CN101838519A - 冷冻机制冷剂 - Google Patents
冷冻机制冷剂 Download PDFInfo
- Publication number
- CN101838519A CN101838519A CN201010167086A CN201010167086A CN101838519A CN 101838519 A CN101838519 A CN 101838519A CN 201010167086 A CN201010167086 A CN 201010167086A CN 201010167086 A CN201010167086 A CN 201010167086A CN 101838519 A CN101838519 A CN 101838519A
- Authority
- CN
- China
- Prior art keywords
- composition
- content
- weight
- tetrafluoroethane
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003507 refrigerant Substances 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 100
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 17
- KLZDCUBZWUSEGO-UHFFFAOYSA-N CC.F.F.F.F.F Chemical compound CC.F.F.F.F.F KLZDCUBZWUSEGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 claims abstract description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000005057 refrigeration Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000003449 preventive effect Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 26
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000009834 vaporization Methods 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- 239000001273 butane Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 trifluoromethoxy pentafluoride ethane Chemical compound 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GQUXQQYWQKRCPL-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorocyclopropane Chemical compound FC1(F)C(F)(F)C1(F)F GQUXQQYWQKRCPL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 101000609457 Trichosanthes kirilowii Trypsin inhibitor 1 Proteins 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ACYQYBAHTSKBLM-UHFFFAOYSA-N difluoromethoxy(trifluoro)methane Chemical compound FC(F)OC(F)(F)F ACYQYBAHTSKBLM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNXBKJFUJUWOCW-UHFFFAOYSA-N methylcyclopropane Chemical compound CC1CC1 VNXBKJFUJUWOCW-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Amplifiers (AREA)
- Saccharide Compounds (AREA)
Abstract
公开了一种制冷剂组合物,该组合物由以下组分组成:(a)五氟乙烷,其含量基于组合物重量为60~70wt%;(b)1,1,1,2-四氟乙烷或1,1,2,2-四氟乙烷或其混合物,其含量基于组合物的重量为26~36wt%;和(c)正丁烷,基于组合物重量的其含量为1~4wt%。
Description
本申请是分案申请,其母案是申请日为2003年12月1日、申请号为200380109220.8和发明名称为“冷冻机制冷剂”的申请。
本发明涉及制冷剂组合物,特别涉及可用于冷冻机的组合物。这种装置特别是由于生产一般温度为1~10℃的冷水或水溶液的装置。
冷冻机需要大量的冷量。当前把R22(CHClF2)用于此目的。然而,由于R22是一种臭氧消耗剂,按照蒙特利尔议定书将要再未来十年停止使用,所以需要替代的制冷剂。
因此,就需要一种与R22的性能相似,但不会消耗臭氧的制冷剂。其中特别涉及到的就是,这种制冷剂的温度/蒸气压关系应该与R22足够相似,使其能够用于R22的设备而无须改变控制系统,此控制系统一般在冷冻机制造厂已被编好程序。
这就特别涉及具有基于膨胀阀输入压力和输出压力的敏感控制器件的系统。这种控制系统是基于R22的性能的。因此,如果R22替代物不具有与R22相类似的温度/蒸气压的性能,该系统将不能正确地操作。
我们使用“相类似”一词,意味着在-40℃~+10℃之间的任何给定的平均蒸发温度下,此替代物的蒸气压的差值不应大于±12%,优选不大于±6%。
另外也是很重要的是,任何这样的制冷剂要具有与R22类似的容量和效率。
“类似的容量”意味着在-35℃~-28℃之间的平均蒸发温度下,其容量比R22低得不超过20%,优选比R22低得不超过10%。“类似的效率”意味着在-35℃~-28℃之间的平均蒸发温度下,其效率比R22低得不超过10%,优选比R22低得不超过5%。
按照本发明,提供一种制冷剂,它包括:
(a)五氟乙烷、三氟甲氧基二氟甲烷或六氟环丙烷,或者其中两种或更多种的混合物,基于组合物重量的其含量为60~70wt%。
(b)1,1,1,2-或1,1,2,2-四氟乙烷、三氟甲氧基五氟乙烷、1,1,1,2,3,3-七氟丙烷或其中两种或更多种的混合物,基于组合物重量的其含量为26~36wt%。
(c)乙烯型不饱和或饱和的烃类,任选含有一个或几个氧原子,其沸点为-12~+10℃,或者这些烃类的混合物,或者一种或几种所述烃类与一种或几种其它烃类的混合物,所述混合物的沸点为-12~10℃,基于组合物重量的其含量为1~4wt%。意外地发现,这样的特定配方具有的性能条件,使其能够用作“偶然到来的”R22替代物。
在一个实施方案中,所述组分(c)的含量基于组合物的重量为约为1%至约4%。在另一个实施方案中,所述组分(c)的含量基于组合物的重量为约3%至4%。
在上面所引用的百分比指的是液相。对于汽相相应的范围如下:
(a)75~87%(b)10~28%和(c)0.9~4.1%,所有的重量都是基于组合物的重量。这些百分比优选既用于液相也用于汽相。
本发明还提供制冷的方法,此方法包括使本发明的组合物冷凝,然后使该组合物在靠近待冷却的物体处蒸发。本发明还提供含有本发明的组合物作为制冷剂的制冷设备。
基于组合物的重量,组分(a)的含量为60~70wt%。优选为62~67wt%,特别是高于64wt%,并且可直至66wt%。组分(a)优选是R125(五氟乙烷)或含有至少一半,特别是含有至少3/4(质量)R125的混合物。组分(a)最优选是只含R125。
基于组合物的重量,组合物中组分(b)的含量为26~36%,特别是28~32%。组分(b)优选是含有至少一半,特别是含有至少3/4(质量)R134a(1,1,1,2-四氟乙烷)的混合物。组分(b)最优选只含R134a。
希望组分(a)和组分(b)的重量比至少为1.5∶1,优选为1.5∶1~3∶1,特别是1.8∶1~2.2∶1。
组分(c)是一种饱和的或乙烯类不饱和烃,任选含有一个或几个氧原子,特别是含有一个氧原子,其沸点为-12℃~+10℃,特别是-12℃~-5℃或其混合物。可以使用的优选的烃具有3~5个碳原子。它们可以是非环状的或环状的。可以使用的非环状烃包括丙烷、正丁烷、异丁烷和甲基乙基醚中的一种或几种。可以使用的环状烃包括甲基环丙烷。优选的烃包括正丁烷和/或异丁烷。组分(c)还可以是这些烃与一种或几种其它烃的混合物,所述混合物具有-12℃~+10℃,特别是-12℃~-5℃的始沸点。可以在此混合物中使用的其它烃类包括戊烷和异戊烷、丙烯、二甲醚、环丁烷、环丁烯和环氧乙烷。
在此组合物中不排除存在至少一种其它的组分。比如虽然此组合物一般应含有3个主要组分,至少也可以存在第4个组分。典型的另一个组分包括其它烃类,特别是含氟烃,比如在大气压下沸点为最高-40℃,优选最高-49℃,特别是在分子中的F/H比至少为1的烃,优选是R23,即三氟甲烷,最优选为R32,即二氟甲烷。一般说来,基于组分(a)、(b)和(c)的重量和,这些另外的成分,其最高含量不超过10wt%,特别是不超过5wt%,更特别不超过2wt%。含氟烃的存在一般对所需的配方性能具有中性的影响。在组合物中,希望一种或几种丁烷,特别是正丁烷或异丁烷占烃的总重量的至少70wt%,优选至少80wt%,更优选至少90wt%。应该了解,优选要避免全卤化碳,使得尽可能降低温室效应,还要避免具有一个或几个比氟更重的卤素原子的卤代烃。这样的卤代烃的总量有利地不应超过2wt%,特别是1wt%,更优选不超过0.5wt%。
按照一个优选的实施方案,组合物含有基于组合物重量62~67wt%的五氟乙烷作为组分(a),含有基于组合物重量3~35wt%的1,1,1,2-四氟乙烷作为组分(b)以及含有丁烷和/或异丁烷作为组分(c),或者包括丁烷和/或异丁烷的烃类组成的所述混合物。当组分(c)是一种混合物时,基于组合物的重量,在混合物中丁烷和/或异丁烷的含量优选为至少50wt%,特别是至少70wt%,更优选为至少80wt%,甚至更优选为至少90wt%。混合物中的其它组分优选是戊烷。
现已发现,本发明的组合物与通常与CFC制冷剂一起使用的矿物润滑剂是高度相容的。因此,本发明的组合物不仅可与全合成润滑剂,比如多元醇酯(POE)、聚亚烷基二醇(PAG)和聚氧亚丙基二醇,或者与氟化油比如在EP-A-399817中叙述的氟化油一起使用,而且还能够与矿物油和烷基苯润滑剂一起使用,这些润滑剂包括环烷油、石蜡油和硅油,以及这些油和润滑剂与全合成润滑剂和氟化油的混合物。
通常可以使用的添加剂包括“极压”和抗磨添加剂、氧稳定和热稳定改善剂、腐蚀抑制剂、粘度指数改善剂、倾点降低剂、清洗剂、抗泡剂和粘度调节剂。适当的添加剂的实例被包括在US-A-4755316中的表D中。
下面的实施例进一步说明本发明。
实施例
用于测试的试样详述如下:
丁烷(3.5%)共混物:R125/134a/600(65.0/31.5/3.5)
异丁烷(3.5%)共混物:R125/134a/600a(64.9/31.7/3.4)
设备和实验
在一次性铝罐(Drukenbehalter-产品3469)中制备每份大约600g的用于测定蒸气压的试样,然后将其完全浸没在恒温水浴中。对于每次测试,都在罐中装入大约600g物料。在任何同一时间最多可以加工两个试样。使用与标定的Isotech TTII指示器相连的经过标定的铂电阻温度计(152777/1B)来测量浴温。使用两个标定过的Druck压力变换器,DR1和DR2来采取压力读数。
浴温设定在所需的最低温度,然后将其放置直至被冷却下来,当温度和压力保持恒定至少15min时,随后将其记录下来。以后每升温5℃取一个温度和压力的读数,至最高50℃,每次的时间要保证它们稳定15min,然后记录下读数。
得到的数据没有给出露点,因此没有给出滑移(glide),
使用REFPROP 6程序可以得到对滑移的近似估计。可以用多项式方程来表示滑移对始沸点的关系。现在可以用此方程式来给出对于实验确定的始沸点的近似滑移。这就有效地使计算的滑移对实验确定的数据进行归一化。然后通过从始沸点方程中得到的温度减去温度滑移就能够估计出露点的压力。
然后使用这些方程得到蒸气/压力表。从始沸点得到的实验方程和从REFPROP 6得到的滑移方程显示在表1中。
注:
1.在此方程x=1/T中,T是始沸点(K):y=ln(p),这里p是饱和蒸气压(psi)。为了将其转化为MPa绝对压力,要乘以0.006895。
2.在此方程x=t中,t是液体温度(始沸点℃),y=滑移(在始沸点压力下,℃)。
3.从interpolation的Ashrae手册得到R22的蒸气压。
在低温(LT)热量计上测定制冷剂的性能
设备和一般操作条件
在低温(LT)热量计上测定制冷剂的性能。LT热量计被固定在装有Shell SD油的Bitzer半球冷凝装置。热的蒸气从压缩机排出,经过油分离器进入冷凝器。借助于填料函截止阀在压缩机出口保持排放压力恒定。这必然对冷凝压力/温度具有影响-系统实际上在低于40℃的温度下冷凝。制冷剂随后就沿着液体管线进入蒸发器。
此蒸发器由15mm的铜的蛇管构成,放置在在隔热良好的32LSS浴的边缘的周围。浴中装满50∶50的乙二醇∶水溶液,由PID控制器控制的3×1kW的加热器给其供热。具有大桨叶的搅拌器保证热量均匀地分布。由自动膨胀阀控制蒸发压力。
制冷剂蒸气通过虹吸管换热器返回到压缩机。
使用Dasylab自动地记录下全部12个温度读数、5个压力读数、压缩机的功率和热量输入。
在40℃的冷凝温度和蒸发器过热8℃(±0.5℃)下进行测试。
对于R22,在蒸发器出口的温度保持在相当于蒸发压力的温度(始沸点)以上8℃。
对于其它制冷剂,蒸发器出口的温度保持在相当于蒸发压力的温度(露点)以上8℃。
取相当于从始沸点表上得到的蒸发器压力的温度加上在该温度下的一半滑移计算出对于这些制冷剂的平均蒸发器温度。
当热量计运行时,开始时将蒸发压力和冷凝压力都设置在相当于浴温的近似值。然后让热量计经过一段时间使条件温度。在此期间内,可以进行粗调,还必须进行监测以确保将足够的热量送入浴中,以避免有任何液体返回到压缩机中。当系统确实稳定下来以后,可以对压力和温度进行细调,直至热量计在对于冷凝压力相当于40℃,蒸发器过热8℃时所需的蒸发压力下稳定(注一从蒸发器第三出口测量过热)。
然后开始运行,运行1小时,在此期间内,除了对冷凝压力可能的微小变化进行微调以补偿环境温度的波动以外,不对系统进行调节。
对于每种制冷剂的特定实验细节
R22:在热量计中加入R22(在受液器中加入3.5kg)。在蒸发温度在-38~-22℃之间得到10个数据点。
丁烷(3.5%)共混物:在受液器中加入大约3.55kg,在平均蒸发温度在-38~-22℃之间得到5个数据点。
异丁烷(3.5%)共混物:在LT-热量计的受液器中加入大约3.48kg共混物。在-38~-22℃之间的平均蒸发温度,得到5个数据点。
结果
得到的结果汇总在表2~4中。
对实验结果的看法和讨论
得到的结果以图的形式显示在图1~图6中。图1显示出对于被研究的共混物与R22的饱和蒸气压。此图显示出,共混物的蒸气压仅稍高于R22。
图2显示出在-30℃的平均蒸发温度下,共混物与R22容量的比较,此温度是这些共混物典型的预期操作温度。在此温度下,丁烷共混物的容量仅比R22低4%,而异丁烷的容量稍差,比R22低5.5%。
得到的COP结果显示在图3中。此图显示出,在-30℃的平均蒸发温度下,两种烃类共混物的COP值都比R22小不到1%。
在图4中,容量被固定在-30℃的蒸发温度下R22的容量。下面可以比较不同制冷剂在此恒定容量下的COP。此图显示出,对此给定的容量,丁烷共混物(2.5%)和异丁烷共混物(3.0%)都比R22更有效。
在图5中显示出烃类共混物的容量与R22之比。两种共混物的线彼此平行,其容量是类似的,只是异丁烷共混物稍低。
图6显示出RX共混物与R22的COP的比较。R22的COP和两种共混物的COP显示出是相似的。烃类共混物的线(和R22)在平均蒸发温度-32℃处彼此交叉,此点表示R22的相对COP增大,而异丁烷共混物的相对COP下降。与前面同样,虽然差别只是很小的。
表1.实验SVP测量的结果和来自REFPROP 6的滑移
说明 | SVP方程(见注1) | 滑移方程(见注2) |
丁烷(3.5%)共混物R125/134a/600(65.0/31.5/3.5) | y=-2347.4682x+12.96325R2=0.99999 | y=-0.02618x+3.51740R2=0.99790 |
异丁烷(3.5%)共混物R125/134a/600a(64.9/31.7/3.4) | y=-2356.045324+12999729R2=0.999956 | y=-0.00001x3-0.000012x2+0.028998x+3.628716 |
R22 | (见注3) | 不能用 |
Claims (8)
1.一种制冷剂组合物,该组合物由以下组分组成:
(a)五氟乙烷,其含量基于组合物重量为60~70wt%;
(b)1,1,1,2-四氟乙烷或1,1,2,2-四氟乙烷或其混合物,其含量基于组合物的重量为26~36wt%;和
(c)正丁烷,基于组合物重量的其含量为1~4wt%。
2.一种制冷剂组合物,该组合物由以下组分组成:
(a)五氟乙烷,其含量基于组合物重量为62~67wt%;
(b)1,1,1,2-四氟乙烷或1,1,2,2-四氟乙烷或其混合物,其含量基于组合物的重量为26~36wt%;
(c)正丁烷,其含量基于组合物重量为3~4wt%;和
(d)至少一种润滑剂。
3.一种制冷剂组合物,该组合物由以下组分组成:
(a)五氟乙烷,其含量基于组合物重量为60~70wt%;
(b)1,1,1,2-四氟乙烷或1,1,2,2-四氟乙烷或其混合物,其含量基于组合物的重量为26~36wt%;
(c)正丁烷,基于组合物重量的其含量为1~4wt%;
(d)至少一种润滑剂;和
(e)至少一种添加剂,其选自“极压”添加剂、抗磨添加剂、氧稳定和热稳定改善剂、腐蚀抑制剂、粘度指数改善剂、倾点降低剂、清洗剂、抗泡剂和粘度调节剂。
4.一种制冷剂组合物,该组合物由以下组分组成:
(a)五氟乙烷,其含量基于组合物重量为60~70wt%;
(b)1,1,1,2-四氟乙烷或1,1,2,2-四氟乙烷或其混合物,其含量基于组合物的重量为26~36wt%;
(c)正丁烷,基于组合物重量的其含量为1~4wt%;
(d)至少一种添加剂,其选自“极压”添加剂、抗磨添加剂、氧稳定和热稳定改善剂、腐蚀抑制剂、粘度指数改善剂、倾点降低剂、清洗剂、抗泡剂和粘度调节剂。
5.按照权利要求2或3的组合物,所述至少一种润滑剂选自矿物油、烷基苯润滑剂、全合成润滑剂和氟化油以及它们的混合物。
6.按照权利要求1的组合物,其中基于组合物的重量,组分(b)的含量为28~32wt%。
7.按照权利要求1~4中任何一项的组合物,其中组分(b)是1,1,1,2-四氟乙烷。
8.含有按照权利要求1~4中任何一项的组合物作为制冷剂的制冷设备。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0227891A GB0227891D0 (en) | 2002-11-29 | 2002-11-29 | Chiller refrigerants |
GB0227891.9 | 2002-11-29 | ||
GB0228306.7 | 2002-12-04 | ||
GB0228306A GB0228306D0 (en) | 2002-12-04 | 2002-12-04 | Chiller refrigerants |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200380109220.8A Division CN1742068B (zh) | 2002-11-29 | 2003-12-01 | 冷冻机制冷剂 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101838519A true CN101838519A (zh) | 2010-09-22 |
Family
ID=32472142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010167086A Pending CN101838519A (zh) | 2002-11-29 | 2003-12-01 | 冷冻机制冷剂 |
Country Status (17)
Country | Link |
---|---|
US (7) | US20060151740A1 (zh) |
EP (2) | EP2258788A3 (zh) |
JP (1) | JP4838513B2 (zh) |
KR (1) | KR101126495B1 (zh) |
CN (1) | CN101838519A (zh) |
AT (1) | ATE532841T1 (zh) |
AU (2) | AU2003285568B2 (zh) |
BR (1) | BR0316696B1 (zh) |
CA (1) | CA2507639C (zh) |
ES (1) | ES2374288T3 (zh) |
HK (1) | HK1087429A1 (zh) |
MX (1) | MXPA05005692A (zh) |
NO (1) | NO20053163L (zh) |
PL (1) | PL208354B1 (zh) |
PT (1) | PT1572829E (zh) |
RU (1) | RU2334776C2 (zh) |
WO (1) | WO2004050787A1 (zh) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0223724D0 (en) | 2002-10-11 | 2002-11-20 | Rhodia Organique Fine Ltd | Refrigerant compositions |
JP4838513B2 (ja) | 2002-11-29 | 2011-12-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 深冷器冷媒 |
EP2455439A3 (en) * | 2003-11-13 | 2014-02-19 | E. I. du Pont de Nemours and Company | Compositions and methods for reducing fire hazard of flammable refrigerants |
JP2007107858A (ja) * | 2005-10-17 | 2007-04-26 | Sanyo Electric Co Ltd | 冷凍装置 |
MX2009006556A (es) * | 2006-12-21 | 2009-06-26 | Du Pont | Composiciones de pentafluoroetano, tetrafluoroetano e hidrocarburo. |
BRPI0719479B8 (pt) * | 2006-12-23 | 2017-06-27 | Du Pont | sistema de transferência de calor, refrigerador, câmara frigorífica, resfriador, expositor de produtos, congelador, equipamento de ar condicionado, método para retroajustar um sistema de transferência de calor e sistema de refrigeração ou condicionamento de ar |
GB201002625D0 (en) * | 2010-02-16 | 2010-03-31 | Ineos Fluor Holdings Ltd | Heat transfer compositions |
US20110017942A1 (en) * | 2008-04-15 | 2011-01-27 | E.I. Du Pont De Nemours And Company | Pentafluoroethane, tetrafluoroethane and n-butane compositions |
GB0906547D0 (en) * | 2009-04-16 | 2009-05-20 | Ineos Fluor Holdings Ltd | Heat transfer compositions |
US8444873B2 (en) | 2009-06-12 | 2013-05-21 | Solvay Fluor Gmbh | Refrigerant composition |
FR2950069B1 (fr) * | 2009-09-11 | 2011-11-25 | Arkema France | Utilisation de compositions ternaires |
GB201002622D0 (en) * | 2010-02-16 | 2010-03-31 | Ineos Fluor Holdings Ltd | Heat transfer compositions |
US20130255302A1 (en) * | 2012-03-30 | 2013-10-03 | James B. Tieken | Cleaning composition and method for refrigeration system |
WO2014004665A2 (en) | 2012-06-27 | 2014-01-03 | Gws Energy, Inc. | Hydrocarbon based refrigerant |
US9879164B2 (en) | 2013-01-25 | 2018-01-30 | Trane International Inc. | Refrigerant additives and compositions |
US8999191B2 (en) | 2013-03-15 | 2015-04-07 | National Refrigerants, Inc. | R22 replacement refrigerant |
US11028300B1 (en) | 2020-09-16 | 2021-06-08 | David L. Couchot | Environmentally friendly refrigerant compositions |
Family Cites Families (85)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB101717A (en) | 1915-10-02 | 1917-08-09 | Charles Frederic Larsen | Improvements in Devices for Lighting Gas and like purposes. |
US3779842A (en) | 1972-04-21 | 1973-12-18 | Macdermid Inc | Method of and composition for dissolving metallic copper |
US3869401A (en) | 1972-12-04 | 1975-03-04 | Du Pont | Stabilized acidic hydrogen peroxide solutions |
US3986970A (en) | 1973-05-02 | 1976-10-19 | The Furukawa Electric Co., Ltd. | Solution for chemical dissolution treatment of tin or alloys thereof |
JPS5177404A (zh) | 1974-12-26 | 1976-07-05 | Fuji Photo Film Co Ltd | |
US4349411A (en) | 1981-10-05 | 1982-09-14 | Bell Telephone Laboratories, Incorporated | Etch procedure for aluminum alloy |
DE3623504A1 (de) | 1986-07-09 | 1988-01-21 | Schering Ag | Kupferaetzloesungen |
JPH0655941B2 (ja) | 1987-10-19 | 1994-07-27 | ダイキン工業株式会社 | 冷 媒 |
US4755316A (en) | 1987-10-23 | 1988-07-05 | Allied-Signal Inc. | Refrigeration lubricants |
JP2576162B2 (ja) | 1987-11-26 | 1997-01-29 | 旭硝子株式会社 | 作動媒体混合物 |
JP2576161B2 (ja) | 1987-11-26 | 1997-01-29 | 旭硝子株式会社 | 作動媒体混合物 |
GB8824571D0 (en) | 1988-10-20 | 1988-11-23 | Ici Plc | Chemical process |
US4944890A (en) | 1989-05-23 | 1990-07-31 | E. I. Du Pont De Nemours And Company | Compositions and process of using in refrigeration |
US5032306A (en) | 1989-09-07 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Fluorinated hydrocarbon lubricants for use with refrigerants in compression refrigeration |
FR2662944B2 (fr) | 1989-11-10 | 1992-09-04 | Atochem | Nouveau melange azeotropique a bas point d'ebullition a base de fluoroalcanes et ses applications. |
US5342501A (en) | 1989-11-21 | 1994-08-30 | Eric F. Harnden | Method for electroplating metal onto a non-conductive substrate treated with basic accelerating solutions for metal plating |
EP0430131A1 (en) | 1989-11-29 | 1991-06-05 | Matsushita Electric Industrial Co., Ltd. | Working fluid |
JP2584337B2 (ja) | 1990-05-11 | 1997-02-26 | 三洋電機株式会社 | 冷媒組成物 |
FR2664044B1 (fr) | 1990-06-29 | 1993-05-14 | Sextant Avionique | Procede et dispositif de determination d'une orientation liee a un systeme mobile, notamment de la ligne de visee dans un viseur de casque. |
DE69106135T3 (de) * | 1990-07-26 | 2004-07-22 | E.I. Du Pont De Nemours And Co., Wilmington | Quasi-azeotrope Mischungen zur Verwendung als Kältemittel. |
GB2247462A (en) | 1990-08-29 | 1992-03-04 | Star Refrigeration | Two component refrigerant |
GB9026512D0 (en) | 1990-12-05 | 1991-01-23 | Star Refrigeration | Multi-component refrigerant |
US5520833A (en) | 1991-06-28 | 1996-05-28 | Idemitsu Kosan Co., Ltd. | Method for lubricating compression-type refrigerating cycle |
MX9203904A (es) | 1991-07-03 | 1993-01-01 | Du Pont | Composicion azeotropica o de tipo azeotropo de pentafluoroetano y propano o isobutano y procedimientos para producir refrigeracion y calor al condensar dicha composicion. |
JP2568774B2 (ja) * | 1991-10-28 | 1997-01-08 | 松下電器産業株式会社 | 作動流体 |
AU3602193A (en) | 1992-02-03 | 1993-09-01 | Allied-Signal Inc. | Novel refrigerant compositions |
EP0565265B1 (en) | 1992-04-04 | 1995-12-13 | Star Refrigeration Ltd. | Refrigerant composition |
US5225034A (en) | 1992-06-04 | 1993-07-06 | Micron Technology, Inc. | Method of chemical mechanical polishing predominantly copper containing metal layers in semiconductor processing |
CN1083508A (zh) | 1992-06-25 | 1994-03-09 | 大湖化学公司 | 含有1,1,1,2,3,3,3,-七氟丙烷的致冷剂混合物 |
US5259979A (en) | 1993-01-13 | 1993-11-09 | Oliver Sales Company | Process for regeneration of cleaning compounds |
GB9319540D0 (en) | 1993-09-22 | 1993-11-10 | Star Refrigeration | Replacement refrigerant composition |
JPH07173460A (ja) | 1993-12-20 | 1995-07-11 | Sanyo Electric Co Ltd | 冷媒組成物および冷凍装置 |
US5417871A (en) * | 1994-03-11 | 1995-05-23 | E. I. Du Pont De Nemours And Company | Hydrofluorocarbon compositions |
BR9503366A (pt) | 1994-07-19 | 1996-02-27 | Nippon Oil Co Ltd | Oleo de refrigerador e composiçao de óleo para uso com um refrigerante de HFC e composiçao de fluido para uso em um refrigeraçao |
GB9415159D0 (en) | 1994-07-27 | 1994-09-28 | Ici Plc | Refrigerant compositions |
GB9415140D0 (en) * | 1994-07-27 | 1994-09-14 | Ici Plc | Refrigerant compositions |
US6251300B1 (en) | 1994-08-03 | 2001-06-26 | Nippon Mitsubishi Oil Corporation | Refrigerator oil compositions and fluid compositions for refrigerator |
US5866030A (en) | 1994-09-07 | 1999-02-02 | Witco Corporation | Enhanced hydrocarbon lubricants for use with immiscible refrigerants |
WO1996015205A1 (en) | 1994-11-16 | 1996-05-23 | E.I. Du Pont De Nemours And Company | Compositions that include a cyclic fluorocarbon |
JP3575089B2 (ja) | 1994-12-12 | 2004-10-06 | 旭硝子株式会社 | 非共沸混合冷媒を形成する方法 |
RU2072382C1 (ru) | 1994-12-26 | 1997-01-27 | Олег Николаевич Подчерняев | Озонобезопасная рабочая смесь |
JPH0925480A (ja) | 1995-07-13 | 1997-01-28 | Sanyo Electric Co Ltd | 作動流体 |
JPH0959611A (ja) | 1995-08-28 | 1997-03-04 | Sanyo Electric Co Ltd | 冷媒組成物 |
AU7239596A (en) | 1995-09-21 | 1997-04-09 | George H. Goble | Drop-in substitutes for dichlorodifluoromethane refrigerant |
KR0184083B1 (ko) | 1995-10-20 | 1999-04-01 | 이기태 | 흡입관 열교환기를 사용하는 냉동기용 혼합냉매 |
CN1083474C (zh) | 1995-10-24 | 2002-04-24 | 顾雏军 | 在热力循环中使用的改进的非共沸工作介质 |
JPH09125052A (ja) | 1995-11-02 | 1997-05-13 | Matsushita Refrig Co Ltd | 冷凍システム |
IT1277085B1 (it) | 1995-12-14 | 1997-11-04 | Ausimont Spa | Composizioni ternarie quasi azeotropiche costituite da fluorocarburi idrogenati e idrocarburi adatte come fluidi refrigeranti |
US5954995A (en) | 1996-03-22 | 1999-09-21 | Goble; George H. | Drop-in substitutes for 1,1,1,2-tetrafluoroethane (R-134a) refrigerant |
US5705086A (en) | 1996-04-16 | 1998-01-06 | Mobil Oil Corporation | Refrigeration oils comprising esters of hindered alcohols |
US5984079A (en) | 1996-07-12 | 1999-11-16 | Electro Scientific Industries, Inc. | Method and apparatus for loading electronic components |
US5958288A (en) | 1996-11-26 | 1999-09-28 | Cabot Corporation | Composition and slurry useful for metal CMP |
GB9624818D0 (en) | 1996-11-28 | 1997-01-15 | Rh Ne Poulenc Chemicals Ltd | Refrigerant composition |
KR100541175B1 (ko) | 1996-11-29 | 2006-01-10 | 닛토덴코 가부시키가이샤 | 열전도성 감압 접착제 및 이를 함유하는 접착 시트류 |
JP3127138B2 (ja) | 1997-01-31 | 2001-01-22 | 昭和電工株式会社 | 混合冷媒の製造方法 |
TW492999B (en) | 1997-01-31 | 2002-07-01 | Showa Denko Kk | Process for preparing mixed cooling-media |
AU755306B2 (en) | 1997-07-15 | 2002-12-12 | E.I. Du Pont De Nemours And Company | Refrigerant compositions |
US6000230A (en) | 1997-08-19 | 1999-12-14 | Showa Denko K.K. | Method for dividing and charging of non-azeotropic mixed refrigerant |
US6222136B1 (en) | 1997-11-12 | 2001-04-24 | International Business Machines Corporation | Printed circuit board with continuous connective bumps |
RU2135541C1 (ru) | 1997-12-10 | 1999-08-27 | Российский научный центр "Прикладная химия" | Композиция хладагента |
JP3754198B2 (ja) | 1997-12-25 | 2006-03-08 | 三洋電機株式会社 | 可燃性冷媒組成物の処理装置 |
US6065305A (en) | 1998-12-30 | 2000-05-23 | Praxair Technology, Inc. | Multicomponent refrigerant cooling with internal recycle |
US6076372A (en) | 1998-12-30 | 2000-06-20 | Praxair Technology, Inc. | Variable load refrigeration system particularly for cryogenic temperatures |
RU2161637C2 (ru) | 1999-02-26 | 2001-01-10 | Беляев Андрей Юрьевич | Композиция хладагента (варианты) |
US6783691B1 (en) * | 1999-03-22 | 2004-08-31 | E.I. Du Pont De Nemours And Company | Compositions of difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and hydrocarbons |
US7258813B2 (en) | 1999-07-12 | 2007-08-21 | E.I. Du Pont De Nemours And Company | Refrigerant composition |
HUP0202739A2 (en) * | 1999-09-30 | 2002-12-28 | Refrigerant Products Ltd | R 22 replacement refrigerant |
ATE270699T1 (de) | 1999-09-30 | 2004-07-15 | Refrigerant Products Ltd | Kuehlmittelzusammensetzung als alternative für r- 12 |
CN1377398A (zh) | 1999-09-30 | 2002-10-30 | 制冷产品有限公司 | Cfc12替代物致冷剂 |
US6629419B1 (en) | 1999-10-04 | 2003-10-07 | Refringerant Products Ltd. | CFC 12 replacement refrigerant |
US6606868B1 (en) | 1999-10-04 | 2003-08-19 | Refrigerant Products, Ltd. | R 22 replacement refrigerant |
US6230519B1 (en) | 1999-11-03 | 2001-05-15 | Praxair Technology, Inc. | Cryogenic air separation process for producing gaseous nitrogen and gaseous oxygen |
KR100340186B1 (ko) * | 1999-11-10 | 2002-06-12 | 박호군 | 디플루오로메탄, 펜타플루오로에탄 및1,1,1-트리플루오로에탄을 포함하는 냉매 혼합물 |
GB2356867A (en) | 1999-12-03 | 2001-06-06 | Rhodia Ltd | Refrigeration Compositions |
US6253577B1 (en) | 2000-03-23 | 2001-07-03 | Praxair Technology, Inc. | Cryogenic air separation process for producing elevated pressure gaseous oxygen |
CN1123618C (zh) | 2000-07-28 | 2003-10-08 | 清华大学 | 一种制冷剂 |
FR2813610B1 (fr) | 2000-09-04 | 2002-10-18 | Atofina | Composition utilisable comme fluide frigorifique |
BR0017337B1 (pt) | 2000-09-19 | 2010-11-03 | composição refrigerante lìquida, e, sistema de refrigeração incorporando um compressor centrìfugo. | |
US6526764B1 (en) | 2000-09-27 | 2003-03-04 | Honeywell International Inc. | Hydrofluorocarbon refrigerant compositions soluble in lubricating oil |
EP1193305A1 (en) | 2000-09-27 | 2002-04-03 | Honeywell International Inc. | Hydrofluorocarbon refrigerant compositions soluble in lubricating oil |
JP2002228307A (ja) * | 2001-02-01 | 2002-08-14 | Matsushita Electric Ind Co Ltd | 混合冷媒充填方法および充填された装置 |
JP2002308085A (ja) | 2001-04-18 | 2002-10-23 | Bosch Braking Systems Co Ltd | 液圧倍力装置 |
JP4018484B2 (ja) | 2002-08-27 | 2007-12-05 | キヤノン株式会社 | カメラ装置およびその制御方法 |
GB0223724D0 (en) | 2002-10-11 | 2002-11-20 | Rhodia Organique Fine Ltd | Refrigerant compositions |
JP4838513B2 (ja) * | 2002-11-29 | 2011-12-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 深冷器冷媒 |
-
2003
- 2003-12-01 JP JP2004570701A patent/JP4838513B2/ja not_active Expired - Fee Related
- 2003-12-01 AU AU2003285568A patent/AU2003285568B2/en not_active Ceased
- 2003-12-01 ES ES03778566T patent/ES2374288T3/es not_active Expired - Lifetime
- 2003-12-01 AT AT03778566T patent/ATE532841T1/de active
- 2003-12-01 PL PL376681A patent/PL208354B1/pl unknown
- 2003-12-01 BR BRPI0316696-1A patent/BR0316696B1/pt active IP Right Grant
- 2003-12-01 KR KR1020057009625A patent/KR101126495B1/ko not_active IP Right Cessation
- 2003-12-01 CN CN201010167086A patent/CN101838519A/zh active Pending
- 2003-12-01 PT PT03778566T patent/PT1572829E/pt unknown
- 2003-12-01 EP EP10010473A patent/EP2258788A3/en not_active Withdrawn
- 2003-12-01 EP EP03778566A patent/EP1572829B1/en not_active Expired - Lifetime
- 2003-12-01 RU RU2005120383/04A patent/RU2334776C2/ru not_active IP Right Cessation
- 2003-12-01 CA CA2507639A patent/CA2507639C/en not_active Expired - Fee Related
- 2003-12-01 US US10/536,987 patent/US20060151740A1/en not_active Abandoned
- 2003-12-01 MX MXPA05005692A patent/MXPA05005692A/es active IP Right Grant
- 2003-12-01 WO PCT/GB2003/005227 patent/WO2004050787A1/en active Application Filing
-
2005
- 2005-06-28 NO NO20053163A patent/NO20053163L/no not_active Application Discontinuation
-
2006
- 2006-07-07 HK HK06107662.6A patent/HK1087429A1/xx not_active IP Right Cessation
-
2007
- 2007-07-31 US US11/831,308 patent/US20080078978A1/en not_active Abandoned
-
2008
- 2008-05-22 US US12/125,671 patent/US7641810B2/en not_active Expired - Fee Related
- 2008-07-11 US US12/171,749 patent/US7713434B2/en not_active Expired - Fee Related
- 2008-07-11 US US12/171,719 patent/US7771610B2/en not_active Expired - Lifetime
-
2009
- 2009-05-19 AU AU2009201977A patent/AU2009201977B2/en not_active Ceased
-
2010
- 2010-06-25 US US12/823,607 patent/US8246851B2/en not_active Expired - Fee Related
-
2012
- 2012-07-09 US US13/544,487 patent/US20120273712A1/en not_active Abandoned
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7641810B2 (en) | Refrigerant compositions | |
US7799240B1 (en) | Refrigerant compositions | |
US20080128650A1 (en) | Refrigerant compositions | |
Llopis et al. | Experimental evaluation of HCFC-22 replacement by the drop-in fluids HFC-422A and HFC-417B for low temperature refrigeration applications | |
CN1742068B (zh) | 冷冻机制冷剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C12 | Rejection of a patent application after its publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100922 |