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WO-2026095228-A1 - CATALYST FOR HYDROCRACKING WASTE PLASTIC PYROLYSIS OIL, METHOD FOR PREPARING SAME, AND METHOD FOR HYDROCRACKING USING SAME

WO2026095228A1WO 2026095228 A1WO2026095228 A1WO 2026095228A1WO-2026095228-A1

Abstract

A catalyst for hydrocracking plastic pyrolysis oil of the present invention comprises: an active ingredient containing Ni and Mo; and a USY zeolite-Al2O3 carrier, wherein the catalyst for hydrocracking plastic pyrolysis oil has the highest light naphtha selectivity.

Inventors

  • YOO, SANG BEOM
  • GU, Sang Seo
  • KIM, GIL HO

Assignees

  • 한화솔루션 주식회사

Dates

Publication Date
20260507
Application Date
20250401
Priority Date
20241028

Claims (15)

  1. It is a plastic pyrolysis oil hydrocracking catalyst in which an active material containing Ni and Mo is supported on a carrier, and Includes mesopores and micropores, A plastic pyrolysis oil hydrocracking catalyst satisfying the following Equations 1 to 3: [Equation 1] 2 ≤ I 2 / I 1 ≤ 5 (In the above equation, I1 is the maximum peak intensity at 825±10 cm⁻¹ obtained by Raman spectroscopic analysis, and I₂ is the maximum peak intensity at 960±10 cm⁻¹ ) [Equation 2] S meso : S micro = 0.9: 1 ~ 3: 1 (In the above formula, S meso is the BET surface area of the mesopore ( m² /g), and S micro is the BET surface area of the micropore ( m² /g)) [Equation 3] S meso52 : S micro52 = 1.5: 1 ~ 5: 1 (In the above formula, S meso52 is the BET surface area ( m² /g) of the mesopore after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar, and S micro52 is the BET surface area ( m² /g) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar.
  2. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst satisfies the following Equations 4 and 5: [Equation 4] V meso : V micro = 3: 1 ~ 5: 1 (In the above formula, V meso is the pore volume of the mesopore ( cm³ /g), and V micro is the pore volume of the micropore ( cm³ /g) [Equation 5] V meso52 : V micro52 = 6: 1 ~ 9: 1 (In the above formula, V meso52 is the pore volume ( cm³ /g) of the mesopore after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar, and V micro52 is the pore volume ( cm³ /g) of the micropores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar.
  3. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst satisfies the following Equations 6 and 7: [Equation 6] 65 ≤ 100 * S meso52 / S meso ≤ 85 (In the above formula, S meso is the BET surface area of the mesopore ( m² /g), and S meso52 is the BET surface area ( m² /g) of the mesopore after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. [Equation 7] 30 ≤ 100 * S micro52 / S micro ≤ 50 (In the above formula, S micro is the BET surface area of the micropore ( m² /g), and S micro52 is the BET surface area ( m² /g) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar.
  4. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst satisfies the following Equations 8 and 9: [Equation 8] 65 ≤ 100 * V meso52 / V meso ≤85 (In the above formula, V meso is the pore volume of the mesopore ( cm³ /g), and V meso52 is the pore volume ( cm³ /g) of the mesopore after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. [Equation 9] 30 ≤ 100 * V micro52 / V micro ≤ 50 (In the above formula, V micro is the pore volume of the micropore ( cm³ /g), and V micro52 is the pore volume ( cm³ /g) of the micropores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar.
  5. In paragraph 1, The above carrier is a plastic pyrolysis oil hydrocracking catalyst comprising a USY zeolite- Al₂O₃ carrier.
  6. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst is a plastic pyrolysis oil hydrocracking catalyst having a naphtha conversion rate of 90% or more after a hydrocracking reaction for 80 hours at a temperature of 420°C and a pressure of 50 bar.
  7. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst is a plastic pyrolysis oil hydrocracking catalyst having a nitrogen content of 1 ppm or less and a sulfur content of 5 ppm or less after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar.
  8. In paragraph 1, The above plastic pyrolysis oil hydrocracking catalyst, after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar, The BET surface area of the mesopore (S meso52 ) is 100 to 200 m² /g, The BET surface area of the micropores (S micro52 ) is 50 to 200 m² /g, The pore volume of the mesopores (V meso52 ) is 0.1 to 0.3 cm³ /g, and A plastic pyrolysis oil hydrocracking catalyst having a micropore volume (V micro52 ) of 0.01 to 0.1 cm³ /g.
  9. A method for manufacturing a plastic pyrolysis oil hydrocracking catalyst according to any one of claims 1 to 8, wherein the method A first support is prepared by supporting a Mo precursor on a USY zeolite-Al2O3 support; A catalyst precursor is prepared by supporting a Ni precursor on the first support above; and Heat-treating the above catalyst precursor; A method for manufacturing a plastic pyrolysis oil hydrocracking catalyst comprising the steps.
  10. In Paragraph 9, A method for manufacturing a plastic pyrolysis oil hydrocracking catalyst, further comprising the step of drying the catalyst precursor prior to the heat treatment.
  11. In Paragraph 9, A method for manufacturing a plastic pyrolysis oil hydrocracking catalyst, wherein the heat treatment is performed at 450 to 650 ℃.
  12. This is a method for the hydrocracking of plastic pyrolysis oil, and the method A method characterized by contacting plastic pyrolysis oil with a plastic pyrolysis oil hydrolysis catalyst according to any one of claims 1 to 8 to hydrolyze the oil.
  13. In Paragraph 12, A method in which the above-mentioned hydrocracking is performed at a temperature of 300 to 500 ℃ and a hydrogen pressure of 30 to 70 bar.
  14. A method for producing naphtha from plastic pyrolysis oil, and the method The method includes the step of supplying plastic pyrolysis oil raw materials to a reactor and bringing them into contact with a catalyst embedded in the reactor to carry out a hydrocracking reaction. The above catalyst is a plastic pyrolysis oil hydrocracking catalyst according to any one of claims 1 to 8, and The above method is a method in which the naphtha conversion rate is 90% or higher after a hydrocracking reaction for 80 hours.
  15. In Paragraph 14, A method in which the above-mentioned hydrocracking is performed at a temperature of 300 to 500 ℃ and a hydrogen pressure of 30 to 70 bar.

Description

Plastic pyrolysis oil hydrocracking catalyst, method for manufacturing the same, and hydrocracking method using the same The present invention relates to a plastic pyrolysis oil hydrocracking catalyst, a method for manufacturing the same, and a hydrocracking method using the same. More specifically, the present invention relates to a plastic pyrolysis oil hydrocracking catalyst capable of maintaining reaction activity even when hydrocracking is performed for more than 80 hours without a catalyst regeneration process or a catalyst replacement process, a method for manufacturing the same, and a hydrocracking method using the same. Plastics are materials whose utility and importance are increasing due to their economic efficiency, plasticity, durability, and versatility; however, they have the disadvantage of being difficult to directly recycle or decompose due to their high chemical stability. For this reason, the disposal process of plastics is emerging as a serious environmental issue, causing problems such as landfill shortages, the formation of marine debris zones, the generation of endocrine disruptors, and accumulation in ecosystems. Consequently, social interest in the recycling of waste plastics is increasing. Pyrolysis is one of the effective alternatives for waste plastic recycling as it can effectively decompose plastics without special pretreatment or equipment. Pyrolysis is a decomposition reaction that converts high-molecular-weight hydrocarbons into low-molecular-weight substances at high temperatures, and it typically proceeds for a short period under oxygen-free conditions. As such, waste plastic pyrolysis oil (WPPO), formed by the pyrolysis of waste plastics, contains large amounts of olefins and trace impurities (S, N, O, Cl), making it difficult to use directly as a chemical raw material. Furthermore, because the composition of the WPPO product is irregular, it is necessary to control the number of carbon atoms to convert it into high-value hydrocarbons. Meanwhile, hydrocracking (HCK) refers to a reaction that converts various hydrocarbons into light hydrocarbons by decomposing them under a catalyst and a high-temperature, high-pressure hydrogen atmosphere. Depending on process conditions, it can produce a variety of petrochemical products such as LPG, gasoline, kerosene, jet fuel, and diesel fuel. It has the advantage of eliminating the need for additional processing steps due to low impurity content. The HCK reaction is a commercially known reaction, and various commercial catalysts are in use. However, since most of these commercial catalysts assume crude oil as the reactant feedstock, it is uncertain whether HCK catalysts can be applied to WPPO instead of crude oil. This is because there are physical property differences between WPPO and crude oil, such as quality variations and a lower calorific value. Furthermore, since the required active sites and metal-support interactions of the catalyst vary depending on the reactant, an understanding of the catalytic reaction mechanism and key design parameters is necessary, along with the feed definition. In addition, most HCK catalysts are known to be easily deactivated by coke deposited during the reaction. Therefore, there is a need to develop HCK that can convert WPPO into high-purity naphtha and has excellent durability. Related prior art is US No. 6217746. FIG. 1 schematically illustrates a hydrolysis process of plastic pyrolysis oil according to one embodiment of the present invention. Figure 2 shows the Raman analysis results of the catalysts used in the examples and comparative examples. Figure 3 shows the change in naphtha conversion rate over time for the examples and comparative examples. Figure 4 shows the results of nitrogen absorption analysis of the catalysts used in the examples and comparative examples. The present invention will be described in more detail below. Where terms such as 'comprising,' 'having,' and 'consisting of' are used in this specification, other parts may be added unless 'only' is used. Where a component is expressed in the singular, it includes cases where it includes the plural unless specifically stated otherwise. In interpreting the components, they are interpreted to include a margin of error even in the absence of a separate explicit statement. In this specification, Raman spectroscopic analysis was performed using a 532 nm laser with the Nanofinder 30 of Tokyo Instruments (Tokyo, Japan). In this specification, the analysis of mesopores and micropores was performed using the N2 physisorption method with the Belsorp Max X of MicrotacBEL (Osaka, Japan). N2 physisorption was performed at -196 ℃, and the pore size distribution was calculated using the Barrett-Joyner-Halenda (BJH) model. Hereinafter, the plastic pyrolysis oil hydrolysis catalyst according to the present invention, the method for manufacturing the same, and the hydrolysis method using the same will be described in detail. Plastic pyrolysis