CN115340849B - An environmentally friendly high-temperature heat pump working fluid - Google Patents
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- 239000012530 fluid Substances 0.000 title description 35
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 8
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
- F25B9/006—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant containing more than one component
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/32—The mixture being azeotropic
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- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
Description
技术领域Technical Field
本发明属于高温热泵技术领域，具体涉及一种适用于高温烘干、制药和电镀加热等应用高温热泵的场所的环保高温热泵工质。The present invention belongs to the technical field of high-temperature heat pumps, and in particular relates to an environmentally friendly high-temperature heat pump working fluid suitable for places where high-temperature heat pumps are used, such as high-temperature drying, pharmaceutical manufacturing and electroplating heating.
背景技术Background Art
在全球终端能源消耗量中，制冷和热泵能源消耗量占了50%，能源消耗量具大。2020年9月我国明确提出了“碳中和，碳达峰”目标，其实质是实现低碳转型，以低碳创新推动可持续发展，要实现这些目标，必须均衡工质的循环性能、安全性和可持续性。同时，热泵可以高效利用工业过程中产生的大量低品位余热，是一项重要的节能减排技术，使用量巨大，但目前高温热泵工质的环保性差，所以寻找合适的高温热泵环保工质十分重要。Refrigeration and heat pumps account for 50% of global terminal energy consumption, which is a large amount of energy consumption. In September 2020, my country clearly put forward the goal of "carbon neutrality and carbon peak", the essence of which is to achieve low-carbon transformation and promote sustainable development with low-carbon innovation. To achieve these goals, it is necessary to balance the cycle performance, safety and sustainability of the working fluid. At the same time, heat pumps can efficiently utilize a large amount of low-grade waste heat generated in industrial processes. It is an important energy-saving and emission reduction technology with a huge amount of usage, but the current high-temperature heat pump working fluid has poor environmental protection, so it is very important to find a suitable high-temperature heat pump environmentally friendly working fluid.
发明内容Summary of the invention
本发明的目的在于提供一种环保高温热泵工质，所述工质具有很强的环保特性，ODP为0，GWP小于20，且提供的新工质制热温度可达110℃。The object of the present invention is to provide an environmentally friendly high-temperature heat pump working fluid, which has strong environmental protection characteristics, an ODP of 0, a GWP of less than 20, and the heating temperature of the new working fluid provided can reach 110°C.
本发明采用如下技术方案：The present invention adopts the following technical solution:
本发明给出了第一种新型环保高温热泵工质，属于二元混合物，各组分所占的质量分数比例为：R1233zd(E)(反式-1-氯-3,3,3-三氟丙烯):1%~54%，R600a(异丁烷):46%~99%。The present invention provides the first new type of environmentally friendly high-temperature heat pump working fluid, which is a binary mixture, and the mass fraction ratio of each component is: R1233zd (E) (trans-1-chloro-3,3,3-trifluoropropene): 1%~54%, R600a (isobutane): 46%~99%.
做进一步优选，各组分所占的质量分数比例为：R1233zd(E):1%~46%，R600a:54%~99%。Further optimization is performed, and the mass fraction ratio of each component is: R1233zd(E): 1%~46%, R600a: 54%~99%.
做进一步优选，各组分所占的质量分数比例为：R1233zd(E):1%~24%，R600a:76%~99%。Further optimization is performed, and the mass fraction ratio of each component is: R1233zd(E): 1%~24%, R600a: 76%~99%.
本发明给出了第二种新型环保高温热泵工质，属于三元混合物，各组分所占的质量分数比例为：R1233zd(E):1%~51%，R600a:1%~60%，R600(正丁烷):39%~98%。The present invention provides a second novel environmentally friendly high-temperature heat pump working fluid, which is a ternary mixture, and the mass fraction ratio of each component is: R1233zd (E): 1%~51%, R600a: 1%~60%, R600 (n-butane): 39%~98%.
做进一步优选，R1233zd(E):1%~15%，R600a:1~15%，R600：84%~98%。Further optimization is performed, R1233zd(E): 1%~15%, R600a: 1~15%, R600: 84%~98%.
做进一步优选，R1233zd(E):1%~11%，R600a:1~4%，R600：85%~98%。Further optimization is performed, R1233zd(E): 1%~11%, R600a: 1~4%, R600: 85%~98%.
本发明所给出的两种混合工质，制备方法为各组分按目标配比在常温下进行物理混合即可。各组分之和为100%。The two mixed working fluids provided in the present invention can be prepared by physically mixing the components at room temperature according to the target ratio. The sum of the components is 100%.
表1给出了本发明涉及的工质R600a、R1233zd(E)和R600和常用的热泵工质R245fa的物性参数。Table 1 shows the physical properties of the working fluids R600a, R1233zd(E) and R600 involved in the present invention and the commonly used heat pump working fluid R245fa.
表1工质物性参数(Tc表示临界温度；Pc表示临界压力)Table 1 Working fluid physical parameters ( Tc represents critical temperature; Pc represents critical pressure)
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1. 混合物各组分的GWP明显低于R245fa，且大气寿命低于R245fa，环保性能很好。1. The GWP of each component of the mixture is significantly lower than that of R245fa, and the atmospheric lifetime is lower than that of R245fa, with good environmental performance.
2. 循环性能优良，新工质的COP与R245fa接近，单位容积制冷量或制热量远高于R245fa。2. The cycle performance is excellent. The COP of the new working fluid is close to that of R245fa, and the cooling capacity or heating capacity per unit volume is much higher than that of R245fa.
3. 排气温度低，无需对所发明工质专门设计压缩机。3. The exhaust gas temperature is low, and there is no need to design a compressor specifically for the invented working fluid.
4. 与润滑油溶解性好，替代传统制冷剂不需要对系统设备进行过多更换。4. It has good solubility in lubricating oil and can replace traditional refrigerants without requiring too much replacement of system equipment.
5. 新工质的充注量小，系统运行相对安全，温度滑移值普遍偏小，补充制冷剂方便。5. The charge amount of the new working fluid is small, the system operation is relatively safe, the temperature glide value is generally small, and it is convenient to replenish the refrigerant.
具体实施方式DETAILED DESCRIPTION
一种环保高温热泵工质，包括二元混合物或三元混合物，所述二元混合物包括如下质量百分数的组分：R1233zd(E):1%~54%、R600a:46%~99%；所述三元混合物包括如下质量百分数的组分：R1233zd(E):1%~51%、R600a:1%~60%以及R600:39%~98%。An environmentally friendly high-temperature heat pump working fluid includes a binary mixture or a ternary mixture, wherein the binary mixture includes the following components in mass percentage: R1233zd(E): 1%~54%, R600a: 46%~99%; the ternary mixture includes the following components in mass percentage: R1233zd(E): 1%~51%, R600a: 1%~60% and R600: 39%~98%.
为了反映本发明给出新工质的优良性能，结合以下的案例与R245fa在相同工况下的性能进行对比。In order to reflect the excellent performance of the new working fluid provided by the present invention, the performance of the new working fluid is compared with that of R245fa under the same working conditions in the following cases.
以下方案中所有涉及的混合工质制取方法为各组分在常温下进行物理混合。The preparation method of the mixed working fluid involved in all the following schemes is to physically mix the components at room temperature.
方案1：取质量分数为1%的R1233zd(E)，99%的R600a。Solution 1: Take 1% R1233zd(E) and 99% R600a by mass.
方案2：取质量分数为46%的R1233zd(E)，54%的R600a。Option 2: Take 46% R1233zd(E) and 54% R600a by mass.
方案3：取质量分数为24%的R1233zd(E)，76%的R600a。Option 3: Take 24% R1233zd(E) and 76% R600a by mass.
方案4：取质量分数为54%的R1233zd(E)，46%的R600a。Option 4: Take 54% R1233zd(E) and 46% R600a by mass.
方案5：取质量分数为17%的R1233zd(E)，83%的R600a。Option 5: Take 17% R1233zd(E) and 83% R600a by mass.
方案6：取质量分数为1%的R600a，1%的R1233zd(E)和98%的R600。Scheme 6: Take 1% R600a, 1% R1233zd(E) and 98% R600 by mass fraction.
方案7：取质量分数为1%的R600a，15%的R1233zd(E)和84%的R600。Scheme 7: Take 1% R600a, 15% R1233zd(E) and 84% R600 by mass fraction.
方案8：取质量分数为15%的R600a，1%的R1233zd(E)和84%的R600。Scheme 8: Take 15% R600a, 1% R1233zd(E) and 84% R600 by mass fraction.
方案9：取质量分数为1%的R600a，60%的R1233zd(E)和39%的R600。Scheme 9: Take 1% R600a, 60% R1233zd(E) and 39% R600 by mass.
方案10：取质量分数为51%的R600a，1%的R1233zd(E)和48%的R600。Scheme 10: Take 51% R600a, 1% R1233zd(E) and 48% R600 by mass.
方案11：取质量分数为11%的R600a，4%的R1233zd(E)和85%的R600。Scheme 11: Take 11% R600a, 4% R1233zd(E) and 85% R600 by mass fraction.
方案12：取质量分数为1%的R600a，4%的R1233zd(E)和95%的R600。Scheme 12: Take 1% R600a, 4% R1233zd(E) and 95% R600 by mass fraction.
方案13：取质量分数为11%的R600a，1%的R1233zd(E)和88%的R600。Scheme 13: Take 11% R600a, 1% R1233zd(E) and 88% R600 by mass fraction.
方案14：取质量分数为51%的R600a，10%的R1233zd(E)和39%的R600。Scheme 14: Take 51% R600a, 10% R1233zd(E) and 39% R600 by mass.
方案15：取质量分数为9%的R600a，10%的R1233zd(E)和81%的R600。Scheme 15: Take 9% R600a, 10% R1233zd(E) and 81% R600 by mass fraction.
方案16：取质量分数为13%的R600a，9%的R1233zd(E)和78%的R600。Scheme 16: Take 13% R600a, 9% R1233zd(E) and 78% R600 by mass fraction.
表2给出了方案1~16的工质和R245fa物性参数及环保性。Table 2 gives the working fluid and R245fa physical properties and environmental performance of Schemes 1 to 16.
表2 方案1~16工质物性参数及其他数据与R245fa的比较(Tc表示临界温度；Pc表示临界压力)Table 2 Comparison of the working fluid physical parameters and other data of Schemes 1 to 16 with R245fa ( Tc represents the critical temperature; Pc represents the critical pressure)
将方案1~16应用于热泵系统与R245fa作比较。热泵工况：蒸发温度50℃，冷凝温度110℃，过热度和过冷度均取为5℃，压缩机的等熵效率取0.8。其理论循环计算参数如表3所示。Schemes 1 to 16 are applied to the heat pump system for comparison with R245fa. Heat pump operating conditions: evaporation temperature 50°C, condensation temperature 110°C, superheat and subcooling are both 5°C, and the isentropic efficiency of the compressor is 0.8. The theoretical cycle calculation parameters are shown in Table 3.
表3 热泵工况中方案1~16工质与R245fa的性能对比Table 3 Performance comparison of schemes 1 to 16 working fluids and R245fa in heat pump conditions
(P0表示蒸发压力；Pk表示冷凝压力；qv表示单位容积制热量；T排表示排气温度；T滑，0和T滑，k分别为蒸发器和冷凝器温度滑移)( P0 represents evaporation pressure; Pk represents condensation pressure; qv represents heating capacity per unit volume; Trow represents exhaust temperature; Tslip ,0 and Tslip ,k represent evaporator and condenser temperature slips, respectively)
结果显示：The results show:
1. 新工质的环保性能很好，混合物的ODP值为0，GWP值小于20，远小于R245fa的GWP值858。1. The new working fluid has excellent environmental performance. The ODP value of the mixture is 0 and the GWP value is less than 20, which is much smaller than the GWP value of R245fa, 858.
2. 在冷凝温度110℃的高温热泵工况中，R245fa的单位容积制热量小于3000kJ/m3，应用在热泵系统中可能会导致压缩机体积偏大，系统占地面积大，而两种新型混合工质的单位容积制热量大于3000kJ/m3，COP是R245fa的85%以上，单位容积制热量是其120%以上，最高可达144%，适合高温热泵工况。2. In high-temperature heat pump conditions with a condensing temperature of 110°C, the heating capacity per unit volume of R245fa is less than 3000kJ/m 3 . Its application in heat pump systems may result in a larger compressor volume and a larger system footprint. The heating capacity per unit volume of the two new mixed refrigerants is greater than 3000kJ/m 3 , and their COP is more than 85% of that of R245fa, while their heating capacity per unit volume is more than 120% and can reach up to 144%, making them suitable for high-temperature heat pump conditions.
3. 新工质与传统润滑油溶解性良好，可直接充入替代传统工质，且在高温工况下，温度滑移值普遍偏小，属于近共沸混合物，补充工质方便。3. The new working fluid has good solubility in traditional lubricating oil and can be directly charged to replace the traditional working fluid. In addition, under high temperature conditions, the temperature glide value is generally small, and it is a near-azeotropic mixture, which makes it easy to replenish the working fluid.
4. 由于工质的相对充注量大致与摩尔质量成正比，新工质在制冷系统中的充注量显著低于R245fa，且R1233zd(E)为不可燃工质，系统的安全性会提高。4. Since the relative charge amount of the working fluid is roughly proportional to the molar mass, the charge amount of the new working fluid in the refrigeration system is significantly lower than that of R245fa, and R1233zd(E) is a non-flammable working fluid, the safety of the system will be improved.
本发明提出了两种新型高温热泵工质，混合工质的环保性优良，GWP值远低于R245fa，且与传统润滑油互溶，工质在系统中充灌量小，冷凝压力低，单位容积制热量远高于R245fa，COP值与R245fa接近，综上所述，本发明所涉及的混合工质在环保性和循环性能上表现良好，可作为新型环保工质用在高温热泵工况中。The present invention proposes two new high-temperature heat pump working fluids. The mixed working fluid has excellent environmental protection performance, a GWP value much lower than R245fa, and is miscible with traditional lubricating oil. The working fluid filling amount in the system is small, the condensing pressure is low, the heating capacity per unit volume is much higher than R245fa, and the COP value is close to R245fa. In summary, the mixed working fluid involved in the present invention performs well in environmental protection and cycle performance, and can be used as a new environmentally friendly working fluid in high-temperature heat pump conditions.
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| US8163196B2 (en) * | 2008-10-28 | 2012-04-24 | Honeywell International Inc. | Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene |
| CN102292408A (en) * | 2009-01-22 | 2011-12-21 | 阿科玛股份有限公司 | Azeotrope and azeotrope-like compositions of e-1-chloro-3,3,3-trifluoropropene and isopropanol |
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| CN115340849A (en) | 2022-11-15 |
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