Hydrodesulfurization process employing a titanium promoted catalyst

Claim 2

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal to said carrier after calcination of said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalysts per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 3

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock containing greater than 50 per cent by volume of materials boiling above about 400° F. which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV-B metal to said carrier after calcination of said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 4

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock containing greater than 50 per cent by volume of materials boiling above about 400° F. which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV-B metal to said carrier after calcination of said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 5

The process of claim 2 wherein the hydrocarbon stock contains substantial quantities of residual components, asphaltic materials and metalliferous contaminants.

Claim 6

The process of claim 2 wherein the hydrocarbon stock boils up to about 950° F.

Claim 7

The process of claim 2 wherein the hydrocarbon stock boils above about 950° F.

Claim 8

The process of claim 1 in which the atomic ratio of Group VIII to Group VI metals is in the range from about 1:0.3 to about 1:5.

Claim 9

The process of claim 6 wherein the atomic ratio of Group VIII to Group VI metals is greater than about 1:0.5.

Claim 10

The process of claim 3 wherein the pressure is less than about 2,000 PSIG.

Claim 11

The process of claim 4 wherein the pressure is in the range from about 500 PSIG to about 3,000 PSIG and the temperature is less than about 800° F.

Claim 12

The process of claim 1 in which the Group VI metal comprises molybdenum, the Group VIII metal comprises nickel, and wherein the Group IV-B metal comprises titanium.

Claim 13

The process of claim 2 in which the Group VI metal comprises molybdenum, the Group VIII metal comprises nickel, and wherein the Group IV-B metal comprises titanium.

Claim 14

The process of claim 4 in which the Group VI metal comprises molybdenum, the Group VIII metal comprises nickel, and wherein the Group IV-B metal comprises titanium.

Claim 15

The process of claim 1 in which the refractory oxide carrier comprises alumina.

Claim 16

The process of claim 2 in which the refractory oxide carrier comprises alumina.

Claim 17

A process for the hydrodesufurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal to said carrier after said Group IV and Group VIII hydrogenating metals had been composited with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 18

A process for the hydrodesufurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal to said carrier after said Group IV and Group VIII hydrogenating metals had been composited with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 19

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal after said Group VI hydrogenating metal had been composited with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 20

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal after said Group VI hydrogenating metal had been composited with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 21

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal to said carrier simultaneously with compositing said Group VI and Group VIII hydrogenating metals with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 22

A process for the hydrodesulfurization of a sulfur-containing hydrocarbon stock selected from the group consisting of naphtha and heavier hydrocarbons which comprises contacting the hydrocarbon stock with hydrogen and a catalyst substantially free of phosphates and consisting essentially of a hydrogenating metal selected from Group VI and a hydrogenating metal selected from Group VIII, both hydrogenating metals being in the sulfided form, supported on a non-zeolitic refractory oxide carrier and promoted with from about 1 to about 10 weight per cent of a Group IV-B metal by the addition of the Group IV metal to said carrier simultaneously with compositing said Group VI and Group VIII hydrogenating metals with said carrier, the contacting being conducted at a temperature from about 500° F. to about 1,000° F., a pressure from about 100 to about 5,000 PSIG, a liquid hourly space velocity from about 0.25 to about 10.0 volumes of hydrocarbon stock per volume of catalyst per hour and a hydrogen feed rate from about 500 to about 10,000 standard cubic feet of hydrogen per barrel of hydrocarbon stock.

Claim 23

The process of claim 1 wherein said non-zeolitic refractory oxide carrier is selected from the group consisting of alumina and silica-stabilized alumina.

Claim 24

The process of claim 2 wherein said non-zeolitic refractory oxide carrier is selected from the group consisting of alumina and silica-stabilized alumina.