Abstract: Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a pre-coking hydrocracking reactor, a separator, and a coking reactor. The colloidal or molecular catalyst promotes upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors in the feedstock, increase hydrogen to carbon ratio in the upgraded material, and decrease boiling points of hydrocarbons in the upgraded material. The methods and systems can be used to upgrade vacuum tower bottoms and other low grade heavy oil feedstocks.

Abstract: 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° C. (975° 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.

Abstract: Methods and systems for hydroprocessing heavy oil feedstocks to form upgraded material use a colloidal or molecular catalyst dispersed within heavy oil feedstock, pre-coking hydrocracking reactor, separator, and coking reactor. The colloidal or molecular catalyst promotes upgrading reactions that reduce the quantity of asphaltenes or other coke forming precursors in the feedstock, increase hydrogen to carbon ratio in the upgraded material, and decrease boiling points of hydrocarbons in the upgraded material. The methods and systems can be used to upgrade vacuum tower bottoms and other low grade heavy oil feedstocks.

Abstract: 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.

Abstract: Hydrocarbon-soluble molybdenum catalyst precursors include a plurality of molybdenum cations and a plurality of carboxylate anions having at least 8 carbon atoms. The carboxylate anions are alicyclic, aromatic, or branched, unsaturated and aliphatic, and can derived from carboxylic acids selected from 3-cyclopentylpropionic acid, cyclohexanebutyric acid, biphenyl-2-carboxylic acid, 4-heptylbenzoic acid, 5-phenylvaleric acid, geranic acid, 10-undecenoic acid, dodecanoic acid, and combinations thereof. The molybdenum salts have decomposition temperatures higher than 210° C. The catalyst precursors can form a hydroprocessing molybdenum sulfide catalyst in heavy oil feedstocks. Also disclosed are methods for making catalyst precursors and hydrocracking heavy oil using active catalysts.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: 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.

Abstract: Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a hydrocracking reactor, and a hot separator. The colloidal or molecular catalyst promotes hydrocracking and other hydroprocessing reactions within the hydrocracking reactor. The catalyst is preferentially associated with asphaltenes within the heavy oil feedstock, which promotes upgrading reactions involving the asphaltenes rather than formation of coke precursors and sediment. The colloidal or molecular catalyst overcomes problems associated with porous supported catalysts in upgrading heavy oil feedstocks, particularly the inability of such catalysts to effectively process asphaltene molecules. The result is one or more of reduced equipment fouling, increased conversion level, and more efficient use of the supported catalyst if used in combination with the colloidal or molecular catalyst.

Abstract: A fixed bed hydroprocessing system, and also a method for upgrading a pre-existing fixed bed hydroprocessing system, involves preliminarily upgrading a heavy oil feedstock in one or more slurry phase reactors using a colloidal or molecular catalyst and then further hydroprocessing the upgraded feedstock within one or more fixed bed reactors using a porous supported catalyst. 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. Asphaltene or other hydrocarbon molecules otherwise too large to diffuse into the pores of the fixed bed catalyst can be upgraded by the colloidal or molecular catalyst.

Abstract: 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.

Abstract: 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.

Abstract: An organically complexed nanocatalyst composition is applied to or mixed with coal prior to or upon introducing the coal into a coal burner in order to catalyze the removal of coal nitrogen from the coal and its conversion into nitrogen gas prior to combustion of the coal. This process leads to reduced NOx production during coal combustion. The nanocatalyst compositions include a nanoparticle catalyst that is made using a dispersing agent that can bond with the catalyst atoms. The dispersing agent forms stable, dispersed, nano-sized catalyst particles. The catalyst composition can be formed as a stable suspension to facilitate storage, transportation and application of the catalyst nanoparticles to a coal material. The catalyst composition can be applied before or after pulverizing the coal material or it may be injected directly into the coal burner together with pulverized coal.

Abstract: 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.

Abstract: 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.