CN106543964B - Stabilizer composition suitable for HFC-161 and mixed working medium containing HFC-161 - Google Patents

Stabilizer composition suitable for HFC-161 and mixed working medium containing HFC-161 Download PDF

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CN106543964B
CN106543964B CN201610910375.0A CN201610910375A CN106543964B CN 106543964 B CN106543964 B CN 106543964B CN 201610910375 A CN201610910375 A CN 201610910375A CN 106543964 B CN106543964 B CN 106543964B
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stabilizer composition
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stabilizer
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CN106543964A (en
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郭智恺
谢品赞
方小青
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Zhejiang Chemical Industry Research Institute Co Ltd
Zhejiang Lantian Environmental Protection Hi Tech Co Ltd
Sinochem Lantian Co Ltd
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Zhejiang Chemical Industry Research Institute Co Ltd
Zhejiang Lantian Environmental Protection Hi Tech Co Ltd
Sinochem Lantian Co Ltd
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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
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses a stabilizer composition suitable for HFC-161 and mixed working media containing HFC-161, which consists of two components, wherein: the first component is one or the combination of two or more than three of 4-methoxyphenol, 2-hydroxy-4-methoxybenzophenone, 4-tert-butylcatechol, 2-bis- (4-hydroxyphenyl) propane and benzophenone; the second component is diethylene glycol dimethyl ether and/or diethylene glycol monomethyl ether. The stabilizer composition provided by the invention can ensure that HFC-161 circulating in a refrigeration system is not decomposed at the high temperature of 175 ℃.

Description

Stabilizer composition suitable for HFC-161 and mixed working medium containing HFC-161
Technical Field
The invention relates to a stabilizer composition, in particular to a stabilizer composition suitable for a refrigerating system containing HFC-161.
Background
HCFC-22 has excellent physicochemical and thermodynamic properties and good use safety and economy, and becomes a refrigerant with the widest application and the highest comprehensive performance in the refrigeration and air-conditioning industry at home and abroad, but HCFC-22 has higher GWP (global warming potential) value and ODP (ozone depletion potential) value, is not environment-friendly and is a substance which is required to be eliminated for a limited period of time.
For the R22 substitute, not only the environmental performance with zero ODP and low GWP is required, but also the service performance similar to the environmental performance is required, and HFC-161 is one of the ideal R22 substitutes at present. The ODP value of HFC-161 is zero, the GWP value is 12, not only the environmental performance is excellent, but also can substitute and use in the system that uses R22 originally directly, the consumption can reduce by 45%, the refrigerating and heating ability is close to R22, the energy efficiency improves more than 10%, have low, advantage such as being few of consumption, energy-conserving of replacing cost.
But HFC-161 is as monofluoro halohydrocarbon, because of the chemical structure property of its own, its stability is inferior to bifluoride or many fluorine substituted halohydrocarbon, it is apt to produce the decomposition phenomenon at the high temperature above 175 duC, the decomposition product will influence the reliability of use and life-span of the system, therefore must add suitable stabilizer among them, guarantee its stability under high temperature, in order to fully utilize HFC-161 excellent performance, expand the field of use, play a positive role in reducing climate change.
No stabilizers suitable for HFC-161 have been reported in the prior art.
Disclosure of Invention
The invention aims to provide a stabilizer composition suitable for HFC-161 and mixed working media containing HFC-161, which can be added into lubricating oil of a compressor of a refrigeration system and can also be directly added into liquid-phase HFC-161, so that the stability of the HFC-161 can be ensured at the high temperature of 175 ℃, the HFC-161 circulating in the refrigeration system can be kept stable, and the stable and normal operation of the refrigeration system can be ensured.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
a stabilizer composition suitable for HFC-161 and HFC-161 containing mixed working fluids, said stabilizer composition consisting of two, wherein:
the first component is one, two or more than three of 4-methoxyphenol (PHA), 2-hydroxy-4-methoxybenzophenone (HMBP), 4-tert-butylcatechol (TBC), 2-bis- (4-hydroxyphenyl) propane (BPA) and Benzophenone (BP);
the second component is diethylene glycol dimethyl ether (abbreviated as "DDM") and/or diethylene glycol methyl ether (abbreviated as "DM").
Preferably, the first component is one, two or three of 4-methoxyphenol, 2-hydroxy-4-methoxybenzophenone and 4-tert-butylcatechol.
The mass ratio of the first component to the second component is preferably 1: 1-2, and more preferably 1: 1.
The stabilizer composition is suitable for a refrigerating system using HFC-161 or mixed working medium containing HFC-161 as a refrigerant, and the mass ratio of the stabilizer composition to lubricating oil applicable to the refrigerating system is preferably 1-5% to 1, and more preferably 2-3% to 1.
The stabilizer composition can be directly added into a liquid-phase HFC-161 or mixed working medium containing HFC-161, and the mass ratio of the stabilizer composition to the HFC-161 or mixed working medium containing HFC-161 is preferably 1-5% to 1, and more preferably 2-3% to 1.
The stabilizer combination provided by the invention has the following advantages:
(1) the stabilizer composition has stable performance, can not be decomposed at the high temperature of 175 ℃, and can not influence the parts of the refrigeration system;
(2) can be added into lubricating oil, has no influence on the performance of the lubricating oil, and can ensure that HFC-161 circulating in a refrigeration system is not decomposed at the high temperature of 175 ℃.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The stabilizer composition is prepared by the steps of combining a first component and a second component which are selected from one, two or more than three of 4-methoxyphenol (PHA), 2-hydroxy-4-methoxybenzophenone (HMBP), 4-tert-butylcatechol (TBC), 2-bis- (4-hydroxyphenyl) propane (BPA) and Benzophenone (BP) according to mass percent, and then adding the liquid composition into compressor lubricating oil of a refrigerating system using HFC-161 or mixed working medium containing HFC-161 as a refrigerant, wherein the mass ratio of the stabilizer composition to the lubricating oil is controlled to be 1-5% to 1, preferably 2-3% to 1. The second preparation method is that the first component and the second component are directly added into HFC-161 or mixed working medium containing HFC-161 in liquid phase according to mass percentage, and the mass ratio of the stabilizer composition to HFC-161 or mixed working medium containing HFC-161 is controlled to be 1 percent to 5 percent, 1 percent, preferably 2 percent to 3 percent to 1 percent.
4-methoxyphenol (PHA) in the above stabilizer composition, formula: c7H8O2(ii) a Molecular weight: 124.14 of the total weight of the mixture; CAS number: 150-76-5; melting point: 55-57 ℃; boiling point: 243 ℃.
2-hydroxy-4-methoxybenzophenone (HMBP) in the above described stabilizer composition has the formula: c14H12O3(ii) a Molecular weight: 228.24, respectively; CAS number: 131-57-7; melting point: 62-64 ℃; boiling point: 150 ℃ and 160 ℃.
4-tert-butylcatechol (TBC) in the above stabilizer composition, formula: c10H14O2Molecular weight: 166.22, respectively; CAS number: 98-29-3; melting point: 56-57 ℃; boiling point: 285 deg.C.
2, 2-bis (4-hydroxyphenyl) propane (BPA) in the above stabilizer composition, formula: c15H16O2Molecular weight: 228.29, respectively; CAS number: 80-05-7; melting point: 155-158 ℃; boiling point: 250 ℃ and 252 ℃.
Benzophenone (BP) of formula C in the above stabilizer composition13H10O, molecular weight 182.22, CAS number: 119-61-9; melting point: 47-49 ℃; boiling point: 305 ℃.
Diethylene glycol dimethyl ether (DDM) of the above stabilizer composition, molecular formula C6H14O3(ii) a Molecular weight 134.18; CAS number: 111-96-6; a liquid; boiling point: 159.76 deg.C.
Diethylene glycol monomethyl ether (DM) in the stabilizer composition has a molecular formula of C5H12O3Molecular weight 120.15, CAS number: 111-77-3; a liquid; boiling point: 194 ℃ is used.
The lubricating oil can be mineral oil such as 3GS, 4GS, and the like and ester oil such as T68, SL32, and the like which are commonly used for a compressor of a refrigeration system.
Example 1: PHA, DDM, HFC-161, 4GS lubricating oils were physically blended in a mass of 1.5 g, 100 g, respectively.
Example 2: TBC, DDM, HFC-161, 3GS lubricating oils were physically blended in a mass of 1.5 grams, 100 grams, respectively.
Example 3: BPA, DM, HFC-161, 4GS lubricating oils were physically blended in the mass ranges of 2.5 g, 100 g, respectively.
Example 4: HMBP, DDM, HFC-161, 4GS lubricating oils were physically blended in masses of 0.5 grams, 100 grams, respectively.
Example 5: BP, DM, HFC-161, T68 lubricants were physically blended in a mass of 1.0 g, 100 g, respectively.
Example 6: the lubricating oils HMBP, DM, HFC-161, SL32 were physically blended in a mass of 1.5 grams, 100 grams, respectively.
Example 7: TBC, DDM, HFC-161 were physically mixed in a mass of 1.5 g, 100 g, respectively.
Example 8: HMBP, DM, HFC-161 were physically mixed in masses of 0.5 grams, 100 grams, respectively.
Example 9: PHA, DDM, HFC-161 were physically mixed in a mass of 2.5 grams, 100 grams, respectively.
Example 10: BP, DM, HFC-161 were physically mixed in a mass of 1.5 g, 100 g, respectively.
Comparative example 1: HFC-161 and 4GS lubricating oils were physically mixed in a mass of 100 g and 100 g, respectively.
Comparative example 2: HFC-161 and T68 lubricating oils were physically blended in a mass of 100 g and 100 g, respectively.
Comparative example 3: 100 grams by mass of HFC-161.
The above examples and comparative examples were sealed in a pressure-resistant container together with metallic materials of iron and copper, and after heat preservation at 175 ℃ for 14 days (336 hours), detection of the acidity and fluoride ion concentration of HFC-161 and detection of the acidity of lubricating oil were carried out to determine whether or not HFC-161 is pyrolyzed by detecting the acidity and fluoride ion concentration, thereby determining the effect of the stabilizer. The specific results are shown in table 1 below.
TABLE 1 test results of acidity and fluoride ion concentration of the experimental samples
Figure BDA0001133850780000041
As can be seen from the table, in comparative examples 1 and 2 in which no stabilizer composition was added, HFC-161 had a certain acidity and a certain fluoride ion concentration was detected, indicating that HFC-161 was decomposed under the experimental conditions. In comparative example 3, although no acidity or fluoride ion was detected in the HFC-161 test sample, the test metal was corroded, which indicates that HFC-161 was also decomposed, but the decomposition product chemically reacted with the test metal, so that no acidity or fluoride ion was detected in the HFC-161 test sample. On the other hand, in examples 1 to 10 using the stabilizer, neither acidity nor fluoride ion was detected, and the acidity of the lubricating oil was satisfactory, so that it was demonstrated that the stabilizer composition of the present invention has a significant inhibitory effect on the pyrolysis of HFC-161 and can be used as a stabilizer for HFC-161.

Claims (5)

1. A refrigerant composition characterized by:
the refrigerant composition consists of HFC-161 and a stabilizer composition, the mass ratio of the stabilizer composition to the HFC-161 is 1 to 5 percent, and the stabilizer composition consists of two components, wherein:
the first component is one or the combination of two or more than three of 4-methoxyphenol, 2-hydroxy-4-methoxybenzophenone, 4-tert-butylcatechol, 2-bis- (4-hydroxyphenyl) propane and benzophenone;
the second component is diethylene glycol dimethyl ether and/or diethylene glycol monomethyl ether;
the mass ratio of the first component to the second component is 1: 1.
2. A refrigerant composition as set forth in claim 1 wherein:
the first component is one, two or three selected from 4-methoxyphenol, 2-hydroxy-4-methoxybenzophenone and 4-tert-butylcatechol.
3. Use of a refrigerant composition as claimed in claim 1 wherein: the stabilizer composition is used for a refrigerating system, and the mass ratio of the stabilizer composition to lubricating oil in the refrigerating system is 1-5% to 1.
4. Use of a refrigerant composition as claimed in claim 3 wherein: the mass ratio of the stabilizer composition to the lubricating oil in the refrigeration system is 2-3% to 1.
5. A refrigerant composition as set forth in claim 1 wherein: in the refrigerant composition, the mass ratio of the stabilizer composition to HFC-161 is 2-3 percent to 1.
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CN104449580B (en) * 2013-09-24 2018-01-26 中化蓝天集团有限公司 A kind of composition containing HFC 161 and stabilizer
CN104388058B (en) * 2014-10-21 2017-07-04 朝阳光达化工有限公司 The two-way temperature refrigerating medium wide of low viscosity ultralow temperature
CN105754682B (en) * 2014-12-18 2019-01-29 上海海立电器有限公司 Compressor and freeze oil and compressor refrigerant mixture
CN106967388A (en) * 2017-03-06 2017-07-21 唐建 A kind of environment-protecting mixed refrigerating agent preparation method for substituting monochlorodifluoromethane
CN110373157B (en) * 2019-07-22 2020-11-10 珠海格力电器股份有限公司 Refrigerant composition and method for preparing same
CN110591799A (en) * 2019-09-25 2019-12-20 曾成 Engine oil composition for repairing, maintaining and refrigerating system and preparation and use method thereof

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CN101052704A (en) * 2004-11-05 2007-10-10 雅宝公司 Stabilized propyl bromide compositions
CN101528887A (en) * 2006-09-01 2009-09-09 纳幕尔杜邦公司 Epoxide and fluorinated epoxide stabilizers for fluoroolefins
CN101765648A (en) * 2007-07-27 2010-06-30 纳幕尔杜邦公司 compositions comprising fluoroolefins and uses thereof
CN102216411A (en) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 Compositions comprising 2,3,3,3-tetrafluoropropene and hydrocarbons and uses thereof
CN102333839A (en) * 2009-02-26 2012-01-25 大金工业株式会社 Refrigerant composition containing hydrofluoropropane with low-global warming potential

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Publication number Priority date Publication date Assignee Title
CN1297472A (en) * 1999-04-02 2001-05-30 日本能源株式会社 Lubricant for vapor compression refrigerator using hydrocarbon coolant
CN101052704A (en) * 2004-11-05 2007-10-10 雅宝公司 Stabilized propyl bromide compositions
CN101528887A (en) * 2006-09-01 2009-09-09 纳幕尔杜邦公司 Epoxide and fluorinated epoxide stabilizers for fluoroolefins
CN101765648A (en) * 2007-07-27 2010-06-30 纳幕尔杜邦公司 compositions comprising fluoroolefins and uses thereof
CN102216411A (en) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 Compositions comprising 2,3,3,3-tetrafluoropropene and hydrocarbons and uses thereof
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Denomination of invention: Stabilizer composition suitable for HFC-161 and mixed working medium containing HFC-161

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