Co-processing route for hydroprocessing polymer waste based material

Abstract

A process for improving a polymer waste-based material is provided. The process includes providing a polymer waste-based feedstock, providing a feedstock obtained from crude oil, mixing the polymer waste-based feedstock, the feedstock obtained from crude oil, and optionally additional feed material to provide a feed mixture, hydroprocessing the feed mixture in an FCC feed hydrotreater to provide a hydrocarbon-containing material, and recovering at least a distillate product and a distillation bottoms product from the hydrocarbon-containing material (step E).

Description

Technical Field

[0001] The present invention generally relates to a route for co-processing polymer-based waste materials and fossil materials, and more specifically to a route employing a hydrotreating process under FCC feed hydrotreating conditions, and to the products obtained in the process. Background Technology

[0002] The purification of polymer waste (e.g., liquefied waste plastics (LWP)) to produce more valuable (pure) substances and the conversion of polymer waste into more valuable materials have been studied for many years. Polymer waste refers to waste materials containing polymers, such as plastic waste, end-life tires, and liquid polymer materials. In practice, polymer waste is often treated in the form of polymer waste-based oils (also known as liquefied polymer waste), such as liquefied waste plastics (LWP) or liquefied end-life tires.

[0003] Oils based on polymer waste can be produced through thermal degradation methods, such as hydrothermal liquefaction (HTL) or pyrolysis of polymer waste. Depending on the source of the polymer waste, it contains varying levels of impurities. Typical impurity components are chlorine, nitrogen, sulfur, and oxygen, with corrosive chlorine being particularly problematic for refining / petrochemical processes. These impurities are also commonly found in post-consumer waste plastics (recycled consumer plastics), which have been identified as a potential large-scale source of polymer waste, in addition to end-of-life tires. Similarly, bromine-containing impurities can be predominantly found in polymer waste obtained from industry (e.g., derived from flame retardants). Furthermore, depending on the actual production process, oils based on polymer waste produced via pyrolysis or hydrothermal liquefaction often contain significant amounts of olefins and aromatics, each of which can cause problems in downstream processes, such as polymerization (or coking) at elevated temperatures.

[0004] Whether polymer-based materials undergo only ordinary refining processes (such as fractionation) or are transferred to typical petrochemical conversion processes (such as steam cracking), polymer-based materials need to meet the impurity levels required by these processes in order to avoid facility degradation, such as reactor corrosion or catalyst poisoning.

[0005] Besides refining, chemically recycling polymer waste back into polymers (or monomers) is an interesting option. This option has attracted significant interest from the petrochemical industry in recent years. New waste directives and the EU Plastics Strategy have set ambitious targets for the recycling of waste plastics (polymer waste), further increasing this interest.

[0006] Therefore, it can be expected that chemical recycling will be an important method for recycling polymer waste back to polymers (plastics) and chemicals in the future.

[0007] Due to existing infrastructure, using polymer-based waste materials as feedstock for crackers (e.g., catalytic crackers, hydrocrackers, or steam crackers) is a promising method for recovering polymers. However, the potential of polymer-based waste materials as cracker feedstocks depends on their quality, and therefore methods for purifying polymer-based waste materials and / or modifying cracking processes to handle varying impurity content in the polymer waste have been proposed.

[0008] WO 2018 / 10443 A1 discloses a steam cracking process including pretreatment of a feedstock primarily composed of alkanes, such as hydrowax, hydrotreated vacuum gas oil, pyrolysis oil from waste plastics, gas oil, or slackwax. Solvent extraction is used for pretreatment to reduce scaling components, such as polycyclic aromatic hydrocarbons and resins.

[0009] US 2016 / 0264874 A1 discloses a process for improving waste plastics, which includes, in sequence, a pyrolysis step, a hydrogenation step, a polishing step, and a fluid cracking step.

[0010] Kawanishi,T.,Shiratori,N.,Wakao,H.,Sugiyama,E.,Ibe,H.,Shioya,M.,&Abe,T., “Upgrading of Light Thermal Cracking Oil Derived from Waste Plastics inOil Refinery.Feedstock recycling of plastics.” Karlsruhe, Karlsruhe (2005), pp. 43-50, discloses a method for hydrotreating a blend of petroleum fractions and light thermal cracking oils from waste plastics to avoid scaling of the heat exchanger before the hydrotreating processor. Summary of the Invention

[0011] The aforementioned existing methods employ complex purification processes, where extraction techniques may result in significant amounts of contaminated extracts or materials that are not yet fully suitable for subsequent processing, leading to scaling and reduced lifespan of processing equipment. A more sustainable process is still needed that allows for the recovery of varying amounts of polymer-based waste materials while generating low levels of waste products.

[0012] The present invention was made in view of the above-mentioned problems, and the object of the present invention is to provide an improved method for improving polymer-based waste materials, and in particular a more flexible method that allows for the efficient recycling of materials of different amounts and / or types of polymer-based waste.

[0013] The method of claim 1 solves the problem of providing an improved method for improving materials based on polymer waste.

[0014] In short, the present invention relates to one or more of the following:

[0015] 1. A method for improving polymer waste-based materials, the method comprising:

[0016] Provide raw materials based on polymer waste (Step A),

[0017] Provide feedstock obtained from crude oil (step B).

[0018] The feedstock, derived from polymer waste, crude oil, and optionally additional feed materials are mixed to provide a feed mixture (step C).

[0019] The feed mixture is hydrogenated in an FCC feed hydrotreating processor to provide a hydrocarbon-containing material (step D), and

[0020] At least the distillate products and the bottom products of distillation are recovered from the hydrocarbon-containing material (step E).

[0021] 2. According to the method of item 1, wherein the feedstock obtained from crude oil includes FCC feedstock.

[0022] 3. The method according to item 1 or 2, wherein the feedstock obtained from crude oil comprises at least one crude oil fraction selected from the following: vacuum gas oil (VGO) fraction, gas oil (GO) fraction, heavy gas oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction, and deasphalted oil (DAO) fraction, preferably selected from the following: vacuum gas oil (VGO) fraction, heavy gas oil (HGO) fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction, and deasphalted oil (DAO) fraction.

[0023] 4. The method according to any of the preceding items, wherein at least 40 wt.% of the feedstock obtained from crude oil is boiled at a temperature of 370°C or higher (40% distillation temperature according to ASTM-D2887).

[0024] 5. The method according to any of the preceding items, wherein at least 45 wt.-%, preferably at least 50 wt.-%, at least 55 wt.-%, at least 60 wt.-%, or at least 65 wt.-%, of the feedstock obtained from crude oil is boiled at a temperature of 370°C or higher.

[0025] 6. The method according to any of the preceding items, wherein the feedstock obtained from crude oil has a 5% boiling point of at least 160°C, preferably at least 170°C, at least 180°C, at least 190°C or at least 200°C (according to ASTM-D2887).

[0026] 7. The method according to any of the preceding items, wherein the feedstock obtained from crude oil has a 95% boiling point of 630°C or lower, preferably 610°C or lower, 590°C or lower, 570°C or lower, or 560°C or lower (according to ASTM-D2887).

[0027] 8. The method according to any of the preceding items, wherein the feedstock obtained from crude oil has a final boiling point of 650°C or lower, preferably 630°C or lower, 620°C or lower, 610°C or lower, or 600°C or lower (according to ASTM-D2887).

[0028] 9. The method according to any of the preceding items, wherein, in step E, at least a heavy gas oil (HGO) fraction is recovered, and the heavy gas oil fraction has a 10% boiling point of at least 300°C, preferably at least 310°C, at least 320°C, at least 330°C, at least 340°C, at least 345°C, at least 350°C, or at least 355°C (according to ASTM-D2887).

[0029] 10. The method according to any one of the preceding items, wherein, when the mass of the obtained heavy fraction (m) H ) and the total mass of liquid hydrocarbon products (m liq The ratio (m) H / m liq When calculating, the yield of the heavy fraction boiling at 350°C or higher obtained in step D is at least 50 wt.%, preferably at least 55 wt.%, at least 60 wt.%, or at least 65 wt.%.

[0030] 11. The method according to any one of the preceding items, wherein, when the mass (m) of the obtained light hydrocarbon fraction is used... L ) and the total mass of hydrocarbon-containing products (m ht The ratio (m) L / m htIn the calculation, the yield of the light hydrocarbon fraction boiling at 150°C or lower obtained in step D is at most 10.0 wt.-%, preferably at most 8.0 wt.-%, at most 6.0 wt.-%, at most 5.0 wt.-%, at most 4.0 wt.-%, at most 3.0 wt.-%, or at most 2.0 wt.-%.

[0031] 12. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a temperature in the range of 300-460°C.

[0032] 13. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a temperature of 320°C or higher, preferably 340°C or higher, or 360°C or higher.

[0033] 14. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a temperature of 455°C or lower, preferably 450°C or lower, 445°C or lower, 440°C or lower, 435°C or lower, 430°C or lower, 425°C or lower, 420°C or lower, 415°C or lower, or 410°C or lower.

[0034] 15. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a hydrogen partial pressure of at least 10 bar, preferably at least 20 bar, at least 25 bar, at least 30 bar, at least 33 bar, at least 35 bar, at least 38 bar or at least 40 bar.

[0035] 16. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a hydrogen partial pressure of up to 100 bar, preferably up to 90 bar, up to 80 bar, up to 70 bar, up to 60 bar, up to 55 bar or up to 50 bar.

[0036] 17. The method according to any one of the preceding items, wherein the FCC feed hydrogenation processor operates for at most 8.0 hours. -1 Preferred up to 6.0h -1 At most 4.0h -1 At most 3.0h -1 At most 2.0h -1 At most 1.5 hours -1 Or at most 1.3h -1 Liquid hourly space velocity (LHSV, m) 3 Liquid feed / m 3 Operation at (catalyst / hour).

[0037] 18. The method according to any one of the preceding items, wherein the FCC feed hydrogenation processor operates for at least 0.2 hours. -1 Preferably at least 0.4h -1 At least 0.6h-1 At least 0.7h -1 At least 0.8h -1 At least 0.9h -1 or at least 1.0h -1 Operating at liquid hourly space velocity (LHSV).

[0038] 19. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates at a ratio (H2 / HC) of up to 800 l / l, preferably up to 600 l / l, up to 500 l / l, up to 350 l / l or up to 300 l / l of hydrogen (H2) to feed mixture (HC).

[0039] 20. The method according to any one of the preceding items, wherein the FCC feed hydrogenation processor operates at a hydrogen (H2) to feed mixture (HC) ratio (H2 / HC) of at least 50 l / l, preferably at least 100 l / l, at least 120 l / l, at least 150 l / l, at least 180 l / l, at least 200 l / l or at least 220 l / l.

[0040] 21. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor uses a catalyst, preferably a supported catalyst.

[0041] 22. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor employs a catalyst, and the catalyst comprises at least one component selected from Group 6, 8 or 10 of the IUPAC periodic table.

[0042] 23. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor employs a catalyst, and the catalyst is a supported catalyst containing Mo and at least one other transition metal on a support.

[0043] 24. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor uses a catalyst, and the catalyst is a supported NiMo catalyst or a supported CoMo catalyst.

[0044] 25. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor uses a catalyst, and the catalyst is a supported catalyst, wherein the support comprises alumina and / or silica.

[0045] 26. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor uses a catalyst, and the catalyst is a supported NiMo catalyst, and the support includes alumina (NiMo / Al2O3).

[0046] 27. The method according to any of the preceding items, wherein the FCC feed hydrotreating processor uses a catalyst, and the catalyst is a supported CoMo catalyst, and the support includes alumina (CoMo / Al2O3).

[0047] 28. The method according to any of the preceding items, wherein the FCC feed hydrogenation processor operates under olefin saturation conditions.

[0048] 29. The method according to any of the preceding items, wherein the FCC feed hydrotreating processor is adjusted such that the ratio (BRh / BRf) of the bromine value (BRh) of the hydrocarbon-containing material to the bromine value (BRf) of the feed mixture is 0.50 or less, preferably 0.40 or less, 0.30 or less, 0.20 or less, 0.10 or less, 0.07 or less, 0.06 or less, 0.05 or less, or 0.04 or less.

[0049] 30. The method according to any one of the preceding items, wherein the method further comprises subjecting at least a portion of the distillation bottom product to fluidized catalytic cracking (FCC) together with the co-feed (FCC co-feed).

[0050] 31. The method according to any of the preceding items, wherein the polymer waste-based feedstock provided in step A is or includes polymer waste-based oil or its fraction.

[0051] 32. The method according to any of the preceding items, wherein the mixing in step C is carried out such that the feed mixture contains at most 50 wt.-%, preferably at most 40 wt.-%, at most 30 wt.-%, or at most 25 wt.-%, of polymer waste-based raw material.

[0052] 33. The method according to any of the preceding items, wherein the mixing in step C is carried out such that the feed mixture contains at least 0.5 wt.-%, preferably at least 1.0 wt.-%, at least 1.5 wt.-%, or at least 2.0 wt.-%, of polymer waste-based raw material.

[0053] 34. The method according to any of the preceding items, wherein the mixing in step C is carried out such that the feed mixture contains at least 25 wt.-%, preferably at least 30 wt.-%, at least 40 wt.-%, at least 50 wt.-%, at least 60 wt.-%, at least 70 wt.-%, or at least 75 wt.-%, of feedstock obtained from crude oil.

[0054] 35. The method according to any of the preceding items, wherein the mixing in step C is carried out such that the feed mixture contains up to 99 wt.% of the feedstock obtained from crude oil.

[0055] 36. The method according to any of the preceding items, wherein the raw material based on polymer waste is or includes liquefied polymer waste or a fraction thereof, such as liquefied waste plastic (LWP) or a fraction thereof, particularly waste plastic pyrolysis oil (WPPO) or a fraction thereof, or liquefied end-of-life tires or a fraction thereof, such as end-of-life tire pyrolysis oil (ELTPO) or a fraction thereof.

[0056] 37. The method according to any of the preceding items, wherein the raw material based on polymer waste is or includes pyrolysis oil raw material or a fraction thereof obtained from the pyrolysis of polymer waste, and / or the raw material based on polymer waste is or includes raw material or a fraction thereof obtained from the hydrothermal liquefaction of polymer waste.

[0057] 38. The method according to any of the preceding items, wherein the feedstock based on polymer waste is a pyrolysis oil feedstock or a fraction thereof.

[0058] 39. The method according to any of the preceding items, wherein the raw material based on polymer waste is a liquefied and pretreated material that has undergone pretreatment after liquefaction.

[0059] 40. The method according to any of the preceding items, wherein the raw material based on polymer waste has a chlorine content of 5 wt.-ppm or higher.

[0060] 41. The method according to any of the preceding items, wherein the raw material based on polymer waste has a chlorine content of 10 wt.-ppm or more, 15 wt.-ppm or more, 20 wt.-ppm or more, 50 wt.-ppm or more, or 100 wt.-ppm or more.

[0061] 42. The method according to any of the preceding items, wherein the raw material based on polymer waste has a chlorine content of 4000 wt.-ppm or less, 3000 wt.-ppm or less, 2000 wt.-ppm or less, 1000 wt.-ppm or less, 500 wt.-ppm or less, 400 wt.-ppm or less, or 200 wt.-ppm or less.

[0062] 43. The method according to any of the preceding items, wherein the raw material based on polymer waste has an olefin content of 10 wt.-% or more, 15 wt.-% or more, 20 wt.-% or more, 30 wt.-% or more, 40 wt.-% or more, or 50 wt.-% or more.

[0063] 44. The method according to any of the preceding items, wherein the raw material based on polymer waste has an olefin content of 85 wt.-% or less, 80 wt.-% or less, 70 wt.-% or less, or 65 wt.-% or less.

[0064] 45. The method according to any of the preceding items, wherein in step E, at least the heavy gas oil (HGO) fraction is recovered.

[0065] 46. ​​The method according to item 45, wherein the HGO fraction has an aromatic compound content of 10 wt.-% or more, 15 wt.-% or more, 20 wt.-% or more, 25 wt.-% or more, 30 wt.-% or more, or 40 wt.-% or more.

[0066] 47. The method according to item 45 or 46, wherein the HGO fraction has an aromatic compound content of 85 wt.-% or less, 80 wt.-% or less, 70 wt.-% or less, or 60 wt.-% or less.

[0067] 48. The method according to any one of items 45 to 47, wherein the HGO fraction has a nitrogen content of 100 wt.-ppm or more, 200 wt.-ppm or more, 300 wt.-ppm or more, 400 wt.-ppm or more, 500 wt.-ppm or more, or 600 wt.-ppm or more.

[0068] 49. The method according to any one of items 45 to 48, wherein the HGO fraction has a nitrogen content of 5000 wt.-ppm or less, 4000 wt.-ppm or less, 3000 wt.-ppm or less, or 2000 wt.-ppm or less.

[0069] 50. The method according to any one of items 45 to 49, wherein the HGO fraction has a sulfur content of 10 wt.-ppm or more, 20 wt.-ppm or more, 30 wt.-ppm or more, 50 wt.-ppm or more, 100 wt.-ppm or more, 200 wt.-ppm or more, 250 wt.-ppm or more, 300 wt.-ppm or more, 350 wt.-ppm or more, or 400 wt.-ppm or more.

[0070] 51. The method according to any one of items 45 to 50, wherein the HGO fraction has a sulfur content of 10,000 wt.-ppm or less, 6,000 wt.-ppm or less, 5,000 wt.-ppm or less, 4,000 wt.-ppm or less, or 3,000 wt.-ppm or less.

[0071] 52. The method according to any of the preceding items, wherein step A of providing the raw material based on polymer waste includes a stage of thermal degradation (e.g., pyrolysis or hydrothermal liquefaction) of the polymer waste.

[0072] 53. The method according to any one of the preceding claims, wherein the FCC feed hydrotreating processor employs a mixed catalyst, and the mixed catalyst comprises at least one supported CoMo catalyst, and the support comprises alumina (CoMo / Al2O3), and CoMo / Al2O3 accounts for at least 60 vol.-% of the total catalyst, more preferably at least 70 vol.-% or at least 80 vol.-%.

[0073] 54. The method according to item 53, wherein the mixed catalyst further comprises at least one supported NiMo catalyst and the support comprises alumina (NiMo / Al2O3).

[0074] 55. The method according to any of the preceding items, wherein the FCC feed hydrotreating processor employs a catalyst, and the catalyst is sulfided in its active form, such as a sulfided NiMo catalyst or a sulfided CoMo catalyst.

[0075] 56. The method according to any of the preceding items, wherein the FCC feed hydrotreating processor employs a catalyst, and the catalyst comprises a sulfided NiMo catalyst and / or a sulfided CoMo catalyst.

[0076] 57. The method according to any of the preceding items, wherein the polymer waste-based feedstock provided in step A is or includes oil based on non-fractionated polymer waste.

[0077] 58. The method according to any of the preceding items, wherein the bottom product of distillation has an aromatic compound content of 10 wt.-% or more, 15 wt.-% or more, 20 wt.-% or more, 25 wt.-% or more, 30 wt.-% or more, or 40 wt.-% or more.

[0078] 59. The method according to any of the preceding items, wherein the bottom product of distillation has an aromatic compound content of 85 wt.-% or less, 80 wt.-% or less, 70 wt.-% or less, or 60 wt.-% or less.

[0079] 60. The method according to any of the preceding items, wherein the bottom product of distillation has a nitrogen content of 100 wt.-ppm or more, 200 wt.-ppm or more, 300 wt.-ppm or more, 400 wt.-ppm or more, 500 wt.-ppm or more, or 600 wt.-ppm or more.

[0080] 61. The method according to any of the preceding items, wherein the distillation bottom product has a nitrogen content of 5000 wt.-ppm or less, 4000 wt.-ppm or less, 3000 wt.-ppm or less, or 2000 wt.-ppm or less.

[0081] 62. The method according to any of the preceding items, wherein the distillation bottom product has a sulfur content of 10 wt.-ppm or more, 20 wt.-ppm or more, 30 wt.-ppm or more, 50 wt.-ppm or more, 100 wt.-ppm or more, 200 wt.-ppm or more, 250 wt.-ppm or more, 300 wt.-ppm or more, 350 wt.-ppm or more, or 400 wt.-ppm or more.

[0082] 63. The method according to any of the preceding items, wherein the distillation bottom product has a sulfur content of 10,000 wt.-ppm or less, 6,000 wt.-ppm or less, 5,000 wt.-ppm or less, 4,000 wt.-ppm or less, or 3,000 wt.-ppm or less.

[0083] 64. The method according to any of the preceding items, wherein, in step E, at least a heavy gas oil (HGO) fraction is recovered, and the heavy gas oil fraction has a 90% boiling point of 620°C or lower, preferably 600°C or lower, 580°C or lower, 560°C or lower, or at least 550°C or lower (according to ASTM-D2887).

[0084] 65. A hydrocarbon mixture obtainable by any of the preceding items.

[0085] 66. The hydrocarbon mixture according to item 65, wherein the hydrocarbon mixture is the HGO fraction obtained in step E.

[0086] 67. A hydrocarbon-containing material obtainable in step D of the method according to any one of claims 1 to 64.

[0087] 68. The hydrocarbon-containing material according to item 67, wherein the hydrocarbon-containing material comprises more than 16 wt.% of a fraction boiling in the range of 150°C to 300°C and at least 60 wt.% of a fraction boiling above 370°C.

[0088] 69. Use of hydrocarbon mixtures according to item 65 or 66 or hydrocarbon-containing materials according to item 67 or 68 as raw materials in the production of fuels (e.g., diesel components, gasoline components, marine fuel components or jet fuel components), as raw materials in the production of chemicals (e.g., solvents), and / or as raw materials in the production of polymers (e.g., polypropylene and / or polyethylene).

[0089] 70. Use of a mixture of hydrocarbons or fractions thereof according to paragraph 65 or 66, or of a hydrocarbon-containing material or fraction thereof according to paragraph 67 or 68, as an FCC feedstock or steam cracking feedstock. Detailed Implementation

[0090] This invention relates to a method for improving polymer-based waste materials, and more specifically to a co-processing route for hydrogenating polymer-based waste materials.

[0091] Raw materials based on polymer waste, such as liquefied products of collected consumer plastics or liquefied products of tires that have reached the end of their service life (end-of-life tires), contain large and varying amounts of contaminants that would be harmful in processes such as steam cracking or other downstream processes (e.g., fluid catalytic cracking (FCC)). These contaminants include, in particular, halogens (primarily chlorine) derived from halogenated plastics (e.g., PVC and PTFE), sulfur derived from crosslinking agents in rubber polymers (e.g., in end-of-life tires), and metallic or metalloid (e.g., Si, Al) contaminants derived from composite materials and additives (e.g., films coated with metals or metal compounds, end-of-life tires, or plastic processing aids). These contaminants can be present in elemental, ionic, or as part of organic or inorganic compounds.

[0092] These impurities / contaminants can lead to coking and / or other (undesirable) side reactions in conventional refineries or petrochemical processes (e.g., steam cracking or FCC), thereby converting the product distribution into lower-value products or even products that must be disposed of (i.e., waste). Similarly, these impurities may have corrosive or degradative effects, thereby reducing the service life of refining equipment.

[0093] The production process of polymer waste-based materials (i.e., polymer waste-based feedstocks) typically involves at least one thermal degradation (e.g., pyrolysis or hydrothermal liquefaction or similar process steps) to provide polymer waste-based oil as polymer waste feedstock. These thermal degradation processes inherently result in polymer waste-based oils with high olefin content. The hydrotreating step of the present invention reduces the olefin content in the polymer waste feedstock (and co-feed, as applicable), and thus produces hydrotreated materials (also known as hydrocarbon-containing materials) with (significantly) reduced olefin content.

[0094] This invention relates to a method for improving materials based on polymer waste. The method of this invention includes the following steps:

[0095] (Step A) Provide raw materials based on polymer waste.

[0096] (Step B) Provide feedstock obtained from crude oil.

[0097] (Step C) Mixing (blending) the polymer waste-based feedstock, the feedstock obtained from crude oil, and optional additional feed materials to provide a feed mixture.

[0098] (Step D) Hydrotreating the feed mixture in an FCC feed hydrotreating processor to provide hydrocarbon-containing material

[0099] (Step E) Recover at least the distillate products and the bottom distillate products from the hydrocarbon-containing material.

[0100] In this invention, the term "polymer waste" refers to organic polymer materials that are no longer suitable for their use or are disposed of for any other reason. Specifically, polymer waste can be solid and / or liquid polymer materials, and is generally (or includes) solid polymer materials. More specifically, polymer waste can refer to end-of-life tires, collected consumer plastics (consumer plastics refer to any organic polymer material in consumer products, even if it does not have the characteristics of "plastic"), and collected industrial polymer waste. For the purposes of this invention, the terms "polymer waste" or "polymer" generally do not cover purely inorganic materials (which are sometimes referred to as inorganic polymers). The polymers in polymer waste can be of natural and / or synthetic origin and can be based on renewable and / or fossil raw materials.

[0101] The terms "polymer waste-based feedstock" or "polymer waste-based material" refer to feedstocks (or raw materials for processes) obtained from polymer waste. Preferably, "polymer waste-based feedstock" (or "polymer waste-based material") specifically refers to oil or oil sample products obtainable from liquefaction (i.e., non-oxidative thermal or thermocatalytic depolymerization of (solid) polymer waste (followed by optional subsequent fractionation and / or purification)). In other words, "polymer waste-based feedstock" or "polymer waste-based material" can also be referred to as "depolymerized polymer waste" or "liquefied polymer waste."

[0102] There are no particular restrictions on the liquefaction method, but the pyrolysis (e.g., rapid pyrolysis) or hydrothermal liquefaction of polymer waste can be mentioned.

[0103] The term "hydrothermal liquefaction (HTL)" refers to the thermal decomposition process that uses subcritical or supercritical water at moderate temperatures and high pressures to convert carbonaceous feedstocks into crude oil-like substances. The term "pyrolysis" refers to the thermal decomposition of materials at high temperatures in a non-oxidizing atmosphere. The term "rapid pyrolysis" refers to the thermochemical decomposition of carbonaceous feedstocks through rapid heating in the absence of oxygen.

[0104] The term "feedstock obtained from crude oil" refers to material (or stream) obtained from crude oil. Typically, the feedstock obtained from crude oil will be a crude oil fraction, which may be further purified / refined or unpurified / unrefined. Preferably, crude oil fractions that have not undergone further purification or processing are used as feedstock obtained from crude oil.

[0105] The term "feed mixture" refers to a mixture of feedstocks at least based on polymer waste and feedstocks derived from crude oil. A feed mixture may also contain one or more additional feed materials besides the polymer waste-based feedstocks and crude oil-derived feedstocks. In other words, "additional feed materials" are neither polymer waste-based feedstocks nor crude oil-derived feedstocks. If two or more polymer waste-based materials (feedstocks) are used in a feed mixture, these are collectively referred to as polymer waste feedstocks. Similarly, if two or more crude oil-derived materials (feedstocks) are used in a feed mixture, these are collectively referred to as crude oil-derived feedstocks.

[0106] The term "hydrotreating" (which is sometimes referred to as "hydroprocessing" hereinafter) refers to the chemical conversion of polymer-based waste feedstocks in the presence of hydrogen in an FCC feed hydrotreating processor to produce hydrocarbon-containing materials. The effluent from an FCC feed hydrotreating processor typically contains unreacted hydrogen, water, various gases, and other compounds derived from heteroatoms or metals (e.g., H₂S, HCl, HBr, NH₃), and, where appropriate, non-reactive components (e.g., carrier gas). At least the gaseous components (and water) are preferably separated as part of the hydrotreating process. In hydrotreating (the hydrotreating process), olefins and aromatic compounds are at least partially saturated and heteroatoms are removed. In other words, hydrotreating is the reaction of organic compounds in the presence of (high-pressure) hydrogen to remove heteroatoms and / or alter the saturation of the organic compounds. The resulting material (after separation of gaseous compounds, water, heteroatom-derived materials, and metal-derived materials) consists primarily of hydrocarbons (molecules composed of hydrogen and carbon atoms) and may contain residual (non-hydrocarbon) impurities. This resulting material is referred to as "hydrocarbon-containing material" in this invention.

[0107] The hydrotreating in this invention is carried out in an FCC feed hydrotreating processor, and this type of FCC feed hydrotreating reactor (and FCC feed hydrotreating process) inherently results in hydrotreating primarily leading to saturation and heteroatom removal, while (hydro)isomerization and / or (hydro)cracking occur only as minor side reactions (if any).

[0108] The term "FCC feed hydrotreating unit" refers to a hydrotreating reactor designed and arranged to pretreat FCC feedstock in a conventional refinery setting. Therefore, the term "FCC feed hydrotreating unit" refers to both the reactor itself and the reaction conditions.

[0109] The term "hydrocarbon-containing material" refers to a material primarily composed of hydrocarbons (i.e., molecules composed of carbon and hydrogen atoms). Specifically, "hydrocarbon-containing material" preferably contains at least 95.0 wt.% carbon (C) and hydrogen (H) atoms, as determined by elemental analysis, relative to the entire material. Other components such as oxygen (O), sulfur (S), and nitrogen (N) may also be present, typically in the form of organic molecules. The content of H and C is preferably at least 97.0 wt.%, at least 98.0 wt.%, or at least 99.0 wt.%.

[0110] The term "distillation" refers to a separation method by evaporation and condensation and encompasses fractional distillation. Distillation can be carried out under elevated pressure, at ambient pressure, and / or under reduced pressure. The result of distillation (the distillation method) is at least one distillate (fraction) and a distillation residue (or bottom product, i.e., the heaviest fraction). Therefore, the recovery in step E can be carried out by distillation or include distillation. Typically, distillation is carried out by fractional distillation and results in multiple distillate fractions with different boiling point ranges. These distillate fractions are typically mixtures of multiple compounds and are specified by their initial boiling point and final boiling point (e.g., xx℃-yy℃, meaning that the fraction begins to boil at xx℃ or higher and completely evaporates at yy℃ or higher). The bottom distillate (bottom product) is typically specified only by its initial boiling point (or starting boiling point) and is recovered without distillation (i.e., from the bottom of the distillation).

[0111] The term "heavy gas oil fraction" or "HGO fraction," which can be recovered in step E of the method of the present invention, refers to the fraction of the product of the hydrotreating step D. Therefore, the HGO fraction is a fraction containing hydrocarbon materials. Furthermore, the HGO fraction is a high-boiling fraction and can be the highest-boiling fraction obtained in the distillation of hydrocarbon materials, or alternatively, it can be an intermediate fraction (i.e., a distillate fraction). Typically, the HGO fraction usually has a high initial boiling point (or initial boiling point). Since the initial boiling point is sometimes difficult to determine, the HGO fraction of the present invention preferably has a 10% boiling point of at least 300°C (according to ASTM-D2887; wt.-%). In the case where the HGO fraction is a highest-boiling fraction, the final boiling point of the HGO fraction corresponds to the final boiling point of the hydrocarbon material; in other words, the HGO fraction can be a bottom fraction of the distillation. The HGO fraction of the present invention preferably has a 90% boiling point of up to 620°C (according to ASTM-D2887; wt.-%).

[0112] This invention is based on the discovery that polymer-based feedstocks and crude oil-derived feedstocks can be co-processed in an FCC feed hydrotreating processor (under FCC feed hydrotreating conditions), and that higher-value (improved) materials can be prepared from other difficult-to-process polymer-based feedstocks. Specifically, co-processing in this particular FCC feed hydrotreating processor allows for the integration of highly diverse and therefore difficult-to-process polymer-based feedstocks into conventional petrochemical processes with minimal effort and cost.

[0113] Specifically, co-processing allows for the easy integration of varying amounts of recycled materials (polymer waste or polymer waste-based materials). Various fractions (i.e., boiling point ranges) of polymer waste-based feedstocks can be used because distillation occurs after hydrotreating, making fractionation of polymer waste-based feedstocks (e.g., polymer waste-based oils) prior to hydrotreating in this invention typically unnecessary. By design, even conventional FCC feed hydrotreating processors are suitable for handling difficult-to-process feedstocks, such as crude oil HGO fractions, and therefore can also handle (highly contaminated) polymer waste-based feedstocks.

[0114] Furthermore, when using liquefied polymer waste, not only can HGO fractions be obtained in high yields, but also a higher proportion of valuable lower boiling point fractions, such as diesel, jet fuel, or gasoline fractions, can be obtained (and fractionated and recovered).

[0115] Preferably, the feedstock obtained from crude oil is an FCC feedstock. This feedstock is best suited for the process because the FCC feed hydrotreating unit (typically the first stage of a conventional FCC unit) is designed for this type of feedstock. Specifically, the feedstock obtained from crude oil preferably includes at least one crude oil fraction selected from: vacuum gas oil (VGO), gas oil (GO), heavy gas oil (HGO), kerosene, light gas oil, atmospheric residue (AR), vacuum residue (VR), and deasphalted oil (DAO). Preferably, the primary (at least 50 wt.%) higher boiling point fractions, namely vacuum gas oil (VGO), heavy gas oil (HGO), atmospheric residue (AR), vacuum residue (VR), and deasphalted oil (DAO), are used, while only lighter fractions (i.e., gas oil (GO), kerosene, and light gas oil) are used, excluding the heavier fractions. For example, at least 40 wt.% of the feedstock obtained from crude oil is boiled at a temperature of 370°C or higher (40% distillation temperature according to ASTM-D2887), or at least 45 wt.%, preferably at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, or at least 65 wt.% of the feedstock obtained from crude oil is boiled at a temperature of 370°C or higher.

[0116] Furthermore, feedstocks obtained from crude oil may have a 5% boiling point (according to ASTM-D2887; wt.-%) of at least 160°C, preferably at least 170°C, at least 180°C, at least 190°C, or at least 200°C and / or a 95% boiling point (according to ASTM-D2887; wt.-%) of 630°C or lower, preferably 610°C or lower, 590°C or lower, 570°C or lower, or 560°C or lower. For example, the final boiling point (according to ASTM-D2887) of feedstocks obtained from crude oil may be 650°C or lower, preferably 630°C or lower, 620°C or lower, 610°C or lower, or 600°C or lower.

[0117] In this invention, "final boiling point" (FBP) refers to the 99.5% boiling point and "initial boiling point" (IBP) refers to the 0.5% boiling point (according to ASTM-D2887; wt.-%).

[0118] The heavy gas oil (HGO) fraction (or distillation bottom fraction) recovered in step E may have a 10% boiling point (according to ASTM-D2887; wt.-%) of at least 300°C, preferably at least 310°C, at least 320°C, at least 330°C, at least 340°C, at least 345°C, at least 350°C, or at least 355°C. This product fraction of the method of the present invention is particularly suitable for processing in conventional downstream cracking processes (e.g., steam cracking processes or, in particular, FCC processes). Lighter fractions containing hydrocarbon materials, which can be obtained as additional (other) products of the method of the present invention, can be used directly for other purposes or can be transferred to other (conventional) petrochemical processes, including those mentioned above for HGO fractions (or distillation bottom products).

[0119] In this invention, when the mass of the obtained heavy fraction (m) H The total mass (m) of the liquid hydrocarbon-containing products obtained in step D. liq The ratio (m) H / m liqIn calculations, the yield of the heavy fraction boiling at 350°C or higher (unless otherwise specified, boiling point and range in this invention refer to the boiling point or range at atmospheric pressure of 101.324 kPa) can be at least 50 wt.-%. "Heavy fraction" is not necessarily the fraction recovered in the method of this invention, but can be a hypothetical fraction that can be obtained, for example, through simulated distillation. This high proportion of high-boiling-point products means that the FCC feed hydrotreating processor operates under conditions of hydrotreating with little or no (hydrocracking). Preferably, the yield of the heavy fraction can be at least 55 wt.-%, at least 60 wt.-%, or at least 65 wt.-%. For this purpose, liquid hydrocarbon products refer to the sum of hydrocarbon products in a hydrocarbon-containing material boiling at 25°C or higher at 1013.25 hPa (absolute) pressure. Therefore, the FCC feed hydrotreating processor produces a large proportion of products within the boiling point range suitable for subsequent FCC (which is a common follow-up unit to FCC hydrotreating units in conventional refineries).

[0120] Similarly, when the mass of the obtained light hydrocarbon fraction (m) L ) and the total mass of hydrocarbon-containing products (m ht The ratio (m) L / m ht In the calculations, the yield of the light hydrocarbon fraction (including gaseous products) boiling at 150°C or lower obtained in step D is preferably at most 10.0 wt.-%. This yield can be at most 8.0 wt.-%, at most 6.0 wt.-%, at most 5.0 wt.-%, at most 4.0 wt.-%, at most 3.0 wt.-%, or at most 2.0 wt.-%. The high yield of this (very) light-boiling hydrocarbon component in the hydrocarbon material obtained in step D will imply high levels of cracking in the FCC feed hydrotreating processor and / or a high proportion of light-boiling components in the feed mixture. However, those skilled in the art will understand that the FCC feed hydrotreating processor can be operated in different ways depending on the desired results of the process at a given time. For example, the FCC feed hydrotreating processor can be operated to achieve a constant sulfur content in the FCC feed, to achieve maximum aromatic saturation in the FCC feed, or even to maximize the production of diesel boiling-range products through the conversion of heavier feed molecules.

[0121] For example, FCC feed hydrotreating processors can operate in a temperature range of 300-460°C. Specifically, suitable operating temperatures are 320°C or higher, preferably 340°C or higher, or 360°C or higher and / or 455°C or lower, preferably 450°C or lower, 445°C or lower, 440°C or lower, 435°C or lower, 430°C or lower, 425°C or lower, 420°C or lower, 415°C or lower, or 410°C or lower. Processing temperatures within this range help ensure good hydrotreating efficiency, low cracking tendency, and low isomerization tendency. In particular, good hydrotreating efficiency results in low amounts of olefins and heteroatom-containing impurities (especially sulfur impurities) and low amounts of aromatic compounds in hydrocarbon-containing materials, thereby causing fewer problems in downstream processes (e.g., coking).

[0122] For example, an FCC feed hydrogenation processor can operate at a hydrogen partial pressure of at least 10 bar, preferably at least 20 bar, at least 25 bar, at least 30 bar, at least 33 bar, at least 35 bar, at least 38 bar, or at least 40 bar and / or up to 100 bar, preferably up to 90 bar, at most 80 bar, at most 70 bar, at most 60 bar, at most 55 bar, or at most 50 bar. These ranges are commonly used in conventional FCC feed hydrogenation processors and help ensure efficient hydrogenation. Unless otherwise specified, the pressure values ​​given in this invention refer to absolute pressure.

[0123] For example, an FCC feed hydrogenation processor can operate for up to 8.0 hours. -1 Optimal version up to 6.0 -1 At most 4.0 -1 At most 3.0h -1 At most 2.0h -1 At most 1.5 hours -1 or at most 1.3 hours -1 and / or at least 0.2h -1 Preferably at least 0.4h -1 At least 0.6h -1 At least 0.7h -1 At least 0.8h -1 At least 0.9h -1 or at least 1.0h -1 Liquid hourly space velocity (LHSV, m) 3 Liquid feed / m 3The catalyst per hour (Catalyst / h) is used for operation. For example, an FCC feed hydrotreating unit can be operated at a hydrogen (H2) to feed mixture (HC) ratio (H2 / HC) of up to 800 l / l, preferably up to 600 l / l, up to 500 l / l, up to 350 l / l, or up to 300 l / l; and / or at least 50 l / l, preferably at least 100 l / l, at least 120 l / l, at least 150 l / l, at least 180 l / l, at least 200 l / l, or at least 220 l / l. These conditions similarly promote efficient hydrotreating.

[0124] The FCC feed hydrotreating processor preferably uses a catalyst. The catalyst can be a supported catalyst. For example, the catalyst may include at least one component selected from Groups 6, 8, or 10 of the IUPAC periodic table. When a supported catalyst is used, it preferably contains Mo and at least one other transition metal on a support. Examples of such supported catalysts are supported NiMo catalysts or supported CoMo catalysts, or mixtures of both. In supported catalysts, the support preferably comprises alumina and / or silica. These catalysts are typically used as sulfidation catalysts to ensure that the catalysts are in their active (sulfided) form. Converting the catalysts to their active (sulfided) form can be achieved by pre-sulfiding them (i.e., before starting the hydrotreating reaction) and / or by adding a sulfur-containing feed (containing sulfur, for example, as an organic or inorganic sulfide). The feed may contain sulfur from the starter, or sulfur additives may be mixed into the feed.

[0125] In a preferred embodiment, the FCC feed hydrogenation processor employs a catalyst, and the catalyst is a supported NiMo catalyst with a support comprising alumina (NiMo / Al2O3), and / or the catalyst is a supported CoMo catalyst with a support comprising alumina (CoMo / Al2O3).

[0126] The use of a catalyst helps ensure efficient hydrotreating and helps reduce the tendency for isomerization and / or cracking. In particular, preferred catalysts help reduce the tendency for isomerization and / or cracking.

[0127] Therefore, step D is preferably carried out in the presence of the catalyst defined above (especially supported Mo-containing catalysts, such as NiMo / Al2O3 and / or CoMo / Al2O3) within the temperature range, hydrogen pressure, LHSV and / or H2 / HC ratio specified above.

[0128] FCC feed hydrotreating processors are typically operated to achieve specific sulfur contents in the FCC feed and, in some cases, to maximize the saturation of aromatic compounds in the FCC feed or to maximize the production of lighter diesel boiling point products through the conversion of heavier feed molecules. Simultaneously, these process conditions also result in the saturation of olefins, which are more reactive than aromatic compounds. The bromine number reduction rate (BRh / BRf) can be given as a measure of the efficiency of olefin saturation conditions. Specifically, in this invention, the FCC feed hydrotreating processor is preferably adjusted such that the ratio (BRh / BRf) of the bromine number (BRh) of the hydrocarbon-containing material to the bromine number (BRf) of the feed mixture is 0.50 or less, preferably 0.40 or less, 0.30 or less, 0.20 or less, 0.10 or less, 0.07 or less, 0.06 or less, 0.05 or less, or 0.04 or less.

[0129] The method of the present invention may further include subjecting at least a portion of the distillation bottom product recovered in step E to fluidized catalytic cracking (FCC). The co-feed (FCC co-feed), which may originate, for example, from another unit within a conventional refinery setting, may be subjected to the FCC process together with the distillation bottom product (fraction). Those skilled in the art will understand that the aforementioned FCC co-feed materials can be available from various sources depending on the precise configuration of the refinery. The suitability of a given FCC co-feed material will depend, for example, on its boiling point range, sulfur content, and aromatic compound content. Suitable FCC co-feed materials may be obtained, for example, from a hydrocracking unit.

[0130] Preferably, the feed mixture contains up to 50 wt.-%, more preferably up to 40 wt.-%, up to 30 wt.-%, or up to 25 wt.-%, of polymer-based raw material. In other words, the mixing in step C is preferably adjusted such that the feed mixture contains up to 50 wt.-%, more preferably up to 40 wt.-%, up to 30 wt.-%, or up to 25 wt.-%, of polymer-based raw material. This adjustment can be suitably achieved by simply mixing the desired amount.

[0131] Typically, mixing (or blending) (step C) can be carried out in a separate container or feed line prior to the FCC feed hydrotreating processor, or mixing can be carried out within the FCC feed hydrotreating processor. Preferably, the polymer-based feedstock and the feedstock obtained from crude oil are mixed prior to entering the FCC feed hydrotreating processor, for example in a feed tank.

[0132] It has been shown that the aforementioned range of polymer waste-based feedstock contents yields favorable results in the final product. Therefore, this invention covers a significant range of blends of polymer waste-based feedstocks with high contents. In other words, due to the combination of features of this invention, the method is suitable for a wide range of polymer waste-based feedstock contents in feed mixtures subjected to FCC hydrogenation. The polymer waste-based feedstock content is preferably no higher than 50 wt.% to ensure easy integration into existing processes.

[0133] To ensure at least some use of the recycled materials (based on polymer waste feedstock) and thus sustainability, the feed mixture preferably contains at least 0.5 wt.%, preferably at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.%. In other words, the mixing in step C is preferably adjusted such that the feed mixture contains at least 0.5 wt.%, preferably at least 1.0 wt.%, at least 1.5 wt.%, or at least 2.0 wt.%.%.

[0134] Preferably, the feed mixture contains at least 25 wt.%, preferably at least 30 wt.%, at least 40 wt.%, at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, or at least 75 wt.% of feedstock obtained from crude oil. In other words, the mixing in step C is preferably adjusted such that the feed mixture contains at least 25 wt.%, preferably at least 30 wt.%, at least 40 wt.%, at least 50 wt.%, at least 60 wt.%, at least 70 wt.%, or at least 75 wt.% of feedstock obtained from crude oil.

[0135] The minimal amount of feedstock derived from crude oil (a conventional feedstock in FCC hydrotreating processes) ensures that the method of this invention can be easily integrated into existing petrochemical processes. Nevertheless, a high degree of sustainability can be achieved if desired.

[0136] The polymer waste-based raw material provided in step A can be polymer waste-based oil. Preferably, the polymer waste-based raw material provided in step A is polymer waste-based oil, more preferably liquefied polymer waste, such as polymer waste liquefied through thermal degradation (e.g., pyrolysis or hydrothermal liquefaction).

[0137] The polymer-based feedstock provided in step A can be a fraction of polymer-based waste oil, particularly a fraction of liquefied polymer-based waste. However, the polymer-based feedstock provided in step A can also be unfractionated polymer-based waste oil, as the FCC feed hydrotreating unit is quite flexible and can even handle such unfractionated (and even unprocessed, i.e., raw or crude) polymer-based waste oil.

[0138] In this invention, the preferred polymer-based feedstock comprises or includes the following: liquefied polymer waste or its fractions, such as liquefied waste plastics (LWP) or its fractions, particularly waste plastic pyrolysis oil (WPPO) or its fractions, or liquefied end-of-life tires or their fractions, such as end-of-life tire pyrolysis oil (ELTPO) or its fractions. More generally, the polymer-based feedstock may comprise or include the following: thermally liquefied polymer waste, such as pyrolysis oil feedstock or its fractions, and / or HTL (hydrothermal liquefaction) polymer waste feedstock or its fractions. In this document, pyrolysis oil feedstock refers to feedstock obtained by the pyrolysis of polymer waste, and HTL (hydrothermal liquefaction) polymer waste feedstock refers to polymer waste feedstock obtained by the hydrothermal liquefaction of polymer waste.

[0139] Thermal liquefaction, such as pyrolysis and / or hydrothermal liquefaction (with subsequent purification, such as separation, if desired), is a common method for preparing liquefied polymer waste. This material is not easily handled, but the method of the present invention is specifically designed to handle even such challenging raw materials. In particular, pyrolysis and hydrothermal liquefaction (HTL) are commonly used techniques, and therefore these types of raw materials are readily available with reasonable effort.

[0140] Liquefied polymer waste can be pretreated after liquefaction to provide polymer waste-based feedstocks. Typical pretreatment methods include separation (e.g., gas-liquid separation), distillation or fractionation, solids removal (e.g., filtration or sedimentation), and extraction techniques such as liquid-liquid extraction (e.g., using organic solvents or water, optionally each containing additives such as extraction aids). For example, pretreatment may include contacting the liquefied polymer waste with an aqueous medium having a pH of at least 7 at a temperature of 200°C or higher, followed by liquid-liquid separation and optionally further separation and / or purification to produce a polymer waste-based feedstock.

[0141] Pretreatment can be particularly beneficial in reducing impurity content, thereby making polymer-based feedstocks more suitable for hydrotreating steps. Advantageously, pretreatment may have already removed some impurities (by means other than hydrotreating) that would otherwise be removed by hydrogenation in the hydrotreating step, thus reducing the total consumption of valuable hydrogen and / or increasing the lifespan of the hydrotreating equipment.

[0142] For example, polymer waste-based feedstocks may have a chlorine content of 5 wt.-ppm or more, such as 10 wt.-ppm or more, 15 wt.-ppm or more, 20 wt.-ppm or more, 50 wt.-ppm or more, or 100 wt.-ppm or more. Suitably, polymer waste-based feedstocks may have a chlorine content of 4000 wt.-ppm or less, 3000 wt.-ppm or less, 2000 wt.-ppm or less, 1000 wt.-ppm or less, 500 wt.-ppm or less, 400 wt.-ppm or less, or 200 wt.-ppm or less. In other words, the method of the present invention is applicable to a wide range of impurities, and it is not necessary or even necessary to completely remove chlorine (or other) impurities before subjecting the polymer waste-based feedstock to an FCC feed hydrogenation treatment step.

[0143] Oils based on polymer waste, particularly those obtained through the thermal degradation of polymer waste, typically exhibit high levels of olefins and / or aromatic compounds. These compounds can lead to coking in downstream processes. However, the FCC feed hydrotreating processor of this invention is capable of handling such challenging feeds and converting most of the problematic compounds, thereby providing an improved material stream that can be used in a variety of downstream processes.

[0144] For example, feedstocks based on polymer waste may have an olefin content of 10 wt.-% or more, 15 wt.-% or more, 20 wt.-% or more, 30 wt.-% or more, 40 wt.-% or more, or 50 wt.-% or more and / or 85 wt.-% or less, 80 wt.-% or less, 70 wt.-% or less, or 65 wt.-% or less.

[0145] In this invention, for example, the distillation bottom product (or HGO fraction) may have an aromatic compound content of 10 wt.-% or more, 15 wt.-% or more, 20 wt.-% or more, 25 wt.-% or more, 30 wt.-% or more, or 40 wt.-% or more and / or 85 wt.-% or less, 80 wt.-% or less, 70 wt.-% or less, or 60 wt.-% or less. Such an aromatic compound content in the resulting distillation bottom product (or HGO fraction) can be achieved through a suitable combination of feedstock and hydrotreating conditions. In particular, the preferred feed mixture of this invention is obtained from relatively high-boiling fractions derived from crude oil and hydrolyzed polymer waste, the former typically having a relatively high aromatic compound content and the latter a relatively high olefin content. Furthermore, the hydrotreating conditions in typical FCC hydrotreating processors prevent a significant reduction in aromatic compound content, instead resulting in olefin hydrogenation.

[0146] In this invention, for example, the distillation bottom product (or HGO fraction) may have a nitrogen content of 100 wt.-ppm or more, 200 wt.-ppm or more, 300 wt.-ppm or more, 400 wt.-ppm or more, 500 wt.-ppm or more, or 600 wt.-ppm or more. Furthermore, the distillation bottom product (or HGO fraction) may have a nitrogen content of 5000 wt.-ppm or less, 4000 wt.-ppm or less, 3000 wt.-ppm or less, or 2000 wt.-ppm or less. The bottom product of distillation (or HGO fraction) may have a sulfur content of 10 wt.-ppm or more, 20 wt.-ppm or more, 30 wt.-ppm or more, 50 wt.-ppm or more, 100 wt.-ppm or more, 200 wt.-ppm or more, 250 wt.-ppm or more, 300 wt.-ppm or more, 350 wt.-ppm or more, or 400 wt.-ppm or more, and / or may have a sulfur content of 10,000 wt.-ppm or less, 6,000 wt.-ppm or less, 5,000 wt.-ppm or less, 4,000 wt.-ppm or less, or 3,000 wt.-ppm or less.

[0147] In one embodiment, step A, which provides the polymer waste-based raw material, includes a step of thermal degradation (e.g., pyrolysis or hydrothermal liquefaction) of the waste plastic. Therefore, a complete method from (solid) polymer waste to improved materials can be provided. The thermal degradation step may also include a post-processing (work-up) stage, such as a separation stage.

[0148] The present invention further provides hydrocarbon mixtures obtainable by the method according to the invention. Specifically, the hydrocarbon mixture may be distillation bottom product, HGO fraction, and / or other fractions obtained in recovery step D.

[0149] The present invention further provides a hydrocarbon-containing material obtained in step D of the method according to the invention. The hydrocarbon-containing material preferably comprises more than 16 wt.% of a fraction boiling in the range of 150°C to 300°C and at least 60 wt.% of a fraction boiling above 370°C.

[0150] In this invention, the olefin content of the distillation bottom product (or HGO fraction) can be, for example, 4 wt.% or less, preferably 3 wt.% or less. The olefin content of the distillation bottom product (or HGO fraction) can be estimated by the bromine value and is used in this invention. The distillation bottom product (or HGO fraction) can, for example, have a bromine value of 10 g Br / 100 g or less, 8 g Br / 100 g or less, 6 g Br / 100 g or less, 5 g Br / 100 g or less, 4 g Br / 100 g or less, 3 g Br / 100 g or less, 2 g Br / 100 g or less, or 1 g Br / 100 g or less.

[0151] The present invention further provides the use of the hydrocarbon mixtures (or hydrocarbon-containing materials obtained in step D) as raw materials in the production of fuels, chemicals and / or polymers (such as polypropylene and / or polyethylene).

[0152] For example, the low- to medium-boiling fractions (e.g., gasoline, diesel, or jet fuel fractions) obtained in step D of the method of the present invention can be used directly or after further post-processing (e.g., polishing) as fuel components. The distillation bottom product (or HGO fraction) can be transferred to conventional petrochemical processes for high-boiling fractions (e.g., FCC) or to steam cracking to provide unsaturated hydrocarbons that can be used as raw materials in polymer or other chemical production.

[0153] Specifically, this invention provides the use of hydrocarbon mixtures obtained in the method of this invention as FCC feedstock, steam cracking feedstock, solvent components, or fuel components (e.g., diesel components, gasoline components, or jet fuel components).

[0154] The invention has been described with reference to specific embodiments. Unless otherwise indicated, each of these preferred embodiments and each of the numerical ranges (preferred to any degree) may be combined with any other embodiment and / or any other numerical range (preferred to any degree), and each of these combinations should be covered within the disclosure of the invention.

[0155] Measurement method used in this invention

[0156] Unless otherwise specified, the following measurement methods may be applied in this invention.

[0157] In this invention, the contents of F, Cl, and Br can be determined according to ASTM-D7359. The iodine (I) content can be determined by XRF (X-ray fluorescence) spectroscopy. The sulfur (S) content can be determined according to ASTM-D7039. For a product containing 0.3-100 mg / kg N and having a boiling point range of approximately 50-400°C and 0.2-10 mg / kg Br, the following methods are used: 2 For samples with a room temperature viscosity of 100 mg / kg / s, the nitrogen (N) content can be determined according to ASTM-D4629. For other types of petroleum samples with an N content of 100 mg / kg or more, ASTM-D5762 can be used. Depending on the characteristics of the sample, the aromatic compound content can be determined according to EN12916 or alternatively according to ASTM-D2549.

[0158] For methods not mentioned above, the methods used in the embodiments may be utilized. In the context of this invention, unless otherwise specified, standards (e.g., ASTM or EN-ISO) refer to the latest version available as of November 30, 2020.

[0159] Example

[0160] In the following description, the invention will be described with reference to embodiments. It should be understood that the embodiments are for illustrative purposes and should not limit the scope of the invention (as defined by the claims). However, the numerical values ​​and ranges disclosed in the embodiments (e.g., the content of compounds or impurities) may be combined with the numerical values ​​and / or ranges disclosed in the above general description to give new numerical ranges.

[0161] Example 1

[0162] WPPO (Waste Plastic Pyrolysis Oil) is prepared by pyrolysis of collected waste plastics and used as a feedstock for polymer-based waste products without further purification or fractionation. The feedstock is a mixture of products from two pyrolysis processes in a 1:1 weight ratio, wherein the first product has a 5-95% boiling range of approximately 95-477°C, and the second product has a 5-95% boiling range of approximately 66-475°C. The feedstock is a conventional fossil fuel (conventional fossil FCC feedstock hydrotreating processor feedstock; IBP: 94.3°C; FBP: 580.2°C; density measured at 15°C: 914 kg / m³). 3 The density measured at 50℃ is 889 kg / m³. 3It is used as a feedstock obtained from crude oil. A feed mixture is prepared by blending WPPO with fossil feedstock, such that the total WPPO content in the feed mixture is 10 wt.-% and the total fossil feedstock content in the feed mixture is 90 wt.-%.

[0163] The feed mixture was subjected to hydrogenation in a laboratory-scale continuous-flow hydrogenation reactor operating under FCC feed hydrogenation processor conditions. The hydrogenation conditions were set at 398°C and 48 bar hydrogen partial pressure (without the addition of inert gas).

[0164] Following hydrotreating, the liquid product was recovered via gas-liquid separation, and the total liquid product was distilled into four different fractions: light naphtha (IBP-150°C), light gas oil (150-300°C), gas oil (300-370°C), and heavy gas oil (370°C-FBP). The distillation yields and analytical results for the different products are shown in Tables 1 to 4. Note that the catalyst (CoMo / Al2O3) in the FCC hydrotreating unit was at the end of its lifetime and sulfided at the start of the experiment. Therefore, the sulfur content of this product may be higher compared to that achievable with a less deactivated catalyst.

[0165] Comparative Example 1

[0166] Except that 100% fossil feedstock was used as a reference sample, the hydrogenation treatment and distillation of Example 1 were repeated. The results are shown in Tables 1 to 4.

[0167] Table 1: Fractionation Yields

[0168]

[0169] Table 2: Detailed analysis of light gas oil fractions (150℃-300℃)

[0170]

[0171] 1) Aromatic compounds - LC refers to the total content of aromatic compounds measured by liquid chromatography according to EN12916 (specified for diesel fractions).

[0172] Table 3: Detailed analysis of gas oil fractions (300℃-370℃)

[0173]

[0174] Table 4: Detailed analysis of heavy gas oil fraction (370℃-FBP)

[0175]

[0176] When compared with the results obtained using WPPO (Comparative Example 1), adding WPPO to the FCC feed hydrotreating processor feed LWP (Example 1) did not cause a surprising negative change in product quality attributable to WPPO. Those skilled in the art will also understand that, depending on how the experiment is conducted, other factors (e.g., catalyst deactivation, process conditions, experiment duration, and the order of test feeds) may affect product quality. Physical properties (e.g., density, viscosity, and cloud point) are affected in a limited manner due to the addition of WPPO. This can be attributed to the more alkane-like nature of the hydrotreated WPPO when compared with conventional FCC hydrotreating processor feeds and the products obtained therefrom. This is also reflected in the aromatic content of all analyzed product fractions – the fraction produced in Example 1 has a lower aromatic content and is therefore more attractive than the product of Comparative Example 1 for applications requiring low aromatic content. Such applications include fluidized catalytic cracking, steam cracking, and use as a diesel fuel.

[0177] Example 2

[0178] Except for recovering the jet fuel fraction (IBP-240°C) excluding the heavier fractions (including HGO as a bottom fraction), the process of Example 1 was repeated. The results are shown in Table 5 below.

[0179] Table 5: Detailed Analysis of Jet Fuel Fractions

[0180]

[0181] As can be seen from Table 5 above, jet fuel fractions are highly suitable as jet fuel components. Specifically, Bocle lubricity reaches values ​​that are traditionally difficult to achieve using sustainable processes.

Claims

1. A method for improving polymer waste-based materials, the method comprising: Step A: Provide raw materials based on polymer waste. Step B: Provide feedstock obtained from crude oil. Step C: Mix the polymer-based waste feedstock, the crude oil-derived feedstock, and optionally additional feed materials to provide a feed mixture. Step D: Hydrotreating the feed mixture in an FCC feed hydrotreating processor to provide a hydrocarbon-containing material, and Step E: Recover at least the distillate product and the bottom product from the hydrocarbon-containing material. In this process, at least a portion of the distillation bottom product is subjected to FCC or steam cracking; The raw material obtained from crude oil includes at least one crude oil fraction selected from the following: vacuum gas oil fraction, heavy gas oil fraction, kerosene fraction, light gas oil fraction, atmospheric residue oil fraction, vacuum residue oil fraction, and deasphalted oil fraction; and In step A, the raw material based on polymer waste is liquefied polymer waste or its fractions.

2. The method according to claim 1, wherein, At least a portion of the distillation bottom product is subjected to FCC co-feed with the FCC feed.

3. The method according to claim 1 or 2, wherein, The distillation bottom product recovered in step E has a boiling point of at least 300°C and a 10% boiling point according to ASTM-D2887.

4. The method according to claim 1 or 2, wherein, When the mass m of the heavy fraction obtained H The total mass m of the liquid hydrocarbon products liq The ratio m H / m liq In calculations, the yield of the heavy fraction boiling at 350°C or higher obtained in step D is at least 50 wt.

5. The method according to claim 1 or 2, wherein, When the mass m of the light fraction obtained L The total mass m of hydrocarbon-containing products ht The ratio m L / m ht When calculating, the yield of the light hydrocarbon fraction at 150°C or lower obtained in step D is at most 10.0 wt.

6. The method according to claim 1 or 2, wherein, The FCC feed hydrogenation processor operates at temperatures ranging from 300 to 460°C.

7. The method according to claim 1 or 2, wherein, The FCC feed hydrogenation processor operates at a hydrogen partial pressure of at least 10 bar, and / or The FCC feed hydrogenation processor operates at a hydrogen partial pressure of up to 100 bar.

8. The method according to claim 1 or 2, wherein, The FCC feed hydrogenation processor uses a catalyst, and the catalyst is a supported catalyst.

9. The method according to claim 8, wherein, The catalyst comprises at least one component selected from Group 6, 8, or 10 of the new periodic table of elements in IUPAC.

10. The method according to claim 1 or 2, wherein, The FCC feed hydrogenation processor uses a catalyst, and the catalyst is a supported catalyst containing Mo and at least one other transition metal on a support.

11. The method according to claim 10, wherein, The supported catalyst is a supported NiMo catalyst or a supported CoMo catalyst, wherein the support includes alumina and / or silica.

12. The method according to claim 10, wherein, The FCC feed hydrogenation processor employs a catalyst, and the catalyst is a supported CoMo catalyst with the support comprising alumina, and / or the catalyst is a supported NiMo catalyst with the support comprising alumina.

13. The method according to claim 1 or 2, wherein, The FCC feed hydrogenation processor operates under olefin saturation conditions.

14. The method according to claim 1 or 2, wherein, The polymer waste-based raw material provided in step A is a fraction of liquefied polymer waste.

15. The method according to claim 1 or 2, wherein, The feed mixture contains up to 50 wt% of the polymer-based waste material, and / or the feed mixture contains at least 0.5 wt% of the polymer-based waste material.

16. The method according to claim 1 or 2, wherein, The feed mixture contains at least 25 wt% of the feedstock obtained from crude oil.

17. The method according to claim 1 or 2, wherein, The raw materials based on polymer waste are pyrolysis oil raw materials obtained from waste plastics and / or pyrolysis oil raw materials obtained from end-of-life tires or their fractions, and / or raw materials obtained from hydrothermal liquefaction of waste plastics and / or end-of-life tires or their fractions.

18. The method according to claim 1 or 2, wherein, Step A, which provides the polymer waste-based raw material, includes a step of thermal degradation of the polymer waste.

19. The method according to claim 18, wherein, The thermal degradation is either pyrolysis or hydrothermal liquefaction.

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