Catalyst for producing basic chemical feedstock from diesel

Abstract

The present invention relates to: a catalyst for converting diesel and kerosene, which are increasingly underutilized, into basic chemical feedstock; and a method for producing the catalyst. The catalyst comprises: a porous zeolite; and phosphorus (P) supported in inner pores and on the surface of the zeolite, wherein the amount of Lewis acid sites in the phosphorus-supporting zeolite is 20 to 100 μmol / g, and basic chemical feedstock are produced through catalytic cracking of hydrocarbon feedstock having a boiling point of 150 °C to 550 °C.

Description

Catalyst for producing basic chemical raw materials from diesel

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

[0002] Diesel is a mixture of hydrocarbons with a boiling point of 250-350°C and is primarily used as fuel for passenger cars, buses, trucks, small and medium-sized ships, and large passenger aircraft. Recently, due to global warming, a global environmental issue, the demand for electric vehicles has surged. This has led to changes in the transportation powertrain and the development of alternative renewable energy sources, which are expected to stagnate or even decline in demand for heavier fuels than naphtha, such as diesel and kerosene. Furthermore, the European Union (EU) has decided to pursue a complete ban on the sale of gasoline and diesel engine vehicles as early as 14 years. Consequently, there is a growing need for technologies that can selectively produce light olefins, a basic chemical raw material, through the cracking of diesel fuel, an amount expected to increase unused in refineries.

[0003] There is no commercially available catalytic technology for converting diesel fuel into basic chemical raw materials yet, and the thermal decomposition reaction itself, which induces hardening through decomposition, is a strongly endothermic reaction, requiring a high temperature reaction of over 500 degrees. In addition, if a solid acid catalyst is used, the amount of energy used to activate the decomposition can be reduced, making catalytic decomposition technology a good candidate.

[0004] Among similar catalytic technologies, the paper '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 the catalytic cracking reaction technology based on BEA zeolite using n-dodecane as a model compound of heavy oil. The paper describes the advantages of the metal-supported catalytic technology by dissolving the silica in the zeolite with a strong alkali and converting it into a hierarchical structure that can three-dimensionally connect the micropores in the zeolite. It was reported that when cobalt-supported BEA with a hierarchical structure was used, the total yield of ethylene, propylene, and butenes could be produced up to 28.6 wt% at a reaction temperature of 400 degrees. However, the above-mentioned similar prior art designed the catalyst only by considering the decomposition characteristics of paraffin, which accounts for about 20% of the components in diesel fuel, and there is no technical consideration for attacking the remaining hydrocarbons corresponding to naphthenes and aromatics.

[0005] Also, in the paper '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, p 3382-3388) which reports on cracking reaction technology through catalytic pyrolysis reaction using heavy gas oil, it was reported that the total yield of ethylene and propylene could be produced up to about 10 wt% at a reaction temperature of 700 degrees using a shaped catalyst containing ZSM-5 zeolite. Although the above prior art induces cracking reaction at a higher temperature than the existing naphtha cracking temperature, there is no description of a specific catalyst structure for improving olefin yield, and only states the possibility of converting heavy gas oil into basic chemical raw materials without any technical consideration for improving the catalyst properties.

[0006] Accordingly, the inventors of the present invention controlled the specific acid site of zeolite, C 10 -C 20 The present invention was completed by discovering that the selectivity of light olefins and BTX as basic chemical raw materials can be increased from diesel, which is composed of a diverse and complex structure.

[0007] The present invention aims to provide a catalyst capable of maximizing the productivity of light olefins and BTX as basic chemical raw materials by controlling acid sites by introducing phosphorus (P) into a specific zeolite in the process of catalytic cracking of diesel to produce light olefins and BTX as basic chemical raw materials, and a method for producing the same.

[0008] In addition, in the present invention, by applying a phosphorus-supported zeolite in which Lewis acid sites, Bronsted acid sites, and total acid sites are controlled within a specific range, C is applied to hydrocarbon raw materials such as diesel and kerosene. 10 -C 20The aim is to provide a catalyst that can increase the selectivity of light olefins and BTX as basic chemical raw materials by targeting hydrocarbons corresponding to naphthenes and aromatics with diverse and complex structures.

[0009] One aspect of the present invention provides a catalyst comprising a porous zeolite having pores; and phosphorus (P) supported on the internal pores of the zeolite and the surface of the zeolite, wherein the phosphorus-supported zeolite has a Lewis acid site amount of 20 to 100 μmol / g and a catalyst for producing a basic chemical raw material through catalytic decomposition of a hydrocarbon raw material having a boiling point of 150°C or more and 550°C or less.

[0010] The above phosphorus (P)-supported zeolite may have a total acid site amount of 200 to 600 μmol / g.

[0011] The above-mentioned P-supported zeolite may satisfy the following equation 1.

[0012] [Formula 1]

[0013] 3 ≤ A2 / A1 ≤ 12

[0014] In the above equation 1, 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.

[0015] The above-mentioned P-supported zeolite may satisfy the following equation 2.

[0016] [Formula 2]

[0017] 0.1 ≤ P / Al < 1.4

[0018] In the above equation 2, P is the content (in moles) of phosphorus supported on the zeolite, and Al is the content (in moles) of aluminum in the zeolite.

[0019] The above 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 having a Si / Al molar ratio of 200 or less.

[0020] The above zeolite may have an average pore size of 3 to 8 Å.

[0021] The hydrocarbon raw material may be kerosene, diesel or a mixture thereof, and the basic chemical raw material may include light olefins including ethylene and propylene and BTX.

[0022] Another aspect of the present invention provides a catalyst for producing basic chemical raw materials through catalytic cracking of hydrocarbon raw materials having a boiling point of 150°C or more and 550°C or less in a fluidized bed reactor, comprising the phosphorus (P)-supported porous zeolite; clay; and an inorganic oxide binder.

[0023] Another aspect of the present invention provides a method for producing the catalyst, comprising the steps of (a) mixing a porous zeolite having pores and a phosphorus (P) compound in a solvent phase in an amount 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.

[0024] The above phosphorus (P) compound may include phosphoric acid, ginseng ammonium salt and / or alkyl phosphate.

[0025] Another aspect of the present invention provides a method for producing a basic chemical raw material by catalytically decomposing a hydrocarbon raw material having a boiling point of 150°C or more and 550°C or less in the presence of the catalyst.

[0026] The above contact decomposition can be performed under reaction conditions of a reaction temperature of 600 to 700°C, a reaction pressure of 0.1 to 5 bar, and a weight ratio of catalyst to reactants of 2 to 20.

[0027] The present invention relates to a catalyst capable of converting diesel and kerosene, which are increasingly likely to be unused, into basic chemical raw materials, and a method for producing the same. As a new technology capable of selectively producing light olefins and BTX, which are basic chemical raw materials, from diesel and kerosene, which are likely to be underused in the future, it is expected to be commercially applied to the oil refining and petrochemical industries.

[0028] Figure 1 is a schematic diagram of a circulating fluidized bed reactor used for manufacturing basic chemical raw materials through diesel catalytic cracking reaction.

[0029] Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used in a manner commonly understood by a person of ordinary skill in the art to which the present invention pertains. Throughout the specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated. Furthermore, the singular includes the plural unless specifically stated otherwise.

[0030] In this specification, 'zeolite' is used with the same meaning as the above 'porous zeolite having pores'.

[0031] One aspect of the present invention provides a catalyst used for producing light olefins and BTX, which are basic chemical raw materials, by catalytically decomposing diesel, kerosene, etc. in the presence of a catalyst according to one aspect of the present invention.

[0032] The catalyst comprises a porous zeolite having pores; and phosphorus supported on the internal pores of the zeolite and the surface of the zeolite; wherein the phosphorus-supported zeolite has a Lewis acid site amount of 20 to 100 μmol / g and is characterized in that it produces a basic chemical raw material through catalytic decomposition of a hydrocarbon raw material having a boiling point of 150°C or higher and 550°C or lower.

[0033] The catalyst of the present invention is a catalyst for catalytic cracking reaction that generates light olefins and BTX as basic chemical raw materials by catalytic cracking of diesel, kerosene, etc., and a solid acid catalyst such as zeolite forms Brønsted and / or Lewis acid sites on the solid surface and can be used in various processes such as catalytic cracking, isomerization, and alkylation of hydrocarbon reactants in the petrochemical industry. Since zeolite has silicon (Si) and aluminum (Al) bonded to each other via oxygen as a bridge, acid sites can be generated therefrom.

[0034] The above-mentioned phosphorus-supported zeolite has a Lewis acid site amount of 20 to 100 μmol / g, and specifically, may be 20 to 50 μmol / g or 30 to 50 μmol / g. In the present invention, by controlling the Lewis acid site amount of the zeolite within a specific range through phosphorus support, it is possible to induce a lightening reaction of diesel, kerosene, etc., thereby improving the selectivity of light olefins and BTX. Specifically, it is necessary to control the Lewis acid sites, Brønsted acid sites, and total acid sites to facilitate the decomposition of hydrocarbons such as isoparaffins, naphthenes, and aromatics contained in high amounts in diesel, kerosene, etc.

[0035] Meanwhile, the phosphorus-supporting method is a simple and easy method that can change the Lewis acid point of zeolite. However, the conventional method of synthesizing zeolite so that the acid point is changed on its own during synthesis, or of removing Si and Al with leaching or acid or base increases the process complexity, making it difficult to reproduce it as a mass production technology in actual industries.

[0036] The above-mentioned 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 controlling the total acid site amount of the zeolite within the above-mentioned range, the production of by-products such as methane, ethane, and propane gas can be reduced, and the selectivity of light olefins and BTX can be improved.

[0037] The above-mentioned zeolite can satisfy the following equation 1.

[0038] [Formula 1]

[0039] 3 ≤ A2 / A1 ≤ 12

[0040] In the above equation 1, 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.

[0041] The above-mentioned 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 controlling the ratio of Lewis acid sites and Bronsted acid sites of the zeolite, C is added to hydrocarbon raw materials such as diesel and kerosene. 10 -C 20 The selectivity of light olefins and BTX as basic chemical raw materials can be increased by targeting hydrocarbons corresponding to naphthenes and aromatics with diverse and complex structures.

[0042] The above-mentioned zeolite can further satisfy the following equation 1-1.

[0043] [Formula 1-1]

[0044] 0.1 ≤ A1 / At ≤ 0.2

[0045] In the above 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.

[0046] The above-mentioned 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-described effect can be further improved by controlling the ratio of Lewis acid sites to the total acid sites of the zeolite.

[0047] 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 sites of zeolite, it receives a proton and becomes pyridinium, which has an emission wavelength of 1540 cm -1 The Lewis acid point of zeolite shares an electron pair with pyridine, resulting in an infrared absorption band at 1450 cm -1 By indicating the absorption band, the acid content can be distinguished according to the type of acid site.

[0048] The above-mentioned zeolite can satisfy the following equation 2.

[0049] [Formula 2]

[0050] 0.1 ≤ P / Al < 1.4

[0051] In the above equation 2, P is the content (in moles) of phosphorus supported on the zeolite, and Al is the content (in moles) of aluminum in the zeolite.

[0052] The above P / Al molar ratio may specifically be 0.1 to 1.2, 0.1 to 1.1, 0.1 to 1.0, 0.2 to 0.9, 0.3 to 0.8, or 0.4 to 0.8. By adjusting the P / Al molar ratio of the phosphorus-supported zeolite catalyst within the above-described range, a catalyst suitable for the catalytic cracking of hydrocarbon raw materials such as diesel and kerosene can be designed. Light olefins and BTX can be produced in a high yield during the catalytic cracking of a mixture containing diesel and kerosene, and it is analyzed that this result is related to the amount of Lewis acid sites of the catalyst. On the other hand, if the content of phosphorus supported is too small, the effect of promoting hydrothermal stability by phosphorus is reduced, and the number of Lewis acid sites neutralized by phosphorus is small, so that the initial acid strength of the catalyst becomes excessively strong, which may cause a problem of a decrease in the yield of light olefins by the catalytic cracking of the mixed raw material. If the phosphorus content is too high, the phosphorus neutralizes an excessive amount of all acid sites, clogging pores and significantly reducing the catalyst's specific surface area. This reduces catalytic activity, lowering the conversion rate of hydrocarbon feedstocks such as diesel and kerosene.

[0053] In addition, in the present invention, in order to increase the selectivity of light olefins and BTX from diesel, kerosene, etc., the acid site is controlled by loading phosphorus on ZSM zeolite, which exhibits the best resolution, and also, through a specific region of P / Al and an optimized pore design, the yield of olefins can be rapidly increased while at the same time relatively reducing the yield of by-products.

[0054] Meanwhile, in the present invention, the content of phosphorus may mean the amount (in moles) of phosphorus oxide (P2O5) calculated according to the stoichiometric equivalent based on the case where all phosphorus precursors supported on zeolite are converted to phosphorus oxide (P2O5) during catalyst production.

[0055] The zeolite of the present invention may have a Si / Al molar ratio of 200 or less, and specifically, 8 to 30, 8 to 25, 8 to 20, or 8 to 15. If the amount of aluminum in the zeolite is excessive, thermal and hydrothermal stability may deteriorate, and conversely, if the amount of silicon is excessive, the amount of acid sites generated by aluminum may decrease, which may reduce catalytic activity, and also is not economical in molecular sieve synthesis. Meanwhile, the zeolite may have a FER, MFI, MEL, BEA, CHA, or MOR structure, and a zeolite having a MEL structure is more preferable because it has a 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, preferably ZSM-11 or ZSM-5, and most preferably ZSM-5. According to this, during the catalytic cracking of hydrocarbon raw materials such as diesel and kerosene, light olefins and BTX can be produced with high selectivity, and at the same time, the amount of byproducts such as carbon monoxide and methane can be minimized.

[0056] The above zeolite may have an average pore size of 3 to 8 Å, 3 to 7 Å, or 4 to 5 Å. Accordingly, the contact time between the reactant and the catalyst can be appropriately controlled, thereby improving the selectivity of light olefins and BTX. If the contact time between the reactant and the catalyst is excessively increased, the side reaction may be accelerated, thereby reducing the selectivity of light olefins. Conversely, if the contact time is too short, the reaction conversion rate may be reduced, resulting in a problem of lowering the yield of light olefins.

[0057] The above hydrocarbon raw material is a hydrocarbon raw material having a boiling point of 150°C or higher and 550°C or lower, and may be kerosene, diesel, or a mixture thereof, and the basic chemical raw material manufactured through catalytic cracking of the hydrocarbon raw material may include light olefins including ethylene and propylene and BTX.

[0058] In general, diesel and kerosene are analyzed to contain a lot of naphthene, aromatics, etc. In the present invention, C is produced through a catalyst design to attack hydrocarbons corresponding to naphthene and aromatics. 10 -C 20 By controlling the specific acid sites of zeolites from diesel, which are composed of diverse and complex structures, the selectivity of light olefins and BTX as basic chemical raw materials can be increased.

[0059]

[0060] Another aspect of the present invention provides a catalyst for producing basic chemical raw materials through catalytic cracking of hydrocarbon raw materials having a boiling point of 150°C or more and 550°C or less in a fluidized bed reactor, the catalyst comprising a phosphorus-supported porous zeolite; clay; and an inorganic oxide binder.

[0061] The above porous zeolite is the same as the phosphorus-supported zeolite according to one embodiment of the present invention, and may be included in an amount of 1 wt% or more and 70 wt% or less based on the total weight of the catalyst.

[0062] The above 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. The clay may be included in the above-mentioned amount to contribute to improving the mechanical strength of the catalyst without contributing to a decrease in the activity of the catalyst.

[0063] The above-mentioned inorganic oxide binder can act as a binder during catalyst molding, and can include, but is not limited to, Al2O3, SiO2, Al2O3-SiO2, or a combination thereof, and can be included in an amount of 5 wt% to 30 wt% based on the total weight of the catalyst. The inorganic oxide binder can be included in the above-mentioned amount to improve the mechanical strength of the catalyst without contributing to a decrease in the activity of the catalyst.

[0064] The above catalyst may further contain phosphoric acid (P2O5). It may be contained in an amount of 1 wt% to 20 wt% based on the total weight of the catalyst. Phosphoric acid (P2O5) may be further contained in the aforementioned amount and may exist on the surface of the inorganic oxide binder and the surface of the clay. Accordingly, by controlling the acid point of the inorganic oxide binder, it is possible to suppress side reactions in which CO, CH4, etc. are excessively generated due to the acid point of the inorganic oxide binder during the thermal decomposition reaction of the raw material, and to prevent the detachment of aluminum from the inorganic oxide binder, thereby maintaining the binding performance of the inorganic oxide binder.

[0065]

[0066] Another aspect of the present invention provides a method for producing a catalyst used in a reaction for producing basic chemical raw materials through catalytic cracking of a hydrocarbon raw material having a boiling point of 150°C or more and 550°C or less.

[0067] The above manufacturing method is characterized by including the steps of (a) mixing a porous zeolite having pores and a phosphorus compound in a solvent phase in an amount 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.

[0068] The method for producing the above catalyst may be a method for producing a catalyst used in a reaction for producing light olefins by catalytic cracking of a mixture containing diesel and methanol according to one aspect of the present invention.

[0069] The above step (a) is a step of supporting a phosphorus compound by mixing a porous zeolite having pores and a phosphorus compound in a solvent phase, and is characterized in that the mixing is performed in the solvent phase so that the P / Al molar ratio is 0.1 to 1.4.

[0070] The porous zeolite having the above pores and the P / Al molar ratio are as described above.

[0071] The above phosphorus compound basically includes phosphorus (P) in its chemical structure and may be a compound that can react with the acid site of the zeolite. For example, it may include phosphoric acid, phosphate ammonium salt and / or alkyl phosphate, and specifically, it may include phosphoric acid (H3PO4), H2NH4PO4, H(NH4)2PO4 and / or an organic phosphite having a size that can penetrate into the pores of the zeolite. Meanwhile, when NaH2PO4, Na2HPO4, Na3PO4, etc. of the sodium phosphate series are used, Na generated during phosphorus loading + This is undesirable because cations may affect the acid sites of zeolite, which may prevent the properties of the solid acid catalyst from being properly implemented.

[0072] The above solvent may be any solvent used in the relevant technical field, and for example, distilled water may be used.

[0073] Methods for supporting phosphorus compounds within zeolite pores and / or on the surface of zeolite generally include impregnating zeolite with a solution containing phosphorus compounds or using chemical vapor deposition (CVD). When using chemical vapor deposition, the phosphorus compound is heated to become a gas, and then the gaseous phosphorus compound diffuses into the pores of the zeolite and reacts with acid sites. However, this may not be suitable for application to the present invention.

[0074] The above step (b) is a step of drying the mixture at 100 to 150°C for 5 to 20 hours, and the solvent is removed so that the phosphorus compound can be uniformly loaded into the internal pores of the zeolite and / or the surface of the zeolite. Since the drying step is performed at 100 to 150°C or 100 to 130°C for 5 to 20 hours or 7 to 15 hours, the phosphorus compound can be uniformly loaded into the zeolite, making it easy to control the retention time of the isobutane gas catalyst of the phosphorus-loaded zeolite of the present invention in the pores and to control the acid site within the catalyst.

[0075] The above drying step (b) may further include a step of evaporating the solvent in the mixture of the above mixing step (a) in an evaporator at room temperature. For example, a rotary evaporator may be used to evaporate the solvent, but the present invention is not limited thereto.

[0076] The above (c) calcination step may be performed at a temperature ranging from 400 to 600°C, for example, from 450 to 550°C, for 2 to 10 hours or 3 to 8 hours; however, the calcination temperature and time are not limited to this range. The amount of acid sites in the catalyst may be reduced by the chemical reaction between aluminum in the zeolite and added phosphorus, and a pore blocking phenomenon may be induced, thereby changing the characteristics of the pores.

[0077]

[0078] Another aspect of the present invention provides a method for producing a basic chemical raw material by catalytically decomposing a hydrocarbon raw material having a boiling point of 150°C or more and 550°C or less in the presence of a catalyst of the present invention.

[0079] The above reaction can be performed in a fluidized bed reactor, and can be performed under reaction conditions of a reaction temperature of 600 to 700°C, a reaction pressure of 0.1 to 5 bar, a weight ratio of catalyst / total reactants (Cat / Oil ratio) of 5 to 50, and an injection flow rate of reactants at a rate of 100 to 500 kg / h based on the hydrocarbon injection amount (hydrocarbon rate).

[0080] The present inventors studied various catalyst compositions for producing basic chemical raw materials including light olefins and BTX through catalytic cracking of hydrocarbon raw materials such as diesel and kerosene, and as a result, invented a catalyst component having high activity / high durability and capable of obtaining high yields of light olefins and BTX, and a method for producing the catalyst.

[0081]

[0082] Hereinafter, preferred embodiments and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0083] Example

[0084] (Examples 1 to 5 and Comparative Example 1)

[0085] (Manufacturing Example 1): Manufacturing of zeolite used in the present invention

[0086] ZSM-5, ZSM-22, NU-87, TNU-9, PST-32, UZSM-35, and NU-88 were manufactured 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 other Y products were commercially available from Albemarle. The internal pore sizes of each type of zeolite are shown in Table 1 below.

[0087] Zeolite typepore size (Å)Y7.4 7.8UZM-356.4 × 6.8, 5.2 × 5.8, 5.2 × 5.2NU-88-

[0088]

[0089] (Manufacturing Example 2): Manufacturing of ZSM-5 zeolite loaded with phosphorus

[0090] 10 g of ZSM-5 (Si / Al=11) zeolite was uniformly 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 support 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. ZSM-5 zeolite in which phosphorus (P) is 0.5 relative to the aluminum (Al) content in the zeolite was prepared and used in this experiment (Example 1).

[0091] By varying the molar ratio of zeolite and phosphoric acid, ZSM-11 zeolite was manufactured in which the phosphorus (P) content was P / Al = 0, 0.7, 1.0, 1.2, and 1.4 relative to the aluminum (Al) content in the zeolite, as described above (Comparative Example 1, Examples 2 to 5).

[0092]

[0093] (Manufacturing Example 3): Manufacturing of a spherical catalyst for fluidized bed reaction using phosphorus-loaded ZSM-5 zeolite

[0094] 32.65 kg of ZSM-5 (Si / Al=11) molecular sieve was 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 additionally added and stirred at room temperature for 30 minutes. After that, a solution in which 55 kg of alumina sol (Al2O3 content 10 wt%) was dispersed was additionally added and stirred for 1 hour, then 33.3 kg of clay was added and thoroughly mixed for 2 hours using a high-viscosity slurry mixer. The slurry was spray formed to obtain a microsphere catalyst having a particle size of 75-200 μm, and the obtained formed catalyst was calcined at 700°C for 5 hours. In order to confirm the hydrothermal stability, the prepared sample was loaded into a reactor, and distilled water was injected at a rate of 0.3 kg / h using a liquid pump, vaporized, and brought into contact with the sample in the form of water vapor. The hydrothermal treatment was performed at 760°C for 24 hours in a 100% steam atmosphere.

[0095]

[0096] Experimental example

[0097] [Experimental Example 1] Manufacturing of Basic Chemical Raw Materials through Diesel Catalytic Decomposition Reaction by Zeolite Type

[0098] 0.1 g of the catalyst manufactured in Manufacturing Example 1 of the present invention was charged into a fixed bed reactor, and diesel was injected at a rate of 2.1 ml / h, and the reaction was performed at a temperature of 600°C and a pressure of 1 bar. The composition of the diesel used in this Example 1 is as shown in Table 2, and the results of the catalytic cracking reaction of diesel are summarized in Table 3.

[0099] Carbon No.n-paraffiniso-paraffinOlefinNaphtheneAromaticsTotalC6-C80.40.70.21.91.34.4C9-C 12 3.19.52.225.37.647.8C 13 -C 19 7.414.92.915.92.941.7C 19 -C 32 2.31.60006Sum13.226.75.243.111.799.9

[0100] (In Table 2, the unit is wt%)

[0101] Zeolite typeThermalYZSM-5ZSM-22NU-87TNU-9PST-32UZM-35NU-88Conversion (wt%)4952.369.551.155.455.448.448.358.3Selectivity (wt%)E+P32.934.118.237.637.534.431.430.234BTX2326.772.728.229.836.819.826.236.3Yield (wt%)E+P16.117.812.619.220.819.115.214.619.8BTX11.314.050.514.416.520.49.612.721.2

[0102] (In Table 3, E is C2H4 and P is C3H6)

[0103] From the results in Table 3, in order to find a zeolite suitable for diesel catalytic cracking reaction, several types of zeolites having an average pore size of 5 Å were selected in consideration of the kinetic diameter of the diesel components in Table 1, and Example 1 was performed. From the results in Table 3, except for UZSM-35, when a catalyst was used, diesel could be converted into basic chemical raw materials by lightening more effectively than in a thermal cracking reaction without a catalyst, and it was confirmed that ZSM-5 zeolite showed the highest conversion rate and the highest selectivity for light olefins and BTX products.

[0104]

[0105] [Experimental Example 2] Manufacture of basic chemical raw materials through diesel catalytic cracking using phosphorus-loaded ZSM-5 zeolite.

[0106] (Evaluation method)

[0107] * Measurement of Lewis acidity, Bronsted acidity, and total acidity

[0108] In order to analyze the total acid site content, Brønsted acid site amount, and Lewis acid site amount of the present invention, pyridine-FTIR analysis was performed using a Nicolet6700 model equipment from Thermo SCIENTIFIC. 0.01 g of the measurement sample was placed in a mold and evenly distributed, and then 3 tons of pressure was applied to manufacture pellets. To measure the IR spectrum at high temperature and vacuum, an in-situ IR cell and CaF2 window made of stainless steel were used. The IR cell was heated to 300°C under reduced pressure, and then pretreated for 1 hour, and pyridine vapor was adsorbed on the sample at 100°C for 30 minutes. After that, the physically adsorbed pyridine was removed by vacuum decompression at the same temperature, and then analysis was performed at 150°C. When pyridine is adsorbed on the Brønsted acid sites of zeolite, it receives a proton and becomes pyridinium, which has an emission wavelength of 1540 cm -1The Lewis acid point of zeolite shares an electron pair with pyridine, resulting in an infrared absorption band at 1450 cm -1 The amount of acid was distinguished according to the type of acid site by indicating the absorption band, and the results are summarized in Table 4 below.

[0109] * Evaluation of catalytic cracking reaction of diesel

[0110] 0.1 g of the catalysts manufactured in Examples 1 to 5 and Comparative Example 1 were charged into a fixed bed reactor, and diesel was injected at a rate of 2.1 ml / h, and the reaction was performed at a reaction temperature of 600°C and a reaction pressure of 1 bar. The composition of the diesel used in Example 1 is as shown in Table 1, and the results of the diesel catalytic cracking reaction are summarized in Table 5 below.

[0111] P / Al (mole ratio)Bronsted acid site amount (A2)Lewis acid site amount (A1)Total acid site amount (At)A2 / A1RatioA1 / AtRatioComparative Example 10454905605.00.16Example 10.5241.648.6290.35.00.17Example 20.7236.834.9271.76.80.13Example 31219.622241.610.00.09Example 41.2130.616146.58.10.11Example 51.46810786.80.13

[0112] (The unit of scatter plot in Table 4 is μmol / g)

[0113] Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 P / Al 0.00.50.711.21.4wt%CH44.73.32.92.32.22.0C2H66.24.54.33.23.02.7C2H47.610.211.610.48.59.1C3H85.14.53.71.80.90.8C3H65.09.612.013.912.58.2C4H 10 0.10.30.30.20.10.0C4H80.61.52.02.72.81.9E+P12.619.823.624.321.01 7.3BTX50.541.335.125.016.512.5Conversion69.568.167.060.649.949.0

[0114] Through the results of the catalytic cracking reactions of Comparative Example 1 and Examples 1 to 5, it was confirmed that as the phosphorus content increased relative to the aluminum content in the zeolite, the total amount of acid sites and Lewis acid sites decreased, thereby suppressing side reactions, and thus the gas components of alkanes (methane, ethane, propane) gradually decreased, and the yield of light olefins, which are more economical than BTX among basic chemical oils, gradually increased.

[0115] Meanwhile, through the results of the contact cracking reaction of Examples 4 and 5, it was confirmed that when the amount of Lewis acid sites of the zeolite was lost by more than 70% (corresponding to P / A = 1.2, 1.4), the conversion rate of diesel was reduced to a level similar to that of a simple thermal cracking reaction, making it difficult to effectively induce a hardening reaction as a catalyst.

[0116]

[0117] [Experimental Example 3] Manufacturing of Basic Chemical Raw Materials through Diesel Catalytic Cracking Reaction Based on Fluidized Bed Reaction

[0118] Based on the results of Experimental Example 2, a circulating fluidized bed reactor, as shown in the schematic diagram in Fig. 1, was prepared to manufacture basic chemical raw materials from diesel using the spherical shaped catalyst obtained from Example 1. The circulating fluidized bed reactor is composed of a riser (a region where the catalytic cracking reaction between diesel and the catalyst takes place), a regenerator (a region where the deactivated catalyst after the catalytic cracking reaction between diesel and the catalyst is regenerated), and a stripper (a region where the product produced after the catalytic cracking reaction between diesel and the catalyst and the catalyst are separated). The reactor has a length of 7 m and a diameter of 1 / 2 inch. The fluidized bed operating conditions and reaction results are summarized in Table 6 below.

[0119] CASE 1CASE 2CASE 3Riser Top (℃)635654673Riser BTM (℃)661678696Cat Inlet T (℃)690710730Diesel Feed Temp (℃)500500500Delta T @ Riser262423Dilution Ratio0.610.620.62Cat / Oil ratio32.133.729.8Residence Time (sec)2.722.62.51System Pressure(psig)252525HC Feed (kg / hr)0.60.60.6Dilution Steam Ratio0.290.290.29Steam feed(kg / hr)171.4171171.1Detail Composition (Yield on Product, wt%)Coke(Flue)0.670.711.06CO, CO2000Hydrogen H20.310.360.36Methane4.656.416.76Ethane3.444.154.37Ethylene14.7616.8917.8Propane2.642.222.33Propylene18.1418.72 19.73C49.28.258.69C5&C6NA2.331.991.68Benzene3.74.374.67Toluene7.347.838.21Xylene5.395.324.87C7&C8NA1.480.920.3C9 + 8.197.988.55

[0120] When the temperature of the riser top, which is the reaction section, was changed from 635°C to 673°C under the condition that the catalyst circulation amount 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 at the same time, BTX was also produced at approximately 17 wt% or more, confirming that basic chemical raw materials can be effectively produced through diesel catalytic cracking reaction using the catalyst developed by the present invention.

[0121]

[0122] While the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, but can be manufactured in various different forms. Those skilled in the art will understand that the present invention can be implemented in other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood to be illustrative in all respects and not restrictive.

Claims

1. Porous zeolite having pores; and A catalyst comprising phosphorus (P) supported on the internal pores of the zeolite and the surface of the zeolite, The Lewis acid site amount of the above-mentioned zeolite is 20 to 100 μmol / g, A catalyst for producing basic chemical raw materials through catalytic decomposition of hydrocarbon raw materials having a boiling point of 150°C or higher and 550°C or lower.

2. In paragraph 1, The above phosphorus (P)-supported zeolite is a catalyst having a total acid site amount of 200 to 600 μmol / g.

3. In paragraph 1, The above P-supported zeolite is a catalyst that satisfies the following equation 1: [Formula 1] 3 ≤ A2 / A1 ≤ 12 In the above equation 1, 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.

4. In paragraph 1, The above P-supported zeolite is a catalyst that satisfies the following equation 2: [Formula 2] 0.1 ≤ P / Al < 1.4 In the above equation 2, P is the content (in moles) of phosphorus supported on the zeolite, and Al is the content (in moles) of aluminum in the zeolite.

5. In paragraph 1, A catalyst comprising at least one zeolite selected from the group consisting of Y, ZSM-5, ZSM-11, ZSM-22, NU-87, TNU-9, PST-32, UZM-35, mordenite, and beta, wherein the zeolite has a Si / Al molar ratio of 200 or less.

6. In paragraph 1, The above zeolite is a catalyst having an average pore size of 3 to 8 Å.

7. In paragraph 1, The above hydrocarbon raw material is kerosene, diesel or a mixture thereof, The above basic chemical raw materials include light olefins including ethylene and propylene and catalysts including BTX.

8. A porous zeolite containing P of the first paragraph; clay; and an inorganic oxide binder, A catalyst for producing basic chemical raw materials through catalytic cracking of hydrocarbon raw materials with a boiling point of 150℃ or higher and 550℃ or lower in a fluidized bed reactor. 9.(a) A step of mixing a porous zeolite having pores and a phosphorus (P) compound in a solvent phase in an amount corresponding to a P / Al molar ratio of 0.1 to 1.1; (b) a step of drying the mixture at 100 to 150°C for 5 to 20 hours; and (c) A method for producing a catalyst of claim 1, comprising a step of calcining the product of the drying step at 400 to 600°C for 2 to 10 hours.

10. In paragraph 9, A method for producing a catalyst, wherein the above-mentioned phosphorus (P) compound comprises phosphoric acid, ginseng ammonium salt and / or alkyl phosphate.

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

12. In paragraph 11, A method in which the above contact decomposition is performed under reaction conditions of a reaction temperature of 600 to 700°C, a reaction pressure of 0.1 to 5 bar, and a weight ratio of catalyst to reactants of 2 to 20.

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