KR20210043334A - Method of Preparing Catalysts for Fischer―Tropsch Synthesis Reaction and Method of Preparing Liquid Fuel Using the Catalysts - Google Patents

Abstract

The present invention relates to a method for preparing a catalyst for a Fischer-Tropsch synthesis reaction. More particularly, the present invention relates to a method for preparing a catalyst for a Fischer-Tropsch synthesis reaction with increased reducibility and dispersion by changing the calcination temperature and calcination gas. In addition, the present invention relates to a method for preparing any one liquid fuel among gasoline, jet oil, or diesel having C5-C20 carbon number by using the Fischer-Tropsch synthesis reaction catalyst prepared by the method.

Description

Method of Preparing Catalysts for Fischer-Tropsch Synthesis Reaction and Method of Preparing Liquid Fuel Using the Catalysts}

The present invention relates to a method for preparing a catalyst for a Fischer-Tropsch synthesis reaction, and more particularly, a method for preparing an excellent Fischer-Tropsch catalyst for a synthesis reaction by changing the firing conditions according to the firing temperature and the firing gas, and the above It relates to a method of manufacturing a liquid fuel using the catalyst for the Fischer-Tropsch synthesis reaction prepared by the manufacturing method.

The Fischer-Tropsch synthesis reaction is a reaction in which a hydrocarbon mixture is prepared through a catalytic chemical reaction using _{synthetic gas (CO + H 2} ) mainly derived from natural gas, coal, and biomass. As the dependence on traditional resources decreases and crude oil prices soar, the demand for non-traditional gas resources such as landfill gas, accompanying gas, and remote gas, which are a kind of natural gas, is increasing, and the demand for clean fuel obtained therefrom is increasing. Recently, the reserves of shale gas have been discovered exponentially around the world, and the Fischer-Tropsch technology, which is a method of making clean liquid fuels using syngas derived from gas resources due to the abundant reserves and potential utilization in the future. This is attracting attention.

In the Fischer-Tropsch synthesis reaction, carbon chain growth occurs on the surface of a solid catalyst in a gaseous reaction product, and a liquid hydrocarbon product is produced, thereby reacting in three phases. Since the reaction is highly exothermic, when the catalyst is filled in a fixed-bed reactor, extreme heat is generated in the catalyst layer, and a diluent having no activity and good thermal stability is mixed to control the exotherm and react.

The main product of the Fischer-Tropsch synthesis reaction, the production mechanism of hydrocarbons, mainly follows the Anderson-Schulz-Folry (ASF) distribution, and is produced in a wide and diverse range from methane with 1 carbon to hydrocarbons with more than 20 carbons. . Due to this ASF distribution, there is a limit to obtaining hydrocarbons in the desired range, so the selectivity of heavy oil or gasoline hydrocarbons, which are mainly liquid fuel hydrocarbons, is limited to a maximum of 48%. Therefore, in order to additionally produce liquid fuel, a wax product having a high boiling point having 20 or more carbon atoms needs a subsequent process of hydrolysis and a dewaxing process.

When Fischer-Tropsch synthesis is performed for the purpose of producing transportation fuel, it is necessary to selectively produce synthetic oil composed _{of medium carbon number (gasoline: C 5} -C ₁₂ , diesel: C ₁₂ ~ C _{20 ).} Make sure that the products of the Tropsey reaction do not follow the ASF distribution law. At this time, by combining the Fischer-Tropsch catalyst and the solid acid catalyst, it is possible to control the carbon number distribution of the Fischer-Tropsch product.

Meanwhile, catalysts currently widely used in the Fischer-Tropsch synthesis reaction include cobalt and iron catalysts. In the case of a cobalt catalyst, the activity is high and the life is good due to the stability of the catalyst, and a linear paraffinic hydrocarbon is produced as a product. Iron catalysts are cheaper than cobalt catalysts, have less selectivity for methane in the high temperature range, and maintain equilibrium even if it is higher or lower than _{H 2 /CO = 2.0, which is optimal for Fischer-Tropsch reaction through aqueous reaction.} There is a great advantage that reaction is possible.

In addition, as a method generally used to disperse an expensive active ingredient, a catalyst is prepared by adding a cobalt component and other activity enhancing substances to alumina, silica, titania, etc. as a support having a high surface area. Specifically, in order to improve the dispersibility of the active ingredient cobalt, a catalyst prepared in a single component or mixed form of the above support is commercially used, but when the particle size of cobalt is similar, the FT reaction according to the type of support Little change in activity has been reported [Applied Catlysis A 161 (1997) 59]. Rather, it has been reported that the activity of the F-T reaction is greatly affected by the dispersibility of the cobalt component and the particle size [Journal of American Chemical Society, 128 (2006) 3956].

In addition, the firing conditions used during the preparation of the cobalt-based catalyst have a great influence on the surface condition of the cobalt species, and determine catalytic properties such as enhancing the activity and stability of the catalyst for the Fischer-Tropsch synthesis reaction.

As a conventional technique, U.S. Patent No. 7585808 discloses a method for preparing a catalyst for Fischer-Tropsch reaction, which is prepared by using ruthenium as a catalytically active metal and treating with triethanolamine to increase catalytic activity. Patent No. 5928983 discloses a cobalt-based Fischer Tropsch catalyst prepared by adding an oxidizing alcohol, an oxidizing aldehyde or an oxidizing ketone, especially glyoxal. A process of activating a catalyst by impregnating and drying a solution containing a multifunctional carboxylic acid represented by (CRR')n-COOH and rhenium has been disclosed.

However, for the development of a Fischer-Tropsch synthetic catalyst that can selectively produce synthetic oil composed _{of medium carbon atoms (gasoline: C 5} -C ₁₂ , diesel: C ₁₂ ~ C ₂₀ ) for the purpose of producing fuel for transportation. In addition, there is still a need for continuous research on enhancing the activity of the catalyst by controlling the calcination gas and temperature in the manufacture of the catalyst.

US Patent No. 7585808 (published on July 27, 2006) U.S. Patent No. 5928983 (Announcement date: 1999.07.27) U.S. Patent No. 5968991 (Announcement date: 1999.10.19)

The main object of the present invention is to solve the above-described problems, and to provide a method for preparing a catalyst for a Fischer-Tropsch synthesis reaction having high selectivity for hydrocarbons of C5 to C20 by changing the firing gas and the firing temperature. have.

It is also an object of the present invention to provide a catalyst for a Fischer-Tropsch synthesis reaction, which is prepared by the above production method and capable of selectively producing C5 to C20 hydrocarbons from synthesis gas.

In addition, it is an object of the present invention to provide a method for producing a liquid fuel comprising a hydrocarbon of C5 to C20 from syngas produced by the above production method.

In order to achieve the above object, the present invention comprises the steps of: (a) mixing a cobalt precursor, an inorganic binder, an acid additive, and a solvent in a catalyst carrier; (b) forming a molding catalyst by extrusion molding the mixture of step (a); (c) drying the shaping catalyst; And (d) calcining the dried shaped catalyst in a nitrogen (N ₂ ) atmosphere; Fischer-Tropsch provides a method for producing a catalyst for synthesis reaction comprising a.

In a preferred embodiment of the present invention, the catalyst carrier in step (a) is alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium diboride, yttria, silicon nitride, titanium nitride, tungsten It may be a carbide, an oxide, a nitride, a sulfide of a metal selected from carbide and boron carbide, or a mixture thereof.

In a preferred embodiment of the present invention, the catalyst carrier in step (a) may be zeolite.

In a preferred embodiment of the present invention, the inorganic binder in the step (a) is a group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite, and combinations thereof. Can be chosen from.

In a preferred embodiment of the present invention, the acid additive in step (a) is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid and perchloric acid, and

It may be selected from the group consisting of a combination thereof.

In a preferred embodiment of the present invention, in the step (a), 1 to 50 parts by weight of cobalt may be mixed with respect to 100 parts by weight of the catalyst carrier.

In a preferred embodiment of the present invention, the sintering of step (d) may be performed at 300° C. to 500° C. for 1 hour to 24 hours.

In addition, an embodiment of the present invention provides a catalyst for a Fischer-Tropsch synthesis reaction, characterized in that it is prepared by the method for preparing a catalyst for the Fischer-Tropsch synthesis reaction.

In a preferred embodiment of the present invention, the catalyst for the Fischer-Tropsch synthesis reaction is prepared by the method for preparing the catalyst for the Fischer-Tropsch synthesis reaction, and the reduction degree may be 68 or more.

In addition, another embodiment of the present invention is a) the step of introducing the catalyst for the Fischer-Tropsch synthesis reaction into the Fischer-Tropsch synthesis reactor; b) injecting syngas in the Fischer-Tropsch synthesis reactor; And c) synthesizing liquid fuel from syngas in the Fischer-Tropsch synthesis reactor.

The catalyst prepared by the method for producing a catalyst according to the present invention has a high CO conversion rate in the Fischer-Tropsch synthesis reaction, as well as a high selectivity for C5 to C20 hydrocarbons, thereby producing liquid fuel from syngas. -It can be usefully used for tropsch synthesis.

1 is a graph for measuring CO conversion and product selectivity of a catalyst according to an embodiment of the present invention.
2 is a graph showing the reducibility of a catalyst according to another embodiment of the present invention.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.

In the entire specification of the present application, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise specified.

The present invention comprises the steps of (a) mixing a cobalt (Co) precursor, an inorganic binder, an acid additive, and a solvent in a catalyst carrier; (b) forming a molding catalyst by extrusion molding the mixture of step (a); (c) drying the shaping catalyst; And (d) calcining the dried shaped catalyst in _{an atmosphere containing nitrogen (N 2} ). It relates to a method for producing a catalyst for a Fischer-Tropsch synthesis reaction comprising.

More specifically, a method for preparing a catalyst for a Fischer-Tropsch synthesis reaction according to the present invention includes a catalyst carrier; Cobalt (Co) precursor; Inorganic binders; Acid additives; And a solvent; by mixing and extrusion molding the catalyst, followed by drying and sintering to prepare a catalyst, it is possible to obtain a catalyst for a Fischer-Tropsch synthesis reaction having high CO conversion and selectivity of a hydrocarbon having a carbon number of C5 or more. .

In the method for preparing a catalyst for a Fischer-Tropsch synthesis reaction according to the present invention, first, a cobalt (Co) precursor, an inorganic binder, an acid additive, and a solvent are mixed with a catalyst carrier to obtain a mixture [Step (a)].

The catalyst carrier can be used without limitation as long as it is a carrier component having an acid point according to the distribution of the desired hydrocarbon product in the Fischer-Tropsch synthesis reaction.For example, alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium Diboride, yttria, silicon nitride, titanium nitride, tungsten carbide and boron carbide of a metal selected from carbides, oxides, nitrides, sulfides, or mixtures thereof, preferably has an affinity with the inorganic-inorganic binder described below. It may be a zeolite, which is a good aluminum silicate hydrate, even more preferably Si/Al ZSM-5 with a ratio of 10 to 200 can be used.

The catalyst carrier according to the present invention is a porous material and contains many pores, so it can effectively improve the reactivity by supporting the catalytic active component in the pores, can sufficiently support the catalytic active component, and has no reactivity with the catalytic active component. It can be selected as a material that is not sensitive to temperature changes.

The catalyst carrier may be pulverized or prepared by a conventional method, and may have an average particle diameter of 1 µm to 500 µm, preferably 10 to 200 µm. If the average particle diameter of the catalyst carrier is less than 1 µm, the mechanical properties of the catalyst may be deteriorated, and at the same time, the support rate of the catalytic active ingredient may decrease due to the small pore size. If it exceeds 500 µm, the fluidity in the mixture is small and the extrusion characteristics decrease. In addition, the surface area may be small, so that the reactivity of the catalytically active component may be lowered.

The cobalt (Co) precursor can be used without limitation as long as it is a cobalt (Co) precursor of a catalytically active component that can be applied to the Fischer-Tropsch synthesis reaction, and as a water-soluble precursor, an oxide salt, oxyhydroxide salt, chloride salt, carbonate, acetate, Citrate, nitrosylnitrate, nitrate. Hydroxide salts. Examples include, but are not limited to, oxalate, carboxylate, sulfate, and alkoxy precursors containing hydrocarbons as fat-soluble precursors, ammonium precursors, and the like.

At this time, the cobalt (Co) in the cobalt (Co) precursor contains 1 part by weight to 50 parts by weight, preferably 10 parts by weight to 20 parts by weight, based on 100 parts by weight of the catalyst carrier in step (a), If the metal of the (Co) precursor is added in an amount of less than 1 part by weight based on 100 parts by weight of the catalyst carrier, the content of the metal supported on the catalyst carrier may be too small to reduce the activity of the reaction. Since the ratio of the amount is small, it is not possible to efficiently prepare the catalyst. If the amount exceeds 50 parts by weight, the amount of metal supported on the catalyst support is too large, and it is not fully supported on the catalyst support during the catalyst production process, so that a part of the metal is leached at the same time. The interaction between the catalyst carrier and the metal is weakened, and thus sintering between the metal particles may occur during a catalytic reaction.

On the other hand, the inorganic binder bonds the catalyst carrier powder to each other to impart cohesion and viscosity, while imparting fluidity and fluidity to the composition to facilitate extrusion. The inorganic-inorganic binder may be one or more selected from the group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite, preferably properties suitable for acidity. You can use boehmite with

In particular, boehmite used as the inorganic binder is a monovalent γ-AlO(OH) having one hydroxyl group (-OH), and has a variety of Al ₂ O ₃ forms depending on heat treatment conditions and methods. This boehmite is high strength, high acidity, high crystallization, high growth _{Al 2} O _{3 compared to Al 2} O ₃ , and has excellent thermal/structural properties as a starting material for gamma/delta/theta/alpha Al ₂ O ₃ It is possible to improve the mechanical properties of the catalyst structure without an inorganic binder and a photocuring agent.

The inorganic binder according to the present invention contains 10 parts by weight to 90 parts by weight, preferably 10 parts by weight to 80 parts by weight, more preferably 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the catalyst carrier powder, If the inorganic binder is mixed with less than 10 parts by weight based on 100 parts by weight of the catalyst carrier powder, the bonding strength of the catalyst carrier powder may decrease, resulting in weak catalyst structure strength, and if it exceeds 90 parts by weight, the porosity in the catalyst structure may be reduced. Can be reduced.

In addition, the acid additive serves to gelatinize a mixture containing a catalyst carrier and a cobalt (Co) precursor, and if it is less than 0.5 parts by weight based on 100 parts by weight of the catalyst carrier, the mixture is not properly gelled and the catalyst has mechanical properties. Falling problems may occur, and if it exceeds 70 parts by weight, the viscosity of the mixture may be high, resulting in a decrease in molding properties, and a problem in that the activity of the prepared catalyst may be decreased. Accordingly, the acid additive is preferably 0.5 parts by weight to 70 parts by weight, preferably 3 parts by weight to 20 parts by weight, based on 100 parts by weight of the catalyst carrier.

On the other hand, the acid additive serves to gelatinize the 3D printing ink composition.

At this time, the acid additive may be at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid, and perchloric acid, and preferably nitric acid.

In addition, the solvent is to improve the strength of the catalyst by uniformly mixing the components contained in the mixture and controlling the viscosity. Polar solvents such as water, methanol, ethanol, propanol, butanol, and acetone can be used, and environmental aspects Water can be preferably used.

The solvent contains 50 parts by weight to 100 parts by weight based on 100 parts by weight of the catalyst carrier. If the solvent is mixed with less than 50 parts by weight based on 100 parts by weight of the catalyst carrier, the viscosity of the mixture becomes high, making it difficult to discharge quantitatively when extruding, and if it exceeds 100 parts by weight, the viscosity of the mixture is too low to ensure proper molding. Problems that cannot be achieved may occur.

As such, a mixture of a catalyst carrier, a cobalt (Co) precursor, an inorganic binder, an acid additive, and a solvent may have a viscosity (at room temperature) of 100 cps to 5,000 cps, preferably 100 cps to 1,000 cps or less. If the viscosity of the mixture is less than 100 cps, it is difficult to maintain its shape after extrusion molding, making it difficult to manufacture a high-precision and high-quality molding catalyst. If it exceeds 5,000 cps, it is difficult to precisely control the molding catalyst, and shrinkage and cracking during firing. Can occur.

Thereafter, the obtained mixture is extrusion-molded to form a shaping catalyst [Step (b)].

The extrusion molding is not particularly limited in the case of an extrusion molding method, apparatus, and conditions typically used in the production of a molding catalyst.

The molding catalyst having a predetermined shape extruded as described above is dried to evaporate the solvent to obtain a dried molding catalyst [Step (c)].

At this time, the drying of the extrusion-molded catalyst is preferably performed at 100° C. to 200° C. for 1 hour to 24 hours, and may be dried using conventional methods such as hot air, constant temperature and humidity, and microwave.

The drying is carried out in the range of 100 to 200 ℃, and if it is less than 100 ℃, the solvent used in the preparation of the catalyst does not evaporate smoothly in the pores of the support, resulting in agglomeration of cobalt (Co) during the sintering of the catalyst. Thus, the dispersibility may be reduced, and if it exceeds 200°C, cobalt components may be agglomerated due to rapid desorption of the solvent in the pores of the support, so it is preferable to maintain the above temperature range.

Finally, firing is performed to improve the inherent strength and hardness of the catalyst carrier to prepare a catalyst for the Fischer-Tropsch synthesis reaction [Step (d)].

The sintering of the dried molding catalyst can be variously changed in consideration of the inherent glass transition temperature according to the type of catalyst carrier.However, in the sintering step, while maintaining the extruded form without cracking of the molding catalyst, CO conversion and carbon number of hydrocarbons of C5 or more In order to obtain a catalyst for a Fischer-Tropsch synthesis reaction having high selectivity, it may be calcined for 1 hour to 24 hours at 300° C. to 500° C. in an atmosphere containing nitrogen (N2).

In the present invention, the dried molding catalyst is calcined in the range of 300 to 600° C., and if the calcining temperature is less than 300° C., an appropriate interaction between cobalt and the support cannot be formed, resulting in a phenomenon in which particles become larger during the reaction. I can. In addition, if it exceeds 600 ℃, the dispersibility decreases due to the increase of the particles of the cobalt component, and the formation of cobalt silicate or cobalt aluminate There is a need to maintain the above sintered area because the CO conversion rate and the selectivity of the hydrocarbon having C5 or more may decrease.

In the present invention, it is preferable that the thermal conductivity of a gas containing nitrogen (N2) generally used is 0.030 w/mK or less based on 300K, and if it is higher than that, the catalytic cobalt particles increase and the activity decreases due to the increase in the thermal conductivity of the calcined gas. Since there is a problem, it must be fired using a firing gas exhibiting a thermal conductivity of 0.030 w/mK or less.

At this time, since the rapid temperature change cannot maintain the shape of the extruded structure due to rapid evaporation and oxidation of the solvent, cracks and voids are generated and the strength is significantly reduced. Therefore, it is recommended to gradually increase the temperature to a temperature of 10 ℃ or less per minute. desirable.

In addition, the present invention provides a catalyst for a Fischer-Tropsch synthesis reaction prepared by the method for preparing a catalyst for the Fischer-Tropsch synthesis reaction described above.

In addition, the catalyst for the Fischer-Tropsch synthesis reaction prepared as described above exhibits high selectivity for hydrocarbons of C5 to C20, and thus can be usefully used in the Fischer-Tropsch synthesis for producing liquid fuel from syngas.

In another aspect of the present invention, a) adding the catalyst for the Fischer-Tropsch synthesis reaction to the Fischer-Tropsch synthesis reactor; b) injecting syngas in the Fischer-Tropsch synthesis reactor; And c) synthesizing liquid fuel from syngas in the Fischer-Tropsch synthesis reactor.

First, prior to step a), a process of improving catalytic activity may be performed by reducing the catalyst according to the present invention in a hydrogen atmosphere (5% H ₂ ) at a temperature at which the catalyst can be reduced (250 to 4000 °C), and _{After mounting the catalyst in the reactor tube, the catalyst may be reduced by flowing 5% hydrogen (H 2} ) gas at 250 to 350° C. for 2 to 10 hours at a rate of 50 to 200 ml/min. After reducing the catalyst in a hydrogen atmosphere, the reduced catalyst is mounted in a fixed bed reactor (step a)).

Subsequently, step b) is a process of injecting syngas into the fixed bed reactor. Specifically, the b) the synthesis gas used in the step as a raw material is a hydrogen (H ₂₎ and carbon monoxide (which contains CO), H ₂ / CO molar ratio of 0.1 to 3 range, preferably H ₂ / CO molar ratio Synthetic gas of 1 to 2 is used. If the molar ratio of H ₂ /CO in the syngas is less than 0.1, the carbon deposition rate increases and the catalyst life may be shortened, and _{if the molar ratio of H 2} /CO exceeds 3, hydrogenation is promoted. As a result, the selectivity of unnecessary methane and short-chain paraffin increases.

In addition, in the step b), the syngas is preferably reacted by being injected into a fixed bed reactor within a range of 1 to 5 MPa. When the pressure is less than 1 MPa, the solubility of the synthesis gas is low, and the reaction activity is low, and when the pressure is 5 MPa or more, the hydrothermal stability of the catalyst is lowered, so that the reaction activity may be lowered.

In step c), the process temperature of the Fischer-Tropsch reaction is in the range of 200 to 260° C., which is a relatively low temperature, and the chain propagation probability can be increased, so that the carbon of the product can be relatively increased. In addition, when considering thermodynamics, generation of olefins and iso paraffin is more advantageous than generation of paraffin. However, when the reaction temperature is less than 200° C., unnecessary high-boiling products are strongly adsorbed to the catalyst, so that selective deactivation may proceed rapidly. On the other hand, if the reaction temperature exceeds 260 ℃, the carbon deposition rate increases, which shortens the life of the catalyst, as well as _{increases the selectivity of methane (C 1} ), which is the cause of lowering the selectivity of the long-chain olefin compound, which is not preferable. .

In addition, according to the present invention, a liquid fuel including any one of gasoline, jet oil, or diesel having C5-C20 carbon atoms can be obtained from the syngas in step (C).

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited by the following examples.

Example 1: N2 400

As for the cobalt (Co) catalyst, boehmite was mixed with ZSM-5, and then nitric acid and distilled water were added to the mixture, and the mixture was stirred uniformly at room temperature and uniformly extruded using an extruder to prepare a molding catalyst. The extruded catalyst was dried at room temperature for 12 hours and then dried at 110° C. for 5 hours in an air atmosphere oven. The sintering was carried out at 400° C. for 5 hours in a nitrogen (N2) atmosphere, and the prepared catalyst was prepared by sieving at 710 µm to 1000 µm, and the Co content of the prepared catalyst was confirmed to be 10 wt.%. I did.

Comparative example 1: air 400

As for the cobalt (Co) catalyst, boehmite was mixed with ZSM-5, and then nitric acid and distilled water were added to the mixture, and the mixture was stirred uniformly at room temperature and uniformly extruded using an extruder to prepare a molding catalyst. The extruded catalyst was dried for 12 hours at room temperature and then dried for 5 hours at 110° C. in an air atmosphere oven. The sintering was carried out at 400° C. for 5 hours in an air atmosphere through which air flows, and the prepared catalyst was 710 μm. It was prepared by sieving to 1000 μm, and it was confirmed that the Co content of the prepared catalyst was 10wt.%.

Comparative example 2: He 400

As for the cobalt (Co) catalyst, boehmite was mixed with ZSM-5, and then nitric acid and distilled water were added to the mixture, and the mixture was stirred uniformly at room temperature and uniformly extruded using an extruder to prepare a molding catalyst. The extruded catalyst was dried at room temperature for 12 hours and then dried in an air atmosphere oven at 110° C. for 5 hours. The sintering was performed at 400° C. for 5 hours in a helium (He) atmosphere, and the prepared catalyst was 710 μm. It was prepared by sieving to 1000 μm, and it was confirmed that the Co content of the prepared catalyst was 10wt.%.

Comparative example 3: NO 400

As for the cobalt (Co) catalyst, boehmite was mixed with ZSM-5, and then nitric acid and distilled water were added to the mixture, and the mixture was stirred uniformly at room temperature and uniformly extruded using an extruder to prepare a molding catalyst. The extruded catalyst was dried at room temperature for 12 hours and then dried at 110° C. for 5 hours in an air atmosphere oven. The sintering was carried out at 400° C. for 5 hours in a nitrogen monoxide (NO) atmosphere, and the prepared catalyst was prepared by sieving at 710 µm to 1000 µm, and the Co content of the prepared catalyst was 10 wt.%. Confirmed.

Experimental example 1: Evaluation of catalytic activity of the catalyst structure

In order to measure the activity of the FT synthesis reaction of the catalyst structures prepared in Examples 1 to 4, the FT synthesis reaction was performed. _{Before the FT synthesis reaction, 5% H 2} /Ar gas was flowed at 100 cc/min to the catalyst structures prepared in Examples 1 to 4 and activated at 400° C. for 5 hours. 0.5 g of the catalyst structures of Examples 1 to 5 activated as described above were charged into a fixed bed reactor, and alumina balls, which are diluents, were charged at the top and bottom of each reactor in order to control the catalyst heat generation of the reactor. The reaction conditions of the reactor were carried out at T = 250 °C, P = 20 bar, SV = 4,000 ml/g.cat/h for 72 hours, and the reaction was carried out using H ₂ /CO = 2.0 volume fraction of syngas. Became. The reaction was measured by measuring the CO conversion rate and the selectivity of the product through On-line GC (TCD, FID), and are shown in Table 1 and FIG. 1 below.

Samples Conversion of CO
(C-mol%) Selectivity (C-mol%) C1 C2-C4 C5+ N2 400 68.75 13.77 10.75 75.48 Air 400 60.55 12.57 9.99 77.44 He 400 49.64 16.51 13.10 70.39 NO 400 41.75 26.13 18.62 55.25

Experimental example 2: Measurement of the reducing property of the catalyst

Hydrogen elevated temperature reduction analysis was used to confirm the degree of reduction according to temperature for the catalysts prepared in Examples 1 to 4. After filling 0.1 g of the catalyst into the U-shaped reactor, fully flow He to remove the impurities remaining in the line, and use 10%H2, 90% Ar to increase the temperature from room temperature to 1173 K at 10 K/min. conductivity detector). Autochem 2910 (micromeritics) was used for this analysis.

As shown in FIG. 2, in general, the first peak near 307 to 477° C. is a peak reduced to Co3O4 → CoO, and the second peak is a peak reduced to CoO → Co. The last and third peak is the peak that changes to Co-Aluminate. When N2 is used as the calcination gas, the formation of Co-Aluminate is small by suppressing the interaction between Support and Co, and the formation of Co-Aluminate is increased when sintering with NO gas.

Experimental example 3: catalytic H2-O2 chemical adsorption ( Chemisorption ) Measure

In order to observe the chemical change of the catalyst and the reduction behavior of the catalyst shown in Examples 1 and 4, the catalyst was subjected to H ₂ -O ₂ chemisorption analysis using the ASAP 2020 analysis equipment of Micomeritics. The catalysts prepared in Examples and 4 were reduced at 400° C. for 4 hours in an H2 atmosphere, and then Ar was flowed for 1 hour and then lowered to 100° C. Then, to find out the degree of _{H 2} uptake, H2 gas was sufficiently flowed to measure the _{H 2 uptake. After the H 2} chemisortion was completed, the catalysts were raised to 400 ℃ to 10 ℃/min, and then He gas was flowed. ₂ Gas was flowed for 3 hours to measure the degree of _{O 2 uptake.} The _{degree of dispersion and reduction of cobalt were calculated using H 2} -O ₂ chemisorption, and the size of cobalt was also measured accordingly. The analysis results of H ₂ -O ₂ chemisorption are shown in Table 2 below.

Notation H2 chemisorption O2 consumption (mmol) degree of reduction (%) ^b dispersion
(%) ^a uncorrected
size (nm) corrected
size (nm) ^a N2 400 5.3 26.5 18.1 679.96 68.3 Air 400 5.6 26.7 17.1 636.27 63.9 He 400 6.0 26.8 15.9 590.65 59.3 NO 400 5.4 29.6 17.9 602.36 60.5

^a Dispersion and cobalt size are calculated results from hydrogen chemisorption experimental values, and were corrected by the degree of reduction.

^b The degree of reduction is a result calculated from the oxygen consumption resulting from the result of dividing the FTS catalyst amount reduced by the following general formula 1 by the theoretical oxygen consumption.

General Formula 1: 3Co + 2O ₂ →Co ₃ O ₄ .

Looking at the degree of reduction in Table 2, the degree of reduction when nitrogen is used as a calcination gas shows a higher value than when air, helium, and NO are used during calcination. From this, if it is used as a sintering gas other than nitrogen, the interaction between cobalt and the support increases _{to form CoAl 2} O ₄ to reduce the reduction of the active material. On the contrary, when nitrogen gas is used, the interaction between cobalt and the support is small, making reduction easier. It shows excellent CO conversion.

As described above, a specific part of the present invention has been described in detail, and it will be apparent to those of ordinary skill in the art that this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. will be. Therefore, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (10)

(a) mixing a cobalt precursor, an inorganic binder, an acid additive, and a solvent with the catalyst carrier;
(b) forming a molding catalyst by extrusion molding the mixture of step (a);
(c) drying the shaping catalyst; And
(d) calcining the dried shaped catalyst in a nitrogen (N ₂ ) atmosphere; Fischer-Tropsch synthesis catalyst manufacturing method comprising a.
The method of claim 1,
The catalyst carrier in the step (a) is a carbide of a metal selected from alumina, zirconia, silica, mullite, silicon carbide, titanium carbide, titanium oxide, titanium diboride, yttria, silicon nitride, titanium nitride, tungsten carbide and boron carbide. , An oxide, a nitride, a sulfide, or a mixture thereof.
The method of claim 1,
The catalyst carrier in the step (a) is a zeolite, characterized in that the Fischer-Tropsch method for producing a catalyst for synthesis reaction.
The method of claim 1,
The inorganic binder in the step (a) is Fischer-, characterized in that it is selected from the group consisting of aluminum trihydroxide, boehmite, and pseudo-boehmite, and combinations thereof. Method for producing a catalyst for the Tropsch synthesis reaction.
The method of claim 1,
The acid additive in step (a) is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, boric acid and perchloric acid, and combinations thereof.
The method of claim 1,
The step (a) is a method for producing a catalyst for a Fischer-Tropsch synthesis reaction, characterized in that 1 to 50 parts by weight of cobalt is mixed with respect to 100 parts by weight of the catalyst carrier.

The method of claim 1,
Fischer-Tropsch method for producing a catalyst for synthesis reaction, characterized in that the firing of step (d) is carried out at 300 ℃ ~ 500 ℃ for 1 hour to 24 hours.
[8] The catalyst for a Fischer-Tropsch synthesis reaction, characterized in that it is produced by the method for producing a catalyst for a Fischer-Tropsch synthesis reaction according to any one of claims 1 to 7.
A catalyst for a Fischer-Tropsch synthesis reaction, characterized in that it is prepared by the method for producing a catalyst for a Fischer-Tropsch synthesis reaction according to any one of claims 1 to 7, and has a reduction degree of 68 or more.
a) adding the catalyst for the Fischer-Tropsch synthesis reaction of any one of claims 1 to 7 into the Fischer-Tropsch synthesis reactor;
b) injecting syngas in the Fischer-Tropsch synthesis reactor; And
c) synthesizing liquid fuel from syngas in the Fischer-Tropsch synthesis reactor.

Images