# US 10,246,388 B2 · Process for the reduction of RfC≡CX impurities in fluoroolefins > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,246,388 B2 - Document ID: US10246388B2 - Status: Granted - Kind: B2 - Application number: 15/609,292 - Filed: 2017-05-31 - Published: 2017-09-21 - Granted: 2019-04-02 - Earliest claimed: 2013-03-15 - Assignees: The Chemours Company Fc, LLC - Applicants: The Chemours Company Fc, LLC - Inventors: Mario Joseph Nappa; Xuehui Sun; David Richard Corbin - Web page: https://patentgrep.com/patent/US10246388B2 ## CPC - C07C 17/389: by adsorption on solids - C07C 17/087: to unsaturated halogenated hydrocarbons - C07C 17/25: by splitting-off hydrogen halides from halogenated hydrocarbons - Y02P 20/582: Recycling of unreacted starting or intermediate materials - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract This disclosure relates to processes which involve: contacting a mixture comprising at least one fluoroolefin and at least one RfC≡CX impurity with at least one zeolite to reduce the concentration of the at least one RfC≡CX impurity in the mixture; wherein Rf is a straight-chain perfluorinated alkyl group, and X is H, F, Cl, Br or I; and the at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that the at least one zeolite is not zeolite 4A. This disclosure also relates to processes for making at least one hydrotetrafluoropropene product selected from the group consisting of CF3CF═CH2, CF3CH═CHF, and mixtures thereof; and relates to processes for making at least one hydrochlorotrifluoropropene product selected from the group consisting of CF3CCl═CH2, CF3CH═CHCl, and mixtures thereof. ## Claims ### Claim 1 A process comprising: contacting a mixture comprising at least one fluoroolefin and at least one RfC≡CX impurity with at least one zeolite to reduce the concentration of said at least one RfC≡CX impurity in said mixture; wherein: (a) Rf is a straight-chain perfluorinated alkyl group, and X is H, F, Cl, Br or I; and (b) said at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that said at least one zeolite is not zeolite 4A. ### Claim 2 (depends on 1) The process of claim 1 wherein the amount of said at least one fluoroolefin in said mixture is at least 90 wt % based on the total weight of said mixture. ### Claim 3 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is selected from the group consisting of CF3CF═CH2, CF3CH═CHF, CF3CH═CH2, CF3CCl═CH2, CF3CH═CHCl, CF3CH═CFCl, CF3CH═CF2, CF3CCl═CHF, CF3CF═CHF, CF3CF═CHCl, CF3CH═CCl2, CF3CCl═CHCl, and mixtures thereof, and wherein said at least one RfC≡CX impurity is selected from the group consisting of CF3C≡CH, CF3C≡CCl, CF3C≡CF, and mixtures thereof. ### Claim 4 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is selected from the group consisting of CF3CF═CH2, CF3CH═CHF, CF3CH═CH2, CF3CCl═CH2, CF3CH═CHCl, CF3CF═CHCl, and mixtures thereof, and wherein said at least one RfC≡CX impurity is selected from the group consisting of CF3C≡CH, CF3C≡CCl, CF3C≡CF, and mixtures thereof. ### Claim 5 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is selected from the group consisting of CF3CF═CH2, CF3CH═CHF, CF3CCl═CH2, CF3CH═CHCl, and mixtures thereof and wherein said at least one RfC≡CX impurity is selected from the group consisting of CF3C≡CH, CF3C≡CCl, and mixtures thereof. ### Claim 6 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is CF3CF═CH2, and wherein said at least one RfC≡CX impurity is selected from the group consisting of CF3C≡CH, CF3C≡CCl, and mixtures thereof. ### Claim 7 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is CF3CF═CH2, and wherein said at least one RfC≡CX impurity is CF3C≡CH. ### Claim 8 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is CF3CH═CHF, and wherein said at least one RfC≡CX impurity is CF3C≡CH. ### Claim 9 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is a mixture of CF3CF═CH2 and CF3CH═CHF, and wherein said at least one RfC≡CX impurity is CF3C≡CH. ### Claim 10 (depends on 1) The process of claim 1 wherein said at least one fluoroolefin is CF3CH═CHCl, and wherein said at least one RfC≡CX impurity is CF3C≡CH. ### Claim 11 (depends on 1) The process of claim 1 wherein said at least one zeolite has a pore opening of at least about 5 Angstroms and a Sanderson electronegativity of no more than about 2.6. ### Claim 12 (depends on 1) The process of claim 1 wherein said at least one zeolite is selected from the group consisting of zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, zeolite AW-500, and mixtures thereof. ### Claim 13 (depends on 1) The process of claim 1 wherein said at least one zeolite is zeolite 5A, zeolite 13X, or mixtures thereof. ### Claim 14 (depends on 1) The process of claim 1 wherein the concentration of said at least one RfC≡CX impurity in said mixture is reduced to 300 ppm or less. ### Claim 15 (depends on 1) The process of claim 1 wherein the amount of said at least one RfC≡CX impurity in said mixture is reduced at least about 20%. ### Claim 16 (depends on 1) The process of claim 1 further comprising recovering said at least one fluoroolefin having reduced concentration of said at least one RfC≡CX impurity. ### Claim 17 A process for making at least one hydrotetrafluoropropene product selected from the group consisting of CF3CF═CH2, CF3CH═CHF, and mixtures thereof, comprising: (a) dehydrohalogenating at least one starting material selected from the group consisting of CF3CFClCH3, CF3CHFCH2Cl, CF3CHClCH2F, CF3CH2CHFCl, CF3CHFCH2F, CF3CH2CF2H, CF3CF2CH3, and mixtures thereof to produce a product mixture comprising CF3C≡CH impurity and said at least one hydrotetrafluoropropene product; (b) contacting said product mixture with at least one zeolite to reduce the concentration of said CF3C≡CH impurity in said product mixture; and (c) recovering said at least one hydrotetrafluoropropene product having reduced concentration of said CF3C≡CH impurity; wherein said at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that said at least one zeolite is not zeolite 4A. ### Claim 18 (depends on 17) The process of claim 17 wherein said at least one hydrotetrafluoropropene product is CF3CF═CH2, and said at least one starting material is selected from the group consisting of CF3CFClCH3, CF3CHFCH2Cl, CF3CHFCH2F, CF3CF2CH3, and mixtures thereof. ### Claim 19 (depends on 18) The process of claim 18 wherein said at least one starting material is CF3CFClCH3. ### Claim 20 (depends on 18) The process of claim 18 wherein said at least one starting material is CF3CHFCH2F. ### Claim 21 (depends on 17) The process of claim 17 wherein said at least one hydrotetrafluoropropene product is CF3CH═CHF, and said at least one starting material is selected from the group consisting of CF3CH2CHF2, CF3CH2CHFCl, CF3CHClCH2F, and mixtures thereof. ### Claim 22 The process of 17 wherein the concentration of said CF3C≡CH impurity in said product mixture is reduced to 300 ppm or less in the contacting step (b). ### Claim 23 (depends on 17) The process of claim 17 wherein the contacting step (b) reduces the amount of said CF3C≡CH impurity in said product by at least about 20% by weight relative to the amount originally present. ### Claim 24 A process for making at least one hydrochlorotrifluoropropene product selected from the group consisting of CF3CCl═CH2, CF3CH═CHCl, and mixtures thereof, comprising: (a) dehydrohalogenating at least one starting material selected from the group consisting of CF3CCl2CH3, CF3CHClCH2Cl, CF3CHClCH2F, CF3CH2CHCl2, CF3CHFCH2Cl, CF3CFClCH3, CF3CH2CHFCl, and mixtures thereof to produce a product mixture comprising CF3C≡CH impurity and said at least one hydrochlorotrifluoropropene product; (b) contacting said product mixture with at least one zeolite to reduce the concentration of said CF3C≡CH impurity in said product mixture; and (c) recovering said at least one hydrochlorotrifluoropropene product having reduced concentration of said CF3C≡CH impurity; wherein said at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that said at least one zeolite is not zeolite 4A. ### Claim 25 (depends on 24) The process of claim 24 wherein said at least one hydrochlorotrifluoropropene product is CF3CH═CHCl, and said at least one starting material is selected from the group consisting of CF3CHClCH2Cl, CF3CH2CHCl2, and mixtures thereof. ### Claim 26 (depends on 24) The process of claim 24 wherein said at least one hydrochlorotrifluoropropene product is CF3CHCl═CH2, and said at least one starting material is selected from the group consisting of CF3CHClCH2Cl, CF3CCl2CH3, and mixtures thereof. ### Claim 27 (depends on 24) The process of claim 24 wherein the concentration of said CF3C≡CH impurity in said product mixture is reduced to 300 ppm or less in the contacting step (b). ### Claim 28 (depends on 24) The process of claim 24 wherein the contacting step (b) reduces the amount of said CF3C≡CH impurity in said product by at least about 20% by weight relative to the amount originally present. ### Claim 29 (depends on 17) The process of claim 17 wherein said at least one zeolite has a pore opening of at least about 5 Angstroms and has a Sanderson electronegativity of no more than about 2.6. ### Claim 30 (depends on 17) The process of claim 17 wherein said at least one zeolite is selected from the group consisting of zeolite 5A, zeolite 13X, zeolite LSX, zeolite AW-300, zeolite AW-500, and mixtures thereof. ### Claim 31 (depends on 17) The process of claim 17 wherein said at least one zeolite is zeolite 5A, zeolite 13X, or mixtures thereof. ### Claim 32 A process for preparing 2,3,3,3-tetrafluoropropene comprising: (i) providing a starting composition including a compound of Formulae I, II, or III: CX2═CCl—CH2X (I); CX3—CCl═CH2 (II); or CX3—CHCl—CH2X (III) wherein X is independently selected from F, Cl, Br, and I, provided that at least one X is not fluorine; (ii) contacting the starting composition with a first fluorinating agent to produce a first intermediate composition including 2-chloro-3,3,3-trifluoropropene and a first chlorine-containing byproduct; (iii) contacting the first intermediate composition with a second fluorinating agent to produce a second intermediate composition including 2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoropropene; (iv) dehydrochlorinating at least a portion of the second intermediate composition including 2-chloro-1,1,1,2-tetrafluoropropane to produce a reaction product including 2,3,3,3-tetrafluoropropene and CF3C≡CH impurity; (v) contacting said reaction product produced in step (iv) with at least one zeolite to reduce the concentration of said CF3C≡CH impurity in said product mixture, wherein said at least one zeolite is selected from the group consisting of zeolites having pore opening of at least 4 Angstroms and no more than about 5 Angstroms, zeolites having pore opening of at least about 5 Angstroms and Sanderson electronegativity of no more than about 2.6, and mixtures thereof; provided that said at least one zeolite is not zeolite 4A; and (vi) recovering said 2,3,3,3-tetrafluoropropene from said product mixture of step (v), said 2,3,3,3-tetrafluoropropene having reduced concentration of said CF3C≡CH impurity present relative to that amount originally present in said reaction product of step (iv).