Energy-saving efficient novel air conditioner refrigerant and preparation method thereof

Abstract

The invention belongs to the technical field of air conditioner refrigerants, and particularly relates to an energy-saving efficient novel air conditioner refrigerant and a preparation method thereof. The invention relates to an energy-saving high-efficiency novel air conditioner refrigerant, which is prepared from the following components in percentage by weight: 20 to 30 percent of propane, 15 to 30 percent of carbon dioxide, 10 to 15 percent of difluoromethane, 10 to 15 percent of pentafluoroethane, 2 to 5 percent of trans-hexafluorobutene, 2 to 5 percent of tetrafluoropropene, 10 to 20 percent of PPG-2000 and 15 to 20 percent of deionized water. The global warming potential value of the refrigerant is remarkably lower than that of traditional Freon and hydrofluorocarbon, the influence on climate change is reduced, chlorine harmful to the ozone layer is not contained, and damage to the ozone layer is avoided; compared with some traditional refrigerants, the refrigerant has low toxicity and is relatively safe during use, meanwhile, the refrigerant can be compatible with an existing refrigerating system to be modified, the requirement for comprehensively replacing equipment is reduced, the refrigerant can provide good thermodynamic performance, and the energy efficiency of the system can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of air-conditioning refrigerants, and in particular relates to an energy-saving and high-efficiency new air-conditioning refrigerant and a preparation method thereof. Background Art

[0002] The earliest refrigeration methods used natural substances such as ice and salt. With the development of industry, mechanical refrigeration technology gradually emerged. In the early 20th century, chemists began to synthesize Freon (CFCs) compounds, which quickly became the main choice of refrigerants due to their excellent thermodynamic properties and stability. In the 1980s, scientists discovered that Freon damaged the ozone layer, causing global climate change issues to attract attention. The signing of the Kyoto Protocol in 1997 prompted the international community to reduce the use of Freon. With the emphasis on environmental impact, alternative refrigerants such as hydrofluorocarbons (HFCs) were developed. Although they do not damage the ozone layer, they still have a greenhouse effect. In recent years, new low global warming potential (GWP) refrigerants such as hydrofluoroolefins (HFOs) have begun to be put into use, committed to reducing the impact of refrigerants on the environment. Countries have successively introduced regulations to restrict the use of high GWP refrigerants, promoting the refrigeration industry to develop in a more environmentally friendly direction.

[0003] Many hydrofluorocarbon (HFCs) refrigerants have high global warming potential and have an adverse impact on climate change. Some refrigerants perform poorly under high or low temperature conditions, which may lead to reduced system efficiency and increased energy consumption. Some refrigerants are flammable or toxic and need to be handled with caution when used, which increases safety risks. Some existing equipment is not suitable for the use of new refrigerants, and the transformation or replacement of equipment requires additional costs and time. Chinese patent publication number CN108148556A discloses an air-conditioning refrigerant that does not contain Freon, but its refrigeration energy consumption is high and the use of hydrofluorocarbons still has a high global warming potential value. Chinese patent publication number CN117844454A discloses an air-conditioning refrigerant composition that has excellent environmental protection effects during use and is less harmful to the body, but still has a small amount of harmful effects on the body and consumes a lot of energy during use.

[0004] In view of the above technical defects, a solution is now proposed. Summary of the invention

[0005] The object of the present invention is to provide a new energy-saving and efficient air-conditioning refrigerant and a preparation method thereof, which has the characteristics of low global warming potential, non-flammability, non-toxicity, energy saving and high efficiency.

[0006] To achieve the above purpose, the present invention adopts the following technical scheme: a new energy-saving and high-efficiency air-conditioning refrigerant is specifically composed of the following percentage components: 20-30% propane, 15-30% carbon dioxide, 10-15% difluoromethane, 10-15% pentafluoroethane, 2-5% trans-hexafluorobutene, 2-5% tetrafluoropropylene, 10-20% PPG-2000, and 15-20% deionized water.

[0007] Furthermore, a method for preparing a new energy-saving and high-efficiency air-conditioning refrigerant comprises the following steps:

[0008] S1: weigh 20-30% propane, 15-30% carbon dioxide, 10-15% difluoromethane, 10-15% pentafluoroethane, 2-5% trans-hexafluorobutene, 2-5% tetrafluoropropylene, 10-20% PPG-2000, and 15-20% deionized water according to the proportion and store for later use;

[0009] S2: Propane, difluoromethane, pentafluoroethane and tetrafluoropropylene are placed in a high-pressure reactor, the pressure is adjusted to 7.8 MPa and mixed, and a vacuum pump is used to evacuate for 30-45 minutes after mixing. After the evacuation is completed, the vacuum valve is closed to maintain the vacuum environment, the temperature is adjusted to minus 20°C, and the mixture is shaken for 20-30 minutes to obtain product A;

[0010] S3: Use a vacuum filter to filter the mixture A into a high-pressure reactor, pump liquid carbon dioxide and deionized water into the high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.8 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 200-300 rpm, and stir at high pressure and low temperature for 1-1.5 hours to obtain product B;

[0011] S4: Pump trans-hexafluorobutene and PPG-2000 into a high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.2 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 400-600 rpm, stir at high pressure and low temperature for 1.5-2 hours, and then let it stand for 20-30 minutes to obtain an energy-saving and high-efficiency new air-conditioning refrigerant.

[0012] Furthermore, the difluoromethane is a colorless transparent difluoromethane liquefied gas; the pentafluoroethane is a colorless transparent pentafluoroethane liquefied gas; the tetrafluoropropylene is a colorless transparent 2,3,3,3-tetrafluoro-1-propylene liquefied gas; the trans-hexafluorobutene is a colorless transparent trans-1,1,1,4,4,4-hexafluoro-2-butene liquefied gas; the propane is a colorless transparent propane liquefied gas; and the carbon dioxide is a colorless transparent carbon dioxide liquefied gas.

[0013] Furthermore, the PPG-2000 is a colorless, transparent, oily, viscous polypropylene glycol liquid.

[0014] In summary, due to the adoption of the above technical scheme, the beneficial effects of the present invention are as follows: the global warming potential value of the refrigerant of the present invention is significantly lower than that of traditional Freon and hydrofluorocarbon, which reduces the impact on climate change, and does not contain chlorine elements that are harmful to the ozone layer and will not cause damage to the ozone layer; compared with some traditional refrigerants, the refrigerant of the present invention has lower toxicity and is relatively safe to use. At the same time, the present invention can be compatible with the existing refrigeration system and reduces the need for comprehensive replacement of equipment. The refrigerant of the present invention can provide good thermodynamic properties and help improve the energy efficiency of the system. DETAILED DESCRIPTION

[0015] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0016] The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials and reagents used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0017] Example 1

[0018] S1: Weigh 400 ml propane, 600 ml carbon dioxide, 200 ml difluoromethane, 200 ml pentafluoroethane, 40 ml trans-hexafluorobutene, 40 ml tetrafluoropropylene, 200 ml PPG-2000, and 300 ml deionized water according to the proportion;

[0019] S2: 400 ml propane, 200 ml difluoromethane, 200 ml pentafluoroethane and 40 ml tetrafluoropropylene are placed in a high-pressure reactor, the pressure is adjusted to 7.8 MPa and mixed, and a vacuum pump is used to evacuate for 45 minutes after mixing. After the evacuation is completed, the vacuum valve is closed to maintain the vacuum environment, the temperature is adjusted to minus 20°C, and the mixture is mixed and shaken for 30 minutes to obtain product A;

[0020] S3: Use a vacuum filter to filter the mixture A into a high-pressure reactor, pump 600 ml of carbon dioxide and 300 ml of deionized water into the high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.8 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 300 rpm, and stir at high pressure and low temperature for 1.5 hours to obtain product B;

[0021] S4: 40 ml of trans-hexafluorobutene and 200 ml of PPG-2000 were pumped into a high-pressure reactor, the pressure of the high-pressure reactor was adjusted to 8.2 MPa and the temperature was adjusted to 4° C., a magnetic stirrer was used, the speed was set to 600 rpm, and the mixture was stirred at high pressure and low temperature for 2 h and then allowed to stand for 30 min to obtain 1.8 L of Example 1.

[0022] Table 1, reagent parameters used in Example 1

[0023] Drug Name source model parameter Propane Chengdu Taiyu Industrial Gas Co., Ltd. 1075 47L carbon dioxide Anhui Yibang Gas Co., Ltd. <![CDATA[CO2]]> 47L Difluoromethane Fluorine Chemical Gas HFC-32 400L Pentafluoroethane Fine Fluorine Technology Co., Ltd. R-125 200L trans-hexafluorobutene Quanzhou Yuji New Material Technology Co., Ltd. 66711-86-2 13.4L Tetrafluoropropylene Zhejiang Huanxin Fluorine Materials Co., Ltd. HFO-1234yf 400L PPG-2000 Jiangsu Haian Petrochemical Plant PPG-2000 1kg

[0024] Example 2

[0025] S1: Weigh 500 ml propane, 400 ml carbon dioxide, 200 ml difluoromethane, 200 ml pentafluoroethane, 100 ml trans-hexafluorobutene, 100 ml tetrafluoropropylene, 200 ml PPG-2000, and 400 ml deionized water according to the proportion;

[0026] S2: 500 ml propane, 200 ml difluoromethane, 200 ml pentafluoroethane and 100 ml tetrafluoropropylene were placed in a high-pressure reactor, the pressure was adjusted to 7.8 MPa for mixing, and after mixing, vacuum was evacuated using a vacuum pump for 45 minutes. After the vacuum was evacuated, the vacuum valve was closed to maintain the vacuum environment, the temperature was adjusted to minus 20°C, and the mixture was mixed and shaken for 30 minutes to obtain product A;

[0027] S3: Use a vacuum filter to filter the mixture A into a high-pressure reactor, pump 400 ml of carbon dioxide and 400 ml of deionized water into the high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.8 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 300 rpm, and stir at high pressure and low temperature for 1.5 hours to obtain product B;

[0028] S4: 100 ml of trans-hexafluorobutene and 200 ml of PPG-2000 were pumped into a high-pressure reactor, the pressure of the high-pressure reactor was adjusted to 8.2 MPa and the temperature was adjusted to 4° C., a magnetic stirrer was used, the speed was set to 600 rpm, and the mixture was stirred at high pressure and low temperature for 2 h and then allowed to stand for 30 min to obtain 1.9 L of Example 2.

[0029] Table 2, reagent parameters used in Example 2

[0030] Drug Name source model parameter Propane Chengdu Taiyu Industrial Gas Co., Ltd. 1075 47L carbon dioxide Anhui Yibang Gas Co., Ltd. <![CDATA[CO2]]> 47L Difluoromethane Fluorine chemical gas HFC-32 400L Pentafluoroethane Fine Fluorine Technology Co., Ltd. R-125 200L trans-hexafluorobutene Quanzhou Yuji New Material Technology Co., Ltd. 66711-86-2 13.4L Tetrafluoropropylene Zhejiang Huanxin Fluorine Materials Co., Ltd. HFO-1234yf 400L PPG-2000 Jiangsu Haian Petrochemical Plant PPG-2000 1kg

[0031] Example 3

[0032] S1: Weigh 600 ml propane, 300 ml carbon dioxide, 300 ml difluoromethane, 300 ml pentafluoroethane, 100 ml trans-hexafluorobutene, 100 ml tetrafluoropropylene, 400 ml PPG-2000, and 400 ml deionized water according to the proportion;

[0033] S2: 600 ml of propane, 300 ml of difluoromethane, 300 ml of pentafluoroethane and 100 ml of tetrafluoropropylene are placed in a high-pressure reactor, the pressure is adjusted to 7.8 MPa for mixing, and after mixing, vacuum is evacuated for 30 minutes using a vacuum pump. After vacuuming, the vacuum valve is closed to maintain the vacuum environment, the temperature is adjusted to minus 20°C, and the mixture is mixed and shaken for 20 minutes to obtain product A;

[0034] S3: Use a vacuum filter to filter the mixture A into a high-pressure reactor, pump 300 ml of carbon dioxide and 400 ml of deionized water into the high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.8 MPa and the temperature to 4°C, use a magnetic stirrer with the speed set to 200 rpm, and stir at high pressure and low temperature for 1 hour to obtain product B;

[0035] S4: 100 ml of trans-hexafluorobutene and 400 ml of PPG-2000 were pumped into a high-pressure reactor, the pressure of the high-pressure reactor was adjusted to 8.2 MPa and the temperature was 4° C., a magnetic stirrer was used, the speed was set to 400 rpm, and high-pressure and low-temperature stirring was performed for 2 h, and then allowed to stand for 30 min to obtain 2.3 L of Example 3.

[0036] Table 3, reagent parameters used in Example 3

[0037] Drug Name source model parameter Propane Chengdu Taiyu Industrial Gas Co., Ltd. 1075 47L carbon dioxide Anhui Yibang Gas Co., Ltd. <![CDATA[CO2]]> 47L Difluoromethane Fluorine chemical gas HFC-32 400L Pentafluoroethane Fine Fluorine Technology Co., Ltd. R-125 200L trans-hexafluorobutene Quanzhou Yuji New Material Technology Co., Ltd. 66711-86-2 13.4L Tetrafluoropropylene Zhejiang Huanxin Fluorine Materials Co., Ltd. HFO-1234yf 400L PPG-2000 Jiangsu Haian Petrochemical Plant PPG-2000 1kg

[0038] Comparative Example 1

[0039] Example 1 of Chinese patent publication number CN108148556A was selected as comparative example 1.

[0040] Comparative Example 2

[0041] Example 1 of the Chinese patent with publication number CN117844454A was selected as comparative example 2.

[0042] Cytotoxicity assay:

[0043] Carbon dioxide was used to dilute Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 to concentrations of 1% and 10%, and Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 of different concentrations were divided into four series, namely, 1% concentration series, 10% concentration series, 100% concentration series and pure carbon dioxide series (blank series); wherein the 1% concentration series, the 10% concentration series and the 100% concentration series respectively comprised Example 1 group, Example 2 group, Example 3 group, Comparative Example 1 group and Comparative Example 2 group, totaling 15 groups, plus one blank series group, totaling 16 groups, and then each group was connected to a carbon dioxide inlet of a cell culture incubator using a rubber hose, and the inlet valve was adjusted to a carbon dioxide content of 5% in the cell culture incubator.

[0044] 1: A cytotoxicity experiment was performed using 293T cells and an MTT kit with a catalog number of M1020 produced by Solarbio to detect the toxic effects of the air-conditioning refrigerants prepared in Example 1, Example 2, Example 3, Comparative Example 1 and Comparative Example 2 on cells.

[0045] 2: The MTT kit used contains MTT solution and Formazan solution.

[0046] 3: Resuscitate and culture 293T cells. Collect logarithmic phase 293T cells one day later, adjust the concentration of cell suspension, and distribute them in 96-well plates, 180ul per well, 3000-10000 cells / well.

[0047] 4: Place the 96-well plate in a constant temperature incubator at 37°C and 5% CO2 for 6 hours. Set up 3 replicate experiments for each group.

[0048] 5: After aspirating the supernatant, add 90ul of fresh culture medium, then add 10ul of MTT solution and continue culturing for 4h.

[0049] 6: Then aspirate the supernatant, add 110ul Formazan solution to each well, place on a shaker and shake for 10 minutes to allow the crystals to fully dissolve. After shaking, transfer the 96-well plate to an ELISA reader and measure the absorbance of each well at 490nm. Take the average value of each group.

[0050] Table 4, MTT cytotoxicity test results

[0051] Grouping Cytotoxicity Cell viability Blank Group Non-toxic / 1% Example 1 Non-toxic / 1% Example 2 Non-toxic / 1% Example 3 Non-toxic / 1%Comparative Example 1 Non-toxic / 1%Comparative Example 2 Non-toxic / 10% Example 1 0.22％ 99.78％ 10% Example 2 0.27％ 99.73％ 10% Example 3 0.17％ 99.83％ 10% Comparative Example 1 2.64％ 97.36％ 10% Comparative Example 2 1.86％ 98.13％ 100% Example 1 1.21％ 98.79％ 100% Example 2 1.23％ 98.77％ 100% Example 3 1.15％ 98.85％ 100% Comparative Example 1 8.45％ 91.55％ 100% Comparative Example 2 5.27％ 94.73％

[0052] It can be seen from Table 4 that the cytotoxicity of Example 1, Example 2 and Example 3 is basically negligible when the dilution ratio is 10%, and there is no cytotoxicity when the dilution ratio is 1%. At the same time, under the condition that no carbon dioxide dilution is used, Comparative Example 1 and Comparative Example 2 have a small amount of cytotoxicity.

[0053] Energy saving experiment:

[0054] 1: Select a model house as the experimental site, and place a commercially available KFR-51LW / BDN8Y-YA400(3)A model vertical air conditioner in the corner of the living room and connect it to the electricity meter.

[0055] 2: Turn on the air conditioner and adjust it to cooling mode, connect the refrigerant pipe to the external unit interface, use an empty cylinder to release the R-23 refrigerant in the original air conditioner external unit, then close the cylinder valve after 30 minutes, and remove the refrigerant pipe after observing that the pressure gauge reading returns to zero;

[0056] 3: Connect the refrigerant cylinder and the refrigerant pipe to the external unit interface, open the three-way valve of the refrigerant cylinder valve and the pressure gauge to fill for 10-15 minutes;

[0057] 4: Adjust the air conditioner temperature to 24℃, use a thermometer to observe the temperature in the room, and record the electricity data for maintaining 24℃ for 1 day. Repeat twice;

[0058] 5: Change the refrigerant in the refrigerant cylinder to Example 2, Example 3, Comparative Example 1 and Comparative Example 2, and repeat steps 2-4, and record the electricity consumption data.

[0059] Table 5, Energy saving experiment results

[0060] Group Energy consumption on the first day Energy consumption on the second day Energy consumption on the third day Average energy consumption Example 1 36.36° 36.34° 36.36° 36.35° Example 2 36.48° 36.47° 36.49° 36.48° Example 3 36.96° 36.94° 36.92° 36.94° Comparative Example 1 38.40° 38.42° 38.44° 38.42° Comparative Example 2 39.60° 39.64° 39.62° 39.62°

[0061] By analyzing Table 5, it can be seen that the air-conditioning refrigerants prepared by Example 1, Example 2 and Example 3 have obvious energy-saving effects compared with the air-conditioning refrigerants prepared by Comparative Example 1 and Comparative Example 2, among which the air-conditioning refrigerant prepared by Example 1 has the best energy-saving effect.

[0062] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A new energy-saving and high-efficiency air-conditioning refrigerant, characterized in that: The invention is composed of the following percentage components: 20-30% propane, 15-30% carbon dioxide, 10-15% difluoromethane, 10-15% pentafluoroethane, 2-5% trans-hexafluorobutene, 2-5% tetrafluoropropylene, 10-20% PPG-2000 and 15-20% deionized water.

2. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The difluoromethane is colorless and transparent liquefied difluoromethane gas.

3. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The pentafluoroethane is colorless and transparent liquefied pentafluoroethane gas.

4. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The tetrafluoropropylene is a colorless and transparent 2,3,3,3-tetrafluoro-1-propylene liquefied gas.

5. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The trans-hexafluorobutene is a colorless and transparent trans-1,1,1,4,4,4-hexafluoro-2-butene liquefied gas.

6. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The PPG-2000 is a colorless, transparent, oily, viscous polypropylene glycol liquid.

7. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The propane is colorless and transparent liquefied propane gas.

8. The energy-saving and high-efficiency new air-conditioning refrigerant according to claim 1 is characterized in that: The carbon dioxide is colorless and transparent liquefied carbon dioxide gas.

9. The method for preparing a new energy-saving and high-efficiency air-conditioning refrigerant according to claim 1, characterized in that: The following steps are involved: S1: weigh 20-30% propane, 15-30% carbon dioxide, 10-15% difluoromethane, 10-15% pentafluoroethane, 2-5% trans-hexafluorobutene, 2-5% tetrafluoropropylene, 10-20% PPG-2000, and 15-20% deionized water according to the proportion and store for later use; S2: Propane, difluoromethane, pentafluoroethane, trifluoromethane and tetrafluoropropylene are mixed in a high-pressure reactor at a pressure of 7.8 MPa. After mixing, a vacuum pump is used to evacuate for 30-45 minutes. After the evacuation is completed, the vacuum valve is closed to maintain the vacuum environment. The temperature is adjusted to minus 20°C, and the mixture is shaken for 20-30 minutes to obtain product A; S3: Use a vacuum filter to filter the mixture A into a high-pressure reactor, pump liquid carbon dioxide and deionized water into the high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.8 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 200-300 rpm, and stir at high pressure and low temperature for 1-1.5 hours to obtain product B; S4: Pump trans-hexafluorobutene and PPG-2000 into a high-pressure reactor, adjust the pressure of the high-pressure reactor to 8.2 MPa and the temperature to 4°C, use a magnetic stirrer, set the speed to 400-600 rpm, stir at high pressure and low temperature for 1.5-2 hours, and then let it stand for 20-30 minutes to obtain an energy-saving and high-efficiency new air-conditioning refrigerant.