E.i. Dupont De Nemours and Company

V N Mallikarjuna Rao

Allen Capron Sievert

Steven Henry Swearingen

Barry Asher Mahler

Mario Joseph Nappa

Leo Ernest Manzer

Munirpallam Appadorai Subramanian

Ralph Newton Miller

Carl G Krespan

Frank J Weigert

William H Manogue

Edwin J Warwas

Francis John Walczak

Michael Keane, Jr

David A Glasscock

Paul S Furmanek

The fluorine content of an acyclic saturated compound of the formula C F X H (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&plus;b&plus;c equals 2n&plus;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.

Process for reducing the fluorine content of hydrofluorocarbons and hydrohalofluorocarbons

A process for the manufacture of CF CF&boxH;CF is disclosed. The process involves contacting 2,3-dichloro-1,1,1,2,3,3-hexafluoropropane with at least 0.1 mole of hydrogen in a reaction vessel of titanium, nickel or iron or their alloys, which is either empty or packed with particles or formed shapes of titanium, nickel or iron or their alloys, at a temperature within the range of from about 350&deg; C. to about 600&deg; C. and for a time sufficient to produce hexafluoropropene. Also disclosed are compositions which comprise hydrogen fluoride in combination with an effective amount of CClF CClFCF to form an azeotrope or azeotrope-like composition with hydrogen fluoride. The compositions contain from about 8.7 to 33.6 mole percent CClF CClFCF .

Process for the production of hexafluoropropylene from CClF2CClFCF3 and azeotropes of CClF2CClFCF3 with HF

Processes for the purification and use of 2-chloro-1,1,1,2,3,3,3-heptafluoropropane and zeotropes thereof with HF

Compositions comprising hydrofluorocarbons and their manufacture

A process is disclosed for producing the pentfluropropenes of the formula CF CX&boxH;CF , where X is H or Cl. The process involves hydrodehalogenating CF CCl CF with hydrogen at an elevated temperature in the vapor phase over a catalyst comprising an elemental metal, metal oxide, metal halide and/or metal oxyhalide (the metal being copper, nickel, chromium and the halogen of said halides and said oxyhalides being fluorine and/or chlorine. Processes for producing the hydrofluorocarbons CF CH CHF , CF CHFCF and CF CH CF are also disclosed which involve (a) hydrodehalogenating CF CCl CF with the hydrogen as indicated above to produce a product comprising CF CCl&boxH;CF , CF CH&boxH;CF , HCl and HF; and (b) either reacting the CF CCl&boxH;CF and/or CF CH&boxH;CF produced in (a) in the vapor phase with hydrogen to produce CF CH CHF , reacting CF CCl&boxH;CF produced in (a) with HF to produce CF CHFCF , or reacting the CF CH&boxH;CF produced in (a) with HF to produce CF CH CF . Azeotrope compositions of CF CHFCH with HF, and a process for recovering HF from a product mixture comprising HF and CF CHFCF are also disclosed. Also disclosed are compositions and a process for producing compositions comprising (c1) CF CHFCF , CF CH CF or CHF CH CF and (c2) at least one saturated halogenated hydrocarbon and/or ether having the formula: C H Cl F O wherein n is an integer from 1 to 4, a is an integer from 0 to 2n&plus;1, b is an integer from 1 to 2n&plus;2&minus;a, and c is 0 or 1, provided that when c is 1 then n is an integer from 2 to 4, and provided that component (c2) does not include the selected component (c1) compound, wherein the molar ratio of component (c2) to component (c1) is between about 1:99 and a molar ratio of HF to component (c1) in an azeotrope or azeotrope-like composition of component (c1) with HF. The process involves (A) combining (i) the azeotropic composition with (ii) the fluorination precursor to component (c2); and (B) reacting a sufficient amount of the HF from the azeotrope or azeotrope-like composition(i) with precursor component (ii) to provide a composition containing components (c1) and (c2) in the desired ratio. The compositions include at least two (c1) compounds, at least one of which is an ether.

Process for the manufacture of 1,1,1,3,3-pentafluoropropene, 2-chloro-pentafluoropropene and compositions comprising saturated derivatives thereof

Process for the production of hexafluoropropylene from CC1F2CC1FCF3 and azeotropes of CC1F2CC1FCF3 with HF

Disclosed are azeotropic compositions comprising CF CHFCF and HF. Also disclosed are compositions and a process for producing compositions comprising (c1) CF CHFCF , CF CH CF , or CHF CH CF , and (c2) at least one saturated halogenated hydrocarbon and or ether having the formula: C H Cl F O wherein n is an integer from 1-4, a is an integer from 0-2n&plus;1, b is an integer from 1-2n&plus;2a, and c is 0 or 1, provided that when c is 1 then n is an integer from 2-4, and provided that component (c2) does not include the selected component (c1) compound, wherein the molar ratio of component (c2) to component (c1) is between about 1:99 and a molar ratio of HF to component (c1) in an azeotrope or azeotrope-like composition of component (c1) with HF. The process involves (A) combining (1) the azeotropic composition with (ii) the fluorination precursor to component (c2); and (B) reacting a sufficient amount of the HF from the azeotrope or azeotrope-like composition (1) with the precursor component (ii) to provide a composition containing components (c1) and (c2) in the desired ratio. The compositions include at least two (c1) compounds, at least one of which is an ether.

Processes for the manufacture of 1,1,1,3,3-pentafluoropropene, 2-chloro-pentafluoropropene and compositions comprising saturated derivatives thereof

A process is disclosed for the manufacture of CF,CF&boxH;CF,, and optionally a least one compound selected from CF,CH,CF,and CF,CHFCHF,. The process involves contacting a reactor feed including a precursor stream of at least one halogenated propane of the formula CX,CH,CH,X,and/or halogenated propene of the formula CX,CH&boxH;CH,X,, where each X is Cl or F and y is 0, 1 or 2 (provided that the average fluorine content of the precursor stream is no more than 5 fluorine substituents per molecule) with HF and Cl,in a chlorofluorination reaction zone containing a fluorination catalyst and operating at a temperature between about 150&deg; C. and 400&deg; C., to produce a reaction zone effluent including HF, HCl and a mixture of reaction products of the precursor feed which contains at least one compound of the formula C,Cl,F,including CClF,CClFCF,and at least one compound of the formula C,HClF,, including CHF,CClFCF,and has an average fluorine content which is at least one fluorine substituent per molecule more than the average fluorine content of the precursor stream. The chlorofluorination reaction zone effluent is distilled to produce (i) a low-boiling component including HCl (and when they are present in the reaction zone effluent, C,F,, C,ClF,and C,HF,), (ii) a hydrogenation feed component containing at least one compo of the formula C,Cl,F,including CClF,CClFCF,and at least one compound of the formnula C,HClF,including CHF,CClFCF,, and an underfluorinated component including halogenated propanes containing at least one chlorine subtituent and from one to five fluorine substituents. The CClF,CClFCF,and CHF,CClFCF,of hydrogenation feed component (ii) is reacted with hydrogen to produce a mixture including CF,CF&boxH;CF,and CF,CHFCHF,and the CF,CF&boxH;CF,from this product mixture is recovered. Underfluorinated component (iii) is returned to the chlorofluorination reaction zone.

Processes for the production of hexafluoropropene and optionally other halogenated hydrocarbons containing fluorine

A highly selective process is disclosed for the hydrogenolysis of 2,2-dichlorohexafluoropropane (i.e., CFC-216aa or CF,CCl,CF,) to 2,2-dihydrohexafluoropropane (i.e., HFC-236fa or CF,CH,CF,) and 2-chloro-2-hydrohexafluoropropane (i.e., 226da or CF,CHClCF,). The process involves reacting the starting material with hydrogen at an elevated temperature of about 300&deg; C. or less in the presence of a catalyst containing a catalytically effective amount of palladium supported on a support of fluorinated alumina and/or aluminum fluoride.

Halofluorocarbon hydrogenolysis

A process is disclosed for the manufacture of CF,CHFCF,containing less than 0.01 ppm (CF,),C&boxH;CF,. The process involves (a) contacting hexafluoropropene in the vapor phase at a temperature of less than about 260&deg; C. with hydrogen fluoride in the presence of a selected fluorination catalyst or produce a product containing less than 10 parts (CF,),C&boxH;CF,per million parts of CF,CHFCF,; and (b) treating the product of (a) as necessary to remove excess (CF,),C&boxH;CF,. Suitable catalysts include: (i) an activated carbon treated to contain from about 0.1 to about 10 weight % added alkali or alkaline earth metals, (ii) three dimensional matrix porous carbonaceous materials, (iii) supported metal catalysts comprising trivalent chromium, and (iv) unsupported chrome oxide prepared by the pyrolysis of (NH,),Cr,O,.

1,1,1,2,3,3,3-heptafluoropropane manufacturing process

A halocarbon product made from the reaction of excess hydrogen fluoride with a halocarbon, containing excess hydrogen fluoride as an azeotrope is purified by fluorination in the presence of additional halocarbon or halo-olefin.

Fluorocarbon purification process

A process is disclosed for changing the fluorine content of halogenated hydrocarbons containing from 1 to 6 carbon atoms, in the presence of a multiphase catalyst. The process involves producing the catalyst by heating a single phase solid catalyst precursor having the formula (NH,),Cr,M,F,(where x is in the range of 0.1 to 1 and M is at least one metal selected from the group consisting of Al, Sc, V, Fe, Ga and In) to about 400&deg; or less to produce a multiphase composition wherein a phase containing crystalline M fluoride is homogeneously dispersed with a phase containing chromium fluoride. Also disclosed are multiphase catalyst compositions consisting essentially of chromium fluoride and a crystalline fluoride of at least one metal selected from the above group (provided the atom percent of Cr is at least equal to the atom percent of the crystalline fluoride metals). Phases of the crystalline fluorides are homogeneously dispersed with phases of the chromium fluoride. Preparation of homogeneously dispersed multiphase catalyst compositions consisting essentially of fluorides of chromium and crystalline fluorides of at least one other metal selected from the above group (the atom percent Cr being at least equal to the atom percent of the other metal(s)) is also disclosed.

Catalysts for halogenated hydrocarbon processing and their preparation and use

A process for producing difluoromethane is disclosed which includes the step of contacting a gaseous mixture containing CH,Cl,and hydrogen fluoride with a catalyst containing a catalytically effective amount of trivalent chromium supported on a carbon having an ash content of less than 0.5 percent by weight, at a temperature of from about 180 &deg; C. to about 375&deg; C. The catalyst and temperature conditions of this process allow the concurrent reaction CCl,CF,with HF to form CCl,FCF,. CH,ClF and unreacted CH,Cl,, each of which may be recovered as an azeotrope with HF, may be recycled.

Production of dihalomethanes containing fluorine and azeotropes of dihalomethanes containing chlorine with HF

This invention relates to a process for the production of vinyl fluoride by dehydrofluorination of 1,1-difluoroethane in the presence of a catalyst containing magnesium and/or zinc.

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Wilmington, DE, United States of America

V N Mallikarjuna Rao