Catalysts for producing basic chemical feedstocks from diesel

Abstract

The present invention relates to a catalyst for converting diesel and kerosene, which are increasingly likely to be unused, into basic chemical feedstocks, and a method for producing the catalyst. The catalyst includes a porous zeolite having pores and phosphorus (P) supported in the internal pores of the zeolite and on the surface of the zeolite. The phosphorus-supported zeolite has a Lewis acid site number of 20 to 100 μmol / g, and the basic chemical feedstocks are produced by catalytic cracking of a hydrocarbon feedstock having a boiling point of 150°C or higher and 550°C or lower.

Description

[Technical Field]

[0001] The present invention relates to a catalyst for catalytic cracking of diesel and kerosene to produce light olefins and BTX as basic chemical raw materials, a method for producing the catalyst, and uses thereof. [Background technology]

[0002] Diesel is a mixture of hydrocarbons with a boiling point between 250 and 350°C and is typically used as fuel for passenger cars, buses, trucks, small and medium-sized ships, and large passenger aircraft. In recent years, global warming, a global environmental issue, has led to a surge in demand for electric vehicles. As a result, demand for heavier fractions than naphtha, such as diesel and kerosene, is expected to stagnate or decline due to related changes in transportation power systems and the development of alternative renewable energy sources. In addition, the European Union (EU) has decided to pursue a plan to completely ban the sale of gasoline and diesel-engine vehicles as early as 14 years from now. Therefore, there is a need for technology development that can selectively produce light olefins, a basic chemical raw material, through the cracking reaction of diesel fractions, which are expected to remain unused in oil refineries in the future.

[0003] There are no examples of catalytic technology that has yet been commercialized to convert diesel fractions into basic chemical feedstocks, and the thermal cracking reaction that induces lighter fuels through cracking is itself a strongly endothermic reaction, requiring a high temperature of over 500°C. Furthermore, the use of solid acid catalysts can reduce the amount of energy required to activate the cracking process, making catalytic cracking technology a suitable candidate technology.

[0004] A similar catalytic technology, "Steam catalytic cracking of n-dodecane over Ni and Ni / Co bimetallic catalyst supported on hierarchical BEA zeolite" (Energy Fuels 2017, Vol. 31, pp. 5482-5490), reports on a catalytic cracking reaction technology based on BEA zeolite using n-dodecane as a model compound for heavy oil. The paper discusses the benefits of this catalyst technology, which uses a strong alkali to dissolve the silica in the zeolite, converting the micropores within the zeolite into a hierarchical structure that allows for three-dimensional connections, thereby supporting metals. When using a cobalt-supported hierarchical BEA, the paper reports that ethylene, propylene, and butene can be produced in a total yield of up to 28.6 wt% at a reaction temperature of 400°C. However, the above-mentioned similar prior art designs catalysts taking into consideration only the cracking characteristics of paraffins, which account for approximately 20% of the components in diesel fraction, and does not take into consideration the technical aspects of cracking the remaining naphthenes and hydrocarbons corresponding to aromatics.

[0005] Additionally, a paper reporting on a cracking reaction technology using catalytic pyrolysis of heavy gas oil, "Cracking performance of gasoline and diesel fractions from catalytic pyrolysis of heavy gas oil derived from Canadian synthetic crude oil" (Energy Fuels 2011, Vol. 25, pp. 3382-3388), reports that a molded catalyst containing ZSM-5 zeolite can produce ethylene and propylene at a total yield of approximately 10 wt% at a reaction temperature of 700°C. Although the above prior art induces a cracking reaction at a temperature higher than the conventional naphtha cracking temperature, it does not explain the specific catalyst structure for improving olefin yields, and only explicitly mentions the possibility of converting heavy gas oil into basic chemical feedstocks without any technical considerations for improving catalyst properties.

[0006] Therefore, the present inventors have developed a method for controlling the specific acid sites of zeolite to achieve the desired C 10 -C 20 The present invention was accomplished by finding that the selectivity of light olefins and BTX as basic chemical raw materials can be increased from diesel, which has a diverse and complex structure ranging from 1 to 100%. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] "Steam catalytic cracking of n-dodecane over Ni and Ni / Co Bimetallic catalyst supported on Hierarchical BEA zeolite",Energy Fuels 2017,vol 31,p5482-5490 [Non-patent document 2] "Cracking performance of gasoline and diesel fractions from catalytic pyrolysis of heavy gas oil derived from Canadian synthetic crude oil", Energy fuels 2011, vol 25, p3382-3388 Summary of the Invention [Problem to be solved by the invention]

[0008] An objective of the present invention is to provide a catalyst that can maximize the productivity of light olefins and BTX as basic chemical raw materials by controlling acid sites through the introduction of phosphorus (P) into a specific zeolite when producing light olefins and BTX as basic chemical raw materials through catalytic cracking of diesel with a catalyst, and a method for producing the catalyst.

[0009] In addition, the present invention applies phosphorus-supported zeolite whose Lewis acid point, Bronsted acid point, and total acid point are adjusted to specific ranges, thereby enabling the production of C zeolite from hydrocarbon feedstocks such as diesel and kerosene. 10 -C 20 The objective of the present invention is to provide a catalyst that can target hydrocarbons corresponding to naphthenes and aromatics, which have diverse and complex structures, and increase the selectivity of light olefins and BTX as basic chemical raw materials. [Means for solving the problem]

[0010] One aspect of the present invention provides a catalyst comprising a porous zeolite having pores and phosphorus (P) supported in the internal pores of the zeolite and on the surface of the zeolite, wherein the phosphorus-supported zeolite has a Lewis acid site number of 20 to 100 μmol / g and the catalyst is used to produce basic chemical raw materials by catalytic cracking of a hydrocarbon raw material having a boiling point of 150°C or higher and 550°C or lower.

[0011] The phosphorus (P)-supported zeolite may have a total acid site amount of 200 to 600 μmol / g.

[0012] The phosphorus (P)-supported zeolite may satisfy the following formula 1:

[0013] [Formula 1] 3≦A2 / A1≦12 In the formula 1, A1 and A2 are the Lewis acid site amount (µmol / g) and Bronsted acid site amount (µmol / g) of the phosphorus-supported zeolite, respectively.

[0014] The phosphorus (P)-supported zeolite may satisfy the following formula 2:

[0015] [Formula 2] 0.1≦P / Al<1.4 In the above formula 2, P is the content (mol) of phosphorus supported on the zeolite, and Al is the content (mol) of aluminum in the zeolite.

[0016] The zeolite may include at least one selected from the group consisting of Y, ZSM-5, ZSM-11, ZSM-22, NU-87, TNU-9, PST-32, UZM-35, mordenite, and beta, each having a Si / Al molar ratio of 200 or less.

[0017] The zeolite may have an average pore size of 3 to 8 Å.

[0018] The hydrocarbon feedstock may be kerosene, diesel, or a mixture thereof, and the base chemical feedstock may include light olefins, including ethylene and propylene, and BTX.

[0019] Another aspect of the present invention provides a catalyst for producing basic chemical raw materials by catalytic cracking of a hydrocarbon feedstock having a boiling point of 150°C or higher and 550°C or lower in a fluidized bed reactor, the catalyst comprising the phosphorus (P)-loaded porous zeolite, clay, and an inorganic oxide binder.

[0020] Another aspect of the present invention provides a method for producing the catalyst, comprising: (a) mixing a porous zeolite having pores and a phosphorus (P) compound in a solvent in amounts corresponding to a P / Al molar ratio of 0.1 to 1.1; (b) drying the mixture at 100 to 150°C for 5 to 20 hours; and (c) calcining the product of the drying step at 400 to 600°C for 2 to 10 hours.

[0021] The phosphorus (P) compound may include phosphoric acid, ammonium phosphate salts, and / or alkyl phosphate salts.

[0022] Another aspect of the present invention provides a method for producing basic chemical raw materials by catalytically cracking a hydrocarbon feedstock having a boiling point of 150° C. or higher and 550° C. or lower in the presence of the catalyst.

[0023] The catalytic cracking may be carried out under reaction conditions of a reaction temperature of 600-700°C, a reaction pressure of 0.1-5 bar, and a weight ratio of catalyst to reactant of 2-20. [Effects of the Invention]

[0024] The present invention relates to a catalyst that can convert diesel and kerosene, which are increasingly likely to be underutilized, into basic chemical raw materials, and a manufacturing method thereof. This is a new technology that can selectively produce light olefins and BTX, which are basic chemical raw materials, from diesel and kerosene, which are likely to become less utilized in the future, and is expected to be commercially applicable to the oil refining and petrochemical industries. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram of a circulating fluidized bed reactor used for the production of basic chemical feedstocks by diesel catalytic cracking reactions. DETAILED DESCRIPTION OF THE INVENTION

[0026] Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used in the same manner as commonly understood by a person of ordinary skill in the art to which this invention pertains. Throughout this specification, when a part "comprises" a certain element, this means that it may further include other elements, not excluding other elements, unless otherwise specified. Furthermore, the singular form "a," "an," or "an" includes the plural form unless otherwise specified in the phrase.

[0027] In this specification, the term "zeolite" is used in the same sense as the above-mentioned "porous zeolite having pores."

[0028] Another aspect of the present invention provides a catalyst for producing light olefins and BTX, which are basic chemical raw materials, by catalytic cracking diesel, kerosene, etc. with the catalyst in the presence of the catalyst according to the aspect of the present invention.

[0029] The catalyst includes a porous zeolite having pores, and phosphorus supported in the internal pores of the zeolite and on the surface of the zeolite, and is characterized in that the phosphorus-supported zeolite has a Lewis acid site amount of 20 to 100 μmol / g, and basic chemical raw materials are produced by catalytic cracking of a hydrocarbon raw material having a boiling point of 150°C or higher and 550°C or lower.

[0030] The catalyst of the present invention is a catalyst for catalytic cracking reaction that produces light olefins and BTX as basic chemical feedstocks by catalytically cracking diesel, kerosene, etc. Solid acid catalysts such as zeolites have Brwensted and / or Lewis acid sites formed on their solid surfaces and can be used in various processes in the petrochemical industry, such as catalytic cracking, isomerization, and alkylation of hydrocarbon reactants. Zeolites are composed of silicon (Si) and aluminum (Al) bonded to each other via oxygen bridges, which allows the acid sites to be generated.

[0031] The phosphorus-supported zeolite has a Lewis acid site amount of 20 to 100 μmol / g, specifically 20 to 50 μmol / g or 30 to 50 μmol / g. In the present invention, by adjusting the Lewis acid site amount of the zeolite to a specific range by supporting phosphorus, it is possible to induce lightening reactions of diesel, kerosene, etc., and improve the selectivity to light olefins and BTX. Specifically, it is necessary to control the Lewis acid sites, Brønsted acid sites, and total acid sites, which facilitate the cracking of hydrocarbons such as isoparaffins, naphthenes, and aromatics, which are contained in high amounts in diesel, kerosene, etc.

[0032] On the other hand, the phosphorus loading method is a simple and easy method that can change the Lewis acid sites of zeolite. Conventional methods such as synthesizing zeolite so that the acid sites are changed during synthesis, or removing Si and Al by leaching or using an acid or base increase the process complexity, making it difficult to reproduce these methods as mass production techniques in industry.

[0033] The phosphorus-supported zeolite may have a total acid site amount of 200 to 600 μmol / g, specifically 200 to 500 μmol / g, 200 to 400 μmol / g, 200 to 300 μmol / g, or 250 to 300 μmol / g. By adjusting the total acid site amount of the zeolite to the above range, it is possible to reduce the production of by-products such as methane, ethane, and propane gas, and improve the selectivity to light olefins and BTX.

[0034] The phosphorus-supported zeolite may satisfy the following formula 1:

[0035] [Formula 1] 3≦A2 / A1≦12 In the formula 1, A1 and A2 are the Lewis acid site amount (µmol / g) and Bronsted acid site amount (µmol / g) of the phosphorus-supported zeolite, respectively.

[0036] The phosphorus-supported zeolite may satisfy 3≦A2 / A1≦12, 3≦A2 / A1≦10, 3≦A2 / A1≦7.5, or 4≦A2 / A1≦7. In the present invention, by adjusting the ratio of Lewis acid sites and Bronsted acid sites of the zeolite, it is possible to add C 10 -C 20 It can target hydrocarbons corresponding to naphthenes and aromatics, which have diverse and complex structures, and increase the selectivity of light olefins and BTX as basic chemical raw materials.

[0037] The phosphorus-supported zeolite may further satisfy the following formula 1-1:

[0038] [Formula 1-1] 0.1≦A1 / At≦0.2 In the formula 1-1, A1 and At are the Lewis acid site amount (µmol / g) and the total acid site amount (µmol / g) of the phosphorus-supported zeolite, respectively.

[0039] The phosphorus-supported zeolite may satisfy 0.1≦A1 / At≦0.2, 0.11≦A1 / At≦0.18, or 0.13≦A1 / At≦0.17. In the present invention, the above-mentioned effects can be further improved by adjusting the ratio of Lewis acid sites to the total acid sites of the zeolite.

[0040] Meanwhile, the total acid site content, Lewis acid site content, and Bronsted acid site content of the present invention can be measured by pyridine-FTIR analysis, but are not limited thereto. For example, when pyridine is adsorbed on the Bronsted acid site of zeolite, it receives a proton and becomes pyridinium, which has an emission wavelength of 1540 cm. -1 The Lewis acid site of the zeolite shares an electron pair with pyridine and exhibits an infrared absorption band at 1450 cm -1 The absorption bands indicate the acid content depending on the type of acid site.

[0041] The phosphorus-supported zeolite may satisfy the following formula 2:

[0042] [Formula 2] 0.1≦P / Al<1.4 In the above formula 2, P is the content (mol) of phosphorus supported on the zeolite, and Al is the content (mol) of aluminum in the zeolite.

[0043] The P / Al molar ratio may be 0.1-1.2, 0.1-1.1, 0.1-1.0, 0.2-0.9, 0.3-0.8, or 0.4-0.8. By adjusting the P / Al molar ratio of the phosphorus-supported zeolite catalyst within the above range, a catalyst suitable for catalytic cracking of hydrocarbon feedstocks such as diesel and kerosene can be designed. Catalytic cracking of a mixture containing diesel and kerosene can produce light olefins and BTX in high yields, and this result is analyzed to be related to the number of Lewis acid sites on the catalyst. On the other hand, if the content of supported phosphorus is too low, the effect of phosphorus in increasing hydrothermal stability is reduced, and the number of Lewis acid sites neutralized by phosphorus is small, resulting in excessively strong initial acid strength of the catalyst, which may result in a reduced yield of light olefins from the catalytic cracking of the mixed feedstock. If the content of supported phosphorus is too high, the phosphorus may excessively neutralize all acid sites, causing pore clogging and a significant decrease in the specific surface area of ​​the catalyst, resulting in a decrease in catalytic activity and a decrease in the conversion rate of hydrocarbon feedstocks such as diesel and kerosene.

[0044] In addition, in the present invention, in order to increase the selectivity of light olefins and BTX from diesel, kerosene, etc., phosphorus is loaded onto ZSM zeolite, which has the best decomposition ability, to adjust the acid sites. Furthermore, by using a specific P / Al region and optimizing the pore design, the yield of olefins can be significantly increased while the yield of by-products can be relatively reduced.

[0045] Meanwhile, in the present invention, the phosphorus content may refer to the amount (mol) of phosphorus oxide (PO) calculated according to the stoichiometric optimum amount, based on the case where all of the phosphorus precursor supported on the zeolite is converted to phosphorus oxide (PO) during the preparation of the catalyst.

[0046] The zeolite of the present invention may have a Si / Al molar ratio of 200 or less, specifically, 8 to 30, 8 to 25, 8 to 20, or 8 to 15. Excessive aluminum content within the zeolite may reduce thermal and hydrothermal stability. Conversely, excessive silicon content may reduce the number of acid sites generated by aluminum, resulting in reduced catalytic activity and making molecular sieve synthesis uneconomical. The zeolite may have an FER, MFI, MEL, BEA, CHA, or MOR structure, with zeolites having an MEL structure being preferred due to their high light olefin selectivity. Specifically, the zeolite of the present invention may include at least one selected from the group consisting of Y, ZSM-5, ZSM-11, ZSM-22, NU-87, TNU-9, PST-32, UZM-35, mordenite, and beta. ZSM-11 or ZSM-5 is preferred, with ZSM-5 being most preferred. This enables the production of light olefins and BTX with high selectivity during catalytic cracking of hydrocarbon feedstocks such as diesel and kerosene, while minimizing the production of by-products such as carbon monoxide and methane.

[0047] The zeolite may have an average pore size of 3-8 Å, 3-7 Å, or 4-5 Å. This allows the contact time between the reactants and the catalyst to be appropriately controlled, thereby improving the selectivity to light olefins and BTX. If the contact time between the reactants and the catalyst is too long, the progression of side reactions may be accelerated, resulting in a decrease in the selectivity to light olefins. Conversely, if the contact time is too short, the reaction conversion rate may be low, resulting in a low yield of light olefins.

[0048] The hydrocarbon feedstock has a boiling point of 150°C or higher and 550°C or lower, and may be kerosene, diesel, or a mixture thereof. Basic chemical feedstocks produced by catalytic cracking of the hydrocarbon feedstock may include light olefins including ethylene and propylene, and BTX.

[0049] Generally, diesel and kerosene are analyzed to contain a large amount of naphthenes and aromatics. In the present invention, a catalyst designed to target hydrocarbons corresponding to naphthenes and aromatics is used to produce C 10 -C 20 By controlling the specific acid sites of zeolites, it is possible to increase the selectivity of light olefins and BTX as basic chemical feedstocks from diesel, which has a diverse and complex structure ranging from 0.1 to 0.2.

[0050] Another aspect of the present invention provides a catalyst for producing basic chemical raw materials by catalytic cracking of a hydrocarbon feedstock having a boiling point of 150°C or more and 550°C or less in a fluidized bed reactor, the catalyst comprising a phosphorus-loaded porous zeolite, clay, and an inorganic oxide binder.

[0051] The porous zeolite may be the same as the phosphorus-supported zeolite according to one aspect of the present invention, and may be contained in an amount of 1% by weight to 70% by weight based on the total weight of the catalyst.

[0052] The clay may be, but is not limited to, montmorillonite, saponite, kaolin, clinoptilolite, bentonite, or a combination thereof, and may be included in an amount of 15 wt% to 50 wt% based on the total weight of the catalyst. By including the clay in the above amount, it is possible to contribute to improving the mechanical strength of the catalyst without contributing to a decrease in the activity of the catalyst.

[0053] The inorganic oxide binder serves as a binder during catalyst molding and may include, but is not limited to, Al2O3, SiO2, Al2O3-SiO2, or a combination thereof, and may be included in an amount of 5 wt% to 30 wt% based on the total weight of the catalyst. By including the inorganic oxide binder in the above amount, it is possible to contribute to improving the mechanical strength of the catalyst without contributing to a decrease in catalyst activity.

[0054] The catalyst may further contain phosphoric acid (P2O5). The content of phosphoric acid (P2O5) may be 1 wt% to 20 wt% based on the total weight of the catalyst. The additional content of phosphoric acid (P2O5) allows it to be present on the surface of the inorganic oxide binder and the surface of the clay. This adjusts the acid sites of the inorganic oxide binder, thereby suppressing side effects such as the generation of excessive CO, CH4, etc. due to the acid sites of the inorganic oxide binder during the thermal decomposition reaction of the raw materials. This also prevents the release of aluminum from the inorganic oxide binder, maintaining the binding performance of the inorganic oxide binder.

[0055] Another aspect of the present invention provides a method for producing a catalyst used in a reaction for producing basic chemical raw materials by catalytic cracking of a hydrocarbon raw material having a boiling point of 150°C or higher and 550°C or lower.

[0056] The production method includes the steps of: (a) mixing a porous zeolite having pores and a phosphorus compound in a solvent in amounts corresponding to a P / Al molar ratio of 0.1 to 1.4; (b) drying the mixture at 100 to 150°C for 5 to 20 hours; and (c) calcining the product of the drying step at 400 to 600°C for 2 to 10 hours.

[0057] The method for producing a catalyst according to one aspect of the present invention may be a method for producing a catalyst used in a reaction for producing light olefins by catalytic cracking a mixture containing diesel and methanol.

[0058] The step (a) is a step of mixing a porous zeolite having pores and a phosphorus compound in a solvent to support the phosphorus compound, and is characterized in that the mixing is performed in the solvent so that the P / Al molar ratio is 0.1 to 1.4.

[0059] The porous zeolite having the pores and the P / Al molar ratio are as described above.

[0060] The phosphorus compound may be a compound that basically contains phosphorus (P) in its chemical structure and can react with the acid sites of the zeolite. For example, it may include phosphoric acid, ammonium phosphate, and / or alkyl phosphate. Specifically, it may include phosphoric acid (H3PO4), H2NH4PO4, H(NH4)2PO4, and / or an organic phosphorus compound (organic phosphite) large enough to penetrate into the pores of the zeolite. Meanwhile, when using sodium phosphates such as NaH2PO4, Na2HPO4, and Na3PO4, the Na generated during phosphorus loading may react with the zeolite. + This is undesirable because the cations may affect the acid sites of the zeolite, preventing the properties of the solid acid catalyst from being fully realized.

[0061] The solvent may be any solvent used in the relevant technical field, for example, distilled water.

[0062] Methods for supporting a phosphorus compound inside the pores of zeolite and / or on the surface of zeolite generally include impregnating the zeolite with a solution containing the phosphorus compound, or chemical vapor deposition (CVD). When using chemical vapor deposition, the phosphorus compound is heated to become gaseous, and then the gaseous phosphorus compound diffuses into the pores of the zeolite and reacts with the acid sites. However, this method may not be suitable for the present invention.

[0063] The step (b) is a step of drying the mixture at 100 to 150°C for 5 to 20 hours, which removes the solvent and allows the phosphorus compound to be uniformly supported in the internal pores of the zeolite and / or on the surface of the zeolite. The drying step is carried out at 100 to 150°C or 100 to 130°C for 5 to 20 hours or 7 to 15 hours, which allows the phosphorus compound to be uniformly supported in the zeolite, and makes it easy to adjust the retention time of isobutane gas in the pores of the phosphorus-supported zeolite catalyst of the present invention and to control the acid sites in the catalyst.

[0064] The drying step (b) may further include a step of evaporating the solvent in the mixture of the mixing step (a) using an evaporator at room temperature. For example, a rotary evaporator may be used for solvent evaporation, but the present invention is not limited thereto.

[0065] The calcination step (c) may be carried out at a temperature of 400 to 600°C, for example, 450 to 550°C, for 2 to 10 hours or 3 to 8 hours, but the calcination temperature and calcination time are not limited to these ranges. The chemical reaction between aluminum in the zeolite and the added phosphorus reduces the amount of acid sites in the catalyst, which induces a pore blocking phenomenon and changes the pore characteristics.

[0066] Another aspect of the present invention provides a process for producing basic chemical raw materials by catalytic cracking a hydrocarbon feedstock having a boiling point of 150° C. or higher and 550° C. or lower in the presence of the catalyst of the present invention.

[0067] The reaction may be carried out in a fluidized bed reactor under the following reaction conditions: a reaction temperature of 600 to 700°C, a reaction pressure of 0.1 to 5 bar, a catalyst / total reactant weight ratio (Cat / Oil ratio) of 5 to 50, and a reactant injection rate of 100 to 500 kg / h based on the hydrocarbon injection rate.

[0068] The present inventors have studied various catalyst compositions for producing basic chemical raw materials including light olefins and BTX by catalytic cracking of hydrocarbon feedstocks such as diesel and kerosene, and as a result have invented a catalyst component that has high activity and durability and can produce light olefins and BTX in high yields, as well as a method for producing said catalyst.

[0069] Preferred examples and comparative examples of the present invention will be described below. However, the following examples are merely preferred examples of the present invention, and the present invention is not limited to the following examples.

[0070] Example (Examples 1 to 5 and Comparative Example 1) (Production Example 1): Production of zeolite used in the present invention ZSM-5, ZSM-22, NU-87, TNU-9, PST-32, UZSM-35, and NU-88 were prepared according to US Patent 4,556,477 (1985), Nature 353 (1991) 417420, J. Am. Chem. Soc. 127 (2007) 10870-10885, Science 373 (2021) 104-107, US Patent 7,922,997 (2011), Journal of Catalysis 215 (2003) 151-170, Journal of Materials Science, 51 (2016) 3735-3749), and the remaining zeolites were commercially available products from Albemarle. The internal pore sizes of each zeolite type are shown in Table 1 below.

[0071] [Table 1]

[0072] (Production Example 2): Production of phosphorus-supported ZSM-5 zeolite Ten grams of ZSM-5 (Si / Al=11) zeolite was homogeneously mixed with an aqueous solution of 0.2 g of phosphoric acid (H3PO4, 85%) and 3.8 g of distilled water, and the solvent was removed using a rotary evaporator to load the phosphoric acid. The sample prepared above was dried at 110°C for 12 hours, calcined at 500°C for 5 hours, and then cooled to room temperature to prepare ZSM-5 zeolite with a phosphorus (P) / aluminum (Al) ratio of P / Al=0.5, which was used in this experiment (Example 1).

[0073] By varying the molar ratio of zeolite and phosphoric acid, ZSM-11 zeolites in which phosphorus (P) relative to the aluminum (Al) content in the zeolite was P / Al = 0, 0.7, 1.0, 1.2, and 1.4 were produced in the same manner as above (Comparative Example 1, Examples 2 to 5).

[0074] (Production Example 3): Production of spherical catalyst for fluidized bed reaction using phosphorus-supported ZSM-5 zeolite 32.65 kg of ZSM-5 (Si / Al=11) molecular sieves were slowly added to 64.24 kg of distilled water while stirring to prepare a molecular sieve slurry. Then, 14.3 kg of 85% phosphoric acid was added and stirred at room temperature for 30 minutes. 55 kg of alumina sol (AlO content: 10 wt%) was added and stirred for 1 hour. Then, 33.3 kg of clay was added and thoroughly mixed in a high-viscosity slurry mixer for 2 hours. The slurry was spray-formed to obtain microsphere catalysts with particle sizes of 75-200 μm. The resulting formed catalysts were calcined at 700°C for 5 hours. To confirm hydrothermal stability, the prepared samples were loaded into a reactor, and distilled water was pumped at a rate of 0.3 kg / h using a liquid pump. The water vapor was then contacted with the samples. Hydrothermal treatment was carried out at 760°C for 24 hours in a 100% steam atmosphere.

[0075] Experimental Example [Experimental Example 1] Production of basic chemical raw materials by catalytic diesel cracking reaction using different types of zeolite 0.1 g of the catalyst prepared in Preparation Example 1 of the present invention was packed into a fixed-bed reactor, and diesel was injected at a rate of 2.1 ml / h at a reaction temperature of 600°C and a reaction pressure of 1 bar. The composition of the diesel used in this Example 1 is shown in Table 2, and the results of the catalytic cracking reaction of diesel are summarized in Table 3.

[0076] [Table 2]

[0077] (In Table 2, the units are wt%) [Table 3]

[0078] (In Table 3, E is C2H4 and P is C3H6) To determine the zeolites suitable for catalytic diesel cracking based on the results in Table 3, various zeolites with an average pore size of 5 Å were selected taking into account the kinetic diameters of the diesel components in Table 2, and then Example 1 was carried out. The results in Table 3 confirmed that, with the exception of UZSM-35, the use of a catalyst enabled diesel to be converted into basic chemical feedstocks by more effectively lightening it than in a thermal cracking reaction without a catalyst, and that ZSM-5 zeolite exhibited the highest conversion rate and the highest selectivity for light olefins and BTX products.

[0079] [Experimental Example 2] Production of basic chemical raw materials by catalytic diesel cracking using phosphorus-loaded ZSM-5 zeolite (Evaluation method) *Measurement of Lewis acid sites, Bronsted acid sites, and total acid sites To analyze the total acid site content, Bronsted acid site content, and Lewis acid site content of the present invention, pyridine-FTIR analysis was performed using a Nicolet 6700 model instrument from Thermo Scientific. 0.01 g of the sample was placed in a mold, uniformly distributed, and then pelleted under 3 tons of pressure. To measure the IR spectrum at high temperatures and in vacuum, a stainless steel in-situ IR cell and CaF2 window were used. The IR cell was heated to 300°C under reduced pressure, followed by pretreatment for 1 hour. Pyridine vapor was then adsorbed onto the sample at 100°C for 30 minutes. The physically adsorbed pyridine was then removed by vacuum decompression at the same temperature, and analysis was then performed at 150°C. When pyridine adsorbs on the Bronsted acid sites of the zeolite, it accepts protons to form pyridinium, with a peak at 1540 cm. -1 The Lewis acid site of the zeolite shares an electron pair with pyridine and exhibits an infrared absorption band at 1450 cm -1 The acid content was determined based on the type of acid site, and the results are summarized in Table 4 below.

[0080] *Evaluation of catalytic cracking reaction of diesel 0.1 g of the catalysts prepared in Examples 1 to 5 and Comparative Example 1 was packed into a fixed-bed reactor, and the diesel was injected at a rate of 2.1 ml / h, at a reaction temperature of 600°C and a reaction pressure of 1 bar. The composition of the diesel used in this Example 1 is shown in Table 2, and the results of the diesel catalytic cracking reaction are summarized in Table 5 below.

[0081] [Table 4]

[0082] (In Table 4, the unit of the amount of acid sites is μmol / g)

[0083] [Table 5]

[0084] From the results of the catalytic cracking reaction in Comparative Example 1 and Examples 1 to 5, it was confirmed that as the phosphorus content relative to the aluminum content in the zeolite increases, the number of total acid sites and Lewis acid sites decreases, thereby suppressing side effects and gradually reducing the gas components of alkanes (methane, ethane, propane), and gradually increasing the yield of light olefins, which are more economical than BTX among the basic chemical fractions.

[0085] On the other hand, from the results of the catalytic cracking reaction in Examples 4 and 5, it was confirmed that when the amount of Lewis acid sites of the zeolite was lost by 70% or more (corresponding to P / A = 1.2, 1.4), the diesel conversion rate decreased to a level similar to that of a simple thermal cracking reaction, making it difficult to effectively induce the lightening reaction as a catalyst.

[0086] [Experimental Example 3] Production of basic chemical raw materials by catalytic diesel cracking reaction based on a fluidized bed reaction Based on the results of Experimental Example 2, a circulating fluidized bed reactor, as shown in the schematic diagram of Figure 1, was prepared to produce basic chemical feedstocks from diesel using the spherical catalyst obtained in Example 1. The circulating fluidized bed reactor consisted of a riser (the area where the catalytic cracking reaction between diesel and the catalyst took place), a regenerator (the area where the catalyst deactivated after the catalytic reaction between diesel and the catalyst is regenerated), and a stripper (the area where the catalyst is separated from the products produced after the catalytic cracking reaction between diesel and the catalyst). The reactor was 7 m long and 1 / 2 inch in diameter. The fluidized bed operating conditions and reaction results are summarized in Table 6 below.

[0087] [Table 6]

[0088] When the temperature of the riser top (reaction section) was changed from 635°C to 673°C under the condition that the catalyst circulation rate was maintained at approximately C / O (Cat / Oil ratio) = 30, the yield of light olefins increased from approximately 32.9 wt% to 37.5 wt%, and BTX was produced at approximately 17 wt% or more. This confirmed that basic chemical feedstocks can be effectively produced through diesel catalytic cracking using the catalyst developed according to the present invention.

[0089] Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various different forms, and a person skilled in the art to which the present invention pertains will understand that the present invention can be embodied in other specific forms without changing the technical concept or essential features of the present invention. Therefore, the above-described embodiments should be understood to be illustrative in all respects and not limiting.

Claims

1. a porous zeolite having pores; A catalyst comprising: phosphorus (P) supported in the internal pores of the zeolite and on the surface of the zeolite; The amount of Lewis acid sites of the phosphorus-supported zeolite is 20 to 100 μmol / g, A catalyst for producing basic chemical raw materials by catalytic cracking of a hydrocarbon raw material having a boiling point of 150°C or more and 550°C or less.

2. 2. The catalyst according to claim 1, wherein the phosphorus (P)-supported zeolite has a total acid site amount of 200 to 600 μmol / g.

3. In the phosphorus (P)-supported zeolite, A1 and A2 are the Lewis acid site amount (μmol / g) and the Bronsted acid site amount (μmol / g) of the phosphorus-supported zeolite, respectively, and [Formula 1] 3≦A2 / A1≦12 The catalyst according to claim 1, wherein

4. The phosphorus (P)-supported zeolite has the following structure, where P is the content (mol) of phosphorus supported on the zeolite and Al is the content (mol) of aluminum in the zeolite: [Formula 2] 0.1≦P / Al<1.4 The catalyst according to claim 1, wherein

5. 2. The catalyst according to claim 1, wherein the zeolite comprises at least one selected from the group consisting of Y, ZSM-5, ZSM-11, ZSM-22, NU-87, TNU-9, PST-32, UZM-35, mordenite, and beta, each having a Si / Al molar ratio of 200 or less.

6. 2. The catalyst of claim 1, wherein the zeolite has an average pore size of 3 to 8 Å.

7. the hydrocarbon feedstock is kerosene, diesel, or a mixture thereof; 10. The catalyst of claim 1, wherein the base chemical feedstock comprises light olefins, including ethylene and propylene, and BTX.

8. A composition comprising the phosphorus (P)-supported porous zeolite according to claim 1, clay, and an inorganic oxide binder, A catalyst for producing basic chemical raw materials by catalytic cracking of hydrocarbon feedstocks having a boiling point of 150°C or more and 550°C or less in a fluidized bed reactor.

9. (a) mixing a porous zeolite having micropores and a phosphorus (P) compound in a solvent in amounts corresponding to a P / Al molar ratio of 0.1 to 1.1; (b) drying the mixture at 100-150°C for 5-20 hours; (c) calcining the product of the drying step at 400 to 600° C. for 2 to 10 hours.

10. The method for producing a catalyst according to claim 9, wherein the phosphorus (P) compound comprises phosphoric acid, an ammonium phosphate, and / or an alkyl phosphate.

11. A method for producing basic chemical raw materials by catalytic cracking a hydrocarbon raw material having a boiling point of 150° C. or higher and 550° C. or lower in the presence of the catalyst according to claim 1.

12. 12. The method according to claim 11, wherein the catalytic cracking is carried out under the reaction conditions of a reaction temperature of 600-700°C, a reaction pressure of 0.1-5 bar, and a weight ratio of catalyst to reactant of 2-20.

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