High temperature heat pump system and method of use

Abstract

Systems and methods of using high temperature heat pumps for recovering heat from chemical process and, in particular, of operating a heat pump integrated into a continuous distillation process, are provided.

Description

TITLE OF THE INVENTION High Temperature Heat Pump System and Method of Use CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional ApplicationNo.63 / 611,456 filed December 18, 2023, the disclosures of which is incorporated herein by reference in its entirety. FIELD OF INVENTION

[0002] The invention relates to using high temperature heat pumps (HTHP) forrecovering heat from chemical process and, in particular, to operating a heat pump integrated into a continuous distillation process. BACKGROUND OF THE INVENTION

[0003] A method for conducting chemical separations is by continuous fractionaldistillation which involves the input of heat at a reboiler to create vapors at the bottom of a tower containing surfaces where liquid and vapor contact. The column typically contains one or more condensers where heat is removed causing vapors to condense with some or all the resulting liquid returned to the column as reflux. Often a large amount of energy is required for the heat input in the form of fossil-fuel derived heat such as steam to the distillation and the amount of heat rejected from the distillation at the condenser are similar and continuous. The rejected heat at the condenser is often removed using a cooling tower or refrigeration machine with little or no recovery of the heat input.

[0004] Conventional industrial heat pumps are much smaller capacity of a fewmillion Btu / h with temperature lifts of approximately 35ºC from a single compression cycle (for example, as disclosed in “Integration of High-Temperature Heat Pumps in Swiss Industrial Processes (HTHP-CH)” presented at the 14th IEA Heat Pump Conference, May 15-18, 2023, Chicago, Illinois; the disclosure of which is hereby incorporated by reference). There is a need in this art for a system and method to recover and supply heat at a temperature of least 100ºC, with a temperature lift of 50ºC and having a megawatt (MW) capacity or more.SUMMARY OF INVENTION

[0005] The instant invention solves problems associated with conventionalsystems and methods by providing a HTHP and distillation column integration. The instant invention can reduce steam inputs in chemical manufacturing, recover heat as well as reduce energy consumption. One aspect of the invention relates to recovering waste heat (for example, heat conventionally rejected to cooling tower water) and upgrade the recovered heat as an input at a column reboiler. For example, the process temperature lift or upgrade can be at least 40ºC, at least 50ºC and, in some cases greater than 80ºC and, in turn supply heat, at a temperature of at least 90ºC, at least 100ºC and, in some cases greater than 200ºC.

[0006] In one aspect of the invention, process heat is extracted from the chemicalmanufacturing process by condensing the distillation column process vapor in the heat pump evaporator (chiller). The process heat plus the heat of compression generated by the compressor of the HTHP is transferred back into the distillation column with a heat exchanger commonly referred to as a distillation reboiler that condenses the heat pump fluid while boiling the distillation liquid, thereby eliminating steam heat input. The cycle is completed once the condensed refrigerant (e.g., working fluid) flows through an expansion device to drop the temperature and pressure to the evaporator condition. The electrical energy required to operate the heat pump is less than the energy value of the resultant heat (for example, approximately about 0.55 MW electricity is used while 2.4 MW is produced). The integration of the HTHP to a distillation column reduces the energy consumption for heating of this unit operation (for example, by approximately 50%, 65% and in some cases at least 77%).

[0007] External heat will typically only be used to start-up the distillation columnfrom ambient temperature. The use of an electrically driven HTHP to provide all the energy input provides the capability for this unit operation to be performed with renewable energy while reducing cooling tower load. External heat can be applied to the distillation column to assist with startup or supplement the heat pump. When the process operation is stabilized, the primary energy input to the distillation process is from closed-loop recompression of the HTHP vapor. The amounts of energy input required for the distillation process will depend on the overall energy balance ofamount of entering, heat recovered, plus the compression heat, less energy leaving the system through material flows and external cooling.

[0008] One aspect of the invention relates to selecting a working fluid for use inthe HTHP. The working fluid can impact vessel working pressure designs, sizing of compressor and other system components, maintenance requirements specific to the refrigerant safety rating, among other HTHP features. A desirable refrigerant has good thermal stability including a high critical temperature and low critical pressure. Environmental and safety requirements include zero ozone depletion potential, low GWP, low to no-flammability, and low to no-toxicity. Performance metrics include high efficiency at the proposed conditions, high volumetric capacity, oil solubility, thermal stability with oil, and refrigerant-oil material compatibility. The working fluid should not cause significant issues should a leak into the process occur. The working fluid needs to have balance of operating pressures, efficiency, and volumetric capacity that equate to economical equipment component sizing (compressor, condenser, evaporator), low electrical consumption, and subsequent operating cost. In this regard, the inventive system and method also solves the undesirable toxicity and flammability dangers caused by ammonia and hydrocarbons. In one aspect of the invention, the inventive system and method are free of ammonia and hydrocarbon.

[0009] One aspect of the invention relates to working fluids comprising at least onefluoroolefin. By fluoroolefin is meant any compound containing carbon, fluorine and optionally, hydrogen or oxygen that also contains at least one double bond. These fluoroolefins may be linear, branched or cyclic.

[0010] Fluoroolefins have a variety of utilities in working fluids, which include useas foaming agents, blowing agents, fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like), to name a few.

[0011] In some embodiments, the working fluid may comprise fluoroolefinscomprising at least one compound with 2 to 12 carbon atoms, in another embodiment, the fluoroolefins comprise compounds with 3 to 10 carbon atoms, andin yet another embodiment the fluoroolefins comprise compounds with 3 to 7 carbon atoms.

[0012] The fluorolefin is a compound selected from the group consisting of:(i) fluoroolefins of the formula E- or Z-R1CH=CHR2 (Formula 1), whereinR1and R2are, independently, C1to C6perfluoroalkyl groups; (ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from: 1,2,3,3,3-pentafluoro-1-propene (CHF=CFCF3), 1,1,3,3,3-pentafluoro- 1-propene (CF2=CHCF3), 1,1,2,3,3-pentafluoro-1-propene (CF2=CFCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF=CFCHF2), 2,3,3,3-tetrafluoro-1-propene (CH2=CFCF3), 1,3,3,3-tetrafluoro-1-propene (CHF=CHCF3), 1,1,2,3- tetrafluoro-1-propene (CF2=CFCH2F), 1,1,3,3-tetrafluoro-1-propene (CF2=CHCHF2), 1,2,3,3-tetrafluoro-1-propene (CHF=CFCHF2), 3,3,3- trifluoro-1-propene (CH2=CHCF3), 2,3,3-trifluoro-1-propene (CHF2CF=CH2); 1,1,2-trifluoro-1-propene (CH3CF=CF2); 1,2,3-trifluoro-1-propene (CH2FCF=CF2); 1,1,3-trifluoro-1-propene (CH2FCH=CF2); 1,3,3-trifluoro-1- propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4- heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4- heptafluoro-1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF3); 1,2,3,3,4,4-hexafluoro- 1-butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF2CF=CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-hexafluoro- 2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2);3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CH2=C(CF3)2); 1,1,1,2,4- pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4-pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2-butene (CHF2CH=CHCF3); 1,1,1,2,3-pentafluoro-2- butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1-butene (CH2=CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3-pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2- butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1-butene (CH2=CFCHFCF3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1- butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF2CHF2); 1,2,3,4,4-pentafluoro-1-butene (CHF=CFCHFCHF2); 3,3,4,4-tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-difluoro-2- (difluoromethyl)-1-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2- methyl-1-propene (CHF=C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1- propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5- decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro- 1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)- 2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1-pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1-pentene(CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1-trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3); 3,3,4,5,5,5- hexafluoro-1-pentene (CH2=CHCF2CHFCF3); 4,4,4-trifluoro-2- (trifluoromethyl)-1-butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6- dodecafluoro-1-hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6- dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro- 2,3-bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5- nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)- 2- butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1- pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2- pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6- octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluoro1- hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5- heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6- heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro- 1-hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3- heptene (CF3CF2CF=CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2- heptene (CF3CH=CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2- heptene (CF3CF=CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3- heptene (CF3CF2CH=CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3- heptene (CF3CF2CF=CHCF2C2F5); pentafluoroethyl trifluorovinyl ether (CF2=CFOCF2CF3); and trifluoromethyl trifluorovinyl ether (CF2=CFOCF3).

[0013] In one embodiment, with respect to Formula 1, examples of R1 and R2groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3) CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment the fluoroolefins of Formula I, have at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 5 carbon atoms in the molecule. Exemplary, non- limiting Formula I compounds are presented in Table 1. Table 1 Structure Chemical NameCF3CH=CHCF3 111444-hexafluorobut-2-ene -Table 1 (continued) Structure Chemical NameCF3CH=CHC(CF3)31,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene-------Table 1 (continued) Structure Chemical NameC2F5CH=CHCF(CF3)(CF2)2C2F51,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-ene[0cyclic fluoroolefins (cyclo-[CX=CY(CZW)n-] (Formula II), wherein X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5). In one embodiment the fluoroolefins of Formula II, have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula II have at least about 4 carbon atoms in the molecule. In yet another embodiment, the fluoroolefins of Formula II have at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2.TABLE 2 Cyclic fluoroolefins Structure Chemical name[00compound of Formula I or formula II, for example, one of the compounds in Table 1 or Table 2, or may comprise a combination of compounds of Formula I or formula II.

[0016] In another embodiment, fluoroolefins may comprise those compoundslisted in Table 3. TABLE 3 Name Structure Chemical nameE / Z-HFO-1132 CFH=CHF E / Z-1,2-difluoroethyleneTABLE 3 (continued) Name Structure Chemical nameHFO-1327ye CHF=CFCF2CF3 1,2,3,3,4,4,4-heptafluoro-1-buteneeeTABLE 3 (continued) Name Structure Chemical nameFC-141-10myy CF3CF=CFCF2CF3 1,1,1,2,3,4,4,5,5,5-decafluoro-2-tTABLE 3 (continued) Name Structure Chemical nameHFO-1447mytm CF3CF=C(CF3)(CH3) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-t1-3- e - l-TABLE 3 (continued) Name Structure Chemical nameHFO-1558mmtzc (CF3)2C=CHCF2CH3 1,1,1,4,4-pentafluoro-2-tifl th l 2 tl-eeel-rormay be prepared by processes known in the art or as described herein.

[0018] Many of the compounds of Formula I, Formula II, Table 1, Table 2, andTable 3 exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the described composition is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, HFO-1225ye is meant to represent the E-isomer, Z-isomer, or anycombination or mixture of both isomers in any ratio, with the Z isomer preferred.

[0019] In some embodiments, the working fluid may further comprise at least onecompound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO2), ammonia (NH3), and iodotrifluoromethane (CF3I).

[0020] In some embodiments, the working fluid may further comprisehydrofluorocarbons comprising at least one saturated compound containing carbon, hydrogen, and fluorine. Of particular utility are hydrofluorocarbons having 1 to 7 carbon atoms and having a normal boiling point of from about -90°C to about 80°C. Hydrofluorocarbons are commercial products available from a number of sources or may be prepared by methods known in the art. Representative hydrofluorocarbon compounds include but are not limited to fluoromethane (CH3F, HFC-41), difluoromethane (CH2F2, HFC-32), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC-125), 1,1,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1,1,1,2-tetrafluoroethane (CF3CH2F, HFC-134a), 1,1,1-trifluoroethane (CF3CH3, HFC-143a), 1,1-difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (CF3CF2CHF2, HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,2,2,3,3,- hexafluoropropane (CHF2CF2CHF2, HFC-236ca), 1,1,1,2,2,3-hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (CF3CHFCHF2, HFC- 236ea), 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa), 2-chloro-1,1,1,2- tetrafluoropropane (HFC-244bb), 1,1,2,2,3-pentafluoropropane (CHF2CF2CH2F, HFC-245ca), 1,1,1,2,2-pentafluoropropane (CF3CF2CH3, HFC-245cb), 1,1,2,3,3- pentafluoropropane (CHF2CHFCHF2, HFC-245ea), 1,1,1,2,3-pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1,1,1,3,3-pentafluoropropane (CF3CH2CHF2, HFC- 245fa), 1,2,2,3-tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1,1,2,2- tetrafluoropropane (CHF2CF2CH3, HFC-254cb), 1,1,2,3-tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1,1,1,2-tetrafluoropropane (CF3CHFCH3, HFC- 254eb), 1,1,3,3-tetrafluoropropane (CHF2CH2CHF2, HFC-254fa), 1,1,1,3- tetrafluoropropane (CF3CH2CH2F, HFC-254fb), 1,1,1-trifluoropropane (CF3CH2CH3, HFC-263fb), 2,2-difluoropropane (CH3CF2CH3, HFC-272ca), 1,2-difluoropropane (CH2FCHFCH3, HFC-272ea), 1,3-difluoropropane (CH2FCH2CH2F, HFC-272fa), 1,1- difluoropropane (CHF2CH2CH3, HFC-272fb), 2-fluoropropane (CH3CHFCH3, HFC- 281ea), 1-fluoropropane (CH2FCH2CH3, HFC-281fa), 1,1,2,2,3,3,4,4- octafluorobutane (CHF2CF2CF2CHF2, HFC-338pcc), 1,1,1,2,2,4,4,4-octafluorobutane (CF3CH2CF2CF3, HFC-338mf), 1,1,1,3,3-pentafluorobutane (CF3CH2CHF2, HFC- 365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3, HFC-43- 10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane (CF3CF2CHFCHFCF2CF2CF3, HFC-63-14mee).

[0021] In some embodiments, working fluids may further comprise fluoroetherscomprising at least one compound having carbon, fluorine, oxygen and optionally hydrogen, chlorine, bromine or iodine. Fluoroethers are commercially available or may be produced by methods known in the art. Representative fluoroethers include but are not limited to nonafluoromethoxybutane (C4F9OCH3, any or all possible isomers or mixtures thereof); nonafluoroethoxybutane (C4F9OC2H5, any or all possible isomers or mixtures thereof); 2-difluoromethoxy-1,1,1,2-tetrafluoroethane (HFOC-236eaEβγ, or CHF2OCHFCF3); 1,1-difluoro-2-methoxyethane (HFOC- 272fbEβγ, or CH3OCH2CHF2); 1,1,1,3,3,3-hexafluoro-2-(fluoromethoxy)propane (HFOC-347mmzEβγ, or CH2FOCH(CF3)2); 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFOC-356mmzEβγ, or CH3OCH(CH3)2); 1,1,1,2,2-pentafluoro-3-methoxypropane (HFOC-365mcEγδ, or CF3CF2CH2OCH3); 2-ethoxy-1,1,1,2,3,3,3-heptafluoropropane (HFOC-467mmyEβγ, or CH3CH2OCF(CF3)2 and mixtures thereof.

[0022] In some embodiments, working fluids may further comprise hydrocarbonscomprising compounds having only carbon and hydrogen. Of particular utility are compounds having 3 to 7 carbon atoms. Hydrocarbons are commercially available through numerous chemical suppliers. Representative hydrocarbons include but are not limited to propane, n-butane, isobutane, cyclobutane, n-pentane, 2- methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 2,2- dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, and cycloheptane.

[0023] In some embodiments, the working fluid may comprise hydrocarbonscontaining heteroatoms, such as dimethylether (DME, CH3OCH3).

[0024] In some embodiments, working fluids may further comprise carbon dioxide(CO2), which is commercially available from various sources or may be prepared by methods known in the art.

[0025] In some embodiments, working fluids may further comprise ammonia(NH3), which is commercially available from various sources or may be prepared by methods known in the art.

[0026] In some embodiments, the working fluid further comprises at least onecompound selected from hydrofluorocarbons, fluoroethers, hydrocarbons, dimethyl ether (DME), carbon dioxide (CO2), ammonia (NH3), and iodotrifluoromethane (CF3I).

[0027] In one embodiment, the working fluid comprises 2,3,3,3-tetrafluoropropene(HFO-1234yf). In another embodiment, the working fluid comprises HFO-1233zd. In one embodiment, the working fluid comprises E / Z-1,3,3,3-tetrafluoropropene (E / Z- HFO-1234ze, preferably E-HFO-1234ze). In another embodiment, the working fluid comprises E / Z-HFO-1336mzz.

[0028] In some embodiments, the working fluid comprises at least one of thecompounds defined in Table 4. TABLE 4 Code Structure Chemical nameCH2═CH2 Ethylene

[0029] One aspect of the invention relates to manufacturing HFOs that utilizedistillation to separate components obtained during the manufacturing process. One specific embodiment of the invention relates to using the instant invention in an HFO- 1234yf manufacturing process that recovers heat employed for separating, for example, HCFC-244bb from HCFO-1233xf. Another specific embodiment of the invention relates to using the instant invention in the HFO-1234yf manufacturing processes described in U.S. Patent Nos.10214669 and 8147709; and HFO-1234ze manufacturing processes described in U.S. Patent Nos.7189884 and 9255046; the disclosure of the foregoing US Patents is hereby incorporated by reference in their entirety. However, there are many applications over a wide variety of industries and, for reasons described herein, the inventive system and method can be used for making a wide range of compounds including HFOs.

[0030] Another aspect of the invention relates to any combination of the foregoingaspects and a system for separating at least two compounds comprising a distillation column and an integrated HTHP, wherein the HTHP receives and provides heat to the distillation column.

[0031] Another aspect of the invention relates to any combination of the foregoingaspects and a system for separating at least two compounds of a mixture, the system comprising a distillation column and an integrated HTHP, wherein the HTHP receives and provides heat to the distillation column and wherein the mixture comprises any of the compounds of Table 1, Table 2, Table 3 and / or Table 4.

[0032] In one embodiment, the present invention relates to a system for separatingat least two compounds of a mixture, the system comprising a distillation column and an integrated HTHP, wherein the HTHP receives and provides heat to the distillation column and wherein the mixture includes a. at least one of 244bb and 1233xf which are to be separated by distillation, such as when HCFO-1233xf is used to produce HCFC- 244bb as disclosed in Patent Nos.10214669, or b. cis-HFO-1234ze, trans-HFO-1234ze and HFC-245fa which are to be separated by distillation, for example as disclosed in US9255046.

[0033] A further aspect of the invention relates to any combination of the foregoingaspects wherein the temperature of the heat provided to the distillation column is greater than the temperature of the heat received by the HTHP.

[0034] A further aspect of the invention relates to any combination of the foregoingaspects wherein the HTHP contains a working fluid comprising at least one member selected from HFO-1234yf, HFO-1234ze, HFO-1233zd, HFO-1336mzz, and blends thereof including those comprising, for example, R-514A, R-515B, R-476A and R- 471A.

[0035] Another aspect of the invention relates to making at least one of HFO-1234yf, HFO-1233zd, HFO-1336mzz and HFO-1234ze using the system of any combination of the foregoing aspects.

[0036] The various aspects and embodiments of the invention can be used aloneor combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG.1 is a schematic drawing of an exemplary HTHP unit to be integrated with a distillation column.

[0038] FIG.2 is a typical pressure enthalpy diagram of Fig.1.

[0039] FIG. 3 is a schematic drawing showing operational details of the HTHPsystem shown in FIG.1 integrated with a distillation column.

[0040] FIG. 4 is a schematic drawing showing multiple HTHP units that can beintegrated with one or more distillation columns. DETAILED DESCRIPTION

[0041] The present invention relates to systems and processes which can reducesteam inputs, recover heat as well as reduce energy consumption by integrating one or more high temperature heat pumps (HTHP), as disclosed herein. Preferably, the working fluid for the inventive systems and processes is selected to have a high critical temperature, low critical pressure, zero ozone depletion potential (ODP), low GWP, low to no-flammability, and low to no-toxicity. In one embodiment, the workingfluid may comprise one or more of the compounds disclosed herein, such as one or more of the compounds of Tables 1, 2, 3 and / or 4.

[0042] In one embodiment, one or more of the HTHP units is associated with orintegrated with one or more distillation columns. In some embodiments, existing chemical process equipment or related processes can be modified / retrofitted to integrate existing distillation columns with one or more HTHPs to reduce steam requirements. High coefficient of performance (COP) and energy efficiency is achieved by coupling, more particularly integrating, the HTHP(s) with distillation process equipment, and provides flexibility in the choice of refrigerant and equipment design while maintaining high reliability required for a continuous operation.

[0043] In some embodiments, one or more HTHP units associated with processheat exchangers providing cooling and heating, especially in energy intensive unit operations such as reactors, provide additional heat recovery beyond what is achievable with direct process-to-process heat exchange or heat exchange with a common utility.

[0044] Before addressing details of the embodiments described below, someterms are defined or clarified.

[0045] As used herein, the terms “comprises,” “comprising,” “includes,” “including,”“has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a 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 process, method, article, or apparatus. Further, unless expressly stated to the contrary, “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 is true (or present).

[0046] The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0047] The transitional phrase “consisting essentially of” is used to define acomposition, 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.’

[0048] Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0049] Also, use of “a” or “an” are employed to describe elements and componentsdescribed herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0050] Where a range of numerical values is recited herein, unless otherwisestated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0051] When an amount, concentration, or other value or parameter is given aseither a range, preferred range, or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0052] Process equipment for producing fluorochemical compounds can rely onone or more reactors, heat exchangers, effluent lines, mass transfer units, contacting vessels (pre-mixers), distillation columns, and feed, transfer and product lines associated with the one or more: reactors, heat exchangers, vessels, distillation columns, separatory columns used in the process. The reactors can be a flow through reactor, a tube reactor, or an autoclave equipped with a temperature and pressure control. The reactor can operate in batch, semi-continuous or continuous modes, preferably in the continuous mode. Various reactor configurations are possible, such as, a horizontally or vertically arranged reactors. Downstream reactions may be carried in a series of reactors operated in non-adiabatic and adiabatic modes.

[0053] The process and / or HTHP equipment disclosed herein should beconstructed of materials resistant to the reactants and or product produced. Preferably, the reactors and components are made of an acid resistant alloy, e.g., nickel, a nickel-based alloys (e.g., Hastelloy®, available from Special Metals Corp.), nickel-chromium alloys commercially available under the trade name of Inconel®(hereafter "Inconel®"), or nickel-copper alloys marketed under the trade name Monel®. Alternatively, containers, piping, or reactors fabricated from less corrosive- resistant metals such as stainless steel or carbon steel may be lined with a fluoropolymer such as poly(tetrafluoroethylene). In addition to the reactors disclosed herein, the preheaters and vaporizers, heat exchangers, feed, transfer and effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and valving associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes of various embodiments disclosed herein should be constructed of materials resistant to corrosion. In certain embodiments the condenser and evaporator tube side materials of construction would be the corrosion resistant materials such as the nickel-based alloys listed above. The remainder of the refrigerant circuit would be standard carbon steel and stainless steel.

[0054] Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0055] Also, use of “a” or “an” are employed to describe elements and componentsdescribed herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0056] As used herein, the term “substantially free” means that less than about0.0001 percent by weight is present (1 ppm).

[0057] As used herein the term “about” in certain embodiments can mean ± 1%, ±2%, ± 3% and up to and including ±10% of an identified value, including all whole numbers and fractions thereof.

[0058] As used herein the term “substantially,” “main” or “major” should beconstrued to mean at least 51 percent.

[0059] Compounds referred to in this disclosure may be referred to by code, basedon fluorochemical naming convention, chemical structure and / or chemical name.

[0060] FIG. 1 exemplifies an HTHP unit that is to be integrated with a chemicalmanufacturing process, as shown in for example FIG.3, to provide heating with the highest efficiency possible, while providing the stable and reliable heat input required to operate the process. For example, the integrated HTHP and distillation column system may be part of a larger system for manufacturing of a composition or compound comprising any of the compounds disclosed herein, such as the compounds of Tables 1, 2, 3 and / or 4. As noted herein, it will be understood by those skilled in the art that one or more HTHPs may be integrated with one or more distillation columns and related process heat exchangers used for heating and cooling.

[0061] Once the HTHP is integrated with a distillation column or manufacturingprocess, the integrated system reduces the amount of steam usage in the process, can provide heat to other unit operations on a given site, as well as provide heat to a secondary heat transfer loop or district heating.

[0062] Integration of the one or more HTHP units with one or more distillationcolumns reduces energy intensity for heating of the distillation processes. More particularly, integrating one or more HTHP units with one or more distillation columnscan reduce total steam consumption for not only the distillation process, but the overall chemical manufacturing process.

[0063] For example, in some embodiments, integrating one or more HTHP unitswith one or more distillation columns can reduce total steam consumption for the manufacturing process by at least about 10%, 20%, 30% or higher or any amount between 10% and 100%, depending on the process and the upper limit of steam reduction, possibly limited by, e.g., design footprint and / or process economics.

[0064] The HTHP can be integrated to any suitable distillation column, forexample, a column with over 50 theoretical separation stages. The HTHP will include first and second heat exchangers comprising an evaporator (process condenser) and condenser (process reboiler). The surface areas of the condenser and / or evaporator can range from several hundred square feet to several thousand square feet, and are selected according to the components being separated (e.g., HCFC-244bb and HCFO-1233xf). These heat exchangers are generally located at the process distillation column site (see Fig.3) as separate equipment pieces, but still part of a closed loop system including the other HTHP components that may be on site near the distillation column or any other part of the system or plant. The HTHP can employ an independent PLC control package that will be integrated into the process DCS (distributed control system) and safety system.

[0065] The inventive system and method achieve a high coefficient of performance(COP) by coupling the heat pump to the distillation process, and provides flexibility in the choice of refrigerant and equipment design while maintaining high reliability required for a continuous operation.

[0066] Referring now to the figures, Fig. 1 illustrate an exemplary HTHP unit to becoupled to a distillation column to form the integrated system of the presentinvention. The HTHP system 100 includes a closed loop 110 filled with a workingfluid connected with and providing fluid communication to and from the compressor120, condenser 130 (process reboiler), economizer 140, evaporator 150 (processcondenser), flow valves 160, 170 and 180 associated with a control system (notshown). Closed loop 110 includes flow lines 190 and 192, and valved lines 194, 196and 198. The loop 110 may be filled with any working fluid, including but not limitedto, for example, HFO-1234yf, E / Z-HFO-1234ze, HFO-1233zd, E / Z-HFO-1336mzz,and blends thereof including R-514A, R-515B, R-476A and R-471A, but preferably a refrigerant that has sufficient volumetric capacity to keep compressor and equipment sizes reasonable, exhibits low flammability or is non-flammable, low to no PFAS, an azeotrope / near azeotrope / or single component fluid that is suitable for use in flooded systems, and / or has positive pressures at the desired evaporating condition and reasonable pressures at the desired condensing condition.

[0067] Referring to Figs. 1 and 2, starting with point P-1, suction gas enters thesuction side of the compressor (P-1) and the refrigerant pressure and temperature are elevated as the working fluid (e.g., refrigerant) travels through the compressor in what could be multiple stages of compression. Point P-4 is depicting a point within the compressor between suction and discharge where working fluid vapor from the economizer is introduced as a side load. The working fluid travels further along the path of compression and is discharged at point P-5 in the form (“state”) of a superheated vapor. The superheated vapor working fluid travels through thedischarge piping 190 and into a heat exchanger 130 (process reboiler) where aprocess fluid (e.g., air, water and the like) is used to condense the superheated vapor working fluid to a liquid. Saturated or subcooled liquid working fluid exits thecondenser at point P-6, passes through line 194, valve 170 and point P-7 to aneconomizer 140, e.g., one or more expansion devices for an expansion process.The working fluid pressure can be dropped in an isenthalpic expansion process.Flash gas from this expansion process is sent via flow line 198 and valve 160 to thecompressor (along point P-2 and P-3 to point P- 4). The remaining liquid leaving the expansion device collects in the economizer and travels to a separate expansion device (not shown) where another isenthalpic expansion process occurs. Theresulting liquid-vapor mixture at point P- 8 travels through flow line 196 and thenvalve 180 at which point it is at the desired temperature to enter the evaporator heatexchanger 150. Process fluid exchanges heat in the evaporator heat exchanger 150with the working fluid (e.g., refrigerant) and the working fluid boils and exits theevaporator heat exchanger 150 (process condenser). The heat recovery cycle iscomplete when the vapor leaves the evaporator heat exchanger 150 through flowline 192 and enters the compressor suction at point P-1.

[0068] Fig. 2 reflects a typical enthalpy cycle for the HTHP of Fig. 1. Referring toFig.2, at state 1, suction gas enters the compressor, and the refrigerant pressureand temperature are elevated as the refrigerant travels through the compressor in what could be multiple stages of compression. State 4 is within the compressor between suction and discharge where refrigerant vapor from the economizer is introduced as a side load. The refrigerant travels further along the path of compression and is discharged at state 5 in the form of a superheated vapor. The refrigerant travels through the discharge piping and into a heat exchanger where a process media is used to condense the superheated vapor refrigerant to a liquid. Saturated or subcooled liquid refrigerant exits the condenser at state 6 and travels to an expansion device. The refrigerant pressure is dropped in an isenthalpic expansion process. Flash gas from this expansion process is sent to the compressor (state 2 to state 3 to state 4). The remaining liquid leaving the expansion device collects in the economizer and travels to a separate expansion device where another isenthalpic expansion process occurs. The resulting liquid- vapor mixture that is now at the desired temperature enters the evaporator heat exchanger. Process fluid exchanges heat in this exchanger with the refrigerant and the refrigerant boils and exits the evaporator. The cycle is complete when the vapor leaving the evaporator enters the compressor suction at state 1.

[0069] Referring to Fig. 3, there is shown an integrated system and processaccording to an embodiment of the present invention. Referring to Fig.3, according to the present invention, the HTHP unit / system (such as, for example, the HTHP of Figs.1 and 2 as described above) is integrated with a distillation column. Process streams from chemical processes, particularly processes to form chemicals such as refrigerants, such as those described in, for example, U.S. Patent Nos.10214669, 8147709, 7189884 and 9255046, the disclosure of each of which is incorporated herein in its entirety, are transferred to distillation columns for separation. Process streams include, but are not limited to, final product stream mixtures, crude product steam mixtures, intermediate product stream mixtures and the like.

[0070] The stream or mixture to be separated, for example process streamsgenerated from the reactor system (not shown), in the form of a liquid is introducedinto the distillation column 302 through, e.g., line 301. Overhead 302a is selectivelyconveyed directly to CTW (cooling tower water) condenser 305 and / or through line302c to and through the tube side of heat pump chiller 350 to reflux tank 306 alongwith discharge from CTW condenser 305. Discharge from reflux tank 306 istransferred via pump 304 to either a recycle line or through line 302b back to thedistillation column 302. Bottoms 302d from column 302 are selectively transferred byappropriate valving (not shown) through line 302e to the tube side of a HTHPcondenser 330 (process reboiler), through line 302f to a reboiler 303. Heat isprovided via the reboiler 303 and HTHP condenser 330 at a location below the entrylocation of the material for separation 301 in distillation column 302. Heat recoveredfrom the overhead of the distillation column 302 is provided through line 302a to theHTHP condenser 330, which upgrades or lifts (increases the temperature) the heatproduced thereby, and the generated heat, in turn, is provided to the distillationcolumn 302. The working fluid is circulated through the closed loop system, whichincludes, in addition to the components specifically discussed in detail above, theshell side of heat pump chiller 350 (process condenser), compressor 340, shell sideof condenser 330, valve 370 which controls flow from the HTHP condenser 330 to atleast the shell side of the economizer 340, valve 360 which controls flow from atleast the tube side of the economizer 340 and to compressor 320.

[0071] Referring to Fig. 4, there is shown a system and process according to anembodiment of the present invention which includes a multiple component HTHPsystem 400, and more particularly an integrated system 400 which includes multipleHTHP units for coupling to one or more distillation columns (not shown). Themulticomponent HTHP system 400 comprises first and second compressors 420,421; first, second and third condensers 430, 431 and 432 (process reboilers); one ormore economizers 440; and first, second and third evaporators 450, 450 and 451(process condensers). It will be understood by those skilled in the art that the systems are not limited to only two compressors, three condensers, or three evaporators. Instead, more or less of each type of process equipment may be utilized. In Fig.4, bottoms from a distillation column (not shown) would be conveyedto and through the tube side of the economizer 440 and overhead from thedistillation column would be conveyed through the tube side of the evaporators 450,450 and 451.

[0072] Referring again to the figures, and in particular Fig. 3, while the inventivesystem and method can be used in connection with manufacturing any suitable material, in one embodiment, the invention can be employed for reducing heat required for manufacturing a refrigerant, such as HFO-1234yf. For example, onestep for making a refrigerant, such as HFO-1234yf, may comprise separating two compounds from each other. The inventive system can reduce the amount of heat required for the separation. That is, by utilizing a HTHP to recover a significant portion, if not all, of the heat rejected at the distillation column condenser and upgrading that heat to a higher temperature to provide all or most of the heat input required at the column reboiler, the need for and use of fossil-fuel derived steam is reduced, if not completely eliminated. This is because the energy produced is greater than the energy input needed to operate the compressor. The heat recovery may occur by installing a suitable evaporator (such as a flooded evaporator) with the refrigerant on the shell-side and the distillation column overhead vapors condensing in the tube-side of the heat pump evaporator. The recovered heat, along with the energy from compression of the refrigerant, is then released at the heat pump condenser which operates as the distillation column reboiler with the process chemicals being boiled while the refrigerant is condensed. The integration of the heat pump into the distillation column with a specific refrigerant working fluid is done so that the refrigerant pressure is maintained higher than the process, in order to provide a predictable leak path, and the chosen refrigerant is compatible with the process if a leak were to occur.

[0073] The invention will be described in greater detail below by way of specificexamples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results. Examples Example 1:

[0074] The system depicted in Fig. 3 is employed for separating HCFC-244bbfrom HCFO-1233xf during manufacture of HFO-1234yf, thereby reducing the heat required for manufacturing HFO-1234yf. The amount of heat required for the separation of HCFC-244bb from HCFO-1233xf (i.e., the energy intensity for heating of the distillation step) is reduced by about 70%, about 75% and, in some cases, by about 77%. The heat pump has a COP (Coefficient-of-Performance) of at least about 4.0, or about 4.1, or in some cases at least 4.27 (or 14.57 Btu / W-hr EER),meaning that the energy produced is over 4 times the amount of energy input needed to operate the compressor. Example 2:

[0075] An integrated HTHP / distillation system is applied to process cooling for afirst stream containing HFO-1243zf, HF and HCl and a second stream containing HFO-1234yf, HCFC-244bb, and HF utilizing an evaporator, cooling the process vapor from approximately 95°C to as low as 50°C. The HTHP fluid vapor is condensed with one or more the heat exchangers, such as related distillation reboilers as described herein, used to purify HFO-1243zf and HFO-1234yf, and distill HF that is recycled in the process. The recovered heat is transferred with heat exchangers that condense the heat pump fluid while boiling the distillation liquid either directly or with an intermediate working fluid. Example 3:

[0076] An integrated HTHP / distillation system is applied where heat is recoveredfrom the process cooling tower water return for the manufacture of HFO-1243zf, HCFO-1233xf, HCFC-244bb, and HFO-1234yf using a large heat exchanger by evaporating the heat pump working fluid. The cooling water is cooled from approximately 50°C to 27°C. The evaporated working fluid is then compressed with a network of two or more parallel compressors with the recovered heat with compression energy transferred into a common heating utility, such as steam or propylene glycol solution at 75°C to 120°C. Example 4:

[0077] A thermodynamic model using NIST Reference Fluid Thermodynamic andTransport Properties (REFPROP) version 10.0.0.98b for refrigerant properties was used to compare heat pump system performance between heat pump working fluids, in accordance with the integrated system of the present invention. The fluids, and more particularly refrigerants, considered were HFO-1336mzzZ, HFO-1336mzzE, HFO-1234zeE, HFO-1234yf, and HFO-1233zdE. Compressor isentropic efficiencies were modeled using the same 60% value across all refrigerants and conditions.

[0078] The modeled system, as shown in Figure 1, includes a compressor,condenser, economizer, and evaporator. Two conditions were considered for thisevaluation. The first condition represents a source heat from a distillation column overheads stream at 100oF which is required to be lifted to a process heating or column reboiler temperature of 194oF. The process heat duty is 8 million BTU per hour. The second condition represents a source heat from process cooling tower return water at 70oF which is required to be lifted to a process heating temperature of 220oF. The required process heat duty is 20 million BTU per hour. Thus, the first condition represents a lower temperature lift and required heating capacity, while the second condition represents a lower source temperature, higher sink temperature and higher heating duty. The conditions are summarized in Table 5. Table 5 Condition 1 Condition 2 UnitsCondensin Tem erature 194 220 ⁰Fr[00pressure, discharge temperature, cooling capacity, system energy use, theoretical displacement, heating coefficient of performance, comparative energy required if steam were used in lieu of the heat pump, and the percent energy reduction of the heat pump versus steam use were modeled and are reported in Tables 6 and 7. Table 6 Condition 1 nTable 6 (continued) Condition 1 System Theoretical Comparative Energy nCondition 2* Suction Discharge Discharge nSystem Theoretical n1234yf was not evaluated at Condition 2.

[0080] Low system energy use is desirable for operating cost and carbon footprint.Generally, refrigerant selection for positive suction pressures is desired so as not to introduce air into the refrigeration system should a leak arise. Discharge pressures should be kept low to reduce the design requirements for equipment and piping. A high cooling capacity for a given heat rejection requirement can be desirable depending on the heat source. Low theoretical compressor displacements are desirable to reduce compressor sizing. High coefficient of performance is desired for the same reason as low system energy use.

[0081] The results indicate that optimum refrigerant selection is dependent uponend user requirements. For both conditions 1 and 2, and all refrigerants, considerable energy reduction is achieved.

[0082] Although certain aspects, embodiments and principals have beendescribed above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Claims

CLAIMS What is claimed is:

1. A system for separating at least two compounds, the system comprising:at least one distillation column, a first reboiler coupled to the at least one distillation column, and at least one high temperature heat pump (HTHP) coupled to the at least one distillation column, wherein the at least one distillation column, first reboiler and at least one HTHP define a closed circulation loop filled with a working fluid, and wherein the at least one HTHP receives heat recovered from the at least one distillation column, performs a temperature lift, and provides heat to the at least one distillation column.

2. The system of Claim 1, wherein a temperature of the heat provided to the atleast one distillation column from the at least one HTHP is greater than a temperature of the heat received by the at least one HTHP.

3. The system of Claim 1 or Claim 2, wherein the HTHP contains a working fluidcomprising at least one member selected from the group consisting of HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1233zd, E-HFO-1336mzz, Z-HFO-1336mzz and blends thereof.

4. The system of Claim 3, wherein the HTHP contains a working fluid comprisingHFO-1234yf, and wherein the at least one distillation column comprises an inlet feed of at least one of HCFC-244bb and HCFO-1233xf.

5. The system of any of Claims 1 to 4, wherein said system includes a singledistillation column and a single HTHP.

6. The system of any of Claims 1 to 4, wherein said system includes more thanone distillation columns.

7. The system of any of Claims 1 to 4 or 6, wherein said system includes morethan one HTHPs.

8. A method for making at least one member selected from the group consistingof HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1233zd, E-HFO-1336mzz, Z- HFO-1336mzz and blends thereof, the method comprising producing an intermediateproduct stream comprising at least a first intermediate compound and second intermediate compound, and feeding the intermediate product stream as a feed for the system of Claim 1 or Claim 2.

9. The method of claim 8, wherein the first and second intermediate compoundare HCFC-244bb and HFO-1233xf.

10. An integrated distillation system comprising: one or more distillation columns, each of said distillation columns comprising a feed line, overhead and bottoms discharge line, and one or more high temperature closed loop heat pump units (HTHP), each of said HTHP units comprising at least first and second heat exchange units, wherein said overhead and bottoms discharge lines of each distillation column are respectively connected to said first and second heat exchange units.

11. The integrated distillation system of Claim 10, wherein said overhead and bottoms discharge lines of each distillation column are respectively connected to a tube side of said first and second heat exchange units.

12. The integrated distillation system of Claim 10 or Claim 11, wherein each HTHP unit further comprises an economizer and a compressor, wherein said compressor, said first heat exchange unit, said economizer and second heat exchange unit are connected in seriatim to form the closed loop, the closed loop being filed with a working fluid.

13. The integrated distillation system of any of Claims 10 to 12, wherein the working fluid comprises at least one member selected from the group consisting of HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1233zd, E-HFO-1336mzz, Z- HFO-1336mzz, and blends thereof, the blend including one selected from the group consisting of R-514A, R-515B, R-476A and R-471A.

14. A process for separating components of a chemical process stream, the process comprising, a) providing the chemical process stream which comprises at least first and second components to be separated, b) conveying the chemical process stream to a distillation column for separation of the first and second components,c) withdrawing an overhead stream from the distillation column and transferring the overhead stream to a condenser-chiller, optionally to a tube side of a condenser-chiller, and d) withdrawing a bottoms stream from the distillation column and transferring the bottoms stream to a condenser-reboiler of a closed loop HTHP, the closed loop HTHP further comprising a compressor and an economizer, and e) continuously circulating a working fluid through the condenser-chiller, optionally through a shell side of the condenser-chiller, and through the condenser-reboiler of the closed loop HTHP, optionally through a shell side of the condenser-reboiler, and through the compressor and the economizer of the closed loop HTHP.

15. A system comprising, a) at least one reaction zone configured to produce at least one product stream, b) a discharge line configured to convey the product stream as a liquid, c) at least one distillation column having an overhead discharge line, a branched bottoms discharge line with one branch connected to a reboiler, and a feed line located between the reboiler and the overhead discharge line for receiving the liquid product stream, and d) a closed loop high temperature heat pump (HTHP) comprising, in seriatim, a compressor, a reboiler condenser, an economizer and chiller-condenser, the closed loop HTHP being filled with a working fluid which circulates through the chiller-condenser and the reboiler condenser, wherein the overhead discharge line and the branched bottoms discharge line of said distillation column are respectively in heat exchange relationship with the working fluid.

16. A retrofitting process comprising, a) integrating a high temperature heat pump (HTHP) with a distillation column, the HTHP containing, in seriatim, a first heat exchanger, acompressor, a second heat exchanger and an economizer which collectively define a closed circulation loop housing a working fluid, b) connecting an overhead line of the distillation column to the first heat exchanger which is returned to an upper portion of the distillation column, c) connecting a branch of a bottoms discharge line of the distillation column to pass a bottoms fraction to the second heat exchanger and back to the distillation column, and d) arranging a liquid feed inlet of the distillation column between an upper portion of the column and above the second heat exchanger of the HTHP.

17. The retrofitting process of claim 16, wherein the working fluid selected from the group consisting of HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1233zd, E-HFO-1336mzz, Z-HFO-1336mzz, R-514A, R-515B, R-476A and R-471A.

18. A distillation process comprising, a) passing a process stream mixture comprising HCFO-1233xf and HCFC-244bb to a distillation column, b) withdrawing an overhead stream from the distillation column at a first temperature and recovering heat from the overhead stream using a working fluid of a high temperature heat pump (HTHP), c) withdrawing a portion of a bottoms stream of the distillation column at a second temperature, d) contacting the withdrawn portion of the bottoms stream with the circulating working fluid of the HTHP and returning the withdrawn portion to the distillation column, wherein heat recovered from the process is less than heat returned to the distillation column by the working fluid.

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