JP4119980B2 - Catalyst for propane dehydrogenation reaction - Google Patents

Description

  The present invention relates to a catalyst used for producing propylene by dehydrogenating propane.

Propylene is one of the most important basic chemicals as a raw material for polypropylene and the like. Conventionally, in order to industrially produce propylene, methods such as separation of petroleum from catalytic cracking gas and propane dehydrogenation are employed. As a catalyst used for the dehydrogenation reaction of propane in the absence of hydrogen, a catalyst mainly composed of chromium oxide has been developed and used industrially. (For example, refer nonpatent literature 1).
However, from the viewpoint of environmental conservation, the development of a safe and high-performance catalyst that does not contain chromium oxide is an important technical development issue.

"Petrochemical process", pages 31-37, edited by the Japan Petroleum Institute, published by Kodansha (2001).

  An object of the present invention is to provide an environment-friendly and high-performance catalyst in a method for producing propylene by dehydrogenating propane.

  As a result of studying the influence of various additives on the catalyst performance, the present inventor unexpectedly found that gallium oxide, aluminum oxide, calcium oxide, and strontium oxide. It has been found that the problem can be solved by a catalyst characterized in that at least one selected from the group consisting of barium oxide, manganese oxide, cerium oxide, lanthanum oxide and yttrium oxide is an essential component.

That is, according to this application, first, it is composed of (1) gallium oxide, (2) aluminum oxide, and (3) calcium oxide, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide, and yttrium oxide. A catalyst comprising at least one oxide selected from the group as an essential component, and when the total catalyst is 100% by weight, the content of each oxide is 5 to 20% by weight in the above order, 60 Provided is a catalyst for dehydrogenation of propane, characterized in that it is ˜94 wt% and 1 to 20 wt%.
Second, there is provided a method for producing propylene, characterized in that propane is brought into contact with the catalyst described in the first.

  The catalyst of the present invention is safe and exhibits high catalytic activity in the propane dehydrogenation reaction. Therefore, propylene can be produced industrially advantageously.

The present invention will be described in detail below.
The catalyst component for the dehydrogenation reaction of propane of the present invention includes (1) gallium oxide, (2) aluminum oxide, and (3) calcium oxide, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide, and yttrium oxide. An essential component is at least one selected from the group consisting of:

  The catalyst of the present invention exhibits excellent performance in producing propylene by dehydrogenation of propane, such as high propylene yield and propylene selectivity, and low carbon deposition on the catalyst.

The ratio of each catalyst component is not particularly limited. When the total catalyst is 100% by weight, (1) gallium oxide is 5 to 20% by weight, (2) aluminum oxide is 60 to 94% by weight, and (3) oxidation is performed. At least one oxide selected from the group consisting of calcium, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide and yttrium oxide is 1 to 20% by weight. In such a quantitative range, by appropriately determining the composition according to the reaction conditions, catalyst performance suitable for the reaction conditions can be obtained.
The dehydrogenation reaction catalyst of the present invention comprises (1) gallium oxide, (2) aluminum oxide, and (3) calcium oxide, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide, and yttrium oxide. Although at least one oxide selected from the group is an essential component, it may contain other substances as long as the performance of the catalyst of the present invention is not impaired. Examples of such a substance include silicon oxide and activated carbon.

  As raw materials for gallium oxide, aluminum oxide, calcium oxide, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide, and yttrium oxide, which are the catalyst components of the present invention, the respective nitrates, hydrochlorides, sulfates, organic acids A salt, a hydroxide, or the like can be used. For the catalyst, a catalyst precursor is prepared by a method such as a coprecipitation method, an impregnation method, a mixing method, a sequential precipitation method, an alkoxide method, or a combination of these methods. It can be manufactured by firing. Although the calcination temperature of a catalyst precursor is not specifically limited, The range of 300-1000 degreeC is preferable and 500-800 degreeC is especially preferable.

  The catalyst thus produced is used as it is or after being granulated or tableted by an appropriate method. The particle diameter and shape of the catalyst can be arbitrarily selected depending on the reaction system and the shape of the reactor. That is, the catalyst according to the present invention can be used in any reaction system such as a fixed bed and a fluidized bed.

  The reaction conditions for producing propylene by the dehydrogenation reaction of propane using the catalyst according to the present invention are such that the reaction temperature is in the range of 500 to 650 ° C, preferably 530 to 630 ° C, the reaction pressure is increased, Either pressure or reduced pressure may be used, and preferably 0.2 to 1.5 atmospheres (absolute pressure). By treating the catalyst with hydrogen in the vicinity of the reaction temperature before the start of the reaction, the catalyst performance in the initial stage after the start of the reaction can be improved. Further, when the activity of the catalyst of the present invention decreases after use for a certain period of time, its performance can be recovered by firing again in air.

Hereinafter, the features of the present invention will be further clarified by giving examples.
Example 1

0.95 g of gallium nitrate hydrate, 14.7 g of aluminum nitrate nonahydrate, and 1.10 g of calcium nitrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.2 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of the catalyst, _{(2 O} 3 Ga) 5 wt% gallium oxide, aluminum oxide _{(Al 2} O 3) 90 wt% and 5 wt% calcium oxide (CaO).

1 g of the obtained catalyst was charged into a reaction tube and heated to a reaction temperature in argon, then a mixed gas consisting of 10% by volume of propane and 90% by volume of argon was passed through the catalyst layer to obtain a pressure of 0.1 MPa, The mixed gas was reacted under the conditions of a mixed gas flow rate of 10 ml / min and a temperature of 550 ° C. The reaction product gas was analyzed by gas chromatography. As a result, after 9 hours of reaction elapsed time, the propylene yield was 33% and the propylene selectivity was 82%, and the amount of carbonaceous material deposited on the catalyst was 1 mg per 1 g of the catalyst amount (see Table 1). .
Example 2

  0.97 g of gallium nitrate hydrate, 35.5 g of aluminum nitrate nonahydrate, and 0.55 g of strontium nitrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.3 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of strontium oxide (SrO).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 33% and the propylene selectivity was 80%, and the amount of carbonaceous material deposited on the catalyst was 9 mg per 1 g of the catalyst amount (see Table 1). .
Example 3

  0.98 g of gallium nitrate hydrate, 35.8 g of aluminum nitrate nonahydrate, and 0.46 g of barium nitrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.4 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of barium oxide (BaO).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction time, the propylene yield was 32% and the propylene selectivity was 79%, and the amount of carbonaceous material deposited on the catalyst was 1 mg per 1 g of the catalyst amount (see Table 1). .
Example 4

0.97 g of gallium nitrate hydrate, 35.3 g of aluminum nitrate nonahydrate, and 0.88 g of manganese nitrate hexahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.7 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of manganese oxide (MnO ₂ ).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 32% and the propylene selectivity was 81%, and the amount of carbonaceous material deposited on the catalyst was 10 mg per gram of catalyst (see Table 1). .
Example 5

0.98 g of gallium nitrate hydrate, 35.8 g of aluminum nitrate nonahydrate, and 0.68 g of cerium nitrate hexahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of cerium oxide (CeO ₂ ).

1 g of the obtained catalyst was charged into a reaction tube, and propane dehydrogenation reaction was carried out in the same manner as in Example 1. As a result, after 9 hours of reaction time, the propylene yield was 30%, the propylene selectivity was 79%, and the amount of carbonaceous material deposited on the catalyst was 16 mg per gram of catalyst (see Table 1). .
Example 6

0.98 g of gallium nitrate hydrate, 35.8 g of aluminum nitrate nonahydrate, and 0.72 g of lanthanum nitrate hexahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 17.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of lanthanum oxide (La ₂ O ₃ ).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction time, the propylene yield was 30%, the propylene selectivity was 79%, and the amount of carbonaceous material deposited on the catalyst was 19 mg per gram of catalyst (see Table 1). .
Example 7

0.97 g of gallium nitrate hydrate, 35.5 g of aluminum nitrate nonahydrate, and 0.91 g of yttrium nitrate hexahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of yttrium oxide (Y ₂ O ₃ ).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 30% and the propylene selectivity was 78%, and the amount of carbonaceous material deposited on the catalyst was 19 mg per gram of catalyst (see Table 1). .
Comparative Example 1

  0.95 g of gallium nitrate hydrate and 36.5 g of aluminum nitrate nonahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 17.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide and 95% by weight of aluminum oxide.

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 30% and the propylene selectivity was 74%, and the amount of carbonaceous material deposited on the catalyst was 21 mg per gram of the catalyst (see Table 1). .
Comparative Example 2

  0.97 g of gallium nitrate hydrate, 35.2 g of aluminum nitrate nonahydrate, and 0.97 g of zinc nitrate hexahydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.3 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of zinc oxide (ZnO).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 26%, the propylene selectivity was 72%, and the amount of carbonaceous material deposited on the catalyst was 25 mg per gram of the catalyst (see Table 1). .
Comparative Example 3

0.98 g of gallium nitrate hydrate, 35.6 g of aluminum nitrate nonahydrate, and 0.58 g of zirconyl nitrate dihydrate were dissolved in distilled water to prepare a 100 ml aqueous solution. On the other hand, 17.4 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of zirconium oxide (ZrO ₂ ).

1 g of the obtained catalyst was filled in a reaction tube, and propane dehydrogenation reaction was performed in the same manner as in Example 1. As a result, after 9 hours of reaction elapsed time, the propylene yield was 29%, the propylene selectivity was 75%, and the amount of carbonaceous material deposited on the catalyst was 24 mg per 1 g of the catalyst amount (see Table 1). .
Comparative Example 4

  37.5 g of aluminum nitrate nonahydrate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution A. On the other hand, 17.5 g of anhydrous sodium carbonate was dissolved in distilled water to prepare a 100 ml aqueous solution, which was designated as solution B. Liquid A and liquid B were each added dropwise simultaneously to 300 ml of room temperature distilled water that was well stirred at a rate of 8 ml / min to obtain a precipitate. The precipitate was aged at room temperature for 1 day, and then filtered and washed to remove sodium in the precipitate. Thereafter, the precipitate was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the fired oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain aluminum oxide. An aqueous solution obtained by dissolving 0.93 g of gallium nitrate hydrate and 1.64 g of magnesium nitrate hexahydrate in 50 ml of distilled water was added to 4.6 g of the obtained aluminum oxide and mixed well. Thereafter, the mixture was dried at 110 ° C. and calcined in air at 600 ° C. for 2 hours. Next, the calcined oxide was crushed and the particle size was adjusted to 250 to 600 μm to obtain a catalyst. The composition of this catalyst was 5% by weight of gallium oxide, 90% by weight of aluminum oxide, and 5% by weight of magnesium oxide (MgO).

  1 g of the obtained catalyst was charged into a reaction tube, and propane dehydrogenation reaction was carried out in the same manner as in Example 1. As a result, after 9 hours of reaction time, the propylene yield was 26% and the propylene selectivity was 75%, and the amount of carbonaceous material deposited on the catalyst was 27 mg per gram of the catalyst (see Table 1). .

Claims (2)

(1) gallium oxide, (2) aluminum oxide, and (3) at least one oxide selected from the group consisting of calcium oxide, strontium oxide, barium oxide, manganese oxide, cerium oxide, lanthanum oxide, and yttrium oxide. , A catalyst composed of metal oxides as essential components, and when the total catalyst is 100 wt%, the content of each oxide is 5 to 20 wt%, 60 to 94 wt% in the above order, A catalyst for dehydrogenation of propane, which is 1 to 20% by weight. A method for producing propylene, comprising contacting propane with the catalyst according to claim 1.