KR20190029912A - A method for producing the higher alkene from butene by using mesoporous aluminosilicate catalyst - Google Patents

Abstract

The present invention relates to a method of producing a high quality of alkene through an oligomerization reaction of butene, and more specifically, to a method of producing a high quality of alkene of a jet fuel region by using a mesoporous aluminosilicate catalyst, on which a mesoporous aluminosilicate catalyst and nickel are supported to promote an oligomerization reaction of butene. Compared to an existing catalyst, the mesoporous aluminosilicate catalyst, on which the mesoporous aluminosilicate catalyst and nickel are supported, of the present invention is effective in improving conversion ratio of butane and yield of a high quality of alkene (an alkene in the C_8-C_16 range) of the jet fuel region. The present invention is expected to be industrially useful by exhibiting excellent performance in the production of the high quality of alkene (the alkene in the C_8-C_16 range) of the jet fuel region by oligomerizing butene.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing an advanced alkene from butene using a mesoporous aluminosilicate catalyst,

The present invention relates to a method for producing a high-quality alkene through a polymerization reaction of butene, and more particularly, to a method for producing a high-quality alkene by the polymerization reaction of butene by using an intermediate alumino silicate catalyst and nickel- To a process for producing advanced alkenes in the aerosol region.

Research on the synthesis of aviation oil using biomass as a raw material is attracting attention. The Alcohol to Jet (ATJ) process for producing alcohols using biomass as a raw material and for manufacturing aviation oil from alcohol has recently begun to attract attention. Particularly, a process for producing aviation oil using butanol as a raw material is attracting attention. This process is a process in which butene is produced through dehydration reaction of butanol, and high alkenes (C ₈ -C ₁₆ Range olefins), and the hydrogenation of higher alkenes.

For the polymerization of butene, a homogeneous catalyst or a heterogeneous catalyst such as zeolite can be used. U.S. Patent No. 8,395,007 reported using bis (cyclopentadienyl) zirconium chloride as a catalyst to synthesize high alkenes ranging from 1-butene to diesel oil fractions. However, since homogeneous catalysts were used, catalyst recovery and reuse were difficult There is a problem.

U.S. Patent No. 9,732,295 reports the use of zirconium metallocenes as catalysts to synthesize higher alkenes ranging from 1-butene to diesel oil fractions. However, since homogeneous catalysts are used, there is a problem that catalyst recovery and reuse are difficult.

U.S. Pat. No. 4,227,992 and U.S. Pat. No. 4,211,640 claim ZSM-11 as a catalyst for olefin polymerization and report the use of other microporous zeolites such as ZSM-12, ZSM-21 and mordenite. British Patent No. 2,106,131 and British Patent No. 2,106,533 reported the use of microporous zeolites, ZSM-5 and ZSM-11, in the oligomerization of light olefins. WO93 / 082780 discloses a method of carrying out the oligomerization reaction of butene using microporous zeolite ZSM-23 as a catalyst. U.S. Patent No. 9,550,706 describes a method for producing high-grade alkenes from butene using ITQ-39 catalyst, a microporous zeolite. The above-mentioned microporous zeolite catalysts have a problem that the diffusion of reactants and products in the pores is likely to be limited because of the small pore size, and the possibility of formation of coke is high.

The present inventors have made efforts to solve the above-mentioned problems, and as a result, they have found that by using an aluminosilicate catalyst having a mesopore catalyst as a heterogeneous catalyst and a mesoporous aluminosilicate bearing nickel, (Alkene in the range of C ₈ to C ₁₆ ) can be produced in a high yield.

Accordingly, an object of the present invention is to provide a method for producing a high-grade alkene in an aerosol region by promoting a polymerization reaction of butene using a mesoporous aluminosilicate catalyst and a nickel-supported mesopore aluminosilicate .

It is to be understood, however, that the technical scope of the present invention is not limited to the above-mentioned problems, and other technical problems can be clearly understood by those skilled in the art from the following description.

Implementing one of the present invention in order to attain the object example was to which the aluminosilicate is a medium pore filled with a fixed catalyst bed reactor through the butene as the reactant advanced alkene of jet fuel region from butene by carrying out predetermined polymerization (C ₈ To C < ₁₆ >).

Another embodiment of the present invention is advanced alkene of jet fuel region from butene by carrying out predetermined polymerization reaction to nickel is passed through the butene as the reactant in which the aluminosilicate in the supported medium pore filled with a fixed catalyst reactor (C ₈ ~ C ₁₆ range of alkenes).

Other details of the embodiments of the present invention are included in the following detailed description.

According to the present invention, since the size of the pores of the mesoporous aluminosilicate catalyst supported on nickel and the pore size of mesoporous aluminosilicate catalyst is 2 to 10 nm, the diffusion of butene oligomer molecules into the catalyst pores is fast, The catalysts were found to be able to reach the surface active sites in the catalysts and to retard the pore clogging due to the formation of coke. In comparison with the conventional catalysts, the conversion of butene and the higher alkenes (C ₈ -C ₁₆ range of alkene) yield. Therefore, the method according to the present invention is expected to be industrially useful because it exhibits excellent performance in producing advanced alkenes (alkenes in the range of C ₈ to C ₁₆ ) in the aerospace region by slightly polymerizing butene.

Hereinafter, the present invention will be described in detail.

As it described above, the present invention was to which the aluminosilicate is a medium pore filled with a fixed catalyst bed reactor through the butene as the reactant in the high alkene (C ₈ ~ C ₁₆ range of jet fuel region from butene by carrying out predetermined polymerization Alkene ").≪ / RTI >

In the present invention, the catalyst is a mesoporous aluminosilicate catalyst and nickel supported mesoporous aluminosilicate catalyst. The mesoporous aluminosilicate catalyst according to the present invention has a surface area of 600 m ² / g to 1000 m ² / g and has a ZSM-5 unit structure, which can promote the oligomerization reaction due to the acid sites, Is 2 to 10 nm, so that the diffusion of the butene molecule or the butene oligomer molecule in the catalyst pores is fast, and it is easy to reach the surface active sites in the catalyst pores. In addition, the mesoporous aluminosilicate catalyst supported with nickel has advantages of mesoporesic aluminosilicate catalyst as well as strong acidity of acid, which can effectively promote the polymerization reaction.

In the present invention, the intermediate-pore aluminosilicate catalyst supported with nickel in the present invention is preferably a catalyst in which the loading amount of nickel is less than 10 wt%, more preferably, less than 5 wt% is used. If a catalyst having a nickel loading of 10 wt% or more is used, the pores of the mesoporous aluminosilicate catalyst are clogged by nickel, and thus the surface area and the pore size of the catalyst are greatly reduced.

The intermediate pore aluminosilicate catalyst and nickel-supported mesoporous aluminosilicate catalyst were prepared by the following polymerization process using 1-butene, 2-butene, or a mixture of 1-butene and 2-butene as reactants Can be applied under the same reaction conditions.

In the present invention, the reaction for producing the advanced alkene in the aerosol region by promoting the polymerization of butene by using the intermediate pore aluminosilicate and nickel-supported aluminosilicate in the present invention is carried out in a reactor packed with a fixed catalyst bed, Is conducted at a reaction temperature of 200 ° C to 550 ° C, preferably 250 ° C to 450 ° C. When the reaction temperature is lower than 200 ° C, the reaction activity is lowered. When the reaction temperature is higher than 550 ° C, And the reaction activity may be lowered. In addition, the flow rate of n-butene and the catalyst ratio is 1 hr ^-1 ~ 50 hr ^-1, and more preferably from WHSV 5 hr ^-1 ~ 30 hr ^-1 to (weigh hour space velocity) WHSV, hr ^-1 is less than 1 The selectivity may be reduced due to the side reaction, and if it exceeds 30 hr <" ¹ >, the contact time may be too short and the activity may be lowered.

In the present invention, the reactor used for the reaction for producing the advanced alkene in the aerosol region by promoting the polymerization of butene by using the intermediate pore aluminosilicate and the nickel-supported mesoporous aluminosilicate has the inner diameter of 1/4 inch (inch) and 10 cm long stainless steel tube. A mass flow regulator was installed between the butene storage tank and the reactor to regulate the flow rate. The temperature of the reactor was adjusted using a customized tubular furnace, and the gaseous products were analyzed by direct connection to gas chromatography after receiving the liquid product. The conversion, selectivity and yield were calculated by the following formulas (1) to (3).

Hereinafter, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited thereto.

[Comparative Example 1]

1 g of a microporous zeolite HZSM-5 catalyst was charged and a butene mixture of 1-butene and 2-butene in a weight ratio of 1: 1.3 was charged at a flow rate of 10.0 g / h, The polymerization was carried out at atmospheric pressure. Analysis of the product by gas chromatography 5 hours after the start of the reaction showed that the butene conversion was 76.9%, the alkene selectivity in the range of C ₈ to C ₁₆ was 64.9%, and the yield of the alkene in the C ₈ to C ₁₆ range was 49.9% .

[Example 1]

To perform the oligomerization reaction of the butene mixture using mesoporous aluminosilicate. The mesoporous aluminosilicate is prepared by using the method of preparing mesoporous material of zeolite skeleton by using zeolite and basic aqueous solution.

First, an aqueous sodium hydroxide solution was prepared by dissolving 15 g of sodium hydroxide in 76.5 g of distilled water, and 33.8 g of HZSM-5 zeolite (ratio of silicon to aluminum = 50) was mixed with an aqueous solution of sodium hydroxide and stirred for 1 hour, Is used as a precursor solution for synthesis. 69 g of hexadecyltrimethylammonium bromide is dissolved in 1050 g of distilled water to prepare a surfactant solution. The surfactant solution is added dropwise to the solution containing HZSM-5 zeolite while stirring for 24 hours. After hydrothermal synthesis in an oven at 100 ° C for 12 hours without stirring, the solution was adjusted to pH 10 with 50% acetic acid at room temperature and dried in a 100 oven for 12 hours. The pH control and drying process described above was repeated two more times. The precipitate thus obtained was collected by vacuum filtration, washed with distilled water, and dried in an oven at 100 ° C for 24 hours. The above-described washing and drying process is repeated two more times. The remaining surfactant is removed by washing with ethanol, dried in an oven at 100 ° C for 24 hours, and then calcined at 550 ° C for 3 hours. (MMZ _ZSM-5 ) having mesopores converted to a hydrogen substitute material by calcination at 500 ° C. for 3 hours is obtained by performing ion exchange using a 1 M ammonium chloride aqueous solution .

A fixed-bed continuous reactor was charged with 1 g of the mesoporous aluminosilicate (MMZ _{ZSM -5} ) catalyst, and a butene mixture of 1-butene and 2-butene in a weight ratio of 1: 1.3 was charged at a flow rate of 10.0 g / h And the polymerization reaction was carried out at 350 ° C and 10 atm. The reaction started is 85.0% 5 hours after the result butene conversion rate by using the gas chromatography analysis of the product, C ₈ ~ C the selectivity to ₁₆ range alkene is the yield of alkene, of 68.0%, C ₈ ~ C ₁₆ range is 57.8% .

[Example 2]

And then carrying out the oligomerization reaction of the butene mixture using the nickel-supported mesoporous aluminosilicate. The mesoporous aluminosilicate prepared above was prepared by using zeolite and a basic aqueous solution as a support in a mesopore of zeolite skeleton, A method in which nickel metal is supported on a support is used.

First, a mesoporous aluminosilicate (MMZ _ZSM-5 ) is prepared in the same manner as in Example 1. A nickel aqueous solution was prepared by adding 0.47 g of nickel nitrate hexahydrate to 5 g of distilled water and then 3 g of alumino silicate (MMZ _ZSM-5 ) having intermediate pores was immersed in the nickel aqueous solution by using a wetting method. The amount of nickel metal supported on the thus prepared catalyst is 3 wt%. After drying in an oven at 100 ° C. for 24 hours, the catalyst was calcined at 550 ° C. for 4 hours to complete a mesoporous aluminosilicate (NiO / MMZ _ZSM-5 ) catalyst carrying nickel.

A fixed-bed continuous reactor was charged with 1 g of the mesoporous aluminosilicate (Ni / MMZ _ZSM-5 ) catalyst on which nickel was supported, and 10.0 g of a butene mixture mixed at a weight ratio of 1-butene and 2-butene of 1: / h, and the polymerization reaction was carried out at 350 ° C and 10 atm. The reaction started is 89.4% 5 hours after the result butene conversion rate by using the gas chromatography analysis of the product, C ₈ ~ C the selectivity to ₁₆ range alkene is the yield of alkene, of 69.1%, C ₈ ~ C ₁₆ range is 61.0% .

catalyst Reaction temperature
(° C) Reaction pressure (bar) WHSV
(hr ^-1 ) Butene
Conversion Rate (%) C ₈ ~ C ₁₆ in the range
Alken selectivity (%) Alken yield (%) in the range of C ₈ to C ₁₆ Comparative Example 1 HZSM-5 350 10 10 76.9 64.9 49.9 Example 1 MMZ _{ZSM -5} 350 10 10 85.0 68.0 57.8 Example 2 Ni / MMZ _{ZSM -5} 350 10 10 89.4 69.1 61.0

As shown in the above Examples and Comparative Examples, when the catalyst according to the present invention was used in comparison with the catalyst used in the conventional polymerization of butene, it was found that the conversion of butene and the yield of alkene in the range of C ₈ to C ₁₆ were improved I could.

Claims (8)

C ₈ ~ C ₁₆ range from butene, characterized in that the aluminosilicate of the mesopores by passing the butene in a reactor filled with a fixed catalyst bed to the reactants subjected to predetermined polymerization to give the alkene ₁₆ range C ₈ ~ C ≪ / RTI > The method of claim 1, wherein the butene is 1-butene, 2-butene, or a method for producing 1-butene and 2 of C ₈ ~ C ₁₆ range, characterized in that a mixture of butene-alkene. The method of claim 1, wherein the predetermined polymerization method for producing a C ₈ ~ C ₁₆ range, characterized in that is carried out at a reaction temperature of 200 ℃ to 550 ℃ alkene. The method of claim 1, wherein the address of the polymerization WHSV (weight hour space velocity) is 1 hr ^-1 to 50 hr ^-1 in the method of producing a alkene of C ₈ ~ C ₁₆ range, characterized. The method of claim 1, wherein the alumino-silicate of the mesopores is method of producing a alkene of C ₈ ~ C ₁₆ range, characterized in that consisting of a ZSM-5 structure unit. 6. The method of claim 5, wherein the production of the intermediate pore aluminosilicate is a C ₈ ~ C ₁₆ range, characterized in that a surface area of 600 to 1000 m ² / g alkenes. The method of claim 1, wherein the alumino-silicate of the mesopores is C ₈ ~ process for producing a C ₁₆ range alkenes, characterized in that aluminosilicates of the mesopores of the nickel is supported. The method of claim 7, wherein the aluminosilicate in the mesopores of the nickel is carried manufacturing method of the ₈ C ~ C ₁₆ range, characterized in that the amount of nickel is less than 10 wt% alkenes.