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KR-20260068085-A - Fischer-Tropsch catalyst

KR20260068085AKR 20260068085 AKR20260068085 AKR 20260068085AKR-20260068085-A

Abstract

The Fischer-Tropsch catalyst comprises a substantially homogeneous mixture of cobalt and alumina, and the catalyst comprises a pore volume (PV) of 0.3 cc/g to 0.5 cc/g and an average pore diameter (PD) in the range of 18 nm to 30 nm. Methods for preparing the Fischer-Tropsch catalyst are also included in the present disclosure.

Inventors

  • 에스피노사, 라파엘 루이스

Assignees

  • 디멘셔널 에너지, 인코포레이티드

Dates

Publication Date
20260513
Application Date
20230913

Claims (20)

  1. As a method for preparing a Fischer-Tropsch catalyst, the method is: A step of mixing a first precursor and a second precursor sufficient to form a mixture, wherein the first precursor comprises cobalt and the second precursor comprises one or more aluminum-containing compounds; A step of mixing a first precursor and a second precursor sufficient to form a structure, and then molding the mixture; A step of drying the structure; A step of calcining the structure sufficient to form a catalyst; and The method includes the step of optionally adding one or more metals to the catalyst; A catalyst comprises a pore volume (PV) and an average pore diameter (PD), and the catalyst in oxide form follows the equation PV 0.5 x PD 0.65 > 2, where PV is measured in cc/g units and PD is measured in nm units.
  2. In Article 1, A method comprising a step of drying the structure, wherein the step of heating at a temperature between 70°C and 180°C.
  3. In Article 1, A method comprising a step of firing the structure, wherein the step of heating at a temperature of less than 500℃.
  4. In Article 1, A method comprising a step of firing the structure, wherein the step of heating at a temperature between 500°C and 725°C.
  5. In Article 1, A method comprising a mixture having a modified Loss on Ignition (MLOI) value between 30 and 60.
  6. In Article 1, A method in which the first precursor comprises cobalt nitrate, the catalyst comprises cobalt oxide, and 25% to 75% by weight of the cobalt oxide in the catalyst prior to reduction is present from the first precursor.
  7. In Article 1, A method wherein the first precursor further comprises a metal salt, the catalyst comprises metal oxide(s), 25% to 75% by weight of the metal oxide(s) in the catalyst prior to reduction is present from the first precursor, and the metal salt comprises one or more of iron and ruthenium.
  8. In Article 1, A method in which the first precursor comprises cobalt nitrate and silver nitrate.
  9. In Article 1, A method in which an aluminum-containing compound comprises one or more of boehmite and alumina.
  10. In Article 1, A method in which the second precursor further comprises one or more of aluminum, silica, silicon, titania, titanium, zirconia, and zirconium.
  11. In Article 1, A method comprising the additional step of adding ruthenium after molding the mixture.
  12. In Article 11, A method in which ruthenium is added by an impregnation step without other metals.
  13. In Article 1, A method in which the fracture strength (CS) of the catalyst is 1.8 kg/mm or higher.
  14. In Article 1, One or more metals are selected from cobalt, ruthenium, and iron.
  15. In Article 1, A method comprising a blend of cobalt and alumina, wherein the catalyst comprises a pore volume (PV) in the range of 0.3 cc/g to 0.5 cc/g and an average pore diameter (PD) in the range of 18 nm to 30 nm.
  16. In Article 1, The catalyst is a non-supported catalyst, method.
  17. In Article 1, A method in which a catalyst is used in a fixed-bed, slurry, boiling-bed, or fluidized-bed Fischer-Tropsch reactor, and the catalyst is used to directly produce or through further processing Fischer-Tropsch primary products, light olefins, gasoline, diesel, paraffin, jet fuel, wax, lubricating oil, drilling fluids, primary olefins, and hydrocarbon-based chemicals.
  18. A Fischer-Tropsch catalyst comprising a substantially homogeneous blend of cobalt and alumina, wherein the catalyst comprises a pore volume (PV) in the range of 0.3 cc/g to 0.5 cc/g and an average pore diameter (PD) in the range of 18 nm to 30 nm.
  19. In Article 18, The pore volume and average pore diameter follow the equation PV 0.5 x PD 0.65 > 2, where PV is measured in cc/g and PD is measured in nm, for the catalyst.
  20. In Article 18, A catalyst in which the weight percentage of cobalt in the catalyst is in the range of about 20 weight% to about 40 weight%.

Description

Fischer-Tropsch catalyst The Fischer-Tropsch process is a catalytic chemical reaction designed to convert carbon monoxide and hydrogen into hydrocarbons of various molecular weights. Depending on the catalyst and operating conditions, hydrocarbons of varying molecular weights can be produced. The Fischer-Tropsch reaction is highly exothermic, and the process may include one or more reactors, separation units, compressors, heat exchangers, and recirculation streams. Reactors used in the Fischer-Tropsch process may include fixed-bed reactors, fluidized-bed reactors, tubular fixed-bed reactors, and slurry-bed reactors. Typically, the input hydrogen and carbon monoxide must be compressed to high pressure before entering the reactor, and the reactor usually contains a catalyst to increase the reaction rate. While many catalysts have been developed for the Fischer-Tropsch reaction, these catalysts can face challenges due to rapid degradation, sintering, and costly and time-consuming formulation processes. Furthermore, catalyst selectivity and activity control remain critical challenges in these catalytic reactions. Therefore, it is desirable to efficiently produce a Fischer-Tropsch catalyst having excellent activity, selectivity, and stability. This written disclosure describes exemplary embodiments that are not limiting and are not exhaustive. The exemplary embodiments illustrated in the drawings are referenced, in which: FIG. 1 illustrates a system (100) for Fischer-Tropsch synthesis according to some embodiments. FIG. 2 illustrates a method (200) for processing feedstock according to some embodiments. FIG. 3 illustrates a method (300) for manufacturing a Fischer-Tropsch catalyst according to some embodiments. FIG. 4 illustrates a method (400) for manufacturing a Fischer-Tropsch catalyst according to some embodiments. FIG. 5A illustrates catalyst pore volumes according to various cobalt weight percentages and calcination temperatures according to some embodiments. FIG. 5B shows a parity plot of predicted pore volume versus experimental pore volume according to some embodiments. FIG. 6A illustrates the effect of cobalt addition before molding according to some embodiments on the final catalyst pore volume. FIG. 6B illustrates the effect of cobalt addition before molding according to some embodiments on the final catalyst pore volume. FIG. 7 illustrates the pore size distribution of a Fischer-Tropsch catalyst according to some embodiments. FIG. 8 illustrates the effect of a pore regulating agent (PRA) on pore size distribution according to some embodiments. FIG. 9A illustrates modified loss on ignition (MLOI) versus pore volume according to some embodiments. FIG. 9B illustrates pore volume versus pore diameter according to some embodiments. FIG. 10 illustrates an apparatus for testing crushing strength according to some embodiments. FIG. 11 illustrates pore diameter versus crushing strength according to some embodiments. FIG. 12 illustrates the temperature programmed reduction (TPR) of various catalysts according to some embodiments. FIG. 13 illustrates the warm-temperature reduction (TPR) of various catalysts having different Ru contents according to some embodiments. FIG. 14 illustrates a predictive plot including an equation factor for activity according to some embodiments. definition As used herein, terms such as "catalyst" and "catalytic material" refer to a material that enables a chemical reaction to proceed at a faster rate or under different conditions (e.g., at a lower temperature) than would otherwise be possible. The catalyst of the present disclosure may be adapted and designed for Fischer-Tropsch catalytic reactions. Additionally, the catalyst of the present invention may comprise a mixture of two or more catalytic materials and other inert materials. The catalytic material used in the present invention may be formed into a desired shape or size. argument The Fischer-Tropsch (FT) process utilizes catalysts to convert carbon monoxide and hydrogen into hydrocarbons of various molecular weights. Catalysts can increase the rate of chemical reactions and/or lower the temperature required to initiate the chemical reaction. An example equation for a reaction in the Fischer-Tropsch process is shown below as Equation 1, where n = 1 or greater. A side reaction in the Fischer-Tropsch process may be a water gas shift reaction, shown as Equation 2. The input ratios of the reactants H₂ and CO can be adjusted using a synthesis gas production process. For example, the Fischer-Tropsch reaction can proceed at temperatures above approximately 180°C and pressures above approximately 20 bar. Conventional catalysts suffer from inefficient selectivity and activity values. Furthermore, these conventional catalysts require extensive formation steps. Therefore, it is desirable to use a catalyst that can maintain high selectivity while reducing unwanted reactions. Embodiments of the present disclosure provide novel Fischer-T