Fixed bed hydroprocessing methods and systems and methods for upgrading an existing fixed bed system

A method of upgrading a pre-existing fixed bed hydroprocessing system, comprising:

• (a) operating a pre-existing fixed bed hydroprocessing system comprising one or more fixed bed reactors, each of which comprises a liquid hydrocarbon phase, a bed of a porous supported catalyst as a solid phase, and hydrogen gas as a gaseous phase;
• and
• (b) constructing and operating one or more slurry phase reactors upstream from at least one fixed bed reactor of the pre-existing fixed bed hydroprocessing system in order to form an upgraded feedstock from a heavy oil feedstock, each slurry phase reactor comprising (i) a liquid phase comprised of a heavy oil feedstock that initially contains asphaltenes and a colloidal or molecular catalyst having a particle size of less than about 100 nm and (ii) a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst catalyzing hydroprocessing reactions that reduce or eliminate the asphaltenes from the heavy oil feedstock prior to introducing an upgraded feedstock from the one or more slurry phase reactors into one or more of the fixed bed reactors, the colloidal or molecular catalyst being prepared by:
• (1) intimately premixing a catalyst precursor composition into a hydrocarbon oil diluent to formed a catalyst precursor mixture and adding the catalyst precursor mixture into the heavy oil feedstock in a manner so that the colloidal or molecular catalyst is formed upon heating the heavy oil feedstock to above the decomposition temperature of the precursor composition;
• and
• (2) heating the catalyst precursor composition within the heavy oil feedstock in order to decompose the catalyst precursor composition and expose it to hydrogen sulfide from the heavy oil feedstock to form a colloidal or molecular catalyst in situ within the heavy oil feedstock;
• and
• (c) introducing the upgraded feedstock from the slurry phase reactor into at least one fixed bed reactor of the pre-existing fixed bed hydroprocessing system to yield an upgraded fixed bed hydroprocessing system comprising one or more slurry phase reactors in combination with the one or more fixed bed reactors, the upgraded feedstock reducing or eliminating fouling and sedimentation within the fixed bed reactor as a result of the colloidal or molecular catalyst having reduced or eliminated the asphaltenes from the heavy oil feedstock in the one or more slurry phase reactors.

A method of upgrading a pre-existing fixed bed hydroprocessing system, comprising:

• (a) operating a pre-existing fixed bed hydroprocessing system comprising one or more pre-existing fixed bed reactors, each of which comprises a liquid hydrocarbon phase, a bed of a porous supported catalyst as a solid phase, and hydrogen gas as a gaseous phase;
• and
• (b) converting at least one of the pre-existing fixed bed reactors into a slurry phase reactor by removing the porous supported catalyst therefrom and replacing it with a colloidal or molecular catalyst formed in situ within a heavy oil feedstock to yield an upgraded fixed bed hydroprocessing system comprising one or more converted slurry phase reactors in combination with one or more remaining fixed bed reactors, each slurry phase reactor comprising (i) a liquid phase comprised of the heavy oil feedstock, which initially contains asphaltenes, and a colloidal or molecular catalyst, which has a particle size of less than about 100 nm, and (ii) a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst catalyzing hydroprocessing reactions that reduce or eliminate the asphaltenes from the heavy oil feedstock prior to introducing an upgraded feedstock from the one or more converted slurry phase reactors into one or more remaining fixed bed reactors, the colloidal or molecular catalyst being prepared by:
• (1) intimately premixing a catalyst precursor composition into a hydrocarbon oil diluent to formed a catalyst precursor mixture and adding the catalyst precursor mixture into the heavy oil feedstock in a manner so that the colloidal or molecular catalyst is formed upon heating the heavy oil feedstock to above the decomposition temperature of the precursor composition;
• and
• (2) heating the catalyst precursor composition within the heavy oil feedstock in order to decompose the catalyst precursor composition and expose it to hydrogen sulfide from the heavy oil feedstock to form a colloidal or molecular catalyst in situ within the heavy oil feedstock;
• and
• (c) introducing the upgraded feedstock from the one or more converted slurry phase reactors into one or more remaining fixed bed reactors to yield an upgraded fixed bed hydroprocessing system comprising the one or more converted slurry phase reactors in combination with the one or more remaining fixed bed reactors, the upgraded feedstock reducing or eliminating fouling and sedimentation within the one or more remaining fixed bed reactors as a result of the colloidal or molecular catalyst having reduced or eliminated the asphaltenes from the heavy oil feedstock in the one or more converted slurry phase reactors.

A method of hydroprocessing a heavy oil feedstock, comprising:

• preparing a heavy oil feedstock comprised of asphaltenes and a substantial quantity of hydrocarbons having a boiling point greater than about 650° F. by mixing an oil soluble catalyst precursor composition and a hydrocarbon oil diluent at a temperature below which a substantial portion of the catalyst precursor composition begins to decompose to form a diluted catalyst precursor mixture, adding the diluted catalyst precursor mixture into the heavy oil feedstock to form a conditioned feedstock comprised of a mixture of the heavy oil feedstock and diluted catalyst precursor mixture, and
• heating the catalyst precursor composition within the heavy oil feedstock in order to decompose the catalyst precursor composition and form a colloidal or molecular catalyst having a particle size of less than about 100 nm in situ within the heavy oil feedstock;
• heating or maintaining the heavy oil feedstock at a hydrocracking temperature within one or more slurry phase reactors to yield an upgraded material, each slurry phase reactor comprising (i) a liquid phase comprised of the heavy oil feedstock and the colloidal or molecular catalyst and (ii) a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst catalyzing hydroprocessing reactions that reduce or eliminate the asphaltenes from the heavy oil feedstock prior to introducing an upgraded feedstock from the one or more slurry phase reactors into one or more other reactors;
• introducing the upgraded feedstock into a guard bed reactor in order to remove at least a portion of the colloidal or molecular catalyst and metal impurities from the upgraded feedstock and thereby form a cleaned upgraded feedstock;
• and
• hydrotreating the cleaned upgraded feedstock within one or more fixed bed hydrotreating reactors to yield a hydrotreated material.

A method of upgrading a pre-existing fixed bed hydroprocessing system, comprising:

• (a) operating a pre-existing fixed bed hydroprocessing system comprising (1) one or more guard bed reactors comprising a liquid hydrocarbon phase and a bed of porous supported catalyst as a solid phase, (2) a plurality of fixed bed reactors downstream from the one or more guard bed reactors, each of which comprises a liquid hydrocarbon phase, a bed of a porous supported catalyst as a solid phase, and hydrogen gas as a gaseous phase, and (3) conduits which fluidly interconnect the one or more guard bed reactors and the fixed bed reactors;
• (b) converting at least one of the pre-existing fixed bed reactors into a slurry phase reactor by removing the porous supported catalyst therefrom and replacing it with a colloidal or molecular catalyst formed in situ within a heavy oil feedstock introduced into the converted slurry phase reactor;
• (c) re-routing at least some of the conduits in order for the converted slurry phase reactor to be upstream from at least one guard bed reactor in order for the heavy oil feedstock introduced into the converted slurry phase reactor to initially by-pass the at least one guard bed reactor initially positioned upstream from the converted slurry phase reactor so that the heavy oil feedstock is introduced into the converted slurry phase reactor prior to being introduced into the at least one guard bed;
• (d) operating the converted slurry phase reactor in order to upgrade a heavy oil feedstock into an upgraded feedstock, the converted slurry phase reactor comprising (i) a liquid phase comprised of the heavy oil feedstock, which initially contains asphaltenes, and the colloidal or molecular catalyst, which has a particle size of less than about 100 nm, and (ii) a gaseous phase comprised of hydrogen gas, the colloidal or molecular catalyst catalyzing hydroprocessing reactions that reduce or eliminate the asphaltenes from the heavy oil feedstock prior to introducing the upgraded feedstock from the converted slurry phase reactor into one or more remaining fixed bed reactors, the colloidal or molecular catalyst being prepared by:
• (1) premixing a catalyst precursor composition into a hydrocarbon oil diluent to formed a catalyst precursor mixture and adding the catalyst precursor mixture into the heavy oil feedstock in a manner so that the colloidal or molecular catalyst is formed upon heating the heavy oil feedstock to above the decomposition temperature of the precursor composition;
• and
• (2) heating the catalyst precursor composition within the heavy oil feedstock in order to decompose the catalyst precursor composition and expose it to hydrogen sulfide from the heavy oil feedstock to form a colloidal or molecular catalyst in situ within the heavy oil feedstock;
• (e) introducing the upgraded feedstock from the converted slurry phase reactor into the at least one guard bed to yield a cleaned upgraded feedstock;
• and
• (f) introducing the cleaned upgraded feedstock from the at least one guard bed into one or more remaining fixed bed reactors to further hydroprocess the cleaned upgraded feedstock.