Catalysts and process for gaseous phase fluorination of aliphatic chlorinated derivatives

Claim 2

A gaseous phase fluorination process which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (II±) oxide having a diameter of between about 100 to 3,000 μm: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated aliphatic hydrocarbons.

Claim 3

The process according to claim 1 wherein the sol contains from 1 to 10% of colloidal silica in proportion to the dry materials.

Claim 4

The process according to claim 1 wherein the sol and/or the solvent contains wetting agents and/or thickening agents.

Claim 5

The process according to claim 1 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 6

A gaseous phase fluorination process which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm, said chromium based catalysts prepared by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated aliphatic hydrocarbons.

Claim 7

A gaseous phase fluorination process which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm, said chromium based catalysts prepared by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated aliphatic hydrocarbons.

Claim 8

The process according to claim 5 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 9

A gaseous phase fluorination process which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activting the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocarbons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated aliphatic hydrocarbons.

Claim 10

A gaseous phase fluorination process which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activting the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocarbons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated aliphatic hydrocarbons.

Claim 11

The process according to claim 7 wherein the sol contains from 1 to 10% of colloidal silica in proportion to the dry materials.

Claim 12

The process according to claim 7 wherein the sol and/or the solvent contains wetting agents and/or thickening agents.

Claim 13

The process according to claim 7 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 14

A gaseous phase fluorination process which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocabons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated alipahtic hydrocarbons.

Claim 15

A gaseous phase fluorination process which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocabons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor for a sufficient time to produce fluorinated or fluorochlorinated alipahtic hydrocarbons.

Claim 16

The process according to claim 11 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 17

A gaseous phase fluorination process for forming symmetric isomers, of fluorinated aliphatic hydrocarbons which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the miscrospheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 18

A gaseous phase fluorination process for forming symmetric isomers, of fluorinated aliphatic hydrocarbons which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the miscrospheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 19

The process according to claim 13 wherein the sol contains from 1 to 10% of colloidal silica in proportion to the dry materials.

Claim 20

The process according to claim 13 wherein the sol and/or the solvent contains wetting agents and/or thickening agents.

Claim 21

The process according to claim 13 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 22

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm, said chromium based catalysts prepared by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 23

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which comprises: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm, said chromium based catalysts prepared by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 24

The process according to claim 17 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 25

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 26

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semi-colloidal suspension of hydroxide of chromium from a mixture comprising an aqueous solution of a chromium salt, ammonia, and hexamethylenetetramine; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting chlorinated aliphatic hydrocarbons with hydrofluoric acid in the presence of said catalyst in a fluidized bed reactor.

Claim 27

The process according to claim 19 wherein the sol contains from 1 to 10% of colloidal silica in proportion to the dry materials.

Claim 28

The process according to claim 19 wherein the sol and/or the solvent contains wetting agents and/or thickening agents.

Claim 29

The process according to claim 19 wherein the gelling of the sol is effected in 2-ethylhexanol.

Claim 30

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocarbons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor.

Claim 31

A gaseous phase fluorination process for forming symmetric isomers of fluorinated aliphatic hydrocarbons which consists essentially of: preparing catalysts having a chromium oxide base consisting essentially of unsupported amorphous chromium (III) oxide having a diameter of between about 100 to 3,000 μm by: (a) forming a sol or semicolloidal suspension of hydroxide of chromium by the reduction of an aqueous solution of chromium trioxide by an alcohol; (b) gelling the sol in the form of microspheres, at an elevated temperature, in an organic solvent that is non-miscible or partially miscible in water; (c) washing the microspheres in ammonia and water; (d) drying the microspheres; and (e) thermally activating the microspheres at a temperature between about 200° and 500° C.; and contacting aliphatic chlorinated hydrocarbons with hydrofluoric acid in the presence of a catalyst in a fluidized bed reactor.

Claim 32

The process according to claim 23 wherein the gelling of the sol is effected in 2-ethylhexanol.