Process for the manufacture of halogen-substituted propanes containing hydrogen and at least five fluorine substituents

A process for producing a C.sub.3 HCl.sub.2 F.sub.5 product comprising the steps of:

• (a) charging a reactor with a fluorinated Cr.sub.2 O.sub.3 catalyst;
• and
• (b) reacting propylene, Cl.sub.2 and HF in the vapor phase at a temperature between about 275.degree.60 C. and 350.degree. C. for a selected contact time in the presence of said catalyst;
• the mole ratio of HF to propylene being from about 10:1 to 60:1 and the mole ratio of Cl.sub.2 to propylene being from about 5:1 to 25:1;
• and said contact time and temperature being chosen to provide a yield of at least about 20 mole percent of CF.sub.3 CCl.sub.2 CF.sub.2 based upon the moles of propylene reacted.

A process for producing a halohydrocarbon product selected from the group of halohydrocarbon products consisting of C.sub.3 HCl.sub.2 F.sub.5, C.sub.3 H.sub.2 ClF.sub.5, C.sub.3 HClF.sub.6, C.sub.3 H.sub.2 F.sub.6, and C.sub.3 HF.sub.7, comprising the steps of:

• (a) charging a reactor with (i) a catalyst consisting essentially of chromium oxide, (ii) a catalyst consisting essentially of chromium oxide in combination with a refractory oxide, (iii) a catalyst consisting essentially of chromium oxide modified with up to 10 percent by weight based upon the weight of chromium in the catalyst of metal selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc and mixtures thereof, (iv) a catalyst consisting essentially of chromium oxide in combination with a refractory oxide and modified with up to 10 percent by weight based upon the weight of chromium in the catalyst of metal selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc and mixtures thereof, or (v) a catalyst consisting essentially of a catalyst of (i), a catalyst of (ii), a catalyst of (iii), or a catalyst of (iv) which has been fluorinated;
• and
• (b) reacting at least one three-carbon reactant selected from the group of reactants consisting of propane, propylene, allene and halogenated acyclic three-carbon hydrocarbons containing at least one less fluorine substitutent than said selected product and at least as many hydrogen substituents as said selected product, at least a stoichiometric amount of Cl.sub.2 and at least a stoichiometric amount of HF in the vapor phase at an elevated temperature for a selected contact time in the presence of said catalyst;
• said contact time and temperature being chosen to provide a yield of at least about 20 mole percent of said selected product based upon the moles of said three-carbon reactants reacted, and to provide a product which comprises one or more products selected from C.sub.3 HCl.sub.2 F.sub.5 products including at least about 10 mole percent CF.sub.3 CCl.sub.2 CHF.sub.2 based upon the moles of three-carbon reactants reacted, C.sub.3 H.sub.2 F.sub.6 products including at least about 10 mole percent CHF.sub.2 CF.sub.2 CHF.sub.2 based upon the moles of three-carbon reactants reacted, and C.sub.3 HF.sub.7 products including at least about 10 mole percent CF.sub.3 CF.sub.2 CHF.sub.2 based upon the moles of three-carbon reactions reacted.