KR20160092547A - Mixed support catalyst for fischer-tropsch synthesis and it used liquid hydrocarbon fabrication method - Google Patents

Mixed support catalyst for fischer-tropsch synthesis and it used liquid hydrocarbon fabrication method Download PDF

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KR20160092547A
KR20160092547A KR1020150012613A KR20150012613A KR20160092547A KR 20160092547 A KR20160092547 A KR 20160092547A KR 1020150012613 A KR1020150012613 A KR 1020150012613A KR 20150012613 A KR20150012613 A KR 20150012613A KR 20160092547 A KR20160092547 A KR 20160092547A
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catalyst
fischer
tropsch synthesis
synthesis reaction
support
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Korean (ko)
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유성식
민선기
노성래
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한국기술교육대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/13—Potassium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a mixed support catalyst for Fischer-Tropsch synthesis reaction and a method for producing liquid hydrocarbons using the same, which comprises a catalyst composed of iron (Fe), copper (Cu) and potassium (K) 2 O 3 ) and silica (SiO 2 ) are mixed with each other to carry out the Fischer Tropsch synthesis reaction, thereby ensuring stable catalytic activity for a long period of time and improving the conversion of carbon monoxide and the formation of liquid hydrocarbons Can be improved.

Description

Technical Field [0001] The present invention relates to a mixed support catalyst for a Fischer-Tropsch synthesis reaction and a method for producing a liquid hydrocarbon using the same,

The present invention relates to a Fischer-Tropsch synthesis reaction mixture capable of improving the conversion of carbon monoxide and the yield of hydrocarbons while ensuring stable catalytic activity for a long period of time by using an iron-based catalyst prepared by mixing a promoter and a support in a Fischer- Support catalyst and a process for producing liquid hydrocarbons using the same.

As is well known, a coal indirect liquefaction system has been developed which can finally produce wax-form synthetic oil through a gasification process, a refining process, and a liquefaction process, using the powder of coal as a main raw material, and to use it as a raw material for fossil fuels

Here, in the liquefaction process, Fischer-Tropsch synthesis reaction (FISCHER-TROPSCH SYNTHESIS) in which purified synthetic gas is reacted on a catalyst to convert it to liquid synthetic oil is applied.

This Fischer-Tropsch synthesis reaction utilizes a variety of catalysts to convert syngas (principally consisting of carbon monoxide and hydrogen) to hydrocarbon mixtures of various chain lengths ranging from methane to wax, which are saturated / unsaturated Hydrocarbons having oxidizing bonds such as hydrocarbons, alcohols, ketones, aldehydes, etc. and olefins containing double bonds.

Among the various reaction products as described above, in order to increase the selectivity to a specific substance and to improve the overall reaction efficiency, research and development of a reaction process and a reaction catalyst have been required, and a metal catalyst having activity in a Fischer- (Fe), nickel (Ni), cobalt (Co), and ruthenium (Ru).

A ruthenium (Ru) is too high in such a metal catalyst, a nickel (Ni) is the methane generation rate is there so high that commercially only iron (Fe) and cobalt (Co) is used, the cobalt catalyst is carbon dioxide (CO 2) contains a large amount (CH 4 ) at high temperatures and can be used only as a low-temperature catalyst. On the other hand, the iron catalyst is the lowest catalyst among the catalysts applied to the Fischer-Tropsch synthesis reaction , The formation of methane is one of the most widely used catalysts because it shows a tendency to be low at high temperatures and high selectivity of olefins in hydrocarbons.

The iron catalyst as described above can be prepared by incorporating one or more cocatalyst which helps adsorption of carbon monoxide (CO) or reduction of iron, and has a specific surface area for dispersion of small metal particles and stabilization of catalyst It is possible to add a support as a structural stabilizer to the iron catalyst.

As the co-catalyst, an alkali metal such as copper (Cu), sodium (Na), potassium (K), ruthenium (Ru), cesium (Cs) or the like is used. In the case of the support, silica (SiO 2 ) 2 O 3 ). In this case, a technique for producing a Fischer-Tropsch synthesis catalyst capable of improving the conversion of carbon monoxide and the yield of hydrocarbons while ensuring stable catalytic activity over a long period of time has been continuously researched and developed.

1. Registration No. 10-1211376 (registered on December 06, 2012): F-T bubble column reactor capable of complex reaction 2. Registration No. 10-1026536 (registered on March 25, 2011): Catalyst of iron series for Fischer-Tropsch synthesis reaction and production method thereof 3. Registration No. 10-0933062 (Registered Nov. 11, 2009): Catalyst for Direct Production of Light Olefins from Synthetic Gases and its Preparation Method

The present invention relates to a process for the production of a Fischer-Tropsch synthesis reaction capable of improving the conversion of carbon monoxide and the yield of liquid hydrocarbons while securing a stable catalytic activity for a long period of time by using an iron-based catalyst prepared by mixing a promoter and a support in a Fischer- A mixed support catalyst and a method for producing a liquid hydrocarbon using the same.

The present invention is by using copper and potassium as co-catalyst which is added to the iron catalyst and adjusting the ratio of silica and alumina used as a support, while ensuring a long time stable catalytic activity increases the conversion rate of carbon monoxide, carbon dioxide (CO 2 ), The selectivity of C1 and C2-C4 is lowered, and the selectivity of C5 + is increased, and a method for producing liquid hydrocarbons using the same is provided.

The objects of the embodiments of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description .

According to one embodiment of the invention, an iron (Fe), copper (Cu), and potassium with catalysts composed of (K), gamma-alumina (γ-Al 2 O 3) and silica (SiO 2) that the support is a mixture consisting of A mixed support catalyst for Fischer Tropsch synthesis reaction may be provided.

In accordance with another embodiment of the invention, an iron (Fe), copper (Cu), and potassium with catalysts composed of (K), gamma-alumina (γ-Al 2 O 3) and silica (SiO 2) that the support is a mixture consisting of by the steps, and hydrogen; and a hydrogen (H 2) and carbon monoxide (CO) for reducing the above mixed support catalyst using an (H 2) for charging the mixture support catalyst in Fischer-Tropsch synthesis reactor a reaction gas of the reduced And performing a Fischer Tropsch synthesis reaction using the mixed support catalyst. The present invention also provides a method for producing a liquid hydrocarbon using a mixed support catalyst for a Fischer Tropsch synthesis reaction.

In the present invention, the conversion of carbon monoxide and the yield of liquid hydrocarbons can be improved while ensuring stable catalytic activity for a long period of time by using an iron-based catalyst obtained by mixing a promoter and a support in a Fischer Tropsch synthesis reaction.

The present invention is by using copper and potassium as co-catalyst which is added to the iron catalyst and adjusting the ratio of silica and alumina used as a support, while ensuring a long time stable catalytic activity increases the conversion rate of carbon monoxide, carbon dioxide (CO 2 ), The selectivity of C1 and C2-C4 is lowered, and the selectivity of C5 + is increased.

FIGS. 1A and 1B are views for explaining characteristics of a mixed support catalyst for a Fischer-Tropsch synthesis reaction according to an embodiment of the present invention;
FIG. 2 is a flow chart showing a process for producing liquid hydrocarbons using a mixed support catalyst for Fischer-Tropsch synthesis reaction according to another embodiment of the present invention.
FIGS. 3A and 3B are diagrams for explaining conversion rates of carbon monoxide and yields of liquid hydrocarbons when producing liquid hydrocarbons according to another embodiment of the present invention; FIGS.

Advantages and features of embodiments of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. The following terms are defined in consideration of the functions in the embodiments of the present invention, which may vary depending on the intention of the user, the intention or the custom of the operator. Therefore, the definition should be based on the contents throughout this specification.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIGS. 1A and 1B are views for explaining characteristics of a mixed support catalyst for a Fischer-Tropsch synthesis reaction according to an embodiment of the present invention.

1A and 1B, a mixed support catalyst for a Fischer-Tropsch synthesis reaction according to an embodiment of the present invention is composed of iron (Fe), copper (Cu), potassium (K) 0.05 to 0.15 parts by weight of copper (Cu), 0.15 to 0.25 parts by weight of potassium (K), and 4.5 to 5.5 parts by weight of a support. Here, each component can be mixed and formed into a powder.

At this time, if copper (Cu) is less than 0.05 part by weight based on 1 part by weight of iron (Fe), there arises a problem that the amount of methane (CH 4 ) is increased, while when it exceeds 0.15 parts by weight, , And copper (Cu) in the range of 0.05-0.15 parts by weight.

In addition, potassium (K) increases the average molecular weight of the hydrocarbon product, inhibits the inactivation of the catalyst, increases the activity of the Fischer Tropsch synthesis reaction and decreases the selectivity of methane (CH 4 ) When the amount of the catalyst is less than 0.15 parts by weight based on 1 part by weight of iron (Fe), the selectivity of methane (CH 4 ) is difficult to decrease. When the amount of the catalyst is more than 0.25 parts by weight, By weight.

On the other hand, the support is advantageous to increase the specific surface area in order to disperse small metal particles and stabilize the catalyst in the production of the catalyst, and is added as a structural stabilizer, thereby performing a support. If the amount of the catalyst is less than 4.5 parts by weight, the amount of the catalyst used is too small to act as a support. If the amount of the catalyst is more than 5.5 parts by weight, there is no effective difference with increasing amount of the catalyst. -5.5 parts by weight.

The support used in the mixed support catalyst as described above is added in an amount of 40-80 wt% of gamma alumina (γ-Al 2 O 3 ) having an equiaxed crystal form and 20-60 wt% of silica (SiO 2 ) Gamma alumina and silica each having a specific surface area of 200-300 m 2 / g can be used.

On the other hand, a powder of 1 kg of iron (Fe), 100 g of copper (Cu), 200 g of potassium (K) and 5 kg of a support were mixed, molded, dried and sintered to prepare a catalyst sample 1 to then prepare a catalyst sample 5, a catalyst sample 1 to the catalyst sample 5 positive measurement, BET and (Brunauer, Emmett, Teller) of the nitrogen gas adsorbed by the adsorption of nitrogen (N 2) to the powder surface, for each formula The result of the BET nitrogen adsorption analysis showing the surface area calculated using the method of FIG.

First, gamma-alumina (γ-Al 2 O 3) : % by weight, the ratio of silica (SiO 2) 100: 0 The catalyst of sample 1, and a BET surface area of 171.93 m 2 / g, pore volume is 0.3725 cm 3 / g , And the average pore diameter is 6.5996 nm.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 75: the 25 The catalyst sample 2, and a BET surface area of 168.82 m 2 / g, pore volume is 0.4725 cm 3 / g , And the average pore diameter is 8.7061 nm.

In addition, gamma-alumina (γ-Al 2 O 3) : % by weight, the ratio of silica (SiO 2) is 50: at 50 A catalyst of sample 3 and a BET surface area of 160.80 m 2 / g, pore volume is 0.4222 cm 3 / g , And the average pore diameter is 8.6695 nm.

On the other hand, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 25: the 75 catalyst sample 4, and a BET surface area of 153.12 m 2 / g, pore volume is 0.5193 cm 3 / g , And the average pore diameter is 11.6254 nm.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 0: In 100 A catalyst sample 5 and a BET surface area of 144.11 m 2 / g, pore volume is 0.5641 cm 3 / g , And the average pore diameter is 12.9306 nm.

Here, although the BET surface area is high in the catalyst sample 1, since the pore volume and the average pore diameter are small, the dispersion of the metal particles and the stabilization effect of the catalyst can not be sufficiently obtained, and the catalyst samples 4 and 5 have the void volume and the average pore diameter However, since the BET surface area is small, the dispersion of the metal particles and the stabilization effect of the catalyst can not be sufficiently obtained.

On the other hand, in the case of Catalyst Samples 2 and 3, it can be seen that BET surface area, pore volume and mean pore diameter are appropriate enough to obtain sufficient dispersion of the metal particles and stabilization of the catalyst.

Referring to such a catalyst sample 1 catalyst to X- ray diffraction results of Figure 1b for the sample 5, similarly to the catalyst in the catalyst sample 1 to sample 5, the diffraction angle (2θ) of gamma silicate (γ-Si 2 O at about 20 DEG 2 ) peaks appear. The peaks of α-Fe 2 O 3 appear at about 25 ㅀ, 33 ㅀ, 36 ㅀ, and 42 각각, respectively. The peaks of alumina (Al 2 O 3 ) It was confirmed by X-ray diffraction analysis that the peak of alpha-iron oxide (alpha -Fe 2 O 3 ), which is known to be active in the Fischer-Tropsch reaction, appears in all of catalyst sample 1 to catalyst sample 5, In the catalyst sample 5 using the 100% gamma-silicate (γ-Si 2 O 2 ) support, there was no alumina (Al 2 O 3 ) peak and in the catalyst sample 1 using the 100% alumina (Al 2 O 3 ) γ-Si 2 O 2 ) peaks do not appear.

Fischer Tropsch synthesis reaction agent mixed catalyst support is gamma-alumina (γ-Al 2 O 3) 40-80 % by weight of silica as a support as described above (SiO 2) should be added in a 20-60% by weight, in which case A BET surface area of 155-170 m 2 / g, a pore volume of 0.4-0.5 cm 3 / g, and an average pore diameter of 7-11 nm, Can be obtained.

Next, a process for producing liquid hydrocarbons using the mixed support catalyst for Fischer-Tropsch synthesis reaction having the above-described structure will be described.

FIG. 2 is a flowchart showing a process of producing liquid hydrocarbons using a mixed support catalyst for a Fischer-Tropsch synthesis reaction according to another embodiment of the present invention.

2, a mixed support catalyst prepared by mixing iron (Fe), copper (Cu), potassium (K), and a support with gamma-alumina (γ-Al 2 O 3 ) and silica (SiO 2 ) Can be charged to the Fischer Tropsch synthesis reactor (step 202).

Here, the iron (Fe), the copper (Cu), the potassium (K) and the support may be formed by mixing powders of the respective components and may be formed by mixing 0.05-0.15 parts by weight 0.15-0.25 parts by weight of potassium (K), and 4.5-5.5 parts by weight of a support. The support is composed of 40-80% by weight of γ-alumina (γ-Al 2 O 3 ) having an equiaxed crystal form and silica 2 ), and gamma alumina (gamma -Al 2 O 3 ) and silica (SiO 2 ) may have a specific surface area of 200-300 m 2 / g, respectively.

This support is gamma-alumina (γ-Al 2 O 3) and silica may be adjusted by adding a weight percent ratio of (SiO 2), the dispersion of metal particles, the purpose of using a support as described in one embodiment of the present invention It is preferable to use a mixed support catalyst having a BET surface area of 155-170 m 2 / g, a pore volume of 0.4-0.5 cm 3 / g and an average pore diameter of 7-11 nm in order to sufficiently obtain the stabilization effect of the catalyst .

The mixed support catalyst charged in the Fischer Tropsch mixer reactor in step 202 may then be reduced using hydrogen (H 2 ) (step 204).

Here, the mixed catalyst support may be treated for 8-12 hours at 250-350 ℃ reduction with hydrogen (H 2).

Next, the Fischer Tropsch synthesis reaction can be performed using the reduced mixed support catalyst using hydrogen (H 2 ) and carbon monoxide (CO) as a reaction gas (Step 206).

Here, the Fischer Tropsch synthesis reaction can be carried out at a pressure of 15-25 bar at 250-350 ° C for 58-62 hours, and the volume ratio of hydrogen and carbon monoxide as the reaction gases can be adjusted to 2: 1, When the ratio is more than 2, the selectivity of methane (CH 4 ) is increased and the selectivity of C 5 + (hydrocarbon having 5 or more carbon atoms) is relatively low, which is not suitable.

Using a mixed support catalyst prepared by mixing, molding, drying and sintering powders of 1 kg of iron (Fe), 100 g of copper (Cu), 200 g of potassium (K) and 5 kg of a support under the conditions of the temperature and pressure described above, The result of performing the Lossy synthesis reaction is shown in FIG. 3A. In the catalyst sample 1 in which the weight% ratio of gamma alumina (γ-Al 2 O 3 ): silica (SiO 2 ) is 100: 0, CO conversion %)) Is 92.5184, and the carbon dioxide selectivity (CO 2 selectivity (%)) and the hydrocarbon selectivity (%) are 50.1212 and 49.8788, respectively.

The distribution of hydrocarbons (c-wt%) in this catalyst sample 1 is 23.36, C2-C4 (hydrocarbon having 2 to 4 carbon atoms) is 21.74, C5 + Is 54.89.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 75: 25 The catalyst sample 2, the carbon monoxide conversion rate is 91.9884, and the carbon dioxide selectivity and a hydrocarbon selected that each 43.4871 and 56.5129 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be C1.05, C2.05, C5 +, and C5 +.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 50: 50 A catalyst of sample 3, the carbon monoxide conversion rate is 81.91, and the carbon dioxide selectivity and is a hydrocarbon selected that respectively 50.46 and 49.54 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 7.52 for C1, 10.23 for C2-C4, and 78.34 for C5 +.

On the other hand, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 25: 75 The catalyst sample 4, the carbon monoxide conversion rate is 79, and the carbon dioxide selectivity and is a hydrocarbon selected that respectively 61.03 and 38.97 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 4.63, C1 to 3.36, and C5 + to be 85.98.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 0: 100 A catalyst sample 5, the carbon monoxide conversion rate is 54.454, and is a carbon dioxide selectivity and a hydrocarbon selected that each 25.8484 and 74.1516 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 14.00 for C1, 11.49 for C2-C4, and 72.80 for C5 +.

The carbon monoxide conversion and yield of the liquid hydrocarbons prepared using Catalyst Sample 1 through Catalyst Sample 5 as described above are as follows: As the catalyst sample 1 to the catalyst sample 5 (that is, the silica ratio becomes higher), the carbon monoxide conversion gradually increases And the ratio of C5 + gradually increased, tends to decrease in the catalyst sample 5, and the selectivity of the hydrocarbon in the catalyst sample 4 is relatively low. As a result, the carbon monoxide conversion and the hydrocarbon selectivity It can be seen that catalyst sample 2 and catalyst sample 3, which are relatively high and have a high ratio of C5 +, are the most suitable combination.

In this way, the gamma-alumina (γ-Al 2 O 3) 40-80 % by weight of silica (SiO 2) using a mixed catalyst support added to a 20-60% by weight of the reaction gas from the Fischer-Tropsch synthesis reactor to a support It is preferable to carry out the reaction at a temperature of 250-350 DEG C and a pressure of 15-25 bar for 58-62 hours while adjusting the volume ratio of hydrogen and carbon monoxide to 2: 1.

On the other hand, the Fischer-Tropsch synthesis reaction can be carried out under different pressure conditions, at a pressure of 35-45 bar at 250-350 ° C for 58-62 hours, and the reaction of n-HEXANE with the reaction gas Can be injected at a molar ratio of 1: 1. Here, the reaction gas can be adjusted to have a volume ratio of 2: 1 by using hydrogen (H 2 ) and carbon monoxide (CO) as reaction gases as described above.

Using a mixed support catalyst prepared by mixing, molding, drying and sintering powders of 1 kg of iron (Fe), 100 g of copper (Cu), 200 g of potassium (K) and 5 kg of a support under different pressure conditions as described above, There results of the synthesis reaction is shown in Figure 3b, gamma-alumina (γ-Al 2 O 3) : silica weight% ratio of 100 (SiO 2): and the zero-catalyst sample 1 the carbon monoxide conversion rate 93.1135, CO The selectivity and selectivity for hydrocarbons are 40.3265 and 59.6735, respectively.

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 22.56 for C1, 20.31 for C2-C4 and 57.13 for C5 +.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 75: 25 The catalyst sample 2, the carbon monoxide conversion rate is 92.3684, and the carbon dioxide selectivity and a hydrocarbon selected that each 42.1598 and 57.8402 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 18.56 for C1, 16.59 for C2-C4 and 64.85 for C5 +.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 50: 50 A catalyst of sample 3, the carbon monoxide conversion rate is 82.56, and the carbon dioxide selectivity and is a hydrocarbon selected that respectively 49.88 and 50.12 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 6.992 for C1, 9.74 for C2-C4, and 83.27 for C5 +.

On the other hand, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 25: 75 The catalyst sample 4, a carbon monoxide conversion rate is 80.56, the carbon dioxide selectivity and a hydrocarbon selectivity of which each 59.63 and 40.37 .

The distribution of hydrocarbons in this catalyst sample 1 is shown to be 4.21 for C1, 3.06 for C2-C4 and 65.19 for C5 +.

In addition, gamma-alumina (γ-Al 2 O 3) : The weight percent ratio of silica (SiO 2) 0: 100 A catalyst sample 5, the carbon monoxide conversion rate is 55.69, and is a carbon dioxide selectivity and a hydrocarbon selected that respectively 24.71 and 75.29 .

The distribution of hydrocarbons in this catalyst sample 1 is found to be 13.88 for C1, 11.03 for C2-C4 and 75.09 for C5 +.

The carbon monoxide conversion and yield of liquid hydrocarbons prepared under different pressure conditions using catalyst sample 1 to catalyst sample 5 as described above will be described. From catalyst sample 1 to catalyst sample 5 (that is, the silica ratio becomes higher), carbon monoxide The conversion rate gradually decreased, and the ratio of C5 + gradually increased, tending to decrease in the catalyst sample 4 and the catalyst sample 5, and the selectivity of hydrocarbon in the catalyst sample 4 was relatively low. , Catalyst sample 2 and catalyst sample 3 having relatively high carbon monoxide conversion and hydrocarbon selectivity and high C5 + ratio are the most suitable combination.

Thus, gamma-alumina as a support (γ-Al 2 O 3) 40-80 % by weight of silica (SiO 2) using a mixed catalyst support added to a 20-60% by weight of normal hexane in the Fischer-Tropsch synthesis reactor ( n-HEXANE) at a molar ratio of 1: 1 to the reaction gas at a pressure of 35-45 bar at 250-350 캜 for 58-62 hours.

Therefore, the present invention uses a catalyst of iron series which is obtained by mixing a co-catalyst containing copper and potassium and a support containing gamma-alumina and silica in a Fischer-Tropsch synthesis reaction, thereby ensuring stable catalytic activity for a long period of time, And the yield of liquid hydrocarbons can be improved.

Further, the present invention uses copper and potassium as co-catalysts to be added to the iron catalyst and adjusts the ratio of silica and gamma-alumina to be used as a support, thereby ensuring stable catalytic activity for a long period of time and increasing the conversion rate of carbon monoxide, 2 ), the selectivity of C1 and C2-C4 is lowered, and the selectivity of C5 + is increased.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be readily apparent that such substitutions, modifications, and alterations are possible.

Claims (17)

Iron consisting of (Fe), copper (Cu), potassium (K) catalyst and a gamma-alumina (γ-Al 2 O 3) and silica mixed support catalyst for the Fischer-Tropsch synthesis reaction in which the support is a mixture consisting of (SiO 2) .
The method according to claim 1,
Wherein 0.05 to 0.15 part by weight of copper (Cu), 0.15 to 0.25 part by weight (K) of potassium (K) are contained in the iron (Fe), copper (Cu), potassium And 4.5-5.5 parts by weight of the support.
The method according to claim 1,
The support, the gamma-alumina (γ-Al 2 O 3) 40-80% by weight and a silica (SiO 2) 20-60% by weight of a Fisher added to Tropsch synthesis reaction mixture for the catalyst support.
The method according to claim 2 or 3,
Wherein the mixed support catalyst for Fischer-Tropsch synthesis reaction is formed by mixing powder of each component.
The method according to claim 1,
Wherein said gamma alumina and silica have a specific surface area of 200-300 m 2 / g, respectively.
The method according to claim 1,
The Fischer-Tropsch synthesis catalyst support had a Fischer-Tropsch synthesis reaction with a BET surface area of 155-170 m 2 / g, a pore volume of 0.4-0.5 cm 3 / g and an average pore diameter of 7-11 nm Mixed support catalyst.
Iron (Fe), copper (Cu), potassium (K) catalyst and a gamma-alumina consisting of (γ-Al 2 O 3) and silica (SiO 2) for mixing the support catalyst is the support is a mixture consisting of a Fischer-Tropsch synthesis reactor ,
Reducing the mixed support catalyst using hydrogen (H 2 )
Performing a Fischer Tropsch synthesis reaction using the mixed support catalyst reduced with hydrogen (H 2 ) and carbon monoxide (CO) as reaction gases
≪ / RTI > wherein the mixed catalyst support comprises a mixed support catalyst for a Fischer Tropsch synthesis reaction.
8. The method of claim 7,
Wherein 0.05 to 0.15 part by weight of copper (Cu), 0.15 to 0.25 part by weight (K) of potassium (K) are contained in the iron (Fe), copper (Cu), potassium And 4.5-5.5 parts by weight of the support.
8. The method of claim 7,
The support may be prepared by mixing liquid hydrocarbons using a mixed support catalyst for Fischer-Tropsch synthesis reaction added with 40-80 wt% of γ-Al 2 O 3 and 20-60 wt% of silica (SiO 2 ) Lt; / RTI >
9. The method of claim 8,
Wherein the mixed support catalyst is prepared by mixing powders of respective components, and a mixed support catalyst for a Fischer-Tropsch synthesis reaction is used for producing liquid hydrocarbons.
8. The method of claim 7,
Wherein the gamma alumina and silica are prepared by using a mixed support catalyst for Fischer-Tropsch synthesis reaction having a specific surface area of 200-300 m 2 / g, respectively.
8. The method of claim 7,
The mixed support catalysts were prepared by using a mixed support catalyst for Fischer-Tropsch synthesis reaction having a BET surface area of 155-170 m 2 / g, a pore volume of 0.4-0.5 cm 3 / g and an average pore diameter of 7-11 nm A method for producing liquid hydrocarbons.
13. The method according to any one of claims 7 to 12,
Wherein the reducing is performed at 250-350 < 0 > C for 8-12 hours.
13. The method according to any one of claims 7 to 12,
Wherein the step of performing the Fischer Tropsch synthesis reaction comprises performing a reaction at a temperature of 250-350 DEG C and a pressure of 15-25 bar for 58-62 hours to prepare a liquid hydrocarbon using a mixed support catalyst for a Fischer Tropsch synthesis reaction.
15. The method of claim 14,
Wherein the Fischer-Tropsch synthesis reaction is carried out using a mixed support catalyst for a Fischer-Tropsch synthesis reaction wherein the volume ratio of hydrogen and carbon monoxide is 2: 1.
13. The method according to any one of claims 7 to 12,
Wherein the step of performing the Fischer-Tropsch synthesis reaction comprises performing a reaction at a temperature of 250-350 DEG C at a pressure of 35-45 bar for 58-62 hours to prepare a liquid hydrocarbon using a mixed support catalyst for a Fischer-Tropsch synthesis reaction.
17. The method of claim 16,
The step of performing the Fischer-Tropsch synthesis reaction comprises preparing a liquid hydrocarbon using a mixed support catalyst for a Fischer-Tropsch synthesis reaction in which normal hexane (n-HEXANE) is injected at a molar ratio of 1: 1 to the reaction gas Way.
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