Hydrofining catalyst for waste plastic oil and preparation method of hydrofining catalyst

Abstract

The present invention discloses a waste plastic oil hydrofining catalyst and a preparation method thereof, the catalyst comprises an active component and a carrier, the total mass of the catalyst is 100%, the active component accounts for 10 wt%-30 wt%, the carrier accounts for 70 wt%-90 wt%, the carrier comprises a Ce (at) Cu-M / Al2O3 composite oxide, and M is an alkali metal oxide or an alkaline earth metal oxide. According to the present invention, the synthesized Ce (at) Cu-CaO / Al2O3 composite oxide is adopted in the carrier material, such that the chlorine resistance of the catalyst is improved, the dispersity and the carbon deposition resistance of the active component on the catalyst surface are significantly improved, the high hydrogenation activity of the catalyst is obtained, the hydrogenation catalysis performance of the catalyst is effectively improved, and the waste plastic oil hydrofining dechlorination effect is improved.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a catalyst for the hydrogenation refining of waste plastic oil and its preparation method. Background Technology

[0002] The plastics consumption market is enormous, and waste plastic disposal faces both opportunities and challenges. Since the 1950s, global plastic production has steadily increased, reaching 368 million tons in 2019, accumulating approximately 6.3 billion tons of waste plastics; it is projected that global plastic production will reach 1.124 billion tons by 2050. This has also generated a large amount of plastic waste. Disposal of waste plastics through landfill and incineration causes severe secondary pollution, resulting in increasingly prominent environmental and health problems and resource waste. Therefore, developing chemical recycling technologies for waste plastics, establishing efficient chemical recycling processes, and truly realizing the resource utilization of low-value waste plastics to eliminate plastic pollution are of great significance.

[0003] In recent years, the main methods for treating waste plastics have included landfilling, incineration, recycling and granulation, and oleochemicals. With the structural adjustment of the petrochemical industry and the booming development of the new energy vehicle sector, the entire petrochemical industry is undergoing transformation and upgrading through "oil conversion" and "oil-to-specialty" conversion. The products converted from waste plastics have shifted from liquid fuels to other more economically valuable fields, such as aromatics and other chemical raw materials, chemicals, and functional materials. Research on fuel-related technologies needs to focus more on types with increasing demand, such as jet fuel. In comparison, utilizing plastics for high-value-added production of chemicals and functional materials has greater development prospects and practical value. Converting waste plastics into fuel oil or chemical raw materials through thermal or catalytic cracking can alleviate the current energy shortage while significantly reducing carbon emissions, and the process does not cause secondary pollution, resulting in high economic benefits. However, chlorides in waste plastic cracking oil can cause rapid catalyst deactivation, thus preventing deep processing applications. Therefore, it is urgent to find a catalyst to remove chlorides from waste plastic cracking oil to achieve deep processing and application.

[0004] Chlorides in waste plastic pyrolysis oil include both organic and inorganic chlorides. Hydrodechlorination catalysts often use noble metals such as Pd, Pt, and Rh as active components because these catalysts achieve good dechlorination results under relatively mild reaction conditions, and the interaction between HCl and noble metals is weak, giving them strong resistance to chlorine poisoning. Although noble metal catalysts exhibit high hydrodechlorination activity and good resistance to chlorine poisoning, they are expensive and easily contaminated by impurities such as sulfur and nitrogen oxides, making them unsuitable for the hydrorefining of low-quality oils like waste plastic pyrolysis oil. Studies have shown that Ni-based catalysts achieve good dechlorination performance and are low in cost. However, chlorine atoms in organochlorides are converted into HCl during hydrogenation, which reacts with Ni active sites to form NiCl2. This leads to the loss of Ni active components on the catalyst surface, severely inhibiting the hydrodesulfurization activity of the catalyst. At the same time, HCl reacts with NH3, a hydrogenation product of nitrides, to form NH4Cl, causing ammonium salts to crystallize in the catalyst bed, destroying the catalyst structure, reducing the specific surface area and pore volume, and hindering the adsorption and reaction of reactants on the catalyst surface.

[0005] CN201610891768.1 discloses a dechlorinating agent and its preparation method. The raw materials include an active component and a carrier. The mass ratio of the carrier to the active component in the dechlorinating agent raw materials is 0.7–1.5, and may also include binders, solvents, and molding aids. The preparation method includes mixing, extruding, and drying the active component, carrier, and molding aids, and further includes calcination to obtain a shaped dechlorinating agent. The obtained dechlorinating agent has high compressive strength and a large chlorine penetration capacity, effectively removing hydrogen chloride from mixed gases, reducing adverse effects on refining units, and enabling the dechlorinating agent to be produced at lower temperatures and in a shorter time, thus reducing energy consumption and production costs.

[0006] CN101992113A discloses a method for preparing a catalyst for the light transformation of waste plastic pyrolysis oil into fuel oil and its application, aiming to reduce the cost of waste plastic pyrolysis fuel oil production and improve fuel oil quality. The method involves treating fly ash (>200 mesh) with a mixed acid solution of 2M / L hydrochloric acid, 2M / L sulfuric acid, 1M / L hydrochloric acid, and 1M / L sulfuric acid; then modifying the fly ash catalyst with metal oxides using an equal-volume impregnation method. The catalyst is then placed in a fixed bed and used in the production of fuel oil from waste plastic pyrolysis oil. The reaction is carried out at a mass hourly space velocity (MHSV) of 1–4 h⁻¹ and a temperature of 400–550 °C, achieving a fuel oil yield of over 72%, demonstrating good results. Summary of the Invention

[0007] The purpose of this invention is to provide a catalyst for the hydrorefining of waste plastic oil, which can remove sulfides, nitrides and chlorides from waste plastic pyrolysis oil.

[0008] The present invention also aims to provide a method for preparing a catalyst for the hydrogenation refining of waste plastic oil.

[0009] To achieve the above objectives, this invention provides a catalyst for the hydrorefining of waste plastic oil, comprising an active component and a support. Based on the total mass of the catalyst (100%), the active component comprises 10wt%–30wt%, and the support comprises 70wt%–90wt%. The support comprises a Ce@Cu-M / Al2O3 composite oxide, wherein M is an alkali metal oxide or an alkaline earth metal oxide. The preparation method of the Ce@Cu-M / Al2O3 composite oxide is as follows:

[0010] (1) Mix template agent, copper source, aluminum source and water to obtain slurry A. The aluminum source is calculated as Al2O3 and the copper source is calculated as CuO. The mass ratio of aluminum source, copper source and template agent is 1:(0.2-0.5):(0.5-1).

[0011] (2) Using an alkali source as a precipitant, add the alkali source, alkali metal or alkaline earth metal source to slurry A, stir, and obtain product B. The molar ratio of aluminum source, alkali metal or alkaline earth metal source and alkali source is 1:(0.2-1):(6-10) based on metal oxides.

[0012] (3) The product B was crystallized, filtered, washed, dried and calcined to obtain the precursor C;

[0013] (4) The precursor C was immersed in an aqueous solution of cerium source, dried and calcined to obtain Ce@Cu-CaO / Al2O3 composite oxide, wherein the cerium source is calculated as CeO2 and the molar ratio of aluminum source to cerium source is 1:(0.05-0.5).

[0014] The waste plastic oil hydrorefining catalyst of the present invention has a crystallization treatment condition of 90-150℃ for 10-72h in step (3).

[0015] The waste plastic oil hydrorefining catalyst of the present invention comprises nickel, molybdenum and phosphorus as active components.

[0016] The waste plastic oil hydrorefining catalyst of the present invention uses a cationic surfactant as the template agent, which is hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium hydroxide.

[0017] The waste plastic oil hydrorefining catalyst of the present invention uses aluminum source as one or more of aluminum nitrate, aluminum sulfate, and sodium aluminate, preferably aluminum sulfate.

[0018] The copper source in the waste plastic oil hydrorefining catalyst of the present invention is a water-soluble copper salt.

[0019] The catalyst for the hydrogenation refining of waste plastic oil described in this invention uses an alkali metal or alkaline earth metal source that is a water-soluble calcium salt, magnesium salt, or potassium salt.

[0020] The waste plastic oil hydrorefining catalyst of the present invention uses an alkaline source that is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, sodium carbonate, and sodium bicarbonate, preferably sodium hydroxide and / or ammonia.

[0021] To achieve the above objectives, the present invention also provides a method for preparing the above-mentioned waste plastic oil hydrorefining catalyst, comprising the following steps:

[0022] The Ce@Cu-M / Al2O3 composite oxide and molding aid were mixed evenly, extruded into strips, dried and calcined to obtain the catalyst support.

[0023] The active component is dissolved in deionized water to obtain a metal impregnation solution. The catalyst support is then impregnated in the impregnation solution, and after curing, drying, and calcination, a hydrorefining catalyst is obtained.

[0024] The preparation method of the waste plastic oil hydrorefining catalyst of the present invention, based on the catalyst support mass of 100%, has a molding aid content of 5wt% to 10wt% and a Ce@Cu-M / Al2O3 composite oxide content of 90wt% to 95wt%. The molding aid includes one or more of guar gum powder, citric acid, oxalic acid, and nitric acid.

[0025] Beneficial effects of this invention:

[0026] The use of synthesized Ce@Cu-CaO / Al2O3 composite oxide in the support material improves the chlorine resistance of the catalyst, significantly enhances the dispersion of the active components on the catalyst surface and the resistance to carbon deposition, and enables the catalyst to achieve higher hydrogenation activity. This effectively improves the hydrogenation catalytic performance of the catalyst and enhances the dechlorination effect of waste plastic oil hydrorefining. Detailed Implementation

[0027] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0028] Example 1

[0029] Preparation of Ce@Cu-CaO / Al2O3 composite oxide materials:

[0030] The feed ratio was Al2O3:CuO:template = 1:0.5:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, then 251.7g of a 20% aluminum sulfate solution and 117.2g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Calcium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:CaO:ammonia = 1:0.5:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 90℃ for 24 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.05, the precursor C was stirred and soaked in 33g of 3% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-CaO / Al2O3 composite oxide material.

[0031] Preparation of hydrorefining catalyst support:

[0032] Based on a carrier weight of 100%, the Ce@Cu-CaO / Al2O3 composite oxide material comprises 90wt%, guar gum powder 3wt%, nitric acid 2wt%, and citric acid 5wt%. 63g of Ce@Cu-CaO / Al2O3 composite oxide material and 2.1g of guar gum powder were mixed evenly, and a mixed solution consisting of 2g of nitric acid (68wt%), 3.5g of citric acid, and 63g of deionized water was added dropwise. The mixture was then kneaded, extruded into strips, dried at 120℃ for 2 hours, and then calcined at 550℃ for 4 hours to produce carrier #1.

[0033] Preparation of hydrorefining catalysts:

[0034] Weigh 20g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 6.1g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label this solution as #1.

[0035] Take 70g of support #1, and add the obtained impregnation solution #1 evenly to support #1. Mix well, let stand for 3h for impregnation, then dry at 120℃ for 3h and calcine at 500℃ for 4h to obtain catalyst #1, with an active component content of 30wt% and a support content of 70wt%.

[0036] Example 2

[0037] Preparation of Ce@Cu-CaO / Al2O3 composite oxide materials:

[0038] The feed ratio was Al2O3:CuO:template = 1:0.5:1 (mass ratio). 60g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 60g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, then 251.7g of a 20% aluminum sulfate solution and 117.2g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Calcium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:CaO:ammonia = 1:0.2:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 120℃ for 48 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.05, the precursor C was stirred and soaked in 33g of 3% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-CaO / Al2O3 composite oxide material.

[0039] Preparation of hydrorefining catalyst support:

[0040] Based on a carrier weight of 100%, the Ce@Cu-CaO / Al2O3 composite oxide material comprises 90wt%, guar gum powder 3wt%, nitric acid 2wt%, and citric acid 5wt%. 63g of Ce@Cu-CaO / Al2O3 composite oxide material and 2.1g of guar gum powder were mixed evenly, and a mixed solution consisting of 2g of nitric acid (68wt%), 3.5g of citric acid, and 63g of deionized water was added dropwise. The mixture was then kneaded, extruded into strips, dried at 120℃ for 2 hours, and then calcined at 550℃ for 4 hours to produce carrier #2.

[0041] Preparation of hydrorefining catalysts:

[0042] Weigh 20g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 6.1g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label this solution as solution #2.

[0043] Take 100g of support #2, add the obtained impregnation solution #2 evenly to support #2, mix evenly, let stand for 3h for impregnation, then dry at 120℃ for 3h, and calcine at 500℃ for 4h to obtain catalyst #2, with an active component content of 23wt% and a support content of 77wt%.

[0044] Example 3

[0045] Preparation of Ce@Cu-CaO / Al2O3 composite oxide materials:

[0046] The feed ratio was Al2O3:CuO:template = 1:0.2:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, and then 251.7g of a 20% aluminum sulfate solution and 46.9g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Calcium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:CaO:ammonia = 1:0.5:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 90℃ for 72 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.5, the precursor C was stirred and soaked in 33g of 30% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-CaO / Al2O3 composite oxide material.

[0047] Preparation of hydrorefining catalyst support:

[0048] Based on a carrier weight of 100%, the Ce@Cu-CaO / Al2O3 composite oxide material is 90wt%, guar gum powder is 3wt%, nitric acid is 2wt%, and citric acid is 5wt%. Take 63g of Ce@Cu-CaO / Al2O3 composite oxide material and 2.1g of guar gum powder, mix them evenly, add dropwise a mixed solution consisting of 2g nitric acid (68wt%), 3.5g citric acid, and 63g deionized water, knead, extrude into strips, dry at 120℃ for 2h, and then calcine at 550℃ for 4h to prepare carrier #3.

[0049] Preparation of hydrorefining catalysts:

[0050] Weigh 23g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 2.4g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label this solution as solution #3.

[0051] Take 120g of support #3, and add the obtained impregnation solution #3 evenly to support #3. Mix well, let stand for 3 hours for impregnation, then dry at 120℃ for 3 hours and calcine at 500℃ for 4 hours to obtain catalyst #3, with an active component content of 20wt% and a support content of 80wt%.

[0052] Example 4

[0053] Preparation of Ce@Cu-CaO / Al2O3 composite oxide materials:

[0054] The feed ratio was Al2O3:CuO:template = 1:0.5:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, and then 251.7g of a 20% aluminum sulfate solution and 117.2g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Calcium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:CaO:ammonia = 1:1:10. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 150℃ for 24 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.2, the precursor C was stirred and soaked in 40g of 10% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-CaO / Al2O3 composite oxide material.

[0055] Preparation of hydrorefining catalyst support:

[0056] Based on a carrier weight of 100%, the Ce@Cu-CaO / Al2O3 composite oxide material comprises 90wt%, guar gum powder 3wt%, nitric acid 2wt%, and citric acid 5wt%. 63g of Ce@Cu-CaO / Al2O3 composite oxide material and 2.1g of guar gum powder were mixed evenly, and a mixed solution consisting of 2g of nitric acid (68wt%), 3.5g of citric acid, and 63g of deionized water was added dropwise. The mixture was then kneaded, extruded into strips, dried at 120℃ for 2 hours, and then calcined at 550℃ for 4 hours to produce carrier #4.

[0057] Preparation of hydrorefining catalysts:

[0058] Weigh 15g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 5.9g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label the solution as solution #4.

[0059] Take 75g of support #4, and add the obtained impregnation solution #4 evenly to support #4. Mix well, let stand for 3 hours, then dry at 120℃ for 3 hours and calcine at 500℃ for 4 hours to obtain catalyst #4, with an active component content of 25wt% and a support content of 75wt%.

[0060] Example 5

[0061] Preparation of Ce@Cu-K2O / Al2O3 composite oxide materials:

[0062] The feed ratio was Al2O3:CuO:template = 1:0.5:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, and then 251.7g of a 20% aluminum sulfate solution and 117.2g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Potassium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:K2O:ammonia = 1:0.5:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 90℃ for 24 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. The precursor C was stirred and soaked in 33g of a 1.5% cerium nitrate aqueous solution for 12h with a molar composition of Al2O3:Ce2O3 = 1:0.05, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-K2O / Al2O3 composite oxide material.

[0063] Preparation of hydrorefining catalyst support:

[0064] Based on a carrier weight of 100%, the Ce@Cu-K2O / Al2O3 composite oxide material is 95wt%, guar gum powder is 3wt%, and nitric acid is 2wt%. Take 66.5g of Ce@Cu-K2O / Al2O3 composite oxide material and 2.1g of guar gum powder, mix them evenly, add dropwise a mixed solution consisting of 2g of nitric acid (68wt%) and 63g of deionized water, knead, extrude into strips, dry at 120℃ for 2h, and then calcine at 550℃ for 4h to prepare carrier #5.

[0065] Preparation of hydrorefining catalysts:

[0066] Weigh 20g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 5.9g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label the solution as No. 5.

[0067] Take 70g of support #5, add the obtained impregnation solution #5 evenly to support #5, mix evenly, let stand for 3h for impregnation, then dry at 120℃ for 3h, and calcine at 500℃ for 4h to obtain catalyst #5, with active component content of 30wt% and support content of 70wt%.

[0068] Example 6

[0069] Preparation of Ce@Cu-MgO / Al2O3 composite oxide materials:

[0070] The feed ratio was Al2O3:CuO:template = 1:0.5:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. The mixture was stirred until the CTAB was uniformly dissolved, then 251.7g of a 20% aluminum sulfate solution and 117.2g of a 20% CuSO4·5H2O solution were added concurrently. The mixture was dynamically treated until a homogeneous slurry A was formed. Magnesium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:MgO:ammonia = 1:0.5:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 90℃ for 24 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.05, the precursor C was stirred and soaked in 33g of 1.5% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@Cu-MgO / Al2O3 composite oxide material.

[0071] Preparation of hydrorefining catalyst support:

[0072] Based on a carrier weight of 100%, the Ce@Cu-MgO / Al2O3 composite oxide material is 95wt%, guar gum powder is 3wt%, and nitric acid is 2wt%. Take 66.5g of Ce@Cu-MgO / Al2O3 composite oxide material and 2.1g of guar gum powder, mix them evenly, add dropwise a mixed solution consisting of 2g of nitric acid (68wt%) and 63g of deionized water, knead, extrude into strips, dry at 120℃ for 2h, and then calcine at 550℃ for 4h to prepare carrier #6.

[0073] Preparation of hydrorefining catalysts:

[0074] Weigh 20g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 5.9g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label the solution as No. 6.

[0075] Take 270g of support #6, and add the obtained impregnation solution #6 evenly to support #6. Mix well, let stand for 3 hours for impregnation, then dry at 120℃ for 3 hours and calcine at 500℃ for 4 hours to obtain catalyst #6, with an active component content of 10wt% and a support content of 90wt%.

[0076] Comparative Example 1

[0077] Preparation of Ce@CaO / Al2O3 composite oxide materials:

[0078] The feed ratio was Al2O3:template = 1:0.5 (mass ratio). 30g of a 25% hexadecyltrimethylammonium bromide (CTAB) solution was placed in a 60℃ constant temperature water bath, and 29g of deionized water was added. After stirring until the CTAB was uniformly dissolved, 251.7g of a 20% aluminum sulfate solution was added, and the mixture was dynamically treated until a homogeneous slurry A was formed. Calcium nitrate and ammonia were added to slurry A according to a molar composition of Al2O3:CaO:ammonia = 1:0.5:6. The pH was adjusted to approximately 8 with sulfuric acid, and the mixture was stirred in a 60℃ constant temperature water bath for 3 hours to obtain mixture B. Mixture B was transferred to a polytetrafluoroethylene-lined crystallization vessel and crystallized at 90℃ for 24 hours. Subsequently, it was filtered, washed, dried at 120℃ for 3 hours, and calcined at 550℃ for 4 hours to obtain precursor C. According to the molar composition Al2O3:Ce2O3=1:0.05, the precursor C was stirred and soaked in 33g of 3% cerium nitrate aqueous solution for 12h, dried at 120℃ for 3h, and calcined at 550℃ for 4h to obtain Ce@CaO / Al2O3 composite oxide material.

[0079] Preparation of hydrorefining catalyst support:

[0080] Based on a carrier weight of 100%, the Ce@CaO / Al2O3 composite oxide material is 90wt%, guar gum powder is 3wt%, nitric acid is 2wt%, and citric acid is 5wt%. Take 63g of Ce@CaO / Al2O3 composite oxide material and 2.1g of guar gum powder, mix them evenly, add dropwise a mixed solution consisting of 2g nitric acid (68wt%), 3.5g citric acid, and 63g deionized water, knead, extrude into strips, dry at 120℃ for 2h, and then calcine at 550℃ for 4h to prepare carrier D1#.

[0081] Preparation of hydrorefining catalysts:

[0082] Weigh 20g of molybdenum trioxide (MoO3 content 99wt%), 9.6g of basic nickel carbonate (NiO content 52wt%), and 5.9-6.1g of phosphoric acid (purity 85wt%) and add them to a 100ml beaker. Add deionized water, stir, and heat until the metal salts are completely dissolved and the solution is clear and transparent. Transfer the solution to a 100ml volumetric flask and dilute to 100ml with deionized water. Label the solution as D1#.

[0083] Take 100g of D1# support and 70g of D1# impregnation solution, add it evenly to D1# support, mix well, let stand for 3h, dry at 120℃ for 3h, and calcine at 500℃ for 4h to obtain catalyst D1#, with active component content of 30wt% and support content of 70wt%.

[0084] Comparative Example 2

[0085] According to the feeding ratio in Example 1, hexadecyltrimethylammonium bromide (CTAB) solution, aluminum sulfate solution, CuSO4·5H2O solution, calcium nitrate and ammonia water are mixed evenly in one go to form slurry A. The pH value is adjusted with sulfuric acid to stabilize at about 8. The mixture is stirred in a constant temperature water bath at 60°C for 3 hours to obtain mixture B.

[0086] The remaining steps are the same as in Example 1, and catalyst D2# is obtained.

[0087] Experimental Example

[0088] Hydrogenation refining was carried out using woven bag pyrolysis oil as raw material at a reaction temperature of 320℃, a pressure of 8 MPa, a hydrogen-to-oil ratio of 500:1, and a space velocity of 1.0 h⁻¹. -1 .

[0089]

[0090] The evaluation results show that, using woven bag pyrolysis liquid as raw material, the chlorine content decreased from 280 mg / kg to below 20, the dechlorination rate reached over 93%, and the sulfur and nitrogen contents were both <10, which meets the standards for plastic oil blending.

[0091] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A waste plastic oil hydrofining catalyst comprising an active component and a support, characterized in that, Based on the total mass of the catalyst (100%), the active component comprises 10wt%–30wt%, and the support comprises 70wt%–90wt%. The support comprises Ce@Cu-M / Al2O3 composite oxide, wherein M is an alkali metal oxide or an alkaline earth metal oxide. The preparation method of the Ce@Cu-M / Al2O3 composite oxide is as follows: (1) Mix template agent, copper source, aluminum source and water to obtain slurry A. The aluminum source is calculated as Al2O3 and the copper source is calculated as CuO. The mass ratio of aluminum source, copper source and template agent is 1:(0.2-0.5):(0.5-1). (2) Using an alkali source as a precipitant, add the alkali source, alkali metal or alkaline earth metal source to slurry A, stir, and obtain product B. The molar ratio of aluminum source, alkali metal or alkaline earth metal source and alkali source is 1:(0.2-1):(6-10) based on metal oxides. (3) The product B was crystallized, filtered, washed, dried and calcined to obtain the precursor C; (4) The precursor C was immersed in an aqueous solution of cerium source, dried and calcined to obtain Ce@Cu-CaO / Al2O3 composite oxide, wherein the cerium source is calculated as CeO2 and the molar ratio of aluminum source to cerium source is 1:(0.05-0.5).

2. The spent plastic oil hydrofining catalyst of claim 1, wherein, In step (3), the crystallization treatment conditions are crystallization treatment at 90-150℃ for 10-72h.

3. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The active components include nickel, molybdenum, and phosphorus.

4. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The template agent is a cationic surfactant, which is hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium hydroxide.

5. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The aluminum source is one or more of aluminum nitrate, aluminum sulfate, and sodium aluminate, with aluminum sulfate being preferred.

6. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The copper source is a water-soluble copper salt.

7. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The alkali metal or alkaline earth metal source is a water-soluble calcium salt, magnesium salt, or potassium salt.

8. The catalyst for the hydrorefining of waste plastic oil according to claim 1, characterized in that, The alkaline source is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, sodium carbonate, and sodium bicarbonate, preferably sodium hydroxide and / or ammonia.

9. The method for preparing the waste plastic oil hydrorefining catalyst according to any one of claims 1-8, characterized in that, Includes the following steps: The Ce@Cu-M / Al2O3 composite oxide and molding aid were mixed evenly, extruded into strips, dried and calcined to obtain the catalyst support; The active component is dissolved in deionized water to obtain a metal impregnation solution. The catalyst support is then impregnated in the impregnation solution, and after curing, drying, and calcination, a hydrorefining catalyst is obtained.

10. The method for preparing the catalyst for the hydrorefining of waste plastic oil according to claim 9, characterized in that, Based on the mass of the catalyst support (100%), the content of the molding aid is 5wt% to 10wt%, and the content of Ce@Cu-M / Al2O3 composite oxide is 90wt% to 95wt%. The molding aid includes one or more of guar gum powder, citric acid, oxalic acid, and nitric acid.

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