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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
• • 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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
• • 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
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
• • 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
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds 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
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
• • 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
  • C10G49/22—Separation of effluents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
  • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4012—Pressure
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV

Definitions

• the present invention relates to a process for treating an oil from the pyrolysis of plastics in order to obtain a hydrocarbon effluent which can be recovered by being directly integrated into a naphtha or diesel storage unit or as a feedstock for a steam cracking unit. More particularly, the present invention relates to a process for treating a charge resulting from the pyrolysis of plastic waste in order to eliminate at least part of the impurities that said charge may contain in relatively large quantities.
• Plastics from the collection and sorting channels can undergo a pyrolysis step in order to obtain, among other things, pyrolysis oils. These plastic pyrolysis oils are usually burned to generate electricity and/or used as fuel in industrial or district heating boilers.
• plastic waste is generally mixtures of several polymers, for example mixtures of polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polystyrene.
• plastics may contain, in addition to polymers, other compounds, such as plasticizers, pigments, dyes or polymerization catalyst residues.
• Plastic waste may also contain, in a minor way, biomass from household waste, for example.
• the treatment of waste on the one hand, in particular storage, mechanical treatment, sorting, pyrolysis, and also the storage and transport of pyrolysis oil on the other hand can also induce corrosion.
• the oils resulting from the pyrolysis of plastic waste contain many impurities, in particular diolefins, metals, in particular iron, silicon, or even halogenated compounds, in particular chlorine-based compounds, heteroelements such as sulphur, oxygen and nitrogen, insolubles, at levels that are often high and incompatible with steam cracking units or units located downstream of steam cracking units, in particular polymerization processes and selective hydrogenation.
• the yields of light olefins sought after for petrochemicals, in particular ethylene and propylene, are highly dependent on the quality of the feeds sent for steam cracking.
• the BMCI Boau of Mines Correlation Index according to Anglo-Saxon terminology
• This index developed for hydrocarbon products derived from crude oils, is calculated from the measurement of the density and the average boiling temperature: it is equal to 0 for a linear paraffin and 100 for benzene. Its value is therefore all the higher when the product analyzed has an aromatic condensed structure, naphthenes having a BMCI intermediate between paraffins and aromatics.
• the yields of light olefins increase when the paraffin content increases and therefore when the BMCI decreases.
• the yields of unwanted heavy compounds and/or coke increase when the BMCI increases.
• Document WO 2018/055555 proposes an overall, very general and relatively complex plastic waste recycling process, ranging from the very stage of pyrolysis of plastic waste to the steam cracking stage.
• the process of application WO 2018/055555 comprises, among other things, a step of hydrotreating the liquid phase resulting directly from pyrolysis, preferably under fairly stringent conditions, in particular in terms of temperature, for example at a temperature of between 260 and 300°C, a stage of separation of the hydrotreatment effluent then a stage of hydrodealkylation of the heavy effluent separated at a temperature which is preferably high, for example between 260 and 400°C.
• the unpublished patent application FR20/01.758 describes a process for treating an oil from the pyrolysis of plastics, comprising: a) the selective hydrogenation of the diolefins contained in the said charge in the presence of hydrogen and a hydrogenation catalyst selective to obtain a hydrogenated effluent; b) hydrotreating said hydrogenated effluent in the presence of hydrogen and a hydrotreating catalyst, to obtain a hydrotreating effluent; c) separation of the hydrotreatment effluent in the presence of an aqueous stream, at a temperature between 50 and 370° C., to obtain a gaseous effluent, an aqueous liquid effluent and a liquid hydrocarbon effluent; d) optionally a step of fractionating all or part of the hydrocarbon effluent from step c), to obtain a gas stream and at least two hydrocarbon streams which may be a naphtha cut and a heavier cut; e) a recycling step comprising a recovery phase of
• step a) of selective hydrogenation and step b) of hydrotreatment are separate steps, carried out under different conditions and in separate reactors.
• step a) of selective hydrogenation is carried out under mild conditions, in particular at a temperature between 100 and 250° C., which can lead to premature deactivation of the catalyst.
• step b) of hydrotreatment is generally carried out at a significantly higher temperature than step a) of selective hydrogenation, in particular at a temperature between 250 and 430° C., this which requires a heating device between these two stages.
• This same step would also make it possible to benefit from the heat of hydrogenation reactions, in particular of a part of the diolefins, so as to have a rising temperature profile in this step and thus being able to eliminate the need for a heating device between the section catalytic hydrogenation section and the catalytic hydrotreating section.
• the invention relates to a process for treating a charge comprising a plastics pyrolysis oil, comprising: a) a hydrogenation stage implemented in a hydrogenation reaction section, implementing at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one catalyst hydrogenation, said hydrogenation reaction section being fed at least by said charge and a gas stream comprising hydrogen, said hydrogenation reaction section being implemented at an average temperature between 140 and 400°C, a pressure partial hydrogen between 1.0 and 10.0 MPa abs. and an hourly volume rate between 0.1 and 10.0 h′ 1 , the temperature at the outlet of the reaction section of step a) being at least 15° C.
• a hydrotreating step implemented in a hydrotreating reaction section, implementing at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrotreatment catalyst, said hydrotreatment reaction section being fed at least by said hydrogenated effluent from step a) and a gas stream comprising hydrogen, said reaction section d the hydrotreatment being implemented at an average temperature between 250 and 430° C., a partial pressure of hydrogen between 1.0 and 10.0 MPa abs.
• a hydrotreated effluent b') optionally a hydrocracking stage implemented in a hydrocracking reaction section, implementing at least one fixed bed having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed at least by said hydrotreated effluent from step b) and/or by the cut comprising compounds having a boiling point above 175° C from step d) and a gas stream comprising hydrogen, said hydrocracking reaction section being implemented at an average temperature between 250 and 450° C., a partial pressure of hydrogen between 1.5 and 20.0 MPa abs.
• step c) a stage of separation, supplied with the hydrotreated effluent from the step b) or by the hydrocracked effluent from step b') and an aqueous solution, said step being carried out at a temperature between 50 and 370° C., to obtain at least one gaseous effluent, one aqueous effluent and one hydrocarbon effluent, d) optionally a step of fractionating all or part of the hydrocarbon effluent from step c), to obtain at least one gaseous effluent and at least at least one cut comprising compounds having a lower or equal boiling point at 175°C and a hydrocarbon cut comprising compounds having a boiling point above 175°C.
• An advantage of the process according to the invention is to purify an oil resulting from the pyrolysis of plastic waste of at least a part of its impurities which makes it possible to hydrogenate it and thus to be able to valorize it in particular by incorporating it directly into the fuel storage unit or by making it compatible with treatment in a steam cracking unit in order to be able to obtain in particular light olefins with increased yields which can be used as monomers in the manufacture of polymers.
• Another advantage of the invention is to prevent risks of clogging and/or corrosion of the processing unit in which the method of the invention is implemented, the risks being exacerbated by the presence, often in large quantities , diolefins, metals and halogenated compounds in plastics pyrolysis oil.
• the process of the invention thus makes it possible to obtain a hydrocarbon effluent resulting from a plastic pyrolysis oil freed at least in part of the impurities of the starting plastic pyrolysis oil, thus limiting the problems of operability, such as the problems of corrosion, coking or catalytic deactivation, which these impurities can cause, in particular in the steam cracking units and/or in the units located downstream of the steam cracking units, in particular the polymerization and hydrogenation units.
• the elimination of at least part of the impurities of the oils resulting from the pyrolysis of plastic waste will also make it possible to increase the range of applications of the target polymers, the incompatibilities of uses being reduced.
• the method comprises step d).
• the method comprises step b′).
• the quantity of the gas stream comprising hydrogen supplying said reaction section of step a) is such that the hydrogen coverage is between 50 and 1000 Nm 3 of hydrogen per m 3 of charge (Nm 3 /m 3 ), and preferably between 200 and 300 Nm 3 of hydrogen per m 3 of charge (Nm 3 /m 3 ).
• the temperature at the outlet of step a) is at least 30° C. higher than the temperature at the inlet of step a).
• at least a fraction of the hydrocarbon effluent resulting from stage c) of separation or at least a fraction of the naphtha cut comprising compounds having a boiling point less than or equal to 175° C. resulting from the step d) of fractionation is sent to step a) of hydrogenation and/or step b) of hydrotreatment.
• At least a fraction of the cut comprising compounds having a boiling point above 175° C. resulting from stage d) of fractionation is sent to stage a) of hydrogenation and/or the stage b) of hydrotreating and/or stage b′) of hydrocracking.
• the method comprises a step aO) of pretreatment of the feed comprising a plastic pyrolysis oil, said pretreatment step being implemented upstream of step a) of hydrogenation and comprises a step of filtration and /or an electrostatic separation step and/or a washing step using an aqueous solution and/or an adsorption step.
• the hydrocarbon effluent resulting from step c) of separation, or at least one of the two liquid hydrocarbon stream(s) resulting from step d), is in whole or in part sent to a step e) of steam cracking carried out in at least one pyrolysis furnace at a temperature of between 700 and 900° C. and at a pressure of between 0.05 and 0.3 relative MPa.
• reaction section of step a) implements at least two reactors operating in switchable mode.
• a stream containing an amine is injected upstream of step a).
• said hydrogenation catalyst comprises a support chosen from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof and a hydro-dehydrogenating function comprising either at least one element from group VIII and at least one element from group VIB, or at least one element from group VIII.
• said hydrotreating catalyst comprises a support chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof, and a hydro-dehydrogenating function comprising at least one element from group VIII and/or at least one element from group VIB.
• the process further comprises a second hydrocracking stage b”) implemented in a hydrocracking reaction section, implementing at least one fixed bed having n catalytic beds, n being an integer greater than or equal to at 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed by the cut comprising compounds having a boiling point above 175° C. resulting from stage d) and a gas stream comprising hydrogen, said hydrocracking reaction section being carried out at a temperature between 250 and 450°C, a hydrogen partial pressure between 1.5 and 20.0 MPa abs. and an hourly volumetric speed between 0.1 and 10.0 h' 1 , to obtain a hydrocracked effluent which is sent to stage c) of separation.
• a second hydrocracking stage b implemented in a hydrocracking reaction section, implementing at least one fixed bed having n catalytic beds, n being an integer greater than or equal to at 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being fed by the cut comprising compounds
• said hydrocracking catalyst comprises a support chosen from halogenated aluminas, combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites and a hydro-dehydrogenating function comprising at least one metal of group VIB chosen from chromium, molybdenum and tungsten, alone or as a mixture, and/or at least one group VIII metal chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum .
• the invention also relates to the product capable of being obtained, and preferably obtained by the process according to the invention.
• the product comprises in relation to the total weight of the product:
• the pressures are absolute pressures, also denoted abs., and are given in absolute MPa (or MPa abs.), unless otherwise indicated.
• the expressions "between .... and " and “between .... and " are equivalent and mean that the limit values of the interval are included in the range of values described . If this was not the case and the limit values were not included in the range described, such precision will be provided by the present invention.
• the different parameter ranges for a given step such as the pressure ranges and the temperature ranges can be used alone or in combination.
• a range of preferred pressure values can be combined with a range of more preferred temperature values.
• particular and/or preferred embodiments of the invention can be described. They may be implemented separately or combined with each other, without limitation of combination when technically feasible.
• group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IIIPAC classification.
• the metal content is measured by X-ray fluorescence.
• a “plastic pyrolysis oil” is an oil, advantageously in liquid form at ambient temperature, resulting from the pyrolysis of plastics, preferably plastic waste originating in particular from collection and sorting channels. It can also come from the pyrolysis of used tires.
• hydrocarbon compounds in particular paraffins, mono- and/or di-olefins, naphthenes and aromatics. At least 80% by weight of these hydrocarbon compounds preferably have a boiling point below 700°C, and more preferably below 550°C. In particular, depending on the origin of the pyrolysis oil, it may comprise up to 70% by weight of paraffins, up to 90% by weight of olefins and up to 90% by weight of aromatics, it being understood that the sum of paraffins, olefins and aromatics is 100% weight of hydrocarbon compounds.
• the density of the pyrolysis oil measured at 15° C. according to the ASTM D4052 method, is generally between 0.75 and 0.99 g/cm 3 , preferably between 0.75 and 0.95 g/cm 3 .
• the plastics pyrolysis oil can also comprise, and most often comprises, impurities such as metals, in particular iron, silicon, halogenated compounds, in particular chlorinated compounds. These impurities may be present in the plastic pyrolysis oil at high levels, for example up to 350 ppm by weight or even 700 ppm by weight or even 1000 ppm by weight of halogen elements (in particular chlorine) provided by halogenated compounds, and up to 100 ppm by weight, or even 200 ppm by weight of metallic or semi-metallic elements. Alkali metals, alkaline earth metals, transition metals, poor metals and metalloids can be assimilated to contaminants of a metallic nature, called metals or metallic or semi-metallic elements.
• the metals or metallic or semi-metallic elements possibly contained in the oils resulting from the pyrolysis of plastic waste, comprise silicon, iron or these two elements.
• the plastic pyrolysis oil may also include other impurities such as heteroelements provided in particular by sulfur compounds, oxygenated compounds and/or nitrogen compounds, at levels generally below 10,000 ppm by weight of heteroelements and preferably below at 4000 ppm weight of heteroelements.
• the charge of the process according to the invention comprises at least one plastic pyrolysis oil.
• Said charge may consist solely of plastic pyrolysis oil(s).
• said charge comprises at least 50% by weight, preferably between 70 and 100% by weight, of plastic pyrolysis oil relative to the total weight of the charge, that is to say preferably between 50 and 100% by weight, preferably between 70% and 100% by weight of plastic pyrolysis oil.
• the feedstock of the process according to the invention can comprise, in addition to plastic pyrolysis oil or oils, a conventional petroleum feedstock or a feedstock resulting from the conversion of biomass which is then co-treated with the pyrolysis oil. of plastics from the load.
• the conventional petroleum feed can advantageously be a cut or a mixture of naphtha, gas oil or vacuum gas oil type cuts.
• the feed resulting from the conversion of the biomass can advantageously be chosen from vegetable oils, algae or algal oils, fish oils, used food oils, and fats of vegetable or animal origin; or mixtures of such fillers.
• Said vegetable oils can advantageously be raw or refined, totally or partly, and derived from plants chosen from rapeseed, sunflower, soy, palm, olive, coconut, copra, castor, cotton , peanut, linseed and crambe oils and all oils derived, for example, from sunflower or rapeseed by genetic modification or hybridization, this list not being exhaustive.
• Said animal fats are advantageously chosen from lard and fats composed of residues from the food industry or from catering industries. Frying oils, various animal oils such as fish oils, tallow, lard can also be used.
• the feed resulting from the conversion of the biomass can also be chosen from feeds resulting from thermal or catalytic conversion processes of biomass, such as oils which are produced from biomass, in particular from biomass lignocellulosic, with various liquefaction methods, such as hydrothermal liquefaction or pyrolysis.
• biomass refers to material derived from recently living organisms, which includes plants, animals and their by-products.
• lignocellulosic biomass refers to biomass derived from plants or their by-products. Lignocellulosic biomass is composed of carbohydrate polymers (cellulose, hemicellulose) and an aromatic polymer (lignin).
• the feed resulting from the conversion of the biomass can also advantageously be chosen from feeds resulting from the paper industry.
• Plastic pyrolysis oil can come from a thermal or catalytic pyrolysis treatment or even be prepared by hydropyrolysis (pyrolysis in the presence of a catalyst and hydrogen).
• Said charge comprising a plastics pyrolysis oil can advantageously be pretreated in an optional pretreatment step aO), prior to step a) of hydrogenation, to obtain a pretreated charge which feeds step a).
• This optional pretreatment step aO) makes it possible to reduce the quantity of contaminants, in particular the quantity of iron and/or silicon and/or chlorine, possibly present in the charge comprising a plastic pyrolysis oil.
• an optional step aO) of pretreatment of the charge comprising a plastic pyrolysis oil is advantageously carried out in particular when said charge comprises more than 10 ppm by weight, in particular more than 20 ppm by weight, more particularly more than 50 ppm by weight of metallic elements, and in particular when said filler comprises more than 5 ppm by weight of silicon, more particularly more than 10 ppm by weight, or even more than 20 ppm by weight of silicon.
• an optional step aO) of pretreating the charge comprising a plastic pyrolysis oil is advantageously carried out in particular when said charge comprises more than 10 ppm by weight, in particular more than 20 ppm by weight, more particularly more than 50 ppm by weight of chlorine.
• Said optional pretreatment step aO) can be implemented by any method known to those skilled in the art which makes it possible to reduce the quantity of contaminants. It may in particular comprise a filtration step and/or an electrostatic separation step and/or a washing step using an aqueous solution and/or an adsorption step. Said optional pretreatment step aO) is advantageously carried out at a temperature between 0 and 150° C., preferably between 5 and 100° C., and at a pressure between 0.15 and 10.0 MPa abs, preferably between 0 .2 and 1.0 MPa abs.
• said optional pretreatment step aO) is implemented in an adsorption section operated in the presence of at least one adsorbent, preferably of the alumina type, having a specific surface greater than or equal to 100 m 2 /g , preferably greater than or equal to 200 m 2 /g.
• the specific surface of said at least one adsorbent is advantageously less than or equal to 600 m 2 /g, in particular less than or equal to 400 m 2 /g.
• the specific surface of the adsorbent is a surface measured by the BET method, i.e. the specific surface determined by nitrogen adsorption in accordance with the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT method.
• said adsorbent comprises less than 1% by weight of metallic elements, preferably is free of metallic elements.
• metallic elements adsorbent means the elements of groups 6 to 10 of the periodic table of elements (new IUPAC classification)
• the residence time of the filler in the adsorbent section is generally between 1 and 180 minutes.
• Said adsorption section of optional step aO) comprises at least one adsorption column, preferably comprises at least two adsorption columns, preferably between two and four adsorption columns, containing said adsorbent.
• an operating mode can be a so-called "swing" operation, according to the accepted Anglo-Saxon term, in which one of the columns is in line, i.e. ie in operation, while the other column is in reserve.
• the absorbent of the online column is used, this column is isolated while the column in reserve is put online, that is to say in operation.
• the spent absorbent can then be regenerated in situ and/or replaced with fresh absorbent so that the column containing it can be brought back online once the other column has been isolated.
• Another mode of operation is to have at least two columns operating in series. When the absorbent of the column placed at the head is used up, this first column is isolated and the used absorbent is either regenerated in situ or replaced by fresh absorbent. The column is then brought back in line in the last position and so on.
• This operation is called permutable mode, or according to the English term "PRS" for Permutable Reactor System or even “lead and lag” according to the Anglo-Saxon term.
• the association of at least two adsorption columns makes it possible to overcome poisoning and/or clogging possible and possibly fast adsorbent under the joint action of metal contaminants, diolefins, gums from diolefins and insolubles possibly present in the pyrolysis oil of plastics to be treated.
• the presence of at least two adsorption columns in fact facilitates the replacement and/or regeneration of the adsorbent, advantageously without stopping the pretreatment unit, or even the process, thus making it possible to reduce the risks of clogging and therefore avoid unit shutdown due to clogging, control costs and limit adsorbent consumption.
• said optional pretreatment step aO) is implemented in a washing section with an aqueous solution, for example water or an acid or basic solution.
• This washing section may include equipment making it possible to bring the load into contact with the aqueous solution and to separate the phases so as to obtain the pretreated load on the one hand and the aqueous solution comprising impurities on the other hand.
• this equipment there may for example be a stirred reactor, a settler, a mixer-settler and/or a co- or counter-current washing column.
• Said optional pretreatment step aO) can also optionally be supplied with at least a fraction of a recycle stream, advantageously from step d) of the process, mixed with or separately from the feed comprising a plastic pyrolysis oil.
• Said optional pretreatment step aO) thus makes it possible to obtain a pretreated feed which then feeds the hydrogenation step a).
• the process comprises a step a) of hydrogenation implemented in a hydrogenation reaction section, implementing at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one hydrogenation catalyst, said hydrogenation reaction section being fed at least by said charge and a gas stream comprising hydrogen, said hydrogenation reaction section being implemented at an average temperature between 140 and 400° C., a partial pressure of hydrogen between 1.0 and 10.0 MPa abs. and an hourly volume rate between 0.1 and 10.0 h′ 1 , the temperature at the outlet of the reaction section of step a) being at least 15° C. higher than the temperature at the inlet of the reaction section of the step a), to obtain a hydrogenated effluent.
• Stage a) is in particular carried out under conditions of hydrogen pressure and temperature making it possible to carry out the hydrogenation of the diolefins and of the olefins at the start of the hydrogenation reaction section while allowing a rising temperature profile so that the temperature at the outlet of the reaction section of step a) is at least 15° C. higher than the temperature at the inlet of the section reaction of step a).
• a necessary quantity of hydrogen is injected so as to allow the hydrogenation of at least some of the diolefins and olefins present in the plastic pyrolysis oil, the hydrodemetallization of at least some of the metals , in particular the retention of the silicon, and also the conversion of at least a part of the chlorine (into HCl).
• the hydrogenation of diolefins and olefins thus makes it possible to avoid or at least limit the formation of "gums", that is to say the polymerization of diolefins and olefins and therefore the formation of oligomers and polymers, which can plug the reaction section of step b) hydrotreatment.
• the hydrodemetallization, and in particular the retention of the silicon during stage a makes it possible to limit the catalytic deactivation of the reaction section of stage b) of hydrotreatment.
• the conditions of step a) in particular the temperature and its rising profile, make it possible to convert at least part of the chlorine.
• Temperature control is therefore important in this step and must respond to an antagonistic constraint.
• the temperature at the inlet and throughout the hydrogenation reaction section must be low enough to allow the hydrogenation of diolefins and olefins at the start of the hydrogenation reaction section.
• the inlet temperature of the hydrogenation reaction section must be high enough to avoid catalyst deactivation.
• the hydrogenation reactions, in particular of some of the olefins and diolefins, being highly exothermic a rising temperature profile is then observed in the hydrogenation reaction section. This higher temperature at the end of said section makes it possible to carry out the hydrodemetallization and hydrodechlorination reactions.
• the temperature at the outlet of the reaction section of step a) is at least higher by 15° C., preferably at least higher than 25° C. and in a particularly preferred manner at least higher than 30° C. entrance to the reaction section of step a).
• the temperature difference between the inlet and the outlet of the reaction section of step a) is understood with the possible injection of any gaseous (hydrogen) or liquid cooling stream (for example the recycling of a stream coming from steps c) and/or d).
• the temperature difference between the inlet and the outlet of the reaction section of step a) is exclusively due to the exothermicity of the chemical reactions carried out in the reaction section and therefore means excluding the use of a heating means ( furnace, heat exchanger etc).
• the temperature at the inlet of the reaction section of step a) is between 135 and 385°C, preferably between 210 and 335°C.
• the temperature at the outlet of the reaction section of step a) is between 150 and 400°C, preferably between 225 and 350°C.
• the invention it is advantageous to carry out the hydrogenation of the diolefins and part of the hydrotreatment reactions in the same stage and at a temperature sufficient to limit the deactivation of the catalyst of stage a) which is manifested by a drop the conversion of diolefins.
• This same step also makes it possible to benefit from the heat of hydrogenation reactions, in particular of a part of the olefins and diolefins, so as to have a temperature profile rising in this step and thus being able to eliminate the need for a heating device. between the catalytic hydrogenation section and the catalytic hydrotreating section.
• Said reaction section implements hydrogenation in the presence of at least one hydrogenation catalyst, advantageously at an average temperature (or WABT as defined below) between 140 and 400° C., preferably between 220 and 350° C. , and particularly preferably between 260 and 330° C., a partial pressure of hydrogen between 1.0 and 10.0 MPa abs, preferably between 1.5 and 8.0 MPa abs and at an hourly volumetric speed ( WH) between 0.1 and 10.0 h′ 1 , preferably between 0.2 and 5.0 h′ 1 , and very preferably between 0.3 and 3.0 h′ 1 .
• an average temperature or WABT as defined below
• WABT average temperature
• WH hourly volumetric speed
• the “average temperature” of a reaction section corresponds to the Weight Average Bed Temperature (WABT) according to the established Anglo-Saxon term, well known to those skilled in the art.
• WABT Weight Average Bed Temperature
• the average temperature is advantageously determined according to the catalytic systems, the equipment, the configuration thereof, used.
• the average temperature (or WABT) is calculated as follows:
• WABT (Tin + Tj ftt jj iS )/2 with Tin: the temperature of the effluent at the inlet of the reaction section and Tout: the temperature of the effluent at the outlet of the reaction section.
• the hourly volume velocity (WH) is defined here as the ratio between the hourly volume flow of the feed comprising the plastics pyrolysis oil, possibly pretreated, by the volume of catalyst(s).
• the hydrogen coverage is defined as the ratio of the volume flow of hydrogen taken under normal conditions of temperature and pressure compared to the volume flow of "fresh" feed, that is to say the feed to be treated, possibly pretreated, without taking into account any recycled fraction, at 15° C. (in normal m 3 , denoted Nm 3 , of H2 per m 3 charging).
• the quantity of the gas stream comprising hydrogen (H2), supplying said reaction section of step a), is advantageously such that the hydrogen coverage is between 50 and 1000 Nm 3 of hydrogen per m 3 of charge ( Nm 3 /m 3 ), preferably between 50 and 500 Nm 3 of hydrogen per m 3 of charge (Nm 3 /m 3 ), preferably between 200 and 300 Nm 3 of hydrogen per m 3 of charge (Nm 3 /m 3 ).
• the quantity of hydrogen necessary allowing the hydrogenation of at least a part of the diolefins and olefins and the hydrodemetallization of at least a part of the metals, in particular the retention of silicon, and also the conversion of at least part of the chlorine (in HCl) is greater than the quantity of hydrogen necessary to carry out the hydrogenation of diolefins as described in FR20/01.758.
• the hydrogenation reaction section of step a) is fed at least by said feed comprising an oil from the pyrolysis of plastics, or by the pretreated feed resulting from the optional pretreatment step aO), and a gas stream comprising hydrogen (H2).
• the reaction section of said step a) can also be additionally supplied with at least a fraction of a recycle stream, advantageously from step c) or from optional step d).
• the reaction section of said step a) comprises between 1 and 5 reactors, preferably between 2 and 5 reactors, and particularly preferably it comprises two reactors.
• the advantage of a hydrogenation reaction section comprising several reactors lies in an optimized treatment of the charge, while making it possible to reduce the risks of clogging of the catalytic bed(s) and therefore to avoid stopping the unit due to to clogging.
• these reactors operate in permutable mode, called according to the English term “PRS” for Permutable Reactor System or even “lead and lag”.
• PRS Permutable Reactor System
• the association of at least two reactors in PRS mode makes it possible to isolate a reactor, to unload the spent catalyst, to reload the reactor with fresh catalyst and to put the said reactor back into service without stopping the process.
• PRS technology is described, in particular, in patent FR2681871.
• the hydrogenation reaction section of step a) comprises two reactors operating in switchable mode.
• reactor internals for example of the filter plate type, can be used to prevent clogging of the reactor(s).
• An example of a filter plate is described in patent FR3051375.
• said hydrogenation catalyst comprises a support, preferably mineral, and a hydro-dehydrogenating function.
• the hydro-dehydrogenating function comprises in particular at least one element from group VIII, preferably chosen from nickel and cobalt, and at least one element from group VI B, preferably chosen from molybdenum and tungsten.
• the total content expressed as oxides of the metal elements of groups VI B and VIII is preferably between 1% and 40% by weight, preferably from 5% to 30% by weight relative to the total weight of the catalyst.
• the metal content is expressed as CoO and NiO respectively.
• the metal content is expressed as MoCh and WO3 respectively.
• the weight ratio expressed as metal oxide between the metal (or metals) of group VI B relative to the metal (or metals) of group VIII is preferably between 1 and 20, and preferably between 2 and 10.
• the reaction section of said step a) comprises for example a hydrogenation catalyst comprising between 0.5% and 12% by weight of nickel, preferably between 1% and 10% by weight of nickel (expressed as oxide of nickel NiO relative to the weight of said catalyst), and between 1% and 30% by weight of molybdenum, preferably between 3% and 20% by weight of molybdenum (expressed as molybdenum oxide MoOs relative to the weight of said catalyst) on preferably a mineral support, preferably on an alumina support.
• a hydrogenation catalyst comprising between 0.5% and 12% by weight of nickel, preferably between 1% and 10% by weight of nickel (expressed as oxide of nickel NiO relative to the weight of said catalyst), and between 1% and 30% by weight of molybdenum, preferably between 3% and 20% by weight of molybdenum (expressed as molybdenum oxide MoOs relative to the weight of said catalyst) on preferably a mineral support, preferably on an alumina support.
• the hydro-dehydrogenating function comprises, and preferably consists of at least one element from group VIII, preferably nickel.
• the nickel oxide content is preferably between 1 and 50% by weight, preferably between 10% and 30% by weight relative to the weight of said catalyst.
• This type of catalyst is preferably used in its reduced form, preferably on a mineral support, preferably on an alumina support.
• the support for said hydrogenation catalyst is preferably chosen from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof.
• Said support may contain doping compounds, in particular oxides chosen from boron oxide, in particular boron trioxide, zirconia, ceria, titanium oxide, anhydride phosphoric and a mixture of these oxides.
• said hydrogenation catalyst comprises an alumina support, optionally doped with phosphorus and optionally boron.
• phosphoric anhydride P2O5 When phosphoric anhydride P2O5 is present, its concentration is less than 10% by weight relative to the weight of the alumina and advantageously at least 0.001% by weight relative to the total weight of the alumina.
• boron trioxide B2O3 When boron trioxide B2O3 is present, its concentration is less than 10% by weight relative to the weight of the alumina and advantageously at least 0.001% relative to the total weight of the alumina.
• the alumina used may for example be a y (gamma) or q (eta) alumina.
• Said hydrogenation catalyst is for example in the form of extrudates.
• step a) can implement, in addition to the hydrogenation catalyst(s) described above, in addition at least one hydrogenation catalyst used in step a) comprising less than 1% by weight of nickel and at least 0.1% by weight of nickel, preferably 0.5% by weight of nickel, expressed as nickel oxide NiO relative to the weight of said catalyst, and less than 5% by weight of molybdenum and at least 0, 1% by weight of molybdenum, preferably 0.5% by weight of molybdenum, expressed as molybdenum oxide MoOs relative to the weight of said catalyst, on an alumina support.
• This catalyst with a low metal content can preferably be placed upstream or downstream of the hydrogenation catalyst(s) described above.
• Said step a) of hydrogenation makes it possible to obtain a hydrogenated effluent, that is to say an effluent with a reduced content of olefins, in particular of diolefins, and of metals, in particular of silicon.
• the content of impurities, in particular of diolefins, of the hydrogenated effluent obtained at the end of stage a) is reduced compared to that of the same impurities, in particular of diolefins, included in the charge of the process.
• Stage a) of hydrogenation generally makes it possible to convert at least 40%, and preferably at least 60% of the diolefins as well as at least 40%, and preferably at least 60% of the olefins contained in the initial charge.
• Step a) also allows the elimination, at least in part, of other contaminants, such as, for example, silicon and chlorine.
• other contaminants such as, for example, silicon and chlorine.
• at least 50%, and more preferably at least 75%, of the chlorine and silicon of the initial charge are eliminated during step a).
• the hydrogenated effluent obtained at the end of stage a) of hydrogenation is sent, preferably directly, to stage b) of hydrotreatment.
• the treatment process comprises a step b) of hydrotreatment implemented in a hydrotreatment reaction section, implementing at least one fixed-bed reactor having n catalytic beds, n being an integer greater than or equal to 1 , each comprising at least one hydrotreating catalyst, said hydrotreating reaction section being fed at least by said hydrogenated effluent from step a) and a gas stream comprising hydrogen, said hydrotreating reaction section being placed in works at an average temperature between 250 and 430° C., a partial pressure of hydrogen between 1.0 and 10.0 MPa abs. and an hourly volume rate between 0.1 and 10.0 h- 1 , the average temperature of the reaction section of stage b) being higher than the average temperature of the hydrogenation reaction section of stage a), to obtain a hydrotreated effluent.
• step b) implements the hydrotreatment reactions well known to those skilled in the art, and more particularly hydrotreatment reactions such as the hydrogenation of aromatics, hydrodesulphurization and hydrodenitrogenation.
• hydrotreatment reactions such as the hydrogenation of aromatics, hydrodesulphurization and hydrodenitrogenation.
• the hydrogenation of the remaining olefins and halogenated compounds as well as the hydrodemetallization are continued.
• Said hydrotreatment reaction section is advantageously carried out at a pressure equivalent to that used in the reaction section of stage a) of hydrogenation, but at an average temperature higher than that of the reaction section of stage a. ) hydrogenation.
• said hydrotreatment reaction section is advantageously implemented at an average hydrotreatment temperature between 250 and 430° C., preferably between 280 and 380° C., at a partial pressure of hydrogen between 1.0 and 10, 0 MPa abs. and at an hourly volume rate (WH) between 0.1 and 10.0 h' 1 , preferably between 0.1 and 5.0 h' 1 , preferably between 0.2 and 2.0 h' 1 , so preferably between 0.2 and 1 hour 1 .
• WH hourly volume rate
• the hydrogen coverage in stage b) is advantageously between 50 and 1000 Nm 3 of hydrogen per m 3 of fresh charge which supplies stage a), and preferably between 50 and 500 Nm 3 of hydrogen per m 3 of fresh feed which feeds stage a), preferably between 100 and 300 Nm 3 of hydrogen per m 3 of fresh feed which feeds stage a).
• the definitions of mean temperature (WABT), WH and hydrogen coverage correspond to those described above.
• Said hydrotreating reaction section is supplied at least with said hydrogenated effluent from step a) and a gas stream comprising hydrogen, advantageously at the level of the first catalytic bed of the first reactor in operation.
• the reaction section of said step b) can also be additionally supplied with at least a fraction of a recycle stream, advantageously from step c) or from optional step d).
• said step b) is implemented in a hydrotreating reaction section comprising at least one, preferably between one and five, fixed-bed reactor(s) having n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, preferably between two and five, said bed(s) each comprising at least one, and preferably not more than ten, catalyst(s) d hydrotreating.
• a reactor comprises several catalytic beds, that is to say at least two, preferably between two and ten, preferably between two and five catalytic beds, said catalytic beds are preferably arranged in series in said reactor.
• step b) When step b) is implemented in a hydrotreating reaction section comprising several, preferably two reactors, these reactors can operate in series and/or in parallel and/or in switchable mode (or PRS) and/or in swing mode.
• PRS switchable mode
• swing mode The various possible operating modes, PRS (or lead and lag) mode and swing mode, are well known to those skilled in the art and are advantageously defined above.
• said hydrotreating reaction section comprises a single fixed-bed reactor containing n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, so favorite between two and five.
• the hydrogenation reaction section of stage a) comprises two reactors operating in switchable mode followed by the hydrotreating reaction section of stage b) which comprises a single fixed-bed reactor.
• said hydrotreating catalyst used in said step b) can be chosen from known catalysts for hydrodemetallization, hydrotreating, silicon capture, used in particular for the treatment of petroleum cuts, and combinations thereof.
• Known hydrodemetallization catalysts are for example those described in patents EP 0113297, EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463.
• Known hydrotreating catalysts are for example those described in patents EP 0113297, EP 0113284, US 6589908, US 4818743 or US 6332976.
• Known silicon capture catalysts are for example those described in patent applications CN 102051202 and US 2007/080099.
• said hydrotreating catalyst comprises a support, preferably mineral, and at least one metallic element having a hydro-dehydrogenating function.
• Said metallic element having a hydro-dehydrogenating function advantageously comprises at least one element from group VIII, preferably chosen from the group consisting of nickel and cobalt, and/or at least one element from group VI B, preferably chosen from the group group consisting of molybdenum and tungsten.
• the total content, expressed as oxides, of the metal elements of groups VIB and VIII is preferably between 0.1% and 40% by weight, preferably from 5% to 35% by weight, relative to the total weight of the catalyst. When the metal is cobalt or nickel, the metal content is expressed as CoO and NiO respectively.
• the metal content is expressed as MoOs and WO3 respectively.
• the weight ratio expressed as metal oxide between the metal (or metals) of group VIB relative to the metal (or metals) of group VIII is preferably between 1.0 and 20, preferably between 2.0 and 10
• the hydrotreating reaction section of step b) of the process comprises a hydrotreating catalyst comprising between 0.5% and 10% by weight of nickel, preferably between 1% and 8% by weight of nickel.
• nickel oxide NiO nickel oxide relative to the total weight of the hydrotreating catalyst
• molybdenum preferably between 3.0% and 29% by weight of molybdenum, expressed as oxide of molybdenum MoOs relative to the total weight of the hydrotreating catalyst, on a mineral support, preferably on an alumina support.
• the support for said hydrotreating catalyst is advantageously chosen from alumina, silica, silica-aluminas, magnesia, clays and mixtures thereof.
• Said support may also contain doping compounds, in particular oxides chosen from boron oxide, in particular boron trioxide, zirconia, ceria, titanium oxide, phosphoric anhydride and a mixture of these oxides.
• said hydrotreating catalyst comprises an alumina support, preferably an alumina support doped with phosphorus and optionally boron.
• phosphoric anhydride P2O5 When phosphoric anhydride P2O5 is present, its concentration is less than 10% by weight relative to the weight of the alumina and advantageously at least 0.001% by weight relative to the total weight of the alumina.
• boron trioxide B2O3 When boron trioxide B2O3 is present, its concentration is less than 10% by weight relative to the weight of the alumina and advantageously at least 0.001% relative to the total weight of the alumina.
• the alumina used may for example be a y (gamma) or (eta) alumina.
• Said hydrotreating catalyst is for example in the form of extrudates.
• said hydrotreating catalyst used in step b) of the process has a specific surface area greater than or equal to 250 m 2 /g, preferably greater than or equal to 300 m 2 /g.
• the specific surface of said hydrotreating catalyst is advantageously less than or equal to 800 m 2 /g, preferably less than or equal to 600 m 2 /g, in particular less than or equal to 400 m 2 /g.
• the specific surface of the hydrotreating catalyst is measured by the BET method, i.e. the specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the periodical 'The Journal of the American Chemical Society', 6Q, 309 (1938).
• Such a surface specific allows to further improve the elimination of contaminants, in particular metals such as silicon.
• the hydrotreating catalyst as described above further comprises one or more organic compounds containing oxygen and/or nitrogen and/or sulfur.
• a catalyst is often designated by the term "additive catalyst".
• the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or even compounds including a furan ring or even sugars.
• stage b) of hydrotreatment allows the hydrogenation of at least 80%, and preferably of all of the olefins remaining after stage a) of hydrogenation, but also the conversion at least in part of other impurities present in the charge, such as aromatic compounds, metal compounds, sulfur compounds, nitrogen compounds, halogenated compounds (in particular chlorinated compounds), oxygenated compounds.
• the nitrogen content at the outlet of step b) is less than 10 ppm by weight.
• Step b) can also make it possible to further reduce the content of contaminants, such as that of metals, in particular the silicon content.
• the metal content at the outlet of step b) is less than 10 ppm by weight, and preferably less than 2 ppm by weight, and the silicon content is less than 5 ppm by weight.
• the process of the invention may comprise a hydrocracking step b′) carried out either directly after step b) of hydrotreating, or after step d) of fractionation on a hydrocarbon cut comprising compounds having a boiling point above 175°C (diesel cut).
• step b′) implements the hydrocracking reactions well known to those skilled in the art, and more particularly makes it possible to convert the heavy compounds, for example compounds having a boiling point above 175° C. into compounds having a boiling point less than or equal to 175° C. contained in the hydrotreated effluent resulting from stage b) or separated during fractionation stage d).
• Other reactions such as hydrogenation of olefins, aromatics, hydrodemetallation, hydrodesulfurization, hydrodenitrogenation, etc. can continue.
• Compounds with a boiling point above 175°C have a high BMCI and contain, compared to lighter compounds, more naphthenic, naphtheno-aromatic and aromatic compounds, thus leading to a higher C/H ratio.
• the process of the invention may comprise a step b′) of hydrocracking implemented in a hydrocracking reaction section, implementing at least one fixed bed having n catalytic beds, n being an integer greater than or equal to to 1, each comprising at least one hydrocracking catalyst, said hydrocracking reaction section being supplied with said hydrotreated effluent from step b) and/or with the cut comprising compounds having a boiling point greater than 175 °C from step d) and a gas stream comprising hydrogen, said hydrocracking reaction section being implemented at an average temperature between 250 and 450°C, a partial pressure of hydrogen between 1.5 and 20.0 MPa abs. and an hourly volumetric speed between 0.1 and 10.0 h' 1 , to obtain a hydrocracked effluent which is sent to stage d) of fractionation.
• said hydrocracking reaction section is advantageously implemented at an average temperature between 250 and 480° C., preferably between 320 and 450° C., at a partial pressure of hydrogen between 1.5 and 20.0 MPa abs ., preferably between 2 and 18.0 MPa abs, and at an hourly volume velocity (WH) between 0.1 and 10.0 h' 1 , preferably between 0.1 and 5.0 h' 1 , preferably between 0.2 and 4 h'1 .
• the hydrogen coverage in stage c) is advantageously between 80 and 2000 Nm 3 of hydrogen per m 3 of fresh charge which supplies stage a), and preferably between 200 and 1800 Nm 3 of hydrogen per m 3 of fresh load which supplies step a).
• the definitions of mean temperature (WABT), WH and hydrogen coverage correspond to those described above.
• said hydrocracking reaction section is implemented at a pressure equivalent to that used in the reaction section of stage a) of hydrogenation or of stage b) of hydrotreatment.
• said step b′) is implemented in a hydrocracking reaction section comprising at least one, preferably between one and five, fixed-bed reactor(s) having n catalytic beds, n being an integer greater than or equal to to one, preferably between one and ten, preferably between two and five, said bed(s) each comprising at least one, and preferably not more than ten, hydrocracking catalyst(s).
• a reactor comprises several catalytic beds, that is to say at least two, preferably between two and ten, preferably between two and five catalytic beds, said catalytic beds are preferably arranged in series in said reactor.
• Stage b) of hydrotreatment and stage b′) of hydrocracking can advantageously be carried out in the same reactor or in different reactors.
• the reactor comprises several catalytic beds, the first catalytic beds comprising the hydrotreating catalyst(s) and the following catalytic beds comprising the hydrocracking catalyst(s).
• the hydrocracking step can be carried out in one (step b') or two steps (step b') and b")).
• the effluent from the first hydrocracking stage b′) is separated, making it possible to obtain a cut comprising compounds having a boiling point above 175° C. (cut diesel) during steps c) and d), which is introduced into the second hydrocracking step b”) comprising a second dedicated hydrocracking reaction section, different from the first hydrocracking reaction section b′).
• This configuration is particularly suitable when it is desired to produce only a naphtha cut.
• the second hydrocracking stage b”) implemented in a hydrocracking reaction section, implementing at least one fixed bed having n catalytic beds, n being an integer greater than or equal to 1, each comprising at least one catalyst hydrocracking, said hydrocracking reaction section being fed by the cut comprising compounds having a boiling point above 175° C. resulting from step d) and a gas stream comprising hydrogen, said reaction section d hydrocracking being implemented at an average temperature between 250 and 450° C., a partial pressure of hydrogen between 1.5 and 20.0 MPa abs. and an hourly volume rate between 0.1 and 10.0 h ⁇ 1 , to obtain a hydrocracked effluent which is sent to stage c) of separation.
• the preferred operating conditions and catalysts used in the second hydrocracking stage are those described for the first hydrocracking stage.
• the operating conditions and catalysts used in the two hydrocracking stages can be identical or different.
• Said second hydrocracking step is preferably carried out in a hydrocracking reaction section comprising at least one, preferably between one and five, fixed-bed reactor(s) having n catalytic beds, n being an integer greater than or equal to one, preferably between one and ten, preferably between two and five, said bed(s) each comprising at least one, and preferably not more than ten, hydrocracking catalyst(s) .
• the hydrocracking step(s) thus does not necessarily make it possible to transform all the compounds having a boiling point above 175° C. (diesel cut) into compounds having a boiling point less than or equal to 175°C (naphtha cut). After fractionation step d), there may therefore remain a greater or lesser proportion of compounds with a boiling point above 175°C.
• at least part of this unconverted cut can be recycled as described below in stage b’) or even be sent to a second hydrocracking stage b”). Another part can be purged.
• said purge may be between 0 and 10% by weight of the cut comprising compounds having a boiling point above 175° C. relative to the incoming feed, and preferably between 0.5 % and 5% weight.
• the hydrocracking step(s) operate(s) in the presence of at least one hydrocracking catalyst.
• the hydrocracking catalyst(s) used in the hydrocracking step(s) are conventional hydrocracking catalysts known to those skilled in the art, of the bifunctional type combining an acid function with a hydro-dehydrogenating agent and optionally at least one binding matrix.
• the acid function is provided by supports with a large surface area (generally 150 to 800 m 2 /g) exhibiting surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites.
• the hydro-function dehydrogenating agent is provided by at least one metal from group VI B of the periodic table and/or at least one metal from group VIII.
• the hydrocracking catalyst(s) comprise a hydro-dehydrogenating function comprising at least one group VIII metal chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum, and preferably among cobalt and nickel.
• said catalyst(s) also comprise at least one metal from group VI B chosen from chromium, molybdenum and tungsten, alone or as a mixture, and preferably from molybdenum and tungsten.
• Hydro-dehydrogenating functions of the NiMo, NiMoW, NiW type are preferred.
• the group VIII metal content in the hydrocracking catalyst(s) is advantageously between 0.5 and 15% by weight and preferably between 1 and 10% by weight, the percentages being expressed as percentage by weight of oxides relative to the total weight of the catalyst.
• the metal is cobalt or nickel, the metal content is expressed as CoO and NiO respectively.
• the group VIB metal content in the hydrocracking catalyst(s) is advantageously between 5 and 35% by weight, and preferably between 10 and 30% by weight, the percentages being expressed as a percentage by weight of oxides relative to the total weight of the catalyst.
• the metal is molybdenum or tungsten
• the metal content is expressed as MoOs and WO3 respectively.
• the hydrocracking catalyst(s) may also optionally comprise at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (chlorine, preferred fluorine), optionally at least one element from group VIIB (preferred manganese), and optionally at least one element from group VB (preferred niobium).
• at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (chlorine, preferred fluorine), optionally at least one element from group VIIB (preferred manganese), and optionally at least one element from group VB (preferred niobium).
• the hydrocracking catalyst(s) comprise at least one amorphous or poorly crystallized porous mineral matrix of the oxide type chosen from aluminas, silicas, silica-aluminas, aluminates, alumina-boron oxide , magnesia, silica-magnesia, zirconia, titanium oxide, clay, alone or as a mixture, and preferably aluminas or silica-aluminas, alone or as a mixture.
• oxide type chosen from aluminas, silicas, silica-aluminas, aluminates, alumina-boron oxide , magnesia, silica-magnesia, zirconia, titanium oxide, clay, alone or as a mixture, and preferably aluminas or silica-aluminas, alone or as a mixture.
• the silica-alumina contains more than 50% weight of alumina, preferably more than 60% weight of alumina.
• the hydrocracking catalyst(s) also optionally comprise a zeolite chosen from Y zeolites, preferably from USY zeolites, alone or in combination, with other zeolites from beta zeolites, ZSM-12, IZM-2, ZSM-22, ZSM-23, SAPO-11, ZSM-48, ZBM-30, alone or as a mixture.
• zeolite is USY zeolite alone.
• the zeolite content in the hydrocracking catalyst(s) is advantageously between 0.1 and 80% by weight, preferably between 3 and 70% by weight, the percentages being expressed as a percentage of zeolite relative to the total weight of the catalyst.
• a preferred catalyst comprises, and preferably consists of, at least one Group VIB metal and optionally at least one non-noble Group VIII metal, at least one promoter element, and preferably phosphorus, at least one Y zeolite and at least one alumina binder.
• An even more preferred catalyst comprises, and preferably consists of, nickel, molybdenum, phosphorus, a USY zeolite, and optionally also a beta zeolite, and alumina.
• Another preferred catalyst includes, and preferably consists of, nickel, tungsten, alumina and silica-alumina.
• Another preferred catalyst includes, and preferably consists of, nickel, tungsten, USY zeolite, alumina and silica-alumina.
• Said hydrocracking catalyst is for example in the form of extrudates.
• the hydrocracking catalyst used in step b”) comprises a hydro-dehydrogenating function comprising at least one noble metal from group VIII chosen from palladium and platinum, alone or as a mixture.
• the noble metal content of group VIII is advantageously between 0.01 and 5% by weight and preferably between 0.05 and 3% by weight, the percentages being expressed as percentage by weight of oxides (PtO or PdO) relative to the weight total catalyst.
• the hydrocracking catalyst as described above further comprises one or more organic compounds containing oxygen and/or nitrogen and/or sulfur.
• a catalyst is often designated by the term "additive catalyst".
• the organic compound is chosen from a compound comprising one or more chemical functions chosen from a carboxylic function, alcohol, thiol, thioether, sulphone, sulphoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea and amide or even compounds including a furan ring or even sugars.
• the preparation of the catalysts of stages a), b), b') or b") is known and generally comprises a stage of impregnation of the metals of group VIII and of group VIB when it is present, and optionally phosphorus and/or or boron on the support, followed by drying, then optionally by calcination.
• the preparation is generally carried out by simple drying without calcination after introduction of the organic compound.
• calcination means a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200°C.
• the catalysts are generally subjected to sulfurization in order to form the active species.
• the catalyst of step a) can also be a catalyst used in its reduced form, thus involving a reduction step in its preparation.
• the gaseous flow comprising hydrogen, which feeds the reaction section of stage a), b), b') or b") may consist of a hydrogen make-up and/or recycled hydrogen obtained in particular of step c) of separation.
• an additional gas stream comprising hydrogen is advantageously introduced at the inlet of each reactor, in particular operating in series, and/or at the inlet of each catalytic bed from the second catalytic bed of the reaction section.
• These additional gas streams are also called cooling streams. They make it possible to control the temperature in the reactor in which the reactions implemented are generally very exothermic.
• each of the steps a), b), b’) or b”) can implement a heating section located upstream of the reaction section and in which the incoming effluent is heated to reach a suitable temperature.
• Said possible heating section may thus comprise one or more exchangers, preferably allowing heat exchange between the hydrotreated effluent and the hydrocracked effluent, and/or a preheating furnace.
• step a) at a relatively high average temperature with a rising profile possibly makes it possible to eliminate the need for a heating device or at least to reduce the caloric requirement between the catalytic hydrogenation section of step a) and the catalytic hydrotreating section of step b).
• the treatment method comprises a step c) of separation, advantageously implemented in at least one washing/separation section, fed at least by the hydrotreated effluent from step b), or the hydrocracked effluent from optional steps b′) and b′′), and an aqueous solution, to obtain at least one gaseous effluent, one aqueous effluent and one hydrocarbon effluent.
• the gaseous effluent obtained at the end of step c) advantageously comprises hydrogen, preferably comprises at least 80% by volume, preferably at least 85% by volume, of hydrogen.
• said gaseous effluent can at least partly be recycled to stages a) of hydrogenation and/or b) of hydrotreating and/or b′) of hydrocracking and/or b”) of hydrocracking, the system of recycling which may include a purification section.
• the aqueous effluent obtained at the end of step c) advantageously comprises ammonium salts and/or hydrochloric acid.
• This separation step c) makes it possible in particular to eliminate the ammonium chloride salts, which are formed by reaction between the chloride ions, released by the hydrogenation of the chlorinated compounds in the HCl form, in particular during steps a) and b). then dissolution in water, and the ammonium ions, generated by the hydrogenation of the nitrogenous compounds in the form of NH3 in particular during step b) and/or provided by injection of an amine then dissolution in water, and thus to limit the risks of clogging, in particular in the transfer lines and/or in the sections of the method of the invention and/or the transfer lines to the steam cracker, due to the precipitation of the ammonium chloride salts. It also eliminates the hydrochloric acid formed by the reaction of hydrogen ions and chloride ions.
• a stream containing an amine such as, for example, monoethanolamine, diethanolamine and/or monodiethanolamine can be injected upstream of stage a) of hydrogenation and/or or between stage a) of hydrogenation and stage b) of hydrotreatment and/or between stage b′) of hydrocracking and stage c) of separation, preferably upstream of stage a ) of hydrogenation in order to ensure a sufficient quantity of ammonium ions to combine the chloride ions formed during the hydrotreatment step, thus making it possible to limit the formation of hydrochloric acid and thus to limit corrosion downstream of the section of seperation.
• an amine such as, for example, monoethanolamine, diethanolamine and/or monodiethanolamine
• step c) of separation comprises an injection of an aqueous solution, preferably an injection of water, into the hydrotreated effluent from step b), or the hydrocracked effluent from steps b′). and b”) optional, upstream of the washing/separation section, so as to at least partially dissolve ammonium chloride salts and/or hydrochloric acid and thus improve the elimination of chlorinated impurities and reduce the risks of clogging due to an accumulation of ammonium chloride salts.
• Separation step c) is advantageously carried out at a temperature of between 50 and 450°C, preferably between 100 and 440°C, more preferably between 200 and 420°C.
• step c) of separation is carried out at a pressure close to that implemented in steps a) and/or b), preferably between 1.0 and 20.0 MPa, so as to facilitate the recycling of 'hydrogen.
• the washing/separation section of step c) can at least partly be carried out in common or separate washing and separation equipment, this equipment being well known (separator drums which can operate at different pressures and temperatures, pumps, heat exchangers heat pumps, washing columns, etc.).
• step c) of separation comprises the injection of an aqueous solution into the hydrotreated effluent from step b), followed by the washing/separation section advantageously comprising a separation phase making it possible to obtain at least one aqueous effluent charged with ammonium salts, a washed liquid hydrocarbon effluent and a partially washed gaseous effluent.
• the aqueous effluent charged with ammonium salts and the washed liquid hydrocarbon effluent can then be separated in a settling flask in order to obtain said hydrocarbon effluent and said aqueous effluent.
• Said partially washed gaseous effluent can be introduced in parallel into a washing column where it circulates countercurrent to an aqueous flow, preferably of the same nature as the aqueous solution injected into the hydrotreated effluent, which makes it possible to eliminate at least part, preferably entirely, of the hydrochloric acid contained in the partially washed gaseous effluent and thus obtaining said gaseous effluent, preferably comprising essentially hydrogen, and an acidic aqueous stream.
• Said aqueous effluent from the settling flask can optionally be mixed with said acid aqueous stream, and be used, optionally mixed with said acid aqueous stream in a water recycling circuit to supply stage c) of separation with said aqueous solution upstream of the washing/separation section and/or in said aqueous stream in the washing column.
• Said water recycling circuit may comprise a make-up of water and/or a basic solution and/or a drain allowing the dissolved salts to be evacuated.
• step c) of separation can advantageously comprise a "high pressure" washing/separation section which operates at a pressure close to the pressure of step a) of hydrogenation and/or of stage b) of hydrotreatment and/or of stage b′) of optional hydrocracking, preferably between 1.0 and 20.0 MPa, in order to facilitate the recycling of hydrogen.
• This possible "upper" section pressure" of step c) can be supplemented by a "low pressure” section, in order to obtain a liquid hydrocarbon fraction devoid of some of the gases dissolved at high pressure and intended to be treated directly in a steam cracking process or optionally be sent in step d) of splitting.
• the gas fraction(s) resulting from step c) of separation may (may) be subject to purification(s) and additional separation(s) with a view to recovering at least one gas rich in hydrogen which can be recycled upstream of stages a) and/or b) and/or b′) and/or b”) and/or light hydrocarbons, in particular ethane, propane and butane, which can advantageously be sent separately or as a mixture to one or more furnaces of step e) of steam cracking so as to increase the overall yield of olefins.
• the hydrocarbon effluent from step c) separation is sent, in part or in whole, either directly to the inlet of a steam cracking unit, or to an optional step d) fractionation.
• the liquid hydrocarbon effluent is sent, in part or in whole, preferably in whole, to a stage d) of fractionation.
• the method according to the invention may comprise a step of fractionating all or part, preferably all, of the hydrocarbon effluent from step c), to obtain at least one gas stream and at least two hydrocarbon streams liquids, said two liquid hydrocarbon streams being at least one naphtha cut comprising compounds having a boiling point less than or equal to 175°C, in particular between 80 and 175°C, and a hydrocarbon cut comprising compounds having a boiling above 175°C.
• Stage d) makes it possible in particular to eliminate the gases dissolved in the liquid hydrocarbon effluent, such as for example ammonia, hydrogen sulphide and light hydrocarbons having 1 to 4 carbon atoms.
• the optional fractionation step d) is advantageously carried out at a pressure of less than or equal to 1.0 MPa abs., preferably between 0.1 and 1.0 MPa abs.
• step d) can be carried out in a section advantageously comprising at least one stripping column equipped with a reflux circuit comprising a reflux drum.
• Said stripping column is fed by the liquid hydrocarbon effluent from step c) and by a stream of steam.
• the liquid hydrocarbon effluent from step c) can optionally be reheated before entering the stripping column.
• the lightest compounds are entrained at the top of the column and in the reflux circuit comprising a reflux drum in which a separation takes place gas/liquid.
• the gaseous phase which includes the light hydrocarbons, is withdrawn from the reflux drum, in a gas stream.
• the naphtha cut comprising compounds having a boiling point of less than or equal to 175° C. is advantageously withdrawn from the reflux drum.
• the hydrocarbon cut comprising compounds having a boiling point above 175° C. is advantageously drawn off at the bottom of the stripping column.
• step d) of fractionation can implement a stripping column followed by a distillation column or only a distillation column.
• the naphtha cut comprising compounds having a boiling point lower than or equal to 175°C and the cut comprising compounds having a boiling point higher than 175°C, optionally mixed, can be sent, in all or part, to a steam cracking unit, after which olefins can be (re)formed to participate in the formation of polymers.
• a steam cracking unit Preferably, only part of said cuts is sent to a steam cracking unit; at least a fraction of the remaining part is optionally recycled in at least one of the process steps and/or sent to a fuel storage unit, for example a naphtha storage unit, a diesel storage unit or a kerosene storage unit, from conventional petroleum feedstocks.
• the naphtha cut comprising compounds having a boiling point less than or equal to 175° C., all or part is sent to a steam cracking unit, while the cut comprising compounds having a boiling point above 175° C. is recycled in stage a) and/or b) and/or b′), and/or sent to a fuel storage unit.
• the optional fractionation step d) can make it possible to obtain, in addition to a gas stream, a naphtha fraction comprising compounds having a boiling point less than or equal to 175° C., preferably between 80 and 175°C, and, a middle distillate cut comprising compounds having a boiling point greater than 175°C and lower than 385°C, and a hydrocarbon cut comprising compounds having a boiling point greater than or equal to 385 °C, called heavy hydrocarbon cut.
• the naphtha cut can be sent, in whole or in part, to a steam cracking unit and/or to the naphtha storage unit from conventional petroleum feedstocks, it can still be recycled;
• the middle distillate cut can also be, in whole or in part, either sent to a steam cracking unit, or to a diesel storage unit from conventional petroleum feedstocks, or even be recycled;
• the heavy cut can be sent, at least in part, to a steam cracking unit, or be recycled.
• the optional step e) of fractionation can make it possible to obtain, in addition to a gas stream, a naphtha cut comprising compounds having a boiling point less than or equal to 175° C., preferably between 80 and 175°C, and a kerosene cut comprising compounds having a boiling point above 175°C and less than or equal to 280°C, a diesel cut comprising compounds having a boiling point above 280°C and less than 385° C. and a hydrocarbon cut comprising compounds having a boiling point greater than or equal to 385° C., referred to as a heavy hydrocarbon cut.
• the naphtha cut can be sent, in whole or in part, to a steam cracking unit and/or to the naphtha pool resulting from conventional petroleum feedstocks, it can also be sent to stage g) of recycling;
• the kerosene cut and/or the diesel cut can also be, in whole or in part, either sent to a steam cracking unit, or respectively to a kerosene or diesel pool resulting from conventional petroleum feedstocks, or sent to stage f) of recycling ;
• the heavy cut can for its part be sent, at least in part, to a steam cracking unit, or be sent to stage f) of recycling.
• the naphtha cut comprising compounds having a boiling point less than or equal to 175° C. resulting from stage d) is fractionated into a heavy naphtha cut comprising compounds having a boiling point between 80 and 175°C and a light naphtha cut comprising compounds having a boiling point below 80°C, at least part of said heavy naphtha cut being sent to an aromatic complex comprising at least one step of reforming the naphtha into to produce aromatic compounds.
• at least a part already cut light naphtha is sent to step e) of steam cracking described below.
• the gas fraction(s) resulting from fractionation stage d) may (may) be subject to purification(s) and additional separation(s) with a view to recovering at least light hydrocarbons, in particular ethane, propane and butane, which can advantageously be sent separately or as a mixture to one or more furnaces of step e) of steam cracking so as to increase the overall yield of olefins.
• At least a fraction of the cut comprising compounds having a boiling point above 175° C. resulting from fractionation step d) can be recovered to form a recycle stream which is sent upstream from or directly towards at least one of the reaction stages of the process according to the invention, in particular towards stage a) of hydrogenation and/or stage b) of hydrotreatment and/or stage b′) of hydrocracking.
• a fraction of the recycle stream can be sent to optional step aO).
• the recycle stream can supply said reaction stages a) and/or b) and/or b') in a single injection or can be divided into several fractions to supply reaction stages a) and/or b) and/or b' ) in several injections, that is to say at the level of different catalytic beds.
• the quantity of the recycle stream of the cut comprising compounds having a boiling point above 175° C. is adjusted so that the weight ratio between the recycle stream and the charge comprising a plastics pyrolysis oil, c that is to say the charge to be treated supplying the overall process, is less than or equal to 10, preferably less than or equal to 5, and preferably greater than or equal to 0.001, preferably greater than or equal to 0.01, and preferably greater than or equal to 0.1.
• the quantity of the recycle stream is adjusted so that the weight ratio between the recycle stream and the charge comprising a plastics pyrolysis oil is between 0.2 and 5.
• At least a fraction of the cut comprising compounds having a boiling point above 175° C. resulting from stage d) of fractionation is sent to stage b′) of hydrocracking when it is present.
• stage b′) of hydrocracking advantageously makes it possible to increase the yield of naphtha cut having a boiling point below 175°C. Recycling also makes it possible to dilute the impurities and on the other hand to control the temperature in the reaction stage(s), in which the reactions involved can be highly exothermic.
• At least a fraction of the cut comprising compounds having a boiling point above 175° C. resulting from stage d) of fractionation is sent to a second stage b”) of hydrocracking when she is here.
• a purge can be installed on the recycle of said cut comprising compounds having a boiling point above 175°C. Depending on the operating conditions of the process, said purge may be between 0 and 10% by weight of the cut comprising compounds having a boiling point above 175° C. relative to the incoming feed, and preferably between 0.5 % and 5%weight. Recycling of the hydrocarbon effluent from step c) and/or of the naphtha cut having a boiling point less than or equal to 175° C. from step d)
• a fraction of the hydrocarbon effluent resulting from step c) of separation or a fraction of the naphtha cut having a boiling point less than or equal to 175° C. resulting from step d) optional of fractionation can be recovered to form a recycle stream which is sent upstream of or directly to at least one of the reaction stages of the process according to the invention, in particular to stage a) of hydrogenation and/or stage b) d hydrotreating.
• a fraction of the recycle stream can be sent to the optional pretreatment step aO).
• the quantity of the recycle stream is adjusted so that the weight ratio between the recycle stream and the charge comprising a plastics pyrolysis oil is that is to say the charge to be treated supplying the overall process, is less than or equal to 10, preferably less than or equal to 5, and preferably greater than or equal to 0.001, preferably greater than or equal to 0.01, and preferably greater than or equal to 0.1.
• the quantity of the recycle stream is adjusted so that the weight ratio between the recycle stream and the charge comprising a plastics pyrolysis oil is between 0.2 and 5.
• a hydrocarbon cut external to the process can be used as recycle stream.
• a person skilled in the art will then know how to choose said hydrocarbon cut.
• reaction (s) in which (the) which (s) of the reactions involved can be strongly exothermic.
• Said hydrocarbon effluent or said hydrocarbon stream(s) thus obtained by treatment according to the process of the invention of an oil for the pyrolysis of plastics exhibit(s) a composition compatible with the specifications of a charge at the inlet of a steam cracking unit.
• composition of the hydrocarbon effluent or of said hydrocarbon stream(s) is preferably such that: - the total content of metallic elements is less than or equal to 5.0 ppm by weight, preferably less than or equal to 2.0 ppm by weight, preferably less than or equal to 1.0 ppm by weight and preferably less than or equal to 0, 5 ppm by weight, with: a content of the element silicon (Si) less than or equal to 1.0 ppm by weight, preferably less than or equal to 0.6 ppm by weight, and a content of the element iron (Fe) less than or equal to 100 ppb weight,
• the sulfur content is less than or equal to 500 ppm by weight, preferably less than or equal to 200 ppm by weight,
• the nitrogen content is less than or equal to 100 ppm by weight, preferably less than or equal to 50 ppm by weight and preferably less than or equal to 5 ppm by weight
• the asphaltene content is less than or equal to 5.0 ppm by weight
• the total chlorine element content is less than or equal to 10 ppm by weight, preferably less than 1.0 ppm by weight,
• the content of olefinic compounds is less than or equal to 5.0% by weight, preferably less than or equal to 2.0% by weight, preferably less than or equal to 0.1% by weight.
• the contents are given in relative weight concentrations, percentage (%) by weight, part(s) per million (ppm) weight or part(s) per billion (ppb) weight, relative to the total weight of the stream considered.
• the process according to the invention therefore makes it possible to treat the pyrolysis oils of plastics to obtain an effluent which can be injected, in whole or in part, into a steam cracking unit.
• the hydrocarbon effluent from step c) of separation, or at least one of the two liquid hydrocarbon stream(s) from step d) optional, can be wholly or partially sent to a step e) steam cracking.
• the gas fraction(s) resulting from step c) of separation and/or d) of fractional and containing ethane, propane and butane can (can) in whole or in part be also sent to step e) of steam cracking.
• Said step e) of steam cracking is advantageously carried out in at least one pyrolysis furnace at a temperature of between 700 and 900° C., preferably between 750 and 850° C., and at a pressure of between 0.05 and 0.3 MPa relative.
• the residence time of the hydrocarbon compounds is generally less than or equal to 1.0 second (denoted s), preferably between 0.1 and 0.5 s.
• water vapor is introduced upstream of the optional steam cracking step e) and after the separation (or the fractionation).
• the quantity of water introduced, advantageously in the form of steam, is advantageously between 0.3 and 3.0 kg of water per kg of hydrocarbon compounds at the inlet of stage e).
• optional step e) is carried out in several pyrolysis furnaces in parallel so as to adapt the operating conditions to the different flows supplying step e) in particular from step d), and also to manage the decoking of the tubes.
• a furnace comprises one or more tubes arranged in parallel.
• An oven can also refer to a group of ovens operating in parallel.
• a furnace can be dedicated to cracking the naphtha cut comprising compounds having a boiling point less than or equal to 175°C.
• step e) of steam cracking includes steam cracking furnaces but also the sub-steps associated with steam cracking well known to those skilled in the art. These sub-steps may include in particular heat exchangers, columns and catalytic reactors and recycling to the furnaces.
• a column generally makes it possible to fractionate the effluent with a view to recovering at least a light fraction comprising hydrogen and compounds having 2 to 5 carbon atoms, and a fraction comprising pyrolysis gasoline, and optionally a fraction comprising pyrolysis oil.
• This steam cracking step e) makes it possible to obtain at least one effluent containing olefins comprising 2, 3 and/or 4 carbon atoms (that is to say C2, C3 and/or C4 olefins), at satisfactory contents, in particular greater than or equal to 30% by weight, in particular greater than or equal to 40% by weight, or even greater than or equal to 50% by weight of total olefins comprising 2, 3 and 4 carbon atoms relative to the weight of the effluent from considered steam cracking.
• Said C2, C3 and C4 olefins can then be advantageously used as polyolefin monomers.
• the process for treating a charge comprising a plastics pyrolysis oil comprises, preferably consists of, the sequence of steps, and preferably in the order given:
• step a) hydrogenation, b) hydrotreatment, c) separation, d) fractionation and recycling of the cut comprising compounds having a boiling point less than or equal to 175° C. in step a) and /or b),
• step b′ hydrocracking and recycling of the effluent from step b′) into step c), and recycling of cut comprising compounds having a boiling point less than or equal to 175° C. in step a) or b).
• All embodiments can comprise and preferably consist of more than one aO pretreatment step. All the embodiments can comprise and preferably consist of more than one step g) of steam cracking.
• Figure 1 shows the diagram of a particular embodiment of the method of the present invention, comprising:
• step d) of fractionating the liquid hydrocarbon fraction 12 making it possible to obtain at least one gaseous fraction 13, a cut 14 comprising compounds having a boiling point less than or equal to 175° C. (naphtha cut) and a cut 15 comprising compounds having a boiling point above 175° C. (diesel cut).
• part of the cut 14 comprising compounds having a boiling point less than or equal to 175° C. is sent to a steam cracking process (not shown). Another part of cut 14 feeds stage a) of hydrogenation (fraction 14a) and stage b) of hydrotreatment (fraction 14b). A part of the cut 15 comprising compounds having a boiling point above 175° C. resulting from stage d) feeds stage b′) of hydrocracking (fraction 15a), another part 15b constitutes the purge.
• FIG. 2 represents the diagram of another particular embodiment of the process of the present invention which is based on the diagram of FIG. 1.
• This diagram notably comprises a second hydrocracking step b”) in which the cut 15 comprising compounds having a boiling point above 175°C from stage d) feeds this second hydrocracking stage b”) (fraction 15a) which is carried out in at least one fixed-bed reactor comprising at least one hydrocracking catalyst and is fed with hydrogen (16).
• the second hydrocracked effluent (17) is recycled in stage c) of separation.
• the other part of the cut 15 constitutes the purge 15b.
• Feedstock 1 treated in the process is a plastics pyrolysis oil (that is to say comprising 100% by weight of said plastics pyrolysis oil) having the characteristics indicated in Table 2.
• Table 2 characteristics of the load
• Charge 1 is subjected to a hydrogenation step a) carried out in a fixed-bed reactor and in the presence of hydrogen 2 and a hydrogenation catalyst of the NiMo on alumina type under the conditions indicated in Table 3.
• Table 3 conditions of stage a) of hydrogenation
• the conditions indicated in Table 3 correspond to conditions at the start of the cycle and the average temperature (WABT) is increased by 1° C. per month so as to compensate for the catalytic deactivation.
• WABT average temperature
• stage a) of hydrogenation is subjected directly, without separation, to a stage b) of hydrotreatment carried out in a fixed bed and in the presence of hydrogen 5, and of a hydrotreatment catalyst of NiMo type on alumina under the conditions presented in table 5.
• the conditions indicated in Table 5 correspond to conditions at the start of the cycle and the average temperature (WABT) is increased by 1° C. per month so as to compensate for the catalytic deactivation.
• WABT average temperature
• stage c) of separation The effluent 6 from stage b) of hydrotreatment is subjected to a stage c) of separation: a flow of water is injected into the effluent from stage b) of hydrotreatment; the mixture is then treated in an acid gas scrubbing column and separator drums to obtain a gas fraction and a liquid effluent.
• the yields of the various fractions obtained after separation are indicated in Table 6 (the yields correspond to the ratios of the quantities by mass of the various products obtained with respect to the mass of feedstock upstream of stage a), expressed as a percentage and noted as % m /m).
• All or part of the liquid fraction obtained can then be upgraded in a steam cracking step in order to form olefins which can be polymerized in order to form recycled plastics.
• the process implemented according to the invention leads to reduced catalytic deactivations during stage a) of hydrogenation and during stage b) of hydrotreatment compared to the catalytic deactivations observed according to the prior art.
• the load to be treated is identical to that described in Example 1 (cf. table 2).
• the charge is subjected to a stage a) of selective hydrogenation carried out in a fixed-bed reactor and in the presence of hydrogen and a selective hydrogenation catalyst of the NiMo on alumina type under the conditions indicated in Table 7.
• stage a) of selective hydrogenation is subjected directly, without separation, to a stage b) of hydrotreatment carried out in a fixed bed and in the presence of hydrogen, a recycled hydrocarbon stream, and a hydrotreating catalyst of the NiMo on alumina type under the conditions presented in Table 9.
• the conditions indicated in table 9 correspond to conditions at the start of the cycle and the average temperature (WABT) is increased by 2° C. per month so as to compensate for the catalytic deactivation.
• WABT average temperature
• stage c) of separation The effluent from stage b) of hydrotreatment is subjected to a stage c) of separation: a flow of water is injected into the effluent from stage b) of hydrotreatment; the mixture is then treated in an acid gas scrubbing column and separator drums to obtain a gas fraction and a liquid effluent.
• Table 10 yields of the different products obtained after separation

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• 2021
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