KR102065344B1 - Catalyst for the Synthesis of Jet Fuel Range Hydrocarbon Through Deoxygenation reaction, manufacturing method thereof - Google Patents

Abstract

The present invention includes a rod-shaped SBA-15 or SBA-16 carrier having a short axis diameter of 1: 1 to 3, and nickel and aluminum supported on the SBA-15 or SBA-16 carrier, and deoxidized from vegetable oil. The present invention relates to a catalyst for preparing an aviation oil for the production of an aviation oil mixture in the fire extinguishing reaction. When using the aviation oil production catalyst according to the present invention, there is an advantage in that a high yield of the aviation oil mixture can be prepared.

Description

Catalyst for preparation of hydrocarbon mixture in the range of aviation oil by deoxygenation, and method for preparing the same. {Catalyst for the Synthesis of Jet Fuel Range Hydrocarbon Through Deoxygenation reaction, manufacturing method}

The present invention relates to a catalyst for preparing a hydrocarbon mixture (C ₈ -C ₁₆ hydrocarbon) in the range of the aviation oil in a high yield in a deoxygenation reaction for the production of aviation oil and a method for producing the same.

As the depletion of fossil fuels such as coal or petroleum has recently become visible, various alternative technologies have been developed to secure energy sources in the future. Since the plant-derived biomass is recognized as an alternative resource that can be directly applied to industrial facilities that are biased to fossil fuels, research and development on this is being actively conducted.

In particular, unlike fuel used for automobiles on the ground, aviation oil used for flight has a feature that must be used in high altitude and low temperature environment of -45 ℃ or less, there is a problem that can not be replaced by sunlight, etc. Accordingly, bio-aviation oils that can be used even at low temperatures by using biomass are attracting more attention.

Typically, the preparation of bio-aviation oil using bio-oil consists of two stages of reaction.

Firstly, the first reaction step is to convert the biooil from the hydrocarbon compound range (C ₁₂ -C ₂₂ ) or the hydrocarbon oil range (C ₈ -C ₁₆ ) through the deoxygenation step. The hydrogenation upgrading reaction, which is a reaction step, produces an aviation oil having a hydrocarbon compound range of 70% or more of the branched hydrocarbon component. In the first deoxidation reaction step, it is very important to convert directly to the range of hydrocarbon compounds corresponding to aviation oil, rather than to the range of hydrocarbon compounds of diesel, it is necessary to develop a catalyst with high activity required. In addition, the latter hydrogenation upgrading reaction converts normal hydrocarbons into branched hydrocarbons in order to give flow characteristics at an extremely low temperature of -40 degrees or less, which is one of important properties required for aviation oil. The present invention corresponds to the first reaction step, the deoxygenation step, and relates to the step of converting to a hydrocarbon compound range of aviation oil through the application of a highly active catalyst.

Typically, the catalyst used in the first step, the deoxygenation reaction, uses a metal supported catalyst in which an active metal is supported on an inorganic carrier. The metal component is a noble metal selected from palladium, platinum, rhodium, and iridium. The active ingredient is used, mainly supporting an excess of platinum or palladium, usually 5 wt%. In addition, as a carrier, a carrier having a very small or irregular shape having a pore size of carbon, silica, aluminum, or the like is mainly used. Therefore, the catalyst supported on the noble metal has a problem that the production cost of the catalyst is very expensive because of using an excessive amount of expensive noble metal, and also due to the pore structure in which nano pores are irregularly formed, a material having a large carbon number of hydrocarbons such as bio oil In the case of the mass transfer to the active site of the metal contained in the catalyst of the catalyst is difficult, the resulting product is also difficult to escape easily out of the pores, there is a problem that the yield of the hydrocarbon compound range (C ₈ -C ₁₆ ) of the aviation oil is low.

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst for the production of aviation oil, which is capable of producing a high yield of hydrocarbon mixtures in the range of aviation oil in deoxygenation by applying a supported catalyst having an appropriate acid strength with inexpensive nickel-based mesopores. It aims to do it.

The present invention is a uniaxial diameter: long axis diameter of 1: 1 to 3 having a rod-shaped mesopore having a mesopore and for the production of aviation oil containing nickel and aluminum supported on the SBA-15 or SBA-16 carrier Using a catalyst, there is provided a catalyst for the production of aviation oil which can produce a high yield of hydrocarbon mixtures in the range of aviation oils during deoxygenation from vegetable oils.

Aluminum included in the aviation oil production catalyst according to an embodiment of the present invention was used to give an appropriate acid point for the cracking reaction, including 1 to 7 moles compared to 100 moles of silica contained in the SBA-15 or SBA-16 carrier. It may be.

Nickel included in the catalyst for aviation oil production according to an embodiment of the present invention was used to impart a function required for the hydrodeoxygenation reaction, and may be included in an amount of 5 to 20 wt% based on the total weight of the SBA-15 or SBA-16 carrier. .

In the catalyst for aviation oil production according to an embodiment of the present invention, an appropriate size is required for the size of the SBA-15 or SBA-16 carrier, and the major axis diameter may be 0.5 to 10 μm.

In the catalyst for aviation oil production according to an embodiment of the present invention, the SBA-15 or SBA-16 carrier may be a mesoporous carrier having an average pore size of 4 to 12 nm.

In the catalyst for aviation oil production according to an embodiment of the present invention, the specific surface area of the SBA-15 or SBA-16 carrier may be a mesoporous carrier having a 600 to 850 m ² / g.

In the deoxygenation reaction according to an embodiment of the present invention, the vegetable oil may include methyl palmitate.

In the deoxygenation reaction according to an embodiment of the present invention, the vegetable oil may include an oil extracted from a deadwood tree.

The present invention also provides a method for producing a catalyst for producing aviation oil described above.

Method for producing a catalyst for aviation oil production according to the present invention, the diameter of the cross-section: length 1: 1 to 3, the introduction of aluminum to contact the aluminum precursor with a rod-shaped SBA-15 or SBA-16 carrier; A nickel introduction step of contacting the aluminum introduced SBA-15 or SBA-16 carrier with a nickel metal precursor; And a reduction step of reducing the SBA-15 or SBA-16 carrier to which nickel is introduced.

The present invention also provides a process for producing aviation oil, using the catalyst for aviation oil production described above.

The method for preparing aviation oil according to the present invention may include the step of selectively preparing an aviation oil mixture having 8 to 16 carbon atoms by reaction of the fatty acid methyl ester having 9 to 17 carbon atoms with the catalyst for preparing aviation oil described above.

In the method for preparing aviation oil according to an embodiment of the present invention, the catalyst for preparing aviation oil may be mixed in an amount of 1 to 10 parts by weight based on 100 parts by weight of fatty acid methyl ester having 9 to 17 carbon atoms.

The present invention is a nano-size by including a rod-shaped mesoporous SBA-15 or SBA-16 carrier having a short axis diameter of 1: 1 to 3, and nickel and aluminum supported on the SBA-15 or SBA-16 carrier. In the case of using other carriers or metals having irregular pores, there is an advantage that a significantly higher yield can be produced in the preparation of hydrocarbon mixtures in the range of aviation oil in the deoxygenation reaction. Furthermore, by producing relatively inexpensive nickel and aluminum, there is an advantage in that hydrocarbon mixtures in the range of aviation oils can be produced in the deoxygenation reaction even at a very low cost of less than 1/10 of the catalyst cost compared to precious metals.

Figure 1 shows the nitrogen adsorption distribution curve of the carrier prepared in the carrier preparation and comparative carrier preparation of the present invention.
Figure 2 shows the pore analysis results and the volume of the pores of the carrier prepared in the carrier preparation example and comparative carrier preparation of the present invention.
Figure 3 shows the carrier prepared in the carrier preparation example and comparative carrier preparation of the present invention through SEM and shown.

Hereinafter, a catalyst for preparing an aviation oil mixture in the deoxygenation reaction according to the present invention will be described in detail. In this case, unless there is another definition in the technical terms and scientific terms used, it has the meaning that is commonly understood by those of ordinary skill in the art, unnecessarily obscure the subject matter of the present invention in the following description Description of known functions and configurations that may be omitted.

In the present invention, the uniaxial diameter (W) is a rod-shaped mesoporous SBA-15 or SBA-16 carrier having a major axis diameter (L) of 1 to 3 and nickel and aluminum supported on the SBA-15 or SBA-16 carrier. It includes, and relates to a catalyst capable of producing a high yield of aviation oil mixture in the deoxygenation reaction from vegetable oil.

Hereinafter, in the present invention, "width" is used in the same sense as "short axis diameter (W)" or "diameter" of the cross section, "length" means the same as "long axis diameter (L)" or "length" of the cross section. Was used.

In addition, in the present invention, "air fuel" means a mixture of the hydrocarbon compound range (C ₈ -C ₁₆ ), and has the same meaning as "bio synthetic oil", "bio aviation oil", "air fuel mixture" or "air fuel oil" Was used.

In addition, in the present invention, the ratio of the number of moles of aluminum (Al ₂ ) to the number of moles of silica (Si) included in the carrier is represented by “Si / Al ₂ ”.

In the deoxygenation reaction according to the present invention, the catalyst is involved in the deoxygenation reaction, which is the first step in the production of bio aviation oil from vegetable oil. Specifically, the catalyst for aviation oil production according to the present invention has the advantage of enabling the conversion of aviation oil to the hydrocarbon compound range (C ₈ -C ₁₆ ) in a high yield by applying to the production of aviation oil mixture in the deoxygenation reaction. Furthermore, without using expensive precious metal catalysts such as platinum or palladium, there is an advantage that the production of aviation oil mixture in the deoxygenation reaction with high efficiency while reducing the cost by producing a high yield bio-synthetic oil.

Specifically, in the deoxygenation reaction according to the present invention, the catalyst for aviation oil production is particularly preferably used in a rod-shaped mesoporous SBA-15 or SBA-16 carrier having a ratio of uniaxial diameter: major axis diameter of 1: 1 to 3: And aluminum is supported. Furthermore, unlike the present invention, even if a carrier of the same material is produced in a round shape such as a carrier, an amorphous carrier, a platelet or a donut having a shape that does not satisfy the diameter: length ratio described above, high yield deoxidation as in the present invention There are differences in the digestion reactions that make aviation oil mixtures difficult. Furthermore, even when the ratio between the short axis diameter and the long axis diameter described above is satisfied, even when a carrier of a material other than SBA-15 or SBA-16 mesoporous carrier is used or a metal other than aluminum and nickel is supported. As described above, there is a disadvantage in that it is difficult to manufacture bio synthetic oil in high yield.

As a result, in the deoxygenation reaction according to the present invention, the catalyst for the production of aviation oil is particularly preferably a rod-shaped SBA-15 or SBA-16 mesoporous carrier having a uniaxial diameter: long axis diameter of 1: 1 to 3 and an appropriate content of nickel and aluminum metal. The synergistic effect of the combination of, has the advantage that can be produced in a high yield in the air fuel mixture in the deoxygenation reaction.

Specifically, in the deoxygenation reaction according to an embodiment of the present invention, the catalyst for aviation oil production may have a short axis diameter: long axis diameter of 1: 1 to 3, specifically 1 to 2.5, and may occur during the deoxygenation process. Since liquid and gaseous products are easily discharged out of the carrier, it is possible to prepare a high yield of aviation oil mixture in the deoxygenation reaction by preventing the rapid decrease in catalytic activity caused by the liquid and gaseous products filled in the pores of the carrier. There is this.

Furthermore, as described above, liquid and gaseous products generated in the deoxygenation process are easily discharged out of the carrier, thereby solving the problem of difficulty in regenerating the catalyst, thereby facilitating reuse of the catalyst in the long term, and reducing the cost of replacing the catalyst. There are advantages to it.

In addition, in the deoxygenation reaction according to an embodiment of the present invention, the SBA-15 or SBA-16 mesoporous carriers used in the catalyst for preparing the aviation oil mixture may have an average pore size of 4 to 12 nm and a specific surface area of 600 To 850 m ² / g, specifically 650 to 840 m ² / g.

When the SBA-15 or SBA-16 mesoporous carrier included in the catalyst for aviation oil production according to an embodiment of the present invention satisfies the above average pore size and specific surface area, the liquid generated in the deoxygenation process as described above and Gas products are easily discharged out of the carrier to prevent deterioration of catalyst activity and to facilitate regeneration. Furthermore, if the pore size is excessively expanded in view of facilitating the regeneration of the catalyst and easily discharging the product of deoxygenation, the specific surface area may be lowered, but the specific surface area may be secured in the above-described range. At the same time, there is an advantage in that the products of deoxygenation are easily discharged to prevent the problem of deterioration of catalyst activity caused by the product not being easily discharged during the process.

Due to these advantages, when the catalyst for aviation oil production that satisfies the above-mentioned average pore size and specific surface area is applied to vegetable oil, specifically methyl palmitate, to be described later, the deoxygenation process falls within the range of C ₈ to C ₁₆ . It is advantageous in that the aviation oil mixture can be prepared in a high yield of 75% or more, preferably 80% or more, which is a carrier, amorphous carrier, platelet or donut having a shape that does not satisfy the diameter: length ratio of the above-mentioned cross section under the same conditions. When deoxygenation is carried out by forming a round catalyst such as this, it can be seen as a result in contrast with the limit of hardly showing a yield of 70% or more. It can be seen that the effect of preparing the mixture of aviation oil can be achieved.

In the catalyst for preparing an aviation oil mixture in the deoxygenation reaction according to an embodiment of the present invention, the major axis diameter of the SBA-15 or SBA-16 mesoporous carrier may be 0.5 to 10 μm, and the minor axis diameter is in the above-described ratio range. Can be satisfied.

For example, the major axis diameter of the SBA-15 or SBA-16 mesoporous carrier may be 0.5 to 5 ㎛, the minor axis diameter may satisfy the above-described ratio range.

For example, the major axis diameter of the SBA-15 or SBA-16 mesoporous carrier may be 1.0 to 3.0 ㎛, the minor axis diameter may satisfy the above ratio range.

While securing a part of the specific surface area by the particle size in the above-described range, it is possible to prevent the problem that the separation of the catalyst from the product after the reaction is difficult due to the excessively fine particle size.

In the deoxygenation reaction according to an embodiment of the present invention, aluminum included in the catalyst for preparing an aviation oil mixture is 1 to 7 moles, more specifically, 100 moles of silica contained in the SBA-15 or SBA-16 mesoporous carrier. 2 to 5 moles may be included. In this case, when the supported aluminum content is more than the above-mentioned range, a large amount of unreacted reactant methyl ester component may remain. When the supported aluminum content is less than the above-mentioned range, hydrocarbons having too low carbon number may be produced. There is a big problem of carbon loss due to unnecessary hydrocarbons.

In the deoxygenation reaction according to an embodiment of the present invention, nickel included in the catalyst for preparing an aviation oil mixture may be 5 to 20 wt% based on the total weight of SBA-15 or SBA-16 mesoporous carrier. In the above-described range, while preventing the problem that the deoxygenation efficiency is lowered because the content of nickel is too low, it is possible to prevent the problem of inhibiting catalytic activity by aggregating a large amount of nickel together.

In the deoxygenation reaction according to an embodiment of the present invention, the vegetable oil to which the catalyst for preparing an aviation oil mixture is applied may specifically include a fatty acid methyl ester having 9 to 17 carbon atoms. More specifically, it can be used as a raw material containing methyl palmitate, and when applying the catalyst for aviation oil production of the present invention with a bio-oil containing methyl palmitate, the deoxygenation process is performed at a significantly higher efficiency to achieve a higher yield There is an advantage to prepare a bio-synthetic oil. In this case, the methyl palmitate may be extracted from the vegetable raw material, but the present invention is not limited thereto, and more specifically, the methyl palmitate to which the catalyst for preparing the aviation oil mixture is applied in the deoxygenation reaction according to an embodiment of the present invention may be used. It may be obtained from the oil extracted from the deadwood, but the present invention is not limited thereto.

In this case, the hydrocarbon compound in the range of aviation oil in the present invention may be a mixture of C ₈ to C ₁₆ hydrocarbon compound through a deoxygenation reaction that is a one-step reaction for the production of aviation oil.

The present invention also provides a method for preparing the above-mentioned catalyst for aviation oil production.

The method for preparing a catalyst for preparing aviation oil according to the present invention may be a manufacturing method for preparing a catalyst for preparing aviation oil used in a deoxygenation reaction from vegetable oil, but the present invention is not limited thereto.

A method for preparing a catalyst for aviation oil production according to the present invention includes introducing an aluminum contacting an aluminum precursor with a rod-shaped SBA-15 or SBA-16 carrier having a cross-sectional diameter: length of 1: 1 to 3; A nickel introduction step of contacting the aluminum introduced SBA-15 or SBA-16 carrier with a nickel metal precursor; And a reduction step of reducing the SBA-15 or SBA-16 carrier to which nickel is introduced.

The method for producing a catalyst for aviation oil production according to the present invention has the advantage of forming a carrier without a precise process by a relatively simple method by forming a rod-shaped carrier having a short axis diameter: long axis diameter of 1: 1 to 3. By sequentially impregnating an aluminum precursor and a nickel precursor There is an advantage to prepare a catalyst. Furthermore, there is an advantage that the bio-derived aviation oil can be provided with high productivity by preparing a catalyst for aviation oil production in the deoxygenation reaction at a relatively low cost. In this case, the production of a rod-shaped SBA-15 or SBA-16 carrier having a short axis diameter: long axis diameter of 1: 1 to 3 may be generally manufactured by a method known to those skilled in the art, and the present invention is limited thereto. no.

The method for preparing a catalyst for aviation oil production according to the present invention serves to promote a cracking reaction at an acid point of the catalyst by generating an acid point, which is an acid characteristic of the catalyst, according to an appropriate acid point, that is, an Al / Si molar ratio.

First, the method for preparing a catalyst for aviation oil production according to the present invention includes an aluminum introduction step of contacting an aluminum precursor with a rod-shaped SBA-15 or SBA-16 carrier having a uniaxial diameter: long shaft diameter of 1: 1 to 3. In this case, the step of contacting the aluminum precursor may be specifically carried out by impregnating the SBA-15 or SBA-16 carrier in a solution in which the aluminum precursor is dissolved, and drying it. More specifically, the solution in which the aluminum precursor is dissolved may be an aqueous solution, but the present invention is not limited thereto.

In this case, the aluminum precursor may be used without limitation in the case of an aluminum compound soluble in a polar solvent, and is not limited to an organic or inorganic precursor. In one specific and non-limiting example, the aluminum precursor may be one or two or more selected from AlCl ₃ , Al (NO ₃ ) ₃ , Al (CH ₃ COO) _3, and hydrates thereof, but the present invention is not limited thereto. .

In addition, the concentration of the solution in which the aluminum precursor is dissolved may vary depending on the amount of the SBA-15 or SBA-16 carrier, the execution time of the aluminum introduction step, and the like. As a specific and non-limiting example, the concentration of the solution in which the aluminum precursor is dissolved may be 1 to 10% by weight, specifically 1.5 to 5% by weight, and the amount of aluminum introduced may be 1 to 7 moles based on 100 moles of silica, More specifically, 2 to 5 moles may be included. In this range, while introducing aluminum into the SBA-15 or SBA-16 mesoporous carrier within a short time, there is an advantage that can prevent the problem affecting the pore or the nickel carried after carrying a large amount of aluminum is supported, but the present invention It is not limited to this.

Next, the method for preparing a catalyst for aviation oil production according to the present invention includes a nickel introduction step of contacting an aluminum-introduced SBA-15 or SBA-16 carrier with a nickel metal precursor. That is, nickel metal promotes a hydrogenation or dehydrogenation reaction upon introduction into such a carrier, thereby giving the function of controlling the hydrocarbon range for preparing the aviation oil mixture in an appropriate deoxygenation reaction.

At this time, the introduction of nickel may also be introduced through a process of impregnating the SBA-15 or SBA-16 carrier with aluminum introduced into a solution in which the nickel precursor is dissolved and firing the same. At this time, the concentration of the nickel precursor may vary depending on the amount of SBA-15 or SBA-16 mesoporous carrier, the type and the impregnation time of the nickel precursor, as a specific example of the concentration of 0.05 to 0.1% by weight based on the aqueous solution Nickel may be introduced through the impregnation of the nickel precursor solution.

In this case, the nickel precursor applied in the nickel introduction step is Ni (NO ₃ ) ₂ , NiCl ₂ , Ni (CH ₃ COO) ₂ And One or two or more selected from these hydrates, etc., but the present invention is not limited thereto.

Next, the method for preparing a catalyst for aviation oil production according to the present invention includes a reduction step of reducing SBA-15 or SBA-16 mesoporous carrier into which nickel is introduced. This reduction step can be used without limitation in the case of a reduction method commonly used in the field of catalysts, the present invention is not limited thereto. As a specific and non-limiting example, the reduction step may be performed by heating a carrier in which nickel is introduced at 150 to 400 ° C. while supplying hydrogen gas, and such heating may be performed for 1 to 10 hours, and hydrogen The gas may be supplied at 30 to 300 ml per minute, but the present invention is not limited thereto.

The present invention also provides a process for producing aviation oil in the deoxygenation reaction from vegetable oils.

This production method according to the present invention comprises the step of preparing a bio-synthetic oil having 8 to 16 carbon atoms by the reaction of the fatty acid methyl ester having 9 to 17 carbon atoms with the catalyst for preparing aviation oil according to an embodiment of the present invention.

The method for preparing aviation oil according to the present invention has an advantage of finally improving the yield by preparing the aviation oil mixture at a high yield through a deoxygenation process in fatty acid methyl ester.

In this case, the catalyst for preparing aviation oil in the deoxygenation reaction to be mixed may be 1 to 10 parts by weight, specifically 2 to 7 parts by weight, based on 100 parts by weight of fatty acid methyl ester having 9 to 17 carbon atoms, but the present invention is limited thereto. It doesn't happen.

Hereinafter, the present invention will first be described with reference to embodiments of the catalyst production for aviation oil production described above, and then by examples of the reaction using the same. The embodiments described below are merely to aid the understanding of the invention, and the present invention is not limited to the embodiments.

(Assessment Methods)

1. Check physical properties

For the physical properties of each carrier used in the catalyst for preparing aviation oil prepared in the following examples and comparative examples, BET analysis and particle size were measured (see Table 1 and FIGS. 1 to 3). In this case, the particle size means a value obtained by obtaining the average size of the particles by the SEM photograph.

2. Evaluation of Reactivity of Catalysts for Air Oil Production

The catalyst for the production of aviation oil prepared in the following examples and comparative examples was applied to the deoxygenation reaction to calculate the conversion of the reactants and to evaluate it as reactive capacity. Specifically, the deoxygenation reaction was carried out in the following manner.

The reactor used a high pressure batch reactor (autoclave), the reaction was carried out in a semi-continuous batch reactor in the form of a mass flow meter to continuously supply hydrogen for the deoxygenation reaction. As a catalyst, 1.0 g of each of the catalysts for preparing aviation oil prepared in the following Examples and Comparative Examples and 30 g of methyl palmitate (97% Acros) as a reactant were introduced into the reactor, and stirred well at 500 rpm or more. Hydrogen was flowed at 300 ° C. for 2 hours to reduce the oxide catalyst. Subsequently, the reaction temperature was raised to the reaction temperature of 280 ° C. At this time, the reactor pressure of hydrogen was maintained at 20 bar and 50 ml / min was flowed to carry out the reaction for 2 hours.

The reaction product was subjected to component analysis via GC. In this case, since the fatty acid ester compound reacts with the filler of the GC column, it is not easy to detect the peak during the GC analysis. Thus, the fatty acid ester compound is analyzed after undergoing a silylation step of the liquid reactant.

At this time, the silylation solution was mixed with 3.068 cc of N, O bis (trimethylsilyl), 12.0 cc of trifluoroacetamide (BSTFA), and 0.04 gram of icosane (eicosane, C ₂₀ H ₄₂ ) as a reference substance. The reaction mixture was used after reacting at 60 ° C. for 1 hour. 0.75 ml of the prepared silylation solution was collected, mixed with 0.5 grams of the reaction product, and reacted at 60 ° C. for 1 hour, followed by component analysis by GC (FID analyzer, GC column: DB-5MS, Ultra inert, 60 mx 0.25 mm, 0.25 μm).

Here, the conversion of the reactants was calculated based on the weight of methyl palmitate after the reaction, based on the weight of the methyl palmitate before the reaction. The yield of the product was also calculated as the ratio of the weight of each product based on the total weight of the converted product after the reaction (see Table 2).

Example 1

Manufacture of catalysts 1 for aviation oil production

First, 4.0 grams of triblock copolymer Pluronic P123 (EO ₂₀ PO ₇₀ EO ₂₀ from Aldrich) was dissolved in 150 grams of 1.6 M HCl (aqueous solution) in a high pressure reactor coated with Teflon and stirred well. Inject 8.50 grams of TEOS (tetraethyl orthosilicate) and stir well for 15 minutes. This mixed solution is allowed to stand at 35 ° C. for 1 day without stirring. The mixture is then placed in a constant temperature oven at 100 ° C. for 1 day for thermal treatment. This product solution was then filtered to separate the white solids, dried at 100 ° C. and finally calcined at 550 ° C. to obtain an SBA-15 carrier having a length / width ratio of 1.6 (carrier preparation example 1).

Aluminum and nickel were sequentially impregnated into the obtained carrier to prepare a catalyst for aviation oil production. Specifically, it was impregnated by wet impregnation using an Al precursor to control the acid point. 5.0 g of the SBA-15 was dissolved in 0.125 grams of Al (NO ₃ ) ₃ .9H ₂ O with Al precursors, 5.0 grams of distilled water. The dissolved solution with was impregnated in a rotary evaporator and then distilled water was evaporated. Subsequently, it was calcined at 500 ° C. to prepare Al-SBA-15 impregnated with aluminum, wherein Si / Al ₂ The molar ratio was 30.

Subsequently, 10 wt% Ni was impregnated based on the prepared Al-SBA-15, and Al was prepared in the solution prepared by dissolving 0.0044 grams of Ni (NO ₃ ) ₂ .6H ₂ O in 5 grams of distilled water at room temperature. Inject 2.0 grams of SBA-15 and stir well at 80 ° C. for 20 hours. The resulting solution was filtered to separate solids, dried at 80 ° C. and finally calcined at 300 ° C. to finally prepare a Ni-Al-SBA-15 catalyst impregnated with 10 wt% Ni. At this time, the Si / Al ₂ molar ratio was 30, 10% Ni-Al-SBA-15 catalyst 1 (L / W = 1.6, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

Example 2

Preparation of catalyst 2 for aviation oil production

Prepared in the same manner as in Example 1, except that Si / Al ₂ A catalyst for preparing aviation oil was prepared by setting the molar ratio to 20, which was 10 wt% Ni / Al-SBA-15 catalyst 2 (L / W = 1.6, Si / Al ₂ = 20).

Example 3

Preparation of catalysts 3 for aviation oil production

Prepared in the same manner as in Example 1, except that Si / Al ₂ A catalyst for preparing aviation oil was prepared by setting the molar ratio to 20, which was 10 wt% Ni / Al-SBA-15 catalyst 3 (L / W = 1.6, Si / Al ₂ = 40).

Example 4

Manufacture of catalysts 4 for aviation oil production

Prepared in the same manner as in Example 1, except that Si / Al ₂ The molar ratio was set to 10 to prepare a catalyst for preparing aviation oil, which was 10 wt% Ni / Al-SBA-15 catalyst 4 (L / W = 1.6, Si / Al ₂ = 10).

Example 5

Manufacture of catalysts 5 for aviation oil production

Prepared in the same manner as in Example 1, except that Si / Al ₂ A catalyst for preparing aviation oil was prepared by setting the molar ratio to 70, which was 10 wt% Ni / Al-SBA-15 catalyst 5 (L / W = 1.6, Si / Al ₂ = 70).

Example 6

Preparation of catalysts 6 for aviation oil production

Prepared in the same manner as in Example 1, but using a SBA-15 carrier having a length / width ratio = 1.8 instead of the SBA-15 carrier having a length / width ratio = 1.6. Specifically, SBA-15 carrier having a length / width ratio = 1.8 is prepared by the following method.

In a high pressure reactor coated with Teflon, 33.6 grams of P123 copolymer was dissolved in 18.3 grams of 0.3 M hydrochloric acid (HCl) aqueous solution and maintained at 35 ° C. 54.2 grams of TEOS solution was then added to the solution, followed by stirring for 1 day. Subsequently, the mixed solution is placed in a constant temperature oven at 100 ° C. for 1 day and heat treated. The product solution was then filtered to separate solids, dried at 100 ° C. and finally calcined at 550 ° C. to obtain SBA-15 having a length / width ratio = 1.8 to prepare a carrier (carrier preparation example 2).

The catalyst for preparing aviation oil prepared by the above method was named 10 wt% Ni / Al-SBA-15 catalyst 6 (L / W = 1.8, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

Example 7

Preparation of catalysts 7 for aviation oil production

Prepared in the same manner as in Example 1, but using a SBA-16 carrier having a three-dimensional cubic Im3m structure having a length / width ratio = 1.0 instead of the SBA-15 carrier having a length / width ratio = 1.6. Specifically, SBA-16 carriers having a length / width ratio = 1.0 are described in J. Phys. Chem. B 108, 11480-11498 (2004).

First, 4.0 grams of F127 (Pluronic® F-127, PEO106PPO70PEO106, Aldrich), a triblock copolymer, are completely dissolved in a polypropylene bottle at 35 ° C in 200 mL of 0.4 M HCl aqueous solution. Then, 19.3 grams of TEOS was added quickly, followed by vigorous stirring for 15 minutes, maintained in a static state for 24 hours, transferred to a Teflon high pressure reactor, and hydrothermally treated at 100 ° C. for 24 hours, followed by solid SBA- 16 product was isolated by filtration and dried in a drying oven under air atmosphere at 100 ° C. and then calcined at 550 ° C. to prepare an SBA-16 carrier having a length / width ratio = 1.0 (carrier preparation 3).

The catalyst for preparing aviation oil prepared by the above method was named 10 wt% Ni / Al-SBA-16 catalyst 7 (L / W = 1.0, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

Example 8

Preparation of catalysts 8 for aviation oil production

Prepared in the same manner as in Example 1, but using a SBA-15 carrier having a length / width ratio = 3.0 instead of the SBA-15 carrier having a length / width ratio = 1.6 (carrier preparation example 4).

The catalyst for preparing aviation oil prepared by the above method is 10 wt% Ni / Al-SBA-15 catalyst 8 (L / W = 3.0, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

(Comparative Example 1)

Manufacture catalyst A for aviation oil production

At 35 ° C, 80 grams of 2.0 M HCl (aqueous solution) are dissolved well with 2.0 grams of triblock copolymer Pluronic P123 surfactant and 0.32 grams ZrOCl ₂ · 8H ₂ O. This solution is then mixed well with 4.2 grams of TEOS and stirred well under these conditions for 15 minutes. It is then allowed to stand at 35 ° C. for 24 hours. Subsequently, the mixed solution is placed in a constant temperature oven at 100 ° C. for 1 day and heat treated. The product solution was then filtered to separate solids, dried at 100 ° C. and finally calcined at 550 ° C. to yield SBA-15 having a length / width ratio = 0.3 (Comparative Carrier Preparation Example 1).

The catalyst for preparing aviation oil prepared by the above method was named 10% Ni-Al-SBA-15 catalyst A (L / W = 0.3, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

(Comparative Example 2)

Manufacture catalyst B for aviation oil production

Dissolve 2.4 grams of P123 surfactant and 1.08 grams NH ₄ F at 20 ° C in 80 mL of 1.75 M HCl (aqueous solution). In addition, a solution of 5.5 grams of TEOS in 38.4 grams of heptane is stirred well with the solution for 4 minutes. Subsequently, the mixture is held at 20 ° C. for 20 hours. Subsequently, the mixed solution is placed in a constant temperature oven at 100 ° C. for 1 day and heat treated. This product solution was then filtered to separate solids, dried at 100 ° C. and finally calcined at 550 ° C. to produce SBA-15 having a length / width ratio of 4.3 (Comparative Carrier Preparation Example 2).

The catalyst for preparing aviation oil prepared by the above method was named 10% Ni-Al-SBA-16 catalyst B (L / W = 4.3, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

(Comparative Example 3)

Manufacture catalyst C for aviation oil

Prepared in the same manner as in Comparative Example 1, but using a SBA-15 carrier having a length / width ratio = 0.9 instead of the SBA-15 carrier having a length / width ratio = 0.3 (Comparative Carrier Preparation Example 3).

The catalyst for preparing aviation oil prepared by the above method was named 10% Ni-Al-SBA-15 catalyst C (L / W = 0.9, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

(Comparative Example 4)

Manufacture catalyst D for aviation oil

Prepared in the same manner as in Comparative Example 1, but using a SBA-15 carrier having a length / width ratio = 3.1 instead of the SBA-15 carrier having a length / width ratio = 0.3 (Comparative Carrier Preparation Example 4).

The catalyst for preparing aviation oil prepared by the above method was named 10% Ni-Al-SBA-15 catalyst D (L / W = 3.1, Si / Al ₂ = 30).

The physical properties of the carrier prepared by the preparation method were measured and the results are shown in Table 1 below.

(Comparative Example 5)

Manufacture catalyst E for aviation oil production

Prepared in the same manner as in Comparative Example 1, a carrier of 3-D cubic la-3d structure was used instead of SBA-15 carrier having a length / width ratio = 0.3. Specifically, the carrier of the 3-D cubic la-3d structure is prepared by the following preparation method (comparative carrier preparation example 5).

First, 16.9 grams of triblock copolymer Pluronic P123 (EO20PO70EO20 from Aldrich) and 18.6 grams of normal butanol (n-butanol) were dissolved in 610 grams of water in a Teflon-coated high-pressure reactor. Aqueous solution). Then 43.6 grams of TEOS is injected while maintaining at 35 ° C. The mixture is stirred well for 1 day while maintaining at 35 ° C., and then heat-treated in a constant temperature oven at 100 ° C. for 1 day. The product solution was then filtered to separate the white solid, dried at 100 ° C., and finally calcined at 550 ° C. to obtain KIT-6, showing a 3-D cubic la-3d structure.

The catalyst for preparing aviation oil prepared by the above method was named 10% Ni-Al-KIT-6 catalyst E (Si / Al ₂ = 30).

(Comparative Example 6)

Manufacture catalyst F for aviation oil

Prepared in the same manner as in Example 1, but impregnated with a catalyst weight of 5% by weight relative to the weight of the carrier using PdCl ₂ instead of 0.0044 grams of Ni (NO ₃ ) ₂ · 6H2O.

The catalyst for aviation oil production prepared by the above production method was named Pd / Al-SBA-15 catalyst F (L / W = 1.6, Si / Al ₂ = 30).

(Examples 9 to 16)

Using each of the catalysts for the production of aviation oil prepared in Examples 1 to 8, the deoxygenation reaction specifically disclosed in the evaluation method was carried out.

As a result, the product yield of each catalyst for aviation oil production, specifically the low boiling point component (%) below C ₈ , the hydrocarbon mixture yield (%) in the aviation oil range and the component (%) of side reaction FFA are calculated and shown in Table 2 below. It was.

(Comparative Examples 7 to 12)

Using each of the catalysts for the production of aviation oil prepared in Comparative Examples 1 to 6, the deoxygenation reaction specifically disclosed in the evaluation method was carried out.

As a result, the product yield of each catalyst for aviation oil production was calculated and shown in Table 2 below.

(Comparative Example 13)

Using a commercial 5 wt% Pd / C catalyst (Adrich), the deoxygenation reaction described specifically in the above evaluation was carried out.

As a result, the product yield of each catalyst for aviation oil production was calculated and shown in Table 2 below.

Observing based on Table 2, it was confirmed that the reactivity performance compared to the same catalyst having a different ratio in the range of 1: 1 to 3 diameter: length ratio of the cross section.

Specifically, by applying the catalyst for the production of aviation oil of the present invention to the deoxygenation reaction, it can be seen that the implementation of the reactant conversion efficiency of more than 99%, as well as the yield of hydrocarbon mixtures in the range of 70% or more aviation oil. That is, the use of the catalyst for aviation oil production according to the present invention has a technical meaning that it is possible to drastically improve the conventional technical limitations.

Further, it can be seen that the reaction activity is superior to Comparative Example 13, a commercial catalyst, in terms of yield of bio-synthetic oil (aircraft oil).

Specifically, as the aviation oil production catalyst of the present invention is applied to the deoxygenation reaction, a side reaction FFA content of less than 1% can be realized.

On the contrary, when the ratio (L / W) according to the present invention is not satisfied, the hydrocarbon mixture yield in the range of 50% or less of aviation oil is realized, and it can be confirmed that it is accompanied by excessive low boiling point component content or excessive side reaction FFA content. have.

In short, the catalyst for aviation oil production according to the present invention can be used in the deoxygenation reaction of vegetable oil to provide a high yield of the desired aviation oil mixture, as well as to provide a very economical way to chemically improve biomass such as vegetable oil. It is expected to be very promising as a catalyst for grading.

Claims (11)

As catalyst for preparing a mixture of aviation oils from vegetable oils,
Minor axis diameter (W): rod-shaped SBA-15 or SBA-16 carrier having a major axis diameter (L) of 1: 1 to 3; And
It includes; and nickel and aluminum supported on the SBA-15 or SBA-16 carrier,
The carrier has a specific surface area of 600 to 850 m ² / g and a major axis diameter of 0.5 to 10 ㎛, aviation oil production catalyst. The method of claim 1,
The aluminum is,
A catalyst for producing aviation oil, which is included in an amount of 1 to 7 moles relative to 100 moles of silica included in the SBA-15 or SBA-16 carrier. The method of claim 1,
The nickel is,
The SBA-15 or SBA-16 will be included in 5 to 20% by weight relative to the total weight of the carrier, a catalyst for aviation oil production. delete The method of claim 1,
The SBA-15 or SBA-16 carrier,
A catalyst for the production of aviation oil, wherein the mesoporous carrier has an average pore size of 4 to 12 nm. delete The method of claim 1,
The vegetable oil,
A catalyst for producing aviation oil, comprising methyl palmitate. The method of claim 7, wherein
The vegetable oil,
A catalyst for producing aviation oil, comprising an oil extracted from the deadwood. A process for preparing a catalyst for preparing an aviation oil mixture from vegetable oil,
Diameter of cross section: aluminum introduction step of contacting the aluminum precursor with a rod-shaped SBA-15 or SBA-16 carrier having a length of 1: 1 to 3;
A nickel introduction step of contacting the aluminum introduced SBA-15 or SBA-16 carrier with a nickel metal precursor; And
It includes; reducing the nickel introduced SBA-15 or SBA-16 carrier;
The carrier has a specific surface area of 600 to 850 m ² / g and a major axis diameter of 0.5 to 10 ㎛, a method for producing a catalyst for aviation oil production. A process for preparing an aviation oil mixture having 8 to 16 carbon atoms by reaction of a fatty acid methyl ester having 9 to 17 carbon atoms and a catalyst for preparing aviation oil according to any one of claims 1 to 3, 5, 7 and 8. It includes ;, Method for producing an aviation oil mixture. The method of claim 10,
The aviation oil production catalyst,
1 to 10 parts by weight relative to 100 parts by weight of fatty acid methyl ester having 9 to 17 carbon atoms, the method for producing an aviation oil mixture.

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