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WO2025068057A1 - Installation de vapocraqueur pour la conversion de déchets plastiques en oléfines - Google Patents

Installation de vapocraqueur pour la conversion de déchets plastiques en oléfines Download PDF

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Publication number
WO2025068057A1
WO2025068057A1 PCT/EP2024/076497 EP2024076497W WO2025068057A1 WO 2025068057 A1 WO2025068057 A1 WO 2025068057A1 EP 2024076497 W EP2024076497 W EP 2024076497W WO 2025068057 A1 WO2025068057 A1 WO 2025068057A1
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Prior art keywords
plastic waste
feedstock
furnace
steam cracker
cracker
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English (en)
Inventor
Shahram Mihan
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Basell Poliolefine Italia SRL
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Basell Poliolefine Italia SRL
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Publication of WO2025068057A1 publication Critical patent/WO2025068057A1/fr
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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
    • 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
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • 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
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • This disclosure relates to an integrated cracker setup for the production of C2-C4 olefins. More specifically, this disclosure relates to an integrated cracker setup based on fed with renewable and plastic waste feedstock.
  • Crackers plants are a crucial aspect of the petrochemical industry. By traditionally “cracking” fossil fuel-based materials they perform the first step in producing downstream products such as resins and plastics.
  • Chemical recycling for example, in the version plastic-to-feedstock includes the steps of collecting plastic waste material, followed by heating the plastic waste material to break down the polymers to obtain smaller organic molecules which are then recirculated in the petrochemical industry.
  • the main effluent from the pyrolysis step is a liquid stream, also called pyrolytic oil, which can be subject to a steam cracking step to generate a gaseous fraction composed by C2- C4 olefins.
  • a liquid stream also called pyrolytic oil
  • the global yields in olefins, particularly ethylene and propylene, in respect of plastic waste feedstock are still at a level of about 35% which is not entirely satisfactory.
  • the present disclosure provides a steam cracker setup comprising: at least one electrical furnace for depolymerizing polyolefin based plastic waste said furnace operating with an efficiency of at least 70% raw gas based on polyolefin content in plastic waste and at least one furnace for renewable feedstock having a final boiling point (FBP) of less than 550°C and optionally, a hydrogenation unit.
  • FBP final boiling point
  • the cracker set-up can comprise: at least one electrical furnace for depolymerizing polyolefin based plastic waste said furnace operating with an efficiency of at least 70% raw gas based on polyolefin content in plastic waste; at least one furnace for renewable feedstock having a final boiling point (FBP) of ⁇ 550°C; and at least one electrical furnace for steam cracking feedstock other than plastic waste and renewable feedstock; a quench/fractionation unit receiving the outputs of said furnaces and generating a light hydrocarbon stream and a heavier liquid stream; a cracker backend separation unit receiving the light hydrocarbon stream from the quench/fractionation unit; optionally a hydrogenation unit fed with the heavier liquid stream from the quench/ fractionation unit and an output connected with the electrical furnace for steam cracking feedstock other than plastic waste and renewable feedstock; said set-up being characterized by the fact that the raw gas of the plastic waste furnace is sent to the cracker backend separation unit by-passing the quench/fractionation unit.
  • FBP final boiling point
  • the cracker setup also include a hydrotreating/hydrocracking unit to upgrade heavy cracker residues as well as pyrolysis oil feed (Pyroil, PFO, HVGO etc).
  • a hydrotreating/hydrocracking unit to upgrade heavy cracker residues as well as pyrolysis oil feed (Pyroil, PFO, HVGO etc).
  • the cracker setup also includes at least a further electrical furnace for feedstock other than plastic waste or renewable feedstock such as for example fossil based feedstock like naphtha or natural gas.
  • Fig. 1 is a block flow diagram showing the integrated steam cracker set-up according to the present disclosure.
  • the electrical furnace for the depolymerization of polyolefin based plastic waste is operated at a temperature ranging from 400 to 750°C with a plastic waste feedstock comprising more than 80% wt of polyolefins based on the polymeric content of the plastic waste feedstock.
  • the plastic waste feedstock is characterized by: (a) a polyolefin content, in particular a total content of polypropylene (PP) and polyethylene (PE) of more than 85 wt.%, more preferably more than 90 wt.%, especially more than 95 wt.% based on the total weight of the polymeric waste material feedstock.
  • a polyolefin content in particular a total content of polypropylene (PP) and polyethylene (PE) of more than 85 wt.%, more preferably more than 90 wt.%, especially more than 95 wt.% based on the total weight of the polymeric waste material feedstock.
  • the upper limit of polyolefin content is 99 wt%, more preferably 98 wt% and especially 97 wt% based on the total amount of plastic waste feedstock.
  • the total ash content of the plastic waste feedstock is preferably less than 10 wt.%, more preferably less than 5 wt.%, and most preferably less than 3 wt.%, determined as residue after heating the polymeric waste material feedstock at 800 °C for 120 hours in air.
  • the plastic waste feedstock is also characterized by (i) a bulk density from 70 to 500 g/1, preferably from 100 to 450 g/1 for cases in which the polymeric waste material feedstock is present in shredded form or a bulk density from 300 to 700 g/1 for cases in which the polymeric waste material feedstock is in pellet form, the bulk density being determined according to DIN 53466, respectively.
  • the plastic waste feedstock is additionally characterized by: (i) a content of total volatiles (TV), measured as the weight loss of a 10 g sample at 100°C after 2 hours at 200 mbar, of less than 4%, preferably less than 3%.
  • TV total volatiles
  • the polymeric waste material feedstock employed in the process of the present disclosure may include essentially all polymeric materials, in particular those materials formed from synthetic polymers.
  • Non-limiting examples include polyolefins other than PE and PP, such as polybutene- 1 and ethylene-propylene elastomers etc., polystyrene, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide, polycarbonate, polyurethane, polyester, natural and synthetic rubber, tires, filled polymers, composites and plastic alloys, plastics dissolved in a solvent, etc.
  • the plastic feedstock preferably consists primarily of polyolefins and the nonpolyolefin polymeric materials may be present only in an amount lower than 10%, preferably lower than 5% based on the total amount of plastic waste feedstock.
  • the polymeric waste material feedstock can be composed of one type of polyolefin waste material or may be a mixture of two or more different polymeric waste materials.
  • the embodiment in which the polyolefin waste material is composed entirely by polyethylene (PE) is particularly preferred.
  • the polymeric waste material feedstock may be provided in a variety of different forms.
  • the polymeric waste material feedstock may be in the form of a powder.
  • the polymeric waste material feedstock may be in the form of pellets, flakes and powders, such as those having a particle size from 1 to 30 mm counting for at least 80wt% of the feedstock (preferably 85%, 90%), preferably from 2 to 20 mm, and more preferably from 2 to 8 mm, or, when in the form of shredded flakes and/or small pieces of film, preferably having a particle size from 1 to 20 mm.
  • having a particles size in a defined range means that 90 wt.% of the particles have a particle size which is in the defined range.
  • the particle size may be determined by sieving or by using a Beckman Coulters LSI 3320 laser diffraction particle size analyzer.
  • the plastic waste material disclosed above mostly consists of plastic material and is generally named after the type of polymer which forms the predominant component of the polymeric waste material.
  • the plastic waste material employed as feedstock in the process of the present disclosure contains more than 50 wt.% of its total weight of the polymeric material, preferably more than 6 wt.% and more preferably more than 70 wt.%.
  • Other components in the polymeric waste material feedstock may, for example, be additives, such as fillers, reinforcing materials, processing aids, plasticizers, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, inks, antioxidants, pigments etc.
  • the polymeric waste materials used in the process of the present disclosure preferably comprises polyolefins and polystyrene, such as high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ethylene- propylene-diene monomer (EPDM), polypropylene (PP), and polystyrene (PS).
  • polyolefins and polystyrene such as high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ethylene- propylene-diene monomer (EPDM), polypropylene (PP), and polystyrene (PS).
  • HDPE high-density polyethylene
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • EPDM ethylene- propylene-diene monomer
  • PP polypropylene
  • PS polystyrene
  • non-polyolefin polymeric waste materials such as polyamide, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), acrylonitrile-butadiene- styrene (ABS), nylon and fluorinated polymers can also be employed in the process of the present disclosure. If present in the polymeric waste material, those polymers are preferably present in an amount of less than 10% and especially less than 5% of the total weight of the dry weight polymeric waste material feedstock.
  • the polymeric waste material is essentially free of thermosetting polymers. Essentially free in this regard is intended to denote a content of thermosetting polymers of less than 10 wt.% and even more preferably less than 5 wt.% of the polymeric waste material feedstock.
  • the polymeric waste materials used in the process of the present disclosure are preferably selected from the group consisting of single plastic waste, mixed plastics waste, rubber waste. Single plastic waste, single virgin plastic off spec, mixed plastics waste, rubber waste or a mixture thereof are preferred. Single virgin plastic off-spec, mixed plastics waste or a mixture thereof are particularly preferred.
  • the polymeric waste material may also contain limited quantities of non-pyrolysable components such as water, glass, stone, metal and the like as contaminants.
  • "Limited quantities” preferably mean an amount of less than 15 wt.%, and more preferably less than 10 wt.% of the total weight of the dry polymeric waste material feedstock.
  • the polymeric waste material can optionally be extruded prior to being employed as feedstock in the process of the present disclosure.
  • the polymeric waste material is pelletized, and the pellets are employed as feedstock in the process of the present disclosure.
  • the polymeric waste material is employed in a molten state, for example at temperatures from 200°C to 300°C.
  • a particularly preferred type of polymeric waste material employed as feedstock in the process of the present disclosure is characterized by the following features: i) A polyolefin content, in particular the content of polypropylene (PP) and/or polyethylene (PE) in the polymeric waste material of more than 80 wt.%, preferably more than 85 wt.%, and more preferably more than 90 wt.%, especially more than 95 wt.% based on the total weight of the polymeric waste material feedstock; ii) The polymeric waste material is a shredded and optionally compacted polymeric waste material in powder, flakes or agglomerate form having a bulk density from 70 to 500 g/1, preferably from 100 to 450 g/1, more preferably 200 to 440g/l, especially 250-400 g/1.
  • PP polypropylene
  • PE polyethylene
  • the polymeric waste material is in pellet, form and has a bulk density from 250 to 700 g/1, the bulk density being determined according to DIN 53466; iii) A total content of volatiles (TV), measured as the weight loss of a 10 g sample at 100 °C and a pressure of 200 mbar after 2 hours of less than 5%, preferably less than 3%, and more preferably less than 2%, especially less than 1%; iv) An amount of polar polymer contaminants in the polymeric waste material of less than 5 wt.%, and more preferably less than 3 wt.%, based on the total weight of the polymeric waste material; v) An amount of cellulose, wood and/or paper in the polymeric waste material of less than 5 wt.%, and more preferably less than 3%, based on the total weight of the polymeric waste material; vi) A total chlorine content of less than 1.0 wt.%, preferably less than 0.5 wt.%, more preferably less than 0.1 wt.%
  • the polymeric waste materials employed as feedstock in the process of the present disclosure is defined by upper limits of minor components, constituents or impurities expressed as percent by weight.
  • the lower limits for the amounts of these components, constituents or impurities in the preferred polymeric waste materials are preferably below the detection limit, or the lower limits are 0.001 wt.% or 0.01 wt.% or 0.1 wt.%, respectively.
  • a variety of techniques are known to separate materials in a polymeric waste stream. Moving beds, drums and screens, and air separators are used to differentiate materials by size, weight and density. Advanced sorting of plastic waste by spectroscopy techniques (MIR, NIR [near-infrared]), X-ray or fluorescence spectroscopy deliver high quality plastic waste streams with high polyolefin content.
  • Automatic Separation Techniques of waste plastics comprise dry sorting technique, electrostatic sorting technique, mechanical sorting method (involves centrifugal force, specific gravity, elasticity, particle shape, selective shredding and mechanical properties) as well as wet sorting technique (e.g. sink float sorting method) and chemical sorting methods.
  • a suitable feedstock to be employed in the process of the present disclosure may be obtained by applying any of the known sorting techniques, as e.g. summarized in B. Ruj et al: Sorting of plastic waste for effective recycling, Int. J. Appl. Sci. Eng. Res 4, 2015, 564-571.
  • the process for the depolymerization of plastic waste material comprises pyrolyzing the plastic waste material at a temperature preferably ranging from 350 to 750°C, preferably from 420 to 700°C, more preferably from 460 to 680°C and especially from 500 to 680°C.
  • the temperature is preferably kept in the range from 500°C to 700°C more preferably in the range from 500 to 600°C.
  • the depolymerization process may be only thermal or thermocatalytic.
  • a catalyst is present, it is chosen from those comprising, as the active component, an acidic compound preferably selected from metal oxides, heteropolyacids, mesoporous silica, aluminosilicates catalysts, such as halloysite and kaolinite, and preferably from zeolites optionally modified.
  • an acidic compound preferably selected from metal oxides, heteropolyacids, mesoporous silica, aluminosilicates catalysts, such as halloysite and kaolinite, and preferably from zeolites optionally modified.
  • particularly preferred zeolites are synthetic Y-type zeolite and ZSM-5.
  • One preferred specific type of catalyst comprises as the active component an acidic compound deposited on a particulate non-porous support with the aid of a coating agent.
  • the catalyst of the present disclosure is in particulate form.
  • particulate non-porous support selected from the group consisting of sand, glass beads and metal particles.
  • the particulate non-porous support may have any shape such as spherical, cylindrical or any non-homogenous shape.
  • the support employed in the catalyst of the present invention is also non-porous. Non-porous within the meaning of the present disclosure is to be understood as being not permeable to gases, such as air, or liquids such as water.
  • Sand is a preferred type of non-porous particulate support, and preferably, has a particle size distribution of:
  • the acidic compound of the catalyst of the present disclosure is preferably selected from the group consisting of Al/Si mixed oxides, AI2O3, aluminosilicates, silica and zeolites.
  • Al/Si mixed oxides which are particularly preferred in the present disclosure, refer to a material comprising a mixture of AI2O3 and SiO2, having a neutral structure.
  • Zeolites which are particularly preferred, as referred to in the present disclosure are understood to be crystalline microporous aluminosilicates which are built up from corner-sharing SiO4- and AIO4- tetrahedrons having the general structure M n +x/n [AlO2]-x(SiO2) y ]+ ZH2O with n being the charge of the cation M, typically an alkaline or alkaline earth metal or hydrogen ion, preferably an ion selected from the group consisting of H + , Na + , Ca2 + , K + and Mg2 + , and z defining the number of water molecules incorporated into the crystal structure.
  • Zeolites differ from mixed Al/Si oxides by their defined pore structure and ionic character.
  • the zeolite employed as the acidic compound is selected from the group consisting of Zeolite Y, Zeolite Beta, Zeolite A, Zeolite X, Zeolite L and mixtures thereof, especially Zeolite Y and Zeolite Beta.
  • the listed zeolites are well-known and commercially available. Particularly preferred are zeolites wherein the metal ion M is substituted by a hydrogen.
  • zeolite-type components include but are not limited to ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS- 2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU-1, NU-10, silicalite- 1 , silicahte-2, boralite-C, boralite-D, BCA, and mixtures thereof.
  • the determination of the SiCh and AI2O3 content of the acidic compound can be carried out by atomic emission spectroscopy using an inductively coupled plasma (ICP-AES).
  • ICP-AES inductively coupled plasma
  • the coating agent employed in the catalyst of the present disclosure is preferably selected from the group consisting of oil, inorganic hydrogel or combinations thereof.
  • inorganic hydrogel preference is given to silica hydrogel.
  • oils employed as the coating agent preference is given to aromatic-free white mineral oil, preferably based on iso-paraffins.
  • the oil employed has a kinematic viscosity at 20°C of 140 to 180 mm 2 /s, preferably 150 to 170 mm 2 /s and/or a kinematic viscosity at 40°C of 40 to 80 mm 2 /s, preferably 50 to 70 mm 2 /s and/or a kinematic viscosity at 100°C of 5 to 15 mm 2 /s, preferably 7 to 10 mm 2 /s.
  • the kinematic viscosity can be determined according to ISO 3104.
  • the preferred amount of coating agent ranges from 1 to 300% preferably from 2 to 150%wt, more preferably from 5 to 100%wt and most preferably 10-80%wt based on amount of acidic compound.
  • the amount to be employed is referred to the dry weight.
  • the active compound is comprised in the catalyst of the present disclosure in an amount of 0.5 to 6 wt.%, preferably 2 to 4 wt.%, based on the total weight of the catalyst.
  • the catalyst of the present disclosure is preferably obtained by mixing the particulate non- porous support and the coating agent and then adding the acidic compound in the form of a powder to the obtained mixture.
  • the mixture may be optionally heat treated to obtain the catalyst.
  • the heat treatment may, for example, be carried out at a temperature of 100 to 800°C, preferably 150 to 600°C.
  • the particulate non-porous support is subjected to a drying step before being mixed with the coating agent.
  • the catalyst is obtained by a process comprising the steps of: (a) mixing the particulate non-porous support and the coating agent; and (b) adding the acidic compound in powder form to the mixture of step (a).
  • the catalyst is characterized as follows: (a) sand as a particulate non-porous support; (b) an Al/Si mixed oxide or a zeolite as acidic compound; and (c) mineral oil or silica hydrogel as coating agent.
  • the catalyst package may include also a cocatalysts, for example a clay, component and/or a solid base component for example a metal hydroxide.
  • a cocatalysts for example a clay, component and/or a solid base component for example a metal hydroxide.
  • the gaseous effluent from the pyrolysis reactor is then collected and separated into a gaseous and a liquid depolymerization product.
  • the collected gaseous fractions may be separated into liquid and gaseous depolymerization products by condensation.
  • the liquid depolymerization product and the gaseous depolymerization product may be further processed.
  • the process of the present disclosure may generate little to no char. Therefore, in preferred embodiments, the residue of the depolymerization process of the present disclosure has a char content of less than 5 wt.%, preferably less than 2 wt.%, based on the total weight of the product.
  • the obtained liquid depolymerization product may be further separated. Therefore, the cracker setup preferably further comprise a step of distilling the liquid depolymerization product.
  • the process of the present disclosure yields a depolymerization product with a high gaseous content.
  • the amount of gaseous depolymerization product is at least 70% wt of the total polyolefin content in the plastic waste, preferably more than 75%wt, more preferably higher than 80% wt and especially higher than 85%wt of the total polyolefin content in the plastic waste.
  • the amount of C2-C4 olefins is equal to or higher than 50%wt based on the total amount of hydrocarbons.
  • the amount of olefinic C2-C4-compounds is equal to or higher than 55% and preferably higher than 60% and especially higher than 65% based on the total amount of hydrocarbons in the gaseous depolymerization product.
  • the percentage of ethylene on the total of olefinic C2-C4 compounds is higher than 28%wt and preferably higher than 30%wt.
  • the amount of C2-C4 hydrocarbons in the gaseous fraction of the depolymerization product is preferably higher than 80% preferably higher than 85% and especially higher than 90% based on the total amount of hydrocarbons.
  • the gaseous product comprising light olefins and light alkanes can be directly transferred to a separation unit in the cracker backend where olefins are separated from the other hydrocarbon components.
  • the gaseous product before being sent to a separation unit, is sent to a cleaning/purification unit for contaminants removal.
  • a cleaning/purification unit for contaminants removal.
  • Such unit which may be comprised of several sections for the removal of contaminants like HC1, HCN, H2S, H2O, NH3, COS, MeCl, MeSH, NOx, etc.
  • a caustic scrubber section is an example of the conventional units usable for this purpose.
  • the gaseous stream coming from the cleaning/purification section can be sent to the quench section of the steam cracker.
  • olefins and the other hydrocarbon components can be subject to different uses.
  • Olefins like ethylene and propylene can be used in polymerization processes and therefore reintroduced in the plastic cycle.
  • Unsaturated C4 hydrocarbons can be either used in polymerization or subject to a steam cracker step, preferably after having been subject to a hydrogenation step in a hydrogenation unit.
  • Saturated hydrocarbons such as ethane, propane and butanes can be sent directly to the additional steam cracking furnace in the conventional way.
  • the liquid depolymerization product obtained from the distillation unit can also be sent to an additional steam cracking furnace. However, subjecting the liquid product to a hydrotreating/hydrocracking step for upgrading the pyrolytic oil is especially preferred.
  • Plastic Waste Depolymerization Furnace [0069] Plastic Waste Depolymerization Furnace [0070] Plastic Waste Depolymerization Furnace [0070] The depolymerization process according to the present disclosure can be carried out in a reactor comprising: (a) feeding devices for introducing polymeric waste material and catalyst into the reactor; (b) a pyrolysis device equipped with heating units, gas discharge units and a solid discharge unit; and (c) a condensation unit.
  • the reactor may comprise more than one pyrolysis unit.
  • any type of reactor used for pyrolysis can be used provided that heating is generated by the use of electricity.
  • any type of reactor used for pyrolysis can be used provided that heating is generated by the use of electricity.
  • screw type fluidized bed, circulating gas phase with and without catalyst, slurry loop or stirred tank, fixed bed, ebulliated bed reactors.
  • It can be for example an agitated vessel with rotating blades or, preferably, a horizontal reactor a screw equipped with a screw for homogenously mixing the polymeric waste material in the pyrolysis device throughout the depolymerization.
  • the residence time of the solids in the pyrolysis device could be well-defined by adjusting the rotational speed of the screw.
  • An example of screw reactor applicable for the present disclosure is described in WO2017/173473, herein enclosed for reference, showing a particular type of screw within which a heating fluid flows.
  • the gas discharge units are distributed throughout the pyrolysis device and are provided with an outlet to discharge the gaseous fraction of the depolymerization and an inlet for introducing cleaning gas into the pyrolysis device.
  • the gas discharge units are equipped with filter membrane to avoid solids to be present in the gaseous fractions after being discharged from the pyrolysis device.
  • the gas discharge units are preferably made of metallic or ceramic grain or fiber materials.
  • the electric furnace working as a depolymerization reactor is of the type described in WO2022/136333 the relevant portion of which is herein enclosed by reference.
  • the heat to the reactor is provided through a circulating molten salt the fusion of which has been obtained by electric heating.
  • the condensation unit comprises several condensers which are preferably operated at different temperatures.
  • the temperatures of the condensers may be set according to the boiling points of the condensates.
  • the polymeric waste feedstock and, if employed, the catalyst are introduced into the pyrolysis unit via at least one feeding device and then heated to achieve depolymerization.
  • the gaseous fractions generated during depolymerization are discharged through the outlet of the gas discharge units and conveyed to the condensation unit for further processing. Any solid residue of the depolymerization is discharged via the solid discharge unit.
  • Cleaning gas for cleaning the gas discharge units and the pyrolysis unit may be introduced through the inlet of the gas discharge units.
  • gaseous fractions generated during pyrolysis are separated into liquid and gaseous depolymerization products, e.g. by condensation.
  • the process of the present disclosure yields a depolymerization product of surprising very high selectivity for the gaseous fraction.
  • the obtained liquid depolymerization product especially when the run is carried out in the presence of a catalyst, shows a surprisingly low content of aromatic compounds and in particular a surprisingly low content of polycyclic aromatic compounds and asphaltanes.
  • the liquid depolymerization product obtained by the process of the present disclosure is accordingly characterized by a low content of aromatic and olefinic components as well as a high degree of purity.
  • the content of aromatic compounds in the obtained liquid depolymerization product is less than 10 mol%, preferably less than 5 mol%, and in particular no more than 3 mol%, the content of aromatic components being measured as contents of aromatic protons in mol% as determined by 1H-NMR -spectroscopy.
  • the liquid depolymerization product obtained by the depolymerization process of the present disclosure is characterized by a low content of olefinic compounds.
  • the content of olefinic compounds in the liquid depolymerization product is preferably less than 7 mol%, more preferably less than 5 mol%, even more preferably less than 3 mol%, based on the total number of hydrocarbon protons; the content of olefinic compounds being determined based on the contents of olefinic protons as determined by 1H-NMR -spectroscopy.
  • the liquid depolymerization product obtained in the process of the present disclosure has preferably a boiling range from 30 to 550°C, more preferably from 50 to 250°C.
  • the depolymerization product may be separated into hydrocarbon fractionations of different boiling ranges, for example a light naphtha fraction mainly containing Cs and Ce hydrocarbons having a boiling range from 30°C and 130°C, a heavy naphtha fraction mainly containing Ce to C12 hydrocarbons having a boiling range from 130°C to 220°C, a kerosene fraction mainly containing C9 to C17 hydrocarbons having a boiling range from 220°C to 270°C or into other high boiling point fractions such as diesel fuel, fuel oil or hydrowax.
  • the liquid depolymerization product contains little to no solid residue.
  • the content of residues of the liquid depolymerization product upon evaporation determined according to ASTM D381, is no more than 5 ppm (w).
  • the gaseous depolymerization product obtained shows a surprisingly low content of low molecular hydrocarbons such as methane or ethane. Rather, it was surprisingly found that the gaseous depolymerization product contained unusually high amounts of higher olefins such as ethylene, propylene, and butenes which are commonly desired for polyolefin production.
  • the amount of olefinic C2-C4-compounds is preferably equal to or higher than 55% and preferably higher than 60% and especially higher than 65% based on the total amount of hydrocarbons in the gaseous depolymerization product.
  • the gaseous depolymerization product obtained by the process of the present disclosure is characterized by a high content of any of ethylene, propylene, and butenes and also by a low content of saturated low molecular hydrocarbons, in particular hydrocarbons of the general formula C n H2n+2 wherein n is a real number ranging from 1 to 4.
  • the gaseous depolymerization product of the process of the present disclosure is characterized by a content of CO of at most 2 wt.%, preferably at most 1 wt.%, more preferably at most 3 wt.%, most preferably at most 2 wt.%, especially at most 0.1 -0.5 wt.%, based on the total weight of the gaseous depolymerization product after step (e) of the process of the present disclosure.
  • the gaseous depolymerization product of the process of the present disclosure is characterized by a content of CO2 of at most 5 wt.%, preferably at most 3 wt.%, more preferably at most 2 wt.%, based on the total weight of the gaseous depolymerization product after step (e) of the process of the present disclosure
  • the gaseous fraction could thus be directly used as feedstock for further processing in a cracker downstream, e.g. a raw gas compressor to obtain purified monomer streams, and thereafter for the subsequent production of polymers, allowing bypassing the highly energy consuming stream cracking ovens usually required while at the same time reducing the output of CO2.
  • a cracker downstream e.g. a raw gas compressor to obtain purified monomer streams
  • the global yield of C2/C3 olefins can range from 60 to 70% wt based on the amount of plastic waste feedstock.
  • the furnace working with the renewable feedstock can be one of those customarily used in the art.
  • the reactor can be the same as that used for the plastic waste furnace, thus for example, also in this case a reactor such as the one disclosed in WO2017/173473 can be used.
  • the liquid output products of this furnace may be merged with the liquid outputs of other furnaces and sent to a fractionation stage.
  • the pyrolysis fuel oil fraction (PFO) may be subject to a hydrotreating/hydrocracking stage and then reintroduced into the a conventional naphta furnace where they can be converted into lighter products including olefins.

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Abstract

Une installation de craquage intégré pour la production d'oléfines en C2-C4 est divulguée sur la base de l'utilisation intégrée d'une charge d'alimentation renouvelable et d'au moins une charge d'alimentation constituée de déchets plastiques, cette dernière étant convertie en un gaz brut avec une efficacité élevée.
PCT/EP2024/076497 2023-09-25 2024-09-20 Installation de vapocraqueur pour la conversion de déchets plastiques en oléfines Pending WO2025068057A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1290042A1 (fr) 2000-05-22 2003-03-12 Basell Polyolefine GmbH Catalyseur de polymerisation pour la production de polyolefines presentant des combinaisons de proprietes excellentes
WO2010050186A1 (fr) 2008-10-31 2010-05-06 財団法人北九州産業学術推進機構 Procédé et appareil pour la fabrication de carburant biodiesel, et catalyseur de décomposition pour la décarboxylation de graisses utilisé dans le procédé
WO2014111598A2 (fr) * 2013-01-21 2014-07-24 Total Research & Technology Feluy Procédé de production de bionaphta à partir de mélanges complexes de graisses et huiles d'origine naturelle
WO2017173473A1 (fr) 2016-04-06 2017-10-12 Next Generation Elements Gmbh Vis sans fin à thermorégulation interne, installation et procédé de mise en oeuvre d'une telle vis sans fin
US20190177626A1 (en) * 2016-10-11 2019-06-13 Sabic Global Technologies B.V. Maximizing high-value chemicals from mixed plastic using different steam-cracker configurations
WO2021163106A1 (fr) * 2020-02-10 2021-08-19 Eastman Chemical Company Recyclage chimique de flux dérivés de plastique dans une zone de séparation de craqueur avec une efficacité énergétique améliorée
WO2022136333A1 (fr) 2020-12-22 2022-06-30 Basell Poliolefine Italia S.R.L. Procédé destiné à la dépolymérisation de déchets de matière plastique
WO2023049027A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Traitement de gaz de pyrolyse comprenant un épurateur caustique
WO2023178157A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Installation de recyclage chimique avec équipement de traitement électrique
WO2023178137A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Procédé et système de recyclage chimique pour la fusion et la pyrolyse de déchets plastiques solides

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1290042A1 (fr) 2000-05-22 2003-03-12 Basell Polyolefine GmbH Catalyseur de polymerisation pour la production de polyolefines presentant des combinaisons de proprietes excellentes
WO2010050186A1 (fr) 2008-10-31 2010-05-06 財団法人北九州産業学術推進機構 Procédé et appareil pour la fabrication de carburant biodiesel, et catalyseur de décomposition pour la décarboxylation de graisses utilisé dans le procédé
WO2014111598A2 (fr) * 2013-01-21 2014-07-24 Total Research & Technology Feluy Procédé de production de bionaphta à partir de mélanges complexes de graisses et huiles d'origine naturelle
WO2017173473A1 (fr) 2016-04-06 2017-10-12 Next Generation Elements Gmbh Vis sans fin à thermorégulation interne, installation et procédé de mise en oeuvre d'une telle vis sans fin
US20190177626A1 (en) * 2016-10-11 2019-06-13 Sabic Global Technologies B.V. Maximizing high-value chemicals from mixed plastic using different steam-cracker configurations
WO2021163106A1 (fr) * 2020-02-10 2021-08-19 Eastman Chemical Company Recyclage chimique de flux dérivés de plastique dans une zone de séparation de craqueur avec une efficacité énergétique améliorée
WO2022136333A1 (fr) 2020-12-22 2022-06-30 Basell Poliolefine Italia S.R.L. Procédé destiné à la dépolymérisation de déchets de matière plastique
WO2023049027A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Traitement de gaz de pyrolyse comprenant un épurateur caustique
WO2023178157A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Installation de recyclage chimique avec équipement de traitement électrique
WO2023178137A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Procédé et système de recyclage chimique pour la fusion et la pyrolyse de déchets plastiques solides

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
B. RUJ ET AL.: "Sorting of plastic waste for effective recycling", INT. J. APPL. SCI. ENG. RES, vol. 4, 2015, pages 564 - 571
ESCHENBACHER ANDREAS ET AL: "Highly selective conversion of mixed polyolefins to valuable base chemicals using phosphorus-modified and steam-treated mesoporous HZSM-5 zeolite with minimal carbon footprint", APPLIED CATALYSIS B. ENVIRONMENTAL, ELSEVIER, AMSTERDAM, NL, vol. 309, 25 February 2022 (2022-02-25), XP086994800, ISSN: 0926-3373, [retrieved on 20220225], DOI: 10.1016/J.APCATB.2022.121251 *
HENRIK THUNMAN ET AL: "Circular use of plastics-transformation of existing petrochemical clusters into thermochemical recycling plants with 100% plastics recovery", vol. 22, 1 December 2019 (2019-12-01), pages 1 - 36, XP055690634, ISSN: 2214-9937, Retrieved from the Internet <URL:https://www.sciencedirect.com/science/article/pii/S2214993719300697> [retrieved on 20200430], DOI: 10.1016/j.susmat.2019.e00124 *
SIMON C.M ET AL: "Pyrolysis of polyolefins with steam to yield olefins", JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, vol. 38, no. 1-2, 1 December 1996 (1996-12-01), NL, pages 75 - 87, XP093084219, ISSN: 0165-2370, DOI: 10.1016/S0165-2370(96)00950-3 *

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