Hydroperoxide decomposition process

Abstract

An improved process for decomposing alkyl or aromatic hydroperoxides to form a decomposition reaction mixture containing the corresponding alcohol and ketone is disclosed. The improvement relates to adding water to a starting hydroperoxide containing mixture, then removing the bulk of said water by a means such that water-soluble impurities are removed along with the water, then decomposing the hydroperoxide by contacting the hydroperoxide with a catalytic amount of a heterogeneous catalyst of Au, Ag, Cu or a sol-gel compound containing particular combinations of Cr, Co, Zr, Ta, Si, Mg, Nb, Al and Ti wherein certain of those metals have been combined with an oxide, such as an inorganic matrix of hydroxides or oxides, or combinations thereof. The catalysts may also optionally be supported on a suitable support member.

Description

field of invention

[0001] This invention relates to an improved catalytic process for the decomposition of alkyl or aryl hydroperoxides to form mixtures containing the corresponding alcohols and ketones. In particular, the invention relates to decomposing hydroperoxides by removing most of the water from the product stream by washing the feedstock with water to remove acidic impurities in addition to contacting with a catalytic amount of a heterogeneous catalyst. Background of the invention

[0002] Industrial processes for the production of cyclohexanol and cyclohexanone mixtures from cyclohexane are generally of commercial importance and are described in the patent literature. According to typical industrial practice, cyclohexane is oxidized to a reaction mixture containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is either decomposed or hydrogenated to a reaction mixture containing cyclohexanol and cyclohexanone in the presence or absence ...

Examples

Embodiment 1

[0050] A feed mixture containing 1.6% CHHP, 0.9% K, 1.9% A, 0.1% water and 0.3% acid was decomposed with 10 g of 1% Au-0.1% Pd catalyst, the remainder of the mixture being cyclohexane. The mixture was fed over the catalyst at 150°C and 150 psig (1.03 MPa) at 8 ml / min. The results are shown in Table I.

[0051] Ventilation time (hours)

Embodiment 2

[0053] This example illustrates the effect of pure water. Increasing water has only a small effect on the conversion ratio, but greatly reduces the K / A ratio. Catalyst and reaction condition are identical with embodiment 1. Different amounts of pure water were added to the feed. The results are shown in Table II

[0054] ventilation time

Embodiment 3

[0056] This example illustrates the effect of water with low levels of acid. Increasing the water / acid mixture has a large effect on conversion and K / A ratio. Catalyst and reaction condition are identical with embodiment 1. Acid % indicates the acid present in the added water, not the percentage in the feed mixture. The results are shown in Table III.

[0057]

field of invention

[0001] This invention relates to an improved catalytic process for the decomposition of alkyl or aryl hydroperoxides to form mixtures containing the corresponding alcohols and ketones. In particular, the invention relates to decomposing hydroperoxides by removing most of the water from the product stream by washing the feedstock with water to remove acidic impurities in addition to contacting with a catalytic amount of a heterogeneous catalyst. Background of the invention

[0002] Industrial processes for the production of cyclohexanol and cyclohexanone mixtures from cyclohexane are generally of commercial importance and are described in the patent literature. According to typical industrial practice, cyclohexane is oxidized to a reaction mixture containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is either decomposed or hydrogenated to a reaction mixture containing cyclohexanol and cyclohexanone in the presence or absence ...

Examples

Embodiment 1

[0050] A feed mixture containing 1.6% CHHP, 0.9% K, 1.9% A, 0.1% water and 0.3% acid was decomposed with 10 g of 1% Au-0.1% Pd catalyst, the remainder of the mixture being cyclohexane. The mixture was fed over the catalyst at 150°C and 150 psig (1.03 MPa) at 8 ml / min. The results are shown in Table I.

[0051] Ventilation time (hours)

Embodiment 2

[0053] This example illustrates the effect of pure water. Increasing water has only a small effect on the conversion ratio, but greatly reduces the K / A ratio. Catalyst and reaction condition are identical with embodiment 1. Different amounts of pure water were added to the feed. The results are shown in Table II

[0054] ventilation time

Embodiment 3

[0056] This example illustrates the effect of water with low levels of acid. Increasing the water / acid mixture has a large effect on conversion and K / A ratio. Catalyst and reaction condition are identical with embodiment 1. Acid % indicates the acid present in the added water, not the percentage in the feed mixture. The results are shown in Table III.

[0057]