Liquid acid alkylation catalyst and isoparaffin-olefin alkylation process

A process for alkylating an isoparaffin with an olefin comprising effecting reaction of isoparaffin and olefin with an alkylation catalyst composition comprising:

• (a) hydrofluoric acid;
• (b) an additive in admixture with said hydrofluoric acid, said additive selected from the group consisting of the compounds having the formula R'--(NO.sub.2), wherein R' is an alkyl, aromatic, alkyl halide, or halide-substituted aromatic group having from about 1 to about 30 carbon atoms, the compounds having the formula R"--COOH wherein R" is C.sub.6 H.sub.5 or CF.sub.3, and the compounds having the formula ROC(O)OR or ##STR8## wherein R is an alkyl or an alkyl halide, or an aromatic or halogenated aromatic group having from about 1 to about 30 carbon atoms, wherein said additive is present in a quantity sufficient to effect deactivation of said hydrofluoric acid for isoparaffin-olefin alkylation such that the catalytic properties of said admixture of said hydrofluoric acid and said additive, in the absence of superacid promoter are characterized by the conversion of a mixed isoparaffin-olefin stream to product containing more than about 0.1 weight percent of alkyl halide;
• and
• (c) a superacid promoter selected from the group consisting of BF.sub.3, AlCl.sub.3, AlBr.sub.3, TaF.sub.5, SbF.sub.5, NbF.sub.5, PF.sub.5, BCl.sub.3, TiF.sub.4, CF.sub.3 SO.sub.3 H, and FSO.sub.3 H in concentration sufficient such that contacting said catalyst composition comprising said hydrofluoric acid, said additive, and said superacid promoter with a mixed isobutane/2-butene feedstream in an isobutane/2-butene molar ratio of more than about 2:1 under alkylation conversion conditions yields a product containing at least 50 percent of the trimethylpentanes obtained by contacting said isobutane/2-butene feedstream with concentrated HF under said alkylation conversion conditions.

A process for alkylating an isoparaffin with an olefin comprising effecting reaction of isoparaffin and olefin with an alkylation catalyst composition comprising:

• (a) at least one Bronsted acid selected from the group consisting of hydrofluoric acid and the halogenated sulfonic acid;
• (b) an additive in admixture with said Bronsted acid, said additive selected from the group consisting of the compounds having the formula R'--(NO.sub.2), wherein R' is an alkyl, aromatic, alkyl halide, or halide-substituted aromatic group having from about 1 to about 30 carbon atoms, the compounds having the formula R"--COOH wherein R" is C.sub.6 H.sub.5 or CF.sub.3 and compounds having the formula ROC(O)OR or ##STR9## wherein R is an alkyl or an alkyl halide, or an aromatic or halogenated aromatic group having from about 1 to about 30 carbon atoms, wherein said additive is present in a quantity sufficient to effect deactivation of said Bronsted acid for isoparaffin-olefin alkylation such that the catalytic properties of said admixture of said Bronsted acid and said additive, in the absence of superacid promoter are characterized by the conversion of a mixed isobutane/2-butene feedstream in an isobutane/2-butene molar ratio of more than about 2:1 under alkylation conversion conditions to product containing less than about 50 weight percent of the trimethylpentanes obtained by contacting said mixed isobutane/2-butene stream with said Bronsted acid under said alkylation conversion conditions;
• and
• (c) a superacid promoter in concentration sufficient such that contacting said liquid alkylation catalyst composition with a mixed isobutane/2-butene feedstream in an isobutane/2-butene molar ratio of more than about 2:1 under alkylation conversion conditions yields a product containing at least 50 weight percent of the trimethylpentanes obtained by contacting said isobutane/2-butene feedstream with said Bronsted acid under said alkylation conversion conditions.

A process for alkylating an isoparaffin with an olefin comprising effecting reaction of isoparaffin and olefin with an alkylation catalyst composition which composition consists essentially of:

• (a) hydrofluoric acid;
• (b) an additive in admixture with said hydrofluoric acid, said additive selected from the group consisting of nitroalkanes and alkyl carbonates, wherein said additive is present in a quantity sufficient to effect deactivation of said Bronsted acid for isoparaffin-olefin alkylation such that the catalytic properties of said admixture of said hydrofluoric acid and said additive, in the absence of superacid promoter are characterized by the conversion of a mixed isoparaffin-olefin stream to product containing more than about 0.1 weight percent of alkyl halide;
• and
• (c) a superacid promoter selected from the group consisting of BF.sub.3, AlCl.sub.3, AlBr.sub.3, TaF.sub.5, SbF.sub.5, NbF.sub.5, PF.sub.5, BCl.sub.3, TiF.sub.4, CF.sub.3 SO.sub.3 H, and FSO.sub.3 H in concentration sufficient such that contacting said catalyst composition comprising said hydrofluoric acid, said additive, and said superacid promoter with a mixed isobutane/2-butene feedstream in an isobutane/2-butene molar ratio of more than about 2:1 under alkylation conversion conditions yields a product containing at least 50 weight percent of the trimethylpentanes obtained by contacting said isobutane/2-butene feedstream with concentrated HF under said alkylation conversion conditions.

A catalyst composition for alkylation of an isoparaffin with an olefin, said catalyst composition consisting essentially of:

• (a) hydrofluoric acid;
• (b) an additive in admixture with said hydrofluoric acid, said additive selected from the group consisting of nitroalkanes and alkyl carbonates, wherein said additive is present in a quantity sufficient to effect deactivation of said hydrofluoric acid for isoparaffin-olefin alkylation such that the catalytic properties of said admixture of said hydrofluoric acid and said additive, in the absence of superacid promoter are characterized by the conversion of a mixed isoparaffin-olefin stream to product containing more than about 0.1 weight percent of alkyl halide;
• and
• (c) a superacid promoter selected from the group consisting of BF.sub.3, AlCl.sub.3, AlBr.sub.3, TaF.sub.5, SbF.sub.5, NbF.sub.5, PF.sub.5, BCl.sub.3, TiF.sub.4, CF.sub.3 SO.sub.3 H, and FSO.sub.3 H in concentration sufficient such that contacting said catalyst composition comprising said hydrofluoric acid, said additive, and said superacid promoter with a mixed isobutane/2-butene feedstream in an isobutane/2-butene molar ratio of more than about 2:1 under alkylation conversion conditions yields a product containing at least 50 percent of the trimethylpentanes obtained by contacting said isobutane/2-butene feedstream with concentrated HF under said alkylation conversion conditions.