Catalyst, method for producing the same, and method for producing liquid fuel

Abstract

To improve a yield of carbon hydride of 5C or more to be produced by using carbon monoxide and hydrogen as raw materials.SOLUTION: A catalyst contains a metallic compound having activity on a Fischer-Tropsch synthetic reaction, has a metal-based catalyst generating carbon hydride from synthetic gas, and a carrier catalyst containing zeolite carrying the metal-based catalyst, and can produce carbon hydride from synthetic gas. The metallic compound contains Co and at least one kind of metal selected from a group consisting of Mn and Ru, a carrying amount of Mn is 1-3 wt.%, a carrying amount of Ru is 0.5-2 wt.%, and a carrying amount of Co is 10-30 wt.%. Zeolite includes zeolite having pores for dissolving chains of generated carbon hydride, the pore is a meso fine pore whose aperture diameter is 2 nm or more and 50 nm or less, and a ratio of Si to Al in zeolite is 2.5 or more and 3.5 or less.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a catalyst, a method for producing the same, and a method for producing a liquid fuel. In particular, the present invention relates to a catalyst for reacting a mixed gas of carbon oxide and hydrogen to produce a liquid fuel, a method for producing the same, and a method for producing a liquid fuel from carbon oxide using this catalyst, and is suitable for application thereto.

Background Art

[0002] In recent years, research and development have been actively conducted to improve the selectivity of target products by controlling complex reaction pathways using a synthesis technique by the Fischer-Tropsch (FT) method for synthesizing liquid hydrocarbons from carbon monoxide (CO) and hydrogen (H2). In addition to cobalt (Co), which is the main catalyst for improving the selectivity of conventional target products, techniques for adding oxide-based promoters and second metal promoters have been proposed (see, for example, Patent Documents 1 and 2).

[0003] In addition, a technique for synthesizing a liquid fuel in one step from synthesis gas, which is a mixed gas of carbon monoxide and hydrogen, without a secondary hydrogenation purification process using a modified mesoporous zeolite cobalt catalyst has been proposed (see, for example, Non-Patent Document 1).

[0004] In Non-Patent Document 1 described above, as a catalyst, a catalyst in which cations in mesopores are lanthanum (La) or potassium (K) and the supported amount of cobalt (Co) is 15% by weight is used for a Y-type zeolite support having mesopores. Such a catalyst has activity in the Fischer-Tropsch synthesis reaction and is called an FT synthesis catalyst for producing hydrocarbon-based liquid fuels.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] [Non-Patent Document 1] ”Integrated tuneable synthesis of liquid fuels via Fischer-Tropsch technology”, Jie Li et al, Nature Catalysis volume 1, pages787-793 (2018) [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] When producing a liquid fuel containing hydrocarbons having 5 to 20 carbon atoms from synthesis gas containing hydrogen (H2) and carbon monoxide (CO) using the above-described FT synthesis catalyst, the selectivity of the liquid fuel is high, but there is a problem that the carbon monoxide conversion rate (hereinafter referred to as CO conversion rate) is low. When the CO conversion rate is low, the yield derived from the product of the conversion rate and the selectivity is low. Therefore, there has been a demand for a highly active catalyst capable of improving the yield of a liquid product composed of hydrocarbons having 5 or more carbon atoms.

[0008] The present invention has been made in view of the above, and an object thereof is to provide a catalyst and a method for producing the same, which can improve the yield of hydrocarbons having 5 or more and 20 or less carbon atoms produced from carbon monoxide and hydrogen as raw materials, and a method for producing a liquid fuel. [Means for Solving the Problems]

[0009] (1) In order to solve the above-described problems and achieve the object, a catalyst according to one aspect of the present invention contains a metal compound having activity in the Fischer-Tropsch synthesis reaction, and is a metal-based catalyst for producing hydrocarbons from synthesis gas and a supported catalyst including zeolite supporting the metal-based catalyst, and is a catalyst capable of producing hydrocarbons from synthesis gas, wherein the metal compound includes cobalt and at least one metal selected from the group consisting of manganese and ruthenium.

[0010] (2) The catalyst according to one aspect of the present invention is characterized in that, in the invention of (1) above, the supported amount of the manganese is 1 wt% or more and 3 wt% or less in the invention of (1) above.

[0011] (3) The catalyst according to one aspect of the present invention is characterized in that, in the invention of (1) or (2) above, the supported amount of the ruthenium is 0.5 wt% or more and 2 wt% or less in the invention of (1) or (2) above.

[0012] (4) The catalyst according to one aspect of the present invention is characterized in that, in any one of the inventions of (1) to (3) above, the supported amount of the cobalt is 10 wt% or more and 30 wt% or less in any one of the inventions of (1) to (3) above.

[0013] (5) The catalyst according to one aspect of the present invention is characterized in that, in any one of the inventions of (1) to (4) above, the zeolite includes zeolite having pores that decompose the carbon chain of the produced hydrocarbons, and the pores are mesopores having a pore diameter of 2 nm or more and 50 nm or less in any one of the inventions of (1) to (4) above.

[0014] (6) The catalyst according to one aspect of the present invention is characterized in that, in the inventions of (1) to (5) above, the molar ratio of silicon to aluminum in the zeolite is 2.5 or more and 3.5 or less in the inventions of (1) to (5) above.

[0015] (7) The method for manufacturing a catalyst according to one aspect of the present invention is a method for manufacturing a catalyst by the invention of any one of (1) to (6) above, and includes a pore formation step of forming mesopores in the supported catalyst, and a catalyst support step of supporting the metal compound on the supported catalyst, wherein the catalyst support step includes a step of supporting, on the supported catalyst, a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium.

[0016] (8) The method for manufacturing a catalyst according to one aspect of the present invention is the invention of (7) above, wherein the catalyst support step includes a melt impregnation step of melt impregnating, on the supported catalyst, a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium.

[0017] (9) The method for manufacturing a catalyst according to one aspect of the present invention is the invention of (8) above, wherein the melt impregnation step is a step of supporting the metal compound containing cobalt on the supported catalyst by the melt impregnation method and then supporting at least one of the metal compound containing manganese and the metal compound containing ruthenium by the melt impregnation method.

[0018] (10) The method for manufacturing a catalyst according to one aspect of the present invention is the invention of (8) above, wherein the melt impregnation step is a step of substantially simultaneously supporting, on the supported catalyst, the metal compound containing cobalt and at least one of the metal compound containing manganese and the metal compound containing ruthenium by the melt impregnation method.

[0019] (11) The method for manufacturing a catalyst according to one aspect of the present invention is the invention of (7) above, wherein the catalyst support step includes an impregnation step of impregnating, after supporting the metal compound containing cobalt on the supported catalyst by the impregnation method, the supported catalyst on which cobalt is supported into at least one of a solution containing manganese and a solution containing ruthenium to impregnate the supported catalyst and the supported catalyst supported on the supported catalyst.

[0020] (12) The method for producing a catalyst according to one aspect of the present invention is, in the invention of (7) above, wherein the catalyst supporting step includes impregnating the supported catalyst with a metal compound containing cobalt by an impregnation method, and immersing the supported catalyst and at least one of the supported catalysts supported on the supported catalyst in at least one of a solution containing manganese and a solution containing ruthenium.

[0021] (13) The method for producing a catalyst according to one aspect of the present invention is, in the invention of (7) above, wherein the catalyst supporting step includes a melt impregnation step of melt impregnating the supported catalyst with a metal compound containing cobalt, and an impregnation step of immersing the supported catalyst having the metal compound containing cobalt supported thereon in at least one of a solution containing manganese and a solution containing ruthenium to impregnate at least one of the supported catalyst and the supported catalysts supported on the supported catalyst.

[0022] (14) The method for producing a catalyst according to one aspect of the present invention is, in any one of the inventions of (7) to (13) above, wherein the supported catalyst is previously cationized or cationized by a cation exchange step using an ion exchange method performed before the catalyst supporting step.

[0023] (15) The method for producing a catalyst according to one aspect of the present invention is, in the invention of (14) above, wherein the cation is at least one cation selected from the group consisting of lanthanum, potassium, lithium, sodium, and cerium.

[0024] (16) The method for producing a liquid fuel according to one aspect of the present invention is to produce a liquid fuel composed of hydrocarbons from synthesis gas by a Fischer-Tropsch synthesis reaction using the catalyst according to any one of the inventions of (1) to (6) above.

Advantages of the Invention

[0025] According to the catalyst, its manufacturing method, and the method for manufacturing a liquid fuel according to the present invention, it is possible to improve the yield of hydrocarbons having 5 to 20 carbon atoms produced from carbon monoxide and hydrogen as raw materials.

Brief Description of the Drawings

[0026]

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Mode for Carrying Out the Invention

[0027] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Note that the present invention is not limited by the embodiment described below. First, in describing an embodiment of the present invention, for the sake of easy understanding of the present invention, the experiments and intensive studies conducted by the present inventors to solve the above problems will be described.

[0028] First, the present inventors examined the problems regarding a catalyst (Co - supported FT synthesis catalyst) in which cobalt (Co) as a metal catalyst was supported on mesopores subjected to cation exchange treatment using Y - type mesoporous zeolite as a support catalyst, which is used as a conventional Fischer - Tropsch (FT) synthesis catalyst. Note that mesopores are pores having a pore diameter of 2 nm or more and 50 nm or less, and having a peak in the range of 10 nm or more and 20 nm or less.

[0029] That is, according to the findings of the present inventors, using the above - described Co - supported Y - type mesoporous zeolite catalyst, hydrocarbons having 5 to 20 carbon atoms (C n H 2n+2) To improve the yield in producing a liquid fuel composed of, increasing the supported amount of cobalt (Co) (also referred to as the catalyst amount) is not preferable because it may block mesopores. Therefore, the present inventor conducted studies on various metal catalysts other than Co and came up with the idea of adding a highly active catalyst. According to the studies of the present inventor, in order to improve the yield of a liquid fuel composed of hydrocarbons having 5 to 20 carbon atoms by adding a highly active metal catalyst, it is desirable to add manganese (Mn) as the metal catalyst. In other words, the present inventor came up with the idea of using a compound containing Co and Mn, which are metal compounds having activity in the Fischer-Tropsch synthesis reaction, as a metal-based catalyst for producing hydrocarbons from synthesis gas containing carbon (C) and hydrogen (H2). Further, as the support catalyst for supporting these Co and Mn, it was found that the zeolite studied is preferable, and particularly Y-type zeolite having mesopores is preferable. Furthermore, from the experiments conducted by the present inventor, it was found that the supported amount of Mn is preferably 1 wt% or more and 3 wt%, more preferably 1.5 wt% or more and 2.5 wt% or less, and the optimum value is preferably about 2.0 wt%.

[0030] When the present inventor produced a liquid fuel using the Co-supported FT synthesis catalyst (MnCo-supported FT synthesis catalyst) with added Mn as described above, it was found that the CO conversion rate did not improve significantly. Therefore, the present inventor conducted further studies, conducted various experiments and intensive studies on metal catalysts capable of improving the CO conversion rate, and came up with a method of adding ruthenium (Ru) to the Co-supported FT synthesis catalyst. When the present inventor conducted an experiment on producing hydrocarbons from synthesis gas using the Co-supported FT synthesis catalyst supporting Ru (RuCo-supported FT synthesis catalyst), it was confirmed that the production of hydrocarbons improved throughout the entire range of carbon numbers and the CO conversion rate improved. Further, as the support catalyst for supporting these Co and Ru, it was found that the zeolite studied is preferable, and particularly Y-type zeolite having mesopores is preferable. Furthermore, from the experiments conducted by the present inventor, it was found that the supported amount of Ru is preferably 0.5 wt% or more and 2.0 wt%, more preferably 0.5 wt% or more and 1.5 wt% or less, and the optimum value is preferably about 1.0 wt%.

[0031] The inventor further advanced the above studies and examined a Co-supported FT synthesis catalyst (RuMnCo-supported FT synthesis catalyst) with the addition of both Mn and Ru, and intensively studied the conditions for maximizing the yield and its effects. When the inventor produced liquid fuel from synthesis gas using the RuMnCo-supported FT synthesis catalyst, it was confirmed that the yield of the liquid fuel was significantly improved. On the other hand, the inventor found that under the conditions for maximizing the yield of hydrocarbons (maximum yield conditions), wax consisting of hydrocarbons with a carbon number exceeding 20 was generated and coated and deposited on the FT synthesis catalyst, and over time, the CO conversion rate decreased.

[0032] The inventor also studied the reduction of wax and came up with an idea to increase hydrocarbons with a small carbon number n to reduce the amount of wax generated. The inventor studied the method for increasing hydrocarbons with a small carbon number and adjusted the ratio of silicon (Si) to aluminum (Al) in zeolite (hereinafter referred to as Si / Al ratio) to strengthen the acid sites on the surface layer, improve the cracking power, decompose the carbon chain, and shift the carbon number distribution to a small carbon number, thereby suppressing the generation of wax in the production of hydrocarbons. Focusing on the amount of wax generated, when the inventor conducted experiments, it was found that as the Si / Al ratio of zeolite, on average for the whole zeolite, typically 2.5 or more and 3.5 or less, preferably 2.7 or more and 3.1 or less, more preferably 2.84 or more and 3.03 or less, and the optimum value is preferably about 2.94.

[0033] Based on the above studies, the inventor came up with an idea that as a metal compound supported on the FT synthesis catalyst, it is preferable to contain cobalt and at least one metal selected from the group consisting of manganese and ruthenium. Also, the inventor came up with an idea to adjust the hydrocarbon distribution by adjusting the Si / Al ratio of zeolite in the range of 2.5 to 3.5. The present invention was devised based on the above intensive studies by the inventor.

[0034] (Examples of Support Catalysts) First, the support catalyst used in the FT synthesis catalyst according to the present embodiment is used as a hydrogenation catalyst and is composed of zeolite, that is, aluminosilicate. In the present embodiment, it is preferably composed of Y-type zeolite. If zeolite is provided on the surface layer, as the support, the intermediate material between the support, and the binder material, activated carbon, silicon carbide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, or a mixture thereof may be included.

[0035] (Method for Manufacturing Catalyst) Next, a method for manufacturing an FT synthesis catalyst, which is a catalyst according to an embodiment devised through the above-mentioned intensive studies, will be described. FIG. 1 is a flowchart for explaining the method for manufacturing an FT synthesis catalyst according to an embodiment.

[0036] As shown in FIG. 1, in the method for manufacturing a catalyst according to an embodiment, first, as a raw material, for example, microporous zeolite powder (manufactured by Tosoh Corporation) composed of Y-type zeolite is prepared. Here, Y-type zeolite with a mass of, for example, 6.7 g, an Si / Al ratio of 2.8, and sodium (Na) ions incorporated in the molecular framework is used. In addition, L-type zeolite can also be used as the zeolite.

[0037] In step ST1, by performing EDTA treatment on Y-type zeolite, mesopores are formed in the zeolite (pore formation step). Also, by desorbing Al from Y-type zeolite, the Si / Al ratio of Y-type zeolite can be increased. Specifically, in step ST1, 6.7 g of zeolite powder is mixed with an EDTA (ethylenediaminetetraacetic acid) aqueous solution having a concentration of 0.07 mol / L and a volume of 100 ml. Next, it is refluxed in a container such as a flask and stirred at a temperature of 100 °C (373 K) for 6 hours. Note that the amount of desorbed Al can be adjusted by adjusting the time of EDTA treatment, so the Si / Al ratio of zeolite can be adjusted. Thereafter, the solid powder is filtered and dried, for example, in an air dryer at 120 °C for 12 hours.

[0038] Next, proceed to step ST2, and perform an alkali treatment, such as sodium hydroxide (NaOH) treatment, on the Y-type zeolite with mesopores formed to expand the mesopores (pore expansion step). Also, by desorbing Si from the Y-type zeolite, the Si / Al ratio of the Y-type zeolite can be decreased. Specifically, for example, in step ST2, the solid powder of the Y-type zeolite is mixed with an aqueous NaOH solution having a concentration of 0.4 mol / L and a volume of 50 ml. Next, the mixture is stirred at a temperature of, for example, 61 °C (338 K) for 30 minutes (0.5 hour).

[0039] Thereafter, proceed to step ST3, and separate the powder in about 5 minutes using a centrifuge with a rotation speed of, for example, 9000 rpm, and perform a drying treatment for 12 hours using an air dryer at 120 °C. As a result, a Y-type mesoporous zeolite (hereinafter, Y meso ) carrier is obtained.

[0040] Next, proceed to step ST4, and perform a cation exchange treatment using, for example, lanthanum (La) as a cation on the Y-type mesoporous zeolite carrier in which sodium (Na) has been previously incorporated as a cation by an ion exchange method (cation exchange step). Note that, in addition to La, potassium (K), lithium (Li), cerium (Ce), etc. can also be used as the cation. Specifically, for example, in step ST4, 1.0 g of the Y-type mesoporous zeolite carrier is mixed with a lanthanum nitrate solution having a concentration of 0.2 mol / L and a volume of 100 ml. Next, the mixture is stirred at a temperature of 80 °C (353 K) for 12 hours to perform the cation exchange treatment. Thereafter, powder separation is performed on the mixture by centrifugation, and a calcination treatment is performed at a temperature of 550 °C (823 K) for 6 hours in an atmospheric pressure atmosphere, whereby a powder of the Y-type mesoporous zeolite La (hereinafter, Y meso -La) carrier is produced.

[0041] Note that the cation exchange amount is adjusted in the range of 0.1% or more and 10% or less depending on temperature and time conditions, and is typically about 1%. Further, in this embodiment, the cation exchange process has been described in the case of using zeolite in which Na is previously incorporated as a cation. However, it is not limited to the case where cations are previously incorporated, and cations may be incorporated into zeolite in which no cations are incorporated.

[0042] Next, proceed to step ST5, and the generated Y meso -La carrier is subjected to a metal catalyst supporting treatment, for example, by a melt impregnation method (catalyst supporting step). Specifically, for example, cobalt nitrate (Co(NO3)2·6H2O), at least one of manganese nitrate (Mn(NO3)2) and ruthenium nitrate (Ru(NO3)3), and Y meso -La carrier powder are kneaded, for example, for 30 minutes (0.5 hour). Then, for example, the kneaded product is put into a container such as a glass bottle and sealed, and melt impregnated at a temperature of 50°C (333K) for 48 hours (melt impregnation step). As a result, a metal compound of at least one of Co, Mn, and Ru is impregnated into the mesopores of the Y meso -La carrier. Note that it is also assumed that the mesopores are shallow or supported on the surface of the mesopores, and Co is exposed from the mesopores. In this case, it is considered that Mn or Ru is supported on the surface and surroundings of the exposed Co.

[0043] Here, the supported amount of Co is, for example, 15% by weight, the supported amount of Mn is, for example, 2% by weight, and the supported amount of Ru is, for example, 1% by weight. Note that the supported amount is the ratio of the mass of the metal in the metal compound having activity in the FT synthesis reaction to the total mass of the catalyst (the total mass of the catalyst for producing hydrocarbons from synthesis gas), assuming that the metal compound having activity in the FT synthesis reaction is finally not completely reduced but is completely reduced.

[0044] After the metal catalyst loading treatment in step ST5, the process proceeds to step ST6 where drying and calcination treatments are performed. As the calcination treatment, for example, nitrogen (N2) gas is passed through at a temperature of 400 °C (673 K) and a flow rate of 40 mL / min for 4 hours to desorb nitrogen (N) and convert it into cobalt oxide, manganese oxide, or ruthenium oxide. This results in an MnCo-supported FT synthesis catalyst (Mn-Co / Y meso -La catalyst), a RuCo-supported FT synthesis catalyst (Ru-Co / Y meso -La catalyst), or a RuMnCo FT synthesis catalyst (Ru-Mn-Co / Y meso -La catalyst). In the ion exchange treatment in step ST4, when potassium (K) is used as the cation, an MnCo-supported FT synthesis catalyst (Mn-Co / Y meso -K catalyst), a RuCo-supported FT synthesis catalyst (Ru-Co / Y meso -K catalyst), or a RuMnCo FT synthesis catalyst (Ru-Mn-Co / Y meso -K catalyst), etc. can be obtained. Also, when other cations such as cerium (Ce) are used as the cation, the "-La" or "-K" parts in each FT synthesis catalyst are replaced by "-Ce" or other cations.

[0045] Thereafter, if necessary, the process proceeds to step ST7, and the physical properties of the FT synthesis catalyst are confirmed by checking the physical properties of the product, for example, by X-ray diffraction or gas chromatography. Specifically, in order to evaluate the reactivity of the catalyst, after filling the produced FT synthesis catalyst into, for example, a tubular reactor, a reduction treatment is carried out by flowing hydrogen gas at a temperature of 400 °C. Thereafter, under the conditions where the temperature is 250 °C and the pressure is 2.0 MPa, synthesis gas is adjusted so that the catalyst mass W (W / F) with respect to the synthesis gas flow rate F becomes, for example, 10 g h / mol, and then brought into contact with the FT synthesis catalyst. Individually, the ratio of hydrogen (H2) to carbon monoxide (CO) in the synthesis gas is set to be from 1 to 2 (H2 / CO = 1 to 2). The compositions of the supplied synthesis gas and the gas discharged from the outlet of the tubular reactor are determined, for example, by gas chromatography (GC method), and the CO conversion rate, CH4 selectivity, selectivity of hydrocarbons having 5 or more carbon atoms (C5+ selectivity), and productivity of liquid hydrocarbons are measured.

[0046] (Modification Example of Metal Catalyst Support Treatment Method) Next, an impregnation method (Impregnation: IM method), which is a modification example of the catalyst support treatment method in step ST5 described above, will be described. FIG. 2 is a flowchart showing the metal catalyst support treatment method according to the modification example.

[0047] That is, in step ST11, cobalt nitrate (Co(NO3)2·6H2O) as a metal compound is melt-impregnated into the powder of the Y meso -La support by the above-described melt impregnation method. In addition to the melt impregnation method, an impregnation method may also be used.

[0048] Thereafter, the process proceeds to step ST12, and a calcination treatment is carried out. As a result, a Co-supported FT synthesis catalyst (Co / Y meso -La catalyst) is obtained. The supported amount of Co is, for example, 15% by weight. Next, the process proceeds to step ST13, and the CO / Y obtained by the calcination treatment mesoImmerse the powder of the -La catalyst in at least one of a manganese nitrate (Mn(NO3)2) solution and a ruthenium nitrate (Ru(NO3)3) solution for impregnation. As a result, at least one of Mn and Ru corresponding to the solution is impregnated into the support catalyst having mesopores and the supported catalyst supported on the support catalyst. Note that the melt impregnation method and the impregnation method may be carried out in parallel.

[0049] Thereafter, proceed to step ST6, and as a firing treatment, for example, by flowing nitrogen (N2) gas at a temperature of 400 °C (673 K) and a flow rate of 40 mL / min for 4 hours, nitrogen (N) is desorbed to obtain cobalt oxide, manganese oxide, or ruthenium oxide. Thus, an MnCo-supported FT synthesis catalyst (Mn-Co / Y meso -La catalyst), an RuCo-supported FT synthesis catalyst (Ru-Co / Y meso -La catalyst), or an RuMnCo FT synthesis catalyst (Ru-Mn-Co / Y meso -La catalyst) is obtained. When these catalysts are collectively referred to, they are called FT synthesis catalysts.

[0050] (Method for producing hydrocarbons) Next, a method for producing hydrocarbons using the FT synthesis catalyst produced as described above, particularly a method for producing a liquid fuel such as jet fuel, will be described. In the method for producing hydrocarbons according to the present embodiment, it is the same as the conventional method for producing a liquid fuel except that a Y-type mesoporous zeolite catalyst supporting at least one of Co, Mn, and Ru described above is used as the FT synthesis catalyst.

[0051] That is, first, hydrogen (H2) gas and carbon monoxide (CO) gas are generated from methane (CH4), water (H2O), oxygen (O2), and carbon dioxide (CO2) in a synthesis gas production process. Next, hydrocarbons (C n H 2n+2 ) are generated from the synthesis gas by the Fischer-Tropsch synthesis method (also referred to as the FT method or the Fischer-Tropsch synthesis reaction method) using the above-described FT synthesis catalyst.

[0052] Subsequently, through the upgrading process, various liquid hydrocarbons are separated and purified into lower olefins (carbon number n = 2 - 4: C2 - C4), naphtha (carbon number n = 5 - 10: C5 - C10), kerosene (carbon number n = 10 - 14: C10 - C14), gas oil (carbon number n = 14 - 20: C14 - C20), wax (carbon number n > 20: C20+), etc. Note that as jet fuel, hydrocarbons with a carbon number n of 8 - 16 (C8 - C16) are mainly used. Also, as liquid fuel, hydrocarbons with a carbon number n of 5 - 20 (C5 - C20) are mainly used. Thus, by the FT process using an FT synthesis catalyst, liquid fuel containing liquid hydrocarbons is produced.

[0053] (Effect of the addition of Mn to the FT synthesis catalyst) Next, the effects of the FT synthesis catalyst produced as described above will be explained. Figures 3 and 4 are graphs showing the hydrocarbon distribution for each catalyst in the generated hydrocarbons to explain the effect of adding manganese (Mn) in the catalyst according to this embodiment. Note that the hydrocarbon distribution in Figures 3 and 4 shows the distribution when hydrocarbons are generated from synthesis gas with an H2 / CO ratio of 2.0 (H2 / CO = 2.0). Also, in the graphs shown in Figures 3 and 4, "Co / Y meso -La" is a Co-supported Y-type mesoporous zeolite La catalyst, that is, a Co / Y meso -La catalyst, which is an FT synthesis catalyst ion-exchanged with La as a cation. Similarly, "Mn-Co / Y meso -La" represents an MnCo-supported Y-type mesoporous zeolite La catalyst, which is an FT synthesis catalyst further supported with Mn. Furthermore, "Mn-Co / Y meso -La-IM" represents an FT synthesis catalyst in which Mn and Co are impregnated and supported by the IM method shown in Figure 2. The same applies to other graphs.

[0054] First, "Co / Y meso -La" in Figure 3 and "Co / Y meso"-K" is an FT synthesis catalyst described in Non-Patent Document 1 as prior art. In this prior art, as described in Non-Patent Document 1, under the condition where the H2 / CO ratio is 1.0 (H2 / CO = 1.0), in a liquid fuel composed of hydrocarbons having 5 to 20 carbon atoms, the selectivity is as high as 72 to 86%, while the CO conversion rate is extremely low at 30 to 40%. When synthesis is carried out under the condition where the H2 / CO ratio is 2.0 (H2 / CO = 2.0) to increase the CO conversion rate, as shown in Figure 3, in "Co / Y meso -La", the CO conversion rate is 62% and in a liquid fuel composed of hydrocarbons having 5 to 16 carbon atoms, the selectivity is 55%. Also, as shown in Figure 4, in "Co / Y meso -K", the CO conversion rate is 78% and in a liquid fuel composed of hydrocarbons having 5 to 16 carbon atoms, the selectivity is 66%.

[0055] In contrast, in the above-described embodiment, from "Mn-Co / Y meso -La" and "Mn-Co / Y meso -La-IM" shown in Figure 3, under the condition where the H2 / CO ratio is 2.0 (H2 / CO = 2.0), in a liquid fuel composed of hydrocarbons having 5 to 20 carbon atoms, the selectivity is 60 to 71% and it can be seen that the CO conversion rate is significantly improved to 75 to 88%. Also, from "Mn-Co / Y meso -K" and "Mn-Co / Y meso -K-IM" shown in Figure 4, under the condition where the H2 / CO ratio is 2.0 (H2 / CO = 2.0), the CO conversion rate does not change significantly at 72 to 82%, but it can be seen that the selectivity is improved to 71 to 78% in a liquid fuel composed of hydrocarbons having 5 to 20 carbon atoms.

[0056] Therefore, when using the FT synthesis catalyst described in Non-Patent Document 1, under the condition that the H2 / CO ratio is 2.0 (H2 / CO = 2.0), both the CO conversion rate and the selectivity of liquid fuel composed of hydrocarbons with carbon numbers of 5 to 16 were low. In contrast, in the above-described embodiment, from FIGS. 3 and 4, by adding about 2% of Mn, the selectivity of liquid fuel with carbon numbers of 5 to 20 can be increased by 5 to 16 points, and it can be seen that the yield obtained by the product of the selectivity and the CO conversion rate (selectivity × CO conversion rate) increases by 11 to 29 points.

[0057] Also, from FIG. 3, in the FT synthesis catalyst on which the metal catalyst is supported by the IM method (see FIG. 2), compared with the FT synthesis catalyst on which the metal catalyst is supported by the melt impregnation method, it can be seen that the selectivity of hydrocarbons with carbon number n of 5 or more (C5+) increases from 60% to 71%. Similarly, it can be seen that the CO conversion rate also improves from 75% to 88%. Further, from FIG. 4, in the FT synthesis catalyst on which the metal catalyst is supported by the IM method, compared with the FT synthesis catalyst on which the metal catalyst is supported by the melt impregnation method, it can be seen that the selectivity of hydrocarbons with carbon number n of 5 or more (C5+) increases from 71% to 78%. That is, from FIGS. 3 and 4, it can be seen that in the FT synthesis catalyst, by supporting Mn by the IM method, it is possible to improve the selectivity and the CO conversion rate of liquid fuel (C5+).

[0058] Also, FIGS. 5 and 6 are graphs showing the CO conversion rate, selectivity, and yield with respect to the supported amount of manganese in the hydrocarbons produced using the catalyst according to this embodiment. FIG. 5 shows the synthesis gas with an H2 / CO ratio of 1.5 (H2 / CO = 1. 5 )), and FIG. 6 is a graph when using synthesis gas with an H2 / CO ratio of 2.0 (H2 / CO = 2 .0).

[0059] From FIG. 6, it can be seen that by adding Mn as a metal catalyst to the FT synthesis catalyst, the selectivity of hydrocarbons with carbon numbers n of 5 to 16 (C5 - C16) and 8 to 16 (C8 - C16), that is, liquid fuels suitable for jet fuel, is improved without reducing the CO conversion rate. Since the selectivity of hydrocarbons with carbon numbers n of 5 to 16 and 8 to 16 is improved without reducing the CO conversion rate, the yields of hydrocarbons with carbon numbers n of 5 to 16 and 8 to 16 can be improved.

[0060] Also, from FIGS. 5 and 6, it can be seen that as the supported amount of Mn supported on the FT synthesis catalyst, if it is greater than 0 wt% and 3 wt% or less, the CO conversion rate and the selectivity and yield of hydrocarbons with carbon numbers n of 5 to 16 and 8 to 16 can be improved. Further, from FIG. 5, it can be seen that as the supported amount of Mn, preferably, it is 1 wt% or more and 3 wt% or less, and more preferably around 2 wt% such as 1.5 - 2.5 wt% is preferred.

[0061] (Effect of addition of Ru to the FT synthesis catalyst) FIGS. 7 and 8 are graphs showing the hydrocarbon distribution for each catalyst in the generated hydrocarbons to explain the effect of adding ruthenium in the catalyst according to this embodiment. As the synthesis gas, synthesis gas with an H2 / CO ratio of 2.0 (H2 / CO = 2.0) is used. From FIGS. 7 and 8, in this embodiment, by adding Ru to the FT synthesis catalyst (Co / Y meso -K catalyst) according to the prior art, it can be seen that the CO conversion rate can be increased to almost 100% in hydrocarbons with carbon numbers n of 5 to 16 (C5 - C16), that is, in liquid fuels.

[0062] Furthermore, from FIG. 8, by using an FT synthesis catalyst in which both Mn and Ru are added and supported as compared with an FT synthesis catalyst supporting only Ru, the selectivity of liquid fuels with carbon numbers n of 5 to 16 can be improved without reducing the CO conversion rate from slightly less than 100%. That is, according to the Ru - Mn - Co / Y meso -La catalyst according to this embodiment, it can be seen that the yield of liquid fuels with carbon numbers of 5 to 16 can be improved.

[0063] Figure 9 is a graph showing the CO conversion rate, selectivity, and yield with respect to the ruthenium loading in the hydrocarbons produced using the catalyst according to the present embodiment. Figure 9 is a graph for the case where synthesis gas with an H2 / CO ratio of 1.5 (H2 / CO = 1.5) is used.

[0064] From Figure 9, it can be seen that when the Ru as a metal catalyst in the FT synthesis catalyst is increased so that the loadings are 0.5 wt%, 1.0 wt%, and 1.5 wt%, the CO conversion rate can be improved up to a loading of about 1.0 wt%. Also, it can be seen that the CO conversion rate can be maintained at a sufficient value up to 1.5 wt%. That is, it can be understood that the Ru loading is preferably 0.5 wt% or more and 1.5 wt% or less, more preferably around 1.0 wt%.

[0065] (Suppression of wax generation) Figure 10 is a graph showing the CO conversion rate in the produced hydrocarbons, the yield of liquid fuels having 5 to 16 carbon atoms (C5 - C16), and the ratio of waxes C16+ which are hydrocarbons mainly composed of waxes having more than 16 carbon atoms, for each Si / Al ratio of the catalyst according to the present embodiment.

[0066] From Figure 10, in the FT synthesis catalyst, by changing the EDTA treatment time from 0 to 6 hours, the Si / Al ratio of the zeolite is adjusted in the range of 2.5 or more and 3.5 or less (Si / Al ratio = 2.5 - 3.5), preferably 2.7 or more and 3.1 or less (Si / Al ratio = 2.7 - 3.1), more preferably 2.84 or more and 3.03 or less (Si / Al ratio = 2.84 - 3.03), it can be seen that the generation of wax can be controlled. The Si / Al ratio can be adjusted by the EDTA treatment time described above. In particular, from Figure 10, it can be seen that by setting the EDTA treatment to 2 hours and making the Si / Al ratio about 2.94, the generation of wax can be suppressed while achieving high values for the yield and CO conversion rate.

[0067] According to the above-described embodiment, the following advantages are achieved with respect to Patent Documents 1 and 2. That is, the technique described in Patent Document 1 uses a cobalt-based catalyst and a silica (SiO2) catalyst support, and the technique described in Patent Document 2 uses a catalyst containing at least one metal or compound selected from the group consisting of ruthenium (Ru), cobalt (Co), and iron (Fe), and a β-zeolite support having an Si / Al ratio of 13 or more. In contrast, in the above-described embodiment, the difference lies in that a zeolite such as Y-type or L-type with an Si / Al ratio of 10 or less using a cobalt-based catalyst is used as the support. Further, according to the catalyst according to the above-described embodiment, the reactivity and selectivity can be improved with respect to the catalysts described in Patent Documents 1 and 2.

[0068] According to the above-described embodiment, the yield of hydrocarbons having 5 to 20 carbon atoms (C5 to C20), preferably 8 to 16 carbon atoms (C8 to C16), that is, jet fuel, produced from carbon monoxide (CO) and hydrogen (H2) as raw materials can be improved.

[0069] Industrially, a catalyst capable of directly producing a liquid fuel such as jet fuel from carbon monoxide and hydrogen can be provided, and the liquid fuel production technology can be provided efficiently and inexpensively. It has been confirmed that the catalyst according to the above-described embodiment has superior catalyst performance compared to the prior art.

[0070] Although the embodiments of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible. For example, the numerical values given in the above-described embodiments are merely examples, and different numerical values may be used as necessary. Combinations of the components of the above-described embodiments and various modification examples as appropriate are also included in the present invention.

[0071] (Modification Example of Method for Supporting Metal Compound) The method for supporting a metal compound having activity for the FT synthesis reaction on a catalyst support is not limited to the selection and treatment methods of the above-described melting impregnation method and impregnation method. For mass production and reduction of manufacturing costs, by optimizing the manufacturing conditions and methods, it is possible to support only by melting impregnation or only by the impregnation method. Furthermore, it is also possible to support Co, Mn, and Ru in a single treatment.

[0072] That is, the catalyst support step may include a melting impregnation step of melt-impregnating a supported catalyst with a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium. Further, the melting impregnation step may be a step of supporting a metal compound containing cobalt on the supported catalyst by the melting impregnation method and then supporting at least one of a metal compound containing manganese and a metal compound containing ruthenium by the melting impregnation method. Or, the melting impregnation step may be a step of substantially simultaneously supporting a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium on the supported catalyst by the melting impregnation method.

[0073] Furthermore, the catalyst support step may include an impregnation step of immersing the supported catalyst on which cobalt has been supported in at least one of a solution containing manganese and a solution containing ruthenium after supporting a metal compound containing cobalt on the supported catalyst by the impregnation method to impregnate the supported catalyst and the supported catalyst supported on the supported catalyst. Or, the catalyst support step may include an impregnation step of supporting a metal compound containing cobalt on the supported catalyst by the impregnation method and immersing it in at least one of a solution containing manganese and a solution containing ruthenium to impregnate at least one of the supported catalyst and the supported catalyst supported on the supported catalyst. Here, the supported catalyst is a catalyst such as Co, Mn, and Ru supported on the supported catalyst.

[0074] (Supported amount of Co) The loading amount of the metal compound having activity for the FT synthesis reaction on the catalyst support is 5 to 50% by mass. For example, when cobalt (Co) is used, it is preferably 10 to 30% by weight, more preferably 15% by weight. When the loading amount range is less than 10% by weight, the FT synthesis activity cannot be fully expressed. When it exceeds 30% by weight, the zeolite pores are blocked and the utilization efficiency of the supported Co decreases.

[0075] Furthermore, further effects and modifications can be easily derived by those skilled in the art. The broader aspects of the present invention are not limited to the specific details and representative embodiments represented and described as above. Therefore, various changes can be made without departing from the spirit or scope of the general inventive concept defined by the appended claims and their equivalents.

Claims

1. A catalyst capable of producing hydrocarbons from synthesis gas, comprising a metal-based catalyst containing a metal compound having activity for the Fischer-Tropsch synthesis reaction and producing hydrocarbons from synthesis gas, and a supported catalyst including a zeolite supporting the metal-based catalyst, wherein the ratio of silicon to aluminum (Si / Al ratio) in the zeolite is 2.5 or more and 3.5 or less, the zeolite includes a zeolite having pores that decompose the carbon chains of the produced hydrocarbons, the pores are mesopores having a pore diameter of 2 nm or more and 50 nm or less, the metal compound includes cobalt, manganese, and ruthenium, the supported amount of ruthenium is 1.0% by weight characterized in that it is a catalyst.

2. A catalyst capable of producing hydrocarbons from synthesis gas, comprising a metal-based catalyst containing a metal compound having activity for the Fischer-Tropsch synthesis reaction and producing hydrocarbons from synthesis gas, and a supported catalyst including a zeolite supporting the metal-based catalyst, wherein the ratio of silicon to aluminum (Si / Al ratio) in the zeolite is 2.5 or more and 3.5 or less, the zeolite includes a zeolite having pores that decompose the carbon chains of the produced hydrocarbons, the pores are mesopores having a pore diameter of 2 nm or more and 50 nm or less, the metal compound includes cobalt and manganese, the supported amount of manganese is 1.5% by weight or more and 2.5% by weight or less characterized in that it is a catalyst.

3. The supported amount of cobalt is 10% by weight or more and 30% by weight or less characterized in that it is the catalyst according to Claim 1.

4. A method for manufacturing a catalyst for manufacturing the catalyst according to Claim 1, comprising a pore formation step of forming mesopores in the supported catalyst, and a catalyst support step of supporting the metal compound on the supported catalyst, wherein the catalyst support step includes a melt impregnation step of supporting a metal compound containing cobalt on the supported catalyst by a melt impregnation method and then melt impregnating a metal compound containing manganese and a metal compound containing ruthenium characterized in that it is a method for manufacturing a catalyst.

5. A method for manufacturing a catalyst for manufacturing the catalyst according to Claim 1, comprising a pore formation step of forming mesopores in the supported catalyst, and a catalyst support step of supporting the metal compound on the supported catalyst, wherein the catalyst support step The method for producing a catalyst includes a melt impregnation step of simultaneously supporting, on the carrier catalyst, a metal compound containing cobalt, a metal compound containing manganese, and a metal compound containing ruthenium by a melt impregnation method. A method for producing a catalyst, characterized in that.

6. A method for producing a catalyst for producing the catalyst according to claim 1, comprising: a pore forming step of forming mesopores in the carrier catalyst; a catalyst supporting step of supporting the metal compound on the carrier catalyst, wherein the catalyst supporting step includes an impregnation step of impregnating the carrier catalyst on which the metal compound containing cobalt has been supported by an impregnation method into a solution containing manganese and a solution containing ruthenium to impregnate the carrier catalyst and the supported catalyst supported on the carrier catalyst. A method for producing a catalyst, characterized in that.

7. A method for producing a catalyst for producing the catalyst according to claim 1, comprising: a pore forming step of forming mesopores in the carrier catalyst; a catalyst supporting step of supporting the metal compound on the carrier catalyst, wherein the catalyst supporting step includes an impregnation step of impregnating the carrier catalyst with the metal compound containing cobalt by an impregnation method and immersing the carrier catalyst in a solution containing manganese and a solution containing ruthenium to impregnate at least one of the carrier catalyst and the supported catalyst supported on the carrier catalyst. A method for producing a catalyst, characterized in that.

8. A method for producing a catalyst for producing the catalyst according to claim 1, comprising: a pore forming step of forming mesopores in the carrier catalyst; a catalyst supporting step of supporting the metal compound on the carrier catalyst, wherein the catalyst supporting step includes a melt impregnation step of melt impregnating the carrier catalyst with a metal compound containing cobalt; and an impregnation step of impregnating the carrier catalyst on which the metal compound containing cobalt has been supported in the melt impregnation step into a solution containing manganese and a solution containing ruthenium to impregnate at least one of the carrier catalyst and the supported catalyst supported on the carrier catalyst. A method for producing a catalyst, characterized in that.

9. The carrier catalyst is previously cationized or cationized by a cation exchange step using an ion exchange method performed before the catalyst supporting step. A method for producing a catalyst according to any one of claims 4 to 8, characterized in that.

10. The cation is at least one cation selected from the group consisting of lanthanum, potassium, lithium, sodium, and cerium. The method for producing a catalyst according to claim 9, characterized in that...

11. Using the catalyst according to any one of claims 1 to 3, producing a liquid fuel composed of hydrocarbons from synthesis gas by a Fischer-Tropsch synthesis reaction The method for producing a liquid fuel, characterized in that...

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