CN111073602A - Composition for improving refrigeration energy efficiency of HFO1234yf - Google Patents
Composition for improving refrigeration energy efficiency of HFO1234yf Download PDFInfo
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- CN111073602A CN111073602A CN201911232768.0A CN201911232768A CN111073602A CN 111073602 A CN111073602 A CN 111073602A CN 201911232768 A CN201911232768 A CN 201911232768A CN 111073602 A CN111073602 A CN 111073602A
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- olefin
- hfo1234yf
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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
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- 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 discloses a composition for improving the refrigeration energy efficiency of HFO1234yf, which comprises a refrigerant HFO1234yf, refrigeration lubricant PVE, solubilizer anhydrous ethanol and a high-polarity metal protective agent, and comprises, by mass, HFO1234 yf: 85%, PVE: 12%, anhydrous ethanol: 1%, and a metal protective agent: 2%, wherein the metal protective agent is selected from chlorinated poly α -olefin or chlorinated alkane, and the chlorinated poly α -olefin is prepared by reacting poly α -olefin with chlorine.
Description
Technical Field
The invention relates to a refrigerant composition, in particular to a composition for improving the refrigeration energy efficiency of HFO1234 yf.
Background
For a china having the automobile industry as the backbone industry and keeping more than 3.2 hundred million motor vehicles, the enormous energy consumption and the resulting environmental problems have attracted great attention from all parties. The air conditioning system as a standard automobile provides comfortable environment for drivers and passengers, and further increases energy consumption and environmental pollution. In order to relieve environmental stress caused by the use of an automobile air conditioner, the direction from function improvement to efficiency improvement of the automobile air conditioner is changed. At present, countries in Europe, America, Japan and the like have already proposed relevant regulations to encourage the application of high-efficiency air conditioning technology, and the automobile air conditioning society in China also proposes a relevant matching method for encouraging the use of high-efficiency air conditioning.
The air conditioner is used for realizing energy transfer, and the same is true of the automobile air conditioner. In summer, the purpose of using the air conditioner is to transfer heat in the driving space of the automobile to the environment. The energy transfer mode of the automobile air conditioner is realized by absorbing heat in a riding space when a circulating refrigerant in an evaporation box is evaporated and discharging the absorbed heat to an environment space outside the riding space by a condenser, and the specific process comprises the following steps: the low-boiling-point liquid-phase refrigerant absorbs heat in the riding environment when being evaporated to be low-temperature and low-pressure refrigerant vapor in the evaporation tank, then the low-temperature and low-pressure refrigerant vapor is pumped into the compression cavity of the compressor to be compressed into high-temperature and high-pressure refrigerant vapor and sent into the condenser, the high-temperature and high-pressure refrigerant vapor exchanges heat with the environment in the condenser, the heat absorbed in the riding environment is released and condensed into liquid refrigerant, and the liquid refrigerant enters the evaporation tank through the throttling device to be evaporated again to absorb heat so as to transfer the heat of the riding space to the environment. In the process, the evaporation tank and the condenser play the roles of absorbing and releasing heat, and the heat exchange efficiency of the absorption and the release of the heat directly determines the quality and the efficiency of the refrigeration performance of the air conditioner. One index that most reflects the Performance Of the cooling efficiency Of an air conditioner is the "Coefficient Of cooling Performance", which is expressed by COP (COP is an abbreviation for Coefficient Of Performance), and it refers to the ratio Of cooling capacity that can be obtained per unit power consumption. The obtained cold quantity refers to the heat quantity absorbed by the evaporation box and is expressed by the refrigerating capacity. The formula is expressed as: COP is the refrigerating capacity/input power, and the coefficient is an important technical and economic index of a refrigerating system (refrigerator). The refrigeration coefficient of performance is large, and the energy utilization efficiency of the refrigeration system is high.
The combination of a tetrafluoropropene (HFO1234yf) refrigerant and a polyvinyl Ether (Poly Vinyl Ether, PVE) refrigeration lubricant oil has been largely used as a refrigeration cycle composition in the latest type of environment-friendly automotive air conditioning system at present. Wherein HFO1234yf absorbs and releases heat to complete heat transfer during system phase change and PVE is responsible for lubricating moving parts such as compressor to avoid excessive wear and failure of the moving parts. However, in the evaporation tank, since the temperature is low and the liquid HFO1234yf is evaporated in a large amount, the viscosity of the liquid composition consisting of HFO1234yf and PVE increases and the fluidity deteriorates, and therefore PVE does not easily flow back to the compressor portion, so that it is necessary to use a higher proportion of PVE in the system. The compressor is mainly used for compressing HFO1234yf gas, when the usage of PVEs in the refrigeration system is increased, the quantity of PVEs sucked into the compression chamber of the compressor is correspondingly increased, the occupation ratio of HFO1234yf gas is correspondingly reduced, and the volumetric efficiency of the compressor is reduced, so that the refrigeration effect of the automobile air conditioner is reduced. And reducing the proportion of the PVE can cause excessive abrasion of metal moving parts of the compressor, thus shortening the service life of the metal moving parts, and an anti-wear agent, an extreme pressure agent and the like are required to be additionally added for enhancing the lubricity and the reliability of the moving parts of the compressor and the like. In addition, the PVEs form an adsorption film on the aluminum pipe wall due to adsorption, and heat in the riding space is conducted to the PVEs with a small amount of HFO1234yf dissolved on the pipe wall through the aluminum pipe wall of the evaporation box, and then the PVEs conduct the heat to the steam of HFO1234yf with lower temperature to complete heat exchange. In the heat conduction process, the heat exchange efficiency of the process is greatly reduced because the PVE film adsorbed on the tube wall has high thermal resistance and certain thickness. In the condenser of another heat exchange component, because more high-temperature liquid HFO1234yf is almost miscible with PVE, the HFO1234yf and PVE composition has low viscosity and high flow speed, and PVE is not easy to accumulate, so its heat exchange efficiency is slightly higher than that of the evaporation tank. Even if the PVEs in the composition have certain polarity, the PVEs can still form a high-strength and certain-thickness oil film with the surface of the aluminum condenser pipe under the conditions of higher temperature, lower viscosity and higher flow speed of the condenser, and the oil film with low thermal conductivity coefficient can prevent the heat transfer in the condenser.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a refrigerant composition, which can effectively protect the parts of a compressor and prolong the service life of the parts of the compressor under the condition of reducing the using amount of refrigeration lubricant in an automobile air-conditioning system, and can better improve the heat conduction effect of a condenser and an evaporation tank and improve the refrigeration coefficient of an air conditioner.
The technical scheme adopted by the invention for solving the technical problems is as follows: a composition for improving the refrigeration energy efficiency of HFO1234yf, which comprises a refrigerant HFO1234yf, a refrigerant lubricant PVE, a solubilizer anhydrous ethanol and a highly polar metal protectant.
The composition comprises the following components in percentage by mass:
HFO1234yf：83～85％
PVE：12～15％
anhydrous ethanol: 1 percent of
Metal protecting agent: 1 to 2 percent.
Wherein the metal protective agent is selected from chlorinated poly α -alkene or chlorinated alkane, and the chlorinated poly α -alkene is prepared from poly α -alkene and chlorine gas by the following specific method:
(1) charging a chlorination reactor with 70% by volume of a commercially available poly α -olefin;
(2) introducing liquid chlorine into a liquid chlorine gasifier through a regulating valve to maintain the pressure of the gasifier at 195-198 kPa, and opening a needle valve of a flow meter to introduce chlorine into a chlorination reactor;
(3) starting an ultraviolet lamp arranged in the chlorination reactor, performing chlorination activation treatment, and controlling the reaction temperature to be 40-60 ℃;
(4) when the reactants in the chlorination reactor are amber, stopping introducing chlorine and turning off the ultraviolet lamp to obtain a crude chlorinated poly α -olefin product;
(5) and (2) feeding the crude chlorinated poly α -olefin into a degassing tower, degassing for 3-4 hours to remove hydrogen chloride contained in the crude chlorinated poly α -olefin and unreacted chlorine, neutralizing the crude chlorinated poly α -olefin by using 40% caustic soda at 100 ℃ until the pH value is 6-7, and finally dehydrating and filtering to obtain the required poly α -olefin.
The amount of chlorine atoms in the chlorinated poly α -olefin can be controlled by controlling the reaction time and the rate of chlorine gas introduction.
The chlorinated alkane can be chlorinated paraffin-40 or chlorinated paraffin-42.
Preferably, the composition comprises the following components in percentage by mass:
HFO1234yf：85％，
PVE：12％，
anhydrous ethanol: 1 percent of the total weight of the mixture,
metal protecting agent: 2 percent.
HFO1234yf of the above-mentioned composition has a molecular formula of CF3CF＝CH2The molecular weight is 114, the boiling point is-29.5 ℃, the critical temperature is 94.7 ℃ and the critical pressure is 3.38 MPa.
The poly α -olefin in the above components is mainly C10, and has a flash point of 260 deg.C, a pour point of-45 deg.C, and a viscosity index of 133 VI.
The chlorinated alkane in the above components has a molecular formula of C25H45Cl7The molecular weight is 594.81, the freezing point is-30 ℃, and the relative density is 1.16g/cm3The flash point was 298.4 ℃.
PVE in the above composition has a molecular formula of CH2OR ═ CH-OR, R is alkyl OR aryl.
The anhydrous ethanol in the above components has molecular formula of CH3CH2-OH, molecular mass 40.07, boiling point 78.3 ℃, critical temperature 243.1 ℃ and critical pressure 6.38 MPa.
Compared with the prior art, the refrigerant composition provided by the invention has the following advantages:
the chlorinated poly α -olefin or chlorinated alkane with higher polarity relative to the frozen lubricating oil can reduce the adsorption of a high thermal resistance frozen lubricating oil film on the surface of a heat exchange aluminum pipe by 'competitive adsorption', because the chlorinated poly α -olefin or chlorinated alkane has low thermal resistance and the adhesion thickness is only molecular, the thermal resistance and the higher heat transfer efficiency are lower, and the viscosity of the solubilizer in the composition can be reduced, so that the frozen lubricating oil in a low-temperature partial evaporation tank can be more easily refluxed and the power consumption of a conveying cycle is reduced, thereby simultaneously effectively improving the heat exchange efficiency of a condenser and an evaporator and the refrigeration performance of an automobile air conditioner.
Detailed Description
The present invention will be described in further detail with reference to examples.
First, experiments were conducted using only HFO1234yf and PVE as circulating compositions, and the optimum usage ratio of PVE was screened when no metal protectant and no solubilizer were introduced into the composition. The ratio of refrigerant to refrigeration lubricant is 60: 40. 65: 35. 70: 30. 75: 25. 80: 20. 85: 15. 84: 16. 83: 17 the refrigeration performance coefficients of the automobile air conditioner are respectively tested under the simulation conditions of the same working conditions, and the results are as follows:
| PVE(％) | 40 | 35 | 30 | 25 | 20 | 17 | 16 | 15 |
| COP | 1.77 | 1.91 | 2.02 | 2.19 | 2.28 | 2.35 | 2.44 | 2.52 |
from the above experimental results, it was found that the energy efficiency ratio was improved correspondingly as the use ratio of the frozen lubricating oil in the circulating composition was decreased. However, when the proportion of the frozen lubricating oil used is reduced to 17%, the noise generated by the refrigeration compressor begins to appear and is more significant as the proportion of the frozen lubricating oil is reduced, and the temperature rise of the refrigeration compressor also begins to rise significantly (the exhaust temperature begins to rise), because the system lubrication conditions of the compressor are deteriorated due to the reduction of the proportion of the frozen lubricating oil used. Therefore, the use ratio of the refrigeration lubricant should be not less than 17% when the metal protectant and solubilizer are not introduced into the composition.
Examples
The refrigerant composition added with metal protective agent chlorinated poly α -olefin or chlorinated alkane and solubilizer absolute ethyl alcohol is prepared by the following steps:
the preparation method comprises the steps of fully mixing PVE and chlorinated poly α -olefin or chlorinated alkane at normal temperature and normal pressure to form a uniform-phase liquid mixture, adding solubilizer absolute ethyl alcohol into the liquid mixture to fully mix the PVE and the chlorinated poly α -olefin or the chlorinated alkane to form a uniform phase, and finally adding refrigerant HFO1234yf into the obtained ternary mixed liquid to fully dissolve the ternary mixed liquid to obtain the refrigerant composition.
Although chlorinated poly α -olefin or chlorinated alkane and PVE can be freely miscible without limitation, the solubility between chlorinated poly α -olefin or chlorinated alkane, PVE, or a mixture comprising the two and refrigerant is limited, and particularly, delamination occurs due to the reduction of the solubility in the low-temperature environment of the evaporation chamber, so that the solubilizer anhydrous ethanol needs to be introduced, and the solubilizer itself does not have a heat transfer effect, so that the solubilizer anhydrous ethanol is used in an amount such that the components are just completely dissolved.
After refrigerant compositions with different mass fraction ratios are prepared according to the method, performance tests are respectively carried out, and the results are shown in table 1, wherein:
testing the heat exchange performance of the condenser and the evaporator: the test is carried out in a closed heat preservation circulating system which comprises a 570mm multiplied by 350mm multiplied by 20mm universal parallel flow automobile air conditioner condenser, a driving device which is a set of variable-frequency variable-speed 4KW motor, a set of heater which can adjust power and has rated maximum electric heating power of 2KW, an SSJ96 air conditioner sliding sheet type circulating pump, a throttling device which is a throttling hole pipe with the diameter of 1.2mm and the length of 50mm, a calorimeter which can control the heat absorption (release) environment to be between 40 ℃ below zero and 85 ℃ and a temperature, pressure and flow transmitter with the capacity of 170L. Comparison of the circulating compositions of the different components, respectively, simulates the heat exchange performance of a mobile composition of 85 ℃ in the condenser to the medium in the calorimeter at a temperature of 32 ℃ and of a mobile composition of 3 ℃ in the evaporator to the medium in the calorimeter at a temperature of 25 ℃ under operating ambient conditions of the automotive air conditioner.
Testing the change of the refrigeration performance coefficient of the automobile air conditioner: the test is carried out in a closed heat preservation circulating system consisting of a universal parallel flow automobile air conditioner condenser with the size of 640mm multiplied by 420mm multiplied by 25mm, a driving device which is a set of variable-frequency variable-speed 4KW motor, a set of heater with adjustable power and rated maximum electric heating power of 6KW, a YFB508, a fixed-displacement reciprocating piston type air conditioner compressor with the displacement of 164cc/r, a popular Passat B5 governing evaporation box, a throttling device which is a throttling hole pipe with the diameter of 1.4mm and the length of 80mm, a calorimeter with the capacity of 220L and capable of controlling the heat absorption (heat release) environment to be between-40 ℃ and 85 ℃, a temperature transmitter, a pressure transmitter, a flow transmitter, a dynamic torque sensor (capable of measuring torque, rotating speed and instantaneous power) and the like. The experiment adopts national standard (GB5773-04) second refrigerant calorimetry to measure the shaft input power and the refrigerating capacity of the refrigerating compressor and obtain the value of the coefficient of performance (COP) according to the measurement. The test compares the COP of different component circulating compositions under the operating condition of simulating an automobile air conditioner at the engine speed of 1800 rpm and the ambient temperature of 35 ℃.
Testing of the composition for changes in the antiwear Properties of metals: the test was carried out on a four-ball machine produced by Shanghai laboratory instruments and factories according to SH/T0189-92 "method for measuring antiwear properties of lubricating oils". The test ball is a chromium alloy steel ball with the diameter of 12.7mm and the material of Gcr15, and the Rockwell hardness of the test ball is HRC64-66 standard special test ball. The experimental parameters of the long grinding experiment are as follows: the test is carried out under the conditions of load 392N, rotating speed 1200 rpm and test time 60 minutes, and the abrasion spot diameter values of the three test balls are used as test reference comparison results. The test compares the ball wear spot diameters of different compositions, respectively, the smaller the value of the ball wear spot diameter, the better the abrasion resistance.
Table 1: examples 1-4 compare performance.
The results show that the addition of the metal protective agent to chlorinate poly α -olefin or chlorinated alkane can effectively reduce the consumption of the refrigeration lubricant, along with the reduction of the consumption, the heat exchange efficiency and the refrigeration efficiency of a condenser and an evaporation tank in an automobile air-conditioning system are improved, and the metal antiwear performance is obviously improved by introducing the chlorinated poly α -olefin or chlorinated alkane, but when the consumption of the refrigeration lubricant is lower than 12 percent, the compressor begins to be abnormal, so the optimal proportion of the refrigerant composition is HFO1234 yf: 85% + PVE: 12% + anhydrous ethanol: 1% + metal protective agent: 2%, under the condition, the consumption of the refrigeration lubricant in the automobile air-conditioning refrigeration system is reduced to 12 percent from the original 17 percent, the heat release efficiency of the condenser and the heat release efficiency of the evaporation tank are respectively improved by 2.87 percent and 7.83 percent, and the COP is improved by 7.89 percent.
The refrigerant composition has the following action principle:
when more polar chlorinated poly α -alkene or chlorinated alkane coexists in liquid state with PVE of lower relative polarity on the heat exchange surface of the condenser or evaporator, chlorinated poly α -alkene or chlorinated alkane is electronegative due to the uneven distribution of electron clouds in the molecule, so that the acting force of the chlorinated poly α -alkene or chlorinated alkane with the metal surface increases the electrostatic association force in addition to the van der Waals force, which is much stronger than the adhesion of the PVE film to the metal surface by the intermolecular van der Waals force alone, therefore, chlorinated poly α -alkene or chlorinated alkane easily replaces the PVE adhered to the metal surface, and the substitution of chlorinated poly α -alkene or chlorinated alkane of lower thermal resistance to the PVE film of higher thermal resistance, which results in greatly improved heat exchange performance of the condenser and evaporator, the substitution of chlorinated poly α -alkene or chlorinated alkane of lower coefficient of friction, which easily generates a chemical protective film between the friction pair of the compressor moving relatively at higher temperature of boundary lubrication, which can both extend the service life of the compressor and provide better lubricity and reduce the friction coefficient of input of PVE, and thus increase the effective heat exchange efficiency of the PVE by the air conditioner, and the condensation of the PVE by the introduction of the PVE.
Claims (3)
1. The composition for improving the refrigeration energy efficiency of the HFO1234yf is characterized by comprising a refrigerant HFO1234yf, a refrigeration lubricant PVE, a solubilizer anhydrous ethanol and a high-polarity metal protective agent, wherein the composition comprises, by mass, 83-85% of HFO1234yf, 12-15% of PVE, 1% of anhydrous ethanol and 1-2% of a metal protective agent, the metal protective agent is selected from chlorinated poly α -olefin or chlorinated alkane, and the chlorinated poly α -olefin is prepared by reacting poly α -olefin with chlorine.
2. The composition for improving the refrigeration energy efficiency of HFO1234yf according to claim 1, wherein said chlorinated poly α -olefin is prepared by the following specific method:
(1) charging poly α -olefin in an amount of 70% by volume of the chlorination reactor;
(2) introducing liquid chlorine into a liquid chlorine gasifier through a regulating valve to maintain the pressure of the gasifier at 195-198 kPa, and opening a needle valve of a flow meter to introduce chlorine into a chlorination reactor;
(3) starting an ultraviolet lamp arranged in the chlorination reactor, performing chlorination activation treatment, and controlling the reaction temperature to be 40-60 ℃;
(4) when the reactants in the chlorination reactor are amber, stopping introducing chlorine and turning off the ultraviolet lamp to obtain a crude chlorinated poly α -olefin product;
(5) and (2) feeding the chlorinated poly α -olefin crude product into a degassing tower, degassing for 3-4 hours to remove hydrogen chloride contained in the chlorinated poly α -olefin crude product and unreacted chlorine, neutralizing the chlorine with 40% caustic soda at 100 ℃ to reach the pH = 6-7, and finally dehydrating and filtering to obtain the required poly α -olefin.
3. The composition for improving the refrigeration energy efficiency of HFO1234yf according to claim 1, wherein the composition is, in terms of mass percent, HFO1234 yf: 85%, PVE: 12%, absolute ethyl alcohol: 1%, metal protecting agent: 2 percent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911232768.0A CN111073602A (en) | 2019-12-05 | 2019-12-05 | Composition for improving refrigeration energy efficiency of HFO1234yf |
| PCT/CN2020/133231 WO2021110008A1 (en) | 2019-12-05 | 2020-12-02 | Composition for improving refrigeration energy efficiency of hfo1234yf |
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| WO2021110008A1 (en) * | 2019-12-05 | 2021-06-10 | 鸿蒙科技(浙江)有限公司 | Composition for improving refrigeration energy efficiency of hfo1234yf |
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