E.i. Dupont De Nemours and Company

V N Rao

Leo E Manzer

Allen Capron Sievert

Mario Joseph Nappa

Frank J Weigert

William H Manogue

Carl G Krespan

Carl S Kellner

David Richard Corbin

Munirpallam Appadorai Subramanian

Ralph Newton Miller

Steven Henry Swearingen

Jan J Lerou

Edwin J Warwas

Michael A Sisk

Richard T Rockwell

Roy Winteringham

Leo Ernest Manzer

Barry Asher Mahler

Ronald James McKinney

Ponnattu Kurian Joseph

Michael Grant Topor

Richard E Fernandez

Pravin Maganlal Desai

William H Gumprecht

William C Seidel

Stanislaw Bogdan Ziemecki

Walter Vladimir Cicha

Vincent Allen Elder

John Gregory Fulcher

Alfred Waterfeld

Joseph Stuart Thrasher

Douglas W Bruhnke

William Robert Williams

Francis John Walczak

Klaus Guenter Wuttke

Norman A Nielsen

Andreas Josef Kornath

Klaws G Wuttke

Eric Boudreaux

Gerald James Vogel

Wu Li

A process is disclosed for increasing the fluorine content of a saturated or olefinic halogenated hydrocarbon starting material of the formula C.sub.n H.sub.a Cl.sub.b F.sub.c, wherein n is an integer from 1 to 6, a is an integer from 0 to to 12, b is an integer from 0 to 13 and c is an integer from 0 to 13. The process involves contacting the starting material in the vapor phase at a temperature in the range of about 150.degree. C. to about 500.degree. C. with HF and a catalytic metal supported on a trivalent lanthanum compound support (the catalytic metal being chromium, cobalt, nickel, zinc, magnesium, copper, silver and/or gold). Certain catalytic compositions including catalytic metal (e.g., chromium, nickel, cobalt, zinc and/or magnesium) supported on a support at trivalent lanthanum compound containing fluoride anion are also disclosed. The atomic ratio of catalytic metal to lanthanum in the compositions is from about 1:1 to 1:999.

Catalytic hydrofluorination processes and catalysts

A process is disclosed for recovering at least one perfluorocycloalkane selected from the group consisting of octafluorocyclobutane, hexafluoro-bis(trifluoromethyl)cyclobutane (1,2 and 1,3; cis and trans), and heptafluoro(trifluoromethyl)cyclobutane from a mixture comprising (a) the perfluorocycloalkane, (b) olefinic impurity and, optionally, (c) saturated chlorine-containing impurity selected from the group consisting of chlorocarbons, hydrochlorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons and mixtures thereof. The process involves (1) contacting the mixture with hydrogen in the presence of a hydrogenation catalyst under conditions suitable for converting at least a portion of the olefinic impurity to a saturated impurity containing at least one fluorine substituent less than the olefin impurity and reducing the chlorine content of at least a portion of the saturated chlorine-containing impurity (if present), and (2) separating said at least one perfluorocycloalkane from the products produced during the hydrogenation of (1).

Process for perfluorocycloalkane purification

A process is disclosed for recovering at least one perhalocycloalkane selected from the group consisting of octafluorocyclobutane, hexafluoro-bis(trifluoromethyl)cyclobutane (1,2 and 1,3; cis and trans), 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane (cis and trans), 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1-chloro-1,2,2,3,3,4-hexafluoro-4-(trifluoromethyl)-cyclobutane, heptafluoro(trifluoromethyl)cyclobutane and chloroheptafluoro-cyclobutane from a mixture comprising (a) the perhalocycloalkane, (b) olefinic impurity and optionally (c) saturated fluorine-containing impurity selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons and mixtures thereof. The process involves (1) contacting the mixture with chlorine under conditions suitable for chlorinating the olefinic impurity, thereby converting the olefinic impurity to a saturated impurity containing at least one chlorine substituent and reducing the hydrogen content of the saturated fluorine-containing impurity (if present), and (2) separating said at least one perhalocycloalkane from the products produced during the chlorination of (1). Also disclosed is a process for producing n-decafluorobutane. The process involves contacting a mixture comprising octafluorocyclobutane (i.e., C-318) and 1,1,1,2,3,4,4,4-octafluorobutene-2 (FC-1318my) with chlorine under conditions suitable for converting the FC-1318my to 2,3-dichloro-1,1,1,2,3,4,4,4-octa-fluorobutane (i.e., CFC-318mbb); separating the C-318 from the CFC-318mbb; and reacting the CFC-318mbb with HF.

Process for perhalocycloalkane purification

A process is disclosed for recovering HF from a product mixture including HF and CF.sub.3 CF.sub.2 CHF.sub.2. The process involves (1) distilling the product mixture to remove all products which have a lower boiling point than the lowest boiling azeotrope containing HF and CF.sub.3 CF.sub.2 CHF.sub.2 ; and (2) distilling the azeotrope to recover HF as an azeotropic composition containing HF and CF.sub.3 CF.sub.2 CHF.sub.2. Also disclosed are compositions of hydrogen fluoride in combination with an effective amount of CF.sub.3 CF.sub.2 CHF.sub.2 to form an azeotrope or azeotrope-like composition with hydrogen fluoride, (e.g., compositions containing from about 57.1 to 67.2 mole percent CF.sub.3 CF.sub.2 CHF.sub.2). A process for producing certain compositions comprising

Compositions comprising CF.sub.3 CF.sub.2 CHF.sub.2 and their manufacture

A process is disclosed for producing the hydrofluorocarbon CF.sub.3 CH.dbd.CF.sub.2. The process involves dehydrofluorinating CF.sub.3 CH.sub.2 CF.sub.3 at an elevated temperature in the vapor phase over a catalyst of (1) aluminum fluoride, (2) fluorided alumina, (3) metal supported on a trivalent aluminum compound containing fluoride anion, (4) lanthanum fluoride, (5) fluorided lanthanum oxide, (6) metal supported on a trivalent lanthanum compound containing fluoride anion, (7) trivalent chromium compounds and/or (8) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum, provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less, to produce a product containing CF.sub.3 CH.dbd.CF.sub.2 and HF. The CF.sub.3 CH.dbd.CF.sub.2 may then be reacted in the vapor phase with hydrogen over a hydrogenation catalyst in the presence of HF to produce CF.sub.3 CH.sub.2 CHF.sub.2.

Process for the manufacture of 1,1,1,3,3-pentafluoropropane

A process is disclosed for recovering HF from a product mixture comprising HF and at least one compound having the formula CF.sub.3 CCl.sub.2+x F.sub.1-x (where x is 0 or 1). The process includes the steps of distilling the product mixture to remove all products which have a lower boiling point than the lowest boiling azeotrope containing HF and said at least one compound; and distilling said azeotrope to recover HF as an azeotropic composition containing HF and said at least one compound. Also disclosed are azeotrope and azeotrope-like compositions which consist essentially of hydrogen fluoride in combination with from about 10 to 27 mole percent CCl.sub.3 CF.sub.3 or from about 35 to 56 mole percent CCl.sub.2 FCF.sub.3.

Azeotropes of chlorofluoroethanes of the formula CF.sub.3 CC1.sub.2+x    ub

A process is disclosed for producing HCFC-133a which includes reacting certain trihaloethene starting materials (e.g., trichloroethene) with HF in the gaseous phase at an elevated temperature in the presence of certain supported metal catalysts containing effective amounts of zinc. A catalyst of metal fluoride on a fluorinated alumina support having an atomic ratio of F to Al of at least 2.7:1 and containing .beta.-aluminum fluoride, is employed.

Process for the manufacture of 2-chloro-1,1,1-trifluoroethane

This invention provides a crystalline chromium fluoride having a cubic crystal structure (i.e., chromium trifluoride having an X-ray diffraction powder pattern as shown in Table I); and a catalytic composition comprising cubic chromium trifluoride. This invention also provides a process for changing the fluorine content of halogenated hydrocarbons containing from one to six carbon atoms, in the presence of a chromium-containing catalyst. The process is characterized by the chromium-containing catalyst comprising cubic chromium trifluoride.

Cubic chromium trifluoride and its use for halogenated hydrocarbon

A process is disclosed for the separation of a mixture of HF and CF.sub.3 CClFCF.sub.3. The process involves placing the mixture in a separation zone at a temperature of from about -30.degree. C. to about 100.degree. C. and at a pressure sufficient to maintain the mixture in the liquid phase, whereby an organic-enriched phase comprising less than 50 mole percent HF is formed as the bottom layer and an HF-enriched phase comprising more than 90 mole percent HF is formed as the top layer. The organic-enriched phase can be withdrawn from the bottom of the separation zone and subjected to distillation in a distillation column to recover essentially pure CF.sub.3 CClFCF.sub.3. The distillate comprising HF and CF.sub.3 CClFCF.sub.3 can be removed from the top of the distillation column while essentially pure CF.sub.3 CClFCF.sub.3 can be recovered from the bottom of the distillation column. The HF-enriched phase can be withdrawn from the top of the separation zone and subjected to distillation in a distillation column. The distillate comprising HF and CF.sub.3 CClFCF.sub.3 can be removed from the top of the distillation column while essentially pure HF can be recovered from the bottom of the distillation column. If desired, the two distillates can be recycled to the separation zone. Also disclosed are compositions of hydrogen fluoride in combination with an effective amount of CF.sub.3 CClFCF.sub.3 to form an azeotrope or azeotrope-like composition with hydrogen fluoride. Included are compositions containing from about 38.4 to 47.9 mole percent CF.sub.3 CClFCF.sub.3. Also disclosed are processes for producing 1,1,1,2,3,3,3-heptafluoropropane. One process uses a mixture comprising HF and CF.sub.3 CClFCF.sub.3 and is characterized by preparing essentially pure CF.sub.3 CClFCF.sub.3 as indicated above, and reacting the CF.sub.3 CClFCF.sub.3 with hydrogen. Another process uses an azeotropic composition as described above, and reacts the CF.sub.3 CClFCF.sub.3 with hydrogen in the presence of HF. Also disclosed is a process for producing hexafluoropropene. This process is characterized by preparing essentially pure CF.sub.3 CClFCF.sub.3 as indicated above, and dehalogenating the CF.sub.3 CClFCF.sub.3.

Process for the production of fluorocarbons

A process is disclosed for producing 1,1,2,2,3,3,4,4-octafluorobutane. The process involves (a) reacting a mixture comprising 2,2,3,3-tetrafluorobutane and chlorine to form a mixture of chloro-compounds wherein compounds of the formula C.sub.4 H.sub.x Cl.sub.6-x F.sub.4 (where x is 0 or 1) comprise at least about 50 mole % of the mixture of chloro-compounds; (b) contacting certain chloro-compounds from (a) and hydrogen fluoride with a fluorination catalyst to form a mixture of fluoro-compounds; and (c) contacting certain fluoro-compounds from (b) and hydrogen with a hydrogenolysis catalyst to produce CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2. Sufficient chloro-compounds formed in (a) and sufficient fluoro-compounds formed in (b) are recycled to provide a selectivity to CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2 of at least about 75% based upon the moles of CH.sub.3 CF.sub.2 CF.sub.2 CH.sub.3 reacted in (a). Also disclosed is a process for the purification of at least one compound selected from the group consisting of CCl.sub.2 F(CF.sub.2).sub.2 CCl.sub.3, CCl.sub.2 F(CF.sub.2).sub.2 CCl.sub.2 F, CCl.sub.2 F(CF.sub.2).sub.2 CClF.sub.2, CClF.sub.2 (CF.sub.2).sub.2 CClF.sub.2, CClF.sub.2 (CF.sub.2).sub.2 CF.sub.3, CHCl.sub.2 (CF.sub.2).sub.2 CCl.sub.2 F, CHClF(CF.sub.2).sub.2 CCl.sub.3, CHCl.sub.2 (CF.sub.2).sub.2 CClF.sub.2, CHClF(CF.sub.2).sub.2 CCl.sub.2 F, CHF.sub.2 (CF.sub.2).sub.2 CCl.sub.3, CHClF(CF.sub.2).sub.2 CClF.sub.2, CHF.sub.2 (CF.sub.2).sub.2 CCl.sub.2 F, CHCl.sub.2 (CF.sub.2).sub.2 CF.sub.3, CHClF(CF.sub.2).sub.2 CF.sub.3, CHF.sub.2 (CF.sub.2).sub.2 CClF.sub.2, CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2, CHF.sub.2 CF.sub.2 CF.sub.2 CH.sub.2 F, CHF.sub.2 CF.sub.2 CF.sub.2 CF.sub.3 and CH.sub.2 FCF.sub.2 CF.sub.2 CF.sub.3 from a mixture of HF and said at least one compound. The purification process involves (a) subjecting the mixture of HF and said compound(s) to a distillation step in which a first distillate is removed; (b) subjecting said first distillate to an additional distillation as described herein; and (c) recovering said compound(s) essentially free of HF as bottoms from either the distillation of (a) or the distillation of (b). New compounds CCl.sub.2 FCF.sub.2 CF.sub.2 CClF.sub.2, CCl.sub.3 CF.sub.2 CF.sub.2 CCl.sub.2 F, CHCl.sub.2 CF.sub.2 CF.sub.2 CCl.sub.3, CHCl.sub.2 CF.sub.2 CF.sub.2 CCl.sub.2 F, CHClFCF.sub.2 CF.sub.2 CCl.sub.3, CHCl.sub.2 CF.sub.2 CF.sub.2 CClF.sub.2, CHClFCF.sub.2 CF.sub.2 CCl.sub.2 F, CHF.sub.2 CF.sub.2 CF.sub.2 CCl.sub.3, CHF.sub.2 CF.sub.2 CF.sub.2 CCl.sub.2 F, CHClFCF.sub.2 CF.sub.2 CF.sub.3, CH.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 Cl and CH.sub.2 ClCF.sub.2 CF.sub.2 CCl.sub.3 are also disclosed, as are compositions which comprise hydrogen fluoride in combination with an effective amount of CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2 to form an azeotrope or azeotrope-like composition with hydrogen fluoride.

Processes for the manufacture and purification of

A process is disclosed for producing the hydrofluorocarbon CF.sub.3 CH.sub.2 CHF.sub.2. The process involves dehydrofluorinating CF.sub.3 CH.sub.2 CF.sub.3 at an elevated temperature in the vapor phase over a catalyst of (1) aluminum fluoride, (2) fluorided alumina, (3) metal supported on a trivalent aluminum compound containing fluoride anion, (4) lanthanum fluoride, (5) fluorided lanthanum oxide, (6) metal supported on a trivalent lanthanum compound containing fluoride anion, (7) trivalent chromium compounds and/or (8) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum, provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less, to produce a product containing CF.sub.3 CH.dbd.CF.sub.2 and HF; and reacting the CF.sub.3 CH.dbd.CF.sub.2 in the vapor phase with hydrogen over a hydrogenation catalyst in the presence of HF to produce CF.sub.3 CH.sub.2 CHF.sub.2.

A process is disclosed for enriching the amount of CFC-114 relative to the amount of CFC-114a from an initial mixture containing both isomers, by contacting said initial mixture with hydrogen chloride in the vapor phase at an elevated temperature in the presence of a catalyst to produce a product mixture containing C.sub.2 Cl.sub.2 F.sub.3 and chlorination products of CCl.sub.2 FCF.sub.3 wherein the weight ratio of CClF.sub.2 CClF.sub.2 to the total C.sub.2 Cl.sub.2 F.sub.4 is higher than the weight ratio of CClF.sub.2 CClF.sub.2 to the total C.sub.2 Cl.sub.2 F.sub.4 in the initial mixture. The chlorination products of CFC-114a (e.g., CCl.sub.3 CF.sub.3) in the product mixture may then be separated from the C.sub.2 Cl.sub.2 F.sub.4 therein (e.g., by distillation).

Process for enriching 1,2-dichloro-1,1,2,2-tetrafluoroethane from a

A process is disclosed for producing 1,12,2,3,3,4,4-octafluorobutane. The process involves chlorination of 2,2,3,3-tetrafluorobutane to form a mixture of chloro-compounds wherein compounds of the formula C.sub.4 H.sub.4 Cl.sub.6-x F.sub.4 (where x is 0 or 1) comprise at least 50 mole % of the mixture of chloro-compounds, followed by hydrofluorination, then hydrogenolysis, and sufficient recycle to provide a selectivity to CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2 of at least about 75% based upon the moles of CH.sub.3 CF.sub.2 CF.sub.2 CH.sub.3 reacted. Also disclosed is a multi-distillation process for the purification of CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2 from a mixture of HF and the compound(s). Also disclosed are certain new halogenated butanes containing fluorine, and a composition which contains HF in combination with an effective amount of CHF.sub.2 CF.sub.2 CF.sub.2 CHF.sub.2 to form an azeotrope or azeotrope-like composition with hydrogen fluoride.

A process is disclosed for preparing a perfluoroalkyl sulfonate of the formula R.sub.a MX.sub.b-c O.sub.g �(SO.sub.3).sub.d (R.sub.f).sub.e !.sub.c. This process involves reacting a reagent of the fonnula R.sub.a MX.sub.b O.sub.g and a second reagent of the formula R'.sub.x E�(SO.sub.3).sub.d (R.sub.f).sub.e !.sub.y, where

Perfluoroalkyl sulfonates, their preparation and use

The fluorine content of an acyclic saturated compound of the formula C.sub.n F.sub.a X.sub.b H.sub.c (wherein each X is independently selected from the group consisting of Cl and Br, and wherein n is 1 to 6, a is 1 to 13, b is 0 to 12, c is 1 to 9, and a+b+c equals 2n+2) is reduced by reacting the acyclic saturated compound with HCl in the vapor phase at an elevated temperature in the presence of a catalyst, the mole ratio of HCl to the acyclic saturated compound being at least about 1:1.

Growing community of inventors

Wilmington, DE, United States of America

V N Rao