Methods for removing chlorides from a plastic pyrolysis stream

Description

1 / 24 “METHODS FOR REMOVING CHLORIDES FROM A PLASTIC PYROLYSIS STREAM” Cross-reference to related orders

[001] This application claims the benefit of priority under U.S. Provisional Patent Application No. 63 / 455,733, filed March 30, 2023, disclosure of which is incorporated herein by reference in full. Background of the Invention

[002] Recycling mixed waste plastics using chemical / monomer recycling is an area of ​​great importance. Although multiple chemical recycling methods are being explored, pyrolysis remains the most technically feasible for integration into the steam cracking value chain. Commercialized plastic pyrolysis processes generally prefer to use polyolefins as feed plastics. However, pure polyolefin waste is rarely available in quantities relevant to full industrial scale-up and / or requires expensive pre-separation implementation to reject other types of plastics (e.g., polystyrene, polyamide, polyethylene terephthalate, polyvinyl chloride, etc.). It has been demonstrated for small and medium-sized pyrolysis plants that the complete exclusion of halogen, nitrogen, and oxygen-containing polymers from feed plastics is not currently possible.

[003] Most plastic pyrolysis plants produce liquids with average amounts of the following components: 50-400 ppmw of chlorides, 1000-4000 ppmw of nitrogen, 2000-20000 ppmw of oxygen, and 100-1000 ppmw of sulfur. These levels are too high for these liquids to be used as feedstocks in steam crackers without being mixed with conventional naphtha. Upgrading pyrolysis liquids to remove impurities is important to ensure consistency with the Petition 870250088025, dated 09 / 29 / 2025, page 36 / 68 2 / 24 specifications for steam cracking naphtha.

[004] The only commercially available solution at scale that allows for the reduction of these impurities to levels of 1-5 ppmw, making these liquids immediate substitutes in naphtha crackers, is hydroprocessing. Hydroprocessing has been standardized in refining and does not require major process adjustments if used on plastic pyrolysis liquids. The only important exception is chlorides / halogens. Hydroprocessing catalysts perform the hydrogenation of N, -O, -S, and -Cl compounds, resulting in the production of the respective NH3, H2O, H2S, and HCl. However, there are problems with higher chloride levels in such units (i.e., above 10 ppmw), including: (1) formation of NH4Cl by the reaction of NH3 and HCl, which deposits and clogs equipment at temperatures below 100 °C; (2) catalyst deactivation; (3) and the need for expensive steel. Therefore, there is a need for alternative and / or improved materials and processes. Brief Description of the Invention

[005] Disclosed and described herein are adsorbents, methods of preparation thereof, and methods of their use in dechlorination processes.

[006] One aspect of the present disclosure relates to a method for removing chlorides from a plastic pyrolysis stream comprising an initial chloride concentration of more than about 10 ppmw. In at least one embodiment, the method comprises: contacting the stream with an alumina adsorbent, the alumina adsorbent comprising the sodium-comprising promoter. In at least one embodiment, a final chloride concentration of the treated stream is less than about 10 ppmw.

[007] In at least one embodiment, concentration Petition 870250088025, dated 09 / 29 / 2025, page 37 / 68 3 / 24 of the final chloride concentration is from about 10 ppmw to about 45 ppmw. In at least one embodiment, the final chloride concentration is from about 45 ppmw to about 250 ppmw.

[008] In at least one embodiment, the promoter is present in about 2% by weight to about 10% by weight based on the total weight of the adsorbent. In at least one embodiment, the promoter comprises sodium in the form of Na2O.

[009] In at least one embodiment, the alumina adsorbent has a BET surface area of ​​about 150 m2 / ga about 300 m2 / g.

[0010] In at least one embodiment, the alumina adsorbent has a total pore volume of about 0.2 mL / g to about 6 mL / g.

[0011] In at least one embodiment, the alumina adsorbent exhibits a bimodal pore size distribution.

[0012] In at least one embodiment, the alumina adsorbent has a density of about 0.5 g / mL to about 1.0 g / mL.

[0013] In at least one embodiment, the alumina adsorbent is in the form of spherical particles. In at least one embodiment, the spherical particles have an average diameter of about 2 mm to about 4 mm. In at least one embodiment, the particles exhibit a lateral crush resistance greater than about 40 N.

[0014] In at least one embodiment, a chloride removal rate is at least about 80%, at least about 85%, or at least about 90% for a pyrolysis stream temperature of 200 °C to 350 °C.

[0015] In at least one embodiment, the alumina adsorbent is regenerative.

[0016] In at least one embodiment, the method Petition 870250088025, dated 09 / 29 / 2025, page 38 / 68 4 / 24 further comprises: subsequently placing the alumina adsorbent in contact with a regeneration stream to regenerate the alumina adsorbent. In at least one embodiment, the regeneration stream comprises hydrogen gas at a temperature of about 450 °C to about 600 °C.

[0017] In at least one embodiment, the regeneration stream comprises oxygen gas at a temperature of about 250 °C to about 350 °C.

[0018] A further aspect of the present disclosure relates to a method of removing chlorides from a plastic pyrolysis stream comprising an initial chloride concentration greater than about 10 ppmw. In at least one embodiment, the method comprises: contacting the stream with an adsorbent, the adsorbent comprising copper oxide, zinc oxide, and alumina. In at least one embodiment, the final chloride concentration of the treated stream is less than about 10 ppmw.

[0019] In at least one embodiment, the final chloride concentration is from about 10 ppmw to about 45 ppmw. In at least one embodiment, the final chloride concentration is from about 45 ppmw to about 250 ppmw.

[0020] In at least one embodiment, copper oxide is present at about 50% by weight to about 80% by weight based on the total weight of the adsorbent.

[0021] In at least one embodiment, zinc oxide is present at about 20% by weight to about 30% by weight based on the total weight of the adsorbent.

[0022] In at least one embodiment, alumina is present at about 3% by weight to about 10% by weight based on the total weight of the adsorbent. Petition 870250088025, dated 09 / 29 / 2025, page 39 / 68 5 / 24

[0023] In at least one embodiment: copper oxide is present from about 50% by weight to about 80% by weight; zinc oxide is present from about 10% by weight to about 40% by weight; and alumina is present as the balance of the adsorbent weight.

[0024] In at least one embodiment, the adsorbent is formed by coprecipitation of copper oxide and zinc oxide in alumina.

[0025] In at least one embodiment, the adsorbent has a BET surface area of ​​about 25 m2 / ga about 150 m2 / g.

[0026] In at least one embodiment, the adsorbent has a total pore volume of about 0.15 mL / g or about 2 mL / g.

[0027] In at least one embodiment, the adsorbent has a density of about 1.0 g / mL to about 3.0 g / mL.

[0028] In at least one embodiment, the adsorbent is in the form of tablets. In at least one embodiment, the tablets have an average length of about 3 mm to about 6 mm and an average width of about 2 mm to about 4 mm.

[0029] In at least one embodiment, the tablets exhibit a lateral crush resistance of more than about 60 N.

[0030] In at least one embodiment, the chloride removal rate is at least about 80%, at least about 85%, or at least about 90% for a pyrolysis stream temperature of 200 °C to 350 °C.

[0031] In at least one embodiment, the adsorbent is regenerative.

[0032] In at least one embodiment, the method further comprises: subsequently placing the adsorbent in contact with the regeneration stream to regenerate the adsorbent. In at least one embodiment, the regeneration stream comprises hydrogen gas in a Petition 870250088025, dated 09 / 29 / 2025, page 40 / 68 6 / 24 temperature of about 450 °C to about 600 °C. In at least one embodiment, the regeneration stream comprises oxygen gas at a temperature of about 250 °C to about 350 °C. Brief Description of the Drawings

[0033] The disclosure described here is illustrated by way of example and not by way of limitation in the attached figures.

[0034] Figure 1 is a graph of the pore volume distribution for a sample prepared according to the embodiments described herein compared to a reference sample.

[0035] Figure 2 is a graph showing chloride removal as a function of temperature for samples prepared according to the embodiments described herein, compared with a reference sample.

[0036] Figure 3 is a graph showing chloride removal as a function of temperature for samples prepared according to the embodiments described herein compared with two reference samples. Detailed Description of the Invention

[0037] The embodiments of the present disclosure relate to processes and compositions for the efficient removal of chlorides from plastic pyrolysis streams (which may be liquid or gaseous streams). For example, certain embodiments utilize an adsorbent comprising a promoter (e.g., sodium) to remove chlorides from a plastic pyrolysis stream (e.g., with an initial chloride concentration of more than about 10 ppmw). Formulations comprising sodium on a high-pore-volume support (e.g., copper- or sodium-promoted high-pore-volume alumina) have been found to be active in removing chlorides (e.g., to levels below 10 ppmw or sub-ppmw). Other embodiments relate to adsorbents comprising precipitated copper oxide on a support (e.g., which may be co-precipitated). Petition 870250088025, dated 09 / 29 / 2025, page 41 / 68 7 / 24 with zinc oxide).

[0038] The described adsorbents may utilize a porous support and one or more active metallic components supported thereon. Exemplary supports include metal oxides, metalloid oxides, activated carbons, and molecular sieves. For example, the support may include titanium oxide, ceria, alumina, silica, zirconia, magnesium oxide, zeolites, or combinations thereof. In at least one embodiment, the supports include silica. In at least one embodiment, the support may include high surface area metal oxides. In at least one embodiment, the support may comprise aluminum oxide. In at least one embodiment, the support may comprise a mixture of titanium dioxide and aluminum oxide.Mixtures of metal oxides, for example, a mixture of titanium dioxide and aluminum oxide, may contain metal oxides in a weight / weight ratio of titanium dioxide to aluminum oxide of any of about 9 / 1, about 8 / 1, about 7 / 1, about 6 / 1, about 5 / 1, about 4 / 1, about 3 / 1, about 2 / 1 or about 1 / 1 to any of about 1 / 2, about 1 / 3, about 1 / 4, about 1 / 5, about 1 / 6, about 1 / 7, about 1 / 8 or about 1 / 9.

[0039] In at least one embodiment, the adsorbent comprises a high-pore-volume support, such as high-pore-volume alumina. In at least one embodiment, the promoter is dispersed in the support, for example, by impregnation. The term “dispersed form” may be synonymous with “dispersed in”, “impregnated in”, “supported by / on”, and the like.

[0040] In at least one embodiment, the promoter material or a precursor of the promoter material is combined with the support to facilitate the impregnation of incipient moisture, and the impregnated support is subsequently dried and calcined. Petition 870250088025, dated 09 / 29 / 2025, page 42 / 68 8 / 24

[0041] The adsorbents described herein can be prepared by a variety of methods. For example, a metal can be dispersed onto a support by means of an incipient moisture technique. “Impregnated” generally means that the materials are “inside” the pores of the support. In at least one embodiment, the metal is precipitated onto the support. In at least one embodiment, the metal can be reduced after being dispersed or precipitated onto the support.

[0042] In at least one embodiment, the adsorbent comprises a promoter (e.g., Na2O), which may be present from about 0.5% by weight to about 20% by weight based on the total weight of the adsorbent. In at least one embodiment, the promoter (e.g., NaO) may be present at about 0.5% by weight, about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight based on the total weight of the adsorbent, or in any range defined by and inclusive of these points (e.g., from about 2% by weight to about 10% by weight).

[0043] In at least one embodiment, the adsorbent comprises copper oxide (e.g., precipitated copper oxide), which may be present from about 50% by weight to about 80% by weight based on the total weight of the adsorbent. In at least one embodiment, the copper oxide may be present at about 50% by weight, about 51% by weight, about 52% by weight, about 53% by weight, about 54% by weight, about 55% by weight, about 56% by weight, about 57% by weight, Petition 870250088025, dated 09 / 29 / 2025, page 43 / 68 9 / 24 approximately 58% by weight, approximately 59% by weight, approximately 60% by weight, approximately 61% by weight, approximately 62% by weight, approximately 63% by weight, approximately 64% by weight, approximately 65% ​​by weight, approximately 66% by weight, approximately 67% by weight, approximately 68% by weight, approximately 69% by weight, approximately 70% by weight, approximately 71% by weight, approximately 72% by weight, approximately 73% by weight, approximately 74% by weight, approximately 75% by weight, approximately 76% by weight, approximately 77% by weight, approximately 78% by weight, approximately 79% by weight, approximately 80% by weight, or in any interval defined by and inclusive of these points (for example, from approximately 65% ​​by weight to approximately 75% by weight).

[0044] In at least one embodiment, the adsorbent comprises zinc oxide (e.g., precipitated zinc oxide), which may be present from about 10% by weight to about 40% by weight based on the total weight of the adsorbent.In at least one embodiment, zinc oxide may be present in about 10% by weight, about 11% by weight, about 12% by weight, about 13% by weight, about 14% by weight, about 15% by weight, about 16% by weight, about 17% by weight, about 18% by weight, about 19% by weight, about 20% by weight, about 21% by weight, about 22% by weight, about 23% by weight, about 24% by weight, about 25% by weight, about 26% by weight, about 27% by weight, about 28% by weight, about 29% by weight, about 30% by weight, about 31% by weight, about 32% by weight, about 33% by weight, about 34% by weight, about 35% by weight, approximately 36% by weight, approximately 37% by weight, approximately 38% by weight, approximately 39% by weight, approximately 40% by weight, or in any range defined by and inclusive of these points (for example, from approximately 15% by weight to approximately 35% by weight).

[0045] The surface area, as discussed herein, is determined by the Brunauer-Emmett-Teller (BET) method in accordance with DIN Petition 870250088025, dated 09 / 29 / 2025, page 44 / 68 10 / 24 ISO 9277:2003-05 (which is a revised version of DIN 66131), which can be called the "BET surface area". The specific surface area is determined by a multipoint BET measurement in the relative pressure range of 0.05-0.3 p / p0. In at least one embodiment, the adsorbent has a BET surface area of ​​approximately 100 m² / g, approximately 110 m² / g, approximately 120 m² / g, approximately 130 m² / g, approximately 140 m² / g, approximately 150 m² / g, approximately 160 m² / g, approximately 170 m² / g, approximately 180 m² / g, approximately 190 m² / g, approximately 200 m² / g, approximately 210 m² / g, approximately 220 m² / g, approximately 230 m² / g, approximately 240 m² / g, approximately 250 m² / g, greater than 250 m² / g, or in any range. defined by and inclusive of these points (e.g., from about 150 m2 / ga to about 200 m2 / g). In at least one embodiment, the BET surface area is at least about 25 m2 / g, at least about 50 m2 / g, or at least about 75 m2 / ga to about 150 m2 / g or more.

[0046] The pore volume and average pore radius, as discussed herein, are determined by the Barrett-Joyner-Halenda (BJH) method. Mercury porosimetry analysis can be used to characterize porosity. Mercury porosimetry applies controlled pressure to a sample immersed in mercury. An external pressure is applied so that the mercury penetrates the voids / pores of the material. The amount of pressure required to penetrate the voids / pores is inversely proportional to the size of the voids / pores. A mercury porosimeter generates pore volume and size distributions from the pressure versus intrusion data generated by the instrument using the Washburn equation: — 4g cos q where D = diameter, P = pressure, g = surface tension of mercury, q = contact angle. For example, porous silica microspheres containing voids / pores with an average size of about 165 nm may have Petition 870250088025, dated 09 / 29 / 2025, page 45 / 68 11 / 24 an average porosity of about 0.8. In at least one embodiment, the alumina adsorbent has a total volume of about 0.1 mL / g, about 0.15 mL / g, about 0.2 mL / g, about 0.3 mL / g, about 0.4 mL / g, about 0.5 mL / g, about 0.6 mL / g, about 0.7 mL / g, about 0.8 mL / g, about 0.9 mL / g, about 1.0 mL / g, about 1.5 mL / g, 2.0 mL / g, about 2.5 mL / g, 3.0 mL / g, approximately 3.5 mL / g, 4.0 mL / g, approximately 4.5 mL / g, 5.0 mL / g, approximately 5.5 mL / g, approximately 6.0 mL / g, more than approximately 6.0 mL / g, or in any range defined by and inclusive of these points (e.g., from approximately 0.3 mL / g to approximately 6 mL / g).

[0047] In at least one embodiment, the adsorbent has a density of about 0.5 g / mL, about 0.6 g / mL, about 0.7 g / mL, about 0.8 g / mL, about 0.9 g / mL, about 1.0 g / mL, about 1.1 g / mL, about 1.2 g / mL, about 1.3 g / mL, about 1.4 g / mL, about 1.5 g / mL, about 1.6 g / mL, about 1.7 g / mL, about 1.8 g / mL, about 1.9 g / mL, about 2.0 g / mL, about 2.1 g / mL, about 2.2 g / mL, about 2.3 g / mL, about 2.4 g / mL, about 2.5 g / mL, approximately 2.6 g / mL, approximately 2.7 g / mL, approximately 2.8 g / mL, approximately 2.9 g / mL, approximately 3.0 g / mL, or in any range defined by and inclusive of these points (for example, approximately 0.7 g / mL to approximately 1.0 g / mL).

[0048] The suitable components may be present in the adsorbent compositions in bulk form, i.e., in continuous form, generally uninterrupted by other materials. The bulk form may contain virtually no other material. Consequently, the adsorbent compositions may be in any suitable final form, for example, spheres, tablets, extrudates, pellets, rods, molds or monoliths, etc., in various shapes and sizes. In at least one embodiment, an adsorbent (for example, an alumina adsorbent with precipitated or impregnated copper) is in the form of spheres or a material Petition 870250088025, dated 09 / 29 / 2025, pp. 46 / 68 12 / 24 extruded, as extruded particles. In at least one embodiment, the extruded particles are elongated and may have an average extruded length (i.e., a major average dimension) of about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, or in any range defined by and inclusive of these points (e.g., from about 3 mm to about 5 mm). In at least one embodiment, the adsorbent particles have a lateral crush resistance greater than about 10 N, greater than about 20 N, greater than about 30 N, greater than about 40 N, greater than about 50 N, greater than about 60 N, greater than about 70 N, greater than about 80 N, greater than about 90 N, or greater than about 100 N.

[0049] The adsorbents described herein may be suitable for removing chlorides and / or other components from feed streams, such as pyrolysis streams from plastics. As used herein, “chlorides” refers to chlorine-containing compounds which may include, but are not limited to, chloroalkanes, chloroalkenes, chloroxygenates, chloronaphthenes and chloroaromatics. Streams suitable for treatment by the adsorbents described herein may include a chloride content greater than about 10 ppmw, up to about 500 ppmw (e.g., about 10 ppmw to about 45 ppmw, or about 100 ppmw to about 250 ppmw), or more.

[0050] In at least one embodiment, the adsorbent exhibits a chloride removal rate of at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, or at least about 99% when in contact with the pyrolysis liquid stream (e.g., having a chloride content of more than about 80 ppmw) at a temperature of about 200 °C to 350 °C. Petition 870250088025, dated 09 / 29 / 2025, page 47 / 68 13 / 24

[0051] In at least one embodiment, the adsorbent is regenerative (i.e., the adsorbent is capable of being regenerated to restore its activity to or near its pre-use activity). In at least one embodiment, the adsorbent can be regenerated by treating the adsorbent with a regeneration stream. In at least one embodiment, the regeneration stream is at a temperature of about 450 °C to about 600 °C and comprises hydrogen gas. In at least one embodiment, the regeneration stream is at a temperature of about 250 °C to about 350 °C and comprises oxygen gas.

[0052] Unless otherwise indicated, all parts and percentages are by weight. The percentage by weight (% by weight), unless otherwise indicated, is based on a whole composition free of any volatiles, i.e., based on the dry solids content.

[0053] The following exemplary embodiments are now described: - Embodiment Example 1: A method for removing chlorides from a plastic pyrolysis stream, comprising an initial chloride concentration greater than about 10 ppmw, the method comprising: contacting the stream with an alumina adsorbent, the alumina adsorbent comprising a sodium promoter, wherein a final chloride concentration of the treated stream is less than about 10 ppmw; - Embodiment 2: The method of Embodiment 1, in which the initial chloride concentration is from about 10 ppmw to about 45 ppmw; - Embodiment 3: The method of Embodiment 1, in which the initial chloride concentration is from about 45 ppmw to about 250 ppmw; - Implementation Method 4: The method of any of the Forms of Petition 870250088025, dated 09 / 29 / 2025, pp. 48 / 68 14 / 24 Previous embodiments, in which the promoter is present at 2% by weight to approximately 10% by weight based on the total weight of the adsorbent; - Embodiment Form 5: The Embodiment Form 4 method, in which the promoter comprises sodium in the form of Na2O; - Embodiment 6: The method of any of the preceding Embodiments, wherein the alumina adsorbent has a BET surface area of ​​about 150 m2 / ga or about 300 m2 / g; - Embodiment 7: The method of any of the preceding Embodiments, wherein the alumina adsorbent has a total pore volume of about 0.2 mL / g to about 6 mL / g; - Embodiment 8: The method of any of the preceding Embodiments, in which the alumina adsorbent exhibits a bimodal pore size distribution; - Embodiment 9: The method of any of the preceding Embodiments, wherein the alumina adsorbent has a density of about 0.5 g / mL to about 1.0 g / mL; - Embodiment 10: The method of any of the preceding Embodiments, in which the alumina adsorbent is in the form of spherical particles; - Embodiment 11: The method of Embodiment 10, in which the spherical particles have an average diameter of about 2 mm to about 4 mm; - Embodiment 12: The method of either Embodiment 10 or Embodiment 11, in which the spherical particles exhibit a lateral crushing resistance greater than about 40 N; - Embodiment 13: The method of any of the preceding Embodiments, in which the chloride removal rate is at least about 80%, at least about 85%, or at least about 90%. Petition 870250088025, dated 09 / 29 / 2025, page 49 / 68 15 / 24 for a pyrolysis flow temperature of 200 °C to 350 °C; - Embodiment 14: The method of any of the preceding Embodiments, in which the alumina adsorbent is regenerative; - Embodiment 15: The method of any of the preceding Embodiments, further comprising: subsequently placing the alumina adsorbent in contact with a regeneration stream to regenerate the alumina adsorbent; Example of Embodiment 16: The method of Embodiment Form 15, in which the regeneration stream comprises hydrogen gas at a temperature of about 450 °C to about 600 °C; Example of Embodiment 17: The method of Embodiment Form 15, in which the regeneration flow comprises oxygen gas at a temperature of about 250 °C to about 350 °C; - Embodiment Example 18: A method for removing chlorides from a pyrolysis stream of plastics, comprising an initial chloride concentration greater than about 10 ppmw, the method comprising: contacting the stream with an adsorbent, the adsorbent comprising copper oxide, zinc oxide and alumina, wherein a final chloride concentration of the treated stream is less than about 10 ppmw; - Embodiment 19: The method of Embodiment 18, in which the initial chloride concentration is from about 10 ppmw to about 45 ppmw; - Embodiment 20: The method of Embodiment 18, in which the initial chloride concentration is from about 45 ppmw to about 250 ppmw; - Embodiment 21: The method of any of the Embodiments 18-20, wherein copper oxide is present in about 50% by weight to about 80% by weight based on the total weight of Petition 870250088025, dated 09 / 29 / 2025, pp. 50 / 68 16 / 24 adsorbent; Example of Embodiment 22: The method of any of the Embodiment Forms 18 to 21, wherein zinc oxide is present at about 20% by weight to about 30% by weight based on the total weight of the adsorbent; Example of Embodiment 23: The method of any of the Embodiment Forms 18 to 22, wherein alumina is present at about 3% by weight to about 10% by weight based on the total weight of the adsorbent; - Embodiment 24: The method of any of Embodiments 18 to 23, wherein: copper oxide is present in about 50% by weight to about 80% by weight; zinc oxide is present in about 10% by weight to about 40% by weight; and alumina is present as the balance of the adsorbent weight; - Embodiment 25: The method of any of Embodiments 18 to 24, in which the adsorbent is formed by the coprecipitation of copper oxide and zinc oxide in alumina; - Embodiment 26: The method of any of the Embodiments 18 to 25, wherein the adsorbent has a BET surface area of ​​about 25 m2 / ga or about 150 m2 / g; - Embodiment 27: The method of any of the Embodiments 18 to 26, wherein the adsorbent has a total pore volume of about 0.15 mL / g or about 2 mL / g; - Embodiment 28: The method of any of Embodiments 18 to 27, in which the adsorbent has a density of about 1.0 g / mL to about 3.0 g / mL; - Embodiment 29: The method of any of the Embodiments 18 to 28, in which the adsorbent is in tablet form; Petition 870250088025, dated 09 / 29 / 2025, pp. 51 / 68 17 / 24 - Embodiment 30: The method of Embodiment 29, in which the tablets have an average length of about 3 mm to about 6 mm, and an average width of about 2 mm to about 4 mm; - Embodiment 31: The method of either Embodiment 29 or Embodiment 30, in which the tablets exhibit a lateral crush resistance greater than about 60 N; - Embodiment 32: The method of any of Embodiments 18 to 20, in which the chloride removal rate is at least about 80%, at least about 85%, or at least about 90% for a pyrolysis stream temperature of 200 °C to 350 °C; - Implementation Method 33: The method of any of the Embodiment Forms 18 to 20, in which the adsorbent is regenerative; - Implementation Method 34: The method of any of the Embodiment Forms 18 to 20, further comprising: subsequently placing the adsorbent in contact with a regeneration stream to regenerate the adsorbent; - Embodiment 35: The method of Embodiment 34, in which the regeneration stream comprises hydrogen gas at a temperature of about 450 °C to about 600 °C; - Embodiment 36: The method of Embodiment 34, in which the regeneration stream comprises oxygen gas at a temperature of about 250 °C to about 350 °C. Illustrative Example(s)

[0054] The following examples are presented to aid in understanding the disclosure and should not, of course, be interpreted as specifically limiting the embodiments described and claimed herein. Such variations of embodiments, including the replacement of all currently known or subsequently developed equivalents, which Petition 870250088025, dated 09 / 29 / 2025, pp. 52 / 68 18 / 24 would be within the competence of the technicians in the field, and changes in the formulation or minor changes in the experimental design should be considered as being within the scope of the embodiments incorporated herein. Example 1: Dechlorination Performance

[0055] Standard dechlorination experiments were performed for several samples (described below) in a flow reactor loaded with approximately 1 mL of a given sample. Dechlorination was performed using a sample of commercial plastic waste pyrolysis oil (PyOil) containing approximately 80 ppmw of chlorides, which were organic chlorides. Before each experiment, the reactor was purged with dry nitrogen, and the samples were dehydrated at 250 °C for one hour at a gas space hour velocity (GHSV) of 1000 h-1. After dehydration, a feed of liquid PyOil was introduced into the reactor at a space hour velocity (LHSV) of 1 h-1 and a total pressure of 50 barg. The reactor temperature was increased to 200 °C at 50 barg to ensure liquid-only flow. Chloride measurements in the effluent liquid stream were performed in the range of 200 to 325 °C with temperature increments of 25 °C.Each temperature increase was maintained for approximately 20 hours to allow the system to balance.

[0056] Sample A was a sodium-promoted alumina formulation with a high volume of macroporous pores with a bimodal pore size distribution in the form of spheres. Without wanting to be bound by theory, it was believed that the unique pore size distribution, which characterizes a macropore volume of approximately 0.3 mL / g, would allow this product to perform highly in removing chlorides from pyrolysis oils from plastic waste. The sodium oxide content was approximately 5.5% by weight based on the total weight of the formulation.

[0057] Reference 1 was sodium-promoted alumina Petition 870250088025, dated 09 / 29 / 2025, pp. 53 / 68 The conventional 19 / 24 sample did not exhibit any appreciable macropore volume (below 0.05 mL / g) or a bimodal pore size distribution in the form of a sphere. The sodium oxide level was approximately 4% by weight. It was observed that the performance of this formulation in removing chlorides from pyrolysis oils of plastic waste was inferior to Sample A.

[0058] Reference 2 was a conventional unpromoted high surface area activated alumina shield in the form of a sphere. It did not exhibit any appreciable macropore volume (below 0.05 mL / g) or bimodal pore size distribution. The performance of this formulation in removing chlorides from residual plastic pyrolysis oils was found to be substantially lower than Sample A.

[0059] Sample B was a formulation based on precipitated copper and zinc oxide in tablet form, with a copper oxide content of approximately 70% by weight and a zinc oxide content of approximately 24.5% by weight balanced by alumina. Without wishing to be bound by theory, it is believed that due to the exceptionally high copper oxide surface area, this formulation shows high performance in removing chlorides from pyrolysis oils of waste plastics.

[0060] The properties of Samples A, B and the reference samples are summarized in Tables 1 and 2. Figure 1 shows the mercury pore volume distributions for Sample A versus Reference 1, demonstrating a significant macropore volume peak.

[0061] The chloride removal performance of Samples A, B, and the reference samples is shown in Figures 2 and 3.

[0062] Figure 2 shows the performance of Samples A and B in removing chlorides from a pyrolysis feed of plastic waste. The experimental conditions were: argon pressure of 50 barg, temperature of 200-325 °C and commercial PyOil feed at 80 ppmw chlorides. Petition 870250088025, dated 09 / 29 / 2025, pp. 54 / 68 20 / 24

[0063] Figure 3 shows the performance of Sample A in removing chlorides from a pyrolysis feed of plastic waste. The experimental conditions were: 50 barg argon pressure, 200-325 °C temperature and commercial PyOil feed at 80 ppmw chlorides. Table 1: Properties Typically Observed of Sample A, References 1 and 2. Sample A Reference 1 Reference 2 Shape 3.2 mm sphere 3.2 mm sphere 3.2 mm sphere LOI (250-1100 °C) % 6.5 6.5 6.5 Surface area m2 / g 250 250 335 Density by volume kg / m3 675 800 750 Crushing strength N 50 125 110 Water pore volume mL / g 0.6 0.45 0.45 Macropore volume (d > 750 A) mL / g 0.3 below 0.05 below 0.05 Composition Na2O % by weight 5.5 4 below 0.25 AlOx % by weight equilibrium equilibrium equilibrium Table 2: Properties Typically Observed of Samples A, B and E Reference 2. Sample A Sample B Reference 2 Shape 3.2 mm sphere 3 mm x 5 mm tablet 3.2 mm sphere LOI (250-1100 °C) % 6.5 17 6.5 Surface area m2 / g 250 70 335 Density by volume kg / m3 675 1450 750 Crushing strength N 50 80 110 Water pore volume mL / g 0.6 0.25 0.45 Composition Na2O % by weight 5.5 below 0.1 below 0.25 CuO % by weight none 70 none Petition 870250088025, dated 09 / 29 / 2025, pp. 55 / 68 21 / 24 ZnO % by weight none 24.5 none AlOx % by weight equilibrium 5.5 equilibrium

[0064] In the preceding description, several specific details are presented, such as specific materials, dimensions, process parameters, etc., to provide a complete understanding of the embodiments of the present disclosure. The particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. The terms “example” or “exemplary” are used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as an “example” or “exemplary” should not necessarily be interpreted as preferential or advantageous in relation to other aspects or designs. Rather, the use of the words “example” or “exemplary” is intended to present concepts in a concrete way. As used in this application, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.”That is, unless otherwise specified, or clear from the context, “X includes A or B” is intended to mean any of the natural inclusive permutations. In other words, if X includes A; X includes B; or X includes both A and B, then “X includes A or B” is satisfied under any of the above cases.

[0065] Furthermore, the use of the terms “a”, “an”, “the” and similar referents in the context of the description of the materials and methods discussed herein (especially in the context of the following claims) should be constructed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context.

[0066] Quotation of value ranges here is intended only to serve as a shorthand method of referring individually to each separate value within the range, unless otherwise indicated herein, and each separate value is incorporated into the descriptive report as if it were. Petition 870250088025, dated 09 / 29 / 2025, pp. 56 / 68 22 / 24 cited individually here. All methods described herein may be performed in any appropriate order unless otherwise indicated or clearly contradicted by the context. Furthermore, any permutations of quoted values ​​are considered to define the limits of the intervals. For example, an interval from 1, 2, or 3 to 4, 5, or 6 is understood as including not only 1 to 4, 1 to 5, 1 to 6, 2 to 4, 2 to 5, etc., but also 1 to 2, 1 to 3, 2 to 3, 4 to 6, etc.

[0067] The term “about” used throughout the text is used to describe and consider small fluctuations that could be introduced through experimental or measurement error (e.g., ± 1%). All numerical values ​​are modified by the term “about” whether explicitly indicated or not. Numerical values ​​modified by the term “numerical values” include the specific value identified. For example, “about 5.0” includes 5.0.

[0068] The term “essentially none” or “substantially none” or “substantially free of” means “not intentionally added” and only trace or inadvertent amounts could be present, for example, < 5% by weight, < 4% by weight, < 3% by weight, < 2% by weight, < 1% by weight, < 0.5% by weight or < 0.25% by weight, based on the weight of the composition referred to, for example, the total adsorbent composition. For example, an adsorbent composition that is substantially lead-free may refer to an adsorbent composition for which lead is below a detectable limit, or its presence has a negligible effect on the adsorbent performance.

[0069] The reference throughout this descriptive report to “a form of embodiment”, “certain forms of embodiment”, “one or more forms of embodiment”, “some form of embodiment” or “some forms of embodiment” means that a specific feature, structure, material or characteristic Petition 870250088025, dated 09 / 29 / 2025, pp. 57 / 68 23 / 24 described in connection with the embodiment is included in at least one embodiment of this disclosure. Thus, the appearance of phrases such as “in one or more embodiments”, “in certain embodiments”, “in one embodiment” or “in some embodiments” in various places throughout this descriptive report does not necessarily refer to the same embodiment of this disclosure. Furthermore, the particular features, structures, materials or characteristics may be combined in any suitable manner in one or more embodiments.

[0070] It is important to understand that the above description is illustrative and not restrictive. Many other embodiments will become apparent to those skilled in the art after reading and understanding the above description. The scope of the disclosure should therefore be determined with reference to the appended claims, together with the full scope of equivalents to which such claims are entitled. The use of any examples or exemplary language (e.g., “such as”) provided herein is intended only to better clarify the materials and methods and does not impose a limitation on the scope unless stated otherwise. No language in the descriptive report should be constructed as an indication of any unclaimed element as essential to the practice of the materials and methods disclosed.

[0071] Although the embodiments disclosed herein have been described with reference to particular embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be evident to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present disclosure without departing from the spirit and scope thereof. Thus, it is intended that the present disclosure includes modifications and variations that are within the scope of the appended claims and their respective provisions. Petition 870250088025, dated 09 / 29 / 2025, pages 58 / 68 24 / 24 equivalents, and the embodiments described above are presented for illustrative purposes only and not as a limitation. Petition 870250088025, dated 09 / 29 / 2025, pages 59 / 68

Claims

1 / 5 Claims 1. A METHOD FOR REMOVING CHLORIDES FROM A PLASTIC PYROLYSIS STREAM comprising an initial chloride concentration greater than about 10 ppmw, characterized by the method comprising: contacting the stream with an alumina adsorbent, the alumina adsorbent comprising a sodium promoter, wherein a final chloride concentration of the treated stream is less than about 10 ppmw.

2. METHOD, according to claim 1, characterized in that the initial chloride concentration is from about 10 ppmw to about 45 ppmw.

3. METHOD, according to claim 1, characterized in that the initial chloride concentration is from about 45 ppmw to about 250 ppmw.

4. METHOD, according to claim 1, characterized in that the promoter is present at 2% by weight to about 10% by weight based on the total weight of the adsorbent.

5. METHOD, according to claim 4, characterized by the promoter comprising sodium in the form of Na2O.

6. METHOD, according to claim 1, characterized in that the alumina adsorbent has a BET surface area of ​​about 150 m2 / g or about 300 m2 / g.

7. METHOD, according to claim 1, characterized in that the alumina adsorbent has a total pore volume of about 0.2 mL / g or about 6 mL / g.

8. METHOD, according to claim 1, characterized by the alumina adsorbent exhibiting a bimodal pore size distribution. Petition 870250088025, dated 09 / 29 / 2025, pp. 60 / 68 2 / 5 9. METHOD, according to claim 1, characterized in that the alumina adsorbent has a density of about 0.5 g / mL to about 1.0 g / mL.

10. METHOD, according to claim 1, characterized in that the alumina adsorbent is in the form of spherical particles.

11. METHOD, according to claim 10, characterized in that the spherical particles have an average diameter of about 2 mm to about 4 mm.

12. METHOD, according to claim 10, characterized in that the spherical particles exhibit a lateral crushing resistance greater than about 40 N.

13. METHOD, according to claim 1, characterized by a chloride removal rate of at least about 80%, at least about 85%, or at least about 90% for a pyrolysis stream temperature of 200 °C to 350 °C.

14. METHOD, according to claim 1, characterized in that the alumina adsorbent is regenerative.

15. METHOD, according to claim 1, characterized by further comprising: subsequently placing the alumina adsorbent in contact with a regeneration stream to regenerate the alumina adsorbent.

16. METHOD, according to claim 15, characterized in that the regeneration stream comprises hydrogen gas at a temperature of about 450 °C to about 600 °C.

17. METHOD, according to claim 15, characterized in that the regeneration stream comprises oxygen gas at a temperature of about 250 °C to about 350 °C.

18. METHOD FOR REMOVING CHLORIDES FROM A PLASTIC PYROLYSIS STREAM Petition 870250088025, dated 09 / 29 / 2025, page 61 / 68 3 / 5 comprising an initial chloride concentration greater than about 10 ppmw, characterized by the method comprising: placing the stream in contact with an adsorbent, the adsorbent comprising copper oxide, zinc oxide and alumina, wherein the final chloride concentration of the treated stream is less than about 10 ppmw.

19. METHOD, according to claim 18, characterized in that the initial chloride concentration is from about 10 ppmw to about 45 ppmw.

20. METHOD, according to claim 18, characterized in that the initial chloride concentration is from about 45 ppmw to about 250 ppmw.

21. METHOD, according to claim 18, characterized in that copper oxide is present in about 50% by weight to about 80% by weight based on the total weight of the adsorbent.

22. METHOD, according to claim 18, characterized in that zinc oxide is present in about 20% by weight to about 30% by weight based on the total weight of the adsorbent.

23. METHOD, according to claim 18, characterized in that alumina is present in about 3% by weight to about 10% by weight based on the total weight of the adsorbent.

24. METHOD, according to claim 18, characterized in that: copper oxide is present in about 50% by weight to about 80% by weight; zinc oxide is present in about 10% by weight to about 40% by weight; and alumina is present as the balance of the adsorbent weight.

25. METHOD, according to claim 18, characterized in that the adsorbent is formed by the coprecipitation of copper oxide and zinc oxide in alumina.

26. METHOD, according to claim 18, characterized in that the adsorbent has a BET surface area of ​​about 25 m2 / g or about 150 m2 / g.

27. METHOD, according to claim 18, characterized in that the adsorbent has a total pore volume of about 0.15 mL / g or about 2 mL / g.

28. METHOD, according to claim 18, characterized in that the adsorbent has a density of about 1.0 g / mL to about 3.0 g / mL.

29. METHOD, according to claim 18, characterized in that the adsorbent is in tablet form.

30. METHOD, according to claim 29, characterized in that the tablets have an average length of about 3 mm to about 6 mm and an average width of about 2 mm to about 4 mm.

31. METHOD, according to claim 29, characterized by the tablets having lateral crush resistance greater than about 60 N.

32. METHOD, according to claim 18, characterized in that a chloride removal rate is at least about 80%, at least about 85%, or at least about 90% for a pyrolysis stream temperature of 200 °C to 350 °C.

33. METHOD, according to claim 18, characterized in that the adsorbent is regenerative.

34. METHOD, according to claim 18, further characterized by comprising: subsequently placing the adsorbent in contact with a regeneration stream to regenerate the adsorbent. Petition 870250088025, dated 09 / 29 / 2025, pp. 63 / 68 5 / 5 35. METHOD, according to claim 34, characterized in that the regeneration stream comprises hydrogen gas at a temperature of about 450 °C to about 600 °C.

36. METHOD, according to claim 34, characterized in that the regeneration flow comprises oxygen gas at a temperature of about 250 °C to about 350 °C. Petition 870250088025, dated 09 / 29 / 2025, pp. 64 / 68

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