Χ-iron carbide complex, preparation method therefor and use thereof

Abstract

The present invention relates to a χ-iron carbide complex, a preparation method therefor and a use thereof. The complex comprises iron carbide and halide ions; the iron carbide includes χ-iron carbide; the halide ions are bromine ions and / or iodide ions; the molar ratio of the χ-iron carbide to the halide ions is 100:(0.1-45); and the number of moles of the χ-iron carbide is based on the number of moles of an iron element contained in the χ-iron carbide. The complex has a monoclinic crystal system structure. The χ-iron carbide complex according to one embodiment of the present invention can be used as a catalyst for a syngas conversion reaction; and by introducing the halide ions, such as bromine ions or iodide ions, to the χ-iron carbide complex, the resulting reaction has a high CO conversion rate and extremely low overall CO2 selectivity, thereby realizing comprehensive optimization of a reaction result.

Description

A χ-iron carbide composite and its preparation method and application Technical Field

[0001] The present invention relates to the conversion of synthesis gas, and in particular to a χ-iron carbide composite capable of being used for the conversion of synthesis gas and a preparation method thereof. Background Art

[0002] my country's primary energy structure is characterized by an abundance of coal, a shortage of oil, and limited natural gas. With the development of my country's economy, its dependence on foreign oil has continued to rise. Syngas, a mixture of CO and H₂ obtained by gasifying coal, natural gas, and biomass, has become increasingly important in recent years. Syngas conversion technology can be used to gasify carbon-containing materials such as coal, natural gas, and biomass to generate syngas, which can then be converted into liquid fuels and high-value chemicals.

[0003] The reaction equation for syngas conversion is as follows:

[0004] (2n+1)H2+nCO→C n H 2n+2 +nH2O (a)

[0005] 2nH2+nCO→C n H 2n +nH2O (b)

[0006] (n+1)H2+2nCO→C n H 2n+2 +nCO2 (c)

[0007] nH2+2nCO→C n H 2n +nCO2 (d)

[0008] Iron-based catalysts are the most affordable and readily available catalysts for syngas conversion. They offer advantages such as high activity, a wide window of applicable conditions, strong sulfur tolerance, simple online catalyst replacement, and suitability for continuous industrial production. However, one of the bottlenecks of conventional syngas conversion technology using iron-based catalysts is their excessively high CO2 selectivity (typically 35-45% of the raw CO converted).

[0009] Professor Enrique Iglesia's paper ("Pathways for CO2 Formation and Conversion During Fischer-Tropsch Synthesis on Iron-Based Catalysts" (Catalysis Letters volume 80, pages 77-86 (2002))) explains that in the reaction of synthesis gas conversion achieved by the Fischer-Tropsch synthesis principle, the production of CO2 has two sources: (1) primary CO2 directly derived from a single Fischer-Tropsch synthesis reaction (see equations (c) and (d) above); and (2) secondary CO2 produced by the water-gas-shift reaction (WGS reaction, CO+H2O→CO2+H2) of H2O and CO at a higher CO conversion rate.

[0010] The prior art discloses a high-purity iron carbide catalyst that can reduce primary CO2 in the Fischer-Tropsch synthesis reaction to near zero while achieving a high space-time conversion rate of CO, thereby reducing the overall CO2 selectivity to less than 5% at low CO conversions (typically below 35%). However, as CO conversion increases, the WGS reaction becomes more intense as the H2O content in the reaction environment rises, leading to an increase in secondary CO2 and ultimately increasing the overall CO2 selectivity at high CO conversions.

[0011] In addition, reducing CO2 selectivity will significantly increase carbon atom utilization efficiency, essentially improving the economic and environmental friendliness of syngas conversion technology. Therefore, how to suppress the water-gas shift side reaction at high CO conversion rates, reduce CO2 selectivity, and improve carbon atom utilization efficiency has become one of the common key issues in the field of syngas conversion. On the other hand, in addition to CO2, another major by-product in the field of syngas conversion is methane. In the reaction, higher CH4 selectivity will jointly reduce the effective product selectivity of the reaction with higher CO2 selectivity.

[0012] Summary of the Invention

[0013] To overcome at least one defect of the above-mentioned prior art, in a first aspect, one embodiment of the present invention provides a χ-iron carbide composite, comprising iron carbide and halide ions, wherein the iron carbide comprises χ-iron carbide, and the halide ions are bromide ions and / or iodide ions; the molar ratio of the χ-iron carbide to the halide ions is 100:(0.1 to 45), and the molar number of the χ-iron carbide is calculated based on the molar number of iron element it contains; wherein the composite has a monoclinic structure.

[0014] In a second aspect, an embodiment of the present invention provides a method for preparing the above-mentioned χ-iron carbide composite, comprising the following steps:

[0015] S1: Under the action of hydrogen, the precursor is reduced and surface purified at a temperature of 260° C. to 470° C. to obtain a reduced product;

[0016] S2: performing a surface passivation treatment on the reduced product in a first gas atmosphere at a temperature of 0° C. to 40° C. to obtain a passivated product; and

[0017] S3: treating the passivation product in a second gas atmosphere at a temperature of 250° C. to 430° C. to form a product containing iron carbide;

[0018] The first gas comprises 1% to 3% by volume of oxygen; the second gas comprises hydrogen and carbon monoxide, and the molar ratio of the hydrogen to the carbon monoxide is (8-90):1;

[0019] The precursor is nano-iron and / or nano-iron compound that has been subjected to a first impregnation treatment with an impregnation solution, and the nano-iron compound can be prepared into nano-iron through a reduction reaction; or,

[0020] The precursor is nano-iron and / or the nano-iron compound, and the passivation product is subjected to a second immersion treatment in the immersion solution and then to the treatment in step S3; or,

[0021] The precursor is nano-iron and / or the nano-iron compound, and the product containing iron carbide is subjected to a third impregnation treatment through the impregnation liquid; the impregnation liquid includes bromide ions and / or iodine ions.

[0022] In a third aspect, an embodiment of the present invention provides a catalyst comprising the above-mentioned χ-iron carbide composite or the χ-iron carbide composite prepared by the above-mentioned preparation method.

[0023] In a fourth aspect, an embodiment of the present invention provides the use of the above-mentioned χ-iron carbide composite, the χ-iron carbide composite obtained by the above-mentioned preparation method, or the above-mentioned catalyst in a synthesis gas conversion reaction.

[0024] In a fifth aspect, an embodiment of the present invention provides the use of the above-mentioned χ-iron carbide composite, the χ-iron carbide composite obtained by the above-mentioned preparation method, or the above-mentioned catalyst in a reaction for synthesizing C, H fuels and / or chemicals based on the Fischer-Tropsch synthesis principle.

[0025] In a sixth aspect, an embodiment of the present invention provides a synthesis gas conversion process, comprising contacting the above-mentioned catalyst with synthesis gas under reaction conditions for reaction.

[0026] The χ-iron carbide composite of one embodiment of the present invention can be used as a catalyst for synthesis gas conversion reactions, especially Fischer-Tropsch synthesis reactions. By introducing halide ions such as bromine or iodine into the χ-iron carbide composite, the reaction has a high CO conversion rate, extremely low total CO2 selectivity, and low CH4 selectivity, thereby achieving comprehensive optimization of the reaction results. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings are only used to illustrate specific embodiments and are not to be considered as limiting the present invention.

[0028] FIG1 is a Mössbauer spectrum of the χ-iron carbide composite CX1 prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] Typical embodiments that embody the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention is capable of various variations in different embodiments without departing from the scope of the present invention, and the descriptions herein are intended to be illustrative rather than limiting.

[0030] One embodiment of the present invention provides a χ-iron carbide composite, comprising iron carbide and halide ions, wherein the iron carbide comprises χ-iron carbide, and the halide ions are bromide ions and / or iodide ions; the molar ratio of χ-iron carbide to halide ions is 100:(0.1-45); herein, the molar number of χ-iron carbide is calculated based on the molar number of iron element it contains; wherein the composite has a monoclinic crystal structure.

[0031] In one embodiment, the average crystallite diameter of the composite is 6 to 35 nm, and further can be 9 to 28 nm.

[0032] In one embodiment, the molar ratio of χ-iron carbide to halide ions can be 100:(0.1-45), further can be 100:(0.5-27), and further can be 100:(7-20), for example, 100:0.5, 100:1, 100:5, 100:7, 100:10, 100:15, 100:20, 100:25, 100:30, 100:40.

[0033] In one embodiment, the χ-iron carbide complex includes a first cation comprising a halide cation that is charge balanced with the halide ions, i.e., the total number of negative charges (or the total number of valences exhibited) of the halide ions is equal to the total number of positive charges of the halide cations.

[0034] In one embodiment, the first cation includes other cations, and the molar ratio of χ-iron carbide to the other cations can be 100:(0.1-23), further can be 100:(0.1-17), and further can be 100:(0.1-12), for example, 100:0.5, 100:1, 100:3, 100:5, 100:10, 100:15, 100:20.

[0035] In one embodiment, the χ-iron carbide complex further includes other anions, and the other cations are capable of maintaining charge balance with the other anions.

[0036] In one embodiment, the halide cations include one or more of a first metal ion and a complex cation. Further, the first metal ion includes one or more of an iron ion (e.g., a divalent or trivalent iron ion), a manganese ion (e.g., a divalent manganese ion), a copper ion (e.g., a monovalent or divalent copper ion), a cobalt ion (e.g., a divalent cobalt ion), a platinum ion (e.g., a divalent, trivalent or tetravalent platinum ion), a lanthanum ion (e.g., a trivalent or tetravalent lanthanum ion), a cerium ion (e.g., a trivalent or tetravalent cerium ion), and a neodymium ion (e.g., a trivalent or tetravalent neodymium ion); and the complex cations include one or more of a hexaamminemanganese ion, a hexaammineferric ion, and a hexaamminecopper ion.

[0037] In one embodiment, the other cations include one or more of the second metal ions. The second metal ions may include one or more of manganese ions, copper ions, cobalt ions, platinum ions, chromium ions, rare earth ions, alkali metal ions, and alkaline earth metal ions; for example, the second metal ions may be manganese ions (e.g., divalent, trivalent, or tetravalent manganese ions), copper ions (e.g., monovalent or divalent copper ions), cobalt ions (e.g., divalent cobalt ions), platinum ions (e.g., divalent, trivalent, or tetravalent platinum ions), chromium ions (e.g., trivalent chromium ions), lanthanum ions (e.g., trivalent or tetravalent lanthanum ions), cerium ions (e.g., trivalent or tetravalent cerium ions), neodymium ions (e.g., trivalent or tetravalent neodymium ions), sodium ions, potassium ions, calcium ions, and barium ions.

[0038] In one embodiment, the other anions include one or more of oxygen ions, complex ions, and acid ions, such as oxygen ions, nitrate, citrate, and gluconate.

[0039] One embodiment of the present invention provides a method for preparing the above-mentioned χ-iron carbide composite, comprising the following steps:

[0040] S1: Under the action of hydrogen, the precursor is subjected to high-temperature treatment at a temperature of 260-470°C for reduction and surface purification to obtain a reduced product;

[0041] S2: subjecting the reduced product to a high-temperature treatment at a temperature of 0 to 40° C. in a first gas atmosphere to perform surface passivation to obtain a passivated product; and

[0042] S3: subjecting the passivation product to a high-temperature treatment at a temperature of 250 to 430° C. in a second gas atmosphere to form iron carbide, thereby obtaining a product containing iron carbide;

[0043] The first gas comprises 1 to 3 vol% oxygen; the second gas comprises hydrogen and carbon monoxide, and the molar ratio of hydrogen to carbon monoxide is (8 to 90):1;

[0044] The precursor is nano-iron and / or nano-iron compound subjected to a first impregnation treatment with an impregnation solution, and the nano-iron compound can be prepared into nano-iron by a reduction reaction; or,

[0045] The precursor is nano-iron and / or nano-iron compound, and the passivation product is subjected to a second impregnation treatment in an impregnation solution before the treatment of step S3; or the precursor is nano-iron and / or nano-iron compound, and the product containing iron carbide is subjected to a third impregnation treatment through an impregnation solution; the impregnation solution includes bromide ions and / or iodide ions.

[0046] In one embodiment, the nano-iron compound includes one or more of nano-iron oxide, nano-magnetite, nano-goethite, and nano-iron hydrated oxide.

[0047] In one embodiment, the nano-iron or nano-iron compound may be nano-iron powder and / or nano-iron particles.

[0048] In one embodiment, the average grain diameter of the nano-iron or nano-iron compound is 6 to 35 nm, and can further be 9 to 28 nm, for example, 10 nm, 12 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 30 nm, or 32 nm.

[0049] In one embodiment, the impregnation solution is prepared by dissolving a solute in a solvent. The solute may include a water-soluble halide, and the halide may include a bromide and / or an iodide. Further, the halide includes one or more bromides and iodides containing manganese, iron, copper, cobalt, molybdenum, or a rare earth metal element. For example, the halide may be one or more of manganese bromide, ferrous bromide, copper bromide, cobalt bromide, molybdenum bromide, manganese iodide, ferrous iodide, copper iodide, rare earth bromide, rare earth iodide, hexaamminemanganese bromide, hexaammineferric bromide, hexaamminecopper bromide, hexaamminemanganese iodide, hexaammineferric iodide, and hexaamminecopper iodide.

[0050] In one embodiment, the concentration of the halide in the impregnation solution may be 0.7 to 7 mol / L, for example, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, or 6 mol / L.

[0051] In one embodiment, the solvent of the impregnation solution includes water and / or ethanol. For example, the solvent may be water or a mixture of ethanol and water.

[0052] In one embodiment, the solute of the impregnation solution further includes other compounds, and the other compounds include one or more salts (organic salts and / or inorganic salts) of manganese, copper, cobalt, molybdenum, rare earth metals, alkali metals, and alkaline earth metals. For example, the other compounds can be one or more of potassium nitrate, sodium nitrate, manganese nitrate, copper nitrate, cobalt nitrate, molybdenum nitrate, calcium nitrate, barium nitrate, rare earth nitrates, potassium carbonate, sodium carbonate, potassium citrate, sodium citrate, manganese citrate, copper citrate, cobalt citrate, molybdenum citrate, calcium citrate, barium citrate, potassium gluconate, sodium gluconate, lithium gluconate, rubidium gluconate, cesium gluconate, manganese gluconate, copper gluconate, and calcium gluconate.

[0053] In one embodiment, the solute components of the impregnation solution do not chemically react with each other, for example, the solute does not include potassium carbonate and calcium nitrate at the same time.

[0054] In one embodiment, the concentration of the other compounds in the impregnation solution may be 0.7-7 mol / L, for example, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, or 6 mol / L.

[0055] In one embodiment, the precursor is nano-iron or a nano-iron compound that is subjected to a first impregnation treatment with an impregnation liquid, and the temperature of the first impregnation treatment, the second impregnation treatment or the third impregnation treatment is 0 to 50°C, and can further be 20 to 30°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C; the time of the first impregnation treatment, the second impregnation treatment or the third impregnation treatment can be 0.1 to 12h, and can further be 0.2 to 10h, and further can be 0.3 to 9h, for example, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h.

[0056] In one embodiment, the material after the first, second, or third impregnation treatment can be dried at 15-40°C and further dried in the dark. The drying temperature can be, for example, 20°C, 25°C, 30°C, or 35°C; the drying time can be 0.5-12 hours. The drying process can be carried out under normal pressure or reduced pressure.

[0057] In one embodiment, the first impregnation treatment, the second impregnation treatment, or the third impregnation treatment may be performed by a slurry impregnation method, a saturation impregnation method, a supersaturation impregnation method, or other feasible impregnation methods.

[0058] In one embodiment, the temperature of the reduction and surface purification treatment in step S1 can be 260-470°C, for example, 300°C, 310°C, 320°C, 350°C, 370°C, 400°C, 420°C, and 450°C; the treatment pressure can be 0.12-10atm, and further can be 0.15-7atm, for example, 0.15atm, 0.2atm, 0.5atm, 0.8atm, 1atm, 1.5atm, 2atm, 5atm, 8atm, and 10atm; the treatment time can be 1.2-25h, and further can be 2-12h, for example, 5h, 8h, 10h, 15h, 20h, and 25h.

[0059] In one embodiment, the gas flow rate of H2 in step S1 can be 600-22000 mL / h / g, and can further be 1200-15000 mL / h / g, for example, 1000 mL / h / g, 1500 mL / h / g, 2000 mL / h / g, 3000 mL / h / g, 5000 mL / h / g, 6000 mL / h / g, 8000 mL / h / g, 10000 mL / h / g, 12000 mL / h / g, and 15000 mL / h / g.

[0060] In one embodiment, the first gas in step S2 includes 1-3 vol% oxygen and 97-99 vol% nitrogen. The oxygen content may be, for example, 1.5 vol%, 2 vol%, 2.5 vol%, or 3 vol%.

[0061] In one embodiment, the temperature of the surface passivation treatment in step S2 can be 0 to 40°C, for example, 1°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C; the treatment pressure can be 0 to 1.5atm, and further can be 0 to 0.09atm, for example, 0.01atm, 0.02atm, 0.05atm, 0.06atm, 0.08atm, 1atm, 1.5atm; the treatment time can be 2 to 60h, and further can be 3 to 45h, for example, 8h, 12h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h.

[0062] In one embodiment, the gas flow rate of the first gas in step S2 can be 500-20000 mL / h / g, and can further be 1200-12500 mL / h / g, for example, 500 mL / h / g, 1000 mL / h / g, 1500 mL / h / g, 2000 mL / h / g, 3000 mL / h / g, 4000 mL / h / g, 5000 mL / h / g, 6000 mL / h / g, 7000 mL / h / g, 10000 mL / h / g, and 15000 mL / h / g.

[0063] In one embodiment, the molar ratio of hydrogen to carbon monoxide in the second gas of step S3 may be 10: 1, 20: 1, 30: 1, 36: 1, 40: 1, 50: 1, 60: 1, or 80: 1. The second gas may be a mixture of hydrogen and carbon monoxide.

[0064] In one embodiment, the treatment temperature of step S3 can be 250-430°C, for example, 280°C, 300°C, 320°C, 330°C, 350°C, 380°C, and 400°C; the treatment pressure can be 0.08-17atm, and can further be 0.15-7atm, for example, 0.1atm, 0.2atm, 0.5atm, 0.8atm, 1atm, 1.2atm, 1.5atm, 1.8atm, 2atm, 2.2atm, 5atm, 8atm, 10atm, and 15atm; the treatment time can be 0.3-24h, and can further be 0.5-6h, for example, 1h, 1.5h, 1.8h, 2h, 2.2h, 5h, 10h, 15h, and 20h.

[0065] In one embodiment, the gas flow rate of the second gas in step S3 can be 250 to 21000 mL / h / g, and can further be 2000 to 17000 mL / h / g, for example, 1000 mL / h / g, 3000 mL / h / g, 5000 mL / h / g, 6000 mL / h / g, 7700 mL / h / g, 8000 mL / h / g, 10000 mL / h / g, 12000 mL / h / g, 15000 mL / h / g, and 16000 mL / h / g.

[0066] In one embodiment, in step S3, the temperature of the system is increased from 0 to 40°C to 250 to 430°C at a heating rate of 0.1 to 5°C / min, and further, the temperature of the system is increased from 0 to 40°C to 260 to 400°C at a heating rate of 0.2 to 2.5°C / min; the heating rate of step S3 can be, for example, 0.5°C / min, 0.8°C / min, 1°C / min, 1.2°C / min, 1.5°C / min, 1.8°C / min, 2°C / min, 2.2°C / min, 3°C / min, or 4°C / min.

[0067] In one embodiment, preferably, steps S1, S2, S3 and the first, second and third immersion treatments can all be performed under light-proof conditions.

[0068] In one embodiment, the preparation method of the χ-iron carbide composite comprises the following steps:

[0069] S0: performing a first impregnation treatment on the nano-iron and / or nano-iron compound using an impregnation liquid to obtain a precursor to be treated;

[0070] S1: Under the action of hydrogen, the precursor is reduced and surface purified at a temperature of 260-470°C to obtain a reduced product;

[0071] S2: passivating the surface of the reduced product in a first gas atmosphere at a temperature of 0 to 40° C. to obtain a passivated product; and

[0072] S3: treating the passivation product in a second gas atmosphere at a temperature of 250-430° C. to form iron carbide, thereby obtaining a product containing iron carbide (ie, a χ-iron carbide composite).

[0073] In another embodiment, the preparation method of the χ-iron carbide composite comprises the following steps:

[0074] S1: Under the action of hydrogen, the precursor (nano-iron and / or nano-iron compound) is reduced and surface-cleaned at a temperature of 260-470° C. to obtain a reduction product;

[0075] S2: passivating the surface of the reduced product in a first gas atmosphere at a temperature of 0 to 40° C. to obtain a passivated product;

[0076] S21: performing a second immersion treatment on the passivation product in an immersion solution; and

[0077] S3: treating the material after the second impregnation treatment in a second gas atmosphere at a temperature of 250-430° C. to form a product containing iron carbide (i.e., a χ-iron carbide composite).

[0078] In another embodiment, the preparation method of the χ-iron carbide composite comprises the following steps:

[0079] S1: Under the action of hydrogen, the precursor (nano-iron and / or nano-iron compound) is reduced and surface-cleaned at a temperature of 260-470° C. to obtain a reduction product;

[0080] S2: passivating the surface of the reduced product in a first gas atmosphere at a temperature of 0 to 40° C. to obtain a passivated product; and

[0081] S3: treating the passivation product in a second gas atmosphere at a temperature of 250 to 430° C. to form iron carbide, thereby obtaining a product containing iron carbide;

[0082] S31: subjecting the product containing iron carbide to a third impregnation treatment to obtain a χ-iron carbide composite.

[0083] One embodiment of the present invention provides a catalyst comprising the above-mentioned χ-iron carbide composite.

[0084] One embodiment of the present invention provides the use of the above-mentioned χ-iron carbide composite or catalyst in a synthesis gas conversion reaction.

[0085] In one embodiment, the synthesis gas conversion reaction may be a Fischer-Tropsch synthesis reaction, or other reactions based on the Fischer-Tropsch synthesis principle, such as a reaction using synthesis gas as a starting material and an alcohol as a final product.

[0086] In one embodiment, the syngas comprises CO and H2.

[0087] One embodiment of the present invention provides the use of the aforementioned χ-iron carbide composite or catalyst in a reaction based on the Fischer-Tropsch synthesis principle for synthesizing C and H fuels and / or chemicals. The Fischer-Tropsch synthesis principle refers to a reaction in which syngas (a mixture of CO and H₂) is used as a feedstock to produce chain hydrocarbons and / or their oxygenated derivatives through CO hydrogenation and carbon chain growth reactions in the presence of a catalyst and appropriate conditions.

[0088] In one embodiment, the above reaction is a Fischer-Tropsch synthesis reaction, and the reaction temperature can be 230-280°C, for example, 240°C, 250°C, 260°C, 270°C, 275°C, 277°C; the reaction pressure can be 2-3.5 MPa, and the molar ratio of H2 / CO can be 1.7-2.15.

[0089] One embodiment of the present invention provides a synthesis gas conversion process, comprising contacting the above-mentioned catalyst with synthesis gas under synthesis gas conversion reaction conditions to react.

[0090] In one embodiment, syngas conversion may be performed in a high temperature and high pressure continuous reactor.

[0091] A chi-iron carbide composite according to one embodiment of the present invention can be used as a catalyst for syngas conversion reactions. By introducing halide ions into the chi-iron carbide, the reaction exhibits high CO conversion, extremely low total CO selectivity, and low CH selectivity. Furthermore, the chi-iron carbide composite catalyst exhibits considerable activity, benefiting from its high space-time CO conversion rate.

[0092] The χ-iron carbide composite of one embodiment of the present invention can be used as a catalyst for synthesis gas conversion reactions, enabling the reaction to maintain extremely low CO2 selectivity while having a high CO conversion rate, while maintaining low CH4 selectivity and high reaction stability. This greatly improves the utilization efficiency of carbon atoms and the selectivity of effective products, breaks through key technical bottlenecks, and can promote the high-end, diversified and low-carbonization of clean synthesis gas conversion, indicating new trends and directions for the development of modern synthesis gas chemical industry.

[0093] The χ-iron carbide composite of one embodiment of the present invention, as a catalyst for the Fischer-Tropsch synthesis reaction, can maintain a continuous and stable reaction for more than 300 hours using a high-pressure continuous reactor under industrial Fischer-Tropsch synthesis reaction conditions, with its CO2 selectivity below 5%, further below 3%; its by-product CH4 selectivity can be maintained below 8.5%, further below 5.5%; the carbon atom utilization efficiency is maintained above 95%, further above 97%; and the effective product selectivity can reach above 86.5%, further above 92%.

[0094] In one embodiment, the Fischer-Tropsch synthesis reaction catalyzed by the χ-iron carbide composite can achieve a CO2 selectivity of <5%, a carbon atom utilization efficiency of >95%, and an effective product selectivity of >88% at a CO conversion rate of more than 70%.

[0095] In this article, the "ions" contained in the complex include all particles that are bound to other particles by covalent bonds and / or ionic bonds. For example, the bromide ion in the complex includes both the bromide ion and the K + Interacting Br - , also including Br atoms that interact with H atoms through covalent bonds.

[0096] The pressure values ​​mentioned in this article are gauge pressure.

[0097] The following further describes the χ-iron carbide composite and its application according to one embodiment of the present invention with reference to the accompanying drawings and specific examples. The test methods involved are as follows:

[0098] 1. The crystal structure and corresponding composition of χ-iron carbide complex were determined by Mössbauer spectrometer (Transmission 57 Fe, 57 Measured by Co(Rh) source sinusoidal velocity spectrometer).

[0099] 2. The average grain size of the χ-iron carbide composite was obtained by XRD testing.

[0100] 3. The elements of χ-iron carbide composite were detected using inductively coupled plasma emission spectrometer (ICP).

[0101] 4. During the synthesis gas conversion reaction, the reaction products are analyzed by gas chromatography (Agilent 7890 gas chromatograph) for calculation of reaction performance such as conversion rate and selectivity. This product refers to the tail gas collected from the tail end of the reactor, including generated hydrocarbon compounds, alcohol compounds, CO2, etc.

[0102] 5.CO conversion rate %, CO2 selectivity %, CH4 selectivity %, carbon atom utilization efficiency %, and effective product selectivity % are calculated using the following formulas:

[0103] CO conversion rate % = [(CO moles in feed - CO moles in discharge) / CO moles in feed] × 100%;

[0104] CO2 selectivity % = [CO2 moles in the discharge / (CO moles in the feed - CO moles in the discharge)] × 100%;

[0105] CH4 selectivity % = [mole number of CH4 in the discharge / (mole number of CO in the feed - mole number of CO in the discharge)] × 100%;

[0106] Carbon atom utilization efficiency % = (1-CO2 selectivity %) × 100%;

[0107] Effective product selectivity % = (1-CO2 selectivity %-CH4 selectivity %) × 100%.

[0108] Example 1

[0109] S1: 5.6 g of nano-iron particles with an average grain diameter of 20 nm were taken and maintained in H2 at a flow rate of 12000 mL / h / g at 370°C and a pressure of 2.0 atm for 2 h to perform reduction and surface purification treatment to obtain a reduced product.

[0110] S2: Cooling the reduction product to 30°C and contacting it with a first gas at this temperature for surface passivation treatment to obtain a passivated product; wherein the system pressure is 0.1atm, the gas flow rate is 7500mL / h / g, and the treatment time is 12h; the first gas includes 2vol% oxygen and 98vol% nitrogen.

[0111] S21: dissolving manganese bromide and potassium nitrate in water to prepare an impregnation solution, wherein the manganese bromide concentration is 6.7 mol / L; mixing the prepared impregnation solution with the passivation product, and performing impregnation treatment by a slurry impregnation method, with an impregnation ratio of Fe:Br:K=100:7:2, an impregnation temperature of 32°C, and an impregnation time of 2 hours; and drying the solid material after impregnation at 25°C for 6 hours.

[0112] S3: The impregnated material was exposed to a second gas atmosphere at a pressure of 2.1 atm and a total gas flow rate of 11,000 mL / h / g. Under these conditions, the system was heated from 30°C to 350°C at a heating rate of 2.0°C / min to prepare carbides. The second gas was a mixture of H2 and CO with a molar ratio of H2 to CO of 50:1. The material was treated at 350°C for 5 hours. After treatment, a χ-iron carbide composite was obtained, labeled CX1.

[0113] Examples 1-1 to 3-8 all used substantially the same raw materials and processes as Example 1 to prepare metallic χ-iron carbide composites, differing only in the amount or type of halide ions or other cations in the impregnation solution. The resulting composites are numbered CX1-1 to CX3-8, using the same serial numbers as in Example 1. Because material loss was minimal during the preparation process, the content of each substance in the resulting composites was essentially the same as the amount of the corresponding raw materials used. Specific content values ​​are shown in Table 1.

[0114] Example 4

[0115] S1: 8.0 g of nano-iron oxide particles with an average grain diameter of 15 nm were taken and maintained in H2 at a flow rate of 8000 mL / h / g at 420°C and a pressure of 3.0 atm for 3 h to perform reduction and surface purification treatment to obtain a reduction product.

[0116] S2: Cooling the reduction product to 35°C and contacting it with a first gas at this temperature for surface passivation treatment to obtain a passivated product; wherein the system pressure is 0.5atm, the gas flow rate is 9500mL / h / g, and the treatment time is 9h; the first gas includes 1.5vol% oxygen and 98.5vol% nitrogen.

[0117] S21: dissolving manganese bromide, potassium citrate, and calcium nitrate in water to prepare an impregnation solution, wherein the manganese bromide concentration is 5.5 mol / L; mixing the prepared impregnation solution with the passivation product, and performing impregnation treatment by a slurry impregnation method, with an impregnation ratio (molar ratio) of Fe:Br:K:Ca=100:7:3:2.7, an impregnation temperature of 37°C, and an impregnation time of 3 hours; and drying the solid material after impregnation at 25°C for 5 hours.

[0118] S3: The impregnated material was exposed to a second gas atmosphere with a system pressure of 3.6 atm and a total gas flow rate of 7700 mL / h / g. Under these conditions, the system was heated from 35°C to 330°C at a heating rate of 2.0°C / min to prepare carbides. The second gas was a mixture of H2 and CO with a molar ratio of H2 to CO of 36:1. The material was treated at 330°C for 5 hours. After the treatment, a χ-iron carbide composite was obtained, which was labeled CX4.

[0119] Example 4-1

[0120] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the H2 flow rate in step S1 is 1200 mL / h / g. The resulting χ-iron carbide composite is labeled CX4-1.

[0121] Example 4-2

[0122] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the H2 flow rate in step S1 is 15000 mL / h / g. The resulting χ-iron carbide composite is labeled CX4-2.

[0123] Example 4-3

[0124] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the H2 flow rate in step S1 is 9000 mL / h / g. The resulting χ-iron carbide composite is labeled CX4-3.

[0125] Example 4-4

[0126] This example uses substantially the same raw materials and process as in Example 1 to prepare a χ-iron carbide composite, with the only difference being that the carbonization temperature in step S3 is 430° C. The resulting χ-iron carbide composite is labeled CX4-4.

[0127] Examples 4-5

[0128] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the carbonization temperature in step S3 is 250° C. The resulting χ-iron carbide composite is labeled CX4-5.

[0129] Examples 4-6

[0130] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the carbonization temperature in step S3 is 360° C. The resulting χ-iron carbide composite is labeled CX4-6.

[0131] Examples 4-7

[0132] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the reduction temperature in step S1 is 470° C. The resulting χ-iron carbide composite is labeled CX4-7.

[0133] Examples 4-8

[0134] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the carbonization pressure in step S3 is 7 atm. The resulting χ-iron carbide composite is labeled CX4-8.

[0135] Examples 4-9

[0136] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the reduction time in step S1 is 12 hours. The resulting χ-iron carbide composite is labeled CX4-9.

[0137] Examples 4-10

[0138] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the carbonization time in step S3 is 6 hours. The resulting χ-iron carbide composite is labeled CX4-10.

[0139] Examples 4-11

[0140] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the reduction pressure in step S1 is 7.0 atm. The resulting χ-iron carbide composite is labeled CX4-11.

[0141] Examples 4-12

[0142] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that the passivation time in step S2 is 45 hours. The resulting χ-iron carbide composite is labeled CX4-12.

[0143] Example 5

[0144] S0: Take 5.6 g of nano-iron particles with an average grain diameter of 20 nm, use the same raw materials and methods as in Example 1 to prepare an impregnation solution, mix the impregnation solution with the nano-iron particles, and perform impregnation treatment by a slurry impregnation method. The impregnation ratio (molar ratio) is Fe:Br:K=100:7:2, the impregnation temperature is 35°C, and the impregnation time is 6 h; the solid material after impregnation is dried at 25°C and 0.05 atm pressure for 5 h to obtain a precursor.

[0145] S1: The precursor prepared in step S0 was kept in H2 at a flow rate of 12000 mL / h / g for 2 h at 370° C. and a pressure of 2.0 atm to perform reduction and surface purification treatment to obtain a reduced product.

[0146] S2: Cooling the reduction product to 30°C and contacting it with a first gas at this temperature for surface passivation treatment to obtain a passivated product; wherein the system pressure is 0.1atm, the gas flow rate is 7500mL / h / g, and the treatment time is 12h; the first gas includes 2vol% oxygen and 98vol% nitrogen.

[0147] S3: The passivation product is brought into contact with a second gas atmosphere. The system pressure is 2.1 atm, and the total gas flow rate is 11,000 mL / h / g. Under these conditions, the system is heated from 30°C to 350°C at a heating rate of 2.0°C / min to prepare carbides. The second gas is a mixture of H2 and CO with a molar ratio of H2 to CO of 50:1. The material is treated at 350°C for 5 hours. After the treatment, a χ-iron carbide composite is obtained, which is labeled CX5.

[0148] Example 6

[0149] S1: 5.6 g of nano-iron particles with an average grain diameter of 20 nm were taken and maintained in H2 at a flow rate of 12000 mL / h / g at 370°C and a pressure of 2.0 atm for 2 h to perform reduction and surface purification treatment to obtain a reduced product.

[0150] S2: Cooling the reduction product to 30°C and contacting it with a first gas at this temperature for surface passivation treatment to obtain a passivated product; wherein the system pressure is 0.1atm, the gas flow rate is 7500mL / h / g, and the treatment time is 12h; the first gas includes 2vol% oxygen and 98vol% nitrogen.

[0151] S3: The passivated product was exposed to a second gas atmosphere at a system pressure of 2.1 atm and a total gas flow rate of 11,000 mL / h / g. Under these conditions, the system was heated from 30°C to 350°C at a heating rate of 2.0°C / min to prepare carbides. The second gas was a mixture of H2 and CO with a molar ratio of H2 to CO of 50:1. The material was treated at 350°C for 5 hours. After treatment, a product containing iron carbide was obtained.

[0152] S31: An impregnation solution was prepared using the same raw materials and methods as in Example 1. The impregnation solution was mixed with a product containing iron carbide and impregnated using a slurry impregnation method. The impregnation ratio (molar ratio) was Fe:Br:K = 100:7.0:2.0, the impregnation temperature was 32°C, and the impregnation time was 2 hours. The solid material after impregnation was dried at 25°C for 9 hours. A χ-iron carbide composite was obtained, labeled CX6.

[0153] Comparative Example 1

[0154] This example uses substantially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, with the only difference being that in step S21, the impregnation ratio (molar ratio) is Fe:Br:K = 100:50.0:2.0. The resulting χ-iron carbide composite is labeled DX1.

[0155] Comparative Example 2

[0156] This example used essentially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite, differing only in that manganese bromide was omitted from the impregnation solution prepared in step S21. This impregnation solution was then used to impregnate the nano-iron particles. The resulting χ-iron carbide composite was labeled D2.

[0157] Comparative Example 3

[0158] This example uses essentially the same raw materials and process as Example 1 to prepare a χ-iron carbide composite. The only difference is that in the preparation of the impregnation solution in step S21, manganese chloride is used in place of manganese bromide in equal amounts. The resulting χ-iron carbide composite is labeled DX3.

[0159] Comparative Example 4

[0160] Using the same raw materials and steps as in steps S1 to S3 of Example 1, but omitting the impregnation step S21, x-iron carbide was obtained, labeled D4.

[0161] Comparative Example 5

[0162] This example uses substantially the same raw materials and processes as Example 1 to prepare a χ-iron carbide composite, with the only difference being that in step S3, the ratio of the second gas atmosphere H2 to CO is 120:1. The resulting χ-iron carbide composite is labeled DX5.

[0163] The χ-iron carbide composites and χ-iron carbide prepared in each example and comparative example were subjected to XRD, Mössbauer spectroscopy and ICP determination, wherein the content of χ-iron carbide is calculated based on 100 mol, and the relevant content refers to the number of moles. Specific results are shown in Table 1.

[0164] The catalytic performance of the χ-iron carbide composites and χ-iron carbide prepared in each example and comparative example was evaluated in a slurry bed continuous reactor. The catalyst loading was 9.0 g. Evaluation conditions: T = 277°C, P = 2.75 MPa, H2:CO = 2.1:1, total (H2 + CO) = 14500 mL / h / g- Fe The reaction was carried out and the reaction products were analyzed by gas chromatography. The reaction performance evaluation data after 24 h and 300 h of reaction are shown in Tables 2 and 3.

[0165] Table 1

[0166] Table 2

[0167] Table 3

[0168] Combining the results of the Examples, Comparative Examples, and Tables 1-3, it can be seen that compared to Example 1, the impregnation solution of Comparative Example 2 does not contain manganese bromide, indicating that the composite prepared in Comparative Example 2 does not contain manganese ions and bromide ions. The results in Table 2 show that although the CO conversion rate of Comparative Example 2 is higher than that of Example 1, its CO2 selectivity of 38.7% is much higher than the CO2 selectivity of 2.3% in Example 1, and its carbon atom utilization (61.3%) and effective product selectivity (57.4%) are much lower than the carbon atom utilization (97.7%) and effective product selectivity (93.5%) in Example 1. Therefore, the composite of Example 1 can improve the overall efficiency of the reaction compared to the composite of Comparative Example 2, achieving optimized comprehensive reaction results.

[0169] Furthermore, Example 1-1 differs from Example 1 in that a different halide, ferrous bromide, is used. The results in Table 2 show that the reaction performance data of Example 1-1 and Example 1 are not much different, indicating that the improvement in performance of Example 1 over Comparative Example 2 is primarily due to the addition of bromide ions rather than manganese ions.

[0170] Furthermore, the main difference between Example 2 and Example 1-2 is that iodide ions are introduced into the prepared composite, rather than bromide ions. The results in Table 2 show that the reaction performance data of Example 2 are not much different from those of Examples 1-2, indicating that the introduction of iodide ions into iron carbide can also improve the overall performance of the reaction. In addition, the difference between Comparative Example 3 and Example 1 is that chloride ions are introduced into the prepared composite, rather than bromide ions. The results in Table 2 show that all the reaction performances of Comparative Example 3 are significantly lower than those of Example 1, and the overall results of the reaction cannot be optimized.

[0171] Furthermore, while bromide ions were also introduced into the iron carbide of Comparative Example 1, the bromide ion content was relatively high, exceeding the range of a molar ratio of χ-iron carbide to halide ions of 100:(0.1-45) specified in one embodiment of the present invention. The results in Table 2 indicate that the CO conversion rate in Comparative Example 1 was only 38.6%, significantly lower than the 81.8% CO conversion rate in Example 1. Furthermore, the carbon atom utilization and effective product selectivity in Comparative Example 1 were significantly lower than those in Example 1. Therefore, when the bromide ion content in the iron carbide composite exceeds a certain range, comprehensive optimization of the reaction results cannot be achieved.

[0172] Furthermore, the difference between Examples 1 to 1-7 mainly lies in the different contents of bromide ions. Combining the results in Tables 2 and 3, the molar ratio of iron carbide (or iron element) to bromide ions in the prepared composite is preferably 100:(7-20).

[0173] Furthermore, the difference between Examples 3 to 3-8 mainly lies in the different contents of other cations. Combining the results in Tables 2 and 3, the molar ratio of iron carbide (or iron element) to other cations in the prepared composite is preferably 100:(0.1-12).

[0174] Furthermore, the results in Table 3 indicate that the reactions catalyzed by the composites of various embodiments of the present invention can maintain stable CO conversion rates, product selectivity, and other characteristics over a prolonged period. Thus, by including halide ions such as bromine or iodine in the χ-iron carbide composite and limiting the halide ion content to a specific range, using it as a catalyst for the Fischer-Tropsch synthesis reaction can improve the overall efficiency of the reaction and optimize the overall reaction results.

[0175] In summary, the χ-iron carbide composite containing halide ions such as bromine or iodine prepared in accordance with the present invention, when used as a catalyst for synthesis gas conversion reactions under industrial conditions, can exhibit ultra-low CO2 selectivity, low CH4 selectivity, extremely high carbon atom utilization efficiency, and selectivity for effective products while maintaining a high CO conversion rate (>60%). Further long-term experiments were conducted. From the data in Table 3 after 300 hours of reaction, it can be seen that the CO conversion rate, product selectivity, carbon atom utilization efficiency, and effective product selectivity of the χ-iron carbide composite of the present invention as a catalyst in a stirred tank remained stable after long-term continuous operation, without significant changes, demonstrating good operational stability. Thus, by using the χ-iron carbide composite of the present invention as a catalyst for synthesis gas conversion reactions, comprehensive optimization of reaction results can be achieved.

[0176] Unless otherwise defined, the terms used in the present invention have the same meanings as those commonly understood by those skilled in the art.

[0177] The embodiments described in the present invention are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art may make various other substitutions, changes and improvements within the scope of the present invention. Therefore, the present invention is not limited to the above-mentioned embodiments, but is only limited by the claims.

Claims

1. A χ-iron carbide composite, comprising iron carbide and halide ions, wherein the iron carbide comprises χ-iron carbide, and the halide ions are bromide ions and / or iodide ions; the molar ratio of the χ-iron carbide to the halide ions is 100:(0.1-45), and the molar number of the χ-iron carbide is calculated by the molar number of iron element contained therein; in, The composite has a monoclinic crystal structure.

2. The composite according to claim 1, comprising a first cation, wherein the first cation comprises other cations, and the molar ratio of the χ-iron carbide to the other cations is 100:(0.1-23), and can further be 100:(0.1-17); and / or, The average crystal grain diameter of the composite is 6-35 nm.

3. The composite according to claim 2, wherein The first cation comprises a halide cation, and the halide cation is capable of maintaining charge balance with the halide ion; and / or, The molar ratio of the χ-iron carbide to the halide ion is 100:(0.5-27); and / or, The complex also includes other anions, and the other cations are capable of maintaining charge balance with the other anions.

4. The composite according to claim 3, wherein The halide cation includes one or more of a first metal ion and a complex cation; and / or, The other cations include one or more of the second metal ions, wherein the second metal ions include one or more of manganese ions, copper ions, cobalt ions, molybdenum ions, chromium ions, rare earth ions, alkali metal ions, and alkaline earth metal ions; and / or, The other anions include one or more of oxygen ions, complex ions, and acid radical ions.

5. The composite according to claim 4, wherein The first metal ion includes one or more of iron ion, manganese ion, copper ion, cobalt ion, molybdenum ion, and rare earth ion; the complex cation includes one or more of hexaammine manganese ion, hexaammine iron ion, and hexaammine copper ion; and / or, The other cations include one or more of manganese ions, copper ions, cobalt ions, molybdenum ions, chromium ions, lanthanum ions, cerium ions, neodymium ions, sodium ions, potassium ions, calcium ions, and barium ions; and / or, The other anions include one or more of oxygen ions, nitrate, citrate, and gluconate.

6. A method for preparing the χ-iron carbide composite according to any one of claims 1 to 5, comprising the following steps: S1: Under the action of hydrogen, the precursor is reduced and surface purified at a temperature of 260° C. to 470° C. to obtain a reduced product; S2: The reduced product is subjected to surface passivation treatment at a temperature of 0°C to 40°C in a first gas atmosphere to obtain a passivated chemical products; and S3: treating the passivation product in a second gas atmosphere at a temperature of 250° C. to 430° C. to form a product containing iron carbide; in, The first gas includes 1 volume % to 3 volume % of oxygen; the second gas includes hydrogen and carbon monoxide, and the molar ratio of the hydrogen to the carbon monoxide is (8-90):1; The precursor is nano-iron and / or nano-iron compound subjected to a first impregnation treatment by an impregnation solution, and the nano-iron compound can be prepared into nano-iron by a reduction reaction; or, The precursor is nano-iron and / or the nano-iron compound, and the passivation product is subjected to a second immersion treatment in the immersion solution and then subjected to the treatment of step S3; or, The precursor is nano-iron and / or the nano-iron compound, and the product containing iron carbide is subjected to a third impregnation treatment through the impregnation liquid; the impregnation liquid includes bromide ions and / or iodine ions.

7. The preparation method according to claim 6, wherein: The nano iron compound comprises one or more of nano iron oxide, nano magnetite, nano goethite and nano iron hydrate oxide; and / or, The impregnation solution is prepared by dissolving a solute in a solvent, wherein the solute comprises a halide, and the halide comprises bromide and / or iodide; and / or, The material after the first impregnation treatment, the second impregnation treatment or the third impregnation treatment is dried at 15-40°C.

8. The preparation method according to claim 7, wherein: The halide includes one or more of bromides and iodides containing manganese, iron, copper, cobalt, molybdenum, and rare earth metal elements; and / or, The solvent comprises water and / or ethanol; and / or, The concentration of the halide in the impregnation solution is 0.7 to 7 mol / L; and / or, The solute also includes other compounds, which include one or more salts of molybdenum, manganese, copper, alkaline earth metals, cobalt, rare earth metals, and alkali metals; wherein no chemical reaction occurs between the components of the solute.

9. The preparation method according to any one of claims 6 to 8, wherein The temperature of the first immersion treatment, the second immersion treatment or the third immersion treatment is 0 to 50° C., and can further be 20 to 30° C.; the time of the first immersion treatment is 0.1 to 12 hours, and can further be 0.2 to 10 hours, and further can be 0.3 to 9 hours.

10. The preparation method according to any one of claims 6 to 9, wherein The treatment pressure in step S1 is 0.12 to 10 atm, and can further be 0.15 to 7 atm; the treatment time is 1.2 to 25 hours, and can further be 2 to 12 hours; and / or, The treatment pressure in step S2 is 0 to 1.5 atm, and can further be 0 to 0.09 atm; the treatment time is 2 to 60 hours. Further, it may be 3 to 45 hours; and / or, The processing pressure of step S3 is 0.08 to 17 atm, and can further be 0.15 to 7 atm; the processing time is 0.3 to 24 hours, and can further be 0.5 to 6 hours.

11. A catalyst comprising the χ-iron carbide composite according to any one of claims 1 to 5 or the χ-iron carbide composite prepared by the preparation method according to any one of claims 6 to 10.

12. Use of the x-iron carbide composite according to any one of claims 1 to 5, the x-iron carbide composite obtained by the preparation method according to any one of claims 6 to 10, or the catalyst according to claim 11 in a synthesis gas conversion reaction.

13. Use of the χ-iron carbide composite according to any one of claims 1 to 5, the χ-iron carbide composite obtained by the preparation method according to any one of claims 6 to 10, or the catalyst according to claim 11 in a reaction for synthesizing C, H fuels and / or chemicals based on the Fischer-Tropsch synthesis principle.

14. A synthesis gas conversion process, comprising contacting the catalyst according to claim 11 with synthesis gas under reaction conditions to react.

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