Sterically hindered hydrofluoroolefins with dipole moment and their blends with sterically hindered-olefins as refrigerants for high temperature heat pumps and working fluid for organic Rankine cycles
A variety of methods and compositions are disclosed, including, in one example, a method that includes compressing a working fluid with a compressor to form a compressed working fluid, wherein the working fluid includes at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and at least one C 5 or C 6 cis olefins, condensing the working fluid to form a condensed working fluid, expanding the working fluid to form an expanded working fluid, and heating the working fluid, wherein heat from a heat source is transferred to a heat sink with the working fluid. In embodiments, the compounds and blends are designed for high temperature heat pump (HTHP) and Organic Rankine Cycle (ORC) applications for waste heat recovery and low-grade renewable (e.g., geothermal & flat panel solar) energy utilization.
1 . A method comprising:
compressing a working fluid to form a compressed working fluid, wherein the working fluid comprises:
at least one C 5 or C 6 cis or (Z) hydrofluoroolefins; and
at least one C 5 or C 6 cis olefins wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins working fluid comprise (Z)-1,1,1,4,4,4-hexafluoro-2-methylbut-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 8:5 to 12:5 or in a ratio of about 7:1 to 11:1 or in a ratio of about 6:5 to 4:5;
condensing the working fluid to form a condensed working fluid,
expanding the working fluid to form an expanded working fluid; and
heating the working fluid, wherein heat from a heat source is transferred to a heat sink with the working fluid.
2 . The method of claim 1 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins is selected from the group consisting of: 2,3-dimethyl-but-2-ene, (Z)-1,1,1,4,4,4-hexafluoro-2-methylbut-2-ene, 2-(difluoromethyl)-1,1,4,4-tetrafluorobut-2-ene, 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene, (Z)-1,1,1,4,4,4-hexafluoro-2-butene, (E)-1,1,1,2,4,4,4-heptafluoro-3-methylbut-2-ene, (Z)-1,1,1,2,4,4,4-heptafluoro-3-methylbut-2-ene, (E)-1,1,1,3,5,5,5-heptafluoro-2-pentene, (Z)-1,1,1,3,5,5,5-heptafluoro-2-pentene, (E)-1,1,1,4,4,4-hexafluoro-2-methylbut-2-ene, and any combinations thereof.
3 . The method of claim 1 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins working fluid comprise (Z)-1,1,1,4,4,4-hexafluoro-2-methylbut-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 8:5 to 12:5.
4 . The method of claim 1 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise (Z)-1,1,1,4,4,4-hexafluoro-but-2-ene and 2-methyl-but-2-ene in a ratio of about 7:1 to 11:1.
5 . The method of claim 1 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise (Z)-1,1,1,4,4,4-hexafluoro-but-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 7:1 to 11:1.
6 . The method of claim 1 , wherein the working fluid after the compressing is in a supercritical phase.
7 . The method of claim 1 , wherein a compressed working fluid is in a subcritical phase.
8 . The method of claim 1 , further comprising flowing the working fluid through at least one device selected from the group consisting of: an evaporator; a flash cooler, a flash economizer, a heat exchanger, and any combination thereof.
9 . The method of claim 1 , further comprising flowing the working fluid and an additional working fluid through a heat exchanger, wherein heat is transferred between the working fluid and the additional working fluid.
10 . The method of claim 1 , wherein the working fluid has a critical temperature greater than 170° C.
11 . The method of claim 1 , wherein the working fluid has a critical pressure less than 35 bar.
12 . A method comprising:
compressing a working fluid to form a compressed working fluid, wherein the working fluid comprises:
at least one C 5 or C 6 cis or (Z) hydrofluoroolefins; and
at least one C 5 or C 6 cis olefins, wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise (Z)-1,1,1,4,4,4-hexafluoro-but-2-ene and 2-methyl-but-2-ene in a ratio of about 7:1 to 11:1 or in a ratio of about 6:5 to 4:5;
condensing the working fluid to form a condensed working fluid,
expanding the working fluid to form an expanded working fluid; and
heating the working fluid, wherein heat from a heat source is transferred to a heat sink with the working fluid.
13 . The method of claim 12 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise (Z)-1.1.1.4.4.4-hexafluoro-but-2-ene and 2-methyl-but-2-ene in a ratio of about 7:1 to 11.1.
14 . The method of claim 12 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefinsil and the at least one C 5 or C 6 cis olefins comprise (Z)-1,1,1,4,4,4-hexafluoro-but-2-ene and 2-methyl-but-2-ene in a ratio of about 6:5 to 4:5.
15 . A method comprising:
compressing a working fluid to form a compressed working fluid, wherein the working fluid comprises:
at least one C 5 or C 6 cis or (Z) hydrofluoroolefins; and
at least one C 5 or C 6 cis olefins, wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2-methyl-but-2-ene in a ratio of about 5:2 to 4:1 or in in a ratio of about 7:11 to 1:1;
condensing the working fluid to form a condensed working fluid,
expanding the working fluid to form an expanded working fluid; and
heating the working fluid, wherein heat from a heat source is transferred to a heat sink with the working fluid.
16 . The method of claim 15 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2-methyl-but-2-ene in a ratio of about 5:2 to 4:1.
17 . The method of claim 15 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2-methyl-but-2-ene in a ratio of about 7:11 to 1:1.
18 . A method comprising:
compressing a working fluid to form a compressed working fluid, wherein the working fluid comprises:
at least one C 5 or C 6 cis or (Z) hydrofluoroolefins; and
at least one C 5 or C 6 cis olefins, wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 5:2 to 4:1 or in a ratio of about 7:11 to 1:1;
condensing the working fluid to form a condensed working fluid,
expanding the working fluid to form an expanded working fluid; and
heating the working fluid, wherein heat from a heat source is transferred to a heat sink with the working fluid.
19 . The method of claim 18 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefinsil and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 5:2 to 4:1.
20 . The method of claim 18 , wherein the at least one C 5 or C 6 cis or (Z) hydrofluoroolefins and the at least one C 5 or C 6 cis olefins comprise 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-but-2-ene and 2,3-dimethyl-but-2-ene in a ratio of about 7:11 to 1:1.