Patent Description:
Petrochemical feeds, such as crude oils, can be converted to chemical intermediates such as ethylene, propylene, butenes, butadiene, and aromatic compounds such as benzene, toluene, and xylene, which are basic intermediates for a large portion of the petrochemical industry. They are mainly obtained through the thermal cracking (sometimes referred to as "steam pyrolysis" or "steam cracking") of petroleum gases and distillates such as naphtha, kerosene, or even gas oil. Additionally, petrochemical feeds may be converted to transportation fuels such a gasoline, diesel, et cetera. However, as demands rise for these basic intermediate compounds and fuels, other production methods must be considered beyond traditional refining operations.

<CIT> and <CIT> disclose methods of processing heavy oil. The use of mesoporous zeolites in hydrocracking catalysts is known from <CIT> and <CIT>.

There is a need for processes that produce transportation fuels from heavy oil feeds, such as crude oil. In one or more embodiments, catalytic treatment processes (sometimes referred to herein as pretreating, hydroprocessing, or hydrotreating) and catalysts for use in such processes are disclosed. In one or more embodiments, the catalyst have enhanced catalytic functionality and, in particular, have enhanced aromatic cracking functionality, and through such catalytic treatment processes, heavy oils may be upgraded and converted to at least transportation fuels by subsequent separation. The separation, such as by distillation, may be performed without any intermediate steps which reduce the final boiling point of the upgraded oil.

The presently-described catalytic treatment processes (for example, the upgrading) may have enhanced catalytic functionality with regards to reducing at least aromatic content, metal content, and nitrogen content in a crude oil feedstock, which may be subsequently refined into desired petrochemical products by a number of different processes disclosed herein. According to one or more embodiments, heavy oils may be treated by four catalysts arranged in series, where the primary function of the first catalyst (that is, the hydrodemetalization catalyst) is to remove metals from the heavy oil, the primary function of the second catalyst (that is, the transition catalyst) is to remove metals, sulfur, and nitrogen from the heavy oil and to provide a transition area between the first and third catalysts, the primary function of the third catalyst (as the hydrodenitrogenation catalyst) is to further remove nitrogen, sulfur, or both, and saturate the aromatics from the heavy oil, and the primary function of the fourth catalyst (that is, the hydrocracking catalyst) is to reduce aromatic content in the heavy oil. The overall pretreatment process may result in one or more of an increased concentration of paraffins, a decreased concentration of polynuclear aromatic hydrocarbons, and a reduced final boiling point of the pretreated oil with respect to the heavy oil feedstock.

Following the hydroprocessing, the upgraded heavy oil is further processed by distillation into at least one or more transportation fuels. For example, the upgraded heavy oil may be directly passed to a separation unit for processing. In additional embodiments, some intermediate steps may by present, but the most heavy portion of the upgraded heavy oil may be retained in the stream that is passed to the separation device.

According to the invention, a heavy oil is processed by a method that includes upgrading at least a portion of the heavy oil to form an upgraded oil, where the upgrading comprises contacting the heavy oil with a hydrodemetalization catalyst, a transition catalyst, a hydrodenitrogenation catalyst, and a hydrocracking catalyst to remove at least a portion of metals, nitrogen, or aromatics content from the heavy oil and form the upgraded oil. The method further comprises passing at least a portion of the upgraded oil to a separation device that separates the upgraded oil into one or more transportation fuels; and where the final boiling point of the upgraded oil is less than or equal to <NUM>.

Additional features and advantages of the technology described in this disclosure will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the technology as described in this disclosure, including the detailed description which follows, the claims, as well as the appended drawings.

For the purpose of the simplified schematic illustrations and descriptions of <FIG>, the numerous valves, temperature sensors, electronic controllers and the like that may be employed and are well known to those of ordinary skill in the art of certain chemical processing operations are not included. Further, accompanying components that are often included in conventional chemical processing operations, such as refineries, such as, for example, air supplies, catalyst hoppers, and flue gas handling are not depicted. It would be known that these components are within the spirit and scope of the present embodiments disclosed. However, operational components, such as those described in the present disclosure, may be added to the embodiments described in this disclosure.

It should further be noted that arrows in the drawings refer to process streams. However, the arrows may equivalently refer to transfer lines that may serve to transfer process steams between two or more system components. Additionally, arrows that connect to system components define inlets or outlets in each given system component. The arrow direction corresponds generally with the major direction of movement of the materials of the stream contained within the physical transfer line signified by the arrow. Furthermore, arrows that do not connect two or more system components signify a product stream which may exit the depicted system or a system inlet stream which may enter the depicted system. Product streams may be further processed in accompanying chemical processing systems or may be commercialized as end products. System inlet streams may be streams transferred from accompanying chemical processing systems or may be non-processed feedstock streams. Additionally, dashed or dotted lines may signify an optional step or stream. For example, recycle streams in a system may be optional. However, it should be appreciated that not all solid lines may represent required transfer lines or chemical streams.

Generally, described in this disclosure are various embodiments of systems and methods for processing heavy oils such as crude oil. According to the invention, the heavy oil processing includes an upgrading process followed by downstream separation into transportation fuels. Generally, the upgrading process may remove one or more of at least a portion of nitrogen, sulfur, and one or more metals from the heavy oil, and may additionally break aromatic moieties in the heavy oil. According to the invention, the heavy oil is treated with a hydrodemetalization catalyst (referred to sometimes in this disclosure as an "HDM catalyst"), a transition catalyst, a hydrodenitrogenation catalyst (referred to sometimes in this disclosure as an "HDN catalyst"), and a hydrocracking catalyst. The HDM catalyst, transition catalyst, HDN catalyst, and hydrocracking catalyst may be positioned in series, either contained in a single reactor, such as a packed bed reactor with multiple beds, or contained in two or more reactors arranged in series.

Embodiments of the pretreatment process, as well as other processes following the pretreatment process, are described herein. The systems utilized following the pretreatment may be referred to as a "chemical processing system," or alternatively as a "post-pretreatment process" or "downstream processing. " It should be understood that any of the disclosed chemical processing systems may be practiced in conjunction with any of the pretreatment processes described herein. For example, <FIG> depict embodiments of pretreatment processing, and <FIG> depicts embodiments of chemical processing systems (i.e., post-pretreatment processing) by separation. It should be appreciated that any of the embodiments of the pretreatment systems, such as those depicted in <FIG> or described with respect to <FIG>, may be utilized with any of the downstream processing configurations described herein, such as those of <FIG>, or any other processing configuration described with respect to <FIG>.

As used in this disclosure, a "reactor" refers to any vessel, container, or the like, in which one or more chemical reactions may occur between one or more reactants optionally in the presence of one or more catalysts. For example, a reactor may include a tank or tubular reactor configured to operate as a batch reactor, a continuous stirred-tank reactor (CSTR), or a plug flow reactor. Example reactors include packed bed reactors such as fixed bed reactors, and fluidized bed reactors. One or more "reaction zones" may be disposed in a reactor. As used in this disclosure, a "reaction zone" refers to an area where a particular reaction takes place in a reactor. For example, a packed bed reactor with multiple catalyst beds may have multiple reaction zones, where each reaction zone is defined by the area of each catalyst bed.

As used in this disclosure, a "separation unit" refers to any separation device that at least partially separates one or more chemicals that are mixed in a process stream from one another. For example, a separation unit may selectively separate differing chemical species from one another, forming one or more chemical fractions. Examples of separation units include, without limitation, distillation columns, flash drums, knock-out drums, knock-out pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, and the like. It should be understood that separation processes described in this disclosure may not completely separate all of one chemical consistent from all of another chemical constituent. It should be understood that the separation processes described in this disclosure "at least partially" separate different chemical components from one another, and that even if not explicitly stated, it should be understood that separation may include only partial separation. As used in this disclosure, one or more chemical constituents may be "separated" from a process stream to form a new process stream. Generally, a process stream may enter a separation unit and be divided or separated into two or more process streams of desired composition. Further, in some separation processes, a "light fraction" and a "heavy fraction" may separately exit the separation unit. In general, the light fraction stream has a lesser boiling point than the heavy fraction stream. It should be additionally understood that where only one separation unit is depicted in a figure or described, two or more separation units may be employed to carry out the identical or substantially identical separation. For example, where a distillation column with multiple outlets is described, it is contemplated that several separators arranged in series may equally separate the feed stream and such embodiments are within the scope of the presently described embodiments.

It should be understood that a "reaction effluent" generally refers to a stream that exits a separation unit, a reactor, or reaction zone following a particular reaction or separation. Generally, a reaction effluent has a different composition than the stream that entered the separation unit, reactor, or reaction zone. It should be understood that when an effluent is passed to another system unit, only a portion of that system stream may be passed. For example, a slip stream may carry some of the effluent away, meaning that only a portion of the effluent enters the downstream system unit.

As used in this disclosure, a "catalyst" refers to any substance which increases the rate of a specific chemical reaction. Catalysts described in this disclosure may be utilized to promote various reactions, such as, but not limited to, hydrodemetalization, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, aromatic cracking, or combinations thereof. As used in this disclosure, "cracking" generally refers to a chemical reaction where a molecule having carbon-carbon bonds is broken into more than one molecules by the breaking of one or more of the carbon-carbon bonds; where a compound including a cyclic moiety, such as an aromatic, is converted to a compound that does not include a cyclic moiety; or where a molecule having carbon-carbon double bonds are reduced to carbon-carbon single bonds. Some catalysts may have multiple forms of catalytic activity, and calling a catalyst by one particular function does not render that catalyst incapable of being catalytically active for other functionality.

It should be understood that two or more process stream are "mixed" or "combined" when two or more lines intersect in the schematic flow diagrams of <FIG>. Mixing or combining may also include mixing by directly introducing both streams into a like reactor, separation unit, or other system component.

It should be understood that the reactions promoted by catalysts as described in this disclosure may remove a chemical constituent, such as only a portion of a chemical constituent, from a process stream. For example, a hydrodemetalization (HDM) catalyst may be present in an effective amount to promote a reaction that removes a portion of one or more metals from a process stream. A hydrodenitrogenation (HDN) catalyst may be present in an effective amount to promote a reaction that removes a portion of the nitrogen present in a process stream. A hydrodesulfurization (HDS) catalyst may present in an effective amount to promote a reaction that removes a portion of the sulfur present in a process stream. Additionally, a hydrocracking catalyst, such as a hydrodearomatization (HDA) catalyst, may present in an effective amount to promote a reaction that reduces the amount of aromatic moieties in a process stream by saturating and cracking those aromatic moieties. It should be understood that, throughout this disclosure, a particular catalyst is not necessarily limited in functionality to the removal or cracking of a particular chemical constituent or moiety when it is referred to as having a particular functionality. For example, a catalyst identified in this disclosure as an HDN catalyst may additionally provide HDA functionality, HDS functionality, or both.

It should further be understood that streams may be named for the components of the stream, and the component for which the stream is named may be the major component of the stream (such as comprising from <NUM> weight percent (wt. %), from <NUM> wt. %, from <NUM> wt. %, from <NUM> wt. %, or even from <NUM> wt. % of the contents of the stream to <NUM> wt. % of the contents of the stream).

It should be understood that pore size, as used throughout this disclosure, relates to the average pore size unless specified otherwise. The average pore size may be determined from a Brunauer-Emmett-Teller (BET) analysis. Further, the average pore size may be confirmed by transmission electron microscope (TEM) characterization.

Referring now to <FIG>, a pretreatment system <NUM> is depicted which includes a generalized hydrotreatment catalyst system <NUM>. It should be understood that additional embodiments of the hydrotreatment catalyst system <NUM> of <FIG> are described in detail in <FIG>. However, it should be understood that the feedstocks, products, recycle streams, et cetera, of the generalized pretreatment system <NUM> of <FIG> apply also to embodiments described with respect to <FIG>.

Referring to <FIG>, according to embodiments of this disclosure, a heavy oil feed stream <NUM> may be mixed with a hydrogen stream <NUM>. The hydrogen stream <NUM> may comprise unspent hydrogen gas from recycled process gas component stream <NUM>, make-up hydrogen from hydrogen feed stream <NUM>, or both, to mix with heavy oil feed stream <NUM> and form a pretreatment catalyst input stream <NUM>. In one or more embodiments, pretreatment catalyst input stream <NUM> may be heated to a process temperature of from <NUM> degrees Celsius (°C) to <NUM>. The pretreatment catalyst input stream <NUM> may enter and pass through the hydrotreatment catalyst system <NUM>. As is described herein, the hydrotreatment catalyst system <NUM> may include a series of reaction zones, including a HDM reaction zone, a transition reaction zone, a HDN reaction zone, and a hydrocracking reaction zone.

The systems and processes described are applicable for a wide variety of heavy oil feeds (in heavy oil feed stream <NUM>), including crude oils, vacuum residue, tar sands, bitumen and vacuum gas oils using a catalytic hydrotreating pretreatment process. If the heavy oil feed is crude oil, it may have an American Petroleum Institute (API) gravity of from <NUM> degrees to <NUM> degrees. For example, the heavy oil feed utilized may be Arab Heavy crude oil. The typical properties for an Arab Heavy crude oil are shown in Table <NUM>.

Still referring to <FIG>, a pretreatment catalyst reaction effluent stream <NUM> may be formed by interaction of the pretreatment catalyst input stream <NUM> with hydrotreatment catalyst system <NUM>. The pretreatment catalyst reaction effluent stream <NUM> may enter a separation unit <NUM> and may be separated into recycled process gas component stream <NUM> and intermediate liquid product stream <NUM>. In one embodiment, the pretreatment catalyst reaction effluent stream <NUM> may also be purified to remove hydrogen sulfide and other process gases to increase the purity of the hydrogen to be recycled in recycled process gas component stream <NUM>. The hydrogen consumed in the process can be compensated for by the addition of a fresh hydrogen from make-up hydrogen feed stream <NUM>, which may be derived from a steam or naphtha reformer or other source. Recycled process gas component stream <NUM> and fresh make-up hydrogen feed stream <NUM> may combine to form hydrogen stream <NUM>. In one embodiment, intermediate liquid product stream <NUM> may be separated in separation unit <NUM> to separate light hydrocarbon fraction stream <NUM> and pretreatment final liquid product stream <NUM>; however, it should be understood that this separation step is optional. In further embodiments, separation unit <NUM> may be a flash vessel. In one embodiment, light hydrocarbon fraction stream <NUM> acts as a recycle and is mixed with fresh light hydrocarbon diluent stream <NUM> to create light hydrocarbon diluent stream <NUM>. Fresh light hydrocarbon diluent stream <NUM> can be used as needed to provide make-up diluent to help further reduce the deactivation of one or more of the catalysts in the hydrotreatment catalyst system <NUM>.

In one or more embodiments, one or more of the pretreatment catalyst reaction effluent stream <NUM>, the intermediate liquid product stream <NUM>, and the pretreatment final liquid product stream <NUM> may have reduced aromatic content as compared with the heavy oil feed stream <NUM>. Additionally, in embodiments, one or more of the pretreatment catalyst reaction effluent stream <NUM>, the intermediate liquid product stream <NUM>, and the pretreatment final liquid product stream <NUM> may have reduced sulfur, metal, asphaltenes, Conradson carbon, nitrogen content, or combinations thereof, as well as an increased API gravity and increased diesel and vacuum distillate yields as compared with the heavy oil feed stream <NUM>.

According to one or more embodiments, the pretreatment catalyst reaction effluent stream <NUM> may have a reduction of at least about <NUM> wt. %, a reduction of at least <NUM> wt. %, or even a reduction of at least <NUM> wt. % of nitrogen with respect to the heavy oil feed stream <NUM>. According to another embodiment, the pretreatment catalyst reaction effluent stream <NUM> may have a reduction of at least about <NUM> wt. %, a reduction of at least <NUM> wt. %, or even a reduction of at least <NUM> wt. % of sulfur with respect to the heavy oil feed stream <NUM>. According to another embodiment, the pretreatment catalyst reaction effluent stream <NUM> may have a reduction of at least about <NUM> wt. %, a reduction of at least <NUM> wt. %, or even a reduction of at least <NUM> wt. % of aromatic content with respect to the heavy oil feed stream <NUM>. According to another embodiment, the pretreatment catalyst reaction effluent stream <NUM> may have a reduction of at least about <NUM> wt. %, a reduction of at least <NUM> wt. %, or even a reduction of at least <NUM> wt. % of metal with respect to the heavy oil feed stream <NUM>.

Still referring to <FIG>, in various embodiments, one or more of the pretreatment catalyst reaction effluent stream <NUM>, the intermediate liquid product stream <NUM>, and the pretreatment final liquid product stream <NUM> may be suitable for use as the separation input stream <NUM> of <FIG> as described subsequently in this disclosure. As used in this disclosure, one or more of the pretreatment catalyst reaction effluent stream <NUM>, the intermediate liquid product stream <NUM>, and the pretreatment final liquid product stream <NUM> may be referred to as an "upgraded oil" which may be downstream processed by the systems of at least <FIG>. The upgraded oils have a final boiling point of less than <NUM>, which may increase efficiency of further conversion in downstream separation. In additional embodiments, the upgraded oil may have a final boiling point of less than or equal to <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or even <NUM>. It should be understood that the final boiling point of the upgraded oil is equal to the final boiling point of the pretreatment reaction catalyst effluent stream <NUM> because only light fractions are removed by subsequent, optional separation steps in pretreatment system <NUM>.

Referring now to <FIG>, according to one or more embodiments, the hydrotreatment catalyst system <NUM> may include or consist of multiple packed bed reaction zones arranged in series (for example, a HDM reaction zone <NUM>, a transition reaction zone <NUM>, a HDN reaction zone <NUM>, and a hydrocracking reaction zone <NUM>) and each of these reaction zones may comprise a catalyst bed. Each of these reaction zones may be contained in a single reactor as a packed bed reactor with multiple beds in series, as shown as a pretreatment reactor <NUM> in <FIG>. In such embodiments, the pretreatment reactor <NUM> comprises an HDM catalyst bed comprising an HDM catalyst in the HDM reaction zone <NUM>, a transition catalyst bed comprising a transition catalyst in the transition reaction zone <NUM>, an HDN catalyst bed comprising an HDN catalyst in the HDN reaction zone <NUM>, and a hydrocracking catalyst bed comprising a hydrocracking catalyst in the hydrocracking reaction zone <NUM>. In other embodiments, the HDM reaction zone <NUM>, transition reaction zone <NUM>, HDN reaction zone <NUM>, and hydrocracking reaction zone <NUM> may each be contained in a plurality of packed bed reactors arranged in series. In further embodiments, each reaction zone is contained in a separate, single packed bed reactor. It should be understood that contemplated embodiments include those where packed catalyst beds which are arranged in series are contained in a single reactor or in multiple reactors each containing one or more catalyst beds. It should be appreciated that when relatively large quantities of catalyst are needed, it may be desirable to house those catalysts in separate reactors.

According to one or more embodiments, the pretreatment catalyst input stream <NUM>, which comprises heavy oil, is introduced to the HDM reaction zone <NUM> and is contacted by the HDM catalyst. Contacting the HDM catalyst with the pretreatment catalyst input stream <NUM> may promote a reaction that removes at least a portion of the metals present in the pretreatment catalyst input stream <NUM>, such as a hydrodemetalization reaction. Following contact with the HDM catalyst, the pretreatment catalyst input stream <NUM> may be converted to an HDM reaction effluent. The HDM reaction effluent may have a reduced metal content as compared to the contents of the pretreatment catalyst input stream <NUM>. For example, the HDM reaction effluent may have at least <NUM> wt. % less, at least <NUM> wt. % less, or even at least <NUM> wt. % less metal as the pretreatment catalyst input stream <NUM>.

According to one or more embodiments, the HDM reaction zone <NUM> may have a weighted average bed temperature of from <NUM> to <NUM>, such as from <NUM> to <NUM>, and may have a pressure of from <NUM> bars to <NUM> bars, such as from <NUM> bars to <NUM> bars. The HDM reaction zone <NUM> comprises the HDM catalyst, and the HDM catalyst may fill the entirety of the HDM reaction zone <NUM>.

The HDM catalyst may comprise one or more metals from the International Union of Pure and Applied Chemistry (IUPAC) Groups <NUM>, <NUM>, or <NUM>-<NUM> of the periodic table. For example, the HDM catalyst may comprise molybdenum. The HDM catalyst may further comprise a support material, and the metal may be disposed on the support material. In one embodiment, the HDM catalyst may comprise a molybdenum metal catalyst on an alumina support (sometimes referred to as "Mo/Al2O3 catalyst"). It should be understood throughout this disclosure that metals contained in any of the disclosed catalysts may be present as sulfides or oxides, or even other compounds.

In one embodiment, the HDM catalyst may include a metal sulfide on a support material, where the metal is selected from the group consisting of IUPAC Groups <NUM>, <NUM>, and <NUM>-<NUM> elements of the periodic table, and combinations thereof. The support material may be gamma-alumina or silica/alumina extrudates, spheres, cylinders, beads, pellets, and combinations thereof.

In one embodiment, the HDM catalyst may comprise a gamma-alumina support, with a surface area of from <NUM> m2/g to <NUM> m2/g (such as, from <NUM> m2/g to <NUM> m2/g, or from <NUM> m2/g to <NUM> m2/g). The HDM catalyst can be best described as having a relatively large pore volume, such as at least <NUM> cm3/g (for example, at least <NUM> cm3/g, or even at least <NUM> cm3/g). The pore size of the HDM catalyst may be predominantly macroporous (that is, having a pore size of greater than <NUM>). This may provide a large capacity for the uptake of metals on the HDM catalyst's surface and optionally dopants. In one embodiment, a dopant can be selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.

In one or more embodiments, the HDM catalyst may comprise from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum), and from <NUM> wt. % to <NUM> wt. % of alumina (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of alumina).

Without being bound by theory, in some embodiments, it is believed that during the reaction in the HDM reaction zone <NUM>, the HDM catalyst promotes the hydrogenation of porphyrin type compounds present in the heavy oil via hydrogen to create an intermediate. Following this primary hydrogenation, the nickel or vanadium present in the center of the porphyrin molecule in the intermediate is reduced with hydrogen and then further reduced to the corresponding sulfide with hydrogen sulfide (H2S). The final metal sulfide is deposited on the HDM catalyst thus removing the metal sulfide from the virgin crude oil. Sulfur is also removed from sulfur-containing organic compounds through a parallel pathway. The rates of these parallel reactions may depend upon the sulfur species being considered. Overall, hydrogen is used to abstract the sulfur which is converted to H2S in the process. The remaining, sulfur-free hydrocarbon fragments remain in the liquid hydrocarbon stream.

The HDM reaction effluent may be passed from the HDM reaction zone <NUM> to the transition reaction zone <NUM> where it is contacted by the transition catalyst. Contact by the transition catalyst with the HDM reaction effluent may promote a reaction that removes at least a portion of the metals present in the HDM reaction effluent stream as well as reactions that may remove at least a portion of the nitrogen present in the HDM reaction effluent stream. Following contact with the transition catalyst, the HDM reaction effluent is converted to a transition reaction effluent. The transition reaction effluent may have a reduced metal content and nitrogen content as compared to the HDM reaction effluent. For example, the transition reaction effluent may have at least <NUM> wt. % less, at least <NUM> wt. % less, or even at least <NUM> wt. % less metal content as the HDM reaction effluent. Additionally, the transition reaction effluent may have at least <NUM> wt. % less, at least <NUM> wt. % less, or even at least <NUM> wt. % less nitrogen as the HDM reaction effluent.

According to embodiments, the transition reaction zone <NUM> has a weighted average bed temperature of about <NUM> to <NUM>. The transition reaction zone <NUM> comprises the transition catalyst, and the transition catalyst may fill the entirety of the transition reaction zone <NUM>.

In one embodiment, the transition reaction zone <NUM> may be operable to remove a quantity of metal components and a quantity of sulfur components from the HDM reaction effluent stream. The transition catalyst may comprise an alumina based support in the form of extrudates.

In one embodiment, the transition catalyst comprises one metal from IUPAC Group <NUM> and one metal from IUPAC Groups <NUM>-<NUM>. Examples of IUPAC Group <NUM> metals include molybdenum and tungsten. Example IUPAC Group <NUM>-<NUM> metals include nickel and cobalt. For example, the transition catalyst may comprise Mo and Ni on a titania support (sometimes referred to as "Mo-Ni/Al2O3 catalyst"). The transition catalyst may also contain a dopant that is selected from the group consisting of boron, phosphorus, halogens, silicon, and combinations thereof. The transition catalyst can have a surface area of <NUM> m2/g to <NUM> m2/g (such as from <NUM> m2/g to <NUM> m2/g or from <NUM> m2/g to <NUM> m2/g). The transition catalyst can have an intermediate pore volume of from <NUM> cm3/g to <NUM> cm3/g (such as <NUM> cm3/g). The transition catalyst may generally comprise a mesoporous structure having pore sizes in the range of <NUM> to <NUM>. These characteristics provide a balanced activity in HDM and HDS.

In one or more embodiments, the transition catalyst may comprise from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum), from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel), and from <NUM> wt. % to <NUM> wt. % of alumina (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of alumina).

The transition reaction effluent may be passed from the transition reaction zone <NUM> to the HDN reaction zone <NUM> where it is contacted by the HDN catalyst. Contact by the HDN catalyst with the transition reaction effluent may promote a reaction that removes at least a portion of the nitrogen present in the transition reaction effluent stream, such as a hydrodenitrogenation reaction. Following contact with the HDN catalyst, the transition reaction effluent may be converted to an HDN reaction effluent. The HDN reaction effluent may have a reduced metal content and nitrogen content as compared to the transition reaction effluent. For example, the HDN reaction effluent may have a nitrogen content reduction of at least <NUM> wt. %, at least <NUM> wt. %, or even at least <NUM> wt. % relative to the transition reaction effluent. In another embodiment, the HDN reaction effluent may have a sulfur content reduction of at least <NUM> wt. %, at least <NUM> wt. %, or even at least <NUM> wt. % relative to the transition reaction effluent. In another embodiment, the HDN reaction effluent may have an aromatics content reduction of at least <NUM> wt. %, at least <NUM> wt. %, or even at least <NUM> wt. % relative to the transition reaction effluent.

According to embodiments, the HDN reaction zone <NUM> has a weighted average bed temperature of from <NUM> to <NUM>. The HDN reaction zone <NUM> comprises the HDN catalyst, and the HDN catalyst may fill the entirety of the HDN reaction zone <NUM>.

The HDN catalyst comprises one or more metals on an alumina support, the alumina support having an average pore size of from <NUM> to <NUM>. In one embodiment, the HDN catalyst includes a metal oxide or sulfide on a support material, where the metal is selected from the group consisting of IUPAC Groups <NUM>, <NUM>, and <NUM>-<NUM> of the periodic table, and combinations thereof. The support material may include gamma-alumina, meso-porous alumina, silica, or both, in the form of extrudates, spheres, cylinders and pellets.

According to one embodiment, the HDN catalyst contains a gamma alumina based support that has a surface area of <NUM> m2/g to <NUM> m2/g (such as from <NUM> m2/g to <NUM> m2/g, or from <NUM> m2/g to <NUM> m2/g). This relatively large surface area for the HDN catalyst allows for a smaller pore volume (for example, less than <NUM> cm3/g, less than <NUM> cm3/g, or even less than <NUM> cm3/g). In one embodiment, the HDN catalyst contains at least one metal from IUPAC Group <NUM>, such as molybdenum and at least one metal from IUPAC Groups <NUM>-<NUM>, such as nickel. The HDN catalyst can also include at least one dopant selected from the group consisting of boron, phosphorus, silicon, halogens, and combinations thereof. In one embodiment, the HDN catalyst may include cobalt, which further promotes desulfurization. In one embodiment, the HDN catalyst has a higher metals loading for the active phase as compared to the HDM catalyst. This increased metals loading may cause increased catalytic activity. In one embodiment, the HDN catalyst comprises nickel and molybdenum, and has a nickel to molybdenum mole ratio (Ni/(Ni+Mo)) of <NUM> to <NUM> (such as from <NUM> to <NUM> or from <NUM> to <NUM>). In an embodiment that includes cobalt, the mole ratio of (Co+Ni)/Mo may be in the range of <NUM> to <NUM> (such as from <NUM> to <NUM> or from <NUM> to <NUM>).

According to another embodiment, the HDN catalyst contains mesoporous alumina, that may have an average pore size of at least <NUM>. For example, the HDN catalyst may comprise mesoporous alumina having an average pore size of at least <NUM>, or even at least <NUM>. HDN catalysts with relatively small average pore size, such as less than <NUM>, may be referred to as conventional HDN catalysts in this disclosure, and may have relatively poor catalytic performance as compared with the presently-disclosed HDN catalysts with larger-sized pores. Embodiments of HDN catalysts with an alumina support having an average pore size of from <NUM> to <NUM> are referred to in this disclosure as "meso-porous alumina supported catalysts. " According to the invention, the mesoporous alumina of the HDN catalyst has an average pore size in a range from <NUM> to <NUM>, <NUM> to <NUM>, from <NUM> to <NUM>, or from <NUM> to <NUM>. According to embodiments, the HDN catalyst may include alumina that has a relatively large surface area, a relatively large pore volume, or both. For example, the mesoporous alumina may have a relatively large surface area by having a surface area of at least about <NUM> m2/g, at least about <NUM> m2/g, at least about <NUM> m2/g, at least about <NUM> m2/g, or even at least about <NUM> m2/g, such as from <NUM> m2/g to <NUM> m2/g, from <NUM> m2/g to <NUM> m2/g, or from <NUM> m2/g to <NUM> m2/g. In one or more embodiments, the mesoporous alumina may have a relatively large pore volume by having a pore volume of at least about <NUM>/g, at least about <NUM>/g, at least <NUM>/g, or even at least <NUM>/g, such as from <NUM>/g to <NUM>/g, from <NUM>/g to <NUM>, or from <NUM>/g to <NUM>/g. Without being bound by theory, it is believed that the mesoporous alumina supported HDN catalyst may provide additional active sites and a larger pore channels that may facilitate larger molecules to be transferred into and out of the catalyst. The additional active sites and larger pore channels may result in higher catalytic activity, longer catalyst life, or both. In one embodiment, the HDN catalyst may include a dopant, which can be selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.

According to embodiments described, the HDN catalyst may be produced by mixing a support material, such as alumina, with a binder, such as acid peptized alumina. Water or another solvent may be added to the mixture of support material and binder to form an extrudable phase, which is then extruded into a desired shape. The extrudate may be dried at an elevated temperature (such as above <NUM>, such as <NUM>) and then calcined at a suitable temperature (such as at a temperature of at least <NUM> or at least <NUM>, such as <NUM>). The calcined extrudates may be impregnated with an aqueous solution containing catalyst precursor materials, such as precursor materials that include Mo, Ni, or combinations thereof. For example, the aqueous solution may contain ammonium heptanmolybdate, nickel nitrate, and phosphoric acid to form an HDN catalyst comprising compounds comprising molybdenum, nickel, and phosphorous.

In embodiments where a meso-porous alumina support is utilized, the meso-porous alumina may be synthesized by dispersing boehmite powder in water at <NUM> to <NUM>. Then, an acid such as HNO3 may be added to the boehmite in water solution at a ratio of HNO3:Al3+ of <NUM> to <NUM> and the solution is stirred at <NUM> to <NUM> for several hours, such as <NUM> hours, to obtain a sol. A copolymer, such as a triblock copolymer, may be added to the sol at room temperature, where the molar ratio of copolymer:Al is from <NUM> to <NUM> and aged for several hours, such as three hours. The sol/copolymer mixture is dried for several hours and then calcined.

According to one or more embodiments, the HDN catalyst may comprise from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum), from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel), and from <NUM> wt. % to <NUM> wt. % of alumina (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of alumina).

In a similar manner to the HDM catalyst, and again not intending to be bound to any theory, it is believed that hydrodenitrogenation and hydrodearomatization may operate via related reaction mechanisms. Both involve some degree of hydrogenation. For the hydrodenitrogenation, organic nitrogen compounds are usually in the form of heterocyclic structures, the heteroatom being nitrogen. These heterocyclic structures may be saturated prior to the removal of the heteroatom of nitrogen. Similarly, hydrodearomatization involves the saturation of aromatic rings. Each of these reactions may occur to a differing extent depending on the amount or type of each catalyst because each catalyst may selectively promote one type of transfer over others and because the transfers are competing.

It should be understood that some embodiments of the presently described methods and systems may utilize HDN catalyst that include porous alumina having an average pore size of at least <NUM>. However, in other embodiments, the average pore size of the porous alumina may be less than about <NUM>, and may even be microporous (that is, having an average pore size of less than <NUM>).

Still referring to <FIG>, the HDN reaction effluent may be passed from the HDN reaction zone <NUM> to the hydrocracking reaction zone <NUM> where it is contacted by the hydrocracking catalyst. Contact by the hydrocracking catalyst with the HDN reaction effluent may promote a reaction that reduces the aromatic content present in the HDN reaction effluent. Following contact with the hydrocracking catalyst, the HDN reaction effluent is converted to a pretreatment catalyst reaction effluent stream <NUM>. The pretreatment catalyst reaction effluent stream <NUM> may have reduced aromatics content as compared to the HDN reaction effluent. For example, the pretreatment catalyst reaction effluent stream <NUM> may have at least <NUM> wt. % less, at least <NUM> wt. % less, or even at least <NUM> wt. % less aromatics content as the HDN reaction effluent.

The hydrocracking catalyst comprises a mesoporous zeolite and one or more metals, the mesoporous zeolite having an average pore size of from <NUM> to <NUM>. The hydrocracking catalyst may comprise one or more metals from IUPAC Groups <NUM>, <NUM>, <NUM>, <NUM>, or <NUM> of the periodic table. For example, the hydrocracking catalyst may comprise one or more metals from IUPAC Groups <NUM> or <NUM>, and one or more metals from IUPAC Groups <NUM>, <NUM>, or <NUM> of the periodic table. For example, the hydrocracking catalyst may comprise molybdenum or tungsten from IUPAC Group <NUM> and nickel or cobalt from IUPAC Groups <NUM>, <NUM>, or <NUM>. The HDM catalyst may further comprise a support material, such as zeolite, and the metal may be disposed on the support material. In one embodiment, the hydrocracking catalyst may comprise tungsten and nickel metal catalyst on a zeolite support that is mesoporous (sometimes referred to as "W-Ni/meso-zeolite catalyst"). In another embodiment, the hydrocracking catalyst may comprise molybdenum and nickel metal catalyst on a zeolite support that is mesoporous (sometimes referred to as "Mo-Ni/meso-zeolite catalyst").

According to embodiments of the hydrocracking catalysts of the hydrotreatment catalytic systems described in this disclosure, the support material (that is, the mesoporous zeolite) is characterized as mesoporous by having average pore size of from <NUM> to <NUM>. By way of comparison, conventional zeolite-based hydrocracking catalysts contain zeolites which are microporous, meaning that they have an average pore size of less than <NUM>. Without being bound by theory, it is believed that the relatively large sized pores (that is, mesoporosity) of the presently-described hydrocracking catalysts allow for larger molecules to diffuse inside the zeolite, which is believed to enhance the reaction activity and selectivity of the catalyst. Because of the increased pore size, aromatic-containing molecules can more easily diffuse into the catalyst, and aromatic cracking may increase. For example, in some conventional embodiments, the feedstock converted by the hydroprocessing catalysts may be vacuum gas oils; light cycle oils from, for example, a fluid catalytic cracking reactor; or coker gas oils from, for example, a coking unit. The molecular sizes in these oils are relatively small compared to those of heavy oils such as crude and atmosphere residue, which may be the feedstock of the present methods and systems. The heavy oils generally are inable to diffuse inside the conventional zeolites and be converted on the active sites located inside the zeolites. Therefore, zeolites with larger pore sizes (that is, mesoporous zeolites) may allow the larger molecules of heavy oils to overcome the diffusion limitation and may promote the reaction and conversion of the larger molecules of the heavy oils.

The zeolite support material is not necessarily limited to a particular type of zeolite. However, it is contemplated that zeolites such as Y, Beta, AWLZ-<NUM>, LZ-<NUM>, Y-<NUM>, Y-<NUM>, LZ-<NUM>, LZ-<NUM>, Silicalite, or mordenite may be suitable for use in the presently-described hydrocracking catalyst. For example, suitable mesoporous zeolites that can be impregnated with one or more catalytic metals such as W, Ni, Mo, or combinations thereof, are described in at least <CIT>; <NPL>; <NPL>; and <NPL>).

In one or more embodiments, the hydrocracking catalyst may comprise from <NUM> wt. % to <NUM> wt. % of a sulfide or oxide of tungsten (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of tungsten or a sulfide or oxide of tungsten), from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel), and from <NUM> wt. % to <NUM> wt. % of mesoporous zeolite (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of zeolite). In another embodiment, the hydrocracking catalyst may comprise from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of molybdenum), from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of an oxide or sulfide of nickel), and from <NUM> wt. % to <NUM> wt. % of mesoporous zeolite (such as from <NUM> wt. % to <NUM> wt. % or from <NUM> wt. % to <NUM> wt. % of mesoporous zeolite).

The hydrocracking catalysts described may be prepared by selecting a mesoporous zeolite and impregnating the mesoporous zeolite with one or more catalytic metals or by comulling mesoporous zeolite with other components. For the impregnation method, the mesoporous zeolite, active alumina (for example, boehmite alumina), and binder (for example, acid peptized alumina) may be mixed. An appropriate amount of water may be added to form a dough that can be extruded using an extruder. The extrudate may be dried at from <NUM> to <NUM> for from <NUM> hours to <NUM> hours and then calcinated at from <NUM> to <NUM> for from <NUM> hours to <NUM> hours. The calcinated extrudate may be impregnated with an aqueous solution prepared with compounds comprising Ni, W, Mo, Co, or combinations thereof. Two or more catalytic metal precursors may be utilized when two catalytic metals are desired. However, some embodiments may include only one of Ni, W, Mo, or Co. For example, the catalyst support material may be impregnated by a mixture of nickel nitrate hexahydrate (that is, Ni(NO3)<NUM>•6H2O) and ammonium metatungstate (that is, (NH4)6H2W12O40) if a W-Ni hydrocracking catalyst is desired. The impregnated extrudate may be dried at from <NUM> to <NUM> for from <NUM> hours to <NUM> hours and then calcinated at from <NUM> to <NUM> for from <NUM> hours to <NUM> hours. For the comulling method, the mesoporous zeolite may be mixed with alumina, binder, and the compounds comprising W or Mo, Ni or Co (for example, MoO3 or nickel nitrate hexahydrate if Mo-Ni is desired).

According to one or more embodiments described, the volumetric ratio of HDM catalyst : transition catalyst HDN catalyst : hydrocracking catalyst may be <NUM>-<NUM> : <NUM>-<NUM> : <NUM>-<NUM> : <NUM>-<NUM>. The ratio of catalysts may depend at least partially on the metal content in the oil feedstock processed.

Now referring to <FIG>, according to additional embodiments, the hydrotreatment catalyst system <NUM> may include multiple packed bed reaction zones arranged in series (for example, a HDM reaction zone <NUM>, a transition reaction zone <NUM>, and a HDN reaction zone <NUM>) and each of these reaction zones may comprise a catalyst bed. Each of these zones may be contained in a single reactor as a packed bed reactor with multiple beds in series, shown as an upstream packed bead hydrotreating reactor <NUM> in <FIG>, and a downstream packed bed hydrocracking reactor <NUM>. In other embodiments, the HDM reaction zone <NUM>, the transition reaction zone <NUM>, and the HDN reaction zone <NUM> may be contained in a plurality of packed bed reactors arranged in series with a downstream packed bed hydrocracking reactor <NUM>. In further embodiments, each reaction zone is contained in a separate, single packed bed reactor. The upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors may include the HDM reaction zone <NUM>, the transition reaction zone <NUM>, and the HDN reaction zone <NUM>. The downstream packed bed hydrocracking reactor <NUM> may include the hydrocracking reaction zone <NUM>. In such embodiments, the HDM reaction zone <NUM>, the transition reaction zone <NUM>, the HDN reaction zone <NUM>, and the hydrocracking reaction zone <NUM> may utilize the respective catalysts, processing conditions, et cetera, disclosed with respect to the system of <FIG>. The configuration of the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors of <FIG> may be particularly beneficial when reaction conditions such as, but not limited to, hydrogen content, temperature, or pressure are different for operation of the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors and the downstream packed bed hydrocracking reactor <NUM>. In such embodiments, a stream <NUM> is passed from the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors to the downstream packed bed hydrocracking reactor <NUM>.

Now referring to <FIG>, according to additional embodiments, the hydrotreatment catalyst system <NUM> may include multiple packed bed reaction zones arranged in series (for example, a HDM reaction zone <NUM>, a transition reaction zone <NUM>, and a HDN reaction zone <NUM>) and each of these reaction zones may comprise a catalyst bed. Each of these zones may be contained in a single reactor as a packed bed reactor with multiple beds in series, shown as an upstream packed bead hydrotreating reactor <NUM> in <FIG>, and a downstream fluidized bed hydrocracking reactor <NUM>. In other embodiments, the HDM reaction zone <NUM>, the transition reaction zone <NUM>, and the HDN reaction zone <NUM> may each be contained in a plurality of packed bed reactors arranged in series with a downstream packed bed hydrocracking reactor <NUM>. In further embodiments, each reaction zone is contained in a separate, single packed bed reactor. The upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors may include the HDM reaction zone <NUM>, the transition reaction zone <NUM>, and the HDN reaction zone <NUM>. The downstream fluidized bed hydrocracking reactor <NUM> may include the hydrocracking reaction zone <NUM>. In such embodiments, the HDM reaction zone <NUM>, the transition reaction zone <NUM>, the HDN reaction zone <NUM>, and the hydrocracking reaction zone <NUM> may utilize the respective catalysts, processing conditions, et cetera, disclosed with respect to the system of <FIG>. The configuration of the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors of <FIG> may be particularly beneficial when reaction conditions such as, but not limited to, hydrogen content, temperature, or pressure are different for operation of the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors and the downstream fluidized bed hydrocracking reactor <NUM>. A process fluid <NUM> may fluidize the hydrocracking catalyst of the hydrocracking reaction zone <NUM>. In such embodiments, a stream <NUM> is passed from the upstream packed bed hydrotreating reactor <NUM> or plurality of upstream packed bed reactors to the downstream fluidized bed hydrocracking reactor <NUM>. The fluidized bed of the embodiment of <FIG> may be beneficial with particular hydrocracking catalysts as compared to the packed bed configurations of <FIG> and <FIG>.

Referring now to <FIG>, the upgraded oil (present in separation input stream <NUM>) is introduced to a separation unit <NUM> which separates the upgraded oil into one or more transportation fuels. For example, the separation input stream <NUM> may be separated into one or more of gasoline <NUM>, kerosene <NUM>, or diesel <NUM>. In one embodiment, such as depicted in <FIG>, a single distillation column separates the contents of the separation input stream <NUM>. In additional embodiments, multiple separation units are utilized for the separation of the separation input stream <NUM> into three or more streams.

In additional embodiments, other process products are contemplated in addition to, or in combination with, the transportation fuels described herein. For example, some fraction of the separation input stream <NUM> may be a non-transportation fuel which may be further processed or recycled in the system for further processing.

The various aspects of methods and systems for the upgrading of a heavy fuel will be further clarified by the following examples. The examples are illustrative in nature, and should not be understood to limit the subject matter of the present disclosure. Conventional catalysts and methods are not according to the invention.

A hydrocracking catalyst comprising mesoporous zeolite as described previously in this disclosure was synthesized. <NUM> of commercial NaY zeolite (commercially available as CBV-<NUM> from Zeolyst) was added in <NUM> milliliters (mL) of <NUM> molar (M) sodium hydroxide (NaOH) solution and was stirred at <NUM> for <NUM> hours. Then, <NUM> of cetyl trimethylammonium bromide (CTAB) was added into prepared mixture while the acidity was controlled at <NUM> pH with <NUM> hydrochloric acid solution. The mixture was aged at <NUM> for <NUM> hours, and then transferred into a Teflon-lined stainless steel autoclave and crystallized at <NUM> for <NUM> hours. Following the crystallization, the sample was washed with deionized water, dried at <NUM> for <NUM> hours, and calcined at <NUM> for <NUM> hours. The as-made sample was ion-exchanged with <NUM> ammonium nitrate (NH<NUM>NO<NUM>) solution at <NUM> for <NUM> hours, followed by a steam treatment (at a flow rate of <NUM> milliliter per minute (mL/min)) at <NUM> for <NUM> hour. Then, the sample was ion-exchanged with <NUM> NH<NUM>NO<NUM> solution again. Finally, the sample was dried at <NUM> for <NUM> hours and calcined at <NUM> for <NUM> hours to form a mesoporous zeolite Y. In a mortar, <NUM> grams (g) of the mesoporous zeolite Y, <NUM> of molybdenum trioxide (MoO<NUM>), <NUM> of nickel(II) nitrate hexahydrate (Ni(NO<NUM>)<NUM>•<NUM><NUM>O), and <NUM> of alumina (commercially available as PURALOX® HP <NUM>/<NUM> from Sasol) were mixed evenly. Then, <NUM> of binder made from alumina (commercially available as CATAPAL® from Sasol) and diluted nitric acid (HNO<NUM>) (ignition of loss: <NUM> wt. %) was added, which pasted the mixture to form a dough by adding an appropriate amount of water. The dough was extruded with an extruder to form a cylindered extrudate. The extrudate was dried at <NUM> overnight and calcinated at <NUM> for <NUM> hours.

A conventional hydrocracking catalyst (including a microporous zeolite) was produced by a method similar to that of Example <NUM> which utilized a commercial microporous zeolite. In a mortar, <NUM> of microporous zeolite (commercially available as ZEOLYST® CBV-<NUM> from Micrometrics), <NUM> of MoO<NUM>, <NUM> of Ni(NO<NUM>)<NUM><NUM><NUM>O, and <NUM> of alumina (commercially available as PURALOX® HP <NUM>/<NUM> from Sasol) were mixed evenly. Then, <NUM> of binder made from boehmite alumina (commercially available as CATAPAL® from Sasol) and diluted nitric acid (HNO<NUM>) (ignition of loss: <NUM> wt. %) was added, which pasted the mixture to form a dough by adding an appropriate amount of water. The dough was extruded with an extruder to form a cylindered extrudate. The extrudate was dried at <NUM> overnight and calcinated at <NUM> for <NUM> hours.

The prepared catalysts of Examples <NUM> and <NUM> were analyzed by BET analysis to determine surface area and pore volume. Additionally, micropore (less than <NUM>) and mesopore (greater than <NUM>) surface area and pore volume were determined. The results are shown in Table <NUM>, which shows the catalyst of Example <NUM> (conventional) had more micropore surface area and micropore pore volume than mesopore surface area and mesopore pore volume. Additionally, the catalyst of Example <NUM> had more mesopore surface area and mesopore pore volume than micropore surface area and micropore pore volume. These results indicate that the catalyst of Example <NUM> was microporous (that is, average pore size of less than <NUM>) and the catalyst of Example <NUM> was mesoporous (that is, average pore size of at least <NUM>).

A mesoporous HDN catalyst was prepared by the method described, where the mesoporous HDN catalyst had a measured average pore size of <NUM>. First, <NUM> of mesoporous alumina was prepared by mixing <NUM> of boehmite alumina powder (commercially available as CATAPAL® from Sasol) in <NUM> of water at <NUM>. Then, <NUM> of <NUM> HNO3 was added with the molar ratio of H+ to Al3+ equal to <NUM> and the mixture was kept stirring at <NUM> for <NUM> hours to obtain a sol. Then, <NUM> of triblock copolymer (commercially available as PLURONIC® P123 from BASF) was dissolved in the sol at room temperature and then aged for <NUM> hours, where the molar ratio of the copolymer to Al was equal to <NUM>). The mixture was then dried at <NUM> overnight and then calcined at <NUM> for <NUM> hours to form a mesoporous alumina.

The catalyst was prepared from the mesoporous alumina by mixing <NUM> (dry basis) of the mesoporous alumina with <NUM> (<NUM> of alumina on dry basis) of acid peptized alumina (commercially available as CATAPAL® from Sasol). An appropriate amount of water was added to the mixture to form a dough, and the dough material was extruded to form trilobe extrudates. The extrudates were dried at <NUM> overnight and calcinated at <NUM> for <NUM> hours. The calcinated extrudates were wet incipient impregnated with <NUM> of aqueous solution containing <NUM> of ammonium heptanmolybdate, <NUM> of nickel nitrate, and <NUM> of phosphoric acid. The impregnated catalyst was dried <NUM> overnight and calcinated at <NUM> for <NUM> hours.

A catalyst was prepared from the conventional alumina by mixing <NUM> (dry basis) of the alumina (commercially available as PURALOX® HP <NUM>/<NUM> from Sasol) with <NUM> (that is, <NUM> of alumina on dry basis) of acid peptized alumina (commercially available as CATAPAL® from Sasol). Appropriate amount of water was added to the mixture to form a dough, and the dough material was extruded to form trilobe extrudates. The extrudates were dried at <NUM> overnight and calcinated at <NUM> for <NUM> hours. The calcinated extrudates were wet incipient impregnated with <NUM> of aqueous solution containing <NUM> of ammonium heptanmolybdate, <NUM> of nickel nitrate, and <NUM> of phosphoric acid. The impregnated catalyst was dried <NUM> overnight and calcinated at <NUM> for <NUM> hours. The conventional HDN catalyst had a measured average pore size of <NUM>.

In order to compare the reaction performance of the catalysts of Example <NUM> and Example <NUM>, both catalysts were tested in a fixed bed reactor. For each run, <NUM> of the selected catalyst was loaded. The feedstock properties, operation conditions, and results are summarized in Table <NUM>. The results showed that the hydrodenitrogenation performance of the catalyst of Example <NUM> is better than that of the conventional catalyst of Example <NUM>.

To compare a conventional catalyst system, which includes the catalyst of Example <NUM> and the catalyst of Example <NUM> with a catalyst system, which includes the catalyst of Example <NUM> and the catalyst of Example <NUM>, experiments were performed in a four-bed reactor system. The four-bed reactor unit included an HDM catalyst, a transition catalyst, an HDN catalyst, and a hydrocracking catalyst, all in series. The feed and reactor conditions were the same as those reported in Table <NUM>. Table <NUM> shows the components and volumetric amount of each component in the sample systems. The <NUM> reactor was utilized for the testing.

Table <NUM> reports the catalytic results for Sample System <NUM> and Sample System <NUM> of Table <NUM> with liquid hourly space velocities of <NUM> hour-<NUM> and <NUM> hour-<NUM>. The results showed that the catalyst system that included the catalysts of Example <NUM> and Example <NUM> (Sample System <NUM>) exhibited a better performance in hydrodenitrogenation, hydrodesulfurization, and conversion of <NUM>+ residues. Only the process using sample system <NUM> with LHSV of <NUM>-<NUM> falls under the scope of the claims.

It is noted that one or more of the following claims utilize the term "where" as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term "comprising.

It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure.

Claim 1:
A method for processing heavy oil, the method comprising:
upgrading at least a portion of the heavy oil to form an upgraded oil, the upgrading comprising contacting the heavy oil with a hydrodemetalization catalyst, a transition catalyst, a hydrodenitrogenation catalyst, and a hydrocracking catalyst to remove at least a portion of metals, nitrogen, or aromatics content from the heavy oil and form the upgraded oil; and
passing at least a portion of the upgraded oil to a separation device that separates the upgraded oil into one or more transportation fuels;
wherein the final boiling point of the upgraded oil is less than or equal to <NUM>;
wherein the hydrocracking catalyst comprises a mesoporous zeolite and one or more metals, the mesoporous zeolite having an average pore size of from <NUM> to <NUM>;
wherein the hydrodenitrogenation catalyst comprises one or more metals on an alumina support, the alumina support having an average pore size of from <NUM> to <NUM>.