Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/02—Multi-step carbonising or coking processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • 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
• • 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
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
• • 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
  • C10G49/12—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 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
  • 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
  • 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
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/005—Coking (in order to produce liquid products mainly)
• • 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
  • C10G2300/1074—Vacuum distillates
• • 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
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/205—Metal content
  • C10G2300/206—Asphaltenes
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/701—Use of spent catalysts
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/708—Coking aspect, coke content and composition of deposits

Definitions

• the invention relates to a process for the hydroconversion of heavy petroleum feedstocks into lighter products, recoverable as fuels and / or raw materials for petrochemicals. More particularly, the invention relates to a process for hydroconversion of heavy petroleum feeds comprising a step of hydroconversion of the feedstock in at least one reactor containing a slurry catalyst and allowing the recovery of the metals in the unconverted residual fraction, in particular those used as catalysts, in order to efficientlyze them in catalytic solutions and to recycle them upstream of the slurry conversion process.
• the method comprises a hydroconversion step, a gas / liquid separation step, a coking step, a combustion step, a metal extraction step, and a catalyst solution (s) preparation step which is / are recycled (s) in the hydroconversion stage.
• the conversion of heavy oil loads into liquid products can be done by heat treatments or by hydrogenation treatments, also called hydroconversion.
• Current research is mainly focused on hydroconversion because heat treatments generally produce poor quality products and a significant amount of coke.
• the hydroconversion of heavy feeds involves the conversion of the feedstock in the presence of hydrogen and a catalyst.
• the commercial processes use depending on the load, fixed bed technology, bubbling bed technology or slurry technology.
• the hydroconversion of heavy charges in fixed bed or bubbling bed is by supported catalysts comprising one or more transition metals (Mo, W, Ni, Co, Ru) on supports of silica / alumina or equivalent type.
• transition metals Mo, W, Ni, Co, Ru
• the fixed bed technology is generally limited because the contaminants cause a rapid deactivation of the catalyst thus requiring a frequency of renewal of the catalytic bed too high and therefore too expensive .
• ebullated bed processes have been developed.
• the conversion level ebullated bed technologies are generally limited to levels below 80% due to the catalytic system employed and the design of the unit.
• Hydroconversion technologies operating with slurry technology provide an attractive solution to the disadvantages encountered in the use of the fixed bed or bubbling bed. Indeed, the slurry technology makes it possible to treat heavy loads heavily contaminated with metals, asphaltenes and heteroatoms, while having conversion rates generally greater than 85%.
• Slurry residue hydroconversion technologies use a dispersed catalyst in the form of very small particles, the size of which is less than 1 mm and preferably of a few tens of microns or less (generally 0.001 to 100 ⁇ m). Due to this small size of the catalysts, the hydrogenation reactions are facilitated by a uniform distribution throughout the reaction zone and the coke formation is greatly reduced.
• the catalysts, or their precursors are injected with the feed to be converted at the inlet of the reactors.
• the catalysts pass through the reactors with the feedstocks and the products being converted, and then are driven with the reaction products out of the reactors. They are found after separation into the heavy residual fraction, such as, for example, the unconverted vacuum residue.
• the catalysts used in slurry are generally sulfurized catalysts preferably containing at least one member selected from the group consisting of Mo, Fe, Ni, W, Co, V and / or Ru.
• Mo molybdenum and tungsten show much more satisfactory performance than nickel, cobalt or ruthenium and even more than vanadium and iron (N. Panariti et al., Applied Catalysis A: General 204 (2000), 203). -213).
• hydroconversion technologies of commercialized heavy slurries are known. Examples include EST technology licensed by ENI, Chevron-Lummus-Global licensed VRSH technology, Intevep-licensed HDH and HDHPLUS technologies, UOP-licensed SRC-Uniflex technology, Headwaters licensed technology (HC) 3, etc. ..
• the small size of the slurry catalysts makes it possible to obtain very high conversion rates, this size is problematic with regard to the separation and the recovery of the catalyst (s) after the reaction. hydroconversion.
• the catalysts are found after separation in the heavy residual fraction, such as unconverted vacuum residue.
• a portion of the vacuum residue containing the unconverted fraction and the catalysts is recycled directly to the hydroconversion reactor to increase conversion efficiency.
• these recycled catalysts generally have no activity or much reduced activity compared to fresh catalyst.
• the vacuum residue is traditionally used as fuel for the production of heat, electricity and ash. These ashes contain metals and are generally dumped. In this case, the metals are not recovered.
• the deactivation of the catalysts requires regular replacement thus creating a demand for fresh catalysts.
• the heavy loads treated contain a high concentration of metals, mainly vanadium and nickel. These metals are largely removed from the charge by settling on the catalysts during the reaction. They are washed away by the catalyst particles leaving the reactor. Similarly, the deactivation of the catalysts is accentuated by the formation of coke, in particular from the high concentration of asphaltenes contained in these feeds.
• the continuous renewal of the catalytic phase finely dispersed in the reaction zone allows the contact of the hydrogen dissolved in the liquid phase to hydrogenate and hydrotrate the injected heavy load.
• the amount of catalytic solution to be injected is quite high which represents relatively high industrial operating costs.
• slurry hydroconversion processes are generally consuming a large amount of catalysts, in particular molybdenum, which has the most active catalyst, but also the most expensive.
• the costs of fresh catalysts, catalyst separation and metal recovery have a major impact on the profitability of such processes.
• the selective recovery of molybdenum and its recycling as a catalyst are two essential elements for the industrial valorization of slurry processes.
• This recovery is also accompanied by those of other metals such as nickel (the one injected and the one recovered in the charge) and the vanadium recovered in the a load whose contents are comparable to that of molybdenum and which can be resold for metallurgical applications.
• patent application US2008 / 0156700 describes a process for separating catalysts in the form of ultrafine particles resulting from a slurry hydroconversion process comprising a step of precipitation or flocculation of a heavy fraction including metal parts by solvents. of heptane type, a step of separating the heavy fraction of the light fraction by centrifugation and a coking step between 350 ° and 550 ° C under an inert atmosphere to obtain coke containing the catalyst. This coke can be subjected to a metal extraction step.
• US Pat. No. 6,155,555 describes a process for recovering metals, in particular molybdenum, from catalysts used in heavy-lift hydroconversion processes.
• This process comprises a coking step between 300 and 1000 ° C, at atmospheric pressure and under an inert atmosphere.
• the coked product is then divided and subjected to one or two stages of combustion in air at temperatures of between 800 and 1900 ° C. in order to sublimate the molybdenum, which then condenses by cooling on the ashes.
• the molybdenum is subsequently recovered by an extraction step using a mixture of ammonia and (NH 4 ) 2 CO 3 .
• 6,511,937 describes a heavy-duty slurry hydroconversion process comprising, after the hydroconversion reaction, a separation step in a high-pressure, low-temperature separator making it possible to separate a very light fraction, a deasphalting step of the entire residual fraction using paraffin C3 to C5 solvents at room temperature, a coking step (427-649 ° C, without air) and / or a combustion step below 649 ° C to produce ash containing the catalyst .
• This catalyst may subsequently be subjected to metal extraction steps and recycled to the process.
• the present invention aims to improve the methods of hydroconversion of heavy loads by slurry technology known by allowing the valuation of a residual unconverted fraction resulting from the conversion to slurry fraction highly concentrated in metals and heteroelements and ultimately including the recovery of said metals in said unconverted fraction and the production of catalytic precursors for recycling upstream of the conversion process in slurry mode.
• the method comprises a hydroconversion step, a gas / liquid separation step, a coking step, a combustion step, a metal extraction step, and a catalyst solution (s) preparation step which is / are recycled (s) in the hydroconversion stage.
• this process comprises a separation making it possible to maximize the light fraction resulting from the hydroconversion reactor and to minimize the residual fraction.
• a moderate combustion step avoiding sublimation metals, made it possible to prepare the extraction of the metals contained in the ashes in such a way that very good recovery rates of recyclable metals in the process are possible.
• the critical stages of this recovery are firstly the concentration of metals on the carbon matrix (via coking) and then the formation of a mineral phase (via the moderate combustion) containing the metallic elements from the catalyst (Mo and Ni). but also the charge (Ni, V and Fe) devoid of carbon.
• An advantage of the method according to the invention is the recovery of an unconverted residual fraction highly concentrated in metals and heteroelements for the recovery of said metals and the production of catalytic precursors for recycling upstream of the conversion process in slurry mode.
• Another advantage is the optimization of the conversion of hydroconversion by a gas / liquid separation after hyd conversion operating under operating conditions close to those of the reactor and allowing the effective separation in a single step of a light fraction comprising the future fuel bases (gases, naphtha, light gas oil or even heavy diesel) of the unconverted residual fraction containing solids such as metals.
• the yield of the light fraction is thus maximized at the same time that the unconverted residual fraction is minimized thereby facilitating the reduced concentration of the metals thereafter.
• Maintaining the operating conditions during the separation also allows the economical integration of a subsequent treatment of hydrotreating and / or hydrocracking of the light fraction without the need for additional compressors.
• Another interest is the coking of the unconverted fraction containing the metals allowing an effective metal concentration.
• Another advantage of the process is the combustion at moderate temperature to separate the organic phase of the inorganic phase containing the metals to facilitate the subsequent extraction of metals from the inorganic phase while avoiding vaporization and / or sublimation (and therefore loss) of metals during combustion.
• Another advantage of the process is that this process does not require a deasphalting step and the disadvantages associated with (handling of solvents, often toxic, need for a recycling of the solvent after extraction ).
• the invention relates to a process for the hydroconversion of heavy petroleum slurry feeds enabling the recovery and recycling of metals in the unconverted residual fraction, in particular those used as catalysts.
• the invention relates to a process for hydroconversion of heavy petroleum feedstocks containing metals comprising:
• step b optionally a fractionation step comprising a vacuum separation of said residual fraction as obtained in step b), and there is obtained a vacuum residue concentrated in metals,
• step b) a step of coking said residual fraction as obtained in step b) and / or said vacuum residue as obtained in step b ') making it possible to obtain a solid effluent containing coke
• the process according to the invention comprises a step of hydroconversion of the feedstock in at least one reactor containing a slurry catalyst and optionally a solid additive.
• Hydroconversion is understood to mean hydrogenation, hydrotreatment, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization and hydrocracking reactions.
• the heavy loads concerned are petroleum hydrocarbon feedstocks such as petroleum residues, crude oils, crude head oils, deasphalted oils, asphalts or desulfaspeating pitches, derivatives of petroleum conversion processes (for example: HCO, FCC slurry, GO heavy / VGO coking, visbreaking residue or similar thermal process, etc.), oil sands or their derivatives, oil shales or their derivatives, or mixtures of such fillers. More generally, herein will be grouped under the term "heavy load” hydrocarbon feeds containing at least 50 wt% of product distilling above 250 ° C and at least 25 wt% distilling above 350 ° C.
• the heavy charges concerned according to the invention contain metals, essentially V and / or Ni, at a rate of generally at least 50 ppm by weight and most often 100-2000 ppm by weight, at least 0.5% by weight of sulfur, and at least 1% by weight of asphaltenes (heptane asphaltenes), often more than 2% by weight or 5% by weight, of 25% by weight or more of asphaltenes attainable; they also contain condensed aromatic structures which may contain heteroelements refractory to conversion.
• the heavy feedstocks concerned are unconventional oils of the heavy crude type (API ° between 18 and 25 and a viscosity of between 10 and 100 cP), the extra heavy mills (API ° between 7 and 20 and viscosity between 100 and 10,000 cP) and oil sands (API ° 7 to 12 ° API and a viscosity of less than 10,000 cP) present in large quantities in the Athabasca region of Canada and the Orinoco Venezuela where reserves are estimated at 1700 Gb and 1300 Gb respectively.
• These unconventional oils are also characterized by high levels of residues under vacuum, asphaltenes and heteroelements (sulfur, nitrogen, oxygen, vanadium, nickel, etc.) which require conversion steps to commercial gasoline type products. specific diesel or heavy fuel oil.
• the heavy charge is mixed with a hydrogen stream and a catalyst as dispersed as possible to obtain a hydrogenating activity as uniformly distributed as possible in the hydroconversion reaction zone.
• a solid additive promoting the hydrodynamics of the reactor is also added.
• This mixture feeds the catalytic hydroconversion section into slurry.
• This section consists of a preheating furnace for the charge and hydrogen and a reaction section consisting of one or more reactors arranged in series and / or in parallel, according to the required capacity. In the case of series reactors, one or more separators may be present on the effluent at the head of each of the reactors.
• hydrogen can feed one, several or all of the reactors in equal or different proportions.
• the catalyst can feed one, several or all the reactors in equal or different proportions.
• the catalyst is kept in suspension in the reactor, flows from the bottom to the top of the reactor with the gas and the feedstock, and is evacuated with the effluent.
• at least one (and preferably all) of the reactors is provided with an internal recirculation pump.
• the operating conditions of the slurry catalytic hydroconversion section are in general a pressure of 2 to 35 Pa, preferably 10 to 25 Pa, a hydrogen partial pressure ranging from 2 to 35 MPa and preferably from 10 to 25 MPa. a temperature of between 300 ° C and 500 ° C, preferably 420 ° C to 480 ° C, a contact time of 0.1 h to 10 h with a preferred duration of 0.5h to 5 h.
• the conversion rate mentioned above is defined as the mass fraction of organic compounds having a boiling point greater than 500 ° C at the inlet of the reaction section minus the mass fraction of organic compounds having a boiling point. greater than 500 ° C at the outlet of the reaction section, all divided by the mass fraction of organic compounds having a boiling point greater than 500 ° C at the inlet of the reaction section.
• the slurry catalyst is in dispersed form in the reaction medium. It can be formed in situ but it is preferable to prepare it outside the reactor and inject it, usually continuously, with the charge.
• the catalyst promotes the hydrogenation of radicals from thermal cracking and reduces coke formation. When coke is formed, it is removed by the catalyst.
• the slurry catalyst is a sulfurized catalyst preferably containing at least one member selected from the group consisting of Mo, Fe, Ni, W, Co, V, Ru. These catalysts are generally monometallic or bimetallic (by combining, for example, a non-noble group VIIIB element (Co, Ni, Fe) and a group VIB element (Mo, W)). NiMo, Ni or Fe catalysts are preferably used.
• the catalysts used may be heterogeneous solid powders (such as natural ores, iron sulphate, etc.), dispersed catalysts derived from water-soluble precursors.
• water soluble dispersed catalyst such as phosphomolybdic acid, ammonium molybdate, or a mixture of Mo or Ni oxide with aqueous ammonia.
• the catalysts used are derived from soluble precursors in an organic phase ("oil soluble dispersed catalyst”).
• the precursors are organometallic compounds such as the naphthenates of Mo, Co, Fe, or Ni or such as multi-carbonyl compounds of these metals, for example 2-ethyl hexanoates of Mo or Ni, acetylacetonates of Mo or Ni , C7-C12 fatty acid salts of Mo or W, etc.
• the catalysts can be used in the presence of a surfactant to improve the dispersion of metals, when the catalyst is bimetallic.
• the catalysts are in the form of dispersed particles, colloidal or otherwise depending on the nature of the catalyst. Such precursors and catalysts that can be used in the process according to the invention are widely described in the literature.
• the catalysts are prepared before being injected into the feed.
• the preparation process is adapted according to the state in which the precursor is and of its nature.
• the precursor is sulfided (ex-situ or in-situ) to form the catalyst dispersed in the feedstock.
• the precursor is mixed with a petroleum feedstock (which may be a part of the feedstock to be treated, an external feedstock, a recycled feedstock, etc.), the mixture is optionally dried at least in part, and then or simultaneously sulphurized by the addition of a sulfur compound (H 2 S preferred) and heated.
• H 2 S sulfur compound
• the preferred solid additives are inorganic oxides such as alumina, silica, mixed Al / Si oxides, supported spent catalysts (for example, on alumina and / or silica) containing at least one group VIII element (such as Ni, Co) and / or at least one group VI B element (such as Mo, W).
• group VIII element such as Ni, Co
• group VI B element such as Mo, W
• the catalysts described in the application US2008 / 177124 Carbonaceous solids with a low hydrogen content (for example 4% hydrogen), possibly pretreated, can also be used. Mixtures of such additives can also be used. Their particle sizes are preferably less than 1 mm.
• the content of any solid additive present at the inlet of the reaction zone of the slurry hydroconversion process is between 0 and 10% by weight and preferably between 1 and 3% by weight, and the content of the catalytic solutions is between 0 and 10% by weight.
• % wt preferably between 0 and 1 wt%.
• the known slurry technology heavy charge hydroconversion processes are EST of ENI operating at temperatures of the order of 400-420 ° C, under pressures of 10-16 MPa with a particular catalyst (molybdenite); (HC) 3 of Headwaters operating at temperatures of the order of 400-450 ° C, at pressures of 10-15 MPa with Fe pentacarbonyl or Mo 2-ethyl hexanoate, the catalyst being dispersed in the form of colloidal particles; HDH and HDHPLUS licensed by Intevep / PDVSA operating at temperatures of the order of 420-480 ° C, at pressures of 7-20 MPa, using a dispersed metal catalyst; Chevron CASH using a Mo or W sulfide catalyst prepared by aqueous means; SRC-Uniflex UOP operating at temperatures of the order of 430-480 ° C, under pressures of 10-15 MPa; VCC developed by Veba and belonging to BP operating at temperatures of the order of 400-480 ° C, at pressures
• HPHT high pressure and high temperature separator
• This separation section is preferably carried out under operating conditions close to those of the reactor, which are in general a pressure of 2 to 35 MPa with a preferred pressure of 10 to 25 MPa, a hydrogen partial pressure ranging from 2 to 35 MPa. and preferably from 10 to 25 MPa and a temperature of between 300 ° C and 500 ° C, preferably 380 ° C to 460 ° C.
• the residence time of the effluent in this separation section is 0.5 to 60 minutes and preferably 1 to 5 minutes.
• the light fraction contains, for the most part, the compounds boiling at at most 300 ° C., or even at most 400 ° C. or 500 ° C .; they correspond to the compounds present in gases, naphtha, light diesel or even heavy diesel.
• the cut contains very predominantly these compounds, because the separation is not made according to a precise cutting point, it is more like a flash. If we had to speak in terms of cutting point, we could say that it is between 200 ° and 400 ° or 450 ° C.
• the valorization of the light fraction is not the subject of the present invention and these methods are well known to those skilled in the art.
• the light fraction obtained after the separation can undergo at least one hydrotreatment and / or hydrocracking step, the objective being to bring the different cuts to the specifications (sulfur content, smoke point, cetane, aromatic content, etc.).
• the light fraction may also be mixed with another feed before being directed to a hydrotreatment and / or hydrocracking section.
• an external cut generally coming from another process existing in the refinery or possibly outside the refinery can be brought before the hydrotreatment and / or the hydrocracking, advantageously the external cut is for example the VGO resulting from the fractionation crude oil (VGO straight-run), conversion-derived VGO, FCC light cycle oil (LCO) or HCO (heavy cycle oil).
• hydration and / or hydrocracking after hydration conversion can be done conventionally via a conventional intermediate separation section (with decompression) using, for example, after the high-pressure high-temperature separator, a low temperature high pressure separator and / or atmospheric distillation and / or vacuum distillation.
• the hydrotreatment and / or hydrocracking section is directly integrated into the hydroconversion section without intermediate decompression.
• the light fraction is sent directly, without additional separation and decompression steps to the hydrotreatment and / or hydrocracking section.
• This last embodiment makes it possible to optimize pressure and temperature conditions, avoids additional compressors and thus minimizes the costs of additional equipment.
• the residual fraction resulting from the separation for example by the separator
• HPHT HPHT
• containing the metals and a fraction of solid particles used as a possible additive and / or formed during the reaction can be directed to a fractionation step.
• This fractionation is optional and comprises a vacuum separation, for example one or more flash flasks and / or, preferably, a vacuum distillation, making it possible to concentrate a metal-rich vacuum residue at the bottom of the flask or column. recover at the head of the column one or more effluents.
• the residual fraction resulting from the decompression-free separation step is fractionated by vacuum distillation into at least one vacuum distillate fraction and a vacuum residue fraction, at least a portion and preferably all of said fraction residue under vacuum being sent to the coking step, at least a portion and preferably all of said vacuum distillate fraction being preferably subjected to at least one hydrotreatment and / or hydrocracking step.
• the liquid effluent (s) of the vacuum distillate fraction thus produced will (are) usually be directed to a small extent to the slurry hydroconversion unit where they can be directly recycled. in the zone reaction or it (s) can (wind) be used for the preparation of catalytic precursors before injection into the load.
• Another part of the effluent (s) is directed towards the hydrotreating and / or hydrocracking section, optionally mixed with other fillers, for example the light fraction derived from the HPHT separator or a vacuum distillate originating from of another unit, in equal or different proportions depending on the quality of the products obtained.
• the objective of the vacuum distillation is to increase the efficiency of the liquid effluents for a subsequent treatment of hydrotreatment and / or hydrocracking and thus to increase the yield of fuel bases. At the same time, the amount of the residual fraction containing the metals is reduced, thus facilitating the concentration of the metals.
• the residual fraction resulting from the no-decompression separation (for example via the HPHT separator) and / or the vacuum residue fraction of the vacuum separation (for example withdrawn at the bottom of the vacuum distillation column) are then directed to a thermal conversion step. coking type. This step has the objective of concentrating the metals in the effluent to be subsequently treated by combustion, by reducing its quantity, and to maximize the liquid effluent yield for the hydrotreatment and / or hydrocracking treatment.
• the coking step may be by delayed coking or by fluid bed coking ("fluid-coking” or "flexi-coking”).
• fluid bed coking the reactor temperature is above 490 ° C, preferably between 500-550 ° C, at atmospheric pressure.
• coking takes place by delayed coking in at least two maturation flasks.
• the load Before being sent to the maturation flask, the load is heated by heating ovens.
• the operating conditions are a temperature at the outlet of the charging furnaces of between 460 and 530 ° C., preferably 480 and 510 ° C.
• the recycle rate of the unconverted fraction of the maturation flask is less than 20% wt. cool, preferably less than 10% by weight.
• Coking takes place under an inert atmosphere. Coking of the fresh load is ensured continuously through regular switching between two maturation balls, one being in the cocking phase while the other is in the decocking phase.
• the delayed coking step produces a solid effluent containing coke (and metals) and a liquid effluent.
• the liquid effluent is generally separated by distillation.
• At least a portion, and preferably all, of the liquid effluent produced during coking and having a boiling point below a temperature of 300 to 400 ° C can be sent to the hydrotreatment and / or hydrocracking section mixed with the light fraction of the HPHT separator and / or with an external cut.
• the liquid effluent produced during coking having a boiling point greater than a temperature of between 300 and 400 ° C. is preferably mixed with the heavy hydrocarbon feedstock upstream of the hydroconversion section. in slurry. It can also be sent to the hydrotreatment and / or hydrocracking section mixed with the light fraction of the HPHT separator and / or with an external cut. It can also be sent to the vacuum distillation stage mixed with the residual fraction of the HPHT separator.
• At least a portion, and preferably all, of the solid effluent containing coke with a high concentration of metals is directed to a moderate combustion step.
• a portion of the solid effluent containing coke may be recycled as an additive in the hydroconversion stage.
• the solid effluent containing coke is directed to a combustion stage at moderate temperature and in the presence of oxygen.
• a preliminary step is required to separate the organic phase (coke) from the inorganic phase containing the metals.
• the objective of the combustion step is to obtain ash containing the easily recoverable metals in the subsequent metal recovery units, by burning the organic phase or carbon phase of the solid effluent at a temperature and pressure that limit the vaporization and / or sublimation of metals, especially that of molybdenum (sublimation temperature of about 700 ° C for Mo0 3 ).
• the step of reducing the organic phase consists of a combustion at moderate temperature in order to concentrate the metals, without significant loss by vaporization and / or sublimation towards the fumes, in a mineral phase which may contain a proportion of organic phase ranging from 0 to 100 wt%, preferably 0 wt% to 40 wt%.
• the operating conditions of this combustion are in general a pressure of from 0.1 to 1 MPa, preferably from 0.1 to 0.5 MPa, a temperature of 200 to 700 ° C., preferably of 400 to 550 ° C.
• the combustion is done in the presence of air.
• the gaseous effluent resulting from the combustion requires purification steps in order to reduce the emission of sulfur and nitrogen compounds into the atmosphere.
• the processes conventionally used by those skilled in the field of air treatment are carried out under the operating conditions necessary to meet the standards in force in the country of operation of such a hydrocarbon feedstock treatment. .
• the solid resulting from the combustion is a mineral phase containing all, or almost all, the metal elements contained in the extract, in the form of ash.
• Ashes from combustion are sent to a metal extraction step in which the metals are separated from one another in one or more substeps. This recovery of the metals is necessary because the simple recycling of the ashes in the hydroconversion stage shows a very weak catalytic activity.
• the metal extraction step makes it possible to obtain several effluents, each effluent containing a specific metal, for example Mo, Ni or V, generally in salt or oxide form.
• Each effluent containing a catalyst metal is directed to a step of preparation of an aqueous or organic solution based on the metal identical to the catalyst or its precursor used in the hydroconversion stage.
• the effluent containing a metal from the feed being non-recoverable as a catalyst (such as vanadium for example) can be recovered outside the process.
• the operating conditions, fluids and / or extraction methods used for the various metals are considered to be known to those skilled in the art and already used industrially, as for example described in Marafi et al., Resources, Conservation and Recycling. 53 (2008) 1-26, US4432949, US4514369, US4544533, US4670229 or US2007 / 0025899.
• the various known metal extraction routes generally include leaching by acidic and / or basic solutions, ammonia or ammonia salts, bioleaching by microorganisms, low temperature heat treatment ( roasting) by sodium or potassium salts, chlorination or the recovery of metals electrolytically.
• the acid leaching may be by inorganic acids (HCl, H 2 SO 4, HNO 3) or organic acids (oxalic acid, lactic acid, citric acid, glycolic acid, phthalic acid, malonic acid, succinic acid, salicylic acid, tartaric acid. ..).
• HCl inorganic acids
• HNO 3 organic acids
• oxalic acid lactic acid, citric acid, glycolic acid, phthalic acid, malonic acid, succinic acid, salicylic acid, tartaric acid. ..
• ammonia, salts of ammonia, sodium hydroxide or Na 2 CO 3 are generally used.
• oxidizing agents H2O2, Fe (N0 3 ) 3 , Al (N0 3 ) 3 ...) may be present to facilitate the extraction.
• the metals in solution they can be isolated by selective precipitation (at different pH and / or with different agents) and / or by extraction agents (oximes, beta-diketone ).
• the metal extraction step according to the invention comprises leaching with at least one acidic and / or basic solution.
• the metals recovered after the extraction step are generally in the form of salt or oxide.
• the preparation of the catalytic solutions for producing the organic or aqueous solutions is known to those skilled in the art and has been described in the hydroconversion part.
• the preparation of catalytic solutions concerns especially molybdenum and nickel metals, vanadium being generally valorized as vanadium pentoxide, or in combination with iron, for the production of ferrovanadium, outside the process.
• the recovered metal recovery rate as a catalyst for the slurry or vanadium hydroconversion process is at least 50 wt%, preferably at least 65 wt% and more generally 70 wt%.
• Figure 1 shows a process of hydroconversion of heavy oil loads incorporating a slurry technology without recovery of metals.
• FIG. 2 describes a process for hydroconversion of heavy petroleum feedstocks according to the invention.
• the installation and the method according to the invention are essentially described. We will not repeat the operating conditions described above.
• charge 1 feeds the catalytic hydroconversion section in slurry A.
• This slurry catalytic hydroconversion section consists of a preheating furnace for charge 1 and hydrogen 2 and a reaction section. consisting of one or more reactors arranged in series and / or in parallel, according to the required capacity.
• the catalyst 4 or its precursor is also injected, as well as the optional additive 3.
• the catalyst 4 is kept in suspension in the reactor, flows from the bottom to the top of the reactor with the feedstock, and is evacuated with the effluent.
• the effluent 5 resulting from the hydroconversion is directed to a high-pressure and high-temperature separation section B which makes it possible to separate a fraction converted into the gaseous state 6, called the light fraction, and a residual unconverted liquid / solid fraction.
• the light fraction 6 can be directed to a hydrotreatment and / or hydrocracking section C.
• An external cut 7 generally coming from another process existing in the refinery or possibly outside the refinery can be brought before the hydrotreatment and / or hydrocracking.
• the unconverted residual fraction 8 containing the catalyst and a solid particle fraction optionally used as an additive and / or formed during the reaction is directed to a fractionation step D.
• Fractionation step D is preferably vacuum distillation.
• the metal-rich vacuum residue is recovered as a very high viscosity fuel or as a solid fuel after pelleting, by example to produce heat and electricity on site or outside or as fuel in cement works. Metals are, a priori, not recovered.
• the effluent (s) 9 thus produced will (are) usually be directed via line 24 to a small extent to the A slurry hydroconversion unit where they can be directly recycled to the reaction zone or it (s) can (wind) be used for the preparation of catalytic precursors before injection in the feedstock 1 and for the other part to the hydrotreating and / or hydrocracking unit C via the line 25 mixed with the effluents 6 and or 7 in equal or different proportions depending on the quality of the products obtained.
• the steps (and reference marks) for hydroconversion, HPHT separation, hydrotreatment and / or hydrocracking and vacuum distillation are identical to FIG. vacuum distillation D is directed to a thermal conversion step of coking type E to concentrate the effluent 10.
• the liquid effluent produced during coking and having a boiling point below a temperature of between 300 and 400 ° C. C (LCGO) 11 may be sent to the hydrotreatment / hydrocracking section C in mixture via line 22 with effluent 6 and / or 7.
• the liquid product having a boiling point greater than a temperature of between 300 and 400 ° C (HCGO) 12 is preferably sent to the slurry conversion section A via line 23 in admixture with feedstock 1. It can also be sent to the hydrotreatment / hydrocracking section C in mixture via line 28 ave c the effluent 6 and / or 7, and / or to the vacuum distillation stage D via the line 29 mixed with the effluent 8.
• the solid effluent containing coke 13 highly concentrated in metals is partially directed and preferably all, to a step of reducing the organic phase by combustion at moderate temperature F to very strongly concentrate the metals, without significant loss by vaporization and / or sublimation to the fumes.
• a smaller portion of the solid effluent 13 can be sent as additive 3 via line 50 in hydroconversion step A.
• the gaseous effluent from combustion 14 requires purification steps (not shown) to reduce the emission of sulfur and nitrogen compounds into the atmosphere.
• the product 15 resulting from the combustion F is a mineral phase containing all, or almost all, the metal elements contained in the solid 13 in the form of ash.
• the product is sent to a metal extraction step G in which the metals are separated from one another in one or more sub-steps.
• the effluent 16 from the extraction G is composed of a molybdenum type metal in the form of salt or oxide.
• This effluent 16 is then directed to a preparation step H of an organic or aqueous solution based on molybdenum 18 identical to the catalyst 4 or its precursor recycled partially or wholly in the hydroconversion step in slurry A via the line 40.
• the effluent 17 from the extraction G is composed of a nickel-type metal in the form of salt or oxide.
• This effluent 17 is then directed to a preparation step I of an organic or aqueous nickel-based solution 19 identical to the catalyst 4 or its precursor recycled partially or wholly in the hydroconversion step in slurry A via the line 41.
• the effluent 20 from the extraction G is composed of a vanadium type metal in salt or oxide form. This effluent can be recovered for example as vanadium pentoxide, or in combination with iron, for the production of ferrovanadium.
• the hydroconversion uses a finely dispersed catalyst of nickel and molybdenum type with a concentration of 160 ppm by weight and 600 ppm by weight respectively. 'hydrogen.
• the industrial unit has a capacity of 50,000 barrels per day and a utilization rate of 90% per year, the quantity of nickel and molybdenum consumed per year is therefore 0.4 and 1.6 kt / year respectively.
• the operating cost is $ 100 million per year.
• the process according to the invention makes it possible to recover a large part of the metals, nickel and molybdenum, present in the unconverted fraction of the effluent resulting from hydroconversion into slurry.
• the recovered metal recovery rate as a catalyst for the slurry hydroconversion process is at least 50 wt%, preferably at least 65 wt%, and more generally 70 wt%.
• This recycling of metals can therefore reduce the operating cost from $ 100 million a year to $ 30 million a year.
• the saving thus achieved is 70 million dollars makes it possible initially to pay the additional investments necessary for the recovery of these metals.
• the vanadium present in the heavy load at 400 ppm wt can be valorized as ferrovanadium.
• the sale of vanadium is estimated, considering an observed average cost of 40 k $ / t on the metal market over the past 5 years, at $ 12 million a year. This sale will also make it possible in the first time to pay the additional investments necessary for the recovery of these metals.
• the recovery of these metals in the unconverted residual fraction reduces the overall quantity of nickel and molybdenum used and thus reduces the environmental impact of the slurry hydroconversion process.
• the amount of additional catalyst is reduced to 0.1 t / year for nickel and 0.5 t / year for molybdenum compared to 0.4 t / year and 1.6 t / year without recycle.

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• 2010
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