Method and apparatus for producing aviation fuel from waste plastic pyrolysis oil

Abstract

The present disclosure provides a method for producing aviation fuel, the method including a first step of subjecting waste plastic pyrolysis oil to an olefin transfer reaction, a second step of subjecting the product of the first step to an olefin branching reaction, a third step of hydrotreating the product of the second step in the presence of a hydrotreating catalyst, and a fourth step of hydrocracking the product of the third step in the presence of a hydrocracking catalyst.

Description

[Technical field]

[0001] The present disclosure relates to a method and an apparatus for producing aviation fuel by refining waste plastic pyrolysis oil. [Background technology]

[0002] Waste plastics are manufactured using petroleum as a raw material, and the recycling rate is low, so most of them are disposed of as garbage. Such wastes are difficult to decompose in natural conditions, and they cause many environmental problems, such as generating large amounts of air pollution and hazardous substances during the incineration process, which has become a social issue.

[0003] The biggest problem with plastics is that they are almost never biodegradable. It takes decades for plastics to decompose in the natural environment, and in the process, they turn into microplastics, which can have a devastating effect on the environment. This has led to a significant increase in the importance of waste plastic processing technology. One of the waste plastic processing technologies is to thermally decompose waste plastics and convert them into fractions, which can then be recycled.

[0004] Compared to fractions produced from crude oil, waste plastic pyrolysis oil contains a higher amount of impurities such as chlorine, nitrogen, and metals, so it cannot be immediately used as a high-value-added fuel such as gasoline or diesel oil and must be refined.

[0005] In addition, the low-temperature properties of fractions containing waste plastic pyrolysis oil vary depending on the hydrocarbon structure. For example, the low-temperature properties appear in the following order: aromatic > naphthene > branched hydrocarbon > linear hydrocarbon. Waste plastic pyrolysis oil is mainly composed of linear hydrocarbons, and its low-temperature properties are relatively inferior to those of general crude oil, which has the same hydrocarbon distribution.

[0006] Unlike automobile fuel, aviation fuel used for flight must be used at high altitudes and in low-temperature environments below -4°C. Therefore, the low-temperature properties of the distillate act as a very important factor in determining the quality of the fuel.

[0007] As a refining process to improve the low-temperature properties of waste plastic pyrolysis oil, a dewaxing process using a precious metal catalyst and a dewaxing process using a strong acid catalyst such as Zeolite or Clay have been carried out, but due to the low low-temperature properties of waste plastic pyrolysis oil, there is a limit to how much can be done to improve the freezing point and pour point, and there is also a problem that the excessive amount of impurities contained in the waste plastic pyrolysis oil causes the catalyst to be inactivated, resulting in a significant decrease in reaction yield. As another method, the low-temperature properties of pyrolysis oil can be further improved by carrying out the reaction under high-temperature reaction conditions of 450°C or more and inducing a hydrocracking reaction simultaneously with the dewaxing reaction, but there is a problem that the yield decreases by more than 50% because the reaction is carried out under excessive conditions.

[0008] In other words, due to the poor low-temperature properties of waste plastic pyrolysis oil, it is difficult to produce aviation fuel that meets the aviation fuel standard JET A-1 or JP-8 standard from the waste plastic pyrolysis oil at a high yield.

[0009] Therefore, there is a need for a method and apparatus for producing aviation fuel that can produce high-quality aviation fuel that meets aviation fuel standards and has a minimized impurity content from waste plastic pyrolysis oil at a high yield. Summary of the Invention [Problem to be solved by the invention]

[0010] The present disclosure aims to provide an aviation fuel production method and production apparatus that can produce aviation fuel that has a freezing point that meets the aviation fuel standards JET A-1 or JP-8 at a high yield through a refining process of waste plastic pyrolysis oil.

[0011] Another object of the present disclosure is to provide an aviation fuel manufacturing method and manufacturing apparatus capable of manufacturing high-quality aviation fuel with minimized impurity content through a refining process of waste plastic pyrolysis oil.

[0012] Another object of the present disclosure is to provide an aviation fuel production method and production apparatus that can operate stably for long periods of time by preventing catalyst inactivation due to impurities during the refining process of waste plastic pyrolysis oil containing impurities including chlorine and nitrogen. [Means for solving the problem]

[0013] The present disclosure provides a method for producing aviation fuel, the method including a first step of subjecting waste plastic pyrolysis oil to an olefin transfer reaction, a second step of subjecting the product of the first step to an olefin branching reaction, a third step of hydrotreating the product of the second step in the presence of a hydrotreating catalyst, and a fourth step of hydrocracking the product of the third step in the presence of a hydrocracking catalyst.

[0014] In one embodiment, the first step may be carried out under a weak acid site catalyst, and the second step may be carried out under a one-dimensional pore structure zeolite (1-D zeolite) catalyst.

[0015] In one embodiment, the weak acid site catalyst may include a titanium oxide catalyst.

[0016] In an embodiment, the weight ratio of the weak acid site catalyst to the 1-D zeolite catalyst may be 60:40 to 90:10.

[0017] In one embodiment, the hydrotreating catalyst in the third step may be a catalyst in which an active metal containing any one or more selected from molybdenum, nickel, cobalt and tungsten is supported on a support.

[0018] In one embodiment, the hydrocracking catalyst in the fourth step may be a catalyst in which an active metal including any one or more selected from molybdenum, nickel, cobalt and tungsten is supported on a zeolite.

[0019] In one embodiment, the freezing point of the produced aviation fuel may be −45° C. or lower and the yield may be 75% or higher.

[0020] In one embodiment, the produced aviation fuel may have a chlorine content of 10 ppm or less and a nitrogen content of 10 ppm or less.

[0021] In one embodiment, the first and second steps may be carried out at a reaction temperature above 300°C.

[0022] In one embodiment, the first and second steps may be carried out in an inert atmosphere under conditions of a reaction pressure of 5 to 70 bar and a GOR (gas / oil ratio) of 100 to 3,000.

[0023] In one embodiment, the third step may be carried out under hydrogen gas conditions at a reaction temperature of less than 300° C., a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3,000.

[0024] In one embodiment, the fourth step may be carried out under hydrogen gas conditions at a reaction temperature of more than 300° C., a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3,000.

[0025] In one embodiment, the method may further include a fifth step of hydrofinishing the product of the fourth step in the presence of a hydrofinishing catalyst under conditions of a reaction temperature of more than 300° C., a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000.

[0026] The present disclosure also provides an apparatus for producing aviation fuel, comprising: a first reactor into which waste plastic pyrolysis oil is flowed and an olefin transfer reaction and an olefin branching reaction are carried out in that order; a second reactor into which the reaction product and hydrogen gas from the first reactor are flowed and subjected to hydrotreating in the presence of a hydrotreating catalyst; and a third reactor into which the reaction product and hydrogen gas from the second reactor are flowed and subjected to a hydrocracking reaction in the presence of a hydrocracking catalyst.

[0027] In one embodiment, the first reactor includes a first region filled with a weak acid site catalyst and a second region filled with a one-dimensional pore structure zeolite (1-D zeolite) catalyst, and the waste plastic pyrolysis oil may be purified by passing through the first region and the second region in sequence.

[0028] In one embodiment, the first to third reactors may be fixed bed continuous reactors.

[0029] In one embodiment, a fourth reactor may be further included, into which the reaction product and hydrogen gas from the third reactor flow and into which a hydrofinishing reaction is carried out in the presence of a hydrofinishing catalyst. Effect of the Invention

[0030] The method for producing aviation fuel according to the present disclosure can produce aviation fuel from waste plastic pyrolysis oil with a high yield, the freezing point of which meets the aviation fuel standard JET A-1 or JP-8.

[0031] The method for producing aviation fuel according to the present disclosure can produce high-quality aviation fuel with minimized impurity content from waste plastic pyrolysis oil.

[0032] The aviation fuel production method and production apparatus disclosed herein provide an aviation fuel production method and production apparatus that can operate stably for long periods of time by preventing catalyst inactivation during the refining process of waste plastic pyrolysis oil containing impurities including chlorine and nitrogen. [Brief description of the drawings]

[0033] [Figure 1] FIG. 1 illustrates an apparatus for producing aviation fuel including a first reactor, a second reactor and a third reactor according to one embodiment of the present disclosure. [Diagram 2] FIG. 2 is a diagram illustrating an apparatus for producing aviation fuel according to one embodiment of the present disclosure, further including a fourth reactor in addition to the apparatus for producing aviation fuel shown in FIG. 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] Unless otherwise defined, technical and scientific terms used herein have the meanings that are commonly understood by one of ordinary skill in the art to which this invention belongs.

[0035] As used herein, the singular forms of the terms "a," "an," and "the" can be construed as including the plural forms as well, unless otherwise indicated.

[0036] Numerical ranges used herein include lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the ranges defined, all values ​​limited therein, and all possible combinations of upper and lower limits of numerical ranges limited in different forms from each other. Unless otherwise specified in the present specification, values ​​outside the numerical ranges that may occur due to experimental error or rounding of values ​​are also included in the defined numerical ranges.

[0037] As referred to in this specification, "comprising" is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," "characterized," and the like, and does not exclude further unrecited elements, materials, or steps.

[0038] In this specification, unless otherwise specified, the unit of % means % by weight, and the unit of % by volume means % by volume at 1 atm and 25°C.

[0039] The ppm unit used in this specification without any special mention means ppm by mass unless otherwise defined.

[0040] Unless otherwise specified, the boiling point (bp) used in this specification means the boiling point at 1 atm and 25°C.

[0041] As described above, waste plastic pyrolysis oil has poor low-temperature properties, making it difficult to produce high-quality aviation fuel with a low freezing point from it. In addition, waste plastic pyrolysis oil contains excessive amounts of impurities including chlorine or nitrogen, making it difficult to use it as is.

[0042] Therefore, the present disclosure provides a method for producing aviation fuel, the method including a first step of subjecting waste plastic pyrolysis oil to an olefin transfer reaction, a second step of subjecting the product of the first step to an olefin branching reaction, a third step of hydrotreating the product of the second step in the presence of a hydrotreating catalyst, and a fourth step of hydrocracking the product of the third step in the presence of a hydrocracking catalyst.

[0043] Through the continuous refining process including the first to fourth steps, high-quality aviation fuel with a solidification point that meets the aviation fuel standard JET A-1 or JP-8 and with minimized impurity content can be produced from the waste plastic pyrolysis oil in a high yield.

[0044] In detail, the waste plastic may be solid or liquid waste related to synthetic polymer compounds such as waste synthetic resin, waste synthetic fiber, waste synthetic rubber, waste vinyl, etc., and the hydrocarbon fraction mixture produced by pyrolyzing the waste plastic may be waste plastic pyrolysis oil. The hydrocarbon fraction mixture may contain impurities such as chlorine compounds, nitrogen compounds, and metal compounds in addition to the hydrocarbon fraction, and may contain, for example, 300 ppm or more of nitrogen, 30 ppm or more of chlorine, 20 vol. % or more of olefins, and 1 vol. % or more of conjugated diolefins.

[0045] The olefins contained in the waste plastic pyrolysis oil may mostly include linear hydrocarbon structures of alpha-olefins. The waste plastic pyrolysis oil may be a mixture of various hydrocarbon fractions, and the hydrocarbon fractions may include, for example, H-Naphtha (up to C8, bp<150°C): Kero (C9-C17, bp150-265°C), LGO (C18-C20, bp265-340°C) and VGO / AR (C21-, bp>340°C). Specifically, the waste plastic pyrolysis oil may contain 70% by weight or more of Kero (C9-C17, bp150-265°C) as the main hydrocarbon fraction.

[0046] The first step of subjecting the waste plastic pyrolysis oil to an olefin transfer reaction converts the linear alpha olefins contained in the waste plastic pyrolysis oil into linear internal olefins, and the second step of subjecting the product of the first step to an olefin branching reaction allows the internal olefins contained in the waste plastic pyrolysis oil to branching.

[0047] In one embodiment, the first step may be carried out under a weak acid site catalyst, and the second step may be carried out under a one-dimensional pore structure zeolite (1-D zeolite) catalyst.

[0048] Conventionally, precious metal catalysts such as Pt and Pd have been used as catalysts for converting linear alpha olefins in various petroleum fractions such as crude oil into linear internal olefins, but the precious metal catalysts are vulnerable to impurities and have a problem of being inactivated by excessive nitrogen impurities contained in waste plastic pyrolysis oil. Therefore, by using a weak acid site catalyst as a catalyst for the olefin transfer reaction, it is possible to prevent the catalyst from being inactivated and effectively improve the reaction efficiency.

[0049] In one embodiment, the weak acid site catalyst may include a titanium oxide catalyst. Examples of the weak acid site catalyst include catalysts having weak acid sites such as γ-Al2O3, kaolin, TiO2, and ZrO2. Among the weak acid site catalysts, titanium oxide catalysts are preferred in consideration of the chain length distribution of the hydrocarbon fraction mixture contained in the waste plastic pyrolysis oil and the conversion yield to linear internal olefins in the presence of impurities such as chlorine and nitrogen. In the case of titanium oxide catalysts, catalyst inactivation is suppressed even in the presence of an excessive amount of impurities, so that the aviation fuel production process can be stably performed for a long period of time and the reaction yield can be improved.

[0050] The second step of subjecting the product of the first step to an olefin branching reaction may be carried out under the catalyst of a zeolite having a one-dimensional pore structure (hereinafter, referred to as 1-D zeolite). When the 1-D zeolite is used, it is possible to maximize the reaction efficiency by suppressing side reactions such as cracking reactions and improving the selectivity of the olefin branching reaction in the presence of impurities such as chlorine and nitrogen. Specifically, the 1-D zeolite may be a zeolite having a 10-membered ring structure such as EU-2, ZSM-23 or ZSM-48 zeolite. The 1-D zeolite may have a BET specific surface area of ​​150 m 2 / g or more, an average pore diameter of 5 nm or more, and a total pore volume of 0.3 cc / g or more. When these ranges are satisfied, the efficiency of the olefin branching reaction can be improved. Specifically, the BET specific surface area is 180 to 400 m 2 / g (more specifically, 200-300m 2 / g), the average pore size may be 6 to 20 nm (more specifically, 7 to 15 nm), and the total pore volume may be 0.4 to 2.0 cc / g (more specifically, 0.5 to 1.3 cc / g).

[0051] In one embodiment, the weight ratio of the weak acid site catalyst to the 1-D zeolite catalyst may be 60:40 to 90:10. Specifically, the weight ratio may be 60:40 to 80:20, and more specifically, the weight ratio may be 60:40 to 70:30.

[0052] The third step, which involves hydrotreating the product of the second step under a hydrotreating catalyst, effectively reduces impurities in the waste plastic pyrolysis oil. The hydrotreating process effectively removes chlorine or nitrogen from the pyrolysis oil, and also removes other impurities such as sulfur, oxygen, and olefins. By removing impurities from the waste plastic pyrolysis oil through the hydrotreating process, catalyst inactivation can be prevented in the hydrocracking process, the refining process can be performed stably for a long period of time, and impurities in the produced aviation fuel can be minimized.

[0053] In one embodiment, the hydrotreating catalyst in the third step may be a catalyst in which an active metal containing any one or more selected from molybdenum, nickel, cobalt, and tungsten is supported on a support. The catalyst may be a catalyst in which an active metal having hydrotreating catalytic activity is supported on a support, and the active metal may contain, for example, any one or more selected from molybdenum, nickel, cobalt, etc. The support may be any one having durability capable of supporting an active metal, and may contain, for example, any one or more selected from alumina, zirconia, titanium, etc. Specifically, the hydrotreating catalyst may be a catalyst in which an active metal containing 0.1 to 10 wt % nickel and 0.1 to 30 wt % molybdenum is supported on a γ-alumina support. However, this is an example of the present disclosure, and the present disclosure is not necessarily limited thereto.

[0054] The product of the third step is subjected to a fourth step of hydrocracking under a hydrocracking catalyst, so that aviation fuel that meets the aviation fuel standard JET A-1 or JP-8 can be finally produced from the waste plastic pyrolysis oil.

[0055] In one embodiment, the hydrocracking catalyst may be a catalyst in which an active metal, including any one or more selected from molybdenum, nickel, cobalt, and tungsten, is supported on a zeolite. The support is preferably a zeolite in terms of cracking reaction activity, and specifically may include ZSM-5, zeolite Y, or beta zeolite. The zeolite may be included in an amount of 10 to 30% by weight based on the total weight of the hydrocracking catalyst.

[0056] In one embodiment, the freezing point of the produced aviation fuel may be -45°C or less, and the yield of aviation fuel may be 75% or more. By the continuous refining process of waste plastic pyrolysis oil including the first to fourth steps, aviation fuel having a freezing point of -45 to -55°C can be produced from the waste plastic pyrolysis oil. Conventionally, in the case of a fraction obtained by a hydrodewaxing process under a general precious metal catalyst, for example, a PtPd / 1-D zeolite catalyst, the freezing point is about -25°C, so it cannot meet the JET A-1 or JP-8 standard. In order to meet this, the reaction can be performed under high temperature reaction conditions of 450°C or more to induce a hydrocracking reaction simultaneously with the hydrodewaxing reaction, thereby further improving the low-temperature properties of the pyrolysis oil, but in this case, there is a problem that the yield is reduced by 50% or more because the reaction is performed under excessive conditions. Therefore, the method for producing aviation fuel including the first to fourth steps of the present disclosure can produce aviation fuel having a freezing point that meets the aviation fuel standard JET A-1 or JP-8 from the waste plastic pyrolysis oil in high yield. Specifically, the freezing point of the aviation fuel may be -50°C or lower (more specifically, -50°C to -60°C), and the yield of the aviation fuel may be 75% or higher (more specifically, 80 or higher and 90 or lower).

[0057] In one embodiment, the produced aviation fuel may have a chlorine content of 10 ppm or less and a nitrogen content of 10 ppm or less. The aviation fuel finally obtained by the aviation fuel production method including the first to fourth steps may be a high-quality aviation fuel having an extremely low impurity content, and may have, for example, chlorine of 10 ppm (weight) or less, nitrogen of 30 ppm (weight) or less, sulfur of 10 ppm (weight) or less, other metal components of 10 ppm (weight) or less, oxygen of 0.1 wt % or less, olefins of 10 volume % or less, and conjugated diolefins of 0.2 volume % or less.

[0058] In one embodiment, the first and second steps may be carried out at a reaction temperature of more than 300°C. When the reaction is carried out in the above temperature range, side reactions such as cracking reactions can be suppressed, thereby minimizing changes in molecular weight distribution and weight loss, and maximizing the efficiency of the olefin migration reaction and olefin branching reaction. The weight loss (weight reduction) may be 5% or less, and carrying out the reaction in a relatively high temperature zone within the above reaction temperature range may be more advantageous in controlling the degree of position migration of the double bond. Specifically, the reaction temperature may be 330 to 430°C, more specifically 330 to 400°C.

[0059] In one embodiment, the first and second steps may be carried out under an inert atmosphere under conditions of a reaction pressure of 5 to 70 bar and a GOR (gas / oil ratio) of 100 to 3000. At a high pressure condition of 70 bar or more, the reaction activity is poor, whereas at a low reaction pressure of 5 bar or less, the raw material may be lost, so it is preferable to adjust the pressure within an appropriate range. In addition, the reaction may be carried out in an inert atmosphere without supplying hydrogen, which is required in a normal dewaxing reaction. For example, various inert carrier gases such as nitrogen, argon, helium, and mixtures thereof may be selected and used without any particular restrictions, and specifically, nitrogen gas may be used. The flow rate of the inert carrier gas is one of the factors for controlling the reaction activity, and since the reaction is carried out by contact between the catalyst and the reactants, the retention time may be considered to control the reaction. Depending on the gas flow rate, the degree of the olefin transfer reaction and the branching transfer reaction and the degree of occurrence of side reactions can be adjusted. Specifically, the reaction pressure is preferably within a range of 5 to 50 bar (more specifically, 10 to 40 bar), and the GOR is preferably within a range of 400 to 2500 (more specifically, 500 to 2000).

[0060] In one embodiment, the third step may be carried out under hydrogen gas at a reaction temperature of less than 300°C, a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000. When the hydrogenation treatment is carried out under the above conditions, the generation of ammonium salt (NH4Cl) can be minimized, and chlorine, nitrogen, and other impurities can be effectively removed. Specifically, the temperature may be 250°C or less (more specifically, 100°C or more and 250°C or less), the reaction pressure may be 30 bar to 90 bar (more specifically, 50 bar to 80 bar), and the GOR may be 400 to 2500 (more specifically, 500 to 2000).

[0061] In one embodiment, the fourth step may be carried out under hydrogen gas under conditions of a reaction temperature of more than 300°C, a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000. When the hydrocracking reaction is carried out under the above conditions, the low-temperature properties of the pyrolysis oil can be effectively improved, and aviation fuel can be obtained in a high yield. In particular, by carrying out the hydrocracking reaction after the first improvement of the low-temperature properties of the pyrolysis oil by the first and second steps, it is possible to obtain aviation fuel having a freezing point characteristic that meets the target aviation fuel standard JET-A or JP-8 in a high yield even if the hydrocracking reaction is carried out under milder conditions. Specifically, the temperature may be 350°C or more (more specifically, 350°C or more and 450°C or less), the reaction pressure may be 30 bar to 90 bar (more specifically, 50 bar to 80 bar), and the GOR may be in the range of 400 to 2500 (more specifically, 500 to 2000).

[0062] In one embodiment, the method may further include a fifth step of hydrofinishing the product of the fourth step under a hydrofinishing catalyst at a reaction temperature of more than 300°C, a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000. The hydrofinishing step can be performed to remove olefins and aromatic components from the fraction in accordance with product-specific requirements, thereby ensuring stability and adjusting the aromatic content and gas hygroscopicity. In particular, when the fourth step is performed at 370°C or higher, olefins are further generated by the cracking reaction, so it is more preferable to perform a fifth step of hydrofinishing to remove them. Specifically, the reaction temperature may be 330°C to 430°C, the reaction pressure may be 10 to 90 bar, and the GOR (gas / oil ratio) may be 500 to 2500.

[0063] The catalyst used in the hydrofinishing step may be a catalyst in which an active metal containing one or more selected from molybdenum, nickel, cobalt, and tungsten is supported on a support. Specifically, the catalyst may be a catalyst in which an active metal having hydrotreating catalytic activity is supported on a support, and the active metal may contain, for example, one or more selected from molybdenum, nickel, cobalt, etc. The support may be any material having durability capable of supporting the active metal, and may contain, for example, alumina, zirconia, and titanium.

[0064] The present disclosure also provides an apparatus for producing aviation fuel, comprising: a first reactor into which waste plastic pyrolysis oil is flowed and an olefin transfer reaction and an olefin branching reaction are carried out; a second reactor into which a reaction product and hydrogen gas from the first reactor are flowed and hydrotreated in the presence of a hydrotreating catalyst; and a third reactor into which the reaction product and hydrogen gas from the second reactor are flowed and a hydrocracking reaction is carried out in the presence of a hydrocracking catalyst.

[0065] In one embodiment, the first reactor includes a first region filled with a weak acid site catalyst and a second region filled with a one-dimensional pore structure zeolite (1-D zeolite) catalyst, and the waste plastic pyrolysis oil can be purified by passing through the first region and the second region in sequence.

[0066] An inert carrier gas may be supplied into the first reactor. As the inert carrier gas, various carrier gases well known in the relevant technical field, such as nitrogen, argon, helium, and mixtures thereof, may be selected and supplied without any particular limitation, and specifically, nitrogen gas may be supplied.

[0067] In one embodiment, the first to third reactors may be fixed bed continuous reactors. Fixed bed reactors have the advantage of high productivity and may be operated in a continuous mode.

[0068] The first to third reactors are filled with catalysts, and waste plastic pyrolysis oil may be introduced into the first reactor as shown in FIG. 1, and then passed through the second and third reactors in order to carry out the purification process.

[0069] Each of the reactors may be connected to a pipe, and a reaction product may be introduced from each reactor through the pipe.

[0070] The second reactor has a reaction zone equipped with a hydrotreating catalyst, into which the reaction products and hydrogen gas from the first reactor are introduced and hydrotreated to remove chlorine and nitrogen from the waste plastic pyrolysis oil, as well as some olefins and other impurities.

[0071] The third reactor contains a reaction zone containing a hydrocracking catalyst, into which the reaction products and hydrogen gas from the second reactor are introduced and hydrocracking is carried out, so that aviation fuel can be obtained from the waste plastic pyrolysis oil.

[0072] In one embodiment, a fourth reactor may be further included, in which the reaction product and hydrogen gas from the third reactor are introduced and a hydrofinishing reaction is carried out under a hydrofinishing catalyst. As shown in FIG. 2, the fourth reactor is further included, so that olefins and aromatic components of the fraction can be removed in accordance with product-specific requirements to ensure stability and adjust the aromatic content and gas hygroscopicity. In particular, when the temperature condition of the third reactor is set to 370° C. or higher, olefins are further generated by the cracking reaction, and it is more preferable to further include a fourth reactor for hydrofinishing in order to remove them.

[0073] For matters not further explained regarding the apparatus for producing aviation fuel, reference may be made to the contents described in the above-mentioned method for producing aviation fuel.

[0074] Hereinafter, the present disclosure will be described in detail with reference to examples. However, these are provided for the purpose of providing a more detailed description, and the scope of the present disclosure is not limited to the following examples.

[0075] Example 1 A hydrocarbon fraction mixture containing high-concentration impurities of 1,000 ppm nitrogen and 700 ppm chlorine was prepared as a raw material for waste plastic pyrolysis oil. The hydrocarbon fraction mixture contained 20% by weight of naphtha (bp 180°C or less, ~C8) and 80% by weight of kerosene (bp 180~220°C, C8~C10), and the total olefin content in the hydrocarbon fraction mixture was 20% by volume.

[0076] Waste plastic pyrolysis oil was introduced into the first reactor to carry out the olefin transfer reaction and olefin branching reaction. Specifically, 70 g of TiO2 catalyst was introduced into the first zone of the first reactor, and 30 g of ZSM-48 zeolite catalyst was introduced and packed into the second zone. The remaining part of the reactor was packed with silica beads, and a thermocouple was installed so as to be in contact with the part packed with the catalyst. Here, 260 ml of zeolite was used as the zeolite. 2 The material used had a BET specific surface area of ​​1.0 mm / g, an average pore diameter of 10 nm, and a total pore volume of 0.83 cc / g.

[0077] Under the condition of N25 bar, the reactor was heated at a rate of 5°C / min and maintained at 250°C for 3 hours to remove water or adsorbed gas present on the catalyst surface. Next, the temperature was raised to 350°C, and the waste plastic pyrolysis oil was added to the reactor at a GOR (N2 / Oil Ratio) of 700 and space velocity (WHSV) of 0.5hr. -1 The reactor was operated under the above conditions, and olefin transfer reaction and olefin branching reaction were carried out.

[0078] The reaction product produced in the first reactor was introduced into the second reactor and then hydrotreated. The inside of the second reactor was filled with NiMo / γ-Al2O3, which is a hydrotreatment catalyst. The reaction product and hydrogen gas were then introduced into the second reactor and then hydrotreated at 230°C, 60 bar, H2 / Oil ratio 860, and LHSV 1h. -1 The waste plastic pyrolysis oil was subjected to hydrotreating under the above conditions, and a reaction product was obtained from which impurities such as chlorine and nitrogen had been removed.

[0079] The reaction product produced in the second reactor was introduced into the third reactor, where it was subjected to hydrocracking. The third reactor was equipped with NiMo / Zeolite (10%) as a hydrocracking catalyst, and the reaction product and hydrogen gas were introduced into the third reactor, and the reaction product and hydrogen gas were then subjected to hydrocracking at 360°C, 60 bar, H2 / Oil ratio 860, and LHSV 1h. -1 A hydrocracking reaction was carried out under the above conditions, and finally a refined oil, aviation fuel, was obtained.

[0080] Example 2 In Example 1, the temperature conditions and pressure conditions of the first reactor, the second reactor, and the third reactor were changed as shown in Table 1 below, and the operation was performed in the same manner as in Example 1, except that aviation fuel, which is a refined oil, was obtained.

[0081] Example 3 In Example 2, aviation fuel, which is a refined oil, was obtained in the same manner as in Example 1, except that the obtained aviation fuel was further subjected to a step of hydrofinishing treatment.

[0082] Example 4 Aviation fuel, which is a refined oil, was obtained in the same manner as in Example 1, except that the first reactor was operated under hydrogen gas, the reaction temperature was changed to 320°C, and the reaction pressure was changed to 70 bar.

[0083] Comparative Example 1 In Example 1, the first reactor of the manufacturing apparatus was omitted, and the waste plastic pyrolysis oil was directly introduced into the second reactor to carry out the reaction. In the same manner as in Example 1, the refined oil, aviation fuel, was obtained.

[0084] Comparative Example 2 An aviation fuel, which is a refined oil, was obtained in the same manner as in Example 1, except that the reaction was carried out without using the third reactor in the production apparatus.

[0085] Comparative Example 3 An aviation fuel, which is a refined oil, was obtained in the same manner as in Example 1, except that the reaction was carried out without using the second reactor in the production apparatus.

[0086] Comparative Example 4 In Example 1, the order of the first and second reactors in the manufacturing apparatus was changed, and the waste plastic pyrolysis oil was first fed into the second reactor for reaction, and the aviation fuel, which is a refined oil, was obtained in the same manner as in Example 1.

[0087] Comparative Example 5 In Example 1, the TiO2 catalyst was omitted in the first reactor of the manufacturing apparatus, and only the 1-D zeolite catalyst was used to carry out the reaction. In the same manner as in Example 1, an aviation fuel, which is a refined oil, was obtained.

[0088] Evaluation example Aviation fuel, a refined oil, was analyzed according to the JET A-1 standard to measure the freezing point and yield.

[0089] ICP and XRF analysis was performed on aviation fuel, a refined oil, to measure the chlorine and nitrogen contents (ppm) and the olefin content (wt%).

[0090] The maximum possible operating time (operating life) without catalyst deactivation was measured while continuing to produce refined oil.

[0091] The measurement results are shown in Table 1 below.

[0092] [Table 1]

[0093] evaluation In relation to the freezing point and yield of the obtained aviation fuel, in Examples 1 and 2, waste plastic pyrolysis oil is subjected to an olefin transfer reaction by TiO2 under N2 gas in a first reactor, an olefin branching reaction by ZSM-48, hydrotreating in a second reactor, and hydrocracking in a third reactor in that order, and it can be confirmed that aviation fuel with a freezing point of -45°C or less can be obtained with a yield of 82% or more. In Example 3, by setting the temperature of the first reactor to -37°C or more, the reaction is further carried out including a hydrofinishing reaction in a fourth reactor, and it can be confirmed that aviation fuel with a freezing point of -48°C can be obtained with a yield of 87%.

[0094] On the other hand, in Example 4, by carrying out the reaction in the first reactor under hydrogen gas, aviation fuel with a freezing point of -35°C was finally obtained at a yield of 70%, and it was confirmed that the freezing point and yield of aviation fuel were lower than those of Example 1, in which the reaction was carried out under N2 gas.

[0095] In relation to the Cl, N, and olefin contents and operating life of the obtained aviation fuel, in the cases of Examples 1 to 4, it was confirmed that the contents of Cl, N, and olefins, which are impurities in the obtained aviation fuel, are all minimized by sequentially carrying out the olefin transfer reaction and olefin branching reaction in the first reactor, the hydrotreating reaction in the second reactor, and the hydrocracking reaction in the third reactor, and therefore it was confirmed that the operating life was also extended to more than 15 days, allowing the aviation fuel production process to be stably performed for a long period of time.

[0096] In Comparative Example 1, the reaction was performed excluding the olefin transfer reaction and olefin branching reaction in the first reactor, and in Comparative Example 2, the reaction was performed excluding the hydrocracking reaction in the third reactor, and it was confirmed that the freezing point of the obtained aviation fuel was significantly reduced to -25°C or higher and the yield was significantly reduced to 65% or less. In addition, the Cl, N, and olefin contents in the aviation fuel obtained in Comparative Example 1 and Comparative Example 2 were 35-38 ppm, 117-125 ppm, and 5-7 wt%, respectively, confirming a deterioration in the quality of the aviation fuel, and therefore, it was confirmed that the operating life was also reduced to 7 days or less.

[0097] In Comparative Example 3, the Cl, N, and olefin contents in the aviation fuel obtained by performing the reaction without the hydrotreatment process in the second reactor were 384 ppm, 754 ppm, and 8 wt%, respectively, indicating a significant deterioration in the quality of the aviation fuel, and therefore, indicating that the operating life was also significantly reduced to less than 3 days.

[0098] In Comparative Example 4, when the first and second reactors were used in the order, i.e., the hydrotreatment process of the waste plastic pyrolysis oil was performed before the olefin transfer reaction and olefin branching reaction, the freezing point of the obtained aviation fuel was confirmed to be -32°C and the yield was 55%, confirming that the reaction order of the present disclosure has a significant effect on the production of aviation fuel. In addition, the Cl, N, and olefin contents in the obtained aviation fuel were 24 ppm, 97 ppm, and 3 wt%, respectively, confirming a deterioration in the quality of the aviation fuel, and therefore, it was confirmed that the operating life was also reduced to 9 days or less.

[0099] In Comparative Example 5, it can be confirmed that the freezing point of the aviation fuel obtained by performing the aviation fuel production process in the first reactor without performing the olefin transfer reaction was reduced to -25°C and the yield was reduced to 63%. In addition, the Cl, N, and olefin contents in the obtained aviation fuel were 26 ppm, 88 ppm, and 3 wt%, respectively, confirming a deterioration in the quality of the aviation fuel, and therefore, it can be confirmed that the operating life was also reduced to 10 days or less.

[0100] Although the examples and comparative examples have been described above, the present invention is not limited to the above examples, and may be embodied in various different forms, and a person having ordinary skill in the art to which the present invention belongs can understand that the present invention may be embodied in other specific forms without changing the technical idea or essential features of the present invention. Therefore, it should be understood that the above-described examples are illustrative in all respects and are not limiting.

Claims

1. A first step of subjecting waste plastic pyrolysis oil to an olefin transfer reaction; a second step of subjecting the product of the first step to an olefin branching reaction; a third step of hydrotreating the product of the second step in the presence of a hydrotreating catalyst; and a fourth step of hydrocracking the product of the third step in the presence of a hydrocracking catalyst.

2. 2. The method for producing aviation fuel according to claim 1, wherein the first step is carried out in the presence of a weak acid site catalyst, and the second step is carried out in the presence of a one-dimensional pore structure zeolite (1-D zeolite) catalyst.

3. The method for producing aviation fuel according to claim 2 , wherein the weak acid site catalyst comprises a titanium oxide catalyst.

4. The method for producing aviation fuel according to claim 2, wherein the weight ratio of the weak acid site catalyst to the 1-D zeolite catalyst is 60:40 to 90:

10.

5. 2. The method for producing aviation fuel according to claim 1, wherein the hydrotreating catalyst in the third step is a catalyst in which an active metal containing any one or more selected from the group consisting of molybdenum, nickel, cobalt and tungsten is supported on a support.

6. 2. The method for producing aviation fuel according to claim 1, wherein the hydrocracking catalyst in the fourth step is a catalyst in which an active metal including any one or more selected from the group consisting of molybdenum, nickel, cobalt, and tungsten is supported on a zeolite.

7. 2. The method for producing aviation fuel according to claim 1, wherein the freezing point of the produced aviation fuel is −45° C. or lower, and the yield is 75% or higher.

8. 2. The method for producing aviation fuel according to claim 1, wherein the chlorine content of the produced aviation fuel is 10 ppm or less and the nitrogen content is 10 ppm or less.

9. 2. A method for producing aviation fuel as claimed in claim 1, wherein the first and second steps are carried out at a reaction temperature above 300°C.

10. The method for producing aviation fuel according to claim 1, wherein the first step and the second step are carried out in an inert atmosphere under conditions of a reaction pressure of 5 to 70 bar and a GOR (gas / oil ratio) of 100 to 3000.

11. 2. The method for producing aviation fuel according to claim 1, wherein the third step is carried out in hydrogen gas under conditions of a reaction temperature of less than 300° C., a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000.

12. 2. The method for producing aviation fuel according to claim 1, wherein the fourth step is carried out in hydrogen gas under conditions of a reaction temperature of more than 300° C., a reaction pressure of 100 bar or less, and a GOR (gas / oil ratio) of 100 to 3000.

13. 2. The method for producing aviation fuel according to claim 1, further comprising a fifth step of hydrofinishing the product of the fourth step in the presence of a hydrofinishing catalyst under conditions of a reaction temperature of more than 300° C., a reaction pressure of not more than 100 bar, and a GOR (gas / oil ratio) of 100 to 3000.

14. a first reactor into which the waste plastic pyrolysis oil is introduced and in which an olefin transfer reaction and an olefin branching reaction are sequentially carried out; a second reactor into which the reaction product and hydrogen gas from the first reactor are flowed and hydrotreated in the presence of a hydrotreatment catalyst; a third reactor into which the reaction product and hydrogen gas from the second reactor are flowed and into which a hydrocracking reaction is carried out in the presence of a hydrocracking catalyst.

15. The apparatus for producing aviation fuel according to claim 14, wherein the first reactor includes a first region filled with a weak acid site catalyst and a second region filled with a zeolite catalyst having a one-dimensional pore structure (1-D zeolite), and the waste plastic pyrolysis oil is refined by passing through the first region and the second region in order.

16. The apparatus for producing aviation fuel according to claim 14, wherein the first reactor, the second reactor, the third reactor and the like are fixed bed continuous reactors.

17. 15. The apparatus for producing aviation fuel according to claim 14, further comprising a fourth reactor into which the reaction product and hydrogen gas from the third reactor are flowed and into which a hydrofinishing reaction is carried out in the presence of a hydrofinishing catalyst.

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