KR20200028751A - Catalyst for fischer-tropsch synthesis reation, method for preparing the same and, method for fischer-tropsch synthesis using the same - Google Patents

Abstract

The present invention relates to a catalyst for Fischer-Tropsch synthesis, a manufacturing method thereof, and a Fischer-Tropsch synthesis reaction for manufacturing liquid hydrocarbons using the same. When the synthesis reaction is induced by using the catalyst of the present invention, catalyst deactivation is suppressed, the catalyst is structurally stable, and a liquid hydrocarbon conversion rate is superior compared to the prior art. The catalyst for Fischer-Tropsch synthesis comprises a support comprising zirconium and phosphorus on silica having mesopores, and a complex metal oxide comprising cobalt supported on the support.

Description

Fischer-Tropsch synthesis reaction catalyst, production method thereof, and Fischer-Tropsch synthesis method using the catalyst TECHNICAL FIELD

The present invention relates to a catalyst for the Fischer-Tropsch synthesis reaction, a method for producing the same, and a method for producing a hydrocarbon through the Fischer-Tropsch synthesis reaction using the catalyst.

 The Fischer-Tropsch (F-T) synthesis method was derived from the technology in 1923 by Fischer and Tropsch to produce synthetic fuel from syngas by coal gasification. In general, the FT reaction is carried out at a reaction temperature of 200 to 350 ° C. and a pressure of 10 to 30 atmospheres using iron and cobalt as active materials. Chain growth in FT synthesis, methanation, aqueous It consists of four main reactions: water gas shift reaction and Boudouard reaction.

Iron-based catalysts were mainly used in the initial F-T reaction, but cobalt-based catalysts are also used to increase the conversion rate of synthetic gas and the yield of liquid fuel. Cobalt-based catalysts have the advantage of high activity, long life, and high yield of liquid paraffinic hydrocarbons while suppressing water gas conversion. In particular, it is used in low temperature Fischer-Tropsch Synthesis reactions because it exhibits similar activity while being cheaper than precious metals such as platinum (Pt) and ruthenium (Ru).

 On the other hand, in the Fischer-Tropsch synthesis reaction, the activity of the cobalt-based catalyst is generally known to be proportional to the number of active sites exposed on the surface. In order to obtain high catalytic activity, an active material such as cobalt is applied on a support having a large specific surface area. The process of evenly dispersing is essential. Silica materials are used in this process.

 However, when silica is used as a support, a strong interaction decreases the reducibility of the cobalt metal, and a phenomenon in which activity decreases during the reaction is observed. New techniques are needed to overcome these problems.

One object of the present invention is to provide a new catalyst for the production of liquid hydrocarbons and reactions using the same.

The Fischer-Tropsch synthesis catalyst for one purpose of the present invention includes a support comprising zirconium and phosphorus on silica having mesopores; And a composite metal oxide containing cobalt supported on the support.

In one embodiment, the support may include zirconium phosphate (zirconium phosphate).

In one embodiment, the support may be that the zirconium phosphate is included in at least a portion of the silica surface having the mesopores.

In one embodiment, the zirconium phosphate may be in the form of a thin film.

In one embodiment, the cobalt may be supported on the zirconium phosphate.

In one embodiment, the support may include 10 to 15 wt% of zirconium based on the silica.

In one embodiment, the support may include 5 to 70 wt% of phosphorus based on the zirconium.

In one embodiment, the catalyst may be one containing 10 to 20 wt% cobalt based on the support.

In one embodiment, the support may have a specific surface area of 200 to 400 m ² / g.

For another purpose of the present invention, a method of preparing a catalyst for Fischer-Tropsch synthesis comprises: a first step of preparing a mixture by mixing and impregnating a support and a cobalt precursor; And a second step of drying and calcining the mixture to prepare a catalyst; and further comprising preparing the support before the first step, wherein preparing the support comprises: a solvent, a zirconium precursor, and phosphorus. Mixing the precursor to prepare a first mixed solution; Preparing a second mixed solution by mixing silica with the first mixed solution; And preparing the support by drying the second mixed solution under reduced pressure.

In one embodiment, the firing process of the second step may be performed at 500 to 600 ° C.

In one embodiment, the support may include 10 to 15 wt% of zirconium based on the silica.

In one embodiment, the support may include 5 to 70 wt% of phosphorus based on the zirconium.

In one embodiment, the catalyst may be one containing 10 to 20 wt% cobalt based on the support.

In one embodiment, the zirconium precursor may be zirconium propoxide (Zirconium (IV) propoxide, Zr (OPr) ₄ ).

In one embodiment, the phosphorus precursor may be phosphorus oxychloride (Phosphorus (V) oxychloride, POCl ₃ ).

In one embodiment, the cobalt precursor may be cobalt nitrate (Cobalt nitrate hexahydrate, Co (NO ₃ ) ₂ · 6H ₂ O).

In one embodiment, the solvent may be one or more of toluene, ethanol, and mixtures thereof.

Another Fischer-Tropsch synthesis method for another object of the present invention is a Fischer-Tropsch synthesis method for producing a liquid hydrocarbon, comprising the steps of placing the catalyst of the present invention inside a reactor; Activating the catalyst by reducing a cobalt oxide of the catalyst with cobalt by supplying a reducing gas into the reactor; And synthesizing the liquid hydrocarbon by supplying a synthesis gas containing hydrogen and carbon monoxide inside the reactor.

In one embodiment, the step of activating the catalyst may be performed at a temperature of 300 to 500 ° C.

In one embodiment, the step of performing the Fischer-Tropsch synthesis reaction may be performed at a reaction temperature of 200 ° C to 300 ° C and a reaction pressure of 10 to 30 bar.

The catalyst of the present invention has a feature that the collapse of the catalyst structure under reduction or reaction conditions is suppressed by using a mesoporous zirconium phosphate / silica support having a regular pore structure, so that deactivation of the catalyst can be suppressed. In addition, by treating the surface of silica with mesopores using zirconium phosphate, the dispersion and reducibility of the active component cobalt is increased and the particle size increase caused by sintering of the cobalt component during the reaction is suppressed, thereby deactivating the reaction and stability of the catalyst. It has an augmenting effect.

1 to 4 are diagrams showing the analysis results of the Fischer-Tropsch synthesis catalyst according to an embodiment of the present invention.

The terms used in the present application are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "include" or "have" are intended to indicate the presence of features, steps, actions, components, parts or combinations thereof described in the specification, one or more other features or steps. It should be understood that it does not preclude the existence or addition possibility of the operation, components, parts or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms such as those defined in a commonly used dictionary should be interpreted as having meanings consistent with meanings in the context of related technologies, and should not be interpreted as ideal or excessively formal meanings unless explicitly defined in the present application. Does not.

The Fischer-Tropsch synthesis catalyst of the present invention includes a support comprising zirconium and phosphorus on silica having mesopores; And a composite metal oxide containing cobalt supported on the support.

In one embodiment, the support may have a regular pore structure, and in one embodiment, the support may be mesoporous silica having medium pores. Without being limited thereto, for example, MCM-41, MCM-48, SBA-15, and KIT-6 may be used.

In one embodiment, the support may include zirconium phosphate (zirconium phosphate). In one embodiment, the support may be a form in which the zirconium phosphate is included in at least a portion of the surface of the silica having the mesopores, the entire silica, or the mesopores of the silica.

In one embodiment, a portion of the zirconium phosphate may be in the form of a thin film, and the other part may be in the form of nanoparticles. In other words, the zirconium phosphate may be dispersed in the form of thin films and / or nanoparticles within the silica surface and / or pores. For example, the support may be a form in which the zirconium phosphate in the form of a thin film or particles is coated on all or part of the surface of the mesoporous silica.

In one embodiment, the cobalt may be supported on the zirconium phosphate. For example, the composite metal oxide may be a structure in which at least a portion of the silica surface having mesopores, zirconium phosphate thin film or zirconium phosphate particles may be included, and on the surface of the zirconium phosphate thin film or particles, cobalt oxide may be included. have.

In one embodiment, the cobalt may be in the form of particles. For example, the cobalt particles may be evenly dispersed on the surface of the zirconium phosphate and / or the surface of the support. For example, the zirconium phosphate and / or the support and the cobalt particles may be physically and / or chemically bound.

In one embodiment, the composite metal oxide may have a pore structure. For example, the pore diameter of the composite metal oxide may be 3 to 10 nm.

In one embodiment, the support may include 10 to 15 wt% of zirconium based on the silica. For example, the support may include 12 wt% of the zirconium based on the silica.

In one embodiment, the support may include 5 to 70 wt% of phosphorus based on the zirconium. For example, when phosphorus is contained in an amount of 4 wt% or less based on zirconium, the effect of increasing the stability of the structure is insignificant while the phase of zirconium phosphate is not formed, thereby causing a problem that the catalyst is deactivated. In addition, when the phosphorus content is 70 wt% or more based on the zirconium, since an inactive chemical species such as cobalt phosphate is generated in addition to zirconium phosphate, a problem of decreasing reactivity may occur. It can show excellent effect.

In one embodiment, the catalyst may include 10 to 20 wt% cobalt based on the support. For example, when 15% by weight of cobalt may be included, and when the content of cobalt is less than 10wt%, catalytic activity is not excellent, and when 20% by weight or more of cobalt is included, structural stability is lowered due to cogging between particles. Problems may occur.

In one embodiment, the support may have a specific surface area of 200 to 400 m ² / g. The larger the specific surface area of the support, the better the catalytic activity, but may be structurally unstable.

The catalyst of the present invention is a catalyst that can be used in the Fischer-Tropsch synthesis reaction and used in the Fischer-Tropsch synthesis reaction for producing liquid hydrocarbons having 5 or more carbon atoms from syngas. In other words, the catalyst is a Fischer-Tropsch synthesis reaction catalyst comprising a composite metal oxide containing cobalt oxidized or reduced on a mesoporous zirconium-phosphate / silica support. The catalyst comprises a mesoporous zirconium-phosphate / silica support, which improves the heat and mass transfer of reactants and products, and at the same time increases the dispersibility and hydrothermal stability of the active material cobalt, greatly inhibiting deactivation than conventionally. There is a characteristic. At this time, since a certain amount of zirconium and phosphorus is included, sintering of the cobalt component during the synthesis reaction is suppressed, so that deactivation of the catalyst can be suppressed.

The production method of the Fischer-Tropsch synthesis catalyst of the present invention comprises a first step of preparing a mixture by mixing and impregnating a support and a cobalt precursor; And a second step of drying and firing the mixture to prepare a catalyst. And the manufacturing method of the catalyst further comprises the step of preparing the support before the first step, wherein the step of preparing the support comprises: mixing a solvent, a zirconium precursor and a phosphorus precursor to prepare a first mixed solution; Preparing a second mixed solution by mixing silica with the first mixed solution; And preparing the support by drying the second mixed solution under reduced pressure.

In one embodiment, in the step of preparing the support, the first mixed solution or the second mixed solution may include zirconium phosphate.

In one embodiment, the firing process of the second step may be performed at 500 to 600 ° C. For example, the firing process may be performed at 550 ℃ for 3 hours or more. In one embodiment, the firing process may be performed after being sufficiently dried at room temperature.

In one embodiment, the support may include 10 to 15 wt% of the zirconium based on the silica, and 5 to 70 wt% of the phosphorus based on the zirconium.

In one embodiment, when the zirconium is 10 wt% or less, zirconium phosphate may not be formed, and when it is 15 wt% or more, zirconium may exist in the form of zirconium oxide (ZrO ₂ ).

In one embodiment, the catalyst may include 10 to 20 wt% of the cobalt based on the support.

In one embodiment, but not limited to, the zirconium precursor is zirconium propoxide (Zirconium (IV) propoxide, Zr (OPr) ₄ ), zirconium oxynitride (ZrO (NO ₃ ) ₂ · xH ₂ O), oxychlorination One or more of zirconium (ZrOCl ₂ xH ₂ O), zirconium sulfate (Zr (SO ₄ ) ₂ ), zirconium chloride (ZrCl ₄ ), and mixtures thereof may be used, and the phosphorus precursor is phosphorus oxychloride (Phosphorus ( V) One or more of oxychloride, POCl ₃ ), phosphorus pentoxide (P ₂ O ₅ ), phosphorus trichloride (Phosphorus (III) trichloride, PCl ₃ ) and mixtures thereof can be used. .

In one embodiment, but not limited to, the cobalt precursor is cobalt nitrate (Cobalt nitrate hexahydrate, Co (NO ₃ ) ₂ · 6H ₂ O), Cobalt chloride hexahydrate, CoCl ₂ · 6H ₂ O), cobalt acetate (Cobalt acetate tetrahydrate, Co (CH ₃ COO) ₂ · 4H ₂ O) and one or more of mixtures thereof may be used.

In one embodiment, the solvent is not limited thereto, but may be one or more of distilled water, toluene, ethanol, and mixtures thereof.

The Fischer-Tropsch synthesis method of the present invention comprises: a Fischer-Tropsch synthesis method for producing a liquid hydrocarbon, the method comprising: disposing the catalyst of the present invention in a reactor; Activating the catalyst by reducing a cobalt oxide of the catalyst with cobalt by supplying a reducing gas into the reactor; And synthesizing the liquid hydrocarbon by supplying a synthesis gas containing hydrogen and carbon monoxide inside the reactor.

In one embodiment, the reactor may be a fixed-bed reactor as a Fischer-Tropsch synthesis reactor, but is not limited thereto.

In one embodiment, the reducing gas may include hydrogen and nitrogen gas. For example, the reducing gas may include hydrogen and nitrogen, for example, about 4 to 7% of hydrogen gas and residual nitrogen gas.

In one embodiment, the step of activating the catalyst may be performed at a temperature of 300 to 500 ° C. For example, the catalyst can be activated by reducing at 400 ° C for 10 hours or more.

In one embodiment, the step of performing the Fischer-Tropsch synthesis reaction may be performed at a reaction temperature of 200 to 300 ° C. and a reaction pressure of 10 to 30 bar. In one embodiment, the reaction temperature of the Fischer-Tropsch synthesis reaction may be 200 to 250 ° C, and the reaction pressure may be 15 to 35 bar. For example, the reaction pressure may be 20 bar.

As follows, a catalyst support was prepared according to one embodiment of the present invention, and a synthetic reaction was performed.

Example 1

According to an embodiment, mesoporous silica having a regular pore structure used as a support was prepared through the following method.

 First, 16.0 g of Pluronic P123 copolymer was added to 150 ml of distilled water and stirred until completely dissolved. Then, 32 ml of an aqueous 37% hydrochloric acid solution was added to 500 ml of distilled water, followed by stirring at 35 ° C.

Then, after confirming that the above Pluronic P123 copolymer was completely dissolved in distilled water, the two solutions were mixed by pouring them into the stirring hydrochloric acid solution at once. Then, after stirring for about 10 minutes, 16.0 g of n-butanol was further added and mixed. At this time, while maintaining the temperature of 35 ℃ stirred for 1 hour, 38.7 g of TEOS (Tetraethyoxysiland) was added to the reaction solution at once, and further stirred at 35 ℃ for 24 hours.

After stirring, the reaction solution was transferred to an autoclave equipped with a Teflon container, and then subjected to a hydrothermal synthesis reaction in a 110 ° C. oven for one day. After completion of the hydrothermal synthesis, the reaction solution was sufficiently cooled and filtered without washing. After the filtration process, it was dried in an oven at 110 ° C for about 30 minutes. After drying, the white powder was heated to 550 ° C. at a heating rate of 1 ° C./min, maintained for 6 hours, and then fired, and finally KIT-6 mesoporous silica in the form of a fine white powder was prepared.

The specific surface area of KIT-6 prepared according to the above example was 642 m ² / g, and the average pore size was 5.2 nm.

 Next, zirconium phosphate nanoparticles were prepared using an impregnation method on the surface of mesoporous silica (KIT-6) prepared according to the above-described embodiment.

At this time, the mass of zirconium supported on the basis of mesoporous silica was adjusted to 12 weight ratio, and the mass of phosphorus was adjusted to 6.36 weight ratio of zirconium. As precursors for zirconium and phosphorus, zirconium propoxide (Zirconium (IV) propoxide, Zr (OPr) ₄ ) and phosphorus oxychloride (Phosphorus (V) oxychloride, POCl ₃ ) were used.

First, zirconium propoxide and phosphorus oxychloride were injected into a solution in which toluene and ethanol were mixed at the same molar ratio. Then, mesoporous silica (KIT-6) prepared above was introduced. The mixed solution was stirred for 30 minutes and maintained at 110 ° C. for 2 hours. After removing the solvent through drying under reduced pressure, it was washed with ethanol and distilled water. After washing, drying was performed at 80 ° C. for 24 hours to prepare zirconium phosphate nanoparticles.

Subsequently, wet impregnation was used to support the cobalt. At this time, the mass of cobalt supported on the basis of mesoporous silica was adjusted to a weight ratio of 15 of the total catalyst, and cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ · 6H ₂ O) was used as a precursor of cobalt. .

First, after drying at room temperature for 12 hours or more, firing was performed at 550 ° C. for 3 hours. The catalyst prepared as described above was designated as CoZrP (0.2) / KIT-6. The specific surface area of the catalyst was 260 m ² / g, and the average pore size was 7.1 nm.

Example 2

The catalyst was synthesized under the same conditions as in Example 1, but the mass of phosphorus was set to 16.9 weight ratio of zirconium. The catalyst was designated CoZrP (0.6) / KIT-6. The specific surface area of the catalyst was 371 m ² / g, and the average pore size was 6.5 nm.

Example 3

The catalyst was synthesized in the same manner as in Example 1, but the mass of phosphorus was set to 67.9 weight ratio of zirconium. The catalyst was designated CoZrP (2) / KIT-6. The specific surface area of the catalyst was 206 m ² / g, and the average pore size was 6.4.

Comparative Example 1

The catalyst was prepared in the same manner as in Example 1, but cobalt was directly supported on the support without treating phosphorus and zirconium separately. The catalyst was designated Co / KIT-6. The specific surface area of the catalyst was 482 m ² / g, and the average pore size was 6.5 nm.

Comparative Example 2

The catalyst was prepared in the same manner as in Example 1, but the mass of phosphorus was set to 0 weight ratio of zirconium. The catalyst was designated CoZrP (0) / KIT-6. The specific surface area of the catalyst was 336 m ² / g, and the average pore size was 3.7 nm.

Comparative Example 3

The catalyst was prepared in the same manner as in Example 1, but the mass of phosphorus was set to 3.28 weight ratio of zirconium. The catalyst was designated CoZrP (0.1) / KIT-6. The specific surface area of the catalyst was 246 m ² / g, and the average pore size was 7.0 nm.

Fischer-Tropsch synthesis reactions were performed using the respective catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3 above.

Before carrying out the Fischer-Tropsch synthesis reaction, the catalysts were subjected to reduction treatment at 400 ° C. for about 12 hours under a H ₂ (5%) / N ₂ reducing gas at a flow rate of 30 ml / min.

In a fixed bed reactor at a synthesis gas pressure of 20 bar, a space velocity of 8000 L / kg cat / h, and 230 ° C., 0.1 g of each of the catalysts prepared above and 1 g of commercial puralox α-Al 2 O 3 are mixed with a diluent, and then synthesized. The reaction was performed while flowing gas (H ₂ + CO) at a flow rate of about 13.33 ml / min.

At this time, the reaction was performed for about 60 hours as a continuous reaction, and the carbon monoxide (CO) conversion rate and selectivity for the product were analyzed at 1 hour intervals using gas chromatography. Then, after the reaction was completed, the liquid product of C ₅₊ or higher (5 or more carbon atoms) was sampled and analyzed using offline gas chromatography.

 The catalysts prepared according to the embodiment and the results of analysis of the Fischer-Tropsch synthesis reaction using the same are shown in Table 1 and FIGS. 1 to 4 below.

division catalyst CO conversion rate (% carbon) Selectivity (% carbon mole)
(C ₁ / C ₂ -C ₄ / C ₅ -C ₁₀ / C ₁₁ -C ₂₀ / C ₂₁₊ ) C ₅ or higher yield (% carbon) Catalyst specific surface area (m ² / g) Pore diameter (nm) Example 1 CoZrP (0.2) / KIT-6 60.4 15.9 / 11.7 / 11.7 / 45.2 / 15.5 43.7 260 7.1 Example 2 CoZrP (0.6) / KIT-6 35.4 16.9 / 13.6 / 22.7 / 35.4 / 11.4 24.6 371 6.5 Example 3 CoZrP (2) / KIT-6 24.5 19.7 / 14.9 / 25.4 / 28.3 / 11.7 16.0 206 6.4 Comparative Example 1 Co / KIT-6 30.0 25.5 / 17.3 / 26.5 / 23.4 / 7.3 17.2 482 6.5 Comparative Example 2 CoZrP (0) / KIT-6 6.8 42.8 / 44.8 / 12.1 / 0.3 / 0 0.8 336 3.7 Comparative Example 3 CoZrP (0.1) / KIT-6 21.9 42.7 / 36.8 / 20.0 / 0.5 / 0 4.5 246 7.0

As described in Table 1, catalysts comprising a support containing P and Zr on the silica surfaces prepared through Examples 1 to 3 are generally liquid hydrocarbons compared to catalysts prepared through Comparative Examples 1 to 3. It can be seen that the yield of (C ₅ or more) was excellent.

1 to 4 are diagrams showing the analysis results according to an embodiment of the present invention. First, FIG. 1 shows the result of X-ray diffraction analysis at a low angle, and it was confirmed that all of the synthesized samples have a regular mesoporous structure. When the surface of the mesoporous silica was treated with zirconium and a small amount of phosphorus (Comparative Examples 2 and 3), a phenomenon in which a part of the mesoporous structure collapsed was observed, but when the phosphorus content was 6.36 wt. It was confirmed (Examples 1 to 3).

Specifically, FIG. 2 shows the result of X-ray diffraction analysis at a wide angle, and it is possible to confirm the oxidation state of the metal oxide. In Examples 1 to 3 and Comparative Examples 1 to 3, peaks representing cobalt oxide (Co ₃ O ₄ ) can be confirmed, and it can be seen that cobalt oxide catalysts were well formed in all catalysts.

Specifically, FIG. 3 shows the results of the Fischer-Tropsch synthesis reaction using the catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and Time On Stream (TOS) for the carbon monoxide conversion rate according to the reaction time. It shows. In the case of Examples 1 to 3 in which the catalyst was prepared so that phosphorus was contained in a weight ratio of 5 to 70 relative to zirconium according to an embodiment of the present invention, the catalytic activity was stably maintained, but a comparative example using pure mesoporous silica In the case of Comparative Examples 2 and 3 in which the content of 1 and phosphorus was contained in a weight ratio of 0 to 4, it was confirmed that the deactivation of the catalyst occurred rapidly or the activity was very small. In the case of the catalyst of Comparative Example 1 without zirconium and phosphorus, it was found that the degree of inactivation was the greatest even though it had the most distinct mesopores. And in Example 1, it was confirmed that the CO conversion rate is the best and the degree of deactivation is also low, so that the catalytic activity is the best and is maintained stably.

4, the results of analyzing the catalysts of Example 1 and Comparative Example 1 with a transmission electron microscope (TEM) are shown. Specifically, the results of observing the particle size change of cobalt and the stability of mesopores before and after the reaction are observed. Is showing. In the case of the catalyst showing stable activity by treating the surface with zirconium phosphate as in Example 1, the sintering of cobalt particles was less before and after the Fischer-Tropsch reaction, and the structure of the mesopores was stable, whereas the comparative example When the surface was not treated as in 1, it was found that the initial activity was high, but the activity was rapidly decreased, and the structure of the mesopores was not stable.

Although described above with reference to the preferred embodiment of the present invention, those skilled in the art may variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

Claims (21)

A support comprising zirconium and phosphorus on silica having mesopores; And
A composite metal oxide containing cobalt supported on the support; containing,
Fischer-Tropsch synthesis catalyst.
According to claim 1,
The support is characterized in that it comprises a zirconium phosphate (zirconium phosphate, zirconium phosphate),
Fischer-Tropsch synthesis catalyst.
According to claim 2,
The support is characterized in that the zirconium phosphate is in a form included in at least a portion of the silica surface having the mesopores,
Fischer-Tropsch synthesis catalyst.
According to claim 3,
The support,
At least a portion of the zirconium phosphate, characterized in that the thin film form,
Fischer-Tropsch synthesis catalyst.
According to claim 3,
Characterized in that the cobalt is supported on the zirconium phosphate,
Fischer-Tropsch synthesis catalyst.
According to claim 2,
The support,
Characterized in that the zirconium is contained 10 to 15wt% based on the silica,
Fischer-Tropsch synthesis catalyst.
The method of claim 6,
The support,
Characterized in that the phosphorus containing 5 to 70wt% based on the zirconium,
Fischer-Tropsch synthesis catalyst.
According to claim 2,
The catalyst,
Characterized in that the cobalt is contained 10 to 20wt% based on the support,
Fischer-Tropsch synthesis catalyst.
According to claim 1,
The support is characterized in that the specific surface area is 200 to 400 m ² / g,
Fischer-Tropsch synthesis catalyst.
A first step of preparing a mixture by mixing and impregnating a support and a cobalt precursor; And
Including a second step of drying and firing the mixture to prepare a catalyst;
Further comprising the step of preparing the support before the first step,
The preparing of the support may include preparing a first mixed solution by mixing a solvent, a zirconium precursor, and a phosphorus precursor;
Preparing a second mixed solution by mixing silica with the first mixed solution; And
Including the step of preparing the support by drying the second mixed solution under reduced pressure;
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 10,
The second step of the firing process is characterized in that carried out at 500 to 600 ℃,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 11,
The support,
Characterized in that the zirconium is contained 10 to 15wt% based on the silica,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 12,
The support,
Characterized in that the phosphorus containing 5 to 70wt% based on the zirconium,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 13,
The catalyst,
Characterized in that the cobalt is contained 10 to 20wt% based on the support,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 10,
The zirconium precursor is zirconium propoxide (Zirconium (IV) propoxide, Zr (OPr) ₄ ), zirconium oxynitrate (ZrO (NO ₃ ) ₂ xH ₂ O), zirconium oxychloride (ZrOCl ₂ · xH ₂ O), Characterized in that at least one of zirconium sulfate (Zr (SO ₄ ) ₂ ), zirconium chloride (ZrCl ₄ ) and mixtures thereof,

Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 10,
The phosphorus precursor is phosphorus oxychloride (Phosphorus (V) oxychloride, POCl ₃ ), phosphorus pentoxide (Phosphorus (V) pentoxide, P ₂ O ₅ ), phosphorus trichloride (Phosphorus (III) trichloride, PCl ₃ ) And mixtures thereof,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 10,
The cobalt precursor is cobalt nitrate hexahydrate (Co (NO ₃ ) ₂ · 6H ₂ O), cobalt chloride hexahydrate (CoCl ₂ · 6H ₂ O), cobalt acetate (Cobalt acetate tetrahydrate, Co (CH ₃ COO) ) ₂ · 4H ₂ O) and mixtures thereof, characterized in that it comprises at least one,
Method for preparing catalyst for Fischer-Tropsch synthesis.
The method of claim 10,
The solvent is characterized in that at least one of toluene, ethanol and mixtures thereof,
Method for preparing catalyst for Fischer-Tropsch synthesis.
In the Fischer-Tropsch synthesis method for producing a liquid hydrocarbon,
Disposing the catalyst according to any one of claims 1 to 9 inside the reactor;
Activating the catalyst by reducing a cobalt oxide of the catalyst with cobalt by supplying a reducing gas into the reactor; And
Including the step of synthesizing the liquid hydrocarbon by supplying a synthesis gas containing hydrogen and carbon monoxide inside the reactor;
Fisher-Tropsch synthesis method.
The method of claim 19,
Activating the catalyst,
Characterized in that it is carried out at a temperature of 300 to 500 ℃,
Fisher-Tropsch synthesis method.
The method of claim 19,
The step of performing the Fischer-Tropsch synthesis reaction,
Characterized in that it is carried out at a reaction temperature of 200 ℃ to 300 ℃, a reaction pressure of 10 bar to 30 bar,
Fisher-Tropsch synthesis method.

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