WO2004099336A1 - Fluide frigorigene environnemental remplacant hcfc-22 - Google Patents

Fluide frigorigene environnemental remplacant hcfc-22 Download PDF

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Publication number
WO2004099336A1
WO2004099336A1 PCT/CN2004/000319 CN2004000319W WO2004099336A1 WO 2004099336 A1 WO2004099336 A1 WO 2004099336A1 CN 2004000319 W CN2004000319 W CN 2004000319W WO 2004099336 A1 WO2004099336 A1 WO 2004099336A1
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Prior art keywords
hfc
hcfc
refrigerant
mass percentage
temperature
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PCT/CN2004/000319
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English (en)
French (fr)
Inventor
Guangming Chen
Zhikai Guo
Xinzheng Guo
Yongmei Xuan
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Zhe Jiang Lantian Environmental Protection Hi-Tech Co. Ltd.
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Application filed by Zhe Jiang Lantian Environmental Protection Hi-Tech Co. Ltd. filed Critical Zhe Jiang Lantian Environmental Protection Hi-Tech Co. Ltd.
Priority to EP04726416.3A priority Critical patent/EP1630216B1/de
Priority to CNB2004800102368A priority patent/CN100500792C/zh
Publication of WO2004099336A1 publication Critical patent/WO2004099336A1/zh
Priority to US11/221,777 priority patent/US7459101B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2205/22—All components of a mixture being fluoro compounds
    • 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
    • C09K2205/40—Replacement mixtures
    • C09K2205/43—Type R22

Definitions

  • the present invention relates to refrigerants, and in particular, to an environmentally friendly refrigerant that replaces HCFC-22.
  • HCFC-22 hydrochlorofluorocarbon (HCFC) refrigerants
  • HCFC-22 has been widely used in air conditioning, low temperature, and food freezing projects due to its excellent comprehensive properties in thermodynamics, chemistry, and physics.
  • HCFC-22 has a certain destructive effect on the ozone layer in the stratosphere of the atmosphere, and its ODP (Ozone Depletion Potential) value is 0.055 (with CFC-11 as the reference value 1.0).
  • ODP Ozone Depletion Potential
  • people have paid more and more attention to this destructive effect of HCFC-22.
  • the Montreal Protocol on Substances that Deplete the Ozone Layer, held in December 1995, the Seventh Congress of the States Parties has advanced the ban period of HCFC-22 in developed countries. In 2020, China will also stop using HCFC-22 from 2030.
  • HCFC-22 there is another serious environmental problem, namely the greenhouse effect of the earth, its global warming potential GWP (Global Warming Potential) value 1700 (C0 2 as a reference value to 1.0), global warming is Big.
  • GWP Global Warming Potential
  • HFC mixed working fluid is usually considered as an alternative working fluid.
  • R407C and R410A are usually used as the main substitute refrigerants for HCFC-22 in the current technology.
  • R407C is a ternary near-azeotropic mixture of R32, R125 and R134a. Its evaporation pressure and condensation pressure are very close to HCFC-22, which is the biggest advantage of R407C replacing HCFC-22. However, the heat transfer characteristics of R407C are poor, and the unit cooling capacity and COP value are both smaller than HCFC-22 under air conditioning conditions. In order to achieve the same cooling capacity as HCFC-22, the condensation area needs to be increased, and the air volume of the condenser also needs to be increased. In this way, the condenser is much larger than the HCFC-22 system.
  • R410A is a binary near-azeotropic mixture of R32 and R125. It has a substantially constant boiling point, which facilitates the charging of refrigerant and the replacement of equipment. Under the condition of air conditioning, the COP value of R410A is about 9% smaller than that of HCFC-22. Its evaporation pressure, condensing pressure and volume cooling capacity are much larger than HCFC-22, and cannot be directly used to replace HCFC-22. Redesign compressors, piping and systems.
  • the object of the present invention is to provide an environmentally friendly refrigerant that replaces HCFC-22.
  • the refrigerant contains three components, HFC-161, HFC-125 and HFC-32, and its mass percentage is:
  • HFC-161 5% -60%
  • HFC-32 5% -50%.
  • the refrigerant of the present invention has the following advantages:
  • Thermal parameters such as operating pressure and pressure ratio are similar to HCFC-22. Under the premise that the main components of the equipment are not changed, the thermal performance such as unit mass cooling capacity and exhaust temperature are better than HCFC-22, COP value Although it is smaller than HCFC-22, it is larger than R410A and R407C. Can be used as a long-term alternative to HCFC-22, and can reduce the amount of filling. detailed description
  • the present invention aims to develop and research a new refrigerant that can be used to replace HCFC-22, so that the newly developed refrigerant not only does not damage the atmospheric ozone layer, but also has a smaller greenhouse effect. In addition, it has the same thermal parameters and thermal properties as HCFC-22, and can be used as a direct replacement for HCFC-22.
  • the present invention provides a novel refrigerant that can be used instead of HCFC-22, which is characterized in that the refrigerant contains fluoroacetamidine (HFC-161), pentafluoroethane (HFC-125), and difluoromethane (HFC- 32)
  • HFC-161 fluoroacetamidine
  • HFC-125 pentafluoroethane
  • HFC- 32 difluoromethane
  • HFC-161 5% -60%
  • HFC-32 5% -50%.
  • the more preferred mass percentage is:
  • HFC-161 30% -60%
  • HFC-32 5% -35%.
  • the more preferred mass percentage is:
  • HFC-161 40% -50%
  • the most preferred mass percentage is:
  • the refrigerant provided by the present invention is prepared by physically mixing the above-mentioned various components in a liquid phase state according to their corresponding proportions.
  • the fluoroacetamidine (HFC-161) in the above components has a molecular formula of CH 3 CH 2 F, a molecular weight of 48.06, a standard boiling point of -37. C, a critical temperature of 102.2 ° C, and a critical pressure of 4.7 MPa.
  • Pentafluoroacetamidine (HFC-125) in the above components has a molecular formula of CHF 2 CF 3 , a molecular weight of 120.02, a standard boiling point of -48.rC, a critical temperature of 66.2 ° C, and a critical pressure of 3.63 MPa.
  • difluoromethane HFC-32
  • HFC-32 has a molecular formula of CH 2 F 2 , a molecular weight of 52.02, a standard boiling point of -51 / TC, a critical temperature of 78.2 Torr, and a critical pressure of 5.78 MPa.
  • Example 1 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 5:50:45.
  • Example 2 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 5:45:50.
  • Example 3 HFC-161, HFC-125 and HFC-32 are physically mixed in a liquid phase at a mass percentage of 25:25:50.
  • Example 4 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 20:40:40.
  • Example 5 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 15:35:50.
  • Example 6 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 50:40:10.
  • Example 7 HFC-161, HFC-125 and HFC-32 were physically mixed in the liquid phase at a mass of 30:35:35.
  • Example 8 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 60: 35: 5.
  • Example 9 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 40:25:35.
  • Example 10 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 45: 50: 5.
  • Example 11 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 15:50:35.
  • Example 12 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 30:50:20.
  • Example 13 HFC-16K HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 60:25:15.
  • Example 14 HFC-161, HFC-125 and HFC-32 were physically mixed in a liquid phase at a mass percentage of 45:37:18.
  • the bubble point temperature and dew point temperature in the table are the saturation temperature at standard atmospheric pressure of 101.325kPa).
  • the temperature slip of all the examples is not large, which belongs to near-azeotropic mixed refrigeration. Compared with R407C, the main replacement of HCFC-22, the agent has less temperature slip.
  • Table 2 compares the environmental performance of the above examples with HCFC-22, R407C, and R410A.
  • the ODP value uses CFC-11 as the reference value 1.0
  • the GWP value uses C0 2 as the reference value 1.0 (100 years). Table 2 Comparison of environmental performance
  • ODP ozone layer depletion potential
  • the global warming potential (GWP) values of the above embodiments are also less than R22, R407C, R410A, only 29 ⁇ 78% of the HCFC-22 GWP value, and 35 ⁇ 97% of the GWP values of the two main substitutes, R407C and R410A. , More in line with the current environmental protection requirements to protect the ozone layer and reduce the effects of global warming. c Thermal parameters and thermal performance
  • Embodiments 1, 2, 3, 4, 5, 7, 9, 11, 12, and 14 although the cooling capacity per unit volume and the power consumption per unit volume are larger than HCFC-22 and R407C, but smaller than R410A, they can be directly The R410A compressor is used with little modification.

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Description

一种替代 HCFG-22的环保型制冷剂
技术领域
本发明涉及制冷剂， 尤其涉及一种替代 HCFC-22的环保型制冷剂。 技术背景
在氢氯氟烃（HCFC)类制冷剂中， 由于 HCFC-22在热力学、 化学和物理等 方面优良的综合性能， 目前已被广泛地应用于空调、 低温和食品冷冻等工程中。
但是 HCFC-22对大气同温层中的臭氧层具有一定的破坏作用， 其消耗臭氧 层潜能 ODP ( Ozone Depletion Potential)值为 0.055 (以 CFC-11作为基准值 1.0)。 近年来人们对 HCFC-22的这种破坏作用已日益重视， 1995年 12月召开的 《关 于消耗臭氧层物质的蒙特利尔协议书》 缔约国第七次代表大会己将发达国家 HCFC-22的禁用期提前到 2020年， 我国也将于 2030年起停止使用 HCFC-22。
此外， HCFC-22 还存在另外一个严重的环境问题， 即对地球的温室效应， 其全球变暖潜能 GWP (Global Warming Potential) 值为 1700 (以 C02作为基准 值 1.0)， 全球变暖效应很大。 1997年召开的关于防止地球变暖京都会议中己经 特别强调要控制温室效应气体的排放。种种现象表明对制冷空调领域中有重要地 位的 HCFC-22的替代工作已是势在必行。
现有研究表明， 没有哪一种纯工质的 COP值和容积制冷量能均优于 R22, 甚至没有接近的， 在这种情况下， 通常考虑采用 HFC的混合工质作为替代工质。 在该原则的指导下， 目前技术中通常使用 R407C和 R410A作为 HCFC-22的主 要替代制冷剂。
R407C是 R32、 R125和 R134a的三元近共沸混合物， 其蒸发压力和冷凝压 力与 HCFC-22非常接近， 这是 R407C替代 HCFC-22的最大优点。但是， R407C 的传热特性较差， 在空调工况下的单位容积制冷量和 COP值都小于 HCFC-22。 为了达到与 HCFC-22相同的冷量， 需要增加冷凝面积， 而且冷凝器风量也需要 增加， 这样， 其冷凝器要比 HCFC-22系统大很多。 由于它是近共沸制冷剂， 在 换热器中可能会发生分馏作用， 从而导致蒸发和冷凝过程中组分随温度、压力而 变化， 在换热器的定压相变过程中还存在约 7°C的温度滑移； 因此， 系统的泄漏 会导致组分的明显改变， 这使得 R407C空调系统的维修和保养存在一定的困难， 同时对其传热性能也会产生一定的影响。
R410A是 R32和 R125的二元近共沸混合物， 它具有基本恒定的沸点， 这给 制冷剂的充灌、 设备的更换提供了方便。 在空调工况下， R410A 的 COP 值比 HCFC-22约小 9%， 其蒸发压力、 冷凝压力以及容积制冷量都比 HCFC- 22大很 多， 不能直接用来替代 HCFC-22, 在使用时要重新设计压缩机、 管路和系统。
此外， R410A与 R407C虽然 ODP值均为 0， 但仍具有较高的 GWP值， 在 全球变暖业已成为紧迫的环境问题的情况下， 较高的 GWP值已日益成为明显的 缺陷， 需要加以改进。 发明内容
本发明的目的是提供一种替代 HCFC-22的环保型制冷剂。
该制冷剂含有 HFC-161、 HFC-125和 HFC-32三种组分, 其质量百分比为：
HFC-161 : 5%-60%
HFC-125 : 25%-50%
HFC-32: 5%-50% 。
本发明的制冷剂与现有技术相比， 具有以下优点：
1 ) 近共沸， 温度滑移小于 R407C。
2 ) 环境性能良好， 不仅消耗臭氧层潜能 ODP 值为零， 而且全球变暧潜能 GWP值大大小于 HCFC-22及其现有的主要替代物 R407C、 R410A, 符合环保要 求， 这是本发明的最大优势。
3 )热工参数如运行压力、 压比与 HCFC-22相近， 在基本不改变设备主要部 件的前提下， 热工性能如单位质量制冷量、 排气温度都要优于 HCFC-22 , COP 值虽然小于 HCFC-22, 但是大于 R410A、 R407C。 可作为 HCFC-22的长期替代 物， 并且可以减少充灌量。 具体实施方式
本发明旨在开发研究一种可用于替代 HCFC- 22的新型制冷剂，使新开发的制 冷剂不仅不破坏大气臭氧层， 而且温室效应更小。此外， 还具有和 HCFC-22相当 的热工参数和热工性能， 可作为 HCFC- 22的直接替代物。 本发明提供的这种可用于替代 HCFC- 22的新型制冷剂，其特征在于该制冷剂 中含有氟乙垸 （HFC-161)、 五氟乙烷 （HFC-125) 和二氟甲烷 （HFC- 32) 这三种 组份， 其质量百分比为：
HFC-161: 5%-60%
HFC-125: 25%-50%
HFC-32: 5%-50% 。
比较优选的质量百分比为：
HFC-161: 30%-60%
HFC-125: 25%-50%
HFC-32: 5%-35% 。
较优选的质量百分比为：
HFC-161: 40%-50%
HFC-125: 30%-45%
HFC-32: 10%-25%
最优选的质量百分比为：
HFC-161: 43%-47%
HFC-125: 36%-40%
HFC-32: 16%-20%
本发明提供的制冷剂，其制备方法是将上述各种组分按照其相应的配比在液 相状态下进行物理混合。
上述组分中的氟乙垸 （HFC-161), 其分子式为 CH3CH2F， 分子量为 48.06， 标准沸点为 -37. C, 临界温度为 102.2°C， 临界压力为 4.7MPa。
上述组分中的五氟乙垸（HFC-125),其分子式为 CHF2CF3，分子量为 120.02, 标准沸点为 -48.rC， 临界温度为 66.2°C, 临界压力为 3.63MPa。
上述组分中的二氟甲垸 （HFC-32), 其分子式为 CH2F2， 分子量为 52.02， 标准沸点为 -51/TC, 临界温度为 78.2Ό, 临界压力为 5.78MPa。
实施例 1: 将 HFC-161、 HFC-125和 HFC-32在液相下按 5: 50： 45的质量 百分比进行物理混合。
实施例 2: 将 HFC-161、 HFC-125和 HFC-32在液相下按 5: 45： 50的质量 百分比进行物理混合。 实施例 3 : 将 HFC-161、 HFC-125和 HFC-32在液相下按 25 : 25： 50的质量 百分比进行物理混合。
实施例 4： 将 HFC-161、 HFC-125和 HFC-32在液相下按 20： 40： 40的质量 百分比进行物理混合。
实施例 5： 将 HFC-161、 HFC-125和 HFC-32在液相下按 15： 35： 50的质量 百分比进行物理混合。
实施例 6: 将 HFC-161、 HFC-125和 HFC-32在液相下按 50: 40： 10的质量 百分比进行物理混合。
实施例 7: 将 HFC-161、 HFC-125和 HFC-32在液相下按 30: 35： 35的质量. 百分比进行物理混合。
实施例 8: 将 HFC-161、 HFC-125和 HFC-32在液相下按 60: 35： 5的质量 百分比进行物理混合。
实施例 9: 将 HFC- 161、 HFC-125和 HFC-32在液相下按 40: 25： 35的质量 百分比进行物理混合。
实施例 10： 将 HFC-161、 HFC-125和 HFC-32在液相下按 45： 50： 5的质量 百分比进行物理混合。
实施例 11 : 将 HFC-161、 HFC-125和 HFC-32在液相下按 15 : 50： 35的质 量百分比进行物理混合。
实施例 12: 将 HFC-161、 HFC-125和 HFC-32在液相下按 30: 50: 20的质 量百分比进行物理混合。
实施例 13： 将 HFC-16K HFC-125和 HFC-32在液相下按 60： 25： 15的质 量百分比进行物理混合。
实施例 14: 将 HFC-161、 HFC-125和 HFC-32在液相下按 45 : 37： 18的质 量百分比进行物理混合。
现将上述实施例的性能与 HCFC-22及其主要替代物 R407C、 R410A进行比 较， 说明本发明的特点和效果。
a. 近共沸 表 1温度滑移的比较 （单位： °c )
Figure imgf000006_0001
(注： 表中的泡点温度和露点温度都是在标准大气压 101.325kPa时的饱和温度） . 从表 1中可以看出，所有实施例的温度滑移都不大，属于近共沸混合制冷剂， 与 HCFC-22现有的主要替代物 R407C相比， 温度滑移要小。
b. 环境性能
表 2比较了上述实施例与 HCFC-22、 R407C、 R410A的环境性能。其中 ODP 值以 CFC-11作为基准值 1.0, GWP值以 C02作为基准值 1.0 ( 100年）。 表 2 环境性能比较
Figure imgf000007_0001
从表 2中可以看出， 上述实施例的臭氧层消耗潜能（ODP)值为零， 对大气 臭氧层没有破坏作用， 这一点要优于 HCFC-22。
不仅如此， 上述实施例的全球变暖潜能 （GWP ) 值也小于 R22、 R407C R410A, 只有 HCFC-22 GWP值的 29~78%, R407C、 R410A这两种主要替代物 GWP值的 35~97%，更符合当前保护臭氧层、减小全球变暖效应的环境保护要求。 c 热工参数及热力性能
表 3 比较了空调工况下 （即蒸发温度 =7°C， 冷凝温度二 55°C， 吸气温度 =18 V， 过冷温度 =50°C )， 上述实施例与 HCFC-22、 R407C、 R410A的热工参数 (即: 蒸发压力 P,>、 冷凝压力 Pk、 压比 f P„、 排气温度 t2) 及相对热力性能 (即: 相 对 C0P、 相对单位质量制冷量 q,,、 相对单位容积制冷量 q„、 相对单位容积耗功量 wv )„ 所说的相对热力性能是指实际热力性能与 HCFC-22热力性能的比值。
表 3 热工参数的比较
Figure imgf000008_0001
从表 3中可见， 在空调工况下， 实施例 6、 8、 10、 13的冷凝压力、 蒸发压 力、 压比与 HCFC-22相近， 而且均处于允许范围， 可直接充灌； 从排气温度来 看， 上述实施例的排气温度要低于 HCFC-22 , 接近或低于 R407C、 R410A; 单 位质量制冷量高于 HCFC-22、 R407C、 R410A, 这意味着可以减少系统制冷剂的 充灌量； COP值均优于 R407C或 R410A， 因此， 这些实施例具有节能效果； 此 外， 它们的单位容积制冷量和单位容积耗功量与 HCFC-22或 R407C相比， 偏差 不大， 这表明这些实施例可直接使用 HCFC-22或 R407C的压缩机， 而基本无需 改动。 在实施例 1、 2、 3、 4、 5、 7、 9、 11、 12、 14中， 虽然单位容积制冷量和 单位容积耗功量大于 HCFC-22 和 R407C, 但小于 R410A, 因此， 可直接使用 R410A的压缩机， 而基本无需改动。

Claims

权 利 要 求 书
1、 一种替代 HCFC- 22的环保型制冷剂， 其特征在于该制冷剂含有 HFC-161、 HFC- 125和 HFC- 32三种组分， 其质量百分比为：
HFC-161 : 5%- 60%
HFC-125: 25%- 50%
HFC-32: 5%-50% 。
2、 根据权利要求 1所述的一种替代 HCFC- 22的环保型制冷剂， 其特征在于 其质量百分比为：
HFC-161 : 30%- 60%
HFC-125: 25%- 50%
HFC-32: 5%- 35% 。
3、 根据权利要求 1所述的一种替代 HCFC-22的环保型制冷剂， 其特征在于 其质量百分比为：
HFC-161 : 40%-50%
HFC-125: 30%- 45%
HFC-32: 10%- 25% 。
4、 根据权利要求 1所述的一种替代 HCFC-22的环保型制冷剂， 其特征在于 其质量百分比为-
HFC-161 : 43%- 47%
HFC-125 : 36%-40%
HFC-32 : 16%- 20% 。
PCT/CN2004/000319 2003-05-07 2004-04-08 Fluide frigorigene environnemental remplacant hcfc-22 WO2004099336A1 (fr)

Priority Applications (3)

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EP04726416.3A EP1630216B1 (de) 2003-05-07 2004-04-08 Umweltfreundlicher kühlmittelersatz für hcfc-22
CNB2004800102368A CN100500792C (zh) 2003-05-07 2004-04-08 一种替代hcfc-22的环保型制冷剂
US11/221,777 US7459101B2 (en) 2003-05-07 2005-09-09 Environmentally friendly alternative refrigerant for HCFC-22

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CN031168566A CN1216118C (zh) 2003-05-07 2003-05-07 一种替代hcfc－22的环保型制冷剂
CN03116856.6 2003-05-07

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US20100101245A1 (en) * 2006-12-23 2010-04-29 E. I. Du Pont De Nemours And Company Fluorinated compositions and systems using such compositions
US20100011791A1 (en) * 2006-12-23 2010-01-21 Roger Nicholas Strickland R422d heat transfer systems and r22 systems retrofitted with r422d
CN101157849A (zh) * 2007-11-09 2008-04-09 浙江蓝天环保高科技股份有限公司 一种环保型制冷剂
JP5243880B2 (ja) * 2008-08-05 2013-07-24 日立電線株式会社 絶縁電線
US20140088017A1 (en) * 2011-05-23 2014-03-27 Yeda Research And Development Co., Ltd. Use of akt phosphorylation as a biomarker for prognosing neurodegenerative diseases and treating same
CN113528091B (zh) * 2020-04-09 2023-03-24 浙江省化工研究院有限公司 一种含hfc-161的环保型制冷组合物

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CN1780892A (zh) 2006-05-31
CN1478849A (zh) 2004-03-03
CN1216118C (zh) 2005-08-24
EP1630216B1 (de) 2017-03-15
US20060001001A1 (en) 2006-01-05
US7459101B2 (en) 2008-12-02
CN100500792C (zh) 2009-06-17
EP1630216A1 (de) 2006-03-01
EP1630216A4 (de) 2010-11-24

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