# US 9,000,238 B2 · Processes for separation of fluoroolefins from hydrogen fluoride by azeotropic distillation

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- Number: US 9,000,238 B2
- Document ID: US9000238B2
- Status: Granted
- Kind: B2
- Application number: 13/587,468
- Filed: 2012-08-16
- Published: 2012-12-06
- Granted: 2015-04-07
- Earliest claimed: 2006-08-24
- Assignees: E. I. Du Pont de Nemours and Company
- Applicants: Jeffrey P. Knapp; Barry Asher Mahler; Donald J. Toton
- Inventors: Jeffrey P. Knapp; Barry Asher Mahler; Donald J. Toton
- Web page: https://patentgrep.com/patent/US9000238B2

## CPC

- C07C 17/38: Separation; Purification; Stabilisation; Use of additives
- C01B 7/196: {by distillation}
- C07C 17/25: by splitting-off hydrogen halides from halogenated hydrocarbons
- C07C 17/383: by distillation
- C07C 17/386: with auxiliary compounds
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

The present disclosure relates to a process for separating a fluoroolefin from a mixture comprising hydrogen fluoride and fluoroolefin, comprising azeotropic distillation both with and without an entrainer. In particular are disclosed processes for separating any of HFC-1225ye, HFC-1234ze, HFC-1234yf or HFC-1243zf from HF.

## Claims

### Claim 1

A process for the purification of HF from a mixture comprising a fluoroolefin and HF, wherein HF is present in a concentration greater than the azeotrope concentration for HF and said fluoroolefin, said process comprising:
a. adding an entrainer to the mixture comprising fluoroolefin and HF thus forming a second mixture;
b. distilling said second mixture in a first distillation step to form a first distillate composition comprising an HF, entrainer, and fluoroolefin, and a first bottoms composition comprising HF;
c. condensing said first distillate composition to form two liquid phases, being i) an entrainer-rich phase and ii) an HF-rich phase; and
d. optionally recycling the HF-rich phase back to the first distillation step;
wherein said fluoroolefin comprises: (i) at least one compound selected from the group consisting of HFC-1225ye, HFC-1234ze, HFC-1234yf, and HFC-1243zf (ii) 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene (CHF═CHCF(CF3)2); and (iii) fluoroolefins of the formula E— or Z—R1CH═CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups and wherein the entrainer is selected from the group consisting of hydrocarbons, chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, fluoroethers, HFPO, SF6, chlorine, hexafluoroacetone, and mixtures thereof.

### Claim 2 (depends on 1)

The process of claim 1 further comprising feeding the entrainer-rich phase of step (c) to a second distillation step and forming a second distillate composition comprising an azeotrope of entrainer and HF and a second bottoms composition comprising HF essentially free of entrainer.

### Claim 3 (depends on 2)

The process of claim 2 further comprising recycling said second distillate composition back to the two liquid phases.

### Claim 4 (depends on 1)

The process of claim 1, wherein said entrainer is selected from the group consisting of:
a. hydrocarbon entrainers comprising at least one compound selected from the group consisting of: methane, ethane, ethylene, acetylene, vinylacetylene, n-propane, propylene, propyne, cyclopropane, cyclopropene, propadiene, n-butane, isobutane, 1-butene, isobutene, 1,3-butadiene, 2,2-dimethylpropane, cis-2-butene, trans-2-butene, 1-butyne, n-pentane, isopentane, neopentane, cyclopentane, 1-pentene, 2-pentene, and mixtures thereof;
b. chlorocarbon entrainers selected from the group consisting of methylene chloride, methyl chloride, and mixtures thereof;
c. chlorofluorocarbon (CFC) entrainers comprising at least one compound selected from the group consisting of: dichlorodifluoromethane (CFC-12), 2-chloro-1,1,2-trifluoroethylene, chloropentafluoroethane (CFC-115), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a), 1,1,2-trichloro-1,2,3,3,3-pentafluoropropane (CFC-215bb), 2,2-dichloro-1,1,1,3,3,3-hexafluoropropane (CFC-216aa), 1,2-dichloro-1,1,2,3,3,3-hexafluoropropane (CFC-216ba), 2-chloro-1,1,1,2,3,3,3-heptafluoropropane (CFC-217ba), 2-chloro-1,1,3,3,3-pentafluoropropene (CFC-1215xc), and mixtures thereof;
d. hydro chlorofluorocarbon (HCFC) entrainers comprising at least one compound selected from the group consisting of: dichlorofluoromethane (HCFC-21), 1,1-dichloro-3,3,3-trifluoroethane (HCFC-123), 1,1-dichloro-1-fluoroethane (HCFC-141 b), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 2-chloro-1,1,1-trifluoroethane (HCFC-133a), 1-chloro-1,1-difluoroethane (HCFC-142b), 2-chloro-1,1-difluoroethylene (HCFC-1122), and mixtures thereof;
e. hydrofluorocarbon (HFC) entrainers comprising at; least one compound selected from the group consisting of: 1,1,2-trifluoroethylene (HFC-1123), 1,1-difluoroethylene (HFC-1132a), 1,1,3,3,3-pentafluoropropene (HFC-1225zc), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), 1,3,3,3-tetrafluoropropene (HFC-1234ze), 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy), 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (HFC-162-13mczy), 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (HFC-162-13mcyz), and mixtures thereof;
f. perfluorocarbon (PFC) entrainers comprising at least one compound selected from the group consisting of: hexafluoroethane (PFC-116), octafluoropropane (PFC-218), 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY-2), hexafluoropropylene (HFP, PFC-1216), hexafluorocyclopropane (PFC-C216), octafluorocyclobutane (PFC-C318), decafluorobutane (PFC-31-10, all isomers), 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (PFC-1316mxx), octafluoro-2-butene (PFC-1318my, cis and trans), hexafluorobutadiene (PFC-2316), and mixtures thereof;
g. fluoroether entrainers comprising at least one compound selected from the group consisting of: trifluoromethyl-difluoromethyl ether (CF3OCHF2, HFOC-125E), 1,1-difluorodimethyl ether, tetrafluorodimethylether (HFOC-134E), difluoromethyl methyl ether (CHF2OCH3, HFOC-152aE), pentafluoroethyl methyl ether, and mixtures thereof; and
h. miscellaneous other compounds selected from the group consisting of HFPO, SF6, chlorine, hexafluoroacetone, PMVE (perfluoromethylvinylether), PEVE (perfluoroethylvinylether), and mixtures thereof.