WO2006033328A1 - Novel structure containing alminosilicate, method for producing same and use thereof - Google Patents

Abstract

Disclosed is a novel structure containing a crystalline porous alminosilicate which is effective as a solid acid catalyst. Also disclosed are a method for producing such a structure and a use thereof. After having a silica structure impregnated with or support an alkali metal and/or a basic nitrogen-containing compound, the surface portion of the silica structure is made to support an aluminum source and the resulting is subjected to crystallization. Consequently, there can be obtained a novel structure wherein a crystalline porous alminosilicate exists in the surface portion, especially in the surface portion from the outermost surface of the structure to the depth of 1-1000 μm and an inorganic carrier exists in the inner portion other than the surface portion.

Description

 Specification

 Novel structure containing aluminosilicate, its production method and its use

 [0001] The present invention relates to a novel structure including aluminosilicate, a method for producing the same, and a use thereof. More specifically, the present invention relates to a structure including a crystalline porous aluminosilicate in a surface layer portion of a structure and an aluminosilicate in which an inorganic support is present in an inner layer excluding the surface layer portion of the structure, a manufacturing method thereof, and a use thereof. .

 Background art

 [0002] A crystalline porous aluminosilicate is a kind of zeolite, and its composition is generally represented by the following formula (1).

[0003] [Chemical 1]

 (Where η is the valence of the cation 、, X is a number in the range of 0.8-2, y is a number greater than 2, and z is a number greater than 0.)

 Its basic structure is represented by SiO with four oxygen atoms at the top centered on silicon.

 The tetrahedron structure is shown by AIO with aluminum instead of silicon.

 The tetrahedrons are regular three-dimensional bonds that share oxygen with each other such that the atomic ratio of oxygen Z (silicon + aluminum) is 2.

[0004] As a result, a three-dimensional skeleton structure having pores of different sizes and shapes is formed by the difference in the bonding method of the tetrahedron.

[0005] Crystalline porous aluminosilicate is known to have solid acidity. The tetrahedron centered on aluminum is negatively charged, and is electrically neutralized by binding to cations such as protons, alkali metals, and alkaline earth metals. Crystalline porous aluminosilicate is used as a solid acid catalyst because it shows Bronsted acidity especially when combined with proton. That is, it is used as a catalyst for catalytic cracking, hydrocracking, aliphatic or aromatic isomerization, olefin or paraffin aromatization and disproportionation. [0006] A crystalline porous aluminosilicate is obtained by hydrothermal synthesis of an aqueous slurry prepared using a silicon source, an aluminum source, an alkali metal component, and a structure-directing agent such as nitrogen-containing or phosphorus-containing compound. It is done. In the conventional manufacturing method, the obtained crystalline porous aluminosilicate is a powder. When a structure containing aluminosilicate is produced, the crystalline porous aluminosilicate alone has poor moldability. It is necessary to add an inorganic binder to the resulting powder to produce a structure containing aluminosilicate.

 [0007] As a method for producing a structure containing an aluminosilicate using zeolite as a binder, for example, a first crystal of zeolite is first produced, and this crystal powder is mixed and molded with silica gel or zole. There is a method in which the added silica gel or sol is zeoliteized (for example, see Patent Document 1).

 [0008] As a method for producing a crystalline porous aluminosilicate structure containing no binder, for example, a silica structure is used as a silicon source, and an aluminate, an alkali metal component, and a tetraalkylammonium component are formed in a silica structure. A method for producing a crystalline aluminosilicate having a ZSM-5 type structure can be mentioned by carrying it on a body and bringing it into contact with saturated water vapor (for example, see Patent Document 2).

 In these methods, aluminum atoms are present in the entire structure, and as a result, acid sites are also present in the entire structure.

 [0010] As a method for causing zeolite to be present in the surface layer portion of the catalyst structure, for example, the surface layer portion of a particulate solid catalyst such as a metal catalyst, an alloy catalyst, an inorganic oxide catalyst, etc. has a molecular sieving action and is substantially inactive. There is a catalyst in which the entire surface is coated with a zeolite film (for example, see Patent Document 3). In this case, the zeolite layer on the surface of the structure is an inactive silicalite having no acid sites.

 Patent Document 1: JP 2001-504084 (Page 10)

 Patent Document 2: Japanese Patent No. 3442348 (Page 3)

 Patent Document 3: Japanese Patent Application Laid-Open No. 2003-62466 (page 3)

 Disclosure of the invention

 Problems to be solved by the invention

[0011] However, the crystalline porous aluminosilicate of Patent Document 1 and Patent Document 2 is Since active sites such as acid sites are present in the entire structure or inside the structure, the reaction raw materials and reaction products in the solid acid catalytic reaction enter the structure through the pores. Therefore, the residence time in the structure of the reaction raw materials and reaction products becomes longer, the excess reaction proceeds at the active site, etc., the selectivity of the target product decreases, and the high boiling point such as coke becomes active in the catalyst. It precipitates on the spots and pores, resulting in poisoning of the active sites and blockage of the pores, resulting in a decrease in catalyst activity and a further decrease in catalyst life.

 [0012] In the method of Patent Document 3, since the entire surface is coated with a substantially inert zeolite membrane having a molecular sieving action on the active point of the catalyst, the reaction raw material and the reaction product in the reaction The object needs to enter the structure through the zeolite pores. Also in this case, the residence time in the structure of the reaction raw material and the reaction product becomes longer, the selectivity of the target product is lowered, high boiling substances such as coke are deposited, poisoning of active sites and pore clogging. As a result, problems such as a decrease in catalyst activity and a decrease in catalyst life occur.

 [0013] In order to solve these problems, a structure in which the reaction product immediately leaves from an acid site, that is, a site having an active site, is required.

 [0014] The present invention has been made in view of the above problems, and its purpose is to provide a crystalline porous aluminosilicate in the surface layer of a structure effective as a solid acid catalyst, and an inorganic support in the structure. It is providing the structure to manufacture, its manufacturing method, and its use.

 Means for solving the problem

[0015] As a result of intensive studies to solve the above problems, the present inventors have found a novel structure containing an aluminosilicate, and have completed the present invention. That is, the gist of the present invention resides in the following (1) to (12).

[0016] (1) A structure characterized in that a crystalline porous aluminosilicate is present in a surface layer portion of the structure, and an inorganic support is present in an inner layer excluding the surface layer portion of the structure.

[0017] (2) The structure according to (1) above, wherein the inorganic support is a crystalline porous silicate.

 [0018] (3) Both crystalline porous aluminosilicate and crystalline porous silicate are M

The structure according to (1) or (2) above, which has an FI-type crystal structure.

[0019] (4) Crystalline porous aluminosilicate from the outer surface of the structure 1 ~: LOOO m deep The structure according to any one of the above (1) to (3), wherein the structure is present in a surface layer portion.

 [0020] (5) The structure according to any one of (1) to (4) above, wherein the structure is spherical.

 [0021] (6) The aluminum Z silicon ratio (atomic ratio) of the crystalline porous aluminosilicate is 0.0001.

The structure according to any one of (1) to (5) above, wherein

[0022] (7) The structure according to any one of (1) to (6) above, wherein the size is 0.9 to LOmm.

 [0023] (8) The structure according to any one of (1) to (7) above, which does not contain a binder.

 [0024] (9) After impregnating or supporting an alkali metal and Z or a basic nitrogen-containing compound on a silica structure, an aluminum source is supported on the surface layer portion of the silica structure, and a crystallization treatment is performed. The method for producing a structure according to any one of the above (1) to (8), wherein:

 [0025] (10) The method for producing a structure as described in (9) above, wherein the aluminum source is supported on the surface layer portion from the outer surface of the silica structure to a depth of 1 to: LOOO μm.

 [0026] (11) A catalyst for aromatization reaction, wherein zinc and Z or gallium are supported on the structure according to any one of (1) to (8) above.

 [0027] (12) A method for producing an aromatic hydrocarbon, characterized in that olefins are aromatized using the catalyst according to (11).

 The invention's effect

[0028] The structure of the present invention has a short residence time in the structure of the reaction raw material and the reaction product because the crystalline porous aluminosilicate effective as a solid acid catalyst is present in the surface layer of the structure. Since the selectivity of the product is high and poisoning of the active sites and clogging of the pores are difficult to occur, the catalyst activity is difficult to decrease, and the catalyst life is long. In particular, it is assumed that crystalline porous aluminosilicate is present in the structure surface layer portion of the present invention, and zinc and Z or gallium are supported on the structure in which the inorganic support is present in the inner layer excluding the structure surface layer portion. The catalyst for aromatization reaction characterized by the presence of crystalline porous aluminosilicate effective as a solid acid catalyst in the surface layer of the structure, Residence time in the catalyst is shortened. Therefore, the accumulation of coke-like substances is reduced, and a high catalytic activity can be maintained for a long time.

 Brief Description of Drawings

 [0029] [Fig. 1] A cross-sectional view of a spherical structure of the present invention.

 FIG. 2 is a cross-sectional view of a cylindrical structure of the present invention

 FIG. 3 is a sectional view of a hollow cylindrical structure according to the present invention.

 FIG. 4 is a cross-sectional view of the plate-like structure of the present invention

 [FIG. 5] Results of aluminum line analysis of the silica structure of Example 1

 [Fig. 6] Results of powder X-ray diffraction measurement of the structure of Example 1

 [FIG. 7] Results of aluminum surface analysis of the structure of Example 1

 [FIG. 8] Results of aluminum line analysis of the structure of Example 1

FIG. 9 shows the result of solid state NMR measurement of ²⁷ A1 of the structure of Example 1.

 FIG. 10 shows the result of line analysis of aluminum in the silica structure of Example 2.

 FIG. 11: Results of powder X-ray diffraction measurement of the structure of Example 2

 [FIG. 12] Results of aluminum surface analysis of the structure of Example 2

 [FIG. 13] Results of aluminum line analysis of the structure of Example 2

 [FIG. 14] Results of aluminum line analysis of the silica structure of Comparative Example 1

 FIG. 15: Results of powder X-ray diffraction measurement of the structure of Comparative Example 1

 [FIG. 16] Results of aluminum line analysis of the structure of Comparative Example 1

 FIG. 17 shows the results of an aluminum line analysis of the silica structure of Example 4.

 FIG. 18: Results of aluminum line analysis of the structure of Example 4

 Explanation of symbols

[0030] 1 Crystalline porous aluminosilicate

 2 Crystalline porous silicate

 BEST MODE FOR CARRYING OUT THE INVENTION

[0031] The present invention is described in detail below.

[0032] The present invention provides a structure in which a crystalline porous aluminosilicate is present in the structure surface layer portion, and an inorganic support is present in an internal layer excluding the structure surface layer portion, a method for producing the structure, and use thereof It is about.

 [0033] The novel structure containing the aluminosilicate of the present invention has a structure in which a crystalline porous aluminosilicate is present in the surface layer portion of the structure and an inorganic support is present in an inner layer excluding the surface layer portion of the structure. It is characterized by having.

 [0034] Here, the structure in the present invention refers to an object formed to resist a load such as its own weight or external force.

 [0035] The crystalline porous aluminosilicate of the present invention is a kind of zeolite and a zeolite-like substance, and the structure thereof is not particularly limited. The structure code defined by the International Society of Zeolite, for example, ABW, AFG, ANA, * BEA, BIK, BOG, BRE, CAN, CAS, CFI, CHA, DAC, DDR, EAB, EDI, EMT, EPI, ERI, ESV, EUO, FAU, FER, FRA, GIS, GME, GOO, HEU, IFR, ITE ゝ JBW, KFI, LAU, LEV, LIO, LOS, LTA, LTL, LTN, MAZ, MEI, MEL, MER, MFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAT, NES ゝ NON, OFF ゝ -PAR, PAU, PHI, RHO, RTS ゝ SFE, SFF ゝ SFG, SOD, SST, ST F, STI, STT, TER, THO, TON, TSC, UFI, VET, Examples include VFI, -WEN, YUG. Zeolite and zeolite analogues that are effective as solid acid catalysts, and also because of the high yield of aromatic hydrocarbons in the aromatization of olefins described below, ANA, * BEA, CAS ゝ CFI, DDR, EMT, EUO, FAU, FER, ITE, LE V, LTA, MAZ, MEI, MEL, MFI, MFS, MOR, MOS, MTF, MTN, MTT, MTW, MWW, NES ゝ NON, OFF ゝ SFE, SFFゝ SFG, SSY, STF, STT, TO N, VFI, etc., more preferably MFI.

 [0036] The inorganic support of the present invention is not particularly limited, and examples thereof include crystalline porous silicate, silica, zirconium, titanium, magnesia, silicon nitride, activated carbon, and clay mineral. Of these, the surface stability of the structure stability Crystalline porous silicate is preferably used.

[0037] Here, the crystalline porous silicate preferably used for the inorganic support is a kind of zeolite and zeolite-like substance, and its basic structure is centered on silicon and four oxygen atoms arranged at the apex. Tetrahedral structural force shown by SiO 3D with regularity It is combined with. As a result, a three-dimensional skeletal structure having pores of different sizes and shapes is formed by the difference in the tetrahedral bonding method. In addition, it is known that crystalline porous silicate does not have solid acidity.

 [0038] The crystalline porous silicate preferably used for the inorganic support of the present invention is not particularly limited, and the structure is a structure code defined by the International Zeolite Society, for example, AST, water BEA, CAS CFI , CON, DDR, DOH, EUO, FAU, FER, GON, IF R, ISV, ITE, ITH, ITW, FER, GON, IFR, ISV, ITE, ITH, ITW, LEV, MA Z, MEI, MEL, MEP , MFI, MFS, MOS, MTF, MTN, MTT, MTW, MWW, NES ゝ NON, OFF ゝ RTE, RTH, RUT, SFE, SFF ゝ SFG, SGT, SSY, STF, STT, TON, VET, VFI, YUG Etc. Since the structure of the present invention is easy to synthesize and the force is further stable, the structure is preferably * BEA, CAS, CFI, DDR, EUO, FAU, FER, ITE, LEV, MAZ, MEI, MEL, MFI, MFS, MOS, MTF, MTN, MTT, MTW, MWW, NES ゝ NON, OFF ゝ SFE, SFF ゝ SFG, S SY, STF, STT, TON, VFI, etc., more preferably MFI Can be mentioned.

 [0039] In the structure of the present invention, the thickness of the layer where the crystalline porous aluminosilicate is present in the surface layer of the structure is preferably 1 to: LOOO / zm, more preferably 1 to 500 μm from the outer surface of the structure. m.

 [0040] In the structure of the present invention, the aluminum Z silicon ratio (atomic ratio) of the crystalline porous aluminosilicate in the surface layer of the structure is preferable because a structure with high crystallinity can be obtained. Or from 0.0001 to 1, more preferably from 0.0005 to 0.5.

 [0041] In the structure of the present invention, the inorganic support in the inner layer excluding the structure surface layer part substantially does not contain aluminum.

 [0042] The shape of the structure of the present invention is not particularly limited. For example, a spherical shape, an elliptical shape, a cylindrical shape, a hollow cylindrical shape, a plate shape, a sheet shape, and a honeycomb shape as shown in Figs. Etc. Among these, the ability to have sufficient reaction activity and the ability to suppress side reactions and coking is preferably spherical, elliptical, cylindrical, hollow cylindrical, and more preferably spherical.

[0043] The size of the structure of the present invention is not particularly limited. Since there is reaction activity and side reactions and coking can be suppressed, structures in the range of 0.1 to LOOmm, more preferably in the range of 0.9 to 10 mm are preferable.

 [0044] In the structure of the present invention, the presence or absence of noinda is not particularly limited, but it can maintain the aromatization reaction activity of the below-described polyolefin, and can further suppress side reactions and coking. Do not include, is preferred!

[0045] The structure of the present invention may be produced by any method. For example, (1) Structure definition of alkali metal and / or basic nitrogen-containing compound, and if necessary, nitrogen-containing or phosphorus-containing compound After impregnating or supporting the agent on the silica structure, the aluminum source is supported on the surface layer of the silica structure, and if necessary, the silica structure is impregnated or supported with a structure-directing agent such as nitrogen-containing compound or phosphorus-containing compound again. And then, a method of crystallization treatment by contact with water vapor or water vapor containing a structure-directing agent such as nitrogen-containing compound or phosphorus-containing compound as necessary. Add to a silica alumina sol containing a structure-directing agent such as nitrogen or phosphorus-containing compound, and crystallize by hydrothermal treatment. (3) Alkali metal on the inorganic support surface layer, optionally containing nitrogen Alternatively, a silica-alumina sol containing a structure-directing agent such as a phosphorus-containing compound is applied, and contacted with water vapor or steam containing a structure-directing agent such as nitrogen-containing or phosphorus-containing compound as necessary for crystallization. It can manufacture by manufacturing methods, such as the method of processing. The method (1) is preferably used because the aluminum source supported on the surface layer of the structure is difficult to diffuse inside.

[0046] In the present invention, the method (1) will be described in more detail. The structure of the silica structure is defined such as alkali metal and Z or basic nitrogen-containing compound, and if necessary, nitrogen-containing or phosphorus-containing compound. After impregnating or supporting the agent, the aluminum source is supported on the surface layer of the silica structure, and after drying, a structure-directing agent such as nitrogen-containing or phosphorus-containing compound is impregnated or supported on the silica structure as necessary. After crystallizing by contact with water vapor or water vapor containing a structure-directing agent such as nitrogen-containing or phosphorus-containing compound as necessary, crystalline porous aluminosilicate exists in the surface layer of the structure. Thus, a structure comprising an inorganic support in the inner layer excluding the surface layer of the structure is obtained. In addition, if necessary, Baking and ion exchange may be performed.

[0047] The silicon source used in the method of the present invention is not particularly limited. For example, a silica structure can be used, and commercially available silica beads can be used. The silica structure body, since it is possible to obtain a high degree of crystallinity structure, preferably a surface area forces ~ 1000 m ² Zg, more preferably used are those of 10 to 500 m ² Zg.

 [0048] The shape of the silica structure is not particularly limited, and for example, a spherical shape, an elliptical shape, a cylindrical shape, a hollow cylindrical shape, a plate shape, a sheet shape, a honeycomb shape, or the like is used. Since there is sufficient reaction activity and side reactions and coking can be suppressed, a spherical shape, an elliptical shape, a cylindrical shape, a hollow cylindrical shape, and more preferably a spherical shape are used.

 [0049] The particle size of the silica structure is not particularly limited. For example, it is preferably in the range of 0.1 to LOOmm, more preferably in the range of 0.9 to LOmm. Things are used.

 [0050] The aluminum source used in the method of the present invention is not particularly limited. For example, aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum carbonate; lithium aluminate, aluminum Aluminates such as sodium oxide, potassium aluminate, rubidium aluminate, cesium aluminate; aluminum alkoxides such as aluminum methoxide, aluminum methoxide, aluminum propoxide, and aluminum butoxide are used. Preferably, aluminum nitrate is used, more preferably aluminum nitrate, because the aluminum source supported on the surface layer of the structure is difficult to diffuse inside.

 [0051] The alkali metal used in the method of the present invention is not particularly limited, and examples thereof include water such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Acids; lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate

Carbonates such as cesium carbonate; acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate; lithium chloride, sodium chloride sodium, potassium salt potassium, rubidium chloride, sodium chloride cesium, etc. Salts such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate are used. When using alkali metal components other than hydroxide, before loading the aluminum source on the silica structure It is preferable to carry out baking to make an acid oxide.

The basic nitrogen-containing compound used in the present invention is not particularly limited, and examples thereof include ammonia, methenoreamine, ethenoreamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, n-Hexylamine, diaminoethane, diaminopropane, diaminobutane, diaminopeptane, diaminohexane, dimethylamine, jetylamine, di-n-propylamine, di-n-butylamine, di-n pentylamine, di-n-hexylamine, diphenylamine , Trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butynoleamine, tri-n-pentylamine, tri-n-hexylamine, triphenylamine, dimethylethylamine Dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, dimethyl-n-pentylamine, dimethyl-n-hexylamine, dimethylphenylamine, jetylmethylamine, di-n-propylmethylamine, diisopropylmethylamine, di -N-Butylmethylamine, diisoptylmethylamine, di-n-pentylmethylamine, di-n-hexylmethylamine, diphenylmethylamine, aziridin, azetidine, pyrrolidine, 1 Methylpyrrolidine, 1-ethylpyrrolidine, l-n-propylpyrrolidine, 1-isopropylpyrrolidine, l-n-butylpyrrolidine, 1-isobutylpyrrolidine, l-n-pentylpyrrolidine, l-n-hexylpyrrolidine, 1- Ferropyrrolidine, piperidine, 1-methylpiperine 1-ethylpiperidine, l-n-propylpiperidine, 1-isopropylpiperidine, 1n-butylpiperidine, 1-isobutylpiperidine, l-n-pentylpiperidine, l-n-hexylpiperidine, 1-phenylpiperidine , 1-methylolylpyrrole, 1-chinololepyrrole, 1 n propinolepyrrole, 1 isopropylpyrrole, l-n-butylpyrrole, 1 isobutylpyrrole, l-n-pentylpyrrole, l-n-hexyl To pyrrole, 1-phenol pyrrole, pyridine, 1 methyl pyridine, 1 ethyl pyridine, l-n-propyl pyridine, 1 isopropyl pyridine, 1 n-butyl pyridine, 1 isobutyl pyridine, l-n-pentyl pyridine, 1 n- Organic amine compounds such as xylpyridine and 1-vinylpyridine; tetramethylamine - © beam, tetraethylammonium ammonium - © beam, tetra n- propyl ammonium - © beam, Tetoraiso propyl ammonium - © beam, tetra n- Buchiruanmo - © beam, tetraisobutyl ammonium - © , Tetra-n-pentyl ammonium, tetra-n-hexyl ammonium, tetra-phenyl ammonium, trimethyl ether ammonium, trimethyl n-propyl ammonium, trimethylisopropyl ammonium , Trimethyl n-butylammonium, trimethylisobutylammonium, trimethyl-n-pentylammonium, trimethyl-n-hexylammonium, trimethylphenol-ammonium, dimethyljetylammonium- N-propyl ammonium, dimethyldiisopropyl ammonium, dimethyl n-butyl ammonium, dimethyldiisobutyl ammonium, dimethyl n-pentyl ammonium, dimethyl n- Hexylammonum, dimethyldiphenol, dimethylamine, methyltriethylamine, methyl N-propyl ammonium, methyl triisopropyl ammonium, methyl tri-n-butyl ammonium, methyl triisobutyl ammonium, methyl tree n-pentyl ammonium, methyl tree n xyl ammonium Methyl trimethyl ammonium, hydroxymethyl trimethyl ammonium, 2 hydroxyethyl trimethyl ammonium, 3 hydroxy n-propyl trimethyl ammonium, 4-hydroxy n n-butyl trimethyl ammonium Nitrate of ammonium salts such as 5-hydroxyl-n-pentyltrimethylammonium, 6-hydroxyl-n-hexyltrimethylammonium, 3-hydroxyphenyltrimethylammonium Salts such as sulfates, acetates, hydroxides and halides are used. Ammonium salt hydroxide is preferably used because the aluminum source supported on the surface layer of the structure is difficult to diffuse inside.

The structure directing agent used in the present invention is not particularly limited, and examples thereof include nitrogen-containing compounds or phosphorus-containing compounds. More specific nitrogen-containing compounds or phosphorus-containing compounds include: For example, methenoreamine, ethenoreamine, n-propylamine, isopropylamine, n-butyramine, isobutylamine, n-pentylamine, n xylamine, diaminoethane, diaminopropane, diaminobutane, diaminopeptane, diaminohexane, dimethylamine, jetylamine, G _n - Puropiruamin, di -n- Buchiruamin, di -n- pentyl Ruamin, Kishiruamin to di one n-, Jifueniruamin, Torimechiruamin, Toryechiruami down, tri one n- Puropiruamin, triisopropyl § Min, tree n- Buchinoreamin, Tri-n-pentyl Min, tree n Kishiruamin, triphenyl § Min, dimethyl E chill § Min, Dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, dimethyl-n-pentylamine, dimethyl-n-hexylamine, dimethylphenylamine, jetylmethylamine, di-n-propylmethylamine, diisopropylmethylamine, Di-n-butylmethylamine, diisobutylmethylamine, di-n-pentylmethylamine, di-n-hexylmethylamine, diphenylmethylamine, aziridine, azetidine, pyrrolidine, 1-methylpyrrolidine, 1- Ethylpyrrolidine, 1-n-propylpyrrolidine, 1-isopropylpyrrolidine, 1-n-butylpyrrolidine, 1-isobutylpyrrolidine, 1-n-pentylpyrrolidine, 1-n-hexylpyrrolidine, 1-phenylpyrrolidine, Piperidine, 1-methyl pipette Jin, -1-E chill piperidine, 1-n-Puropirupi Bae lysine, 1-isopropyl piperidine, 1 _n - Buchirubiperijin, 1 isobutyl bi Peri gin, 1 n-pentyl piperidine, cyclohexyl piperidine 1-n-to, 1-full Enylpiperidine, 1-n-pentylolepyrrole, 1-methinorepyrrolone, 1-ethinorepyrrolone, 1 n propinolepyrrole, 1 isopropylpyrrole, 1-n-butylpyrrole, 1 isobutylpyrrole, 1-n-pentinorepyrrole, 1-n— Hexylpyrrole, 1-phenylpyrrole, pyridine, 1-methylpyridin, 1 ethylpyridine, 1-n-propylpyridine, 1 isopropylpyridine, 1-n-butylpyridine, 1 isobutylpyridine, 1-n-pentylpyridine, 1 — N-hexyl pyridine, 1-phenylpyridine and other organic amine compounds; tetra Chiruanmo - © beam, Te tiger ethyl Honoré ammonium - © beam, tetra _n - propyl ammonium - © beam, tetraisopropyl ammonium Yuumu, tetra n- Buchiruanmo - © beam, tetraisobutyl ammonium - © beam, tetra n- Penchiruanmo - © , Tetra n-hexyl ammonium, tetraphenyl ammonium, trimethyl ether ammonium, trimethyl n-propyl ammonium, trimethyl isopropyl ammonium, trimethyl n-butyl ammonium , Trimethylisobutylammonium, trimethyl-n-pentylammonium, trimethyl-n-hexylammonium, trimethylphenol-ammonium, dimethyljetylammonium, dimethyldi-n-propylammonium Dimethyldiisopropyl ammonium, dimethylbenzene n-butyl ammonium, dimethyl Diisobutyl ammonium, dimethyldiol n-pentyl ammonium, dimethyldiol n-hexyl ammonium, dimethyldiphenyl ammonium, methyltriethyl ammonium, methyltri-n-propyl ammonium , Methyltri Isopropyl ammonium, methyl tri-n-butyl ammonium, methyl triisobutyl ammonium, methyl tri-n-pentyl ammonium, methyl tri-n-hexyl ammonium, methyl tri-fluoromethane , Hydroxymethyl trimethyl ammonium, 2-hydroxyethyl trimethyl ammonium, 3-hydroxy 1 n propyl trimethyl ammonium, 4-hydroxy 1 n-butyl trimethyl ammonium, 5-hydroxy 1 Ammonium salts such as n-pentyltrimethylammonium, 6-hydroxyl-n-hexyltrimethylammonium, 3-hydroxyphenyltrimethylammonium, nitrates, sulfates, acetic acid salts, hydroxides, salts such as Harogeni匕物; tetramethyl phosphonium - © beam, tetraethyl Hosuhoniumu, tetra _n - propyl phosphonyl © , Tetraisopropyl phosphonium, tetrar n-butyl phosphonium, tetraisobutyl phosphonium, tetra n-pentylphosphonium, tetra-n-xinolephosphonium, tetraphenylphosphonium, trimethinoletinol phosphonium, Trimethyl-n-propyl phosphor, trimethyl-isopropyl phosphor, trimethyl-n-butyl phosphor, trimethyl-isobutyl phosphor, trimethyl-n-pentyl phosphor, trimethyl-n-xyl phosphor, trimethylenol Ninolephosphonium, Dimethinolegetinolephosphonium, Dimethinoresin n Propinolefos Phosphorus, Dimethyldiisopropyl Phosphorum, Dimethyldi n-butylphosphonium, Dimethyldiisobutylphosphonium, Dimethyldi n-pentylphos -Um, dimethyl n-hexylphosphome, dimethyldiphenylphosphome, methyltriethrephosphonium, methyltri-npropynolephosphonium, methyltriisopropinorephospho-mume, methyltri-n-butylphosphome, Methyl triisobutyl phosphor, methyl tri-n-pentyl phosphor, methyl tri-n-hexyl phosphor, methyl tri-phenol phosphor, hydroxymethyl trimethyl phosphate, 2-hydroxy Etyl trimethyl phosphor, 3-hydroxy-1-n-propyl trimethyl phosphor, 4-hydroxy n-butyl trimethyl phosphor, 5-hydroxy n-pentyl trimethyl phosphor, 6-hydroxy n-xyl trimethyl Norephosphonium, 3-hydroxyphenol-trimethylphosphonium Phosphonium salts such as nitrates, sulfates, acetates, hydroxides, halides, etc. are used. Among these structure-directing agents, a structure having a high degree of crystallinity can be obtained. Therefore, organic amine compounds and ammonium salts are preferable. Is used.

 In the present invention, the order of impregnation or loading of the aluminum source, the alkali component, the basic nitrogen-containing compound, and the structure directing agent on the silica structure as the silicon source is not particularly limited. Since the aluminum source supported on the surface layer of the structure is difficult to diffuse inside, the order of the alkali metal and Z or basic nitrogen-containing compound, structure directing agent, aluminum source or alkali metal and Z or A basic nitrogen-containing compound, an aluminum source, and a structure directing agent are preferred in this order. The alkali metal may be supported after the aluminum source is supported.

 [0055] In the present invention, the method for supporting an alkali metal and Z or a basic nitrogen-containing compound on a silica structure as a silicon source is not particularly limited, but a substance is applied to a silica carrier or the like. A conventionally known method for supporting, for example, an impregnation method, a deposition method, an ion exchange method or the like is used. If necessary, drying and baking may be performed. The amount of alkali metal and Z or basic nitrogen-containing compound supported on the silica structure, which is the silicon source, is not limited, but a structure with high crystallinity can be obtained. Metal and Z or basic nitrogen-containing compounds Z silicon ratio (atomic ratio) of 0.00015 to 1.5 is preferable In addition to the above effects, an aluminum source supported on the surface layer of the structure is included. It is difficult to diffuse to the surface, more preferably in the range of 0.000075-0.75.

 In the present invention, the method for supporting the structure directing agent on the silica structure as the silicon source is not particularly limited, but a conventionally known method for supporting a substance on a silica support or the like, for example, For example, an impregnation method, a deposition method, an ion exchange method, or the like is used. The amount of impregnation or loading of the structure-directing agent is preferably in the range of ο to ι.0 in terms of the structure-directing agent Z silicon ratio (molar ratio).

In the present invention, the method for supporting the aluminum source on the silica structure as the silicon source is not particularly limited. For example, the aluminum source is dissolved in a solvent and heated. There is a method in which the silica carrier impregnated or supported with the alkali metal and Z or basic nitrogen-containing compound described above is added instantaneously and heated and stirred. As the solvent, any solvent can be used as long as the aluminum source is dissolved. For example, alcohols such as water, methanol and ethanol can be used. The amount of the solvent is not particularly limited. For example, since the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside, it is preferable that the amount of the silica structure that is a silicon source is fine. More than the pore volume, more preferably silica The amount is 1 to 5 times the pore volume of the silica structure as the source. The heating temperature of the solution in which the aluminum source is dissolved is not particularly limited, but is preferably 30 to: LOO ° because, for example, the aluminum source held on the surface layer of the structure is difficult to diffuse inside. C, more preferably 50 to 95 ° C. The heating and stirring temperature is not particularly limited, but is preferably 30 to 100 ° C., more preferably 50 to 95, for example, because the aluminum source supported on the surface layer portion of the structure is difficult to diffuse inside. ° C. The heating and stirring time is not particularly limited, but is preferably 1 minute to 10 hours, more preferably 5 minutes to 5 hours, because, for example, the aluminum source supported on the surface layer of the structure is difficult to diffuse inside. Between. The ratio of the alkali metal and Z or basic nitrogen-containing compound supported on the silica structure, which is the silicon source, and the aluminum source is not particularly limited. For example, aluminum supported on the surface layer of the structure Since it is possible to obtain a structure with a high degree of crystallinity that is difficult for the source to diffuse into the interior, it is preferable that the alkali metal and Z or basic nitrogen-containing compound have a ratio of the aluminum source (element ratio) of 1 to 100. More preferably, it is 3 to 50. After loading, the solvent is removed by operations such as decantation, filtration, heating or heating under reduced pressure. Thereafter, drying and baking may be performed. Further, if necessary, the structure-directing agent may be impregnated again into the structure and dried.

 In the method of the present invention, it is preferable that the aluminum source is supported on the silica structure as the silicon source at a position of 1 to 1000 μm from the outer surface of the silica structure. It is preferably carried at a position of 0 μm.

 [0059] In the method of the present invention, the aluminum Z silicon ratio (atomic ratio) of the crystalline porous aluminosilicate in the surface layer of the structure is preferable because a structure with a high degree of crystallinity can be obtained. Or from 0.0001 to 1, more preferably from 0.0005 to 0.5.

[0060] In the present invention, the method for crystallizing the structure is not particularly limited. For example, the structure is preferably crystallized by contacting with water vapor. The temperature of the water vapor is not particularly limited, but if a crystalline porous aluminosilicate is produced, a structure with a high degree of crystallinity can be obtained. Therefore, it is preferably 80 to 260 ° C, more preferably Is in the range of 100-230 ° C. The contact time with water vapor is not particularly limited, but a structure with a high degree of crystallinity can be obtained. Preferably, it is in the range of 2 hours to 80 days.

 [0061] The method of contacting with saturated water vapor and the apparatus therefor are not particularly limited as long as the structure is produced. For example, silica in which an aluminum source and an alkali metal are supported in the air of a pressure vessel is used. It can be manufactured by installing the structure, adding water to the bottom of the container, sealing it, and then heating it in a thermostat. The amount of water to be added is not particularly limited, but since a structure having a high degree of crystallinity can be obtained, the amount of water is 0.1 lwt% or more with respect to the weight of the silicon force structure as a silicon source. preferable.

 [0062] The structure obtained in the present invention may be washed with water, dried, and calcined or ion-exchanged if necessary.

 [0063] The use of the structure of the present invention is not particularly limited, but is preferably used as a catalyst carrier or a catalyst of a system that reacts with a solid acid catalyst.

 [0064] Examples of supported elements when the structure of the present invention is also used as a catalyst support include periodic group 1 elements such as lithium, sodium, potassium, rubidium, and cesium; beryllium, magnesium, Periodic table group 2 elements such as calcium, strontium, and norm; Periodic table group 3 elements such as scandium, yttrium, lanthanoids, and actinoids; Group 4 elements of the periodic table such as titanium and zirconium-um; Vanadium, niobium, and tantalum Periodic table of Group 5 elements such as Chromium, Molybdenum, Tungsten, etc. Group 6 element of Periodic Tables such as Manganese, Rhenium, etc. Group 8 elements of Periodic Table such as Iron, Ruthenium, Os-um, Cobalt Periodic Table Group 9 elements such as nickel, palladium and platinum; Group 11 Elements of Periodic Table such as copper, silver and gold; Periodic Table Group 12 elements such as boron, aluminum, gallium, indium and thallium; Group 13 Elements Periodic table such as germanium, tin and lead; Periodic Table 15 groups such as antimony and bismuth Element; One or more elements such as group 16 elements of periodic table such as sulfur and tellurium are included.

[0065] Further, as a reaction system using the structure of the present invention as a catalyst for reacting with a solid acid catalyst, for example, catalytic cracking reaction of light oil and heavy oil; hydrocracking of heavy oil Reaction: Catalytic reforming of heavy fractions of petroleum naphtha such as cyclohexane dehydrogenation, cyclopentene isomerism dehydrogenation, paraffin cyclization dehydration, norafine isomerization, norafine hydrocracking, etc. ; Butane, pentane, hexane, butene, pentene, hexene, xylene, etc. Isomerization reaction of alkanes and alkenes; aromatization reaction of methane, ethane, propane, butane, pentane, hexane, ethylene, propylene, butene, pentene, hexene, etc .; benzene, alkylbenzene, naphthalene, phenol, thiophene, Alkylation reaction of pyridine, etc. with aromatics such as ethylene, propylene, butene, pentene, hexene, methanol, ethanol, propanol, butanol, ethyl chloride, propyl chloride, butyl chloride and other olefins and alcohol halogenated alkyls; toluene, Ethylbenzene, propylbenzene, butylbenzene, xylene, jetylbenzene, dipropylbenzene, dibutylbenzene, trimethylbenzene, triethylbenzene, tripropylbenzene, tributylbenzene, etc. Alkyl aromatic isomerization, disproportionation, transalkylation, de al Kill reaction, ethylene, propylene, butene, pentene, Orefin polymerization reaction such as cyclohexene and the like to. Among these systems, it is preferable to use as a catalyst for aromatization reaction.

 [0066] When the structure of the present invention is used as a catalyst for aromatization reaction, it is characterized in that it supports zinc and Z or gallium.

 [0067] In this case, the amount of zinc and Z or gallium supported on the structure is not particularly limited, but is preferably 0.01 to 30% by weight, more preferably based on the total weight of the structure. 1 to 25% by weight. The state of supporting zinc or gallium supported on the structure is not particularly limited, and for example, it is supported in the state of oxide, nitrate, chloride or the like. Zinc or gallium used in the aromatic reaction catalyst of the present invention can be used alone or in combination. In particular, it is easy to obtain raw materials and the structure can be easily prepared. Is preferably used.

 [0068] The method for preparing the aromatization reaction catalyst of the present invention is not particularly limited, and any method may be used as long as the aromatization reaction applied catalyst of the present invention can be prepared. Although a preferable aspect is shown below as a preparation method of the catalyst for aromatization reaction of this invention, this invention is not limited to this.

[0069] In the method for preparing an aromatization reaction catalyst of the present invention, for example, a crystalline porous aluminosilicate is present in advance in a structure surface layer portion, and an inorganic support is present in an internal layer excluding the structure surface layer portion. Prepare the aforementioned structure that exists and add zinc and Z or gallium to this structure And a method of preparing it by supporting.

 [0070] The composition of the crystalline porous aluminosilicate is generally represented by the following formula (1).

[0071] [Chemical 2]

 (Where η is the valence of the cation 、, X is a number in the range of 0.8-2, y is a number greater than 2, and z is a number greater than 0.)

 On the other hand, the structure prepared by the above method has crystalline porous aluminosilicate in the surface layer portion of the structure. The composition of the crystalline porous aluminosilicate is represented by the following formula (2), and the cation is a sodium ion (hereinafter, a structure having a composition in which the cation becomes a sodium ion is referred to as a sodium type).

[0072] [Chemical 3]

 aNa 0-A1 O -bSiO -cH O (2)

 2 2 3 2 2

 (Here, a is a number in the range of 0.8 to 2, b is a number of 2 or more, and c is a number of 0 or more.) The aromatic reaction catalyst used in the present invention has high catalytic activity. The cation in the formula (1) is preferably a hydrogen ion, that is, a proton (hereinafter, a structure having a composition in which the cation becomes a hydrogen ion is referred to as a proton type). The method for converting the sodium type to the proton type is not particularly limited, and examples include a method in which a sodium type structure is ion-exchanged with ammonium chloride and then calcined in air. . Here, the ion exchange in the salt / ammonium can be carried out in accordance with a conventional method. In the case of firing, there is oxygen or oxygen diluted with an inert gas such as nitrogen, helium or argon. Or, it should be performed at 100 to 1,000 ° C in an air atmosphere.

[0073] By the above method, the structure of the aromatization reaction catalyst used in the present invention is obtained.

. The catalyst for aromatization reaction of the present invention is prepared by supporting zinc and Z or gallium on the above structure. Here, although it does not specifically limit as zinc, For example, salts, such as zinc metal, zinc oxide, zinc hydroxide, zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate, zinc oxalate; And organic zinc compounds such as zinc. Of these, salts are preferably used because they are easy to support and the yield of aromatic hydrocarbons is high in the aromatization of olefins, and more preferably, nitrate. Lead is used. Further, the gallium is not particularly limited, but examples thereof include salts such as gallium chloride, gallium bromide, gallium nitrate, and gallium oxide; or organic gallium compounds such as acetylacetonate gallium and gallium ethoxide. Can be mentioned. Of these, salts are preferably used, and gallium nitrate is more preferably used because it is easy to support and has a high yield of aromatic hydrocarbons in the aromatization of olefin.

 [0074] Usable support methods, such as impregnation support method, ion exchange method and coprecipitation method, which are not particularly limited in the method of supporting zinc and Z or gallium on the structure, can be used, preferably impregnation support. The law is good. When preparing an aromatization reaction catalyst by the impregnation support method, for example, impregnating the above-mentioned solution containing zinc or gallium into the structure, drying and further firing treatment! ヽ For aromatization reaction A method for preparing the catalyst is mentioned.

 [0075] After the loading, the solvent is removed by an operation such as decantation, filtration, heating or heating under reduced pressure according to a conventional method in an impregnation method or an ion exchange method. Drying after removal of the solvent can be carried out using dry heat or reduced pressure. When firing, oxygen, oxygen diluted with an inert gas such as nitrogen, helium, or argon, or air may be performed at 100 to 1,000 ° C. Here, the order in which zinc and Z or gallium are supported on the structure is not particularly limited, and may be supported on the proton type structure or on the amorphous structure. Then, it may be prepared by subsequent baking treatment.

[0076] In the present invention, for example, a metal other than zinc and gallium may be further supported on the reaction catalyst for aromatization as long as it does not interfere with the aromatization of olefin. Periodic Table Group 1 elements such as lithium, sodium, potassium, rubidium and cesium; Periodic Table Group 2 elements such as beryllium, magnesium, calcium, strontium and norium; Periodic Tables such as scandium, yttrium, lanthanoids and actinoids Group 3 elements; Periodic table of titanium, zirconium, etc. Group 4 elements; Periodic table of vanadium, niobium, tantalum, etc. Group 5 elements; Periodic table of chromium, molybdenum, tungsten, etc. Group 6 elements; Manganese, rhenium, etc. Periodic Table Group 7 elements; Periodic Table Group 8 elements such as iron, ruthenium, and osmium; Periodic Table 9 Group elements such as cobalt, rhodium, and iridium; Kell, palladium, periodic table Group 10 element such as platinum; copper, silver, periodic table group 11 elements such as gold, zinc, periodic table group 12 elements such as cadmium, boron, Al Periodic table group 13 elements such as minium, gallium, indium and thallium; periodic table group 14 elements such as germanium, tin and lead; periodic table group 15 elements such as antimony and bismuth; periodic table group 16 elements such as sulfur and tellurium These metals are mentioned.

 [0077] Aromatics in which zinc and Z or gallium are supported on a structure in which crystalline porous aluminosilicate is present in the surface layer portion of the structure of the present invention, and an inorganic support is present in an inner layer excluding the surface layer portion of the structure The catalyst for the oxidization reaction is also used in a method for producing an aromatic hydrocarbon by aromatizing olefin.

 [0078] The olefin is not particularly limited as long as the compound contains a double bond, and examples thereof include ethylene, propylene, butene, pentene, hexene, heptene, otaten, nonene, and decene. Can be mentioned.

 [0079] In the present invention, in addition to the above olefin, paraffins such as ethane, propane, butane, pentane, hexane, heptane, octane and nonane; and Z or cyclopentane, cyclopentene, methylcyclopentane, cyclohexane A naphthene such as xylene, methylcyclopentene, cyclohexene, cycloheptene, cyclootaten, cyclohexagen, etc. may be mixed. These paraffins and naphthenes can be used as a raw material for aromatization, but the rate of aromatization is slower than olefin, so the amount of paraffins and naphthenes mixed is preferably 50% by weight based on the total weight. Less than, more preferably less than 30% by weight. These olefins can be used alone or in combination of two or more. As the mixture, each of the above-mentioned mixtures, or the C fraction of a thermal decomposition product such as naphtha, butadiene was removed from the C fraction.

 4 4

 Distillate (S (hereinafter abbreviated as “Svent”) C4 or raffinate 1), fraction obtained by removing butadiene and i-butene from the above C fraction (referred to as SS-C4 or raffinate 2)

Four

 C fractions of pyrolysis products such as naphtha, fractions excluding the C fractions

 5 5

 And the like (S—C5), pyrolysis gasoline, raffinate obtained by BTX extraction from pyrolysis gasoline, FCC cracked gas, FCC cracked gasoline, and rough rice obtained by extracting BTX from reformate.

[0080] The reaction mode in the production of aromatic hydrocarbons by aromatization of olefins of the present invention is not particularly limited, and can be performed in any reaction mode. For example, fixed bed gas flow It can be carried out by a continuous type, a fixed bed liquid phase flow type, or a suspension bed batch type. Of these, the fixed bed liquid phase flow system is preferred because aromatic hydrocarbons can be obtained efficiently and the aromatization reaction can be carried out under mild conditions. The reaction temperature is not particularly limited, but is preferably 300 to 700 ° C, more preferably 400 to 600 ° C, because it can be efficiently converted into an aromatic hydrocarbon. The reaction pressure is not particularly limited, but is usually preferably 0.01 to 50 MPa in absolute pressure, and more preferably 0.05 to 30 MPa. The liquid hourly space velocity during the fixed-bed liquid-phase flow reactor (LHSV), since it can efficiently convert the aromatic hydrocarbons, preferably 0. 01~: LOOhr ^_1, more preferably 0.5 5 it is a 20hr ^{_ 1.} Here, the liquid hourly space velocity (LHSV) represents the total volume of olefin, norafine and naphthene supplied per unit time (hr) per unit catalyst volume.

 [0081] The olefin raw material may be used as it is or diluted with an inert gas.

 The inert gas is not particularly limited, and examples thereof include nitrogen, helium, and argon. These inert gases are not only used alone but also used in combination of two or more. Is also possible.

 Here, examples of the generated aromatic hydrocarbon include benzene, toluene, xylene, styrene, cumene, propylbenzene, trimethylbenzene, indene, naphthalene, diisopropylbenzene, biphenyl and the like. These aromatic hydrocarbons are separated by known separation methods and used as petrochemical, pharmaceutical and agricultural chemical raw materials. In addition, the ability to produce olefins, norafines and naphthenes having 1 to 12 carbon atoms as unreacted raw materials and as side-reactive products. You can also use it as a part.

 [0083] Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.

 [0084] Measurement methods used in the following examples are shown.

 [0085] (Confirmation of crystal state of structure)

The crystal state of the obtained structure was measured at a voltage of 40 kV and a current of 200 mA using a powder X-ray diffraction measurement device (XRD) (manufactured by Mac Science, trade name: M18XHF). [0086] (Measurement of aluminum depth distribution and silicon Z aluminum ratio) PolyZBed (R) 812 (manufactured by Polysciences, Inc.), Nadic Methyl Anhydride (Polysciences, Inc. ), Dodecenylsuccinic Anhydride (Polysciences, Inc.), 2, 4, 6Tris (dimethylaminomethyl) phenol (Polysciences, Inc.) Using the X-ray microanalyzer (EPMA) (trade name EP M-810, manufactured by Shimadzu Corporation), the obtained sample was subjected to line analysis and surface analysis in the depth direction of the particle cross section at a voltage of 20 kV and a current of ΙΟηΑ. The carrying ratio was calculated from the specific force.

 [0087] (Confirmation of aluminum in zeolite framework structure)

^{27 As} measured by A1 solid-state NMR (trade name GSX-270, manufactured by JEOL Ltd.), the chemical shift attributed to 4-coordinated aluminum in the zeolite framework structure (σ) = a peak measured in the range of 50 to 70 ppm. This was confirmed by a peak measured in the range of chemical shift (σ) = 0 to: LOppm attributed to off-lattice hexacoordinated aluminum deviating from the skeletal structure.

 [0088] (Measurement of aluminum content)

 The amount of aluminum was calculated by quantitative analysis with an inductively coupled plasma optical emission spectrometer (ICP) (Kyoto Koken, trade name ICP—AES UOP-1 markll).

 [0089] (Measurement of coke production)

 After completion of the reaction, about 10 mg of the catalyst was placed on a thermobalance (SEIKO SSCZ5200), and the temperature was raised to 800 ° C in 10 ° CZ minutes under an air atmosphere. The reduced weight from 300 ° C to 700 ° C with respect to the catalyst weight at 700 ° C was taken as the amount of coke produced.

 Example 1

[0090] 20 wt% tetra-n-propyl ammonium hydroxide aqueous solution 12.2 g (tetra-n-propyl pyramonium hydroxide Z silicon = 0.07 (molar ratio)) to 0.3 g of sodium hydroxide (sodium Z silicon ratio) = 0.04 (atomic ratio)) was added and dissolved. Silica beads (“Carrier Tart Q-50” manufactured by Fuji Silysia Chemical Ltd., particle shape: spherical, particle diameter: 1.7 to 4. Omm, surface area: 80 m ² Zg, average pore diameter 50 nm) llg is added to this aqueous solution. The silica beads were impregnated with an aqueous solution.

[0091] Next, aluminum nitrate 9 hydrate 0.4 g (sodium Z aluminum = 6.7 (atomic ratio ;)) Was dissolved in 12 ml of water and heated to 75 ° C., and then the silica beads impregnated with sodium hydroxide and tetrapropyl ammonium hydroxide were added and stirred for 30 minutes. After stirring, it was dried under reduced pressure, and dried under a nitrogen atmosphere at 80 ° C for 5 hours.

[0092] FIG. 5 shows the result of aluminum line analysis of the obtained spherical silica structure. The supported aluminum was found to be present within 230 μm from the outer surface of the silica beads.

 [0093] Put 0.5 g of water in a Teflon (registered trademark) pressure vessel, and raise a Teflon (registered trademark) dish so that it does not touch the water. Ammonium hydroxide and silica beads carrying an aluminum source were added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 8 hours for crystallization treatment.

[0094] After that, after washing with distilled water, drying was performed overnight at 110 ° C, followed by firing in air at 540 ° C.

[0095] As a result of powder X-ray diffraction measurement of the obtained structure (Fig. 6), it was found to be MFI structure.

 Also, from the results of aluminum surface analysis and line analysis (Figs. 7 and 8), aluminum is present within 230 m from the outer surface of the obtained structure. The aluminum Z-silicon ratio (atomic ratio) of the surface layer of the structure was 0. 020, about 250 m from the outer surface of the structure, and aluminum was below the detection limit from the center.

[0096] As a result of solid state NMR measurement of ²⁷ A1 (FIG. 9), only a peak in the chemical shift (σ) range of 50 to 70 ppm was confirmed, and it was found that aluminum was present in the zeolite framework structure. .

 [0097] From this, there is a crystalline porous aluminosilicate with an MFI structure with a thickness of 230 μm in the surface layer of the structure, and the inner layer excluding the structure surface layer has a crystalline porous structure with an MFI structure. It was found to be a spherical structure with a particle size of 1.7 to 4. Omm.

 Example 2

[0098] 20 wt% tetra-n-propyl ammonium hydroxide aqueous solution 12.2 g (tetra-n-propyl pyramonium hydroxide Z silicon = 0.07 (molar ratio)) to sodium hydroxide 0.5 g (sodium Z silicon ratio) = 0.07 (atomic ratio)) was added and dissolved. Silica beads ("Carrier Tart Q-50" manufactured by Fuji Silysia Chemical Ltd., particle shape: spherical, particle size: 1.7 to 4. Omm, surface area: 80 m ² Zg, average pore size 50 nm) 1 lg was added, and silica beads were impregnated with an aqueous solution.

 [0099] Next, 0.4 g of aluminum nitrate nonahydrate (sodium Z aluminum = 11.7 (atomic ratio)) was dissolved in 12 ml of water, heated to 75 ° C, sodium hydroxide, tetra Silica beads impregnated with propyl ammonium hydroxide were added and stirred for 30 minutes. After stirring, the supernatant was removed, dried under reduced pressure, and then dried under a nitrogen atmosphere at 80 ° C for 5 hours. Figure 10 shows the results of aluminum line analysis of the resulting silicic force structure. It was found that the supported aluminum was present within 20 m from the outer surface of the silica beads.

 [0100] Put 0.5g of water in a Teflon (registered trademark) pressure vessel, wake up a Teflon (registered trademark) dish so that it does not touch the water, and then add sodium hydroxide, tetra-n-propyl. Ammonium hydroxide and silica beads carrying an aluminum source were added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C. for 8 hours for crystallization treatment.

 [0101] Then, after washing with distilled water, drying at 110 ° C overnight, and firing at 540 ° C in air.

 [0102] As a result of the powder X-ray diffraction measurement of the obtained structure (Fig. 11), it was found to be an MFI structure. In addition, from the results of aluminum surface analysis and line analysis (Figs. 12 and 13), aluminum was present within 20 m from the outer surface of the obtained structure, and as a result of component analysis of local parts by EPMA. The aluminum Z silicon ratio (atomic ratio) in the surface layer of the structure was 0.0016, and the aluminum was below the detection limit near 200 m from the outer surface of the structure and near the center.

[0103] As a result of solid-state NMR measurement of ²⁷ A1, only a peak in the chemical shift (σ) range of 50 to 70 ppm was confirmed, and it was remarkable that aluminum was present in the zeolite framework structure.

 [0104] From this, there is a crystalline porous aluminosilicate with an MFI structure with a thickness of 20 μm on the surface of the structure, and the inner layer excluding the surface of the structure has a crystalline porous structure with an MFI structure. It was found to be a spherical structure with a particle size of 1.7 to 4. Omm, which is an inorganic support of silicate.

 Comparative Example 1

[0105] Aluminum nitrate 9 hydrate 0.4 g (sodium Z aluminum = 6.7 (atomic ratio)) dissolved in 12 ml of water was dissolved in silica beads ("Carrier Tart Q-" manufactured by Fuji Silysia Chemical Ltd.) 50 ”, particle shape: spherical, particle diameter: 1.7 to 4. Omm, surface area: 80 m ² Zg, average pore diameter 50 nm) Add llg, impregnate silica beads with aqueous solution, and stir for 2 hours , Evaporated to dryness and dried at 110 ° C.

 [0106] Next, 12.2 g of tetra-n-propylammonium hydroxide (tetra-n-propylammonium hydroxide / silicon = 0.07 (molar ratio)), 0.3 g of sodium hydroxide (sodium Z) Silica beads carrying an aluminum source were added to an aqueous solution in which a silicon ratio = 0.04 (atomic ratio)) was dissolved, and the mixture was stirred for 2 hours and then evaporated to dryness. It was dried for 5 hours in a nitrogen atmosphere at 80 ° C. FIG. 14 shows the results of aluminum line analysis of the obtained silica structure. The supported aluminum was uniformly supported on the silica beads.

 [0107] Put 0.5 g of water in a Teflon (registered trademark) pressure vessel, wake up a Teflon (registered trademark) dish so that it does not come in contact with water, and hydrate sodium hydroxide, tetrapropyl ammonium hydro Silica beads llg carrying oxide and aluminum sources were added, the pressure vessel was sealed, and the pressure vessel was heated at 180 ° C for 8 hours for crystallization treatment.

 [0108] Then, after washing with distilled water, drying at 110 ° C overnight, and firing at 540 ° C.

 [0109] As a result of the powder X-ray diffraction measurement of the obtained structure (FIG. 15), it was found to be an MFI structure. Also, aluminum was present in the entire structure from the results of line analysis (Fig. 16). Example 3

 [0110] The structure obtained in Example 1 was immersed in a 20-fold weight ImolZL salt / ammonium aqueous solution and allowed to stand at 80 ° C for 1.5 hours. The structure was then filtered off and removed from the salt water solution. After repeating this operation three more times, the resulting structure was washed with water and dried overnight at 120 ° C. to obtain an amorphous structure.

 [0111] Zinc nitrate hexahydrate 4. A solution of 4 g dissolved in llg of water is sprinkled on 10 g of dried ammonium structure, and then water is evaporated at 50 ° C in vacuum to impregnate and support zinc nitrate. It was. The structure supporting zinc nitrate was fired in an electric furnace at 500 ° C. for 5 hours in an air stream to obtain 9.0% by weight of zinc and a proton type structure.

[0112] 10 ml of the structure was filled into a reaction tube, the temperature was set to 530 ° C, the internal pressure was set to 0.5 MPa—G, and 1-butene was supplied at LHSV = 2.7 h ^_1 to aromatize the reaction. Carried out. The results are shown in Table 1. The amount of coke produced was as low as 1.1%. Comparative Example 2

 [0113] Sodium type ZSM-5 was prepared according to Japanese Examined Patent Publication No. 46-10064. 76 g of 30 wt% silica sol (trade name, colloidal silica N, manufactured by Nissan Chemical Industries, Ltd.) was mixed with 108 g of 2.2 mol / l tetra-n-propyl ammonium hydroxide aqueous solution. Next, 3.2 g of sodium aluminate was dissolved in 54 ml of water, and this aqueous solution and the solution were put in a SUS autoclave. The mixture was heated at 150 ° C. with stirring for 6 days. After cooling, the produced slurry was filtered off and washed with 100 ml of distilled water, and this washing operation was repeated 5 times. Next, after drying at 110 ° C. and baking at 540 ° C. in the air, white sodium-type ZSM 5 was obtained. As a result of powder X-ray diffraction measurement, it was found to have MFI type, that is, ZSM-5 type structure. The obtained ZSM-5 had an aluminum Z silicon ratio (atomic ratio) of 0.051.

 [0114] Sodium-type ZSM-5 was stirred in 20-fold weight ImolZL of ammonium chloride aqueous solution and left at 80 ° C for 1.5 hours. The structure was then filtered off and removed from the salt water solution. After repeating this operation three more times, the obtained ZSM-5 was washed with water and dried at 120 ° C. to obtain an amorphous ZSM-5 powder. Mix 2.0g of the powder, 4.4g of zinc nitrate hexahydrate, and 27.3g of 30wt% silica sol (manufactured by Nissan Chemical Co., Ltd., trade name Colloidal Sil N), and then evaporate water at 80 ° C. The white viscous material was extruded using a syringe. The compact is pulverized and sieved to a columnar size of about 3 mm, dried at 120 ° C, and baked in an electric furnace at 500 ° C for 5 hours in an air stream. % Of ZSM-5 supported in a proton form.

 [0115] As a result of aluminum line analysis, aluminum was uniformly dispersed inside the structure. Thus, the resulting structure was a crystalline aluminum silicate uniformly dispersed inside the structure.

[0116] Charge 10 ml of the ZSM-5 into the reaction tube, set the temperature to 530 ° C, set the internal pressure to 0.5 MPa-G, and supply ¹ -butene at LHSV = 2.7 h ^_1 for aromatization The reaction was carried out. The results are shown in Table 1. The amount of coke produced was 27.1%, and the butene turnover rate decreased rapidly.

[0117] [Table 1] Example 3 Comparative Example 2

 Elapsed time 2. O h r 3. O h r 1. O h r 2. O h r 3. O h r

1-butene conversion (%) 92. 9 93. 3 91. Ξ 86. 3 46. 9 24. 4 Selectivity (%)

Hydrogen 0. 3 0. 8 0. 8 0. 9 1. 2 0. 5 Soot gas ¹ > 68. 1 74. 0 68. 3 70. 7 81. 5 89. 0 Benzene 1. 5 1. 1. 4 2. 8 0. 6 0. 2 Tolenene 14. 1 10. 5 12. 8 12. 0 5. 3 2. 0 Xylene 11. 9 9. 9 12. 3 11. 4 8. 9 5. 8 Other fragrances Family 4. 1 3. 6 4. 4 2. 2 2. 5 2. 5

 o

 B TX yield (%) 25. 5 20. 1 24. 2 22. 5 7. 0 1. 9 Coke production (%) 1. 1 27. 1

 1) Aliphatic hydrocarbon having 15 carbon atoms Example 4

[0118] Silica beads ("Carrier Tart Q-40C" manufactured by Fuji Silysia Chemical Co., Ltd., particle shape: spherical, particle diameter: 1. 7 4. Omm, surface area: 73m ² / g, average pore diameter 40nm) Silica beads were impregnated with 21.0 g of a tetra-n-propyl ammonium hydroxide aqueous solution of IN (tetra-n-propyl ammonium hydroxide Z silicon = 0.10 (molar ratio)) under reduced pressure. After stirring for 10 minutes, the solvent was evaporated under reduced pressure at 70 ° C. for 3 hours.

 [0119] Next, 1.3 g of aluminum nitrate nonahydrate (tetrapropyl ammonium hydroxide / aluminum = 6 (atomic ratio)) was dissolved in 10 ml of ethanol, heated to 50 ° C, and then tetrapropyl. The silica beads impregnated with ammonium hydroxide were added and stirred for 20 minutes. After stirring, it was dried under reduced pressure and calcined in air at 540 ° C for 5 hours.

 [0120] Fig. 17 shows the results of aluminum line analysis of the obtained silica structure. It was found that the supported aluminum was present within the outer surface force of silica beads of 400 μm.

 [0121] Next, 12.2 g of the silica beads carrying aluminum previously obtained was added to 14.2 g of 1N tetra-n-propylammonium hydroxide aqueous solution (tetra-n-propylammonium hydroxide Z silicon = 0.07 (molar ratio)) was impregnated with 0.3 g of sodium hydroxide sodium salt (sodium Z silicon ratio = 0.04 (atomic ratio)) under reduced pressure and stirred at normal pressure for 20 hours. After stirring, the solvent was evaporated under reduced pressure at 50 ° C for 1 hour, and then dried under a nitrogen atmosphere at 80 ° C for 5 hours.

[0122] Put 0.5g of water into a Teflon (registered trademark) pressure vessel and avoid touching the water. (Registered Trademark) dish, put sodium hydroxide, tetra-n-propyl ammonium hydroxide, silica beads carrying aluminum source on it, seal the pressure vessel, and put the pressure vessel at 180 ° Crystallization was performed by heating at C for 20 hours.

[0123] Thereafter, after washing with distilled water, drying was performed at 110 ° C overnight, followed by firing in air at 540 ° C.

[0124] As a result of powder X-ray diffraction measurement of the obtained structure, the structure was found to have an MFI structure. From the results of the line analysis (Fig. 18), aluminum also has an external surface force of 400 m or less, and as a result of the component analysis of the local part by EPMA, the surface layer of the structure was obtained. The ratio of aluminum to silicon (atomic ratio) was 0.02, and from the center, aluminum was below the detection limit.

[0125] From this, there is a crystalline porous aluminosilicate with an MFI structure with a thickness of 400 μm in the surface layer of the structure, and the inner layer excluding the surface layer of the structure has a crystalline porous structure with an MFI structure. It was found to be a spherical structure with a particle size of 1.7 to 4. Omm, which is an inorganic support for porous silicate.

 Example 5

 [0126] The structure obtained in Example 4 was immersed in a 20-fold weight ImolZL salt / ammonium aqueous solution and allowed to stand at 80 ° C for 1.5 hours. Next, the structure was taken out from the salt water solution. After repeating this operation three more times, the resulting structure was washed with water and dried overnight at 120 ° C. to obtain an amorphous structure.

 [0127] Zinc nitrate hexahydrate Ammonium-type structure obtained by drying an aqueous solution of 3.5 g in 7.7 g of water 8. After impregnation in Og, the water was evaporated at 50 ° C under reduced pressure to remove zinc nitrate. Impregnation was supported. The structure supporting zinc nitrate was fired in an electric furnace at 540 ° C. for 5 hours under air flow to obtain a structure in which 9.0% by weight of zinc was supported and became a proton type.

[0128] The reaction tube was filled with 10 ml of the structure, the temperature was set to 530 ° C, the internal pressure was set to 0.5 MPa—G, and 1-butene was supplied at LHSV = 2.7 h ^_1 to aromatize the reaction. Carried out. The results are shown in Table 2.

[0129] [Table 2] Example 5

 Elapsed time 3. O h r 10 h r 20 h r

 1-butene conversion (%) 99. 3 99. 2 98. 8 Selectivity (%)

 Hydrogen 1. 6 1. 5 1. 5 Light gas 47. 8 47. 0 47.2 Benzene 6. 3 6. 2 6. 1 Tonorene 23. 0 22. 7 22.2 Xylene 13. 2 13. 2 13. 7 Other aromatics 8. 1 9. 4 9. 3

 B T X Yield (%) 42. 2 41. 8 41. 5

 1) Aliphatic hydrocarbons having 1 to 5 carbon atoms Although the present invention has been described in detail and with reference to specific embodiments, various changes and modifications can be made without departing from the spirit and scope of the present invention. It will be apparent to those skilled in the art what can be done.

 [0130] This application is a Japanese patent application filed on September 21, 2004 (Japanese Patent Application No. 2004-273182), a Japanese patent application filed on May 18, 2005 (Japanese Patent Application No. 2005-145711), and August 2005. This is based on the Japanese patent application (Japanese Patent Application 2005-238648) filed in Japan, the contents of which are incorporated herein by reference.

 Industrial applicability

[0131] The structural body of the present invention has a crystalline porous aluminosilicate effective as a solid acid catalyst in the surface layer portion of the structural body, so that the residence time of the reaction raw material and reaction product in the structural body is short. Since the selectivity of the product is high and poisoning of the active sites and clogging of the pores are difficult to occur, the catalyst activity is difficult to decrease, and the catalyst life is long. In particular, it is assumed that crystalline porous aluminosilicate is present in the structure surface layer portion of the present invention, and zinc and Z or gallium are supported on the structure in which the inorganic support is present in the inner layer excluding the structure surface layer portion. The catalyst for aromatization reaction characterized by the fact that the crystalline porous aluminosilicate, which is effective as a solid acid catalyst, is present in the surface layer of the structure, shortens the residence time of the olefin raw material and the reaction product in the catalyst. . Therefore, the accumulation of coke-like substances is reduced and high Long catalytic activity and long-lasting effect! The industrial value of the present invention is remarkable.

Claims

The scope of the claims  [I] A structure characterized in that a crystalline porous aluminosilicate is present in the surface layer of the structure, and an inorganic support is present in an inner layer excluding the surface layer of the structure.  [2] The structure according to claim 1, wherein the inorganic support is a crystalline porous silicate.  [3] The structure according to claim 1 or 2, wherein the difference between the crystalline porous aluminosilicate and the crystalline porous silicate is an MFI type crystal structure. [4] The structure according to any one of [1] to [3], wherein the crystalline porous aluminosilicate is present in a surface layer part from the outer surface of the structure to a depth of 1 to: LOOO μm. [5] The structure according to any one of claims 1 to 4, wherein the structure is spherical. 6. The structure according to any one of claims 1 to 5, wherein the crystalline porous aluminosilicate has an aluminum Z silicon ratio (atomic ratio) of 0.0001 to 1. [7] The structure according to any one of [1] to [6], wherein the size is 0.9 to: LOmm.  [8] The structure according to any one of claims 1 to 7, wherein the structure does not include a noinder. [9] The method is characterized in that an alkali metal and Z or a basic nitrogen-containing compound are impregnated or supported on a silica structure, and then an aluminum source is supported on the surface layer portion of the silica structure and subjected to crystallization treatment. A method for manufacturing a structure according to any one of claims 1 to 8.  10. The method for producing a structure according to claim 9, wherein the aluminum source is supported on the surface layer part from the outer surface of the silica structure to a depth of 1 to L000 μm.  [II] A catalyst for aromatization reaction, wherein zinc and Z or gallium are supported on the structure according to any one of claims 1 to 8.  [12] A process for producing an aromatic hydrocarbon, wherein the olefin is aromatized using the catalyst according to claim 11.