Preparation of tertiary butyl alcohol

Claim 3

A metal according to Claim 1 characterised in that the bidentate ligand has the formula: wherein R and R′ may be the same or different and are selected from hydrogen, methyl, ethyl, propyl, phenyl and chlorophenyl.

Claim 4

A method according to claim 1 characterised in that said metal phthalocyanine catalyst or a metal porphine compound is promoted with an amine or/and an mercaptan.

Claim 5

A method according to claim 1 characterised in that said metal phthalocyanine catalyst is promoted with a free radical inhibitor and/or a mercaptan, with a base or with borate, said metal being selected from Groups IB, VIIB or VIIIB of the Periodic Table.

Claim 6

A method according to claim 4 characterised in that the t- butyl charge stock is in solution with t -butyl alcohol.

Claim 7

A method according to claim 5 characterised in that the t - butyl alcohol solution consists of a soluble ruthenium catalyst and a 2,2′-dipyridyl or bis(salicylidene)ethylenediamine bidentate ligand.

Claim 8

A method according to claim 6 characterised in that the said soluble ruthenium catalyst compound is ruthenium acetylacetonate.

Claim 11

A method according to claim 5 characterised in that the t -butyl alcohol solution consists of a chloroferric a manganeous or a cobalt phthalocyanine catalyst and a soluble rhenium compound selected from rhenium heptoxide-­p-dioxane ammonium, rhenium tetroxide or rhenium decacarbonyl.

Claim 13

A method according to claim 11 characterised in that said base is an inorganic base having a pH greater than 7.5 when 0.10 mole is dissolved in 1 litre of water.

Claim 14

A method according to claim 11 or claim 12 characterised in that said base is an alkali metal carbonate, bicarbonate, acetate or hydrogen phosphate.

Claim 15

A method according to claim 13 characterised in that said base is sodium acetate, potassium acetate, sodium bicarbonate, lithium bicarbonate, lithium carbonate or sodium hydrogen phosphate.

Claim 17

A method according to claim 15 characterised in that the borate is lithium borate, sodium borate, magnesium borate, calcium borate, barium borate or zinc borate.

Claim 18

A continuous method for preparing t -butyl alcohol according to any of the preceding claims wherein the isobutane is continuously reacted with molecular oxygen in a reaction zone under liquid phase oxidation reaction conditions to provide an initial reaction mixture comprising unreacted isobutane and isobutane oxidation reaction products, principally t -butyl hydroperoxide and t -­butyl alcohol characterised in that it comprises: (a) conducting said reaction in the presence of catalyst, (b) continuously recovering t -butyl alcohol from said t -butyl alcohol fraction.

Claim 19

A method according to claim 17 comprising a solution of t-butyl hydroxide in t-butyl alcohol which contains from about 5 to about 30 wt.% of butyl hydroperoxide wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that it comprises: (a) 0.001 to about 5 wt % based on the weight of the t -butyl hydroperoxide of a soluble rhenium catalyst compound and about 1 to about 3 parts by weight, based on the weight of the rhenium compound, of a bidentate ligand selected from 2,2′-dipyridyl and bis(salicylidene)ethylenediamine. (b) conducting said hydroperoxide decomposition reaction in the presence of said thus-prepared hydroperoxide decomposition catalyst in said hydroperoxide decomposition zone in liquid phase with agitation under reaction conditions including a temperature within the range of about 30° to about 80°C. and autogeneous pressure, and (c) continuously removing a stream of said hydroperoxide conversion product from said hydroperoxide conversion zone. (d) said bidentate ligand having the formula as claimed in claim 2.

Claim 20

A continuous method according to claim 18 characterised in that (a) the oxidation reaction conditions include a temperature within the range of about 135°C to about 155°C, a pressure of about 300 to about 800 psig., and a holding time of about 2 to 6 hours to provide an initial reaction mixture comprising unreacted isobutane and isobutane oxidation reaction products, principally t -butyl hydroperoxide and t -butyl alcohol, (b) continuously separating unreacted isobutane from said initial reaction mixture to provide a charge stock, (c) continuously feeding said charge stock to a hydroperoxide decomposition zone, adding said decomposition catalyst, and (d) continuously conducting a catalytic hydroperoxide decomposition reaction in said hydroperoxide decomposition zone in liquid phase with agitation under reaction conditions at a temperature within the range of about 30o to about 80°C. and autogenous pressure, to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product.

Claim 22

A method according to claim 17 wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that said hydroperoxide decomposition reaction is conducted: (a) in the presence of about 0.001 to about 5 wt.%, based on the weight of said charge stock of an iron (III) or manganese (III) porphine catalyst, by contacting said t -butyl hydroperoxide in said hydroperoxide decomposition zone in liquid phase with agitation with said hydroperoxide decomposition catalyst in solution in said t -butyl alcohol under reaction conditions including a temperature within the range of about 20° to about 125°C. and autogeneous pressure, (b) continuously removing a stream of said hydroperoxide conversion product from said hydroperoxide conversion zone; and (c) continuously separating said hydroperoxide conversion product stream into an isobutane fraction and a t -butyl alcohol fraction.

Claim 23

A method according to claim 21 characterised in that the decomposition reaction is conducted in the additional presence of from about 0.2 to about 5 parts by weight, per part of said porphine catalyst of a C₁-C₁₈-alkyl thiol.

Claim 24

A method according to claim 21 characterised in that the reaction is conducted in the additional presence of from about 0.2 to about 5 parts by weight per part of said porphine catalyst of a heterocyclic amine.

Claim 26

A method according to claim 17 wherein the solution of t -butyl hydroperoxide and t - alcohol contains from about 10 to about 40 wt.% of t -butyl hydroperoxide, wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that it comprises: (a) adding from about 0.001 to about 5 wt.%, based on the weight of the t -butyl hydroperoxide of chloroferric phthalocyanine or cobalt phthalocyanine and about 0.2 to about 1 parts by weight, based on the weight of the phthalocyanine of a rhenium compound selected from rhenium heptoxide-p-dioxane, ammonium rhenium tetroxide or rhenium decacarbonyl to said charge stock as said hydroperoxide decomposition catalyst, (b) conducting said hydroperoxide decomposition reaction in the presence of said thus-prepared hydroperoxide decomposition catalyst in said hydroperoxide decomposition zone in liquid phase with agitation reaction conditions including a temperature within the range of about 20° to about 40°C, and autogeneous pressure, and (c) continuously removing a stream of said hydroperoxide conversion product from said hydroperoxide conversion zone.

Claim 27

A method according to claim 17, wherein said t -butyl hydroperoxide is continuously brought into contact with a catalytically effective amount of a phthalocyanine catalyst in a reaction zone under liquid phase reaction conditions including a temperature within the range of about 20° to about 120°C and a pressure of about 0 to about 1000 psig, characterised in that it comprises: (a) using, as said reduction catalyst, about 0.001 to about 5 wt.%, based on the weight of the charge stock, of a metal phthalocyanine catalyst, the metal of said metal phthalocyanine catalyst being a heavy metal selected from IB, Group VIIB and Group VIIIB of the Periodic Table, and (b) promoting the catalytic activity of said metal phthalocyanine catalyst with from 0.2 to 5 parts by weight, per part of said metal phthalocyanine catalyst of imidazole and (c) continuously removing a stream of said conversion product from said reaction zone.

Claim 28

A method according to claim 26 characterised in that the stream is continuously separated into an isobutane fraction and a t -butyl alcohol fraction, the t -butyl alcohol is removed from said t -butyl alcohol fraction, and said isobutane fraction is continuously recycled to said reaction zone.

Claim 29

A method according to claim 17 containing a solution of t -butyl hydroperoxide in t -butyl alcohol with about 2 to about 90 wt.%. of t -butly hydroperoxide wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that it comprises: (a) adding from about 0.001 to about 5 wt.%, based on the weight of the t -butyl hydroperoxide of chloroferric phthalocyanine, about 1 to about 1.5 parts by weight, per part of the chloroferric phthalocyanine of 2,3-dihydroxynaphthalene and about 1 to about 20 parts by weight, per part of 2,3-­dihydroxynaphthalene of a C₁-C₁₈ alkyl thiol to said charge stock as said hydroperoxide decomposition catalyst, (b) conducting said hydroperoxide decomposition reaction in the presence of said thus-prepared hydroperoxide decomposition catalyst in said hydroperoxide decomposition zone in liquid phase with agitation under reaction conditions including a temperature within the range of about 20° to about 125°C. and autogenous pressure, and (c) continuously removing a stream of said hydroperoxide conversion product from said hydroperoxide conversion zone.

Claim 30

A method according to claim 17 comprising a solution of t -­butyl hydroperoxide in t -butyl alcohol which contains from about to about 30 wt.% of t -butyl hydroperoxide wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that it comprises: (a) adding to said charge stock as said hydroperoxide decomposition catalyst from about 0.001 to about 5 wt.%, based on the weight of the t -butyl hydroperoxide of chloroferric phthalocyanine and about 1 to about 5 parts by weight, based on the weight of the chloroferric phthalocyanine of an alkali metal base of an organic or inorganic acid having a pH greater than about 7.5 when 0.10 mole is dissolved in 1 litre of water. (b) conducting said hydroperoxide decomposition reaction in the presence of said thus-prepared hydroperoxide decomposition catalyst in said hydroperoxide decomposition zone in liquid phase with agitation under reaction conditions including a temperature within the range of about 20° to about 125°C. and autogenous pressure. (c) continuously removing a stream of said hydroperoxide conversion product from such hydroperoxide conversion zone.

Claim 31

A method according to claim 29 characterised in that said chloroferric phthalocyanine derives from lithium, sodium or potassium acetate, carbonate, bicarbonate or hydrogen phosphate.

Claim 32

A method according to claim 17 comprising a solution of t -butyl hydroperoxide in t -butyl alcohol which contains from about 2 to about 90 wt% of t -butyl hydroperoxide wherein unreacted isobutane is continuously separated from said initial reaction mixture to provide a charge stock comprising a solution of said t -butyl hydroperoxide in said t -butyl alcohol, wherein said charge stock is continuously charged to a hydroperoxide decomposition zone, and wherein a catalytic hydroperoxide decomposition reaction is continuously conducted in said decomposition reaction zone to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, to provide a hydroperoxide conversion product, characterised in that it comprises: (a) adding from about 0.001 to about 5 wt.%, based on the weight of the t -butyl hydroperoxide of chloroferric phthalocyanine and about 1 to 6 parts by weight per part of the chloroferric phthalocyanine of a borate of a metal of Group IA, Group IIA or Group IIB of the Periodic Table to said charge stock as said hydroperoxide decomposition catalyst. (b) conducting said hydroperoxide decomposition reaction in the presence of said thus-prepared hydroperoxide decomposition catalyst in said hydroperoxide decomposition zone in liquid phase with agitation under reaction conditions including a temperature within the range of about 20° to about 125°C. and autogenous pressure. (c) continuously removing a stream of said hydroperoxide conversion product from said hydroperoxide zone.

Claim 33

A method according to claim 30 comprising a solution of t -butyl hydroperoxide in t -butyl alcohol which contains from about 20 to about 50 wt.% of t -butyl hydroperoxide characterised in that it comprises adding (a) about 1 to 6 parts by weight, per part of the chloroferric phthalocyanine of a lithium, sodium, magnesium, zinc, or calcium borate to said charge stock as said hydroperoxide decomposition catalyst.

Claim 34

A method according to claim 1 wherein a t -butyl hydroperoxide charge is continuously brought into contact with a catalytically effective amount of a reduction catalyst in a reaction zone in liquid phase under reaction conditions including a temperature within the range of about 20° to about 120°C. and a pressure of 0 to about 1000 psig. to convert said t -butyl hydroperoxide to decomposition products, principally t -butyl alcohol, characterised in that it comprises: (a) using, as a reaction catalyst, about 0.001 to about 5 wt.%, based on the weight of the charge stock, of a metal phthalocyanine catalyst, (b) promoting the catalytic activity of said metal phthalocyanine catalyst with from about 0.2 to about 5 parts by weight, per part of said metal phthalocyanine catalyst of imidazole, and (c) recovering said t -butyl alcohol from the products of said reaction.

Claim 35

A method according to claim 33 characterised in that it comprises promoting the catalytic activity of said metal phthalocyanine catalyst with imidazole, said imidazole being used in an amount correlated with said reaction conditions and said metal phthalocyanine catalyst sufficient to provide at least about a 90% conversion of said t -butyl hydroperoxide and selectivity of said t -butyl hydroperoxide to t -butyl alcohol or at least about 90% on the basis of t -butyl peroxide charged.

Claim 36

A method according to claim 33 characterised in that it comprises: (a) using, as said reduction catalyst, about 0.001 to about 5 wt.%, based on the weight of the charge stock, of a metal phthalocyanine catalyst, the metal of said metal phthalocyanine catalyst being a heavy metal selected from Group IB, Group VIIB and Group VIIIB of the Periodic Table, and (b) promoting the catalytic activity of said metal phthalocyanine catalyst with from about 0.2 to about 5 parts by weight, per part of said metal phthalocyanine catalyst of imidazole.

Claim 38

A method according to claim 1 characterised in that it comprises: (a) preparing a t -butyl alcohol solution of said t -­butyl hydroperoxide containing from about 1 to about 80 wt.% of said t -butyl hydroperoxide, (b) adding a soluble amount of a metal phthalocyanine catalyst and a rhenium compound soluble in said t -­butyl alcohol to said solution as said hydroperoxide decomposition catalyst to thereby promote the substantially selective decomposition of said t -butyl hydroperoxide to t -butyl alcohol, and (c) recovering t -butyl alcohol from the products of said hydroperoxide decomposition reaction.

Claim 39

A method according to claim 1 characterised in that it comprises: (a) preparing a t -butyl alcohol solution of a chloroferric phthalocyanine catalyst promoted with 2,3-di-hydroxynaphthalene and dodecane thiol, (b) charging said t -butyl alcohol solution of said borate, said thiol and said chloroferric phthalocyanine catalyst to said hydroperoxide decomposition reaction zone as said hydroperoxide decomposition catalyst, and (c) recovering said t -butyl alcohol from the products of said hydroperoxide decomposition reaction.

Claim 40

A method according to claim 1 characterised in that it comprises: (a) preparing a t -butyl alcohol solution of said t -­butyl hydroperoxide containing from about 2 to about 50 wt.% of said t -butyl hydroperoxide, (b) adding a soluble amount of a metal phthalocyanine catalyst and a base soluble in said t -butyl alcohol to said solution as said hydroperoxide decomposition catalyst to thereby promote the substantially selective decomposition of said t -butyl hydroperoxide to t -butyl alcohol (c) recovering t -butyl alcohol from the products of said hydroperoxide decomposition reaction, and (d) said metal being selected from Group IB, Group VIIB or Group VIIIB of the Perodic Table.