JP2009119319A - Catalyst for aromatizing lower hydrocarbon and method for preparing aromatic compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for aromatizing lower hydrocarbons having an improved stability of life of its catalytic activities such as conversion of methane to aromatic hydrocarbons, the rate of producing benzene, the rate of producing naphthalene, and the rate of producing BTX (the aggregate rate of producing benzene, toluene and xylene). <P>SOLUTION: The catalyst for aromatizing lower hydrocarbons is constituted by keeping molybdenum and copper supported by a zeolite comprised of a metallosilicate having been treated with a silane compound having a molecular diameter greater than the micropore diameter of the zeolite and comprising an amino group that selectively reacts with Bronsted acid points present in the zeolite and a straight chain hydrocarbon group. The amount of molybdenum supported by the zeolite is 2 to 12% by weight relative to the whole catalyst subsequent to its calcination, and the molecular ratio of copper relative to molybdenum each supported by the zeolite, namely X as defined by the equation: (Cu:Mo=X:1), is 0.01 to 0.8. The silane compound, for example, is a 3-aminoproxyl-triethoxysilane (APTES). APTES is added for treating the zeolite therewith in such an amount that the content thereof in the whole catalyst subsequent to its calcination becomes 2.5% by weight or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to advanced utilization of natural gas, biogas, and methane hydrate mainly composed of methane. Natural gas, biogas, and methane hydrate are considered to be the most effective energy resources as a countermeasure against global warming, and there is an increasing interest in their utilization technologies. Methane resources are attracting attention as the next generation of new organic resources and hydrogen resources for fuel cells, taking advantage of cleanliness. In particular, the present invention relates to a catalytic chemical conversion technique for efficiently producing aromatic compounds mainly composed of benzene and naphthalene, which are raw materials for chemical products such as plastics, and high-purity hydrogen gas from methane, and a method for producing the catalyst. About.

  As a method of producing an aromatic compound such as benzene and hydrogen from methane, a method of reacting methane in the presence of a catalyst is known. As the catalyst at this time, molybdenum supported on ZSM-5-based zeolite is effective (Non-patent Document 1). However, even when these catalysts are used, there are problems that carbon deposition is large and the conversion rate of methane is low.

In order to solve this problem, for example, a catalyst in which a catalyst material such as Mo (molybdenum) disclosed in Patent Documents 1 to 3 is supported on a porous metallosilicate has been proposed. In Patent Documents 1 to 3, lower hydrocarbons are efficiently converted into aromatic compounds by using a catalyst in which a metal component is supported on a porous metallosilicate having a 7 angstrom pore diameter as a carrier. Accompanyingly, it has been confirmed that high purity hydrogen can be obtained. According to the patent document, molybdenum, cobalt, iron or the like is supported on the carrier as the metal component. Patent Document 4 discloses a lower hydrocarbon aromatization catalyst obtained by treating zeolite made of metallosilicate with a silane compound and then supporting molybdenum. According to this aromatization catalyst, the production rate of specific aromatic compounds such as benzene and toluene can be stabilized.
JOURNAL OF CATALYSIS, 1997, pp. 165, pp. 150-161 JP 10-272366 A Japanese Patent Laid-Open No. 11-60514 JP 2004-269398 A JP 2007-14894 A

  As a method for producing an aromatic compound such as benzene and hydrogen from methane, a catalyst in which molybdenum is supported on ZSM-5 is effective as a method for reacting methane in the presence of a catalyst.

  However, even when this catalyst is used, carbon is often deposited. The catalyst performance deteriorates in a short time due to the deposition of carbon. The methane conversion rate (utilization rate of methane used for producing aromatic compounds and hydrogen) is low. Since the catalysts such as Patent Document 1 to Patent Document 3 do not sufficiently improve this problem, development of a more excellent catalyst is desired in order to further increase the production efficiency of the aromatic compound.

  In order to utilize a catalyst for reforming methane to benzene, it is essential to improve the conversion rate of methane, but in order to increase the conversion rate of methane, it is necessary to raise the reaction temperature when methane gas is introduced. In a catalyst such as Patent Document 1 to Patent Document 3, when the reaction temperature with the raw material gas is increased, the active life of the catalyst is significantly reduced.

  Further, according to the aromatization catalyst of Patent Document 4, the production rate of the aromatic compound can be stabilized, but from the viewpoint of mass production of the aromatic compound, methane conversion rate, benzene production rate, naphthalene production rate and BTX Further improvement of the active life stability of the production rate (total production rate of benzene, toluene and xylene) is desired.

  Therefore, a lower hydrocarbon aromatization catalyst for solving the above problems is a catalyst that reacts with a lower hydrocarbon and carbon dioxide gas to produce an aromatic compound, and a zeolite composed of a metallosilicate is converted into a pore of the zeolite. After treatment with a silane compound having an amino group and a linear hydrocarbon group, which has a molecular diameter larger than the diameter and selectively reacts with the Bronsted acid point of the zeolite, molybdenum and copper are supported.

  According to this lower hydrocarbon aromatization catalyst, the active life stability of methane conversion rate, benzene formation rate, naphthalene formation rate and BTX formation rate (total formation rate of benzene, toluene and xylene) is improved. Carbon dioxide gas to be reacted with the catalyst may be replaced with carbon monoxide gas. The amount of carbon dioxide added is preferably in the range of 0.5 to 6% with respect to the entire reaction gas. The active life stability of the methane conversion rate, the benzene formation rate, the naphthalene formation rate and the BTX formation rate is reliably improved.

  Examples of the metallosilicate include ZSM-5 and MCM-22, which are porous metallosilicates having pores having a diameter of 4.5 to 6.5 angstroms.

  Examples of the silane compound include APTES (3-Aminoproxy-trioxysilane). The silane compound may be subjected to the silane treatment so that the added amount of the silane compound after the calcination is less than 2.5% by weight, for example, 0.5% by weight with respect to the total amount of the catalyst. The active lifetime stability of the methane conversion rate, benzene formation rate, naphthalene formation rate and BTX formation rate is reliably improved.

  The molybdenum has a supported amount of 2 to 12% by weight based on the total amount of the catalyst after calcination, and the copper has a molar ratio Cu: Mo = X: 1 with molybdenum of 0.01 to 0.8. It is good to carry so that it may become. The active lifetime stability of the methane conversion rate, benzene formation rate, naphthalene formation rate and BTX formation rate is reliably improved.

  The firing temperature at the time of firing after supporting molybdenum and copper on the metallosilicate is preferably 550 to 800 ° C. If the carbon dioxide gas is excessive or insufficient (less than 0.5%), the oxidizing action of the deposited coke is lowered and the active life stability is lowered. Conversely, if it is excessive (6% or more), hydrogen is oxidized by the direct oxidation reaction of methane gas. And carbon monoxide is produced excessively, and the methane gas concentration required for the reaction is lowered, so that the amount of benzene produced is lowered. Therefore, the methane conversion rate, the benzene production rate, the naphthalene production rate, and the BTX production rate can be efficiently stabilized by setting the amount of carbon dioxide added to the reaction gas in the range of 0.5 to 6%.

  According to the above invention, the active life stability of methane conversion rate, benzene production rate, naphthalene production rate and BTX production rate (total production rate of benzene, toluene and xylene) is improved. Therefore, the production amount of useful aromatic compounds such as benzene and toluene increases.

  The lower hydrocarbon aromatization catalyst according to the invention contains at least one selected from molybdenum and a compound thereof as a catalyst material. In producing the aromatic compound, the lower hydrocarbon aromatization catalyst is reacted with carbon dioxide in addition to the lower hydrocarbon.

  This lower hydrocarbon aromatization catalyst is composed of a metallosilicate zeolite having a molecular diameter larger than the pore diameter of the zeolite and an amino group and a linear hydrocarbon that selectively reacts with the Bronsted acid point of the zeolite. After treatment with a silane compound having a group, molybdenum and copper are supported.

  The carrier carrying the metal component substantially includes a porous metallosilicate having pores with a diameter of 4.5 to 6.5 angstroms. Molybdenum component and copper component are dried and fired after adding silanized metallosilicate to impregnated aqueous solution prepared with copper acetate or copper nitrate and ammonium molybdate to impregnate metallosilicate with molybdenum component and copper component If it uses, it will carry | support to the said metallosilicate.

  Catalyst stability can be obtained by supporting a molybdenum component and a copper component on a metallosilicate that has been silane-treated with a silane compound, such as the lower hydrocarbon aromatization catalyst. In particular, the active life stability of methane conversion rate, benzene production rate, naphthalene production rate and BTX production rate (total production rate of benzene, toluene and xylene) is improved.

  The lower hydrocarbon aromatization catalyst of the present invention will be described based on the following examples.

1. Production of lower hydrocarbon aromatization catalyst (hereinafter abbreviated as catalyst) (Comparative Example 1)
The catalyst of Comparative Example 1 employs ammonium type ZSM-5 (SiO ₂ / Al ₂ O ₃ = 25 to 70) as a metasilicate, and only molybdenum is supported thereon.

(1) Blending Blending of inorganic components: ZSM-5 (82.5 wt%), clay (10.5 wt%), glass fiber (5 wt%)
Total formulation: inorganic component (76.5 wt%), organic binder (17.3 wt%), moisture (24.3 wt%)
(2) Molding The inorganic component, organic binder, and moisture were blended at the blending ratio, and mixed and kneaded by a kneading means (kneader). Next, this mixture was molded into a rod shape (diameter 2.4 mm × length 5 mm) with a vacuum extrusion molding machine. The extrusion pressure at the time of molding at this time was set to 2 to 8 MPa.

(3) Impregnation of molybdenum and copper An impregnation aqueous solution prepared with an acetic acid cylinder and ammonium molybdate is stirred, and a molded product containing ZSM-5 which has undergone the molding step is added to this stirred impregnation aqueous solution to form molybdenum. After impregnating the molded body with a component and a copper component, it was subjected to the following drying and firing steps. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight with respect to the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.1: It was set to 1.0.

(4) Drying and calcination The drying process was performed at 70 ° C. for about 12 hours in order to remove moisture added during the molding process. In the firing step, firing was performed in air at 550 ° C. for 5 hours. The firing temperature in the firing step was in the range of 550 to 800 ° C. This is because the strength of the carrier is lowered at 550 ° C. or lower, and the property (activity) is lowered at 800 ° C. or higher. The temperature increase rate and temperature decrease rate in the firing step were set to 90 to 100 ° C./hour. At this time, in order to prevent the organic binder added at the time of molding from burning instantaneously, the binder was removed by performing temperature keeping for about 2 to 6 hours twice in a temperature range of 250 to 450 ° C. This is because when the temperature increase rate and the temperature decrease rate are equal to or higher than the above rate and the keep time for removing the binder is not secured, the binder burns instantaneously and the strength of the fired body decreases.

(5) Carbonization treatment The fired body is heated to 700 ° C. in 2 hours under a flow of a mixed gas of CH ₄ and H ₂ (mixed molar ratio of methane / hydrogen = 1/4), and this state is maintained for 3 hours. Then, the atmosphere was switched to a reaction gas of CH _{4 and} the temperature was raised to 780 ° C.

(Comparative Example 2)
The catalyst of Comparative Example 2 was produced in the same manner as the catalyst formulation and production process of Comparative Example 1 except that copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.3: 1.0.

  In the impregnation step, an impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and a molded product containing ZSM-5 that has undergone the molding step according to Comparative Example 1 is added to the stirred impregnated aqueous solution, and molybdenum is added. The molded body was impregnated with a component and a copper component. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of molybdenum is 6% by weight based on the total amount of the catalyst after calcination, and the supported amount of copper is copper: molybdenum = 0.3: It was set to 1.0.

(Comparative Example 3)
The catalyst of Comparative Example 3 was produced in the same manner as the catalyst formulation and production process of Comparative Example 1 except that copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.45: 1.0.

  In the impregnation step, the impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and a molded body containing ZSM-5 that has undergone the molding step according to Comparative Example 1 is added to the stirred impregnated aqueous solution. The molded body was impregnated with a copper component. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight based on the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.45: It was set to 1.0.

(Comparative Example 4)
The catalyst of Comparative Example 4 was produced in the same manner as the catalyst formulation and production process of Comparative Example 1 except that copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.6: 1.0.

  In the impregnation step, an impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and a molded body containing ZSM-5 that has undergone the molding step according to Comparative Example 1 is added to the stirred impregnated aqueous solution. The molded body was impregnated with a component and a copper component. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight with respect to the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.6: It was set to 1.0.

Example 1
The catalyst of Example 1 was the same as that of Comparative Example 1 except that the molded body containing ZSM-5 was silane-treated with a silane compound and then copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.15: 1.0. It was manufactured by the same method as the blending and manufacturing process.

  In the silane treatment step, ZSM-5 that has undergone the molding step according to Comparative Example 1 is included in the dissolved ethanol so that the addition amount of APTES as a silane compound is 0.5% by weight with respect to the total amount of the catalyst after calcination. The molded body was impregnated for a predetermined time, dried, and then fired at 550 ° C. for 6 hours and treated with the silane compound.

  In the impregnation step, the impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and the molded product that has undergone the silane treatment step is added to the stirred impregnated aqueous solution, so that the molybdenum component and the copper component are molded. The body was impregnated. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight based on the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.15: It was set to 1.0.

(Example 2)
The catalyst of Example 2 was the same as that of Comparative Example 1 except that the molded body containing ZSM-5 was silane-treated with a silane compound and then copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.3: 1.0. It was manufactured by the same method as the manufacturing process (molding, drying, firing and carbonization treatment).

  In the silane treatment step, a molding containing ZSM-5 that has undergone the molding step according to Comparative Example 1 in ethanol in which APTES as the silane compound is dissolved in an amount of 0.5% by weight based on the total amount of the catalyst after calcination. The body was impregnated for a predetermined time, dried, and then calcined at 550 ° C. for 6 hours and treated with the silane compound.

  In the impregnation step, the impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and the molded product that has undergone the silane treatment step is added to the stirred impregnated aqueous solution, so that the molybdenum component and the copper component are molded. The body was impregnated. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of molybdenum is 6% by weight based on the total amount of the catalyst after calcination, and the supported amount of copper is copper: molybdenum = 0.3: It was set to 1.0.

(Example 3)
The catalyst of Example 3 was the same as that of Comparative Example 1 except that the molded body containing ZSM-5 was silane-treated with a silane compound and then copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.45: 1.0. It was manufactured by the same method as the manufacturing process (molding, drying, firing and carbonization treatment).

  In the silane treatment step, ZSM-5 that has undergone the molding step according to Comparative Example 1 is included in the dissolved ethanol so that the addition amount of APTES as a silane compound is 0.5% by weight with respect to the total amount of the catalyst after calcination. The molded body was impregnated for a predetermined time, dried, and then fired at 550 ° C. for 6 hours and treated with the silane compound.

  In the impregnation step, the impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and the molded product that has undergone the silane treatment step is added to the stirred impregnated aqueous solution, so that the molybdenum component and the copper component are molded. The body was impregnated. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight based on the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.45: It was set to 1.0.

Example 4
The catalyst of Example 4 was the same as that of Comparative Example 1 except that the molded body containing ZSM-5 was silane-treated with a silane compound and then copper and molybdenum were supported at a molar ratio of copper: molybdenum = 0.6: 1.0. It was manufactured by the same method as the manufacturing process (molding, drying, firing and carbonization treatment).

  In the silane treatment step, a molding containing ZSM-5 that has undergone the molding step according to Comparative Example 1 in ethanol in which APTES as the silane compound is dissolved in an amount of 0.5% by weight based on the total amount of the catalyst after calcination. The body was impregnated for a predetermined time, dried, and then calcined at 550 ° C. for 6 hours and treated with the silane compound.

  In the impregnation step, the impregnated aqueous solution prepared with copper acetate and ammonium molybdate is stirred, and the molded product that has undergone the silane treatment step is added to the stirred impregnated aqueous solution, so that the molybdenum component and the copper component are molded. The body was impregnated. Then, after drying this, it baked in air at 550 degreeC for 5 hours, and obtained the ZSM-5 support | carrier which carry | supported molybdenum and copper. In the preparation of the aqueous impregnation solution, the supported amount of copper was 6% by weight with respect to the total amount of the catalyst after calcination, and the supported amount of copper was copper: molybdenum = 0.6: It was set to 1.0.

2. Evaluation of Catalysts of Comparative Examples and Examples Evaluation methods of the catalysts of Comparative Examples and Examples will be described.

Inconel 800H gas contact part calorizing treatment reaction tube (inner diameter 18 mm) of a fixed bed flow type reactor was filled with 14 g of the catalyst to be evaluated (zeolite ratio 82.50%). Then, carbon dioxide mixed methane gas (the molar ratio of methane and carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3) is supplied as a reaction gas to the reaction tube, and the reaction space velocity = 3000 ml / g-MFI / The catalyst and the reaction gas were reacted under the conditions of h (CH ₄ gas flow base), a reaction temperature of 780 ° C., a reaction time of 24 hours, and a reaction pressure of 0.3 MPa. At this time, the product was analyzed, and the methane conversion rate, benzene production rate, naphthalene production rate, and BTX production rate were examined over time. The product was analyzed using TCD-GC and FID-GC.

  Methane conversion rate, benzene production rate, naphthalene production rate and BTX production rate are defined as follows.

“Methane conversion rate (%)” = [(“raw methane flow rate” − “unreacted methane flow rate”) / “raw methane flow rate”] × 100
“Benzene production rate” = “nmol number of benzene produced per second per 1 g of catalyst”.

  “Naphthalene production rate” = “nmol number of naphthalene produced per second per 1 g of catalyst”.

  “BTX production rate” = “total number of nmols of benzene, toluene and xylene produced per second per gram of catalyst”.

  FIG. 1 shows changes over time in the methane conversion rate when the catalysts of Comparative Examples 1 to 4 and Examples 1 to 4 are reacted with the carbon dioxide mixed methane gas. As is clear from the comparison of changes over time in the methane conversion rate when the catalysts of Examples 1 to 4 are reacted and when the catalysts of Comparative Examples 1 to 4 are reacted, silanes as in Examples 1 to 4 are used. It can be seen that when the treatment is performed, the active life stability of the methane conversion rate is improved as compared with the catalysts of Comparative Examples 1 to 4 in which the silane treatment is not performed.

  FIG. 2 shows changes with time of the benzene production rate when the catalysts of Comparative Examples 1 to 4 and Examples 1 to 4 are reacted with the carbon dioxide mixed methane gas. As is clear from the comparison of changes over time in the methane conversion rate when the catalysts of Examples 1 to 4 are reacted and when the catalysts of Comparative Examples 1 to 4 are reacted, silanes as in Examples 1 to 4 are used. It can be seen that when the treatment is performed, the active life stability of the benzene production rate is improved as compared with the catalysts of Comparative Examples 1 to 4 in which the silane treatment is not performed.

  FIG. 3 shows changes over time in the naphthalene production rate when the catalysts of Comparative Examples 1 to 4 and Examples 1 to 4 are reacted with the carbon dioxide mixed methane gas. As is clear from the comparison of changes over time in the methane conversion rate when the catalysts of Examples 1 to 4 are reacted and when the catalysts of Comparative Examples 1 to 4 are reacted, silanes as in Examples 1 to 4 are used. It can be seen that when the treatment is performed, the active lifetime stability of the naphthalene production rate is improved as compared with the catalysts of Comparative Examples 1 to 4 in which the silane treatment is not performed.

  FIG. 4 shows changes over time in the BTX generation rate when the catalysts of Comparative Examples 1 to 4 and Examples 1 to 4 are reacted with the carbon dioxide mixed methane gas. As is clear from the comparison of changes over time in the methane conversion rate when the catalysts of Examples 1 to 4 are reacted and when the catalysts of Comparative Examples 1 to 4 are reacted, silanes as in Examples 1 to 4 are used. It can be seen that when the treatment is performed, the active life stability of the BTX generation rate is improved as compared with the catalysts of Comparative Examples 1 to 4 in which the silane treatment is not performed.

  Table 1 shows methane conversion rate, benzene production rate, naphthalene production rate and BTX when each catalyst of Comparative Examples 1 to 4 and Examples 1 to 4 was reacted with the carbon dioxide mixed methane gas for 3 hours, 10 hours and 24 hours. Disclose the production rate. Comparing the comparative example and the example with respect to the activity characteristics in various reaction time zones, particularly the activity characteristics after 24 hours of reaction, Examples 2 to 4 are comparative examples 2 to 4 in which the supported amount of copper with respect to molybdenum is the same. Even when compared with, the silane treatment gives higher methane conversion rate, benzene production rate, naphthalene production rate, BTX production rate and higher activity than the catalyst according to the comparative example.

  As described above, the catalyst according to the invention in which molybdenum and copper are supported after silane treatment of the metasilicate improves the active life stability of the methane conversion rate, benzene formation rate, naphthalene formation rate, benzene, toluene, etc. BTX production rate which is a useful component of can be stably obtained.

  In the above-described embodiment, ZSM-5 is adopted for the metasilicate on which the metal component is supported. However, even when MCM-22 is applied, the same effects as in the above-described embodiment are obtained. Further, in the above examples, the supported amount of molybdenum is 6% by weight with respect to the total amount of the catalyst after calcination. The effect is similar to the example. Furthermore, in the said Example, although the molar ratio with respect to the molybdenum of the supported copper is 0.15-0.6, even if the said molar ratio is 0.01-0.8, the above-mentioned Example and The same effect is produced. Moreover, in the said Example, although the silane compound is added so that the addition amount may be 0.5 weight% with respect to the catalyst whole quantity after baking, if the addition amount is less than 2.5 weight%, it is the above-mentioned. The same effects as those of the embodiment are obtained. Further, in the above example, the aromatic compound is produced in the evaluation method by reacting with a reaction gas in which the molar ratio of methane to carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3. Even if the amount of the gas added is in the range of 0.5 to 6% with respect to the entire reaction gas, the same effect as in the above-described embodiment is obtained.

Methane conversion when each catalyst of Comparative Examples 1 to 4 and Examples 1 to 4 is reacted with carbon dioxide mixed methane gas (molar ratio of methane to carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3) Change in rate over time. Benzene production when each catalyst of Comparative Examples 1 to 4 and Examples 1 to 4 is reacted with carbon dioxide mixed methane gas (molar ratio of methane to carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3) Change in speed over time. Naphthalene generation when each catalyst of Comparative Examples 1 to 4 and Examples 1 to 4 is reacted with carbon dioxide mixed methane gas (molar ratio of methane to carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3) Change in speed over time. BTX generation when each catalyst of Comparative Examples 1 to 4 and Examples 1 to 4 is reacted with carbon dioxide mixed methane gas (molar ratio of methane to carbon dioxide is methane: carbon dioxide (carbon dioxide) = 100: 3) Change in speed over time.

Claims (9)

A catalyst that reacts with lower hydrocarbons and carbon dioxide to produce an aromatic compound,
After treating a zeolite comprising a metallosilicate with a silane compound having an amino group and a linear hydrocarbon group, which has a molecular diameter larger than the pore diameter of the zeolite and selectively reacts with the zeolite's Bronsted acid point A lower hydrocarbon aromatization catalyst characterized by supporting molybdenum and copper.   The molybdenum has a supported amount of 2 to 12% by weight based on the total amount of the catalyst after calcination, and the copper has a molar ratio Cu: Mo = X: 1 with molybdenum of 0.01 to 0.8. The lower hydrocarbon aromatization catalyst according to claim 1, wherein the lower hydrocarbon aromatization catalyst is supported as follows.   The lower hydrocarbon aromatization catalyst according to claim 1 or 2, wherein the firing temperature after firing molybdenum and copper on the metallosilicate is 550 to 800 ° C.   4. The lower hydrocarbon aromatization catalyst according to claim 1, wherein the metallosilicate is ZSM-5 or MCM-22. 5.   5. The lower hydrocarbon aromatization catalyst according to claim 1, wherein the silane compound is APTES (3-Aminopropyl-triethoxysilane).   6. The lower hydrocarbon aromatization catalyst according to claim 5, wherein the APTES is subjected to a silane treatment such that the addition amount thereof is less than 2.5 wt% with respect to the total amount of the catalyst after calcination.   The lower hydrocarbon aromatization catalyst according to claim 6, wherein the APTES is subjected to silane treatment so that the amount of the APTES added is 0.5 wt% with respect to the total amount of the catalyst after calcination. Production of an aromatic compound, characterized in that a reaction gas containing lower hydrocarbon and carbon dioxide gas is reacted with a catalyst obtained by supporting molybdenum and copper on a metallosilicate carrier and then calcined to produce an aromatic compound Method.   The method for producing an aromatic compound according to claim 8, wherein the amount of carbon dioxide added is in the range of 0.5 to 6% with respect to the total reaction gas.

Images