CN114574275A - Mixture of refrigerator oil and fire retardant suitable for refrigerating system - Google Patents

Mixture of refrigerator oil and fire retardant suitable for refrigerating system Download PDF

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Publication number
CN114574275A
CN114574275A CN202210232285.6A CN202210232285A CN114574275A CN 114574275 A CN114574275 A CN 114574275A CN 202210232285 A CN202210232285 A CN 202210232285A CN 114574275 A CN114574275 A CN 114574275A
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China
Prior art keywords
mixture
oil
working medium
flame retardant
combustible
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CN202210232285.6A
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Inventor
杨昭
吕子建
陈裕博
张勇
贺红霞
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Tianjin University
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Tianjin University
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Publication of CN114574275A publication Critical patent/CN114574275A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • 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

Abstract

The invention relates to a mixture of refrigerating machine oil and a flame retardant, which is suitable for a refrigerating system and consists of polyol ester oil and a flame retardant 2-bromo-3, 3, 3-trifluoropropene in the refrigerating system. The mass percentage of the polyol ester oil is 80-95%; the proportion of the 2-bromo-3, 3, 3-trifluoropropene is 5-20%. The mixture of the refrigerator oil and the flame retardant replaces the traditional refrigerator oil and is matched with HFCs and HFOs flammable working media for use. In traditional refrigerator oil, the mixture has strong fire extinguishing characteristic, and when the mixture is used in a refrigeration system in cooperation with a combustible working medium, the explosion risk of the combustible working medium during leakage can be reduced, and the safety of the refrigeration system is improved, so that the popularization and the use of environment-friendly combustible working media can be promoted. The invention can replace the refrigeration working medium with higher GWP value as soon as possible, and promotes the popularization of environment-friendly working medium in the low-temperature field, thereby achieving the purposes of protecting the environment and improving the system safety.

Description

Mixture of refrigerator oil and fire retardant suitable for refrigerating system
Technical Field
The invention relates to the technical field of refrigerator oil products in a refrigerating system, in particular to a mixture of refrigerator oil and a flame retardant suitable for the refrigerating system.
Background
Energy and environmental problems are the main focus of attention in the current social development, and in the field of refrigeration and air conditioning, the refrigeration working medium brings comfort and convenient life to people and also causes very serious environmental problems. In early researches, it is found that chlorofluorocarbon (CFCs) and Hydrochlorofluorocarbon (HCFCs) refrigeration working media can continuously consume ozone layer substances through a chain reaction, so that the phenomenon of holes in an Antarctic ozone layer is caused. But as a substitute of CFCs and HCFCs working media, Hydrofluorocarbons (HFCs) refrigerating working media have strong greenhouse effect although the ozone layer depletion potential value is zero. Therefore, in order to deal with the increasingly severe environmental problems, international society has issued a series of regulations and policies to gradually reduce and eliminate working media harmful to the environment. The current alternative new generation of environment-friendly working media are mainly classified into the following 3 types: natural working substances, low GWP HFCs, unsaturated olefins (HFOs). Wherein the natural working medium mainly comprises: hydrocarbons (e.g., R290, R600a, R600, etc.), R744, R717, R718, etc., and low GWP HFCs include primarily: r32, R152a, R161, and the like, unsaturated olefins include: r1234yf, R1234ze (E), etc. However, most of the new generation of environment-friendly working media with the low-temperature chamber effect have flammability. In the face of a continuously severe environment protection policy, a combustible working medium with excellent environment protection advantages is a main trend of future application. However, these flammable and explosive refrigerant have the risk of leakage and explosion during use, and in order to improve the safety of flammable refrigerant in application and reduce the risk of explosion, research on the explosion suppression technology of flammable refrigerant is urgently needed.
At present, aiming at the explosion suppression technology of combustible working media, flame-retardant working media are mainly added into the combustible working media and are matched into mixed refrigerants, such as nonflammable working media R513A (R1234yf/R134a) developed for suppressing the flammability of R1234yf and the like. When the flame-retardant working medium and the combustible working medium are mixed for use, although the flammability of the combustible working medium can be effectively weakened or even inhibited, meanwhile, the addition of the flame-retardant working medium can affect the environmental protection characteristic, the thermal physical property and the system performance of the combustible working medium, for example, the flame-retardant working medium HFCs generally have higher GWP value, and the difference between the physical properties of the HFOs working medium and the HCs of the combustible working medium is larger. Therefore, the existing flame retardant technology cannot effectively inhibit the flammability of the flammable working medium and also considers the requirements of environmental protection and the performance of the system.
Therefore, a new explosion suppression technology is needed to be found to reduce the risk of combustible working medium leakage and explosion and to take the environmental protection characteristic and the system performance into consideration.
Disclosure of Invention
In a refrigeration system, a compressor is a core component of the refrigeration system, and the compressor usually contains refrigerating machine oil, so that in order to facilitate oil return of the system, the refrigeration working medium and the lubricating oil need to have excellent intersolubility. In current applications, hydrocarbon working fluids are suitable for mineral oils, while HFCs and HFOs working fluids are more suitable for polyol ester oils. In the operation process of the refrigerating system, because the refrigerating working medium and the adaptive refrigerating machine oil have good intersolubility, the refrigerating machine oil can flow along with the refrigerating working medium, when the refrigerating system leaks, the high-pressure working medium in the system can wrap and carry the part of the refrigerating machine oil to release together, the area near the leakage point is the area with the maximum concentration distribution of the leaked working medium, and if the refrigerating working medium in the system is combustible gas, the area near the leakage point is the area with the most easy explosion risk. In addition, because the refrigerating machine oil has a low flash point, the existence of the refrigerating machine oil can promote the combustion of combustible working media. The invention relates to a method for controlling the leakage of a refrigerating system, which is characterized in that the process characteristics of the refrigerating system when leakage occurs are comprehensively considered, the refrigerating machine oil and a fire retardant are mixed into a mixture according to a certain proportion, wherein the refrigerating machine oil and the fire retardant have good intersolubility, when a combustible working medium leaks, the fire retardant in the mixture flows out along with the refrigerating machine oil, when the combustible working medium near a leakage port meets a potential ignition source to be combusted, the combustibility of the combustible working medium and the refrigerating machine oil is timely inhibited due to the existence of the fire retardant in the refrigerating machine oil, and therefore, the purposes of reducing the leakage explosion risk of the combustible working medium and improving the safety of the system are achieved.
The technical scheme of the invention is as follows:
a mixture of refrigerating machine oil and flame retardant for refrigerating system is prepared from polyol ester oil and 2-bromo-3, 3, 3-trifluoropropene (molecular formula: CF)3CBr＝CH2) And (4) forming.
The polyol ester oil is a mixture consisting of a plurality of chemical components, the main components of the polyol ester oil are dibasic ester and polyol ester, and the main manufacturers and models of the polyol ester oil are Emkarate RL32 and Emkarate RL68H, and Solest LT-32 and Solest 68. The polyol ester oil is a lubricating oil commonly used in a refrigeration system, and has good intersolubility with HFCs and HFOs working substances, wherein the commonly used HFCs and HFOs working substances mainly comprise R32 (molecular formula: CH)2F2) R152a (molecular formula: CH (CH)3CHF2) R161 (molecular formula: CH (CH)3CH2F) And R1234yf (formula: CH (CH)2＝CF2CF3) And the like.
The fire retardant is of various types, but is suitable for the invention and needs to be screened and weighed, and according to various tests and researches, the invention provides the fire retardant 2-bromo-3, 3, 3-trifluoropropene which is a high-efficiency fire extinguishing agent, has the ozone depletion potential of 0.0028 and the greenhouse effect potential of 0.005, and has small influence on the ozone layer destruction, so that the 2-bromo-3, 3, 3-trifluoropropene has the advantages of both fire extinguishing property and environmental protection property.
The mass percentage of the polyol ester oil in the mixture is 80-95%; the proportion of the 2-bromo-3, 3, 3-trifluoropropene is 5-20%.
The mixture of the refrigerator oil and the flame retardant is suitable for a vapor compression refrigeration system and mainly covers the field of low-temperature refrigeration.
The polyol ester oil and the flame retardant 2-bromo-3, 3, 3-trifluoropropene have good intersolubility, and compared with the traditional refrigerator oil, the mixture prepared by mixing the polyol ester oil and the flame retardant 2-bromo-3, 3, 3-trifluoropropene has excellent flame retardant property and fire extinguishing property when being used as the refrigerator oil, and is particularly suitable for a refrigerating system filled with flammable working mediums such as HFCs (high frequency refrigerant systems), HFOs (high frequency vapor hydrocarbons) and the like. Therefore, when the refrigerating machine oil prepared by proportioning the polyol ester oil and the flame retardant 2-bromo-3, 3, 3-trifluoropropene is applied to a refrigerating system, the risk of combustible working medium leakage and explosion can be reduced, and the safety of the system is improved.
The invention has the following advantages and beneficial effects:
the mixture of the refrigerator oil and the flame retardant can replace the traditional refrigerator oil and is matched with HFCs and HFOs flammable working media for use. Compared with the traditional refrigerating machine oil, the mixture has stronger fire extinguishing characteristic, and when the mixture is matched with a combustible working medium in a refrigerating system for use, the explosion risk of the combustible working medium during leakage can be reduced, and the safety of the refrigerating system is improved, so that the popularization and the use of the environment-friendly combustible working medium can be promoted. The acquisition of the patent can replace a refrigeration working medium with a higher GWP value as soon as possible, and promote the popularization of environment-friendly working media in the low-temperature field, thereby achieving the purposes of protecting the environment and improving the system safety.
Detailed Description
The invention relates to a preparation method of refrigerator oil and a flame retardant, which is prepared by physically mixing polyol ester oil and 2-bromo-3, 3, 3-trifluoropropene according to different mass percentages.
Since polyol ester oil is a type of refrigeration motor oil, its major manufacturers and models are Emkarate RL32 and Emkarate RL68H, and Solest LT-32 and Solest 68, Luborun. In the examples, Emkarate RL32 produced by American ice bear is taken as an example.
Refrigerant media which can be adapted to the polyol ester oils and 2-bromo-3, 3, 3-trifluoropropene mixtures described above are mainly R32, R152a, R161, R1234yf, etc., in the examples R1234yf is given as an example.
Specific examples are given below in which the proportions of the components are given in mass percent and the sum of the mass percent of the components in each mixture is 100%.
The specific embodiment is as follows:
example 1, a refrigerator oil was prepared by mixing 95% polyol ester oil and 5% 2-bromo-3, 3, 3-trifluoropropene.
Example 2, 90% by mass of polyol ester oil and 10% by mass of 2-bromo-3, 3, 3-trifluoropropene were mixed and used as a refrigerating machine oil.
Example 3 polyol ester oil in a mass fraction of 85% and 2-bromo-3, 3, 3-trifluoropropene in a mass fraction of 15% were mixed and used as a refrigerator oil.
Example 4, 80% by mass of polyol ester oil and 20% by mass of 2-bromo-3, 3, 3-trifluoropropene were mixed and used as a refrigerating machine oil.
TABLE 1 physical Properties of polyol ester oils
Figure BDA0003538924050000041
TABLE 2 influence of the mixture on the explosion limit of the combustible working substance
Figure BDA0003538924050000042
The physical property parameters of the polyol ester oil are shown in table 1. Flammability tests were conducted on the above examples according to the testing method of flammability limits of Refrigerants set by the American society of heating, refrigeration and air Conditioning Engineers (ASHRAE), Designation and Safety classification of reflagers. The experimental device mainly comprises three parts: reaction vessel, gas distribution system and ignition system. The reaction vessel is a 12L spherical glass flask, precise gas distribution is carried out according to the Dalton partial pressure law, the ignition device adopts a voltage controller with the output voltage of 15KV, the discharge current is 30mA, and the ignition duration is 0.4 s. The flammability of the gas is judged by the experimental phenomenon after the flammable gas is ignited, and the judgment standard is as follows: by observing the propagation phenomenon of the combustion flame, when the flame extends upwards and outwards, whether the maximum fan angle with the position of the electric spark as the center of a circle and the wall of the container reached by the flame as the boundary reaches 90 degrees is taken as a standard. When the fan angle is less than 90 degrees, the gas is not combustible, and when the fan angle is equal to or greater than 90 degrees, the gas is combustible. According to the experimental method and the experimental standard, the influence of the mixture on the upper flammability limit and the lower flammability limit of combustible working medium R1234yf is experimentally tested, and as shown in Table 2, the mass of the mixture in each group of experiments is about 1g, and the mixture is atomized by a plunger pump under high pressure and then sprayed into a reaction vessel.
In example 1, the addition of the mixture increased the lower flammability limit of R1234yf from 7.2% to 7.8%, the upper flammability limit decreased from 12% to 11.8%, and the flammability limit of R1234yf decreased from 4.8% to 4.0%, indicating that the addition of 5% 2-bromo-3, 3, 3-trifluoropropene in the mixture reduced the flammability of R1234 yf.
In example 2, the addition of the mixture increased the lower flammability limit of R1234yf from 7.2% to 8.3%, the upper flammability limit decreased from 12% to 11.4%, and the flammability limit of R1234yf decreased from 4.8% to 3.1%, indicating that the addition of 10% 2-bromo-3, 3, 3-trifluoropropene to the mixture further attenuated the flammability of R1234 yf.
In example 3, the addition of the mixture increased the lower flammability limit of R1234yf from 7.2% to 9.2%, the upper flammability limit decreased from 12% to 10.9%, and the flammability limit of R1234yf decreased from 4.8% to 1.7%, indicating that the addition of 15% 2-bromo-3, 3, 3-trifluoropropene to the mixture further attenuated the flammability of R1234 yf.
In example 4, the addition of the mixture increased the lower flammability limit of R1234yf from 7.2% to 10.3% and the upper flammability limit from 12% to 10.3%, with R1234yf being flammable only at a concentration of 10.3% by volume, indicating that the addition of 20% 2-bromo-3, 3, 3-trifluoropropene to the mixture further attenuated the flammability of R1234 yf.
The examples show that the mixture can effectively increase the lower combustion limit and lower the upper combustion limit of combustible working medium R1234yf, and gradually narrow the combustible limit range, thereby weakening the combustion of combustible gas.
According to the introduction, the mixture of the refrigerator oil and the flame retardant can inhibit the combustion of combustible gas, and can reduce the risk of combustible working medium leakage and explosion when applied to a refrigeration system.
The present invention relates to a mixture of refrigerating machine oil commonly used in refrigeration system and a fire retardant. In recent years, with the continuous aggravation of environmental problems, refrigeration working media which have a harmful effect on the environment are gradually eliminated, and combustible working media become a new application trend by virtue of excellent environmental protection performance. Therefore, in order to reduce the risk of leakage and explosion of the combustible working medium in the using process, the invention provides a flame-retardant method, which is characterized in that a flame retardant with higher fire extinguishing efficiency is adapted to the refrigerating machine oil commonly existing in a refrigerating system to form a mixture and is applied to the refrigerating system. When the refrigerating system leaks, the combustible working medium can be released together with the mixture, and when the mixture meets an ignition source, the flame retardant contained in the mixture can inhibit the combustion reaction of the combustible working medium, so that the aim of extinguishing a fire or reducing the explosion risk is fulfilled.
The above description is only for the preferred embodiment of the present invention, but the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes and modifications without departing from the inventive concept of the present invention, which falls into the protection scope of the present invention.

Claims (4)

1. A mixture of refrigerating machine oil and flame retardant suitable for a refrigerating system is characterized by consisting of polyol ester oil and flame retardant 2-bromo-3, 3, 3-trifluoropropene in the refrigerating system.
2. The mixture of refrigerant oil and flame retardant for use in a refrigeration system of claim 1, wherein the polyol ester oil is present in the mixture in an amount of 80% to 95% by weight; the proportion of the 2-bromo-3, 3, 3-trifluoropropene is 5-20%.
3. A refrigerant oil and flame retardant mixture suitable for use in a refrigeration system as claimed in claim 1 wherein the polyol ester oil comprises Emkarate RL32, Emkarate RL68H, luobu Solest LT-32 or Solest 68 from american bear.
4. The refrigerator oil and flame retardant mixture suitable for use in a refrigeration system of claim 1 is suitable for use in a vapor compression refrigeration system, encompassing cryogenic refrigeration.
CN202210232285.6A 2022-03-09 2022-03-09 Mixture of refrigerator oil and fire retardant suitable for refrigerating system Pending CN114574275A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015136981A1 (en) * 2014-03-14 2015-09-17 三菱電機株式会社 Compressor and refrigeration cycle system
CN105408442A (en) * 2013-08-14 2016-03-16 中央硝子株式会社 Heat transmission method and high-temperature heat pump device
CN107841290A (en) * 2016-09-19 2018-03-27 福特全球技术公司 Suitable for fixed or mobile air conditioner system R 744 and R 1234yf refrigerant mixture
CN110832051A (en) * 2018-06-13 2020-02-21 日立江森自控空调有限公司 Refrigerant composition and refrigeration cycle device using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105408442A (en) * 2013-08-14 2016-03-16 中央硝子株式会社 Heat transmission method and high-temperature heat pump device
WO2015136981A1 (en) * 2014-03-14 2015-09-17 三菱電機株式会社 Compressor and refrigeration cycle system
CN107841290A (en) * 2016-09-19 2018-03-27 福特全球技术公司 Suitable for fixed or mobile air conditioner system R 744 and R 1234yf refrigerant mixture
CN110832051A (en) * 2018-06-13 2020-02-21 日立江森自控空调有限公司 Refrigerant composition and refrigeration cycle device using same

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