KR950007579B1 - Catalyst for preparing ethylene from methane, method for production thereof, and method for preparing ethylene - Google Patents

Abstract

A supported catalyst [MaS; M is a compound selected from Ru3(CO)12, Rh6(CO)16, Rh2(OCOCH3)4, RuCl3xH2O, S is an inorganic carrier selected from alpha-alumina, gamma-alumina, activated carbon, silica, TiO2, MgO, ZnO, ZrO2, a is 5.0-10.0 wt. % of a metal in the catalyst to prepare ethylene was prepared from methane. Thus, 0.64 g of TiO2 and 0.110 g (0.172 mmole) of Ru3(CO)12 were stirred for 30 min in 15 ml n-hexane, and dried for 12 hr in a vacuum dryer to give Ru3(CO)12/TiO2 (7.51 wt.% of Ru) catalyst.

Description

Inorganic supported catalyst for producing ethylene from methane, preparation method thereof and preparation method of ethylene

This application is the following general formula (I)

[Formula 1]

It supported the production of ethylene mugiche from methane catalyst (in which M is _{Ru 3 (CO) 12, Rh} 6 represented by _{(CO) 16, Rh 2 (} OCOCH 3) 4, RuCl 3 · xH is a compound alternatively from ₂ O, S is The inorganic carrier used was an alternative dimji among α-alumina, γ-alumina, activated carbon, silica, TiO ₂ , MgO, ZnO, ZrO ₂ , and a is the weight percentage of the metal in the catalyst.

M and S were added to a solvent, the mixture was stirred at room temperature, the solvent was distilled under reduced pressure, and the residue was vacuum dried to prepare an inorganic dimji catalyst for producing ethylene.

Wherein M is a compound selected from among Ru ₃ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh ₂ (OCOCH ₃ ) ₄ , RuCl ₃ .xH ₂ O, and S is an inorganic carrier used as α-alumina, one carrier selected from γ-alumina, activated carbon, silica, TiO ₂ , MgO, ZnO, ZrO ₂ ).

The present invention relates to a method for producing ethylene which is reacted at 500 to 750 ° C. and 1 atm to 10 atm in the presence of methane, nitrogen and a catalyst (I) represented by the general formula MaS.

Conventionally, there are very few documents, patents, and the like for a catalyst capable of producing methanol by reacting with methanol. All of them have the disadvantage of generating carbon dioxide as a byproduct as catalysts for oxidative coupling reactions.

Conventional synthesis of ethylene and ethane by carbohydrate reaction of methane has been carried out at a relatively high temperature (temperature range of 1500-1550 ° C.). The reaction has been carried out by thermal or electrical cracking reaction methods. Therefore, since the reaction temperature is a high temperature, there is a big disadvantage in the device cost, energy supply, etc. necessary for maintaining the temperature, in particular, because the corrosion of the reactor must be taken into consideration, there is a big problem in the material selection of the reactor and the device.

In the present invention, in order to solve these problems, a catalyst suitable for the present reaction was prepared by supporting a metal cluster compound on an inorganic compound support, and the reaction conditions such as reaction temperature, reaction pressure, etc., were greatly reduced according to the reaction.

In addition, by using the general formula MaS (I), which is the catalyst of the present application, the method of synthesizing a lower hydrocarbon such as ethylene can be greatly simplified, and the productivity can be greatly improved.

The present invention is described in detail as follows.

In order to prepare a catalyst suitable for ethylene synthesis from methane, various catalysts in which the cluster compound was supported on an inorganic carrier were prepared. At this time, the preparation and purification of the catalyst was very simple compared to the preparation method of the catalyst.

In the present invention, unlike the conventional method, the reaction temperature can be greatly reduced to 500 to 750 ° C., and by-products are not generated at all, thereby simplifying the process. In synthesizing lower hydrocarbons such as ethylene, it was synthesized in a yield of 1.09% using Ru ₃ (CO) ₁₂ / α-alumina (6.86 wt% Ru). That is, by using a heterogeneous catalyst, the reaction conditions such as reaction temperature and reaction pressure can be further relaxed, and the reaction apparatus can be simplified.

The inorganic carrier supported catalyst preparation method of the present invention is as follows.

First, the carrier is dried in a vacuum dryer, and a mixture of a metal cluster (0.10.-0.90 m mole) compound and a carrier (0.5-1 g) is added to a solvent (mixed solvent of dichloromethane and acetone), and then immersed by stirring at room temperature. The immersed catalyst is then dried in a vacuum dryer to room temperature to obtain a catalyst.

Inorganic carriers used herein are α-alumina, γ-alumina, activated carbon, silica, TiO ₂ , MgO, ZnO, ZrO ₂ . The catalytic compounds used simultaneously were Ru ₃ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh ₂ (OXOCH ₃ ) ₄ , RuCl ₃ .xH ₂ O.

According to the experiments of the present inventors, the most suitable carriers for the production of C ₂ compounds such as ethylene are α-alumina, TiO ₂ , and the Group VIII metal is ruthenium.

The reaction conditions carried out in the presence of the novel catalyst described in the present invention are as follows. The dilution ratio of nitrogen to methane is 1 to 6, preferably 1 to 3, in molar ratio. Reaction temperature is 500-800 degreeC, Preferably it is 500-700 degreeC.

The concentration of the metal in the catalyst is 5 to 10 wt%, preferably 4 to 7 wt%. The space velocity of the raw material gas is in the range of 100 to 5,000 hr ⁻¹ , preferably in the range of 500 to 2,000 hr ⁻¹ . The reaction pressure is usually 1 to 10 atmospheres, preferably 1 to 5 atmospheres.

In this application, yield, conversion and selectivity as ethylene are defined by the following equation.

[Equation 1]

[Equation 2]

[Equation 3]

Reactants and products were analyzed by gas chromatography.

An embodiment is described in detail as follows.

Example 1

_{TiO 2 0.64g, Ru 3 (CD} ) 12 0.110g (0.172mmole) with stirring for 30 minutes at room temperature, was added to 15ml of n- hexane, and then, after the solvent was distillated under reduced pressure for 12 hours to dry in a vacuum dryer to Ru ₃ ( CO) ₁₂ / TiO ₂ (7.51 wt% Ru) was prepared.

Example 2

0.65 g of TiO ₂ , 0.109 g (0.525 mmol) of RuCl ₃ · xH ₂ O were added to 20 ml of methanol, stirred for 30 minutes, and the solvent was distilled under reduced pressure, followed by drying in a vacuum dryer for 12 hours to give RuCl ₃ · xH ₂ O / A catalyst of TiO ₂ (7.55 wt% Ru) was prepared.

Example 3

_{TiO 2 0.61g, Rh 2 (OCOCH} 3) 4 0.102g (0.232mmole) was added to a stirred 30ml of ethanol for 30 minutes, then the solvent was distillated under reduced pressure for 12 hours to dry in a vacuum dryer to Ru ₂ (OCOCH ₃₎ A catalyst of ₄ / TiO ₂ (7.07 wt% Rh) was prepared.

Example 4

0.62g TiO ₂ , Ru ₆ (CO) ₁₆ 0.11g (0.103mmole) was added to 20ml of dichloromethane, stirred for 30 minutes, the solvent was distilled under reduced pressure and dried in a vacuum dryer for 12 hours, and then Rh ₆ (CO) ₁₆ A catalyst of / TiO ₂ (9.32 wt% Rh) was prepared.

Example 5

0.65g SiO ₂ , Ru ₃ (CO) ₁₆ 0.11g (0.172mmole) was added to 30ml of dichloromethane and 10ml of acetone, stirred for 30 minutes, the solvent was distilled under reduced pressure and dried in a vacuum dryer for 12 hours to give Ru ₃ A catalyst of (CO) ₁₂ / SiO ₂ (7.43 wt% Ru) was prepared.

Example 6

0.67 g of α-Al ₂ O ₃ , 0.10 g (0.156 mmol) of Ru ₃ (CO) ₁₂ were added to 30 ml of dichloromethane and 10 ml of acetone, stirred for 30 minutes, and the solvent was distilled under reduced pressure, followed by 12 hours in a vacuum dryer. It was dried to prepare a catalyst of Ru ₃ (CO) ₁₂ / γ-Al ₂ O ₃ (6.17wt% Ru).

Example 7

0.65 g of α-Al ₂ O ₃ and 0.10 g (0.156 mmol) of Ru ₃ (CO) ₁₂ were added to 30 ml of dichloromethane and 10 ml of acetone, stirred for 30 minutes, and the solvent was distilled under reduced pressure, followed by 12 hours in a vacuum dryer. It was dried to prepare a catalyst of Ru ₃ (CO) ₁₂ / α-Al ₂ O ₃ (6.86wt% Ru).

Example 8

Activated carbon 0.65g, Ru ₃ (CO) ₁₂ 0.10g (0.156mmole) was added to 30ml of dichloromethane and 10ml of acetone, stirred for 30 minutes, the solvent was distilled under reduced pressure and dried in a vacuum dryer for 12 hours to give Ru ₃ ( CO) _{12 /} carbon (6.83 wt% Ru) was prepared.

Example 9

_{ZrO 2 0.66g, Ru 3 (CO} ) 12 0.11g (0.172mmole) was added to acetone in dichloromethane 10ml and 30ml of 30 min. Stirring was then, after the solvent was distillated under reduced pressure for 12 hours to dry in a vacuum dryer during ₃ Ru A catalyst of (CO) ₁₂ / ZrO ₂ (7.47 wt% Ru) was prepared.

Example 10

MgO 0.67g, Ru ₃ (CO) ₁₂ 0.11g (0.172mmole) was added to 30ml of dichloromethane and 10ml of acetone, stirred for 30 minutes, the solvent was distilled under reduced pressure and dried in a vacuum dryer for 12 hours to give Ru ₃ ( CO) ₁₂ / ZrO ₂ (7.29 wt% Ru) was prepared.

Example 11

0.70 g of γ-Al ₂ O ₃ , 0.16 g of Ru ₆ (CO) _{16 was} added to 30 ml of dichloromethane and 10 ml of acetone, stirred for 30 minutes, and the solvent was distilled under reduced pressure, followed by 12 hours in a vacuum dryer. Drying produced a catalyst of Rh ₆ (CO) ₁₆ / γ-Al ₂ O ₃ (8.35 wt% Ru).

Example 12

0.70 g SiO ₂ , Ru ₆ (CO) ₁₆ 0.11 g (0.103 mmol) was added to 30 ml of dichloromethane and 10 ml of acetone and stirred for 30 minutes. The solvent was distilled under reduced pressure and dried in a vacuum dryer for 12 hours to give Ru ₆ A catalyst of (CO) ₁₆ / SiO ₂ (8.23 wt% Ru) was prepared.

Example 13

4.82 g of SiO _{2 and} 5.30 g (0.023 mmol) of amino propyl triethoxy silane were added to 125 ml of toluene, refluxed for 4 hours, cooled to room temperature, filtered and dried in a vacuum dryer for 12 hours. It was. 1.04 g of supported silica and 0.12 g (0.187 mmol) of Ru ₃ (CO) ₁₂ were added to 15 ml of dichloromethane, stirred for 3 hours, filtered and dried in a vacuum dryer for 12 hours, followed by Ru ₃ (CO) ₁₂ / SiO ₂ (5.05 wt% Ru) catalyst was prepared.

Example 14

2.41 g of γ-Al ₂ O _{3 and} 2.65 g (0.012 mmol) of amino propyl triethoxy silane were added to 62.5 ml of toluene, refluxed for 4 hours, cooled to room temperature, filtered and vacuumed. It was dried in a drier for 12 hours. 0.86 g of supported γ-Al ₂ O ₃ and 0.10 g (0.156 mmol) of Ru ₃ (CO) ₁₂ were added to 15 ml of dichloromethane, stirred for 3 hours, filtered and dried in a vacuum dryer for 12 hours, followed by Ru ₃ (CO ) ₁₂ / γ-Al ₂ O ₃ (5.23 wt% Ru) was prepared.

Example 15

2.42 g of MgO and 2.66 g (0.012 mmol) of amino propyl triethoxy silane were added to 625 ml of toluene, refluxed for 4 hours, cooled to room temperature, filtered and dried in a vacuum dryer for 12 hours. . 0.72 g of supported MgO, 0.11 g (0.172 mmol) of Ru ₃ (CO) ₁₂ were added to 15 ml of dichloromethane, stirred for 3 hours, filtered and dried in a vacuum dryer for 12 hours, followed by Ru ₃ (CO) ₁₂ / MgO ₂ (6.75 wt% Ru) was prepared.

Example 16

ZnO 2.56g, 2.57g (0.012mmole) of aminopropyl triethoxy silane was added to 62.5ml of toluene, refluxed for 4 hours, cooled to room temperature, filtered and dried in a vacuum dryer for 12 hours. It was. 0.16 g (0.172 mmol) of supported ZnO 0.76 g Ru ₃ (CO) ₁₂ was added to 15 ml of dichloromethane, stirred for 3 hours, filtered and dried in a vacuum dryer for 12 hours, followed by Ru ₃ (CO) _{12 /} ZnO (6.42). wt% Ru) was prepared.

Example 17

2.65 g of TiO ₂ and 2.57 g (0.012 mmol) of amino propyl triethoxy silane were added to 62.5 ml of toluene, refluxed for 4 hours, cooled to room temperature, filtered and filtered for 12 hours in a vacuum dryer. Dried. 0.79 g of supported TiO ₂ , 0.10 g (0.156 mmole) of Ru ₃ (CO) ₁₂ were added to 15 ml of dichloromethane, stirred for 3 hours, filtered and dried in a vacuum dryer for 12 hours, followed by Ru ₃ (CO) ₁₂ / TiO ₂ (5.66 wt% Ru) was prepared.

Example 18

In the presence of the catalyst prepared in Example 1, a continuous fixed bed flow reactor (inner diameter: 0.95 cm, length: 30 cm, material: stainless steel 316) was added at a flow rate of 10.0 ml / min methane and 10.0 ml / min nitrogen and space velocity. The reaction was continuously carried out under the reaction conditions of 1,200 hr ⁻¹ and 1 atm, and the results of gas chromatography analysis were as shown in Table 1 and Table 2 below.

TABLE 1

TABLE 2

Example 19

Except for using RuCl ₃ · xH ₂ O / TiO ₂ (7.55wt% Ru) which is the catalyst prepared in Example 2, the results were carried out in the same manner as in Example 18 are shown in Table 3.

TABLE 3

Example 20

Except for using Rh ₂ (OCOCH ₃ ) ₄ / TiO ₂ (7.07wt% Ru) prepared in Example 3, the results were carried out in the same manner as in Example 18 are shown in Table 4.

TABLE 4

Example 21

Except for using the catalyst prepared in Example 4 Rh ₂ (CO) ₁₆ / TiO ₂ (9.32wt% Ru), the results were carried out in the same manner as in Example 18 are shown in Table 5.

TABLE 5

Example 22

Except for using the catalyst prepared in Example 5 Ru ₃ (CO) ₁₂ / SiO ₂ (7.43wt% Ru), the results were carried out in the same manner as in Example 16 are shown in Table 6.

TABLE 6

Example 23

Except for using Ru ₃ (CO) ₁₂ / γ-Al ₂ O ₃ (6.17wt% Ru) which is the catalyst prepared in Example 6, the results were carried out in the same manner as in Example 18 are shown in Table 7.

TABLE 7

Example 24

Except for using Ru ₃ (CO) ₁₂ / α-Al ₂ O ₃ (6.86wt% Ru) which is the catalyst prepared in Example 7, the results were carried out in the same manner as in Example 18 are shown in Table 8.

TABLE 8

Example 25

Except for using Ru ₃ (CO) _{12 /} carbon (6.83wt% Ru) which is the catalyst prepared in Example 8, the results were carried out in the same manner as in Example 18 are shown in Table 9.

TABLE 9

Example 26

Except for using Ru ₃ (CO) ₁₂ / ZrO ₂ (7.10wt% Ru) which is the catalyst prepared in Example 9, the results were carried out in the same manner as in Example 18 are shown in Table 10.

TABLE 10

Example 27

Except for using Ru ₃ (CO) _{12 /} MgO (7.29wt% Ru) which is the catalyst prepared in Example 10, the results were carried out in the same manner as in Example 18 are shown in Table 11.

TABLE 11

Example 28

Table 12 shows the results of the same procedure as in Example 18, except that Rh ₆ (CO) ₁₆ / γ-Al ₂ O ₃ (8.35 wt% Rh), which is the catalyst prepared in Example 11, was used.

TABLE 12

Example 29

Table 13 shows the results of the same procedure as in Example 18, except that Rh ₆ (CO) ₁₆ / SiO ₂ (8.23 wt% Ru), which is the catalyst prepared in Example 12, was used.

TABLE 13

Example 30

Except for using Ru ₃ (CO) ₁₂ / SiO ₂ (5.05wt% Ru) which is the catalyst prepared in Example 13, the results were carried out in the same manner as in Example 18 are shown in Table 14.

TABLE 14

Example 31

Except for using Ru ₃ (CO) ₁₂ / γ-Al ₂ O ₃ (5.23wt% Ru) which is the catalyst prepared in Example 14, the results were carried out in the same manner as in Example 18 are shown in Table 15.

TABLE 15

Example 32

Except for using Ru ₃ (CO) _{12 /} MgO (6.75wt% Ru) which is the catalyst prepared in Example 15, the results were carried out in the same manner as in Example 18 are shown in Table 16.

TABLE 16

Example 33

Except for using Ru ₃ (CO) _{12 /} ZnO (6.42wt% Ru) which is a catalyst prepared in Example 16, the results were carried out in the same manner as in Example 18 are shown in Table 17.

TABLE 17

Example 34

Except for using Ru ₃ (CO) ₁₂ / TiO ₂ (5.66wt% Ru) which is a catalyst prepared in Example 17, the results were carried out in the same manner as in Example 18 are shown in Table 18.

TABLE 18

As can be seen from Table 1 to Table 18, since no by-products are generated, the product is easy to stagnate, and the reaction temperature is lowered, thereby saving energy and shortening the time required for simplified production.

Claims (5)

Formula (I) Emile alkylene preparative mugiche supported catalyst from methane represented by the formula (wherein M is _{Ru 3 (CO) 12, Rh} 6 (CO) 16, Rh 2 (OCOCH 3) 4, RuCl 3 · xH is a compound alternatively from ₂ O, S Is the inorganic carrier used, and is an alternative of α-alumina, γ-alumina, activated carbon, silica, TiO ₂ , MgO, ZnO, ZrO ₂ , and a is 5.0 to 10.0 weight percent as the metal in the catalyst. M and S were added to the solvent, the mixture was stirred at room temperature, the solvent was distilled under reduced pressure, and the residue was dried in vacuo. A method of preparing an inorganic supported catalyst for preparing ethylene from methane (where M is Ru ₃ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh ₂ (OCOCH ₃ ) ₄ , RuCl ₃ xH ₂ O S is an inorganic carrier used, and is an alternative carrier of α-alumina, γ-alumina, activated carbon, silica, TiO ₂ , MgO, ZnO, ZrO ₂ , and a is 5.0-10.0 wt% as the metal in the catalyst. to be. A process for producing ethylene, characterized in that the reaction is carried out at 500 to 750 ° C., 1 atm to 10 atm in the presence of methane, nitrogen, and a catalyst represented by monolithic MaS (I). The method of claim 3, wherein the molar ratio of methane and nitrogen is 1 to 6. The method of claim 3, wherein the space velocity is 1,000 to 3,000 hr ^-1 .