Patent Application
20250196121
The present disclosure relates to a catalyst, a method for producing the catalyst, and a method for producing a liquid fuel, and is particularly suitable for application to a catalyst for producing a liquid fuel by reacting a mixed gas of carbon oxide and hydrogen, a method for producing the catalyst, and a method for producing a liquid fuel from carbon oxide using the catalyst.
In the related art, research and development for improving selectivity of an intended product by controlling a complicated reaction path using a synthesis technique based on a Fischer-Tropsch (FT) method in which a liquid hydrocarbon is synthesized from carbon monoxide (CO) and hydrogen (H2) has been actively conducted. A technique in an oxide-based co-catalyst or a secondary metal co-catalyst is added alongside cobalt (Co), which is a conventional main catalyst, to improve the selectivity of the intended product has been proposed (see, for example, Japanese Translation of PCT International Application Publication No. 2019-529065 and Japanese Patent Laid-Open No. 2015-131768).
In addition, a technique in which by using a modified meso-form zeolite cobalt catalyst, a liquid fuel is synthesized in one stage without secondary hydrogenation refining treatment from a synthesis gas that is a mixed gas of carbon monoxide and hydrogen has been proposed (see, for example, Non Patent Literature 1: “Integrated tuneable synthesis of liquid fuels via Fischer-Tropsch technology”, Jie Li et al, Nature Catalysis volume 1, pages 787-793 (2018)).
In Non Patent Literature 1 described above, a
catalyst in which with respect to a Y-type zeolite carrier having mesopores, lanthanum (La) or potassium (K) is used as cations in the mesopores, and the supported amount of cobalt (Co) is 15 wt % is used as a catalyst. Such a catalyst has activity in a Fischer-Tropsch synthesis reaction, and is referred to as a FT synthesis catalyst for producing a hydrocarbon-based liquid fuel.
When using the above-described FT synthesis catalyst, a liquid fuel containing a hydrocarbon having a carbon number of 5 to 20 is produced from a synthesis gas containing hydrogen (H2) and carbon monoxide (CO), there is a problem that while the selectivity of the liquid fuel is high, the carbon monoxide conversion ratio (hereinafter, CO conversion ratio) is low. If the CO conversion ratio is low, the yield derived as a product of a conversion ratio and a selectivity decreases. Therefore, a highly active catalyst capable of improving the yield of a liquid product including a hydrocarbon having a carbon number of 5 or more has been desired.
Therefore, there is a need for a catalyst capable of improving the yield of a hydrocarbon having a carbon number of 5 or more and 20 or less and produced using carbon monoxide and hydrogen as raw materials, a method for producing the catalyst, and a liquid fuel production method.
In some embodiments, provided is a catalyst which is capable of producing a hydrocarbon from a synthesis gas. The catalyst includes: a metallic catalyst containing a metal compound having activity in a Fischer-Tropsch synthesis reaction, the metallic catalyst being configured to produce the hydrocarbon from the synthesis gas; and a carrier catalyst containing zeolite supporting the metallic catalyst, the metal compound containing cobalt, and at least one metal selected from the group consisting of manganese and ruthenium, and a supported amount of the ruthenium being 0.5 wt % or more and 2 wt % or less.
In some embodiments, provided is a catalyst production method for producing the catalyst. The method includes: a pore forming step of forming mesopores in a carrier catalyst; and a catalyst supporting step of supporting a metal compound on the carrier catalyst, the catalyst supporting step including a melt impregnation step of supporting the metal compound containing cobalt on the carrier catalyst by a melt impregnation method, and then melt-impregnating the carrier catalyst with the metal compound containing manganese and the metal compound containing ruthenium.
In some embodiments, provided is a catalyst production method for producing the catalyst. The method includes: a pore forming step of forming mesopores in a carrier catalyst; and a catalyst supporting step of supporting a metal compound on the carrier catalyst, the catalyst supporting step including a melt impregnation step of supporting, on the carrier catalyst, the metal compound containing the cobalt, the metal compound containing the manganese, and the metal compound containing the ruthenium substantially in parallel by a melt impregnation method.
In some embodiments, provided is a catalyst production method for producing the catalyst. The method includes: a pore forming step of forming mesopores in a carrier catalyst; and a catalyst supporting step of supporting a metal compound on the carrier catalyst, the catalyst supporting step including an impregnation step of supporting the metal compound containing cobalt on the carrier catalyst by an impregnation method, and then immersing the carrier catalyst supporting the cobalt in a solution containing manganese and a solution containing ruthenium to impregnate the carrier catalyst and the supported catalyst supported on the carrier catalyst with the solution containing the manganese and the solution containing the ruthenium.
In some embodiments, provided is a catalyst production method for producing the catalyst. The method includes: a pore forming step of forming mesopores in a carrier catalyst; and a catalyst supporting step of supporting a metal compound on the carrier catalyst, the catalyst supporting step including an impregnation step of supporting the metal compound containing cobalt on the carrier catalyst by an impregnation method, and immersing the carrier catalyst supporting the cobalt 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 with at least one of the solution containing the manganese and the solution containing the ruthenium.
In some embodiments, provided is a catalyst production method for producing the catalyst. The method includes: a pore forming step of forming mesopores in a carrier catalyst; and a catalyst supporting step of supporting a metal compound on the carrier catalyst, the catalyst supporting step including: a melt impregnation step of melt-impregnating the carrier catalyst with the metal compound containing cobalt; and an impregnation step of immersing the carrier catalyst supporting the metal compound containing the cobalt, which is obtained in the melt impregnation step, 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 with at least one of the solution containing the manganese and the solution containing the ruthenium.
In some embodiments, a liquid fuel production method includes producing a liquid fuel including a hydrocarbon from a synthesis gas by a Fischer-Tropsch synthesis method using the catalyst.
The above and other features, advantages and technical and industrial significance of this disclosure will be better understood by reading the following detailed description of presently preferred embodiments of the disclosure, when considered in connection with the accompanying drawings.
Hereinafter, an embodiment of the disclosure will be described with reference to the drawings. In addition, the disclosure is not limited by an embodiment described below. First, in describing an embodiment of the disclosure, experiments and intensive studies conducted by the present inventor for solving the above-described problems will be described in order to facilitate understanding of the disclosure.
First, the present inventor has conducted studies on problems concerning a catalyst which is used as a conventional FT (Fischer-Tropsch) synthesis catalyst and in which with Y-type mesoporous zeolite as a carrier catalyst, cobalt (Co) as a metal catalyst is supported in cation-exchanged mesopores (a Co-supported FT synthesis catalyst). Note that the mesopores are pores having an opening diameter of 2 nm or more and 50 nm or less, and have a peak in the range of 10 nm or more and 20 nm or less.
That is, according to the findings by the present inventor, when the above-described Co-supported Y-type mesoporous zeolite catalyst is used, and the supported amount (also referred to as a catalyst amount) of cobalt (Co) is increased for improving the yield in production of a liquid fuel including a hydrocarbon (CnH2n+2) having a carbon number n of 5 to 20, the mesopores may be blocked, which is not preferable. Therefore, the present inventor has conducted studies on various metal catalysts other than Co, and arrived at the addition of a highly active catalyst. According to the studies by the present inventor, it is desirable to add manganese (Mn) as a metal catalyst for improving the yield of a liquid fuel including a hydrocarbon having a carbon number of 5 to 20 by adding a highly active metal catalyst. In other words, the present inventors have arrived at the use of a compound containing Co and Mn, which is a metal compound having activity in a Fischer-Tropsch synthesis reaction, as a metallic catalyst for producing a hydrocarbon from a synthesis gas containing carbon (C) and hydrogen (H2). In addition, it has been found that among the carrier catalysts that support Co and Mn, the zeolite studied is preferable, and in particular, Y-type zeolite having mesopores is preferable. Further, from the experiments conducted by the present inventor, it has been 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 %.
The present inventor has produced a liquid fuel using the above Co-supported FT synthesis catalyst to which Mn is added (a MnCo-supported FT synthesis catalyst), and the present inventor has found that the CO conversion ratio is not significantly improved. Therefore, the present inventor has further conducted studies, conducted various experiments and intensive studies on a metal catalyst capable of improving the CO conversion ratio, and devised a method in which ruthenium (Ru) is added to a Co-supported FT synthesis catalyst. The present inventor has conducted an experiment of producing a hydrocarbon from a synthesis gas using a Co-supported FT synthesis catalyst supporting Ru (a RuCo-supported FT synthesis catalyst), and confirmed that the production of the hydrocarbon is improved over the entire carbon number range, leading to improvement of the CO conversion ratio. In addition, it has been found that among the carrier catalysts supporting both Co and Ru, the zeolite under study is the preferred choice, with Y-type zeolite containing mesopores being particularly advantageous. Further, from the experiment conducted by the present inventor, it has been 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 %.
The present inventor has further advanced the above studies, and conducted studies on a Co-supported FT synthesis catalyst (RuMnCo-supported FT synthesis catalyst) obtained by adding Mn and Ru in combination, and has diligently conducted studies on conditions for maximizing the yield, and the effects thereof. The present inventor has produced a liquid fuel from a synthesis gas using a RuMnCo-supported FT synthesis catalyst, and confirmed considerable improvement of the yield of the liquid fuel. On the other hand, the present inventor has found that under the conditions for maximizing the yield of a hydrocarbon (maximum yield conditions), a wax including a hydrocarbon having a high carbon number of more than 20 is produced, covers the FT synthesis catalyst, and is deposited thereon, and the CO conversion ratio decreases with the lapse of time.
The present inventor has also conducted studies on reduction of the amount of wax, and has devised increasing the amount of a hydrocarbon with a low carbon number, which has a small carbon number n, for reducing the amount of wax produced. The present inventor has conducted studies on a method for increasing the amount of a hydrocarbon having a low carbon number. Additionally, a method has been developed to adjust the silicon-to-aluminum (Si/Al) ratio in zeolite, thereby enhancing the acid sites on the surface layer. This strengthening improves the cracking efficiency, facilitating the decomposition of carbon chains and shifting the carbon number distribution toward lower carbon number. This enables suppression of production of wax in the production of hydrocarbon. The present inventor has conducted experiments with attention paid to the amount of wax produced, and it has been found that the Si/Al ratio of zeolite, as an average over the zeolite, is typically 2.5 or more and 3.5 or less, preferably 2.7 or more and 3.1 or less, and more preferably 2.84 or more and 3.03 or less, and the optimum value is preferably about 2.94.
The present inventor has found, on the basis of the above studies, that cobalt and at least one metal selected from the group consisting of manganese and ruthenium are preferably contained as a metal compound supported on the FT synthesis catalyst. In addition, the present inventor has devised adjusting the hydrocarbon distribution by adjusting the Si/Al ratio of zeolite within the range of 2.5 to 3.5. The disclosure has been devised on the basis of the above intensive studies by the present inventor.
First, the carrier catalyst used for the FT synthesis catalyst according to the present embodiment is used as a hydrogenation catalyst, and includes zeolite, that is, aluminosilicate, and preferably Y-type zeolite in the present embodiment. When zeolite is provided on the surface layer, activated carbon, silicon carbide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide or a mixture thereof may be contained as the support, an intermediate material between the support and the zeolite, and a binder material.
Next, a method for producing a FT synthesis catalyst that is a catalyst according to an embodiment, which has been devised by the above-described intensive studies, will be described.
As shown in
In Step ST1, EDTA treatment is performed on the Y-type zeolite to form mesopores in the zeolite (pore forming step). In addition, the Si/Al ratio of the Y-type zeolite can be increased by eliminating Al from the Y-type zeolite. Specifically, in Step ST1, the zeolite powder 6.7 g in mass is mixed with an EDTA (ethylenediaminetetraacetic acid) aqueous solution with a concentration of 0.07 mol/L and a volume of 100 ml. Next, in a vessel such as a flask, the mixture is refluxed and stirred at a temperature of 100° C. (373 K) for six hours. Note that adjustment of the time of EDTA treatment enables adjustment of the amount of elimination of Al, so that the Si/Al ratio of the zeolite can be adjusted. Thereafter, the solid powder is filtered and dried with, for example, an air dryer at 120° C. for 12 hours.
Next, the process proceeds to Step ST2, where alkali treatment, for example, sodium hydroxide (NaOH) treatment is performed on the Y-type zeolite in which mesopores are formed, thereby expanding the mesopores (pore expanding step). In addition, the Si/Al ratio of the Y-type zeolite can be decreased by eliminating Si from the Y-type zeolite. Specifically, for example, in Step ST2, the solid powder of the Y-type zeolite is mixed with a NaOH aqueous solution with a concentration of 0.4 mol/L and a volume of 50 ml. Next, the mixture is stirred, for example, at a temperature of 61° C. (338 K) for 30 min (0.5 hours).
Thereafter, the process proceeds to Step ST3, where powder is separated in about five minutes using, for example, a centrifuge at a rotation speed of 9000 rpm, and drying treatment is performed for 12 hours using, for example, an air dryer at 120° C. By this, a Y-type mesoporous zeolite (hereinafter, Ymeso) carrier is obtained.
Next, the process proceeds to Step ST4, where by an ion-exchange method, cation-exchange treatment using, for example, lanthanum (La) as a cation is performed on the Y-type mesoporous zeolite carrier in which sodium (Na) is coordinated as a cation in advance (cation-exchange step). Note that as the cation, not only La but also potassium (K), lithium (Li), cerium (Ce) or the like can be used. Specifically, for example, in Step ST4, a Y-type mesoporous zeolite carrier 1.0 g in mass is mixed with a lanthanum nitrate solution with 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 cation-exchange treatment. Thereafter, the mixture is centrifuged to separate powder, and subjected to firing treatment in an air atmospheric pressure atmosphere at a temperature of 550° C. (823 K) for six hours to produce powder of a Y-type mesoporous zeolite La (hereinafter, Ymeso-La) carrier.
The cation exchange amount is adjusted within the range of 0.1% or more and 10% or less depending on temperature and time conditions, and is typically about 1%. In addition, in the present embodiment, a cation-exchange step where zeolite in which Na is coordinated as a cation in advance is used is described, but the disclosure is not limited to a case where a cation is coordinated in advance, and a cation may be coordinated to zeolite in which a cation has not been coordinated.
Next, the process proceeds to Step ST5, where metal catalyst supporting treatment is performed on the produced Ymeso-La carrier by, for example, 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 powder of a Ymeso-La carrier are kneaded for, for example, 30 minutes (0.5 hours). Thereafter, for example, a vessel such as a glass bottle is charged with the kneaded product, and sealed, followed by melt impregnation at a temperature of 50° C. (333 K) for 48 hours (melt impregnation step). By this, the Ymeso-La carrier is impregnated with a metal compound of Co and at least one of Mn and Ru in the mesopores. Note that there may be cases where Co is exposed from the mesopores due to shallowness of the mesopores or support on the surfaces of the mesopores. In this case, Mn or Ru may be supported on the surface or the periphery of Co.
Here, the supported amount of Co is, for example, 15 wt %, the supported amount of Mn is, for example, 2 wt %, and the supported amount of Ru is, for example, 1 wt %. The supported metal compound having activity in a FT synthesis reaction is not always reduced by 100% ultimately, but when it is assumed to be reduced by 100%, the supported amount is a ratio of the mass of 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 that produces a hydrocarbon from a synthesis gas).
After the metal catalyst supporting treatment in Step ST5, the process proceeds to Step ST6, where drying treatment and firing treatment are performed. As the firing treatment, for example, nitrogen (N2) gas is circulated at a temperature of 400° C. (673 K) and a flow rate of 40 mL/min for four hours, thereby eliminating nitrogen (N) to form cobalt oxide, manganese oxide or ruthenium oxide. By this, a MnCo-supported FT synthesis catalyst (Mn—Co/Ymeso-La catalyst), a RuCo-supported FT synthesis catalyst (Ru—Co/Ymeso-La catalyst), or a RuMnCoFT synthesis catalyst (Ru—Mn—Co/Ymeso-La catalyst) is obtained. Note that when potassium (K) is used as a cation in the ion-exchange treatment in Step ST4, a MnCo-supported FT synthesis catalyst (Mn—Co/Ymeso-K catalyst), a RuCo-supported FT synthesis catalyst (Ru—Co/Ymeso-K catalyst), a RuMnCoFT synthesis catalyst (Ru—Mn—Co/Ymeso-K catalyst), or the like is obtained. In addition, when another cation such as cerium (Ce) is used as the cation, the moiety of “—La” or “—K” in each FT synthesis catalyst is replaced with “—Ce” or the other cation.
Thereafter, if necessary, the process proceeds to Step ST7, where the physical properties of the product are confirmed by, for example, X-ray diffraction or gas chromatography to confirm the physical properties of the FT synthesis catalyst. Specifically, for evaluating the reactivity of the catalyst, for example, a tubular reactor is filled with the produced FT synthesis catalyst, and hydrogen gas at a temperature of 400° C. is circulated to perform reduction treatment. Thereafter, under conditions of a temperature of 250° C. and a pressure of 2.0 MPa, the synthesis gas is brought into contact with the FT synthesis catalyst by adjusting the flow rate so that the catalyst mass W to the synthesis gas flow rate F (W/F) is, for example, 10 gh/mol. Note that the ratio of hydrogen (H2) to carbon monoxide (CO) in the synthesis gas is set to 1 to 2 (H2/CO=1 to 2). The compositions of the synthetic gas supplied and the gas discharged from the outlet of the tubular reactor are analyzed using methods such as gas chromatography (GC). This allows for the measurement of key parameters, including the CO conversion ratio, CH4 selectivity, selectivity for hydrocarbons with a carbon number of five or greater (C5+ selectivity), and the productivity of liquid hydrocarbons.
Next, an impregnation method (Impregnation: IM method), which is a modification of the above-described catalyst carrying treatment in Step ST5, will be described.
That is, in Step ST11, the Ymeso-La carrier powder produced in Step ST4 shown in
Thereafter, the process proceeds to Step ST12, where firing treatment is performed. By this, a Co-supported FT synthesis catalyst (Co/Ymeso-La catalyst) is obtained. Note that the supported amount of Co is, for example, 15 wt %. Next, the process proceeds to Step ST13, where the CO/Ymeso-La catalyst powder obtained by the firing treatment is immersed in at least one of a manganese nitrate (Mn(NO3)2) solution and a ruthenium nitrate (Ru(NO3)3) solution, thereby being impregnated. By this, the carrier catalyst having mesopores and the supported catalyst supported on the carrier catalyst are impregnated with at least one of Mn and Ru corresponding to the solution. Note that the melt impregnation method and the impregnation method may be carried out in parallel.
Thereafter, the process proceeds to Step ST6, where as the firing treatment, for example, nitrogen (N2) gas is circulated at a temperature of 400° C. (673 K) and a flow rate of 40 mL/min for four hours, thereby eliminating nitrogen (N) to form cobalt oxide, manganese oxide or ruthenium oxide. By the above, a MnCo-supported FT synthesis catalyst (Mn—Co/Ymeso-La catalyst), a RuCo-supported FT synthesis catalyst (Ru—Co/Ymeso-La catalyst), or a RuMnCoFT synthesis catalyst (Ru—Mn—Co/Ymeso-La catalyst) is obtained. Note that these catalysts may be collectively referred to as a FT synthesis catalyst.
Next, a method for producing a hydrocarbon using a FT synthesis catalyst produced as described above, in particular, a method for producing a liquid fuel such as jet fuel will be described. The method for producing a hydrocarbon according to the present embodiment is the same as a conventional method for producing a liquid fuel except that the above-described Y-type mesoporous zeolite catalyst supporting Co and at least one of Mn and Ru is used as a FT synthesis catalyst.
That is, first, hydrogen (H2) gas and carbon monoxide (CO) gas are produced from methane (CH4), water (H2O), oxygen (O2) and carbon dioxide (CO2) by a synthesis gas production step. Next, a hydrocarbon (CnH2n+2) is produced from the synthesis gases by a Fischer-Tropsch synthesis method (also referred to as a FT method or a Fischer-Tropsch synthesis reaction method) using the above-described FT synthesis catalyst.
Subsequently, various liquid hydrocarbons are separated and refined into lower olefins (carbon number n=2 to 4: C2-C4), naphtha (carbon number n=5 to 10: C5-C10), kerosene (carbon number n=10 to 14: C10-C14), light oil (carbon number n=14 to 20: C14-C20), wax (carbon number n>20: C20+) and the like by an upgrading step. Note that as the jet fuel, a hydrocarbon having a carbon number n of 8 to 16 (C8-C16) is mainly used. In addition, as the liquid fuel, a hydrocarbon having a carbon number n of 5 to 20 (C5-C20) is mainly used. By the above, a liquid fuel containing a liquid hydrocarbon is produced by a FT method using a FT synthesis catalyst.
Next, effects of the FT synthesis catalyst produced as described above will be described.
First, “Co/Ymeso-La” in
On the other hand, from “Mn—Co/Ymeso-La” and “Mn—Co/Ymeso-La-IM” shown in
Therefore, when the FT synthesis catalyst described in Non Patent Literature 1 is used, both the CO conversion ratio and the selectivity of a liquid fuel including a hydrocarbon having a carbon number of 5 to 16 are low under the condition of a H2/CO ratio of 2.0 (H2/CO=2.0). On the other hand, it can be seen from
In addition, it can be seen from
From
In addition, it can be seen from
Effects of addition of Ru to FT synthesis catalyst
Further, from
In addition,
From
From
The embodiment described above has the following advantages over Patent Literature 1 and 2. That is, in the technique described in Patent Literature 1, a cobalt-based catalyst and a silica (SiO2) catalyst carrier are used, and in the technique described in Patent Literature 2, a catalyst containing at least one metal selected from the group of ruthenium (Ru), cobalt (Co), and iron (Fe) or a compound and a β-type zeolite carrier having a Si/Al ratio of 13 or more are used. On the other hand, the embodiment described above is different in that the carrier is zeolite of Y type, L type or the like with a Si/Al ratio of 10 or less in which a cobalt-based catalyst is used. In addition, the catalyst according to the embodiment described above can improve reactivity and selectivity as compared to the catalysts described in Patent Literature 1 and 2.
According to the embodiment described above, it is possible to improve the yield of a hydrocarbon having a carbon number of 5 or more and 20 or less (C5-C20), preferably a hydrocarbon having a carbon number of 8 or more and 16 or less (C8-C16), which is produced using carbon monoxide (CO) and hydrogen (H2) as raw materials, that is a jet fuel.
From an industrial point of view, it is possible to provide a catalyst capable of directly producing a liquid fuel such as jet fuel from carbon monoxide and hydrogen, and a technique for producing a liquid fuel can be provided efficiently and inexpensively. The catalyst according to the embodiment described above has been confirmed to be superior in catalyst performance to conventional techniques.
The embodiments of the disclosure have been described in detail above, the disclosure is not limited to the embodiments described above, and it is possible to make various modifications based on the technical idea of the disclosure. For example, the numerical values given in the embodiments described above are merely examples, and numerical values different from those given above may be used as necessary. The disclosure also includes components formed by appropriately combining those of the embodiments and modifications described above.
The method for supporting a metal compound having activity in a FT synthesis reaction on a catalyst carrier is not limited to the selection and treatment method of the above-described melt impregnation method and impregnation method, and it is also possible to perform the support only by melt impregnation or only by the impregnation method by optimizing the conditions and method for production for mass production and reduction of production cost, or to use a method in which Co, Mn and Ru are supported by one treatment.
That is, the catalyst supporting step may include a melt impregnation step of melt-impregnating the carrier catalyst with a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium. The melt impregnation step may be a step of supporting a metal compound containing cobalt on a carrier catalyst by a melt impregnation method, and then supporting at least one of a metal compound containing manganese and a metal compound containing ruthenium by a melt impregnation method. Alternatively, the melt impregnation step may be a step of supporting a metal compound containing cobalt and at least one of a metal compound containing manganese and a metal compound containing ruthenium on a carrier catalyst substantially in parallel by a melt impregnation method.
Further, the catalyst supporting step may include an impregnation step of supporting a metal compound containing cobalt on a carrier catalyst by an impregnation method, and then immersing the carrier catalyst supporting cobalt in at least one of a solution containing manganese and a solution containing ruthenium, thereby impregnating the carrier catalyst and the supported catalyst supported on the carrier catalyst. Alternatively, the catalyst supporting step may include an impregnation step of supporting a metal compound containing cobalt on a carrier catalyst by an impregnation method, and immersing the carrier catalyst supporting cobalt in at least one of a solution containing manganese and a solution containing ruthenium, thereby impregnating at least one of the carrier catalyst and the supported catalyst supported on the carrier catalyst. Here, the term “supported catalyst” refers to catalysts such as Co, Mn and Ru supported on the carrier catalyst.
The supported amount of the metal compound having activity in the FT synthesis reaction on the catalyst carrier is 5 to 50 wt %. For example, when cobalt (Co) is used, the content is preferably 10 to 30 wt %, and more preferably 15 wt %. If the supported amount is in the range of less than 10 wt %, the FT synthesis activity cannot be sufficiently exhibited, and if the supported amount is in the range of more than 30 wt %, the zeolite pores are blocked, so that the efficiency in utilization of supported Co decreases.
In addition, further effects and modifications can be easily derived by those skilled in the art. The broader aspects of the disclosure are not limited to the specific details and representative embodiments presented and described above. Accordingly, various changes can be made without departing from the spirit or scope of the general inventive concept which is defined by the appended claims and their equivalents.
The catalyst, the method for producing the catalyst, and the method for producing a liquid fuel according to the disclosure are suitable for application to a catalyst for producing a liquid fuel by reacting a mixed gas of carbon oxide and hydrogen, a method for producing the catalyst, and a method for producing a liquid fuel from carbon oxide using the catalyst.
The catalyst, the method for producing the catalyst, and the liquid fuel production method according to the disclosure enables improvement of the yield of a hydrocarbon having a carbon number of 5 or more and 20 or less, the hydrocarbon being produced using carbon monoxide and hydrogen as raw materials.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the disclosure in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-139985 | Sep 2022 | JP | national |
This application is a continuation of International Application No. PCT/JP2023/026834, filed on Jul. 21, 2023 which claims the benefit of priority of the prior Japanese Patent Application No. 2022-139985, filed on Sep. 2, 2022, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2023/026834 | Jul 2023 | WO |
| Child | 19063960 | US |
