KR101386629B1 - Granule-Type Catalyst Composition, Preparation Method Thereof and Preparation Method of Liquid Hydrocarbon using the same - Google Patents

Abstract

The present invention relates to a shaped catalyst composition suitable for a fixed-bed Fischer-Tropsch reaction and selectively increases aviation oil, and a method for preparing a hydrocarbon using the same, wherein copper and manganese are the active ingredients that can act as a promoter in the composition of the iron component. The component is included in the alumina bead support in an appropriate composition and concentration to form 100 Fe-αCu-βMn as a molding catalyst. The copper component (α) is about 5-15%, and the manganese component (β) is about 0.5-10%. It is. Therefore, when the FT reaction is performed using the catalyst of such a composition, the conversion rate of carbon monoxide is maintained at 90% or more during the FT reaction using the synthesis gas, and the hydrocarbon selectivity corresponding to the aviation oil (C ₁₁ -C ₁₇ ) is It is possible to get more than 30%.

Description

Granular-Type Catalyst Composition, Preparation Method Thereof and Preparation Method of Liquid Hydrocarbon using the same

One embodiment of the present invention relates to a method for preparing a catalyst composition used in the Fischer-Tropsch synthesis reaction and a method for producing liquid hydrocarbon using the same.

Fischer-Tropsch (FT) synthesis is a technique for producing hydrocarbon compounds using synthesis gas from alternative materials such as biomass, natural gas, coal, etc. This FT synthesis reaction is carried out by German scientist Fischer and Tropsch. The reaction for producing a hydrocarbon using a catalyst was first developed.

However, this technology has recently attracted new attention in terms of developing clean fuels from petroleum substitute raw materials in the era of high oil prices caused by the depletion of petroleum resources and the increase in oil demand. In particular, various catalysts have been developed to increase the activity or to be associated with the reaction process compared to the conventionally known FT reaction.

As a known representative catalyst, a catalyst mainly containing cobalt and iron as an active ingredient is used. The former is called a cobalt based iron catalyst. In addition, based on the reaction temperature, it is classified into a low temperature Fischer-Tropsch (LTFT) that performs the reaction at 250 ° C. or lower and a high temperature Fischer-Tropsch (HTFT) that reacts at a temperature of 300 ° C. or higher. [Andrei Y et al, Chem Rev., 1007, 2007, pp 1672].

The former contains the cobalt component as an active ingredient of the catalyst, which is advantageous for the production of a wax which is excellent in catalyst activity and a high molecular weight hydrocarbon, and has an advantage of maintaining a long life, but as a disadvantage, a reactor is manufactured for controlling the heat of reaction. And it is difficult to operate the slurry bubble bed (slurry bubble bed) process, and is easily poisoned by sulfur compounds, such as loss of activity as well as about 200 times more expensive than the iron-based catalyst has the disadvantage.

In particular, the synthesis gas manufacturing process is limited because it is very sensitive to the ratio of the components of the synthesis gas (hydrogen: carbon monoxide = 2: 1), the synthesis gas manufacturing cost is expensive in the case of including a post-treatment process.

On the other hand, the latter high temperature FT reaction mainly uses an iron catalyst having a catalyst composition containing iron as an active ingredient, which has a shorter catalyst life than the cobalt catalyst, but is inexpensive. Endothelial toxicity by sulfur compound has strong advantage.

In particular, cobalt-based catalysts have been applied to prepare an oil fraction of waxes having high molecular weight hydrocarbons, while iron-based catalysts are known to be advantageous for producing hydrocarbons having relatively low molecular weight by reacting at high temperatures.

In addition, due to the activity related to the water gas conversion reaction, hydrogen can be additionally generated during the reaction, so the reaction is excellent in a wide range of synthesis gas component ratio (H 2 / CO = 0.7 to 2.0), and is used even in the presence of carbon dioxide. It has the possible advantages.

The present invention aims to develop a catalyst suitable for a fixed bed FT reaction capable of selectively producing aviation oil. Typical methods for obtaining aviation oil from such known alternative raw materials are described in US 2009/0013590 A1 and US 5,378,348 (1995). As shown in), a wax having a large hydrocarbon molecular weight is first prepared by the FT reaction, and a hydrocarbon fraction having a low molecular weight is produced through a cracking and isomerization step using hydrogen, which is a post-stage step, and then a boiling point of aviation oil. Distillation process is used to separate into the boiling point.

However, this process requires the use of expensive cobalt-based catalysts to apply to the fluidized bed process suitable for LTFT to produce waxes of high molecular weight. The cost of hydrogen is a big problem. Therefore, if the FT process is developed to produce an appropriate oil containing a lot of aviation oil can solve this problem mentioned above.

Therefore, it is very important to find a new catalyst system capable of maximizing aviation oil in order to develop a process in which aviation oil is selectively contained by the related FT process.

Therefore, the present inventors have reviewed the prior art known in this respect, and I want to refer to the previous research related to the iron-based catalyst which is inexpensive and the catalyst included as an active ingredient is advantageous for producing low-boiling hydrocarbons.

Application of iron-based catalysts for Fischer-Tropsch synthesis reactions is known for the composition and preparation of a variety of active ingredients, the typical manufacturing method is mainly prepared by the precipitation method, including a variety of promoters in the iron precursor in aqueous solution. It can also be prepared by the spray-drying method, which can improve the abrasion resistance of the catalyst and improve the physical strength of the catalyst without significantly affecting the activity of the catalyst [Industrial & Engineering Chemistry Research 40 (2001) pp 1065.

In general, iron-based catalysts are prepared by including one or more promoters, which can increase the adsorption capacity of carbon monoxide (CO) or overcome the low reducibility of iron components. In particular, the addition of potassium to the iron component is known to increase the yield of waxes with increased molecular weight of hydrocarbons. In addition, in the case of the copper component added as a promoter, it is known that there is an effect of improving the reducibility of iron.

However, although the copper component has the effect of increasing the Fischer-Tropsch reaction rate than potassium by promoting the reducibility of iron, it has the property of reducing the activity of the water gas conversion reaction, iron- without using a support to compensate for this- A method of selectively synthesizing hydrocarbons at a high conversion rate of carbon monoxide using copper and metal elements of Groups 1A or 2A as a promoter has been reported [US Pat. No. 5,118,715].

U.S. Patent 4,340,503 discloses a method for synthesizing a hydrocarbon using an iron supported catalyst. The catalyst was prepared by supporting an iron component and a potassium component using a silicate carrier without an alumina component, and a catalyst was prepared from a synthesis gas using the fluidized bed reactor. C ₂ -C ₄ It is a method of synthesizing olefin of oil.

In addition, WO 01/97968 A2 is a patent applied to a method for preparing an iron catalyst by precipitation method and FT reaction, and precipitates various iron precursors such as nitrate form in the presence of alkali. ammonium hydroxide) was used, and potassium oxide (K ₂ O) was used as a promoter of the reaction to improve performance, and the appropriate amount was in the range of 0.1 to 0.5 weight ratio based on Fe 100.

Korean Patent Publication No. 2008-0112703 discloses a method for synthesizing hydrocarbon by supercritical reaction of syngas, using Fe / Cu / Al / K = 100/6/16/4 (weight ratio) as a catalyst composition. In the hydrocarbon composition obtained by the characteristics of the supercritical reaction conditions, the selectivity of olefin was high. However, this process requires high additional olefin selectivity, which requires an additional step of converting the paraffinic hydrocarbons suitable for aviation oil through an isomerization step followed by hydrogen injection.

In addition, Korean Patent Laid-Open Publication Nos. 10-2010-0133766 and 10-2009-0116181 show that the iron-based catalyst composition is used in the support containing cerium-zirconium in the composition containing iron as co-catalyst, manganese and potassium in the composition of iron. A method of impregnation was proposed, and the catalyst composition for improving the yield of high-boiling hydrocarbons and light hydrocarbons was lowered by lowering the selectivity of the side reactant methane in the fixed bed reactor as compared to the case of using cerium and zirconium alone as a support. have.

A method for the selective preparation of aviation oil by the Fischer Drops reaction has been published [Fuel 89 (2010) pp 2088]. This study relates to a catalyst composition that selectively increases aviation oil by the FT reaction. It is considered to be the only result of previous studies.

That is, the catalyst composition containing iron as an active ingredient and Cu, Ca, Mg, and K as various cocatalyst ingredients was examined. That is, the hydrocarbon range (C ₁₁ -C ₁₇ ) of the aviation fraction was about 17% when the iron component without the promoter was used alone, and the selectivity of the aviation fraction when nitrogen was included in the synthesis gas. Showed a tendency to increase slightly.

However, this result is that since the catalyst form has a powder form, in order to apply it to a commercial fixed bed reaction, it is necessary to carry out a molding process, which is a process of making the powder form to an appropriate particle size.

Therefore, in order to apply to the fixed bed catalytic reactor, the FT reaction is a rapid exothermic reaction. Therefore, in order to remove the heat of reaction appropriately, a considerable amount of various organic or inorganic binders are included, and molding to a certain size using an extruder is required. Korean Chem. Eng. Res., 5 (2011), pp 37]. This process reduces the catalytic activity, such as conversion of the reaction, and requires additional process costs for catalyst formation.

One object of the present invention is to provide a method for producing a molded catalyst composition used in the Fischer-Tropsch synthesis reaction.

Another object of the present invention is to provide a method for producing liquid hydrocarbon using the molding catalyst composition according to the present invention.

In order to achieve such a problem of the present invention, the method for producing a molding catalyst composition according to an embodiment of the present invention, Fe (NO ₃ ) ₃ · 9H ₂ O, Cu (NO ₃ ) ₂ acting as an active ingredient Dissolving 3H ₂ O and Mn (NO ₃ ) ₃ · 9H ₂ O in distilled water at a predetermined weight ratio to prepare a precursor aqueous solution, injecting alumina beads into a rotary evaporator, and stirring at a predetermined temperature and pressure; Injecting the precursor aqueous solution into the rotary evaporator to impregnate the alumina beads and the precursor aqueous solution to form a mixture, vaporizing the mixture, and drying the vaporized mixture.

According to an example related to the present invention, the stirring may be performed by stirring at a speed of 400 rpm while maintaining an air pressure of about 100 torr at a temperature of about 40 ° C.

According to an example related to the present invention, the active ingredient has a composition of 100 Fe-αCu-βMn, wherein α may be 5 intrinsic 10% by weight, and β may be 0.5 to 15% by weight.

According to an example related to the present invention, the total content of the active ingredient may be 5 to 15% by weight based on the weight of the alumina beads.

In addition, another embodiment of the present invention in order to realize the above object, after the charge of the molding catalyst composition in a fixed bed reactor comprising a step of reducing treatment under a hydrogen atmosphere and the step of injecting synthesis gas into the reduced fixed bed reactor; The molding catalyst composition is dissolved in Fe (NO ₃ ) ₃ · 9H ₂ O, Cu (NO ₃ ) ₂ · 3H ₂ O and Mn (NO ₃ ) ₃ · 9H ₂ O in distilled water at a predetermined weight ratio to form a precursor aqueous solution. Preparing, injecting alumina beads into a rotary evaporator, stirring at a predetermined temperature and pressure, and injecting the precursor aqueous solution into the rotary evaporator to impregnate the alumina beads and the precursor aqueous solution to form a mixture. Fischer-Tropsch synthesis reaction, characterized in that the formed catalyst composition comprising the step of vaporizing the mixture and the vaporized mixture Using discloses a method for producing a liquid hydrocarbon.

According to an example related to the present invention, the step of injecting the synthesis gas into the reduced-treated fixed bed reactor, the reaction temperature is 220-350 ℃, the reaction pressure is 10-30 atm, the space velocity is 1000-3000 L / It can be made under the condition of kgcat / hr.

Molding catalyst composition according to at least one embodiment of the present invention, a manufacturing method and a method of producing a liquid hydrocarbon using the same according to the above-described configuration is to increase the selectivity of the aviation oil by directly using a molding catalyst suitable for the fixed bed FT reaction The composition of the molding catalyst can be obtained.

The catalyst composition has a form of 100 Fe-αCu-βMn in which alumina beads contain iron, copper, and manganese as appropriate, and maintains a conversion rate of carbon monoxide more than 90% during FT reaction, and in aviation oil (C ₁₁ -C ₁₇ ). In order that the corresponding hydrocarbon selectivity can be obtained 30% or more, the copper component (α) is composed of about 5-10%, and the manganese component (β) is composed of about 0.5-15%.

As such, it was possible to prepare a molding catalyst composition which greatly increases the selectivity of aviation oil in a fixed bed FT reaction using a synthesis gas obtained from a petroleum substitute raw material. In addition, the molding step including the appropriate binder and the complicated steps such as drying and firing can be omitted, and thus, the formation catalyst having excellent selectivity of aviation oil and strong strength could be prepared.

Therefore, according to the present invention, since it gives the characteristic of selectively producing the aviation oil which is the most expensive oil among the petroleum oil, the burden of the cracking and isomerization process of the rear end is reduced, and the advantage that the selective production of high value oil is possible. have.

1 is a graph showing the TPR analysis of the catalyst prepared according to the embodiments of the present invention.
Figure 2 is a table showing the results of the BET analysis of the representative catalyst composition of the molded catalyst with the Mn content changed.

Hereinafter, the molding catalyst composition according to the present invention, a method for producing the same, and a method for producing liquid hydrocarbon using the same will be described in more detail.

Looking at the patents known to date, after producing a wax with a large hydrocarbon molecular weight by the FT process, after the cracking and isomerization step using hydrogen, which is a post-stage process to produce a small molecular weight fraction, the separation of the aviation oil using a distillation process Doing.

However, this process requires the use of expensive cobalt-based catalysts in a fluidized bed process suitable for LTFT to produce waxes of high molecular weight, and in the latter process, excess hydrogen is used to produce waxes with low boiling fractions at high temperatures and pressures. Hydrogen costs and process costs are big issues.

Therefore, there is no patent for a catalyst composition for selectively increasing the aviation oil by the FT reaction. Looking at the known literature, it shows the highest selectivity of the aviation oil when the iron component is used alone, and the value is about 17%. There is a low problem. In general, the results of previous studies have been published focusing on the increase of hydrocarbon yield of C ₅ ⁺ or more with carbon number of 5 or more by selectively reducing side reactions.

Therefore, in order to selectively prepare aviation oil by FT reaction, it is very important to find a composition of a catalyst having a combination of active materials suitable for this.

In particular, the composition of most known FT catalyst is mainly limited to the powder form and the content of the active ingredient is also very high problem, such as 80%. Therefore, the powder-type catalyst has a high pressure in the catalyst layer in a fixed bed FT reaction process of a predetermined size or more, and has a constant size because fine powder catalyst particles are continuously discharged out of the catalyst layer by hydrocarbon components and water, which are reaction products during the reaction process. Therefore, a molding catalyst having a strength capable of suppressing a phenomenon that the catalyst breaks down depending on the height in the catalyst layer should be used.

However, this molding process has to produce a molding catalyst through an excessive binder and a complicated manufacturing step, there is a problem that the included binder affects the reaction to lower the yield. In addition, conventionally known catalyst production method is the active ingredient in the excess of 80% (for example, Fe / Cu / Al / K = 100/6/16/4 (weight ratio)) of the active ingredients, such as iron and various cocatalysts There is a problem in preparing a catalyst by including.

This excess is the introduction of the active ingredient can promote the reaction activity, that is, the conversion rate of CO, etc., but the cost of the production of the catalyst is expensive, when the excess active ingredient is applied to the fixed bed FT reactor to control the heat of reaction due to rapid exothermic reaction This may indicate a big problem.

The present invention relates to compositions of shaped catalysts for the production of hydrocarbons which can selectively increase the aviation fraction by means of a Fischer-Tropsch synthesis reaction using syngas.

As a catalyst composition, as a molding binder, bead-type alumina (UOP product, D-201, specific surface area 350 m ² / g, apparent density 0.75 g / cm ³ , average particle size 1.5 mm) is available. Most appropriately, the molding carrier is characterized by containing 5-20% of active ingredient.

When a molding binder other than alumina is used as a molding binder, for example, silica gel, silica-alumina, or zeolite, there is a problem in that some acid points are present or the surface area is small so that the selectivity of aviation oil is lower than that of alumina beads. .

In addition, when the content of the active ingredient is too low, the reaction rate, which is the conversion rate according to the reaction time, is too slow. When the content of the active ingredient is too high, it is difficult to control the exothermic generated during the reaction, so that the reaction temperature is rapidly increased, so that There is a problem that the deactivation proceeds rapidly.

The active ingredient is appropriately composed of a complex active ingredient containing copper and manganese at the same time based on the iron component, 5 to 15% copper and 5 to 15% manganese based on the iron component. Is appropriate. If only a certain amount of copper components based on 100 by weight of the iron component or if only the potassium component is contained in the iron component there is a problem that the conversion rate of carbon monoxide is 50% or less.

In addition, even when iron and copper are simultaneously contained in the iron component, if the copper and manganese components are too low (less than 5%) or too high (more than 5%), the low boiling point hydrocarbon component C ₁₀ or less is too large and relatively aerospace. There is a problem that the selectivity of oil is poor.

In addition, the method of impregnating into a molding binder is very important, and the method of impregnating the precursor by dissolving the precursor in aqueous solution and continuously impregnating the catalyst pre-injected in a rotary evaporator under constant temperature and reduced pressure is relatively uniform. Impregnation was possible and advantageous.

Molding catalyst manufacturing method is described in more detail as follows. First, a method of preparing an aqueous metal nitride salt solution dissolves a predetermined amount of Fe (NO ₃ ) ₃ · 9H ₂ O, Cu (NO ₃ ) ₂ · 3H ₂ O, and Mn (NO ₃ ) ₃ · 9H ₂ O in a predetermined amount of distilled water. Manufacture.

Subsequently, alumina beads are first injected into the rotary evaporator, and the temperature is kept constant at 40 ° C., and the pressure is stirred at 400 rpm while maintaining a constant vacuum at 100 torr. The precursor solution is then slowly injected into the rotary evaporator to constantly wet the surface of the beads while the aqueous solution evaporates to impregnate the precursor into the beads.

After completion of the dropping, the aqueous solution was completely vaporized and removed at 70 ° C. Subsequently, the mixture was first dried at 110 ° C. for 24 hours and then calcined at 550 ° C. for 5 hours. The iron oxide thus prepared has a composition of Fe—Cu—Mn in the form of beads.

The activity experiment of the reaction using such a catalyst was carried out by the method used in the activity experiment of a general fixed bed catalytic reaction.

In other words, it was carried out using a fixed bed reactor made of 3/8 inch stainless steel (SUS-316). The precursor was filled with 0.5 g of a molding catalyst and reduced for 12 hours under hydrogen (5% H ₂ / He) at 450 ° C. Reduce the form of the active ingredient involved.

Subsequently, the synthesis gas [mole ratio of carbon monoxide: hydrogen: argon (internal standard) = 28.4: 57.3: 5] was introduced into the reactor at a typical reaction temperature of 270 to 330 ° C. (more preferably around 300 ° C.). Comparative experiments were conducted under constant reaction pressure of 15 atm and space velocity of 2,400 cc / g.cat · hr. The reaction activity was confirmed by gas chromatography (GC) analysis after confirming that the activity of the catalyst was stabilized and maintained, which was the result after about 60 hours had elapsed.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example  1 - 3 and Comparative Example  1-3

In order to prepare a molding catalyst suitable for the FT fixed bed reaction, first, an aqueous metal nitride salt solution was prepared, and Fe (NO ₃ ) ₃ · 9H ₂ O and Cu (NO ₃ ) ₂ · 3H ₂ O and Mn ( NO ₃ ) ₃ · 9H ₂ O is dissolved to prepare a precursor aqueous solution. The amount of each component, based on 100 Fe by weight ratio, the Cu and Mn composition ratio depends on the amount of each component presented in the Examples and Comparative Examples.

Subsequently, 100 g of alumina beads are first introduced into the rotary evaporator, and the temperature is maintained at 40 ° C., the pressure is 100 torr, and the stirring speed is constant at 400 rpm. Subsequently, the precursor solution is slowly injected into the rotary evaporator, and the aqueous solution is evaporated while the solution is constantly wetted on the surface of the beads, and the precursor is impregnated into the beads. After the dropping is completed for 2 hours, the aqueous solution is completely vaporized and removed at 70 ° C.

This is followed by first drying at 110 ° C. for 24 hours and calcining at 550 ° C. for 5 hours. The iron oxide thus prepared was in the form of beads, and the active ingredient was composed of Fe-αCu-βMn, and kept constant at 10wt% based on alumina beads (Al-bead), and the composition of each active ingredient was based on 100% Fe. The content of Cu and Mn was changed as in Examples 1-7.

The prepared catalyst was analyzed by specific surface area analysis and temperature programmed reduction (TPR) analysis to find that the catalyst was well prepared.

The activity experiment of the reaction using this catalyst was carried out using a fixed bed reactor made of 3/8 inch stainless steel (SUS-316), filled with 0.5 g of the catalyst and under a hydrogen (5% H ₂ / He) atmosphere at 450 ° C. After reducing for 12 hours, the synthesis gas [mole ratio of carbon monoxide: hydrogen: argon (internal standard) = 28.4: 57.3: 5] at 270 ~ 330 ℃ (more preferably around 300 ℃) at 100 cc / min The reaction was carried out under the conditions of a reaction pressure of 15 atm and a space velocity of 2,400 cc / g.cat · hr while being injected into the reactor.

The reaction activity was confirmed by GC analysis that the activity of the catalyst remained stable, which was the result after about 72 hours had elapsed.

CO conversion rate was calculated by the CO molar number ratio after the reaction, based on the molar amount of CO injected into the initial product, and then the selectivity to aviation oil is FT reaction air fraction from the heavier components on the basis of the CO conversion (C ₁₁ - A value obtained by GC analysis of a hydrocarbon corresponding to C ₁₇ ), which includes some alcohols, ester compounds, and aldehyde compounds, but ignores them, and also calculates the selectivity by carbon weight ratio. It is not a value.

Examples 1 to 7 and Comparative Examples 1 to 7 of Table 1 are results obtained by changing the composition of the catalyst and the type of the support.

<Table 1>

Here, silica beads were used by Japan Fuji company Q-10 (average particle size 1 mm, specific surface area 250 m ² / g).

In addition, the molded silica-alumina beads were SIRALOX 30 Trilobe Extrudate (average particle size 1.5mm, specific surface area 225 m ² / g), and the molded zeolite beads were formed in an injection molding machine using bentite and alumina sol in the zeolite powder. The product was prepared directly (average particle size 1.5 mm, specific surface area 125 m ² / g) and used.

Example  5-8 and Comparative Example  7 - 9

In Examples 9 to 11 and Comparative Examples 8 to 11 of Table 2, the composition of the catalytically active component was kept constant at 100Fe-6Cu-7Mn, which is the same composition as in Example 5, based on the weight of the alumina beads when impregnated with the alumina beads. This is the result of FT reaction in a fixed bed reactor after the catalyst was prepared by changing the weight of the active ingredient and the catalyst preparation method. In Comparative Example 9, a method of preparing a molding catalyst by immersion instead of impregnation was applied. In this method, a certain amount of alumina beads is first injected into a beaker, and the precursor solution is injected into the amount of the alumina beads soaked, and the solution is deposited in the pores of the alumina beads in a vacuum state, and then filtered. Drying and firing steps were carried out in the same manner as in Example 1.

<Table 2>

Example  12-16 and Comparative Example  12-16

Examples 12-16 and Comparative Examples 12-16 of Table 3 show examples of reacting by changing reaction temperature, reaction pressure, and space velocity, which are reaction conditions, in a fixed bed catalytic reactor based on Example 11.

<Table 3>

Hereinafter, a method of preparing liquid hydrocarbon using Fischer-Tropsch synthesis reaction according to the present invention will be described in detail step by step.

First, the first step according to the present invention is a step of charging the iron-based catalyst prepared by the method for preparing the catalyst in a fixed bed reactor and then reducing the mixture under a hydrogen atmosphere.

In this case, the fixed bed reactor may be made of stainless steel (SUS-316) and the like, the hydrogen is preferably containing 4-6% by weight of helium.

Next, the second step according to the present invention is the step of injecting the synthesis gas into the fixed bed reactor reduced in the first step.

The synthesis gas may be a material consisting of carbon monoxide, hydrogen, argon or carbon dioxide, methane, and the like.

In addition, the synthesis gas of the second stage is preferably injected after the fixed bed reactor is maintained at a reaction temperature of 220-350 ℃. If the reaction temperature is less than 220 ℃, there is a problem that the carbon monoxide conversion is lowered and the olefin selectivity is increased, and if the reaction temperature is higher than 350 ℃, the carbon monoxide conversion and lower olefin selection in terms of energy efficiency in the Fischer-Tropsch synthesis reaction There is a problem that does not get. In addition, the syngas is preferably injected into the fixed bed reactor under conditions of 1000-3000 L / kgcat / hr space velocity. If the space velocity is less than 1000 L / kgcat / hr, the production of carbon dioxide, which is a side reaction, may be increased. If the space velocity exceeds 3000 L / kgcat / hr, the conversion rate of carbon monoxide may decrease rapidly. . The reaction pressure is advantageously carried out at 10 to 30 atmospheres of FT reaction. If the pressure is less than 10 atmospheres, the carbon monoxide conversion rate drops sharply. If the pressure is too high above 30 atmospheres, it must be pressurized through the high pressure booster of syngas. As a result, an increase in the apparatus cost due to the high pressure reaction is economically problematic.

The molding catalyst composition described above, a method for producing the same, and a method for producing a liquid hydrocarbon using the same are not limited to the configuration and method of the embodiments described above, and the embodiments may be modified in various ways. All or some of the embodiments may be optionally combined.

Claims (8)

Fe (NO ₃ ) ₃ · 9H ₂ O, Cu (NO ₃ ) ₂ · 3H ₂ O and Mn (NO ₃ ) ₃ · 9H ₂ O, which act as active ingredients, are dissolved in distilled water at a predetermined weight ratio to prepare a precursor solution. step;
Injecting alumina beads into a rotary evaporator and stirring under constant temperature and pressure;
Injecting the precursor aqueous solution into the rotary evaporator to impregnate the alumina beads and the precursor aqueous solution to form a mixture;
Vaporizing the mixture; And
Method for producing a molding catalyst composition comprising the step of drying the vaporized mixture. The method of claim 1,
The stirring step is a method for producing a molding catalyst composition, characterized in that the stirring step at a speed of 400 rpm while maintaining a pressure of 100 torr at 40 ℃ temperature. The method of claim 1,
The composition ratio of the active ingredient is by weight, Fe: Cu: Mn = 100: α: β, wherein α is 5 to 10, β is 0.5 to 15 method for producing a molded catalyst composition. The method of claim 1,
Wherein the total content of the active ingredient has a weight of 5 to 15% based on the weight of the alumina beads. The method of claim 1,
The drying step,
Method of producing a molded catalyst composition, characterized in that the step of drying first at 110 ℃ for 22 hours to 26 hours, and then calcined (calcination) at 550 ℃ for 4 hours to 6 hours. Charging the shaped catalyst composition into a fixed bed reactor and reducing the mixture under a hydrogen atmosphere; And
Injecting syngas into the reduced fixed bed reactor;
The molding catalyst composition,
Dissolving Fe (NO ₃ ) ₃ .9H ₂ O, Cu (NO ₃ ) ₂ .3H ₂ O and Mn (NO ₃ ) ₃ .9H ₂ O in distilled water at a predetermined weight ratio to prepare a precursor aqueous solution;
Injecting alumina beads into a rotary evaporator and stirring under constant temperature and pressure;
Injecting the precursor aqueous solution into the rotary evaporator to impregnate the alumina beads and the precursor aqueous solution to form a mixture;
Vaporizing the mixture; And
Method for producing a liquid hydrocarbon using the Fischer-Tropsch synthesis reaction, characterized in that the molding catalyst composition formed by drying the vaporized mixture. The method according to claim 6,
Injecting the synthesis gas into the fixed bed reactor,
The reaction temperature is 220-350 ℃, the reaction pressure is 10-30 atm, the space velocity is a production method of liquid hydrocarbon, characterized in that made in the conditions of 1000-3000 L / kgcat / hr. Molding catalyst composition prepared according to any one of the preceding claims used in Fischer-Tropsch synthesis reaction for producing liquid hydrocarbons.

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