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KR-20260065077-A - METHOD FOR PRETREATMENT OF WASTE PLASTIC PYROLYSIS OIL AND METHOD FOR REMOVING STICKY SUBSTANCES USING THE SAME

KR20260065077AKR 20260065077 AKR20260065077 AKR 20260065077AKR-20260065077-A

Abstract

The present invention discloses a method for pretreating plastic pyrolysis oil. The method comprises: a first step of treating plastic pyrolysis oil with activated carbon to obtain a first pretreated product; and a second step of performing a first hydrogenation treatment on the first pretreated product at 150 to 250°C to obtain a second pretreated product.

Inventors

  • 이나현
  • 이동호
  • 김학민
  • 배영광

Assignees

  • 한화솔루션 주식회사

Dates

Publication Date
20260508
Application Date
20241031

Claims (15)

  1. This is a method for pre-treating plastic pyrolysis oil, and the method is A first step of obtaining a first pre-treated product by treating plastic pyrolysis oil with activated carbon; and A second step of obtaining a second pretreated product by performing a first hydrogenation treatment on the first pretreated product at 150 to 250 ℃; A plastic pyrolysis oil pretreatment method comprising
  2. In paragraph 1, A plastic pyrolysis oil pretreatment method in which the first hydrogenation treatment is performed in the presence of a supported catalyst in which a metal catalyst comprising Ni and Mo is supported on γ- Al₂O₃ .
  3. In paragraph 1, A method for pre-treating plastic pyrolysis oil, wherein the activated carbon has a BET of 300 to 700 m2/g, a total pore volume of 0.1 to 0.5 mL/g, and an average pore diameter of 0.5 to 1.2 nm.
  4. In paragraph 1, A plastic pyrolysis oil pretreatment method, wherein the first step is performed at 200 to 300 ℃.
  5. In paragraph 1, A plastic pyrolysis oil pretreatment method comprising the step of recovering and reusing the activated carbon.
  6. In paragraph 1, A plastic pyrolysis oil pretreatment method comprising the additional step of filtering the plastic pyrolysis oil before performing the first hydrogenation treatment.
  7. In paragraph 1, The above method is a plastic pyrolysis oil pretreatment method that removes adhesive substances from plastic pyrolysis oil.
  8. Plastic pyrolysis oil pretreated by the method of any one of claims 1 to 7, wherein the pyrolysis oil has a sticky substance reduction rate of 60% or more and an olefin reduction rate of 30% or more.
  9. A method for removing adhesive substances from plastic pyrolysis oil, and the method Treat plastic pyrolysis oil with activated carbon; and Hydrogenating the plastic pyrolysis oil treated with the above-mentioned activated carbon at 150 to 250 ℃; Includes steps, The above method is a method for removing sticky substances from plastic pyrolysis oil, wherein the olefin reduction rate according to Formula 1 below is 30% or more: [Equation 1] 100 * (W 0 -W 1 )/W 0 (In Equation 1 above, W0 is the initial olefin content of the plastic pyrolysis oil, and W1 is the olefin content of the product)
  10. In Paragraph 9, A method for removing sticky substances from plastic pyrolysis oil, wherein the activated carbon has a BET of 300 to 700 m2/g, a total pore volume of 0.1 to 0.5 mL/g, and an average pore diameter of 0.5 to 1.2 nm.
  11. In Paragraph 9, A method for removing sticky substances from plastic pyrolysis oil, wherein the step of treating with the activated carbon is performed at 200 to 300 ℃.
  12. In Paragraph 9, A method for removing sticky substances from plastic pyrolysis oil, further comprising the step of filtering the plastic pyrolysis oil before performing the above hydrogenation treatment.
  13. A method for producing naphtha comprising the step of hydrotreating or hydrocracking the pretreated plastic pyrolysis oil of claim 8.
  14. In Paragraph 13, The above method is a naphtha production method that involves hydrogenation cracking after hydrogenation treatment.
  15. In Paragraph 13, The above hydrogenation treatment is performed at a pressure of 5 to 200 bar and a temperature of 300 to 450 ℃, and A method for producing naphtha, wherein the above-mentioned hydrogenation cracking is performed at a pressure of 2 to 100 bar and a temperature of 400 to 600 ℃.

Description

Method for Pretreatment of Waste Plastic Pyrolysis Oil and Method for Removing Sticky Substances Using the Same The present invention relates to a method for pretreating plastic pyrolysis oil and a method for removing sticky substances using the same. More specifically, the present invention relates to a method for pretreating plastic pyrolysis oil and a method for removing sticky substances using the same, which can prevent catalyst deactivation and fouling by removing sticky substances in the pretreatment or hydrocracking of plastic pyrolysis oil. 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 amounts of impurities (S, N, O, Cl), making it difficult to use directly as a chemical raw material. In addition, because the composition of the WPPO products is irregular, it is necessary to control the number of carbon atoms to convert them into high-value hydrocarbons. Accordingly, methods of hydrogenation or hydrocracking are being used to chemically upgrade plastic pyrolysis oil. However, there is a problem in that sticky substances are generated during the hydrotreatment or hydrocracking process of plastic pyrolysis oil, which deactivates the catalyst or causes fouling in the catalyst and reactor. Therefore, it is necessary to remove the sticky substance before the above-mentioned hydrogenation or hydrocracking process. Related prior art is US No. 6217746. FIG. 1 schematically illustrates a plastic pyrolysis oil pretreatment process according to one embodiment of the present invention. FIG. 2 schematically illustrates a plastic pyrolysis oil pretreatment process according to another embodiment of the present invention. FIG. 3 schematically illustrates a plastic pyrolysis oil pretreatment process according to another embodiment of the present invention. FIG. 4 is a schematic flowchart illustrating a method for producing naphtha according to one embodiment of the present invention. 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 the following, a plastic pyrolysis oil pretreatment method according to the present invention and a method for removing sticky substances using the same will be described in detail. Method for pre-treating plastic pyrolysis oil and a method for removing adhesive substances using the same In this specification, 'plastic pyrolysis oil' refers to waste plastic pyrolysis oil (WPPO) formed by pyrolyzing waste plastic. In this specification, the term 'sticky substance' includes diolefins in plastic pyrolysis oil, unsaturated groups substituted on aromatic compounds, monoolefins, etc. In this specification, 'hydrotreating' refers to hydrotreating (HDT), which means a reaction in which olefins are hydrogenated and impurities are removed in a catalyst and a hydrogen atmosphere. In this specification, 'hydrocracking' refers to hydrocracking (HCK), which means a reaction in which a substance is decomposed in a catalyst and a hydrogen atmosphere to be converted into a light hydrocarbon. One aspect of the present invention relates to a method for pretreating plastic pyrolysis oil. The method comprises: a first step of treating plastic pyrolysis oil with activated carbon to obtain a first pretreated product; and a second step of performing a first hydrogenation treatment on the first pretreated product at 150 to 250°C to obtain a second pretreated product. FIG. 1 schematically illustrates a plastic pyrolysis oil pretreatment process according to one embodiment of the present invention. The first step is performed in a first reactor (10)