Zeolite catalyst for producing aromatic compound, method for producing aromatic compound, and apparatus for producing aromatic compound

Abstract

A catalyst for synthesizing an aromatic compound from an alcohol, an alkene, and / or an ether, the catalyst containing a zeolite wherein when A is the integral value of the peak intensity in a chemical shift region from 90.0 ppm to 54.0 ppm and B is the integral value of the peak intensity in a chemical shift region from 54.0 ppm to 20.0 ppm in the solid 27Al-NMR spectrum, the ratio A / B is 1.0 or more.

Description

Zeolite catalyst for aromatic compound production, method for producing aromatic compounds, and apparatus for producing aromatic compounds

[0001] The present invention relates to a catalyst containing zeolites for the production of aromatic compounds, and to a method and apparatus for producing aromatic compounds using zeolites.

[0002] Aromatic compounds such as benzene, toluene, and xylene are generally produced by decomposing light naphtha obtained from petroleum refining in a pyrolysis reactor and separating and purifying the aromatic compounds from the resulting pyrolysis products, or by cyclization and dehydrogenation of heavy naphtha obtained from petroleum refining in a catalytic reforming reactor and separating and purifying the aromatic compounds from the resulting reformate. In these production methods, aromatic compounds are produced using petroleum, a fossil resource, as a raw material, and involve reactions under high pressure and high temperature. Therefore, conventionally, the production of aromatic compounds has involved the use of CO2, a greenhouse gas. ２ It was something that could not be manufactured without the discharge of large quantities of waste.

[0003] On the other hand, from the perspective of its impact on the global environment, bioethanol derived from plants and animals has been attracting attention in recent years. Bioethanol is a renewable resource produced by saccharifying and fermenting biomass resources such as waste wood, herbs, rice straw, wheat, corn, sugarcane, sugar beets, rice, and potatoes. Bioethanol is often used as fuel for internal combustion engines as a renewable energy source, but in recent years, with the demand for further improvement in carbon neutrality, its use as an industrial raw material has also been increasing. If a technology can be established to produce aromatic compounds with high selectivity from ethanol that can be supplied as a renewable resource, it will be possible to stably supply aromatic compounds as a resource with a low environmental impact.

[0004] International Publication No. 2008 / 080910

[0005] However, although there are currently known technologies for producing aromatic compounds from alcohols, including ethanol, using zeolites as catalysts (for example, Patent Document 1), none of these technologies have been sufficiently efficient in producing aromatic compounds compared to aliphatic compounds.

[0006] The object of the present invention is to provide a catalyst, a method for producing aromatic compounds, and an apparatus for producing aromatic compounds that can efficiently synthesize aromatic compounds (particularly monocyclic aromatic compounds such as benzene, toluene, and xylene) from alcohols, alkenes, and / or ethers in higher yields.

[0007] The present invention is as follows: [1] A catalyst for synthesizing aromatic compounds from alcohols, alkenes and / or ethers, which is a solid ２７ A catalyst comprising a zeolite such that, in an Al-NMR spectrum, when A is the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm and B is the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm, the ratio A / B is 1.0 or greater. [2] The catalyst according to [1], wherein the molar ratio of silicon to aluminum in the zeolite is 10.0 or greater. [3] The catalyst according to either [1] or [2], wherein the molar ratio of silicon to aluminum in the zeolite is 200.0 or less. [4] The catalyst according to any one of [1] to [3] for synthesizing aromatic compounds from C1-C4 alcohols, C2-C4 alkenes and / or C2-C8 ethers. [5] The catalyst according to any one of [1] to [3] for synthesizing aromatic compounds from ethanol. [6] The catalyst according to any one of [1] to [5] above, wherein the aromatic compound is a monocyclic aromatic compound. [7] The catalyst according to any one of [1] to [6] above, wherein the zeolite is a zeolite having a 10-membered ring pore structure. [8] The catalyst according to any one of [1] to [6] above, wherein the zeolite is a pentasil-type zeolite having a 10-membered ring pore structure. [9] The catalyst according to any one of [1] to [6] above, wherein the zeolite is an MFI-type zeolite.

[10] Solid ２７A method for producing an aromatic compound, comprising a synthesis step of contacting an alcohol, an alkene and / or an ether with a zeolite having a ratio A / B of 1.0 or more, where A is the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm in the Al-NMR spectrum and B is the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm.

[11] The method for producing an aromatic compound according to

[10] , wherein the molar ratio of silicon to aluminum in the zeolite is 10.0 or more.

[12] The method for producing an aromatic compound according to

[10] or

[11] , wherein the molar ratio of silicon to aluminum in the zeolite is 200.0 or less.

[13] The method for producing an aromatic compound according to any one of

[10] to

[12] , wherein the synthesis step involves contacting the zeolite with an alcohol having 1 to 4 carbon atoms, an alkene having 2 to 4 carbon atoms and / or an ether having 2 to 8 carbon atoms to synthesize an aromatic compound.

[14] The method for producing an aromatic compound according to any one of

[10] to

[12] , wherein the synthesis step involves contacting the zeolite with ethanol to synthesize an aromatic compound.

[15] The method for producing an aromatic compound according to any one of

[10] to

[14] , wherein the aromatic compound is a monocyclic aromatic compound.

[16] The method for producing an aromatic compound according to any one of

[10] to

[15] , wherein the zeolite is a zeolite having a 10-membered ring pore structure.

[17] The method for producing an aromatic compound according to any one of

[10] to

[15] , wherein the zeolite is a pentasil-type zeolite having a 10-membered ring pore structure.

[18] A method for producing an aromatic compound according to any one of

[10] to

[15] , wherein the zeolite is an MFI type zeolite.

[19] A method for producing an aromatic compound according to any one of

[10] to

[18] , wherein the contact temperature of the alcohol, alkene and / or ether with respect to the zeolite in the synthesis step is in the range of 350°C to 600°C.

[20] A method for producing an aromatic compound according to any one of

[10] to

[19] , wherein the contact pressure of the alcohol, alkene and / or ether with respect to the zeolite in the synthesis step is in the range of 0.05 MPaG to 4.00 MPaG.

[21] A method for producing an aromatic compound according to any one of

[10] to

[20] above, wherein the synthesis step involves contacting the zeolite with an alcohol, an alkene and / or an ether in a fixed-bed reactor, a fluidized-bed reactor or a moving-bed reactor to synthesize an aromatic compound.

[22] Solid. ２７An aromatic compound manufacturing apparatus comprising a zeolite having a ratio A / B of 1.0 or more, wherein the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm in the Al-NMR spectrum is A, and the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm is B, and the apparatus comprising a synthesis means for synthesizing an aromatic compound by contacting the zeolite with an alcohol, an alkene and / or an ether.

[23] The aromatic compound manufacturing apparatus according to

[22] , wherein the molar ratio of silicon to aluminum in the zeolite is 10.0 or more.

[24] The aromatic compound manufacturing apparatus according to

[22] and

[23] , wherein the molar ratio of silicon to aluminum in the zeolite is 200.0 or less.

[25] The apparatus for producing aromatic compounds according to any one of

[22] to

[24] , wherein the synthesis means synthesizes an aromatic compound by contacting the zeolite with an alcohol having 1 to 4 carbon atoms, an alkene having 2 to 4 carbon atoms and / or an ether having 2 to 8 carbon atoms.

[26] The apparatus for producing aromatic compounds according to any one of

[22] to

[24] , wherein the synthesis means synthesizes an aromatic compound by contacting the zeolite with ethanol.

[27] The apparatus for producing aromatic compounds according to any one of

[22] to

[26] , wherein the aromatic compound is a monocyclic aromatic compound.

[28] The apparatus for producing aromatic compounds according to any one of

[22] to

[27] , wherein the zeolite is a zeolite having a 10-membered ring pore structure.

[29] The apparatus for producing aromatic compounds according to any one of

[22] to

[27] , wherein the zeolite is a pentasil-type zeolite having a 10-membered ring pore structure.

[30] The apparatus for producing aromatic compounds according to any one of

[22] to

[27] above, wherein the zeolite is an MFI type zeolite.

[31] The apparatus for producing aromatic compounds according to any one of

[22] to

[30] above, wherein the contact temperature of the alcohol, alkene and / or ether with respect to the zeolite in the synthesis means is in the range of 350°C to 600°C.

[32] The apparatus for producing aromatic compounds according to any one of

[22] to

[31] above, wherein the contact pressure of the alcohol, alkene and / or ether with respect to the zeolite in the synthesis means is in the range of 0.05 MPaG to 4.00 MPaG.

[33] The apparatus for producing an aromatic compound according to any one of the above

[22] to

[32] , wherein the synthesis means brings the zeolite into contact with an alcohol, an alkene and / or an ether in a fixed-bed reactor, a fluidized-bed reactor or a moving-bed reactor to synthesize an aromatic compound.

[0008] According to the present invention, an aromatic compound (particularly a monocyclic aromatic compound such as benzene, toluene and xylene) can be efficiently synthesized with a higher yield from an alcohol, an alkene and / or an ether.

[0009] FIG. 1 shows an X-ray diffraction (XRD) spectrum of a zeolite produced using pentaerythritol (PET). FIG. 2 shows a solid state of a zeolite produced using pentaerythritol (PET) ２７ Al-NMR chart. FIG. 3 shows an X-ray diffraction spectrum of a zeolite produced using 1,3-propanediol (PDO). FIG. 4 shows a solid state of a zeolite produced using 1,3-propanediol (PDO) ２７ Al-NMR chart. FIG. 5 shows an X-ray diffraction spectrum of a zeolite produced using tert-butanol (TBO). FIG. 6 shows a solid state of a zeolite produced using tert-butanol (TBO) ２７ Al-NMR chart. FIG. 7 shows an X-ray diffraction spectrum of a zeolite produced using 1,3-propanediol (PDO) and hydrofluoric acid (HF). FIG. 8 shows a solid state of a zeolite produced using 1,3-propanediol (PDO) and hydrofluoric acid (HF) ２７ Al-NMR chart. FIG. 9 shows an X-ray diffraction spectrum of a zeolite produced using tetrapropylammonium hydroxide (TPA) and hydrofluoric acid (HF). FIG. 10 shows a solid state of a zeolite produced using tetrapropylammonium hydroxide (TPA) and hydrofluoric acid (HF) ２７ Al-NMR chart. FIG. 11 shows an X-ray diffraction spectrum of a zeolite produced using ethylene glycol (EGO). FIG. 12 shows a solid state of a zeolite produced using ethylene glycol (EGO) ２７The Al-NMR chart is shown. Figure 13 shows the X-ray diffraction spectrum of the zeolite prepared using 1,4-butanediol (BDO). Figure 14 shows the solid state of the zeolite prepared using 1,4-butanediol (BDO). ２７ The Al-NMR chart is shown. Figure 15 shows the X-ray diffraction spectrum of the zeolite prepared using tetrapropylammonium hydroxide (TPA). Figure 16 shows the solid state of the zeolite prepared using tetrapropylammonium hydroxide (TPA). ２７ The Al-NMR chart is shown.

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0011] The catalyst of this embodiment is a catalyst for synthesizing aromatic compounds from alcohols, alkenes, and / or ethers. The catalyst of this embodiment is a solid ２７ The present invention includes zeolites (hereinafter sometimes referred to as "zeolites in this embodiment") in which, in an Al-NMR (nuclear magnetic resonance) spectrum, the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm is A, and the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm is B, the ratio A / B is 1.0 or greater.

[0012] The method for producing aromatic compounds according to this embodiment includes a synthesis step of synthesizing aromatic compounds by contacting the catalyst or zeolite according to this embodiment with an alcohol, an alkene, and / or an ether. The apparatus for producing aromatic compounds according to this embodiment has the catalyst or zeolite according to this embodiment and includes synthesis means for synthesizing aromatic compounds by contacting the catalyst or zeolite with an alcohol, an alkene, and / or an ether.

[0013] By using the catalyst of this embodiment, the method for producing aromatic compounds of this embodiment, or the apparatus for producing aromatic compounds of this embodiment, aromatic compounds (particularly monocyclic aromatic compounds such as benzene, toluene, and xylene) can be efficiently synthesized from alcohols, alkenes, and / or ethers in higher yields.

[0014] The catalyst of this embodiment is a solid ２７ In the Al-NMR spectrum, if A is the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm, and B is the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm, then the zeolite contains such a ratio A / B is 1.0 or greater.

[0015] Zeolite refers to a crystalline aluminosilicate composed of an anionic skeleton and a cationic metal, having a three-dimensional network structure with pores (channels) and cavities.

[0016] solid zeolite ２７ In Al-NMR measurements, the peaks on the spectrum exhibit different chemical shift positions depending on the chemical structure around the aluminum atom. When multiple peaks with different chemical shifts are located close together, they overlap and are detected, resulting in peaks that reflect the distribution of the molecular structure (see, for example, Toshiyuki Yokoi, Hiroshi Mochizuki, Seitaro Namba, Junko N. Kondo, and Takashi Tatsumi, J. Phys. Chem. C, vol 119, No. 27, 15303 (2015)).

[0017] The present inventors investigated zeolite catalysts for producing aromatic compounds from alcohols, alkenes, and / or ethers, and found that using alcohols or the like as raw materials for producing the zeolite catalyst improves the selectivity of monocyclic aromatic compounds such as benzene, toluene, and xylene (BTX) contained in the resulting aromatic compound. The estimated mechanism will be described in detail below, using a 10-membered ring zeolite catalyst as an example, although this is not intended to be a limitation.

[0018] Ten-membered ring zeolites, such as MFI-type zeolites, have a three-dimensional pore structure in which straight channels and zigzag channels intersect within the ten-membered ring. The diameter of the ten-membered ring pores is approximately 5.5 Å, but the intersections of the pores are large spaces of about 10 Å.

[0019] And, using molecules that tend to be present in intersections, Al ３＋ Although the countercation should be able to exist uniformly within the pores, the intersection is occupied by the molecule in question, so as a result, the Al atoms can be selectively located in straight channels or zigzag channels, rather than in the intersection.

[0020] Conventional zeolites are known to have an A / B ratio of less than 1.0 (especially around 0.8) because aluminum atoms within the zeolite framework are largely distributed in the intersections. On the other hand, the present inventors have found that by adding alcohols and / or fluoride-containing compounds to the general raw materials used in zeolite production during the zeolite manufacturing stage, aluminum within the zeolite framework is selectively distributed in the straight channels and / or zigzag channels, making it possible to produce zeolites with an A / B ratio of 1.0 or higher, such as the zeolite in this embodiment.

[0021] When reactions proceed through intersections, sequential reactions occur in a broad reaction field, potentially leading to the formation of bulkier aromatic compounds. On the other hand, when reactions proceed through straight or zigzag channels, the pores within the 10-membered ring are of a suitable size for the shape-selective formation of monocyclic aromatic compounds such as BTX. This suppresses side reactions and improves the selectivity of monocyclic aromatic compounds. In 10-membered ring zeolite catalysts, acid sites are selectively located in the straight and zigzag channels of the 10-membered ring, which is thought to improve the yield of monocyclic aromatic compounds. Thus, while aluminum in zeolites is known to be involved in the synthesis of monocyclic aromatic compounds, it is estimated that in zeolites with an A / B ratio of 1.0 or higher, the proportion of aluminum present near the narrower spaces of the pore structure that can serve as reaction fields is higher compared to conventional zeolites. This may have enabled the synthesis of aromatic compounds in higher yields.

[0022] From the viewpoint of further improving the production efficiency and selectivity of aromatic compounds, the ratio A / B is preferably 1.10 or higher, 1.20 or higher, 1.30 or higher, 1.40 or higher, 1.50 or higher, and 1.60 or higher. Furthermore, the upper limit of the ratio A / B is not particularly limited, but could be, for example, 5.00 or lower, 4.50 or lower, 4.00 or lower, 3.50 or lower, 3.00 or lower, 2.50 or lower, 2.30 or lower, or 2.00 or lower.

[0023] The zeolite included in the catalyst of this embodiment is, for example, a zeolite having an 8-membered ring pore structure such as AEI type zeolite, ANA type zeolite, CHA type zeolite, ERI type zeolite, GIS type zeolite, KFI type zeolite, LTA type zeolite, NAT type zeolite, PAU type zeolite, YUG type zeolite, DDR type zeolite; AEL type zeolite, EUO type zeolite, FER type zeolite, HEU type zeolite, MEU type zeolite, MEL type zeolite, MFI type zeolite, NES type zeolite, TON type zeolite, WEI type zeolite. Examples include zeolites having a 10-membered ring pore structure, such as MWW-type zeolites; zeolites having a 12-membered ring pore structure, such as AFI-type zeolites, ATO-type zeolites, BEA-type zeolites, CON-type zeolites, FAU-type zeolites, GME-type zeolites, LTL-type zeolites, MOR-type zeolites, MSE-type zeolites, MTW-type zeolites, OFF-type zeolites, and YFI-type zeolites; and zeolites having a 14-membered ring pore structure, such as CLO-type zeolites, VFI-type zeolites, AET-type zeolites, CFI-type zeolites, and DON-type zeolites. Here, a zeolite indicated by a three-letter structural code means a zeolite belonging to that structural code, and is characterized by having at least one XRD peak in its XRD (X-ray diffraction) pattern that allows for structural identification as a zeolite belonging to that structural code. The structural code is defined by the Structure Committee of the International Zeolite Association.

[0024] The zeolite contained in the catalyst of this embodiment is preferably a zeolite having a 10-membered ring pore structure, and more preferably a pentasil-type zeolite having a 10-membered ring pore structure, from the viewpoint of further improving the efficiency of aromatic compound production. A pentasil-type zeolite is a zeolite having a structure in which 5-membered oxygen rings are linked. The zeolite contained in the catalyst of this embodiment is particularly preferably MFI-type zeolite, FER-type zeolite, or MEL-type zeolite, and most preferably MFI-type zeolite. An MFI-type zeolite is a zeolite from which a peak based on the MFI-type zeolite structure is obtained when XRD is measured.

[0025] The molar ratio of silicon to aluminum (silicon / aluminum) in the zeolite contained in the catalyst of this embodiment is preferably 5.0 or higher, more preferably 6.0 or higher, even more preferably 8.0 or higher, even more preferably 10.0 or higher, and particularly preferably 20.0 or higher, from the viewpoint of further improving the efficiency of aromatic compound production. The molar ratio (silicon / aluminum) is preferably 200.0 or lower, more preferably 100.0 or lower, even more preferably 70.0 or lower, even more preferably 50.0 or lower, and particularly preferably 30.0 or lower, from the viewpoint of further improving the efficiency of aromatic compound production. ２ ) and aluminum is aluminum oxide (Al ２ O ３ ) as molar ratio SiO ２ : Al ２ O ３ When converted to this ratio, it is preferably 10.0:1 to 400.0:1, more preferably 12.0:1 to 200.0:1, even more preferably 16.0:1 to 140.0:1, and particularly preferably 20.0:1 to 100.0:1. The molar ratio of aluminum to silicon can be calculated, for example, from measurement results such as ICP-AES (inductively coupled plasma emission spectroscopy).

[0026] The zeolite contained in the catalyst of this embodiment may have metals supported on it, such as Group 3 elements like lanthanum and europium; Group 7 elements like manganese and rhenium; Group 8 elements like iron and ruthenium; Group 9 elements like cobalt, rhodium, and iridium; Group 10 elements like nickel, palladium, and platinum; Group 11 elements like copper, silver, and gold; Group 12 elements like zinc and cadmium; and Group 13 elements (but from the 4th period onward) like gallium and indium. The form of metal support is not particularly limited, and examples include a form in which the metal is supported as a metal ion by ion exchange at acid sites present on the surface and / or within the pore structure of the zeolite, a form in which the metal is supported as a metal oxide on the surface and / or within the pore structure of the zeolite, or both of these forms, but the form in which the metal is supported as a metal ion is preferred.

[0027] The zeolite contained in the catalyst of this embodiment may be a single type or a mixture of two or more types. In addition to the zeolite having an A / B ratio of 1.0 or higher, the catalyst of this embodiment may also contain zeolites other than the said zeolite.

[0028] The BET specific surface area of ​​the zeolite contained in the catalyst of this embodiment is not particularly limited, but is 100 m². ２ / g to 800m ２ It is preferable that it be / g, and 150m ２ / g ~ 600m ２ It is more preferable that it be / g, 200m ２ / g to 500m ２ It is even more preferable that the value is / g. The BET specific surface area can be measured by a BET multipoint method based on nitrogen adsorption measurement using nitrogen as the adsorbent gas, in accordance with JIS Z 8830:2013.

[0029] The outer surface area of ​​the zeolite contained in the catalyst of this embodiment is not particularly limited, but is 5 m². ２ / g to 150m ２ It is preferable that it be / g, 10m ２ / g to 120m ２ It is more preferable that it be / g, 15m ２ / g to 100m ２It is even more preferable that it be / g, 15m ２ / g ~ 60m ２ It is even more preferable that the value is / g. The external surface area can be calculated by the t-plot method based on nitrogen adsorption measurement.

[0030] The micropore volume of the zeolite contained in the catalyst of this embodiment is not particularly limited, but is preferably 0.01 mL / g to 1 mL / g, more preferably 0.05 mL / g to 0.7 mL / g, and even more preferably 0.1 mL / g to 0.5 mL / g. The micropore volume can be calculated by the t-plot method based on nitrogen adsorption measurement in accordance with JIS Z 8831:2010.

[0031] The acid content of the zeolite contained in the catalyst of this embodiment is preferably 0.1 mmol / g to 2.5 mmol / g, preferably 0.3 mmol / g to 2 mmol / g, and more preferably 0.5 mmol / g to 1.5 mmol / g. The acid content is, for example, NH ３ - In a TPD apparatus, the material is dried in a helium atmosphere at 500°C for 1 hour, then cooled to 100°C, and ammonia is adsorbed in a 7.5 vol% ammonia / helium mixed atmosphere for 1 hour. Finally, the temperature is increased from 100°C to 700°C at a rate of 10°C / min in a helium atmosphere, and the amount of ammonia desorbed can be determined from this. The amount of acid used here is calculated by performing waveform decomposition using the DFP method, with the obtained peaks treated as a Gaussian distribution, defining the peak around 200°C as desorption from a weak acid and the peak around 400°C as desorption from a strong acid, and then calculating from the remaining amount of desorption after excluding the amount of desorption from the weak acid.

[0032] The catalyst or zeolite of this embodiment is not particularly limited, but can be produced by a method including, for example, a step (A) of hydrothermally reacting a raw material mixture containing water, a silicon source, an aluminum source, and a compound containing alcohols and / or fluoride, and a step (B) of calcining the reaction product obtained in step (A) to obtain zeolite.

[0033] The amount of water used in the raw material mixture in step (A) is preferably 5 to 300 mole equivalents, more preferably 10 to 200 mole equivalents, and even more preferably 15 to 100 mole equivalents, relative to 1 mole equivalent of silicon atoms in the silicon source.

[0034] Examples of silicon sources used in the raw material mixture of process (A) include silica gel, colloidal silica, water glass, sodium silicate, potassium silicate, fumed silica, tetramethyl orthosilicate, tetraethyl orthosilicate, tetramethoxysilane, ethyl silicate, methyl silicate, amorphous silica, etc.

[0035] Examples of aluminum sources used in the raw material mixture of process (A) include aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum hydroxide, aluminum chloride, sodium aluminate, potassium aluminate, aluminum oxide, alumina sol, boehmite, and organoaluminum compounds.

[0036] The ratio of silicon source to aluminum source used in the raw material mixture of step (A) is preferably 5:1 to 200:1, more preferably 6:1 to 100:1, even more preferably 8:1 to 70:1, and particularly preferably 10:1 to 50:1, as the molar ratio of silicon atoms in the silicon source to aluminum atoms in the aluminum source. ２ ): Aluminum oxide (Al ２ O ３ When converted to a molar ratio, it is preferably 10:1 to 400:1, more preferably 12:1 to 200:1, even more preferably 16:1 to 140:1, and particularly preferably 20:1 to 100:1.

[0037] The alcohols used in the raw material mixture in step (A) are organic compounds having a hydroxyl group, such as alcohols whose constituent atoms are hydrogen, carbon, and oxygen. The alcohols used in the raw material mixture in step (A) may be monohydric alcohols, dihydric alcohols, or trihydric or higher alcohols, but dihydric alcohols are preferred from the viewpoint of further improving the production efficiency and production selectivity of aromatic compounds.

[0038] The alcohols used in the raw material mixture in step (A) are preferably monohydric alcohols having a branched chain structure (branched monohydric alcohols), dihydric alcohols or trihydric or higher alcohols having a branched chain structure (branched polyhydric alcohols), or dihydric alcohols or trihydric or higher alcohols not having a branched chain structure (linear polyhydric alcohols). From the viewpoint of further improving the production efficiency and production selectivity of aromatic compounds, linear polyhydric alcohols are more preferable. The alcohols used in the raw material mixture in step (A) are preferably alcohols having 2 to 20 carbon atoms, more preferably alcohols having 2 to 12 carbon atoms, even more preferably alcohols having 2 to 8 carbon atoms, and even more preferably alcohols having 2 to 6 carbon atoms.

[0039] Examples of alcohols used in the raw material mixture of step (A) include branched monohydric alcohols such as tert-butanol (tert-butyl alcohol) and tert-pentanol (tert-pentyl alcohol); branched polyhydric alcohols such as pentaerythritol, glycerol, trimethylolethane, and trimethylolpropane; and linear polyhydric alcohols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, and triethylene glycol. Among these, the alcohols used in the raw material mixture of step (A) are preferably pentaerythritol, 1,3-propanediol, tert-butanol, ethylene glycol, and 1,4-butanediol, and more preferably pentaerythritol, 1,3-propanediol, ethylene glycol, and 1,4-butanediol.

[0040] The amount of alcohols used in the raw material mixture in step (A) is preferably 0.05 to 10 molar equivalents, more preferably 0.1 to 5 molar equivalents, and even more preferably 0.2 to 2 molar equivalents, relative to 1 molar equivalent of silicon atoms in the silicon source.

[0041] The fluoride-containing compounds used in the raw material mixture of step (A) are preferably hydrofluoric acid, ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, mono(C1-C3)alkylammonium fluoride, di(C1-C3)alkylammonium fluoride, tri(C1-C3)alkylammonium fluoride, tetra(C1-C3)alkylammonium fluoride, and tetrapropylammonium fluoride; more preferably hydrofluoric acid, ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, and tetrapropylammonium fluoride; even more preferably hydrofluoric acid, ammonium fluoride, sodium fluoride, and potassium fluoride; even more preferably hydrofluoric acid and ammonium fluoride; and particularly preferably hydrofluoric acid. The amount of fluoride-containing compounds used in the raw material mixture of step (A) is the amount of fluoride ions (F － Based on the above, the amount is preferably 0.01 to 5 molar equivalents, more preferably 0.05 to 2 molar equivalents, and even more preferably 0.07 to 0.8 molar equivalents, relative to 1 molar equivalent of silicon atoms in the silicon source.

[0042] When a fluoride-containing compound is used as the raw material mixture in step (A), for example, an ammonium salt and alcohols may be used as raw materials to obtain the fluoride-containing compound. The ammonium salt and alcohols may be used individually or as a mixture of two or more. Tetrapropylammonium hydroxide (TPA) is preferred as the ammonium salt. The alcohols are preferably pentaerythritol, 1,3-propanediol, tert-butanol, ethylene glycol, and 1,4-butanediol, and more preferably pentaerythritol, 1,3-propanediol, ethylene glycol, and 1,4-butanediol.

[0043] Since aluminum in the zeolite can be more readily present in straight channels and / or zigzag channels, it is preferable to use one or more selected from the group consisting of fluoride-containing compounds and alcohols as the raw material mixture in step (A).

[0044] The raw material mixture in step (A) may further contain an alkali source. Examples of alkali sources include hydroxides, carbonates, sulfates, chlorides, bromides, silicates, and iodides of alkali metals or alkaline earth metals, with hydroxides being preferred. Examples of hydroxides include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; and alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.

[0045] The amount of alkali source used in the raw material mixture of step (A) is preferably 0.01 to 5 mole equivalents, more preferably 0.05 to 2 mole equivalents, and even more preferably 0.07 to 0.8 mole equivalents, based on alkali metal atoms or alkaline earth metal atoms, relative to 1 mole equivalent of silicon atoms in the silicon source.

[0046] The raw material mixture in step (A) may further contain seed crystals. The seed crystals are, for example, zeolites, and are preferably MFI-type zeolites when producing MFI-type zeolites. The amount of seed crystals used should be sufficiently small compared to the silicon and aluminum sources, and should be within the range of the general amount used when seed crystals are used in zeolite production.

[0047] The reaction temperature (hydrothermal treatment temperature) for the hydrothermal reaction in step (A) is preferably 100°C or higher, more preferably 120°C to 250°C, and even more preferably 150°C to 200°C, from the viewpoint of efficiently promoting the crystallization of the zeolite. The reaction time (hydrothermal treatment time) for the hydrothermal reaction in step (A) is preferably 3 hours to 500 hours, more preferably 6 hours to 200 hours, even more preferably 12 hours to 150 hours, and even more preferably 15 hours to 50 hours.

[0048] The hydrothermal reaction in step (A) is preferably carried out under pressurized conditions with the raw material mixture sealed in a pressure vessel. The pressure during the hydrothermal reaction (hydrothermal treatment pressure) is, for example, 0 MPaG or higher, preferably 0.1 MPaG to 4.0 MPaG, and more preferably 0.4 MPaG to 1.5 MPaG, from the viewpoint of further improving the crystallinity of the zeolite.

[0049] The hydrothermal reaction in step (A) may be carried out while stirring the raw material mixture, or it may be carried out in a static state. When the hydrothermal reaction in step (A) is carried out while stirring, the stirring speed is not particularly limited, but can be set to, for example, 10 rpm to 1000 rpm, and 10 rpm to 100 rpm is preferred.

[0050] The reaction product obtained in step (A) can be recovered as a solid from the solid-liquid separation after the hydrothermal reaction. Methods for recovering the solid include separation and recovery using filtration means and separation and recovery using centrifugal sedimentation means.

[0051] The reaction product obtained in step (A) may be washed with water or the like.

[0052] The reaction product obtained in step (A) may be dried. The drying method is preferably by heating. The drying temperature after the hydrothermal reaction is preferably 50°C to 200°C, more preferably 60°C to 150°C, and even more preferably 60°C to 120°C. The drying time after the hydrothermal reaction is preferably 1 hour to 100 hours, more preferably 2 hours to 50 hours, and even more preferably 5 hours to 24 hours.

[0053] The firing temperature in step (B) is preferably 300°C or higher, more preferably 400°C to 800°C, and even more preferably 450°C to 700°C. The firing time in step (B) is preferably 1 hour to 100 hours, more preferably 2 hours to 50 hours, and even more preferably 5 hours to 24 hours. The firing atmosphere in step (B) may be an aerobic atmosphere such as air, oxygen, or a mixed gas of these with nitrogen.

[0054] The zeolite obtained in step (B) may be subjected to ion exchange treatment for the purpose of removing alkali metals or alkaline earth metals. As an ion exchange treatment, for example, a method of contacting the zeolite obtained in step (B) with an aqueous solution of ammonium salt can be used.

[0055] The ion exchange treatment time is preferably 0.5 hours or more, and more preferably 1 hour or more, from the viewpoint of sufficiently diffusing the ammonium salt aqueous solution into the pore structure of the zeolite. The upper limit of the ion exchange treatment time is not particularly limited, but for example, it is 24 hours. The ion exchange treatment temperature is, for example, 50°C to 100°C.

[0056] Examples of ammonium salts used in ion exchange treatment include ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride, ammonium nitrate, and ammonium acetate. Ammonium ions (NH₄) in aqueous solutions of ammonium salts. ４ ＋ The concentration should be, for example, between 0.1 M and 4 M.

[0057] The zeolite after ion exchange treatment may be washed with water or the like.

[0058] The zeolite after ion exchange treatment may be dried. The drying method is preferably by heating. The drying temperature after ion exchange treatment is preferably 50°C to 200°C, more preferably 60°C to 150°C, and even more preferably 60°C to 120°C. The drying time after ion exchange treatment is preferably 1 hour to 100 hours, more preferably 2 hours to 50 hours, and even more preferably 5 hours to 24 hours.

[0059] The zeolite may be calcined after ion exchange treatment. The calcination temperature after ion exchange treatment is preferably 300°C or higher, more preferably 400°C to 800°C, and even more preferably 450°C to 700°C. The calcination time after ion exchange treatment is preferably 1 hour to 100 hours, more preferably 2 hours to 50 hours, and even more preferably 5 hours to 24 hours. The calcination atmosphere after alkali removal treatment may be an aerobic atmosphere such as air, oxygen, or a mixed gas of these with nitrogen.

[0060] The catalyst of this embodiment may be used as is, using the zeolite obtained by the above method (i.e., the zeolite in this embodiment), or it may be molded into a specific form before use. The form of the catalyst of this embodiment is not particularly limited, but examples include powder, spherical, ring-shaped, tablet-shaped, granular, cylindrical, columnar, polygonal tubular, polygonal prismatic, elliptical, trefoil-shaped, tetralob-shaped, etc.

[0061] The catalyst in this embodiment may contain a mixture of zeolite, an inorganic binder, an organic binder, a molding aid, and the like.

[0062] The inorganic binder is not particularly limited, but examples include silica, silica-alumina, alumina, titania, carbon, clay, and ceramics. The inorganic binder may be used alone or in combination of two or more types.

[0063] The organic binder is not particularly limited, but examples include methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethylene glycol, phenolic resin, epoxy resin, etc. The organic binder may be used alone or in combination of two or more types.

[0064] The molding aids are not particularly limited, but examples include ethylene glycol, dextrin, fatty acids, fatty acid soaps, and polyalcohols. The molding aids may be used individually or in combination of two or more.

[0065] The catalyst or zeolite of this embodiment is useful for synthesizing aromatic compounds from alcohols, alkenes, and / or ethers.

[0066] The alcohol used in the synthesis of aromatic compounds is an organic compound having a hydroxyl group, such as an aliphatic alcohol such as a linear or branched alkyl alcohol. The alcohol used in the synthesis of aromatic compounds may be a monohydric alcohol, a dihydric alcohol, or a trihydric or higher alcohol, but a monohydric alcohol is preferred from the viewpoint of easy availability of raw materials produced from renewable resources.

[0067] Specific examples of alcohols used in the synthesis of aromatic compounds include linear primary alcohols such as methanol, ethanol, 1-propanol (n-propyl alcohol), 1-butanol (n-butyl alcohol), 1-pentanol, and 1-hexanol; and branched alcohols such as 2-methyl-1-propanol (isobutyl alcohol), 2-methyl-1-butanol, 3-methyl-1-butanol, 2,2-dimethyl-1-propanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, and 2-ethyl-1-butanol. Examples of secondary alcohols include linear primary alcohols such as 2-propanol (isopropyl alcohol), 2-butanol (sec-butyl alcohol), 2-pentanol, 3-pentanol, 3-methyl-2-butanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, and 3,3-dimethyl-2-butanol; and tertiary alcohols such as 2-methyl-2-propanol (tert-butyl alcohol), 2-methyl-2-butanol (tert-pentyl alcohol), 2-methyl-2-pentanol, 3-methyl-3-pentanol, and 2,3-dimethyl-2-butanol. The alcohols used in the synthesis of aromatic compounds may be used individually or in combination of two or more.

[0068] The alcohol used in the synthesis of aromatic compounds is preferably an alcohol having 1 to 8 carbon atoms, more preferably an alcohol having 1 to 4 carbon atoms, and even more preferably an alcohol having 2 to 4 carbon atoms, from the viewpoint of ease of availability and further improvement of the efficiency of aromatic compound production. Particularly preferred is ethanol from the viewpoint of a method that can utilize biomass fuel.

[0069] Alkenes used in the synthesis of aromatic compounds are hydrocarbon compounds having a straight-chain or branched carbon-carbon double bond. Alkenes used in the synthesis of aromatic compounds may have one carbon-carbon double bond in one molecule, two carbon-carbon double bonds in one molecule, or three or more carbon-carbon double bonds in one molecule. However, from the viewpoint of suppressing side reactions, manufacturing efficiency, and availability, alkenes having one carbon-carbon double bond in one molecule are preferred.

[0070] Specific examples of alkenes used in the synthesis of aromatic compounds include linear alkenes such as ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutene, 1-pentene, cis-2-pentene, trans-2-pentene, 1-hexene, cis-2-hexene, trans-2-hexene, cis-3-hexene, and trans-3-hexene; and 2-methyl-1-butene, 2-methyl- Examples of branched alkenes include 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, (E)-3-methyl-2-pentene, (Z)-3-methyl-2-pentene, (E)-4-methyl-2-pentene, (Z)-4-methyl-2-pentene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene, 2-ethyl-1-butene, and 2,3-dimethyl-2-butene. The alkenes used in the synthesis of aromatic compounds may be used individually or in combination of two or more.

[0071] The alkenes used in the synthesis of aromatic compounds are preferably C2-C8 alkenes, more preferably C2-C4 alkenes, from the viewpoint of easy availability of raw materials produced from renewable resources, and particularly preferably C3 or C4 alkenes, from the viewpoint of suppressing side reactions.

[0072] The ethers used in the synthesis of aromatic compounds are organic compounds having ether bonds, such as aliphatic ethers like linear or branched dialkyl ethers. The ethers used in the synthesis of aromatic compounds may have one ether bond per molecule, two ether bonds per molecule, or three or more ether bonds per molecule. However, from the viewpoint of ease of acquisition and further improvement of the efficiency of aromatic compound production, ethers having one ether bond per molecule are preferred.

[0073] Specific examples of ethers used in the synthesis of aromatic compounds include linear ethers such as dimethyl ether, diethyl ether, ethyl methyl ether, di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, and di-n-hexyl ether; and branched ethers such as diisopropyl ether, diisobutyl ether, di-sec-butyl ether, di-tert-butyl ether, di-tert-pentyl ether, ethyl isopropyl ether, ethyl tert-butyl ether, ethyl tert-pentyl ether, and isopropyl tert-butyl ether. The ethers used in the synthesis of aromatic compounds may be used individually or in combination of two or more types.

[0074] The ether used in the synthesis of aromatic compounds is preferably an ether having 2 to 16 carbon atoms, more preferably an ether having 2 to 8 carbon atoms, even more preferably an ether having 4 to 8 carbon atoms, and particularly preferably a diethyl ether, from the viewpoint of ease of availability and further improvement of the efficiency of the production of aromatic compounds.

[0075] In a preferred embodiment, the catalyst of this embodiment is a catalyst for synthesizing aromatic compounds from C1-C8 alcohols, C2-C8 alkenes and / or C2-C6 ethers, preferably a catalyst for synthesizing aromatic compounds from C1-C4 alcohols, C2-C4 alkenes and / or C2-C8 ethers, more preferably a catalyst for synthesizing aromatic compounds from C2-C4 alcohols, C2-C4 alkenes and / or C4-C8 ethers, even more preferably a catalyst for synthesizing aromatic compounds from C2-C4 alcohols, and particularly preferably a catalyst for synthesizing aromatic compounds from ethanol.

[0076] The aromatic compounds to be synthesized in this embodiment can be produced by a method that includes a synthesis step of contacting the catalyst or zeolite of this embodiment with an alcohol, an alkene, and / or an ether to synthesize the aromatic compounds. Alternatively, the aromatic compounds to be synthesized in this embodiment can be produced by an apparatus that has the catalyst or zeolite of this embodiment and is equipped with synthesis means for contacting the catalyst or zeolite with an alcohol, an alkene, and / or an ether to synthesize the aromatic compounds.

[0077] From the viewpoint of the efficiency of producing aromatic compounds, the contact temperature (reaction temperature) of the alcohol, alkene, and / or ether with the catalyst or zeolite of this embodiment during the synthesis of aromatic compounds is preferably 350°C or higher, more preferably 400°C or higher, even more preferably 420°C or higher, even more preferably 450°C or higher, and particularly preferably 470°C or higher. Furthermore, from the viewpoint of the selectivity and efficiency of producing aromatic compounds, the above contact temperature is preferably 650°C or lower, more preferably 600°C or lower, even more preferably 550°C or lower, even more preferably 530°C or lower, and particularly preferably 520°C or lower. When the above contact temperature exceeds 650°C, the formation of hard coke tends to increase.

[0078] The contact pressure (reaction pressure) of the alcohol, alkene, and / or ether with the catalyst or zeolite in this embodiment during the synthesis of aromatic compounds is preferably 0 MPaG or higher, and more preferably 0.05 MPaG or higher, from the viewpoint of the efficiency of producing aromatic compounds. From the viewpoint of the selectivity of producing aromatic compounds, the above contact pressure is preferably 4.00 MPaG or lower, more preferably 2.00 MPaG or lower, even more preferably 1.00 MPaG or lower, and particularly preferably 0.50 MPaG or lower.

[0079] For supplying alcohols, alkenes, and / or ethers to the synthesis means for the synthesis of aromatic compounds, a gas-phase flow system in which they are continuously supplied in the gas phase is preferred.

[0080] The amount of alcohol, alkene, and / or ether supplied to the catalyst or zeolite in this embodiment in the synthesis means is not particularly limited, but the weight space velocity (i.e., the ratio of the supply rate (weight / hour) of alcohol, alkene, and / or ether to the weight of the catalyst) is, for example, 0.01h. －１ ~100h －１ It is within the range, preferably 0.05h －１ ~50h －１ It is within the range of, and more preferably 0.1h －１ ~10h －１ It is within the range, and particularly preferably 0.5h －１ ~5h －１ It is within the range.

[0081] The synthesis means for the synthesis of aromatic compounds may be supplied with an inert gas such as nitrogen, helium, argon, water vapor, or liquefied petroleum gas (LPG) along with the alcohol, alkene, and / or ether. The amount of inert gas supplied to the synthesis means is not particularly limited, but is, for example, 0% to 95% by volume, preferably 0% to 80% by volume, relative to 100% by volume of the total amount of alcohol, alkene, and / or ether and inert gas supplied to the synthesis means.

[0082] The synthesis method for the synthesis of aromatic compounds may be any known synthesis method used in a gas-phase reaction system using a solid catalyst, and can be selected from various reactors such as fixed-bed reactors, fluidized-bed reactors, moving-bed reactors, boiling-bed reactors, and suspension-bed reactors. However, fixed-bed reactors, fluidized-bed reactors, or moving-bed reactors are preferred, and fixed-bed reactors are particularly preferred because they are easier to design and manufacture, and allow for more stable synthesis of aromatic compounds. Furthermore, the synthesis method for the synthesis of aromatic compounds may be a single-tube reactor or a multi-tube reactor. The aromatic compounds to be synthesized in this embodiment can be synthesized by contacting the catalyst or zeolite of this embodiment with an alcohol, alkene, and / or ether, preferably in a fixed-bed reactor, in a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor, and particularly preferably in a fixed-bed reactor.

[0083] In the synthesis of aromatic compounds using the catalyst of this embodiment, in one embodiment, when the starting material is an alcohol, the reaction can proceed from the alcohol to the aromatic compound via intermediates such as alkenes and ethers, which are alcohol dehydrates. In the synthesis of aromatic compounds using the catalyst of this embodiment, in one embodiment, multiple aromatic compounds are produced simultaneously along with non-aromatic compounds such as alkanes. The method for synthesizing aromatic compounds using the catalyst of this embodiment is characterized by a high production rate of aromatic compounds (especially monocyclic aromatic compounds), particularly benzene, toluene, and xylene (i.e., o-xylene, m-xylene, and p-xylene). The catalyst of this embodiment is useful for the synthesis of monocyclic aromatic compounds, and is particularly useful for the synthesis of benzene, toluene, or xylene. The aromatic compounds synthesized by the catalyst of this embodiment are preferably monocyclic aromatic compounds, and are particularly preferably benzene, toluene, or xylene.

[0084] In the synthesis of aromatic compounds using the catalyst of this embodiment, the total production ratio of benzene, toluene, and xylene one hour after the start of the reaction is 30 atoms or more in a preferred embodiment, 35 atoms or more in a more preferred embodiment, 38 atoms or more in an even more preferred embodiment, and 40 atoms or more in a particularly preferred embodiment, based on the number of carbon atoms of the synthetic raw materials: alcohol, alkene, and / or ether.

[0085] Furthermore, in the synthesis of aromatic compounds using the catalyst of this embodiment, the total production ratio of benzene, toluene, and xylene after 3 hours from the start of the reaction is 27 atoms or more in a preferred embodiment, 30 atoms or more in a more preferred embodiment, 35 atoms or more in an even more preferred embodiment, and 38 atoms or more in a particularly preferred embodiment, based on the number of carbon atoms of the synthetic raw materials: alcohol, alkene, and / or ether.

[0086] Furthermore, in the synthesis of aromatic compounds using the catalyst of this embodiment, the total production ratio of benzene, toluene, and xylene after 5 hours from the start of the reaction is 20 atoms or more in a preferred embodiment, 28 atoms or more in a more preferred embodiment, 30 atoms or more in an even more preferred embodiment, and 33 atoms or more in a particularly preferred embodiment, based on the number of carbon atoms of the raw material alcohol, alkene, and / or ether. The catalyst of this embodiment exhibits even greater durability even when used for extended periods. As a result, by using the catalyst of this embodiment, it is possible to suitably produce benzene, toluene, and xylene over long periods of time.

[0087] In the synthesis of aromatic compounds using the catalyst of this embodiment, the total production ratio of C1-C4 alkanes is 60 atom% or less in a preferred embodiment, 40 atom% or less in a more preferred embodiment, 38 atom% or less in an even more preferred embodiment, and 37 atom% or less in a particularly preferred embodiment, based on the number of carbon atoms of the synthetic raw materials: alcohol, alkene and / or ether.

[0088] In the synthesis of aromatic compounds using the catalyst of this embodiment, the total production ratio of organic compounds having 5 or more carbon atoms, excluding monocyclic aromatic compounds such as benzene, toluene, and xylene, is 20 atoms or less in a preferred embodiment, 15 atoms or less in a more preferred embodiment, 10 atoms or less in an even more preferred embodiment, and 7 atoms or less in a particularly preferred embodiment, based on the number of carbon atoms of the synthetic raw materials: alcohol, alkene, and / or ether.

[0089] In the synthesis of aromatic compounds using the catalyst of this embodiment, the conversion rate of alcohols, alkenes, and / or ethers is 60 atoms or more in a preferred embodiment, 70 atoms or more in a more preferred embodiment, 80 atoms or more in an even more preferred embodiment, 90 atoms or more in an even more preferred embodiment, 95 atoms or more in an even more preferred embodiment, and 99 atoms or more in a particularly preferred embodiment, based on the number of carbon atoms.

[0090] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, room temperature and ambient temperature refer to 25°C ± 5°C. Unless otherwise specified, the temperature condition is room temperature (25°C ± 5°C), and unless otherwise specified, the pressure condition is atmospheric pressure (0.1 MPa).

[0091] [Example 1: Production of zeolite using pentaerythritol (PET)] In a Teflon® beaker, 35.12 g of water, 1.00 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), 6.80 g of pentaerythritol (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), and 1.50 g of aluminum nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent) were added in order and stirred at room temperature for 30 minutes. Then, 15.0 g of 40% by mass of colloidal silica aqueous solution (manufactured by Sigma-Aldrich, HS-40) was added and stirred at room temperature for another 30 minutes. Subsequently, Silicalite-1 (structural formula: Si ９６ O １９２0.30 g was added and stirred at room temperature for 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbid liquid was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 10 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries, and the powder was dispersed in the aqueous solution of ammonium nitrate using 100 cc of aqueous solution of ammonium nitrate for every 1 g of the obtained powder. The solution was heated and stirred at 80°C for 3 hours and then filtered. The same procedure was repeated once more on the filtered powder. After filtering, the powder was washed with water, dried at 80°C, and calcined in an electric furnace at 550°C for 10 hours to obtain powder. The powder was then ground in an agate mortar until uniform to obtain powdered MFI-type zeolite.

[0092] (1) XRD Measurement XRD measurements were performed on the obtained zeolite. A powder X-ray diffractometer (Rigaku RINT Ultima III) was used, with an accelerating current and voltage of 40 mA and 40 kV, a CuKα radiation source (λ = 1.5405 Å), a continuous scan measurement mode, a measurement range of 2θ = 3° to 50°, a scan condition of 4.0° / min, and a semiconductor detector D / teX Ultra. The obtained XRD pattern is shown in Figure 1.

[0093] (2) Solid ２７ Al-NMR analysis and calculation of ratio A / B for the obtained zeolite solid ２７ Al-NMR analysis was performed. The obtained zeolite was filled into an NMR sample tube and measured using an ECA600 instrument (manufactured by JEOL Ltd.) under the following NMR analysis conditions. (NMR analysis conditions) Observed nuclei: ２７ Al Resonance frequency of observed nucleus: 156.4 MHz Measurement temperature: Room temperature Pulse sequence: Single pulse excitation pulse width: 0.1 μs Waiting time after FID measurement until next pulse application: 0.1 seconds Magic angle rotation speed: 15 kHz Number of integrations: 10,000 Measurement range: 240 to -160 ppm External standard: Al(NH) ４ (SO ４ )２ 12H ２ O (Chemical shift -0.54 ppm)

[0094] The obtained data is subjected to FFT (Fast Fourier Transform) to determine the solid ２７ Al-NMR spectra were obtained. ２７ The Al-NMR spectrum was analyzed using the software "Delta" (manufactured by JEOL Ltd.). The region from chemical shift 90.0 ppm to 20.0 ppm was integrated beforehand, and then the region was divided into two parts: from 90.0 ppm to 54.0 ppm and from 54.0 ppm to 20.0 ppm. The area, which is the integrated value, is calculated as the range enclosed above and below the spectrum and baseline. The baseline was set so that it touches the spectrum at 90.0 ppm and 20.0 ppm, and the baseline from 90.0 ppm to 54.0 ppm and the baseline from 54.0 ppm to 20.0 ppm are on a straight line. The ratio A / B was calculated when the integrated value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm was taken as A, and the integrated value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm was taken as B. As a result, the ratio A / B was 1.94. Also, the obtained solid... ２７ The Al-NMR chart is shown in Figure 2.

[0095] (3) Calculation of silicon / aluminum molar ratio based on ICP The molar ratio of silicon to aluminum (silicon / aluminum) in the obtained zeolite was calculated from the ICP-AES measurement results. The obtained zeolite was dissolved by the alkaline fusion method with lithium tetraborate to prepare a sample, and the sample was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using an Agilent Technologies ICP emission spectrometer 5100, and the silicon / aluminum molar ratio was determined from the obtained Si and Al measurements. As a result, the silicon / aluminum molar ratio was 24.9.

[0096] (4) Measurement of BET specific surface area, external surface area and micropore volume The BET specific surface area, external surface area and micropore volume were measured for the obtained zeolite. The BET specific surface area, external surface area and micropore volume were measured by nitrogen adsorption measurement. Nitrogen adsorption measurement was performed using a nitrogen adsorption apparatus (BELSORP-MAX manufactured by Nippon Bell Co., Ltd., measurement temperature -196°C, pretreatment vacuum drying at 350°C for 3 hours). The BET specific surface area was determined by applying the BET multipoint method based on nitrogen adsorption measurement in accordance with JIS Z 8830:2013. The external surface area was determined by applying the t-plot method based on nitrogen adsorption measurement in accordance with JIS Z 8831:2010. The micropore volume was determined by applying the t-plot method based on nitrogen adsorption measurement in accordance with JIS Z 8831:2010. As a result, the BET specific surface area was 393 m². ２ / g, outer surface area 47m ２ The concentration was 0.22 mL / g, and the micropore volume was 0.22 mL / g.

[0097] (5) Measurement of acid content The acid content of the obtained zeolite was measured. The acid content was measured using NH ３ - A TPD instrument (BELCAT-A, manufactured by Bell Corporation Japan) and a gas analyzer (BELCAT-A, TCD, manufactured by Bell Corporation Japan) were used. The sample was powdered and placed in a cell. The temperature was raised to 500°C at 10°C / min under a helium atmosphere, dried for 1 hour, then cooled to 100°C, and ammonia was adsorbed in an ammonia / helium mixed atmosphere (ammonia concentration 29 vol%) for 30 minutes. After that, the temperature was raised from 100°C to 610°C at 10°C / min under a helium atmosphere, and the desorbed ammonia was analyzed with a gas analyzer. The obtained peaks were treated as Gaussian distributions, and waveform decomposition was performed by the DFP method. The peak around 200°C was identified as desorption from a weak acid, and the peak around 400°C was identified as desorption from a strong acid. The acid content of the sample was calculated from the remaining desorption amount after removing the amount of desorption from the weak acid. As a result, the acid content was 0.59 mmol / g.

[0098] [Example 2: Production of Zeolite Using 1,3-Propanediol (PDO)] In a Teflon® beaker, 35.12 g of water, 1.00 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), 3.80 g of 1,3-propanediol (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), and 1.50 g of aluminum nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent) were added in order and stirred at room temperature for 30 minutes. Then, 15.0 g of 40% by mass of colloidal silica aqueous solution (manufactured by Sigma-Aldrich, HS-40) was added and stirred at room temperature for another 30 minutes. Subsequently, Silicalite-1 (structural formula: Si ９６ O １９２ 0.30 g was added and stirred at room temperature for 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbid liquid was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 10 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries, and the powder was dispersed in the aqueous solution of ammonium nitrate using 100 cc of aqueous solution of ammonium nitrate for every 1 g of the obtained powder. The solution was heated and stirred at 80°C for 3 hours and then filtered. The same procedure was repeated once more on the filtered powder. After filtering, the powder was washed with water, dried at 80°C, and calcined in an electric furnace at 550°C for 10 hours to obtain powder. The powder was then ground in an agate mortar until uniform to obtain powdered MFI-type zeolite. The obtained zeolite was subjected to XRD measurement in the same manner as in Example 1. The results are shown in Figure 3. The ratio A / B was calculated in the same manner as in Example 1, and the result was 1.75. ２７ The Al-NMR chart is shown in Figure 4. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, resulting in a value of 24.2. The BET specific surface area, outer surface area, micropore volume, and acid content were measured in the same manner as in Example 1, resulting in a BET specific surface area of ​​470 m². ２ / g, outer surface area 50m ２ The values ​​were per g, micropore volume was 0.31 mL / g, and acid content was 0.63 mmol / g.

[0099] [Example 3: Production of Zeolite Using tert-Butanol (TBO)] In a Teflon® beaker, 35.12 g of water, 1.00 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), 3.70 g of tert-butanol (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), and 1.50 g of aluminum nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent) were added in order and stirred at room temperature for 30 minutes. Then, 15.0 g of 40% by mass of colloidal silica aqueous solution (manufactured by Sigma-Aldrich, HS-40) was added and stirred at room temperature for another 30 minutes. Subsequently, Silicalite-1 (structural formula: Si ９６ O １９２ 0.30 g was added and stirred at room temperature for 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbid liquid was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 10 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries, and the powder was dispersed in the aqueous solution of ammonium nitrate using 100 cc of aqueous solution of ammonium nitrate for every 1 g of the obtained powder. The solution was heated and stirred at 80°C for 3 hours and then filtered. The same procedure was repeated once more on the filtered powder. After filtering, the powder was washed with water, dried at 80°C, and calcined in an electric furnace at 550°C for 10 hours to obtain powder. The powder was then ground in an agate mortar until uniform to obtain powdered MFI-type zeolite. The obtained zeolite was subjected to XRD measurement in the same manner as in Example 1. The results are shown in Figure 5. The ratio A / B was calculated in the same manner as in Example 1, and the result was 1.38. ２７ The Al-NMR chart is shown in Figure 6. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, resulting in a value of 26.0. The BET specific surface area, outer surface area, micropore volume, and acid content were measured in the same manner as in Example 1, resulting in a BET specific surface area of ​​472 m². ２ / g, outer surface area 37m ２ The values ​​were per g, micropore volume was 0.27 mL / g, and acid content was 0.63 mmol / g.

[0100] [Example 4: Production of Zeolite Using 1,3-Propanediol (PDO) and Hydrofluoric Acid (HF)] In a Teflon® beaker, 34.53 g of water, 3.80 g of 1,3-propanediol (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), 1.00 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent), and 1.50 g of aluminum nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent) were added in order, and the mixture was stirred at room temperature for 30 minutes. Then, 15.00 g of 40% by mass colloidal silica aqueous solution (manufactured by Sigma-Aldrich, HS-40) and 1.09 g of 46% by mass hydrofluoric acid aqueous solution (manufactured by Morita Chemical Industries) were added in order, and the mixture was stirred at room temperature for another 30 minutes. Subsequently, Silicalite-1 (structural formula: Si ９６ O １９２ 0.30 g of ) was added and stirred at room temperature for 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbidity was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 6 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries, and the powder was dispersed in the aqueous solution of ammonium nitrate using 100 cc of aqueous solution of ammonium nitrate for 1 g of the obtained powder, heated and stirred at 80°C for 3 hours, and then filtered. The same operation was repeated once more on the filtered powder. After washing the filtered powder with water, it was dried at 100°C for 5 hours and calcined in an electric furnace at 550°C for 6 hours to obtain an MFI-type zeolite catalyst. The obtained zeolite was measured for XRD in the same manner as in Example 1. The results are shown in Figure 7. The ratio A / B was calculated in the same manner as in Example 1, resulting in 1.98. Furthermore, the obtained solid... ２７ The Al-NMR chart is shown in Figure 8. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, resulting in a value of 22.4. The BET specific surface area, outer surface area, micropore volume, and acid content were measured in the same manner as in Example 1, resulting in a BET specific surface area of ​​445 m². ２ / g, outer surface area 37m ２ The values ​​were 0.28 mL / g, micropore volume 0.28 mL / g, and acid content 0.96 mmol / g.

[0101] [Example 5: Production of Zeolite Using Tetrapropylammonium Hydroxide (TPA) and Hydrofluoric Acid (HF)] In a Teflon® beaker, 30.04 g of water, 4.23 g of a 40% by mass aqueous solution of tetrapropylammonium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries), and 1.50 g of aluminum nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, special grade reagent) were added in sequence and stirred at room temperature for 30 minutes. Then, 5.00 g of a 40% by mass aqueous solution of colloidal silica (manufactured by Sigma-Aldrich, HS-40) and 0.36 g of a 46% by mass aqueous solution of hydrofluoric acid (manufactured by Morita Chemical Industries) were added in sequence and stirred at room temperature for a further 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbidity was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 6 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries. The powder was dispersed in 100 cc of the aqueous solution of ammonium nitrate for every 1 g of the obtained powder, heated and stirred at 80°C for 3 hours, and then filtered. The same procedure was repeated once more on the filtered powder. After washing the filtered powder with water, it was dried at 100°C for 5 hours and calcined in an electric furnace at 550°C for 6 hours to obtain an MFI-type zeolite catalyst. The obtained zeolite was subjected to XRD measurement in the same manner as in Example 1. The results are shown in Figure 9. The ratio A / B was calculated in the same manner as in Example 1, and the result was 1.48. The obtained solid ２７ The Al-NMR chart is shown in Figure 10. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, resulting in a value of 25.7. The BET specific surface area, outer surface area, micropore volume, and acid content were measured in the same manner as in Example 1, resulting in a BET specific surface area of ​​466 m². ２ / g, outer surface area 28m ２ The values ​​were 0.31 mL / g, micropore volume 0.31 mL / g, and acid content 0.55 mmol / g.

[0102] [Example 6: Production of Zeolite Using Ethylene Glycol (EGO)] In a Teflon® beaker, 35.12 g of water and 3.10 g of ethylene glycol (EGO) (manufactured by Fujifilm Wako Pure Chemical Industries) were added in sequence and stirred at room temperature for 30 minutes. Then, 15 g of 40% by mass colloidal silica aqueous solution (manufactured by Sigma-Aldrich, HS-40) was added in sequence and stirred at room temperature for another 30 minutes. Subsequently, Silicalite-1 (structural formula: Si ９６ O １９２ 0.30 g of ) was added and stirred at room temperature for 2 hours. The obtained solution was added to a Teflon® inner tube in a stainless steel pressure vessel and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was 40 rpm. The obtained turbidity was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 6 hours. A 2.5 M aqueous solution of ammonium nitrate was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Industries, and the powder was dispersed in the aqueous solution of ammonium nitrate using 100 cc of aqueous solution of ammonium nitrate for every 1 g of the obtained powder. The solution was heated and stirred at 80°C for 3 hours and then filtered. The same procedure was repeated once more on the filtered powder. The filtered powder was washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 6 hours to obtain an MFI-type zeolite catalyst. XRD measurements were performed on the obtained zeolite in the same manner as in Example 1. The results are shown in Figure 11. The ratio A / B was calculated in the same manner as in Example 1, and the result was 2.15. Furthermore, the obtained solid... ２７ The Al-NMR chart is shown in Figure 12. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, resulting in a value of 21.9. The BET specific surface area, outer surface area, micropore volume, and acid content were measured in the same manner as in Example 1, and the BET specific surface area was found to be 450 m². ２ / g, outer surface area 20m ２ The values ​​were 0.24 mL / g, micropore volume 0.24 mL / g, and acid content 0.62 mol / g.

[0103] [Example 7: Production of zeolite using 1,4-butanediol (BDO)] In a Teflon (registered trademark) beaker, 35.12 g of water and 4.50 g of 1,4-butanediol (BDO) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added sequentially, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 15 g of a 40 mass% colloidal silica aqueous solution (HS-40, manufactured by Sigma-Aldrich) was added sequentially, and the mixture was further stirred at room temperature for 30 minutes. Subsequently, 0.30 g of silicalite-1 (structural formula: Si ９６ O １９２ ) was added, and the mixture was stirred at room temperature for 2 hours. The resulting solution was added to a Teflon (registered trademark) inner tube in a stainless steel pressure-resistant container, and heated and stirred at 170°C for 24 hours in a hydrothermal synthesis apparatus. The rotation speed during heating and stirring was set to 40 rpm. The obtained turbid liquid was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 6 hours. A 2.5 M aqueous ammonium nitrate solution was prepared using special grade ammonium nitrate manufactured by FUJIFILM Wako Pure Chemical Corporation. 100 cc of the aqueous ammonium nitrate solution was used per 1 g of the obtained powder to disperse the powder in the aqueous ammonium nitrate solution. After heating and stirring at 80°C for 3 hours, filtration was performed. The same operation was repeated once more on the filtered powder. After washing the filtered powder with water, it was dried at 100°C for 5 hours and calcined in an electric furnace at 550°C for 6 hours to obtain an MFI-type zeolite catalyst. XRD measurement was performed on the obtained zeolite in the same manner as in Example 1. The results are shown in Figure 13. The ratio A / B was calculated in the same manner as in Example 1, and the result was 2.06. In addition, the obtained solid ２７ Al-NMR chart is shown in Figure 14. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, and the result was 22.2. The BET specific surface area, external surface area, micropore volume, and acid amount were measured in the same manner as in Example 1. The results were as follows: BET specific surface area 452 m ２ / g, external surface area 20 m ２ / g, micropore volume 0.24 mL / g, and acid amount 0.67 mol / g.

[0104] [Comparative Example 1: Production of zeolite using tetrapropylammonium hydroxide (TPA)] In a Teflon (registered trademark) beaker, 0.50 g of aluminum nitrate nonahydrate (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Corporation) and 16.92 g of 40 mass% tetrapropylammonium hydroxide aqueous solution (manufactured by Fujifilm Wako Pure Chemical Corporation) were added sequentially, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 6.94 g of tetraethyl orthosilicate (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Corporation) was added, and the mixture was further stirred at room temperature for 2 hours. The resulting solution was added to a Teflon (registered trademark) inner tube placed in a stainless steel pressure-resistant container, and heated and stirred at 170°C for 240 hours in a hydrothermal synthesizer. The rotation speed during heating and stirring was set to 40 rpm. The obtained turbid liquid was filtered, washed with water, dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 10 hours. A 2.5 M ammonium nitrate aqueous solution was prepared using ammonium nitrate (special grade reagent) manufactured by Fujifilm Wako Pure Chemical Corporation. For 1 g of the obtained powder, 100 cc of the ammonium nitrate aqueous solution was used to disperse the powder in the ammonium nitrate aqueous solution, and after heating and stirring at 80°C for 3 hours, filtration was performed. The same operation was repeated once more for the filtered powder. After washing the filtered powder with water, it was dried at 100°C for 5 hours, and calcined in an electric furnace at 550°C for 10 hours to obtain a powder, which was pulverized in an agate mortar until uniform to obtain a powdery MFI-type zeolite. XRD measurement was performed on the obtained zeolite in the same manner as in Example 1. The results are shown in Figure 15. The ratio A / B was calculated in the same manner as in Example 1, and the result was 0.82. Also, the obtained solid ２７ Al-NMR chart is shown in Figure 16. The silicon / aluminum molar ratio was calculated in the same manner as in Example 1, and the result was 30.4. BET specific surface area, external surface area, micropore volume and acid amount were measured in the same manner as in Example 1. The results were 418 m ２ / g, external surface area 73 m ２ / g, micropore volume 0.29 mL / g, and acid amount 0.32 mmol / g.

[0105] [Test Example 1: Production of Aromatic Compounds] A fixed-bed gas-phase flow reactor with a stainless steel reaction tube (inner diameter Φ4 mm, length 270 mm) was used. 100 mg of zeolite obtained in the examples and comparative examples was packed into the middle section of the stainless steel reaction tube, and pre-treatment by heating was carried out at 520°C for 1 hour under Ar flow. Thereafter, the catalyst layer was heated using a ceramic tubular furnace, and while controlling the temperature to 500°C, raw material ethanol was pumped at a flow rate of 2.1 microliters / minute to start the synthesis of aromatic compounds.

[0106] The reaction outlet was connected to a gas chromatograph, and the products were analyzed online. Product analysis was performed at 1 hour, 3 hours, and 5 hours after the start of the reaction. The analysis was performed using a gas chromatograph (Shimadzu Corporation, product name GC-2014) equipped with an FID detector and a capillary column (Agilent, product name HPPLOTQ) as the separation column. The total amount of saturated hydrocarbons (alkanes) with 1 to 4 carbon atoms, the total amount of unsaturated aliphatic hydrocarbons (alkenes) with 2 to 4 carbon atoms, the total amount of benzene, toluene, and xylene, and the total amount of other hydrocarbons with 5 or more carbon atoms were calculated based on the carbon atoms of the starting material (atom%).

[0107] The molar ratios of the raw materials for the examples and comparative examples, the silicon / aluminum molar ratio based on ICP, the ratio A / B, and the results of the test examples are summarized in the table below.

[0108]

[0109] As shown in the table above, in the examples where zeolites with an A / B ratio of 1.0 or higher were used as catalysts for the synthesis of aromatic hydrocarbons, the production rates of aromatic compounds such as benzene, toluene, and xylene were higher compared to the comparative examples where zeolites with an A / B ratio of less than 1.0 were used. Furthermore, even after 3 and 5 hours from the start of the reaction, the production rates of aromatic compounds such as benzene, toluene, and xylene remained higher, indicating that zeolites with an A / B ratio of 1.0 or higher are more durable.

[0110] The catalyst of the present invention is useful for the industrial production of aromatic compounds, which are basic chemicals, because it can efficiently synthesize aromatic compounds (particularly monocyclic aromatic compounds such as benzene, toluene, and xylene) from alcohols, alkenes, and / or ethers in higher yields. In particular, the catalyst of the present invention can also be used to produce aromatic compounds from bioethanol, a renewable resource obtained from biomass, and is a technology that can contribute to the reduction of greenhouse gases.

Claims

1. A catalyst for synthesizing aromatic compounds from alcohols, alkenes and / or ethers, which is a solid ２７ A catalyst containing a zeolite in which, in the Al-NMR spectrum, A is the integral value of the peak intensity in the region from chemical shift 90.0 ppm to 54.0 ppm, and B is the integral value of the peak intensity in the region from chemical shift 54.0 ppm to 20.0 ppm, and the ratio A / B is 1.0 or greater.

2. The catalyst according to claim 1, wherein the molar ratio of silicon to aluminum in the zeolite is 10.0 or more.

3. The catalyst according to claim 1 or 2, wherein the molar ratio of silicon to aluminum in the zeolite is 200.0 or less.

4. The catalyst according to any one of claims 1 to 3 for synthesizing aromatic compounds from C1-C4 alcohols, C2-C4 alkenes and / or C2-C8 ethers.

5. A catalyst according to any one of claims 1 to 3 for synthesizing aromatic compounds from ethanol.

6. The catalyst according to any one of claims 1 to 5, wherein the aromatic compound is a monocyclic aromatic compound.

7. The catalyst according to any one of claims 1 to 6, wherein the zeolite is a zeolite having a 10-membered ring pore structure.

8. The catalyst according to any one of claims 1 to 6, wherein the zeolite is a pentasil-type zeolite having a 10-membered ring pore structure.

9. The catalyst according to any one of claims 1 to 6, wherein the zeolite is an MFI-type zeolite.

10. Solid ２７ A method for producing aromatic compounds, comprising a synthesis step of contacting an alcohol, an alkene and / or an ether with a zeolite having a ratio A / B of 1.0 or greater, where A is the integral value of the peak intensity in the chemical shift region from 90.0 ppm to 54.0 ppm and B is the integral value of the peak intensity in the chemical shift region from 54.0 ppm to 20.0 ppm in an Al-NMR spectrum.

11. The method for producing an aromatic compound according to claim 10, wherein the molar ratio of silicon to aluminum in the zeolite is 10.0 or more.

12. The method for producing an aromatic compound according to claim 10 or 11, wherein the molar ratio of silicon to aluminum in the zeolite is 200.0 or less.

13. The method for producing an aromatic compound according to any one of claims 10 to 12, wherein the synthesis step involves contacting the zeolite with an alcohol having 1 to 4 carbon atoms, an alkene having 2 to 4 carbon atoms, and / or an ether having 2 to 8 carbon atoms to synthesize an aromatic compound.

14. A method for producing an aromatic compound according to any one of claims 10 to 12, wherein the synthesis step involves contacting the zeolite with ethanol to synthesize an aromatic compound.

15. The method for producing an aromatic compound according to any one of claims 10 to 14, wherein the zeolite is a zeolite having a 10-membered ring pore structure.

16. The method for producing an aromatic compound according to any one of claims 10 to 14, wherein the zeolite is an MFI-type zeolite.

17. A method for producing an aromatic compound according to any one of claims 10 to 16, wherein the contact temperature of the alcohol, alkene and / or ether with the zeolite in the synthesis step is in the range of 350°C to 600°C.

18. A method for producing an aromatic compound according to any one of claims 10 to 17, wherein the contact pressure of the alcohol, alkene and / or ether with respect to the zeolite in the synthesis step is in the range of 0.05 MPaG to 4.00 MPaG.

19. A method for producing an aromatic compound according to any one of claims 10 to 18, wherein the synthesis step involves contacting the zeolite with an alcohol and / or ether in a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor to synthesize an aromatic compound.

20. Solid ２７ An aromatic compound production apparatus comprising a zeolite having a ratio A / B of 1.0 or greater, where A is the integral value of the peak intensity in the chemical shift region from 90.0 ppm to 54.0 ppm and B is the integral value of the peak intensity in the chemical shift region from 54.0 ppm to 20.0 ppm in an Al-NMR spectrum, and a synthesis means for synthesizing aromatic compounds by contacting the zeolite with an alcohol, an alkene and / or an ether.

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