WO1997015637A1

WO1997015637A1 - Refrigerant

Info

Publication number: WO1997015637A1
Application number: PCT/CN1996/000093
Authority: WO
Inventors: Mingshan Zhu; Lizhong Han; Xiaoyu Zhao; Mao Ye
Original assignee: Tsinghua University; Beijing Inoue Qinghua Freeze Technology Co. Ltd.
Priority date: 1995-10-20
Filing date: 1996-10-18
Publication date: 1997-05-01
Also published as: AU7276996A

Abstract

A refrigerant comprising component A and component B, in which component A with non-inflammability or incombustibility is 10-95 wt.%, and one or more compounds selected from the group consisting of iodotrifluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and chlorodifluoromethane; component B with flammability is 5-90 wt.%, and one or more compounds selected from the group consisting of methane, ethane, propane, cyclopropane, butane, isobutane, difluoromethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, dimethyl ether, fluoroethane, propene and ethyl ether. While component A is only 1,1,1,2-tetrafluoroethane, component B is not difluoromethane alone; while component A is only pentafluoroethane, component B is not difluoromethane alone; while component A is the mixture of pentafluoroethane and 1,1,1,2-tetrafluoroethane, component B is not difluoromethane alone. Optionally, component A contains 1,1,1,2,3,3,3-heptafluoropropane and/or 1,1,2,2-tetrafluoroethane. The advantage of this refrigerant is better than the replacements of CFC-12 and HCFC-22 in environment effect, heat working parameter, heat working property, etc. This invention also provides methods of the refrigerant in cooling, heating and temperature controlling.

Description

发明领域本发明涉及制冷剂及其在制冷、空调、热泵和温控器等设备中的使用方法. 背景技术现有技术中，作为冰箱、冰柜、汽车空调、空调、热荥和温控器等装置的制冷剂，长期以来大都使用 CFC-12和 HCFC-22. 由于它具有低毒性、不可燃、无腐蚀、与其他材料相兼容等特点，多年来被广泛用于上述制冷、空调、热泵等***及其他一些领域. 但从 1974 年发现氟氣烃 (CFC)与氢代氟氣烃 (HCFC)类物质对大气臭氧层有严重破坏作用以来，引起了国际上日益广泛的重视，并决定逐步限制 CFCs和 HCFCs的生产和使用. 目前，作为替代 CFC-12的主要制冷剂为 1, 1,2-四氟乙烷 (HFC- 134a)，其优点是不破坏臭氧层，热工性能与 CFC- 12相近，其应用技术也日趋成熟，但在推广使用 HFC- 134a时，却带来了一系列与 CFC-12不同的要求.例如对制冷***中的一些主要设备、冷冻油及工艺等方面都提出了一系列新的要求，因而在实际使用中有诸多不便之处；另外，其温室效应 GWP值还较高. 所以尚不理想。近年来，德国使用某些碳氢化合物如异丁烷代替 CFC-12，其优点是热工性能好，但其可燃、易爆性始终成为推广应用的主要障碍。对其进行防爆处理的耗资较大，而且有光雾反应. 作为替代 HCFC- 22 , 现有下列几种主要方法：（1)美国联合信号公司的 R410A(HFC- 32/HFC-125 , 重量百分数 50/50)共沸混合物，但其冷凝压力提高了 60%, 单位容积制冷量增大 40%，故需重新设计压缩机和制冷空调***；（2)杜邦和 I.CI 公司的 R407C(HFC- 32/HFC- 134a, 重量百分数 23/25/52)，其 COP有可能要降低 10%左右， ***需重新优化，温室效应也较大；（3)日本大金株式会社的 HFC- 32/HFC-134a (重量百分数 30/70)混合物，但具可燃性；（4)美国大湖化学公司 HFC-227ea/HFC-32 的混合物（重量百分数 30/70) (CN1083508A) , 但其温室效应大。本发明旨在克服现有技术的不足，开发可替代 CFC- 12和 HCFC-22的制冷剂. 发明内容本发明的上述目的是通过提供下述制冷剂混合物来实现的。本发明提供一种制冷剂，该制冷剂包含下列组分：组分 A为选自下列组中的一种或多种具灭火性或不可燃性的化合物:三氟碘甲烷 (CF₃I， FC-1311) , 五氟乙烷 (CHF'CF HFC- 125) , 1， 1, 2-四氟乙烷 (CH₂FC , HFC-134a)和一氣二氟代甲烷 (CHCl , HCFC-22) , 其含量为制冷剂总重量的 10-95%; 优选为 40-95%; 组分 Β为选自下列组中的一种或多种具可燃性的化合物：甲烷 (HC50) , 乙垸 (HC170) , 丙烷（HC290) ,环丙垸 (C270) ,丁垸（HC600) ,异丁烷（HC600a) ,二氟甲烷（CH , HFC-32) , 1, 1-二氟乙烷 (CHF₂-CH₃， HFC-152a) , 1, 1, 1-三氟乙烷 (CFCH , HFC-143a)，二甲醸 (CH K^, E170) , 一氟乙烷（OhCHaF, HFC-161)和丙烯 (CH;CH H₂， R1270) , 其含量为制冷剂总重量的 5-90¾；其前题条件是，当组分 A仅为 1, 1，2-四氟乙烷((：1^ ^ HFC- 134a)时，组分 B不单独是二氟甲垸 (CH;F₂， HFC-32); 当组分 A 仅为五氟乙烷 (CH CF^, HFC- 125)时，组分 B不单独是二氟甲烷（CH ， HFC-32)；且，当组分 A为五氟乙烷 (CHF₂CF₃， HFC- 125)和 1, 1, 2-四氟乙烷 (CH!FCF^ HFC- 134a)的组合时，组分 B不单独是二氟甲烷 (CH:F₂， HFC-32) . 本发明所提供的制冷剂是可以按常规方法进行制备的，如将上述各组分按其相应的配比在液相状态下进行物理混合即可. 在一个实施方案中，本发明制冷剂的组分 A 中还可含有 1, 1, 1， 2， 3, 3， 3-七氟丙烷 (CFJCHFCF]' HFC-227ea)和 /或 1，1，2，2-四氟乙烷（(：1^(1^, HCFC-134). 借助计箅机的模型已知，这些化合物对平流层的臭氧没有影响或影响很小，即它们的臭氧破坏潜能 (0DP)为零或小于 0.03. 本发明还提供了利用上述混合物产生制冷、供热和温控的方法. 因此，本发明的一个方面是提供新型的、环境上可接受的制冷剂，该制冷剂可应用于制冷、供热和温控的应用中. 本发明的另一个特点是组分 A的化合物具有灭火性或不可燃性，其与组分 B的可燃性化合物结合，便产生了具有所需的制冷、供热和温控性能的不燃的制冷剂混合物。因此，本发明的另一方面是提供了一种不燃的制冷剂。本发明的第三个特点是上述制冷剂能提供与 CFC- 12或 HCFC-22相当或更好的能量效率 (COP) ,并且有基本相同的容积制冷量，而且在制冷、供热等应用中具有与 CFC- 12或 HCFC - 22 相当的热工参数，如冷凝压力、蒸发压力、压缩机排气温度等，因此，本发明的第三方面是提供有效、而且不需对现有设备作重大改动、并可直接进行充灌的制冷剂。在一个实施方案中，具有本发明上述特殊优点的制冷剂的组分 A 为三氟碘甲烷 (FC- 1311) , 组分 B为丙烷 (HC290) , 其含量分别为制冷剂重量的 80-95¾和 5-60%, 优选为 80- 85¾和 15-20%; 在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为三氟碘甲烷 (FC-1311) , 组分 B为丙烷 (HC290)和 1， 1-二氟乙烷 (HFC- 152a) , 其含量分别为制冷剂重量的 60-90%， 3- 10%和 5-30%, 优选为 60- 75¾， 3- 5¾和 20-35%; 在又一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A 为三氟碘甲烷 (FC-1 311)和 1， 1 , 1 , 2, 3, 3, 3-七氟丙烷 (HFC- 227ea)，组分 B为丙烷 (HC290) , 其含量分别为制冷剂重量的 55-85%， 5-25%和 5-20%, 优选为 65- 80¾， 5-25%和 10-18%; 在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A 为三氣碘甲烷 (FC-1 311)和 1， 1， 1 , 2， 3, 3, 3-七氟丙垸 (HFC-227ea) , 所述的组分 B为 1， 1-二氟乙垸 (HFC- 152a) , 其含量分别为制冷剂重量的 40-80%, 3-30%和 7-50%, 优选为 40-60%, 和 30-50%; 在又一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为一氣二氣代甲烷 (HCFC-22) , 所述的组分 B 为 1，1-二氟乙烷 (HFC-152a)，其含量分别为制冷剂重量的 40-60%和 40-60%; 在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为一氯二氟代甲烷（HCFC- 22)和 1， 1， 1， 2, 3， 3, 3-七氟丙烷 (HFC-227ea)或三氟碘甲烷 (FC-1 311 ) , 所述的组分 B为 1， 1 -二氟乙烷（HFC-152a)，其含量分别为制冷剂重量的 15- 50¾, 2- 30和 30-65X; 在再一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为一氣二氟代甲烷 (HCFC-22)和 1 , 1， 1， 2-四氟乙烷 (HFC-1 34a) ,所述的组分 B为 1， 1 -二氟乙垸 (HFC-152a)，其含量分别为制冷剂重量的 5-35%, 10-60%和 30-65%. 上述制冷剂混合物可以 ik容易地用于代替冰箱、冰柜和汽车空调***中的 CFC-12 . 在再一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为五氟乙烷 FIELD OF THE INVENTION The present invention relates to a refrigerant and a method of using the same in equipment such as refrigeration, air conditioners, heat pumps, and thermostats. BACKGROUND OF THE INVENTION In the prior art, refrigerators, freezers, automobile air conditioners, air conditioners, thermostats, and thermostats, etc. Most of the refrigerants used in the device have been CFC-12 and HCFC-22 for a long time. Because of its low toxicity, non-flammability, non-corrosion, and compatibility with other materials, it has been widely used in the above-mentioned refrigeration, air conditioning, heat pumps, etc. Systems and some other fields. However, since the discovery of fluorocarbons (CFCs) and hydrofluorocarbons (HCFCs) in the atmosphere has severely damaged the ozone layer in the atmosphere, it has drawn increasing international attention and decided to gradually restrict Production and use of CFCs and HCFCs. At present, the main refrigerant used as an alternative to CFC-12 is 1,1,2-tetrafluoroethane (HFC-134a), which has the advantage of not damaging the ozone layer, and its thermal performance is similar to that of CFC-12. Similar, its application technology is becoming more and more mature, but when promoting the use of HFC-134a, it brings a series of different requirements from CFC-12. For example, some major equipment, refrigeration oil and processes in the refrigeration system A series of new requirements have been put forward in other aspects, so there are many inconveniences in actual use; in addition, the GWP value of its greenhouse effect is still high, so it is not ideal. In recent years, Germany has used certain hydrocarbons such as isobutane instead of CFC-12. The advantage is that it has good thermal performance, but its flammability and explosiveness have always become the main obstacles to popularization and application. Explosion-proof treatment is costly and has a haze reaction. As an alternative to HCFC-22, the following main methods are available: (1) R410A (HFC-32 / HFC-125, United States Signal Corporation), weight percent 50/50) azeotropic mixture, but its condensing pressure has increased by 60%, and the refrigeration capacity per unit volume has increased by 40%. Therefore, the compressor and refrigeration and air-conditioning system need to be redesigned; (2) R407C (HFC) from DuPont and I.CI -32 / HFC- 134a, weight percentage 23/25/52), its COP may be reduced by about 10%, the system needs to be re-optimized, and the greenhouse effect is also large; (3) HFC- 32 / HFC-134a (weight percentage 30/70) mixture, but flammable; (4) American Great Lakes Chemical Company HFC-227ea / HFC-32 mixture (weight percentage 30/70) (CN1083508A), but its greenhouse effect is large. The present invention aims to overcome the shortcomings of the prior art and develop refrigerants that can replace CFC-12 and HCFC-22. SUMMARY OF THE INVENTION The above object of the present invention is achieved by providing the following refrigerant mixture. The present invention provides a refrigerant comprising the following components: Component A is one or more compounds having fire extinguishing or nonflammable properties selected from the group consisting of: trifluoroiodomethane (CF ₃ I, FC-1311), pentafluoroethane (CHF'CF HFC- 125), 1,1,2-tetrafluoroethane (CH ₂ FC, HFC-134a) and monogas difluoromethane (CHCl, HCFC-22) , Its content is 10-95% of the total weight of the refrigerant; preferably 40-95%; component B is one or more flammable compounds selected from the group consisting of: methane (HC50), acetamidine ( HC170), Propane (HC290), Cyclopropane (C270), Butane (HC600), Isobutane (HC600a), Difluoromethane (CH, HFC-32), 1, 1-Difluoroethane (CHF ₂ -CH ₃ , HFC-152a), 1, 1, 1-trifluoroethane (CFCH, HFC-143a), dimethylfluorene (CH K ^, E170), monofluoroethane (OhCHaF, HFC-161), and propylene (CH ; CH H ₂ , R1270), whose content is 5-90¾ of the total weight of the refrigerant; the precondition is that when component A is only 1,1,2-tetrafluoroethane ((: 1 ^ ^ HFC- 134a), component B is not alone difluoromethane (CH; F ₂ , HFC-32); when component A is only pentafluoroethane (CH CF ^, HFC- 125), component B is not Difluoromethane (CH, HFC-32) alone; and when component A is pentafluoroethane (CHF ₂ CF ₃ , HFC- 125) and 1, 1, 2-tetrafluoroethane (CH! FCF ^ In the combination of HFC-134a), component B is not alone difluoromethane (CH: F ₂ , HFC-32). The refrigerant provided by the present invention can be prepared by conventional methods, such as the above components Physical mixing can be performed in the liquid phase according to its corresponding proportion. In one embodiment, component A of the refrigerant of the present invention may further contain 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (CFJCHFCF] 'HFC-227ea) and / or 1,1,2,2-tetrafluoroethane ((: 1 ^ (1 ^, HCFC-134). Models based on calculators are known for advection Layer of ozone has no effect or little effect, that is, their ozone destruction potential (0DP) is zero or less than 0.03. The present invention also provides a method for generating refrigeration, heating and temperature control using the above mixture. Therefore, one of the present invention One aspect is to provide a novel, environmentally acceptable refrigerant, which can be used in refrigeration, heating and temperature control applications. Another feature of the present invention is that the compound of component A is fire extinguishing or non-flammable In combination with the flammable compound of component B, a non-combustible refrigerant mixture with the required cooling, heating and temperature control performance is produced. Therefore, another aspect of the present invention is to provide a non-combustible refrigerant The third feature of the present invention is that the above-mentioned refrigerant can provide energy efficiency (COP) equivalent to or better than that of CFC-12 or HCFC-22, and has substantially the same volumetric cooling capacity, and is also used for cooling, heating, etc. Application equivalent to CFC-12 or HCFC-22 Parameters, such as condensing pressure, evaporating pressure, and compressor exhaust temperature, etc. Therefore, the third aspect of the present invention is to provide an effective refrigerant that does not require major changes to existing equipment and can be directly charged. In one embodiment, the component A of the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311), and the component B is propane (HC290), the contents of which are 80-95 ¾ of the weight of the refrigerant, respectively. And 5-60%, preferably 80-85¾ and 15-20%; in another embodiment, component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311), the group Sub-B is propane (HC290) and 1, 1-difluoroethane (HFC-152a), the contents of which are respectively the weight of the refrigerant 60-90%, 3- 10%, and 5-30%, preferably 60-75¾, 3--5¾, and 20-35%; in yet another embodiment, a group of refrigerants having the above-mentioned special advantages of the present invention Fraction A is trifluoroiodomethane (FC-1 311) and 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (HFC-227ea), component B is propane (HC290), and their contents are refrigerants 55-85%, 5-25% and 5-20% by weight, preferably 65-80¾, 5-25% and 10-18%; in another embodiment, in the refrigerant having the above-mentioned special advantages of the present invention The component A is three gas iodomethane (FC-1 311) and 1, 1, 1, 2, 3, 3, 3- heptafluoropropane (HFC-227ea), and the component B is 1, 1 -Difluoroacetamidine (HFC-152a), whose content is 40-80%, 3-30% and 7-50%, preferably 40-60%, and 30-50% of the weight of the refrigerant; in another In the embodiment, the component A in the refrigerant having the above-mentioned special advantages of the present invention is monogas digasmethane (HCFC-22), and the component B is 1,1-difluoroethane (HFC-152a) , The content of which is 40-60% and 40-60% of the weight of the refrigerant; in another embodiment, the component A in the refrigerant having the above-mentioned special advantages of the present invention is Monochlorodifluoromethane (HCFC-22) and 1, 1, 1, 2, 2, 3, 3, 3-heptafluoropropane (HFC-227ea) or trifluoroiodomethane (FC-1 311), component B as described Is 1, 1-difluoroethane (HFC-152a), and its contents are 15-50 ¾, 2- 30, and 30-65X, respectively, according to the weight of the refrigerant; Component A in the agent is monogas difluoromethane (HCFC-22) and 1, 1, 1, 2-tetrafluoroethane (HFC-1 34a), and the component B is 1, 1-difluoro Dioxin (HFC-152a), its content is 5-35%, 10-60% and 30-65% of the weight of the refrigerant. The above refrigerant mixture can be easily used in place of refrigerators, freezers and automotive air conditioning systems CFC-12. In yet another embodiment, the component A in the refrigerant having the above-mentioned special advantages of the present invention is pentafluoroethane

(HFC-125) , 所述的组分 B为一氟乙烷 (HFC- 161)，其含量分别为制冷剂重量的 10-95%, 5-90%, 优选为 40-60%, 60-40%; 在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为三氟碘甲烷 (FC-1311)和 1 , 1 , 2-四氟乙烷（HFC- 1 34a) , 所述的组分 B为三氟甲烷（HFC- 32)，其含量分别为制冷剂重量的 5-40%， 15-60%和 10- 50%, 优选为 10- 35¾， 35-60%和 15- 35X; 在又一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为三氣碘甲烷 (FC-1 311) , 所述的组分 B为二氟甲烷 (HFC-32)和 1 , 1-二氟乙烷 (HFC-152a)，其含量分别为 10-80%, 10-50X和 10-40%, 优选为 40-65%, 20- 40¾和 5-25%; 在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为五氟乙烷 (HFC-125), the component B is monofluoroethane (HFC-161), and its content is 10-95%, 5-90%, preferably 40-60%, 60- 40%; In another embodiment, component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311) and 1, 1, 2-tetrafluoroethane (HFC-1 34a ), The component B is trifluoromethane (HFC-32), the content of which is 5-40%, 15-60% and 10-50% of the weight of the refrigerant, preferably 10-35¾, 35-60 % And 15-35X; In yet another embodiment, the component A in the refrigerant having the above-mentioned special advantages of the present invention is triiodoiodomethane (FC-1 311), and the component B is difluoromethane ( HFC-32) and 1, 1-difluoroethane (HFC-152a), the contents of which are 10-80%, 10-50X and 10-40%, preferably 40-65%, 20-405% and 5- 25%; In another embodiment, component A in the refrigerant having the above-mentioned special advantages of the present invention is pentafluoroethane

(HFC-125) , 所述的组分 B为环丙烷 (C270)和一氟乙烷 (HFC-161) , 其含量分别为制冷剂重量的 1 0-70%, 5- 20%和 20-50%, 优选为 40-60%, 10- 20¾和 25- 45¾4；在另一个实施方案中，具有本发明上述特殊优点的制冷剂中的组分 A为三氟捵甲烷 (FC-131 1)和五氟乙烷（HFC-125) ,所述的组分 B为一氣乙垸（HFC-161) ,其含量分别为制冷剂重量的 5- 50%, 20- 60%和 20-60%，优选为 5- 15%, 30- 50%和 40- 55%. 上述制冷剂混合物可以很容易地用于代替空调***中的 HCFC-22 . 应该理解，本发明的制冷剂混合物中还可以包含另外的、非干扰性的组分，例如润滑油等，以便生成新的混合制冷剂。任何这样的混合物都包含在本发明的范围中. 本发明的制冷剂混合物在制冷和 /或供热应用中都有用。在本发明的一个实施方案中，即蒸气压缩制冷或供热的实施方案中，可以使用本发明的制冷剂混合物，如果需要的话，可以在有适当润滑油的情况下使用. 在本发明的另一个实施方案中，即在温控器的实施方案中可以使用本发明的制冷剂混合物. 通过下列实施例可以更完全地说明不发明，而下列实施例应当理解为包含在本发明内，但只是举例性的，而不是对本发明的暇制. 本发明的最佳实施方式实施例 1 -4 实施例 1 (HFC-125), the component B is cyclopropane (C270) and monofluoroethane (HFC-161), the content of which is 10-70%, 5- 20% and 20- 50%, preferably 40-60%, 10-20-20¾ and 25-45¾4; in another embodiment, component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoromethane (FC-131 1) And pentafluoroethane (HFC-125), the component B is monogas acetamidine (HFC-161), the content of which is 5-50%, 20-60% and 20-60% of the weight of the refrigerant, It is preferably 5-15%, 30-50% and 40-55%. The above refrigerant mixture can be easily used to replace HCFC-22 in air conditioning systems. It should be understood that the refrigerant mixture of the present invention may also contain other non-interfering components, such as lubricating oil, etc., in order to generate new Mixed refrigerant. Any such mixture is included within the scope of the present invention. The refrigerant mixture of the present invention is useful in refrigeration and / or heating applications. In one embodiment of the present invention, that is, the embodiment of vapor compression refrigeration or heating, the refrigerant mixture of the present invention can be used, if necessary, can be used in the case of a suitable lubricant. In another of the present invention In one embodiment, that is, the refrigerant mixture of the present invention can be used in the embodiment of the thermostat. The non-invention can be more fully explained through the following examples, and the following examples should be understood to be included in the present invention, but only Exemplary, not for the leisure of the present invention. The best embodiment of the present invention Example 1-4 Example 1

将重量百分比分别为 80%的 FC-1 31 1和 20%的 HC290在液相进行物理混合，得制冷剂 1 . 实施例 2 Embodiment 1 FC-1 31 1 and 20% HC290, which are 80% by weight, were physically mixed in a liquid phase to obtain a refrigerant 1. Example 2

将重量百分比分别为 70¾的 (：-131 1 、 10¾的 HC290和 20%的 HFC- 152a在液相下混合，得制冷剂 2 . 实施例 3 Example 3 was mixed 70% of HC290 (-131 1, 10¾ of HC290 and 20% of HFC-152a in a liquid phase to obtain a refrigerant 2. Example 3

将重量百分比分别为 70%的 FC-1 31 1 、 20%的 HC290和 10%的 HFC- 227ea在液相下混合，得制冷剂 3 。实施例 4 70% of FC-1 31 1, 20% of HC290 and 10% of HFC-227ea were mixed in the liquid phase to obtain a refrigerant 3. Example 4

将重量百分比分别为 50¾的 FC- 1 311 、 40%的 HFC_152a 和 10¾的 HFC- 227ea在液相下混合，得制冷剂 4 。在冰箱的设计工况下，计箅得出上述实施例制备的制冷剂的热工性能，并列于表 1中. 表 1 FC-1 311, 40% HFC_152a, and HFC-227ea of 10¾ were mixed in a liquid phase to obtain a refrigerant 4 by weight. Under the design conditions of the refrigerator, the thermal performance of the refrigerant prepared in the above example was calculated and listed in Table 1. Table 1

*: 均为与 CFC-12的相应比值，下同。将本发明的制冷剂混合物与现有技术中的 CFC-12 , HFC-134&和异丁烷进行比较，本发明的优点将更为明了（以本发明中的一种为例） . a. 环境性能本发明的制冷剂混合物的臭氧破坏潜能 (0DP)为零，其温室效应系数 (GWP) < 50 ，无光雾反应 (V0C)。由此可见，本发明的制冷剂混合物完全符合保护臭氧层、不影响温室效应、无光雾反应的环保要求. 本发明的制冷剂混合物与 CFC-12及其替代物 HFC-1 34a和异丁烷的比较结果如表 2所示. 表 2

*: The corresponding ratios to CFC-12, the same below. Comparing the refrigerant mixture of the present invention with the prior art CFC-12, HFC-134 & and isobutane, the advantages of the present invention will be more clear (take one of the present invention as an example). A. Environment Performance The refrigerant destruction potential (0DP) of the refrigerant mixture of the present invention is zero, its greenhouse effect coefficient (GWP) is <50, and there is no haze reaction (VOC). It can be seen that the refrigerant mixture of the present invention fully meets the environmental protection requirements of protecting the ozone layer, not affecting the greenhouse effect, and having no haze reaction. The refrigerant mixture of the present invention and CFC-12 and its substitute HFC-1 34a and isobutane The comparison results are shown in Table 2. Table 2

b. 热工参数在冰箱的设计工况下，本发明的制冷剂混合物在蒸发器、冷凝器内的制冷剂的压力值、压缩机的压比以及排气温度与 CFC- 12十分相近，而且除排气温度略高外，其他均优于目前 CFC-12的替代物 HFC- 134a和异丁烷，例如，异丁烷的蒸发压力小于 1个大气压，处于真空运行，易漏人空气； HFC- 1 34a 与异丁烷的压比均高于本发明的制冷剂混合物，因此，使用本发明的制冷剂混合物时. 压缩机的容积效率比它们高。比较结果如表 3所示. 表 3

b. Thermal parameters Under the design conditions of the refrigerator, the refrigerant pressure value of the refrigerant mixture in the evaporator and condenser, the pressure ratio of the compressor and the exhaust temperature of the refrigerant mixture of the present invention are very similar to CFC-12, and Except that the exhaust temperature is slightly higher, the other alternatives are HFC-134a and isobutane, which are better than the current CFC-12. For example, the evaporation pressure of isobutane is less than 1 atmosphere, and it is in vacuum operation, which is easy to leak air; HFC -1 The pressure ratio of 34a to isobutane is higher than the refrigerant mixture of the present invention. Therefore, when using the refrigerant mixture of the present invention, the volumetric efficiency of the compressor is higher than them. The comparison results are shown in Table 3. table 3

c. 热工性能本发明的制冷剂混合物的热工性能 (COP与制冷量)优于 CFC- 12 , 参见表 4。容积制冷量约等于 CFC-12 . 这表明本发明的制冷剂可以直接使用原 CFC-12的压缩机而不需改动，而异丁烷的容积制冷量很小，原压縮机必须改造。表 4 c. Thermal performance The thermal performance (COP and cooling capacity) of the refrigerant mixture of the present invention is better than CFC-12, see Table 4. The volumetric refrigeration capacity is approximately equal to CFC-12. This shows that the refrigerant of the present invention can directly use the original CFC-12 compressor without modification, while the volumetric refrigeration capacity of isobutane is very small, and the original compressor must be modified. Table 4

通过以上实施例就可以发现，本发明所提供的制冷剂混合物不仅热工性能良好，且不破坏臭氣层，不产生温室效应，无光雾反应，且无毒，符合环保要求. 经计箅本发明的制冷剂 2的滑移温度小于 1°C , 故该制冷剂是一种不可燃的亚沸混合物，可适用于原冷冻油并直接灌注，其压缩机与***中的主要部件不需改动，生产线不需改造。在性能上优于现有的其他替代物，完全可作为长期性替代 CFC- 12的制冷剂. 冰箱热工性能试验表明，本发明制冷剂 2的降温速度、启动性能、冷冻室与储藏室温度等热工性能完全符合中国国家标准 GB8059. 1-87，且比原 CFC-12节能；制冷剂充灌量减少 20%左右。实施例 5-1 0 重量百分比 50¾的 HFC-125和 50%的 HFC-161在液相下混合，得制冷剂 5 ,用于空调热泵***，替代 HCFC- 22 . 实施例 6

Through the above examples, it can be found that the refrigerant mixture provided by the present invention not only has good thermal performance, but also does not damage the odor layer, does not produce a greenhouse effect, has no haze reaction, and is non-toxic, and meets environmental protection requirements. The slip temperature of the refrigerant 2 of the present invention is less than 1 ° C, so the refrigerant is a non-flammable sub-boiling mixture, which can be applied to the original refrigerating oil and directly filled. The compressor and the main components in the system do not need No modification is required for the production line. Its performance is better than other existing alternatives, and it can be used as a long-term refrigerant to replace CFC-12. Thermal performance tests of refrigerators show that the cooling speed, start-up performance, temperature of freezer and storage room of refrigerant 2 of the present invention Isothermal performance fully complies with Chinese national standard GB8059. 1-87, and is more energy efficient than the original CFC-12; the refrigerant charge and discharge volume is reduced by about 20%. Example 5-1 0 50% by weight of HFC-125 and 50% of HFC-161 are mixed in a liquid phase to obtain refrigerant 5, which is used in an air-conditioning heat pump system instead of HCFC-22. Example 6

用重量百分比 5¾的 FC-1 31 1 、 45%的 HFC-125和 50%的 HFC-161在液相下混合，得制冷剂 6 , 用于空调热泵***，替代 HCFC-22 . 实施例 7 Using FC-1 31 1, 45% HFC-125, 50% HFC-161 and 50% HFC-161 mixed in liquid phase to obtain refrigerant 6, which is used in air-conditioning heat pump system instead of HCFC-22. Example 7

用重量百分比 50%的 HFC-125 、 1 的 C270和 35¾的 HFC-161在液相下混合，得制冷剂 7 , 用于空调热泵***，替代 HCFC-22 , 实施例 8 50% by weight of HFC-125, 1 C270 and 35¾ HFC-161 are mixed in the liquid phase to obtain refrigerant 7, which is used in air-conditioning heat pump systems instead of HCFC-22. Example 8

用重量百分比 50¾的 HFC-125、的 R1270和 20%的 C270在液相下混合，得制冷剂 8，用于空调热泵***，替代 HCFC- 22 . 实施例 9 Mix 50% HFC-125, R1270 and 20% C270 in liquid phase to obtain refrigerant 8, which is used in air-conditioning heat pump system instead of HCFC-22. Example 9

用重量百分比 45%的 HFC- 125、 ⁵%的 E170和 50%的 HFC- 161在液相下混合，得制冷剂 9 , 用于空调热泵***，替代 HCFC-22 . 实施例 10 Example 4 mixed with 45% by weight of HFC-125, ⁵ % of E170 and 50% of HFC-161 in the liquid phase to obtain refrigerant 9, which is used in an air-conditioning heat pump system instead of HCFC-22. Example 10

用重量百分比 50%的 HFC-125、 5%的 HFC- 152a和 45%的 HFC-161在液相下混合，得制冷剂 10，用于空调热泵***，替代 HCFC-22 . 在空调热泵***的设计工况下，计箅得到上述实施例 5-10制备的制冷剂的热工性能，并列于表 5中. 表 5 50% by weight of HFC-125, 5% of HFC-152a and 45% of HFC-161 are mixed in the liquid phase to obtain refrigerant 10, which is used in air-conditioning heat pump systems instead of HCFC-22. Under the design conditions, the thermal performance of the refrigerant prepared in the above-mentioned Example 5-10 was calculated and listed in Table 5.

注： *均为与 HCFC-22的相应比值，下同。本发明与现有技术相比，具有以下优点和有益效果（以本发明的实施例 5制备的制冷剂 5为例）： a. 环境性能本制冷剂的臭氧破坏潜能 (0DP)为零，其温室效应系数 (GWP)数为 1600 . 由此可见，本发明的制冷剂完全符合保护臭氧层的要求，温室效应与 HCFC- 22 相当. 表 6 给出了与 HCFC-22及其他替代物的比较. 表 6 Note: * All are corresponding ratios with HCFC-22, the same below. Compared with the prior art, the present invention has the following advantages and beneficial effects (taking the refrigerant 5 prepared in Example 5 of the present invention as an example): a. Environmental performance The ozone destruction potential (0DP) of the refrigerant is zero, and The greenhouse effect coefficient (GWP) number is 1600. It can be seen that the refrigerant of the present invention fully meets the requirements for protecting the ozone layer, and the greenhouse effect is equivalent to HCFC-22. Table 6 shows the comparison with HCFC-22 and other alternatives. Table 6

制冷剂 HCFC-22 R410A R407C HFC-32 /HFC-1 34a 制冷剂 5 Refrigerant HCFC-22 R410A R407C HFC-32 / HFC-1 34a Refrigerant 5

0DP 0. 05 0 0 0 00DP 0. 05 0 0 0 0 0

GWP 1700 1900 1600 1 100 约 1600 b. 热工参数在空调热泵***的设计工况下，由实施例 5制备的制冷剂 5的蒸发器、冷凝器内的制冷剂的压力值、压缩机压比以及排气温度与 HCFC- 22十分相近，而且排气温度最低，温度滑移比 R407C与 HFC-32/HFC- 134a的要小。比较结果列于表 7中。 GWP 1700 1900 1600 1 100 about 1600 b. Thermal parameters Under the design conditions of the air-conditioning heat pump system, the refrigerant pressure of the refrigerant 5 prepared in Example 5 and the pressure value of the refrigerant in the condenser, the pressure ratio of the compressor, and the exhaust gas temperature are compared with HCFC-22. Very similar, and the exhaust temperature is the lowest, the temperature slip is smaller than that of R407C and HFC-32 / HFC-134a. The comparison results are shown in Table 7.

c 热工性能由实施例 5制备的制冷剂 5的热工性能与 HCFC- 22基本相当，而且在各种替代物中，本发明的制冷剂 5的 COP最高，冷量最大，意味着充灌量最小，参见表 8。这表明制冷剂 5可以直接充灌. 表 8 c Thermal performance The thermal performance of the refrigerant 5 prepared in Example 5 is basically equivalent to that of HCFC-22, and among various alternatives, the refrigerant 5 of the present invention has the highest COP and the largest cooling capacity, which means charging and filling The minimum amount, see Table 8. This shows that refrigerant 5 can be charged directly. Table 8

实施例 11-12 实施例 11 Examples 11-12 Example 11

用重量百分比 30%的 FC-1311 、 25%的 HFC- 32和 45%的 HFC- 134a在液相下混合，得制冷剂 11 , 用于空调热泵***，替代 HCFC-22. 实施例 12 30% of FC-1311, 25% of HFC-32, and 45% of HFC-134a were mixed in a liquid phase to obtain a refrigerant 11 for use in an air-conditioning heat pump system instead of HCFC-22. Example 12

用重量百分比 55¾的 FC-1311 . 30%的 HFC-32和 15%的 HFC- 134a在液相下混合，得制冷剂 12 , 用于空调热泵***，替代 HCFC-22. 在空调热泵***的设计工况下，计箅得到上述由实施例 11和 12制备的制冷剂 11和 12的环境性能、热工参数和热工性能，并将其与 HCFC-22及其他替代物的比较列于表 9-11 中。表 9. 环境性能的比较

表 9说明本发明的制冷剂 11和 12不仅 0DP为零，而且 GWP比其他三种替代物均小。表 10. 热工参数的比较 Use FC-1311 with a weight percentage of 55¾. 30% HFC-32 and 15% HFC-134a are mixed in the liquid phase to obtain refrigerant 12, which is used in air-conditioning heat pump systems instead of HCFC-22. In the design of air-conditioning heat pump systems Under the working conditions, the environmental performance, thermal parameters and thermal performance of the refrigerants 11 and 12 prepared in Examples 11 and 12 were calculated according to the calculations, and the comparison with HCFC-22 and other substitutes is shown in Table 9. -11 in. Table 9. Comparison of environmental performance

Table 9 illustrates that the refrigerants 11 and 12 of the present invention not only have zero ODP, but also have a smaller GWP than the other three alternatives. Table 10. Comparison of thermal parameters

表 1 1表明，本发明的制冷剂 1 1和 12不仅与 HCFC- 22的热工性能相近，而且均优于其他三种替代物。实施例 1 3-16 实施例 1 3

Table 11 shows that the refrigerants 11 and 12 of the present invention are not only similar to the thermal performance of HCFC-22, but also better than the other three alternatives. Example 1 3-16 Example 1 3

用重量百分比 52¾的 HCFC-22和 48%的 HFC - 152a在液相下混合，得到制冷剂 1 3 ,用于冰箱、冰柜等***，作为过渡性替代 CFC-12 . 实施例 14 HCFC-22 with a weight percentage of 52¾ and 48% HFC-152a are mixed in a liquid phase to obtain a refrigerant 1 3, which is used in a refrigerator, a freezer and other systems as a transitional replacement for CFC-12. Example 14

用重量百分比 20¾的 HCFC-22 、 20¾的 HFC- 227ea和 60¾的 HFC- 152a在液相下混合，得到制冷剂 14 , 用于冰箱、冰柜等***，作为过渡性替代 CFC-12 。实施例 15 HCFC-22 with 20¾, HFC-227ea with 20¾ and HFC-152a with 60¾ are mixed in liquid phase to obtain refrigerant 14 for use in refrigerators, freezers and other systems as a transitional replacement for CFC-12. Example 15

用重量百分比 41%的 HCFC- 22 、 5%的 FC-1311和 54%的 HFC- 152a在液相下混合，得到制冷剂 15 , 用于冰箱、冰柜等***，作为过渡性替代 CFC-12 。实施例 16 41% by weight of HCFC-22, 5% of FC-1311, and 54% of HFC-152a were mixed in the liquid phase to obtain Refrigerant 15, which was used in refrigerators, freezers and other systems as a temporary replacement for CFC-12. Example 16

用重量百分比 5¾的 HCFC-22 、 50¾的 HFC- 1 34a和 45%的 HFC- 152a在液相下混合，得钊制冷刑 16 , 用于冰箱、冰柜等***，作为过渡性替代 CFC-12。在冰箱***的设计工况下，计箅得到上述由实施例 1 3， 14 , 15制备的制冷剂 1 3， 14和 I ⁵的环境性能、热工参数和热工性能，并将其与 HCFC-12的比较列于表 12中。表 12 Mix 55% of HCFC-22, 50¾ of HFC-1 34a and 45% of HFC-152a in the liquid phase to obtain Zhao Refrigeration Penalty 16 is used in refrigerators, freezers and other systems as a transitional replacement for CFC-12. Under the design conditions of the refrigerator system, the environmental performance, thermal parameters and thermal performance of the refrigerants 1 3, 14 and I ⁵ prepared in Examples 1 3, 14 and 15 described above were calculated and compared with HCFC The comparison of -12 is listed in Table 12. Table 12

冰箱热工性能试验表明，本发明制冷剂 1 3的降温速度、启动性能、冷冻室与储藏室温度等热工性能完全符合中国国家标准 GB8059. 1 -87，且比原 CFC- 12节能；制冷剂充灌量减少 10%左右。由上述对本发明所作的详细说明和参考本发明的实施例，显然可对本发明进行改进和变化，但这些改变和变化均不能偏离所附的权利要求所规定的本发明的范围。工业实用性本发明提供的制冷剂混合物可长期性或过渡性地替代现有的 CFC- 12和 HCFC-22制冷剂，用于制冷、空调、热泵等设备的制造中。 The thermal performance test of the refrigerator shows that the thermal performance such as the cooling speed, start-up performance, and temperature of the freezer and storage compartments of the refrigerant of the present invention completely complies with the Chinese national standard GB8059. The filling volume of the agent was reduced by about 10%. From the foregoing detailed description of the invention and with reference to the embodiments of the invention, it is apparent that modifications and changes can be made to the invention, but these changes and changes must not depart from the scope of the invention as defined by the appended claims. Industrial Applicability The refrigerant mixture provided by the present invention can replace the existing CFC-12 and HCFC-22 refrigerants in a long-term or transient manner, and is used in the manufacture of refrigeration, air-conditioning, heat pump and other equipment.

Claims

权利要求 Rights request

1、 .一种制冷剂，其特征在于该制冷剂包含下列组分：组分 A为选自下列组中的一种或多种具灭火性或不可燃性的化合物：三氟碘甲烷，五氟乙烷， 1， 1， 2-四氟乙垸和一氣二氟代甲垸其含量为制冷剂总重量的 10-95%; 组分 B为选自下列组中的一种或多种具可燃性的化合物：甲烷，乙烷，丙烷，环丙垸，丁垸，异丁烷，二氟甲烷， 1，1-二氟乙烷， 1, 1, 1-三氟乙烷，二甲酸，一氟乙垸，丙烯, 其含量为制冷剂总重量的 5-90¾；其前题条件是，当组分 A仅为 1, 1, 2-四氟乙烷时，组分 B不单独是二氟甲垸；当组分 A仅为五氟乙烷时，组分 B不单独是二氣甲垸；且，当组分 A为五氟乙垸和 1, 1, 2-四氟乙烷的组合时，组分 B不单独是二氟甲烷. 1. A refrigerant, characterized in that the refrigerant contains the following components: Component A is one or more compounds having fire-extinguishing or non-flammable properties selected from the group consisting of: trifluoroiodomethane, five The content of fluoroethane, 1,1,2-tetrafluoroacetamidine and monogas difluoroformamidine is 10-95% of the total weight of the refrigerant; component B is one or more selected from the group consisting of Flammable compounds: methane, ethane, propane, cyclopropane, butane, isobutane, difluoromethane, 1,1-difluoroethane, 1, 1, 1-trifluoroethane, dicarboxylic acid, Monofluoroacetam, propylene, whose content is 5-90¾ of the total weight of the refrigerant; the prerequisite is that when component A is only 1, 1, 2-tetrafluoroethane, component B is not alone. Formamidine; When component A is only pentafluoroethane, component B is not alone digas formamidine; and when component A is pentafluoroacetamidine and 1,1,2-tetrafluoroethane When combined, component B is not alone difluoromethane.

2、如权利要求 1的制冷剂，其特征在于，在组分 A中还可含有 1, 1， 1,2， 3, 3, 3-七氟丙垸和 /或 1， 1, 2， 2-四氟乙垸。 2. The refrigerant according to claim 1, characterized in that component A further contains 1, 1, 1,2, 3, 3, 3- heptafluoropropane and / or 1, 1, 2, 2 -Tetrafluoroacetamidine.

3、如权利要求 1或 2的制冷剂，其特征在于:组分 A的含量为制冷剂总重量的 40-95¾。 3. The refrigerant according to claim 1 or 2, characterized in that the content of component A is 40-95¾ based on the total weight of the refrigerant.

4、如权利要求 1的制冷剂，其特征在于： 4. The refrigerant according to claim 1, characterized in that:

所述的组分 A为三氟捵甲烷，组分 B为丙垸，其含量分别为制冷剂重量的 80-95¾和 5-20%. The component A is trifluoromethane, and the component B is propidium, and the contents thereof are 80-95¾ and 5-20%, respectively, based on the weight of the refrigerant.

5、如权利要求 4的制冷剂，其特征在于： 5. The refrigerant according to claim 4, characterized in that:

所述的三氟捵甲烷和丙烷的含量分别为制冷剂重量的 80- 85%和 15-20%。 The trifluoromethane and propane content are 80-85% and 15-20% of the weight of the refrigerant, respectively.

6、如权利要求 1的制冷剂，其特征在于： 6. The refrigerant according to claim 1, characterized in that:

所述的组分 A为三氟碘甲烷，所述的组分 B为丙垸和 1， 1-二氟乙烷，其含量分别为制冷剂重量的 60-90%, 3- 10¾和5-30¾. The component A is trifluoroiodomethane, and the component B is propidium and 1, 1-difluoroethane, the contents of which are 60-90%, 3- 10¾ and 5- 30¾.

7、如权利要求 6的制冷剂，其特征在于： 7. The refrigerant according to claim 6, characterized in that:

所述的三氟碘甲烷，丙垸和 1, 1-二氟乙垸的含量分别为制冷剂重量的 60- 75%, 3-5% 和 20-35%。 The trifluoroiodomethane, propidium and 1, 1-difluoroacetamidine content are 60-75%, 3-5% and 20-35% of the weight of the refrigerant, respectively.

8、如权利要求 2的制冷剂，其特征在于： 8. The refrigerant according to claim 2, characterized in that:

所述的组分 A为三氟碘甲垸和 1， 1, 1， 2, 3, 3， 3-七氟丙烷，所述的组分 B为丙烷，其含量分别为制冷剂重量的 55-85%, 5- 25%和 5-20%。 The component A is trifluoroiodomethane and 1, 1, 1, 2, 3, 3, 3- heptafluoropropane, and the component B is propane, and the content thereof is 55-85% by weight of the refrigerant. , 5- 25% and 5-20%.

9、如权利要求 8的制冷剂，其特征在于：所还的三氟碘甲烷、 1， 1， 1， 2， 3, 3, 3-七氟丙垸和丙烷的含量分别为制冷剂重量的 65- 80%, 5- 25¾和 10-18%, 9. The refrigerant according to claim 8, characterized in that: The content of trifluoroiodomethane, 1, 1, 1, 2, 3, 3, 3-heptafluoropropane and propane are 65-80%, 5- 25¾ and 10-18% of the weight of the refrigerant, respectively.

10、如权利要求 2的制冷剂，其特征在于： 10. The refrigerant according to claim 2, characterized in that:

所述的组分 A为三氣碘甲烷和 1, 1, 1, 2, 3, 3, 3-七氟丙垸，所述的组分 B为 1， 1-二氟乙烷，其含量分别为制冷剂重量的 40- 80¾， 3-30%和 7-50%。 The component A is three gas iodomethane and 1, 1, 1, 2, 3, 3, 3- heptafluoropropane, and the component B is 1, 1-difluoroethane, and their contents are respectively It is 40-80¾, 3-30% and 7-50% of refrigerant weight.

Π、如权利要求 10的制冷剂，其特征在于： The refrigerant according to claim 10, characterized in that:

所述的三氟碘甲烷、 1， 1， 1, 2， 3, 3， 3-七氟丙烷和 1, 1-二氟乙烷的含量分别为制冷剂重量的 40-60%, 5- 15%和 30-50%. The content of the trifluoroiodomethane, 1, 1, 1, 2, 3, 3, 3-heptafluoropropane and 1, 1-difluoroethane are 40-60%, 5- 15% and 30-50%.

12、如权利要求 1的制冷剂，其特征在于： 12. The refrigerant according to claim 1, characterized in that:

所述的组分 A为五氟乙烷，所述的组分 B为一氟乙烷，其含量分别为制冷剂重量的 10-95%, 5-90¾. The component A is pentafluoroethane, and the component B is monofluoroethane, the content of which is 10-95%, 5-90¾ of the weight of the refrigerant, respectively.

13、如权利要求 12的制冷剂，其特征在于： 13. The refrigerant according to claim 12, characterized in that:

所述的五氟乙烷和一氟乙烷的含量分别为制冷剂重量的 40-60%, 60-40%. The content of pentafluoroethane and monofluoroethane are 40-60% and 60-40% of the weight of the refrigerant, respectively.

14、如权利要求 1的制冷剂，其特征在于： 14. The refrigerant according to claim 1, characterized in that:

所述的组分 A为三氟碘甲烷和 1, 1， 2-四氟乙烷，所述的组分 B为三氟甲烷，其含量分别为制冷剂重量的 5-40%, 15- 60%和 10-50%. The component A is trifluoroiodomethane and 1,1,2-tetrafluoroethane, and the component B is trifluoromethane, the content of which is 5-40%, 15-60 of the weight of the refrigerant, respectively. % And 10-50%.

15、如权利要求 14的制冷剂，其特征在于： 15. The refrigerant according to claim 14, characterized in that:

所述的三氟碘甲烷、 1, 1， 2-四氟乙烷和三氟甲烷的含量分别为制冷剂重量的 10- 35%, 35-60%和 15-35%. The trifluoroiodomethane, 1, 1, 2-tetrafluoroethane and trifluoromethane content are 10-35%, 35-60% and 15-35% of the weight of the refrigerant, respectively.

16、如权利要求 1的制冷剂，其特征在于： 16. The refrigerant according to claim 1, characterized in that:

所述的组分 A为三氟碘甲烷，所述的组分 B为二氟甲烷和 1, 1-二氟乙烷，其含量分别为 10-80%， 10-50%和 10-40%. The component A is trifluoroiodomethane, and the component B is difluoromethane and 1, 1-difluoroethane, the contents of which are 10-80%, 10-50%, and 10-40%, respectively. .

Π、如权利要求 16的制冷剂，其特征在于： The refrigerant according to claim 16, characterized in that:

所述的三氟碘甲烷、二氟甲烷和 1，1-二氟乙垸的含量分别为 40-65%, 20-40%和 5- The trifluoroiodomethane, difluoromethane and 1,1-difluoroacetamidine content are 40-65%, 20-40% and 5-

25%。 25%.

18、如权利要求 1的制冷剂，其特征在于： 18. The refrigerant according to claim 1, characterized in that:

所述的组分 A为五氟乙垸，所述的组分 B为环丙烷和一氟乙烷，其含量分别为制冷剂重量的 10-70%, 5-20¾和20-50¾. The component A is pentafluoroacetamidine, and the component B is cyclopropane and monofluoroethane, the content of which is 10-70%, 5-20¾ and 20-50¾, respectively, based on the weight of the refrigerant.

19、如权利要求 18的制冷剂，其特征在于： 19. The refrigerant according to claim 18, wherein:

所述的五氟乙烷、环丙烷和一氟乙烷的含量分别为制冷剂重量的 40-60%, 10- 20%和 25- 45¾。 The contents of the pentafluoroethane, cyclopropane and monofluoroethane are 40-60%, 10-20% and 25-45¾ of the weight of the refrigerant, respectively.

20、如权利要求 1的制冷剂，其特征在于： 20. The refrigerant according to claim 1, characterized in that:

所述的组分 A为三氟碘甲烷和五氟乙烷，所述的组分 B为一氟乙垸，其含量分别为制 ^刑直量的 5-50%, 20- 60%和 20-60%。 The component A is trifluoroiodomethane and pentafluoroethane, and the component B is monofluoroacetamidine, the contents of which are respectively ^ 5-50%, 20-60% and 20-60% of the sentence.

21、如权利要求 20的制冷剂，其特征在于： - 所述的三氟碘甲烷、五氟乙垸和一氟乙烷的含量分别为制冷剂重量的 5-15%， 30-50% 和 40-55%. 21. The refrigerant according to claim 20, characterized in that:-the content of said trifluoroiodomethane, pentafluoroacetamidine and monofluoroethane is 5-15%, 30-50% and 40-55%.

22、如权利要求 1的制冷剂，其特征在于： 22. The refrigerant according to claim 1, characterized in that:

所述的组分 A为一氯二氟代甲垸，所述的组分 B为 1, 1-二氟乙烷，其含量分别为制冷剂重量的 40-60%和 40-60%; The component A is monochlorodifluoroformamidine, and the component B is 1, 1-difluoroethane, the content of which is 40-60% and 40-60% of the weight of the refrigerant, respectively;

23、如权利要求 2的制冷剂，其特征在于： 23. The refrigerant according to claim 2, characterized in that:

所述的组分 A为一氣二氟代甲烷和 1， 1， 1, 2, 3, 3, 3-七氟丙垸或三氟碘甲烷，所述的组分 B为 1, 1-二氟乙烷，其含量分别为制冷剂重量的 15-50%, 2-30%和 30-65%; The component A is monogas difluoromethane and 1, 1, 1, 2, 3, 3, 3- heptafluoropropane or trifluoroiodomethane, and the component B is 1, 1-difluoro Ethane, its content is 15-50%, 2-30% and 30-65% of the weight of the refrigerant;

24、如权利要求 1的制冷剂，其特征在于： 24. The refrigerant according to claim 1, characterized in that:

所述的组分 A为一氯二氣代甲烷和 1, 1, 1, 2-四氟乙烷，所述的组分 B为 1， 1-二氟乙烷，其含量分别为制冷剂重量的 5-35%, 10-60%和 30-65%. The component A is monochlorodigasmethane and 1, 1, 1, 2-tetrafluoroethane, and the component B is 1, 1-difluoroethane, and the contents are respectively the weight of the refrigerant 5-35%, 10-60% and 30-65%.

25、一种产生冷却作用的方法，它包括对如权利要求 1-24之一的制冷剂进行蒸气压缩制冷. 25. A method for generating a cooling effect, comprising vapor-compression refrigeration of a refrigerant according to any one of claims 1-24.

26、一种产生供热作用的方法，它包括对如权利要求 1-24之一的制冷剂进行蒸气压缩供热. 7、一种用于控温作用的方法，它包括对如权利要求 1-24之一的制冷剂吸热或放热后利用饱和压力温度对应关系进行控温. 26. A method for generating a heating effect, which comprises vapor-compression heating of a refrigerant according to one of claims 1 to 24. 7. A method for controlling a temperature, which includes providing a heating effect as claimed in claim 1 One of the refrigerants in -24 uses the saturation pressure-temperature correspondence relationship to control the temperature after absorbing or releasing heat.