KR102295224B1 - Catalyst for Dehydroaromatization of Methane and Production Method of BTX from Methane Using Said Catalyst - Google Patents

Abstract

The present invention relates to a catalyst capable of improving the yield of BTX (benzene, toluene, and xylene) in the dehydroaromatication reaction of methane, and a method for producing BTX using the same, and more particularly, to a zeolite that does not support a metal A catalyst capable of increasing the selectivity of BTX in the dehydroaromatization reaction of methane by mixing and using a zeolite supported with a transition metal and a method for producing BTX using the same.

Description

Catalyst for dehydroaromatization of methane and method for preparing an aromatic compound using the same {Catalyst for Dehydroaromatization of Methane and Production Method of BTX from Methane Using Said Catalyst}

The present invention provides a catalyst capable of improving the BTX yield in the dehydroaromatization of methane, a method for producing BTX through the dehydroaromatization of methane using the catalyst, and BTX (benzene, toluene and xylene) using the catalyst It relates to a manufacturing method.

Recently, as the problem of environmental pollution has received great attention around the world, attempts to break free from dependence on crude oil are being actively carried out. Methane is a component of greenhouse gas, and related research is being conducted to efficiently utilize methane. Methane is a light hydrocarbon known as a component of shale gas and natural gas, and although it can be useful industrially, it is currently mostly used as a fuel due to the absence of a process that can secure low reactivity and economical efficiency. However, with the recent development of shale gas and natural gas mining technology in China and North America, which is expected to improve methane supply stability, attempts to produce high value-added products through direct conversion of methane, which are relatively price-competitive, have begun. is in progress Among them, a representative example may be the production of BTX (benzene, toluene and xylene) through dehydrogenation aromatization.

On the other hand, since natural gas is expected as an effective energy in preparation for global warming, interest in technology using natural gas is increasing. In general, natural gas is 1 to 10% _{ethane (C 2} H ₆ ), less than 5% _{propane (C 3} H ₈ ), less than 2% _{butane (C 4} H ₁₀ ), less than 1% _{pentane (C 5} H _{12 )} And hexane (C ₆ H ₁₄ ) contains less than 0.5%, methane (CH ₄ ) contains 70 to 98% as a main component.

In the use of natural gas, methane gas, which is a main component, receives high attention, and ethane contained in natural gas is also removed when the natural gas is poured into a storage in a liquefied form or when the natural gas is transported through a pipe or the like.

In addition, BTX is a key material in the manufacture of synthetic resins, detergents, and rubber, and its industrial value is very high, so the demand for it is increasing recently. Currently, the process of manufacturing BTX is manufactured through naphtha reforming, separation, and refining processes, and it is not economically efficient because it is a process incidental to the crude oil distillation process. Due to this, new process development is required, and with the development of new approaches for manufacturing high value-added products using light paraffin over the past 10 years, the development of a high value-added process for light paraffin mixed gas using methane as the main reactant shows great potential. have.

In Japan, Meidensha Corporation conducted a study on the aromatization of light hydrocarbons using methane as the main reactant, and used a ZSM-5 catalyst on which molybdenum and copper were supported (Patent Document 1).

Mitsui Chemicals Inc. of Japan conducted a study to increase the BTX production yield by successively using two fixed bed reactors using a ZSM-5 catalyst supported with molybdenum (Patent Document 2).

The difficulty of this study is that dehydroaromaticization of methane is an endothermic reaction that is not spontaneous and requires high thermal energy, whereas coke deposition increases in a high temperature reaction, making it difficult to commercialize (Non-Patent Document 1).

6CH ₄ -> C ₆ H ₆ + 9H ₂ (Scheme 1)

There have been various attempts to solve this problem, when a low-cost alcohol (methanol, ethanol) is added to remove _{hydrogen (H 2} ) obtained as a product in the dehydrogenation aromatic reaction of methane according to Scheme 1, the added alcohol By accelerating the reaction of removing hydrogen by reacting with the hydroxyl group of the hydrogen, the dehydroaromatization reaction of methane is promoted. Since the thermodynamically dehydroaromatic reaction of methane is more spontaneous and the energy required is also reduced, it can bring about the effect of producing BTX at a lower temperature.

At CSIR-National Chemical Laboratory in India, the reaction equilibrium was improved at 500°C by simultaneous reaction of methane and methanol using a molybdenum-zinc-containing H-ZSM-5 catalyst (Non-Patent Document 2), and molybdenum at Indian Institute of Technology in India It was reported that a methane conversion rate of 9.0% and a xylene selectivity of 19% at 600°C using a -containing H-ZSM-5 catalyst (Non-Patent Document 3).

However, when using the molybdenum-containing H-ZSM-5 catalyst for the dehydroaromatication reaction of methane, the catalyst is coked by the coke deposits, thereby reducing the activity of the catalyst within a short time, and thus the production cycle is shortened. It also irreversibly shortens the life of the catalyst.

Therefore, in order to solve the above problems, the present inventors have completed the present invention from the fact that the BTX yield is improved in the dehydroaromatization of methane by using the catalyst complex in which molybdenum (Mo) is supported on the existing HZSM-5.

US Patent Registration No. 8278237 (published on Jan. 21, 2010) US Patent Registration No. 9169171 (published on May 9, 2013)

J.J. Spivey, G. Hutchings, Chem. Soc. Rev. 43, (2014) 792 V.R. Choudhary, K.C. Mondal, S.A. Mulla, Angew. Chem. Int. Ed. 44, (2005) 4381-4385 S. Majhi, K.K. Pant, J. Ind. Eng. Chem. 20 (2014) 2364-2369

The present invention is to solve the above problems, and to provide a catalyst with an improved yield in producing BTX from methane and a method for producing BTX from methane using the same.

In order to solve the above problems, the present invention is a catalyst for the dehydroaromatization of methane, wherein the dehydroaromatization reaction of methane includes an oxygenated carbon compound as a reactant, and the catalyst includes a metal unsupported zeolite and a transition metal supported zeolite It provides a complex catalyst that

In an embodiment of the present invention, the transition metal is selected from Mo, Ga, Ni, Cu, Zn, Sn, Fe, V, Cr, Sb, W, Co, Pt, Pd, In, Ag, Re, and Ru. It may be 1 type or 2 or more types of metals.

In the present invention, the zeolite may be a zeolite having an MFI structure and/or a MWW structure, the Si/Al molar ratio of the transition metal-supported zeolite is in the range of 10 to 1000, and the Si/Al molar ratio of the non-metal supported zeolite is 10 to 1000 It can be characterized as a range.

In another embodiment of the present invention, the transition metal content of the transition metal-supported zeolite may be 0.5 to 20 wt%, and the non-metal-supported zeolite is 15 to 80 wt% with respect to the transition metal-supported zeolite. characterized by mixing.

In the present invention, the oxygen-containing carbon compound may be an organic oxide having 1 to 4 carbon atoms, and the organic oxide is methanol, ethanol, propanol, propanediol, butanol, butanediol, glycerol, acetic acid, acrylic acid, methanol, ethanal, propane It may be at least one selected from al, butanal, dimethyl ether, diethyl ether, and acetone.

In another embodiment of the present invention, there is provided a method for preparing an aromatic compound from a mixture of methane and an oxygenated carbon compound using the catalyst of the present invention.

In the present invention, the molar ratio of methane and oxygen-containing carbon compound may be in the range of 1: 0.03 to 1: 5, and the temperature of the reaction for generating an aromatic compound from the mixture of methane and oxygen-containing carbon compound is 400 to 700 ℃, pressure is 1 to 15 atm, GHSV may be 1,000 to 50,000.

According to the present invention, aromatic compounds (benzene, toluene, and xylene), which are rapidly in demand worldwide, can be easily produced from methane. In addition, currently aromatic compounds are produced by the naphtha reforming process and separation and refining process, and the raw material naphtha has low price stability due to its high dependence on crude oil. It is possible to obtain economic benefits by producing phosphorus aromatic compounds, and has the advantage of actively coping with future market changes.

1 is a graph showing carbon conversion according to reaction time in the dehydrogenation and aromatization reaction of methane according to Comparative Example 1 and Examples 1 and 2;
2 shows the selectivity of each product ((a): aliphatic compound, (b) aromatic compound) according to reaction time in the dehydrogenation aromatization reaction of methane according to Comparative Example 1. FIG.
3 shows the selectivity of each product ((a): aliphatic compound, (b) aromatic compound) according to reaction time in the dehydrogenation aromatization reaction of methane according to Example 1. FIG.
4 shows the selectivity of each product ((a): aliphatic compound, (b) aromatic compound) according to reaction time in the dehydrogenation aromatization reaction of methane according to Example 2. FIG.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

Throughout this specification, when a part "includes" a component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the detailed description of the principle of the preferred embodiment of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

The present invention provides a catalyst for the dehydroaromatization reaction of methane, wherein the dehydroaromatization reaction of methane includes an oxygenated carbon compound as a reactant, and the catalyst is a metal-free MFI-structured zeolite and an active metal. It is characterized in that it is a composite catalyst simultaneously containing a supported MFI-structured zeolite.

In the dehydrogenation aromatization reaction of methane of the present invention, an oxygen-containing carbon compound is used as a reactant in order to promote the dehydrogenation aromatization reaction of methane by removing hydrogen, which is produced by the dehydrogenation aromatization reaction of methane according to Scheme 1 below. used

6CH ₄ -> C ₆ H ₆ + 9H ₂ (Scheme 1)

Preferably, an organic oxide having 1 to 4 carbon atoms can be used as the oxygen-containing carbon compound. Examples of the organic oxide include, but are not limited to, monohydric alcohols or polyhydric alcohols such as methanol, ethanol, propanol, propanediol, butanol, butanediol, and glycerol; acids such as acetic acid and acrylic acid; aldehydes such as methanal, ethanal, propanal, and butanal; ethers such as dimethyl ether and diethyl ether; Ketones such as acetone can be used, and the dehydrogenation and aromatization reaction of methane can be accelerated by using such an organic oxide as an additive.

In addition, in the present invention, the catalyst in the dehydrogenation aromatization reaction of methane is at least one of metal-free MFI and MWW zeolite, and the transition metal-supported MFI and transition metal-supported MWW zeolite. It is characterized in that it is a complex catalyst containing at least one of them at the same time.

That is, the composite catalyst simultaneously contains at least one of MFI and MWW structure type zeolite not supported with any metal and at least one of MFI and MWW structure type zeolite supported with a transition metal, thereby dehydrogenation reaction mechanism of methane In this case, two catalyst components having different working effects are allowed to act simultaneously.

Therefore, in the dehydroaromatization reaction of methane, the present invention uses a composite catalyst including a metal unsupported zeolite and a transition metal supported zeolite at the same time, whereby the catalyst is rapidly deactivated by coke deposits during the dehydroaromatication reaction of methane. In addition to improving the problems, the yield of aromatic compounds from methane is improved, so that high value-added aromatic compounds can be effectively produced from inexpensive methane.

The zeolite may be a zeolite having an MFI structure or a MWW structure, and the transition metal is Mo, Ga, Ni, Cu, Zn, Sn, Fe, V, Cr, Sb, W, Co, Pt, Pd, In, Ag, It may be any one or more of Re and Ru, preferably Mo.

Hereinafter, a method for supporting a transition metal according to the present invention on a zeolite will be described, but the above description is only an example and is not limited thereto. can

First, when the transition metal precursor is supported using a solvent, one of known precursors that can be dissolved in the solvent may be selected and used. For example, when the transition metal is molybdenum and the solvent is water, ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O) may be used. In addition, when using a chemical vapor deposition method, etc., a precursor that can be easily vaporized may be used, for example, when the transition metal is molybdenum, molybdenum oxide (MoO ₃ ) may be used.

In addition, in order to support the transition metal precursor in the MFI structure type zeolite, a transition metal precursor is dissolved in a solvent to prepare a transition metal precursor solution, and as a solvent used at this time, it is preferable to use water, methanol, ethanol, or a mixture thereof. It is not limited to this. In addition, depending on the situation, in order to control the dispersion degree of the transition metal, it is possible to perform pH adjustment using an appropriate pH adjusting agent.

Then, after adding the MFI structure type zeolite to the transition metal precursor solution, the prepared catalyst precursor solution is maintained at room temperature to 50° C. for 1 to 10 hours so that the transition metal precursor is sufficiently supported in the zeolite.

In addition, the MFI-structured zeolite on which the transition metal precursor is supported is dried at 80 to 150° C. to remove the solvent remaining in the catalyst. Drying can be carried out under normal pressure or vacuum.

Finally, the dried transition metal precursor is subjected to a step of calcining the supported zeolite, for example, it is preferable to prepare the catalyst by calcining at 400 °C to 700 °C for 1 hour to 10 hours. If the calcination temperature is 400 ° C. or less than 1 hour, the catalyst properties do not change and the catalyst is only in a dry state, and there is a problem that the catalyst activity is lowered because chemical bonding of the catalyst is not made. Since particle dispersibility deteriorates, it is preferable to maintain the above range.

At this time, it is preferable that the zeolite on which the transition metal is supported is of a proton type. By using a proton-substituted zeolite, in the dehydrogenation reaction of methane, it acts as a site to which the active metal in the form of an oxide is bound, so that the active metal is highly dispersed and This is because not only can it be stabilized, but it can also act as an acid site and provide a function for oligomerization and aromatization of dimerized methane.

It is preferable to use at least one of a zeolite having an MFI structure and a MWW structure as the zeolite.

MFI zeolites may consist of three or four pentasil units linked together by oxygen bridges, forming pentasil chains. At this time, the pentasil unit is composed of 8 5-membered rings, each vertex is aluminum or silicon, and oxygen is bonded between these vertices, and accordingly, the pentasil chain is connected to each other by an oxygen bridge and has 10 ring holes. A corrugated sheet may be formed. ZSM-5, a type of MFI zeolite, can be hydrothermal synthesized by reacting silicon oxide with sodium aluminate at high temperature and high pressure in the presence of a tetraalkylammonium compound.

The MFI-structured zeolite is not limited thereto, but may be any one or more selected from Silicalite-1, ZSM-5, and TS-1.

The Si/Al ratio of the metal-unsupported MFI structure zeolite may be in the range of 10 to 1000, preferably 20 to 750, and more preferably 25 to 140. Most preferably, it may be 30-50.

The Si/Al ratio of the metal-supported MFI structure zeolite may be in the range of 10 to 1000, preferably 20 to 750, and more preferably 50 to 300. Most preferably, it may be 100-200.

The MWW framework structure is characterized by two independent pore systems. Specifically, one pore structure is a 10-membered ring pore (4.0 Å × 5.5 Å), which is sinusoidal, and the other is a cocoon-type supercage (7.1 Å × 18.2 Å) consisting of 10-membered rings and 12 rings. Six supercages are connected in two dimensions.

The zeolite of the MWW structure is not limited thereto, but may be exemplarily one selected from MCM-22, ERB-1, ITQ-1, PSH-3, SSZ-25, and the like.

The Si/Al ratio of the metal unsupported MWW structure zeolite may be in the range of 10 to 1000, preferably 20 to 750, and more preferably 25 to 140. Most preferably, it may be 30-50.

The Si/Al ratio of the metal-supported MWW structure zeolite may be in the range of 10 to 1000, preferably 20 to 750, and more preferably 50 to 300. Most preferably, it may be 100-200.

The transition metal content of the transition metal-supported zeolite may be 0.5 to 20 wt%.

The metal unsupported zeolite may contain 15 to 80 wt% with respect to the transition metal supported zeolite, and when it is within the above range, the aromatization yield is high, and catalyst stability is also increased. Preferably 30 to 65 wt% may be used.

In addition, the present invention provides a method for producing an aromatic compound from methane and an oxygen-containing carbon compound in the presence of a catalyst for the methane aromatization reaction.

At this time, the molar ratio of the methane and the oxygen-containing carbon compound used as a reactant is preferably in the range of 1:0.03 to 1:5, and the reaction temperature in the methane aromatization reaction is preferably 400 to 700°C.

In addition, in the present invention, the reaction pressure may be 1 to 15 atm, and the GHSV may be 1,000 to 50,000.

At this time, the composite catalyst comprising the non-metal supported catalyst and the transition metal supported catalyst according to the present invention maintains catalytic activity according to the reaction time, thereby improving the life of the catalyst.

Hereinafter, with reference to the accompanying drawings and examples, the complex catalyst for the aromatization reaction of methane according to the present invention and a method for producing an aromatic compound using the same will be described in detail.

In addition, since the configuration shown in the embodiments and drawings described in this specification is only the most preferred embodiment of the present invention and does not represent all the technical spirit of the present invention, various It should be understood that there may be equivalents and variations.

Preparation Example 1: Preparation of Mo-HZSM-5 (140) catalyst

Ammonium-form ZSM-5 (NH ₄ -ZSM-5, Si/Al=140) zeolite was purchased from Zeolyst (model name CBV 28014) and was calcined at 550°C for 12 hours to convert to H-from ZSM-5 make it H-ZSM-5 is dried in an oven at 100° C. for 12 hours before use, and then used to prepare the catalyst. The amount of the Mo precursor is quantified so that the mass ratio of the transition metal oxide after calcination is 6wt% relative to the H-ZSM-5 mass, and then dispersed and dissolved in a solvent. Mo precursor solution was supported on dried H-ZSM-5 using the impregnation method and maintained at 30°C for 3 hours so that the transition metal was sufficiently supported in the zeolite pores, and the solvent was completely removed by vacuum drying at 120°C. do. The solvent-removed Mo-supported zeolite is calcined at 500° C. for 4 hours to remove impurities and to prepare a Mo oxide-supported zeolite catalyst.

Preparation Example 2: Preparation of Mo-HZSM-5 (140) / HZSM-5 (11.5) catalyst

The Mo oxide-supported H-ZSM-5 zeolite catalyst was prepared by the method of Preparation Example 1. Ammonium-form ZSM-5 (NH ₄ -ZSM-5, Si/Al=11.5) zeolite was purchased from Zeolyst (model name CBV 2314) and was calcined at 550°C for 12 hours to convert to H-from ZSM-5 use it Mo-HZSM-5(140)/HZSM-5(11.5) catalyst is prepared through the following method. Mo-supported ZSM-5 and metal non-supported HZSM-5 were mixed in a weight ratio of 3:1.

H-ZSM-5 (Si/Al=140) on which Mo oxide in powder form is supported and H-ZSM-5 in powder form (Si/Al=11.5) are each molded. After grinding the molded body into particles of a certain size, uniformly dispersed and mixed using a mechanical mixing method to prepare a composite catalyst.

Preparation Example 3: Preparation of Mo-HZSM-5 (140) / HZSM-5 (40) catalyst

Mo-HZSM-5(140)/HZSM-5(40) catalyst was prepared in the same manner as in Preparation Example 2, except that the Si/Al of HZSM-5 on which Mo was not supported was 40.

Comparative Example 1

The catalyst of Preparation Example 1 was pulverized to a size of 30 to 70 mesh in a 3/8” Quartz reactor, 0.4 g was filled in the reactor, and an inert gas was flowed thereto, and the temperature was raised to 575°C. Then, while maintaining the same temperature _{, a mixed gas having a molar ratio of CH 4} /H ₂ = 2 of methane and hydrogen was flowed at 1 atm at a rate of 10 ml/min for 3 hours so that the catalyst undergoes passivation due to reduction and carbonization. .

After that, in order to proceed with the reaction, the supply of the mixed gas of methane and hydrogen was stopped, and the reaction pressure was 1 atm, and the GHSV was 2850 ml/g-cat/h of a mixture of methane and methanol in a molar ratio of 1:1. It was supplied to the reactor to proceed with dehydrogenation and aromatization of methane.

The gas containing the product and reactant at the rear end of the reactor was analyzed by FID and TCD detectors of online gas chromatography, and the results are shown in Table 1 and FIGS. 1 and 2 .

Total carbon conversion is the total number of carbon moles of methanol and methane in the product divided by the total number of carbon moles of methanol and methane in the reactant, and carbon selectivity is the number of moles of carbon in a specific reactant divided by moles of carbon in the total product. divided and calculated.

Example 1

The same experiment was performed except that the catalyst in Comparative Example 1 was replaced with that of Preparation Example 2, and the results are shown in Table 1 and FIGS. 1 and 3 .

Example 2

The same experiment was performed except that the catalyst in Comparative Example 1 was replaced with that of Preparation Example 3, and the results are shown in Table 1 and FIGS. 1 and 4 .

division total carbon
Conversion rate (%) Selectivity (%) COx Aliphatics Aromatics Benzene Toluene Xylene Comparative Example 1 63.2 1.7 71.5 26.8 3.0 9.0 12.2 Example 1 67.5 1.5 69.2 29.3 3.8 11.6 12.2 Example 2 64.5 3.1 62.2 34.6 4.0 11.7 15.3

Table 1 shows the average carbon conversion and product selectivity for 8 hours after the start of the reaction. Overall, it can be seen that the selectivity of BTX is higher in the examples of the present application, and it can be confirmed that the catalyst of the present invention can be usefully used in the methane dehydrogenation aromatization reaction.

1 shows carbon conversion rates in Comparative Example 1 and Examples 1 and 2.

As can be seen from FIG. 1 , it is confirmed that the degree of deactivation of the catalyst does not differ significantly in the case of each reaction.

2 to 4 show the product selectivity of Comparative Example 1, Example 1, and Example 2, respectively.

Unlike the carbon conversion rate, it was confirmed that the selectivity of the aromatic compound in the dehydroaromatization reaction of methane was relatively increased when the Mo-HZSM-5 (140) /HZSM-5 (11.5) catalyst according to Example 1 was used. It was possible (comparison of FIGS. 2 and 3), and in particular, it is confirmed that the rate at which the selectivity of toluene is deactivated with time is significantly reduced.

2 and 4, in the case of using the Mo-HZSM-5(140) /HZSM-5(40) catalyst according to Example 2, the degree of deactivation was compared with that of the Mo-HZSM-5(140) alone catalyst. Although the deactivation tendency of other products is similar, it can be seen that the selectivity of aromatic compounds by reaction time is significantly increased compared to the case of using only Mo-HZSM-5(140). The activity in the initial stage of the reaction also showed a high rate of increase in the selectivity of toluene and benzene in Example 2, and the selectivity of para-xylene is also stably high.

In addition, when comparing Example 1 and Example 2 (FIGS. 3 and 4), the product distribution is increased by adjusting the Si/Al ratio of the zeolite mixed with the transition metal-supported Mo-HZSM-5 (140). you can see the change.

That is, it can be seen that the selectivity of the product can be controlled by adjusting the Si/Al ratio.

As described above, the present invention has been described with reference to the accompanying drawings and embodiments, but this is only exemplary, and that various modifications and equivalent other embodiments are possible therefrom by those of ordinary skill in the art. will understand Therefore, the technical protection scope of the present invention should be defined by the following claims.

Claims (11)

In the catalyst for dehydroaromatization of methane,
The dehydroaromatization reaction of methane includes an oxygen-containing carbon compound as a reactant,
The catalyst is selected from among molybdenum (Mo), chromium (Cr), and tungsten (W) belonging to group VIB on the periodic table in at least one zeolite selected from the MFI structure and the MWW structure, and at least one zeolite selected from the MFI and MWW structure. Catalyst for dehydroaromatization of methane, characterized in that it is a composite catalyst comprising at least one supported zeolite.
delete delete The method of claim 1,
The Si/Al molar ratio of the zeolite in which at least one selected from molybdenum (Mo), chromium (Cr), and tungsten (W) belonging to group VIB of the periodic table is supported on one or more zeolites selected from the MFI and MWW structures is in the range of 10 to 1000 and the Si/Al molar ratio of at least one zeolite selected from the metal-unsupported MFI structure and the MWW structure is in the range of 10 to 1000. Catalyst for dehydroaromatization of methane.
The method of claim 1,
The transition metal content of the zeolite in which at least one selected from molybdenum (Mo), chromium (Cr), and tungsten (W) belonging to group VIB of the periodic table is supported on at least one zeolite selected from the MFI and MWW structures is 0.5 to 20 wt% Catalyst for dehydroaromatization of methane, characterized in that.
The method of claim 1,
At least one zeolite selected from the metal-unsupported MFI structure and the MWW structure is at least one selected from among molybdenum (Mo), chromium (Cr), and tungsten (W) belonging to group VIB on the periodic table in at least one zeolite selected from the MFI and MWW structure. Catalyst for dehydroaromatization of methane, characterized in that it is mixed in an amount of 15 to 80 wt% with respect to the supported zeolite.
The method of claim 1,
The oxygen-containing carbon compound is a catalyst for dehydroaromatization of methane, characterized in that it is an organic oxide having 1 to 4 carbon atoms.
8. The method of claim 7,
The organic oxide is characterized in that at least one selected from methanol, ethanol, propanol, propanediol, butanol, butanediol, glycerol, acetic acid, acrylic acid, methanal, ethanal, propanal, butanal, dimethyl ether, diethyl ether, and acetone. Catalyst for dehydroaromatic reaction of methane.
In the presence of a catalyst for dehydroaromatization of methane of any one of claims 1, 4 to 8,
A method for producing an aromatic compound from a mixture of methane and oxygen-containing carbon compounds.
10. The method of claim 9,
A method for producing an aromatic compound from a mixture of methane and oxygen-containing carbon compound, characterized in that the molar ratio of methane and oxygen-containing carbon compound is in the range of 1: 0.03 to 1: 5.
10. The method of claim 9,
A method for producing an aromatic compound from a mixture of methane and oxygen-containing carbon compounds, characterized in that the reaction temperature is 400 to 700 ° C, the reaction pressure is 1 to 15 atm, and the GHSV is 1,000 to 50,000 ml/g-cat/h.

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