WO2024083783A1 - Charge d'hydrocarbures dérivée de déchets plastiques mixtes - Google Patents

Charge d'hydrocarbures dérivée de déchets plastiques mixtes Download PDF

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Publication number
WO2024083783A1
WO2024083783A1 PCT/EP2023/078761 EP2023078761W WO2024083783A1 WO 2024083783 A1 WO2024083783 A1 WO 2024083783A1 EP 2023078761 W EP2023078761 W EP 2023078761W WO 2024083783 A1 WO2024083783 A1 WO 2024083783A1
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mol
weight
feed stream
stream
ppm
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PCT/EP2023/078761
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English (en)
Inventor
Robert C. Schucker
Jason LOILAND
Dustin Farmer
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Sabic Global Technologies B.V.
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Publication of WO2024083783A1 publication Critical patent/WO2024083783A1/fr

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    • 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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products

Definitions

  • the present invention is directed to a process and a system of producing a hydrocarbon feedstock comprising an oligomeric product derived from waste plastic material and is particularly suitable for fluidized catalytic cracking.
  • the invention further relates to such hydrocarbon feedstock and its associated properties.
  • Fluidized Catalytic Cracking is one of the processes of obtaining gasoline and other high valued chemicals such as ethylene and propylene from a hydrocarbon feedstock.
  • gasoline and other high valued chemicals such as ethylene and propylene
  • industry practitioners and governmental agencies have been exploring the option of producing gasoline and other high valued chemicals through a reliable and an economical feed source.
  • One of the challenges faced by operators of FCC units is the need of making the FCC process more operationally efficient and cost effective by increasing the extent of conversion of the hydrocarbon feedstock to obtain high valued chemical products while keeping the extent of coke formation to an acceptable level.
  • One possible approach can be to partially substitute expensive feed like vacuum gas oil with a material which is available in relative abundance and can therefore lower the cost of feedstock procurement. Further, it is desirable that the high valued chemicals such as propylene, butylene are produced at desired productivity while managing the extent of coke formation. Managing the coke formation is particularly beneficial as catalyst regeneration and productivity can be kept at an efficient level. As an additional consideration, FCC operators are often faced with the challenge of dealing with hydrocarbon feed having undesirably high amounts of inorganic material and chlorine. Unless such species are removed from the hydrocarbon feed, the presence of such species tend to adversely affect the FCC operation.
  • Some of the possible technologies to treat plastic waste can be technologies based on thermal cracking or catalytic cracking of plastic waste, since these technologies allow the treatment of mixtures of different types of plastics without the need of separation by polymer types, resulting in the generation of hydrocarbons suitable for producing high value chemicals.
  • thermal cracking has been investigated at the laboratory and pilot plant level, for the treatment of plastic waste.
  • ordinary processes of thermal cracking generate low quality and unstable hydrocarbons having a wide range of boiling points, which render such processes inefficient and uneconomical for waste plastic treatment.
  • FCC fluidized catalytic cracking
  • EP3878926A1 discloses a suspension comprising of a (1) vacuum gas oil and (2) between 1 and 15 wt% of a powder of plastic particles, comprising particles obtainable by cryogenic milling of waste polyethylene and/or waste polypropylene and having a size of smaller than 500 micron.
  • one of the object of the present invention is to provide a hydrocarbon feed stream derived, at least in part, from waste plastic material, which is suitable to be used as a feedstock for fluidized catalytic cracking (FCC) so as to produce high value chemicals at desired conversion and yield while mitigating the extent of coke formation.
  • FCC fluidized catalytic cracking
  • It is yet another objective of the present invention is to improve product conversion and reduce coke formation during fluidized catalytic cracking over traditional FCC feed such as VGO. It is yet another objective of the invention to produce hydrocarbon feed suitable to be used in an FCC unit with minimal energy consumption. It is yet another objective of the present invention to produce one or more cracked hydrocarbon product in an energy efficient manner at high conversion and minimal coke formation using a fluidized catalytic cracking process.
  • FIG. 1 is a schematic diagram illustrating an embodiment of the present invention, where a process involving a step of diluting the product stream (J) once obtained, with an additional vacuum gas oil feed (AV) in a blending unit (E) and subsequently obtaining the feed stream (H)
  • AV vacuum gas oil feed
  • FIG. 2 is a schematic diagram illustrating an embodiment of the present invention, where a process involving a step of passing the product stream (J) once obtained, into a separation unit (C) prior to blending with the additional vacuum gas oil feed (AV) in the blending unit (E), to obtain the hydrocarbon feed stream (H).
  • FIG. 3 is a schematic diagram illustrating an embodiment of the present invention, where a process involving the step of supplying the waste plastic feed stream (W) and a vacuum gas oil feed (V) to a de-chlorination unit (B) and forming a stream (D) which is subsequently introduced to the thermal cracking unit (A) to obtain the product stream (J).
  • the schematic diagram further illustrates that the product stream (J) is subsequently diluted with an additional vacuum gas oil feed (AV) in a blending unit (E) to subsequently obtain the hydrocarbon feed stream (H).
  • FIG. 3 is a schematic diagram illustrating an embodiment of the present invention, where a process involving the step of supplying the waste plastic feed stream (W) and a vacuum gas oil feed (V) to a de-chlorination unit (B) and forming a stream (D) which is subsequently introduced to the thermal cracking unit (A) to obtain the product stream (J).
  • the schematic diagram further illustrates that the product stream (J) is subsequently diluted with
  • FIG. 4 is a schematic diagram illustrating an embodiment of the present invention, where a process involving the use of a de-chlorination unit (B), a separation unit (C), and obtaining the hydrocarbon feed stream (H).
  • the hydrocarbon feed stream (H) is subsequently introduced into the fluidized catalytic cracker (FCC).
  • FIG. 5-7 is a graphical representation to show that when the hydrocarbon feed stream (R1-R6) from the example section, comprising oligomeric product (Ol) is used as a feed in fluidized catalytic cracking, the use of such a feed resulted in a decrease in coke at constant conversion compared to a traditional FCC feed comprising only of vacuum gas oil (VGO).
  • VGO vacuum gas oil
  • FIG. 8-10 is a graphical representation to show that when the hydrocarbon feed stream (R1-R6) from the example section, comprising the oligomeric product (Ol) is used as a feed in fluidized catalytic cracking, the use of such a feed results in an increase in propylene (C3 olefin) yield at constant conversion compared to a traditional FCC feed comprising only of vacuum gas oil (VGO).
  • VGO vacuum gas oil
  • FIG. 11-13 is a graphical representation to show that when the hydrocarbon feed stream (R1-R6) from the example section, comprising the oligomeric product (Ol) is used as a feed in fluidized catalytic cracking, the use of such feed resulted in an increase in butenes (C4 olefins) yield at constant conversion compared to a traditional FCC feed comprising only of vacuum gas oil (VGO).
  • VGO vacuum gas oil
  • the product stream (J) comprises an oligomeric product (Ol) derived from the one or more polymers (Pl), further wherein the oligomeric product (Ol) has a weight average molecular weight of > 1,000 g/mol and ⁇ 20,000 g/mol, preferably > 1,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol, as determined with gel permeation
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of > 0 and ⁇ 20.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H)
  • the invention relates to a process for producing a hydrocarbon feed stream (H), comprising the steps of:
  • a thermal cracking unit (ii) supplying the waste plastic feed stream (W) and optionally a vacuum gas oil feed (V) to a thermal cracking unit (A) to thermally crack at least a portion of the waste plastic feed stream (W) and forming a product stream (J), wherein the product stream (J) comprises an oligomeric product (Ol) derived from the one or more polymers (Pl), further wherein the oligomeric product (Ol) has a weight average molecular weight of > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography; and
  • the invention relates to a process for producing a hydrocarbon feed stream (H), comprising the steps of:
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of > 2.0 wt.% and ⁇ 10.0 wt.% and the product stream (J) comprises the oligomeric product (Ol) having a weight average molecular weight of > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography.
  • the blending of product stream (J) with an additional vacuum gas oil feed (AV) results in obtaining the hydrocarbon feed stream (H), which when subjected to fluidized catalytic cracking results in higher conversion to commercially valuable hydrocarbons.
  • the inventors propose to combine hydrocarbon feed such as VGO with the oligomeric product stream, as a route to chemically recycle plastics, leading to the production of circular polymers and gasoline components at high conversion rate.
  • hydrocarbon feed such as VGO
  • oligomeric product stream as a route to chemically recycle plastics
  • the VGO also plays a role as a ‘solvent’ for the product stream (J), which comprises the oligomeric product (Ol).
  • the hydrocarbon feed stream (H) is suitable for other types of hydrocarbon cracking such as steam cracking.
  • VGO vacuum gas oil
  • vacuum gas oil feed is referred to as additional vacuum gas oil feed, it should be understood that it may be the first use of vacuum gas oil in the process if vacuum gas oil is optionally not present in the thermal cracking step.
  • the weight average molecular weight may be measured by any suitable gel permeation chromatography method.
  • the weight average molecular weight is determined with gel permeation chromatography using polystyrene standard in accordance with ASTM D5296-11.
  • Oligomeric product (Ol) is determined with gel permeation chromatography using polystyrene standard in accordance with ASTM D5296-11.
  • the oligomeric product (Ol) has a higher weight average molecular weight than vacuum gas oil and typical pyoil and pyoil derived products.
  • the contribution from vacuum gas oil is not considered.
  • the product stream (J) is substantially free of pyoil or pyrolysis products.
  • the product stream (J) comprises 0.0 wt.% of pyoil or pyrolysis products.
  • the oligomeric product (Ol) has a higher weight average molecular weight than pyoil or products derived from pyrolysis of waste plastics.
  • Pyrolysis oil including that made from plastic feedstock, is commonly understood to have a weight average molecular weight of less than 1000 g/mol, more likely to be less than 600 g/mol even more likely to be less than 400 g/mol and more likely to be about 200 g/mol, and would require an energy intensive process to produce it resulting in increased capital expenditure as well as operational expenditure to produce such low molecular weight species.
  • paraffin boiling points as the basis to estimate average molecular weight of the pyoil sample is likely to provide higher than actual molecular weights for the pyoil samples and the actual average molecular weights are very likely lower than those shown in Table 1.
  • the conversion to obtain oligomeric product (Ol) requires lower energy requirements than a process involving pyrolysis, which depolymerizes a polymeric material to a significantly larger degree than what is practiced in the present invention. Therefore, the process of thermal cracking to obtain the oligomeric product (Ol) is not only energy efficient and environmentally less harmful but also renders the process economically efficient in terms of lower capital and operational costs.
  • oligomeric product (Ol) Some depolymerization of plastic is necessary for obtaining the oligomeric product (Ol), as there may be compatibility and processing issues during cracking in the FCC unit of a hydrocarbon feed stream (H) comprising oligomeric product (Ol) having high weight average molecular weight, such as that of most plastics.
  • the oligomeric product (Ol) can have a weight average molecular weight as low as 1,000 g/mol, to fully realize the advantages of the present invention, it is preferable to use one with a higher weight average molecular weight, preferably > 2,000 g/mol, preferably > 8,000 g/mol, preferably > 9,000 g/mol, and preferably > 12,000 g/mol, may be even more preferable, but after considering the amount of plastic sought to be processed.
  • the product stream (J) comprises > 90.0 wt.%, preferably > 95.0 wt.%, preferably > 98.0 wt.%, preferably > 99.0 wt.%, preferably > 99.5 wt.%, preferably 100.0 wt.% of the oligomeric product (Ol), with regard to the total weight of the product stream (J).
  • the process of the present invention comprises a step of supplying the waste plastic feed stream (W) and the vacuum gas oil feed (V) to the thermal cracking unit (A), to thermally crack at least a portion of the waste plastic feed stream (W) and forming the product stream (J).
  • the waste plastic feed stream (W) and the vacuum gas oil feed (V) may be blended together to form a thermal cracking stream and subsequently introduced into the thermal cracking unit (A).
  • the waste plastic feed stream (W) and the vacuum gas oil feed (V) may be blended in an amount such that the thermal cracking stream has > 80 wt.%, more preferably > 90 wt.% of the thermal cracking stream.
  • waste plastic feed stream (W) and the vacuum gas oil feed (V) may be introduced separately into the thermal cracking unit (A) and subsequently cracked under conditions of thermal cracking.
  • the schematic diagram illustrates an embodiment of the invention, involving the steps of supplying the waste plastic feed stream (W) and the vacuum gas oil feed (V) to a thermal cracking unit (A) to thermally crack at least a portion of the waste plastic feed stream (W) and forming the product stream (J).
  • the product stream (J) is subsequently diluted with an additional vacuum gas oil feed (AV) in a blending unit (E) and obtaining the hydrocarbon feed stream (H)
  • vacuum gas oil feed is referred to as additional vacuum gas oil feed, it should be understood that it could be the first use of vacuum gas oil in the process if vacuum gas oil is optionally not present in the thermal cracking step.
  • the blending unit (E) may be a mixing chamber where the product stream (J) and additional vacuum gas oil feed (AV) are blended.
  • the blending unit (E) may be system of conduits which enables the product stream (J) to be combined additional vacuum gas oil feed (AV).
  • the product stream (J) obtained from the thermal cracking unit (A) is blended with the additional vacuum gas oil feed (AV) to obtain the hydrocarbon feed stream (H) having a sufficient amount of vacuum gas oil and the oligomeric product (Ol) suspended in the vacuum gas oil.
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content in an amount of ⁇ 20.0 wt.%, preferably ⁇ 15.0 wt.%, preferably ⁇ 10.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of > 0.5 wt.% and ⁇ 20.0 wt.%, preferably > 0.5 wt.% and ⁇ 15.0 wt.%, preferably > 0.5 wt.% and ⁇ 10.0 wt.%, preferably > 1.0 wt.% and ⁇ 8.0 wt.%, preferably > 2.0 wt.% and ⁇ 10.0 wt.%, preferably > 2.0 wt.% and ⁇ 5.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H)
  • the hydrocarbon feed stream (H) has a vacuum gas oil content of > 80.0 wt.%, preferably > 85.0 wt.%, preferably > 90.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the hydrocarbon feed stream (H) has a vacuum gas oil content of > 80.0 wt.% and ⁇ 99.5 wt.%, preferably > 85.0 wt.% and ⁇ 99.5 wt.%, preferably > 90.0 wt.% and ⁇ 99.5 wt.%, preferably > 92.0 wt.% and ⁇ 99.0 wt.%, preferably > 90.0 wt.% and ⁇ 98.0 wt.%, preferably > 95.0 wt.% and ⁇ 98.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the additional VGO feed serves as a solvent for the oligomeric product (Ol). If the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of > 20.0 wt.%, the solubility of the oligomer will not be sufficient for further processing in the FCC unit. On the other hand, if the amount of oligomeric product (Ol) is ⁇ 0.5 wt.%, the desired conversion to cracked products through FCC operation will not be at desired levels.
  • the hydrocarbon feed stream (H) is particularly suited for fluidized catalytic cracker unit (FCC).
  • FCC fluidized catalytic cracker unit
  • the hydrocarbon feed stream (H) comprises:
  • the oligomeric product (Ol) having a weight average molecular weight of > 1,000 g/mol and ⁇ 20,000 g/mol, > 1,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol, as determined with gel permeation chromatography.
  • hydrocarbon feed stream (H) comprises:
  • the oligomeric product (Ol) having a weight average molecular weight of > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol, as determined with gel permeation chromatography.
  • hydrocarbon feed stream (H) comprises:
  • the oligomeric product (Ol) has a weight average molecular weight of > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 10,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography
  • the atomic chlorine may be measured by any suitable method. Preferably as determined in accordance with ASTM UOP 779-08.
  • the present inventors found that for the hydrocarbon feed stream (H), when used as a feedstock in a fluidized catalytic cracker (FCC), the feedstock conversion is desirably high while minimizing the extent of coke formation.
  • the inventors found that the hydrocarbon feed stream (H) at similar levels of conversion, produces higher yields of polyolefins as compared to traditional FCC feedstock comprising substantially only of vacuum gas oil (VGO). This is particularly surprising as often high feed conversion leads to increased formation of coke.
  • the invention now enables a skilled person of not only improving the efficiency of a fluidized catalytic cracking process but also a method of effectively using waste plastic materials.
  • the invention relates to a hydrocarbon feed stream (H) obtainable by the process of the present invention.
  • the hydrocarbon feed stream (H) comprises:
  • the oligomeric product (Ol) having a weight average molecular weight of > 1,000 g/mol and ⁇ 20,000 g/mol, preferably > 1,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography.
  • the hydrocarbon feed stream (H) comprises (i) a vacuum gas oil content of > 80.0 wt.% and ⁇ 99.5 wt.%, preferably > 85.0 wt.% and ⁇ 99.5 wt.%, preferably > 90.0 wt.% and ⁇ 99.5 wt.%, preferably > 92.0 wt.% and ⁇ 99.0 wt.%, preferably > 90.0 wt.% and ⁇ 98.0 wt.%, preferably > 95.0 wt.% and ⁇ 98.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H) and (ii) an oligomeric product (Ol) content of > 0.5 wt.% and ⁇ 20.0 wt.%, preferably > 0.5 wt.% and ⁇ 15.0 wt.%, preferably > 0.5 wt.% and ⁇ 10.0 wt.%, preferably > 1.0 wt.%
  • the hydrocarbon feed stream (H) obtainable by the process of the present invention comprises:
  • the oligomeric product (Ol) having a weight average molecular weight of > 1,000 g/mol and ⁇ 20,000 g/mol, preferably > 1,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and
  • ⁇ 15,000 g/mol preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography; and
  • the invention relates to one or more cracked hydrocarbon products obtainable by a process comprising the steps of:
  • ⁇ 15,000 g/mol preferably > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography;
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of ⁇ 20.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the invention relates to one or more cracked hydrocarbon products obtainable by a process comprising the steps of:
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of ⁇ 20.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the atomic chlorine may be measured by any suitable method. Preferably as determined in accordance with ASTM UOP 779-08.
  • the hydrocarbon feed stream (H) when obtained from the process of the present invention has a suitable content of inorganic material, a suitable atomic chlorine content and an oligomeric product having a suitable weight average molecular weight.
  • the content of inorganic material and atomic chlorine is kept within a desirable limit so as to prevent poisoning of the catalyst system in the FCC unit and prevent corrosion of the equipment from the hydrochloric acid generated from a chlorine containing feed.
  • the waste plastic feed stream (W) comprising the polymer (Pl) may be derived, at least in part, from a waste plastic material.
  • waste plastic material include mixed plastic waste (MPW), waste plastic film, agricultural waste, waste generated from construction material, post-industrial waste, post-consumer waste and waste from material recycle facilities (MRFs).
  • the vacuum gas oil feed (V) may be any distillate product obtained when distilling under vacuum the distillation residue of an atmospheric distillation of a crude petroleum feedstock.
  • distillate product means any product not being the residue or bottom product of the vacuum distillation.
  • a suitable vacuum gas oil has an API gravity of between 19 and 23and an initial boiling point between 255 and 300 °C, a 10% boiling point of between 343 and 393 °C, a 50% boiling point of between 438 and 465 °C, a 90 % boiling point of between 500 and 560 °C and a final boiling point of between 527 and 582 °C.
  • the API gravity may be measured by any suitable method such as ASTM D4052.
  • the boiling point of vacuum gas oil may be measured by any suitable method such as ASTM DI 160.
  • the one or more polymer (Pl) may be at least one polymer selected from polyethylene, polypropylene, PS (Polystyrene); PVC (Polyvinyl chloride); PET (Polyethylene terephthalate); PUT (Polyurethanes), PP&A fibres (Polyphthalamide fibres), polyvinylidene chloride, ABS (acrylonitrile-butadiene-styrene), nylon, aramid, fluorinated polymers, and combinations thereof.
  • the one or more polymer (Pl) is at least one polymer selected from polypropylene or polyethylene.
  • the polymer (Pl) is polyethylene.
  • the polyethylene may be a low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE).
  • the polymer (Pl) is a low density polyethylene (LDPE).
  • the polymer (Pl) is a low density polyethylene (LDPE) derived from a waste plastic film.
  • the one or more polymer (Pl) is a mixture of polyethylene and polypropylene.
  • the one or more polymer (Pl) may have a weight average molecular weight of > 40,000 g/mol and ⁇ 500,000 g/mol, preferably > 50,000 g/mol and ⁇ 200,000 g/mol, preferably > 50,000 g/mol and ⁇ 150,000 g/mol as determined with gel permeation chromatography.
  • the oligomeric product (Ol) is derived from the one or more polymer (Pl).
  • the one or more polymer (Pl) under conditions of thermal cracking is depolymerized to form the oligomeric product (Ol) having a weight average molecular weight lower than that of the one or more polymer (Pl).
  • the thermal cracking unit (A) may be operated at a temperature of > 350 °C and ⁇ 500 °C, preferably at a temperature of > 370°C and ⁇ 450 °C, preferably at a temperature of > 375 °C and ⁇ 400 °C and at a feed residence time of > 10.0 minutes and ⁇ 80.0 minutes, preferably > 15.0 minutes and ⁇ 60.0 minutes, preferably > 25.0 minutes and ⁇ 60.0 minutes.
  • the thermal cracking unit (A) may be operated at a temperature of > 350 °C and ⁇ 400 °C and at a feed residence time of > 25.0 minutes and ⁇ 60.0 minutes.
  • the thermal cracking unit (A) may be operated at a temperature of > 375 °C and ⁇ 400 °C and at a feed residence time of > 40.0 minutes and ⁇ 60.0 minutes.
  • the thermal cracking of the one or more polymer (Pl) is carried out at a temperature of > 375 °C and ⁇ 400 °C and at a feed residence time of > 40.0 minutes and ⁇ 60.0 minutes. At such operating conditions the polymer (Pl) is only partially depolymerized.
  • feed residence time means the residence time of the waste plastic feed stream (W) and optionally the vacuum gas oil feed (V) inside the thermal cracking unit (A).
  • the thermal cracking unit (A) is configured to operate in a manner such that when the feed residence time is high, the feed comprising the waste plastic feed stream (W) and optionally the vacuum gas oil feed (V) is subjected to a lower cracking temperature. On the other hand, when the feed residence time is low, the feed comprising the waste plastic feed stream (W) and optionally the vacuum gas oil feed (V) is subjected to a higher cracking temperature.
  • the product stream (J) may be passed through a separation unit (C) prior to blending the product stream (J) with the additional vacuum gas oil feed (AV) such that the product stream (J) being blended with the additional vacuum gas oil feed (AV) has a total inorganic material content of ⁇ 1.0 wt.%, preferably ⁇ 0.8 wt.%, preferably ⁇ 0.5 wt.%, preferably 0.0 wt.%, with regard to the total weight of the product stream (J).
  • the separation unit (C) is configured to remove inorganic material from the product stream (J) so that the feed stream (H) has desirably low inorganic material content.
  • the inorganic material is preferred to be kept low so as to prevent a possible deactivation of the catalyst in the FCC unit.
  • Non-limiting examples of inorganic material include calcium carbonate (CaCCh), inorganic anti-oxidant, light stabilizers, polymerization catalyst residue, titanium dioxide, silicon based materials, which are typically additives present in polymers.
  • CaCCh calcium carbonate
  • inorganic anti-oxidant inorganic anti-oxidant
  • light stabilizers light stabilizers
  • polymerization catalyst residue titanium dioxide
  • silicon based materials which are typically additives present in polymers.
  • the separation unit (C) may be any suitable separation apparatus such as a centrifuge separator or a membrane separation unit.
  • the centrifuge separator may be operated at a temperature of about 150 °C or lower while the membrane separation unit can be operated at about 400 °C or lower.
  • the process involves the step of supplying the waste plastic feed stream (W) and the vacuum gas oil feed (V) to a thermal cracking unit (A) to thermally crack at least a portion of the waste plastic feed stream (W) and forming a product stream (J).
  • the product stream (J) is passed through a separation unit (C) prior to blending with the additional vacuum gas oil feed (AV) in the blending unit (E) and obtaining the hydrocarbon feed stream (H).
  • the waste plastic feed stream (W) being supplied to the thermal cracking unit (A) has an atomic chlorine content of ⁇ 50.0 ppm by weight, preferably ⁇ 40.0 ppm by weight, preferably ⁇ 30.0 ppm by weight, preferably ⁇ 10.0 ppm by weight, preferably ⁇ 0.5 ppm by weight, preferably 0.0 ppm by weight.
  • the atomic chlorine may be measured by any suitable method. Preferably as determined in accordance with ASTM UOP 779-08.
  • the waste plastic feed stream (W) may be passed through a de-chlorination unit (B) to reduce the atomic chlorine content in the waste plastic feed stream (W).
  • the process of the present invention comprises a step of passing the waste plastic feed stream (W) and optionally the vacuum gas oil feed (V) through a de-chlorination unit (B) prior to being supplied to the thermal cracking unit (A), such that the waste plastic feed stream (W) being supplied to the thermal cracking unit (A) has an atomic chlorine content of ⁇ 50.0 ppm by weight, preferably ⁇ 40.0 ppm by weight, preferably ⁇ 30.0 ppm by weight, preferably ⁇ 10.0 ppm by weight, preferably ⁇ 0.5 ppm by weight, preferably 0.0 ppm by weight.
  • the process comprises a step of passing both the waste plastic feed stream (W) and the vacuum gas oil feed (V) in the de-chlorination unit (B) and obtaining a stream (D); and supplying the stream (D) to the thermal cracking unit (A), wherein the stream (D) has an atomic chlorine content of ⁇ 50.0 ppm by weight, preferably ⁇ 40.0 ppm by weight, preferably ⁇ 30.0 ppm by weight, preferably ⁇ 10.0 ppm by weight, preferably ⁇ 0.5 ppm by weight, preferably 0.0 ppm by weight.
  • the stream (D) obtained from the de-chlorination unit (B) and comprises the waste plastic feed stream (W) and the vacuum gas oil feed (V).
  • the de-chlorination unit is configured to receive a stream with high concentration of atomic chlorine.
  • the waste plastic feed stream (W) being introduced in the dechlorination unit (B) may have an atomic chlorine content of ⁇ 6,000 ppm by weight, preferably ⁇ 2,000 ppm by weight, preferably ⁇ 1,000 ppm, preferably ⁇ 500 ppm by weight, preferably ⁇ 200 ppm by weight.
  • the atomic chlorine may be measured by any suitable method. Preferably as determined in accordance with ASTM UOP 779-08.
  • the de-chlorination unit (B) may be operated at a temperature of > 250 °C and ⁇ 400 °C, preferably at a temperature of > 275 °C and ⁇ 325 °C and at a feed residence time of > 10.0 minutes and ⁇ 80.0 minutes, preferably > 15.0 minutes and ⁇ 60.0 minutes.
  • the process involves supplying the waste plastic feed stream (W) and the vacuum gas oil feed (V) in the de-chlorination unit (B) and forming a stream (D). Subsequently, introducing the stream (D) to the thermal cracking unit (A) and obtaining the product stream (J). The product stream (J) is further diluted with the additional vacuum gas oil feed (AV) in the blending unit (E) and obtaining the hydrocarbon feed stream (H).
  • the process further comprises the step of introducing the hydrocarbon feed stream (H) in a fluidized catalytic cracker unit (FCC) operating under conditions suitable for cracking the hydrocarbon feed stream (H) in presence of a catalyst and obtaining a product stream (FP) comprising one or more cracked hydrocarbon products.
  • FCC Fluidized Catalytic Cracker
  • the invention relates to a process for producing one or more cracked hydrocarbon products comprising the steps of:
  • the product stream (J) comprises an oligomeric product (Ol) derived from the one or more polymers (Pl), further wherein the oligomeric product (Ol) has a weight average molecular weight of > 1,000 g/mol and ⁇ 20,000 g/mol, > 1,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 15,000 g/mol, preferably > 2,000 g/mol and ⁇ 10,000 g/mol, preferably > 8,000 g/mol and ⁇ 18,000 g/mol, preferably > 9,000 g/mol and ⁇ 18,000 g/mol, preferably > 12,000 g/mol and ⁇ 18,000 g/mol as determined with gel permeation chromatography;
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of ⁇ 20.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H).
  • the hydrocarbon feed stream (H) has an oligomeric product (Ol) content of > 0.5 wt.% and ⁇ 20.0 wt.%, preferably > 0.5 wt.% and ⁇ 15.0 wt.%, preferably > 0.5 wt.% and ⁇ 10.0 wt.%, preferably > 1.0 wt.% and ⁇ 8.0 wt.%, preferably > 2.0 wt.% and ⁇ 5.0 wt.%, with regard to the total weight of the hydrocarbon feed stream (H)
  • the fluidized catalytic cracker unit may be operated at catalyst to oil weight ratio ranging from > 3: 1 to ⁇ 10: 1 and at a temperature ranging from > 450 °C and ⁇ 750 °C, preferably > 500 °C and ⁇ 650 °C.
  • the reaction time of the feed in contact with the catalyst during the fluidized catalytic cracking ranges from > 15 and ⁇ 75 seconds, preferably > 45 and ⁇ 65 seconds.
  • the pressure may be maintained at atmospheric pressure.
  • catalyst to oil weight ratio means the ratio of the weight of the catalyst to the amount of feed that is introduced in the fluidized catalytic cracker unit for cracking (hydrocarbon feed stream (H)).
  • the catalyst may be an equilibrium catalyst (E-CAT) comprising at least one of USY zeolite, X-type zeolite, mordenite, Faujasite, nano-crystalline zeolites, MCM mesoporous materials, SBA-15, a silica-alumino phosphate, a gallophosphate, a titanophosphate, ZSM-5 zeolite, RE-Y zeolite, RE-USY zeolite, and CREY zeolite.
  • E-CAT equilibrium catalyst
  • the cracked hydrocarbon products are selected from ethylene, propylene, C4-C30 hydrocarbons, and C6-C30 aromatics, gasoline, LPG, diesel oil, heavy oil, dry gas.
  • the hydrocarbon feed stream (H) is converted to cracked hydrocarbon products at a conversion of at least > 73.0 % at a catalyst to oil weight ratio of 4.5.
  • the hydrocarbon feed stream (H) is converted to cracked hydrocarbon products at a conversion of at least > 75.0 % at a catalyst to oil weight ratio of 6.0.
  • the hydrocarbon feed stream (H) is converted to cracked hydrocarbon products at a conversion of at least > 76.0 % at a catalyst to oil weight ratio of 9.1.
  • conversion as used herein can be determined by:
  • Dry gas comprises C1-C2 hydrocarbons.
  • Gasoline includes light naphtha, which includes C5-C6 hydrocarbons having boiling point in the range of 30-90 °C and heavy naphtha which includes Ce- C12 hydrocarbons having boiling point in the range of 90-200 °C.
  • the invention relates to the use of the hydrocarbon feed stream (H) as a feed for improving product conversion of a fluidized catalytic cracking process.
  • product conversion means conversion to one or more cracked hydrocarbon using fluidized catalytic cracking.
  • the process of the present invention comprises the step of (a) introducing the waste plastic feed stream (W) and the vacuum gas oil feed (V) in the de-chlorination unit (B) and obtaining a stream (D); (b) introducing the stream (D) to the thermal cracking unit (A) and obtaining the product stream (J); (c) passing the product stream (J) into a separation unit (C); (d) blending the resultant stream from step (c) with the additional vacuum gas oil feed (AV) in a blending unit (E) and obtaining the hydrocarbon feed stream (H). Hydrocarbon feed stream (H) is then fed to and processed in FCC unit (FCC).
  • FCC FCC unit
  • the invention relates to a system suitable for producing the hydrocarbon feed stream (H).
  • the system comprises:
  • thermo cracking unit A configured to receive the waste plastic feed stream (W) and optionally vacuum gas oil (VGO) feed (V) to produce the product stream (J);
  • a de-chlorination unit B
  • the de-chlorination unit (B) is in fluid communication with the thermal cracking unit (A) and wherein the de-chlorination unit is positioned upstream of the thermal cracking unit (A) and wherein the de-chlorination unit (B) is configured to receive the waste plastic feed stream (W) and optionally the vacuum gas oil (VGO) feed (V);
  • a blending unit (E) configured to blend at least a portion of the product stream (J) stream obtained from the thermal cracking unit (A) and at least a portion of the additional vacuum gas oil feed (AV) to obtain the hydrocarbon feed stream (H);
  • a separation unit (C) optionally, a separation unit (C), wherein the separation unit (C) is in fluid communication with the thermal cracking unit (A) and the blending unit (E) such that the separation unit (C) is positioned downstream to the thermal cracking unit (A) and upstream to the blending unit (E).
  • the invention relates to a system suitable for producing one or more cracked hydrocarbon products.
  • the system suitable for producing the one or more cracked hydrocarbon products comprises:
  • thermo cracking unit A configured to receive the waste plastic feed stream (W) and optionally vacuum gas oil (VGO) feed (V) to produce the product stream (J);
  • a de-chlorination unit B
  • the de-chlorination unit (B) is in fluid communication with the thermal cracking unit (A) and wherein the de-chlorination unit is positioned upstream of the thermal cracking unit (A) and wherein the de-chlorination unit (B) is configured to receive the waste plastic feed stream (W) and optionally the vacuum gas oil (VGO) feed (V);
  • a blending unit (E) configured to blend at least a portion of the product stream (J) stream obtained from the thermal cracking unit (A) and at least a portion of the additional vacuum gas oil feed (AV) to obtain the hydrocarbon feed stream (H);
  • a separation unit (C) optionally, a separation unit (C), wherein the separation unit (C) is in fluid communication with the thermal cracking unit (A) and the blending unit (E) such that the separation unit (C) is positioned downstream to the thermal cracking unit (A) and upstream to the blending unit (E);
  • a fluidized catalytic cracker unit (e) a fluidized catalytic cracker unit (FCC), wherein the fluidized catalytic cracker unit (FCC) is configured to receive the hydrocarbon feed stream (H) and produce one or more cracked hydrocarbon products.
  • Operation of a commercial scale fluidized catalytic cracker unit may be evaluated in an ACE (Advanced Catalyst Evaluation) unit as described in the patent U.S. 6,069,012 incorporated by reference.
  • the thermal cracking unit may be an autoclave reactor.
  • Process - Six hydrocarbon feed stream samples (R1-R6) were prepared using the following approach: Approximately 30 grams of shredded black mulch film was placed into an autoclave (thermal cracking unit), which was then sealed and flushed with nitrogen. The temperature was set to the desired operating set point but the stirrer was not started until the temperature of 150 °C was reached (which is above the melting point of the LDPE polymer). At this point, the stirrer was turned on to 250 RPM and held at that value until the end of the run. Thermal cracking was carried out at three different temperatures (375°C, 390 °C for 60 minutes each and 410 °C for 30 minutes) and the product stream (J) was obtained for each of the six samples.
  • FIG. 5-7 show that when the inventive hydrocarbon feed stream (R1-R6) comprising oligomeric product (Ol) is used as a feed in fluidized catalytic cracking, the use of such a feed resulted in a decrease in coke at constant conversion compared to a traditional FCC feed comprising only of vacuum gas oil (VGO).
  • VGO vacuum gas oil
  • FIG. 11-13 show that when the hydrocarbon feed stream (R1-R6) comprising the oligomeric product (Ol) is used as a feed in fluidized catalytic cracking, there is a significant increase in butenes (C4 olefins) yield at constant conversion compared to a traditional FCC feed comprising only of vacuum gas oil (VGO).
  • VGO vacuum gas oil

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Abstract

L'invention concerne un procédé et un système de production d'une charge hydrocarbures comprenant un produit oligomère dérivé de déchets de matière plastique, une telle charge d'hydrocarbures étant particulièrement appropriée pour un craquage catalytique fluidisé. L'invention concerne en outre une telle charge d'hydrocarbures et ses propriétés associées.
PCT/EP2023/078761 2022-10-19 2023-10-17 Charge d'hydrocarbures dérivée de déchets plastiques mixtes WO2024083783A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6069012A (en) 1997-05-23 2000-05-30 Kayser Technology, Inc. Versatile fluidized bed reactor
EP3878926A1 (fr) 2020-03-09 2021-09-15 Michiel Cramwinckel Suspension d'un déchet plastique et d'un gazole sous vide, sa préparation et son utilisation dans fcc
US20210301210A1 (en) * 2020-03-30 2021-09-30 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene via refinery fcc feed pretreater and fcc units
WO2022130052A1 (fr) * 2020-12-18 2022-06-23 Sabic Global Technologies B.V. Procédé de dépolymérisation d'un plastique mixte solide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6069012A (en) 1997-05-23 2000-05-30 Kayser Technology, Inc. Versatile fluidized bed reactor
EP3878926A1 (fr) 2020-03-09 2021-09-15 Michiel Cramwinckel Suspension d'un déchet plastique et d'un gazole sous vide, sa préparation et son utilisation dans fcc
US20210301210A1 (en) * 2020-03-30 2021-09-30 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene via refinery fcc feed pretreater and fcc units
WO2022130052A1 (fr) * 2020-12-18 2022-06-23 Sabic Global Technologies B.V. Procédé de dépolymérisation d'un plastique mixte solide

Non-Patent Citations (1)

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Title
MISKOLCZI N. ET AL: "Hydrocarbons obtained by waste plastic pyrolysis: Comparative analysis of decomposition described by different kinetic models", FUEL PROCESSING TECHNOLOGY, vol. 104, 1 December 2012 (2012-12-01), NL, pages 96 - 104, XP093032044, ISSN: 0378-3820, DOI: 10.1016/j.fuproc.2012.04.031 *

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