Process for the production of fluorinated alkenes and intermediates

Abstract

An integrated process for producing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene and uses of the products produced in this process.

Description

TITLE PROCESS FOR THE PRODUCTION OF FLUORINATED ALKENES AND INTERMEDIATES FIELD

[0001] The present application relates to an integrated process of preparing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene. BACKGROUND

[0002] A growing public awareness of the environmental impacts from the extraction,transportation and use of fossil fuels are motivating a new environmental sustainability driver in the form of regulations and reduction in output of CO2 equivalence in the atmosphere. In particular, new environmental regulations on refrigerants have forced the refrigeration and air-conditioning industry to look for new refrigerants with low global warming potentials (GWPs). Replacement refrigerants with low global warming potentials (GWP) and ozone depletion potential (ODP) for both existing and new applications in thermal management segments will need to adhere to these new regulations.

[0003] Certain hydrofluoroolefins, such as E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene(E-C2F5CH=CHC2F5, E-HFO-153-10mczz), are believed to meet both goals. Inparticular, E-isomer of 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be useful in heattransfer fluid applications (e.g., immersion cooling systems, data-center cooling systems or thermal management solution for EV batteries). Accordingly, the present applicationprovides new processes for preparing E-HFO-153-10mczz.SUMMARY

[0004] Disclosed is an integrated process for the preparation of E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, E-C2F5CH=CHC2F5 (also referred to herein as E-HFO-153-10mczz, or more simply E-153-10mczz) in a series of interrelated steps beginning withethylene and 1,1,1-trichloro-2,2,2-trifluoroethane, CF3CCl3 (CFC-113a) as starting materials and subsequently using HF as fluorinating agent.

[0005] In one embodiment of this invention, there is provided a process for thepreparation of E-HFO-153-10mczz comprising: Step 1 wherein Step 1 comprisescontacting ethylene with CFC-113a in the presence of a catalyst system comprising a metal and an organic ligand in a reactor, to obtain a process mixture (I) comprising 2,2,4-trichloro-1,1,1-trifluorobutane (CH2ClCH2CCl2CF3,HCFC-353maf); Step 2 wherein Step 2 comprises contacting HCFC-353maf with HF in the presence of a fluorination catalyst in a reactor to obtain a process mixture (II) comprising 3,3,4,4,4-pentafluoro-1- butene (CF3CF2CH=CH2, HFO-1345zf); Step 3 wherein Step 3 comprises contacting HFO-1345zf with CFC-113a in the presence of a catalyst system comprising a metal and an organic ligand in a reactor to obtain a process mixture (III) comprising 3,5,5- trichloro-1,1,1,2,2,6,6,6-octafluorohexane (CF3CF2CHClCH2CCl2CF3, HCFC-548mafd); and Step 4 wherein Step 4 comprises contacting HCFC-548mafd with HF in the presence of a fluorination catalyst in a reactor to obtain a process mixture (IV)comprising E-1,1,1,4,4,5,5,6,6,6-decafluoro-3-hexene (E-C2F5CH=CHC2F5, E-HFO-153-10mczz).

[0006] In certain embodiments of the process of this invention the process furthercomprises performing one or more optional steps.

[0007] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1; or between Steps 2 and 3, separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprisingStep 2 intermediates and feeding the recycle stream (2a) to Step 2; or between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO- 1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3; orfollowing Step 4, separating E-HFO-153-10mczz from the process mixture (IV), whereinthe process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0008] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1.

[0009] In one embodiment, the process further comprises, between Steps 2 and 3,separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2. In one embodiment, the Step 2 intermediates comprise one or more isomers of dichlorotrifluorobutenes (HCFO-1343 isomers), and / or one or more isomers of chlorotetrafluorobutenes (HCFO-1344 isomers). In one embodiment, the Step 2 intermediates comprise one or more isomers of dichlorotrifluorobutenes (HCFO-1343 isomers). In one embodiment, the Step 2 intermediates comprise one or more isomers of chlorotetrafluorobutenes (HCFO-1344 isomers).

[0010] In one embodiment, the process further comprises, between Steps 3 and 4,separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO- 1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zfand feeding the recycle stream (3a) to Step 3.

[0011] In one embodiment, the process further comprises, following Step 4,separating E-HFO-153-10mczz from the process mixture (IV), wherein the processmixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV) E- HFO-153-10mczz, providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4. In one embodiment, the Step 4 intermediates comprise one or more isomers of chlorononafluorohexene (HCFO-1539 isomers). In one embodiment, the Step 4 intermediates comprise 2-chloro-1,1,1,2,5,5,6,6,6- nonafluorohex-3-ene (HCFO-1539mbzz, CF3CFClCH=CHCF2CF3).

[0012] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2. In one embodiment, the process further comprises, between Steps 1 and 2, separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1; and between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3.

[0013] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1;and following Step 4, separating E-HFO-153-10mczz from the process mixture (IV),wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0014] In one embodiment, the process further comprises, between Steps 2 and 3,separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II),providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3.

[0015] In one embodiment, the process further comprises, the process furthercomprises, between Steps 2 and 3, separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; andfollowing Step 4, separating E-HFO-153-10mczz from the process mixture (IV), whereinthe process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0016] In one embodiment, the process further comprises, between Steps 3 and 4,separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3; and followingStep 4, separating E-HFO-153-10mczz from the process mixture (IV), wherein theprocess mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0017] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO- 1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3.

[0018] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1;and between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream(3a) to Step 3; and following Step 4, separating E-HFO-153-10mczz from the processmixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0019] In one embodiment, the process further comprises, between Steps 2 and 3,separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; between Steps 3 and 4, separating HCFC-548mafd and CFC- 113a from the process mixture (III), providing a recycle stream (3) comprising CFC- 113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO-1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding therecycle stream (3a) to Step 3; and following Step 4, separating E-HFO-153-10mczzfrom the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV),providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0020] In one embodiment, the process further comprises, between Steps 1 and 2,separating HCFC-353maf and CFC-113a from the process mixture (I) and providing a recycle stream (1) comprising CFC-113a and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating HFO-1345zf from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating HCFC-548mafd and CFC-113a from the process mixture (III), providing a recycle stream (3) comprising CFC-113a and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted HFO- 1345zf, and the process further comprises, between Steps 3 and 4, separating unreacted HFO-1345zf from the process mixture (III), providing a recycle stream (3a) comprising unreacted HFO-1345zf and feeding the recycle stream (3a) to Step 3; andfollowing Step 4, separating E-HFO-153-10mczz from the process mixture (IV), whereinthe process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

[0021] The present disclosure provides a process for the preparation of fluids usefulin thermal management systems, in particular wherein the fluids are hydrofluoroolefins. More particularly, the present disclosure provides a process to produce thehydrofluoroolefin E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz; E-C2F5CH=CHC2F5) and intermediates useful in its production.

[0022] Any of the embodiments of the invention discussed herein can be used aloneor in combination with each other. It will be understood by those skilled in the art that different embodiments discussed herein can be combined and form part of the invention. It will also be understood by those skilled in the art that certain aspects of different embodiments discussed herein can be combined and form part of the invention.

[0023] The present invention involves 4 steps as illustrated in Figure 1.

[0024] Step 1 comprises contacting CFC-113a with ethylene in the presence of acatalyst system comprising a metal and an organic ligand to obtain a process mixture (I) comprising HCFC-353maf, wherein the process is performed at a temperature of about 80 to about 150°C, a pressure of about 50 to 150 psig. Preferably, the temperature is in the range of about 85 to about 125°C, or in the range of about 95 to about 115°C.

[0025] The process mixture (I) is fed through a series of continuous distillationcolumns or batch distillation columns to isolate the unreacted CFC-113a for recycle back to the reactor and provide a final product Step 1, which is used as starting material in Step 2.

[0026] Step 1 operates with an excess of CFC-113a, providing unreacted CFC-113a,which may be recycled to the process after separation from the process mixture (I).

[0027] Step 2 comprises contacting HCFC-353maf produced in accordance with Step1 (final product Step 1) with HF in the presence of a hydrofluorination catalyst to obtain a process mixture (II) comprising HFO-1345zf, wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig. Preferably, thetemperature is in the range of about 300 to about 380°C. Preferably the pressure is in the range from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig.

[0028] The process mixture (II) is fed through a series of purification steps includingdistillation, liquid-liquid phase separation, absorption water to remove residual acid, neutralizing with base and drying in to provide a final product Step 2, which is used as starting material in Step 3.

[0029] Step 2 operates with an excess of HF, such that the process mixture (II)comprises unreacted HF. In one embodiment, the process disclosed herein further comprises separating unreacted HF from the process mixture (II) to provide a recycle stream (2), which is recycled to the process of Step 2.

[0030] The process mixture (II) may further comprise one or more Step 2intermediates formed in the conversion of HCFC-353maf to HFO-1345zf of Step 2. The Step 2 intermediates may include one or more isomers of HCFO-1343 and HCFO-1344. The Step 2 intermediates may be separated from the process mixture (II) and subsequently recycled to the process of Step 2.

[0031] Step 3 comprises reacting contacting CFC-113a with HFO-1345zf, in thepresence of a catalyst system comprising a metal and an organic ligand to obtain a process mixture (III) comprising HCFC-548mafd, wherein the process is performed at a temperature of about 85 to about 165°C, preferably about 125 to about 155°C, more preferably in the range of 135-150°C, and a pressure of about 50 psig to 170 psig or 100 psig to 165 psig or preferably 125 psig to 155 psig or more preferably 135 psig to 150 psig.

[0032] The process mixture (III) is fed through a series of continuous distillationcolumns or batch distillation columns to provide a final product Step 3, which is used as starting material in Step 4. Step 4 is performed with an excess of CFC-113a, such that the process mixture (III) comprises unreacted CFC-113a.

[0033] Step 3 operates with an excess of CFC-113a, providing unreacted CFC-113a,which may be recycled to the process after separation from the process mixture (III). Inaddition, process mixture (III) may further comprise unreacted HFO-1345zf, which may also be recycled and introduced to the process of Step 3.

[0034] Step 4 comprises contacting HCFC-548mafd with HF in the presence of afluorination catalyst in a reactor to obtain a process mixture (IV) comprising E-HFO-153-10mczz, wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 300 to about 380°C. Preferably the pressure is in the range of from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig.

[0035] The process mixture (IV) is fed through a series of purification steps includingdistillation, liquid-liquid phase separation, absorption water to remove residual acid, neutralizing with base and drying in to provide a final product Step 4, which can be used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among other uses.

[0036] Step 4 operates with an excess of HF, providing unreacted HF andintermediates such as HCFO-1539, which may be recycled to the process after separation from the process mixture (IV). BRIEF DESCRIPTION OF THE FIGURES

[0037] Figure 1 illustrates reaction processes as set forth herein for the integratedprocess of this invention.

[0038] Figure 2 illustrates a flow diagram for a process useful to prepare HCFC-353maf according to an embodiment of Step 1 of this invention.

[0039] Figure 3 illustrates a flow diagram for a process useful to prepare HFO-1345zfaccording to an embodiment of Step 2 of this invention.

[0040] Figure 4 illustrates a flow diagram for a process useful to prepare HCFC-548mafd according to an embodiment of Step 3 of this invention.

[0041] Figure 5 illustrates a flow diagram for a process useful to prepare E-HFO-153-10mczz according to an embodiment of Step 4 of this invention.DETAILED DESCRIPTION

[0042] The present invention relates to an integrated process to prepare E-HFO-153-10mczz in a series of interrelated steps beginning with ethylene and CFC-113a as starting materials. General Terms

[0043] Compounds may be referred to herein by the compound name (e.g., 2,2,4-trichloro-1,1,1-trifluorobutane, or 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane, or E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene) or ASHRAE designation (e.g., HCFC-353maf,or HFO-1345zf, HCFC-548mafd, or E-HFO-153-10mczz) or chemical formula (e.g.,CF3CCl2CH2CH2Cl, or CF3CF2CH=CH2, CF3CF2CHClCH2CCl2CF3, or E-C2F5CH=CHC2F5) and optionally prefaced by “CFC”, “HCFC”, “HFC”, “CFO”, “HCFO”, or “HFO”, meaning “chlorofluorocarbon”, “hydrochlorofluorocarbon”, “hydrofluorocarbon”, “chlorofluoroolefin”, “hydrochlorofluoroolefins”, or “hydrofluoroolefin”. The absence of the preface does not change the meaning of the compound.

[0044] The term “isomers” is used to represent one or more compounds having therecited chemical formula that are identified using standard analytical techniques (GC and GC-mass spectrometry). The isomers may include one or more compounds having the recited chemical formula, such as linear, branched and cyclic compounds). Alternatively, isomers may include unsaturated compounds (having a double bond) or cyclic compounds having the same chemical formula or multiple unsaturations (two or more double bonds) or combinations with cyclic structures.

[0045] In addition, with respect to compounds having unsaturation (double bond), thecompound may have “E-” and “Z-” isomers. If neither “E-” nor “Z-” are identified, the compound disclosed may contain one or both isomers. Specific isomers are identified as “E-” or “Z-”. For example, CFO-1316mxx may include one or both of E-CFO- 1316mxx and Z-CFO-1316mxx, whereas specific isomers are identified as “E-CFO- 1316mxx” and “Z-CFO-1316mxx”.

[0046] In reference to Step 1 and Step 3, a “catalyst system” comprises a metal andan organic ligand. The catalyst system promotes the addition of alkyl halides to olefins. By “promotes the addition of alkyl halides to olefins” is meant herein the catalyst system catalyzes or initiates the reaction of an alkyl halide with an olefin.

[0047] 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 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. 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 are true (or present).

[0048] 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.

[0049] 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”.

[0050] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwisestated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0051] 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.

[0052] 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. 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.

[0053] The term “compound” as used herein is meant to include all stereoisomers,geometric isomers, tautomers, and isotopes of the structures or chemical described. Compounds herein identified by name or structure as one particular tautomeric form are intended to include other tautomeric forms unless otherwise specified.

[0054] When an amount, concentration, or other value or parameter is given as eithera 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.

[0055] As used herein the term “about” in certain embodiments can be quantified tomean ± 1%, ± 2%, ± 3% up to and including ±10% of the stated value, and all whole numbers and fractions therebetween.Process Description Step 1

[0056] In the present invention, Step 1 provides a process for preparing HCFC-353maf comprising contacting CFC-113a with ethylene in the presence of a catalyst system comprising a metal and an organic ligand to obtain a process mixture comprising HCFC-353maf, wherein the process is performed at a temperature of about 80°C to about 150°C, a pressure of about 50 psig to 150 psig.80 to about 150°C, a pressure of about 50 to 150 psig. Preferably, the temperature is in the range of about 85 to about 125°C, or in the range of about 95 to about 115°C.

[0057] In one embodiment, Step 1 of the process of this invention is performed at aconversion of CFC-113a of less than 100%, such as from 30-80% conversion of the CFC-113a.

[0058] In one embodiment of Step 1, the process is performed at a conversion of lessthan 80% of the CFC-113a. In one embodiment, the process is performed at a conversion of 30-80% of the CFC-113a. In one embodiment, the process of Step 1 is performed at a conversion of 40-70% of the CFC-113a. In one embodiment, the process of Step 1 is performed at a conversion of 50-70% of the CFC-113a.

[0059] In one embodiment, the process of this invention is performed in the presenceof an excess of CFC-113a.

[0060] When the process of this invention is performed at a conversion of CFC-113aof less than 100% such as from 30-80% or when an excess of CFC-113a is used, the process mixture (I) produced comprises HCFC-353maf and CFC-113a. In these embodiments, the CFC-113a present in the process mixture may be and is preferably separated from the process mixture (I) and recycled to the process. Step 2

[0061] In the present invention, Step 2 provides a process for preparing HFO-1345zfcomprising contacting HCFC-353maf with HF in the presence of a fluorination catalystin a reactor to obtain a process mixture comprising HFO-1345zf, wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 300 to about 380°C. Preferably the pressure is in the range of HCFC-353maf with HF are from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig, such as about 80 psig.

[0062] Step 2 of the process of the present invention is preferably performed in thepresence of an oxygen-containing gas, which may be co-fed with the starting material HCFC-353maf and / or HF. The oxygen-containing gas may be, for example, air.

[0063] In Step 2 of the present invention, it has been found particularly advantageousto perform the process of contacting HCFC-353maf with HF in the presence of a fluorination catalyst in a reactor at a temperature of about 250-450°C. At lower temperatures, 300°C the oxygen is less effective at removing carbon deposits from the catalyst resulting in faster deactivation. Higher temperatures increase the rate of fluorination of the catalyst also deactivating the catalyst. Step 3

[0064] In the present invention, Step 3 provides a process for preparing HCFC-548mafd comprising contacting CFC-113a with HFO-1345zf in the presence of a catalyst system comprising a metal and an organic ligand to obtain a process mixture comprising HCFC-548mafd, wherein the process is performed at a temperature of about 85 to about 165°C, preferably about 125 to about 155°C a pressure of about 50 psig to 170 psig or 100 psig to 165 psig or 125 psig to 155 psig or 135 psig to 150 psig.

[0065] In one embodiment of Step 3 of the process of this invention, Step 3 isperformed at a conversion of less than 80% of CFC-113a. In one embodiment, the process of Step 3 is performed at a conversion of 30-80% of CFC-113a. In one embodiment, the process of Step 3 is performed at a conversion of 40-70% of CFC- 113a. In one embodiment, the process of Step 3 is performed at a conversion of 50- 70% of the CFC-113a.

[0066] In one embodiment, the process of Step 3 of this invention is performed in thepresence of an excess of CFC-113a.

[0067] When the process of Step 3 of this invention is performed at a conversion ofCFC-113a of less than 100% such as from 30-80% or when an excess of CFC-113a is used, the product produced comprises HCFC-548mafd and CFC-113a. In these embodiments, the CFC-113a present in the process mixture is separated and recycled to the process in Step 3. Step 4

[0068] In one embodiment, the present invention provides a process for preparing E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (E-HFO-153-10mczz, E- C2F5CH=CHC2F5)comprising contacting HCFC-548mafd with HF in the presence of a fluorination catalyst in a reactor.

[0069] In the present invention, Step 4 provides a process for preparing E-HFO-153-10mczz comprising contacting HCFC-548mafd with HF in the presence of a fluorinationcatalyst in a reactor to obtain a process mixture (IV) comprising E-HFO-153-10mczz,wherein the process is performed at a temperature of about 250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 300 to about 380°C. Preferably the pressure is in the range of HCFC-548mafd with HF are from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig, such as about 80 psig.

[0070] Step 4 of the process of the present invention is preferably performed in thepresence of an oxygen-containing gas, which may be co-fed with the starting material HCFC-548mafd and / or HF. The oxygen-containing gas may be, for example, air. Catalyst System – Step 1 and Step 3

[0071] Steps 1 and 3 of the process of this invention both involve the reaction of CFC-113a (CF3CCl3) with an olefin to produce a hydrofluorochloroalkane. Many metals have been found to promote the addition of haloalkanes to olefins with good selectivity. Of particular interest are catalyst systems wherein the metal is selected from the groupconsisting of iron, copper, ruthenium and nickel and of particular practical interest here are catalyst systems comprising iron or copper. The conditions for Steps 1 and 3, including the presence of a catalyst system comprising a metal and an organic ligand, temperature and pressure are similar for Steps 1 and 3 and the description below applies generally to both Steps 1 and 3, unless otherwise noted.

[0072] Steps 1 and 3 may use the same or different catalyst systems, including thesame or different metal and / or organic ligand. The metal for Step 1 and Step 3 may comprise iron, copper, ruthenium or nickel.

[0073] In one embodiment of the process of this invention, the metal for Step 1comprises iron. In one embodiment, the metal for Step 1 comprises copper. In one embodiment of the process of this invention, the metal for Step 3 comprises iron. In one embodiment, the metal for Step 3 comprises copper.

[0074] In one embodiment of the process of Step 1 or Step 3 of this invention, themetal is or comprises iron powder, iron wire, iron screen or iron turnings. In one embodiment, the metal comprises iron powder. In one embodiment, the metal comprises iron wire. In one embodiment, the metal comprises iron screen. In one embodiment, the metal comprises iron turnings.

[0075] In one embodiment of Step 1 or Step 3 of the process of this invention, themetal is or comprises an iron salt such as ferric chloride or ferrous chloride. In one embodiment, the metal comprises ferric chloride. In one embodiment, the metal comprises ferrous chloride. In one embodiment of Step 1, the metal comprises ferrous chloride. In one embodiment of Step 1, the metal comprises ferric chloride. In one embodiment of Step 1, the metal comprises ferric chloride and ferrous chloride. In one embodiment of Step 3, the metal comprises ferrous chloride. In one embodiment of Step 3, the metal comprises ferric chloride. In one embodiment of Step 3, the metal comprises ferric chloride and ferrous chloride.

[0076] In one embodiment of Step 1 or Step 3 of the process of this invention, themetal is or comprises copper. The copper may be in the form of a copper salt such as copper(I) chloride or copper(II) chloride. Other copper salts may also be used includingcopper(I) bromide, copper(II) bromide, copper(I) iodide, copper(II) acetate and copper(II) sulfate. In one embodiment, the metal comprises copper(I) chloride . In one embodiment, the metal comprises copper(II) chloride. In one embodiment of Step 1, the metal comprises copper(I) chloride. In one embodiment of Step 1, the metal comprises copper(II) chloride. In one embodiment of Step 1, the metal comprises copper(I) chloride and copper(II) chloride. In one embodiment of Step 3, the metal comprises copper(I) chloride. In one embodiment of Step 3, the metal comprises copper(II) chloride. In one embodiment of Step 3, the metal comprises copper(I) chloride and copper(II) chloride.

[0077] In one embodiment of Step 1 or Step 3 of the process of this invention, theorganic ligand is an organophosphorus compound. In one embodiment of Step 1 or Step 3 of the process of this invention, the organic ligand is an organonitrogen compound.

[0078] In one embodiment, when the organic ligand is an organophosphoruscompound, the metal is iron. In one embodiment, when the organic ligand is an organonitrogen compound, the metal is copper.

[0079] When the organic ligand is an organophosphorus compound, the organicligand may be selected from the group consisting of phosphine, phosphinite, phosphonate, phosphite, phosphine oxide or phosphate, and mixtures of two or more thereof. When the organic ligand is an organonitrogen compound, the organic ligand may be selected from the group consisting of an amine, a nitrile, an amide, a thiamide, and mixtures of two or more thereof.

[0080] Steps 1 and 3 may use the same or different organic ligand.

[0081] In one embodiment of Step 1 or Step 3 of the process of this invention, themetal is iron and the organic component comprises an organophosphorus compound. The organophosphorus compound may be a phosphine, phosphinite, phosphonate, phosphite, a phosphine oxide or a phosphate, each comprising one or more alkyl or aryl groups. In one embodiment, the organophosphorus compound includes compounds having a structural formula as follows: PR1R2R3 where each R1, R2, and R3 isindependently aryl, alkyl, aryloxy or alkoxy. In another embodiment, the organophosphorus compound includes compounds having a structural formula as follows: O=PR1R2R3 where each R1, R2,and R3 is independently selected to be aryloxy or alkoxy.

[0082] In one embodiment of Step 1 or Step 3 of the process of this invention, themetal of the catalyst system comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate or trialkyl phosphine or triaryl phosphine.

[0083] In one embodiment of Step 1 or Step 3 of the process of this invention, theprocess is performed in the presence a catalyst system comprising iron and a trialkyl phosphate. In one embodiment of Step 1 or Step 3, the metal of the catalyst system comprises iron and the organic ligand is trialkyl phosphate wherein the trialkyl phosphate is a tris(C1-6 alkyl)phosphate. In one embodiment, the metal of the catalyst system is iron and the organic ligand is tributyl phosphate.

[0084] In one embodiment of Step 1 or Step 3 of the process of this invention, themetal of the catalyst system is iron and the organic ligand of the catalyst system comprises a phosphine. In one embodiment of Step 1 or Step 3, the phosphine comprises an alkylphosphine or arylphosphine. In one embodiment of Step 1 or Step 3, the phosphine is chosen from triphenyl phosphine and tributyl phosphine. In one embodiment of Step 1 or Step 3, the organic ligand is tributyl phosphine. In one embodiment of Step 1 or Step 3, the organic ligand is triphenyl phosphine.

[0085] In one embodiment of Step 1 or Step 3 of the process of this invention, theprocess is performed in the presence of a catalyst system wherein the metal of the catalyst system comprises copper and the organic ligand of the catalyst system is a nitrogen-containing organic ligand.

[0086] When the metal of the catalyst system is copper, the organic ligand of thecatalyst system may comprise an organonitrogen compound. For example, the organonitrogen compound may be selected from the group consisting of an amine, a nitrile, or an amide, or combinations of two or more thereof. The amine may be selected from the group consisting of monoalkyl amine, dialkylamine, trialkyl amine andcyclic amine. The amine may be selected from the group consisting of tert-butylamine,n-butylamine, sec-butylamine, 2-propylamine, benzylamine, tri-n-butylamine,ethanolamine, piperidine and pyridine. In one embodiment the amine is tert-butylamine.The nitrile may be selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, benzonitrile, and phenylacetonitrile. In one embodiment, the nitrile is acetonitrile. The amide may be selected from the group consisting of hexamethylphosphoramide and dimethylformamide. In one embodiment, the amide is hexamethylphosphoramide.

[0087] When the metal is copper, the organic ligand may comprise a nitrogen-containing heterocyclic compound. Suitable heterocyclic compounds include those selected from the group consisting of imidazoles, imidazolines, oxadiazoles, oxazoles, oxazolines, isoxazoles, thiazoles, thiazolines, pyrrolines, pyridines, trihydropyrimidines, pyrazoles, triazoles, triazolium salts, isothiazoles, tetrazoles, tetrazolium salts, thiadiazoles, pyridazines, pyrazines, oxazines and dihydrooxazine. In certain embodiments, the heterocyclic compound is selected from the group having Formula (I) or Formula (II) as follows: where E is selected from O, S, Se, CH2 and N(R8a); R5ais selected from the group consisting of CH3 and C2H5 (and is preferably CH3); R6aand R7aare selected from the group consisting of H, CH3, C6H5 (i.e., phenyl), CH2C6H5, CH(CH3)2, and fused phenyl; L is selected from the group consisting of O, S, Se, N(R8a), C6H4-, 2,6-pyridyl-, -OC6H4-C6H4O-, -CH2CH2OCH2CH2- and -(CH2)P-, where p is an integer from 0 to 6; and each R8ais selected from the group consisting of H andCmH2m+1 where m is an integer from 1 to 6. The bond between each pair of carbon atoms respectively attached to R6aand R7a(as represented by the dashed bond lines in Formula (I) and Formula (II) can be either a single or a double bond.

[0088] In one embodiment of the process of this invention, the metal of the catalystsystem is copper and the organic ligand of the catalyst system comprises an organonitrogen compound. In one embodiment of the process of this invention, when the metal is or comprises copper and the organic ligand is an organonitrogen compound and the organonitrogen compound is an amine.

[0089] In the present invention, the concentration of the metal of the catalyst systemas discussed herein refers to the concentration of the metal, based on ICP analysis of the process mixture (I) or process mixture (III), for Step 1 or Step 3, respectively.

[0090] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, ranges from 300 ppmw to 3000 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 300 ppmw to 3000 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 300 ppmw to 3000 ppmw.

[0091] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw.

[0092] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, rangesfrom 750 ppmw to 2000 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 750 ppmw to 2000 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 750 ppmw to 2000 ppmw.

[0093] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, ranges from 800 ppmw to 1800 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 800 ppmw to 1800 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 800 ppmw to 1800 ppmw.

[0094] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, ranges from 1000 ppmw to 1500 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 1000 ppmw to 1500 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 1000 ppmw to 1500 ppmw.

[0095] In one embodiment of Step 1 or Step 3 of this invention, the concentration ofthe metal from the catalyst system in the process mixture (I) or (III), respectively, ranges from 1200 ppmw to 1400 ppmw of metal and the metal is iron or copper. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is iron and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 1200 ppmw to 1400 ppmw. In one embodiment, the metal of the catalyst system in Step 1 or Step 3 is copper and the concentration of the metal in the process mixture (I) or (III), respectively, ranges from 1200 ppmw to 1400 ppmw.

[0096] In one embodiment of the process of Step 1 or Step 3 of this invention, theconcentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a trialkyl phosphate. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a tri(C1-6 alkyl)phosphate. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises tributyl phosphate.

[0097] In one embodiment of the process of Step 1 or Step 3 of this invention, theconcentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises a phosphine. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises an alkylphosphine or arylphosphine. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises triphenyl phosphine or tributyl phosphine. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises triphenyl phosphine. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750-2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises iron and the organic ligand of the catalyst system comprises tributyl phosphine.

[0098] In one embodiment of the process of Step 1 or Step 3 of this invention, theconcentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750 to 2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises copper and the organic ligand of the catalyst system is an alkyl amine. In one embodiment of the process of Step 1 or Step 3 of this invention, the concentration of the metal of the catalyst system in the process mixture (I) or (III), respectively, ranges from 500 ppmw to 2500 ppmw or 750 to 2000 ppmw or 800 ppmw to 1800 ppmw or 1000 ppmw to 1500 ppmw and the metal comprises copper and the organic ligand of the catalyst system is tributyl amine.

[0099] In one embodiment of the process of Step 1 or Step 3 of this invention, theprocess is performed with a molar excess of CFC-113a. A molar excess of molar excess of CFC-113a used is based on 1 molar equivalent of ethylene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, or greater than 10 molar equivalents of CFC-113a is used based on 1 molar equivalent of ethylene.

[0100] In one embodiment of Step 1 or Step 3 of the process of this invention, there isprovided a reaction system comprising a reactor and a distillation system downstreamof the reactor. The reaction systems for Step 1 and Step 3 include feed lines to introduce reactants to the reactors. The feed lines include a feed line for a reactant ethylene feed or a reactant feed comprising HFO-1345zf for each of Step 1 and Step 3, respectively, and for each of Steps 1 and 3, a fresh reactant CFC-113a feed, an organic ligand feed and a recycled CFC-113a feed. There is also a feed of metal to introduce metal to the reactor, such as from a bed. Any of the feeds may be combined and introduced to the reactor as a single feed. In certain embodiments, the fresh reactant CFC-113a feed and recycled CFC-113a fee, for Step 1 and Step 3, are combined in a single feed for CFC-113a to be introduced to the respective reactor for each of Steps 1 and 3. In addition, in certain embodiments for Step 1 or Step 3, the organic ligand is combined with the fresh reactant CFC-113a feed or the recycled CFC-113a feed prior to introducing the reactor for the particular Step.

[0101] The following applies to both Step 1 and Step 3.

[0102] The reaction system further comprises an exit stream from the reactor, whichprovides the process mixture. In certain embodiments, the reaction system comprises a distillation system to separate the desired product from the reactor process mixture. The distillation system may comprise multiple distillation columns, evaporator / condenser to facilitate separating reactants, components of the catalyst system, and by- products from the reactor process mixture.

[0103] The reactor process mixture may proceed through a mechanism to separate aportion of the reaction process mixture, which is preferably cooled and then recycled to the reactor.

[0104] In one embodiment, the distillation system comprises a distillation column toseparate a stream comprising reactants from the process mixture. In Step 1, the separated reactants comprise CFC-113a and optionally, ethylene. In Step 3, the separated reactants comprise CFC-113a.

[0105] In one embodiment, after separating CFC-113a from the process mixture (I) or(III) (for Step 1 or Step 3, respectively), the distillation system comprises one or moreadditional distillation columns to separate the desired product (HCFC-353maf in Step 1 and HCFC-548mafd in Step 3) from the remaining process mixture.

[0106] For example, in one embodiment for Step 1, the distillation system comprisesa distillation column to remove compounds having boiling points below ethylene from the process mixture. In another embodiment for Step 1, the distillation system comprises a distillation column to remove compounds having boiling points above the boiling point of HCFC-353maf.

[0107] For example, in one embodiment for Step 3, downstream of the distillationcolumn to separate CFC-113a from the process mixture, the distillation system comprises a distillation column to remove compounds having boiling points below HCFC-548mafd from the process mixture. In another embodiment for Step 3, the reaction system comprises a distillation column to remove compounds having boiling points above the boiling point of HCFC-548mafd.

[0108] The distillation system for Steps 1 and 3 may further comprise one or morepurge lines to remove material from the process mixtures. For example, a purge line may be used to remove high boiling components from the process mixture. “High boiling components” comprises compounds having boiling points above the desired products produced in Steps 1 and 3.

[0109] Following the distillation system, the reaction system of Step 1 provides apurified product comprising HCFC-353maf. The reaction system of Step 1 may comprise a storage tank to store the purified HCFC-353maf. The purified HCFC- 353maf product (final product Step 1) is used in Step 2 as starting material to produce HFO-1345zf.

[0110] Following the distillation system, the reaction system of Step 3 provides apurified product comprising HCFC-548mafd. The reaction system of Step 3 may comprise a storage tank to store the purified HCFC-548mafd. The purified HCFC- 548mafd product (final product Step 3) is used in Step 4 as starting material to produce 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153-10mczz).Conditions - Step 2 and Step 4

[0111] Steps 2 and 4 of the process of this invention are both fluorination reactions inwhich a hydrochlorofluoroalkane is dehydrochlorinated and fluorinated to produce a hydrofluoroolefin. The components and conditions for Steps 2 and 4, such as the fluorination catalyst, temperature and pressure are similar and the description below applies generally to both Steps 2 and 4, unless otherwise noted.

[0112] The process of Steps 2 and 4 are generally performed at a temperature ofabout 250-450°C, a pressure of about 0 to 200 psig. Preferably, the temperature is in the range of about 300 to about 380°C. Preferably the pressure is in the range of from about 30 to 180 psig or about 40 to 150 psig, or about 60-120 psig, such as about 80 psig. The ratio of HF to organic mol ratio is in the range of 3:1 to 50:1.

[0113] In the process of this invention, Steps 2 and 4 are preferably performed in thepresence of an oxygen-containing gas, which may be co-fed with the starting material HCFC-353maf or HCFC-548mafd, respectively and / or HF. The oxygen-containing gas may be, for example, air or oxygen or oxygen-enriched air.

[0114] In the present invention, it has been found particularly advantageous toperform the processes of Steps 2 and 4 with an excess of HF in the presence of a fluorination catalyst in a reactor at a temperature of about 250-450°C. For these processes, it has been found that at lower temperatures, the oxygen is less effective at removing carbon deposits from the fluorination catalyst resulting in faster deactivation. Higher temperatures increase the rate of fluorination of the fluorination catalyst also deactivating the fluorination catalyst. Thus a balance must be found to address fluorination catalyst deactivation from both carbon deposits as well as fluorination of the fluorination catalyst. The O2 concentration is preferred in the range 0.2 mol% to 10 mol%, More preferred in the range of 0.2 mol% to 5 mol%. Fluorination Catalyst – Step 2 and Step 4

[0115] The fluorination catalyst used in Steps 2 and 4 of the process of this inventioncomprises one or more metals, metal oxides, metal oxyfluorides or metal fluorides. Ametal oxide catalyst preferably forms a metal (oxy)fluoride having Lewis acid character. Examples of metals suitable for use in the fluorination catalyst is chosen from one or more of metals selected from Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

[0116] In certain embodiments, the fluorination catalyst comprises one or more of Al,Zr, Cr, Co, Ni and Zn.

[0117] In one embodiment, the fluorination catalyst comprises chromium oraluminum. In one embodiment the fluorination catalyst comprises chromium or aluminum and one or more of Zn, Zr, Co, and Ni.

[0118] Certain metal oxide or metal fluoride fluorination catalysts may contain one ormore additional metals selected from the group consisting of Li, Na, K, Ca, Mg, and Cs. The additional metal may be present in smaller amounts (such as in an amount of less than 2000 or less than 1000 or less than 500 or less than 100 or less than 10 ppm).

[0119] In certain embodiments, the fluorination catalyst comprises aluminum. Thealuminum may be present in the form of aluminum oxide, aluminum fluoride or aluminum oxyfluoride. In certain embodiments the fluorination catalyst comprises Al and further comprises one or more of Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce. In certain embodiments the fluorination catalyst comprises Al and one or more of Zn, Zr, Cr, Co, and Ni.

[0120] In certain embodiments, the fluorination catalyst comprises chromium. Thechromium may be present in the form of chromium oxide, chromium chloride, chromium fluoride or chromium oxyfluoride. Chromium may be in the form of Cr(III), such as Cr2O3. In certain embodiments the fluorination catalyst comprises Cr and further comprises one or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce. In certain embodiments the fluorination catalyst comprises Cr and one or more of Zn, Zr, Co, and Ni.

[0121] In one embodiment, the fluorination catalyst comprises Cr2O3. In oneembodiment, the fluorination catalyst comprises Cr2O3 and one or more of Zn, Zr, Co, K, Na and Ni. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zn. Inone embodiment, the fluorination catalyst comprises Cr2O3 and Co. In one embodiment, the fluorination catalyst comprises Cr2O3 and Ni. In one embodiment, the fluorination catalyst comprises Cr2O3 and Zr.

[0122] In one embodiment, the fluorination catalyst comprises Cr2O3 and at least oneof Zn, Zr, Co, and Ni, wherein the amount of Zn, Zr, Co, and / or Ni ranges from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Zn wherein the amount of Zn is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Zr wherein the amount of Zr is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Co wherein the amount of Co is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3. In one embodiment the fluorination catalyst comprises Cr2O3 and Ni, wherein the amount of Ni is in the range of from about 100 ppm to about 10% by weight, based on weight of Cr2O3.

[0123] In one embodiment, the fluorination catalyst comprises Al2O3. In oneembodiment, the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn. In one embodiment, the fluorination catalyst comprises Al2O3 and Zr. In one embodiment, the fluorination catalyst comprises Al2O3 and Cr. In one embodiment, the fluorination catalyst comprises Al2O3 and Co. In one embodiment, the fluorination catalyst comprises Al2O3 and Ni.

[0124] In one embodiment, the fluorination catalyst comprises Al2O3 and at least oneof Zn, Zr, Cr, Co, and Ni, wherein the amount of Zn, Zr, Cr, Co, and / or Ni ranges from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Zn wherein the amount of Zn is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Zr wherein the amount of Zr is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Cr wherein the amountof Cr is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Co wherein the amount of Co is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3. In one embodiment the fluorination catalyst comprises Al2O3 and Ni, wherein the amount of Ni is in the range of from about 100 ppm to about 10% by weight, based on weight of Al2O3.

[0125] The fluorination catalyst may be on a support (“supported”) or unsupported ora mixture of a support with the fluorination catalyst. If a support is present, suitablesupports include AlF3, alumina, fluorinated alumina or activated carbon. In oneembodiment, the fluorination catalyst comprises chromium oxide and alumina.

[0126] The fluorination catalyst may comprise a metal oxide or metal oxyhalidessupported on chromia or alumina, for example oxides of zinc, iron, magnesium or nickel.The fluorination catalyst may comprise a metal oxides / halides / oxyhalides, or mixedmetal oxides / halides / oxyhalides supported on carbon, wherein the metal is chosen fromone or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni,Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

[0127] In one embodiment, the fluorination catalyst is a chromium-based catalyst,such as chromium oxide (Cr2O3) or fluorinated chromium oxide, or chromium chloride, or chromium fluoride, which catalyst may either be unsupported, or supported on a support such as activated carbon, graphite, fluoride graphite, or alumina fluoride. The chromium fluorination catalyst may either be used alone, or in the presence of a co- catalyst selected from nickel, cobalt, manganese, potassium, sodium or zinc. In one embodiment, optionally a chromium fluorination catalyst is high surface area chromium oxide, or chromium / nickel on alumina fluoride (Cr / Ni / AlF3), or chromium halide on carbon, the preparation of which is reported in European Patent EP486333. In another embodiment, the fluorination catalyst is fluorinated Guignet’s green catalyst.

[0128] In one embodiment, the fluorination catalyst comprises Al2O3. In oneembodiment, the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni. In one embodiment, the fluorination catalyst comprises Al2O3 and Zn, or Al2O3 and Cr, or Al2O3 and Co, or Al2O3 and Ni, or Al 2O3 and Zr.

[0129] In one embodiment, the fluorination catalyst comprises chromium supportedon AlF3, alumina, fluorinated alumina or activated carbon. In one embodiment, the fluorination catalyst comprises chromium supported on alumina.

[0130] In one embodiment, the fluorination catalyst comprises zinc supported on AlF3,alumina, fluorinated alumina or activated carbon. In one embodiment, the fluorination catalyst comprises zinc supported on alumina.

[0131] The physical shape of the fluorination catalyst is not critical and may, forexample, include pellets, extrudates, powders, or granules.

[0132] In one embodiment, the fluorination catalyst is shaped into a form, such asgranulated, or pressed into pellets. A variety of methods generally known in the art, may be used that are suitable to provide, for example, a packed bed of catalyst in a flow reactor.

[0133] In one embodiment for Step 2 and / or Step 4, the process of this inventioncomprises activating the fluorination catalyst in a prefluorination treatment prior to contacting HF with HCFC-353maf and / or HCFC-548mafd, respectively, in the presenceof the fluorination catalyst. Activation of the fluorination catalyst is preferably carried outon the final shape of the catalyst, in the event the catalyst is shaped into a form. Itshould be understood that while the term “fluorination catalyst” is used to refer to metal oxides, including Cr2O3 and Al2O3, metal halide, including CrCl3, CrF3 herein, the metal oxide may undergo a prefluorination step to generate the active catalyst in situ.

[0134] In one embodiment for Step 2 or Step 4 of the process of this invention, thefluorination catalyst undergoes a prefluorination treatment by passing HF, with or without an inert diluent such as nitrogen, over the fluorination catalyst at a temperature within the range of about 250 to 450°C prior to use.

[0135] In a particular embodiment for Step 2 or Step 4 of the process of this invention,the fluorination catalyst comprises chromium and the fluorination catalyst is activated before use, by a procedure comprising heating the fluorination catalyst to a temperature of from 350°C to 400°C under a flow of nitrogen for a period of time, then heating thefluorination catalyst under a flow of HF and nitrogen or air for an additional period of time in one embodiment of a prefluorination treatment.

[0136] In one embodiment of the process of Step 2 of this invention, the processcomprises activating the fluorination catalyst in a prefluorination treatment prior to contacting HCFC-353maf with HF in the presence of the fluorination catalyst. Activation of the fluorination catalyst is preferably carried out on the final shape of the fluorination catalyst, in the event the fluorination catalyst is shaped into a form.

[0137] In one embodiment of the process of Step 4 of this invention, the processcomprises activating the fluorination catalyst in a prefluorination treatment prior to contacting HCFC-548mafd with HF in the presence of the catalyst. Activation of the fluorination catalyst is preferably carried out on the final shape of the fluorination catalyst, in the event the fluorination catalyst is shaped into a form.

[0138] After use for a period of time, the activity of the fluorination catalyst used inSteps 2 and 4 may decrease. When this occurs, the fluorination catalyst may be regenerated, wherein a regenerating step comprises treating the fluorination catalyst with oxygen or air at elevated temperature in the absence of organic materials. In Step 2 of the process, organic materials comprise HCFC-353maf and / or HFO-1345zf. InStep 4 of the process, organic materials comprise HCFC-548mafd and / or E-153-10mczz. Reaction conditions

[0139] In one embodiment for the processes involved in Steps 2 and 4 of thisinvention, suitable temperatures are from about 250°C to about 450°C, preferably from about 300°C to about 380°C. Temperature ranges are set to advantageously protect the fluorination catalyst from deactivation. It has been found that operating at temperatures outside of the recited ranges results in faster deactivation of the fluorination catalyst. For example, it is believed at lower temperatures, carbon containing compounds deposit remains on the surface of the fluorination catalyst. In addition, at higher temperatures, the fluorination catalyst is more susceptible to becoming fluorinated in a way that also results in fluorination catalyst deactivation.Thus, a balance must be found to address fluorination catalyst deactivation from both carbon containing compounds deposits as well as fluorination of the fluorination catalyst.

[0140] In one embodiment, suitable pressures for the process of the reaction ofHCFC-353maf with HF in Step 2 and HCFC-548mafd with HF in Step 4 are from about 0 to 200 psig, preferably from about 30 to 180 psig or about 40 to 150 psig, or about 60- 120 psig. Pressure ranges are set to achieve desired conversion and product selectivity as well as to enhance separation and recovery of HCl component of the process mixture. At lower pressures, the recovery of HCl is more complex or more expensive. In addition, at pressures, the catalyst is found the rate of catalyst deactivation increases. Furthermore, pressure also impacts reaction rate, product selectivity and productivity., again, a balance is found to control the processes of Steps 2 and 4 to improve performance of the fluorination catalyst and improve separation to produce the final products.

[0141] In the process of this invention, it is preferred to have a molar ratio of HF toorganic reactant from about 3:1 to about 50:1. In Step 2, the organic reactant is HCFC- 353maf. In Step 4, the organic reactant is HCFC-548mafd. In Step 2, the ratio of HF to 353maf may be from about 3:1 to about 50:1, preferably from about 10:1 to about 45:1, more preferred, 15:1 to 40:1. In Step 4, the ratio of HF to 548mafd may be from about 3:1 to about 50:1, preferably from about 10:1 to about 45:1, more preferred, 15:1 to 40:1.

[0142] In Steps 2 and 4 of the process of this invention, an oxygen-containing gassuch as air, oxygen or oxygen-enriched air is optionally added. Preferably oxygen is added. The oxygen amount added ranges from about 0 to about 10 mole% based on the feed. The feed in Step 2 comprises HCFC-353maf. The feed in Step 4 comprises HCFC-548mafd. Preferably the amount of oxygen added in the process of this invention is greater than 0% and less than 10 mole%, such as from about 0.2 mole % to about 5 mole%, or about 1 mole%. An amount of oxygen added in the process such as in the range of about 0.2 mole % to about 5 mole%, improves life of the fluorination catalyst. In the absence of added oxygen the rate of fluorination catalyst deactivationincreases. It is also important to avoid adding too much oxygen in the process. A higher concentration of oxygen, particularly greater than 15 mole% oxygen results in lower yield as there is an increase in the formation of oxygenated byproducts. In addition, a higher concentration of oxygen presents a flammability risk. A balance is achieved to enhance overall efficiency of the processes herein.

[0143] In Steps 2 and 4 of the process of this invention, the contact time can bechosen from a range of contact times, such as from as low as about 1 second to 180 seconds. In one embodiment, contact time is from 5 seconds to 180 seconds or from 5 to 120 seconds or from 5 to 60 seconds, or from 10 to 25 seconds, such as about 15 seconds. It should be appreciated that shorter contact times reduces conversion to HFO-1345zf or HFO-153-10mczz for Steps 2 and 4, respectively. However longer contact times may be undesirable as they may increase formation of byproducts (lower yield, selectivity) for a given set of reaction conditions. A balance is achieved to enhance overall efficiency of the processes herein.

[0144] Preferably, the fluorination reactions of Steps 2 and 4 are carried out in thevapor phase. However, it will be understood by those skilled in the art that the fluorination of HCFC-353maf and / or HCFC-548mafd may, alternatively, be performed in the liquid phase.

[0145] In one embodiment, the starting material for Step 2 (comprising HCFC-353maf) or the starting material for Step 4 (comprising HCFC-548mafd) may be pre-mixed with the HF, and then introduced into the reactor to form a reaction productcomprising HFO-1345zf or HFO-153-10mczz, respectively. In some embodiments, the fluorination catalyst may optionally also be pre-mixed with HF and the starting material for Step 2 or Step 4. In another embodiment, the HF may be separately added from fluorination catalyst and starting material to the reactor.

[0146] In some embodiments, the processes of Steps 2 and 4 may be conducted in areactor or reaction zone which is operating in batch, semi-batch, semi-continuous, or continuous modes.

[0147] In one embodiment of the process of this invention, the process of Step 2involves reacting HCFC-353maf with an excess of HF (HF to organic of 3:1 to about 50:1, preferably from about 10:1 to about 45:1, more preferred, 15:1 to 40:1). In one embodiment, the fluorination catalyst comprises chrome oxide (Cr2O3 and the catalyst is dried and partially fluorinated with HF before use. The operating temperature is about 300°C to about 380°C and the operating pressure is about 0 to about 200 psig. The process further comprising adding about 0.2 mole % to about 5 mole % or 0.5 to 2 mole % oxygen in the feed (based on the feed of 353maf) to maintain / increase catalyst life. In one embodiment, in a continuous process, the reactor is shut down periodically to regenerate the fluorination catalyst. Shut down may occur once every 12 months, 6 months, 3 months, 30 days or once every 20 days or once every 15 days, such as once every 18 days. The reactor has a heat transfer system to achieve and maintain a target operating temperature.

[0148] Specific conditions of temperature, pressure, HF:organic ratio, oxygenconcentration and contact time are provided for Step 2 and Step 4, wherein the organic with respect to Step 2 is 353maf and the organic with respect to Step 4 is 548mafd. It has been found that the recited conditions provide limit disadvantages of operating outside of the recited conditions. Disadvantages include one or more of catalyst deactivation, increased difficulties to recover product, increased byproducts (loss of yield, loss of selectivity), lower conversion, need for larger reactor.

[0149] After exiting the reactor in this Step 2, the product stream comprising HFO-1345zf and HCl undergoes distillation to remove HCl. The product stream further comprises unreacted HF as the process uses an excess of HF. The unreacted HF in the product stream is then recovered and recycled back to the reactor. The intermediates such as HCFO-1343 isomers and HCFO-1344 isomers can be also recycled back to reactor. HF recovery may comprise a combination of distillation and liquid-liquid phase separation. When the product stream comprises residual acids, residual acids may be removed from the product stream by absorbing by Al2O3, or absorbing into an aqueous which optional contains dilute base (such as alkali metal hydroxide, including, but not limited to KOH). Following removal of acids, the productstream is then dried, for example, using molecular sieves. The dried HFO-1345zf may undergo a final distillation to provide purified product comprising HFO-1345zf, available for use.

[0150] In one embodiment of the process of this invention, the process of Step 4involves reacting HCFC-548mafd with an excess of HF (HF to organic of about 10:1 toabout 30:1) in a vapor phase reactor, producing a product stream comprising E-153-10mczz and HCl. In one embodiment, the fluorination catalyst comprises chrome oxide (Cr2O3). The fluorination catalyst is dried and partially fluorinated with HF before use. The operating temperature is about 300°C to about 380°C and the operating pressure is about 0 to about 200 psig. The process further comprising adding 0.5 to 2% mole % oxygen in the feed (based on the feed of HCFC-548mafd) to maintain / increase catalyst life. In one embodiment, in a continuous process, the reactor is shut down periodically to regenerate fluorination catalyst. Shut down may occur once every 6 months, 3 months, 30 days or once every 20 days or once every 15 days, such as once every 18 days. The reactor has a heat transfer system to achieve and maintain a target operating temperature.

[0151] In Step 4, the feeds may further comprise a recycle stream comprising HCFC-548mafd and intermediates and byproducts. The recycle stream may comprise one or more of HFO-1539mbzz (CF3CFClCH=CHCF2CF3), HCFO-152-10mcxz (CF3CF2CCl=CHCF2CF3), HFO-2536mxzzx (CF3CCl=CHCH=CClCF3), C6H2ClF9 isomers. C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers. Intermediates may comprise one or more of C6H2ClF9 isomers. C6HClF8 isomers, C6H2Cl2F8 isomers, C6HCl2F7 isomers and C6HCl3F6 isomers.

[0152] After exiting the reactor, the product stream from Step 4 comprising E-HFO-153-10mczz and HCl undergoes distillation to remove HCl. The product stream further comprises unreacted HF as the process uses an excess of HF. The unreacted HF in the product stream is then recovered and recycled back to the reactor. The intermediates such as 1539 can be also recycled back to reactor. HF recovery may comprise a combination of distillation and liquid-liquid phase separation. When the product stream comprises residual acids, residual acids may be removed from the product stream byabsorbing by Al2O3 or absorbing into an aqueous phase optionally containing dilute base (such as alkali metal hydroxide, including, but not limited to KOH). Following removal of acids, the product stream is then dried, for example, using molecular sieves.The dried E-HFO-153-10mczz may undergo a final distillation or other purificationmethod such as adsorption to provide purified product comprising E-HFO-153-10mczz,available for use.

[0153] Carbon steel may be acceptable for ambient temperature feed systems andstorage tanks. The reactor and high temperature portions of the equipment, including the HCl column, are preferably constructed of an alloy such as Inconel or Hastelloy.

[0154] The products from the reactions of Steps 2 and 4 of the process of thisinvention may be purified in a series of additional steps.

[0155] In one embodiment of the process of Step 2 of this invention, the processmixture II is cooled, such as through heat exchangers and is then treated in distillation columns to remove HCl (a product of the reaction). Following removal of HCl, HF may be removed in a distillation column or a phase separation. Since HF is a reactant in the process, the removed HF is recycled to as the recycled HF feed. The intermediates such as HCFO-1343 isomers and HCFO-1344 isomers can also be separated and recycled back to step 2 reactor.

[0156] After removing HCl and HF from the process mixture (II), a distilled processstream II is provided which is treated with adsorption of Al2O3 or an aqueous in an absorber, in which remaining HF is absorbed into an aqueous phase which optionally contains a base such as KOH, providing a scrubbed process stream II.

[0157] The scrubbed process stream II is then dried by passing through a dryingagent. The drying agent may be, for example, molecular sieves, providing a dried process stream II.

[0158] The dried process stream II is distilled using one or more distillation columnsto provide a purified product comprising HFO-1345zf. The purified product may comprise greater than 95% or greater than 98% or greater than 99% or greater than 99.5% HFO-1345zf.

[0159] In one embodiment of the process of Step 4 of this invention, the processmixture IV is cooled, such as through heat exchangers and is then treated in distillation columns to remove HCl (a product of the reaction). Following removal of HCl, HF may be removed in a distillation column. Since HF is a reactant in the process, the removed HF is recycled to as the recycled HF feed.

[0160] After removing HCl and HF from the process mixture IV, a distilled processstream II is provided which is treated with a Al2O3 bed or an aqueous in an absorber, in which remaining HF is absorbed into an aqueous phase which optionally contains a base such as using KOH, providing a scrubbed process stream IV.

[0161] The scrubbed process stream IV is then dried by passing through a dryingagent. The drying agent may be, for example, molecular sieves, providing a dried process stream IV.

[0162] The dried process stream IV is distilled using one or more distillation columnsto provide a purified product comprising E-HFO-153-10mczz. The purified product maycomprise greater than 95% or greater than 98% or greater than 99% or greater than99.5% E-HFO-153-10mczz.Description of the Figures

[0163] Figure 1 illustrates an integrated reaction process as disclosed herein forproducing E-HFO-153-10mczz, E-C2F5CH=CHC2F5. Steps 1-4 provide a process toprepare E-HFO-153-10mczz from CFC-113a and ethylene. Step 1 is a liquid phaseprocess which produces HCFC-353maf. Step 2 is a vapor phase fluorination process using the product of Step 1 to produce HFO-1345zf. Step 3 is a second liquid phase process, which produces HCFC-548mafd using the product produced from Step 2. Step 4 is a second vapor phase process, which using the product produced from Step 3to produce E-HFO-153-10mczz. Details of the process steps are disclosed herein.

[0164] Figure 2 provides a flow diagram for a process useful to prepare 2,2,4-trichloro-1,1,1-trifluorobutane according to an embodiment of this invention. In Figure 1,there is provided a reaction system 100 which includes reactor 101 and distillationsystem downstream of reactor 101. In the reaction system 100, reactant ethylene 102and fresh reactant CFC-113a feed 103 are introduced to reactor 101. In addition,organic ligand 104 component of the catalyst system described herein is alsointroduced to reactor 101. A cooled recycled process stream 110 is also introduced toreactor 101. Reactor 101 may be pre-loaded with metal component of the catalystsystem (iron or copper based), which is not illustrated in Figure 1. While certain reactants (ethylene, fresh and recycled CFC-113a and organic ligand) are illustrated asbeing separately introduced to reactor 101, it should be understood that two or more ofthe reactants can be combined, including combining into a single feed stream along withcooled recycled process stream 110 from metal solids bed 105.

[0165] The metal component of the catalyst system described herein may be fed frommetal bed 105 to reactor 101. Metal solids bed 105 contains additional metal (iron orcopper). The additional metal may be any form of solid, metal (0) or metal salt. In one particular embodiment, the metal bed contains iron (0) which not only serves as asource of metal, but also is able to reduce Fe3+ that may be produced in reactor 101 toFe2+.

[0166] A vent condenser (not shown) may be attached to reactor 101 to remove inertmaterials. The vent condenser may be operated periodically.

[0167] Process stream 106 exits reactor 101 proceeds through pump 130. Processstream 106 is split following pump 130 into a first portion 107 and a second portion 108.First portion 107 of process stream 106 proceeds through heat exchanger 109 to coolfirst portion 107 of process stream 106. After cooling first portion 107 of process stream106 proceeds through metal solids bed 105, allowing introducing additional metal to thestream, which exits metal solids bed 105 as recycled process stream 110.

[0168] A second portion 108 of process stream 106 comprising unreacted startingmaterials, product and byproducts proceeds to first distillation column 112a. Lowboilers are removed overhead from column 112a, providing separated stream 111.“Low boilers” may comprise ethylene and components having a boiling point below theboiling point of ethylene. Separated stream 111 proceeds through heat exchanger 113to evaporator 114 then condenser 115. A purge 116 may be removed from evaporator114. Purge 116 may comprise undissolved metal, metal chlorides.

[0169] From condenser 115, a stream of noncondensables is removed at 117 and thecondensed stream 118 proceeds to second distillation column 112b after pump 131.Noncondensables may comprise nitrogen, ethylene, anhydrous HCl, hydrogen, and low boiling fluorinated compounds.

[0170] In distillation column 112b, condensed stream 118 is separated into stream119 comprising CFC-113a and components having a boiling point below HCFC-353mafand a stream 120 comprising HCFC-353maf and components having a boiling pointabove HCFC-353maf.

[0171] Stream 119 proceeds to third distillation column 112c, from which CFC-113a isseparated from components having a boiling point below HCFC-353maf to providerecycle CFC-113a stream 121. A purge may be removed from the bottom of thirddistillation column 112c.

[0172] In distillation column 112d, stream 120 comprising HCFC-353maf andcomponents having a boiling point above HCFC-353maf is separated into stream 122comprising purified HCFC-353maf from the column.

[0173] As illustrated in Figure 1, a purge stream 124 of high boilers is removed fromdistillation column 112d and purified stream comprising HCFC-353maf is removed asproduct stream 122 as final product. The final product comprising HCFC-353maf maybe stored in tank 123 for future use, such as, for example, in the manufacture of3,3,4,4,4-pentafluorobut-1-ene (HFO-1345zf).

[0174] Additional components not shown in Figure 1 may include heat exchangers,pumps, vacuum equipment for distillation columns and evaporator.

[0175] As illustrated in Figure 1, a purge stream 124 of high boilers is removed fromdistillation column 112d and purified stream comprising HCFC-353maf is removed asproduct stream 122 as final product. The final product comprising HCFC-353maf maybe stored in tank 123 for future use, such as, for example, in the manufacture of3,3,4,4,4-pentafluorobut-1-ene (HFO-1345zf).

[0176] Additional components not shown in Figure 1 may include heat exchangers,pumps, vacuum equipment for distillation columns and evaporator.

[0177] Figure 3 provides a flow diagram for a process useful to prepare 3,3,4,4,4-pentafluoro-1-butene according to an embodiment of this invention. In Figure 3, there isprovided a process system 200 which includes reactor system 201 and purificationsystem 202. In reactor system 201, reactant 353maf feed 203, fresh reactant HF feed204 and recycled HF feed stream 205 are mixed into a single feed stream 206 and fedthrough a series of heat exchangers (207a, 207b and 207c) and introduced to reactor209 in feed stream 208. Heat exchanger 207a vaporizes feed stream 206. Heatexchanger 207b is a process-to-process heat exchanger in which stream from heatexchanger 207a is heated using the heat from reactor process stream 210. The heatedfeed stream from heat exchanger 207b proceeds through preheater heat exchanger207c to provide reactor feed stream 208.

[0178] Reactor feed stream 208 enters tubular reactor 209, which contains solidfluorination catalyst (not shown). Feed stream 208 reacts in reactor 209 in the presenceof solid fluorination catalyst in a vapor phase reaction to produce reactor processstream 210.

[0179] Reactor process stream 210 passes through heat exchanger 207b, thuscooling stream 210 and providing process stream 211. Process stream 211 is furthercooled by passing through heat exchanger 212, providing process stream 213, whichenters purification system 202.

[0180] Purification system 202 comprises distillation columns, absorbers, scrubbersand dryers.

[0181] Process feed stream 213 is distilled in HCl distillation column 214 to removeHCl generated in reactor 209. HCl is removed overhead in stream 215. Distilled stream216 then enters HF distillation column 217, in which HF is removed. A recycle streamcomprising HF 218 is removed from column 217. A portion of stream 218 is mixed withreactant HCFC-353maf feed 203 and fresh reactant HF feed 204 as recycled HF feedstream 205. A purge stream comprising HF 219 is removed from stream 218.

[0182] After HCl and HF distillation columns, process stream 220 enters absorber221. Water is fed to absorber 221 as stream 222. A solution of HF in water is removedfrom absorber 221 in stream 223. Treated stream 224 from absorber 221 is circulatedthrough column 225 in a process step for scrubbing stream 224 with base throughscrubber 226, such as, for example, using an aqueous solution of KOH. Spent KOHsolution 227 is removed from scrubber 226 and column 225. The process streamfollowing scrubbing is removed from column 225 in stream 228, which is then dried bypassing through drying agent column 229. The drying agent may be, for example,molecular sieves. Dried process stream 230 exits drying agent column 229 for furtherpurification.

[0183] Dried process stream 230 enters low boiler distillation column 231 in which lowboilers are removed overhead and pass through a condenser in stream 232. From lowboiler distillation column 231, the process stream 233 passes to distillation column 234,from which high boilers are purged in stream 236 and product stream 235 comprising1345zf is provided. Product stream 235 comprising 1345zf may be stored in tank 237for future or immediate use in manufacture of other fluorochemicals, including, forexample, 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd) and E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (HFO-153-10mczz).

[0184] Pumps such as illustrated with feed streams 203, 204 and 205 are used tointroduce and / or circulate materials (reactants, intermediates, products) throughreaction system 200. Heat exchangers such as illustrated at 207a-d are used tomanage temperature through reaction system 200.

[0185] Additional components not shown in Figure 3 may include purge lines, heatexchangers, pumps, and vacuum equipment for distillation columns.

[0186] Figure 4 provides a flow diagram for a process useful to prepare HCFC-548mafd according to an embodiment of this invention. In Figure 4, there is provided areaction system 300 which includes reactor 301 and a distillation system downstream ofreactor 301. In this system, reactant HFO-1345zf feed 302 and fresh reactant CFC-113a feed 303 are introduced to reactor 301. In addition, organic ligand 304 componentof the catalyst system described herein is also introduced to reactor 301. Recycledprocess stream 313 is also introduced to reactor 301. Reactor 301 contains catalystsystem (iron- or copper-based), which is not illustrated in Figure 4. Metal is fed frombed 305 to reactor 301 along with cooled recycled process stream 310. While certainreactants (HFO-1345zf, fresh and recycled CFC-113a and organic ligand) are illustratedas being separately introduced to reactor 301, it should be understood that two or moreof the reactants can be combined, including combining into a single feed stream alongwith cooled recycled process stream 310 from metal solids bed 305.

[0187] The metal component of the catalyst system described herein may be fed frommetal solids bed 305 to reactor 301. Metal solids bed 305 contains additional metal(iron or copper). The additional metal may be any form of solid, metal (0) or metal salt.In one particular embodiment, the metal solids bed 305 contains iron (0) which not onlyserves as a source of metal, but also is able to reduce Fe3+that may be produced inreactor 301 to Fe2+.

[0188] A vent condenser may be attached to reactor 301 to remove inert materials,such as nitrogen.

[0189] Process stream 306 exits reactor 301 proceeds through pump 330. Processstream 306 is split following pump 330 into a first portion 307 and a second portion 308.First portion 307 of process stream 306 proceeds through heat exchanger 309 to coolfirst portion 307 of process stream 306. After cooling, first portion 307 of process stream306 proceeds through metal solids bed 305, allowing introducing additional metal to thestream, which exits metal solids bed 305 as cooled recycled process stream 310, whichincludes unreacted reactant (CFC-113a and HFO-1345zf), as well as a portion of the catalyst system.

[0190] A second portion 308 of process stream 306 comprising reactants (CFC-113aand HFO-1345zf), product (HCFC-548mafd) and byproducts proceeds to first distillationcolumn 312a. An overhead stream 311 is removed. The overhead stream 311 maycomprise, for example, noncondensable gases, such as nitrogen or anhydrous HCl. Aliquid distillate stream is removed from column 312a and recycled to reactor 301 ascooled recycled process stream 313. Cooled recycled process stream 313 comprisesreactants (CFC-113a and HFO-1345zf). A separated stream 314 is taken from thebottom of column 312a. Separated stream 314 proceeds through heat exchanger 315to evaporator 316 then condenser 317. A purge 318 may be removed from evaporator316.

[0191] From condenser 317, an overhead stream 319 is removed. Overhead stream319 comprises inert gases such as N2, residual reactants such as HFO-1345zf, or otherimpurities. A condensed stream 320 proceeds from condenser 317 through pump 331to second distillation column 312b.

[0192] In distillation column 312b, condensed stream 320 is separated into stream321 comprising CFC-113a and components having a boiling point below HCFC-548mafd and stream 322 comprising HCFC-548mafd and components having a boilingpoint above HCFC-548mafd.

[0193] Stream 321 proceeds to third distillation column 312c, in which CFC-113a isseparated from components having a boiling point below HCFC-548mafd to providerecycle CFC-113a stream 323. A purge may be removed from both the top and thebottom of third distillation column 312c. As illustrated, purge stream 324, maycomprise, among others, HFC-123. As illustrated, purge stream 325 may compriseCFC-113.

[0194] In distillation column 312d, stream 322 comprising HCFC-548mafd andcomponents having a boiling point above HCFC-548mafd is separated into stream 326comprising purified HCFC-548mafd from column 312d.

[0195] As illustrated in Figure 1, a purge stream 328 may be removed from distillationcolumn 312d and purified stream comprising HCFC-548mafd is removed as productstream 326 as final product. The final product comprising HCFC-548mafd may bestored in tank 327 for future or immediate use in manufacture of 1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene (HFO-153-10mczz).

[0196] Additional components not shown in Figure 4 may include purge lines, heatexchangers, pumps, and vacuum equipment for distillation columns.

[0197] Figure 5 provides a flow diagram for a process useful to prepare E-HFO-153-10mczz according to an embodiment of this invention. In Figure 5, there is provided aprocess system 400 which includes reactor system 401 and purification system 402. Inreactor system 401, reactant 548mafd feed 403, fresh reactant HF feed 404 andrecycled HF feed stream 405 are mixed into a single feed stream 406 and fed through aseries of heat exchangers (407a, 407b and 407c) and introduced to reactor 409 in feedstream 408. Heat exchanger 407a vaporizes feed stream 406. Heat exchanger 407b isa process-to-process heat exchanger in which stream from heat exchanger 407a isheated using the heat from reactor process stream 410. The heated feed stream fromheat exchanger 407b proceeds through preheater heat exchanger 407c to providereactor feed stream.

[0198] Reactor feed stream 408 enters tubular reactor 409, which contains solidfluorination catalyst (not shown). Feed stream 408 reacts in reactor 409 in the presenceof solid fluorination catalyst in a vapor phase reaction to produce reactor processstream 410.

[0199] Reactor process stream 410 passes through heat exchanger 407b, thuscooling stream 410 and providing process stream 411. Process stream 411 is furthercooled by passing through heat exchanger 412, providing process stream 413, whichenters purification system 402.

[0200] Purification system 402 comprises distillation columns, absorbers, scrubbers,and dryers.

[0201] Process feed stream 413 is distilled in HCl distillation column 414 to removeHCl generated in reactor 409. HCl is removed overhead in stream 415. Distilled stream416 then enters HF distillation column 417, in which HF is removed. A recycle streamcomprising HF 418 is removed from column 417. A portion of stream 418 is mixed withreactant 548mafd feed 403 and fresh reactant HF feed 404 as recycled HF feed stream405. A purge stream comprising HF 419 is removed from stream 418.

[0202] After HCl and HF distillation columns, process stream 420 enters absorber421. Water is fed to absorber 421 as stream 422. A solution of HF in water is removedfrom absorber 421 in stream 423. Treated stream 424 from absorber 421 is circulatedthrough column 425 in a process step for scrubbing stream 424 with base throughscrubber 426, such as, for example, using an aqueous solution of KOH. Spent KOHsolution 427 is removed from scrubber 426 and column 425. The process streamfollowing scrubbing is removed from column 425 in stream 428, which is then dried bypassing through drying agent column 429. The drying agent may be, for example,molecular sieves. Dried process stream 430 exits drying agent column 429 for furtherpurification.

[0203] Dried process stream 430 enters low boiler distillation column 431 in which lowboilers are removed overhead and pass through a condenser in stream 432. From lowboiler distillation column 431, the process stream 433 passes to distillation column 434,from which high boilers are purged in stream 436 and product stream 435 comprising E-153-10mczz is provided. Product stream 435 comprising E-153-10mczz may be storedin tank 437 for future or immediate use in manufacture of other fluorochemicals or usedin heat transfer applications, such as, for example, in power cycles, high temperature heat pumps and immersion cooling.

[0204] Pumps such as illustrated with feed streams 403, 404 and 405 are used tointroduce and / or circulate materials (reactants, intermediates, products) throughreaction system 400. Heat exchangers such as illustrated at 407a-d are used tomanage temperature through reaction system 400.

[0205] Additional components not shown in Figure 5 may include purge lines, heatexchangers, pumps, and vacuum equipment for distillation columns.

[0206] The final product Step 4 can be used as a heat transfer medium, working fluid,along or combined with other components suitable for use as the heat transfer medium or working fluid to carry heat to and from a source. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back, or vice versa. Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high temperature heat pumps, mobile refrigerators, mobile air conditioning units, electric storage cooling systems, battery cooling, immersion cooling systems, data-center cooling systems, and combinations thereof.

[0207] In some embodiments the final product Step 4 can be used for immersioncooling is used to cool electronic devices, such as datacenter servers, insulated-gate bipolar transistor (IGBT) devices, telecommunication infrastructure, military electronics, televisions (TVs), cell phones, monitors, drones, automotive batteries, powertrains for electric vehicles (EVs), avionics devices, power devices and displays. Immersion cooling systems are heat transfer devices wherein there is no compressor, and the heat transfer medium possesses suitable dielectric properties. Generally, the object to be cooled is at least partially immersed in (in direct contact with) the heat transfer fluid contained in a vessel. In some embodiments, the heat transfer fluid may evaporate and condense in the vessel. In other embodiments, there may be no phase transition involved.

[0208] In one embodiment, the final product Step 4 prepared as disclosed herein canbe used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, among other uses. In one embodiment, the composition disclosed herein is used as a heat transfer fluid. In one embodiment the use as a heat transfer fluid is in a refrigeration system. In one embodiment the use as a heat transfer fluid is in a high temperature heat pump. In one embodiment the use as a heat transfer fluid is in a power cycle, such as an organic Rankine cycle.

[0209] In one embodiment, the final product Step 4 prepared as disclosed herein canbe used in an immersion cooling unit including an immersion cell, defining an internal cavity, is provided. An electronic or electrical component is positioned in the internal cavity. A working fluid partially fills the internal cavity and at least partially immerses the heat generating electronic or electrical device. A condensing coil is positioned inside the cavity above the working fluid.

[0210] In one embodiment of this invention, an immersion cooling unit comprises: animmersion cell, defining an internal cavity; i) an electrical component in the internal cavity; ii) a working fluid partially filling the internal cavity; iii) a condensing coil, positioned in the internal cavity above the electrical component; wherein the working fluid at least partially immerses the electrical component; and wherein the working fluidcomprises, consists essentially of, or consists of the final product Step 4 prepared as disclosed herein.

[0211] Unless otherwise defined, all technical and scientific terms used herein havethe same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0212] The following Examples are provided to illustrate certain aspects of theinvention and shall not limit the scope of the appended claims. EXAMPLES

[0213] In the following Examples, the letter “T” designates temperature; the letter “P”designates pressures. All temperatures are provided in degrees Celsius (°C).

[0214] Unless otherwise stated, all analyses for products in the following Exampleswere performed using GC / MS FID and results are reported in GC FID Area%. Step 1 Example 1

[0215] To a 600 ml pressure reactor, equipped with a gas entrainment stirrer, coolingloop, thermocouple well and diptube, was added 8.73 grams of iron wire. The wire was secured to the cooling loop. The reactor was closed and flushed with nitrogen. Then a solution of CFC-113a (504 grams, 2.69 moles) and tributyl phosphate (17.97 grams, 0.0672 moles) was added through diptube of the reactor. The solution was deoxygenated and heated to 95°C. Ethylene gas (28 grams, 1 mole) was then slowly fed by mass flow controller through diptube at a rate such that the pressure did not to exceed 305 psig. After about 4 hours, the ethylene flow was stopped and the pressurewas allowed to stabilize below 55 psig. The reactor was then cooled, sampled and analyzed by GC / MS and converted to mole%. Results are provided below in Table 1. TABLE 1 Compound Chemical Formula GC Area%ethylene CH2=CH2 1.95CFC-113a CF3CCl3 45.3HCFC-353maf CF3CCl2CH2CH2Cl 43.6HCFC-593 isomer C6H8Cl3F3 0.59HCFC-593mafff CF3CCl2CH2CH2CH2CH2Cl 0.16CFO-1316mxx CF3CCl=CClCF3 0.30CFC-316maa CF3CCl2CCl2CF3 0.10Other Compounds 8.00Example 2

[0216] Iron wire (250 grams) was installed inside a 1-gallon C-276 autoclave whichwas then filled half full of liquid from a previous run. The autoclave was agitated at 1500 rpm and maintained at 105°C internal temperature using an electric heater on the body and an internal cooling coil. During one period of operation, CFC-113a (431 grams / hr) and tributylphosphate (0.159 ml / min) were fed continuously into the autoclave headspace. Ethylene (45 to 48 grams / hr) was continuously added via a submerged dip tube as required to maintain the autoclave internal pressure at 100 psig. Liquid was continuously removed from the bottom of the autoclave as required to maintain the liquid level at 50%. The liquid from the autoclave was collected over 24 hours then analyzed by GC (FID) and is reported as mole %. The run was repeated, and the results of the runs are provided in Table 2. TABLE 2 Compound Chemical Formula Run 1 Run 2mole % ethylene CH2=CH2 0.08 0.085CFC-114a CF3CFCl2 1.955 2.04HCFC-123 CF3CHCl2 0.24 0.23Compound Chemical Formula Run 1 Run 2CFC-113a CF3CCl3 33.415 36.375HCFC-363maf CF3CCl2CH2CH3 0.21 0.191-chlorobutane CH2ClCH2CH2CH3 0.075 0.00HCFC-353maf CF3CCl2CH2CH2Cl 58.53 56.25HCFC-593 isomers C6H8Cl3F3 0.18 0.14HCFC-593mafff CF3CCl2CH2CH2CH2CH2Cl 1.235 1.095HCFC-593syme CH2ClCH2CCl(CF3)CH2CH2Cl 2.025 1.685C8H11Cl2F3 0.04 0.04tributylphosphate C12H27O4P 0.845 0.79Other compounds 1.16 1.01Example 3

[0217] Example 2 was repeated except ethylene was continuously added via asubmerged dip tube as required to maintain the autoclave internal pressure at 125 psig. In comparison to Example 2, conversion of CFC-113a and HCFC-353maf selectivity were similar (less than 5% difference). Thus, operating at a pressure of 125 psig showed consistently good results. Example 4 – Comparison

[0218] Example 2 was repeated except ethylene was continuously added via asubmerged dip tube as required to maintain the autoclave internal pressure at 175 psig. In comparison to Example 2, conversion of CFC-113a decreased by about 10% and the HCFC-353maf selectivity decreased by about 20%. Example 5

[0219] A product produced in accordance with Example 2, Run 2, was purified usingmethods disclosed herein of including distillation. The composition after purification is provided in Table 4.TABLE 4 Compound Chemical Formula GC Area%HCFC-353maf CH2ClCH2CCl2CF3 99.72HCFO-1343 isomers C6H8Cl3F3 0.04HCFC-131 CH2FCCl3 0.03HCFC-343 isomers C4H3F3Cl4 0.031-chlorobutene CF3CCl2CH2CH2CH2CH2Cl 0.021-butanol CF3CCl=CClCF3 0.02C6H2Cl3F7 isomers C6H2Cl3F7 0.011,3-dichlorobutane CH2ClCH2CHClCH3 0.012-butoxyethanol C4H9OCH2CH2OH < 0.01Other Compounds 0.11Step 2 Example 6

[0220] Into an Into an Inconel (0.5 inch OD) tube reactor was added 4 cc of chromiumoxide catalyst (12 / 20 mesh). The reaction was run by feeding liquid HCFC-353maf into a heated chamber where it vaporized and mixed with HF and N2. The process mixture was then allowed to pass through the reactor. Part of the reactor effluent was passed through a series of valves and analyzed by GC-FID-MS. Part of the reactor effluent was also be passed through a caustic scrubber, dried over a desiccant and trap in a dry ice acetone trap. The trapped material was then analyzed by NMR to give HFO-1345zf composition listed in Table 3.TABLE 3 Compound Chemical Formula NMR mole % 1345zf CF3CF2CH=CH2 43.11%E-1335zd CF3CF2CH=CHCl 12.50%Z-1335mxz CF2HCH=CClCF3 11.60% 356mff CF3CH2CH2CF3 10.21%1353mxz CH3CH=CClCF3 7.93%1343mxz CH2ClCH=CClCF3 7.52%1345mzz CF2HCH=CHCF3 7.13%353maf CF3CCl2CH2CH2Cl 0.00%Example 7

[0221] Into an Inconel (0.5 inch OD) tube reactor was added 6 cc of 2.5 wt% zinc-impregnated alumina oxide catalyst (12 / 20 mesh). The reaction was run by feeding liquid HCFC-353maf (“feed”) into a heated chamber where it vaporized and mixed with HF and N2. The process mixture was then allowed to pass through the reactor heated at 285°C to 325°C. A portion of the reactor effluent was passed through a series of valves and analyzed by GCMS. The conditions are provided in Table 4. For each set of conditions in Table 4, 5 GC analyses were taken. These results (averaged 5 GC analyses, area %) are provided in Table 5. TABLE 4 Condition Temperature,Contact time Molar ratio of °C (seconds) N2:HF:feed 1310 15.3 0 : 25.3 : 12 310 10.9 9.3 : 25.3 : 13 325 10.7 9.3 : 25.3 : 14 285 16.1 0 : 25.3 : 1TABLE 5 Condition 1345zf 353maf 13441343 1336 Other isomers isomers isomers compounds GC FID Area % 195.8794% 0.0000% 1.6406% 0.0000% 0.4761% 2.4473%2 86.7588% 0.0000% 6.6134% 0.6027% 0.4098% 5.6592%3 84.8460% 0.0000% 7.5002% 0.6299% 0.5418% 6.5610%4 75.4958% 0.9959% 13.3079% 3.5538% 0.0000% 6.5053%Example 8

[0222] Into an Inconel (0.5 inch OD) tube reactor was added 6 cc of 12-20 mesh 20%CrCl3 / C catalyst. The catalyst was activated with HF starting from 150°C and raising the temperature to end at 450°C. HCFC-353maf was fed by a pump and was passed through a vaporizer at 150°C with 4.6 sccm N2 and then mixed with HF. Reaction test conditions are provided in Table 6 below. The process mixture flowed through the reactor containing the catalyst. Part of the reactor effluent was passed through a GC sample loop and analyzed by GC-MS-FID. The GC (FID) results (area %) are provided in Table 7. TABLE 6 Temperature, 353maf feed, HF feed, N2 feed, Air feed, P, °C ml / hr sccm sccm sccm psig 260 0.1 8 4.6 0 0270 0.1 8 4.6 0 0TABLE 7 Compound GC Area%260°C 270°CHFO-1345zf 75.8183% 45.0412%CFC-13 0.0046% 0.0026%HFC-23 0.0039% 0.0023%HFC-347 isomers 1.1466% 0.4112%HCFC-353maf 0.6403% 4.5976%HCFC-355 isomers 0.9913% 0.0000%HCFC-355 isomers 0.1361% 0.0837%HCFO-1335 isomers 1.6212% 0.568%HCFO-1335 isomers 2.3968% 1.5776%HFO-1336 isomers 0.2212% 0.1410%E-HCFO-1343mxz 0.3658% 0.7115%Z-HCFO-1343mxz 6.6028% 31.7556%HCFO-1344 isomers 0.7042% 5.8206%HCFO-1344 isomers 0.0118% 0.0069%HCFO-1344 isomers 3.1490% 11.1224%E-HFO-1345mzz 1.4294% 0.5950%Z-HFO-1345mzz 0.1610% 0.0520%HCFO-1353 isomers 4.2904% 2.0901%HCFO-1353 isomers 0.2476% 0.3187%Other compounds 0.7736% 0.9292%Example 8a

[0223] In the course of Example 8, the amount of HFO-1345zf formed was found todecrease over time at 270°C as shown in Table 9, below. After 10 hr operation at 270°C, the organic feed was stopped. The catalyst was regenerated using air at the conditions shown in Table 9, below. After air regeneration, the test was resumed at 315°C and 335°°C with co-feeding air. The GC (FID, area %) results at 315°C and 335°C are provided in Table 10. As seen from the results in Table 11, the activity of catalyst was maintained well at 335°C with co-feed of air. TABLE 8 Time Temp GC FID area%hr °C 1345zf 1343 353maf Otherisomers compounds 1.25 260 70.4% 9.04% 1.20% 19.31%2.50 260 60.2% 8.29% 1.24% 30.22%3.75 260 47.2% 7.13% 1.09% 44.63%5.00 260 75.3% 11.6% 1.82% 11.23%6.25 260 75.4% 9.83% 1.62% 13.15%7.50 260 74.4% 8.55% 1.40% 15.68%8.75 260 75.5% 6.42% 1.01% 17.09%10.00 260 75.0% 5.71% 0.95% 18.32%11.25 260 74.9% 5.84% 0.83% 18.44%12.50 260 74.6% 7.39% 0.70% 17.32%13.75 260 65.43% 14.10% 0.87% 19.60%15.00 260 59.73% 20.38% 1.38% 18.50%16.25 270 52.41% 27.04% 2.59% 17.96%17.50 270 45.44% 32.96% 3.53% 18.07%18.75 270 38.70% 37.71% 4.92% 18.67%Time Temp GC FID area%hr °C 1345zf 1343 353maf Otherisomers compounds20.00 270 31.83% 42.08% 6.99% 19.10%21.25 270 25.88% 44.60% 9.80% 19.72%22.50 270 22.39% 45.57% 12.34% 19.69%23.75 270 16.57% 47.12% 15.52% 20.79%25.00 270 14.45% 46.30% 18.51% 20.75%26.25 270 12.57% 44.87% 21.39% 21.17%27.50 270 8.33% 44.27% 25.07% 22.33%28.75 270 6.49% 43.62% 28.24% 21.65%30.00 270 4.67% 42.56% 31.19% 21.58%TABLE 9 T353maf HF N2 Air P°C ml / hr sccm sccm sccm psig350 0 0 12 12 0350 0 24 12 0 0400 0 24 12 0 0450 0 24 12 0 0450 0 24 0 0 0315 0 0 25 0 0315 0.15 12 4.6 4.5 0335 0.15 12 4.6 4.5 0TABLE 10 Compound GC area %315°C 335°CHFO-1345zf 64.3685% 58.9238%CFC-13 0.6518% 0.8209%HFC-23 0.5313% 0.4178%CFC-115 0.1143% 0.1910%HFC-143a 0.2906% 0.3096%HFO-1234yf / HFC-245cb 0.3293% 0.4085%HFO-1234ze 0.5549% 0.4595%HCFC-345 isomers 0.1719% 0.1495%HFC-347 isomers 3.0946% 2.3971%HCFC-353maf 1.2326% 1.4726%HCFC-355 isomers 1.2235% 5.2454%HCFO-1325 isomers 0.8718% 1.0074%HCFO-1326mxz 0.7700% 0.7696%HCFO-1335 isomers 4.5721% 3.8533%HCFO-1335mxz 7.5839% 7.0669%HFO-1336 1.3753% 0.9901%E-HCFO-1343mxz 0.2443% 1.0106%Z-HCFO-1343mxz 5.3337% 10.9610%HCFO-1344 isomers 3.5150% 0.0663%HCFO-1344 isomers 0.7195% 1.4394%E-HFO-1345mzz 0.4762% 0.3120%Z-HFO-1345mzz 0.1805% 0.1278%HCFO-1353 isomers 0.6349% 0.6124%C7H5F7 isomers 0.0404% 0.0498%TABLE 11Time Temp GC area%hr °C 1345zf 1343Other isomers 353mafcompounds1.25 315 38.68% 1.33% 1.69% 58.29%2.50 315 63.00% 1.56% 0.41% 35.03%3.75 315 61.20% 2.51% 0.39% 35.90%5.00 315 59.40% 4.33% 0.81% 35.46%6.25 315 59.38% 6.67% 1.34% 32.61%7.50 315 51.95% 12.19% 3.70% 32.16%8.75 315 47.52% 15.50% 5.26% 31.72%0.00 315 69.28% 10.06% 3.62% 17.04%1.25 315 44.23% 19.40% 6.99% 29.38%2.50 315 41.57% 21.63% 7.96% 28.83%3.75 315 31.83% 26.67% 12.70% 28.80%5.00 315 40.24% 22.65% 8.67% 28.45%6.25 335 56.59% 11.16% 1.51% 30.73%7.50 335 54.94% 12.48% 1.72% 30.86%8.75 335 58.32% 11.64% 1.61% 28.44%0.00 335 66.35% 8.32% 0.89% 24.45%1.25 335 64.90% 9.21% 1.10% 24.79%2.50 335 52.63% 15.29% 2.84% 29.24%3.75 335 51.44% 16.06% 3.24% 29.26%5.00 335 50.48% 15.84% 3.05% 30.63%6.25 335 52.38% 15.58% 3.07% 28.97%7.50 335 55.31% 13.53% 2.33% 28.83%8.75 335 54.21% 14.62% 2.84% 28.34%0.00 335 52.67% 15.84% 3.22% 28.27%Example 9

[0224] Into an Inconel (0.5 inch OD) tube reactor was added 6 cc of 12-20 mesh 6%zinc doped chromium oxide (Cr2O3). The catalyst was activated by treating HF starting from 150°C and ending at 450°C. 353maf was fed by a pump and went through a vaporizer at 150°C with 4.6 sccm N2 and then mixed with HF. The molar ratio of HF to 353maf was 28.91:1. Reaction test conditions are provided in Table 12 below. The process mixture flowed through the reactor containing the catalyst. Part of the reactor effluent was passed through a GC sample loop and analyzed by GC / MS(FID). The GC results are provided in Table 13. The product from this Example was collected and the GC analysis is in Table 14. TABLE 12 Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig1.25 0.1 8 4.6 0 260 02.50 0.1 8 4.6 0 260 03.75 0.1 8 4.6 0 260 05.00 0.1 8 4.6 0 260 06.25 0.1 8 4.6 0 260 07.50 0.1 8 4.6 0 260 08.75 0.1 8 4.6 0 260 010.00 0.1 8 4.6 0 260 011.25 0.1 8 4.6 0 260 012.50 0.1 8 4.6 0 260 013.75 0.1 8 4.6 0 260 015.00 0.1 8 4.6 0 260 016.25 0.1 8 4.6 0 260 017.50 0.1 8 4.6 0 260 018.75 0.1 8 4.6 0 260 020.00 0.1 8 4.6 0 260 021.25 0.1 8 4.6 0 260 022.50 0.1 8 4.6 0 260 0TABLE 13Time GC area%hr 1345zf 1343Other isomers 353mafcompounds1.25 73.58% 4.54% 10.72% 11.15%2.50 70.59% 9.97% 5.90% 13.54%3.75 70.55% 9.51% 6.04% 13.91%5.00 73.93% 7.26% 6.52% 12.29%6.25 78.56% 6.16% 5.21% 10.07%7.50 74.24% 9.96% 3.13% 12.68%8.75 82.26% 3.51% 6.58% 7.65%10.00 76.57% 7.37% 3.90% 12.16%11.25 77.62% 6.57% 4.55% 11.25%12.50 78.93% 5.18% 5.42% 10.46%13.75 76.29% 6.35% 6.45% 10.91%15.00 76.88% 6.18% 6.00% 10.94%16.25 73.72% 9.70% 4.56% 12.03%17.50 77.16% 5.97% 5.99% 10.87%18.75 83.93% 3.32% 4.87% 7.87%20.00 75.52% 8.39% 4.52% 11.57%21.25 72.95% 11.06% 3.58% 12.41%22.50 77.25% 7.34% 4.31% 11.09%TABLE 14 Compound GC FID area%HFO-1345zf 77.6898%CFC-13 0.0009%HFC-23 0.0011%HFC-143a 0.0067%HCFC-345 0.0976%HFC-347 isomers 0.2222%HCFC-355 isomers 1.4824%HCFC-353maf 4.3658%HFO-1325 isomers 0.0440%HCFO-1335 isomers 0.5600%HCFO-1335 isomers 0.5302%Z-HCFO-1343mxz 10.7833%E-HCFO-1343mxz 0.1585%HCFO-1344 isomers 0.5065%HCFO-1344 isomers 2.1625%HCFO-1344 isomers 0.1511%E-HFO-1345mzz 0.4129%Z-HFO-1345mzz 0.0466%HCFO-1353 isomers 0.4932%Other compounds 0.2843%Example 10

[0225] The process of Example 9 was repeated at 315°C, 325°C and 335°C with airco-feed. The conditions are provided in Table 15. GC (FID, area%) analysis results in Table 16 show catalyst activity is stable with air co-feed. TABLE 15 Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig2.5 0.1 8 4.6 3 315 05 0.1 8 4.6 3 315 07.5 0.1 8 4.6 3 315 010 0.1 8 4.6 3 315 012.5 0.1 8 4.6 3 315 015 0.1 8 4.6 3 315 017.5 0.1 8 4.6 3 315 020 0.1 8 4.6 3 315 022.5 0.1 8 4.6 3 315 025 0.1 8 4.6 3 315 027.5 0.1 8 4.6 3 315 030 0.1 8 4.6 3 315 032.5 0.1 8 4.6 3 315 035 0.1 8 4.6 3 315 037.5 0.1 8 4.6 3 315 040 0.1 8 4.6 3 315 042.5 0.1 8 4.6 3 325 045 0.1 8 4.6 3 325 047.5 0.1 8 4.6 3 325 050 0.1 8 4.6 3 325 0Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig52.5 0.1 8 4.6 3 325 055 0.1 8 4.6 3 325 057.5 0.1 8 4.6 3 335 060 0.1 8 4.6 3 335 062.5 0.1 8 4.6 3 335 065 0.1 8 4.6 3 335 067.5 0.1 8 4.6 3 335 070 0.1 8 4.6 3 335 072.5 0.1 8 4.6 3 335 0TABLE 16 Time GC FID area%hr 1345zf 1343 isomers 353maf Othercompounds2.5 71.47% 7.19% 8.23% 13.12%5 75.85% 4.66% 11.62% 7.87%7.5 73.49% 8.20% 6.44% 11.88%10 75.12% 7.93% 5.98% 10.97%12.5 79.11% 6.46% 5.22% 9.21%15 77.01% 8.48% 4.46% 10.04%17.5 79.18% 7.79% 3.85% 9.18%20 78.74% 8.26% 3.84% 9.16%22.5 78.19% 8.87% 3.36% 9.58%25 80.60% 7.52% 3.63% 8.25%27.5 76.32% 10.47% 3.07% 10.14%30 75.42% 11.69% 2.64% 10.25%Time GC FID area%hr 1345zf 1343 isomers 353maf Othercompounds32.5 75.62% 11.51% 2.52% 10.35%35 78.52% 10.02% 2.62% 8.84%37.5 77.65% 10.80% 2.32% 9.23%40 78.01% 10.87% 2.10% 9.02%42.5 86.32% 2.93% 7.71% 3.04%45 79.00% 9.26% 1.83% 9.91%47.5 79.50% 9.23% 1.71% 9.56%50 78.20% 10.12% 1.59% 10.09%52.5 74.44% 12.89% 1.46% 11.21%55 78.73% 9.83% 1.55% 9.90%57.5 78.05% 9.08% 1.50% 11.37%60 81.86% 6.91% 1.68% 9.54%62.5 77.14% 9.86% 1.46% 11.53%65 81.13% 7.50% 1.58% 9.79%67.5 79.27% 8.67% 1.41% 10.65%70 79.27% 8.67% 1.41% 10.65%72.5 78.99% 9.06% 1.24% 10.70%Example 11

[0226] The processes of Examples 9 and 10 was repeated with lower HF / HCFC-353maf mol ratio at 20:1. Deactivation of catalyst was observed faster than the previous test when HCFC-353maf mol ratio was at 29:1. The conditions are provided in Table 17. GC analysis results in Table 18 show deactivation of catalyst was observed faster than the previous test when HF / HCFC-353maf mol ratio was at 29:1.TABLE 17 Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig1.25 0.22 12 4.6 4.5 335 02.5 0.22 12 4.6 4.5 335 03.75 0.22 12 4.6 4.5 335 05 0.22 12 4.6 4.5 335 06.25 0.22 12 4.6 4.5 335 07.5 0.22 12 4.6 4.5 335 08.75 0.22 12 4.6 4.5 335 010 0.22 12 4.6 4.5 335 011.25 0.22 12 4.6 4.5 335 012.5 0.22 12 4.6 4.5 335 013.75 0.22 12 4.6 4.5 335 015 0.22 12 4.6 4.5 335 016.25 0.22 12 4.6 4.5 335 017.5 0.22 12 4.6 4.5 335 0TABLE 18Time GC FID area %hr 1345zf 1343 353mOther isomers afcompounds1.25 70.89% 12.02% 0.00% 17.09%2.5 76.04% 8.65% 0.00% 15.31%3.75 63.95% 13.86% 0.00% 22.20%5 65.06% 16.44% 0.00% 18.50%6.25 61.49% 16.54% 0.00% 21.97%7.5 64.99% 17.68% 0.00% 17.33%8.75 61.95% 19.62% 0.00% 18.43%10 58.51% 20.20% 0.00% 21.29%11.25 56.67% 23.99% 0.00% 19.35%Time GC FID area %hr 1345zf 1343 35Other isomers 3mafcompounds 12.5 54.51% 24.96% 0.00% 20.53%13.75 51.45% 26.17% 0.00% 22.38%15 50.60% 26.89% 0.00% 22.51%16.25 46.26% 30.08% 0.00% 23.67%17.5 44.03% 28.48% 0.00% 27.49%Example 12

[0227] The catalyst from Example 11 was treated with air for regeneration and thentesting was resumed at 335°C with HCFC-353maf mol ratio at 29:1. The conditions are provided in Table 19. GC (FID, area %) analysis results in Table 20 show activity of catalyst resumed and the catalyst stayed stable. TABLE 19 Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig2.5 0 0 12 12 350 01 0 24 12 0 350 01 0 24 12 0 400 01 0 24 12 0 450 01 0 24 0 0 450 01.5 0 0 25 0 335 02.75 0.15 12 4.6 4.5 335 04 0.15 12 4.6 4.5 335 05.25 0.15 12 4.6 4.5 335 06.5 0.15 12 4.6 4.5 335 07.75 0.15 12 4.6 4.5 335 09 0.15 12 4.6 4.5 335 010.25 0.15 12 4.6 4.5 335 011.5 0.15 12 4.6 4.5 335 0Time 353maf HF N2 Air T Phr ml / hr sccm sccm sccm °C psig12.75 0.15 12 4.6 4.5 335 014 0.15 12 4.6 4.5 335 015.25 0.15 12 4.6 4.5 335 016.5 0.15 12 4.6 4.5 335 017.75 0.15 12 4.6 4.5 335 019 0.15 12 4.6 4.5 335 020.25 0.15 12 4.6 4.5 335 021.5 0.15 12 4.6 4.5 335 022.75 0.15 12 4.6 4.5 335 024 0.15 12 4.6 4.5 335 0TABLE 20Time GC area%hr 1345zf 1343s 3Other isomer 53mafCompounds2.75 87.88% 4.98% 0.06% 7.08%4 87.50% 4.96% 0.03% 7.51%5.25 88.02% 4.65% 0.06% 7.27%6.5 88.74% 4.36% 0.02% 6.88%7.75 86.70% 5.31% 0.02% 7.97%9 86.08% 5.54% 0.02% 8.36%0.25 91.44% 0.14% 0.00% 8.42%11.5 87.11% 5.10% 0.03% 7.76%2.75 87.25% 4.98% 0.03% 7.74%14 86.43% 5.44% 0.01% 8.12%5.25 90.36% 4.97% 0.03% 4.64%16.5 86.51% 5.49% 0.01% 7.99%7.75 87.03% 5.35% 0.09% 7.53%19 87.35% 5.06% 0.12% 7.47%0.25 85.77% 5.67% 0.02% 8.54%Time GC area%hr 1345zf 1343Other isomers 353mafCompounds 21.5 75.84% 4.24% 0.00% 19.92%22.75 87.77% 4.70% 0.00% 7.53%24 87.91% 4.72% 0.04% 7.33%Example 13

[0228] In a 1” Hastelloy C tube reactor chromium oxide catalyst was loaded andactivated by HF treatment. Then HCFC-353maf and HF were fed at mol ratio of 1:20 at 80 psig pressure with co-fed of 0.2-0.4mol% O2 in the temp range 340-350°C with contact time around 22 seconds. The product was scrubbed by a caustic solution and then collected and analyzed by GC. The result of GC analysis is provided in Table 21. TABLE 21 Compound GC Area %HFO-1345zf 43.2%HFO-1345 isomers 0.574%HCFO-1233xf 0.117%E- HCFO-1335dz 0.623%E- HCFO-1344fzb 4.79%E- HCFO-1335mxz 1.45%HCFO-1335 isomers 0.159%HCFC-355 isomers 0.403%Z- HCFO-1344mxz 4.99%Z- HCFO-1344myz 4.58%HCFO-1344 isomers 0.120%HCFO-1343 isomers 0.210%HCFO-1343 isomers 0.187%Z- HCFO-1343mxz 33.7%HCFO-1343 isomers 2.26%HCFO-1343 isomers 2.04%Other compounds 0.611%

[0229] This product was further distilled and a purified product was analyzed by GC-MS-TCD which revealed additional byproducts as showed in Table 22. TABLE 22 Compound GC TCD area%HFO-1234yf 0.0023%HCFO-1327 isomers 0.0009%CF3CF2CHO 0.0045%E-HFO-1336mzz 0.0742%HFO-1336yf 0.2657%HFO-1336ze 0.0418%HFO-1345zf 99.4085%Z-HFO-1336mzz 0.0189%HCFC-244 isomers 0.0121%HCFO-1233xf 0.1550%HCFO-1233zd 0.0073%Other compounds 0.0087%

[0230] A distillation cut collected at 65°C was analyzed by NMR to further identify thestructure of intermediate compounds. The result of analysis and structure of intermediates identified are provided in Table 23. TABLE 23 Compound Name Mole percent(mole%)Compound Name 47.21Z-HCFO- 1344mxz Z-2-chloro-1,1,1,4-tetrafluoro-2-butene 43.10Z-HCFO- 1344myz Z-4-chloro-1,1,1,2-tetrafluoro-2-butene 3.92E-HCFO- 1344mxz E-2-chloro-1,1,1,4-tetrafluoro-2-butene 3.59E-HCFO- 1344myz E-4-chloro-1,1,1,2-tetrafluoro-2-butene 0.58Compound Name Mole percent(mole%)HCFC-355of 4-chloro-1,1,1,2,2-pentafluorobutane 0.44HCFO- 1343maz 3,3-dichloro-4,4,4-trifluoro-1-butene 0.100E-HCFO- 1344mxy E-2-chloro-1,1,1,3-tetrafluoro-2-butene 0.010Z-HCFO- 1344mxy Z-2-chloro-1,1,1,3-tetrafluoro-2-butene 1.07Step 3 Example 14

[0231] To a dry 400 ml shaker tube was added 9.56 g of iron powder, 4.25 g of irontrichloride, 18.23 g of triphenylphosphine, and 343 g of R113a. The solution was degassed with N2 pressure / vacuum sweep. While under vacuum, the tube was placed in dry ice and 100 g of HFO-1345zf was added. The tube was heated to 110°C until pressure stabilized. The reactor was cooled, unloaded, and the reaction mixture was analyzed by GC / MS (FID). Results are provided in Table 24. TABLE 24 Chemical Name Formula GC Area %HFO-1345zf CF3CF2CH=CH2 19.2648%CFC-113a CF3CCl3 28.0933%CFO-1316mxx CF3CCl=CClCF3 0.1670%CFC-316maa CF3CCl2CCl2CF3 0.0613%1-chlorobutane C4H9Cl 1.3676%HCFO-1547mafz CF3CCl2CH2CH=CFCF3 2.6030%HCFC-548mafd CF3CF2CHClCH2CCl2CF3 42.3580%triphenylphosphine P(C6H5)3 1.5645%Other compounds 4.4818%Example 15Purification of 3,5,5-Trichloro-1,1,1,2,2,6,6,6-octafluorohexane (HCFC-548mafd)

[0232] The product from Example 1 is purified according to methods disclosed hereinto provide a product comprising the composition disclosed in Table 25. TABLE 25 Chemical Name GC Area %5,5-dichloro-1,1,1,2,6,6,6- 0.2500% heptafluoro-2-hexene (1547mafz) 3,5,5-trichloro-1,1,1,2,2,6,6,6- 99.5000% octafluorohexane (548mafd) Other compounds 0.2500%Example 16

[0233] Iron wire was added to a 1-gallon C-276 autoclave and secured to an internalcooling coil. The autoclave was pre-charged with the liquid from a previous run, which produced HCFC-548mafd. The autoclave was agitated at 1500 rpm and heated to a 150°C internal temperature using an electric heater on the body and an internal cooling coil. CFC-113a (329.8 g / hr) and tributylphosphate (9.7 g / hr) were continuously fed into the autoclave headspace. HFO-1345zf (203.7 g / hr average) was fed to the autoclave through a dip tube as required to maintain the pressure at 165 psig. Liquid was taken off the bottom of the autoclave as required to maintain the autoclave liquid level at about 75% full. The liquid residence time was 5.6 hours. The liquid from the autoclave was collected for over 24 hours then analyzed by GC. The CFC-113a conversion was 61.7% and the HFO-1345zf conversion was 77.1%. The CFC-113a selectivity to 548mafd was 90.9% and the selectivity of HFO-1345zf to 548mafd was 89.9%. The autoclave productivity to 548mafd was 135.5 g / liter-hr. In addition to CFC-113a, HFO- 1345zf and HCFC-548mafd, the composition further comprised C10H6Cl3F13 isomers, CF3CCl2CH2CH=CFCF3 (HCFO-1547mafz), and 1-chlorobutane.Example 17

[0234] A 1-gallon C-276 autoclave containing immobilized iron wire was pre-chargedwith the liquid from a previous run. The autoclave was agitated at 1500 rpm and heated to 150°C internal temperature using an electric heater on the body. CFC-113a (284.4 g / hr) and TBP (8.4 g / hr) were continuously fed into the autoclave headspace. HFO- 1345zf (154.0 g / hr average) was fed into the autoclave through a dip tube as required to maintain the pressure at 145 psig. Liquid was taken off the bottom of the autoclave as required to maintain the autoclave liquid level at about 80% full. The liquid residence time was 7.2 hours. The liquid from the autoclave was collected for over 24 hours then analyzed by GC. The CFC-113a conversion was 56.3% and the HFO-1345zf conversion was 78.6%. The CFC-113a selectivity to HCFC-548mafd was 92.0% and the HFO-1345zf selectivity to HCFC-548mafd was 92.8%. The autoclave productivity to HCFC-548mafd was 103.5 g / liter-hr. Comparison Example

[0235] Example 17 was repeated except HFO-1345zf was continuously added via asubmerged dip tube as required to maintain the autoclave internal pressure at 175 psig. In comparison to Example 17, conversion of CFC-113a decreased by about 10% and the HCFC-548mafd selectivity decreased by about 20%. Thus, lower pressure showed improved results. Example 18

[0236] Iron wire was added to a 1-gallon C-276 autoclave and secured to the internalcooling coil. The autoclave was pre-charged with the liquid from a previous run. The autoclave was agitated at 1500 rpm and heated to a 140°C internal temperature using an electric heater on the body and an internal cooling coil. CFC-113a (258.4 g / hr) and TBP (6.3 g / hr) were continuously fed into the autoclave headspace. HFO-1345zf (122.4 g / hr average) was fed to the autoclave through a dip tube as required to maintain the pressure at 135 psig. Liquid was taken off the bottom of the autoclave as required to maintain the autoclave liquid level at about 75% full. The liquid residence time was 8.1 hours. The autoclave was operated for over 4 days then a liquid sample was collectedand analyzed by GC. The CFC-113a conversion was 51.1% and the HFO-1345zf conversion was 78.4%. The CFC-113a selectivity to HCFC-548mafd was 90.2%, and the selectivity of HFO-1345zf to HCFC-548mafd was 95.3%. The autoclave productivity to HCFC-548mafd was 87.8 g / liter-hr. Example 19

[0237] Iron wire (258 grams) was installed into a 1-gallon C-276 autoclave which wasthen filled with liquid from the previous run. The autoclave was agitated at 1500 rpm and maintained at 140°C internal temperature using an electric heater on the body and an internal cooling coil. During one period of operation, CFC-113a (179.4 g / hr) and TBP (5.6 g / hr) were fed continuously into the autoclave headspace. HFO-1345zf (88.6 g / hr) was continuously added via a submerged dip tube as required to maintain the autoclave internal pressure at 135 psig. Liquid was continuously removed from the bottom of the autoclave as required to maintain a liquid volume of 2.4 liters. The reactor was allowed to reach steady state conditions. The liquid composition in the autoclave was 8.6 mol% HFO-1345zf, 39.6 mol% CFC-113a, 43.4 mol% HCFC-548mafd and 8.4 mol% other compounds. The CFC-113a conversion was 54.2% and the HFO-1345zf conversion was 84.6%. Selectivity from CFC-113a to HCFC-548mafd was 92.7% and selectivity from HFO-1345zf to HCFC-548mafd was 92.1%. Reactor productivity was 66.3 g HCFC-548mafd / liter-hr. Step 4 Example 20

[0238] Into an Inconel (0.5 inch OD) tube reactor was added 4 cc of chromium oxidecatalyst (12 / 20 mesh). The reaction was run by feeding liquid HCFC-548mafd into a heated chamber where it vaporized and mixed with HF and N2. The reaction mixture was then allowed to pass through the reactor. Part of the reactor effluent was passed through a series of valves and analyzed by GC / MS / FID. Part of the reactor effluent can also be passed through a caustic scrubber, dried over a desiccant and trap in a dry iceacetone trap. The trapped material is then analyzed by NMR to give E-153-10mczzcomposition listed in Table 26 below. TABLE 26 Chemical Name Compound Chemical Formula GC FIDArea % E-1,1,1,2,2,5,5,6,6,6- E-153-E-CF3CF2CH=CHCF2CF3 82.4878%decafluorohex-3-ene 10mczz 2-chloro-1,1,1,2,5,5,6,6,6-1539mbzz CF3CFClCH=CHCF2CF3 5.8649%nonafluorohex-3-ene 3-chloro- 152- CF3CF2CCl=CHCF2CF3 2.5736% 1,1,1,2,2,5,5,6,6,6- 10mcdz decafluorohex-3-ene 2,5-dichloro-1,1,1,6,6,6-2536mxzzx CF3CCl=CHCH=CClCF3 2.2272%hexafluorohexa-2,4-diene 2-chloro-1,1,1,5,6,6,6-2537mxzzy CF3CCl=CHCH=CFCF3 1.6498%heptafluorohexa-2,4-diene 2,4-dichloro-1538mxzd CF3CCl=CHCHClCF2CF3 1.4435%1,1,1,5,5,6,6,6- octafluorohex-2-ene 1,1,1,2,2,3,5,5,6,6,6- 152- CF3CF2CF=CHCF2CF3 1.1631% undecafluorohex-3-ene 11mcyz 2-chloro- 152-10mdz CF3CCl=CHCF2CF2CF3 0.9981% 1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene 2,3,5-trichloro-1528mdcxx CF3CHClCF2CCl=CCl-CF3 0.9074%1,1,1,4,4,6,6,6- octafluorohex-2-ene 1-chloro-3,3,4,4,5,5- Cyclic-- 0.6846% hexafluoro-2- CF2CF2CF2C(CF3)CCl- (trifluoromethyl)cyclopent- 1-ene 3,5,5-trichloro-548mafd CF3CF2CHClCH2CCl2CF3 0.0000%1,1,1,2,2,6,6,6- octafluorohexane Example 21

[0239] The product produced in Example 19 was purified using methods disclosedherein of including distillation. The composition after purification is provided in Table 27.TABLE 27 Chemical Name Compound Chemical Formula AnalyzedGC FID Area % E-1,1,1,2,2,5,5,6,6,6- E-153-E-CF3CF2CH=CHCF2CF399.5% decafluoro-3-hexene 10mczz 2-chloro-1539mbzz CF3CFClCH=CHCF2CF3 0.20%1,1,1,2,5,5,6,6,6- nonafluorohex-3-ene 1,1,1,2,2,3,5,5,6,6,6-152-11mcz CF3CF2CF=CHCF2CF3 0.10%undecafluorohex-3-ene Example 22Hydrofluorination of HCFC-548mafd to E-HFO-153-10mczz, using 4%Zn / Al2O3 catalyst

[0240] 6ml (12-20 mesh) of 4% Zn / Al2O3 catalyst is loaded into a 12 inches longInconel (0.5 inch OD) tube reactor. The catalyst is activated by HF starting from 150°C and raising to 450°C. The reaction of HCFC-548mafd-with HF reaction was tested at conditions listed in Table 28 below. HCFC-548mafd was fed by a pump and went through a vaporizer at 200°C with N2 and then is mixed with HF and flow through the reactor with catalyst bed. The reactor effluent is analyzed by a GC-MS-FID and shows E-HFO-153-10mczz, was produced at high concentration at various conditions. Results are provided in Table 29. TABLE 28 Sample Time T P (psig)548mafd N2HF (hours)_(ml / hr) (sccm) (sccm) 11.25 280 1.3 0.15 3.09 6.132 2.50 280 1.4 0.15 3.09 6.103 3.75 280 1.1 0.15 3.09 6.064 5.00 280 1 0.15 3.09 6.065 6.25 280 0.9 0.15 3.09 6.066 7.50 280 0.9 0.15 3.09 6.137 8.75 300 0.9 0.15 3.09 6.178 10.00 300 0.9 0.15 3.09 6.14Sample Time548mafd N2HF (hours)_ T P (psig)(ml / hr) (sccm) (sccm) 911.25 300 0.9 0.15 3.09 6.1610 12.50 315 0.9 0.15 3.09 6.1711 13.75 315 0.9 0.15 3.09 6.1412 15.00 315 0.9 0.15 3.09 6.1013 16.25 330 0.9 0.15 3.09 6.1614 17.50 330 0.9 0.15 3.09 6.1215 18.75 330 0.9 0.15 3.04 6.0516 20.00 345 0.9 0.15 3.02 6.04TABLE 29Sample 548mafd E-153- 1233xf C6H2F8C6H2F8 1539 1539 1539 C6H2ClF7 C6H2ClF7 Other 10mczz isomers isomers isomers isomers isomers isomers compounds GC-FID area% 10.00 67.08 0.00 14.83 6.79 0.00 0.00 0.00 3.08 0.00 8.222 0.00 75.15 0.00 6.88 0.00 0.00 0.00 0.00 4.49 0.00 13.493 2.58 24.69 0.00 11.87 3.27 31.19 4.42 0.33 15.06 4.34 2.254 13.74 17.67 0.04 3.97 1.06 38.50 4.39 1.11 11.41 3.61 4.545 8.67 23.96 0.06 5.65 1.11 37.47 4.24 0.72 10.17 3.34 4.676 7.54 41.82 0.10 3.93 0.77 23.74 2.89 0.68 8.73 3.64 6.277 4.87 48.53 0.11 3.86 0.77 23.61 2.78 0.44 7.33 3.00 4.818 7.12 44.12 0.09 3.79 0.70 24.87 2.91 0.64 7.90 3.29 4.649 2.02 63.96 0.12 2.65 0.59 11.62 1.51 0.21 5.43 2.83 9.2010 2.15 63.92 0.15 2.62 0.58 11.67 1.51 0.22 5.52 2.92 8.9111 2.02 64.68 0.12 2.58 0.00 11.54 2.06 0.22 5.39 2.83 8.6212 0.51 71.56 0.25 1.99 0.00 5.32 1.25 0.15 3.61 2.22 13.2913 0.60 71.03 0.18 1.99 0.39 5.57 0.86 0.18 3.67 2.26 13.4614 0.56 71.43 0.18 1.96 0.39 5.44 0.85 0.18 3.58 2.20 13.4215 0.28 71.09 0.29 2.17 0.32 3.83 0.45 0.30 2.98 1.83 16.75Example 23Production, Purification of E-153-10mczz and analysis of E-153-10mczz product

[0241] In a 1” Hastelloy C tube reactor Cr2O3 catalyst was loaded and activated by HFtreatment. Then HCFC-548mafd and HF were fed at mol ratio of 1:40 at 30 psig pressure with co-fed of 0.2 mol% O2at a temperature of 320°C with contact time around 13 seconds. The product was scrubbed by a caustic and collected. The crude product was analyzed by GC-MS-FID. The result of GC analysis is provided in Table 30. TABLE 30 Compound FID area%125 0.0020%115 0.0032%C6F10 isomers 0.0128%C6F10 isomers 0.0207%C6F10 isomers 0.115%C5HF9 isomers 0.0321%C6F12 isomers 0.0984%Z-152-11mcyz 0.739%E-153-10mczz 82.0%C6HF11 isomers 0.0399%C6HF11 isomers 0.0080%C6HF11 isomers 0.0082%Z-152-11myz 0.0981%C6HF11 isomers 0.0306%C6H2F12 isomers 0.130%C6ClF9 isomers 0.203%C6H2F10 isomers 0.125%C5HClF8 isomers 0.0630%C6H2F10 isomers 0.226%C6HClF10 isomers 1.30%C6HClF10 isomers 0.691%C6H2ClF9 isomers 7.64%C5HF9 isomers 0.152%C6H2ClF9 isomers 0.228%C6H2ClF9 isomers 0.621%C6HClF8 isomers 0.0715%C6H2ClF9 isomers 0.101%C6H2ClF7 isomers 0.194%Compound FID area%C6Cl2F10 isomers 0.126%C6HCl2F9 isomers 0.310%C6HClF10 isomers 0.247%C6HCl2F9 isomers 0.296%C6H2Cl2F8 isomers 0.983%C6Cl2F8 isomers 0.102%C6HCl2F7 isomers 0.169%C6HCl2F7 isomers 0.133%C6HCl2F7 isomers 0.125%C6H2Cl2F6 isomers 0.311%C6HCl3F6 isomers 0.178%Other compounds 2.08%

[0242] This crude E-153-10mczz was purified in a series of distillation columns,absorbers, scrubbers and dryers as described according to Figure 5. The purified product was analyzed by NMR and GC-MS-FID to determine the composition.

[0243] The composition is provided in Table 31 and Table 32.TABLE 31 NMR analysis Compound Formula Name Mole %E-1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene E-C2F5CH=CHC2F5 E-153-10mczz 98.6Z-1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene Z-CF3CF2CF=CHCF2CF3 Z-152-11mcyz 1.22Z-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene Z-CF3CF=CHCF2CF2CF3 Z-152-11myz 0.14TABLE 32 GC-MS-FID analysis Compounds FID area%C6F10 isomers 0.0002%C6F10 isomers 0.0009%1336 isomers 0.0007%C5HF9 isomers 0.0004%C6F12 isomer / C5H2F8 isomers / other 0.0058% compound(s) C6F12 isomers 0.0009%Z-152-11mcyz 0.8153%E-153-10mczz 99.0528%Z-152-11myz 0.0083%C6F10 isomers 0.0040%C6F8 isomers 0.0036%153-10mzz 0.0069%C6HF9 isomers 0.0095%C6HF9 isomers 0.0008%C6ClF9 isomers 0.0060%C6HF9 isomers 0.0019%C6HF9 isomers 0.0022%HCFO-1326mxz 0.0015%C6HClF10 isomers 0.0009%C6H2ClF9 isomers 0.0004%C5HClF8 isomers 0.0073%C5HClF8 isomers 0.0009%HCFC-346mdf 0.0028%Other compounds 0.0661%COMPOUNDS

[0244] Compounds disclosed herein are provided in Table 33.TABLE 33 Name Formula Compound1,1,1,4,4,5,5,6,6,6- decafluoro-2-hexene C2F5CH=CHC2F5 HFO-153-10mzzE-1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene E-C2F5CH=CHC2F5 E-HFO-153-10mczzZ-1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene Z-C2F5CH=CHC2F5 Z-HFO-153-10mczz1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene CF3CF2CF=CHCF2CF3 HFO-152-11mcyzZ-1,1,1,2,2,3,5,5,6,6,6- undecafluoro-3-hexene Z-CF3CF2CF=CHCF2CF3 Z-HFO-152-11mcyzZ-1,1,1,2,4,4,5,5,6,6,6- undecafluoro-2-hexene Z-CF3CF=CHCF2CF2CF3 Z-HFO-152-11myz1,3,3,3-tetrafluoropropene CF3CH=CHF HFO-1234ze2,3,3,3-tetrafluoropropene CF3CF=CH2 HFO-1234yfheptafluorobutene isomers C4HF7 HFO-1327 isomers1,1,1,4,4,4-hexafluoro-2- butene CF3CH=CHCF3 HFO-1336mzz1,3,3,4,4,4-hexafluoro-1- butene CF3CF2CH=CHF HFO-1336ze2,3,3,4,4,4-hexafluoro-1- butene CF3CF2CF=CH2 HFO-1336yfE-1,1,1,4,4,4-hexafluoro- 2-butene CF3CH=CHCF3 E-HFO-1336mzzZ-1,1,1,4,4,4-hexafluoro- 2-butene CF3CH=CHCF3 Z-HFO-1336mzzhexafluorobutene isomers C4H2F6 HFO-1336 isomers3,3,4,4,4-pentafluorobut- 1-ene CH2=CHCF2CF3 HFO-1345zf1,1,4,4,4-pentafluoro-2- butene CF3CH=CHCHF2 HFO-1345mzzE-1,1,4,4,4-pentafluoro-2- butene E-CF3CH=CHCHF2 E-HFO-1345mzzZ-1,1,4,4,4-pentafluoro-2- butene Z-CF3CH=CHCHF2 Z-HFO-1345mzznonafluoropentene C5HF9 HFO-1429 isomersoctafluoropentene C5H2F8 HFO-1438 isomers1-chloro-3,3,3- trifluoropropene CF3CH=CHCl HCFO-1233zdName Formula Compound2-chloro-3,3,3- trifluoropropene CF3CCl=CH2 HCFO-1233xfdichloropentafluorobutene isomers C4HCl2F5 HCFO-1325 isomers2-chloro-1,1,1,4,4,4- hexafluoro-2-butene CF3CCl=CHCF3 HCFO-1326mxz1,1,1,4,4-pentafluoro-3- chlorobutene CF3CH=CClCF2H HCFO-1335mxz1-chloro-3,3,4,4,4- pentafluoro-1-butene CF3CF2CH=CHCl HCFO-1335dzchloropentafluorobutene isomers C4H2ClF5 HCFO-1335 isomersE-2-chloro-1,1,1,4,4- pentafluoro-2-butene E-CF3CCl=CHCF2H E-HCFO-1335mxzZ-1-chloro-1,1,4,4,4- pentafluoro-2-butene CF2ClCH=CHCF3 Z-HCFO-1335lzz1,3-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl HCFO-1343mxz3,3-dichloro-4,4,4- trifluoro-1-butene CF3CCl2CH=CH2 HCFO-1343mazE-1,2-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl E-HCFO-1343mxzE-1,3-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl E-HCFO-1343mxzZ-1,2-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl Z-HCFO-1343mxzZ-1,3-dichloro-4,4,4- trifluoro-2-butene CF3CCl=CHCH2Cl Z-HCFO-1343mxzdichlorotrifluorobutene isomers C4H3Cl2F3 HCFO-1343 isomers2-chloro-1,1,1,3- tetrafluoro-2-butene CF3CCl=CFCH3 HCFO-1344mxy2-chloro-1,1,1,4- tetrafluoro-2-butene CF3CCl=CHCH2F HCFO-1344mxz3-chloro-3,4,4,4- tetrafluoro-1-butene CF3CClFCH=CH2 HCFO-1344fzb4-chloro-1,1,1,2- tetrafluoro-2-butene CF3CF=CHCH2Cl HCFO-1344myzE-2-chloro-1,1,1,3- tetrafluoro-2-butene E-CF3CCl=CFCH3 E-HCFO-1344mxyName Formula CompoundE-2-chloro-1,1,1,4- tetrafluoro-2-butene E-CF3CCl=CHCH2F E-HCFO-1344mxzE-4-chloro-1,1,1,2- tetrafluoro-2-butene E-CF3CF=CHCH2Cl E-HCFO-1344myzZ-2-chloro-1,1,1,3- tetrafluoro-2-butene Z-CF3CCl=CFCH3 Z-HCFO-1344mxyZ-2-chloro-1,1,1,4- tetrafluoro-2-butene Z-CF3CCl=CHCH2F Z-HCFO-1344mxzZ-4-chloro-1,1,1,2- tetrafluoro-2-butene Z-CF3CF=CHCH2Cl Z-HCFO-1344myzchlorotetrafluorobutene isomers C4H3ClF4 HCFO-1344 isomers3-chloro-4,4,4-trifluoro-2- butene CF3CCl=CHCH3 HCFO-1353mxzchlorotrifluorobutene isomers C4H4ClF3 HCFO-1353 isomerstetrachlorohexa- fluoropentene C5Cl4F6 HCFO-1416 isomers2,3,5-trichloro- 1,1,1,4,4,6,6,6-octafluoro- CF3CCl=CClCF2CHClCF3 HCFO-1528mdcxx 2-hexene 2,4-dichloro- 1,1,1,5,5,6,6,6-octafluoro- CF3CCl=CHCHClCF2CF3 HCFO-1538mxzd 2-hexene 2-chloro-1,1,1,2,5,5,6,6,6- nonafluoro-3-hexene CF3CClF=CHCH2CF2CF3 HCFO-1539mbzzchloro-nonafluorohexene isomers C6H3ClF9 HCFO-1539 isomers5,5-dichloro-1,1,1,2,6,6,6- heptafluoro-2-hexene CF3CCl2CH2CH=CFCF3 HCFO-1547mafz2-chloro- 1,1,1,4,4,5,5,6,6,6- CF3CCl=CHCF2CF2CF3 HCFO-152-10mdz decafluoro-2-hexene 3-chloro- 1,1,1,2,2,5,5,6,6,6- CF3CF2CCl=CHCF2CF3 HCFO-152-10mcxz decafluoro-3-hexene 2,5-dichloro-1,1,1,6,6,6-hexafluorohexa-2,4-diene CF3CCl=CHCH=CClCF3 HCFO-2536mxzzx2-chloro-1,1,1,5,6,6,6- heptafluorohexa-2,4- CF3CCl=CHCH=CFCF3 HCFO-2537mxzzy dieneName Formula Compound2,3-dichloro-1,1,1,4,4,4- hexafluoro-2-butene CF3CCl=CClCF3 CFO-1316mxxtrifluoromethane CHF3 HFC-231,1,1,2,2- pentafluoroethane CF3CHCF2 HFC-1251,1,2,2-tetrafluoroethane CHF2CHF2 HFC-1341,1,1-trifluoroethane CF3CH3 HFC-143a1,1,1,2,2,3,3- heptfluoropropane CF3CF2CHF2 HFC-227ca1,1,1,3,3,3- hexafluoropropane CF3CH2CF3 HFC-236fa1,1,1,2,2- pentafluoropropane CF3CF2CH3 HFC-245cb1,1,1,2,2,4,4,4- octafluorobutane CF3CH2CF2CF3 HFC-338mfheptafluorobutane isomers C4H3F7 HFC-347 isomers1,1,1,4,4,4- hexafluorobutane CF3CH2CH2CF3 HFC-356mffdodecafluorohexane C6H2F12 HFC-53-12 isomers2,2-dichloro-1,1,1- trifluoroethane CF3CHCl2 HCFC-1231-chloro-1,2,2,2- tetrafluoroethane CHClFCF3 HCFC-1241,1,2-trichloro-2- fluoroethane CHCl2CHClF HCFC-1312-chloro-1,1,1- trifluoroethane CF3CH2Cl HCFC-133achlorotetrafluoropropane isomers C3H3F4Cl HCFC-244 isomerstetrachlorotrifluorobutane isomers C4H3F3Cl4 HCFC-343 isomers2-chloro-1,1,1,4,4,4- hexafluorobutane CF3CH2CHClCF3 HCFC-346mdfdichloropentafluorobutane isomers C4H3Cl2F5 HCFC-345 isomers2,2,4-trichloro-1,1,1- trifluorobutane CH2ClCH2CCl2CF3 HCFC-353maf4-chloro-1,1,1,2,2- pentafluorobutane CF3CF2CH2CH2Cl HCFC-355ofchloropentafluorobutane isomers C4H4ClF5 HCFC-355 isomersName Formula Compound2,2-dichloro-1,1,1- trifluorobutane CF3CCl2CH2CH3 HCFC-363maf3,5,5-trichloro- 1,1,1,2,2,6,6,6- CF3CF2CHClCH2CCl2CF3 HCFC-548mafd octafluorohexane 1,3,6-trichloro-3-trifluoromethylpentane CH2ClCH2CCl(CF3)CH2CH2Cl HCFC-593syme1,5,5-trichloro-6,6,6- trifluorohexane CF3CCl2CH2CH2CH2CH2Cl HCFC-593maffftrichlorotrifluorohexane isomers C6H8Cl3F3 HCFC-593 isomerschlorotrifluoromethane CClF3 CFC-131,1,1-trichloro-2,2,2- trifluoroethane CF3CCl3 CFC-113a1,1-dichloro-1,2,2,2- tetrafluoroethane CF3CFCl2 CFC-114a1-chloro-1,1,2,2,2- pentafluoroethane CClF2CF3 CFC-1152,2,3,3-tetrachloro- 1,1,1,4,4,4- CF3CCl2CCl2CF3 CFC-316maa hexafluorobutane C5H2F8 C5H2F8 isomers C5HF9 C5HF9 isomers C5HClF8 C5HClF8 isomers C6H4F6 C6H4F6 isomers C6F8 C6F8 isomers C6H2F8 C6H2F8 isomers C6HF9 C6HF9 isomers C6F10 C6F10 isomers C6H2F10 C6H2F10 isomers C6H10 C6H10 isomers C6HF11 C6HF11 isomers C6F12 C6F12 isomers C6H2ClF7 C6H2ClF7 isomers C6HClF8 C6HClF8 isomers C6ClF9 C6ClF9 isomers C6H2ClF9 C6H2ClF9 isomers C6HClF10 C6HClF10 isomersName Formula CompoundC6ClF11 C6ClF11 isomers C6HCl2F7 C6HCl2F7 isomers C6HCl2F9 C6HCl2F9 isomers C6H2Cl3F7 C6H2Cl3F7 isomers C6HCl3F8 C6HCl3F8 isomers C6Cl3F7 C6Cl3F7 isomers C6Cl4F6 C6Cl4F6 isomers C7H5F7 C7H5F7 isomers C10H6Cl3F13 C10H6Cl3F13 isomers

Claims

CLAIMS What is claimed is:

1. A process for the preparation of E-1,1,1,2,2,5,5,6,6,6-decafluorohex-3-enecomprising: Step 1 wherein Step 1 comprises contacting ethylene with 1,1,1-trichloro-2,2,2- trifluoroethane in the presence a catalyst system comprising a metal and an organic ligand to obtain a process mixture (I) comprising 2,2,4-trichloro-1,1,1- trifluorobutane; Step 2 wherein Step 2 comprises contacting 2,2,4-trichloro-1,1,1- trifluorobutane with HF in the presence of a fluorination catalyst to obtain a process mixture (II) comprising 3,3,4,4,4-pentafluoro-1-butene and optionally one or more intermediates; Step 3 wherein Step 3 comprises contacting 3,3,4,4,4-pentafluoro-1-butene with 1,1,1-trichloro-2,2,2-trifluoroethane in the presence of a catalyst system comprising a metal and an organic ligand to obtain a process mixture (III) comprising 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane; and Step 4 wherein Step 4 comprises contacting 3,5,5-trichloro-1,1,1,2,2,6,6,6- octafluorohexane with HF in the presence of a fluorination catalyst to obtain a process mixture (IV) comprising E-1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene.

2. The process of claim 1, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; or between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the processmixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; or between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3; or following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

3. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1.

4. The process of claim 2, wherein the process further comprises, between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3,separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

5. The process of claim 4, wherein, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

6. The process of claim 5, wherein the Step 2 intermediates comprise one or more isomers of dichlorotrifluorobutenes, or one or more isomers of chlorotetrafluorobutenes.

7. The process of claim 6, wherein the Step 2 intermediates comprise one or more isomers of dichlorotrifluorobutenes.

8. The process of claim 6, wherein the Step 2 intermediates comprise one or more isomers of chlorotetrafluorobutenes.

9. The process of claim 6, wherein the Step 2 intermediates comprise one or more isomers of dichlorotrifluorobutenes and one or more isomers of chlorotetrafluorobutenes.

10. The process of claim 2, wherein the process further comprises, between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1- trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

11. The process of claim 10, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

12. The process of claim 2, wherein the process further comprises, following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

13. The process of claim 12, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

14. The process of claim 13, wherein the Step 4 intermediates comprise one or more isomers of chlorononafluorohexene.

15. The process of claim 14, wherein the Step 4 intermediates comprise 2-chloro- 1,1,1,2,5,5,6,6,6-nonafluorohex-3-ene.

16. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HFfrom the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

17. The process of claim 16, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

18. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; and between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6- octafluorohexane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4- pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

19. The process of claim 18, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

20. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; and following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

21. The process of claim 20, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4 22. The process of claim 2, wherein the process further comprises, between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating 3,5,5-trichloro- 1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro- 2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally,wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1- butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

23. The process of claim 22, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

24. The process of claim 22, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

25. The process of claim 23, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

26. The process of claim 2, wherein the process further comprises between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

27. The process of claim 26, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

28. The process of claim 26, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

29. The process of claim 27, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

30. The process of claim 2, wherein the process further comprises between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1- trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3; andfollowing Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

31. The process of claim 30, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

32. The process of claim 30, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

33. The process of claim 31, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

34. The process of claim 2, wherein between Steps 1 and 2, separating 2,2,4-trichloro- 1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2- trifluoroethane and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2)to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating 3,5,5-trichloro- 1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro- 2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1- butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

35. The process of claim 34, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

36. The process of claim 34, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

37. The process of claim 35, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

38. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; and between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6- octafluorohexane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4- pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3; and following Step 4, separating 1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

39. The process of claim 38, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

40. The process of claim 39, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

41. The process of claim 39, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating theStep 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

42. The process of claim 2, wherein the process further comprises, between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; between Steps 3 and 4, separating 3,5,5-trichloro- 1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1-trichloro-2,2,2-trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro- 2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1- butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4-pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3; and following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

43. The process of claim 42, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3,separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

44. The process of claim 42, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

45. The process of claim 42, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

46. The process of claim 43, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

47. The process of claim 43, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

48. The process of claim 44, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

49. The process of claim 46, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

50. The process of claim 2, wherein the process further comprises, between Steps 1 and 2, separating 2,2,4-trichloro-1,1,1-trifluorobutane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (I) and providing a recycle stream (1) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (1) to Step 1; and between Steps 2 and 3, separating 3,3,4,4,4-pentafluoro-1-butene from the process mixture (II), wherein the process mixture (II) comprises HF and optionally Step 2 intermediates, and the process further comprises, separating HF from the process mixture (II), providing a recycle stream (2) comprising HF, and feeding the recycle stream (2) to Step 2, optionally wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3, separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2; and between Steps 3 and 4, separating 3,5,5-trichloro-1,1,1,2,2,6,6,6-octafluorohexane and 1,1,1-trichloro-2,2,2- trifluoroethane from the process mixture (III), providing a recycle stream (3) comprising 1,1,1-trichloro-2,2,2-trifluoroethane and feeding the recycle stream (3) to Step 3, and optionally, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3; and following Step 4, separating 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene from the process mixture (IV), wherein the process mixture (IV) comprises HF and optionally Step 4 intermediates, and separating HF from the process mixture (IV), providing a recycle stream (4) comprising HF, and feeding the recycle stream (4) comprising to Step 4, and optionally, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

51. The process of claim 50, wherein the process mixture (II) further comprises Step 2 intermediates, and the process further comprises, between Steps 2 and 3,separating the Step 2 intermediates from the process mixture (II), providing a recycle stream (2a) comprising Step 2 intermediates and feeding the recycle stream (2a) to Step 2.

52. The process of claim 50, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

53. The process of claim 50, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

54. The process of claim 51, wherein the process mixture (III) comprises unreacted 3,3,4,4,4-pentafluoro-1-butene, and the process further comprises, between Steps 3 and 4, separating unreacted 3,3,4,4,4-pentafluoro-1-butene from the process mixture (III), providing a recycle stream (3a) comprising unreacted 3,3,4,4,4- pentafluoro-1-butene and feeding the recycle stream (3a) to Step 3.

55. The process of claim 51, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

56. The process of claim 52, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

57. The process of claim 54, wherein the process mixture (IV) further comprises Step 4 intermediates, and the process further comprises, following Step 4, separating the Step 4 intermediates from the process mixture (IV), providing a recycle stream (4a) comprising Step 4 intermediates and feeding the recycle stream (4a) to Step 4.

58. The process of any of claims 1-57, wherein the catalyst system in Step 1 comprises iron or copper and an organic ligand.

59. The process of any of claims 1-57, wherein the catalyst system in Step 3 comprises iron or copper and an organic ligand.

59. The process of claim 58 or 59, wherein the catalyst system comprises iron.

60. The process of claim 58 or 59, wherein the catalyst system comprises copper.

61. The process of claim 59, wherein the organic ligand is selected from the group consisting of a phosphine, phosphinite, phosphonate, phosphite, a phosphine oxide or a phosphate, and mixtures of two or more thereof.

62. The process of any of claims 1-61, wherein the fluorination catalyst used in Step 2 or 4, independently, comprises one or more metals, metal oxides, metal oxyfluoride or metal fluorides.

63. The process of claim 62, wherein the fluorination catalyst is chosen from one or more of Al, Sc, Y, Ti, Zr, Hf, V Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, La and Ce.

64. The process of claim 63, wherein the fluorination catalyst comprises one or more of Al, Zr, Cr, Co, Ni and Zn.

65. The process of claim 63, wherein the fluorination catalyst comprises Al2O3.

66. The process of claim 65, wherein the fluorination catalyst comprises Al2O3 and one or more of Zn, Zr, Cr, Co, and Ni.

67. The process of claim 63, wherein the fluorination catalyst comprises Cr2O3.

68. The process of claim 67, wherein the fluorination catalyst comprises Cr2O3 and one or more of Al, Zn, Zr, Co, and Ni.

69. The process of claim 63, the fluorination catalyst comprises chromium supported on AlF3, alumina, fluorinated alumina or activated carbon.

70. The process of claim 63, wherein the fluorination catalyst comprises zinc supported on AlF3, alumina, fluorinated alumina or activated carbon.

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