Catalyst for hydrocracking waste plastic pyrolysis oil, method for preparing same, and method for hydrocracking using same

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.

Description

Plastic pyrolysis oil hydrocracking catalyst, method for manufacturing the same, and hydrocracking method using the same

[0001] 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.

[0002]

[0003] 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.

[0004] 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.

[0005] 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.

[0006] In addition, most HCK catalysts are known to be easily deactivated by coke deposited during the reaction.

[0007] Therefore, there is a need to develop HCK that can convert WPPO into high-purity naphtha and has excellent durability.

[0008] Related prior art is US No. 6217746.

[0009]

[0010] The objective of the present invention is to provide a plastic pyrolysis oil hydrocracking catalyst capable of producing naphtha from waste plastic pyrolysis oil (WPPO) and a method for manufacturing the same.

[0011] Another objective of the present invention is to provide a plastic pyrolysis oil hydrocracking catalyst capable of converting waste plastic pyrolysis oil (WPPO) into high-purity naphtha, and a method for manufacturing the same.

[0012] Another objective of the present invention is to provide a durable plastic pyrolysis oil hydrolysis catalyst and a method for manufacturing the same.

[0013] Another objective of the present invention is to provide a plastic pyrolysis oil hydrocracking catalyst capable of maintaining a naphtha conversion rate of 90% or more after a hydrocracking reaction for 80 hours, and a method for manufacturing the same.

[0014] Another objective of the present invention is to provide a plastic pyrolysis oil hydrocracking catalyst having a nitrogen content of 1 ppm or less and a sulfur content of 5 ppm or less in the produced naphtha, and a method for manufacturing the same.

[0015] Another objective of the present invention is to provide a method for producing naphtha using the plastic pyrolysis oil hydrocracking catalyst.

[0016] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0017]

[0018] 1. One aspect of the present invention relates to a plastic pyrolysis oil hydrocracking catalyst. The plastic pyrolysis oil hydrocracking catalyst is a plastic pyrolysis oil hydrocracking catalyst in which an active material comprising Ni and Mo is supported on a carrier, comprises mesopores and micropores, and satisfies the following Formulas 1 to 3:

[0019] [Equation 1]

[0020] Approximately 2 ≤ I2 / I1 ≤ Approximately 5

[0021] (In the above equation, I1 is 825±10 cm obtained by Raman spectroscopic analysis) -1 It is the maximum peak intensity at, and I2 is 960±10cm -1 (It is the maximum peak intensity in...)

[0022]

[0023] [Equation 2]

[0024] S meso : S micro = approx. 0.9:1 ~ approx. 3:1

[0025] (In the above formula, S meso is the BET surface area of ​​the mesopore (m 2 / g) and, S micro is the BET surface area of ​​the micropore (m 2 / g)im)

[0026]

[0027] [Equation 3]

[0028] S meso52 : S micro52 = approx. 1.5:1 ~ approx. 5:1

[0029] (In the above formula, S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g) and,

[0030] S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction at 420°C and 50 bar pressure for 52 hours. 2 / g)im).

[0031] 2. In the above embodiment 1, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following formulas 4 and 5:

[0032]

[0033] [Equation 4]

[0034] V meso : V micro = approx. 3:1 ~ approx. 5:1

[0035] (In the above equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and,

[0036] V micro is the pore volume of micropores (cm²) 3 / g)im)

[0037]

[0038] [Equation 5]

[0039] V meso52 : V micro52 = approx. 6:1 ~ approx. 9:1

[0040] (In the above equation, V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) and,

[0041] V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g)im).

[0042] 3. In the above 1 to 2 embodiments, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following formulas 6 and 7:

[0043] [Equation 6]

[0044] Approximately 65 ≤ 100 * S meso52 / S meso ≤ About 85

[0045] (In the above formula, S meso is the BET surface area of ​​the mesopore (m 2 / g) and,

[0046] S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g)im)

[0047]

[0048] [Equation 7]

[0049] Approximately 30 ≤ 100 * S micro52 / S micro ≤ About 50

[0050] (In the above formula, S micro is the BET surface area of ​​the micropore (m 2 / g) and,

[0051] S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 2 / g)im).

[0052] 4. In the above 1 to 3 embodiments, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following formulas 8 and 9:

[0053] [Equation 8]

[0054] Approximately 65 ≤ 100 * V meso52 / V meso ≤ approx. 85

[0055] (In the above equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and,

[0056] V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) Im)

[0057]

[0058] [Equation 9]

[0059] Approximately 30 ≤ 100 * V micro52 / V micro ≤ About 50

[0060] (In the above equation, V micro is the pore volume of micropores (cm²) 3 / g) and,

[0061] V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g)im).

[0062] 5. In the above 1 to 4 embodiments, the carrier may include a USY zeolite-Al2O3 carrier.

[0063]

[0064] 6. In the above 1 to 5 embodiments, the plastic pyrolysis oil hydrocracking catalyst may have a naphtha conversion rate of about 90% or more after hydrocracking reaction for 80 hours at a temperature of 420°C and a pressure of 50 bar.

[0065] 7. In the above 1 to 6 embodiments, the plastic pyrolysis oil hydrocracking catalyst may have a nitrogen content of about 1 ppm or less and a sulfur content of about 5 ppm or less after hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar.

[0066] 8. In the above embodiments 1 to 7, after the hydrocracking reaction of the plastic pyrolysis oil catalyst for 52 hours at a temperature of 420°C and a pressure of 50 bar, the BET surface area (S) of the mesopores meso52 ) is about 100 to 200 m 2 / g, BET surface area of ​​micropores (S micro52 ) is about 50 to 200 m 2 / g, pore volume of mesopores (V meso52 ) is about 0.1 to 0.3 cm 3 / g, and micropore volume (V micro52 ) is about 0.01 to 0.1 cm 3 / g can be.

[0067] 9. Another aspect of the present invention relates to a method for manufacturing a plastic pyrolysis oil hydrocracking catalyst. The method is a method for manufacturing a plastic pyrolysis oil hydrocracking catalyst of embodiments 1 to 8 above, and comprises the steps of: supporting a Mo precursor on a USY zeolite-Al2O3 carrier to prepare a first carrier; supporting a Ni precursor on the first carrier to prepare a catalyst precursor; and heat-treating the catalyst precursor.

[0068] 10. In the above 9 embodiments, the step of drying the catalyst precursor before the heat treatment may be further included.

[0069] 11. In the above 9 to 10 embodiments, the heat treatment can be performed at approximately 450 to 650 ℃.

[0070] 12. Another aspect of the present invention relates to a method for hydrolyzing plastic pyrolysis oil. The method comprises the step of hydrolyzing plastic pyrolysis oil by contacting it with a plastic pyrolysis oil hydrolysis catalyst of the 1 to 8 embodiments above.

[0071] 13. In the above 12 embodiments, the hydrocracking can be performed at a temperature of about 300 to 500 ℃ and a hydrogen pressure of about 30 to 70 bar.

[0072] 14. Another aspect of the present invention relates to a method for producing naphtha from plastic pyrolysis oil. The method comprises the step of supplying plastic pyrolysis oil raw material to a reactor and bringing it into contact with a catalyst embedded in the reactor to perform a hydrocracking reaction, wherein the catalyst is the plastic pyrolysis oil hydrocracking catalyst of the 1 to 8 embodiments above, and the method is characterized by having a naphtha conversion rate of about 90% or more after hydrocracking reaction for 80 hours.

[0073] 15. In the above 14 embodiments, the hydrocracking can be performed at a temperature of about 300 to about 500 ℃ and a hydrogen pressure of about 30 to 70 bar.

[0074]

[0075] The present invention has the effect of providing a plastic pyrolysis oil hydrocracking catalyst and a method for manufacturing the same, and a method for producing naphtha using said plastic pyrolysis oil hydrocracking catalyst, which enables the production of naphtha from waste plastic pyrolysis oil (WPPO), can convert waste plastic pyrolysis oil (WPPO) into high-purity naphtha, has excellent durability, has a nitrogen content of about 1 ppm or less and a sulfur content of about 5 ppm or less in the produced naphtha, and can maintain a naphtha conversion rate of about 90% or more after a hydrocracking reaction for 80 hours.

[0076]

[0077] FIG. 1 schematically illustrates a hydrolysis process of plastic pyrolysis oil according to one embodiment of the present invention.

[0078] Figure 2 shows the Raman analysis results of the catalysts used in the examples and comparative examples.

[0079] Figure 3 shows the change in naphtha conversion rate over time for the examples and comparative examples.

[0080] Figure 4 shows the results of nitrogen absorption analysis of the catalysts used in the examples and comparative examples.

[0081]

[0082] 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.

[0083] In interpreting the components, they are interpreted to include a margin of error even in the absence of a separate explicit statement.

[0084] In this specification, Raman spectroscopic analysis was performed using a 532 nm laser with the Nanofinder 30 of Tokyo Instruments (Tokyo, Japan).

[0085] 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.

[0086]

[0087] 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.

[0088]

[0089] Plastic pyrolysis oil hydrolysis catalyst and method for manufacturing the same

[0090] In the present invention, 'plastic pyrolysis oil' refers to waste plastic pyrolysis oil (WPPO) formed by pyrolyzing waste plastic.

[0091] In the present invention, '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.

[0092] The plastic pyrolysis oil hydrocracking catalyst of the present invention is characterized by having an excellent naphtha conversion rate, and in particular, being able to maintain a naphtha conversion rate of about 90% or more even after a hydrocracking reaction for 80 hours.

[0093] In addition, the naphtha converted as described above may have a nitrogen content of about 1 ppm or less, preferably about 0.5 ppm or less, more preferably about 0 ppm, and a sulfur content of about 5 ppm or less, preferably about 1 ppm or less, more preferably about 0.5 ppm or less, most preferably about 0.1 ppm or less. As such, not only can high-quality naphtha be obtained with only a single reaction without additional processes, but the nitrogen and sulfur removal performance is also excellent, so WPPO can be recycled into high-value raw materials at the lowest possible cost.

[0094] The above plastic pyrolysis oil hydrocracking catalyst is one in which an active material containing Ni and Mo is supported on a carrier.

[0095] In a specific example, the plastic pyrolysis oil hydrocracking catalyst satisfies the following Formula 1:

[0096] [Equation 1]

[0097] Approximately 2 ≤ I2 / I1 ≤ Approximately 5

[0098] (In the above equation, I1 is 825±10 cm obtained by Raman spectroscopic analysis) -1 It is the maximum peak intensity at, and I2 is 960±10cm -1 (It is the maximum peak intensity in...)

[0099] Within the above range, the active substance Mo can minimize mutual bonding with the carrier, making it advantageous to convert to the active site sulfide, and a large amount of octahedral Mo and mesopores can exist.

[0100] In a specific example, the I2 / I1 value may be about 2 to about 4.5, for example, about 2.05 to about 4.2. In a specific example, the I2 / I1 value may be 2.05, 2.1, 2.5, 2.75, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2.

[0101] The above plastic pyrolysis oil hydrocracking catalyst includes mesopores and micropores.

[0102] In one embodiment, the plastic pyrolysis oil hydrocracking catalyst has a mesopore BET surface area (S meso ) is about 120 to about 250 m 2 / g, for example, about 150 to about 220 m 2 / g may be. In the above range, resistance to coke deposition is excellent. In a specific example, the plastic pyrolysis oil hydrocracking catalyst has a mesopore BET surface area (S meso ) is 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215 m 2 / g can be.

[0103] After hydrolysis of the above plastic pyrolysis oil hydrocracking catalyst at a temperature of 420°C and a pressure of 50 bar for 52 hours, the BET surface area (S) of the mesopores meso52 ) is about 100 to about 200 m 2 / g, for example, about 110 to about 180 m 2 It can be / g. Within the above range, it can have excellent durability and naphtha conversion rate. In a specific example, the BET surface area (S of the mesopore) of the above example meso52 ) is 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180 m 2 / g can be.

[0104] In addition, the BET surface area of ​​the micropores (S micro ) is about 100 to about 250 m 2 / g, for example, about 120 to about 220 m 2 / g may be. In a specific example, the BET surface area (S of the micropore) of the micropore micro) is 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220 m 2 / g can be.

[0105] After hydrolysis of the above plastic pyrolysis oil hydrocracking catalyst at a temperature of 420°C and a pressure of 50 bar for 52 hours, the BET surface area of ​​the micropores (S micro52 ) is about 50 to about 200 m 2 / g, for example, about 55 to about 130 m 2 It can be / g. Within the above range, it can have excellent durability and naphtha conversion rate. In a specific example, the BET surface area (S of the micropore) of the micropore micro52 ) is 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130 m 2 / g can be.

[0106] The above plastic pyrolysis oil hydrocracking catalyst satisfies the following Equation 2.

[0107]

[0108] [Equation 2]

[0109] S meso : S micro = approx. 0.9:1 ~ approx. 3:1

[0110] (In the above formula, S meso is the BET surface area of ​​the mesopore (m 2 / g) and, S micro is the BET surface area of ​​the micropore (m 2 / g)im)

[0111] The above S meso / S micro When α is approximately 0.9 to approximately 3, coke deposition can be prevented and excellent durability can be achieved. In a specific example, the above S meso / S microThe value may be approximately 0.94 to 2.5, for example, approximately 0.98 to 2. In a specific example, the above S meso / S micro The values ​​can be 0.99, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0. Within the above range, the naphtha conversion rate can be maintained at approximately 90% or higher even after a hydrocracking reaction for 80 hours.

[0112] In addition, the above plastic pyrolysis oil hydrocracking catalyst satisfies the following Equation 3.

[0113] [Equation 3]

[0114] S meso52 : S micro52 = approx. 1.5:1 ~ approx. 5:1

[0115] (In the above formula, S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g) and,

[0116] S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 2 / g)im).

[0117] The above S meso52 / S micro52 When is about 1.5 to about 5, the mesopore content, which has excellent resistance to coke deposition, is sufficient, so the naphtha conversion rate can be maintained at about 90% or more even after a hydrocracking reaction for 80 hours. In a specific example, the above S meso52 / S micro52 The value can be approximately 1.8 to 4, for example, approximately 2 to 3.5. It has superior durability within the above range. In a specific example, the above S meso52 / S micro52The value can be 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5.

[0118] In a specific example, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following Equation 6:

[0119] [Equation 6]

[0120] Approximately 65 ≤ 100 * S meso52 / S meso ≤ About 85

[0121] (In the above formula, S meso is the BET surface area of ​​the mesopore (m 2 / g) and,

[0122] S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g)im)

[0123] If the above Equation 6 is satisfied, excellent durability and a naphtha conversion rate of approximately 90% or more can be maintained even after a hydrocracking reaction for 80 hours. In a specific example, the above 100 * S meso52 / S meso It can be 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85.

[0124] In a specific example, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following Equation 7:

[0125]

[0126] [Equation 7]

[0127] Approximately 30 ≤ 100 * S micro52 / S micro ≤ About 50

[0128] (In the above formula, S micro is the BET surface area of ​​the micropore (m 2 / g) and,

[0129] S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 2 / g)im).

[0130] If the above Equation 7 is satisfied, excellent durability and a naphtha conversion rate of approximately 90% or more can be maintained even after a hydrocracking reaction for 80 hours. In a specific example, the above 100 * S micro52 / S micro It can be 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50.

[0131] The above plastic pyrolysis oil hydrocracking catalyst has a mesopore pore volume (V meso ) is about 0.15 to about 0.5 cm 3 / g, in specific examples, about 0.2 to about 0.35 cm 3 It can be / g. In the above range, resistance to coke deposition is excellent. In a specific example, the pore volume (V) of the mesopore is meso ) is 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35 m 3 / g can be.

[0132] The pore volume (V) of the mesopores after the hydrolysis reaction of the above plastic pyrolysis oil hydrocracking catalyst at a temperature of 420°C and a pressure of 50 bar for 52 hours meso52 ) is about 0.1 to about 0.3 cm 3 / g, for example, about 0.15 to about 0.3 cm 3It can be / g. Within the above range, excellent durability and naphtha conversion rate can be achieved. In a specific example, the pore volume (V) of the mesopore is the same. meso52 ) is 0.15, 0.18, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30 cm 3 / g can be.

[0133] The pore volume (V) of the micropores after the hydrocracking reaction of the above plastic pyrolysis oil hydrocracking catalyst at a temperature of 420°C and a pressure of 50 bar for 52 hours micro52 ) is about 0.01 to about 0.1 cm 3 / g, in specific examples, about 0.02 to about 0.05 cm 3 / g may be used. In a specific example, the pore volume (V) of the micropores above micro52 ) is 0.02, 0.03, 0.04, 0.05 cm 3 / g can be.

[0134] In one embodiment, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following Equation 4:

[0135] [Equation 4]

[0136] V meso : V micro = approx. 3:1 ~ approx. 5:1

[0137] (In the above equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and,

[0138] V micro is the pore volume of micropores (cm²) 3 / g)im)

[0139] The above V meso / V micro When is about 3 to about 5, the mesopore content, which has excellent resistance to coke deposition, is sufficient to prevent deactivation and can have excellent durability. In a specific example, the above V meso / Vmicro The value may be approximately 3.1 to 4.5, for example, approximately 3.2 to 4. Within the above range, the naphtha conversion rate can be maintained at approximately 90% or higher even after a hydrocracking reaction for 80 hours. In a specific example, the above V meso / V micro The values ​​can be 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0.

[0140] In one embodiment, the plastic pyrolysis oil hydrocracking catalyst may satisfy the following Equation 5:

[0141] [Equation 5]

[0142] V meso52 : V micro52 = approx. 6:1 ~ approx. 9:1

[0143] (In the above equation, V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) and,

[0144] V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction at 420°C and 50 bar pressure for 52 hours. 3 / g)im).

[0145] The above V meso52 / V micro52 When V is 6 to 9, pore clogging by coke is minimized even after the reaction, so the naphtha conversion rate can be maintained at approximately 90% or higher even after 80 hours of hydrocracking reaction. In a specific example, the above V meso52 / V micro52 The value can be approximately 6.5 to 8.5, for example, approximately 7 to 8. It has superior durability within the above range. In a specific example, the above V meso52 / V micro52 The values ​​can be 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0.

[0146] In addition, the above plastic pyrolysis oil hydrocracking catalyst can satisfy the following Equations 8 and 9:

[0147] [Equation 8]

[0148] Approximately 65 ≤ 100 * V meso52 / V meso ≤ approx. 85

[0149] (In the above equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and,

[0150] V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) Im)

[0151] If the above Equation 8 is satisfied, excellent durability can be achieved, and a naphtha conversion rate of approximately 90% or higher can be maintained even after a hydrocracking reaction for 80 hours. In a specific example, the above 100 * V meso52 / V meso The values ​​can be 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85.

[0152]

[0153] [Equation 9]

[0154] Approximately 30 ≤ 100 * V micro52 / V micro ≤ About 50

[0155] (In the above equation, V micro is the pore volume of micropores (cm²) 3 / g) and,

[0156] V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g)im).

[0157] If the above Equation 9 is satisfied, excellent durability and a naphtha conversion rate of approximately 90% or more can be maintained even after a hydrocracking reaction for 80 hours. In a specific example, the above 100 * V micro52 / V micro The values ​​can be 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50.

[0158]

[0159] The above Equations 2 to 9 can be controlled by the type of carrier (zeolite, Al2O3, etc.) and ratio, etc. For example, the distribution of mesopores and micropores of the carrier can be controlled through the SAR ratio of the zeolite or the zeolite / Al2O3 ratio, the catalyst synthesis method, etc.

[0160] In a specific example, the weight ratio of Ni to Mo in the active material may be about 1:1 to about 1:3, and in a specific example, the weight ratio of Ni to Mo may be about 1:1.5 to about 1:2.5. High naphtha selectivity can be achieved within the above range. In a specific example, the weight ratio of Ni to Mo may be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5. The active material may further include Co, W, etc.

[0161] The above carrier may include a USY zeolite-Al2O3 carrier. According to a specific example, the silica-to-alumina (SAR) ratio of the USY zeolite may be about 30 to about 60, for example, about 40 to about 55. In a specific example, the silica-to-alumina (SAR) ratio of the USY zeolite may be 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55. Additionally, the ratio of the USY zeolite to the Al2O3 carrier may be about 0.5 to about 2. Excellent durability may be achieved within the above range. In a specific example, the ratio of the USY zeolite to the Al2O3 carrier may be 0.5, 0.7, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. The carrier may be in the form of pellets and may have an average diameter of about 1.5 mm.

[0162] The above plastic pyrolysis oil hydrocracking catalyst can be manufactured by incipient impregnation. In a specific example, it can be manufactured by including the steps of: supporting a Mo precursor on a USY zeolite-Al2O3 carrier to prepare a first carrier; supporting a Ni precursor on the first carrier to prepare a catalyst precursor; and heat-treating the catalyst precursor.

[0163] The above Ni precursor may be Ni(NO3)26H2O, Ni(OCOCH3)24H2O, etc.

[0164] The above Mo precursor is (NH4)6Mo7O 24 2H2O) can be used.

[0165] In a specific example, the Mo precursor is dissolved in a solvent and then supported on a carrier. Once the Mo support is complete, a Ni precursor is introduced and supported on the carrier. After the support is complete, drying can be performed at approximately 90 to approximately 130°C for approximately 1 to 5 hours. Once the drying is complete, heat treatment can be performed to produce a plastic pyrolysis oil hydrocracking catalyst. In a specific example, the heat treatment can be performed at approximately 450 to approximately 650°C, for example, approximately 480 to approximately 600°C. Within this range, residual impurities are removed and Ni and Mo oxides are formed.

[0166] Since the plastic pyrolysis oil hydrocracking catalyst of the present invention has excellent durability, the naphtha conversion rate can be maintained at approximately 90% or more even after a hydrocracking reaction for approximately 80 hours at a temperature of approximately 420°C and a pressure of approximately 50 bar.

[0167]

[0168] Hydrocracking method and production method of light naphtha

[0169] Another aspect of the present invention relates to a method for hydrolyzing plastic pyrolysis oil. The method comprises the step of hydrolyzing plastic pyrolysis oil by contacting it with a plastic pyrolysis oil hydrolysis catalyst.

[0170] FIG. 1 schematically illustrates a hydrolysis process of plastic pyrolysis oil according to one embodiment of the present invention.

[0171] As described above, plastic pyrolysis oil raw material (WPPO) is introduced into the reactor (10), and the plastic pyrolysis oil hydrolysis catalyst described above is embedded in the reactor (10). In addition, hydrogen is injected into the reactor (10), and the hydrogen pressure inside the reactor is maintained at approximately 30 to 70 bar.

[0172] The above reactor (10) is equipped with a raw material tank, a gas flow regulator, a pump, a pump control valve, and a cooler, and a continuous fixed-bed reactor may be used.

[0173] The plastic pyrolysis oil raw material (WPPO) introduced into the reactor (10) comes into contact with the catalyst, and a hydrocracking reaction is carried out. The hydrocracking reaction can be performed at a temperature of about 300 to about 500°C. There is an advantage that the naphtha conversion rate is maintained at a high level within this range.

[0174] Since the plastic pyrolysis oil hydrocracking catalyst of the present invention has a high naphtha conversion rate, the amount of naphtha (light naphtha) in the product (P) produced by the hydrocracking reaction may be about 90 wt% or more, for example, about 92 wt% or more, and in a specific example, about 95 wt% or more.

[0175] In addition, the naphtha may have a nitrogen content of about 1 ppm or less, preferably about 0.5 ppm or less, more preferably about 0 ppm, and a sulfur content of about 5 ppm or less, preferably about 1 ppm or less, more preferably about 0.5 ppm or less, most preferably about 0.1 ppm or less. As the impurity content is extremely low, no additional processing is required, and high-purity light naphtha can be obtained in a single step.

[0176]

[0177] The present invention is to be explained more specifically below through examples and comparative examples; however, these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0178]

[0179] Examples

[0180] The specifications of the catalysts used in the examples and comparative examples are as follows:

[0181] (1) Catalyst 1

[0182] It was prepared by the incipient impregnation method, in which a metal precursor is supported on a carrier using a hot air coating machine and a solution spray tank. (NH4)6Mo7O was used as the Mo precursor. 24 2H2O) was mixed with distilled water and stirred at 45°C for at least 30 minutes. After the Mo precursor was completely dissolved, it was supported onto an ultra-stable zeolite Y (USY)-Al2O3 mixed support in pellet form using a hot air coating machine. Once Mo support was complete, Ni(NO3)26H2O was added, and Ni support was carried out using the same method. The catalyst precursor contained 5 wt% Ni and 10 wt% Mo supported on the USY-Al2O3 support. Subsequently, the catalyst precursor was dried at 105°C for 3 hours. After drying was complete, heat treatment was performed at 550°C for 3 hours. The BET and pore volume of the prepared catalyst are shown in Table 1, and the results of Raman spectroscopic analysis are shown in Figure 2.

[0183] (2) Catalyst 2 ~ Catalyst 4

[0184] The catalyst was prepared in the same manner as the above catalyst 1, except that the mesopores and micropores were controlled by adjusting the ratio of the USY-Al2O3 support. The BET and pore volume of the prepared catalyst are shown in Table 1, and the results of Raman spectroscopic analysis are shown in Figure 2.

[0185]

[0186] BET(m 2 / g) Pore volume (cm²) 3 / g)Mesomicroscopic 2 values ​​(S meso / S micro )Mesomicroscopic 4-value V meso / V micro Catalyst 11601700.940.300.093.33 Catalyst 21701501.130.350.122.92 Catalyst 3703400.210.100.180.56 Catalyst 4180802.250.400.0410

[0187] The catalyst prepared in the above preparation example was sulfidated for 12 hours using a mixed solution of diesel and dimethyl disulfide (DMDS) mixed in a 10:1 ratio under conditions of LHSV (Liquid hourly space velocity) 0.5, GOR (H2 gas to oil ratio) 700, pressure 50 bar, and temperature 400 ℃, and then hydrocracking was performed according to the following method.

[0188] Example 1

[0189] The feed consisted of an oil mixture of waste plastic pyrolysis oil (WPPO, Saehan Recycle) and commercial diesel in a 1:1 ratio. The nitrogen content of the feed was 1,573 ppm, and the sulfur content was 72 ppm. Hydrocracking (HCK) was carried out using the above feed and Catalyst 1 under conditions of a Liquid Hourly Space Velocity (LHSV) of 0.5, a Gas-to-Oil Ratio (GOR) of 700, a hydrogen pressure of 50 bar, and 420°C. The hydrocracking reaction (HCK) was performed at 8-hour intervals for 4 to 80 hours, after which the products were analyzed. The results of the analysis by time are shown in Figure 3. As shown in Figure 3, the naphtha conversion rate was over 89% after 52 hours, and it was confirmed to be even higher, exceeding 90%, after 60 hours. It was maintained at over 90% even after 80 hours. In addition, the nitrogen content was 0 ppm, and the sulfur content was 0.5 ppm.

[0190]

[0191] Example 2

[0192] The procedure was carried out in the same manner as Example 1 above, except that catalyst 2 was used. Both the initial naphtha ratio and the naphtha ratio after 52 hours were 90% or higher, and maintained 90% or higher even after 80 hours.

[0193]

[0194] Comparative Example 1

[0195] The procedure was carried out in the same manner as Example 1 above, except that catalyst 3 was used. The initial naphtha ratio was low at 80%, and due to rapid deactivation, the naphtha ratio decreased significantly to 50% after 52 hours of reaction.

[0196]

[0197] Comparative Example 2

[0198] The procedure was carried out in the same manner as Example 1 above, except that catalyst 4 was used. Although the initial naphtha ratio was high at 90%, it was confirmed that durability decreased to 77% after 52 hours of reaction.

[0199]

[0200] To analyze the pore structure of the catalyst, nitrogen adsorption and desorption analysis was performed before the reaction and after 52 hours of hydrogenation, and the results are shown in Figure 4 and Table 2 below.

[0201]

[0202] BET(m 2 / g) Pore volume (cm²) 3 / g) Naphtha conversion rate 3) I2 / I1 Mesomicro S meso / S micro Mesomicro V meso / V micro 80h52h Example 1 Catalyst 1 Before 1) 1601700.940.300.093.3393892.2hu 2) 1206020.220.037.33 Formula 6~ Formula 97535.3-73.333.3-Example 2 Catalyst 2 Pre- 1) 1701501.130.350.113.1891902.9hu 2) 140682.210.290.047.25 Formula 6~ Formula 982.345.3-82.835.7-Comparative Example 1 Catalyst 3 1) 703400.210.100.180.56-523.7hu 2)401500.270.080.0810 Formula 6~Formula 957.144.1-8044.4-Comparative Example 2 Catalyst 4 Pre- 1) 180802.250.400.0410-771.2hu 2) 1300∞0.250∞Equation 6~Equation 972.20-62.50-

[0203] jeon 1) : Before the hydrolysis reaction

[0204] after 2) : After 52 hours of hydrolysis reaction

[0205] Naphtha conversion rate 3) : Naphtha conversion rate after 80 and 52 hours of reaction

[0206]

[0207] As shown in Table 2 above, the specific surface area and pore volume of the catalyst both decreased after the reaction. It can be confirmed that the ratio of mesopores to micropores and the maximum peak intensity ratio (I2 / I1) by Raman spectroscopic analysis in the case of Examples 1-2 of the present invention is 90% or higher even after 80 hours of hydrocracking reaction. On the other hand, it can be seen that Comparative Example 1-2, which did not satisfy any of Equations 1 to 3, showed a significantly reduced naphtha conversion rate after 52 hours of hydrocracking reaction.

[0208]

[0209] The results of the TNS analysis after performing the hydrolysis reaction (HCK) for 52 hours are shown in Table 3.

[0210]

[0211] Nitrogen (ppm) Sulfur (ppm) Raw Material 157372 Example 100.5 Example 200.1 Comparative Example 12.00.4 Comparative Example 23.30.7

[0212] From the results of the above examples and comparative examples, it can be confirmed that when a hydrocracking reaction is carried out using waste plastic pyrolysis oil (WPPO) as a raw material using the catalyst according to the present invention, the nitrogen and sulfur impurities are at the 0 ppm level. Therefore, it can be confirmed that the catalyst of the present invention can produce high-purity naphtha with only a single process.

[0213]

[0214] Simple variations or modifications of the present invention can be easily implemented by those skilled in the art, and all such variations or modifications are considered to be within the scope of the present invention.

Claims

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 ≤ I2 / I1 ≤ 5 (In the above equation, I1 is 825±10 cm obtained by Raman spectroscopic analysis) -1 It is the maximum peak intensity at, and I2 is 960±10cm -1 (It is the maximum peak intensity in...) [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 (m 2 / g) and, S micro is the BET surface area of ​​the micropore (m 2 / g)im) [Equation 3] S meso52 : S micro52 = 1.5: 1 ~ 5: 1 (In the above formula, S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g) and, S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 2 / g)im) . 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 equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and, V micro is the pore volume of micropores (cm²) 3 / g)im) [Equation 5] V meso52 : V micro52 = 6:1 ~ 9:1 (In the above equation, V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) and, V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g)im) . 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 (m 2 / g) and, S meso52 is the BET surface area (m²) of the mesopores after a hydrocracking reaction for 52 hours at a temperature of 420°C and a pressure of 50 bar. 2 / g)im) [Equation 7] 30 ≤ 100 * S micro52 / S micro ≤ 50 (In the above formula, S micro is the BET surface area of ​​the micropore (m 2 / g) and, S micro52 is the BET surface area (m) of micropores after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 2 / g)im) . 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 equation, V meso is the pore volume of a mesopore (cm²) 3 / g) and, V meso52 is the pore volume (cm²) of mesopores after a hydrolysis reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g) Im) [Equation 9] 30 ≤ 100 * V micro52 / V micro ≤ 50 (In the above equation, V micro is the pore volume of micropores (cm²) 3 / g) and, V micro52 is the pore volume of micropores (cm²) after a hydrocracking reaction for 52 hours at a temperature of 420℃ and a pressure of 50 bar. 3 / g)im) . In paragraph 1, The above carrier is a plastic pyrolysis oil hydrocracking catalyst comprising a USY zeolite-Al2O3 carrier. 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. 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. 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, BET surface area of ​​mesopores (S meso52 ) is 100 to 200 m 2 / g, BET surface area of ​​micropores (S micro52 ) is 50 to 200 m 2 / g, Pore ​​volume of mesopores (V meso52 ) is 0.1 to 0.3 cm 3 / g, and Micropore pore volume (V) micro52 ) is 0.01 to 0.1 cm 3 Plastic pyrolysis oil hydrolysis catalyst that is / g 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. 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. In Paragraph 9, A method for manufacturing a plastic pyrolysis oil hydrocracking catalyst, wherein the heat treatment is performed at 450 to 650 ℃. 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. 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. 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. 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.

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