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
  • 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
  • C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
  • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
• • 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
  • C10G45/04—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 characterised by the catalyst used
  • C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • 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
  • C10G45/16—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 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
  • C10G45/18—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 "moving-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
  • 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
  • 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
  • C10G47/28—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "moving-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
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
• • 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
• • 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
  • C10G2300/1011—Biomass
• • 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 the field of the hydroconversion of feedstocks comprising a fraction of vegetable and/or animal oil, in particular used as a cooking oil, and a heavy fraction of hydrocarbons, in particular a heavy fraction of hydrocarbons containing a of at least 50% by weight, preferably at least 80% by weight, having a boiling point of at least 300°C.
• the heavy hydrocarbon fraction can be a crude oil or be obtained from the distillation and/or the refining of a crude oil, typically a topped crude oil, a residue from the atmospheric and/or vacuum distillation of a crude oil .
• the heavy hydrocarbon fraction is of the vacuum residue type composed of at least 50% by weight, preferably at least 80% by weight of hydrocarbons having a boiling point of at least 450°C. .
• the present invention relates to a process for the hydroconversion of such a mixed feed, comprising at least one hydroconversion step implementing one or more reactors operating in a bubbling bed or in an entrained bubbling hybrid bed, and preferably two steps successive hydroconversion, with a view to producing materials of higher quality, with a lower boiling point, for example for the purposes of producing fuels, or chemical products, while allowing the recovery of used vegetable oil or animal.
• the hydrotreatment and/or hydroconversion of vegetable or animal oils leads to the production of fuel bases of excellent quality, in particular in terms of smoke point of kerosene cuts and cetane number of gas oil cuts.
• the hydrocarbons produced during the conversion are obtained mainly by decarboxylation and/or decarbonylation of the monoglycerides, diglycerides and triglycerides contained in the used vegetable oils and animal fats which are then converted into paraffins.
• patent US20060186020 is known relating to a process for the fixed-bed hydrotreatment of a mixed feed composed of between 1 and 75% by weight of vegetable oil and the balance of hydrocarbon of fossil origin. Hydrotreating vegetable oil generates heat important due to rapid deoxygenation reactions. This exotherm is particularly difficult to control in a fixed bed and can be the cause of clogging at the inlet of the catalytic bed due to the formation of unwanted compounds such as gums.
• the operating conditions of temperature (320°C-400°C) and hourly space velocity WH (0.5-2h -1 ) disclosed in patent US20060186020 do not allow thermal cracking of the hydrocarbon to be envisaged. fossil in parallel with the conversion of vegetable oil.
• Patent WO2008151792 is also known in which is described an ebullated bed hydroconversion process comprising a supported catalyst and a nano-dispersed catalyst capable of treating heavy hydrocarbon feedstocks and in particular vegetable oils.
• This patent does not mention the possibility of carrying out co-treatment of vegetable oil or animal fat with a hydrocarbon feedstock of the fossil type.
• the injection of a vegetable oil feedstock or a pure animal fat in such a process is likely to lead to a conversion of the feedstock entirely, or in large part, into products which will be in gas form under the operating conditions of the process.
• a small quantity of liquid, or even an absence of liquid is operationally impossible for the operation of an ebullated bed reactor.
• a small amount of liquid, or even no liquid is also a problem in controlling the exotherm generated by the conversion of vegetable oil.
• the present invention relates to the field of the recovery of heavy loads that are difficult to recover such as petroleum residues, which generally contain high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon and asphaltenes, in order to convert them into lighter products that can be used as fuels, for example to produce gasoline or diesel, or raw materials for the petrochemical industry.
• heavy loads that are difficult to recover such as petroleum residues, which generally contain high levels of impurities such as metals, sulfur, nitrogen, Conradson carbon and asphaltenes, in order to convert them into lighter products that can be used as fuels, for example to produce gasoline or diesel, or raw materials for the petrochemical industry.
• the inventors have demonstrated that, surprisingly, it was possible to incorporate a fraction of vegetable and/or animal oil, in particular used oil, into a heavy hydrocarbon charge, typically a vacuum residue, traditionally treated in a process hydroconversion in bubbling bed or entrained bubbling hybrid, and thus increase the overall conversion of the feed, improve the yields of the fuels of interest, while maintaining good operation of the process and good stability of the unconverted fraction.
• a fraction of vegetable and/or animal oil, in particular used oil into a heavy hydrocarbon charge, typically a vacuum residue, traditionally treated in a process hydroconversion in bubbling bed or entrained bubbling hybrid, and thus increase the overall conversion of the feed, improve the yields of the fuels of interest, while maintaining good operation of the process and good stability of the unconverted fraction.
• the present invention thus proposes a process for the hydroconversion of a heavy charge of hydrocarbons, in particular of the vacuum residue type, in a bubbling bed or entrained bubbling hybrid, said charge including a fraction of vegetable and/or animal oil, in particular used cooking oil, thus allowing the production of base fuels and other recoverable hydrocarbons, and therefore the recovery of said fraction.
• the present invention proposes, according to a first aspect, a process for the hydroconversion of a feed comprising a vegetable and/or animal oil fraction and a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the sum of the fraction of vegetable and/or animal oil and of the heavy fraction of hydrocarbons forming 100% by weight of said charge, the process comprising the following successive steps:
• step (c) optionally a step of separating part or all of said first effluent resulting from step (b), to form at least one heavy cut boiling mainly at a temperature greater than or equal to 350° C.;
• step (d) optionally a second hydroconversion step in a second hydroconversion section comprising at least one second bubbling bed or bubbling-entrained hybrid bed hydroconversion reactor of part or all of said first effluent resulting from the step (b) or optionally of said heavy cut from step (c), said second hydroconversion reactor comprising a second supported porous catalyst and operating in the presence of hydrogen, to produce a second hydroconverted effluent; step (b) and optional step (d) being carried out at an absolute pressure between 2 MPa and 38 MPa, at a temperature between 405°C and 550°C, at an hourly space velocity relative to the volume of each hydroconversion reactor comprised between 0.05 h 1 and 10 h 1 , and with a quantity of hydrogen comprised between 50 Nm 3 /m 3 and 5000 Nm 3 /m 3 ,
• step (e) a step of fractionating all or part of said first hydroconverted effluent from step (b) or said second hydroconverted effluent from step (d), in a fractionation section, to produce at least one liquid product which mainly boils at a temperature greater than or equal to 350°C, said heavy liquid product containing a residual fraction which boils at a temperature greater than or equal to 540°C.
• step (a) the vegetable and/or animal oil fraction and the heavy hydrocarbon fraction of the feed are mixed beforehand before their introduction into said at least a first hydroconversion reactor of the first hydroconversion section.
• step (a) the vegetable and/or animal oil fraction and the heavy hydrocarbon fraction of the feed are introduced separately into said at least one first reactor hydroconversion of the first hydroconversion section.
• step (a) comprises a step of preheating the heavy hydrocarbon fraction, preferably to a temperature between 280° C. and 450° C., and optionally a step for preheating the vegetable and/or animal oil fraction, preferably at a temperature comprised between ambient temperature and 350°C, before the feed is introduced into the first hydroconversion reactor of the first hydroconversion section .
• the filler comprises between 1% and 50% by weight of the vegetable and/or animal oil fraction and between 50% and 99% by weight of the heavy hydrocarbon fraction. .
• the filler comprises between 5% and 30% by weight, preferably between 5% and 20% by weight, of the vegetable and/or animal oil fraction, and between 70 % and 95% by weight, preferably between 80% and 95% by weight, of the heavy hydrocarbon fraction.
• the vegetable and/or animal oil fraction of the feed is a vegetable oil, preferably chosen from the list consisting of rapeseed, soybean, sunflower, palm, palm kernel, olive, copra, castor, cotton, peanuts, flax, crambe, Purghère, or a mixture thereof.
• the heavy fraction of hydrocarbons of the feed is chosen from the list consisting of a crude oil, a topped crude oil, an atmospheric residue or a vacuum residue resulting from the distillation atmospheric and/or vacuum of a crude oil or an effluent from a thermal conversion, hydrotreating, hydrocracking or hydroconversion unit, an aromatic fraction extracted from a lubricant production unit, a deasphalted oil from a deasphalting unit, an asphalt from a deasphalting unit, a residual fraction from the direct liquefaction of coal, a vacuum distillate from the direct liquefaction of coal, or a mixture thereof.
• the feed consists of a vegetable oil fraction and a heavy hydrocarbon fraction consisting of a vacuum residue, preferably a vacuum residue from the primary fractionation of a crude oil.
• the fraction of vegetable and/or animal oil is a used oil, preferably a used cooking oil.
• the method comprises the separation step (c) separating part, or all, of the first hydroconverted effluent from step (b) to produce at least the heavy cut boiling predominantly at a temperature greater than or equal to 350° C., and comprising the second stage of hydroconversion (d) of said heavy cut.
• an additional vegetable and/or animal oil fraction is introduced into said at least second bubbling-bed or bubbling-entrained hybrid-bed hydroconversion reactor.
• the hydroconversion reactor(s) of first hydroconversion section in step (b), and optionally in hydroconversion step (d), are reactors with bubbling-entrained hybrid bed, said method further comprising a step of introducing a catalyst precursor into the charge, preferably molybdenum 2-ethylhexanoate, before injecting said charge into said at least one first bubbling-entrained hybrid bed reactor of the first hydroconversion section such that a colloidal or molecular catalyst, preferably comprising molybdenum disulfide, is formed when said feed reacts with sulfur.
• the first hydroconversion catalyst, and optionally the second hydroconversion catalyst contains at least one non-noble group VIII metal chosen from nickel and cobalt, preferably nickel, and at least one metal from group VIB chosen from molybdenum and tungsten, preferably molybdenum, and comprising an amorphous support, preferably alumina.
• FIG. 1 schematically illustrates an embodiment of the hydroconversion process according to the invention.
• FIG. 2 schematically illustrates another embodiment of the hydroconversion process according to the invention.
• the different ranges of given parameter values can be used alone or in combination.
• a preferred range of pressure values may be combined with a more preferred range of temperature values, or a preferred range of values for one compound or chemical element may be combined with a more preferred range of values for another chemical compound or element.
• hydroconversion refers to a process whose main purpose is to reduce the boiling point range of a feed comprising at least 50% of a heavy fraction of hydrocarbons having a boiling point of at least minus 300°C, or even at least 450°C, and wherein a substantial portion of the feed is converted to products with lower boiling point ranges than the original feed.
• 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.
• other reactions typically associated with hydrotreating may occur, such as, among others, the removal of sulfur or nitrogen from the feed, or the saturation of olefins, and as defined more broadly below.
• hydrotreating commonly referred to as “HDT” refers to a milder operation whose primary purpose is to remove impurities such as sulfur, nitrogen, oxygen, halides, and trace metals from 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 notably includes hydrodesulphurization reactions (commonly called “HDS”), hydrodenitrogenation reactions (commonly called “HDN”) and hydrodemetallization reactions (commonly called “HDM”), accompanied by hydrogenation reactions, hydrodeoxygenation (commonly called “HDO”), hydrodearomatization, hydroisomerization, hydrodealkylation, hydrocracking, hydrodeasphalting and Conradson carbon reduction.
• Hydrotreating is most often carried out using a fixed bed reactor, although other reactors can also be used for hydrotreating, for example an ebullated bed hydrotreating reactor.
• 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 at least one inlet through which feed and hydrogen can be introduced and one 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 through thermal decomposition.
• hydroconversion reactors include, but are not limited to, entrained bed reactors, also called "slurry" reactors according to English terminology (three-phase reactors - liquid, gas, solid - in which the solid phases and liquid can behave as a 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 reactors (three-phase reactors with downward trickling of liquid feed over a fixed bed of supported catalyst with hydrogen typically flowing simultaneously with the liquid, but possibly countercurrently in some cases) .
• entrained bed reactors also called "slurry" reactors according to English terminology (three-phase reactors - liquid, gas, solid - in which the solid phases and liquid can behave as a 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
• hybrid bed and “hybrid bubbling bed” and “bubbling-entrained 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 referred to as the "slurry catalyst” - being carried 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, e.g. 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 feed, non-volatile liquid fraction, background, residue, or other feed or product in which the catalyst may be present. 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 numerous interconnected channels or pores and (ii) fine particles of an active catalyst such as sulphides of cobalt, nickel, tungsten, molybdenum , or mixed sulphides of these elements (eg NiMo, CoMo, etc.), dispersed in the pores.
• Supported catalysts are commonly produced as cylindrical extrudates ("pellets") or spherical solids, although other shapes are possible.
• the object of the invention is to propose a process for the hydroconversion of a feed consisting of a vegetable and/or animal oil fraction 102 and a heavy hydrocarbon fraction 101 containing a portion of at least 50% by weight having a boiling point of at least 300°C, and containing sulfur and nitrogen, the process comprising the following successive steps: (a) conditioning and introducing said feed into a first hydroconversion section
• step (c) optionally a step of separating part or all of said first effluent resulting from step (b), to form at least one heavy cut boiling mainly at a temperature greater than or equal to 350° C.;
• step (d) optionally a second hydroconversion step in a second hydroconversion section comprising at least one second bubbling bed or bubbling-entrained hybrid bed hydroconversion reactor of part or all of said first effluent resulting from the step (b) or optionally of said heavy cut from step (c), said second hydroconversion reactor comprising a second supported porous catalyst and operating in the presence of hydrogen, to produce a second hydroconverted effluent; step (b) and optional step (d) being carried out at an absolute pressure between 2 MPa and 38 MPa, at a temperature between 405°C and 550°C, at an hourly space velocity relative to the volume of each hydroconversion reactor comprised between 0.05 h 1 and 10 h 1 , and with a quantity of hydrogen comprised between 50 Nm 3 /m 3 and 5000 Nm 3 /m 3 ,
• step (e) a step of fractionating all or part of said first hydroconverted effluent from step (b) or said second hydroconverted effluent from step (d), in a fractionation section 30, to produce at least one product heavy liquid 106b which mainly boils at a temperature greater than or equal to 350°C, said heavy liquid product containing a residual fraction which boils at a temperature greater than or equal to 540°C.
• the feed comprises a vegetable and/or animal oil fraction and a heavy hydrocarbon fraction.
• the sum of the vegetable and/or animal oil fraction and the heavy hydrocarbon fraction is equal to 100% by weight of the feed sent to the first hydroconversion stage.
• the feed consists of a vegetable and/or animal oil fraction and a heavy hydrocarbon fraction.
• the process according to the invention is thus specific to the hydroconversion of a mixture of a vegetable and/or animal oil and a heavy fraction of hydrocarbons of fossil origin.
• the feed does not include other fractions, such as biomass such as algae, lignocellulosic biomass, or one or more constituents of lignocellulosic biomass chosen from the group formed by cellulose, hemicellulose and lignin.
• biomass such as algae, lignocellulosic biomass, or one or more constituents of lignocellulosic biomass chosen from the group formed by cellulose, hemicellulose and lignin.
• these other fillers generally require the implementation of specific steps for their treatment, which are not the subject of the present invention.
• the vegetable and/or animal oil fraction constitutes between 1% and 50% by weight of the filler (total weight of the filler), preferably between 5% and 30% by weight of the filler, and more preferably between 5 % and 20% load weight.
• the heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300°C, preferably at least 450°C, and containing sulfur, Conradson carbon, metals, nitrogen, and asphaltenes, constitutes between 50% and 99% by weight of the charge, preferably between 70% and 95% by weight of the charge, and more preferably between 80% and 95% by weight of the charge .
• the vegetable and/or animal oil fraction of the feedstock of the process according to the invention comprises one or more vegetable oils, or one or more animal fats, or mixtures of such feedstocks in all proportions. Mention may be made, for example, of rapeseed, soybean, sunflower, palm, palm kernel, olive, copra, castor, cotton, peanut, flax, crambe, Purgh Guatemala (jatropha ). This non-exhaustive list also includes all oils obtained by genetic modification or hybridization. Waste oils, such as frying oils, as well as all waste oils and fats from the catering industries, can also be used. As regards animal fats, mention may be made, without being limiting, of fish oils, tallow, lard.
• animal fat and “animal oil” are used interchangeably in the present description, the only difference between a fat and an oil relating to the state of the fatty substance at room temperature: liquid for an oil and solid for a fat.
• These vegetable and/or animal oils can be crude or refined, totally or in part.
• the distinction between a crude or refined vegetable oil refers to its mode of extraction, mainly under pressure for a crude oil (typically a single cold pressing without additives) and generally using a solvent for an oil refined.
• the vegetable and/or animal oil fraction thus defined contains monoglycerides, diglycerides, triglycerides and/or fatty acid structures, the fatty chains of which have a carbon number generally between 8 and 25 (ie the number of carbon atoms of fatty acid).
• the vegetable and/or animal oil fraction thus mainly consists of these monoglyceride, diglyceride, triglyceride and/or fatty acid compounds. Essentially constituted by means that it comprises at least 80% by weight of said compounds, or even at least 85% by weight, 90% by weight, or even 95% by weight of said compounds.
• These vegetable and/or animal oils may contain phospholipids up to 5% by weight, free fatty acids up to 5% by weight (fatty acids not linked to a glycerol), unsaponifiables up to 5% by weight such as sterols, triterpene alcohols, vitamins up to 1% by weight such as tocopherols, colored compounds up to 100 ppm such as carotenoids, various metals and minerals up to 200 ppm, sulfur compounds up to at contents of the order of 2000 ppm, and nitrogen compounds up to contents of 2% by weight.
• used vegetable or animal (edible) oils may also contain triglyceride polymers, for example at levels of a few % by weight, e.g. 5% by weight, which are precursors to the formation of gums.
• These vegetable and/or animal oils have low aromatic contents, generally less than 5% by weight.
• the density at 15°C of these vegetable and/or animal oils is generally between 850 kg/m 3 and 970 kg/m 3 , and their kinematic viscosity at 40°C is typically between 20 mm 2 /s and 400 mm 2 /s, more generally between 30 mm 2 /s and 50 mm 2 /s.
• the heavy hydrocarbon fraction of the feedstock of the process according to the invention is a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 300° C., preferably of at least 350°C, and even more preferably at least 375°C.
• This heavy hydrocarbon fraction of the feed may be a crude oil, or come from the refining of a crude oil or from the treatment of another fossil hydrocarbon source in a refinery.
• the heavy hydrocarbon fraction of the feed is a crude oil, a topped crude oil or consists of atmospheric residues and/or vacuum residues resulting from the atmospheric and/or vacuum distillation of a crude oil .
• the heavy hydrocarbon fraction of the feed may also consist of atmospheric and/or vacuum residues from the atmospheric and/or vacuum distillation of effluents from thermal conversion, hydrotreatment, hydrocracking and/or hydroconversion.
• the heavy hydrocarbon fraction of the feed is a heavy hydrocarbon fraction containing a portion of at least 50% by weight having a boiling point of at least 450° C., preferably of at least 500°C, and even more preferably at least 540°C.
• the heavy hydrocarbon fraction of the feed consists of one or more vacuum residues.
• Vacuum tailings can come directly from crude oil, or from other refining units, such as tailings hydrotreating, tailings hydrocracking, and tailings visbreaking, among others.
• the vacuum residues are vacuum residues from the vacuum distillation column of the primary fractionation of crude oil (called "straight run", or "SR" for short, according to the English terminology). Saxon).
• the heavy hydrocarbon fraction of the charge can also consist of aromatic cuts extracted from a lubricant production unit, deasphalted oils from a deasphalting unit also called DAO (raffinates from the deasphalting unit), asphalt from a deasphalting unit (residues from the deasphalting unit).
• DAO deasphalted oils from a deasphalting unit also called DAO (raffinates from the deasphalting unit)
• asphalt from a deasphalting unit refsidues from the deasphalting unit
• the heavy hydrocarbon fraction of the feed can also consist of a settling oil or a recycle oil (which typically has a boiling range of 360°C to 550°C), for example a catalytic cracking effluent in FCC fluidized bed as a heavy recycling oil (HCO for Heavy cycle Oil in English) or an oil in the form of mud called “slurry” (SLO for Slurry Oil in English).
• a settling oil or a recycle oil which typically has a boiling range of 360°C to 550°C
• HCO Heavy cycle Oil in English
• SLO oil in the form of mud
• the heavy fraction of hydrocarbons of the feed can also be a residual fraction resulting from the direct liquefaction of coal (an atmospheric residue and/or a vacuum residue resulting for example from the H-Coal® process), a vacuum distillate from the direct liquefaction of coal, such as the H-Coal® process.
• the heavy hydrocarbon fraction comprises, and may consist of, at least one of the following feedstocks, alone or as a mixture: a crude oil, a topped crude oil, an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation of a crude oil (preferably from the primary fractionation of crude oil), an atmospheric residue or a vacuum residue from the atmospheric or vacuum distillation obtained during from a direct coal liquefaction process, and preferably is a vacuum residue from the vacuum distillation of a crude oil (preferably from the primary fractionation of crude oil).
• the heavy hydrocarbon fraction of the feed treated according to the invention contains impurities, such as sulfur and nitrogen. It may also contain impurities such as metals, Conradson's carbon and asphaltenes, in particular C 7 asphaltenes which are insoluble in heptane.
• the metal contents can be greater than or equal to 20 ppm by weight, preferably greater than or equal to 100 ppm by weight.
• the sulfur content may be greater than or equal to 0.1% by weight, or even greater than or equal to 0.5% or 1%, and may be greater than or equal to 2% by weight.
• the nitrogen content is usually between 1 ppm and 8000 ppm by weight, more generally between 200 ppm and 8000 ppm by weight, for example between 2000 ppm and 8000 ppm by weight.
• the rate of asphaltenes C 7 (compounds insoluble in heptane according to the ASTM D 6560 standard, also corresponding to the NF T60-115 standard) can amount to at least 1% by weight and is often greater than or equal to 3 % by weight (with the exception of a heavy fraction of hydrocarbons comprising essentially a DAO).
• C 7 asphaltenes are compounds known to inhibit the conversion of residual cuts, both by their ability to form heavy hydrocarbon residues, commonly called coke, and by their tendency to produce sediments which severely limit the operability of the units. hydrotreating and hydroconversion.
• the Conradson carbon content may be greater than or equal to 3% by weight, or even at least 5% by weight.
• the Conradson carbon content is defined by the ASTM D 482 standard and represents, for those skilled in the art, a well-known evaluation of the quantity of carbon residues produced after pyrolysis under standard temperature and pressure conditions.
• the process according to the invention comprises a step (a) of conditioning and introducing the charge into a first hydroconversion section 20 comprising at least a first reactor in an ebullated bed or in a hybrid bed comprising a first porous supported catalyst of hydro conversion.
• Step a) does not include transformation of the filler, in particular of the vegetable and/or animal oil fraction, aimed at significantly changing its composition, in particular the distribution of the molecular weight of said fraction, for example by a hydroforming in the presence of hydrogen and a catalyst, under pressure.
• the vegetable and/or animal oil fraction 102 can be mixed beforehand with the heavy hydrocarbon fraction 101 of the feed before entering the first reactor. hydroconversion to the first hydroconversion step (b).
• the two fractions can be heated beforehand to ensure that they are in the liquid state before being mixed, by means of any heating device known to those skilled in the art.
• only the heavy hydrocarbon fraction 101 can be heated, in particular if the vegetable and/or animal oil fraction is liquid and pumpable at ambient temperature.
• This mixing can be carried out in a dedicated capacity 10 as represented in FIG. 1, the mixing being able to be active (eg a pump with a propeller or a turbine rotor) or not, or directly by the connection of the two conduits transporting the products.
• the homogeneity of the mixture can be ensured by installing an in-line static mixer, a technology well known to those skilled in the art.
• a more homogeneous charge 114 is introduced into the first hydroconversion reactor, which is for example favorable to good fluidization of the catalyst, and to good hydrodynamic operation of the reactor in general. It can also allow the use of common equipment, such as furnaces, feed distributors, hydrogen mixers with the feed, for example of the T-shaped type (“T-mixer”), which can help reduce investment costs.
• Another possibility, represented in FIG. 2, is the separate injection of the vegetable and/or animal oil fraction 102 and the heavy hydrocarbon fraction 101 into the first hydroconversion reactor at the first hydroconversion stage. (b).
• This mode of injection may be preferred to avoid any problem which would be linked to chemical incompatibility between the two fractions (risk of demixing or precipitation of asphaltenes for example), or to avoid possible accelerated clogging of the preheating furnace ( high levels of triglyceride polymers in used vegetable or animal oil may lead to the formation of gum).
• the feedstock, and in particular the heavy hydrocarbon fraction 101 of the feedstock is heated to a temperature suitable for the hydroconversion in the first hydroconversion reactor, that is to say so as to advantageously reach a target temperature in the first hydroconversion reactor.
• a preheating step in the present description The preheating of the heavy hydrocarbon fraction is preferably carried out at a temperature between 280° C. and 450° C., even more preferably between 300° C. and 400° C., and even more preferably between 320° C. and 365° C. vs.
• This preheating can also include the heating of the vegetable and/or animal oil fraction 102, in particular if said fraction is injected separately from the fraction 101 into the first hydroconversion reactor, however preferably at a lower temperature than for the heavy hydrocarbon fraction 101.
• the vegetable and/or animal oil fraction 102 can be heated to a temperature between room temperature, eg 15°C, and 350°C, preferably between 100°C and 350°C, more preferably between 100°C and 250°C, and even more preferably between 150 °C and 250°C.
• said vegetable and/or animal oil fraction can be preheated by simple contact with the heavy hydrocarbon fraction. 101, or alternatively the vegetable and/or animal oil fraction can be heated before it is mixed with the fraction 101 by any suitable heating means known to those skilled in the art.
• preheating furnace comprising for example at least one heating compartment, and / or tubes in which the charge flows, a mixer of the charge with H2, any type of suitable heat exchangers, for example tubular or spiral heat exchangers in which the charge flows, etc.
• the feed Before its introduction into the first hydroconversion reactor, the feed undergoes a pressurization step to be adapted to the pressure operated in the first hydroconversion reactor, for example using a suitable pump.
• This pressurizing step is preferably carried out before the preheating step.
• the fraction of vegetable oil and/or animal fat can undergo a filtration step, before its mixing with the heavy hydrocarbon fraction 101 or its introduction separately from the heavy hydrocarbon fraction 101 into the first hydroconversion reactor, to eliminate impurities which may be naturally present in vegetable oils and animal fats, in particular to eliminate solid particles.
• the charge Prior to its introduction into the first hydroconversion reactor, the charge may be mixed with an entrained catalyst precursor 104, for example the heavy hydrocarbon fraction 101 may be mixed with an entrained catalyst precursor 104, as represented in FIGS. and 2, so that during the formation of an entrained catalyst, in particular by reaction with sulphur, the entrained catalyst will comprise a colloidal or molecular catalyst dispersed in the charge.
• an entrained catalyst precursor 104 for example the heavy hydrocarbon fraction 101 may be mixed with an entrained catalyst precursor 104, as represented in FIGS. and 2, so that during the formation of an entrained catalyst, in particular by reaction with sulphur, the entrained catalyst will comprise a colloidal or molecular catalyst dispersed in the charge.
• the entrained catalyst precursor 104 can also be mixed with the vegetable and/or animal oil fraction 102 before mixing the latter with the heavy hydrocarbon fraction 101 (not shown in FIG. 1), or even be mixed with the charge 114 formed by the mixture of said fractions 101 and 102 (not represented in FIG. 2), in the same way as described below for a mixture between the heavy hydrocarbon fraction 101 and the entrained catalyst precursor 104, at except for the temperature of mixing with the vegetable and/or animal oil fraction 102 which is preferably less than or equal to 250° C. (and in any case preferably at a temperature below a temperature at which a substantial portion of the catalyst precursor begins to decompose).
• the catalyst precursor is not part of the feed as defined above which comprises exclusively the vegetable and/or animal oil fraction and the heavy fraction of hydrocarbons.
• the entrained catalyst precursor may be selected from any metal catalyst precursor known to those skilled in the art capable of forming a colloidally or molecularly dispersed catalyst (i.e. the entrained catalyst) by the presence of hydrogen and/or H 2 S and/or any other source of sulfur, and allowing the hydroconversion of the feed after its injection into the first hydroconversion reactor.
• the catalyst precursor is advantageously an oil-soluble catalyst precursor, containing at least one transition metal.
• the catalyst precursor preferably comprises an oil-soluble organometallic compound or complex.
• the catalyst precursor 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 preferably has a decomposition temperature (temperature below which the catalyst precursor is substantially chemically stable) in a range of 100°C to 350°C, more preferably in a range of 150°C. 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 selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and pentacarbonyl iron. These compounds are non-limiting examples of oil-soluble catalyst precursors.
• the catalyst precursor comprises Mo 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 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 fraction at a temperature below 250°C.
• One skilled in the art can choose a mixing temperature profile that results in the mixing of the chosen precursor, without substantial thermal decomposition prior to the formation of the colloidal or molecular catalyst.
• Catalyst precursor 104 preferably an oil-soluble catalyst precursor
• Catalyst precursor 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.
• Catalyst precursor 104 may be premixed with a diluent to form a dilute precursor mixture, said premix preferably being carried out at a temperature below a temperature at which a substantial portion of the catalyst precursor begins to decompose, preferably between the ambient temperature, e.g. 15°C, and 300°C, more preferably between 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, and advantageously for a time period of 1 second to 30 minutes.
• the ambient temperature e.g. 15°C, and 300°C, more preferably between 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, and advantageously for a time period of 1 second to 30 minutes.
• the catalyst precursor diluent may be a hydrocarbon oil composed of hydrocarbons of which at least 50% by weight, relative to the total weight of the hydrocarbon oil, have a boiling point of between 180° C. and 540° C. vs.
• hydrocarbon diluents suitable for diluting the precursor include, but are not limited to, a vacuum gas oil known as "VGO" (for Vacuum Gas Oil according to the English terminology, and which typically has a range of boiling from 360°C to 524°C), a decant oil or a recycle oil (which typically has a boiling range of 360°C to 550°C), for example a fluidized bed catalytic cracking effluent FCC such as Heavy Cycle Oil (HCO) or Light Cycle Oil (LCO), pyrolysis oil from a hydrocracker, light diesel (which typically has a boiling range of 200°C to 360°C), atmospheric residues, vacuum residues (which typically have a boiling range of greater than or equal to 524°C), deas
• the diluted precursor can be mixed with the heavy hydrocarbon fraction 101, 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, preferably 1 second to 10 minutes, and even more preferably within a range of 2 seconds to 3 minutes.
• a mixing time (or dwell time for mixing) of 1 second includes instant mixing.
• the weight ratio of catalyst precursor 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 further more preferably in a range of about 1:100 to about 1:5 (e.g. 1:100, 1:50, 1:30, or 1:10).
• Premixing the catalyst precursor 104 with a hydrocarbon diluent greatly facilitates complete and intimate mixing of the precursor into the heavy hydrocarbon fraction, particularly in the relatively short period of time required for large-scale industrial operations to be economically viable. .
• the dilute precursor is preferably combined with the hydrocarbon heavy fraction and mixed for sufficient time and in a manner to disperse the catalyst precursor throughout the heavy fraction so that the catalyst precursor is completely/intimately mixed with the heavy hydrocarbon fraction.
• hydrocarbons In order to obtain sufficient mixing before formation of the colloidal or molecular catalyst, the dilute precursor and the heavy fraction are more preferably mixed 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. 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 104 and hydrocarbon heavyweight 101 include, but are not limited to, high shear mixing such as in a pump with a turbine impeller or impeller, 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, high shear, multiple static in-line mixers in combination with high shear in-line mixers followed by recirculation pumping into the buffer tank, combinations of the above followed by one or more multi-stage centrifugal pumps.
• high shear mixing such as in a pump with a turbine impeller or impeller
• multiple static in-line mixers such as in a pump with a turbine impeller or impeller
• multiple static in-line mixers such as in a pump with a turbine impeller or impeller
• multiple static in-line mixers such as in a pump with a turbine impeller or impeller
• the heavy hydrocarbon fraction 101 and the dilute precursor are preferably mixed and conditioned at a temperature in a range of 50°C to 200°C, more preferably in a range from 75°C to 175°C.
• the gauge pressure is between 0 MPa and 25 MPa, more preferably between 0.01 MPa and 5 MPa.
• the step of preheating the heavy hydrocarbon fraction, before the feed is introduced into the first hydroconversion reactor, as detailed above, advantageously causes a release of the sulfur contained in the heavy hydrocarbon fraction which can combine with the catalyst precursor metal.
• the colloidal or molecular catalyst can form, or at least begin to form, in situ in the heavy hydrocarbon fraction during this preheating step.
• sulfur In order to form the colloidal or molecular catalyst, sulfur must be available (e.g. as PS) to combine with the metal of the dispersed catalyst precursor composition.
• the entrained catalyst can also form in the hydroconversion step (b).
• the final activated catalyst can be formed in situ by heating said heavy fraction to a temperature sufficient to release the sulfur therefrom.
• a source of sulfur can thus be P S dissolved in the heavy hydrocarbon fraction, or HÎS contained in the hydrogen recycled to the hydroconversion reactor, or P S originating from organic sulfur molecules present in the hydroconversion reactor.
• the heavy fraction of hydrocarbons or optionally introduced beforehand into said heavy fraction e.g. injection of dimethyl disulphide, thioacetamide, any hydrocarbon feedstock containing sulfur of the mercaptan type, sulphides, petroleum containing sulphur, diesel containing sulfur, sulfur-containing vacuum distillate, sulfur-containing residue).
• a source of sulfur can be sulfur compounds in the heavy hydrocarbon fraction or a sulfur compound added to said heavy fraction.
• step (b) The temperature during the preheating of the heavy hydrocarbon fraction and/or the temperature in step (b) allows the formation of the catalyst of metal sulphide type.
• the metal concentration of the catalyst, preferably in Mo, in the charge is preferably between 5 ppm and 500 ppm by weight of the charge, more preferably between 10 ppm and 300 ppm by weight, more preferably between 10 ppm and 175 ppm by weight, even more preferably between 10 ppm and 75 ppm by weight, and even more preferably between 10 ppm and 50 ppm by weight.
• the colloidal or molecular catalyst comprises molybdenum disulfide.
• the charge is introduced, whether the fractions which compose it are separated (101 and 102) or mixed (114) according to step (a), into the first hydroconversion reactor of the first section hydroconversion 20, together with hydrogen (flow not shown).
• Said first reactor comprises a porous supported first hydroconversion catalyst.
• the first hydroconversion step (b) is carried out under conditions making it possible to obtain a first hydroconverted effluent 105.
• Said first hydroconverted effluent 105 contains the conversion products, in particular said first effluent has a reduced content of hydrocarbons having a point of boiling point of at least 300° C., or at least 350° C., 375° C., 450° C., 500° C., or even 540° C. depending on the nature of the charge.
• Said first hydroconverted effluent 105 may also have a reduced content of sulfur, and/or metals, and/or nitrogen, and/or Conradson carbon, and/or asphaltenes, depending on the reactions implemented in the first reactor of hydroconversion and feedstock composition.
• Step (b) is preferably carried out under an absolute pressure of between 2 MPa and 38 MPa, more preferably between 5 MPa and 25 MPa, and even more preferably, between 6 MPa and 20 MPa, at a temperature between 405°C and 550°C, more preferably between 405°C and 500°C, more preferably between 405°C and 450°C, and even more preferably between 410°C and 435°C .
• the hourly space velocity (WH) relative to the volume of each reactor is preferably between 0.05 h 1 and 10 h 1 .
• the WH is between 0.1 h 1 and 10 h 1 , more preferably between 0.1 h 1 and 5 h 1 , even more preferably between 0.15 h 1 and 2 h 1 , and even more preferably between 0.15 h 1 and 1 h 1 .
• the WH is between 0.05 h 1 and 0.49 h 1 , preferably between 0.1 h 1 and 0.49 h 1 .
• the overall WH that is to say the liquid feed rate sent to step b) relative to the volume of all the reactors if several hydroconversion reactors are put into implemented in step b), is between 0.05 h 1 and 0.09 h 1 .
• the quantity of hydrogen mixed with the charge is preferably between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of liquid charge, preferably between 100 Nm 3 /m 3 and 2000 Nm 3 / m 3 and very preferably between 200 Nm 3 /m 3 and 1000 Nm 3 /m 3 .
• the first hydroconversion section 20 comprises one or more bubbling or hybrid bed reactors, containing at least one first supported hydroconversion catalyst, the reactors possibly being arranged in series and/or in parallel. At this stage, at least one first supported hydroconversion catalyst is therefore maintained in the reactor or reactors.
• the first hydroconversion section 20 comprises one or more hydroconversion reactors, which can be in series and/or in parallel, operating in an ebullated bed, as used for the H -Oil®, as described, for example, in patents US4521295 or US4495060 or US4457831 or US4354852, in the article Aiche, March 19-23, 1995, Houston, Texas, article number 46d, "Second generation ebullated bed technology", or in chapter 3.5 "Hydroprocessing and Hydroconversion of Residue Fractions" of the book “Catalysis by Transition Metal Sulphides", Technip Publishing, 2013.
• each reactor is operated in a fluidized bed known as an ebullating bed.
• Each reactor advantageously comprises a recirculation pump which makes it possible to maintain the porous supported solid catalyst in a bubbling bed by continuous recycling of at least part of a liquid fraction withdrawn at the level of the upper part of the reactor and reinjected at the level of the lower part of the reactor.
• the ebullated bed reactor preferably comprises at least one inlet located at or near the lower part of the reactor through which the charge is introduced together with the hydrogen, and in particular two inlets in the case where the vegetable and/or animal oil fraction of the feed is introduced separately from the heavy hydrocarbon fraction, and an outlet port at or near the top of the reactor through which the first hydroconverted effluent 105 is withdrawn.
• the reactor also preferably comprises an inlet and an outlet for the supported catalyst as already described above in connection with the means for injecting and withdrawing the supported catalyst.
• the ebullated bed reactor further includes an expanded catalyst zone comprising the porous supported catalyst.
• the ebullated 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 feed to the ebullated bed reactor is continuously recirculated 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 pump.
• a recycle line in communication with a boil pump.
• At the top of the recycle conduit is preferably 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" feed and additional hydrogen gas.
• the first supported hydroconversion catalyst used in the first hydroconversion step (b) may contain one or more elements from groups 4 to 12 of the periodic table of elements, which may or may not be supported. It is advantageous to use a catalyst comprising an amorphous support, such as silica, alumina, silica-alumina, titanium dioxide or combinations of these structures, and very preferably alumina.
• the first supported catalyst may contain at least one non-noble group VIII metal selected from nickel and cobalt, and preferably nickel, said group VIII element preferably being used in combination with at least one selected group VIB metal. among molybdenum and tungsten, and preferably the Group VIB metal is molybdenum.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.
• the first supported hydroconversion catalyst used in the first hydroconversion step (b) comprises an alumina support and at least one metal from group VIII chosen from nickel and cobalt, preferably nickel, and at least one metal of group VIB chosen from molybdenum and tungsten, preferably molybdenum.
• the first supported hydroconversion catalyst comprises nickel as a Group VIII element and molybdenum as a Group VIB element.
• non-noble group VIII metal in particular nickel
• metal oxide in particular NiO
• metal content of group VIB, in particular molybdenum is advantageously between 1% and 30% expressed by weight of metal oxide (in particular of molybdenum trioxide IVloOs), and preferably between 4% and 20% weight.
• the metal contents are expressed as weight percentage of metal oxide relative to the weight of the catalyst.
• This first 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 catalysts are well known to those skilled in the art.
• the first hydroconversion section 20 comprises one or more hybrid bed reactors (ie bubbling-entrained hybrid beds), simultaneously comprising at least one first supported hydroconversion catalyst which is maintained in the reactor and at least one entrained catalyst which enters the reactor with the feed and which is entrained outside the reactor with the effluents.
• a colloidal or molecular catalyst also called catalyst dispersed, entrained or slurry, may have formed upstream or formed in situ in the hybrid bed hydroconversion reactor.
• entrained catalysts are well known to those skilled in the art.
• the hybrid bed reactor comprises a solid phase which comprises a porous supported catalyst in the form of an expanded bed, a liquid hydrocarbon phase comprising the charge containing the colloidal or molecular catalyst dispersed therein, and a gas phase comprising 'hydrogen.
• the hybrid bed reactor is an ebullated bed hydroconversion reactor as described above, but comprising, in addition to the porous supported catalyst in the form of an expanded bed maintained in the reactor, the molecular or colloidal catalyst carried out of the reactor with the hydroconverted liquid effluent 105.
• the operation of the hybrid bed hydroconversion reactor is based on that of the bubbling bed reactor already described, and further implies that the colloidal or molecular catalyst is dispersed throughout the charge in the reactor at hybrid bed, including both in the expanded catalyst zone and in the supported catalyst free zones, and therefore available to stimulate upgrading reactions in what constitute catalyst free zones in conventional ebullated bed reactors.
• 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.
• a colloidal or molecular catalyst in a hybrid bed reactor can also make it possible to operate the hydroconversion at higher temperatures than in the case of an ebullated bed reactor (catalyst(s) supported ) alone (s), without entrained catalyst), while remaining within the temperature ranges given above for step (b).
• a different first supported hydroconversion catalyst can be used in each reactor of the first hydroconversion section, the supported catalyst specific to each reactor being adapted to the feed sent into this reactor.
• several types of first catalyst supported are used in each reactor.
• the first supported hydroconversion catalyst when it is used, can be partly replaced by fresh supported catalyst, and/or used supported catalyst but with activity catalyst greater than the used supported catalyst to be replaced, and/or the regenerated supported catalyst, and/or the rejuvenated supported catalyst (catalyst from a rejuvenation zone in which most of the metals deposited are removed, before sending the catalyst spent and rejuvenated in a regeneration zone in which the carbon and the sulfur which it contains are eliminated, thus increasing the activity of the catalyst), by withdrawing the spent supported catalyst preferably at the bottom of the reactor, and by introducing the supported catalyst from replacement either at the top or at the bottom of the reactor.
• This replacement of spent supported catalyst is preferably carried out at regular time intervals, and preferably in bursts or almost continuously. This withdrawal and this replacement are carried out using a withdrawal and injection device advantageously allowing the continuous operation of this hydroconversion step.
• One of the essential aspects of the invention lies in the capacity of the hydroconversion reactor operating in a bubbling or bubbling-entrained hybrid bed to manage the specific exotherms associated with the treatment of a feed comprising a fraction of vegetable and/or animal oil, due in particular to the liquid mixing and therefore to a uniform temperature in the reactor as explained above.
• the use of a heavy fraction of hydrocarbons in combination with the fraction of vegetable and/or animal oil makes it possible to guarantee the presence of a sufficient liquid phase in the reactor for its correct operation, and to ensure good operability of the boiling or hybrid bed hydroconversion process.
• hydroconversion reactor operating in a bubbling or bubbling-entrained hybrid bed also makes it possible to operate under more severe conditions than those, for example, operated in a reactor with a fixed bed of catalyst, making it possible in particular to increase the conversion overall load composed of the vegetable and/or animal oil fraction and the heavy hydrocarbon fraction, and to improve the yield of certain cuts obtained in the effluent hydroconverted, in particular gasoline, kerosene and diesel fuel cuts, and more particularly the diesel fuel cut.
• Another advantage of the invention linked to the use of a hydroconversion reactor operating in a bubbling or bubbling-entrained hybrid bed, is to allow the hydroconversion unit to have a long cycle time (without stopping the unit to replace the catalyst(s), in particular thanks to the system for adding fresh catalyst and withdrawing used catalyst without stopping the hydroconversion unit made possible by the operation of such a type of reactor.
• step (b) when step (b) is implemented in one or more hybrid bed reactors, the charge or the entrained catalyst precursor can be premixed with an organic additive, before the charge is introduced into the first hydroconversion reactor of the first hydroconversion section 20, in particular in order to minimize fouling of the installations before the hydroconversion in the hybrid bed reactor(s).
• the organic additive mixed with the filler, allows better solubility of the catalyst precursor entrained in the filler, avoiding or reducing fouling in particular due to metal deposits in the installations upstream of the hydroconversion reactor, such as in the heaters, and thus improving the dispersion of the entrained catalyst, thus generating an increased availability of the metallic active sites, promoting the hydrogenation of free radicals which are precursors of coke and sediments, and generating a substantial reduction in the fouling of the installations.
• Said organic additive which is neither a catalyst nor a catalyst precursor (eg it contains no metal), has at least one carboxylic acid function and/or at least one ester function and/or at least one anhydride function. 'acid.
• the organic additive can be 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), dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride, and mixtures thereof.
• the organic additive is preferably added during the mixing step so that the molar ratio of organic additive to the active metal(s) of the catalyst precursor composition (eg Mo) is between 0 , 1:1 and 20:1, more preferably between 0.75:1 and 7:1, and even more preferably between 1:1 and 5:1.
• the molar ratio of organic additive to the active metal(s) of the catalyst precursor composition eg Mo
• the method according to the invention further comprises a separation step (c), which separates part, or all, of the first hydroconverted effluent 105, to produce at least two cuts, one of which heavy cut mainly boiling at a temperature greater than or equal to 350°C.
• the other cut(s) are light and medium cut(s).
• the light cut thus separated mainly contains gases (H 2 , H 2 S, NH 3 , and Ci-C 4 ), naphtha (or gasoline, cut which boils at a temperature below 150°C), kerosene (cut which boils between 150° C. and 250° C.), and at least part of the diesel (or gas oil, fraction which boils between 250° C. and 350° C., or even 375° C.).
• the light cut can then be sent at least partially to a fractionation unit (not shown in the figures) where the light gases are extracted from said light cut, 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 to the first hydroconversion stage (b), and/or to the second hydroconversion stage (d) if it is implemented.
• the recovered hydrogen gas can also be used in other refinery facilities.
• the optional separation step (c) is implemented in a separation section (not shown in the figures), which includes any separation means known to those skilled in the art.
• Said separation section 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 distillation under vacuum, and is preferably made up of a single expansion tank, commonly called a “hot separator”.
• the method further comprises a second hydroconversion step, in at least a second bubbling bed or hybrid bed reactor comprising a second porous supported catalyst, in the presence of hydrogen, of part or all of the first effluent 105 resulting from stage (b), or optionally of the heavy cut resulting from stage (c).
• This second hydroconversion step is carried out so as to produce a second hydroconverted effluent.
• Said second hydroconverted effluent advantageously contains a greater quantity of conversion products than the first hydroconverted effluent, and in particular an even lower content of hydrocarbons having a boiling point of at least 300° C., or of at least 350° C.
• the second hydroconverted effluent may be provided with reduced Conradson carbon residue, and optionally with reduced sulfur, and/or nitrogen, and/or metals, and/or asphaltenes.
• an additional vegetable and/or animal oil fraction can be introduced into said at least second reactor, in addition to said part or all of the first effluent 105 resulting from step (b) , or optionally the heavy cut from step (c). Said fraction of additional vegetable and/or animal oil can be introduced into the second reactor mixed with or separated from the first effluent 105, or optionally from the heavy cut resulting from stage (c).
• Said fraction of additional vegetable and/or animal oil can be preheated and/or put under pressure before said mixing or said introduction separately into the second reactor, in a manner similar to what has been described in step (a) .
• Said additional vegetable and/or animal oil fraction may be identical to or different from the vegetable and/or animal oil fraction 102 making up the charge of the first hydroconversion reactor of the first hydroconversion section 20 in step ( b).
• the second hydroconversion step is carried out in a manner similar to that described for the first hydroconversion step (b), and is 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 details mentioned below.
• the second hydroconversion step is carried out in at least a second ebullated or hybrid bed reactor. It is preferably carried out in one or more bubbling bed reactors if the first hydroconversion step is also carried out in one or more bubbling bed reactors, and it is preferably carried out in one or more hybrid bed reactors if the first step hydroconversion is carried out in one or more hybrid bed reactors.
• the operating conditions may be similar or different from those in the hydroconversion step (d), the temperature remaining in the range between 405° C. and 550° C., preferably between 405° C. °C and 500°C, more preferably between 405°C and 450°C, even more preferably between 410°C and 435°C, and the amount of hydrogen introduced into the reactor remains in the range between 50 Nm 3 / m 3 and 5,000 Nm 3 /m 3 of liquid filler, preferably between 100 Nm 3 /m 3 and 3,000 Nm 3 /m 3 , and even more preferably between 200 Nm 3 /m 3 and 2,000 Nm 3 /m 3 .
• the other pressure and WH parameters are in ranges identical to those described for the hydroconversion step (d).
• the operating temperature at the second hydroconversion step (d) may be higher than the operating temperature at the first hydroconversion step (b). This may allow more complete conversion of the load not yet converted.
• the hydroconversion of liquid products from the first hydroconversion stage and the conversion of the feed are accentuated, as well as hydrotreating reactions such as hydrodesulfurization and hydrodenitrogenation, among others.
• the operating conditions are chosen to minimize the formation of solids (eg coke).
• the second porous supported hydroconversion catalyst used in the second hydroconversion reactor may be the same as that used in the first hydroconversion reactor(s) of the first hydroconversion section 20, or may be another porous supported catalyst as well. suitable for the hydroconversion of the treated feed, as defined for the first supported catalyst used in the first hydroconversion step (b).
• This fractionation step (e) separates part or all of said hydroconverted effluent into several fractions including at least one heavy liquid product 106b boiling mainly at a temperature above 350° C., preferably above 500° C. and preferably above at 540°C.
• the heavy liquid product 106b contains a part boiling at a temperature above 540° C., called the residual fraction (or vacuum residue), which is the unconverted part.
• the heavy liquid product 106b can contain a part of the gas oil fraction boiling between 250° C. and 375° C. and a part boiling between 375° C. and 540° C. (also called vacuum distillate).
• This fractionation step therefore produces at least two products including the heavy liquid product 106b as described above, the other product(s) 106a being light and intermediate cut(s).
• the fractionation section 30 includes any separation means known to those skilled in the art.
• the fractionating section 30 can thus comprise one or more following separation equipment: one or more flash drums arranged in series, and preferably a sequence of at least two successive flash drums, one or more steam stripping columns and/or hydrogen, an atmospheric distillation column, a vacuum distillation column.
• this splitting step (e) is performed by linking at least two successive flash balloons.
• the fractionation section 30 can also receive, in addition to part or all of the hydroconverted liquid effluent, one or more additional effluents such as one or more hydrocarbon feedstocks external to the process (e.g. distillates atmospheric and/or vacuum residues, atmospheric and/or vacuum residues), part of the heavy cut from the separation step (c) if it is implemented, part of one or more of the cuts intermediates from the fractionation step (e), part of a DAO or a light or heavy fraction of a DAO if a deasphalting step (fl) is carried out.
• one or more additional effluents such as one or more hydrocarbon feedstocks external to the process (e.g. distillates atmospheric and/or vacuum residues, atmospheric and/or vacuum residues), part of the heavy cut from the separation step (c) if it is implemented, part of one or more of the cuts intermediates from the fractionation step (e), part of a DAO or a light or heavy fraction of a DAO if a deasphal
• the hydroconversion process comprises a deasphalting step (fl), in a deasphalter, of part or all of said heavy liquid product 106b obtained in the fractionation step (e), with at least one hydrocarbon solvent, to produce a DAO deasphalted oil and a residual asphalt (“SDA” stage for Solvent DeAsphalting in English).
• a deasphalting step (fl) is carried out under conditions well known to those skilled in the art. job.
• the solvent/feed (volume/volume) ratios entering the deasphalter are generally between 3/1 and 16/1, and preferably between 4/1 and 8/1.
• the deasphalter comprises at least one extraction column, and preferably only one (eg as implemented in the SolvahlTM process) in which the solvent/feed (volume/volume) ratios entering the deasphalter are low preferences, typically between 4/1 and 8/1, or even between 4/1 and 6/1.
• part of the heavy residue fraction e.g. part of the heavy liquid product 106b and/or part of the residual asphalt, or part of the DAO
• a purge on the recycled stream can be implemented, generally to prevent certain compounds from accumulating at excessive levels.
• Examples 2 and 3 illustrate the performance of an H-Oil® process with a feed comprising a fraction of used cooking oil and a heavy fraction, as defined below, with implementation of a pre-step of homogenization of the medium (optional step), making it possible to convert said oil into lighter hydrocarbons of the light or middle distillate type which can be upgraded in the refinery.
• Example 4 illustrates the performance of this same process when the charge is used cooking oil, without the addition of heavy petroleum fraction. Examples 1 and 4 are therefore references to which Examples 2 and 3 can be compared.
• the heavy fraction (I) of the feed is a so-called straight-run vacuum residue (RSV-SR) originating directly from the distillation of a crude oil.
• the used cooking oil fraction (II) of the feed is a used cooking oil of vegetable origin.
• Procedure of example 1 The batch reactor is charged with a predefined mass of catalyst and with 100% weight of RSV-SR (fraction I of the charge), previously heated to 100-150°C to make it less viscous .
• the hydroconversion catalyst is a NiMo catalyst on alumina.
• the reactor is closed, purged with nitrogen, purged with hydrogen, then pressurized with hydrogen to a pressure of approximately 3 MPa.
• the reactor is then heated to 100°C.
• stirring is started at 500 rev.min -1 .
• the temperature is brought from 100° C. to the reaction temperature and, in parallel, the stirring is gradually brought from 500 to 1000 rpm .
• the pressure in the reactor is instantly adjusted to the target value by adding Hî.
• the batch reactor is first charged with the same mass of catalyst as for Example 1 and with 90% by weight of RSV-SR (fraction I of the charge), previously heated to 100° C. (approximately) to make it less viscous, then the 10% weight of used cooking oil (fraction II of the filler) is added.
• the reactor is closed, purged with nitrogen, purged with hydrogen, then pressurized with hydrogen to a pressure of about 3 MPa.
• the reactor is then heated to 100°C. At this temperature, stirring is started at 500 rev.min -1 . Gradually, the temperature is brought from 100° C. to 200° C. and, in parallel, the stirring is gradually brought from 500 to 1000 rpm . At 200° C., the pressure in the reactor is then 4 MPa.
• a stage of one hour at this temperature is respected, although this step is optional, in order to ensure the good dispersion of the used cooking oil (fraction II of the load) in the RSV-SR (load I ).
• the batch reactor is heated up to the reaction temperature, at which temperature the pressure in the reactor is instantly adjusted to the target value by adding I-. At this point, the reaction time is counted down.
• the reactor is cooled rapidly to stop the reaction, the stirring is stopped when the reactor is at ambient temperature, and the liquid effluent and the gases are sampled for analysis.
• Example 3 The procedure of Example 3 is in all respects similar to that of Example 2, with the difference that the proportions of RSV-SR and used cooking oil are now 50% by weight/50% by weight respectively. .
• the batch reactor is charged with a predefined mass of catalyst and with 100% weight of used cooking oil (fraction II).
• the reactor is closed, purged with nitrogen, purged with hydrogen, then pressurized with hydrogen to a pressure of about 3 MPa.
• the reactor is then heated to 100°C.
• stirring is started at 500 rev.min 1 .
• the temperature is brought from 100° C. to the reaction temperature and, in parallel, the stirring is gradually brought from 500 to 1000 rev.min 1 .
• the pressure in the reactor is instantly adjusted to the target value by adding I-.
• the reaction time is counted down.
• the reactor is cooled rapidly to stop the reaction, the stirring is stopped when the reactor is at ambient temperature, and the liquid effluent and the gases are sampled for analysis.
• the conversion of the 540°C+ cut is calculated by mass difference between the feed and the total liquid effluent, such as:
• experiment 3 demonstrates that with 50% by weight of used vegetable oil, the gaseous flow of reaction products increases by more than 10% by weight in the hydroconversion process compared to that of reference experiment 1.
• 100% VR-SR weight 100% VR-SR weight.
• Experiment 4 with 100% by weight of used cooking oil sees its flow rate of gaseous products increase by more than 20% by weight. This can lead to a risk on the hydrodynamics in the reactor and on the amount of liquid fraction available to be recycled and to keep the catalyst in suspension. It is therefore preferable to maintain the rate of incorporation of vegetable oils below a certain threshold during co-treatment in a hydroconversion reactor with residue and, similarly, to prefer co-treatment at a 100% weight load. vegetable oil (possibly used).

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• 2022
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