Headwaters Heavy Oil, LLC

Headwaters Technology Innovation, LLC

Hydrocarbon Technology & Innovation, LLC

Cetamax Ventures Ltd.

Alberta Research Council Incorporated

Alberta Oil Sands Technology and Research Authority

Roger Kai Lott

Lap-Keung Lee

Yu-Hwa Chang

Lap Keung Lee

Kin Meng Chan

Kamalul Arifin Yusof

Shahrul Niza Bin Abdul Rahim

Md Asraff Bin Abdul Karim

Richard Anthony McFarlane

Haibo Huang

Baki Ozum

Theodore J Cyr

Leszek Lewkowicz

Peter C Quinn

Methods and systems for mixing a catalyst precursor with a heavy oil feedstock preparatory to hydroprocessing the heavy oil feedstock in a reactor to form an upgraded feedstock. Achieving very good dispersion of the catalyst precursor facilitates and maximizes the advantages of the colloidal or molecular hydroprocessing catalyst. A catalyst precursor and a heavy oil feedstock having a viscosity greater than the viscosity of the catalyst precursor are provided. The catalyst precursor is pre-mixed with a hydrocarbon oil diluent, forming a diluted catalyst precursor. The diluted precursor is then mixed with at least a portion of the heavy oil feedstock so as to form a catalyst precursor-heavy oil feedstock mixture. Finally, the catalyst precursor-heavy oil feedstock mixture is mixed with any remainder of the heavy oil feedstock, resulting in the catalyst precursor being homogeneously dispersed on a colloidal and/or molecular level within the heavy oil feedstock.

Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock

Systems for mixing a catalyst precursor with a heavy oil feedstock preparatory to hydroprocessing the heavy oil feedstock in a reactor to form an upgraded feedstock. Achieving very good dispersion of the catalyst precursor facilitates and maximizes the advantages of the colloidal or molecular hydroprocessing catalyst. A catalyst precursor and a heavy oil feedstock having a viscosity greater than the viscosity of the catalyst precursor are provided. The catalyst precursor is pre-mixed with a hydrocarbon oil diluent, forming a diluted catalyst precursor. The diluted precursor is then mixed with at least a portion of the heavy oil feedstock so as to form a catalyst precursor-heavy oil feedstock mixture. Finally, the catalyst precursor-heavy oil feedstock mixture is mixed with any remainder of the heavy oil feedstock, resulting in the catalyst precursor being homogeneously dispersed on a colloidal and/or molecular level within the heavy oil feedstock.

Mixing systems for introducing a catalyst precursor into a heavy oil feedstock

A system and method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system includes forming metal sulfide catalyst particles in situ within the heavy oil feedstock. The metal sulfide catalyst particles are formed in situ by (1) premixing a catalyst precursor with a hydrocarbon diluent to form a diluted precursor mixture, (2) mixing the diluted precursor mixture with the heavy oil feedstock to form a conditioned feedstock, and (3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil feedstock to form metal sulfide catalyst particles in situ in the heavy oil feedstock. The in situ formed metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Systems and methods for hydroprocessing heavy oil

A hydrocracking system is upgraded by modifying an existing ebullated bed initially utilizing a supported ebullated bed catalyst to thereafter utilize a dual catalyst system that includes metal sulfide catalyst particles and supported ebullated bed catalyst. The upgraded hydrocracking system achieves at least one of: (1) hydroprocess lower quality heavy oil; (2) increase conversion of higher boiling hydrocarbons that boil at 524&#xb0; C. (975&#xb0; F.) or higher; (3) reduce the concentration of supported ebullated bed catalyst required to operate an ebullated bed reactor at a given conversion level; and/or (4) proportionally convert the asphaltene fraction in heavy oil at the same conversion level as the heavy oil as a whole. The metal sulfide catalyst may include colloidal or molecular catalyst particles less than 1 micron in size and formed in situ within the heavy oil using a catalyst precursor well-mixed within the heavy oil and decomposed to form catalyst particles.

Method for upgrading ebullated bed reactor and upgraded ebullated bed reactor

A hydroprocessing system involves introducing heavy oil and in situ formed metal sulfide catalyst particles, or a catalyst precursor capable of forming metal sulfide catalyst particles in situ within the heavy oil, into a hydroprocessing reactor. The metal sulfide catalyst particles are formed in situ by 1) premixing a catalyst precursor with a hydrocarbon diluent to form a precursor mixture, 2) mixing the precursor mixture with heavy oil to form a conditioned feedstock, and 3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil to form the metal sulfide catalyst particles in situ in the heavy oil. The in situ formed metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Systems for hydroprocessing heavy oil

High energy (e.g., ultrasonic) mixing of a hydrocarbon feedstock and reactants comprised of an oxidation source, acid, and optional catalyst yields a liquid hydrocarbon product having increased cetane number. Ultrasonic mixing creates cavitation, which involves formation and violent collapse of micron-sized bubbles, which greatly increases reactivity of the reactants. Cavitation substantially increases cetane number compared to reactions carried out using conventional mixing processes, such as simple mechanical stirring. An aqueous mixture comprising water and acid can be pretreated with ozone or other oxidizer using ultrasonic cavitation prior to reacting the pretreated mixture with a hydrocarbon feedstock to promote cetane-increasing reactions. Controlling temperature inside the reactor promotes beneficial cetane-increasing reactions while minimizing formation of water-soluble sulfones.

Method and system for oxidatively increasing cetane number of hydrocarbon fuel

High energy (e.g., ultrasonic) mixing of a liquid hydrocarbon feedstock and reactants comprised of an oxidation source, catalyst and acid yields a diesel fuel product or additive having substantially increased cetane number. Ultrasonic mixing creates cavitation, which involves the formation and violent collapse of micron-sized bubbles, which greatly increases the reactivity of the reactants. This, in turn, substantially increases the cetane number compared to reactions carried out using conventional mixing processes, such as simple mechanical stirring. Alternatively, an aqueous mixture comprising water and acid can be pretreated with an oxidation source such as ozone and subjected to ultrasonic cavitation prior to reacting the pretreated mixture with a liquid hydrocarbon feedstock.

A hydroprocessing method and system involves introducing heavy oil and well-dispersed metal sulfide catalyst particles, or a catalyst precursor capable of forming the well-dispersed metal sulfide catalyst particles in situ within the heavy oil, into a hydroprocessing reactor. The well-dispersed or in situ metal sulfide catalyst particles are formed by 1) premixing a catalyst precursor with a hydrocarbon diluent to form a precursor mixture, 2) mixing the precursor mixture with heavy oil to form a conditioned feedstock, and 3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil to form the well-dispersed or in situ metal sulfide catalyst particles. The well-dispersed or in situ metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Method for efficiently operating an ebbulated bed reactor and an efficient ebbulated bed reactor

Methods for hydrocracking a heavy hydrocarbon feedstock (e.g., heavy oil and/or coal resid) employ a catalyst composed of well dispersed metal sulfide catalyst particles (e.g., colloidally or molecularly dispersed catalyst particles, such as molybdenum sulfide), which provide an increased concentration of metal sulfide catalyst particles within lower quality materials requiring additional hydrocracking. In addition to increased metal sulfide catalyst concentration, the systems and methods provide increased reactor throughput, increased reaction rate, and higher conversion of asphaltenes and lower quality materials. Increased conversion of asphaltenes and lower quality materials also reduces equipment fouling, enables processing of a wider range of lower quality feedstocks, and leads to more efficient use of a supported catalyst if used in combination with the well dispersed metal sulfide catalyst particles.

Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker

A hydrocracking system involves introducing a heavy oil feedstock and a colloidal or molecular catalyst, or a catalyst precursor capable of forming the colloidal or molecular catalyst, into a hydrocracking reactor. The colloidal or molecular catalyst is formed in situ within the heavy oil feedstock by 1) premixing the catalyst precursor with a hydrocarbon diluents to form a catalyst precursor mixture, 2) mixing the catalyst precursor mixture with the heavy oil feedstock, and 3) raising the temperature of the feedstock to above the decomposition temperature of the catalyst precursor to form the colloidal or molecular catalyst. The colloidal or molecular catalyst catalyzes upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment. The colloidal or molecular catalyst can be the sole or primary hydrocracking catalyst in a stand-alone hydrocracking reactor or it can be used together with a porous supported catalyst within a fixed bed or ebullated bed reactor.

Methods and systems for hydrocracking a heavy oil feedstock using an in situ colloidal or molecular catalyst

A hydrocracking system involves introducing a heavy oil feedstock and a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into a hydrocracking reactor. The colloidal or molecular catalyst is formed in situ within the heavy oil feedstock by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst. The colloidal or molecular catalyst catalyzes upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment. At least a portion of a resid fraction containing residual colloidal or molecular catalyst is recycled back into the hydrocracking reactor to further upgrade the recycled resid fraction portion and provide recycled colloidal or molecular catalyst within the hydrocracking reactor.

Methods for hydrocracking a heavy oil feedstock using an in situ colloidal or molecular catalyst and recycling the colloidal or molecular catalyst

Systems for hydrocracking a heavy oil feedstock employ a colloidally or molecularly dispersed catalyst (e.g., molybdenum sulfide) which provide for concentration of the colloidally dispersed catalyst within the lower quality materials requiring additional hydrocracking. In addition to increased catalyst concentration, the inventive systems and methods provide increased reactor throughput, increased reaction rate, and of course higher conversion of asphaltenes and lower quality materials. Increased conversion levels of asphaltenes and lower quality materials also reduces equipment fouling, enables the reactor to process a wider range of lower quality feedstocks, and can lead to more efficient use of a supported catalyst if used in combination with the colloidal or molecular catalyst.

Systems for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker

An ebullated bed hydroprocessing system, and also a method for upgrading an existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a catalyst precursor capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the catalyst precursor to form the colloidal or molecular catalyst in situ. The improved ebullated bed hydroprocessing system includes at least one ebullated bed reactor that employs both a porous supported catalyst and the colloidal or molecular catalyst to catalyze hydroprocessing reactions involving the feedstock and hydrogen. The colloidal or molecular catalyst provides catalyst in what would otherwise constitute catalyst free zones within the ebullated bed hydroprocessing system. Asphaltene or other hydrocarbon molecules too large to diffuse into the pores of the supported catalyst can be upgraded by the colloidal or molecular catalyst. A slurry phase reactor may be positioned upstream from one or more ebullated bed reactors or converted from an existing ebullated bed reactor.

Methods and systems for hydrocracking a heavy oil feedstock using, a colloidally or molecularly dispersed catalyst (e.g., molybdenum sulfide) which provide for concentration of the colloidally dispersed catalyst within the lower quality materials requiring additional hydrocracking. In addition to increased catalyst concentration, the inventive systems and methods provide increased reactor throughput, increased reaction rate, and of course higher conversion of asphaltenes and lower quality materials. Increased conversion levels of asphaltenes and lower quality materials also reduces equipment fouling, enables the reactor to process a wider range of lower quality feedstocks, and can lead to more efficient use of a supported catalyst if used in combination with the colloidal or molecular catalyst.

An ebullated bed hydroprocessing system, and also a method for upgrading a pre-existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst in situ. The improved ebullated bed hydroprocessing system includes at least one ebullated bed reactor that employs both a porous supported catalyst and the colloidal or molecular catalyst to catalyze hydroprocessing reactions involving the feedstock and hydrogen. The colloidal or molecular catalyst provides catalyst in what would otherwise constitute catalyst free zones within the ebullated bed hydroprocessing system. Asphaltene or other hydrocarbon molecules too large to diffuse into the pores of the supported catalyst can be upgraded by the colloidal or molecular catalyst. A slurry phase reactor may be positioned upstream from one or more ebullated bed reactors or converted from a pre-existing ebullated bed reactor.

Growing community of inventors

Edmonton, Canada

Roger Kai Lott