Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
  • C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
  • C10G45/20—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles according to the "fluidised-bed" technique
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1003—Waste materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1077—Vacuum residues

Definitions

• the present invention relates to a process for the conversion of heavy hydrocarbon feedstocks in the presence of hydrogen, a catalyst system comprising a porous supported catalyst and a colloidal or molecular catalyst, and an organic additive.
• the present invention relates to a process for the hydroconversion of heavy hydrocarbon feedstocks containing a fraction of at least 50% by weight having a boiling point of at least 300° C., and in particular heavy hydrocarbon feedstocks comprising a significant amount of asphaltenes and/or fractions with a boiling point above 500°C, such as crude oils or heavy hydrocarbon fractions resulting from the atmospheric and/or vacuum distillation of a crude oil, to give higher quality, lower boiling point materials.
• the method specifically comprises the premixing of said charge with an organic additive, before being brought into contact with the catalysts, these catalysts operating in one or more hybrid ebullated bed reactors, in order to allow the upgrading of said low quality charge while minimizing plant fouling prior to hydroconversion in hybrid ebullated bed reactor(s).
• Converting heavy hydrocarbon feedstocks into useful end products requires extensive processing, including reducing the boiling point of the heavy feedstock, increasing the hydrogen-to-carbon ratio, and removing impurities such as metals , sulfur, nitrogen and high carbon compounds.
• Catalytic hydroconversion is commonly used for heavy hydrocarbon feedstocks and is generally implemented using three-phase reactors in which the feedstock is brought into contact with hydrogen and a catalyst.
• the catalyst can be used in the form of a fixed bed, a moving bed, an ebullating 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” from the book “Heavy Crude Oils: From Geology to Upgrading, An OverView”, published by Éditions Technip in 2011.
• the reactor includes an upward flow of liquid and gas.
• the choice of technology depends generally the nature of the feed to be treated and in particular its metal content, its tolerance to impurities and the conversion aimed at.
• Some heavy feedstock hydroconversion processes are based on hybrid technologies combining the use of different types of catalyst beds, for example hybrid processes using bubbling bed and entrained bed technologies, or fixed bed and driven bed, thus generally taking advantage of each technology.
• a “bubbling-entrained hybrid bed” process also referred to herein as a “hybrid swirling bed” or simply “hybrid bed” process, is defined herein as referring to the application of a swirled bed comprising an entrained catalyst, in addition to a supported catalyst maintained in the ebullated bed, which can be seen as a hybrid operation of an ebullated bed and an entrained bed.
• the hybrid bed is in a way a mixed bed of two types of catalysts of necessarily different particle size and/or density, one type of catalyst being maintained in the reactor and the other type of catalyst, the entrained catalyst, being carried out of the reactor with the effluents.
• Such a hybrid bed hydroconversion process is known to improve upon the traditional ebullated bed process, particularly since the addition of entrained catalyst reduces the formation of sediment and coke precursors in the hydroconversion reactor system.
• the entrained catalyst therefore reacts with free radicals in these areas, forming stable molecules, and thus helps to control and reduce the formation of sediments and coke precursors. Since the formation of coke and sediment is the main cause of the deactivation of conventional catalysts and the fouling of hydroconversion installations, such a hybrid process makes it possible to increase the life of the supported catalyst and prevents fouling. downstream installations, such as separation vessels, distillation columns, heat exchangers etc.
• PCT application WO2012/088025 describes such a hybrid process for upgrading heavy loads using ebullated bed technology and a catalytic system composed of a supported catalyst and an entrained catalyst.
• the ebullated bed reactor includes the two kinds of catalysts having different characteristics, the first catalyst having a size larger than 0.65 mm and occupying an expansion area, and the second catalyst having an average size of 1 to 300 ⁇ m and being used in suspension.
• the second catalyst is introduced into the bubbling bed with the feed and passes through the reactor from the lower part towards the upper part. It is prepared either from unsupported catalysts, or by grinding supported catalysts (grain size between 1 and 300 ⁇ m).
• Patent document US2005/0241991 also relates to such a hybrid bed hydroconversion process for heavy hydrocarbon feedstocks, and describes one or more bubbling bed reactors, which can operate in hybrid mode with the addition of an organosoluble metal precursor. dispersed in the load.
• the addition of the catalyst precursor which can be pre-diluted in vacuum gas oil (VGO), is carried out in a stage of intimate mixing with the charge for the preparation of a conditioned charge before its introduction into the first ebullated bed reactor or in subsequent ebullated bed reactors.
• VGO vacuum gas oil
• the catalyst precursor typically molybdenum 2-ethylhexanoate, forms a colloidal or molecular catalyst (e.g.
• the applicant's European patent application EP3723903 also describes a hybrid bed hydroconversion process for heavy hydrocarbon feedstocks, in which the dispersed solid catalyst is obtained from at least one salt of a heteropolyanion combining molybdenum with at least a metal chosen from cobalt and nickel in a structure of the Strandberg, Keggin, lacunar Keggin or substituted lacunar Keggin type, improving the hydrodeasphalting and leading to the reduction of the formation of sediments.
• Entrained catalysts for the hydroconversion of a heavy hydrocarbon feedstock, and in particular colloidal or molecular catalysts formed by the use of soluble catalytic precursor, are well known.
• metal compounds such as organosoluble compounds (eg molybdenum naphthenate or molybdenum octoate as cited in US4244839, US2005/0241991, US2014/0027344) or water-soluble compounds (eg phosphomolybdic acid cited in patents US3231488, US4637870 and US4637871; ammonium heptamolybdate cited in patent US6043182, salts of a heteropolyanion as cited in FR3074699), can be used as dispersed catalyst precursors and form catalysts.
• the dispersed catalyst precursor is generally mixed with the filler to form an emulsion.
• the dissolution of the dispersed catalyst precursor (generally molybdenum), optionally activated by cobalt or nickel in an acid medium (in the presence of H 3 PO 4 ) or in a basic medium (in the presence of NH 4 OH), has been the subject of numerous studies and patents.
• fouling can also appear in the installations upstream, as soon as the heavy hydrocarbon charge containing the catalyst precursor is heated before it is introduced into the hydroconversion reactor.
• the entrained catalyst in known hybrid processes is known to reduce fouling from coke precursors and sediments in the hydroconversion reactor and in downstream facilities
• the Another hitherto unresolved operational problem is the fouling observed in upstream facilities containing the heavy hydrocarbon feedstock mixed with the catalyst precursor, such as in a preheater.
• fouling due to coke precursors and sediments can still occur in downstream facilities in some cases, showing that the performance of entrained catalyst addition can still be improved.
• an objective of the present invention is to provide a hybrid hydroconversion process using a colloidal or molecular catalyst formed by the use of a soluble catalytic precursor, solving the problem of fouling, in particular in installations upstream of the hydroconversion reactor, in particular in a device for preheating the hydrocarbon feedstock before its conversion in the reactor(s) s) hydroconversion hybrid(s).
• the objective of the present invention is to provide a hybrid hydroconversion process for the recovery of heavy hydrocarbon feedstocks allowing one or more of the following effects: reduced fouling of equipment, more efficient treatment of asphaltene molecules, reduction in the formation of coke precursors and sediments, increased conversion rate, ability for the reactor to process a wider range of lower grade hydrocarbon feedstocks, elimination of catalyst-free zones in the ebullated bed reactor and downstream processing facilities, operation longer between maintenance shutdowns, more efficient use of supported catalyst, increased throughput of heavy hydrocarbon feedstock, and increased production rate of converted products.
• a reduction in the frequency of stopping and starting process equipment implies a reduction in the pressure and temperature cycles of process equipment, and this significantly increases process safety and extends the useful life of installations. expensive.
• the present invention provides, according to a first aspect, a process for the hydroconversion of a heavy hydrocarbon feedstock containing a fraction of at least 50% by weight having a boiling point of at least 300°C, and containing metals and asphaltenes, comprising the following steps:
• step (b) preparing a second conditioned heavy hydrocarbon feedstock by mixing a catalyst precursor composition with the first conditioned heavy hydrocarbon feedstock of step (a) such that a colloidal or molecular catalyst is formed when reacted with sulfur;
• step (c) heating the second conditioned heavy hydrocarbon feedstock from step (b) in at least one preheater;
• step (d) introducing said second heated conditioned heavy hydrocarbon feedstock of step (c) into at least one bubbling-entrained hybrid bed reactor comprising a porous supported hydroconversion catalyst, and operating said bubbling-entrained hybrid bed reactor in presence of hydrogen and under hydroconversion conditions to produce an upgraded material, and wherein the colloidal or molecular catalyst is formed in situ in the second heavy hydrocarbon charge conditioned in step (c) and/or in step (d).
• step (a) comprises mixing said organic chemical compound and said heavy hydrocarbon feedstock in a dedicated vessel of an active mixing device.
• step (a) comprises (a1) injecting said organic chemical compound into a conduit conveying said heavy hydrocarbon feedstock to the bubbling-entrained hybrid bed reactor.
• step (a) is carried out at a temperature between room temperature and 300° C., preferably between 70° C. and 200° C., and the residence time of the organic chemical compound with said heavy hydrocarbon charge before step (b) is between 1 second and 10 hours.
• the organic chemical compound is chosen 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.
• the organic chemical compound comprises 2-ethylhexanoic acid, and is preferably 2-ethylhexanoic acid.
• the organic chemical compound comprises ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate, and is preferably ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.
• the catalyst precursor composition comprises an oil-soluble organometallic or bimetallic compound or complex, preferably an oil-soluble organometallic compound or complex selected from the group consisting of 2-ethylhexanoate molybdenum, molybdenum naphthanate, vanadium naphthanate, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl, and is preferably molybdenum 2-ethylhexanoate.
• the molar ratio between said organic chemical compound added in step (a) and the active metal(s), preferably molybdenum, of the composition of catalyst precursor added in step (b), in said second conditioned heavy hydrocarbon feed is between 0.1:1 and 20:1.
• the colloidal or molecular catalyst comprises molybdenum disulfide.
• step (b) comprises (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 dilute precursor mixture; and (b2) mixing said diluted precursor mixture with the first conditioned heavy hydrocarbon feedstock.
• step (bl) is carried out at a temperature between room temperature and 300° C. and for a time period of 1 second to 30 minutes
• step (b2) is carried out at a temperature between room temperature and 300°C and for a time period of 1 second to 30 minutes.
• step (c) comprises heating to a temperature between 280°C and 450°C, more preferably between 300°C and 400°C, and even more preferably between 320°C and 365°C.
• the heavy hydrocarbon feedstock comprises at least one of the following feedstocks: a crude oil, bitumen from bituminous sands, atmospheric distillation column bottoms, vacuum distillation column bottoms, residues , visbreaker bottoms, coal tar, heavy oil from oil shale, liquefied coal, heavy bio-oils, and heavy oils including plastic waste and/or plastic pyrolysis oil.
• the heavy hydrocarbon feedstock has sulfur in a content greater than 0.5% by weight, a Conradson carbon residue of at least 0.5% by weight, C 7 asphaltenes at a content greater than 1% by weight, of transition and/or post-transition metals and/or metalloids at a content greater than 2 ppm by weight, and of alkali metals and/or alkaline-earth metals at a content greater than 2 ppm in weight.
• step (d) of hydroconversion is implemented under an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 300° C. and 550° C., at a volumetric speed hourly WH relative to the volume of each hybrid reactor comprised between 0.05 h 1 and 10 h 1 and under a quantity of hydrogen mixed with the charge entering the hybrid bed reactor comprised between 50 and 5,000 Nm 3 /m 3 dump.
• the concentration of catalyst metal, preferably molybdenum, in the second conditioned hydrocarbon feed is in a range of 5 ppm to 500 ppm by weight of the heavy hydrocarbon feed.
• the method comprises a step (e) of subsequent processing of the recovered material, said step (e) comprising:
• a second stage of hydroconversion in a second bubbling-entrained hybrid bed reactor of at least part of, or all, the recovered material resulting from the hydroconversion stage (d) or optionally of a heavy fraction liquid which predominantly boils at a temperature greater than or equal to 350°C resulting from an optional separation step separating some or all of the upgraded material resulting from the hydroconversion step (d), said second reactor with a bubbling-entraining hybrid bed comprising a porous supported second catalyst and operating in the presence of hydrogen and under hydroconversion conditions to produce a hydroconverted liquid effluent having a reduced Conradson carbon residue, and optionally a reduced amount of sulfur, and/or nitrogen, and/or metals,
• said hydroconversion step (d) and said second hydroconversion step are carried out under an absolute pressure comprised between 2 MPa and 38 MPa, at a temperature comprised between 300°C and 550°C, at an hourly volume rate WH with respect to the volume of each bubbling-entrained hybrid bed reactor comprised between 0.05 h 1 and 10 h 1 and under an amount of hydrogen mixed with the feed entering each bubbling-entrained hybrid bed reactor comprised between 50 and 5000 Nm 3 /m 3 load.
• FIG. 1 is a functional diagram illustrating the principle of the hybrid bed hydroconversion process according to the invention.
• Figure 2 is a block diagram illustrating an example of a hybrid bed hydroconversion process and system according to the invention.
• FIG. 3 is a graph showing the fouling tendency of examples of conditioned hydrocarbon feedstocks as prepared in the hybrid bed hydroconversion process according to the invention and according to the prior art.
• the object of the invention is to provide hybrid bed hydroconversion processes and systems for improving the quality of a heavy hydrocarbon feedstock.
• Such processes and systems for heavy hydrocarbon feedstock hydroconversion employ a dual catalyst system that includes a molecular or colloidal catalyst dispersed in the heavy hydrocarbon feedstock and a porous supported catalyst. They also employ an organic additive mixed with the heavy hydrocarbon feed, before using the dual catalyst system in one or more bubbling bed reactors, each of which comprises a solid phase comprising an expanded bed of a porous supported catalyst, a phase of liquid hydrocarbon comprising the heavy hydrocarbon feedstock, the colloidal or molecular catalyst dispersed therein and the organic additive, and a gaseous phase comprising gaseous hydrogen.
• the hybrid bed hydroconversion methods and systems of the invention reduce the fouling of the installations, and in particular the fouling in the installations upstream of the hydroconversion reactor(s), in particular in the preheating installations of the feed before its conversion in the hybrid hydroconversion reactor(s), and can effectively treat the asphaltenes, reduce or eliminate the formation of coke precursors and sediments, increase the conversion rate in particular by allowing to perform the high temperature hydroconversion, and eliminate catalyst-free zones that would otherwise exist in conventional ebullated bed hydroconversion reactor(s) and downstream processing facilities.
• the hybrid bed hydroconversion processes and systems of the invention also allow more efficient use of the porous supported catalyst, and the combined dual catalyst system.
• hydroconversion refers to a process the primary purpose of which is to reduce the boiling point range of a heavy hydrocarbon feedstock and in which a substantial portion of the feedstock is converted to products with lower boiling point ranges. boiling points lower than those of the original charge. Hydroconversion generally involves the fragmentation of larger hydrocarbon molecules into smaller molecular fragments having a lower number of carbon atoms and a higher hydrogen to carbon ratio. The reactions implemented during hydroconversion make it possible to reduce the size of hydrocarbon molecules, mainly by cleavage of carbon-carbon bonds, in the presence of hydrogen in order to saturate the cut bonds and the aromatic rings.
• hydroconversion occurs typically involves the formation of hydrocarbon free radicals during fragmentation primarily by thermal cracking, followed by capping of the free radical ends or fragments with hydrogen in the presence of active catalyst sites.
• hydroconversion process other reactions typically associated with "hydrotreating” may occur, such as the removal of sulfur and nitrogen from the feed as well as the saturation of olefins.
• hydrocracking is often used as a synonym for "hydroconversion” in English terminology, although “hydrocracking” rather refers to a process similar to a hydroconversion but in which the cracking of hydrocarbon molecules is primarily a catalytic cracking, that is to say cracking occurring in the presence of a hydrocracking catalyst possessing a phase responsible for the cracking activity, for example acid sites such as contained in a clay or zeolites.
• hydrocracking which can be translated as “hydrocracking” generally refers to this last definition (catalytic cracking), and its use is for example rather reserved for the case of vacuum distillates as hydrocarbon feedstocks to be converted, whereas the French term “hydroconversion” is generally reserved for the conversion of heavy hydrocarbon feedstocks such as atmospheric and vacuum residues (but not only).
• hydrotreating refers to a milder operation whose primary purpose is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace metals from the feed and to saturate olefins and/or stabilize hydrocarbon free radicals by reacting them with hydrogen rather than allowing them to react with themselves.
• the main purpose is not to change the boiling point range of the feed.
• Hydrotreating is most often carried out using a fixed bed reactor, although other hydroprocessing reactors can also be used for hydrotreating, for example a fixed bed hydrotreating reactor. bubbling.
• hydroprocessing generally refers to both “hydroconversion"/"hydrocracking" and “hydrotreating” processes.
• hydroconversion reactor refers to any vessel in which the hydroconversion of a feedstock is the primary purpose, e.g. cracking the feedstock (i.e. reducing the d point range boiling), in the presence of hydrogen and a hydroconversion catalyst.
• Hydroconversion reactors typically include an inlet through which heavy hydrocarbon feedstock and hydrogen can be introduced and an outlet from which upgraded material can be withdrawn.
• hydroconversion reactors are also characterized by possessing sufficient thermal energy to cause larger hydrocarbon molecules to break down into smaller molecules by thermal decomposition.
• hydroconversion reactors include, but are not limited to, entrained bed reactors, also known as "slurry" reactors (three-phase reactors - liquid, gas, solid - in which the solid and liquid phases can behave like homogeneous phase), bubbling bed reactors (three-phase fluidized reactors), moving-bed reactors (three-phase reactors with downward movement of the solid catalyst and upward or downward flow of liquid and gas), and fixed bed (three-phase reactors with liquid feedstock trickling down a fixed bed of supported catalyst with hydrogen typically flowing simultaneously with the liquid, but possibly countercurrently in some cases).
• entrained bed reactors also known as "slurry” reactors (three-phase reactors - liquid, gas, solid - in which the solid and liquid phases can behave like homogeneous phase)
• bubbling bed reactors three-phase fluidized reactors
• moving-bed reactors three-phase reactors with downward movement of the solid catalyst and upward or downward flow of liquid and gas
• fixed bed three-phase reactors with liquid feedstock trickling down a fixed bed of
• hybrid bed and “hybrid bubbling bed” and “entrained-bubbling hybrid bed” for a hydroconversion reactor refer to a bubbling bed hydroconversion reactor comprising an entrained catalyst in addition to the porous supported catalyst maintained in the bubbling bed reactor.
• these terms thus refer to a process comprising hybrid operation of an ebullated bed and an entrained bed in at least one and the same hydroconversion reactor.
• the hybrid bed is a mixed bed of two types of catalysts of necessarily different particle size and/or density, one type of catalyst - the "porous supported catalyst” - being maintained in the reactor and the other type of catalyst - the "entrained catalyst", also commonly called “slurry catalyst” - being entrained out of the reactor with the effluents (upgraded feed).
• the entrained catalyst is a colloidal catalyst or a molecular catalyst, as defined below.
• colloidal catalyst and “colloidally dispersed catalyst” refer to catalyst particles having a particle size which is colloidal, eg less than 1 ⁇ m in size (diameter), preferably less than 500 nm in size, more preferably less than 250 nm in size, or less than 100 nm in size, or less than 50 nm in size, or less than 25 nm in size, or less than 10 nm in size, or less than 5 nm in size.
• colloidal catalyst includes, but is not limited to, molecular or molecularly dispersed catalyst compounds.
• molecular catalyst and “molecularly dispersed catalyst” refer to catalyst compounds that are substantially “dissolved” or completely dissociated from other catalyst compounds or molecules in a heavy hydrocarbon feedstock, non-volatile liquid fraction, a bottoms fraction, residues, or other feed or product in which the catalyst may be found. They also refer to very small catalyst particles or sheets that contain only a few catalyst molecules joined together (e.g. 15 molecules or less).
• porous supported catalyst refers to catalysts that are typically used in conventional bubbling bed and fixed bed hydroconversion systems, including catalysts designed primarily for hydrocracking or hydrodemetallization and catalysts designed primarily for hydrotreating.
• Such catalysts typically comprise (i) a catalyst support having a large surface area and many interconnected channels or pores and (ii) fine particles of an active catalyst such as sulphides of cobalt, nickel, tungsten, and/or or molybdenum dispersed in the pores.
• Supported catalysts are commonly produced as cylindrical extrudates ("pellets") or spherical solids, although other shapes are possible.
• upgraded when used to describe a feedstock which is or has been subjected to hydroconversion, or a resulting material or product, refer to the one or more of the following characteristics: a reduction in the molecular weight of the filler, a reduction in the boiling point range of the filler, a reduction in the concentration of asphaltenes, a reduction in the concentration of hydrocarbon free radicals , a reduction in the Conradson carbon residue, an increase in the H/C atomic ratio of the charge, and a reduction in the amount of impurities, such as sulfur, nitrogen, oxygen, halides, and metals .
• impurities such as sulfur, nitrogen, oxygen, halides, and metals .
• conditioned feedstock and “conditioned heavy hydrocarbon feedstock” refer to the heavy hydrocarbon feedstock to be treated in at least one hybrid bed hydroconversion reactor, feedstock in which an organic additive has been combined (here “first conditioned feedstock ”, or charge in which such an organic additive has been combined and then a catalyst precursor composition has been combined and mixed sufficiently so that, when of the formation of the catalyst, in particular by reaction with sulphur, the catalyst will comprise a colloidal or molecular catalyst dispersed in the charge (here “second conditioned charge”.
• FIG. 1 is a functional diagram schematically illustrating the principle of the hybrid bed hydroconversion process 100 according to the invention. It differs in particular from a conventional hybrid bed process, as described for example in document US2005/0241991, in that it comprises the addition of an organic additive to the filler before mixing it with a precursor composition of catalyst.
• organic chemical compound and “organic additive” are used interchangeably in the present description to designate the chemical compound comprising at least one carboxylic acid function and/or at least one ester function and/or one acid anhydride function added to the heavy hydrocarbon feedstock in step (a) and described in detail below.
• a heavy hydrocarbon feedstock 101 containing a fraction of at least 50% by weight having a boiling point of at least 300° C., and containing metals and asphaltenes is treated in a process of hydroconversion 100 comprising the following steps:
• step (b) preparing a second conditioned heavy hydrocarbon feedstock 105 by mixing a catalyst precursor composition 104 with the first conditioned heavy hydrocarbon feedstock 103 of step (a) such that a colloidal or molecular catalyst is formed when 'it reacts with sulphur; (c) heating the second conditioned heavy hydrocarbon feedstock from step (b) in at least one preheater;
• step (d) introducing the second heated conditioned heavy hydrocarbon feedstock 106 of step (c) into at least one bubbling-entrained hybrid bed reactor comprising a porous supported hydroconversion catalyst and operating said bubbling-entrained hybrid bed reactor in the presence of hydrogen and under hydroconversion conditions to produce an upgraded material 107.
• the recovered material 107 may be further processed in an optional step (e).
• the colloidal or molecular catalyst is formed in situ in the second heavy hydrocarbon feedstock conditioned in stage (c) and/or in stage (d).
• FIG. 2 schematically illustrates an example of a hybrid bed hydroconversion system 200 according to the invention, said system being described in detail later in the description, after the description of the general process.
• heavy hydrocarbon feedstock refers to crude oils, oil sands bitumen, bottoms and residuals from refinery processes (e.g. visbreaker bottoms), and any other lower grade material that contains a substantial amount of high boiling hydrocarbon fractions and/or which includes a significant amount of asphaltenes which can deactivate a solid supported catalyst and/or cause or result in the formation of coke precursors and sediments.
• the heavy hydrocarbon feedstock 101 can thus comprise at least one of the following feedstocks: a crude oil, bitumen from bituminous sands, bottoms of atmospheric distillation columns, bottoms of vacuum distillation columns, residues, bottoms of visbreaker, coal tar, heavy oil from oil shale, liquefied coal, heavy bio-oils, and heavy oils including plastic waste and/or plastic pyrolysis oil.
• Plastic pyrolysis oils are oils obtained by the pyrolysis of plastics, preferably waste plastics, and can be obtained by treatment by catalytic, thermal pyrolysis or can be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen).
• the heavy hydrocarbon charge treated contains hydrocarbon fractions among which at least 50% by weight, preferably at least 80% by weight have a boiling point of at least 300° C., preferably of at least 350° C. or at least 375°C.
• crude oils or heavy hydrocarbon fractions resulting from the atmospheric and/or vacuum distillation of a crude oil can also be atmospheric and/or vacuum residues, and in particular atmospheric and/or vacuum residues resulting from hydrotreatment, hydrocracking and/or hydroconversion. They can also be vacuum distillates, fractions originating from a catalytic cracking unit such as fluidized bed catalytic cracking (FCC), a coking or visbreaking unit.
• FCC fluidized bed catalytic cracking
• these are vacuum residues.
• these residues are fractions in which at least 80% by weight have a boiling point of at least 450°C or more, and most often of at least 500°C or 540°C.
• Aromatic fractions extracted from a lubricant production unit, deasphalted oils (raffinates from a deasphalting unit), and asphalt (residues from a deasphalting unit) are also suitable as feed.
• the feed can also be a residual fraction from a direct liquefaction of coal (vacuum distillate and/or atmospheric and/or vacuum residue from, for example, an H-Coal process, registered trademark), from a pyrolysis of coal or bituminous shale residues, or of a residual fraction originating from the direct liquefaction of lignocellulosic biomass alone or mixed with coal and/or a petroleum fraction (referred to herein as “heavy bio-oils”).
• a direct liquefaction of coal vacuum distillate and/or atmospheric and/or vacuum residue from, for example, an H-Coal process, registered trademark
• a pyrolysis of coal or bituminous shale residues or of a residual fraction originating from the direct liquefaction of lignocellulosic biomass alone or mixed with coal and/or a petroleum fraction (referred to herein as “heavy bio-oils”).
• heavy hydrocarbon feedstocks include, but are not limited to, Lloydminster Crude Oil, Cold Lake Bitumen, Athabasca Bitumen, Urals Crude Oil, Arabian Heavy Crude Oil, Arabian Crude Oil Light, atmospheric distillation column bottoms, vacuum distillation column bottoms, bottoms (or “tails"), bottoms pitch, vacuum bottoms, solvent deasphalting pitch, and liquid fractions not volatiles which remain after subjecting crude oils, bitumen from oil sands, liquefied coal, oil shale, or coal tar feeds to distillation, hot separation, and the like and which contain end fractions boiling point and/or asphaltenes.
• the heavy hydrocarbon feeds treated in the process and the system according to the invention contain metals and asphaltenes, in particular C 7 asphaltenes, and other impurities such as sulfur and nitrogen.
• asphaltene refers to the fraction of a heavy hydrocarbon feedstock which is typically insoluble in paraffinic solvents such as propane, butane, pentane, hexane, and heptane and which comprises sheets of compounds fused rings held together by heteroatoms such as sulfur, nitrogen, oxygen and metals.
• Asphaltenes broadly include a wide range of complex compounds having 80 to 160,000 carbon atoms. Asphaltenes are operationally defined as "C 7 asphaltenes", i.e.
• C 7 asphaltenes are compounds known to inhibit the conversion of residual fractions, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which greatly limit the exploitability of hydrotreating and hydroconversion units.
• the heavy hydrocarbon charge 101 can typically have sulfur at a content greater than 0.5% by weight, a Conradson carbon residue of at least 3% by weight, C 7 asphaltenes at a content greater than 1% by weight , transition and/or post-transition metals and/or metalloids at a content greater than 2 ppm by weight, and alkali metals and/or alkaline-earth metals at a content greater than 2 ppm by weight.
• fillers 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 a content may be higher than 2 ppm by weight, or greater than 20 ppm by weight, and even greater than 100 ppm by weight, and also in alkali metals (e.g. Na) and/or in alkaline-earth metals, the content of which may be greater than 2 ppm in weight, even greater than 5 ppm by weight, and even greater than 7 ppm by weight.
• impurities such as metals, in particular transition metals (e.g. Ni, V) and/or post-transition metals, and/or metalloids, for which a content may be higher than 2 ppm by weight, or greater than 20 ppm by weight, and even greater than 100 ppm by weight, and also in alkali metals (e.g. Na) and/or in alkaline-earth metals,
• the sulfur content is in fact generally greater than 0.5% by weight, and even greater than 1% by weight, or even greater than 2% by weight.
• the content of C 7 asphaltenes can in fact be at least 1% by weight, and even greater than 3% by weight.
• Conradson carbon residue is in fact generally greater than 3% by weight, and even at least 5% by weight.
• Conradson carbon residue is defined by ASTM D 482 and represents the amount of carbon residue produced after pyrolysis under standard conditions of temperature and pressure.
• Step (a) comprises mixing said heavy hydrocarbon feedstock 101 with an organic chemical compound 102 comprising at least one carboxylic acid function and/or at least one ester function and/or one acid anhydride function. This mixture forms what is referred to herein as the first conditioned heavy hydrocarbon charge 103.
• step (b) of thorough/intimate mixing is carried out before step (b) of thorough/intimate mixing with a catalyst precursor composition which will lead to the formation of a colloidal or molecular catalyst dispersed in the heavy hydrocarbon feedstock when it is reacted. with sulfur.
• step (a) of mixing such an organic additive and the heavy hydrocarbon feedstock, before step (b), improves the hydroconversion process in a bubbling-entrained hybrid bed, in particular by reducing the fouling of the installations, in particular upstream of the hydroconversion reactor in the installation for heating the load in step (c).
• the organic additive when mixed with the heavy hydrocarbon feedstock, allows better solubility of the colloidal or molecular catalyst precursor in the feedstock, avoiding or reducing fouling in particular due to metal deposits in installations upstream of the hydroconversion reactor such as in the heating installation, and thus improving the dispersion of the colloidal or molecular catalyst formed in step (c) and/or in a subsequent step, thus generating increased availability of the sites metallic active ingredients, promoting the hydrogenation of free radicals which are precursors of coke and sediments, and generating a substantial reduction in the fouling of the installations.
• the organic additive is the organic additive
• the organic additive 102 having at least one carboxylic acid function and/or at least one ester function and/or at least one acid anhydride function preferably comprises at least 6 carbon atoms, and more preferably at least 8 carbon atoms.
• the organic additive 102 is neither a catalyst precursor nor a catalyst.
• the organic additive 102 does not contain any metal.
• organic additive examples 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, dimethyl suberate, monomethyl, hexanoic anhydride, caprylic anhydride.
• the organic additive is an organic chemical compound chosen from the group consisting of the list of specific compounds described above, and mixtures thereof.
• the organic additive is an organic chemical compound comprising at least one carboxylic acid function, and more preferably chosen from the group consisting of 2-ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
• the organic additive comprises, or consists of, 2-ethylhexanoic acid.
• the organic additive can be an organic chemical compound comprising at least one ester function and/or one acid anhydride function, and for example chosen 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 caprylic anhydride.
• the organic additive comprising at least one ester function and/or one acid anhydride function comprises, or consists of, ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate or mixtures thereof, and preferably is ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.
• This step (a) of mixing the organic additive 102 with the heavy hydrocarbon feedstock 101 forming the first conditioned heavy hydrocarbon feedstock 103 is implemented before a step (b) of complete/intimate mixing with a catalyst precursor composition which will lead to the formation of the colloidal or molecular catalyst dispersed in the heavy hydrocarbon charge.
• the organic additive is preferably added such that the molar ratio of organic additive to active metal(s) of the catalyst precursor composition added in step (b) is within a range of about 0 , 1:1 to about 20:1, more preferably in a range of about 0.75:1 to about 7:1, and even more preferably in a range of about 1:1 to about 5:1. "approximately” refers to an approximation of ⁇ 5%, preferably ⁇ 1%.
• the catalyst precursor composition added in step (b) comprises Mo, eg molybdenum 2-ethylhexanoate, and the organic additive is preferably added such that the molar ratio of organic additive to Mo of the catalyst precursor composition added in step (b) either in a range of about 0.1:1 to about 20:1, more preferably in a range of about 0.75:1 to about 7:1, and even more preferably in a range of about 1:1 to about 5:1.
• Mixture with organic additive is preferably added such that the molar ratio of organic additive to Mo of the catalyst precursor composition added in step (b) either in a range of about 0.1:1 to about 20:1, more preferably in a range of about 0.75:1 to about 7:1, and even more preferably in a range of about 1:1 to about 5:1.
• the mixture of the organic additive and the heavy hydrocarbon filler is advantageously implemented in a first conditioner mixer 210.
• the first conditioning mixer 210 can comprise an active mixing device, any type of injection system for pipes or any type of in-line mixer as detailed below.
• the preparation of the first conditioned heavy hydrocarbon charge 103 comprises mixing said organic additive 102 and said heavy hydrocarbon charge 101 in a dedicated tank of an active mixing device (forming the first conditioning mixer 210 ).
• active mixing device refers to a mixing device comprising a moving part, e.g. a stirring rod, for actively mixing the components.
• Such a configuration makes it possible in particular to increase the dispersion of the colloidal or molecular catalyst formed at a later stage.
• the use of a dedicated tank also makes it possible to achieve a high residence time.
• the preparation of the first conditioned heavy hydrocarbon feedstock 103 comprises injecting said organic chemical compound 102 into a pipe conveying said heavy hydrocarbon feedstock 101 to the bubbling-entrained hybrid bed reactor.
• the first conditioner mixer 210 thus comprises, in such a configuration, the part of the pipe in which the mixing is carried out, and possibly additional systems to facilitate the mixing, such as for example static in-line mixers as described later in section 1. step (b).
• Such a configuration makes it possible in particular to reduce the investments in installations and the space required, in comparison with a mixture in a dedicated tank.
• the residence time of the organic additive with the heavy hydrocarbon feedstock, before mixing with the catalyst precursor composition in step (b) forming the second conditioned heavy hydrocarbon feedstock 105 is preferably between 1 second and 10 hours. , more preferably between 1 second and 1 hour, and even more preferably between 1 second and 30 minutes.
• a mixing time (or dwell time for mixing) of 1 second includes instant mixing.
• the mixture of the organic additive and the heavy hydrocarbon filler is preferably carried out between room temperature, eg 15° C., and 300° C., more preferably between 70° C. and 200° C., for example at 150° C. .
• the temperature at which the mixture is implemented is advantageously the actual temperature of the stream of heavy hydrocarbon feedstock 101.
• the temperature in step (a) should preferably be below a decomposition temperature of the catalyst precursor composition.
• the pressure for mixing step (a) is also advantageously the actual pressure of the heavy hydrocarbon feed stream 101.
• the gauge pressure for mixing step (a) is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa.
• fillers which are solid or extremely viscous at room temperature
• such fillers can advantageously be heated in order to soften them and create a filler having a sufficiently low viscosity to allow good mixing of the organic additive, and in particular with the catalyst precursor composition in additional step (b).
• decreasing the viscosity of the heavy hydrocarbon feedstock will reduce the time required to fully and thoroughly mix the catalyst precursor composition into the first feedstock conditioned in step (b).
• the feedstock should not be heated to a temperature beyond which significant thermal decomposition of the catalyst precursor composition occurs, prior to 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 a colloidal or molecular catalyst.
• step (a) the mixing of the heavy hydrocarbon feedstock 101 with the organic additive 102 can be done for the heavy hydrocarbon feedstock 101, in part or in whole.
• the mixing step (a) is implemented between the organic additive 102 and the entire stream of heavy hydrocarbon feedstock 101 sent to the hydroconversion system.
• the mixing step (a) is implemented between the organic additive 102 and part of the stream of heavy hydrocarbon feedstock 101 sent to the hydroconversion.
• the preparation of the first conditioned heavy hydrocarbon charge 103 can be implemented by mixing at least part of the flow of said heavy hydrocarbon feedstock 101, for example at least 50% by weight of the flow of said heavy hydrocarbon feedstock 101, with the organic additive 102.
• the complementary part of the stream of said heavy hydrocarbon charge 101 can be reincorporated once the catalyst precursor composition has been added (step (b)), that is to say mixed with the second conditioned heavy hydrocarbon charge before its preheating to step (c).
• the first conditioned hydrocarbon feed 103 is then mixed with a catalyst precursor composition 104 to form a second heavy conditioned hydrocarbon feed 105.
• the catalyst precursor composition is selected from any metal catalyst precursor known to those skilled in the art capable of forming colloidally or molecularly dispersed catalyst (i.e., entrained catalyst) by presence of hydrogen and/or H2S and/or any other sulfur source, and allowing the hydroconversion of a heavy hydrocarbon feedstock after injection into said heavy hydrocarbon feedstock.
• the catalyst precursor composition is advantageously an oil-soluble catalyst precursor composition containing at least one transition metal.
• the catalyst precursor composition preferably comprises an oil-soluble organometallic compound or complex.
• the catalyst precursor composition may comprise an oil-soluble organometallic or bimetallic compound or complex comprising one or two of the following metals: Mo, Ni, V, Fe, Co or W, or mixtures of such compounds/complexes.
• the oil-soluble catalyst precursor composition preferably has a decomposition temperature (temperature below which the catalyst precursor composition is substantially chemically stable) in a range of 100°C to 350°C, more preferably in a range of 150°C to 300°C, and most preferably in a range of 175°C to 250°C.
• the oil-soluble organometallic compound or complex is preferably chosen from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum naphthanate vanadium, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl.
• the catalyst precursor composition comprises molybdenum and, for example, comprises a compound selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, and molybdenum hexacarbonyl.
• a presently preferred catalyst precursor composition comprises, or consists of, molybdenum 2-ethylhexanoate (also commonly referred to as molybdenum octoate).
• molybdenum 2-ethylhexanoate contains 15% by weight molybdenum and has a sufficiently high decomposition temperature or decomposition temperature range to avoid substantial thermal decomposition when mixed with a heavy hydrocarbon feedstock at a temperature below 250°C.
• One skilled in the art can, by following the present invention, select a mixing temperature profile which results in the mixing of a selected precursor composition, without substantial thermal decomposition prior to the formation of the colloidal or molecular catalyst.
• the mixture of the catalyst precursor composition and the first conditioned heavy hydrocarbon feedstock is carried out in a second conditioning mixer 220.
• Catalyst precursor composition 104 preferably an oil-soluble catalyst precursor composition
• Catalyst precursor composition 104 can be premixed with a hydrocarbon stream of diluent to form a dilute precursor mixture, as described in US2005/0241991, US10822553 or US10941353 and recalled below.
• step (b) comprises:
• (b1) premixing the catalyst precursor composition 104 with a hydrocarbon oil (diluent) to form a dilute precursor mixture, said premixing preferably being carried out at a temperature below a temperature at which a portion substantial portion of the catalyst precursor composition begins to decompose, preferably between room temperature, eg 15°C, and 300°C, and preferably over a time period of 1 second to 30 minutes; and (b2) mixing said diluted precursor mixture with the first conditioned heavy hydrocarbon feedstock 103, preferably at a temperature between room temperature, eg 15°C, and 300°C, and advantageously for a time period of 1 second to 30 minutes.
• suitable hydrocarbon diluents include, but are not limited to, vacuum gas oil known as "VGO” (which typically has a boiling range of 360°C to 524°C), settling oil or recycle oil (which typically has a boiling range of 360°C to 550°C), light gas oil (which typically has a boiling range of 200°C to 360°C), vacuum residues (which typically have a boiling range of 524°C+), deasphalted oils, and resins.
• VGO vacuum gas oil known as "VGO”
• settling oil or recycle oil which typically has a boiling range of 360°C to 550°C
• light gas oil which typically has a boiling range of 200°C to 360°C
• vacuum residues which typically have a boiling range of 524°C+
• deasphalted oils and resins.
• the hydrocarbon diluent is preferably a VGO.
• the weight ratio of catalyst precursor composition 104 to hydrocarbon oil diluent is preferably in a range of about 1:500 to about 1:1, more preferably in a range of about 1:150 to about 1:2, and even more preferably in a range of about 1:100 to about 1:5 (e.g. 1:100, 1:50, 1:30, or 1:10).
• the catalyst precursor composition 104 is more preferably mixed with the hydrocarbon diluent at a temperature 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 the dilute precursor mixture.
• the actual temperature at which the dilute precursor mixture is formed will generally depend largely on the decomposition temperature of the specific precursor composition being used.
• the catalyst precursor composition 104 is more preferably mixed with the hydrocarbon oil diluent for a period of time in a range of 1 second to 10 minutes, and even more preferably in a range of 2 seconds to 3 minutes.
• Actual mixing time depends, at least in part, on temperature (i.e. which affects the viscosity of fluids) and mixing intensity.
• the mixing intensity depends, at least in part, on the number of stages, e.g. for the static in-line mixer.
• Premixing the catalyst precursor composition 104 with a hydrocarbon diluent prior to mixing the diluted precursor mixture with the heavy hydrocarbon feedstock greatly facilitates thorough and intimate mixing of the precursor composition into the feedstock, particularly in the relatively short period of time required for large-scale industrial operations to be economically viable.
• a dilute precursor mixture shortens the overall mixing time by (1) reducing or eliminating solubility differences between the more polar catalyst precursor composition and the heavy hydrocarbon feed, (2) reducing or eliminating rheology differences between the catalyst precursor composition and the heavy hydrocarbon feedstock, and/or (3) breaking up the catalyst precursor molecules to form a solute in a hydrocarbon oil diluent that is much more easily dispersed in the heavy hydrocarbon feedstock. It is particularly advantageous to first form a mixture of dilute precursor in the case where the heavy hydrocarbon feedstock contains water (e.g. condensed water). 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 catalyst particles of micron or larger size.
• water e.g. condensed water
• the hydrocarbon oil diluent is preferably substantially water-free (i.e. contains less than 0.5 wt% water, preferably less than 0.1 wt% water, and more preferably less than 750 wppm of water) to prevent the formation of substantial amounts of catalyst particles of micrometer size or larger.
• the diluted precursor mixture is then combined with the first conditioned heavy hydrocarbon feedstock 103 and mixed for a sufficient time and so as to disperse the catalyst precursor composition throughout the feedstock to provide a second conditioned heavy hydrocarbon feedstock 105 in which the catalyst precursor composition is completely/intimately mixed with the heavy hydrocarbon feedstock.
• the dilute precursor mixture and the heavy hydrocarbon feedstock are more preferably mixed for a period of time within a range of 1 second to 10 minutes, and even more preferably within a range of 2 seconds to 3 minutes.
• Increasing the shear force and/or energy of the mixing process generally reduces the time required to achieve thorough/intimate mixing.
• Examples of mixing apparatus that can be used to effect thorough/intimate mixing of catalyst precursor composition 104 and first conditioned heavy hydrocarbon feedstock 103 include, but are not limited to, high shear mixing such as a mixture created in a pump with a propeller or turbine rotor; multiple static in-line mixers; multiple static in-line mixers in combination with high shear in-line mixers; multiple static in-line mixers in combination with high shear in-line mixers; multiple static in-line mixers in combination with high shear in-line mixers followed by recirculation pumping in the buffer tank; combinations of the above devices followed by one or more multi-stage centrifugal pumps.
• high shear mixing such as a mixture created in a pump with a propeller or turbine rotor
• multiple static in-line mixers such as a mixture created in a pump with a propeller or turbine rotor
• multiple static in-line mixers such as a mixture created in a pump with a propeller or turbine rotor
• continuous rather than discontinuous mixing in successive batches can be implemented using high-energy pumps having several compartments in which the catalyst precursor composition 104 and the first conditioned heavy hydrocarbon feedstock 103 are churned and mixed as part of the pumping process itself.
• the mixing apparatus previously described can also be used for the premix step (b1) discussed above in which the catalyst precursor composition 104 is mixed with the hydrocarbon oil diluent to form the precursor mixture. of catalyst.
• the dilute precursor blend 104 may be initially blended with 20% of the first conditioned heavy hydrocarbon feedstock, the resulting blended first conditioned heavy hydrocarbon feedstock may be blended with an additional 40% of the first conditioned heavy hydrocarbon feedstock, and the 60 resulting % of mixed conditioned first heavy hydrocarbon feedstock may be mixed with the remaining 40% of conditioned first heavy hydrocarbon feedstock in accordance with good engineering practice of gradual dilution, to fully disperse the catalyst precursor composition 104 in the hydrocarbon feedstock heavy. Mixing time in the appropriate mixing devices or methods described herein should also be used for the stepwise dilution approach.
• the first conditioned heavy hydrocarbon feedstock 103 and the dilute precursor mixture are preferably mixed and conditioned at a temperature within a range of 50°C to 200°C, more preferably within a range of 75°C to 175°C, to provide the second conditioned hydrocarbon charge.
• the gauge pressure is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa. Step (c): heating of the second conditioned heavy hydrocarbon charge
• the second conditioned heavy hydrocarbon charge 105 formed in step (b) is then heated in at least one preheating device 230, before being introduced into the hybrid bed reactor for the hydroconversion.
• the second conditioned hydrocarbon charge 105 is sent to the at least one preheating device 230, optionally pressurized by a pump.
• the preheating device comprises any heating means capable of heating a heavy hydrocarbon charge known to a person skilled in the art.
• the preheating device can comprise a furnace comprising at least one preheating compartment, and/or tubes in which the hydrocarbon charge flows, a mixer of the second hydrocarbon charge conditioned with H2, any type of suitable heat exchangers , for example tubular or spiral heat exchangers in which the oil feed flows, etc.
• This pre-heating of the second conditioned heavy hydrocarbon charge then makes it possible to reach a target temperature in the hydroconversion reactor in the subsequent step (d).
• the second conditioned hydrocarbon charge 105 is more preferably heated in the preheater 230 to a temperature within a range of 280°C to 450°C, even more preferably within a range of 300°C to 400°C, and even more preferably in a range of 320°C to 365°C, in particular in order to later reach a target temperature in the hydroconversion reactor in step (d).
• the skin temperature of the preheater e.g. the skin temperature of the steel shell of a compartment or tubes of a furnace or heat exchanger(s), can reach from 400°C to 650°C .
• Mixing the heavy hydrocarbon feedstock with the organic additive in step (a) avoids or reduces fouling that can occur in the preheater at these high temperatures.
• the second conditioned charge is heated to a temperature which is 100° C. lower than the hydroconversion temperature in the hybrid hydroconversion reactor, preferably 50° C. lower than the hydroconversion temperature.
• the conditioned hydrocarbon feed may be heated in step (c) to a temperature in the range of 310°C to 340°C.
• the absolute pressure is between atmospheric pressure (eg 0.101325 MPa) and 38 MPa, preferably between 5 MPa and 25 MPa, and preferably between 6 MPa and 20 MPa.
• the heating in step (c) advantageously causes the second conditioned hydrocarbon charge to release sulfur which can combine with the metal of the catalyst precursor composition.
• the colloidal or molecular catalyst is formed, or at least begins to form, in situ in the second heavy hydrocarbon charge conditioned in this step (c) of heating in the preheating device 230.
• sulfur In order to form the colloidal or molecular catalyst, sulfur must be available (e.g. as HS) to combine with the metal of the dispersed catalyst precursor composition.
• step (c) The general formation of the colloidal or molecular catalyst in situ in the second conditioned heavy hydrocarbon charge is described in detail below, as well as the conditions required for such formation in step (c) and / or step (d) .
• the final activated catalyst can be formed in situ by heating the second conditioned heavy hydrocarbon feedstock to a temperature sufficient to release the sulfur therefrom.
• a source of sulfur can thus be hhS dissolved in the heavy hydrocarbon feedstock, or hhS contained in hydrogen recycled to the hybrid bed hydroconversion reactor for hydroconversion, or hhS originating from sulfur-containing organic molecules present in the feed or possibly introduced beforehand into the heavy hydrocarbon feed (injection of dimethyl disulphide, thioacetamide, any hydrocarbon feed containing sulfur of the mercaptan type, sulphides, oil containing sulphur, diesel containing sulfur, of vacuum distillate containing sulfur, of residue containing sulfur), such injection being rare and reserved for very atypical heavy hydrocarbon feedstocks.
• a sulfur source can be sulfur compounds in the feed or a sulfur compound added to the feed.
• the formation of the colloidal or molecular dispersed catalyst is carried out at a total gauge pressure of between 0 MPa and 25 MPa.
• a molecularly dispersed catalyst may form upon reaction with sulfur to form the metal sulfide compound. Under certain circumstances, weak agglomeration may occur resulting in colloidal sized catalyst particles.
• the second conditioned hydrocarbon feedstock 105 is preferably heated to a temperature within a range of room temperature, e.g. 15°C, to 500°C, more preferably within a range of 200°C. at 500°C, even more preferably in a range of 250°C to 450°C, and even more preferably in a range of 300°C to 435°C.
• step (c) and/or (d) allows the formation of the catalyst of metal sulphide type.
• the colloidal or molecular catalyst can thus be formed, at least in part, during this heating step (c), before the second heated conditioned hydrocarbon charge is introduced into the hybrid bed hydroconversion reactor in step (d ).
• the colloidal or molecular catalyst can also be formed in situ in the hybrid bed hydroconversion reactor itself in step (d), in particular either completely or partly in the case where it has started to form at step (c).
• the concentration of catalyst metal, preferably molybdenum, in the conditioned hydrocarbon feed is preferably in a range of 5 ppm to 500 ppm by weight of the heavy hydrocarbon feed 101, more preferably in a range of 10 ppm to 300 ppm by weight, more preferably in a range of 10 ppm to 175 ppm by weight, even more preferably in a range of 10 ppm to 75 ppm by weight, and even more preferably in a range of 10 ppm to 50 ppm by weight.
• the catalyst metal can become more concentrated as volatile fractions are removed from a non-volatile residue fraction.
• the colloidal or molecular catalyst tends to be very hydrophilic, the individual particles or molecules will tend to migrate towards the more hydrophilic fragments or molecules in the heavy hydrocarbon feed, in particular the asphaltenes. While the highly polar nature of the catalyst compound causes or allows the colloidal or molecular catalyst to associate with asphaltene molecules, it is the general incompatibility between the highly polar catalyst compound and the hydrophobic heavy hydrocarbon feedstock that requires the aforementioned intimate or complete mixing of the oil-soluble catalyst precursor composition into the heavy hydrocarbon feedstock prior to formation of the colloidal or molecular catalyst.
• the colloidal or molecular catalyst comprises molybdenum disulfide.
• a nanoscale crystal of molybdenum disulfide has 7 molybdenum atoms sandwiched between 14 sulfur atoms, and the total number of molybdenum atoms exposed at the edge, thus available for catalytic activity, is greater than in a micron-sized crystal of molybdenum disulfide.
• small catalyst particles as in the present invention i.e. a colloidal or molecular catalyst, with improved dispersion, results in more catalyst particles and catalyst sites. distributed more evenly throughout the hydrocarbon charge.
• molybdenum disulfide particles of nanometer size or smaller are believed to associate intimately with asphaltene molecules.
• the second heated conditioned charge 106 is then introduced, optionally pressurized by a pump, in particular if it has not already been pressurized before step (c), into at least one bubbling-entrained hybrid bed reactor 240 together with hydrogen 201, and is operated under hydroconversion conditions to produce an upgraded material 107.
• the colloidal or molecular catalyst can form in situ in the hybrid bed hydroconversion reactor itself in step (d), if it is not fully formed or not formed at all during the process. step (c).
• the second heated conditioned feedstock 106 already contains the colloidal or molecular catalyst, in part or in whole, when it is introduced. in the at least one bubbling-entrained hybrid bed reactor 240.
• the bubbling-entrained hybrid bed reactor 240 comprises a solid phase which comprises a porous supported catalyst in the form of an expanded bed, a liquid hydrocarbon phase comprising said second heated conditioned heavy hydrocarbon feedstock 106 containing the colloidal or molecular catalyst dispersed therein. -ci, and a gas phase comprising hydrogen.
• the ebullated-entrained hybrid bed reactor 240 is an ebullated bed hydroconversion reactor comprising the molecular or colloidal catalyst entrained from the reactor with the effluents (upgraded feed), in addition to a porous supported catalyst, in the form of an expanded bed, maintained in the bubbling bed reactor.
• the operation of the hybrid bed hydroconversion reactor is based on that of an ebullated bed reactor as used for the H-OilTM process, as described, for example, in patents US4521295 or US4495060 or US4457831 or US4354852 or in the article Aiche, March 19-23, 1995, Houston, Texas, article number 46d, "Second generation ebullated bed technology".
• the bubbling bed reactor can comprise a recirculation pump which makes it possible to maintain the porous supported solid catalyst in a bubbling bed by continuous recycling of at least a part of a liquid fraction withdrawn at the level from the upper part of the reactor and reinjected at the level of the lower part of the reactor.
• the hybrid bed reactor preferably has an inlet located at or near the bottom of the hybrid bed reactor through which the heated second conditioned feed 106 is introduced together with the hydrogen 201, and an outlet at the at or near the top of the reactor from which the upgraded material 107 is withdrawn.
• the hybrid bed reactor further includes an expanded catalyst zone comprising the 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 located above the expanded catalyst zone.
• the colloidal or molecular catalyst is dispersed throughout the charge in the hybrid bed reactor, including both the expanded catalyst zone and the zones free of supported catalyst, and therefore available to stimulate upgrading reactions in which forms catalyst-free zones in conventional ebullated bed reactors.
• the feed in the hybrid bed reactor continuously recirculates from the upper supported catalyst-free zone to the lower supported catalyst-free zone by means of a recycle line in communication with a boil-out pump.
• a recycle line in communication with a boil-out pump.
• At the top of the recycle conduit is a funnel-shaped recycle cup through which feed is drawn from the upper supported catalyst-free zone.
• the internal recycle feed is mixed with fresh heated second conditioned feed 106 and additional hydrogen gas 201.
• the porous supported hydroconversion catalyst when it is spent, can be partially replaced by fresh catalyst, by withdrawing the spent catalyst preferably at the level of the lower part of the reactor. , and by introducing fresh catalyst either at the level of the upper part or at the level of the lower part of the reactor.
• This replacement of spent catalyst is preferably carried out at regular time intervals, and preferably in bursts or virtually continuously.
• openings inlet and outlet tubes in the expanded catalyst zone can be used to introduce/withdraw fresh and spent supported catalyst respectively.
• the presence of colloidal or molecular catalyst in the hybrid bed reactor provides additional catalytic hydrogenation activity, both in the expanded catalyst zone, in the recycle line, and in the lower and upper supported catalyst-free zones.
• Free radical capping on the exterior of the porous supported catalyst minimizes the formation of sediment and coke precursors, which are often responsible for the deactivation of the supported catalyst. This can allow a reduction in the amount of porous supported catalyst that would otherwise be required to carry out a desired hydroconversion reaction. This can also reduce the rate at which the porous supported catalyst must be drawn off and replenished.
• the porous supported hydroconversion catalyst used in hydroconversion step (d) may contain one or more elements from Groups 4 to 12 of the Periodic Table of Elements, which are supported.
• the support of the porous supported catalyst can advantageously be an amorphous support, such as silica, alumina, silica/alumina, titanium dioxide or combinations of these structures, and most preferably alumina.
• the catalyst may contain at least one Group VIII metal selected from nickel and cobalt, preferably nickel, said Group VIII element being preferably used in combination with at least one Group VIB metal selected from molybdenum and tungsten; preferably, the Group VIB metal is molybdenum.
• the groups of chemical elements can 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).
• Group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the porous supported hydroconversion catalyst used in hydroconversion step (d) comprises an alumina support and at least one Group VIII metal chosen from nickel and cobalt, preferably nickel, and at least one Group VIB metal selected from molybdenum and tungsten, preferably molybdenum.
• the porous supported hydroconversion catalyst comprises nickel as a Group VIII element and molybdenum as a Group VIB element.
• the metal content of the non-noble group VIII, in particular nickel is advantageously between 0.5% and 10% by weight, expressed as weight of metal oxide (in particular NiO), and preferably between 1% and 6% by weight, and the content of Group VIB metal, in particular of molybdenum, is advantageously between 1% and 30% by weight, expressed by weight of metal oxide (in particular of molybdenum trioxide MOO3), and preferably between 4% and 20% by weight.
• the contents of the metals are expressed as percentage by weight of metal oxide relative to the weight of the porous supported catalyst.
• This porous supported catalyst is advantageously used in the form of extrudates or beads.
• the balls have, for example, a diameter of between 0.4 mm and 4.0 mm.
• the extrudates have, for example, a cylindrical shape with a diameter between 0.5 mm and 4.0 mm and a length between 1 mm and 5 mm. Extrudates can also be objects of a different shape such as trilobes, regular or irregular tetralobes, or other multilobes.
• Porous supported catalysts of other shapes can also be used.
• the size of these different forms of porous supported catalysts can be characterized by means of the equivalent diameter.
• the equivalent diameter is defined as six times the ratio between the volume of the particle and the outer surface area of the particle.
• the porous supported catalyst used in the form of extrudates, beads or other shapes, thus has an equivalent diameter of between 0.4 mm and 4.4 mm. These porous supported catalysts are well known to those skilled in the art.
• said second heated conditioned feedstock 106 is generally converted under conventional conditions for the hydroconversion of a heavy hydrocarbon feedstock.
• the hydroconversion step (d) is carried out under an absolute pressure of between 2 and 38 MPa, preferably between 5 and 25 MPa and preferably between 6 and 20 MPa, 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, and even more preferably between 410°C and 435°C.
• the hourly volume velocity (WH), or liquid hourly space velocity (LHSV) in English, of the load relative to the volume of each hybrid reactor is between 0.05 h 1 and 10 h 1 , preferably between 0.10 h 1 and 2 h 1 and preferably between 0.10 h 1 and 1 h 1 .
• the WH is between 0.05 h 1 and 0.09 h 1 .
• the WH 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.
• the quantity of hydrogen mixed with the heavy hydrocarbon feedstock 106 is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid heavy hydrocarbon feedstock, such as between 100 and 3000 Nm 3 /m 3 and preferably between 200 and 2000 Nm 3 /m 3 .
• the hydroconversion step (d) is implemented in one or more hybrid bed hydroconversion reactors, which can be in series and/or in parallel.
• the recovered material 107 can be processed further.
• Examples of such further processing include, without limitation, at least one of the following: separation of hydrocarbon fractions from the upgraded material, deeper hydroconversion in one or more bubbling-entrained hybrid bed reactors or additional bubbling bed to produce further upgraded material, fractionation of the further upgraded material into hydrocarbon fractions, deasphalting of at least part of the upgraded material 107 or of a heavy liquid fraction resulting from fractionation of the upgraded material or further upgraded material, guard bed purification of the upgraded or further upgraded material to remove at least a portion of the colloidal or molecular catalyst and metallic impurities.
• hydrocarbon fractions that can be produced from the upgraded material 107 can be sent to different processes in the refinery, and details of these post-treatments are not described here since they are generally known to those skilled in the art. art and will complicate the description unnecessarily.
• gaseous fractions, naphtha, middle distillates, VGO, DAO can be sent to hydrotreating, steam cracking, fluidized bed catalytic cracking (FCC), hydrocracking, extraction lubricating oil, etc.
• residues atmospheric or vacuum residues
• Heavy ends, including residues can also be recycled in the hydroconversion process, for example in the hybrid bed reactor.
• the method further comprises:
• Said second hydroconversion step is carried out in a manner similar to that which has been described for the hydroconversion step (d), and its description is therefore not repeated here. This applies in particular to the operating conditions, to the equipment used, to the porous supported hydroconversion catalysts used, with the exception of the specifications mentioned below.
• the second hydroconversion step is carried out in a second bubbling-entrained hybrid bed reactor 260 similar to hybrid bed reactor 240.
• the operating conditions may be similar or different from those in the hydroconversion step (d), the temperature remaining in the range between 300°C and 550°C, preferably between 350 °C and 500°C, more preferably between 370°C and 450°C, more preferably between 400°C and 440°C, and even more preferably between 410°C and 435°C, and the amount of hydrogen introduced into the reactor remains in the range comprised between 50 and 5000 Nm 3 /m 3 of liquid feed, preferably between 100 and 3000 Nm 3 /m 3 , and even more preferably between 200 and 2000 Nm 3 /m 3 .
• the other pressure and WH parameters are in ranges identical to those described for the hydroconversion step (d).
• the porous supported hydroconversion catalyst used in the second hybrid bed reactor 260 can be the same as that used in the hybrid bed reactor 240, or can also be another porous supported catalyst also suitable for the hydroconversion of heavy hydrocarbon feedstocks. , as defined for the supported catalyst used in hydroconversion step (d).
• the optional separation step separating some or all of the upgraded material 107 to produce at least two fractions comprising the heavy liquid fraction 203 which boils predominantly at a temperature greater than or equal to 350°C, is carried out. works in a separation section 250.
• the other moiety(s) 202 are light and intermediate moiety(s).
• the light fraction thus separated mainly contains gases (H2, H2S, NH3, and C 1 -C 4 ), naphtha (fraction which boils at a temperature below 150°C), kerosene (fraction which boils between 150°C and 250°C), and at least a part of diesel (fraction which boils between 250°C and 375°C).
• the light fraction can then be sent at least partially to a fractionation unit (not represented in FIG. 2) where the light gases are extracted from said light fraction, for example by passing through a flash drum.
• the gaseous hydrogen thus recovered which may have been sent to a purification and compression installation, can advantageously be recycled in the hydroconversion stage (d).
• the recovered hydrogen gas can also be used in other refinery facilities.
• Separation section 250 includes any separation means known to those skilled in the art. It may comprise one or more flash drums arranged in series, and/or one or more vapor and/or hydrogen stripping columns, and/or an atmospheric distillation column, and/or a vacuum distillation column , and preferably consists of a single expansion tank, commonly referred to as a “hot separator”.
• the other moiety(s) 206 are light and intermediate moiety(s).
• the heavy liquid fraction 207 contains a fraction which boils at a temperature above 540°C, called the vacuum residue (which is the unconverted fraction). It may contain a part of the diesel fraction which boils between 250°C and 375°C and a fraction which boils between 375°C and 540°C, called vacuum distillate.
• Fractionation section 270 may include one or more flash drums arranged in series, and/or one or more vapor and/or hydrogen stripping columns, and/or an atmospheric distillation column, and/or a vacuum distillation, and preferably consists of a set of several flash drums in series and atmospheric and vacuum distillation columns.
• the present invention also relates to an ebullated-entrained bed system 200 configured to hydroconvert the heavy hydrocarbon feedstock 101 as detailed above.
• FIG. 2 schematically illustrates an example of a hybrid bed hydroconversion system according to the invention.
• Said system 200 comprises:
• the first conditioning mixer 210 configured to prepare a first conditioned heavy hydrocarbon charge 103 by mixing said heavy hydrocarbon charge 101 with an organic chemical compound 102 comprising at least one carboxylic acid function and/or at least one ester function and/or one anhydride function acid;
• a second conditioning mixer 220 configured to prepare a second conditioned heavy hydrocarbon feedstock 105 by mixing a catalyst precursor composition
• At least one preheating device 230 configured to heat the second conditioned load
• the at least one bubbling-entrained hybrid bed reactor 240 configured to include:
• an expanded catalyst bed comprising a solid phase which comprises a porous supported catalyst as a solid phase
• liquid hydrocarbon-based phase comprising said second heated conditioned heavy hydrocarbon-based charge 106 containing the colloidal or molecular catalyst dispersed therein;
• Said at least one bubbling-entrained hybrid bed reactor 240 is configured to operate in the presence of hydrogen and under hydroconversion conditions to cause thermal cracking of hydrocarbons in said second conditioned heavy hydrocarbon feedstock to provide upgraded material 107.
• Said at least one preheater 230 and/or said at least one bubbling-entrained hybrid bed reactor 240 are also configured to form the colloidal or molecular catalyst in said second conditioned heavy hydrocarbon feedstock.
• the following example illustrates, without limiting the scope of the invention, some of the performances of the method and of the system according to the invention, in particular the reduced fouling of the installations, in comparison with a method and a system according to the prior art.
• the example is based on a test using an analytical device, called the Alcor Hot Liquid Process Simulator, or HLPS, simulating the fouling effect of atmospheric residues (AR) in heat exchangers.
• the AR is pumped through a heater tube (laminar flow tube-in-shell heat exchanger) under controlled conditions and fouling deposits are formed on the heater tube.
• the temperature of the AR exiting the heat exchanger is related to the effect of deposits on the efficiency of the heat exchanger.
• the decrease in AR liquid outlet temperature from its initial maximum value is called Delta T and is correlated to the amount of deposits.
• the HLPS test can be used to evaluate the fouling tendency of different ARs by comparing the decreasing slope of the AR liquid outlet temperature obtained under identical test conditions.
• the effectiveness of an organic additive can also be determined by comparing the test results of a neat sample (without an organic additive) to the sample mixed with the organic additive. Three samples are tested: sample 1 is a mixture of a heavy hydrocarbon feedstock and a molecular or colloidal catalyst according to the prior art, and samples 2 and 3 are mixtures according to the invention of a hydrocarbon feedstock heavy with an organic additive, in addition to the same molecular or colloidal catalyst.
• the heavy hydrocarbon charge (“Charge”) is an atmospheric residue (AR) whose main composition and properties are given in Table 1 below.
• Sample 1 is a mixture of the Charge (AR) and a catalyst precursor composition (CPC) which is molybdenum 2-ethylhexanoate, the molybdenum 2-ethylhexanoate being diluted in a gas oil under vacuum (VGO) to form a CPC solution.
• CPC catalyst precursor composition
• VGO The composition of VGO is given in Table 1 above.
• the CPC solution is obtained by mixing molybdenum 2-ethylhexanoate with VGO, at a temperature of 70° C. for a period of time of 30 minutes.
• the molybdenum content in the CPC solution containing VGO is 3500 ppm by weight.
• the CPC solution is then mixed with the Filler (AR) at a temperature of 70°C and for a time period of 30 minutes.
• Sample 2 is a mixture of the Charge (AR) with the same solution of CPC (2-ethylhexanoate of molybdenum diluted with VGO) as in sample 1, and with an organic additive which is acid 2-Ethylhexanoic acid (2EHA).
• the CAS number for 2EHA is 149-57-5.
• the Charge is first mixed with the organic additive 2EHA, for a period of time of 30 min, and at a temperature of 70° C., to form a first conditioned charge.
• the first conditioned charge is mixed with the CPC solution, obtained as detailed for sample 1, at a temperature of 70°C and for a time period of 30 minutes, to form a second conditioned charge which is the sample 2.
• the Mo content in sample 2 is 315 ppmw (see Table 2 below).
• the concentration of the organic additive 2EHA is 5827 ppmw (see Table 2 below).
• Sample 3 is a mixture of Charge (AR) with the same solution of CPC (2-ethylhexanoate of molybdenum diluted with VGO) as in samples 1 and 2, and with an organic additive which is the ethyl octanoate (EO).
• the CAS number for EO is 106-32-1.
• the Charge is first mixed with the organic additive EO, for a time period of 30 min, and at a temperature of 70° C., to form a first conditioned charge.
• the first conditioned charge is mixed with the CPC solution, obtained as detailed for sample 1, at a temperature of 70°C and for a time period of 30 minutes, to form a second conditioned charge which is the sample 3.
• the Mo content in sample 3 is 315 ppmw (see Table 2 below).
• the concentration of the organic additive EO in sample 3 is equal to 7340 ppm by weight (see table 2 below).
• the HLPS test conditions are given in Table 3 below.
• Table 3 The results of the test for the different samples (Si for sample 1, S 2 for sample 2, S 3 for sample 3) are shown in the graph of Figure 3.
• the X axis represents the time in hours
• the Y axis represents the temperature difference DT between the temperature of the oil mixture (sample) exiting the tube at a time t [T Huiie s o ni e l t and the maximum temperature of the oil mixture (sample) oil
• sample 1 exiting the tube [THoil Outlet] Max * Dt — [THuile outletlt " [THoil Outlet] Max *
• Samples 2 and 3 which contain an organic additive, eg 2EHA or EO, according to the invention have a lower Delta T than sample 1, showing that the fouling behavior is significantly reduced under the action of said organic additive.

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