Hybrid boiling-entrained bed hydroconversion of heavy hydrocarbon feedstocks involving premixing the heavy hydrocarbon feedstock with organic additives - Patents.com

Abstract

The present invention relates to a method for the hydroconversion of heavy feedstocks, comprising the steps of: (a) preparing a first conditioned feedstock (103) by mixing said heavy hydrocarbon-based feedstock (101) with an organic chemical compound (102) containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group; (b) preparing a second conditioned feedstock (105) by mixing a catalyst precursor composition (104) with the first conditioned feedstock from step (a), thereby preparing said second conditioned feedstock (105). (c) heating the second conditioned feedstock in at least one preheater; (d) introducing the heated second conditioned feedstock (106) from step (c) into at least one hybrid boiling-entrained bed reactor containing a porous supported hydroconversion catalyst, said reactor being operated under hydroconversion conditions in the presence of hydrogen to produce an upgraded material (107); wherein the colloidal or molecular catalyst is formed during step (c) and / or step (d).

Description

[Technical field]

[0001] The present invention relates to a process for the conversion of heavy oil feedstock in the presence of a catalyst system comprising hydrogen, a porous supported catalyst and a colloidal or molecular catalyst, and an organic additive.

[0002] In particular, the present invention relates to a process for the hydroconversion of heavy oil feedstocks containing at least 50 wt.% of a fraction boiling at least 300° C., particularly heavy oil feedstocks containing significant amounts of asphaltenes and / or fractions boiling above 500° C., such as heavy hydrocarbon fractions resulting from crude oil or atmospheric and / or vacuum distillation of crude oil, to produce lower boiling and higher quality materials.

[0003] The method specifically involves premixing the feedstock with an organic additive prior to contact with catalysts which are operated in one or more hybrid ebullated bed reactors to enable upgrading of the low quality feedstock while minimizing fouling in the facility prior to hydroconversion in the hybrid ebullated bed reactor(s). [Background technology]

[0004] Conversion of heavy oil feedstocks into useful end products requires extensive processing, which includes lowering the boiling point of the heavy oil, increasing the hydrogen to carbon ratio, and removing impurities such as metals, sulfur, nitrogen, and high carbon content compounds.

[0005] Catalytic hydroconversion is commonly used for heavy oil feedstocks and is generally carried out using a three-phase reactor in which the feedstock is contacted with hydrogen and a catalyst. In this reactor, the catalyst can be used in the form of a fixed bed, a moving bed, an ebullated bed or an entrained bed, as described, for example, in Chapter 18 "Catalytic Hydrotreatment and Hydroconversion: Fixed Bed, Moving Bed, Ebullated Bed and Entrained Bed" of the book "Heavy Crude Oils: From Geology to Upgrading, An Overview" published in 2011 by Editions Technip. In the case of an ebullated or entrained bed, the reactor contains an upward flow of liquid and gas. The choice of technology generally depends on the nature of the feedstock for the treatment process, in particular its metal content, its tolerance to impurities and the targeted conversion rate.

[0006] Some heavy feedstock hydroconversion processes are based on hybrid technologies that mix the use of different catalyst bed types, e.g., using ebullated and entrained bed technologies, or fixed and entrained bed technologies, and therefore generally take advantage of each technology.

[0007] For example, it is known from the art to simultaneously use, in the same hydroconversion reactor, a supported catalyst maintained in an ebullated bed in the reactor and a smaller sized spouted catalyst, also commonly known as a "slurry" catalyst. The spouted catalyst is removed from the reactor entrained with the effluent. This entrainment of the second catalyst is made possible in particular by the appropriate density and the appropriate particle size of the slurry catalyst. Hence, the "hybrid ebullated-spouted bed" process, also referred to herein as the "hybrid ebullated bed" or simply the "hybrid bed" process, is defined herein as referring to the implementation of an ebullated bed containing a spouted catalyst in addition to a supported catalyst maintained in the ebullated bed, which can be understood as a hybrid operation of ebullated beds and spouted beds. A hybrid bed is in a sense a mixed bed of two types of catalysts, necessarily of different particle sizes and densities, one type of catalyst being maintained in the reactor and the other type of catalyst, the slurry catalyst, being removed from the reactor entrained with the effluent.

[0008] Such hybrid bed hydroconversion processes are known to improve upon traditional ebullated bed processes, particularly because the addition of slurry catalyst reduces the formation of sediment and coke precursors in the hydroconversion reactor system.

[0009] Indeed, it is known that during the operation of an ebullated bed reactor for upgrading heavy oil, the heavy oil is heated to a temperature at which the heavy oil feedstock, typically the high boiling fractions of the heavy oil feedstock having high molecular weight and / or low hydrogen / carbon ratio (examples of which are the class of complex compounds collectively referred to as "asphaltenes"), tend to undergo thermal cracking to form free radicals with reduced chain length. These free radicals have the potential to react with other free radicals, or other molecules, to produce coke precursors and sediments. While the reactor already contains a supported catalyst maintained therein, the slurry catalyst passing through the reactor provides additional catalytic hydrogenation activity, especially in zones of the reactor that generally do not contain a supported catalyst. The slurry catalyst therefore contributes to controlling and reducing the formation of sediments and coke precursors, as it reacts with the free radicals in these zones to form stable molecules. Since coke and sediment formation are the primary causes of deactivation of conventional catalysts and fouling of hydroconversion equipment, such hybrid methods allow for extending the lifespan of supported catalysts and prevent fouling of downstream equipment such as separation vessels, distillation columns, heat exchangers, etc.

[0010] For example, PCT application (Patent Document 1) describes such a hybrid process for upgrading heavy feedstocks using ebullated bed technology and a catalyst system comprising a supported catalyst and a slurry catalyst. The ebullated bed reactor contains two types of catalysts with different characteristics: the first catalyst has a size of more than 0.65 mm and occupies the expansion zone, and the second catalyst has an average size of 1-300 μm and is used in suspension. The second catalyst is introduced with the feed to the ebullated bed and passes through the reactor from bottom to top. It is prepared from unsupported bulk catalyst or by grinding a supported catalyst (granule size 1-300 μm).

[0011] US Patent No. 5,399,933 also relates to such a hybrid bed hydroconversion process for heavy oils and discloses one or more ebullated bed reactors, which can be operated in a hybrid manner by the addition of a dispersed organosoluble metal precursor in the feedstock. The addition of the catalyst precursor can be pre-diluted in vacuum gas oil (VGO) at an intimate mixing stage with the feedstock to prepare a conditioned feedstock, which is then introduced into the first or subsequent ebullated bed reactor. It is demonstrated that the catalyst precursor, typically molybdenum 2-ethylhexanoate, once heated, forms a colloidal or molecular catalyst (e.g., dispersed molybdenum sulfide) by reaction with H2S from the hydrodesulfurization of the feedstock. Such a process suppresses the formation of coke precursors and sediments that could otherwise deactivate the supported catalyst and foul the ebullated bed reactor and downstream equipment.

[0012] The European patent application (Patent Document 3) from the applicant also discloses a hybrid bed hydroconversion process for heavy oils, in which a dispersed solid catalyst is obtained from at least one salt of a heteropolyanion combining molybdenum and at least one metal selected from cobalt and nickel in a Strandberg, Keggin, defective Keggin or substituted defective Keggin structure, which improves hydrodeasphalting and leads to a reduction in the formation of sediments.

[0013] Slurry catalysts for heavy oil hydroconversion, especially colloidal or molecular catalysts formed by the use of soluble catalyst precursors, are well known in the art. It is particularly known that certain metal compounds, such as organic soluble compounds (e.g., molybdenum naphthenate or molybdenum octanoate cited in US Pat. Nos. 4,399,623, 4,497,511) or water-soluble compounds (e.g., phosphomolybdic acid cited in US Pat. Nos. 5,893,111, 5,971,121, 5,971,131, 5,971,141, 5,971,152, and salts of heteropolyanions cited in US Pat. No. 5,133,313, 5,971,161, 5,971,171, 5,971,192, 5,971,181, 5,971,192 ...

[0014] In addition to fouling due to coke precursors and sediments that can occur in the hybrid bed reactor and downstream equipment, the inventors have observed that fouling can also occur in upstream equipment as soon as the heavy oil feedstock containing the catalyst precursor is heated prior to introduction into the hydroconversion reactor.

[0015] Such fouling in equipment upstream of hydroconversion reactors, particularly in equipment for heating heavy oil feedstock mixed with catalyst precursors of certain colloidal or molecular catalysts, appears to be primarily related to metal and carbon buildup on the walls and can limit the operability of the equipment.

[0016] Thus, while the slurry catalysts in known hybrid processes, such as those cited above, are known to reduce fouling due to coke precursors and sediments in hydroconversion reactors and downstream equipment, the fouling observed in upstream equipment containing heavy oil feedstock mixed with catalyst precursors, such as preheating devices, constitutes another operational problem that has not been solved so far. It has also been observed that fouling due to coke precursors and sediments can still occur in downstream equipment in some cases, indicating that the feasibility of adding slurry catalysts can still be improved. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] International Publication No. 2012 / 088025 [Patent Document 2] US Patent Application Publication No. 2005 / 0241991 [Patent Document 3] European Patent Application Publication No. 3723903 [Patent Document 4] U.S. Pat. No. 4,244,839 [Patent Document 5] US Patent Application Publication No. 2005 / 0241991 [Patent Document 6] US Patent Application Publication No. 2014 / 0027344 [Patent Document 7] U.S. Pat. No. 3,231,488 [Patent Document 8] U.S. Pat. No. 4,637,870 [Patent Document 9] U.S. Pat. No. 4,637,871 [Patent Document 10] U.S. Patent No. 6,043,182 [Patent Document 11] French Patent Application Publication No. 3074699 Summary of the Invention [Means for solving the problem]

[0018] (Objectives and Summary of the Invention) Within the above context, the object of the present invention is to provide a hybrid hydroconversion process implementing a colloidal or molecular catalyst formed by the use of a soluble catalyst precursor, specifically addressing the problem of fouling in the equipment upstream of the hydroconversion reactor, in particular in the pre-heating devices of the feedstock prior to conversion in one or more hybrid hydroconversion reactors.

[0019] More generally, it is an aim of the present invention to provide a hybrid hydroconversion process for upgrading heavy oil feedstocks that enables one or more of the following effects: reduced equipment fouling, more efficient processing of asphaltene molecules, reduced formation of coke precursors and sediments, improved conversion levels, and improved solubility in the feedstock. Increased operating efficiency, enabling the reactor to process a wider range of lower quality feedstocks, elimination of catalyst free zones in ebullated bed reactors and downstream processing equipment, longer operation between maintenance shut downs, more efficient use of supported catalysts, increased throughput of heavy oil feedstocks, and increased rates of production of converted products. Reducing the frequency of shut down and start up of processing vessels means that processing equipment pressure and temperature cycling is reduced, which significantly increases the safety of the process and extends the useful life of expensive equipment.

[0020] Therefore, in order to achieve at least one of the above targeted objectives, inter alia, the present invention provides, according to a first aspect, a process for the hydroconversion of a heavy oil feedstock containing at least 50 wt.% of a fraction with a boiling point of at least 300° C. and containing metals and asphaltenes, the process comprising the following steps: (a) preparing a first conditioned heavy oil feedstock by blending said heavy oil feedstock with an organic chemical compound containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group; (b) preparing a second conditioned heavy oil feedstock by mixing a catalyst precursor composition with the first conditioned heavy oil feedstock from step (a) in a manner such that a colloidal or molecular catalyst is formed when reacted with sulfur; (c) heating the second conditioned heavy oil feedstock from step (b) in at least one preheating device; (d) introducing the heated second conditioned heavy oil feedstock from step (c) into at least one hybrid boiling-entrained bed reactor containing a hydroconversion porous supported catalyst, and operating the hybrid boiling-entrained bed reactor under hydroconversion conditions in the presence of hydrogen to produce an upgraded material; Here, the colloidal or molecular catalyst is formed in situ within the second conditioned heavy oil feedstock in step (c) and / or step (d).

[0021] According to one or more embodiments, step (a) comprises mixing the organic chemical compound and the heavy oil feedstock in a dedicated vessel of an active mixing device.

[0022] According to one or more embodiments, step (a) comprises injecting the organic chemical compound into a pipe carrying the heavy oil feedstock towards a hybrid boiling-entrained bed reactor.

[0023] According to one or more embodiments, the temperature at which step (a) is carried out is between room temperature and 300°C, preferably between 70°C and 200°C, and the residence time of the organic chemical compound with the heavy oil feedstock prior to step (b) is between 1 second and 10 hours.

[0024] According to one or more embodiments, the organic chemical compound is selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride, and mixtures thereof.

[0025] According to one or more embodiments, the organic chemical compound includes, and preferably is, 2-ethylhexanoic acid.

[0026] According to one or more embodiments, the organic chemical compound includes ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate, preferably ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.

[0027] According to one or more embodiments, the catalyst precursor composition comprises an oil-soluble organometallic or bimetallic compound or complex, preferably the oil-soluble organometallic compound or complex is selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octanoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl, preferably molybdenum 2-ethylhexanoate.

[0028] According to one or more embodiments, the molar ratio between the organochemical compound added in step a) and the one or more active metals of the catalyst precursor composition added in step (b), preferably molybdenum, in the second conditioned heavy oil feedstock is comprised between 0.1:1 and 20:1.

[0029] According to one or more embodiments, the colloidal or molecular catalyst includes molybdenum disulfide.

[0030] According to one or more embodiments, step (b) includes: (b1) premixing the catalyst precursor composition with a hydrocarbon oil diluent at a temperature below a temperature at which a substantial portion of the catalyst precursor composition begins to thermally decompose to form a diluted precursor mixture; and (b2) mixing the diluted precursor mixture with a first conditioned heavy oil feedstock.

[0031] According to one or more embodiments, step (b1) is carried out at a temperature comprised between room temperature and 300°C for a period comprised between 1 second and 30 minutes, and step (b2) is carried out at a temperature comprised between room temperature and 300°C for a period comprised between 1 second and 30 minutes.

[0032] According to one or more embodiments, step (c) includes heating at a temperature between 280°C and 450°C, more preferably between 300°C and 400°C, and most preferably between 320°C and 365°C.

[0033] According to one or more embodiments, the heavy oil feedstock comprises at least one of the following feedstocks: heavy crude oil, oil sands bitumen, atmospheric bottoms, vacuum bottoms, residual oil, visbreaker bottoms, coal tar, heavy oil derived from oil shale, liquefied coal, heavy bio-oil, and heavy oil containing plastic waste and / or plastic pyrolysis oil.

[0034] According to one or more embodiments, the heavy oil feedstock has a sulfur content of greater than 0.5 wt%, a Conradson carbon residue of at least 0.5 wt%, a C7 asphaltenes content of greater than 1 wt%, transition and / or post-transition and / or metalloid metals content of greater than 2 ppm by weight, and alkali and / or alkaline earth metals content of greater than 2 ppm by weight.

[0035] According to one or more embodiments, the hydroconversion step (d) is carried out at a pressure between 2 MPa and 38 MPa absolute, at a temperature between 300° C. and 550° C., with a liquid hourly space velocity (LHSV) of 0.05 h relative to the volume of each hybrid reactor. -1 ~10h -1 The amount of hydrogen mixed with the feedstock entering the hybrid bed reactor is 50-5000 Nm 3 / m 3 (Feedstock) is carried out as follows.

[0036] According to one or more embodiments, the concentration of the catalytic metal, preferably molybdenum, in the second conditioned oil feedstock is in the range of 5 ppm to 500 ppm by weight based on the weight of the heavy oil feedstock.

[0037] According to one or more embodiments, the method includes a step (e) of further processing the upgraded material, said step (e) including: - a second hydroconversion step, in which at least a part or all of the upgraded material resulting from hydroconversion step (d) or optionally a liquid heavy fraction boiling mainly at a temperature equal to or greater than 350°C resulting from an optional separation step for separating a part or all of the upgraded material resulting from hydroconversion step (d) is hydroconverted in a second hybrid boiling-entrained bed reactor, said second hybrid boiling-entrained bed reactor comprising a second porous supported catalyst and operated under hydroconversion conditions in the presence of hydrogen to produce a hydroconverted liquid effluent having reduced Conradson carbon residue and optionally reduced amounts of sulfur, and / or nitrogen, and / or metals; - fractionating a portion or all of said hydroconverted liquid effluent in a fractionation section to produce at least one heavy fraction boiling primarily at a temperature above 350°C, said heavy fraction containing a residual fraction boiling at a temperature above 540°C; - optionally, a step of deasphalting in a deasphalter of part or all of said heavy fraction with at least one hydrocarbon solvent, resulting in a deasphalted oil (DAO) and residual asphalt; Wherein, the hydroconversion step (d) and the second hydroconversion step are carried out under an absolute pressure of 2 to 38 MPa, a temperature of 300°C to 550°C, a liquid hourly space velocity (LHSV) of 0.05 h relative to the volume of each hybrid boiling-entrained bed reactor, -1 ~10h -1 The amount of hydrogen mixed with the feedstock entering each hybrid boiling-entrained bed reactor is 50-5000 Nm 3 / m 3 (Feedstock) is carried out as follows.

[0038] Other objects and advantages of the present invention will become apparent on reading the following description of particular exemplary embodiments of the invention, given by way of non-limiting example, this description being made with reference to the attached drawings, in which: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] (List of Drawings) FIG. 1 is a block diagram illustrating the principle of a hybrid bed hydroconversion process according to the present invention.

[0040] FIG. 2 is a block diagram illustrating an example of a hybrid bed hydroconversion process and system according to the present invention.

[0041] FIG. 3 is a graph showing the fouling trends of example conditioned oil feedstocks as prepared in hybrid bed hydroconversion processes according to the present invention and the prior art.

[0042] (Description of the embodiment) It is an object of the present invention to provide a hybrid bed hydroconversion process and system for improving the quality of heavy oil feedstocks.

[0043] Such methods and systems for hydroconversion of heavy oil feedstocks use a dual catalyst system comprising a molecular or colloidal catalyst dispersed within the heavy oil feedstock and a porous supported catalyst. They also use an organic additive mixed with the heavy oil feedstock, and then operate the dual catalyst system in one or more ebullated bed reactors, each of which contains a solid phase comprising an expanded bed of the porous supported catalyst, a liquid hydrocarbon phase comprising the heavy oil feedstock, the colloidal or molecular catalyst dispersed therein, and the organic additive, and a gas phase comprising hydrogen gas.

[0044] The hybrid bed hydroconversion method and system of the present invention can reduce equipment fouling, particularly in equipment upstream of the hydroconversion reactor(s), particularly in equipment for preheating the feedstock prior to conversion in the hybrid hydroconversion reactor(s), effectively treat asphaltenes, reduce or eliminate the formation of coke precursors and sediments, increase conversion levels, particularly by allowing hydroconversion to operate at higher temperatures, and eliminate catalyst free zones that would otherwise exist in conventional ebullated bed hydroconversion reactor(s) and downstream processing equipment. The hybrid bed hydroconversion method and system of the present invention also allows for more efficient use of porous supported catalysts and hybrid dual catalyst systems.

[0045] (term) Some definitions are given below, however further details as to what is defined hereinafter will be given further in the description.

[0046] The term "hydroconversion" refers to a process in which the main objective is to reduce the boiling range of a heavy oil feedstock, and a significant portion of the feedstock is converted to products with a boiling range lower than that of the original feedstock. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments with fewer carbon atoms and higher hydrogen-to-carbon ratios. The reactions carried out during hydroconversion allow the size of the hydrocarbon molecules to be reduced, mainly by breaking carbon-carbon bonds in the presence of hydrogen, saturating the broken bonds and aromatic rings. The mechanism by which hydroconversion occurs typically involves the formation of hydrocarbon free radicals during fragmentation, mainly by pyrolysis, followed by capping of the ends or portions of the free radicals with hydrogen in the presence of active catalytic sites. Of course, other reactions, typically associated with "hydroprocessing", may occur during hydroconversion processing, such as the removal of sulfur and nitrogen from the feedstock and the saturation of olefins.

[0047] The term "hydrocracking" is often used as a synonym of the English term "hydroconversion", but "hydrocracking" refers rather to a process similar to hydroconversion, but where the cracking of the hydrocarbon molecules is mainly catalytic cracking, i.e. cracking that takes place in the presence of hydrocracking catalysts that have acid sites as contained in the phase responsible for the cracking activity, for example clays or zeolites. According to the French term, for example, hydrocracking, which can be translated as "hydrocraquage", generally refers to this last definition (catalytic cracking), and its usage is reserved for the case of, for example, rather vacuum distillates as the oil feedstock to be converted, whereas the French term "hydroconversion" is generally reserved for the conversion of heavy oil feedstocks such as atmospheric and vacuum residues (but not only).

[0048] The term "hydrotreating" would refer to a milder operation in which the primary objective is to remove impurities, such as sulfur, nitrogen, oxygen, halides, and trace metals, from the feedstock and to saturate olefins and / or stabilize the hydrocarbon free radicals by reacting them with hydrogen rather than reacting them with themselves. The primary objective is not to change the boiling range of the feedstock. Hydrotreating is most often carried out using fixed bed reactors, although other hydrotreating reactors can also be used for hydrotreating, an example being an ebullated bed hydrotreating reactor.

[0049] The term "hydroprocessing" is intended to refer broadly to both "hydroconversion" / "hydrocracking" and "hydrotreating" processes.

[0050] The term "hydroconversion reactor" is intended to refer to any vessel in which the primary purpose is the hydroconversion of a feedstock, e.g., cracking (i.e., reducing the boiling range) of the feedstock in the presence of hydrogen and a hydroconversion catalyst. Hydroconversion reactors typically include an inlet port through which heavy oil feedstock and hydrogen may be introduced, and an outlet port through which upgraded materials may be withdrawn. Specifically, hydroconversion reactors are also characterized by having sufficient thermal energy to cause the fragmentation of larger hydrocarbon molecules into smaller molecules by thermal cracking. Examples of hydroconversion reactors include, but are not limited to, slurry bed reactors, also known as entrained bed reactors (three-phase liquid, gas, solid reactors, where the solid and liquid phases can behave like homogeneous phases), ebullated bed reactors (three-phase fluidized reactors), moving bed reactors (three-phase reactors with downward movement of solid catalyst and upward or downward flow of liquid and gas), and fixed bed reactors (three-phase reactors in which liquid is trickled downward onto a fixed bed of solid supported catalyst and hydrogen typically co-flows with the liquid, although in some cases it flows counter-currently in some cases).

[0051] The terms "hybrid bed" and "hybrid ebullated bed" and "hybrid entrained-ebullated bed" for hydroconversion reactors are intended to refer to ebullated bed hydroconversion reactors that contain an entrained bed catalyst in addition to a porous supported catalyst maintained in the ebullated bed reactor. Similarly, for hydroconversion processes, these terms are intended to refer thus to processes that include at least a hybrid operation of ebullated bed and entrained bed in the same hydroconversion reactor. A hybrid bed is necessarily a mixed bed of two types of catalysts of different particle sizes and / or densities, one type of catalyst - the "porous supported catalyst" - is maintained in the reactor and the other type of catalyst - the "entrained catalyst" (also commonly referred to as "slurry catalyst") - is entrained with the effluent (upgraded feedstock) and leaves the reactor. In the present invention, the entrained catalyst is a colloidal or molecular catalyst as defined below.

[0052] The terms "colloidal catalyst" and "colloidally dispersed catalyst" refer to catalyst particles having a particle size that is colloidal in size, e.g., a size (diameter) of less than 1 μm, preferably a size of less than 500 nm, more preferably a size of less than 250 nm, or a size of less than 100 nm, or a size of less than 50 nm, or a size of less than 25 nm, or a size of less than 10 nm, or a size of less than 5 nm. The term "colloidal catalyst" includes, but is not limited to, molecular or molecularly dispersed catalyst compounds.

[0053] The terms "molecular catalyst" and "molecularly dispersed catalyst" are intended to refer to catalyst compounds that are essentially "dissolved" or completely dissociated from other catalyst compounds or molecules in the heavy oil hydrocarbon feedstock, non-volatile liquid fraction, bottoms fraction, residual oil, or other feedstock or product in which the catalyst may be found. It is also intended to refer to very small catalyst particles or slabs that contain only a few catalyst molecules bound together (e.g., 15 molecules or less).

[0054] The terms "porous supported catalyst", "solid supported catalyst", and "supported catalyst" refer to catalysts typically used in conventional ebullated bed and fixed bed hydroconversion systems, including catalysts designed primarily for hydrocracking or hydrodemetallization and catalysts designed primarily for hydrotreating. Such catalysts typically contain (i) a catalyst support having a high surface area and numerous interconnected channels or pores, and (ii) fine particles of active catalyst, e.g., sulfides of cobalt, nickel, tungsten, and / or molybdenum, dispersed within the pores. Supported catalysts are typically manufactured as cylindrical pellets or spherical solids, although other shapes are possible.

[0055] The terms "upgrade," "upgrading," and "upgraded," when used to describe a feedstock or resulting material or product that has been subjected to or co-treated with hydroconversion, shall refer to one or more of the following: reduction in the molecular weight of the feedstock, reduction in the boiling range of the feedstock, reduction in the concentration of asphaltenes, reduction in the concentration of hydrocarbon free radicals, reduction in Conradson carbon residue, increase in the H / C atomic ratio of the feedstock, and reduction in the amount of impurities such as sulfur, nitrogen, oxygen, halides, and metals.

[0056] The terms "conditioned feedstock" and "conditioned heavy oil feedstock" refer to a heavy oil feedstock to be processed at least in a hydroconversion hybrid bed reactor, the feedstock having an organic additive combined therewith (herein the "first conditioned feedstock"), or a feedstock having such an organic additive combined therewith and then combined with a catalyst precursor composition and thoroughly mixed such that upon formation of the catalyst, in particular by reaction with sulfur, the catalyst comprises colloidal or molecular catalyst dispersed within the feedstock (herein the "second conditioned feedstock").

[0057] In the following, the term "comprise" is synonymous with (meaning the same as) "include" and "contain" and is inclusive or open and does not exclude other unspecified elements. The term "comprise" will be understood to include the exclusive and closed term "consist".

[0058] The terms “comprised between ... and ...” and “in the ... to ... range” and “in a range of ... to ...” mean that, unless otherwise specified, the values ​​at both ends of the interval are included in the stated range of values.

[0059] In the following detailed description, numerous specific details are presented to convey a more thorough understanding of the method and system according to the present invention. However, it will be apparent to one skilled in the art that the method and system may be used without all of these specific details. In other cases, well-known features have not been described in detail so as not to unnecessarily complicate the description.

[0060] 1 is a block diagram that illustrates in a schematic manner the principle of a hybrid bed hydroconversion process (100) according to the present invention, which differs from conventional hybrid bed processes, such as those disclosed in US 2005 / 0241991, in particular in that it involves the addition of an organic additive to the feedstock prior to mixing with the catalyst precursor composition.

[0061] The terms "organic chemical compound" and "organic additive" are used interchangeably herein to designate a chemical compound containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group, which is added to the heavy oil feedstock in step (a) and is described in more detail below.

[0062] According to the present invention, a heavy oil feedstock (101) containing at least 50 wt.% of a fraction boiling at least 300° C. and containing metals and asphaltenes is treated in a hydroconversion process (100) comprising the following steps: (a) preparing a first conditioned heavy oil feedstock (103) by blending said heavy oil feedstock (101) with an organic chemical compound (102) containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group; (b) preparing a second conditioned heavy oil feedstock (105) by mixing a catalyst precursor composition (104) with the first conditioned heavy oil feedstock (103) from step (a) such that upon reaction with sulfur a colloidal or molecular catalyst is formed; (c) heating the second conditioned heavy oil feedstock from step (b) in at least one preheating device; (d) introducing the heated second conditioned heavy oil feedstock (106) from step (c) into at least one hybrid boiling-entrained bed reactor containing a hydroconversion porous supported catalyst, said hybrid boiling-entrained bed reactor being operated under hydroconversion conditions in the presence of hydrogen to produce an upgraded material (107).

[0063] The upgraded material (107) may be further processed in optional step (e).

[0064] In the hydroconversion process according to the present invention, the colloidal or molecular catalyst is formed in situ within the second conditioned heavy oil feedstock in step (c) and / or step (d).

[0065] Each of the steps, flows and materials involved are now detailed below.

[0066] Some of the reference numbers listed below refer to FIG. 2, which illustrates, in schematic form, an example of a hybrid bed hydroconversion system (200) according to the present invention, which is described in detail later in this specification after the general method description.

[0067] (Heavy oil feedstock) The term "heavy oil feedstock" is intended to refer to heavy crude oil, oil sands bitumen, bottoms of the barrel and residual oils left over from refinery processing (e.g., visbreaker bottoms), and any other lower quality material that contains significant amounts of high boiling hydrocarbon fractions and / or contains significant amounts of asphaltenes that can deactivate solid supported catalysts and / or cause or result in the formation of coke precursors and sediments.

[0068] The heavy oil feedstock (101) can therefore comprise at least one of the following feedstocks: heavy crude oil, oil sands bitumen, atmospheric bottoms, vacuum bottoms, residual oil, visbreaker bottoms, coal tar, heavy oil from oil shale, liquefied coal, heavy bio-oil, and heavy oil containing plastic waste and / or plastic pyrolysis oil.

[0069] Plastic pyrolysis oil is an oil obtained from the pyrolysis of plastics, preferably plastic waste, and may be obtained from thermal, catalytic pyrolysis processes or alternatively may be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen).

[0070] In particular, the heavy oil feedstock being treated contains at least 50% by weight, preferably at least 80% by weight, of the hydrocarbon fraction having a boiling point of at least 300°C, preferably at least 350°C or at least 375°C.

[0071] These are heavy hydrocarbon fractions obtained from crude oil or from atmospheric and / or vacuum distillation of crude oil. They can also be atmospheric and / or vacuum residues, in particular atmospheric and / or vacuum residues obtained from hydrotreating, hydrocracking and / or hydroconversion. They can also be vacuum distillates, fractions from catalytic cracking units, for example fluid catalytic cracking (FCC), coking or visbreaking units.

[0072] Preferably, they are vacuum residues. Generally, these residues are fractions for which at least 80% by weight has a boiling point above 450° C., frequently at least 500° C. or at least 540° C.

[0073] Aromatic fractions extracted from lubricant production units, deasphalted oil (raffinate from a deasphalting unit), and asphalt (residue from a deasphalting unit) are also suitable feedstocks.

[0074] The feedstock can also be a residual fraction from direct coal liquefaction (vacuum distillate and / or atmospheric and / or vacuum residue, e.g., from the H-Coal® process), a residue from coal pyrolysis or shale oil, or a residual fraction from direct liquefaction of lignocellulosic biomass, alone or in admixture with coal and / or petroleum fractions (referred to herein as "heavy bio-oil").

[0075] Examples of heavy oil feedstocks include, but are not limited to, Lloydminster heavy oil, Cold Lake bitumen, Athabasca bitumen, Urals crude oil, Arabian heavy crude oil, Arabian light crude oil, atmospheric bottoms, vacuum bottoms, resid (or "residual"), resid pitch, vacuum residue, solvent deasphalted pitch, and the non-volatile liquid fraction remaining after crude oil, bitumen from tar sands, liquefied coal, oil shale, or coal tar feedstocks have been subjected to distillation, high temperature separation, etc. and which contains higher boiling fractions and / or asphaltenes.

[0076] All these feedstocks can be used alone or in mixtures.

[0077] The heavy oil feedstocks treated in the method and system according to the invention contain metals and asphaltenes, in particular C7 asphaltenes, and other impurities such as sulfur and nitrogen. The term "asphaltenes" refers to the fraction of heavy oil feedstocks that are typically insoluble in paraffinic solvents such as propane, butane, pentane, hexane, and heptane and contain sheet-like condensed ring compounds held together by heteroatoms such as sulfur, nitrogen, oxygen, and metals. Asphaltenes broadly include a wide range of complex compounds having carbon atoms ranging from 80 to 160,000. Asphaltenes are operationally defined as "C7 asphaltenes", i.e., heptane-insoluble compounds according to standard ASTM D 6560 (which also corresponds to standard NF T60-115), and any content in asphaltenes is referred to herein as C7 asphaltenes. C7 asphaltenes are compounds known to inhibit the conversion of residual fractions both by their ability to form heavy hydrocarbon residues commonly known as coke and by their tendency to produce sediments that severely limit the operability of hydrotreating and hydroconversion units.

[0078] The heavy oil feedstock (101) may typically have a sulfur content of greater than 0.5 wt%, a Conradson carbon residue of at least 3 wt%, a C7 asphaltenes content of greater than 1 wt%, transition and / or post-transition and / or metalloid metals content of greater than 2 ppm by weight, and alkali and / or alkaline earth metals content of greater than 2 ppm by weight.

[0079] These types of feedstocks are in fact generally rich in impurities, such as metals, in particular transition metals (e.g. Ni, V) and / or post-transition metals and / or metalloids, for which the contents can be greater than 2 ppm by weight, or greater than 20 ppm by weight, or even greater than 100 ppm by weight, and also rich in alkali metals (e.g. Na) and / or alkaline earth metals, for which the contents can be greater than 2 ppm by weight, or even greater than 5 ppm by weight, or even greater than 7 ppm by weight.

[0080] The sulfur content is in fact generally greater than 0.5% by weight, or even greater than 1% by weight, or even greater than 2% by weight.

[0081] The C7 asphaltenes content can in fact be as low as 1 wt.% and even greater than 3 wt.%.

[0082] The Conradson carbon residue is in practice generally greater than 3% by weight and even a minimum of 5% by weight. The Conradson carbon residue is defined by the ASTM D 482 standard and represents the amount of carbon residue resulting after pyrolysis under standard conditions of temperature and pressure.

[0083] These contents are expressed as weight percent of the total weight of the feed.

[0084] (Step (a): Preparation of the first conditioned heavy oil feedstock: heavy oil feedstock + organic additives) Step (a) comprises blending said heavy oil feedstock (101) with an organic chemical compound (102) containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group, forming what is referred to herein as a first conditioned heavy oil feedstock (103).

[0085] This step is followed by step (b) of thoroughly / intimately mixing with a catalyst precursor composition, which when reacted with the sulfur will lead to the formation of a colloidal or molecular catalyst dispersed within the heavy oil.

[0086] The inventors have shown that such a mixing step (a) prior to step (b) between the organic additive and the heavy oil feedstock improves the hybrid boiling-entrained bed hydroconversion process by in particular reducing the fouling of the equipment upstream of the hydroconversion reactor, in particular in the feed heating equipment of step c).

[0087] Without being bound by any theory, the organic additive is mixed with the heavy oil feedstock to allow better solubility of the colloidal or molecular catalyst precursor in the feed, avoiding or reducing fouling especially due to metal deposition in equipment upstream of the hydroconversion reactor, such as in heating equipment, thus improving the dispersion of the colloidal or molecular catalyst formed in step c) and / or in subsequent steps, thus resulting in greater availability of metal active sites, advantageously promoting the hydrogenation of free radicals which are precursors of coke and sediment, resulting in a considerable reduction in fouling of the equipment.

[0088] (Organic additives) The organic additive (102) having at least one carboxylic acid group and / or at least one ester group and / or anhydride group preferably contains at least 6 carbon atoms, more preferably at least 8 carbon atoms.

[0089] Typically, the organic additive (102) is neither a catalyst precursor nor a catalyst.

[0090] In particular, the organic additive (102) does not contain any metals.

[0091] Examples of organic additives include, but are not limited to, 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride. Advantageously, the organic additive is an organic chemical compound selected from the group consisting of the list of specific compounds listed immediately above, and mixtures thereof.

[0092] Preferably, the organic additive is an organic chemical compound containing at least one carboxylic acid group, more preferably selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

[0093] More preferably, the organic additive comprises or consists of 2-ethylhexanoic acid.

[0094] The organic additive may be an organic chemical compound containing at least one ester and / or anhydride group, for example selected from the group consisting of ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, and / or from the group consisting of hexanoic anhydride and capric anhydride.

[0095] More preferably, the organic additive containing at least one ester and / or anhydride group comprises or consists of ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate or mixtures thereof, preferably ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.

[0096] This step (a) of mixing the organic additive (102) with the heavy oil feedstock (101) forming the first conditioned heavy oil feedstock (103) is followed by step (b) of thoroughly / intimately mixing with a catalyst precursor composition which will lead to the formation of a colloidal or molecular catalyst dispersed within the heavy oil.

[0097] The organic additive is preferably added such that the molar ratio of the organic additive to the one or more active metals of the catalyst precursor composition added in step (b) is in the range of about 0.1:1 to about 20:1, more preferably in the range of about 0.75:1 to about 7:1, and even more preferably in the range of about 1:1 to about 5:1. The term "about" is intended to refer to approximations of ±5%, preferably ±1%.

[0098] Advantageously, the catalyst precursor composition added in step (b) comprises Mo, for example molybdenum 2-ethylhexanoate, and the organic additive is preferably added such that the molar ratio of the organic additive to Mo in the catalyst precursor composition added in step (b) is in the range of from about 0.1:1 to about 20:1, more preferably in the range of from about 0.75:1 to about 7:1, even more preferably in the range of from about 1:1 to about 5:1.

[0099] (mixed with organic additives) Mixing of the organic additive and the heavy oil feedstock is advantageously carried out in a first conditioner mixer (210).

[0100] The first conditioner mixer (210) may include an active mixing device as described below, any type of injection system for a pipe, or any type of in-line mixer.

[0101] According to one or more embodiments, the preparation of the first conditioned heavy oil feedstock (103) comprises mixing said organic additive (102) and said heavy oil feedstock (101) in a dedicated vessel of an active mixing device (forming a first conditioner mixer (210)).

[0102] The term "active mixing device" is intended to refer to a mixing device that contains moving parts, such as a stirring rod, and actively mixes the ingredients.

[0103] Such an arrangement makes it possible in particular to increase the dispersion of the colloidal or molecular catalyst formed in a later stage. The use of dedicated vessels also allows for long residence times.

[0104] According to one or more embodiments, the preparation of the first conditioned heavy oil feedstock (103) comprises injecting said organic chemical compound (102) into a pipe carrying said heavy oil feedstock (101) towards a hybrid boiling-entrained bed reactor. The first conditioner mixer (210) thus comprises the section of pipe where mixing is performed in such a configuration, and optionally includes additional systems to aid in mixing, such as a static in-line mixer as further described in step (b).

[0105] Such an arrangement can particularly reduce capital investment and required footprint compared to mixing in a dedicated vessel.

[0106] The residence time of the organic additive with the heavy oil feedstock prior to mixing with the catalyst precursor composition in step (b) to form the second conditioned heavy oil feedstock (105) is preferably from 1 second to 10 hours, more preferably from 1 second to 1 hour, even more preferably from 1 second to 30 minutes. In this description, a mixing time (or residence time for mixing) of 1 second includes instantaneous mixing.

[0107] Mixing of the organic additive and the heavy oil feedstock is preferably carried out at room temperature, for example between 15°C and 300°C, more preferably between 70°C and 200°C, for example 150°C.

[0108] The temperature at which the mixing occurs is advantageously the actual temperature of the heavy oil feed stream (101).

[0109] The temperature in step (a) should preferably be below the decomposition temperature of the catalyst precursor composition.

[0110] The pressure for the mixing step (a) is also advantageously the actual pressure of the heavy oil feed stream (101). Preferably, the gauge pressure for the mixing stage (a) is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa.

[0111] In the case of heavy oil feedstocks that are solid or extremely viscous at room temperature, such feedstocks may be advantageously heated to soften them and create feedstocks with sufficiently low viscosity to allow good mixing of the organic additives, particularly with the catalyst precursor composition in the additional step (b). In general, reducing the viscosity of the heavy oil feedstock will reduce the time required to effect complete and intimate mixing of the catalyst precursor composition in the first conditioned feedstock in step (b). However, the feedstock should not be heated beyond a temperature at which significant thermal decomposition of the catalyst precursor composition occurs until after thorough and complete mixing with the catalyst precursor composition in step (b). Premature thermal decomposition of the catalyst precursor composition generally results in the formation of micron-sized or larger catalyst particles rather than colloidal or molecular catalyst.

[0112] The blending of the heavy oil feedstock (101) with the organic additive (102) in step (a) can be done partially or completely with the heavy oil feedstock (101).

[0113] According to one or more preferred embodiments, the mixing step (a) is carried out between the organic additive (102) and the entire stream of heavy oil feedstock (101) sent to the hydroconversion system. According to one or more variants, the mixing step (a) is carried out between the organic additive (102) and a portion of the stream of heavy oil feedstock (101) sent to the hydroconversion. This preparation of the first conditioned heavy oil feedstock (103) can be carried out by blending at least a portion of said stream of heavy oil feedstock (101), for example at least 50 wt. % of said stream of heavy oil feedstock (101), with the organic additive (102). The complementary portion of said stream of heavy oil feedstock (101) can be recombined once the catalyst precursor composition has been added (step (b)), i.e. mixed with the second conditioned heavy oil feedstock before its preheating in step (c).

[0114] Step (b): Preparation of Second Conditioned Heavy Oil Feedstock: Mixing with Catalyst Precursor Composition The first conditioned oil feedstock (103) is then mixed with a catalyst precursor composition (104) to form a second conditioned heavy oil feedstock (105).

[0115] (Catalyst precursor composition) The catalyst precursor composition is selected from any metal catalyst precursor known to the skilled artisan that is capable of forming a colloidally or molecularly dispersed catalyst (i.e., a slurry catalyst) in the presence of hydrogen and / or H2S and / or any other sulfur source, and that enables the hydroconversion of said heavy oil feedstock after injection into said heavy oil feedstock.

[0116] The catalyst precursor composition is advantageously an oil-soluble catalyst precursor composition containing at least one transition metal.

[0117] The catalyst precursor composition preferably comprises an oil-soluble organometallic compound or complex.

[0118] The catalyst precursor composition may comprise an oil-soluble organometallic or bimetallic compound or complex containing one or two of the following metals, or a blend of such compounds / complexes: Mo, Ni, V, Fe, Co, or W.

[0119] The oil-soluble catalyst precursor composition preferably has a decomposition temperature (the temperature at which the catalyst precursor composition is substantially chemically stable) in the range of from 100°C to 350°C, more preferably in the range of from 150°C to 300°C, and most preferably in the range of from 175°C to 250°C.

[0120] The oil-soluble organometallic compound or complex is preferably selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octanoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl.

[0121] These compounds are non-limiting examples of oil soluble catalyst precursor compositions.

[0122] More preferably, the catalyst precursor composition comprises molybdenum, for example a compound selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate and molybdenum hexacarbonyl.

[0123] A presently preferred catalyst precursor composition comprises or consists of molybdenum 2-ethylhexanoate (also commonly known as molybdenum octoate), which typically contains 15% by weight molybdenum and has a high enough decomposition temperature or range to avoid substantial thermal decomposition when mixed with heavy oil feedstocks at temperatures below 250°C.

[0124] One of skill in the art, following the disclosure herein, can select a mixing temperature profile that results in mixing of the selected precursor composition without substantial thermal decomposition prior to the formation of the colloidal or molecular catalyst.

[0125] (Mixing with catalyst precursor composition) Mixing of the catalyst precursor composition and the first conditioned heavy oil feedstock occurs in a second conditioner mixer (220).

[0126] The catalyst precursor composition (104), preferably an oil soluble catalyst precursor composition, can be premixed with a diluent hydrocarbon stream to form a diluted precursor mixture, as described in US2005 / 0241991, US10822553 or US10941353 and recalled below.

[0127] According to one or more preferred embodiments, step (b) comprises: (b1) premixing the catalyst precursor composition (104) with a hydrocarbon oil (diluent) to form a diluted precursor mixture; said premixing is preferably carried out at a temperature below the temperature at which a substantial portion of the catalyst precursor composition begins to decompose, preferably at room temperature, e.g., between 15° C. and 300° C., advantageously for a period of from 1 second to 30 minutes; and (b2) mixing said diluted precursor mixture with the first conditioned heavy oil feedstock (103), preferably at room temperature, for example at a temperature between 15°C and 300°C, advantageously for a period of from 1 second to 30 minutes.

[0128] Examples of suitable hydrocarbon diluents include, but are not limited to, vacuum gas oil, also known as "VGO" (typically having a boiling range of 360°C to 524°C), decant or cycle oil (typically having a boiling range of 360°C to 550°C), light gas oil (typically having a boiling range of 200°C to 360°C), vacuum residue (typically having a boiling temperature of 524°C+), deasphalted oil, and resin. The hydrocarbon diluent is preferably VGO.

[0129] The mass ratio of catalyst precursor composition (104) to hydrocarbon oil diluent is preferably within the range of about 1:500 to about 1:1, more preferably within the range of about 1:150 to about 1:2, and even more preferably within the range of about 1:100 to about 1:5 (e.g., 1:100, 1:50, 1:30, or 1:10).

[0130] The catalyst precursor composition (104) is more preferably mixed with a hydrocarbon diluent at a temperature comprised between room temperature, e.g., 15° C. and 200° C., even more preferably between 50° C. and 200° C., even more preferably between 75° C. and 150° C., and even more preferably between 75° C. and 100° C. to form a diluted precursor mixture.

[0131] It will be appreciated that the actual temperature at which the diluted precursor mixture is formed will typically depend greatly on the decomposition temperature of the particular precursor composition utilized.

[0132] The catalyst precursor composition (104) is more preferably mixed with the hydrocarbon oil diluent for a period within the range of from 1 second to 10 minutes, and even more preferably within the range of from 2 seconds to 3 minutes.

[0133] The actual mixing time depends, at least in part, on the temperature (i.e., temperature affects the viscosity of the fluid) and on the intensity of the mixing, which depends, at least in part, on the number of stages, e.g., the number of stages for an in-line static mixer.

[0134] While it is within the scope of the present invention to blend the catalyst precursor composition (104) directly with the first conditioned heavy oil feedstock, care must be taken when mixing the components for a period of time sufficient to thoroughly / intimately blend the catalyst precursor composition within the feedstock prior to forming the catalyst, however, long mixing times, e.g., 24 hours of mixing, may be prohibitively expensive for certain commercial operations.

[0135] Premixing the catalyst precursor composition (104) with a hydrocarbon diluent and then blending the diluted precursor mixture with a heavy oil feedstock greatly aids in thoroughly and intimately blending the precursor composition within the feedstock, especially in the relatively short time periods required to make large scale commercial operations economically viable.

[0136] Forming a diluted precursor mixture shortens the overall mixing time by (1) reducing or eliminating the difference in solubility between the more polar catalyst precursor composition and the heavy oil feedstock; (2) reducing or eliminating the difference in rheology between the catalyst precursor composition and the heavy oil feedstock; and / or (3) breaking down the catalyst precursor molecules to form solutes in the hydrocarbon oil diluent that disperse much more easily in the heavy oil feedstock. Forming a diluted precursor mixture first is particularly advantageous in cases where the heavy oil feedstock contains water (condensate). Otherwise, the greater affinity of water for the polar catalyst precursor composition can cause localized agglomeration of the catalyst precursor composition, resulting in poor dispersion and the formation of micron-sized or larger catalyst particles. The hydrocarbon oil diluent is preferably substantially water-free (i.e., contains less than 0.5% water by weight, preferably less than 0.1% water by weight, more preferably less than 750 ppm water by weight) to prevent the formation of substantial amounts of micron-sized or larger catalyst particles.

[0137] The diluted precursor mixture is then combined with the first conditioned heavy oil feedstock (103) and mixed for a sufficient time to disperse the catalyst precursor composition throughout the feedstock to yield a second conditioned heavy oil feedstock (105), wherein the catalyst precursor composition is thoroughly / intimately mixed with the heavy oil feedstock.

[0138] To obtain sufficient mixing of the catalyst precursor composition in the heavy oil feedstock prior to forming the colloidal or molecular catalyst, the diluted precursor mixture and the heavy oil feedstock are more preferably mixed for a period within the range of 1 second to 10 minutes, most preferably within the range of 2 seconds to 3 minutes. Increasing the intensity and / or shear energy of the mixing method generally shortens the time required to achieve complete / intimate mixing.

[0139] Examples of mixing devices that may be used to achieve thorough / intimate mixing of the catalyst precursor composition (104) and the first conditioned heavy oil feedstock (103) include, but are not limited to, high shear mixing, e.g., mixing produced by a pump with a propeller or turbine impeller; multiple static in-line mixers; multiple static in-line mixers in combination with an in-line high shear mixer; multiple static in-line mixers in combination with an in-line high shear mixer followed by a pump around a surge vessel; a combination of the above devices followed by one or more multi-stage centrifugal pumps. According to one embodiment, continuous rather than batch mixing may be performed using a high energy pump having multiple chambers in which the catalyst precursor composition (104) and the first conditioned heavy oil feedstock (103) are churned and mixed as part of the pumping process itself. The aforementioned mixing equipment may be used for the premixing step (b1) above, in which the catalyst precursor composition (104) is mixed with a hydrocarbon oil diluent to form a catalyst precursor mixture.

[0140] Alternatively, the diluted precursor mixture (104) may be first mixed with 20% of the first conditioned heavy oil feedstock, the resulting mixed first conditioned heavy oil feedstock may be mixed with another 40% of the first conditioned heavy oil feedstock, and the resulting 60% of the mixed first conditioned heavy oil feedstock may be mixed with the remaining 40% of the first conditioned heavy oil, per good engineering practice of staged dilution, to fully disperse the catalyst precursor composition (104) in the heavy oil feedstock. The mixing times in the appropriate mixing devices or methods described herein should still be used in the staged dilution approach.

[0141] The first conditioned heavy oil feedstock (103) and the diluted precursor mixture are preferably mixed and conditioned at a temperature in the range of 50° C. to 200° C., more preferably in the range of 75° C. to 175° C. to give a second conditioned oil feedstock. Preferably, the gauge pressure is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa.

[0142] (Step (c): Heating the second conditioned heavy oil feedstock) The second conditioned oil feedstock (105) formed in step (b) is then heated in at least one preheating device (230) before being introduced into the hybrid bed reactor for hydroconversion.

[0143] The second conditioned oil feedstock (105) is sent to at least one pre-heating device (230) and optionally pressurized by a pump.

[0144] The preheating device includes any heating means capable of heating the heavy oil feedstock known to one skilled in the art. The preheating device may include a furnace including at least a preheating chamber, and / or a tube through which the oil feed flows, a mixer of the second conditioned oil feedstock with H2, any type of suitable heat exchanger, such as a tube or spiral type heat exchanger through which the oil feed flows, etc.

[0145] This pre-heating of the second conditioned heavy oil feedstock then enables the target temperature in the hydroconversion reactor to be achieved later in step (d).

[0146] The second conditioned oil feedstock (105) is more preferably heated in a pre-heating device (230) to a temperature in the range of 280°C to 450°C, even more preferably in the range of 300°C to 400°C, and most preferably in the range of 320°C to 365°C, in particular to subsequently reach the target temperature in the hydroconversion reactor in step (d).

[0147] The skin temperatures of the preheating devices, e.g. the skin temperatures of the furnace chambers or tubes or the steel shell of the heat exchanger(s), can reach 400° C. to 650° C. Mixing the heavy oil feedstock with organic additives at step (a) avoids or reduces fouling that can occur in the preheating devices at these high temperatures.

[0148] According to one or more embodiments, the second conditioned feedstock is heated to a temperature 100° C. below the hydroconversion temperature in the hybrid hydroconversion reactor, preferably 50° C. below the hydroconversion temperature. For example, for a hydroconversion temperature in the range of 410° C. to 440° C., the conditioned oil feedstock may be heated to a temperature in the range of 310° C. to 340° C. at step (c).

[0149] The absolute pressure is comprised between atmospheric pressure (for example 0.101325 MPa) and 38 MPa, preferably between 5 MPa and 25 MPa, preferably between 6 MPa and 20 MPa.

[0150] This heating in step (c) advantageously causes the second conditioned oil feedstock to liberate sulfur which can combine with metals of the catalyst precursor composition.

[0151] According to one or more embodiments, during this step (c) of heating in the preheating device (230), a colloidal or molecular catalyst is formed, or at least begins to form, in situ within the second conditioned heavy oil feedstock.

[0152] To form a colloidal or molecular catalyst, sulfur must be available (eg, as H2S) to combine with the metals from the dispersed catalyst precursor composition.

[0153] In situ formation of colloidal or molecular catalyst in second conditioned heavy oil feedstock The general formation of the colloidal or molecular catalyst in situ within the second conditioned heavy oil feedstock is described in detail below along with the conditions required for such formation in step (c) and / or step (d).

[0154] In cases where the heavy oil feedstock contains sufficient or excess sulfur, the final activated catalyst may be formed in situ by heating the second conditioned heavy oil feedstock to a temperature sufficient to liberate sulfur therefrom.

[0155] The source of sulfur can therefore be H2S dissolved in the heavy oil feedstock, or H2S contained in the hydrogen recycled to the hybrid bed hydroconversion reactor for hydroconversion, or H2S coming from organic sulfur molecules present in the feedstock or possibly previously introduced into the heavy oil feedstock (injection of any sulfur-containing hydrocarbon feedstock of the type dimethyl disulfide, thioacetamide, thiols, sulfides, sulfur-containing petroleum, sulfur-containing gas oil, sulfur-containing vacuum distillate, sulfur-containing residue, etc.), such injections being rare and reserved for very special heavy oil feedstocks.

[0156] Thus, the source of sulfur can be sulfur compounds within the feedstock or sulfur compounds added to the feedstock.

[0157] According to one or more embodiments, the formation of the dispersed colloidal or molecular catalyst is carried out with an overall gauge pressure of 0 MPa to 25 MPa.

[0158] Due to the thorough / intimate mixing in step (b), molecularly dispersed catalyst may be formed upon reaction with sulfur to form metal sulfide compounds. In some circumstances, minor agglomeration may occur, yielding colloidal sized catalyst particles. Failure to mix thoroughly, by simply adding together, typically results in the formation of large agglomerates of metal sulfide compounds, typically micron sized or larger.

[0159] To form the metal sulfide catalyst, the second conditioned oil feedstock (105) is preferably heated to a temperature within the range of room temperature, for example, from 15°C to 500°C, more preferably from 200°C to 500°C, even more preferably from 250°C to 450°C, and even more preferably from 300°C to 435°C.

[0160] The temperature used in steps (c) and / or (d) allows for the formation of a metal sulfide catalyst.

[0161] A colloidal or molecular catalyst may thus be formed, at least in part, during this heating step (c), after which the heated second conditioned oil feedstock is introduced into a hybrid bed hydroconversion reactor in step (d).

[0162] The colloidal or molecular catalyst may also be formed in situ in step (d), particularly within the hybrid bed hydroconversion reactor itself, either in whole or in part if it begins to form in step (c).

[0163] The concentration of the catalyst metal, preferably molybdenum, in the conditioned oil feedstock is preferably in the range of 5 to 500 ppm by weight of the heavy oil feedstock (101), more preferably in the range of 10 to 300 ppm by weight, more preferably in the range of 10 to 175 ppm by weight, even more preferably in the range of 10 to 75 ppm by weight, and most preferably in the range of 10 to 50 ppm by weight.

[0164] The catalytic metals may become more concentrated as the volatile fraction is removed from the non-volatile residual fraction.

[0165] Colloidal or molecular catalysts tend to be very hydrophilic, so that individual particles or molecules will tend to migrate toward the more hydrophilic moieties or molecules, particularly asphaltenes, within the heavy oil feedstock. While the high polarity of the catalyst compounds causes or enables the colloidal or molecular catalysts to associate with the asphaltene molecules, it is the general incompatibility between the highly polar catalyst compounds and the hydrophilic heavy oil feedstock that necessitates the aforementioned intimate or complete mixing of the oil-soluble catalyst precursor composition within the heavy oil feedstock prior to the formation of the colloidal or molecular catalyst.

[0166] Preferably, the colloidal or molecular catalyst comprises molybdenum disulfide.

[0167] Theoretically, a nanometer-sized crystal of molybdenum disulfide has 7 molybdenum atoms sandwiched between 14 sulfur atoms, and the total number of molybdenum atoms exposed at the edges and therefore available for catalytic activity is greater than in micron-sized crystals of molybdenum disulfide. In practice, forming small catalyst particles, i.e., colloidal or molecular catalysts, with increased dispersion as in the present invention results in more catalyst particles and more uniformly distributed catalytic sites throughout the oil feedstock. Furthermore, nanometer-sized or smaller molybdenum disulfide particles are believed to be intimately associated with asphaltene molecules.

[0168] (Step (d): Hydroconversion of the heated second conditioned heavy oil feedstock) The heated second conditioned feedstock (106) is then optionally pressurized, particularly by a pump if not already pressurized prior to step (c), and introduced together with hydrogen (201) into at least one hybrid boiling-entrained bed reactor (240) and operated at hydroconversion conditions to produce the upgraded material (107).

[0169] As stated above, the colloidal or molecular catalyst, if not fully formed or not formed at all in step (c), can be formed in situ in the hybrid bed hydroconversion reactor itself in step (d).

[0170] If the colloidal or molecular catalyst is formed in situ in the second conditioned heavy oil feedstock in step (c), the heated second conditioned feedstock (106) already contains, in part or entirely, the colloidal or molecular catalyst when it enters the at least one hybrid boiling-entrained bed reactor (240).

[0171] The hybrid boiling-entrained bed reactor (240) comprises a solid phase comprising a porous supported catalyst in the form of an expanded bed, a liquid hydrocarbon phase comprising the heated second conditioned heavy oil feedstock (106) having colloidal or molecular catalyst dispersed therein, and a gas phase comprising hydrogen.

[0172] The hybrid ebullating-entrained bed reactor (240) is an ebullating bed hydroconversion reactor that contains a molecular or colloidal catalyst in addition to a porous supported catalyst maintained in the ebullating bed reactor in the form of an expanded bed, where the molecular or colloidal catalyst is entrained with the effluent (upgraded feedstock) leaving the reactor.

[0173] According to one or more embodiments, the operation of the hybrid bed hydroconversion reactor is based on the operation of an ebullated bed reactor, such as that used for the H-Oil® process, as described, for example, in patents US4521295 or US4495060 or US4457831 or US4354852 or in the paper Aiche, March 19-23, 1995, Houston, Texas, paper number 46d, “Second generation ebullated bed technology”. In this implementation, the ebullated bed reactor can include a recirculation pump, which makes it possible to maintain the porous supported solid catalyst as an ebullated bed by continuous recycling of at least a portion of the liquid fraction withdrawn at the top of the reactor and reinjected at the bottom of the reactor.

[0174] The hybrid bed reactor preferably includes an inlet port at or near the bottom of the hybrid bed reactor through which the heated second conditioned feedstock (106) is introduced along with hydrogen (201) and an outlet port at or near the top of the reactor through which the upgraded material (107) is withdrawn. The hybrid bed reactor further includes an expanded catalyst zone containing a porous supported catalyst. The hybrid bed reactor also includes a lower supported catalyst-free zone located below the expanded catalyst zone and an upper supported catalyst-free zone above the expanded catalyst zone. Colloidal or molecular catalyst is dispersed throughout the feedstock in the hybrid bed reactor and includes both the expanded catalyst zone and the supported catalyst-free zone, making it available to promote the upgrading reaction in what would constitute the catalyst-free zone in a conventional ebullated bed reactor. The feedstock in the hybrid bed reactor is continuously recirculated from the upper supported catalyst-free zone to the lower supported catalyst-free zone by a recycle channel in communication with the ebullated pump. At the top of the recycle channel is a funnel-shaped recycle cap through which the feed is drawn from the top supported catalyst freesorn. The internal recycle feed is blended with fresh heated second conditioned feed (106) and make-up hydrogen gas (201).

[0175] As known and described, for example, in patent FR3033797, the porous supported hydroconversion catalyst may be partially replaced with fresh catalyst when it is worn out, by withdrawing the used catalyst, preferably at the bottom of the reactor, and introducing fresh catalyst either at the top or bottom of the reactor. This replacement of the used catalyst is preferably carried out at regular time intervals, preferably in portions or substantially continuously. These withdrawals / replacements are carried out using devices that advantageously allow the continuous functioning of this hydroconversion step. For example, inlet and outlet tubes opening into the expanded catalyst zone may be used to introduce / withdraw fresh and used supported catalyst, respectively.

[0176] The presence of colloidal or molecular catalyst in the hybrid bed reactor provides additional catalytic hydrogenation activity in both the expanded catalyst zone, the recycle channel, and the lower and upper supported catalyst free zones. Capping of the free radicals on the outside of the porous supported catalyst minimizes the formation of sediment and coke precursors that often cause supported catalyst deactivation. This can allow for a reduction in the amount of porous supported catalyst that would otherwise be needed to carry out the desired hydrotreating reactions. It can also reduce the rate at which the porous supported catalyst must be withdrawn and replenished.

[0177] The hydroconversion porous supported catalyst used in hydroconversion step (d) may contain one or more elements from groups 4 to 12 of the Periodic Table of the Elements, which are deposited on a support. The support of the porous supported catalyst can advantageously be an amorphous support, such as silica, alumina, silica / alumina, titanium dioxide or a combination of these structures, highly preferably alumina.

[0178] The catalyst may contain at least one metal from group VIII selected from nickel and cobalt, preferably nickel, said element from group VIII being preferably used in combination with at least one metal from group VIB selected from molybdenum and tungsten; preferably, the metal from group VIB is molybdenum.

[0179] In this specification, groups of chemical elements may be given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor in chief DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to metals in columns 8, 9 and 10 according to the new IUPAC classification.

[0180] Advantageously, the hydroconversion porous supported catalyst used in the hydroconversion step (d) comprises an alumina support and at least one metal from group VIII selected from nickel and cobalt, preferably nickel, and at least one metal from group VIB selected from molybdenum and tungsten, preferably molybdenum. Preferably, the hydroconversion porous supported catalyst comprises nickel as an element from group VIII and molybdenum as an element from group VIB.

[0181] The content of metals from non-noble group VIII, in particular nickel, expressed as the weight of metal oxide (in particular NiO), is advantageously between 0.5% and 10% by weight, preferably between 1% and 6% by weight, and the content of metals from group VIB, in particular molybdenum, expressed as the weight of metal oxide (in particular molybdenum trioxide MoO3), is advantageously between 1% and 30% by weight, preferably between 4% and 20% by weight. The metal contents are expressed as the percentage by weight of metal oxide relative to the weight of the porous supported catalyst.

[0182] The porous supported catalyst is advantageously used in the form of extrudates or beads. The diameter of the beads is, for example, between 0.4 mm and 4.0 mm. The extrudates have, for example, a cylindrical form, the diameter of which is between 0.5 mm and 4.0 mm, and the length of which is between 1 mm and 5 mm. The extrudates may have different shapes, for example trilobes, regular or irregular tetralobes, or other multilobe bodies. Other forms of the porous supported catalyst may also be used.

[0183] The size of these various forms of porous supported catalysts may be characterized by their equivalent diameter, which is defined as six times the ratio between the volume of the particle and the external surface area of ​​the particle. The equivalent diameter of the porous supported catalysts used in extrudate, bead or other forms is therefore between 0.4 mm and 4.4 mm. These porous supported catalysts are well known to those skilled in the art.

[0184] In the hydroconversion step (d), the heated second conditioned feedstock (106) is generally converted under conventional conditions for the hydroconversion of heavy oil feedstocks.

[0185] According to one or more embodiments, the hydroconversion step (d) is carried out at a pressure between 2 and 38 MPa, preferably between 5 and 25 MPa, preferably between 6 and 20 MPa absolute, and at a temperature between 300°C and 550°C, preferably between 350°C and 500°C, preferably between 370°C and 450°C, more preferably between 400°C and 440°C, even more preferably between 410°C and 435°C.

[0186] According to one or more embodiments, the liquid hourly space velocity (LHSV) of the feedstock relative to the volume of each hybrid reactor is 0.05 h -1 ~10h -1 , preferably 0.10h -1 ~2h -1 , preferably 0.10h -1 ~1h -1 According to another embodiment, the LHSV is 0.05h -1 ~0.09h -1LHSV is defined as the liquid feed volumetric flow rate at room temperature and atmospheric pressure (typically 15° C. and 0.101325 MPa) per reactor volume.

[0187] According to one or more embodiments, the amount of hydrogen mixed with the heavy oil feedstock (106) is about 100% by mass per cubic meter (m ) of liquid heavy oil feedstock. 3 ) preferably 50 to 5000 standard cubic meters (Nm 3 ), e.g. 100~3000Nm 3 / m 3 , preferably 200 to 2000 Nm 3 / m 3 It is.

[0188] According to one or more embodiments, the hydroconversion step (d) is carried out in one or more hybrid bed hydroconversion reactors, which can be in series and / or in parallel.

[0189] (Step (e): Further processing of the upgraded material from hydroconversion step (d)) The upgraded material (107) may be further processed.

[0190] Examples of such further processing include at least one of the following, but are not limited to: separation of the hydrocarbon fraction of the upgraded material, further hydroconversion in one or more supplemental hybrid boiling-entrained bed reactors or ebullated bed reactors to produce a further upgraded material, fractionation of a hydrocarbon cut of the further upgraded material, deasphalting of at least a portion of the upgraded material (107) or the heavy liquid fraction resulting from fractionation of the upgraded material or the further upgraded material, purifying the upgraded material or the further upgraded material in a guard bed to remove at least a portion of the colloidal or molecular catalyst and metal impurities.

[0191] The various hydrocarbon fractions that may result from the upgraded material (107) may be sent to different processing methods in the refinery, but the details of these post-processing operations are not described here, since they are generally known to those skilled in the art and would unnecessarily complicate the description. For example, gas fractions, naphtha, middle distillates, VGO, DAO may be sent to processing methods such as hydrotreating, steam cracking, fluid catalytic cracking (FCC), hydrocracking, lube oil extraction, etc., and the residues (atmospheric or vacuum residues) may also be post-processed or used for other applications, such as gasification, bitumen production. The heavy fractions, including the residues, may be recycled to hydroconversion processing methods, for example to a hybrid bed reactor.

[0192] According to one or more embodiments, as illustrated in FIG. 2, the processing method further includes: - a second hydroconversion step in a second hybrid boiling-entrained bed reactor (260) for hydroconverting in the presence of hydrogen (204) a liquid heavy fraction (203) boiling predominantly at a temperature equal to or greater than 350° C. resulting from at least a part or all of the upgraded material resulting from hydroconversion step (d) or optionally from an optional separation step for separating a part or all of the upgraded material resulting from hydroconversion step (d); said second hybrid boiling-entrained bed reactor (260) contains a second porous supported catalyst and is operated under hydroconversion conditions; producing a hydroconverted liquid effluent (205) having a reduced heavy residue fraction, a reduced Conradson carbon residue content, and optionally reduced amounts of sulfur, and / or nitrogen, and / or metals; - fractionating a portion or all of said hydroconverted liquid effluent (205) in a fractionation section (270); producing at least one heavy fraction (207) boiling primarily at a temperature above 350°C; said heavy fraction containing a residual fraction boiling at a temperature above 540°C; - optionally deasphalting a portion or all of said heavy fraction (207) with at least one hydrocarbon solvent in a deasphalter (280); producing a deasphalted oil (DAO) (208) and a residual asphalt (209).

[0193] Said second hydroconversion step is carried out similarly to the steps described for hydroconversion step (d), the description of which is therefore not repeated here, this applies in particular to the operating conditions, the equipment used, the hydroconversion porous supported catalyst used, except for the specifications given below.

[0194] With respect to the hydroconversion step (d), the second hydroconversion step is carried out in a second hybrid boiling-entrained bed reactor (260) similar to the hybrid bed reactor (240).

[0195] In this additional hydroconversion step, the operating conditions may be similar to or different from those in hydroconversion step (d), the temperature is still in the range of 300°C to 550°C, preferably 350°C to 500°C, more preferably 370°C to 450°C, more preferably 400°C to 440°C, even more preferably 410°C to 435°C, and the amount of hydrogen introduced into the reactor is still in the range of 50 to 5000 Nm 3 / m 3 Liquid feedstock, preferably 100-3000 Nm 3 / m 3 , and even more preferably 200 to 2000 Nm 3 / m 3 The other pressure and LHSV parameters are within the same ranges as described for the hydroconversion step (d).

[0196] The hydroconversion porous supported catalyst used in the second hybrid bed reactor (260) may be the same as that used in the hybrid bed reactor (240) or it may be another porous supported catalyst that is also suitable for the hydroconversion of heavy oil feedstocks, as defined for the supported catalyst used in hydroconversion step (d).

[0197] An optional separation step in which some or all of the upgraded material (107) is separated into at least two fractions, including a heavy liquid fraction (203) primarily boiling at a temperature above 350° C., occurs in separation section (250).

[0198] The other fraction or fractions (202) are light and intermediate fraction or fractions. The light fraction thus separated contains mainly gas (H2, H2S, NH3, and C1-C4), naphtha (fraction boiling below 150°C), kerosene (fraction boiling between 150°C and 250°C), and at least part of diesel (fraction boiling between 250°C and 375°C). The light fraction may then be sent, at least in part, to a fractionation unit (not shown in Figure 2) in which light gases are extracted from said light fraction, for example by passing through a flash drum. The gaseous hydrogen thus recovered may be sent to purification and compression installations, which may advantageously be recycled to the hydroconversion step (d). The gaseous hydrogen thus recovered may also be used in other installations of the refinery.

[0199] The separation section (250) includes any separation means known to those skilled in the art, which may include one or more flash drums arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or atmospheric and / or vacuum distillation columns, and is preferably constituted by a single flash drum, commonly known as a "hot separator."

[0200] The fractionation step separates some or all of the hydroconverted liquid effluent from the second hydroconversion step into at least two fractions including at least one heavy liquid fraction (207) boiling primarily at a temperature above 350° C., preferably above 500° C., preferably above 540° C., in a fractionation section (270) including any separation means known to those skilled in the art. The other fraction(s) (206) are one or more light middle distillates.

[0201] The heavy liquid fraction (207) contains a fraction boiling at temperatures above 540° C., called vacuum residue (this is the unconverted fraction). It may contain a part of the diesel fraction boiling between 250° C. and 375° C., and a fraction boiling between 375° C. and 540° C., called vacuum distillate.

[0202] The fractionation section (270) can include one or more flash drums arranged in series, and / or one or more steam and / or hydrogen stripping columns, and / or atmospheric distillation columns, and / or vacuum distillation columns, and is preferably comprised of a set of several flash drums and atmospheric and vacuum distillation columns in series.

[0203] If it is desired to recycle a portion of the heavy resid fraction (e.g., a portion of the heavy liquid fraction (207) and / or a portion of the residual asphalt (209), or a portion of the DAO (208)) back through the hydroconversion system (e.g., to or upstream of the hybrid bed reactor (240)), it may be advantageous to leave the colloidal or molecular catalyst in the resid, and / or the residual asphalt fraction. A purge on the recycled streams may generally be performed to prevent the accumulation of excessive levels of some compounds.

[0204] The present invention also relates to a bubbling-entrained bed system (200) configured for hydroconversion of a heavy oil feedstock (101) as detailed above. The reference numbers listed below refer to Figure 2, which illustrates, in a schematic manner, an example of a hybrid bed hydroconversion system according to the present invention. Said system (200) comprises: - a first conditioner mixer (210), configured to prepare a first conditioned heavy oil feedstock (103) by mixing said heavy oil feedstock (101) with an organic chemical compound (102) containing at least one carboxylic acid group and / or at least one ester group and / or anhydride group; - a second conditioner mixer (220) configured to prepare a second conditioned heavy oil feedstock (105) by mixing a catalyst precursor composition (104) with said first conditioned heavy oil feedstock (103); - at least one preheating device (230); configured to heat the second conditioned feedstock (105); - at least one hybrid boiling-entrained bed reactor (240); configured to include: - an expanded catalyst bed containing a solid phase, the solid phase comprising a porous supported catalyst as the solid phase; - a liquid hydrocarbon phase comprising said second heated conditioned heavy oil feedstock (106), said second heated conditioned heavy oil feedstock (106) containing a colloidal or molecular catalyst dispersed therein; and - A gaseous phase containing hydrogen.

[0205] The at least one hybrid boiling-entrained bed reactor (240) is configured to operate at hydroconversion conditions in the presence of hydrogen to effect thermal cracking of hydrocarbons in the second conditioned heavy oil feedstock to provide an upgraded material (107).

[0206] The at least one preheating device (230) and / or the at least one hybrid boiling-entrained bed reactor (240) are also configured to form a colloidal or particle-like catalyst within the second conditioned heavy oil feedstock.

[0207] Details regarding each apparatus / device / section used in the boiling-entrained bed system have already been given above in relation to the method and will not be repeated.

[0208] (Example) The following examples illustrate some of the performance qualities of the method and system according to the invention, in particular the reduced fouling of equipment compared to prior art methods and systems, but do not limit the scope of the invention.

[0209] The examples are based on tests using an analytical device called the Alcor Hot Liquid Process Simulator, or HLPS, which simulates the fouling effect of atmospheric residues (AR) in a heat exchanger. The AR is pumped under controlled conditions through a heater tube (a laminar flow tube-in-shell heat exchanger), and fouling deposits form on the heater tube. The temperature of the AR leaving the heat exchanger is related to the effect of the deposits on the efficiency of the heat exchanger. The decrease in the AR liquid outlet temperature from its initial maximum is called Delta T and correlates with the amount of deposits. The higher the rate of decrease in Delta T, the greater the fouling and amount of deposits.

[0210] The HLPS test can be used to evaluate the fouling tendency of different ARs by comparing the slope of decrease in AR liquid outlet temperature obtained under identical test conditions. The effectiveness of organic additives can also be determined by comparing the test results from neat samples (without organic additives) with samples blended with organic additives.

[0211] Three samples are tested: Sample 1 is a blend of heavy oil feedstock and a molecular or colloidal catalyst according to the prior art, and Samples 2 and 3 are blends according to the invention of the same molecular or colloidal catalyst plus heavy oil feedstock and organic additives.

[0212] The heavy oil feedstock ("feed") is an atmospheric residue (AR), the main composition and properties of which are given in Table 1 below.

[0213] [Table 1]

[0214] Sample 1: Sample 1 is a blend of a feed (AR) and a catalyst precursor composition (CPC), which is molybdenum 2-ethylhexanoate, which is diluted in vacuum gas oil (VGO) to form a CPC solution.

[0215] The composition of VGO is given in Table 1 above.

[0216] The CPC solution is obtained by mixing molybdenum 2-ethylhexanoate with VGO for a period of 30 minutes at a temperature of 70° C. The molybdenum content in the solution of CPC containing VGO is 3500 ppm by weight.

[0217] The solution of CPC is then mixed with the feed (AR) at a temperature of 70° C. for a period of 30 minutes.

[0218] The Mo content in Sample 1 is 315 ppm by weight (see Table 2 below).

[0219] (Sample 2): Sample 2 is a blend of the same CPC solution (2-ethylhexanoic acid molybdenum diluted with VGO) in the feed (AR) as in Sample 1 and an organic additive, which is 2-ethylhexanoic acid (2EHA). The CAS number of 2EHA is 149-57-5.

[0220] The feed is first mixed with an organic additive, 2EHA, for a period of 30 minutes at a temperature of 70° C. to form a first conditioned feedstock.

[0221] The first conditioned feedstock is then mixed with a solution of CPC obtained as detailed for Sample 1 at a temperature of 70° C. for a period of 30 minutes to form a second conditioned feedstock, Sample 2.

[0222] The content of Mo in Sample 2 is 315 ppm by weight (see Table 2 below).

[0223] The concentration of the organic additive 2EHA is 5827 ppm by weight (see Table 2 below).

[0224] 2EHA / Mo molar ratio=12.3

[0225] (Sample 3): Sample 3 is a blend of the feed (AR) with the same CPC solution (molybdenum 2-ethylhexanoate diluted with VGO) as in Samples 1 and 2, and an organic additive, which is ethyl octanoate (EO). The CAS number for EO is 106-32-1.

[0226] Feed F is first mixed with organic additive EO for a period of 30 minutes at a temperature of 70° C. to form a first conditioned feedstock.

[0227] The first conditioned feedstock is then mixed with the CPC solution obtained as described for Sample 1 at a temperature of 70° C. for a period of 30 minutes to form a second conditioned feedstock, Sample 3.

[0228] The content of Mo in Sample 3 is 315 ppm by weight (see Table 2 below).

[0229] The concentration of the organic additive EO in sample 3 is equal to 7340 ppm by weight (see Table 2 below).

[0230] EO / Mo molar ratio=13.0

[0231] [Table 2]

[0232] The Mo content in the samples was determined by ASTM D7260. The acid and ester organic additive contents were determined by weighing.

[0233] The HLPS test conditions are given in Table 3 below.

[0234] [Table 3]

[0235] The results of the tests of the different samples (S1 for sample 1, S2 for sample 2, S3 for sample 3) are shown in the graph in Figure 3. The X-axis represents time in hours and the Y-axis represents the temperature [T Oil Out ] t and the maximum temperature of the oil blend (sample) exiting the tube [T Oil Out ] Max The temperature difference ΔT between Oil Out ] t -[T Oil Out ] Max .

[0236] The results show that Sample 1 has a strong fouling tendency since its Delta T drops rapidly. Samples 2 and 3 according to the present invention, which contain organic additives such as 2EHA or EO, ​​have lower Delta T than Sample 1, indicating that the fouling behavior is significantly reduced under the action of the organic additives. [Brief description of the drawings]

[0237] [Figure 1] FIG. 1 is a block diagram illustrating the principle of a hybrid bed hydroconversion process according to the present invention. [Diagram 2] FIG. 1 is a block diagram illustrating an example of a hybrid bed hydroconversion process and system according to the present invention. [Diagram 3] 1 is a graph showing the fouling trends of example conditioned oil feedstocks as prepared in a hybrid bed hydroconversion process according to the present invention and the prior art.

Claims

1. A method for the hydroconversion of a heavy oil feedstock (101) containing at least 50% by weight of a fraction having a boiling point of at least 300 °C and containing metals and asphaltenes, the method comprising the following steps: (a) preparing a first conditioned heavy oil feedstock (103); by blending the heavy oil feedstock (101) with an organic chemical compound (102) containing at least one carboxylic acid group and / or at least one ester group and / or acid anhydride group; (b) preparing a second conditioned heavy oil feedstock (105); by mixing a catalyst precursor composition (104) with the first conditioned heavy oil feedstock (103) from step (a) such that a colloidal or molecular catalyst is formed when it reacts with sulfur; (c) heating the second conditioned heavy oil feedstock from step (b) in at least one preheating device; (d) introducing the heated second conditioned heavy oil feedstock (106) from step (c) into at least one hybrid fluidized - jet bed reactor containing a hydroconversion porous supported catalyst, operating the hybrid fluidized - jet bed reactor under hydroconversion conditions in the presence of hydrogen to produce an upgraded material (107); wherein a colloidal or molecular catalyst is formed in - situ within the second conditioned heavy oil feedstock in step (c) and / or step (d).

2. The method according to claim 1, wherein step (a) comprises mixing the organic chemical compound (102) and the heavy oil feedstock (101) in a dedicated vessel of an active mixing device.

3. The method according to claim 1, wherein step (a) comprises injecting the organic chemical compound (102) into a pipe that conveys the heavy oil feedstock (101) towards a hybrid fluidized - jet bed reactor.

4. The temperature during step (a) is between room temperature and 300 °C, preferably between 70 °C and 200 °C, and the residence time of the organic chemical compound with the heavy oil feedstock before step (b) is between 1 second and 10 hours. The method according to any one of claims 1 - 3.

5. The method according to any one of claims 1 to 3, wherein the organic chemical compound (102) is selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride, and mixtures thereof.

6. The method according to claim 5, wherein the organic chemical compound (102) contains 2-ethylhexanoic acid and is preferably 2-ethylhexanoic acid.

7. The method according to claim 5, wherein the organic chemical compound (102) contains ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate and is preferably ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.

8. The method according to claim 1, wherein the catalyst precursor composition (104) contains an oil-soluble organometallic or bimetallic compound or complex, and preferably, the oil-soluble organometallic compound or complex is selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthenate, vanadium naphthenate, vanadium octanoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl, and is preferably molybdenum 2-ethylhexanoate.

9. The molar ratio between the organic chemical compound (102) added in step a) and one or more active metals, preferably molybdenum, of the catalyst precursor composition (104) added in step (b) in the second condition-adjusted heavy oil feedstock is included between 0.1:1 and 20:

1. The method according to claim 1.

10. The method according to claim 1, wherein the colloidal or molecular catalyst contains molybdenum disulfide.

11. The method according to claim 1, wherein step (b) includes: (b1) preliminarily mixing the catalyst precursor composition with a hydrocarbon oil diluent at a temperature below the temperature at which a substantial portion of the catalyst precursor composition begins to thermally decompose to form a diluted precursor mixture; and (b2) mixing the diluted precursor mixture with the first condition-adjusted heavy oil feedstock.

12. Perform step (b1) at a temperature between room temperature and 300 °C for a period of 1 second to 30 minutes, and perform step (b2) at a temperature included between room temperature and 300 °C for a period of 1 second to 30 minutes, the method according to claim 11.

13. Step (c) includes heating, and the temperature at that time is 280 °C to 450 °C, more preferably 300 °C to 400 °C, even more preferably 320 °C to 365 °C, the method according to claim 1.

14. The heavy oil feedstock (101) includes at least one of the following feedstocks: heavy crude oil, oil sand bitumen, atmospheric column bottom oil, vacuum column bottom oil, residual oil, visbreaker bottom oil, coal tar, heavy oil derived from oil shale, liquefied coal, heavy bio-oil, and heavy oil containing plastic waste and / or plastic pyrolysis oil, the method according to claim 1.

15. The heavy oil feedstock (101) contains sulfur at a content exceeding 0.5% by weight, Conradson residual carbon at a minimum of 0.5% by weight, C ７ the method according to claim 1, having asphaltenes at a content exceeding 1% by weight, transition metals and / or post-transition metals and / or metalloid metals at a content exceeding 2 ppm by weight, and alkali and / or alkaline earth metals at a content exceeding 2 ppm by weight.

16. The hydrogenation conversion step (d) is carried out under an absolute pressure of 2 MPa to 38 MPa, at a temperature of 300 °C to 550 °C, with a liquid hourly space velocity (LHSV) of 0.05 h －１ to 10 h －１ in the amount of hydrogen of 50 to 5000 standard cubic meters (Nm ３ ) / cubic meter (m ３ ) of the feedstock, which is mixed with the feedstock entering the hybrid bed reactor, according to the method of claim 1.

17. The concentration of the metal of the catalyst, preferably molybdenum, in the second condition-adjusted oil feedstock (105) is within the range of 5 weight ppm to 500 weight ppm based on the weight of the heavy oil feedstock, the method according to claim 1.

18. Further include step (e) of further processing the upgraded material, and said step (e) includes the following: the method according to claim 1: - A second hydroconversion step; in a second hybrid fluidized - jet bed reactor (260), at least a part or all of the upgraded material resulting from the hydroconversion step (d) or, optionally, from an optional separation step of separating a part or all of the upgraded material resulting from the hydroconversion step (d), hydroconvert the liquid heavy fraction mainly boiling at a temperature of 350 °C or higher; said second hybrid fluidized - jet bed reactor (260) includes a second porous supported catalyst and is operated under hydroconversion conditions in the presence of hydrogen (204) to produce a hydroconverted liquid effluent (205) with a reduced Conradson carbon residue content and, optionally, a reduced amount of sulfur, and / or nitrogen, and / or metal; - A step of fractionating a part or all of the hydroconverted liquid effluent (205) in a fractionation section (270); producing at least one heavy fraction (207) mainly boiling at a temperature of 350 °C or higher, said heavy fraction containing a residual fraction boiling at a temperature of 540 °C or higher; - In some cases, in the deasphalting unit (280), a step of deasphalting part or all of the heavy fraction (207) with at least one hydrocarbon solvent; producing deasphalted oil (DAO) and residual asphalt; Here, the hydrogenation conversion step (d) and the second hydrogenation conversion step are carried out under an absolute pressure of 2 to 38 MPa, at a temperature of 300°C to 550°C, with a liquid hourly space velocity (LHSV) of 0.05 h －１ to 10 h －１ and with the amount of hydrogen mixed with the feedstock entering each hybrid boiling-jetting bed reactor being 50 to 5000 standard cubic meters (Nm ３ 3) / cubic meter (m ３ 3) of the feedstock.

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