Texaco Inc.

Abb Lummus Global Inc.

David E Sherwood, Jr

Pei-Shing E Dai

Bobby R Martin

Burton H Bartley

Roy E Pratt

Gerald V Nelson

Randall Hughes Petty

Govanon Nongbri

Charles N Campbell, Ii

Eugene P Dai

Johnnie R Hardee, Jr

Joseph A Durkin

Laurence D Neff

Charles N Campbell

Michael K Porter

John A Lemen

Low pressure process for the hydroconversion of heavy hydrocarbons

A process for converting a charge of heavy hydrocarbons containing components boiling above 1000.degree. F. to a product containing a decreased content of components boiling above 1000.degree. F. and decreased sediment content employing a NiMo catalyst having a specified pore distribution under hydroconversion conditions is disclosed. The process includes contacting the charge of heavy hydrocarbon with hydrogen in the presence of a heterogeneous catalyst supported on alumina and containing .ltoreq.2.5 wt % of silica and bearing 2.2 to 6 wt % of a Group VIII metal oxide, 7 to 24 wt % of a Group VIB metal oxide and 0.3 to 2 wt % of a loaded phosphorus oxide, the phosphorous being loaded onto the catalyst as aqueous phosphoric acid. The catalyst also may be characterized by having a Total Surface Area of 175 to 205 m.sup.2 /g, a Total Pore Volume of 0.82 to 0.98 cc/g, and a Pore Diameter Distribution wherein 29.6 to 33.0% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG., 67.0 to 70.4% of the Total Pore Volume is present as micropores of diameter less than 250 .ANG., .gtoreq.65% of the micropore volume is present as micropores of diameter .+-.25 .ANG. about a pore mode by volume of 110 to 130 .ANG., less than 0.05 cc/g of micropore volume is present in micropores with diameters less than 80 .ANG..

Hydroconversion process employing a phosphorus loaded NiMo catalyst with

A process for hydrotreating a hydrocarbon feed containing components boiling above 1000.degree. F. and sulfur, metals and carbon residue utilizing a heterogeneous catalyst having a specified pore size distribution, median pore diameter by surface area and pore mode by volume, to give a product containing a decreased content of components boiling above 1000.degree. F. and decreased sulfur, metals and carbon residue is disclosed. The process includes contacting the hydrocarbon feed with hydrogen in the presence of the catalyst at isothermal hydroconversion conditions. The catalyst includes an porous alumina support containing less than or equal to 2.5 wt % silica on the finished catalyst basis, and bearing 2.2 to 6 wt % of a Group VIII metal oxide, 7 to 24 wt % of a Group VIB metal oxide and preferably less than 0.2 wt % of a phosphorous oxide. The catalyst may be characterized as having a Total Surface Area of 215 to 245 m.sup.2 /g, a Total Pore Volume of 0.82 to 0.98 cc/g, a Median Pore Diameter by Surface Area of 91 to 104 .ANG., and a Pore Diameter Distribution in which 22.0 to 33.0% of the total Pore Volume is present as macropores of a diameter greater than 250 .ANG., 67.0 to 78.0% of the Total Pore Volume is present as micropores of a diameter less that 250 .ANG.. Greater than or equal to 65% of the micropore volume is present as micropores having a diameter +/-25 .ANG. about a Pore Mode by volume of 86-99 .ANG.. Less than 0.08 cc/g of the micropore volume is present in micropores with diameters less than 80 .ANG..

Hydroconversion process employing catalyst with specified pore size

A process for hydrotreating a charge hydrocarbon feed containing components boiling above 1000.degree. F. and sulfur, metals, and carbon residue, to provide product containing decreased levels of components having a boiling point greater than 1000.degree. F., decreased levels of sulfur, particularly decreased sulfur contents in the unconverted 1000.degree. F.+ boiling point products, and reduced sediment, which comprises:

Disclosed is a catalyst comprising a porous alumina support bearing 2.5-6 wt % of a non-cobalt Group VIII metal oxide, 14.5-25 wt % of a Group VI-B metal oxide, and 0-4 wt % of a phosphorus oxide, said catalyst having a Total Surface Area of 240-320 M.sup.2 /g, Pore Volume of 0.65-0.90 cc/g, and a Pore Diameter Distribution whereby 50-62.8% of the Total Pore Volume is present as micropores of diameter 55-115 .ANG., 27.5-37% of the Total Pore Volume is present in large pores of a diameter greater than 160 .ANG. and 20-30.5% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG..

Heavy hydrocarbons are hydrotreated to increase content of components boiling below 1000.degree. F. by contact with Group VIII non-noble metal oxide and Group VI-B metal oxide on alumina having a Total Surface Area of 150-240 m.sup.2 /g, a Total Pore Volume, (TPV) of 0.7-0.98, and a Pore Diameter Distribution whereby .ltoreq.20% of the TPV is present as primary micropores of diameter .ltoreq.100 .ANG., at least about 34% of TPV is present as secondary micropores of diameter of about 100 .ANG.-200 .ANG., and about 26%-46% of the TPV is present as mesopores of diameter .gtoreq.200 .ANG..

Catalyst with specified pore size distribution

A novel zeolite characterized by a large number of secondary pores, a substantially decreased Lattice Constant of below about 24.19 .ANG., and a substantially decreased Acid Site Density is attained by hydrothermal and acid-treating of an ultrastable Y-zeolite.

Synthesis of zeolites

Heavy oils may be hydrotreated in the presence of a porous alumina support bearing metals of Group VIII, excluding cobalt, and VI-B and optionally phosphorus, the catalyst having a Total Surface Area of 240-320 m.sup.2 /g, a Total Pore Volume of 0.65-0.9 cc/g, and a Pore Diameter Distribution whereby 50-62.8% of the Total Pore Volume is present as micropores of diameter 55-115 .ANG. and 20-30.5% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG.. The heavy oils and hydrogen are contacted with the catalyst such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed. The process is particularly effective in achieving desired levels of hydroconversion of feedstock components having a boiling point greater than 1000.degree. F. to products having a boiling point less than 1000.degree. F.

Disclosed is a hydrotreating catalyst which comprises a porous alumina support bearing metals of Group VIII and VI-B and optionally phosphorus, the catalyst having a Total Surface Area of 240-310 m.sup.2 /g, a Total Pore Volume of 0.5-0.75 cc/g, and a Pore Diameter Distribution whereby 63-78% of the Total Pore Volume is present as micropores of diameter 55-115 .ANG. and 11-18% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG., said catalyst being particularly effective in achieving desired levels of hydroconversion of feedstock components having a boiling point greater than 1000.degree. F. to products having a boiling point less than 1000.degree. F.

Hydrodesulfurization of a cracked naphtha is effected in the presence of, as catalyst, an alkali metal, a metal of Group VIII, and a metal of Group VI-B on an alumina support containing a hydrotalcite-like composition.

Hydrotalcite-containing catalyst composition

Spent or inactive alumina-supported catalysts removed from a catalytic hydrotreating process and having carbonaceous and metallic deposits thereon are reactivated. After a solvent wash to remove process oils, the spent catalyst is contacted with steam at a temperature of 1000.degree. to about 1250.degree. F. for a period of about 2 to about 5 hours to form a reactivated catalyst suitable for reuse in a catalytic hydrotreating process. Optionally, the steam-treated catalyst can be regenerated by contact with an oxygen-containing gas at a temperature of about 700.degree. to about 900.degree. F. to remove carbon deposits from the catalyst, or, alternatively, the steam-treated catalyst can be acid-leached to remove undesired metals and then contacted with an oxygen-containing gas at an elevated temperature to remove carbon deposits.

Method for the reactivation of spent alumina-supported hydrotreating

Hydrodesulfurization of a cracked naphtha is effected in the presence of, as catalyst, a non-noble metal of Group VIII and a metal of Group VI-B on an alumina support containing a hydrotalcite-like composition. The process of the instant invention gives high levels of hydrodesulfurization compared to prior art magnesia-containing catalysts and lower levels of olefin saturation, and less octane reduction in the desulfurized gasoline.

Hydrodesulfurization process

Heavy hydrocarbons are hydrotreated to increase content of components boiling below 1000.degree. F. by contact with Group VIII non-noble metal oxide and Group VI-B metal oxide on alumina having a Total Surface Area of 150-240 m.sup.2 /g, a Total Pore Volume, (TPV) of 0.7-0.98, and a Pore Diameter Distribution whereby .ltoreq.20% of the TPV is present as primary micropores of diameter .ltoreq.100 .ANG., at least about 34% of TPV is present as secondary micropores of diameter of about 100 .ANG.-200 .ANG., and about 26%-46% of the TPV is present as mesopores of diameter &gt;200 .ANG..

A mild hydrocracking process for the hydrodemetallation (HDM), hydrodesulfurization (HDS) and hydroconversion (HC) of hydrocarbon feedstocks such as residuum feedstocks which provides increased conversion and increased yields of middle distillates is disclosed. The process utilizes a catalyst comprising about 1.0 to about 6.0 wt. % of an oxide of a Group VIII metal, about 12.0 to about 25.0 wt. % of an oxide of molybdenum and 0 to about 5.0 wt. % of an oxide of phosphorus supported on a porous alumina support containing about 0.1 to about 10.0 wt. % of lithium oxide.

Mild hydrocracking of heavy hydrocarbon feedstocks employing lithia

Heavy oils may be hydrotreated in the presence of a porous alumina support bearing metals of Group VIII and VI-B and optionally phosphorus, the catalyst having a Total Surface Area of 165-230 m.sup.2 /g, a Total Pore Volume of 0.5-0.8 cc.g, and a Pore Diameter Distribution whereby less than about 5% the Total Pore Volume is present as primary micropores of diameter less than 80 .ANG., and secondary micropores of diameter of +20 .ANG. of a Pore Mode of 100-135 .ANG. are present in amount of at least about 65% of the micropore volume having pores with diameter less than 250 .ANG., and 22-29% of the Total Pore Volume is present as macropores of diameter &gt;250 .ANG.. The process of the instant invention is particularly effective in achieving desired levels of hydrodemetallation, hydrodesulfurization, and hydrocracking of asphaltenes in the fraction of hydrotreated/hydrocracked petroleum resid product having a boiling point greater than 1000.degree. F.

Growing community of inventors

Beaumont, TX, United States of America

David E Sherwood, Jr