WO2015199855A1 - Application de mélanges de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane dans des refroidisseurs ayant un compresseur de type à vis - Google Patents

Application de mélanges de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane dans des refroidisseurs ayant un compresseur de type à vis Download PDF

Info

Publication number
WO2015199855A1
WO2015199855A1 PCT/US2015/032236 US2015032236W WO2015199855A1 WO 2015199855 A1 WO2015199855 A1 WO 2015199855A1 US 2015032236 W US2015032236 W US 2015032236W WO 2015199855 A1 WO2015199855 A1 WO 2015199855A1
Authority
WO
WIPO (PCT)
Prior art keywords
working fluid
trifluoropropene
chloro
mixture
cooling capacity
Prior art date
Application number
PCT/US2015/032236
Other languages
English (en)
Inventor
Konstantinos Kontomaris
Original Assignee
The Chemours Company Fc, Llc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Chemours Company Fc, Llc filed Critical The Chemours Company Fc, Llc
Publication of WO2015199855A1 publication Critical patent/WO2015199855A1/fr

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B39/00—Evaporators; Condensers
    • F25B39/02—Evaporators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • F25B1/04—Compression machines, plants or systems with non-reversible cycle with compressor of rotary type
    • F25B1/047—Compression machines, plants or systems with non-reversible cycle with compressor of rotary type of screw type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12—Inflammable refrigerants

Definitions

  • This invention relates to the advantageous use of certain mixtures of 1 -chloro-3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3-pentafluoro- propane as the working fluid in chillers having a screw-type compressor.
  • compositions (mixtures) of 1 -chloro-3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3- pentafluoropropane for use in a wide variety of refrigeration systems including air-conditioning, refrigeration, heat-pump, chiller, HVAC systems, and the like (p. 6, second paragraph).
  • This publication also discloses that for the chiller application, those with centrifugal compressors are
  • chillers with centrifugal compressors and flooded type evaporators are preferred, and even more preferred, are the chillers with centrifugal compressors and flooded type evaporators, (p. 7, last paragraph).
  • the publication discloses additional applications of the compositions, as follows: propellants, blowing agents, foaming agent, solvents, de-fluxing agents, degreasers, flushing agents, and the like (pp. 8 and 9).
  • the present invention involves the discovery of unexpected
  • One embodiment of the present invention comprises the process for operating a chiller to provide a cooling effect, comprising compressing a working fluid by reducing its volume, condensing the compressed working fluid, expanding the condensed working fluid, and evaporating the expanded working fluid to provide said cooling effect, said working fluid comprising a mixture of 1 -chloro-3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3- pentafluoropropane, said mixture exhibiting a volumetric cooling capacity that is at least 2.5% greater than the volumetric cooling capacity of said 1 - chloro-3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3-pentafluoropropane by themselves and a temperature glide during at least one of said condensing and said evaporating that is no greater than 0.25°C.
  • the compressing of the working fluid by reducing its volume denotes according to the present invention that compressing is obtained by a screw-type compressor.
  • a chiller comprising a screw-type compressor for compressing a working fluid, means for condensing said compressed working fluid, means for expanding said condensed working fluid, and means for evaporating said expanded working fluid, said working fluid comprising a mixture of 1 - chloro-3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3-pentafluoropropoane, said mixture exhibiting a volumetric cooling capacity that is at least 2.5% greater than the volumetric cooling capacity of said 1 -chloro-3,3,3- trifluoropropene and 1 ,1 ,1 ,2,3-pentafluoropropane by themselves and a temperature glide during at least one of condensation by said
  • condensation means and evaporation by said evaporation means that is no greater than 0.25°C.
  • the composition of the most preferred mixture used in either the process and apparatus embodiments mentioned above or in both such embodiments comprises 60 to 65 wt% of said 1 -chloro-3,3,3-trifluoropropene and 40 to 35 wt% of said 1 ,1 ,1 ,2,3-pentafluoropropane to total 100 wt%.
  • the improvement in volumetric cooling capacity of the mixture is preferably at least 4.0% greater than the volumetric cooling capacity of said 1 -chloro- 3,3,3-trifluoropropene and 1 ,1 ,1 ,2,3-pentafluoropropane by themselves.
  • the temperature glide exhibited by the mixture during at least one of said condensing or condensation and said evaporating or evaporation is preferably no greater than 0.15°C.
  • the amount of temperature glide preferably applies to both condensing (condensation) and evaporating (evaporation).
  • the preferred chiller having a screw-type compressor also has flooded heat exchangers.
  • the condensing and evaporating steps are carried out using a flooded heat exchanger in at least one of these steps.
  • the means for condensing and the means for evaporating comprise a flooded heat exchanger in at least one of these means.
  • Another embodiment of the present invention is wherein both the condensing and evaporating steps and both the means for condensing and means for evaporating are carried out or comprise flooded heat exchangers.
  • Fig .1 is a plot of volumetric cooling capacity vs. composition of the working fluids based on data reported in the Table of the Example below.
  • HCFO-1233zd 1 -chloro-3,3,3- trifluoropropene
  • HFC- 245eb 1 ,1 ,1 ,2,3-pentafluoropropane
  • HCFO-1233zd is the E-isomer, i.e. E-HCFO-1233zd, sometimes referred to as the trans isomer.
  • E-isomer is also referred to herein simply as 1 -chloro-3,3,3- trifluoropropene or as 1233zd.
  • the volumetric cooling capacity of the mixtures used in the present invention is at least 5% greater than the volumetric cooling capacity of either of the 1233zd and 245eb components of the mixture by itself, more preferably at least 6% greater.
  • Sample calculation of % improvement in volumetric cooling capacity taken from the values reported for Blend C in the Table is as follows:
  • the glide is no greater than 0.20°C, more preferably no greater than 0.15°C, and most preferably, no greater than 0.10°C.
  • Each of the glides exhibited by mixtures used in the present invention disclosed herein applies to either the glide during the condensation step or the glide during the evaporation step in the chiller operation, and preferably to both steps.
  • Each of these glides also applies to each of the improvements in volumetric cooling capacity disclosed herein.
  • the mixtures used in the present invention are prepared by mixing together the 1233zd and 245eb in the proportions desired to obtain the combination of volumetric cooling capacity improvement and low glide desired.
  • compositions of mixtures used in the present invention include those wherein the minimum amount of 1233zd includes the following: 50 wt%, 55 wt%, and 60 wt% and wherein the maximum amount of 1233zd is 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt% and 65 wt%, with 245eb being present in the mixture in an amount to total 100 wt% for the combination of 1233zd and 245eb in each mixture.
  • Each of these minimum amounts of 1233zd can be combined with any of these maximum amounts of 1233zd to define the 1233zd wt% range in the mixture, the combination of 1233zd and 245eb in each mixture totaling 100 wt%.
  • Of particular utility in the process for operating a chiller are nonflammable mixtures containing more than about 36 wt% E-1233zd.
  • non-flammable mixtures with from about 36 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 64 wt% HFC-245eb; or from about 37 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 80 wt% E- 1233zd and from about 20 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 65 wt% E-1233zd and from about 35 wt% to about 63 wt% HFC-245eb.
  • examples of mixture In the process for operating a chiller, examples of mixture
  • compositions used in the present invention include the following: mixtures comprising 50 to 90 wt% of 1233zd and 50 to 10 wt% of 245eb, to total 100%; mixtures comprising 50 to 80 wt% of 1233zd and 50 to 20 wt% of 245eb, to total 100%; mixtures comprising 55 to 70 wt% of 1233zd and 45 to 30 wt% of 245eb, to total 100%; and the 60-65/40-35 mixture mentioned above.
  • the mixture composition is selected to achieve the improvement in volumetric cooling capacity and low glide desired, whether for the condensation step or the evaporation step or both. Another consideration as discussed in Example 1 is the GWP and ODP desired for the mixture.
  • the GWP becomes smaller as shown in Table 1 in the Examples.
  • the ODP of 1233zd is small, but somewhat greater than the zero OPD of 245eb, whereby the increasing amount of 1233zd in the mixture results in a positive value for ODP as disclosed in the Examples.
  • non-flammable mixtures containing more than about 36 wt% E-1233zd and less than about 64 wt% HFC-245eb.
  • nonflammable mixtures with from about 36 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 64 wt% HFC-245eb; or from about 37 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 80 wt% E-1233zd and from about 20 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 65 wt% E-1233zd and from about 35 wt% to about 63 wt% HFC-245eb.
  • the 1233zd and 245eb are the essential components of the mixture used as the working fluid in the present invention.
  • Other ingredients can be present in the mixture such as one or more lubricants, compatibilizers, UV dyes, solubilizing agents, tracers, free-radical scavengers, or antioxidants.
  • the chillers used in the present invention include the conventional process steps and equipment means to accomplish compression, condensation, expansion and evaporation of the working fluid, with the proviso that the compression is accomplished by using a screw type compressor.
  • Screw type compressors useful in the present invention are disclosed in the book entitled 2008 ASHRAE Handbook, HVAC Systems and Equipment, S I Edition, Published by the American Society of Heating, Refrigeration, and Air Conditioning Engineers, Inc. (2008) on pp 37.18 to 37.19. These compressors include compressors wherein the volume reduction and accompanying compression of the working fluid are accomplished by a single screw compressor or a twin screw compressor.
  • the working fluid as a vapor is drawn into the screw(s) of the compressor for compression by volume reduction produced by the reduction in volume of the space available within the grooves of the screw(s) as the vapor passes through the compressor to the discharge port of the compressor.
  • the evaporation of the working fluid in the evaporator of the chiller cools a heat transfer medium, and the cooled heat transfer medium is transported out of the evaporator to the body to be cooled, whereby the chiller communicates its cooling effect to the environment.
  • the heat transfer medium is water.
  • examples of working fluids include the following: mixtures comprising 50 to 90 wt% of 1233zd and 50 to 10 wt% of 245eb, to total 100%; mixtures comprising 50 to 80 wt% of 1233zd and 50 to 20 wt% of 245eb, to total 100%; mixtures comprising 55 to 70 wt% of 1233zd and 45 to 30 wt% of 245eb, to total 100%; and the 60-65/40-35 mixture mentioned above.
  • nonflammable mixtures containing more than about 36 wt% E-1233zd and less than about 64 wt% HFC-245eb.
  • non-flammable mixtures with from about 36 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 64 wt% HFC-245eb; or from about 37 wt% to about 90 wt% E-1233zd and from about 10 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 80 wt% E-1233zd and from about 20 wt% to about 63 wt% HFC-245eb; or from about 37 wt% to about 65 wt% E- 1233zd and from about 35 wt% to about 63 wt% HFC-245eb.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase "consisting essentially of is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • the term 'consisting essentially of occupies a middle ground between “comprising" and 'consisting of.
  • the screw type compressor operates using a twin screw.
  • PR is the ratio of the absolute discharge pressure to the absolute inlet pressure for the twin screw compressor.
  • COPcool is the coefficient of performance for cooling, i.e. the amount of heat received by the working fluid divided by the energy required to operate the screw type compressor.
  • Vol Cool Cap is the volumetric cooling capacity.
  • Glide-Cond is the glide occurring during condensation of the working fluid and Glide-Evap is the glide occurring during evaporation of the working fluid.
  • Glide, whether during condensation or during evaporation, is the absolute value of the temperature difference between the starting and ending temperatures of the phase-change step by the working fluid.
  • Nonflammable Blend B offers 4.35% higher volumetric cooling capacity than neat HCFO-1233zd, but with glide values that would be considered excessively high for chillers, especially using flooded heat exchangers. Based on the excessive glide obtained for Blend B, the minimum amount of 1233zd in the Blend is preferably at least 50 wt%.
  • the volumetric cooling capacity exceeds that of 100 wt% 1233zd, and the glide-Cond is 0.14°C and the glide-Evap is 0.22°C.
  • the peak volumetric cooling capacity of 6.96% resides in the same Blend (Blend C) as the smallest glide temperatures for the Blends. According to the curve in Fig. 1 , the peak volumetric cooling capacity of the mixture occurs at 62-63 wt% 1233zd, the remainder to total 100 wt% being 38-37 wt% 245eb.
  • the ODP for the mixtures used in the present invention is also low.
  • the ODP for 245eb is 0, while for 1233zd, it has been reported to be 0.00034.
  • the ODP is 0.00020 (calculation:
  • compositions for use in the processes and chillers according to the present invention were tested according to ASTM E681 to determine flammability.
  • the test procedure was run at a temperature of 60°C and 50.0% relative humidity in a 12 liter flask with standard ignition (IE tungsten electrodes offset from center with a 0.25 inch gap, 15 kv with a 0.4 second duration.
  • IE tungsten electrodes offset from center with a 0.25 inch gap, 15 kv with a 0.4 second duration For those compositions that were found to be flammable, the lower flammability limit (LFL) and upper flammability limit (UFL) are indicated in Table 2.
  • compositions with more than about 36 wt% E-1233zd will be nonflammable.
  • the data indicates that compositions from Example 1 including B, BC, C, CD and D will be non-flammable.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

La présente invention comprend (a) un procédé de fonctionnement d'un refroidisseur pour fournir un effet de refroidissement, consistant à comprimer un fluide de travail dans un compresseur de type à vis, à condenser le fluide de travail comprimé, à dilater le fluide de travail condensé, et à évaporer le fluide de travail dilaté pour fournir ledit effet de refroidissement, ledit fluide de travail comprenant un mélange de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane, ledit mélange présentant une capacité de refroidissement volumétrique qui est au moins 2,5 % supérieure à la capacité de refroidissement volumétrique desdits 1-chloro-3,3,3-trifluoropropène et 1,1,1,2,3-pentafluoropropane par eux-mêmes et un glissement de température pendant ladite condensation et/ou ladite évaporation qui ne dépasse pas 0,25 °C, et (b) un appareil refroidisseur comportant le compresseur de type à vis pour comprimer le fluide de travail. Selon ladite invention, pendant la condensation par des moyens de condensation et/ou l'évaporation du fluide de travail lors de l'évaporation par des moyens d'évaporation, le mélange présente la même amélioration de la capacité de refroidissement volumétrique et le même faible glissement de température tels que mentionnés sous (a).
PCT/US2015/032236 2014-06-26 2015-05-22 Application de mélanges de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane dans des refroidisseurs ayant un compresseur de type à vis WO2015199855A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462017335P 2014-06-26 2014-06-26
US62/017,335 2014-06-26

Publications (1)

Publication Number Publication Date
WO2015199855A1 true WO2015199855A1 (fr) 2015-12-30

Family

ID=53434455

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/032236 WO2015199855A1 (fr) 2014-06-26 2015-05-22 Application de mélanges de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane dans des refroidisseurs ayant un compresseur de type à vis

Country Status (1)

Country Link
WO (1) WO2015199855A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009114398A1 (fr) * 2008-03-07 2009-09-17 Arkema Inc. Utilisation de r-1233 dans des refroidisseurs de liquides
WO2011022260A1 (fr) 2009-08-17 2011-02-24 Arkema Inc. Composition azéotrope et de type azéotrope de 1-chloro-3,3,3-trifluoropropène et de hfc-245eb
WO2011130237A1 (fr) * 2010-04-16 2011-10-20 E. I. Du Pont De Nemours And Company Composition comportant du 2,3,3,3-tétrafluoropropène et du 1,1,1,2-tétrafluoroéthane, refroidisseurs les contenant et procédés de production de refroidissement dans ceux-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009114398A1 (fr) * 2008-03-07 2009-09-17 Arkema Inc. Utilisation de r-1233 dans des refroidisseurs de liquides
WO2011022260A1 (fr) 2009-08-17 2011-02-24 Arkema Inc. Composition azéotrope et de type azéotrope de 1-chloro-3,3,3-trifluoropropène et de hfc-245eb
WO2011130237A1 (fr) * 2010-04-16 2011-10-20 E. I. Du Pont De Nemours And Company Composition comportant du 2,3,3,3-tétrafluoropropène et du 1,1,1,2-tétrafluoroéthane, refroidisseurs les contenant et procédés de production de refroidissement dans ceux-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"2008 ASHRAE Handbook, HVAC Systems and Equipment", 2008, AMERICAN SOCIETY OF HEATING, REFRIGERATION, pages: 37.18 - 37.19

Similar Documents

Publication Publication Date Title
US4303536A (en) Nonazeotropic refrigerant composition containing monachlorodifluoromethane, and method of use
EP2313471B1 (fr) Composition de type azéotrope de 1,1,1,2-tétrafluoropropène et de 1,1,1,2-tétrafluoroéthane
EP3140362B1 (fr) Compositions de transfert de chaleur à faible prg
US20100139314A1 (en) Refrigerant compositions and use thereof in low temperature refrigeration systems
US20190153282A1 (en) Low gwp heat transfer compositions
CN110628389B (zh) 一种含cf3i的低可燃或不可燃混合制冷剂
CN110684509B (zh) 一种环保混合制冷剂及换热系统
CN110878194B (zh) 一种含r13i1的环保混合制冷剂及换热系统
CN112195015B (zh) 混合制冷剂及制冷系统
CN101270275A (zh) 一种混合制冷剂、其制备方法及用途
WO2015199855A1 (fr) Application de mélanges de 1-chloro-3,3,3-trifluoropropène et de 1,1,1,2,3-pentafluoro-propane dans des refroidisseurs ayant un compresseur de type à vis
CN110591652B (zh) 一种热传递组合物及换热系统
CN110591650B (zh) 一种适用于离心式制冷机组的热传递组合物
KR19990053764A (ko) 냉동/공기조화기용 혼합냉매 조성물
KR100616770B1 (ko) 알32를 함유하는 근공비성 3원 혼합냉매
CN112745804A (zh) 一种低温混合工质及其应用
KR100616773B1 (ko) 알32를 함유하는 공비 및 근공비성 2원 혼합냉매
CN110628387A (zh) 一种低可燃性热传递组合物及换热系统
CN101161757A (zh) 一种适用于单级压缩制冷系统的环保型共沸制冷剂
CN114891483B (zh) 一种混合制冷剂和空调系统
KR100669091B1 (ko) 근공비성 3원 혼합냉매
KR100633733B1 (ko) 근공비성 3원 혼합냉매
WO1998008911A1 (fr) Compositions refrigerantes
KR100616772B1 (ko) 근공비성 3원 혼합냉매
WO2022018591A1 (fr) Fluides frigorigènes mixtes à prp réduit destinés à être utilisés dans une réfrigération à ultra-basse température

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15730318

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15730318

Country of ref document: EP

Kind code of ref document: A1