbon refrigerants represented by R290 have been used as the most refrigerant in the initial stage of the development of refrigeration technology, but have been eliminated by synthetic refrigerants because of their flammability and their flammability not well solved when science and technology have lagged behind. As the hydrocarbon refrigerant typically represents R290 and the mixed hydrocarbon refrigerant thereof has good thermal physical properties and ODP value of 0, the excellent energy-saving and environment-friendly performance with extremely low GWP value is more and more widely concerned, but the explosiveness thereof becomes the maximum resistance of large-scale popularization and application thereof. Therefore, the improvement of the safety of the use of the hydrocarbon refrigerant is directly related to the popularization and the use of the hydrocarbon refrigerant.
At present, on the basis of ensuring the basic performance of the hydrocarbon refrigerant, the following two aspects are mainly provided for improving the use safety of the hydrocarbon refrigerant:
adding a flame retardant or an antiknock agent into R290 so as to reduce the possibility of explosion, wherein the patent with the application number of CN201210064427 is that HFC227ea is added into R290 according to the proportion of 12 to 1-15 as a flame retardant, but the GWP value of the HFC227ea is as high as 3220, and the HFC227ea belongs to a substance to be regulated by a Montreal Jiali amendment; CN201010141092 uses trifluoroiodomethane with a weight ratio of 1-10% as a flame and explosion suppression agent, and the trifluoroiodomethane is expensive and hundreds of times of the price of the common refrigerant, and is not suitable for the refrigerant industry with huge use amount. CN201410508003 adds an explosion inhibitor which is 1-5 percent of the total mass of the paraffin hydrocarbon refrigerant in the paraffin hydrocarbon refrigerant, wherein the explosion inhibitor is formed by mixing one or more than one of tetramethyl lead, tetraethyl lead and iron pentacarbonyl in any proportion, but the tetramethyl lead, the tetraethyl lead and the iron pentacarbonyl belong to highly toxic substances and are strictly controlled.
The patent with application number of CN200910214514 takes gas with special odor as a warning agent, wherein the molar concentration of propane is 70-99%, the rest is hydrogen sulfide, CN201010154844 is 0.3-5% of tetrahydrothiophene in R290, CN200510029292 is also 0.5% of tetrahydrothiophene THT in weight percentage in a mixed hydrocarbon refrigerant taking R290 and R600a as main components, and CN201210276788 is also 0.1-10 ppm of warning agent in total mass in a paraffin hydrocarbon refrigerant, and the warning agent is formed by mixing 4-80% of thiophene derivatives and other substances in mass percentage. The tetrahydrothiophene and thiophene derivatives, like hydrogen sulfide, all contain sulfur, and the presence of sulfur in a refrigeration system can cause corrosion of copper and copper alloy materials in the refrigeration system, thereby causing serious damage.
Disclosure of Invention
The invention aims to provide a hydrocarbon refrigerant with a warning function and application thereof. The purpose is to improve the refrigeration and heating efficiency, have excellent environmental protection, good thermal stability, good storage stability, compatibility with the pipeline material and good safety, and be suitable for various equipment such as refrigeration, freezing and refrigeration, air conditioning, heat pump and the like.
The technical scheme for solving the technical problems is as follows: the hydrocarbon refrigerant with the warning effect comprises 10-250 ppm of the hydrocarbon refrigerant and a warning agent, wherein the warning agent comprises 50-100 parts by mass of ethyl acrylate, 0-45 parts by mass of methyl acrylate and 0-5 parts by mass of 3-ethyl-2-methylpyrazine.
The invention has the beneficial effects that: compared with the prior art, the warning agent provided by the invention is applied to the hydrocarbon refrigerant for the first time, and has the following advantages: (1) high olfaction resolution: the main component of the warning agent is ethyl acrylate, the theoretical olfactory threshold value of the warning agent is only 0.00026ppm, the warning agent has pungent and pungent odor, the odor of common substances in the surrounding environment, such as the odor of gas, sewer, food decay and the like, is obviously distinguished, and the warning effect is obvious; (2) high stability: ethyl acrylate (molecular formula: C) 5 H 8 O 2 ) Methyl acrylate (molecular formula: c 4 H 6 O 2 ) And 3-ethyl-2-methylpyrazine (formula: c 7 H 10 N 2 ) The acrylic acid ethyl ester has good chemical stability, although the acrylic acid ethyl ester has a certain polymerization tendency at the temperature higher than 10 ℃, the polymerization tendency of the acrylic acid methyl ester is far weaker than that of the acrylic acid ethyl ester, the 3-ethyl-2-methylpyrazine has no polymerization tendency, and the addition of the acrylic acid ethyl ester and the 3-ethyl-2-methylpyrazine can effectively improve the polymerizability of the acrylic acid ethyl ester and greatly improve the stability of a mixture; (3) the safety is good: in the warning agent used by the invention, both ethyl acrylate and 3-ethyl-2-methylpyrazine have been used as food additives, and methyl acrylate does not cause harm to human bodies at all under the condition of the using amount of the warning agent; (4) good compatibility with materials: the hydrocarbon refrigerant and the warning agent have good compatibility with pipelines made of copper, iron, aluminum and the like, do not generate corrosiveness, have good compatibility with common non-metallic materials such as perfluorinated rubber, tetrafluoroethylene/propylene copolymer, teflon/polytetrafluoroethylene, perfluorinated rubber and the like, and are beneficial to long-term use of refrigerating equipment; the warning agent used in the invention has the advantages of small dosage, wide raw material source, low cost, economy and practicality.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the warning agent is 50-120 ppm of the quality of the hydrocarbon refrigerant.
The beneficial effect of adopting the further scheme is that: at this amount, the warning agent achieves superior results.
Further, every 100 parts by mass of the warning agent comprises 60-80 parts by mass of ethyl acrylate, 10-40 parts by mass of methyl acrylate and 0-5 parts by mass of 3-ethyl-2-methylpyrazine.
The coating further comprises p-hydroxyanisole, wherein the mass of the p-hydroxyanisole is 20-50ppm of the mass of the ethyl acrylate, and/or the mass of the p-hydroxyanisole is 20-80ppm of the mass of the methyl acrylate.
The beneficial effect of adopting the further scheme is that: hydroxyanisole acts as a stabilizer for ethyl acrylate and/or methyl acrylate.
Further, the hydrocarbon refrigerant is an olefin-paraffin hydrocarbon refrigerant, an olefin-olefin hydrocarbon refrigerant, or a paraffin hydrocarbon refrigerant.
Further, every 100 parts by mass of the alkene-alkane hydrocarbon refrigerant is composed of 10-100 parts by mass of propylene and 0-90 parts by mass of isobutane, or every 100 parts by mass of the alkene-alkane hydrocarbon refrigerant is composed of 0-20 parts by mass of propylene and 80-100 parts by mass of butane; or every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 75-90 mass parts of propylene and 10-25 mass parts of ethane, or every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 75.5-87 mass parts of propylene, 1-4 mass parts of propane and 12-20.5 mass parts of ethane.
Further, the olefin-olefin hydrocarbon refrigerant is composed of 90 to 96 parts by mass of propylene and 4 to 10 parts by mass of ethylene per 100 parts by mass of the olefin-olefin hydrocarbon refrigerant.
Further, each 100 parts by mass of the paraffin hydrocarbon refrigerant consists of 10 to 100 parts by mass of propane and 0 to 90 parts by mass of isobutane, or each 100 parts by mass of the paraffin hydrocarbon refrigerant consists of 5 to 25 parts by mass of propane and 95 to 75 parts by mass of butane, or each 100 parts by mass of the paraffin hydrocarbon refrigerant consists of 45 to 55 parts by mass of butane, 22 to 45 parts by mass of isobutane and 10 to 26 parts by mass of pentane, or each 100 parts by mass of the paraffin hydrocarbon refrigerant consists of 37 to 63 parts by mass of butane, 0.5 to 62.5 parts by mass of pentane and 0.5 to 62.5 parts by mass of isopentane, or each 100 parts by mass of the paraffin hydrocarbon refrigerant consists of 80 to 85 parts by mass of isobutane, 1 to 12 parts by mass of pentane and 8 to 19 parts by mass of isopentane.
The beneficial effect of adopting the above further scheme is: by adjusting the proportion of the hydrocarbon refrigerant to olefin-alkane hydrocarbon refrigerant, olefin-olefin hydrocarbon refrigerant or alkane hydrocarbon refrigerant, the refrigeration and heating efficiency can be improved.
According to the preparation method of the hydrocarbon refrigerant with the warning effect, the components in parts by mass are mixed at normal temperature to obtain the hydrocarbon refrigerant, and then the warning agent is added into the hydrocarbon refrigerant in proportion to obtain the hydrocarbon refrigerant with the warning effect.
Based on the application of the hydrocarbon refrigerant with the warning effect, the hydrocarbon refrigerant with the warning effect is applied to refrigeration equipment, freezing and refrigerating equipment, an air conditioner or a heat pump.
The beneficial effect who adopts above-mentioned scheme is: the invention is suitable for various equipment such as refrigeration, freezing and refrigeration, air conditioner, heat pump and the like.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The raw materials of the hydrocarbon refrigerant are all commercial hydrocarbon refrigerants, and all components meet the requirements of the hydrocarbon refrigerant; the component determination method of the hydrocarbon refrigerant is in accordance with petrochemical industry standard SH/T0614-1995.
The evaluation of the warning odor and the warning intensity of the hydrocarbon refrigerant finished product is divided into 7 grades of 0 grade (no odor way), 1 grade (weak), 2 grade (weak), 3 grade (general), 4 grade (strong), 5 grade (strong) and 6 grade (strong). In order to accurately judge the efficacy of the invention, the following two methods are adopted for olfactory evaluation of the hydrocarbon refrigerant of the invention:
the first method comprises the following steps: a sealed steel pipeline with the length of 2m is selected, firstly, odorless hydrocarbon refrigerant is added into the pipeline at the room temperature of about 20 ℃ to serve as blank value comparison, secondly, a warning agent is added into the hydrocarbon refrigerant according to the metering requirement to carry out a test, during the test, the hydrocarbon refrigerant gas in the pipeline leaks out of the pipeline through the tail end of the sealed pipeline, and meanwhile, 5 independent testees evaluate the warning odor and the warning intensity of the hydrocarbon refrigerant containing the warning odor in the aspect of olfaction.
The second method comprises the following steps: the mixed hydrocarbon refrigerant with a certain amount of warning agent is filled into the air conditioner, the air conditioning system runs for 24 hours, then the refrigerant in the air conditioner leaks into a room, and 5 independent testees evaluate the warning odor and the warning intensity of the hydrocarbon refrigerant containing the warning odor in the aspect of smell under the leakage point.
Example 1
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 10ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 10 parts by mass of propane and 90 parts by mass of isobutane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 2
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 50ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 100 parts by mass of propane and 0 part by mass of isobutane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 3
A hydrocarbon refrigerant having a warning function, comprising a paraffin hydrocarbon refrigerant, and a warning agent in an amount of 100ppm based on the total mass of the paraffin hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 50 parts by mass of propane and 50 parts by mass of isobutane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 4
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 10ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 5 parts by mass of propane and 95 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 5
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 50ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 25 parts by mass of propane and 75 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 6
A hydrocarbon refrigerant having warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 100ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 15 parts by mass of propane and 85 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 7
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is formed by mixing 10 parts of propane and 90 parts of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 8
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is formed by mixing 100 parts of propane and 0 part of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 9
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 120ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 70 parts of propane and 30 parts of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 10
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 5 parts by mass of propane and 95 parts by mass of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 11
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 25 parts by mass of propane and 75 parts by mass of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 80ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 12
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 120ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 20 parts by mass of propane and 80 parts by mass of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
In examples 1 to 12, in consideration of safety of a hydrocarbon refrigerant using paraffin, when a hydrocarbon refrigerant comprising 10 to 100 parts by mass of propane and 0 to 90 parts by mass of isobutane was subjected to a first olfactive evaluation method, the amount of ethyl acrylate, which is a warning agent having a warning intensity of class 1 and accounts for the total mass of the hydrocarbon refrigerant, was about 2.0ppm when 25% of the lower Limit of Flammability (LFL) of the refrigerant was reached in the air; for hydrocarbon refrigerant composed of 5-25 parts by mass of propane and 95-75 parts by mass of butane, when the lower limit of combustion (LFL) is 25% in air, the amount of ethyl acrylate which is taken as a warning agent and accounts for the total mass of the hydrocarbon refrigerant and achieves the warning strength of level 1 of the hydrocarbon refrigerant is about 1.64-1.72 ppm.
In examples 1 to 12, when the second olfactory evaluation method is used, in consideration of safety of using a hydrocarbon refrigerant due to interaction (e.g., dissolution) of a warning agent with a material such as lubricating oil in an air conditioner, etc., the amount of ethyl acrylate, which is a warning agent having a warning intensity of class 1 and accounts for the total mass of the hydrocarbon refrigerant, is about 10ppm when the hydrocarbon refrigerant composed of 10 to 100 parts by mass of propane and 0 to 90 parts by mass of isobutane reaches 25% of the lower Limit of Flammability (LFL) in air; for hydrocarbon refrigerant composed of 5-25 parts by mass of propane and 95-75 parts by mass of butane, when the lower limit of combustion (LFL) is 25% in air, the amount of ethyl acrylate which is taken as a warning agent and accounts for the total mass of the hydrocarbon refrigerant and achieves the warning strength of grade 1 of the mixed hydrocarbon refrigerant is about 10 ppm.
Example 13
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 10ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 10 parts by mass of propylene and 90 parts by mass of isobutane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 14
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 50ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 100 parts of propylene and 0 part of isobutane in parts by mass; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 15
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 100ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 38 parts by mass of propylene and 62 parts by mass of isobutane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 16
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 10ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 0 part by mass of propylene and 100 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 17
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 50ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 19 parts by mass of propylene and 81 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 18
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 100ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 11 parts by mass of propylene and 89 parts by mass of butane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 19
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 20ppm of the total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is formed by mixing 10 parts of propylene and 90 parts of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 80ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 20
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent which accounts for 80ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is formed by mixing 90 parts of propylene and 10 parts of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 21
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 120ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is formed by mixing 70 parts of propylene and 30 parts of isobutane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 60ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 22
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 20ppm of the total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 20 parts by mass of propylene and 80 parts by mass of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 23
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent which accounts for 80ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 15 parts by mass of propylene and 85 parts by mass of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 65ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 24
The hydrocarbon refrigerant with warning function contains alkene-alkane refrigerant and warning agent accounting for 120ppm of total mass of the alkene-alkane refrigerant, wherein: the alkene-alkane refrigerant is a mixed hydrocarbon refrigerant consisting of 12 parts by weight of propylene and 88 parts by weight of butane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 25ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 65ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
In examples 13 to 24, when the first olfactory assessment method was employed, considering the safety of the use of hydrocarbon refrigerants, for refrigerants consisting of 10 to 100 parts by mass of propylene and 0 to 90 parts by mass of isobutane, when 25% of the lower Limit of Flammability (LFL) was reached in the air, the amount of ethyl acrylate, which is a warning agent accounting for the total mass of the refrigerant and achieving a level 1 warning intensity, was all around 2.0ppm to 1.66 ppm; for hydrocarbon refrigerant composed of 5-25 parts by mass of propylene and 95-75 parts by mass of butane, when the lower limit of combustion (LFL) is 25% in air, the amount of the warning agent ethyl acrylate accounting for the total mass of the hydrocarbon refrigerant, when the mixed hydrocarbon refrigerant reaches the level 1 warning strength, is about 1.62 ppm.
In examples 13 to 24, in the case of the second olfactory sensation evaluation method, in view of safety of using a hydrocarbon refrigerant due to interaction (e.g., dissolution) of a warning agent with a material such as lubricating oil in an air conditioner, the amount of ethyl acrylate which is a warning agent and accounts for the total mass of the refrigerant, and which has a level 1 warning strength, is about 10ppm when 25% of the lower Limit of Flammability (LFL) of the hydrocarbon refrigerant is reached in air, in the hydrocarbon refrigerant comprising 10 to 100 parts by mass of propylene and 0 to 90 parts by mass of isobutane; for hydrocarbon refrigerant composed of 5-25 parts by mass of propylene and 95-75 parts by mass of butane, when the lower limit of combustion (LFL) is 25% in air, the amount of ethyl acrylate which is taken as a warning agent and accounts for the total mass of the hydrocarbon refrigerant and achieves the level 1 warning strength of the hydrocarbon refrigerant is about 10 ppm.
Example 25
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 10ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 75 parts by mass of propylene and 25 parts by mass of ethane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 26
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 50ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 90 parts by mass of propylene and 10 parts by mass of ethane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 27
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 100ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 83 parts by mass of propylene and 17 parts by mass of ethane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 35ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 28
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 10ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 90 parts by mass of propylene and 10 parts by mass of ethylene; the warning agent is ethyl acrylate, and the ethyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 29
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 50ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 96 parts by mass of propylene and 4 parts by mass of ethylene; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 30
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 100ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 92 parts by weight of propylene and 8 parts by weight of ethylene; the warning agent is ethyl acrylate, and the ethyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 31
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 20ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is formed by mixing 75 parts of propylene and 25 parts of ethane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 80ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 32
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 80ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is formed by mixing 85 parts of propylene and 15 parts of ethane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 65ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 33
The hydrocarbon refrigerant with warning function comprises the hydrocarbon refrigerant and a warning agent accounting for 120ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is formed by mixing 87 parts of propylene and 13 parts of ethane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 25ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 34
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 20ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 94 parts by mass of propylene and 6 parts by mass of ethylene; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 75ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 35
The hydrocarbon refrigerant with warning function contains the hydrocarbon refrigerant and a warning agent accounting for 80ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 96 parts by mass of propylene and 4 parts by mass of ethylene; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 36
The hydrocarbon refrigerant with warning function comprises the hydrocarbon refrigerant and a warning agent accounting for 120ppm of the total mass of the hydrocarbon refrigerant, wherein: the hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 92 parts by mass of propylene and 8 parts by mass of ethylene; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 45ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
In examples 25 to 36, when the first olfactory assessment method is employed, in view of safety in use of a hydrocarbon refrigerant, for a hydrocarbon refrigerant comprising 75 to 90 parts by mass of propylene and 10 to 25 parts by mass of ethane, the amount of ethyl acrylate as a warning agent in the total mass of the hydrocarbon refrigerant, which gives a level 1 warning intensity when 25% of the lower Limit of Flammability (LFL) is reached in air, is about 1.73ppm to 1.69 ppm; when the mixed hydrocarbon refrigerant composed of 90-96 parts by mass of propylene and 4-10 parts by mass of ethylene reaches 25% of the lower limit of combustion (LFL) in air, the amount of ethyl acrylate which is a warning agent and accounts for the total mass of the hydrocarbon refrigerant, and the mixed hydrocarbon refrigerant reaches 1-grade warning strength, is about 1.74ppm-1.70 ppm.
In examples 25 to 36, in the case of the second olfactory evaluation method, in view of safety of the use of the hydrocarbon refrigerant due to interaction (e.g., dissolution) of the warning agent with a material such as lubricating oil in an air conditioner, etc., the amount of ethyl acrylate as a warning agent in the total mass of the hydrocarbon refrigerant, which gives a level 1 warning strength, is about 10ppm when 25% of the lower Limit of Flammability (LFL) is reached in the air for the hydrocarbon refrigerant composed of 75 to 90 parts by mass of propylene and 10 to 25 parts by mass of ethane; for hydrocarbon refrigerant composed of 90-96 parts by mass of propylene and 4-10 parts by mass of ethylene, when the lower limit of combustion (LFL) is 25% in air, the amount of ethyl acrylate which is taken as a warning agent and accounts for the total mass of the hydrocarbon refrigerant and achieves the level 1 warning strength of the hydrocarbon refrigerant is about 10 ppm.
Example 37
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 10ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 55 parts by mass of butane, 22 parts by mass of isobutane and 23 parts by mass of pentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 38
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 50ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 50 parts by mass of butane, 40 parts by mass of isobutane and 10 parts by mass of pentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 39
A hydrocarbon refrigerant having a warning function, comprising a paraffin hydrocarbon refrigerant, and a warning agent in an amount of 100ppm based on the total mass of the paraffin hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 50 parts by mass of butane, 31 parts by mass of isobutane and 19 parts by mass of pentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 40
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is formed by mixing 50 parts of butane, 24 parts of isobutane and 26 parts of pentane according to mass percentage; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
EXAMPLE 41
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is formed by mixing 45 parts of butane, 45 parts of isobutane and 10 parts of pentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 42
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 120ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is formed by mixing 45 parts of butane, 29 parts of isobutane and 26 parts of pentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 43
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 55 parts by mass of butane, 35 parts by mass of isobutane and 10 parts by mass of pentane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 44
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 55 parts by mass of butane, 24 parts by mass of isobutane and 21 parts by mass of pentane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 80ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
In examples 37 to 44, in consideration of safety in use of the hydrocarbon refrigerant when the first olfactory sensation assessment method was employed, the amount of ethyl acrylate as a warning agent in the total mass of the hydrocarbon refrigerant, which gave a level 1 warning intensity, was about 1.83ppm to 1.86ppm when the amount of ethyl acrylate as a warning agent in the total mass of the hydrocarbon refrigerant reached 25% of the lower Limit of Flammability (LFL) in the air for the hydrocarbon refrigerant consisting of 45 to 55 parts by mass of butane, 22 to 45 parts by mass of isobutane and 10 to 26 parts by mass of pentane.
In examples 37 to 44, in the case of the second olfactory assessment method, in view of safety of the use of the hydrocarbon refrigerant due to interaction (e.g., dissolution) of the warning agent with a material such as lubricating oil in an air conditioner, etc., the amount of ethyl acrylate, which is a warning agent and accounts for the total mass of the hydrocarbon refrigerant, that achieves a level 1 warning intensity when the hydrocarbon refrigerant consisting of 45 to 55 parts by mass of butane, 22 to 45 parts by mass of isobutane and 10 to 26 parts by mass of pentane reaches 25% of the lower Limit of Flammability (LFL) in air is about 10 ppm.
Example 45
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 10ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 37 parts by mass of butane, 62.5 parts by mass of pentane and 0.5 part by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 46
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 50ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 37 parts by mass of butane, 32 parts by mass of pentane and 31 parts by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 47
A hydrocarbon refrigerant having warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 100ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 45 parts by mass of butane, 30 parts by mass of pentane and 25 parts by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 48
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 50 parts of butane, 25 parts of pentane and 25 parts of isopentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 49
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 55 parts of butane, 23 parts of pentane and 22 parts of isopentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 50
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 120ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 63 parts of butane, 19 parts of pentane and 18 parts of isopentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 70ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 51
A hydrocarbon refrigerant having warning effect, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 63 parts by weight of butane, 0.5 part by weight of pentane and 36.5 parts by weight of isopentane; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 80ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
In examples 45 to 51, in consideration of safety of use of the hydrocarbon refrigerant when the first olfactory sensation assessment method was employed, for the hydrocarbon refrigerant composed of 37 to 63 parts by mass of butane, 0.5 to 62.5 parts by mass of pentane and 0.5 to 62.5 parts by mass of isopentane, when 25% of the lower Limit of Flammability (LFL) was reached in the air, the amount of ethyl acrylate, which is a warning agent having a level 1 warning strength and accounts for the total mass of the hydrocarbon refrigerant, was about 1.80ppm to 1.97 ppm.
In examples 45 to 51, in the case of the second olfactory evaluation method, the amount of ethyl acrylate as a warning agent in the total mass of the hydrocarbon refrigerant, which has reached a warning intensity of class 1, is about 10ppm when the amount of ethyl acrylate as a warning agent is 25% of the lower Limit of Flammability (LFL) in the air, in the hydrocarbon refrigerant comprising 37 to 63 parts by mass of butane, 0.5 to 62.5 parts by mass of pentane and 0.5 to 62.5 parts by mass of isopentane, in view of the safety of the hydrocarbon refrigerant used, for example, due to the interaction (e.g., dissolution) of the warning agent with a material such as lubricating oil in an air conditioner.
Example 52
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 10ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 80 parts by mass of isobutane, 12 parts by mass of pentane and 8 parts by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 53
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 50ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 80 parts by mass of isobutane, 1 part by mass of pentane and 19 parts by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
Example 54
A hydrocarbon refrigerant having a warning function, comprising a paraffin hydrocarbon refrigerant, and a warning agent in an amount of 100ppm based on the total mass of the paraffin hydrocarbon refrigerant, wherein: the alkane hydrocarbon refrigerant is a mixed hydrocarbon refrigerant consisting of 82 parts by mass of isobutane, 9 parts by mass of pentane and 9 parts by mass of isopentane; the warning agent is ethyl acrylate, and the ethyl acrylate contains 40ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 5 warning intensity.
Example 55
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 20ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 85 parts of isobutane, 7 parts of pentane and 8 parts of isopentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 20ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 1 warning intensity.
Example 56
A hydrocarbon refrigerant having a warning function, comprising a paraffinic hydrocarbon refrigerant, and a warning agent in an amount of 80ppm based on the total mass of the paraffinic hydrocarbon refrigerant, wherein: the paraffin hydrocarbon refrigerant is formed by mixing 85 parts of isobutane, 1 part of pentane and 14 parts of isopentane in percentage by mass; the warning agent is formed by mixing 50% of ethyl acrylate, 45% of methyl acrylate and 5% of 3-ethyl-2-methylpyrazine in percentage by mass of the total amount of the warning agent, wherein the ethyl acrylate contains 30ppm of p-hydroxyanisole as a stabilizer, and the methyl acrylate contains 50ppm of p-hydroxyanisole as a stabilizer. This embodiment can achieve a level 3 warning intensity.
In examples 52 to 56, in consideration of safety in use of the hydrocarbon refrigerant when the first olfactory sensation assessment method was employed, the amount of ethyl acrylate, which is a warning agent accounting for the total mass of the hydrocarbon refrigerant and having a warning intensity of class 1, was about 2.02ppm to 2.04ppm when the lower Limit of Flammability (LFL) in the air was 25% of the mass of the hydrocarbon refrigerant consisting of 80 to 85 parts by mass of isobutane, 1 to 12 parts by mass of pentane and 8 to 19 parts by mass of isopentane.
In examples 52 to 56, in the case of the second olfactory sensation evaluation method, in view of safety of the use of the hydrocarbon refrigerant due to interaction (e.g., dissolution) of the warning agent with a material such as lubricating oil in the air conditioner, the amount of ethyl acrylate, which is a warning agent and accounts for the total mass of the hydrocarbon refrigerant, when the amount of ethyl acrylate, which is a warning agent having a level 1 warning strength, is about 10ppm in the hydrocarbon refrigerant composed of 80 to 85 parts by mass of isobutane, 1 to 12 parts by mass of pentane and 8 to 19 parts by mass of isopentane in the air and reaches 25% of the lower Limit of Flammability (LFL).
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The hydrocarbon refrigerant with the warning effect is characterized by comprising 10-250 ppm of the hydrocarbon refrigerant and a warning agent, wherein the warning agent is composed of 50-100 parts by mass of ethyl acrylate, 0-45 parts by mass of methyl acrylate and 0-5 parts by mass of 3-ethyl-2-methylpyrazine.
2. The hydrocarbon refrigerant with warning effect as claimed in claim 1, wherein the warning agent is 50-120 ppm of the mass of the hydrocarbon refrigerant.
3. The hydrocarbon refrigerant with warning effect according to claim 1, wherein the warning agent comprises 60 to 80 parts by mass of ethyl acrylate, 15 to 40 parts by mass of methyl acrylate and 0 to 5 parts by mass of 3-ethyl-2-methylpyrazine per 100 parts by mass of the warning agent.
4. The hydrocarbon refrigerant with warning effect according to any one of claims 1 to 3, further comprising p-hydroxyanisole, wherein the mass of the p-hydroxyanisole is 20-50ppm of the mass of the ethyl acrylate, and/or the mass of the p-hydroxyanisole is 20-80ppm of the mass of the methyl acrylate.
5. The hydrocarbon refrigerant with warning effect according to any one of claims 1 to 3, wherein the hydrocarbon refrigerant is an alkene-alkane hydrocarbon refrigerant, an alkene-alkene hydrocarbon refrigerant, or a paraffin hydrocarbon refrigerant.
6. The hydrocarbon refrigerant with warning effect as claimed in claim 5, wherein every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 10-100 mass parts of propylene and 0-90 mass parts of isobutane, or every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 0-20 mass parts of propylene and 80-100 mass parts of butane; or every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 75-90 mass parts of propylene and 10-25 mass parts of ethane, or every 100 mass parts of the alkene-alkane hydrocarbon refrigerant consists of 75.5-87 mass parts of propylene, 1-4 mass parts of propane and 12-20.5 mass parts of ethane.
7. The hydrocarbon refrigerant with warning effect as claimed in claim 5, wherein the olefin-olefin hydrocarbon refrigerant is composed of 90 to 96 parts by mass of propylene and 4 to 10 parts by mass of ethylene per 100 parts by mass of the olefin-olefin hydrocarbon refrigerant.
8. The hydrocarbon refrigerant with warning effect according to claim 5, wherein the paraffin hydrocarbon refrigerant consists of 10 to 100 parts by mass of propane and 0 to 90 parts by mass of isobutane per 100 parts by mass of the paraffin hydrocarbon refrigerant, or consists of 5 to 25 parts by mass of propane and 95 to 75 parts by mass of butane per 100 parts by mass of the paraffin hydrocarbon refrigerant, or consists of 45 to 55 parts by mass of butane, 22 to 45 parts by mass of isobutane and 10 to 26 parts by mass of pentane per 100 parts by mass of the paraffin hydrocarbon refrigerant, or consists of 37 to 63 parts by mass of butane, 0.5 to 62.5 parts by mass of pentane and 0.5 to 62.5 parts by mass of isopentane per 100 parts by mass of the paraffin hydrocarbon refrigerant, or consists of 80 to 85 parts by mass of isobutane, 1 to 12 parts by mass of pentane and 8 to 19 parts by mass of isopentane per 100 parts by mass of the paraffin hydrocarbon refrigerant.
9. The method for preparing a hydrocarbon refrigerant with a warning effect according to any one of claims 1 to 8, wherein the components are mixed at normal temperature to obtain the hydrocarbon refrigerant, and then the warning agent is added into the hydrocarbon refrigerant in proportion to obtain the hydrocarbon refrigerant with the warning effect.
10. The use of the hydrocarbon refrigerant with warning effect according to any one of claims 1 to 8, wherein the hydrocarbon refrigerant with warning effect is used in a refrigeration apparatus, a freezing and refrigerating apparatus, an air conditioner or a heat pump.
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