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
  • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • 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
  • 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
  • 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
  • C10G49/002—Apparatus for fixed bed hydrotreatment 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
  • 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
  • C10G49/02—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 characterised by the catalyst used
  • C10G49/04—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 characterised by the catalyst used containing nickel, cobalt, 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step 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
  • 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
  • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1003—Waste materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/70—Catalyst aspects
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the present invention relates to a process for treating an oil from the pyrolysis of plastics in order to obtain a hydrocarbon effluent whose composition is compatible with a feed supplying a steam cracking unit. More particularly, the present invention relates to a process for treating a feedstock resulting from the pyrolysis of plastic waste, in order to at least partially remove impurities, in particular olefins (mono-, diolefins), metals, in in particular silicon, and halogens, in particular chlorine, which said feed can contain in relatively large quantities, and so as to hydrogenate the feed in order to be able to upgrade it in a steam cracking unit with increased yields of light olefins.
• impurities in particular olefins (mono-, diolefins)
• metals in in particular silicon
• halogens in particular chlorine
• Plastics from collection and sorting channels can undergo a pyrolysis step in order to obtain, among other things, pyrolysis oils. These plastic pyrolysis oils are typically 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 even polymerization catalyst residues.
• Plastic waste can also contain, in a minor way, biomass, for example from household waste.
• the oils obtained from the pyrolysis of plastic waste contain many impurities, in particular diolefins, metals, in particular silicon, or halogenated compounds, in particular chlorine-based compounds, heteroelements such as sulfur. , oxygen and nitrogen, insolubles, at levels often high and incompatible with steam cracking units or units located downstream of steam cracking units, in particular polymerization processes and hydrogenation processes selective.
• impurities can generate problems of operability and in particular problems of corrosion, coking or catalytic deactivation, or even problems of incompatibility in the uses of the target polymers.
• the presence of diolefins can also lead to problems of instability of the pyrolysis oil characterized by the formation of gums. This phenomenon is generally limited by proper storage of the charge. The gums and the insolubles possibly present in the pyrolysis oil can generate clogging problems in the processes.
• the yields of light olefins desired for the petrochemical industry in particular ethylene and propylene, strongly depend on the quality of the feeds sent to the steam cracking.
• the BMCI Boau of Mines Correlation Index
• the yields of light olefins increase when the paraffin content increases and / or when the BMCI decreases.
• the yields of unwanted heavy compounds and / or coke increase with increasing BMCI.
• Document WO 2018/055555 proposes an overall and very general plastic waste recycling process, ranging from the actual stage of pyrolysis of plastic waste to the steam cracking stage.
• the process of application WO 2018/055555 comprises, inter alia, a step of hydrotreating the liquid phase resulting directly from pyrolysis, preferably under fairly severe conditions, particularly in terms of temperature, for example at a temperature between 260 and 300 ° C, a stage of separation of the hydrotreatment effluent then a stage of hydrodelakylation of the heavy effluent separated at a preferably high temperature, for example between 260 and 400 ° C.
• the present invention aims to overcome these drawbacks and participate in the recycling of plastics, by proposing a process for treating an oil resulting from the pyrolysis of plastics in order to purify it and hydrotreat it in order to obtain a hydrocarbon effluent with a reduced content of impurities.
• the composition of which is compatible with a feed supplying a steam cracking unit leads to improved yields of light olefins during the steam cracking stage, while in particular reducing the risks of clogging during stages of treatment of carbon oils.
• pyrolysis of plastics such as those described in the prior art, and the formation of coke in large quantities and / or the risks of corrosion encountered during the steam cracking stage of oils for pyrolysis of plastics.
• the invention relates to a process for treating a feed comprising an oil for pyrolysis of plastics, comprising at least the following steps: a) a selective hydrogenation step carried out in a reaction section supplied with said feed and a gas stream comprising hydrogen, in the presence of at least one selective hydrogenation catalyst, at a temperature between 100 and 250 ° C, a partial pressure of hydrogen between 1.0 and 10.0 MPa abs.
• a hydrotreatment step implemented in a hydrotreatment reaction section, comprising a fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, arranged in series and each comprising at least one catalyst hydrotreatment, said hydrotreatment reaction section being fed at the level of the first catalytic bed with said hydrogenated effluent from step a) and a gas stream comprising hydrogen and carried out at a temperature between 250 and 430 ° C, a partial pressure of hydrogen between 1.0 and 10.0 MPa abs.
• step c) a separation step, fed with the hydrotreatment 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, a aqueous effluent and a hydrocarbon effluent.
• the advantage of the process of the invention is to provide a precise sequence of operations which makes it possible to rid an oil obtained from the pyrolysis of plastic waste of at least part of its impurities, to hydrogenate it in order to make it in particular compatible with treatment in a steam cracking unit in order to be able to recreate light olefins with increased yields which can be used as monomers in the manufacture of polymers.
• the invention also makes it possible to prevent risks of clogging and / or corrosion of the treatment unit in which the process of the invention is implemented, the risks being exacerbated by the presence, often in large quantities, of diolefins. , metals and halogen compounds in oil from the pyrolysis of plastics.
• the process of the invention thus makes it possible to obtain an effluent obtained from an oil for the pyrolysis of plastics freed at least in part from the impurities of the oil from the pyrolysis of the starting plastics, thus limiting the problems of operability, such as corrosion, coking or catalytic deactivation problems, which can be caused by these impurities, in the steam cracking units and / or in the units located downstream from the steam cracking units, in particular the polymerization and selective hydrogenation units.
• the elimination of at least part of the impurities from the oils obtained 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.
• Another advantage of the invention is that it participates in the recycling of plastics and in the preservation of fossil resources, by allowing the recovery of the oils resulting from their pyrolysis in a steam cracking unit. It allows, in fact, the purification and the hydrotreatment of these oils which can then be introduced into a steam cracker to obtain olefins and thus to re-manufacture polymers.
• the process also makes it possible to obtain naphtha and / or diesel cuts from feed comprising oils from the pyrolysis of plastics, cuts that the refiner could directly integrate respectively into the naphtha pool and / or the diesel pool obtained by refining crude oil.
• a "plastic pyrolysis oil” is an oil, advantageously in liquid form at room temperature, obtained from the pyrolysis of plastics, preferably of plastic waste originating in particular from collection and sorting channels. It comprises in particular a mixture of hydrocarbon compounds, in particular paraffins, mono- and / or di-olefins, or also optionally naphthenes and aromatics, these hydrocarbon compounds preferably having a boiling point of less than 700 ° C and preferably less than 550 ° C.
• the oil from the pyrolysis of plastics can comprise, and most often comprises, in addition, impurities such as metals, in particular silicon and iron, halogen compounds, in particular chlorine compounds.
• impurities can be present in the pyrolysis oil of plastics 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 supplied by halogenated compounds, up to 100 ppm weight, or even 200 ppm weight of metallic or semi-metallic elements.
• Alkali metals, alkaline earths, transition metals, poor metals and metalloids can be likened to contaminants of a metallic nature, called metals or metallic or semi-metallic elements.
• the metals or metallic or semi-metallic elements, optionally contained in the oils obtained from the pyrolysis of plastic waste comprise silicon, iron or these two elements.
• the oil from the pyrolysis of plastics can also comprise other impurities such as heteroelements provided in particular by sulfur compounds, oxygen compounds and / or nitrogen compounds, at contents generally less than 10,000 ppm by weight of heteroelements and preferably less. at 4000 ppm weight of heteroelements.
• the pressures are absolute pressures, also denoted abs., And are given in absolute MPa (or abs. MPa).
• 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 preferred pressure value range can be combined with a more preferred temperature value range.
• the invention relates to a process for treating a feed comprising an oil for pyrolysis of plastics, comprising the following stages: a) a selective hydrogenation stage advantageously carried out in a fixed bed in which the feed and hydrogen are placed in contact in the presence of at least one selective hydrogenation catalyst, said selective hydrogenation being carried out at a temperature between 100 and 250 ° C, preferably between 110 and 200 ° C, preferably between 130 and 180 ° C, a pressure partial hydrogen between 1.0 and 10.0 MPa abs., and an hourly volume speed between 1.0 and 10.0 h-1, advantageously in at least one reactor, preferably in at least two reactors and so preferred in two reactors in series permutable PRS (Permutable Reactor System) type, to obtain at least one effluent with a reduced diolefin content, also called hydrogenated effluent; b) a hydrotreatment step carried out in a fixed bed in which the hydrogenated effluent from selective hydrogenation step a) is brought into contact with hydrogen in the
• an additional gas stream comprising hydrogen being advantageously introduced at the inlet of each catalytic bed from the second catalytic bed, to obtain at least one hydrotreatment effluent.
• step b) a step of separating the hydrotreatment effluent from step b), comprising a washing / separation section supplied with the hydrotreatment effluent from step b) and advantageously an aqueous stream, said separation step being carried out at a temperature between 50 and 370 ° C, preferably between 100 and 340 ° C, preferably between 200 and 300 ° C, to obtain at least one gaseous effluent, an aqueous effluent and an effluent hydrocarbon.
• the feed for the process according to the invention comprises at least one oil for the pyrolysis of plastics.
• Said charge may consist solely of oil (s) from the pyrolysis of plastics.
• said filler comprises at least 50% by weight, preferably between 75 and 100% by weight, of plastic pyrolysis oil, that is to say preferably between 50 and 100% by weight, preferably between 70% and 100% by weight of oil from the pyrolysis of plastics.
• the feed for the process according to the invention may comprise, among other things, one or more oil (s) from the pyrolysis of plastics, a conventional petroleum feed, which is then co-treated with the pyrolysis oil of plastics from the feed.
• the oil for pyrolysis of plastics of said feed comprises hydrocarbon compounds, advantageously paraffinic, and impurities such as in particular mono- and / or diolefins, metals, in particular silicon and iron, halogenated compounds, in particular chlorinated compounds, heteroelements provided by sulfur compounds, oxygenates and / or nitrogen compounds.
• impurities are often present in often high contents, for example up to 350 ppm by weight or even 700 ppm by weight or even 1000 ppm by weight of halogen elements supplied by halogenated compounds, up to 100 ppm by weight, or even 200 ppm by weight of 'metallic or semi-metallic elements.
• Said feed comprising a plastic pyrolysis oil can advantageously be pretreated in a pretreatment stage ao), prior to selective hydrogenation stage a) of selective hydrogenation, to obtain a pretreated feed which feeds stage a).
• This pretreatment step ao) makes it possible to reduce the quantity of contaminants, in particular the quantity of silicon, optionally present in the load comprising an oil for pyrolysis of plastics.
• a step ao) of pretreatment of the feed comprising an oil for pyrolysis of plastics is advantageously carried out in particular when said feed comprises more than 50 ppm by weight, in particular more than 20 ppm by weight, more particularly more than 10 ppm by weight, or even more.
• Said pretreatment step ao) is carried out prior to selective hydrogenation step a), in an adsorption section supplied by said feed comprising a plastic pyrolysis oil and operating at a temperature between 0 and 150 ° C.
• adsorbent preferably alumina type, having a specific surface greater than or equal to 100 m2 / g, preferably greater than or equal to 200 m2 / g.
• the specific surface of said at least adsorbent is advantageously less than or equal to 600 m2 / g, in particular less than or equal to 400 m2 / g.
• the specific surface of the adsorbent is a surface measured by the BET method, that is to say the specific surface determined by adsorption of nitrogen in accordance with standard ASTM D 3663-78 established using the BRUNAUER-EMMETT method -TELLER described in the periodical 'The Journal of the American Chemical Society ", 6Q, 309 (1938).
• said adsorbent comprises less than 1% by weight of metallic elements, preferably is free of metallic elements. of the adsorbent means the elements of groups 6 to 10 of the periodic table of the elements.
• Said adsorption section comprises at least one adsorption column, preferably comprises two adsorption columns, containing said adsorbent.
• one operating mode can be an operation called "in swing", according to the English term, in which one of the columns is in line while the other. column is in reserve.
• the absorbent in the in-line column is used up, that column is isolated while the reserve column is placed in-line.
• the spent absorbent can then be regenerated in-situ and / or replaced with fresh absorbent to be put back on line once the other column has been isolated.
• Another mode of operation is to have the two columns operating in series, when the absorbent from the overhead column is used up, this first column is isolated and the spent absorbent is either regenerated in-situ or replaced with absorbent fresh. The column is then brought back to line in the second position and so on.
• This operation is called "lead and lag", according to the English term.
• the association of two adsorption columns makes it possible to overcome the possible and possibly rapid poisoning and / or clogging of the adsorbent under the joint action of metal contaminants, diolefins, gums derived from diolefins. and insolubles optionally present in the pyrolysis oil of plastics to be treated.
• the method comprises a step a) of selective hydrogenation is carried out in the presence of hydrogen, under conditions of hydrogen pressure and temperature such as to maintain the liquid phase and with a quantity of soluble hydrogen just necessary for the selective hydrogenation of the diolefins present in the oil from the pyrolysis of plastics.
• the selective hydrogenation of the diolefins in the liquid phase thus makes it possible to avoid or at least limit the formation of “gums”, that is to say the polymerization of the diolefins and therefore the formation of oligomers and polymers, which can stopper the reaction section of the next hydrotreatment step.
• Said selective hydrogenation step a) makes it possible to obtain a hydrogenated effluent, that is to say an effluent with a reduced content of diolefins, or even free of diolefins.
• said step a) of selective hydrogenation is implemented a reaction section supplied with said feed comprising an oil for pyrolysis of plastics, or by the pretreated feed resulting from the optional pretreatment step ao), and a gas stream comprising hydrogen (H2).
• Said reaction section implements a selective hydrogenation, preferably in a fixed bed, in the presence of at least one selective hydrogenation catalyst, advantageously at a temperature between 100 and 250 ° C, preferably between 110 and 200 ° C, of preferably between 130 and 180 ° C, a partial pressure of hydrogen between 1.0 and 10.0 MPa abs. and at an hourly volume velocity (WH) between 1.0 and 10.0 h-1.
• the hourly volume speed (WH) is defined as the ratio between the hourly volume flow rate of the feed comprising the plastic pyrolysis oil, optionally pretreated, by the volume of catalyst (s).
• the quantity of the gas stream feeding said reaction section of step a) is advantageously such that the hydrogen coverage is between 1 and 50 Nm3 of hydrogen per m3 of feed (Nm3 / m3), preferably between 5 and 20 Nm3 of hydrogen per m3 of load (Nm3 / m3).
• 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 rate of charge at 15 ° C (in normal m3, noted Nm3, of H2 per m3 of charge) .
• the gas stream comprising hydrogen, which feeds the reaction section of step a), can consist of additional hydrogen and / or recycled hydrogen, in particular from step c) of separation.
• the reaction section of said step a) comprises at least one reactor.
• the reaction section comprises at least 2 reactors and, in a preferred manner, comprises two reactors which operate in a switchable system also called according to the English term “PRS” for Permutable Reactor System.
• PRS Permutable Reactor System
• 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 at least selective hydrogenation catalyst comprises a support, preferably inorganic, and a hydro-dehydrogenating function.
• the hydro-dehydrogenating function comprises in particular 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 VIB, preferably chosen from the group consisting of molybdenum and tungsten.
• the total content of oxides of the metal elements of groups VIB and VIII (that is to say the sum of the metal elements of groups VIB 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 weight ratio expressed in metal oxide between the metal (or metals) of group VIB 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 a selective hydrogenation catalyst comprising between 0.5% and 10% by weight of nickel, preferably between 1% and 5% by weight of nickel (expressed as nickel oxide NiO by 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 Mo03 relative to the weight of said catalyst) on a support preferably mineral.
• the support of said at least selective hydrogenation catalyst is preferably chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and their mixtures.
• Said support may also contain doping compounds, in particular oxides chosen from the group consisting of boron oxide, in particular boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide and a mixture of these oxides.
• said at least selective hydrogenation catalyst comprises an alumina support, preferably doped with phosphorus and optionally boron.
• phosphorus pentoxide P205 When phosphorus pentoxide P205 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. When boron trioxide B205 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 can be a g (gamma) or h (eta) alumina.
• Said selective hydrogenation catalyst is for example in the form of extrudates.
• At least one selective hydrogenation catalyst used in step a) comprises 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 Mo03 by relative to the weight of said catalyst, on an alumina support, in order to hydrogenate the diolefins as selectively as possible.
• the feed which comprises an oil from the pyrolysis of plastics, optionally pretreated can be mixed with the gas stream comprising hydrogen, prior to the reaction section.
• Said feed optionally mixed with the gas stream, can also be heated, for example by heat exchange in particular with the hydrotreatment effluent, before the reaction section to reach a temperature close to the temperature used in the reaction section. that it feeds.
• Step a) converts at least 90% and preferably at least 99% of the diolefins contained in the initial charge. Step a) also allows the removal, at least in part, of other contaminants, such as, for example, silicon.
• the hydrogenated effluent is preferably sent directly to stage b) of hydrotreatment.
• the treatment process comprises a stage b) of hydrotreatment, advantageously in a fixed bed, of said hydrogenated effluent resulting from stage a) in the presence of hydrogen and of at least one hydrotreatment catalyst, for obtain a hydrotreatment effluent.
• said step b) is carried out in a hydrotreatment reaction section comprising a fixed bed reactor having n catalytic beds, n being an integer greater than or equal to 1, preferably between 2 and 10, so preferred between 2 and 5, arranged in series and each comprising at least one hydrotreatment catalyst.
• Said reaction section is fed, advantageously at the level of the first catalytic bed, with said hydrogenated effluent resulting from step a) and a gas stream comprising hydrogen.
• said hydrotreatment reaction section is carried out at a pressure equivalent to that used in the reaction section of step a) of selective hydrogenation, but at a higher temperature than that of the reaction section of step a) selective hydrogenation.
• said hydrotreatment reaction section is advantageously carried out at a 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 speed (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 preferred between 0.2 and 0.8 h-1.
• the hourly volume speed (WH) is defined as the ratio between the hourly volume flow rate of the hydrogenated effluent from step a) per volume of catalyst (s).
• the hydrogen coverage in step b) is advantageously between 50 and 1000 Nm3 of hydrogen per m3 of hydrogenated effluent from step a), and preferably between 50 and 500 Nm3 of hydrogen per m3 of hydrogenated effluent resulting from stage a) of selective hydrogenation, preferably between 100 and 300 Nm 3 of hydrogen per m3 of hydrogenated effluent resulting from stage a) of selective hydrogenation.
• the hydrogen coverage is defined here as the ratio of the volume flow rate of hydrogen taken under normal temperature and pressure conditions compared to the volume flow rate of hydrogenated effluent from step a) (in normal m3, noted Nm3, from H2 per m3 of hydrogenated effluent from step a)).
• the hydrogen can be made up of make-up and / or recycled hydrogen, in particular from step c) of separation.
• an additional gas stream comprising hydrogen is advantageously introduced at the inlet of each catalytic bed from the second catalytic bed.
• These additional gas streams are also called cooling streams. They make it possible to control the temperature in the hydrotreatment reactor in which the reactions carried out are generally very exothermic.
• said at least hydrotreatment catalyst used in said step b) can be chosen from known hydrodemetallation, hydrotreatment and silicon capture catalysts, used in particular for the treatment of petroleum fractions, and their combinations.
• Known hydrodemetallation catalysts are for example those described in patents EP 0113297, EP 0113284, US 5221656, US 5827421, US 7119045, US 5622616 and US 5089463.
• Known hydrotreatment 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, US 2007/080099.
• said at least hydrotreatment catalyst comprises a support, preferably inorganic, and at least one metallic element having a hydro-dehydrogenating function.
• Said at least 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 in the group consisting of molybdenum and tungsten.
• the total content of 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 weight ratio expressed in metal oxide between the metal (or metals) of group VI B relative to the metal (or metals) of group VIII is preferably between 1.0 and 20, more preferably between 2.0 and 10.
• the hydrotreatment reaction section of step b) of the process comprises a hydrotreatment catalyst comprising between 0.5% and 10% by weight of nickel, preferably between 1% and 5% by weight of nickel, expressed as nickel oxide NiO relative to the total weight of the hydrotreating catalyst, and between 1.0% and 30% by weight of molybdenum, preferably between 3.0% and 20% by weight of molybdenum, expressed as molybdenum oxide Mo03 relative to the total weight of the hydrotreatment catalyst, on an inorganic support.
• the support for said at least hydrotreating catalyst is advantageously chosen from the group consisting of alumina, silica, silica-aluminas, magnesia, clays and their mixtures.
• Said support may also contain doping compounds, in particular oxides chosen from the group consisting of boron oxide, in particular boron trioxide, zirconia, ceria, titanium oxide, phosphorus pentoxide and a mixture of these oxides.
• said at least hydrotreating catalyst comprises an alumina support, more preferably an alumina support doped with phosphorus and optionally boron.
• phosphorus pentoxide P205 When phosphorus pentoxide P205 is present, its concentration is less than 10% by weight based on the weight of the alumina and preferably at least 0.001% by weight based on the total weight of the alumina. When boron trioxide B205 is present, its concentration is less than 10% by weight relative to the weight of the alumina and preferably at least 0.001% relative to the total weight of the alumina.
• the alumina used can be y (gamma) or h (eta) alumina.
• Said hydrotreatment catalyst is, for example, in the form of extrudates.
• said at least hydrotreatment catalyst used in step b) of the process has a specific surface area greater than or equal to 250 m2 / g, preferably greater than or equal to 300 m2 / g.
• the specific surface of said hydrotreatment catalyst is advantageously less than or equal to 800 m2 / g, preferably less than or equal to 600 m2 / g, in particular less than or equal to 400 m2 / g.
• the specific surface of the hydrotreatment catalyst is measured by the BET method, that is to say the specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established using the BRUNAUER-EMMETT method. TELLER described in the periodical 'The Journal of the American Chemical Society', 6Q, 309 (1938). Such a specific surface makes it possible to further improve the removal of contaminants, in particular metals such as silicon.
• step b) can implement a heating section located upstream of the hydrotreatment reaction section and in which the hydrogenated effluent from step a) is heated to reach a temperature suitable for hydrotreatment. , that is to say a temperature between 250 and 370 ° C.
• Said optional heating section can thus comprise one or more exchangers, preferably allowing heat exchange between the hydrogenated effluent and the hydrotreatment effluent, and / or a preheating furnace.
• the hydrotreatment step b) allows the total hydrogenation of the olefins present in the initial feed and those optionally obtained after the selective hydrogenation step a), but also the conversion at least in part of other impurities present.
• the charge such as aromatic compounds, metal compounds, sulfur compounds, nitrogen compounds, halogen compounds (in particular chlorine compounds), oxygenates ...
• Step b) can also make it possible to further reduce the content of contaminants, such as that of metals, especially the silicon content.
• the treatment process comprises a separation step c), advantageously carried out in at least one washing / separation section, supplied at least with the hydrotreatment effluent from step b), for obtain at least one gaseous effluent, one aqueous effluent and one hydrocarbon effluent.
• the gaseous effluent advantageously comprises hydrogen, preferably comprises essentially hydrogen, that is to say comprises at least 90% by volume, preferably at least 95% by volume, preferably at least 99% by volume , hydrogen.
• said gaseous effluent which preferably contains essentially the hydrogen can at least in part be recycled to stages a) of selective hydrogenation and / or b) of hydrotreatment, the recycling system possibly comprising a purification section.
• the aqueous effluent advantageously comprises ammonium salts and / or hydrochloric acid.
• Said hydrocarbon effluent comprises hydrocarbon compounds and advantageously corresponds to the pyrolysis oil of plastics of the feed, or to the pyrolysis oil of plastics and of the conventional petroleum feed fraction co-treated with the pyrolysis oil, freed from at least in part of its impurities, in particular of its olefinic (di- and mono-olefin), metallic, halogenated impurities.
• 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 during step b), and the ammonium ions. , generated by the hydrogenation of the nitrogen compounds during step b) and / or provided by injection of an amine, and thus limit the risk of clogging, in particular in the transfer lines and / or in the sections of the process of the invention and / or the transfer lines to the steam cracker, due to the precipitation of ammonium chloride salts. It also removes hydrochloric acid formed by the reaction of hydrogen ions and chloride ions.
• a stream of amines can be injected upstream of stage a) of selective hydrogenation, between stage a) of selective hydrogenation and stage b) hydrotreatment and / or between hydrotreatment step b) and separation step c), preferably upstream of selective hydrogenation step a), in order to ensure a sufficient quantity of ions ammonium 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 separation section.
• the separation step c) comprises an injection of an aqueous solution into the hydrotreatment effluent from step b), upstream of the washing / separation section, so as to dissolve at least in part ammonium chloride salts and / or hydrochloric acid and thus improve the elimination of chlorinated impurities and reduce the risk of blockages due to an accumulation of ammonium chloride salts.
• Step c) of separation is advantageously carried out between 50 and 370 ° C, preferably between 100 and 340 ° C, preferably between 200 and 300 ° C.
• step c) separation is carried out at a pressure close to that used in steps a) and / or b), 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 flasks which can be operated at different pressures and temperatures, pumps, exchangers heat, washing columns, etc.).
• the separation step c) comprises the injection of an aqueous solution into the effluent of hydrotreatment resulting from step b) followed by the washing / separation section advantageously comprising a separation phase making it possible to obtain at least one aqueous stream loaded with ammonium salts, a washed liquid hydrocarbon stream and a partially washed gaseous stream.
• the aqueous stream loaded with ammonium salts and the washed liquid hydrocarbon stream can then be separated in a settling flask in order to obtain said hydrocarbon effluent and said aqueous effluent.
• Said partially washed gaseous flow can in parallel be introduced into a washing column where it circulates countercurrently to an aqueous flow, preferably of the same nature as the aqueous solution injected into the hydrotreatment effluent, which makes it possible to eliminate less in part, preferably in full, the hydrochloric acid contained in the partially washed gas stream and thus obtain 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 acidic aqueous stream, and be used, optionally mixed with said acidic 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 flow in the washing column.
• Said water recycling circuit may include a make-up of water and / or a basic solution and / or a purge allowing the dissolved salts to be removed.
• the separation step c) can advantageously comprise a “high pressure” washing / separation section. which operates at a pressure close to the pressure of step a) of selective hydrogenation and / or of step b) of hydrotreatment, in order to facilitate the recycling of hydrogen.
• This optional “high pressure” section of step c) can be completed by a “low pressure” section, in order to obtain a liquid hydrocarbon fraction devoid of part of the gases dissolved at high pressure and intended to be treated directly in the gas. a steam cracking process or optionally be sent to fractionation step d).
• the hydrocarbon effluent resulting from separation step c) is sent either directly to the inlet of a steam cracking unit, or to an optional fractionation step d).
• the liquid hydrocarbon effluent is sent to a fractionation step d).
• the method according to the invention can comprise, preferably comprises, a step of fractionation of the hydrocarbon effluent, to obtain at least one gas stream and at least two hydrocarbon streams having different boiling points from one another.
• Said fractionation step d) can for example make it possible to obtain a naphtha cut with a boiling point of less than 150 ° C, in particular between 80 and 150 ° C, and a hydrocarbon cut with a boiling point of greater than 150 ° C.
• step d) makes it possible, in particular under the action of a flow of water vapor, in particular to eliminate the gases dissolved in the hydrocarbon-based liquid effluent, such as for example ammonia , hydrogen sulfide and light hydrocarbons having 1 to 4 carbon atoms.
• gases dissolved in the hydrocarbon-based liquid effluent such as for example ammonia , hydrogen sulfide and light hydrocarbons having 1 to 4 carbon atoms.
• the optional fractionation step d) is advantageously carried out at a pressure 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 comprising a stripping column equipped with a reflux circuit comprising a reflux flask. Said stripping column is fed with the liquid hydrocarbon effluent from step c) and by a stream of water vapor.
• 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 flask in which gas / liquid separation takes place.
• the gas phase which comprises the light hydrocarbons, is withdrawn from the reflux flask, in a gas stream.
• At least a fraction of the liquid phase is advantageously withdrawn from the reflux flask, in a hydrocarbon stream with a relatively low boiling point, for example a naphtha cut with a boiling point of less than 150 ° C.
• fractionation step d) can implement a stripping column followed by a distillation column or only a distillation column.
• Said hydrocarbon streams for example the naphtha cut with a boiling point below 150 ° C and the cut with a boiling point above 150 ° C, optionally mixed, can be sent to a steam cracking unit, at the end of which olefins can be (re) formed to participate in the formation of polymers.
• the naphtha stream for example with a boiling point of less than 150 ° C, can, according to another method, be sent to a naphtha pool, that is to say to the naphtha effluents, resulting from more conventional petroleum feedstocks, produced in the same refinery in which the process according to the invention is implemented, the hydrocarbon stream with a boiling point above 150 ° C., for its part, being sent to a steam cracking unit.
• step d) leads to obtaining a naphtha cut (in particular with a boiling point below 150 ° C), a diesel cut (in particular with a boiling point between 150 ° C and 385 ° C) and a heavy cut (especially with a boiling point above 385 ° C), the naphtha cut can be sent to the naphtha pool produced in the same refinery and the diesel cut can also either be sent to a steam cracking unit with the heavy cut, or to a diesel pool produced in the refinery.
• a naphtha cut in particular with a boiling point below 150 ° C
• a diesel cut in particular with a boiling point between 150 ° C and 385 ° C
• a heavy cut especially with a boiling point above 385 ° C
• the process for treating a feed comprising an oil for pyrolysis of plastics preferably comprises: sequence of the steps described above, and preferably in the order given, that is to say: the pretreatment step ao), the selective hydrogenation step a), the step b) of hydrotreatment, step c) of separation and optionally step d) of fractionation, to produce a treated plastic pyrolysis oil of composition compatible with the input of a steam cracking unit.
• the composition of the hydrocarbon effluent or of said hydrocarbon streams 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 silicon (Si) element content less than or equal to 1.0 ppm by weight, preferably less than or equal to 0.6 ppm by weight, and an iron element (Fe) content less than or equal to 100 ppb by weight, the content of sulfur 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 500 ppm by weight, preferably less than or equal to 200 ppm by weight, the asphaltenes content is less or equal to 5.0 ppm by weight, the total content of chlorine element is less than or equal to 50 ppb by weight, the content of olefinic compounds (mono- and di-olefins) is less than or equal to 5.0% by weight, preferably less or equal to 2.0% by weight, preferably less than or equal to 0.5% by weight.
• Si silicon
• Fe iron element
• the contents are given in relative weight concentrations, percentage (%) 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 oils from the pyrolysis of plastics to obtain an effluent which can be injected into a steam cracking unit.
• the process according to the invention thus makes it possible to recover the oils from the pyrolysis of plastics, while at the same time reducing the formation of coke and thus the risks of clogging and / or of premature loss of activity of the catalyst (s) used in the processing unit. steam cracking, and reducing the risk of corrosion.
• the hydrocarbon effluent from step c) of separation, or at least one of the two hydrocarbon streams from step d) optional, can be sent to a step e) of steam cracking.
• Said steam cracking step e) is advantageously carried out in at least one pyrolysis furnace at a temperature between 700 and 900 ° C, preferably between 750 and 850 ° C, and at a pressure 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 (noted s), preferably between 0.1 and 0.5 s.
• water vapor is introduced upstream of optional steam cracking step e) and after separation (or fractionation).
• the quantity of water introduced, advantageously in the form of water vapor is between 0.3 and 3.0 kg of water per kg of hydrocarbon compounds at the inlet of step e).
• optional step e) is carried out in several pyrolysis ovens in parallel.
• a furnace comprises one or more tubes arranged in parallel.
• a furnace can also refer to a group of furnaces operating in parallel. For example, a furnace can be dedicated to cracking a hydrocarbon stream comprising compounds having a boiling point lower than 150 ° C, in particular between 80 and 150 ° C, and another furnace dedicated to the hydrocarbon stream comprising compounds having a boiling point greater than 150 ° C.
• This step of e) of steam cracking makes it possible to obtain at least one effluent, in particular an effluent by hydrocarbon stream sent to step e) of steam cracking, containing olefins comprising 2, 3 and / or 4 carbon atoms (c ' ie C2, C3 and / or C4 olefins), in 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 olefins total comprising 2, 3 and 4 carbon atoms relative to the weight of the steam cracking effluent considered.
• Said C2, C3 and C4 olefins can then be advantageously used as polyolefin monomers.
• the process for treating a feed comprising an oil for pyrolysis of plastics preferably comprises: sequence of the steps described above, and preferably in the order given, that is to say: the pretreatment step ao), the selective hydrogenation step a), the step b) of hydrotreatment, step c) of separation, optionally step d) of fractionation, and step e) of steam cracking.
• FIG. 1 represents the diagram of an embodiment of the process of the present invention, comprising: a stage a) of selective hydrogenation of a hydrocarbon feed resulting from the pyrolysis of plastics 1, in the presence of a rich gas in hydrogen 2 and optionally of an amine supplied by stream 3, produced in at least one fixed bed reactor comprising at least one selective hydrogenation catalyst, to obtain an effluent 4; a step b) of hydrotreating the effluent 4 from step a), in the presence of hydrogen 5, carried out in at least one fixed bed reactor comprising at least one hydrotreatment catalyst, to obtain a hydrotreated effluent 6; a step c) of separating the effluent 6 carried out in the presence of an aqueous washing solution 7 and making it possible to obtain at least one fraction 8 comprising hydrogen, an aqueous fraction 9 containing dissolved salts, and a fraction hydrocarbon liquid 10.
• FIG. 2 shows a variant of the implementation of the process according to the invention shown in Figure 1.
• the liquid hydrocarbon fraction 10, obtained at the end of step c ) is sent to a fractionation step d) making it possible to obtain at least one gaseous fraction 11, a fraction comprising naphtha 12 and a hydrocarbon fraction 13.
• Figure 3 shows a variant of the implementation of the process according to the invention shown in Figure 2.
• the hydrocarbon feed resulting from the pyrolysis of plastics 1 undergoes a step ao) of pretreatment, prior to step a) of selective hydrogenation.
• the then pretreated feed 14 feeds step a) of selective hydrogenation.
• step d) the fraction comprising naphtha 12 and / or the hydrocarbon fraction 13 is / are sent to a steam cracking process.
• the feed treated in the process is a plastic pyrolysis oil (that is to say comprising 100% by weight of said plastic pyrolysis oil) having the characteristics indicated in Table 2.
• Table 2 load characteristics
• Load 1 is subjected to a step a) of selective hydrogenation carried out in a fixed bed reactor and in the presence of hydrogen 2 and of a selective hydrogenation catalyst of the NiMo type on alumina under the conditions indicated in Table 3. .
• Table 3 conditions of step a) of selective hydrogenation
• step a) of selective hydrogenation all of the diolefins initially present in the feed were converted.
• 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 5 and of a hydrotreatment catalyst of NiMo type on alumina under the conditions presented in Table 4.
• the effluent 6 from hydrotreatment step b) is subjected to a separation step c): a stream of water is injected into the effluent from hydrotreatment step b); the mixture is then treated in an acid gas washing column, separator flasks. Then the liquid effluent obtained is sent to a fractionation step d) which comprises a stripping column.
• a separation step c) a stream of water is injected into the effluent from hydrotreatment step b); the mixture is then treated in an acid gas washing column, separator flasks. Then the liquid effluent obtained is sent to a fractionation step d) which comprises a stripping column.
• Table 5 The yields of the various fractions obtained after separation and fractionation are shown in Table 5 (the yields corresponding to the ratios of the mass quantities of the various products obtained relative to the mass of feedstock upstream of step a), expressed as a percentage and noted% m / m).
• the PI-150 ° C and 150 ° C + liquid fractions both exhibit compositions compatible with a steam cracking unit since: - they do not contain olefins (mono- and di-olefins); they have very low chlorine element contents (respectively an undetected content and a content of 25 ppb by weight) and below the limit required for a steam cracker charge (£ 50 ppb by weight); the metal contents, in particular iron (Fe), are also very low (metal contents not detected for the PI-150 ° C fraction and ⁇ 1 ppm by weight for the 150 ° C + fraction; Fe contents not detected for the PI-150 ° C fraction and 50 ppb weight for the 150 ° C + fraction) and below the limits required for a steam cracker charge (£ 5.0 ppm by weight, very preferably £ 1 ppm by weight for metals; £ 100 ppb weight for Fe); - finally they contain sulfur ( ⁇ 2 ppm by weight for the PI-150 ° C fraction and
• the mixture of the two liquid fractions also has very low contents of olefins and of contaminants (in particular of metals, chlorine, sulfur, nitrogen) making the composition compatible with a steam cracking unit.
• the PI-150 ° C and 150 ° C + liquid fractions obtained are therefore then sent to a steam cracking step where the liquid fractions are cracked under different conditions (see Table 7).
• the PI + mixture can also be sent directly to a steam cracking step according to the conditions mentioned in Table 7.
• the process according to the invention makes it possible to achieve overall mass yields of ethylene and propylene respectively of 34.7% and 18.9% relative to the mass quantity of initial plastic pyrolysis oil type charge.
• the specific sequence of steps upstream of the steam cracking step makes it possible to limit the formation of coke and to avoid the corrosion problems that would have arisen if the chlorine had not been removed.
• the fractionation step includes in addition to a stripping column a distillation section so as to obtain a diesel cut that can be integrated directly into a diesel pool, that is to say meeting the specifications requested for a diesel and in particular the specification of the T90 D86 at 360 ° C.
• the load to be treated is identical to that described in Example 1 (see Table 2).
• Table 11 gives the characteristics of the cuts 150-385 ° C and 385 ° C +, and the commercial specifications EN-590 of a diesel. Table 11: characteristics of cuts 150-385 ° C and 385 ° C + and commercial specifications EN-590
• Table 11 shows that the 150-385 ° C cut qualifies to be sent directly to the diesel pool.
• the hydrocarbon feed of pyrolysis oil type identical to that used in Example 1 is sent directly to a steam cracking step.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=69700116

Family Applications (1)

Country Status (10)

Families Citing this family (26)

Citations (2)

Family Cites Families (37)

• 2019
  • 2019-12-02 FR FR1913625A patent/FR3103822B1/fr active Active
• 2020
  • 2020-11-16 CA CA3155475A patent/CA3155475A1/fr active Pending
  • 2020-11-16 WO PCT/EP2020/082213 patent/WO2021110395A1/fr not_active Ceased
  • 2020-11-16 EP EP20804555.9A patent/EP4069802A1/de active Pending
  • 2020-11-16 CN CN202080083763.0A patent/CN114729264A/zh active Pending
  • 2020-11-16 KR KR1020227017930A patent/KR20220106135A/ko active Pending
  • 2020-11-16 US US17/781,078 patent/US12365842B2/en active Active
  • 2020-11-16 AU AU2020395451A patent/AU2020395451A1/en active Pending
  • 2020-11-16 JP JP2022532599A patent/JP7724216B2/ja active Active
• 2022
  • 2022-04-21 ZA ZA2022/04518A patent/ZA202204518B/en unknown

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events