Texaco Inc.

Govanon Nongbri

Gerald V Nelson

Roy E Pratt

Pei-Shing E Dai

David E Sherwood, Jr

Scott M Sayles

Glenn A Clausen

Lalit S Shah

Charles H Schrader

Jeffrey B Harrison

MIchael P Bellinger

William B Livingston

David E Self

Kamlesh B Vakil

Pei-Sing Dai, Deceased

Stanley M Farabee

The invention is a process for producing hydrocarbons from hydrogen and carbon monoxide by reacting hydrogen and carbon monoxide in the presence of a particulate solid catalyst and a substantially inert liquid medium. This reaction takes place in a reactor vessel adapted for the reaction of gases in the presence of a substantially inert liquid medium and a bed of solid particulate catalyst. The hydrogen gas and carbon monoxide gas are introduced at a plurality of locations within the reactor vessel. Bubbles of gas flow upward through the bed of solid catalyst particles and substantially inert liquid medium at sufficient velocity to expand the bed to a volume greater than its static volume. This velocity creates a turbulent reaction zone wherein liquid, gas, and solid catalyst are present and are in a state of motion.

Process for optimizing hydrocarbon synthesis

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

An improvement has been discovered in an ebullated bed process. A residual hydrocarbon oil feedstock is hydrocracked to yield a product oil. The amount of sediment in the product oil is controlled by adjusting hydrogen partial pressure according to an algorithm. A change in temperature and residence time is avoided.

Ebullated bed 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 VIB metal oxide on alumina having a Total Surface Area of 175-220 m.sup.2 /g, a Total Pore Volume (TPV) of 0.6-0.8, and a Pore Diameter Distribution whereby .ltoreq.33% of the TPV is present as primary micropores of diameter .ltoreq.100 .ANG., at least about 41% of TPV is present as secondary micropores of diameter of about 100 .ANG.-200 .ANG., and about 16%-26% of the TPV is present as mesopores of diameter .gtoreq.200 .ANG.. Phosphorus containing compounds are avoided during catalyst preparation.

Catalyst for residual conversion demonstrating reduced toluene insolubles

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..

Hydroconversion process employing catalyst with specified pore size

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.

Hydroconversion catalyst with specified pore size distribution

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% of 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.

An improved method of controlling catalyst inventory in the reactor of an ebullated bed process has been discovered. Pressure differentials are measured to calculate a catalyst inventory characterization factor. This factor is calculated by means of a new algorithm. Aged catalyst is withdrawn and fresh catalyst added in an amount to reestablish the value of the factor. The catalyst to oil ratio is maintained despite changes in bed ebullation, gas and liquid holdups, oil residence time and conversion.

Catalyst inventory control in an ebullated bed process

In an ebullated bed process, it has been found that in switching from one sediment yielding feedstock to a second sediment yielding feedstock that the transient sediment concentration has caused unit shutdowns with lost production. A method has been found which avoids these high transient sediment concentrations. Fresh addition is substituted for regenerated catalyst addition until the average carbon on catalyst in the bed drops to 22 wt% basis carbon free catalyst. Second feedstock is added incrementally and sediment in the product analyzed. After full second feedstock rate is achieved, first feedstock is reduced incrementally with sediment analysis. Higher unit utilization is achieved with the corresponding increased yearly production.

Method for controlling sedimentation in an ebulated bed process

In a two stage catalytic cracking process a heavy cycle gas oil fraction (HCGO) nominal boiling range 600.degree. F. to 1050.degree. F., API gravity of -10.degree. to +10.degree. and 65 to 95 vol % aromatics is recycled to extinction between an ebullated bed hydrocracking zone and fluidized catalytic cracking zone to yield a liquid fuel and lighter boiling range fraction as the light fraction from each zone. The catalyst in the fluidized catalytic cracking zone is maintained at a micro activity 68 to 72 while cracking a virgin gas oil to HCGO. HCGO is then mixed with vacuum residuum and hydrocracked in an ebullated bed reactor. The mid range fraction is recycled to the fluidized catalytic cracking zone. The 1000.degree. F..sup.+ fraction is blended with a fuel oil.

Growing community of inventors

Port Neches, TX, United States of America

Govanon Nongbri