JP7295614B2 - Catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, apparatus for producing aromatic compounds having said catalyst structure, and method for producing catalyst structure for producing aromatic compounds - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, an aromatic compound production apparatus having the catalyst structure, and a method for producing a catalyst structure for producing aromatic compounds, particularly petroleum. Aromatic compound production catalyst structure used for producing aromatic compounds from oil by-produced in fluidized catalytic cracking of reforming, an aromatic compound production apparatus equipped with the catalyst structure, and aromatic compound production The present invention relates to a method for manufacturing a catalyst structure for a vehicle.

In refineries of petroleum complexes, petrochemical raw materials called naphtha and various fuels such as heavy oil, light oil, kerosene, gasoline, and LP gas are manufactured from crude oil. Crude oil is a mixture of various impurities in addition to the above-mentioned petrochemical raw materials and various fuels, so a process of distilling and separating each component contained in the crude oil is required.

Therefore, in a petroleum refining process, crude oil is heated on trays in a column of an atmospheric distillation unit by utilizing the boiling point difference of each component to separate each component, and each substance after separation is concentrated. As a result, low boiling point substances such as LP gas and naphtha are removed from the upper tray of the atmospheric distillation unit, and high boiling point substances such as heavy oil are removed from the bottom of the atmospheric distillation unit. Various fuel products are manufactured by subjecting the separated and concentrated substances to secondary treatments such as desulfurization.

Fluid catalytic cracking (FCC), which is one of the above secondary treatments, cracks high boiling point hydrocarbons such as vacuum gas oil and atmospheric residual oil at a reaction temperature of about 500 to 550 ° C with a solid acid catalyst. , a process for producing high-octane gasoline. Cracked gas oil (LCO: Light Cycle Oil) produced by FCC contains a large amount of polycyclic aromatic compounds such as naphthalene compounds with low utility value, and hydrocracking produces benzene, toluene, and xylene (BTX). Since it is possible to produce aromatic hydrocarbons such as FCC, effective use of FCC by-product cracked oil, which is a by-product of FCC, is being attempted.

Conventionally, as a method for producing aromatic hydrocarbons from LCO using a catalyst, a fixed bed reaction process or a fluidized bed reaction process using a catalyst based on ZSM-5 is used to produce aromatic hydrocarbons. (Non-Patent Document 1).

Further, as another method for producing aromatic hydrocarbons from LCO using a catalyst, a first catalyst containing a crystalline aluminosilicate containing gallium and/or zinc and phosphorus, and a crystalline aluminosilicate containing phosphorus Using a catalyst for producing monocyclic aromatic hydrocarbons consisting of a mixture with a second catalyst containing A method for doing so is disclosed (Patent Document 1).

WO2012/091099

Takashiro Muroi, "Present and Prospects of Petrochemical Catalysts", Industrial Materials, Nikkan Kogyo Shimbun, January 1, 2017, Vol. 65, No. 1, pp. 31-32

However, in the techniques of Non-Patent Document 1 and Patent Document 1, since one or more types of catalysts simply composed of zeolite compounds are used, aromatic hydrocarbons are produced from FCC by-product LCO using the catalysts. Then, there is a problem that the catalytic activity is lowered due to the formation of coke, and aromatic hydrocarbons cannot be stably produced. That is, when monocyclic aromatic hydrocarbons are produced from heavy feedstock containing polycyclic aromatic hydrocarbons, a large amount of carbonaceous matter precipitates on the catalyst and the activity decreases quickly. It is necessary to frequently regenerate the catalyst for removal.
In addition, when adopting a circulating fluidized bed process that efficiently repeats reaction-catalyst regeneration for the production of monocyclic aromatic hydrocarbons, at least the catalyst regeneration temperature must be higher than the reaction temperature, and the temperature environment of the catalyst becomes more severe.
When a zeolite compound is used as a catalyst under such severe conditions, the hydrothermal deterioration of the catalyst progresses and the reaction activity decreases with time. However, in the zeolite catalysts of Non-Patent Document 1 and Patent Document 1, measures for improving hydrothermal stability are not taken, and there is concern about a decrease in catalytic activity.

An object of the present invention is to provide a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil capable of suppressing a decrease in catalytic activity and realizing efficient aromatic compound production processing, and the catalyst structure. An object of the present invention is to provide an aromatic compound production apparatus provided with a body and a method for producing a catalyst structure for aromatic compound production.

As a result of intensive research to achieve the above object, the present inventors have found that the catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil has a porous structure composed of a zeolite-type compound. A fragrance comprising a carrier and at least one solid acid contained in the carrier, the carrier having channels communicating with each other, and the solid acid present in at least the channels of the carrier. The present inventors have found that it is possible to obtain a catalyst structure capable of suppressing the functional deterioration of the solid acid in the production stage of the group compound and realizing a long life, and have completed the present invention based on such knowledge.

That is, the gist and configuration of the present invention are as follows.
[1] a carrier having a porous structure composed of a zeolite-type compound;
at least one solid acid inherent in the carrier; and
with
the carrier has passages that communicate with each other;
A catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, wherein the solid acid is present in at least the passage of the carrier.
[2] The passage is defined by the framework structure of the zeolite-type compound, and any of the one-dimensional, two-dimensional, and three-dimensional pores, and the one-dimensional, two-dimensional, and three-dimensional pores. Produced from FCC by-product cracked oil according to [1] above, characterized in that it has an enlarged diameter portion different from any of them, and the solid acid is present at least in the enlarged diameter portion catalyst structure for producing aromatic compounds.
[3] The FCC subsidiary according to [2] above, wherein the enlarged diameter portion communicates with a plurality of holes that constitute any one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole. A catalyst structure for producing aromatic compounds produced from biodegradable oil.
[4] The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to [1] or [2] above, wherein the solid acid is fine particles having a catalytic function.
[5] From the FCC by-product cracked oil according to [4] above, wherein the average particle size of the solid acid is larger than the average inner diameter of the passage and is equal to or less than the inner diameter of the enlarged diameter portion A catalyst structure for producing an aromatic compound produced.
[6] The above [1]-[ 5], a catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil.
[7] An aromatic compound produced from FCC by-product cracked oil according to any one of [4] to [6], wherein the fine particles have an average particle size of 0.1 nm to 50 nm. catalyst structure for
[8] A catalyst structure for aromatic compounds produced from FCC by-product cracked oil according to [7] above, wherein the solid acid has an average particle size of 0.5 nm to 14.0 nm. .
[9] FCC byproduct decomposition according to any one of [4] to [8] above, characterized in that the ratio of the average particle size of the fine particles to the average inner diameter of the passage is 0.06 to 500. A catalyst structure for producing aromatic compounds produced from oil.
[10] The ratio of the average particle diameter of the fine particles to the average inner diameter of the passage is 0.1 to 36. Aromatics produced from FCC by-product cracked oil according to [9] above Catalyst structure for compound production.
[11] Produced from FCC by-product cracked oil according to [10] above, wherein the ratio of the average particle size of the fine particles to the average inner diameter of the passage is 1.7 to 4.5 A catalyst structure for producing aromatic compounds.
[12] the passage has an average inner diameter of 0.1 nm to 1.5 nm;
The catalyst for producing aromatic compounds produced from FCC by-product cracked oil according to any one of [2] to [11] above, wherein the inner diameter of the expanded diameter portion is 0.5 nm to 50 nm. Structure.
[13] The aroma produced from the FCC by-product cracked oil according to any one of [1] to [12] above, further comprising at least one catalytic substance retained on the outer surface of the carrier. Catalyst structures for the production of family compounds.
[14] The above [13], wherein the content of the at least one solid acid present in the carrier is higher than the content of the at least one catalytic substance retained on the outer surface of the carrier. A catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to 1.
[15] A catalyst for producing aromatic compounds produced from FCC by-product cracked oil according to any one of [1] to [14] above, wherein the zeolite-type compound is a silicate compound. Structure.
[16] Aromatics produced from the FCC by-product cracked oil according to any one of [1] to [15], characterized by having a cylindrical, leaf-shaped, dumbbell-shaped, or ring-shaped pellet shape Catalyst structure for compound production.
[17] A catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to [16] above, characterized in that the catalyst structure has an average particle size of 100 μm to 15 cm.
[18] An aromatic compound production apparatus having a catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to any one of [1] to [17] above.
[19] A calcination step of calcining the precursor material (B) in which the precursor material (A) for obtaining a porous structure carrier composed of a zeolite-type compound is impregnated with a metal-containing solution;
a hydrothermal treatment step of hydrothermally treating the precursor material (C) obtained by firing the precursor material (B);
A method for producing a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, characterized by comprising:
[20] The FCC secondary according to [19] above, characterized in that 50 to 500% by mass of a nonionic surfactant is added to the precursor material (A) before the firing step. A method for producing a catalyst structure for producing aromatic compounds produced from biodegradable oil.
[21] impregnating the precursor material (A) with the metal-containing solution by adding the metal-containing solution to the precursor material (A) in multiple portions before the firing step; A method for producing a catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to [19] or [20] above.
[22] When the precursor material (A) is impregnated with the metal-containing solution before the firing step, the amount of the metal-containing solution added to the precursor material (A) is In terms of the ratio (atomic ratio Si/M) of silicon (Si) constituting the precursor material (A) to the metal element (M) contained in the metal-containing solution added to (A), A method for producing a catalyst structure for producing an aromatic compound produced from FCC by-product cracked oil according to any one of [19] to [21] above, characterized in that the adjustment is made to have a value of 10 to 1000.
[23] Production of an aromatic compound produced from the FCC by-product cracked oil according to [19] above, characterized in that the precursor material (C) and a structure-directing agent are mixed in the hydrothermal treatment step. a method for producing a catalyst structure for
[24] The method for producing a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to [19] above, wherein the hydrothermal treatment step is performed in a basic atmosphere.

According to the present invention, there is provided a catalyst structure for producing aromatic compounds derived from FCC by-product cracked oil, capable of suppressing a decrease in catalytic activity and realizing efficient aromatic compound production processing, and the catalyst structure. It is possible to provide an aromatic compound production apparatus and a method for producing an aromatic compound production catalyst structure.

FIG. 1 schematically shows the internal structure of a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to an embodiment of the present invention, and FIG. is a perspective view (partially shown in cross section), and FIG. 1(b) is a partially enlarged sectional view. 2A and 2B are partially enlarged cross-sectional views for explaining an example of the function of the catalyst structure of FIG. FIG. 3 is a flow chart showing an example of a method for manufacturing the catalyst structure of FIG. FIG. 4 is a schematic diagram showing a modification of the catalyst structure of FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[Structure of catalyst structure]
FIG. 1 is a diagram schematically showing the configuration of a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to an embodiment of the present invention. ), and (b) is a partially enlarged sectional view. Note that the catalyst structure in FIG. 1 shows an example thereof, and the shape, dimensions, etc. of each component according to the present invention are not limited to those in FIG.

As shown in FIG. 1(a), a catalyst structure 1 for producing aromatic compounds produced from FCC by-product cracked oil (hereinafter simply referred to as a catalyst structure) has a porous structure composed of a zeolite-type compound. and at least one solid acid 20 inherent in the carrier 10 .

Solid acid 20 is a substance that performs one or more functions by itself or in cooperation with carrier 10 . Further, specific examples of the above functions include a catalytic function, a light emitting (or fluorescent) function, a light absorbing function, an identification function, and the like. The solid acid 20 is, for example, a catalytic substance having a catalytic function, and is preferably fine particles. In addition, when the solid acid 20 is a catalytic substance, the carrier 10 is a carrier that supports the catalytic substance. In the catalyst structure 1, a plurality of solid acids 20, 20, .

The carrier 10 has a porous structure, and as shown in FIG. 1(b), preferably has a plurality of holes 11a, 11a, . Here, the solid acid 20 is present in at least the passages 11 of the carrier 10 and preferably held in at least the passages 11 of the carrier 10 .

With such a configuration, movement of the solid acid 20 within the carrier 10 is regulated, and aggregation of the solid acids 20, 20 is effectively prevented. As a result, the reduction in the effective surface area of the solid acid 20 can be effectively suppressed, and the function of the solid acid 20 can be maintained over a long period of time. That is, according to the catalyst structure 1, it is possible to suppress deterioration in function due to aggregation of the solid acid 20, and to extend the life of the catalyst structure 1. In addition, since the life of the catalyst structure 1 is extended, the replacement frequency of the catalyst structure 1 can be reduced, the amount of waste of the used catalyst structure 1 can be greatly reduced, and resource saving can be achieved. .

Normally, when a catalyst structure is used in a fluid (eg, heavy oil, reformed gas such as _NOx, etc.), it may be subject to external forces from the fluid. In this case, if the solid acid is only adhered to the outer surface of the carrier 10, there is a problem that it tends to separate from the outer surface of the carrier 10 under the influence of the external force from the fluid. On the other hand, in the catalyst structure 1, the solid acid 20 is held at least in the passages 11 of the carrier 10, so the solid acid 20 is less likely to separate from the carrier 10 even if it is affected by the external force of the fluid. That is, when the catalyst structure 1 is in the fluid, the fluid flows from the holes 11a of the carrier 10 into the passages 11. Therefore, the speed of the fluid flowing in the passages 11 is It is considered to be slower than the speed of the fluid flowing on the outer surface of the carrier 10 . Due to the influence of such flow path resistance, the pressure that the solid acid 20 held in the passage 11 receives from the fluid is lower than the pressure that the solid acid receives from the fluid outside the carrier 10 . Therefore, it is possible to effectively prevent the solid acid 20 inherent in the carrier 11 from leaving, and it is possible to stably maintain the function of the solid acid 20 for a long period of time. It is believed that the flow path resistance as described above increases as the passage 11 of the carrier 10 has a plurality of bends and branches and the inside of the carrier 10 has a more complicated three-dimensional three-dimensional structure. .

In addition, the passage 11 is defined by the framework structure of the zeolite-type compound, and any of the one-dimensional, two-dimensional, and three-dimensional pores, and the one-dimensional, two-dimensional, and three-dimensional pores It is preferable to have an enlarged diameter portion 12 different from each. At this time, the solid acid 20 is preferably present at least in the enlarged diameter portion 12 , and more preferably enclosed in at least the enlarged diameter portion 12 . The one-dimensional pore here means a tunnel-shaped or cage-shaped pore that forms a one-dimensional channel, or a plurality of tunnel-shaped or cage-shaped pores that form a plurality of one-dimensional channels (a plurality of one-dimensional pores). channel). A two-dimensional pore refers to a two-dimensional channel in which a plurality of one-dimensional channels are two-dimensionally connected, and a three-dimensional pore refers to a three-dimensional channel in which a plurality of one-dimensional channels are three-dimensionally connected. Point.
As a result, the movement of the solid acid 20 within the carrier 10 is further restricted, and separation of the solid acid 20 and aggregation of the solid acids 20, 20 can be prevented more effectively. Inclusion refers to a state in which the solid acid 20 is included in the carrier 10 . At this time, the solid acid 20 and the carrier 10 do not necessarily have to be in direct contact with each other, and another substance (for example, a surfactant or the like) is interposed between the solid acid 20 and the carrier 10. , the solid acid 20 may be indirectly held on the carrier 10 .

Although FIG. 1(b) shows the case where the solid acid 20 is enclosed in the expanded diameter portion 12, it is not limited to this configuration. It may exist in the passage 11 in a state of protruding to the outside. Moreover, the solid acid 20 may be partially embedded in a portion of the passage 11 other than the enlarged diameter portion 12 (for example, an inner wall portion of the passage 11), or may be held by fixing or the like.
Moreover, it is preferable that the diameter-enlarging portion 12 communicates with a plurality of holes 11a, 11a forming any one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole. As a result, separate passages different from the one-dimensional, two-dimensional, or three-dimensional holes are provided inside the carrier 10, so that the function of the solid acid 20 can be exhibited more effectively.

Further, the passage 11 is formed three-dimensionally inside the carrier 10 including a branched portion or a confluence, and the enlarged diameter portion 12 is preferably provided at the branched portion or the confluence of the passage 11. .

The average inner diameter D _F of the passages 11 formed in the carrier 10 is calculated from the average value of the short diameter and long diameter of the holes 11a constituting any one of the one-dimensional, two-dimensional and three-dimensional holes. It is 0.1 to 1.5 nm, preferably 0.5 to 0.8 nm.
Further, the inner diameter D _E of the expanded diameter portion 12 is, for example, 0.5 to 50 nm, preferably 1.1 to 40 nm, more preferably 1.1 to 3.3 nm. The inner diameter D _E of the expanded diameter portion 12 depends on, for example, the pore diameter of the precursor material (A) described later and the average particle diameter D _C of the solid acid 20 to be clathrated. The inner diameter D _E of the expanded diameter portion 12 is large enough to contain the solid acid 20 .

Carrier 10 is composed of a zeolite-type compound. Examples of zeolite-type compounds include zeolite (aluminosilicate), cation-exchanged zeolite, silicate compounds such as silicalite, zeolite-related compounds such as aluminoborates, aluminoarsenates, and germanates, and molybdenum phosphate. phosphate-based zeolite-like substances, and the like. Among them, the zeolite-type compound is preferably a silicate compound.

The skeleton structure of the zeolite type compound is FAU type (Y type or X type), MTW type, MFI type (ZSM-5), FER type (ferrierite), LTA type (A type), MWW type (MCM-22). , MOR type (mordenite), LTL type (L type), BEA type (beta type), etc., preferably MFI type, more preferably ZSM-5. A zeolite-type compound is formed with a plurality of pores having a pore size corresponding to each skeleton structure. be.

The solid acid 20 will be described in detail below.
When the solid acid 20 is fine particles, the fine particles may be held in the passage 11 in the state of primary particles, or may be held in the passage 11 in the state of secondary particles formed by aggregation of the primary particles. There is In any case, the average particle size D _C of the fine particles is preferably greater than the average inner diameter D _F of the passage 11 and equal to or less than the inner diameter D _E of the expanded diameter portion 12 (D _F <D _C ≦D _E ). . Such a solid acid 20 is preferably enclosed by the enlarged diameter portion 12 within the passage 11 , and movement of the solid acid 20 within the carrier 10 is restricted. Therefore, even when the solid acid 20 receives an external force from the fluid, the movement of the solid acid 20 within the carrier 10 is suppressed, and the enlarged diameter portions 12, 12, . can be effectively prevented from coming into contact with each other.

Further, when the solid acid 20 is fine particles, the average particle diameter D _C of the fine particles is preferably 0.1 to 50 nm, more preferably 1.0 nm, for both primary particles and secondary particles. It is at least 30 nm, more preferably 0.5 nm to 14.0 nm, particularly preferably 1.0 to 3.3 nm. Also, the ratio of the average particle diameter D _C of the solid acid 20 to the average inner diameter D _F of the passage 11 (D _C /D _F ) is preferably 0.06 to 500, more preferably 0.1 to 36. , more preferably 1.1 to 36, particularly preferably 1.7 to 4.5.
Further, when the solid acid 20 is fine particles, the metal element (M) of the fine particles is preferably contained in an amount of 0.5 to 2.5% by mass with respect to the catalyst structure 1. It is more preferable that the content is 0.5 to 1.5% by mass. For example, when the metal element (M) is Zn, the content (% by mass) of the Zn element is represented by {(mass of Zn element)/(mass of all elements in catalyst structure 1)}×100. .

Specific examples of the solid acid 20 include metal oxides and their hydrates, sulfides, metal salts, composite oxides, and heteropolyacids. As metal oxides, iron oxide (FeOx), zinc oxide (ZnO), aluminum oxide ( _Al2O3 ), zirconium oxide ( _ZrO2 ), titanium oxide ( _{TiO2 )} , selenium trioxide ( _SeO3 ), dioxide Selenium ( _SeO2 ), tellurium trioxide ( _TeO3 ), tellurium dioxide ( _TeO2 ), tin dioxide (SnO2) _, manganese oxide ( _Mn2O7 ), technetium oxide ( _{Tc2O7 )} and rhenium oxide ₍ Re ₂ O ₇ ). Sulfides also include cadmium sulfide (CdS) and zinc sulfide (ZnS). Metal salts also include magnesium sulfate (MgSO ₄ ), iron sulfate (FeSO ₄ ), and aluminum chloride (AlCl ₃ ). Further, composite oxides include SiO ₂ —TiO ₂ , SiO ₂ —MgO and TiO ₂ —ZrO ₂ . In addition, heteropolyacids include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid. Only one kind of these solid acids 20 may be used, or a plurality of kinds may be used in combination. In addition, the solid acid 20 is distinguished from the zeolite-type compound that constitutes the carrier 10 . Solid acid 20 does not include, for example, zeolites.
In this specification, the “metal oxide” (as a material) constituting the fine particles refers to an oxide containing one metal element (M) and a composite oxide containing two or more metal elements (M). It is a generic term for oxides containing one or more metal elements (M).

Further, the ratio of silicon (Si) constituting the carrier 10 to the metal element (M) constituting the solid acid 20 (atomic ratio Si/M) is preferably 10 to 1000, more preferably 50 to 200. is more preferred. If the above ratio is more than 1000, the activity may be low and the action as a solid acid may not be sufficiently obtained. On the other hand, when the ratio is less than 10, the ratio of the solid acid 20 becomes too large, and the strength of the carrier 10 tends to decrease. The solid acid 20 referred to here refers to a solid acid existing inside or supported by the carrier 10 and does not include a solid acid adhering to the outer surface of the carrier 10 .

[Function of catalyst structure]
As described above, the catalyst structure 1 comprises a carrier 10 having a porous structure and at least one solid acid 20 present in the carrier. The catalyst structure 1 exhibits a function according to the function of the solid acid 20 when the solid acid 20 inherent in the carrier comes into contact with the fluid. Specifically, the fluid in contact with the outer surface 10a of the catalyst structure 1 flows into the carrier 10 through the holes 11a formed in the outer surface 10a, is guided into the passage 11, and moves through the passage 11. , exits the catalyst structure 1 through another hole 11a. When the fluid comes into contact with the solid acid 20 held in the passage 11 on the path along which the fluid moves through the passage 11 , a reaction (catalytic reaction) occurs according to the function of the solid acid 20 . In addition, the catalyst structure 1 has a molecular sieving ability due to the porous structure of the carrier. The catalyst structure 1 has molecular sieving ability to permeate predetermined molecules contained in, for example, an olefin fraction by-produced in FCC.

First, the molecular sieving ability of catalyst structure 1 will be described with reference to FIG. As shown in FIG. 2( a ), a compound composed of molecules (e.g., benzene, propylene) having a size equal to or smaller than the pore diameter of the hole 11 a , in other words, an inner diameter of the passage 11 or smaller, penetrates into the carrier 10 . be able to. On the other hand, a compound composed of molecules having a size exceeding the pore diameter of the pores 11 a (for example, mesitylene) cannot penetrate into the carrier 10 . In this way, when the fluid contains multiple types of compounds, the reaction of the compounds that cannot penetrate into the carrier 10 is regulated, and the compounds that can penetrate into the carrier 10 can react.

Among the compounds produced in the carrier 10 by the reaction, only compounds composed of molecules having a size equal to or smaller than the pore diameter of the pores 11a can exit the carrier 10 through the pores 11a and are obtained as reaction products. On the other hand, compounds that cannot exit the carrier 10 through the pores 11a can be expelled from the carrier 10 by converting them into compounds composed of molecules having a size that allows them to exit the carrier 10. . Thus, by using the catalyst structure 1, a specific reaction product can be selectively obtained.

In the catalyst structure 1, as shown in FIG. 2(b), the solid acid 20 is preferably included in the enlarged diameter portion 12 of the passage 11. As shown in FIG. When the solid acid 20 is fine particles, if the average particle size D _C of the solid acid 20 is larger than the average inner diameter D _F of the passage 11 and smaller than the inner diameter D _E of the expanded diameter portion 12 (D _F <D _C <D _E ), a small passageway 13 is formed between the solid acid 20 and the enlarged diameter portion 12 . Therefore, the fluid that has entered the small passage 13 comes into contact with the solid acid 20, as indicated by the arrows in FIG. 2(b). Since each solid acid 20 is enclosed in the expanded diameter portion 12, movement within the carrier 10 is restricted. This prevents aggregation of the solid acids 20 within the carrier 10 . As a result, a large contact area between the solid acid 20 and the fluid can be stably maintained.

Next, a case where the solid acid 20 has a catalytic function will be described. When the molecules that have entered the passage 11 come into contact with the solid acid 20, they are reacted by a hydrocracking reaction to produce an aromatic compound. For example, using a solid acid 20 as a catalyst and using a polycyclic aromatic compound such as naphthalene (C ₁₀ H ₈ ) as a raw material, BTX (benzene (C ₆ H ₆ ), toluene (C ₆ H ₅ (CH ₃ )), xylene (C ₆ H ₄ (CH ₃ ) ₂ )) and other monocyclic aromatic compounds are produced. By performing the hydrocracking treatment using the catalyst structure including the solid acid catalyst in this way, it is possible to improve, for example, the yield of BTX and the conversion rate of naphthalene.

In addition, when removing coke attached to the aromatic compound-producing catalyst structure 1 by heating in order to restore the catalytic activity of the catalyst structure 1, a metal element in the skeleton of the carrier 10, for example, a metal element in the zeolite skeleton Even in an environment where Al elements (active sites) may desorb and cause hydrothermal deterioration, the catalytic function of the solid acid 20 is hardly affected by the heating, and the hydrothermal stability as a solid acid catalyst is high. Furthermore, since the solid acid 20 is enclosed in the expanded diameter portion 12 of the carrier 10, even if the solid acid 20 is affected by heat during the coke removal treatment, it is difficult for the solid acid 20 to move within the carrier 10. The occurrence of agglomeration (sintering) is suppressed.

[Method for producing catalyst structure]
FIG. 3 is a flow chart showing a method for manufacturing the catalyst structure 1 of FIG. An example of a method for producing a catalyst structure will be described below, taking as an example the case where the solid acid inherent in the carrier is metal oxide fine particles.

(Step S1: preparation process)
As shown in FIG. 3, first, a precursor material (A) for obtaining a carrier having a porous structure composed of a zeolite-type compound is prepared. The precursor material (A) is preferably a regular mesoporous material, and can be appropriately selected according to the type (composition) of the zeolite compound that constitutes the carrier of the catalyst structure.

Here, when the zeolite-type compound constituting the carrier of the catalyst structure is a silicate compound, the ordered mesoporous material has pores with a pore diameter of 1 to 50 nm in one, two, or three dimensions. It is preferably a compound composed of a Si—O skeleton having a uniform size and regularly developed. Such regular mesoporous materials can be obtained as various synthetic products depending on the synthesis conditions. 16, MCM-41 and the like, among which MCM-41 is preferred. The pore diameter of SBA-1 is 10 to 30 nm, the pore diameter of SBA-15 is 6 to 10 nm, the pore diameter of SBA-16 is 6 nm, the pore diameter of KIT-6 is 9 nm, and the pore diameter of FSM-16 is 3 nm. ˜5 nm, and the pore size of MCM-41 is 1-10 nm. Examples of such ordered mesoporous materials include mesoporous silica, mesoporous aluminosilicate, mesoporous metallosilicate, and the like.

Precursor material (A) may be either commercially available or synthetic. Synthesis of the precursor material (A) can be carried out by a known method for synthesizing ordered mesoporous materials. For example, a mixed solution containing raw materials containing constituent elements of the precursor material (A) and a templating agent for defining the structure of the precursor material (A) is prepared, and the pH is adjusted as necessary. , perform hydrothermal treatment (hydrothermal synthesis). After that, the precipitate (product) obtained by the hydrothermal treatment is recovered (for example, filtered), washed and dried as necessary, and further calcined to obtain a powdery ordered mesoporous material. A precursor material (A) is obtained. Here, as the solvent of the mixed solution, for example, water, an organic solvent such as alcohol, or a mixed solvent thereof can be used. The raw material is selected according to the type of carrier, and examples thereof include silica agents such as tetraethoxysilane (TEOS), fumed silica, and quartz sand. As the templating agent, various surfactants, block copolymers, etc. can be used, and it is preferable to select them according to the type of synthetic material of the regular mesoporous material. is preferably a surfactant such as hexadecyltrimethylammonium bromide. The hydrothermal treatment can be carried out, for example, in a closed vessel under conditions of 80 to 800° C., 5 hours to 240 hours, and 0 to 2000 kPa. The calcination treatment can be performed, for example, in the air at 350 to 850° C. for 2 to 30 hours.

(Step S2: impregnation step)
Next, the prepared precursor material (A) is impregnated with a metal-containing solution to obtain a precursor material (B).

The metal-containing solution may be any solution as long as it contains a metal component (for example, metal ions) corresponding to the metal element (M) that constitutes the metal oxide fine particles of the catalyst structure. ) can be prepared by dissolving a metal salt containing Examples of such metal salts include metal salts such as chlorides, hydroxides, oxides, sulfates and nitrates, with nitrates being preferred. As the solvent, for example, water, an organic solvent such as alcohol, or a mixed solvent thereof can be used.

The method for impregnating the precursor material (A) with the metal-containing solution is not particularly limited. It is preferable to divide and add little by little each time. In addition, from the viewpoint of making it easier for the metal-containing solution to penetrate into the pores of the precursor material (A), a surfactant is added as an additive to the precursor material (A) in advance before adding the metal-containing solution. It is preferable to add. Such an additive has the function of coating the outer surface of the precursor material (A), suppresses the metal-containing solution added thereafter from adhering to the outer surface of the precursor material (A), It is believed that the contained solution is more likely to penetrate into the pores of the precursor material (A).

Examples of such additives include nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether. Since these surfactants have a large molecular size and cannot penetrate into the pores of the precursor material (A), they do not adhere to the inside of the pores and prevent the metal-containing solution from entering into the pores. not considered to be a hindrance. As a method for adding the nonionic surfactant, for example, it is preferable to add 50 to 500% by mass of the nonionic surfactant to the precursor material (A) before the baking step described later. If the amount of the nonionic surfactant added to the precursor material (A) is less than 50% by mass, the above suppressing action is difficult to manifest, and the nonionic surfactant is added to the precursor material (A) in an amount of 500% by mass. Adding more than % by mass is not preferable because the viscosity increases too much. Therefore, the amount of the nonionic surfactant added to the precursor material (A) is set within the above range.

In addition, the amount of the metal-containing solution added to the precursor material (A) is the amount of the metal element (M) contained in the metal-containing solution impregnated into the precursor material (A) (that is, the amount of the precursor material (B ) is preferably adjusted as appropriate in consideration of the amount of the metal element (M) to be incorporated in ). For example, before the firing step to be described later, the addition amount of the metal-containing solution added to the precursor material (A) is set to In terms of the ratio of silicon (Si) constituting the precursor material (A) (atomic ratio Si/M), it is preferably adjusted to be 10 to 1000, and adjusted to be 50 to 200. is more preferable. For example, if a surfactant is added as an additive to the precursor material (A) before adding the metal-containing solution to the precursor material (A), the addition of the metal-containing solution to the precursor material (A) By setting the amount to 50 to 200 in terms of the atomic ratio Si/M, the metal element (M) of the metal oxide fine particles is contained at 0.5 to 2.5% by mass with respect to the catalyst structure. can be made In the state of the precursor material (B), the amount of the metal element (M) present inside the pores is the same under conditions such as the metal concentration of the metal-containing solution, the presence or absence of the above additives, and other conditions such as temperature and pressure. If so, it is roughly proportional to the amount of the metal-containing solution added to the precursor material (A). Moreover, the amount of the metal element (M) inherent in the precursor material (B) is in a proportional relationship with the amount of the metal element constituting the metal oxide fine particles inherent in the carrier of the catalyst structure. Therefore, by controlling the addition amount of the metal-containing solution to be added to the precursor material (A) within the above range, the inside of the pores of the precursor material (A) can be sufficiently impregnated with the metal-containing solution. , the amount of the metal oxide fine particles to be incorporated in the carrier of the catalyst structure can be adjusted.

After impregnating the precursor material (A) with the metal-containing solution, a washing treatment may be performed as necessary. As the cleaning solution, water, an organic solvent such as alcohol, or a mixed solution thereof can be used. Moreover, it is preferable that the precursor material (A) is impregnated with the metal-containing solution, washed as necessary, and then dried. Drying treatments include natural drying for about one night and high-temperature drying at 150° C. or less. In addition, when the precursor material (A) is subjected to the firing treatment described later in a state in which a large amount of water contained in the metal-containing solution and the water in the washing solution remains, the ordered mesoporous material of the precursor material (A) Since there is a risk that the skeletal structure of is broken, it is preferable to dry sufficiently.

(Step S3: Firing step)
Next, the precursor material (B) in which the metal-containing solution is impregnated in the precursor material (A) for obtaining a carrier having a porous structure composed of a zeolite-type compound is calcined to obtain a precursor material (C). get

The calcination treatment is preferably carried out, for example, in the air at 350 to 850° C. for 2 to 30 hours. By such a calcination treatment, the metal component impregnated in the pores of the ordered mesoporous material undergoes crystal growth to form metal oxide fine particles in the pores.

(Step S4: hydrothermal treatment step)
Next, a mixed solution is prepared by mixing the precursor material (C) and a structure-directing agent, and the precursor material (C) obtained by calcining the precursor material (B) is hydrothermally treated to obtain a catalyst structure. get a body

The structure-directing agent is a templating agent for defining the skeleton structure of the carrier of the catalyst structure, and for example, a surfactant can be used. The structure-directing agent is preferably selected according to the skeleton structure of the carrier of the catalyst structure. is preferred.

Mixing of the precursor material (C) and the structure-directing agent may be performed during the main hydrothermal treatment step or before the hydrothermal treatment step. The method for preparing the mixed solution is not particularly limited, and the precursor material (C), the structure-directing agent, and the solvent may be mixed at the same time, or the precursor material (C) and the structure-directing agent may be mixed together in the solvent. Each dispersion solution may be mixed after dispersing each of the agents into individual solutions. As the solvent, for example, water, an organic solvent such as alcohol, or a mixed solvent thereof can be used. Moreover, it is preferable that the mixed solution is adjusted in pH with an acid or a base before the hydrothermal treatment.

The hydrothermal treatment can be carried out by a known method, and is preferably carried out in a closed vessel under treatment conditions of 80 to 800° C., 5 hours to 240 hours, and 0 to 2000 kPa. Also, the hydrothermal treatment is preferably performed in a basic atmosphere. Although the reaction mechanism here is not necessarily clear, by performing hydrothermal treatment using the precursor material (C) as a raw material, the skeletal structure of the precursor material (C) as an ordered mesoporous substance gradually collapses. While the position of the metal oxide fine particles inside the pores of the precursor material (C) is generally maintained, a new skeleton structure (porous structure) is formed as a support for the catalyst structure by the action of the structure-directing agent. be done. The catalyst structure obtained in this manner comprises a carrier having a porous structure and metal oxide fine particles contained in the carrier, and the carrier has passages in which a plurality of pores communicate with each other due to the porous structure of the carrier, At least part of the metal oxide fine particles exists in the passages of the carrier.
In the present embodiment, in the hydrothermal treatment step, a mixed solution is prepared by mixing the precursor material (C) and the structure-directing agent, and the precursor material (C) is hydrothermally treated. Alternatively, the precursor material (C) may be hydrothermally treated without mixing the precursor material (C) and the structure-directing agent.

The precipitate (catalyst structure) obtained after the hydrothermal treatment is preferably subjected to washing treatment, drying treatment and calcination treatment as necessary after collection (for example, filtration). As the cleaning solution, water, an organic solvent such as alcohol, or a mixed solution thereof can be used. Examples of the drying treatment include natural drying for about one night, high-temperature drying at 150° C. or less, and the like. If the calcination treatment is performed with a large amount of moisture remaining in the precipitate, the skeleton structure of the catalyst structure as a carrier may be broken, so it is preferable to dry the precipitate sufficiently. Further, the calcination treatment can be performed, for example, in the air under the treatment conditions of 350 to 850° C. for 2 to 30 hours. The structure-directing agent adhering to the catalyst structure is burned off by such a calcination treatment. In addition, the catalyst structure can be used as it is without subjecting the recovered precipitate to a calcining treatment, depending on the purpose of use. For example, when the environment in which the catalyst structure is used is a high-temperature environment in an oxidizing atmosphere, the structure-directing agent is burned away by exposure to the environment for a certain period of time. In this case, since a catalyst structure similar to that obtained by calcining is obtained, it is not necessary to perform calcining.

[Modification of catalyst structure 1]
FIG. 4 is a schematic diagram showing a modification of the catalyst structure 1 of FIG.
The catalyst structure 1 in FIG. 1 comprises a carrier 10 and a solid acid 20 contained in the carrier 10, but is not limited to this configuration. For example, as shown in FIG. 10 may further comprise at least one catalytic material 30 retained on the outer surface 10a.

This catalytic material 30 is a material that performs one or more functions. The function of the catalyst material 30 may be the same as or different from the function of the solid acid 20 . Specific examples of the functions of the catalyst material 30 are the same as those described for the solid acid 20 . The catalytic substance 30 preferably has a catalytic function, in which case the catalytic substance 30 is preferably a solid acid. When the catalytic substance 30 is a solid acid, the catalytic substance 30 may be the same substance as the solid acid 20, or may be a different substance. In particular, when the catalyst material 30 is a solid acid, the content of the solid acid held in the catalyst structure 2 can be increased compared to the catalyst structure 1, further promoting the catalytic reaction by the solid acid. be able to.

In this case, the content of the solid acid 20 inherent in the carrier 10 is preferably greater than the content of the catalytic substance 30 retained on the outer surface 10a of the carrier 10. As a result, the function of the solid acid 20 held inside the carrier 10 becomes dominant, and the function of the solid acid is stably exhibited.

As described above, according to this embodiment, the carrier 10 has the passages 11 formed so that the plurality of holes 11a, 11a, . Since it is present in the passage 11, the predetermined substance to be reformed can be selectively penetrated by the molecular sieving ability of the porous skeleton structure, and the predetermined molecule is hydrogenolyzed by the catalytic function of the solid acid 20, and the predetermined compounds can be obtained. In addition, the movement of the solid acid 20 within the carrier 10 is regulated, and the detachment of the solid acid 20 can be prevented.
Further, even if the solid acid 20 is heated during the coke removal treatment, the catalytic function of the solid acid 20 and aggregation of the solid acids 20 can be suppressed. Therefore, by repeatedly performing the coke removal treatment by heating, the catalytic activity inherent in the catalyst structure 1 for producing an aromatic compound can be maintained. is high, and a decrease in catalytic activity can be suppressed. Therefore, compared with the conventional hydrocracking process, it is possible to suppress a decrease in catalytic activity and realize an efficient aromatic compound production process.

Further, since the average particle diameter D _C of the solid acid 20 is larger than the average inner diameter D _F of the passage 11 and equal to or smaller than the inner diameter D _E of the enlarged diameter portion 12 , the solid acid 20 is contained inside the enlarged diameter portion 12 . The clathration can be ensured, and aggregation of the solid acids 20 can be reliably prevented. Moreover, since a large effective surface area as a catalyst can be secured, the catalytic function of the solid acid 20 can be maximized.

In particular, the yield of aromatic compounds can be improved by using the catalyst structure 1 when producing aromatic compounds such as BTX, which is a base material for gasoline and various chemical products, as an effective use of petroleum.

In the above, the catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to the embodiment of the present invention has been described, but the present invention is not limited to the described embodiment, and the technology of the present invention Various modifications and changes are possible based on the idea.

For example, in the above embodiment, the appearance of the catalyst structure is powder, but it is not limited to this, and may be in the form of a cylinder, a leaf, a dumbbell column, or a ring-shaped pellet. The method of molding the catalyst structure to obtain the above shape is not particularly limited, but a general method such as extrusion molding, tableting molding, or granulation in oil can be used. Alternatively, for example, after the catalyst powder is compacted with a uniaxial press to produce a catalyst structure, the catalyst compact is crushed and passed through a sieve to obtain at least one secondary particle having a desired secondary particle diameter. A method for obtaining a structured catalyst structure may be provided. A state in which the catalyst structure is granulated by the above method can be referred to as a catalyst structure or a catalyst compact. When the catalyst structure is granulated, for example, a catalyst structure having an average particle diameter (or an average equivalent circle diameter) of 100 μm to 15 cm can be formed. When the size of the catalyst structure is increased to several centimeters or more, a binder such as alumina may be mixed and molded. When the catalyst structure or the catalyst molded body has the above shape and dimensions, the catalyst layer is prevented from being clogged with a heavy oil fraction or the like when desulfurizing crude oil, heavy oil, or a fraction obtained by distilling crude oil. be able to.

For example, an aromatic compound production apparatus having a catalyst structure for producing aromatic compounds derived from the FCC by-product cracked oil may be provided. This aromatic compound production apparatus includes, for example, a reactor in which a hydrocracking reaction is performed, a polycyclic aromatic compound supply unit that supplies a polycyclic aromatic compound to the reactor, and a polycyclic aromatic compound produced by the hydrocracking reaction. and a monocyclic aromatic compound discharge part for discharging the monocyclic aromatic compound. A catalyst structure for producing aromatic compounds can be used in a reactor of an apparatus having such a configuration.
That is, by supplying a polycyclic aromatic compound to the catalyst structure, these can be hydrocracked. For example, using the catalyst structure in an aromatic compound production apparatus, the polycyclic aromatic compound is By carrying out hydrocracking in the aromatic compound manufacturing apparatus, the same effect as described above can be obtained.

(Examples 1 to 288)
[Synthesis of precursor material (A)]
A mixed aqueous solution is prepared by mixing a silica agent (tetraethoxysilane (TEOS), manufactured by Wako Pure Chemical Industries, Ltd.) and a surfactant as a template agent, and the pH is adjusted as appropriate. Hydrothermal treatment was performed at 350° C. for 100 hours. After that, the produced precipitate is filtered off, washed with water and ethanol, and further calcined in the air at 600° C. for 24 hours to obtain the precursor material (A) having the types and pore sizes shown in Tables 1 to 6. Obtained. The following surfactants were used according to the type of the precursor material (A) (“type of precursor material (A): surfactant”).
・ MCM-41: hexadecyltrimethylammonium bromide (CTAB) (manufactured by Wako Pure Chemical Industries, Ltd.)
・ SBA-1: Pluronic P123 (manufactured by BASF)

[Production of precursor materials (B) and (C)]
Next, according to the metal element (M) constituting the solid acid fine particles of the types shown in Tables 1 to 6, a metal salt containing the metal element (M) is dissolved in water to obtain a metal-containing aqueous solution. prepared. The following metal salts were used according to the type of solid acid fine particles (“solid acid fine particles: metal salt”).
・ ZnOx: zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
・AlOx: Aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ZrOx: Zirconyl nitrate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.)

Next, the metal-containing aqueous solution is added to the powdery precursor material (A) little by little in multiple portions, dried at room temperature (20° C.±10° C.) for 12 hours or more, and precursor material (B) is obtained. got

In addition, when the condition of the presence or absence of additives shown in Tables 1 to 6 is "Yes", polyoxyethylene (15) as an additive is added to the precursor material (A) before adding the metal-containing aqueous solution. Pretreatment was performed by adding an aqueous solution of oleyl ether (NIKKOL BO-15V, manufactured by Nikko Chemicals Co., Ltd.), and then a metal-containing aqueous solution was added as described above. In addition, when the condition for the presence or absence of additives is "absence", pretreatment with additives as described above is not performed.

The amount of the metal-containing aqueous solution added to the precursor material (A) is determined by the ratio of silicon (Si) constituting the precursor material (A) to the metal element (M) contained in the metal-containing aqueous solution ( Numerical values when converted to the atomic number ratio (Si/M) were adjusted to the values shown in Tables 1-6.

Next, the precursor material (B) impregnated with the metal-containing aqueous solution obtained as described above was calcined in the air at 600° C. for 24 hours to obtain the precursor material (C).

[Synthesis of catalyst structure]
The precursor material (C) obtained as described above was mixed with the structure-directing agents shown in Tables 1 to 6 to prepare a mixed aqueous solution, which was heated in a sealed container at 80 to 350 ° C. Tables 1 to 6. Hydrothermal treatment was performed under the pH and time conditions shown in . After that, the generated precipitate is filtered off, washed with water, dried at 100° C. for 12 hours or more, and further calcined in the air at 600° C. for 24 hours to obtain solids as carriers and catalyst substances shown in Tables 1 to 6. Catalyst structures having acid fine particles were obtained (Examples 1 to 288).

(Comparative example 1)
In Comparative Example 1, MFI-type silicalite was mixed with cobalt oxide powder (II, III) (manufactured by Sigma-Aldrich Japan G.K.) having an average particle size of 50 nm or less. A catalyst structure to which cobalt fine particles were attached was obtained. MFI-type silicalite was synthesized in the same manner as in Examples 52 to 57, except for the step of adding metal.

(Comparative example 2)
In Comparative Example 2, MFI-type silicalite was synthesized in the same manner as in Comparative Example 1, except that the step of adhering cobalt oxide fine particles was omitted.

[evaluation]
The catalyst structures of Examples 1 to 288 and the silicalites of Comparative Examples 1 and 2 were subjected to various property evaluations under the conditions shown below.

[A] Observation of cross-section For the catalyst structures of Examples 1 to 288 and the silicalite of Comparative Example 1, observation samples were prepared by a pulverization method and observed using a transmission electron microscope (TEM) (TITAN G2, manufactured by FEI). , a cross-sectional observation was performed.

As a result, it was confirmed that in the catalyst structures of the above examples, the catalyst substance was contained and held inside the carrier made of silicalite or zeolite. On the other hand, in the silicalite of Comparative Example 1, the solid acid fine particles adhered only to the outer surface of the carrier, and did not exist inside the carrier.
In the above examples, the catalyst structures in which the solid acid fine particles are ZnO fine particles were cut out by FIB (focused ion beam) processing, and subjected to SEM (SU8020, manufactured by Hitachi High-Technologies Corporation), EDX (X-Max, (manufactured by Horiba, Ltd.) was used to perform cross-sectional elemental analysis. As a result, Zn element was detected from inside the carrier.
From the results of cross-sectional observation by TEM and SEM/EDX, it was confirmed that ZnOx fine particles were present inside the carrier.

[B] Average inner diameter of carrier passages and average particle size of solid acid fine particles 500 arbitrarily selected carrier passages in the TEM image taken by cross-sectional observation performed in the above evaluation [A], and the major diameter of each And the short diameter was measured, the inner diameter was calculated from the average value (N=500), and the average inner diameter was obtained to obtain the average inner diameter _DF of the carrier passages. Similarly, with regard to the solid acid microparticles, 500 solid acid microparticles are arbitrarily selected from the above TEM image, the particle size of each is measured (N=500), the average value is obtained, and the solid acid The average particle diameter of fine particles was defined as _DC . The results are shown in Tables 1-6.
In addition, in order to confirm the average particle diameter and dispersion state of the catalyst substance, analysis was performed using SAXS (small angle X-ray scattering). Measurements by SAXS were performed using Spring-8 beamline BL19B2. The obtained SAXS data was fitted with a spherical model by the Guinier approximation method to calculate the particle size. Particle size was measured for catalyst structures in which the solid acid particulates were _ZrO2 particulates. For comparison, ZrO ₂ fine particles (manufactured by Nippon Shokubai Co., Ltd.), which is a commercial product, were observed and measured by SEM.
As a result, _ZrO2 fine particles of various sizes in the range of about 5 nm to 25 nm exist randomly in the commercial product, whereas the average particle size obtained from the TEM image is 1.2 nm to 2.0 nm. In the catalyst structure of each example, a scattering peak with a particle size of 10 nm or less was also detected in the SAXS measurement results. From the SAXS measurement results and SEM/EDX cross-sectional measurement results, it was found that catalytic substances with particle sizes of 10 nm or less were present inside the carrier in a highly dispersed state with a uniform particle size.

[C] Relationship between the amount of metal-containing solution added and the amount of metal clathrated inside the support A catalyst structure was prepared by enclosing solid acid fine particles inside a carrier, and then the amount (% by mass) of the metal enclosed inside the carrier of the catalyst structure produced with the above-mentioned addition amount was measured. In this measurement, the catalyst structures with atomic ratios Si/M = 100, 200, and 1000 are the same as the catalyst structures with atomic ratios Si/M = 100, 200, and 1000 in Examples 1 to 288, respectively. The catalyst structure with the atomic ratio Si/M = 50 was prepared by adjusting the amount of the metal-containing solution added by the method of No., except that the amount of the metal-containing solution added was changed. = 100, 200 and 1000 catalyst structures.
The amount of metal was quantified by ICP (high frequency inductively coupled plasma) alone or by combining ICP and XRF (X-ray fluorescence analysis). XRF (energy dispersive X-ray fluorescence spectrometer "SEA1200VX", manufactured by SSI Nanotechnology Co., Ltd.) was performed under the conditions of a vacuum atmosphere and an acceleration voltage of 15 kV (using a Cr filter) or an accelerating voltage of 50 kV (using a Pb filter). .
XRF is a method of calculating the amount of metal present based on fluorescence intensity, and a quantitative value (in terms of mass %) cannot be calculated using XRF alone. Therefore, the metal content of the catalyst structure to which the metal was added at Si/M = 100 was quantified by ICP analysis, and the metal content of the catalyst structure to which the metal was added at Si/M = 50 and less than 100 was the result of XRF measurement. and calculated based on the ICP measurement results.
As a result, it was confirmed that at least within the range of 50 to 1000 for the atomic number ratio Si/M, the amount of metal clathrated in the structure increased as the amount of the metal-containing solution added increased. .

[D] Performance Evaluation The catalytic ability (performance) of the solid acid fine particles (catalyst material) was evaluated for the catalyst structures of the above examples and the silicalite of the comparative example. The results are shown in Tables 1-6.

(1) Catalytic activity Catalytic activity was evaluated under the following conditions.

First, 0.5 g of the catalyst structure was filled in the reactor, and the properties (density, kinematic viscosity, distillation properties) and composition in Table 1 described in WO 2012/091099 were obtained at 600 ° C. for 2 hours. A hydrocracking reaction was performed to obtain aromatic hydrocarbons having 6 to 8 carbon atoms from feedstock oil having the same properties and composition.

After completion of the reaction, the components of the collected product gas and product liquid were analyzed by gas chromatography/mass spectrometry (GC/MS). The generated gas analyzer is TRACE 1 310GC (manufactured by Thermo Fisher Scientific Co., Ltd., detector: thermal conductivity detector), and the generated liquid analyzer is TRACE DSQ (Thermo Fisher Scientific Fick Co., Ltd., detector: mass detector, ionization method: EI (ion source temperature 250° C., MS transfer line temperature 320° C., detector: thermal conductivity detector) was used.

Furthermore, the yield (mol%) of aromatic hydrocarbons having 6 to 8 carbon atoms was determined based on the above analysis results.

In this example, when the yield of aromatic hydrocarbons having 6 to 8 carbon atoms contained in the product liquid is 20 mol% or more, the catalyst activity (decomposition) is judged to be excellent, If it is 15 mol% or more and less than 20 mol%, it is judged that the catalytic activity is good, and it is judged to be "○". When the amount was less than 10 mol %, the catalytic activity was judged to be inferior (improper) and was judged to be "x".

(2) Durability (service life)
Durability was evaluated under the following conditions.
First, the catalyst structure used in evaluation (1) was collected and heated at 650° C. for 12 hours to prepare a heated catalyst structure. Next, using the obtained heated catalyst structure, a hydrocracking reaction is performed to obtain aromatic hydrocarbons having 6 to 8 carbon atoms from the raw material oil in the same manner as in evaluation (1), and The components of the produced gas and produced liquid were analyzed in the same manner as in evaluation (1).

Based on the obtained analysis results, the yield (mol%) of aromatic hydrocarbons having 6 to 8 carbon atoms was determined in the same manner as in evaluation (1). Then, how much the yield of the compound by the catalyst structure after heating is maintained with respect to the yield of the compound by the catalyst structure before heating (yield obtained in evaluation (1)). evaluated. Specifically, the yield of the compound by the catalyst structure after heating (determined by evaluation (2)) is compared with the yield of the compound by the catalyst structure before heating (yield determined by evaluation (1)). The percentage (%) of the yield) was calculated.

In this example, the yield of the compound obtained by the catalyst structure after heating (yield determined in evaluation (2)) was the yield of the compound obtained by the catalyst structure before heating (determined in evaluation (1)). Yield), the durability (heat resistance) is judged to be excellent when 80% or more is maintained, and the case where 60% or more and less than 80% is maintained is durability ( It is determined that the durability (heat resistance) is not good, but the pass level (acceptable) is determined to be "○" when 40% or more and less than 60% is maintained. Δ”, and the case where it was reduced to less than 40% was judged to be inferior (improper) in durability (heat resistance) and was evaluated as “x”.

Performance evaluations similar to evaluations (1) and (2) were also performed for Comparative Examples 1 and 2. Comparative Example 2 is the carrier itself and does not have solid acid fine particles. Therefore, in the above performance evaluation, only the carrier of Comparative Example 2 was filled instead of the catalyst structure. Table 6 shows the results.

As is clear from Tables 1 to 6, the catalyst structures (Examples 1 to 288) in which it was confirmed that the solid acid fine particles were held inside the carrier by cross-sectional observation were simply solid acid fine particles outside the carrier. Compared to the catalyst structure that is only attached to the surface (Comparative Example 1) or the carrier itself that does not have any solid acid fine particles (Comparative Example 2), the amount of aromatics having 6 to 8 carbon atoms from the feedstock oil It has been found to exhibit excellent catalytic activity in the hydrocracking reaction to obtain hydrocarbons, and to have excellent durability as a catalyst.

On the other hand, the silicalite of Comparative Example 1, in which the solid acid fine particles were attached only to the outer surface of the carrier, compared with the carrier itself of Comparative Example 2, which did not have any solid acid fine particles, had 6 carbon atoms from the raw material oil. Although the catalytic activity in the hydrocracking reaction to obtain the aromatic hydrocarbons of No. 1 to 8 was improved, the durability as a catalyst was inferior to that of the catalyst structures of Examples 1 to 288.

In addition, the carrier itself of Comparative Example 2, which does not have any catalyst substance, shows almost no catalytic activity in the hydrocracking reaction for obtaining aromatic hydrocarbons having 6 to 8 carbon atoms from the feed oil. Both catalyst activity and durability were inferior compared to the 288 catalyst structure.

1 Catalyst structure 10 Carrier 10a Outer surface 11 Passage 11a Hole 12 Expanded diameter portion 20 Solid acid 30 Catalyst material D _C Average particle size D _F Average inner diameter D _E inner diameter

Claims (21)

a carrier having a porous structure composed of a zeolite-type compound;
at least one solid acid inherent in the carrier; and
with
the carrier has passages that communicate with each other;
The passageway is defined by the framework structure of the zeolite-type compound, and any one of the one-dimensional, two-dimensional, and three-dimensional pores. having a different enlarged diameter portion from each other,
The average particle size of the solid acid is greater than the average inner diameter of the passageway, wherein the average inner diameter of the passageway constitutes any one of the one-dimensional pore, the two-dimensional pore and the three-dimensional pore. It is calculated from the average value of the short diameter and long diameter of the hole,
The average particle size of the solid acid is 0.5 nm to 50 nm,
A catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, wherein the solid acid is included in at least the expanded diameter portion of the carrier. The FCC by-product cracked oil according to claim 1, wherein the enlarged diameter portion communicates with a plurality of holes constituting any one of the one-dimensional hole, the two-dimensional hole, and the three-dimensional hole A catalyst structure for producing an aromatic compound produced. 3. The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to claim 1 or 2, wherein said solid acid is fine particles having a catalytic function. 4. The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to claim 3, wherein the average particle size of said solid acid is equal to or smaller than the inner diameter of said enlarged diameter portion. 5. Any one of claims 1 to 4, wherein the metal element (M) of the solid acid is contained in an amount of 0.5 to 2.5% by mass with respect to the catalyst structure for producing an aromatic compound. 2. A catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to claim 1. 2. The catalyst structure for aromatic compounds produced from FCC by-product cracked oil according to claim 1 , wherein said solid acid has an average particle size of 0.5 nm to 14.0 nm. Produced from FCC by-product cracked oil according to any one of claims 3 to 6 , wherein the ratio of the average particle size of the solid acid to the average inner diameter of the passage is 1.1 to 500 A catalyst structure for producing aromatic compounds. The ratio of the average particle size of the solid acid to the average inner diameter of the passage is 1.1 to 36. For producing aromatic compounds produced from FCC by-product cracked oil according to claim 7 . catalyst structure. Aromatic compounds produced from FCC by-product cracked oil according to claim 8 , wherein the ratio of the average particle size of the solid acid to the average inner diameter of the passage is 1.7 to 4.5. Manufacturing catalyst structure. The average inner diameter of the passage is 0.1 nm to 1.5 nm,
The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to any one of claims 1 to 9 , wherein the inner diameter of the enlarged diameter portion is 0.5 nm to 50 nm. body. For producing aromatic compounds produced from FCC by-product cracked oil according to any one of claims 1 to 10 , further comprising at least one catalytic substance held on the outer surface of the carrier. catalyst structure. 12. The FCC of claim 11 , wherein the content of said at least one solid acid contained within said support is greater than the content of said at least one catalytic material retained on the outer surface of said support. A catalyst structure for producing aromatic compounds produced from by-product cracked oil. The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to any one of claims 1 to 12 , wherein the zeolite type compound is a silicate compound. Catalyst for producing aromatic compounds produced from FCC by-product cracked oil according to any one of claims 1 to 13 , characterized in that it has a cylindrical, leaf-like, dumbbell column-like, or ring-like pellet shape. Structure. 15. The catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to claim 14 , wherein the catalyst structure has an average particle size of 100 μm to 15 cm. An aromatic compound production apparatus comprising a catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to any one of claims 1 to 15 . a calcination step of calcining the precursor material (A) , which is an ordered mesoporous material for obtaining a carrier having a porous structure composed of a zeolite-type compound, impregnated with a metal-containing solution (B); ,
a hydrothermal treatment step of mixing the precursor material (C) obtained by sintering the precursor material (B) with a structure-directing agent and performing hydrothermal treatment;
A method for producing a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil, characterized by comprising: From the FCC by-product cracked oil according to claim 17 , characterized in that 50 to 500% by mass of a nonionic surfactant is added to the precursor material (A) before the firing step. A method for producing a catalyst structure for producing aromatic compounds. The precursor material (A) is impregnated with the metal-containing solution by adding the metal-containing solution to the precursor material (A) in multiple batches before the firing step. 19. A method for producing a catalyst structure for producing aromatic compounds produced from the FCC by-product cracked oil according to claim 17 or 18 . When the precursor material (A) is impregnated with the metal-containing solution before the firing step, the amount of the metal-containing solution added to the precursor material (A) is 10 to 1000 in terms of the ratio (atomic ratio Si/M) of silicon (Si) constituting the precursor material (A) to the metal element (M) contained in the metal-containing solution added to The method for producing a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to any one of claims 17 to 19 , characterized in that the adjustment is made so that 18. The method for producing a catalyst structure for producing aromatic compounds produced from FCC by-product cracked oil according to claim 17 , wherein the hydrothermal treatment step is performed under a basic atmosphere.

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