Pre-treatment of a bi-functional catalyst for the production of c2 to c5 hydrocarbons

Abstract

A process for producing C2 to C5 hydrocarbons, the process comprising introducing a feed stream comprising hydrogen and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor, and converting the feed stream into a product stream comprising C2 to C5 hydrocarbons in the presence of a shaped mixed catalyst in the reaction zone. The shaped mixed catalyst comprises a metal oxide catalyst component comprising nickel oxide, gallium oxide, and zirconium oxide; a microporous catalyst component is a molecular sieve having 8-MR (member ring) pore openings; and wherein the mixed catalyst is reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C.

Description

Technical Field

[0001] This disclosure relates to methods for efficiently converting various carbon-containing streams into C2 to C5 hydrocarbons. Specifically, this disclosure relates to the preparation of mixed catalysts, the prepared mixed catalysts, and the application of process methods to achieve high carbon conversion rates and desired product yields. Background Technology

[0002] For many industrial applications, hydrocarbons are used or serve as starting materials to produce plastics, fuels, and a variety of downstream chemicals. These hydrocarbons include C2 to C5 alkanes, such as ethane, propane, butane, and pentane. Various methods have been developed for producing these lower hydrocarbons, including petroleum cracking and various synthetic methods.

[0003] Synthetic methods for converting feed carbon into desired products, such as hydrocarbons, are known. Different types of catalysts, as well as different types of feed streams and the proportions of feed stream components, have been studied.

[0004] Many of these synthetic methods exhibit low carbon conversion rates, and much of the feed carbon remains unconverted and exits the process in the same form as the feed carbon, or is converted to CO2. Furthermore, these synthetic methods can exhibit low stability over time, and the catalysts rapidly lose their activity or selectivity for the carbon conversion of the desired products. Therefore, there is a need for methods and catalytic systems that increase the yield of C2 to C5 hydrocarbons, especially as operating times increase. Summary of the Invention

[0005] The embodiments of this disclosure address these and other needs through the preparation of mixed catalysts and / or shaped mixed catalysts and methods of using such catalysts. In one embodiment, the mixed catalyst comprises a combination of a metal oxide catalyst component and a microporous catalyst component, wherein the mixed catalyst is reduced in a hydrogen-containing atmosphere. In another embodiment, the shaped mixed catalyst comprises a mixed catalyst as provided herein and a binder to provide a single catalyst body, wherein the shaped mixed catalyst is reduced in a hydrogen-containing atmosphere as discussed herein. The mixed catalyst and / or shaped mixed catalyst can be used in methods for preparing C2 to C5 hydrocarbons, wherein a feed stream containing hydrogen and a carbon-containing gas (such as syngas) forms C2 to C5 hydrocarbons. The metal oxide catalyst component and the microporous catalyst component can be operated in series, such that the mixed catalyst and / or shaped mixed catalyst can directly and selectively convert a feed stream containing hydrogen and a carbon-containing gas (such as syngas) into C2 to C5 hydrocarbons having a high alkane / olefin ratio.

[0006] According to one or more aspects of this disclosure, a method for preparing C2 to C5 hydrocarbons includes introducing a feed stream comprising hydrogen and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into a reaction zone of a reactor, and converting the feed stream into a product stream comprising C2 to C5 hydrocarbons in the reaction zone in the presence of a mixed catalyst and / or a shaped mixed catalyst. The mixed catalyst comprises a metal oxide catalyst component and a microporous catalyst component, the metal oxide catalyst component including nickel oxide, gallium oxide, and zirconium oxide; the microporous catalyst component is a molecular sieve having 8-MR (membered ring) pore openings, wherein the mixed catalyst is reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C. In embodiments, the mixed catalyst may further comprise a binder to provide a shaped mixed catalyst, wherein the binder includes alumina, zirconium oxide, or mixtures thereof. In embodiments, as discussed herein, the shaped mixed catalyst can be reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C.

[0007] According to one or more other aspects of this disclosure, a method for preparing a mixed catalyst includes mixing a metal oxide catalyst component and a microporous catalyst component, the metal oxide catalyst component including nickel oxide, gallium oxide, and zirconium oxide, and the microporous catalyst component being a molecular sieve having 8-MR (membered ring) pore openings; and reducing the mixed catalyst in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C. As described herein, the mixed catalyst may also contain a binder to provide a shaped mixed catalyst, wherein the binder includes alumina, zirconium oxide, or mixtures thereof, and wherein the shaped mixed catalyst can be reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C.

[0008] Further features and advantages will be set forth in the following detailed description, and in part will be apparent to those skilled in the art from those description or will be recognized by practice of the embodiments described herein, including the following detailed description and claims.

[0009] It should be understood that both the foregoing general description and the following detailed description describe various implementation schemes and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. Detailed Implementation

[0010] Reference will now be made in detail to embodiments of methods for preparing and / or shaping mixed catalysts, and methods for forming C2 to C5 hydrocarbons from a feed stream containing hydrogen and carbon-containing gases using the aforementioned catalysts. As used herein, “carbon-containing gas” means a gas selected from carbon monoxide, carbon dioxide, and mixtures thereof. As used herein, “synthesis gas” means a gas containing both hydrogen and carbon-containing gases.

[0011] For the implementation scheme, the method for preparing C2 to C5 hydrocarbons includes introducing a feed stream comprising hydrogen and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof into the reaction zone of a reactor; and converting the feed stream into a product stream comprising C2 to C5 hydrocarbons in the reaction zone in the presence of a mixed catalyst and / or a shaped mixed catalyst. The mixed catalyst and the shaped mixed catalyst can be formed by methods for preparing mixed catalysts and shaped mixed catalysts as described herein.

[0012] As used herein, “C2 to C5 hydrocarbons” includes C2 to C5 alkenes and / or C2 to C5 alkanes and subsets of these carbon ranges, such as C2 to C5 hydrocarbons, including C2 to C5 alkenes and / or C2 to C5 alkanes, wherein “C2 to C5 hydrocarbons” as used herein may be replaced by any of C2 to C5 alkenes, C2 to C5 alkanes, C2 to C5 hydrocarbons and / or C2 to C5 alkenes. “C2 to C5 hydrocarbons” may also include straight-chain and branched alkanes and alkenes.

[0013] In one embodiment, the mixed catalyst comprises a metal oxide catalyst component and a microporous catalyst component. The metal oxide catalyst component includes nickel oxide, gallium oxide, and zirconium oxide; the microporous catalyst component is a molecular sieve with 8-MR pore openings. In another embodiment, the mixed catalyst is reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C. This disclosure also includes embodiments in which the mixed catalyst is a shaped mixed catalyst comprising a binder, the binder including alumina, zirconium oxide, or mixtures thereof. That is, the shaped mixed catalyst is a subset of the mixed catalysts provided herein, wherein the reduction treatment of this disclosure is equally applicable to mixed catalysts and / or shaped mixed catalysts.

[0014] For implementation schemes, the mixed catalysts provided herein may be present in the form of a physical mixture, which is a loose mixture or physically / mechanically pressed together in a tableting manner; or in an extruded form (e.g., the mixed catalyst also contains a binder as provided herein to allow the mixed catalyst to be extruded), as discussed herein. It should be understood that when a binder is present with the mixed catalyst, the term "mixed catalyst" as used herein also includes the term "shaped mixed catalyst" and may be interchanged / substituted with "shaped mixed catalyst". Thus, the method for preparing C2 to C5 hydrocarbons as discussed herein includes converting a feed stream into a product stream containing C2 to C5 hydrocarbons in the reaction zone of a reactor in the presence of a shaped mixed catalyst, wherein the shaped mixed catalyst comprises a metal oxide catalyst component and a microporous catalyst component, the metal oxide catalyst component including nickel oxide, gallium oxide, and zirconium oxide; the microporous catalyst component being a molecular sieve having 8-MR (membered ring) pore openings; and wherein the shaped mixed catalyst is reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C, wherein all terms and phrases are as defined and discussed herein.

[0015] The use of blended catalysts and / or shaped blended catalysts is known in the field of hydrocarbon products such as diesel or aromatic compounds. However, many known blended catalysts and / or shaped blended catalysts are inefficient for both the formation of C2 to C5 hydrocarbons, C2 to C5 alkanes, and C2 to C5 olefins from feed streams containing hydrogen and carbon-containing gases, because they exhibit low feed carbon conversion and / or rapid deactivation during use, for example by increasing methane production. This results in low and unstable C2 to C5 hydrocarbon productivity over a given set of operating conditions and a given time period. Known shaped blended catalysts for the production of C2 to C5 alkanes exhibit increasing C2 to C5 olefin selectivity over time. In contrast, the blended catalysts and / or shaped blended catalysts disclosed and described herein exhibit significantly higher and more stable C2 to C5 alkanes selectivity at comparable levels of total CO conversion and hydrocarbon productivity, compared to blended catalysts and / or shaped blended catalysts that do not undergo re-reduction at temperatures from 450°C to 750°C in a hydrogen-containing atmosphere according to this disclosure. The preparation and composition of such mixed catalysts and / or shaped mixed catalysts used in the embodiments are discussed below.

[0016] In summary, mixed catalysts and / or shaped mixed catalysts tightly couple the independent reactions on each of the two independent catalysts. In the first step, a feed stream containing hydrogen (H2) and a carbon-containing gas selected from the group consisting of carbon monoxide (CO), carbon dioxide (CO2), or a mixture of CO and CO2, such as syngas, is converted into intermediates, such as oxygenated hydrocarbons. In subsequent steps, these intermediates are converted into a product stream containing hydrocarbons (primarily short-chain hydrocarbons, such as C2 to C5 hydrocarbons). The continuous formation and consumption of intermediate oxygenated compounds formed in the first step by the reaction in the second step ensures that there are no thermodynamic limitations on the conversion.

[0017] In one or more embodiments, the metal oxide catalyst component may include zirconium oxide, wherein the zirconium oxide acts as a metal oxide support. The term "metal oxide support" may refer to a support material on which other components of the metal oxide catalyst component (e.g., nickel oxide, gallium oxide, and optionally rare earth oxides (e.g., lanthanum oxide)) are supported. In some embodiments, the zirconium oxide of the metal oxide catalyst component may include micropores. The term "micropore" may refer to a pore of material in which one or more pores have a diameter less than 2 nm. In some embodiments, the zirconium oxide of the metal oxide catalyst component may include mesopores. The term "mesopore" may refer to a pore of material in which one or more pores have a diameter of 2 nm to 50 nm. In some embodiments, the zirconium oxide of the metal oxide catalyst component may include macropores. The term "macropore" may refer to a pore of material in which one or more pores have a diameter greater than or equal to 80 nm.

[0018] For various implementations, zirconia can have a macroporosity fraction of less than 0.3. The term "macroporosity fraction" refers to the ratio of the macropore volume of zirconia to the total pore volume of pores smaller than 500 nm. To test the macroporosity fraction, mercury intrusion porosimetry can be used, where the porosity of zirconia is measured by immersing the material in mercury and applying controlled pressure to the system, allowing the mercury to permeate into the pores of the material. Based on the pressure required to force mercury into certain pores of the zirconia, the pore diameter and pore volume can be calculated. The correlation between pore diameter and the associated pressure can be achieved using Equation I, where D is the diameter of the zirconia pore, P is the pressure required for mercury to permeate the zirconia pore, γ is the surface tension of mercury, and θ is the contact angle between zirconia and mercury.

[0019] (Formula I)

[0020] For each embodiment, zirconia may have a macroporosity fraction of less than 0.3, such as less than 0.25, less than 0.20, less than 0.15, or even less than 0.10. In one or more embodiments, the macroporosity fraction may be 0.05 to 0.25, 0.10 to 0.25, or 0.10 to 0.20. In another embodiment, the macroporosity fraction may be 0.05 to 0.25, 0.05 to 0.20, 0.05 to 0.15, or 0.0 to 0.10. In yet another embodiment, the macroporosity fraction may be 0.10 to 0.30, 0.15 to 0.30, 0.20 to 0.30, or 0.25 to 0.30.

[0021] In one embodiment, the metal oxide catalyst component includes nickel oxide, gallium oxide, and zirconium oxide (ZrO2). In another embodiment, the metal oxide catalyst component includes nickel oxide, gallium oxide, rare earth oxides, and zirconium oxide (ZrO2). As used herein, "rare earth oxide" refers to an oxide containing a rare earth element, including scandium, yttrium, and elements with atomic numbers from 57 to 71, such as, but not limited to, samarium, gadolinium, dysprosium, lanthanum, cerium, and neodymium. For example, in another embodiment, the metal oxide catalyst component includes gallium oxide, nickel oxide, lanthanum oxide, and zirconium oxide (ZrO2).

[0022] As used herein, in the embodiments disclosed and described herein, the zirconium oxide used in the metal oxide catalyst component of the formed mixed catalyst is "phase-pure zirconium oxide," which is defined herein as zirconium oxide in which no other materials are intentionally added during formation. Therefore, "phase-pure zirconium oxide" comprises zirconium oxide having small amounts of components other than zirconium (including oxides other than zirconium oxide) that are unintentionally present in the zirconium oxide as a natural part of the zirconium oxide formation process, such as hafnium (Hf). Therefore, unless otherwise specifically stated, the terms "zirconium oxide" and "phase-pure zirconium oxide" are used interchangeably herein.

[0023] Unbound by any specific theory, it is believed that the high surface area of ​​zirconium oxide allows nickel oxide, gallium oxide catalysts, and optional rare earth oxides, acting as part of a shaped mixed catalyst, to convert carbonaceous components into C2 to C5 hydrocarbons. It is believed that nickel oxide, gallium oxide, and optional rare earth oxides, along with zirconium oxide, facilitate mutual activation, thereby increasing the yield of C2 to C5 hydrocarbons.

[0024] In some embodiments, the metal oxide catalyst component includes gallium oxide. As used herein, "gallium oxide" refers to gallium in various oxidation states. In some embodiments, gallium oxide may be deposited on the surface of zirconium oxide or form a solid solution with zirconium oxide. In other embodiments, gallium oxide may include, but is not limited to, Ga₂O₃, GaO(OH), and Ga₅O. 7-(OH). Gallium oxide may also include polymorphs of Ga₂O₃, such as monoclinic (β-Ga₂O₃), rhombohedral (α-Ga₂O₃), defect spinel (γ-Ga₂O₃), cubic (δ-Ga₂O₃), or orthorhombic (ε-Ga₂O₃) structures. In other embodiments, gallium oxide may include gallium in more than one oxidation state. For example, individual gallium particles may be in different oxidation states. Gallium oxide is not limited to gallium comprising a uniform oxidation state.

[0025] In embodiments, the metal oxide catalyst component includes nickel oxide. As used herein, "nickel oxide" refers to nickel in various oxidation states. In embodiments, nickel oxide may be deposited on the surface of zirconium oxide or form a solid solution with zirconium oxide. In other embodiments, nickel oxide may include, but is not limited to, NiO and Ni2O3. Nickel oxide may also include polymorphs of NiO, such as rock salt structures or hexagonal NiO structures. In other embodiments, nickel oxide may include nickel in more than one oxidation state. For example, individual nickel may be in different oxidation states. Nickel oxide is not limited to nickel containing a uniform oxidation state.

[0026] In the implementation scheme, the reduced mixed catalyst contains Ni 0 Alloys of Ni and Ga, or intermetallic compounds of Ni and Ga. Alloys and intermetallic compounds may include, but are not limited to, NiGa, Ni5Ga3, and Ni3Ga1.

[0027] In the embodiments disclosed herein, the composition of the metal oxide catalyst component is expressed as a millimole (mmol) / weight ratio of nickel, gallium metal, and optionally rare earth oxides relative to pure zirconium oxide (considering the stoichiometry of ZrO2). For example, the metal oxide catalyst component comprises 6 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel per 100 g zirconium oxide, and 5 mmol of gallium per 100 g zirconium oxide to 80 mmol of gallium per 100 g zirconium oxide. Other values ​​are possible. For example, according to embodiments, the metal oxide catalyst component comprises 6 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel, such as 7 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel, 8 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel, 10 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel, 12 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel, or 15 mmol of nickel per 100 g zirconium oxide to 20 mmol of nickel. In some embodiments, the metal oxide catalyst component comprises 6 mmol to 18 mmol of nickel per 100 g of zirconium oxide, such as 6 mmol to 16 mmol of nickel per 100 g of zirconium oxide, 6 mmol to 15 mmol of nickel per 100 g of zirconium oxide, 6 mmol to 12 mmol of nickel per 100 g of zirconium oxide, or 6 mmol to 10 mmol of nickel per 100 g of zirconium oxide. In some embodiments, the metal oxide catalyst component comprises 7 mmol of nickel to 18 mmol of nickel per 100 g of zirconium oxide, such as 8 mmol of nickel to 18 mmol of nickel per 100 g of zirconium oxide, 10 mmol of nickel to 18 mmol of nickel per 100 g of zirconium oxide, 12 mmol of nickel to 18 mmol of nickel per 100 g of zirconium oxide, or 14 mmol of nickel to 18 mmol of nickel per 100 g of zirconium oxide. In some embodiments, the metal oxide catalyst component includes 10 mmol nickel per 100g zirconium oxide to 18 mmol nickel per 100g zirconium oxide, such as 12 mmol nickel per 100g zirconium oxide to 18 mmol nickel per 100g zirconium oxide, 14 mmol nickel per 100g zirconium oxide to 18 mmol nickel per 100g zirconium oxide, or 16 mmol nickel per 100g zirconium oxide to 18 mmol nickel per 100g zirconium oxide.

[0028] According to the embodiments, the metal oxide catalyst component comprises 5 mmol gallium to 80 mmol gallium per 100 g zirconium oxide, such as 10 mmol gallium to 80 mmol gallium per 100 g zirconium oxide; 15 mmol gallium oxide to 80 mmol gallium per 100 g zirconium oxide; 20 mmol gallium oxide to 80 mmol gallium per 100 g zirconium oxide; 25 mmol gallium oxide to 80 mmol gallium per 100 g zirconium oxide; or 30 mmol gallium oxide to 80 mmol gallium per 100 g zirconium oxide. In some embodiments, the metal oxide catalyst component comprises 5 mmol gallium oxide to 75 mmol gallium per 100 g zirconium oxide, such as 5 mmol gallium oxide to 70 mmol gallium per 100 g zirconium oxide, 5 mmol gallium oxide to 65 mmol gallium per 100 g zirconium oxide, 5 mmol gallium oxide to 60 mmol gallium per 100 g zirconium oxide, or 5 mmol gallium oxide to 55 mmol gallium per 100 g zirconium oxide. In some embodiments, the metal oxide catalyst component includes 10 mmol gallium to 75 mmol gallium per 100 g zirconium oxide, such as 15 mmol gallium to 70 mmol gallium per 100 g zirconium oxide. In some embodiments, the metal oxide catalyst component includes 5 mmol gallium per 100g zirconium oxide to 50 mmol gallium per 100g zirconium oxide, such as 10 mmol gallium per 100g zirconium oxide to 45 mmol gallium per 100g zirconium oxide, 15 mmol gallium per 100g zirconium oxide to 40 mmol gallium per 100g zirconium oxide, 20 mmol gallium per 100g zirconium oxide to 35 mmol gallium per 100g zirconium oxide, 25 mmol gallium per 100g zirconium oxide to 30 mmol gallium per 100g zirconium oxide, 50 mmol gallium per 100g zirconium oxide to 80 mmol gallium per 100g zirconium oxide, 55 mmol gallium per 100g zirconium oxide to 75 mmol gallium per 100g zirconium oxide, or 60 mmol gallium per 100g zirconium oxide to 70 mmol gallium per 100g zirconium oxide.

[0029] Examples of rare earth oxides for the embodiments disclosed herein include, but are not limited to, lanthanum oxide. For the embodiments disclosed herein, the composition of the metal oxide catalyst component is expressed as a mmol / w ratio of lanthanum oxide metal to pure zirconium oxide (considering ZrO2 stoichiometry). In one or more embodiments, the composition of the metal oxide catalyst component is expressed as mmol of lanthanum per 100 g (g) of zirconium oxide. According to embodiments, the metal oxide catalyst component, when present, comprises 1 mmol to 40 mmol of lanthanum per 100 g of zirconium oxide, 5 mmol to 40 mmol of lanthanum per 100 g of zirconium oxide, 10 mmol to 40 mmol of lanthanum per 100 g of zirconium oxide, or 15 mmol to 40 mmol of lanthanum per 100 g of zirconium oxide. In some embodiments, the metal oxide catalyst component comprises 1 mmol to 35 mmol of lanthanum per 100 g of zirconium oxide, such as 1 mmol to 30 mmol of lanthanum per 100 g of zirconium oxide, 1 mmol to 25 mmol of lanthanum per 100 g of zirconium oxide, 1 mmol to 20 mmol of lanthanum per 100 g of zirconium oxide, or 1 mmol to 15 mmol of lanthanum per 100 g of zirconium oxide. In some embodiments, the metal oxide catalyst component includes 1 mmol of lanthanum oxide to 30 mmol of lanthanum per 100g of zirconium oxide, such as 1 mmol of lanthanum to 25 mmol of lanthanum per 100g of zirconium oxide, 2 mmol of lanthanum to 20 mmol of lanthanum per 100g of zirconium oxide, 5 mmol of lanthanum to 15 mmol of lanthanum per 100g of zirconium oxide, 5 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide, 5.50 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide, 6 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide, 7 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide, 8 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide, or 9 mmol of lanthanum to 10 mmol of lanthanum per 100g of zirconium oxide.

[0030] In view of the above, a method for preparing a nickel oxide, gallium oxide, and zirconium oxide metal oxide catalyst component for a mixed catalyst is carried out by initial wet impregnation. In this method, an aqueous mixture of nickel precursor materials and gallium precursor materials is added to zirconium oxide powder in doses (such as dropwise) while the zirconium oxide particles are stirred and mixed. In an embodiment, the nickel precursor material may be nickel nitrate (Ni(NO3)2), and the gallium precursor material may be gallium nitrate (Ga(NO3)3). In other embodiments, nickel oxide and gallium oxide may be deposited or distributed on zirconium oxide by CVD methods. However, the method for preparing the nickel oxide, gallium oxide, and zirconium oxide metal oxide catalyst component for a mixed catalyst is not particularly limited, and any method that can apply a fine layer of nickel oxide and gallium oxide to the zirconium oxide surface can be used according to the embodiment. It should be understood that the total amount of nickel and gallium precursors mixed with the zirconium oxide particles will be determined based on the desired target amount of nickel and gallium in metal oxide form in the catalyst component.

[0031] Furthermore, in view of the above, a method for preparing a shaped mixed catalyst of gallium oxide, nickel oxide, rare earth oxide (e.g., lanthanum oxide), and zirconium oxide metal oxide catalyst components is also carried out by a pre-wetting impregnation method. In this method, while stirring and mixing zirconium oxide particles, an aqueous mixture of gallium precursor material (in an embodiment, it may be gallium nitrate (Ga(NO3)3)); nickel precursor material (in an embodiment, it may be nickel nitrate (Ni(NO3)2)); and lanthanum precursor material (in an embodiment, it may be lanthanum nitrate (La(NO3)3)) is added to the zirconium oxide powder in a dosage (e.g., dropwise). In other embodiments, gallium oxide, nickel oxide, and lanthanum oxide can be deposited or distributed on the zirconium oxide by a CVD method. However, the method for preparing the shaped mixed catalyst of gallium oxide, nickel oxide, lanthanum oxide, and zirconium oxide metal oxide catalyst components is not particularly limited, and any method that can apply a fine layer of gallium oxide, nickel oxide, and lanthanum oxide to the zirconium oxide surface can be used according to the embodiments. It should be understood that the total amount of gallium precursor, nickel precursor and lanthanum precursor mixed with zirconium oxide particles will be determined based on the desired target amount of gallium, nickel and lanthanum in the form of metal oxides in the catalyst composition.

[0032] As previously discussed, according to some embodiments, the zirconia particles comprise zirconia particles having a crystalline structure. In some embodiments, the zirconia particles comprise zirconia particles having a monoclinic crystal structure. In one or more embodiments, the zirconia particles are substantially composed of or consist of crystalline zirconia particles, and in some embodiments, the zirconia particles are substantially composed of or consist of monoclinic zirconia particles. According to some embodiments, the BET surface area of ​​the zirconia particles is greater than or equal to 5 square meters per gram (m²). 2 / g), such as greater than 10m 2 / g, greater than 20m 2 / g, greater than 30m 2 / g, greater than 40m 2 / g, greater than 50m 2 / g, greater than 60m 2 / g, greater than 70m 2 / g, greater than 80m 2 / g, greater than 90m 2 / g, greater than 100m 2 / g, greater than 110m 2 / g, greater than 120m 2 / g, greater than 130m 2 / g, or greater than 140m 2 / g. According to some implementation schemes, the maximum BET surface area of ​​the zirconium oxide particles is 150m². 2 / g. Therefore, in some embodiments, the BET surface area of ​​the zirconium oxide particles is 5m². 2 / g to 150m 2 / g, 10m 2 / g to 150m 2 / g、20m 2 / g to 150m 2 / g, such as 30m 2 / g to 150m 2 / g、40m 2 / g to 150m 2 / g, 50m 2 / g to 150m 2 / g、60m 2 / g to 150m 2 / g、70m 2 / g to 150m 2 / g、80m 2 / g to 150m 2 / g、90m 2 / g to 150m 2 / g, 100m 2 / g to 150m 2 / g、110m 2 / g to 150m 2 / g、120m 2 / g to 150m 2 / g, 130m 2 / g to 150m 2 / g, or 140m 2 / g to 150m 2 / g. In some embodiments, the BET surface area of ​​the zirconium oxide particles is 5m².2 / g to 140m 2 / g, such as 5m 2 / g to 130m 2 / g、5m 2 / g to 120m 2 / g、5m 2 / g to 110m 2 / g、5m 2 / g to 100m 2 / g、5m 2 / g to 90m 2 / g、5m 2 / g to 80m 2 / g、5m 2 / g to 70m 2 / g、5m 2 / g to 60m 2 / g、5m 2 / g to 50m 2 / g、5m 2 / g to 40m 2 / g、5m 2 / g to 30m 2 / g、5m 2 / g to 20m 2 / g, or 5m 2 / g to 10m 2 / g. In some embodiments, the BET surface area of ​​the zirconium oxide particles is 10m². 2 / g to 140m 2 / g、20m 2 / g to 130m 2 / g、30m 2 / g to 120m 2 / g、40m 2 / g to 110m 2 / g, 50m 2 / g to 100m 2 / g、60m 2 / g to 90m 2 / g, or 70m 2 / g to 80m 2 / g.

[0033] For the implementation scheme, once the nickel precursor, gallium precursor (and optionally rare earth precursor), and zirconium oxide particles are thoroughly mixed, the metal oxide catalyst component can be dried at a temperature below 200 degrees Celsius (°C), such as below 175°C, below 150°C, below 100°C, or about 85°C. After drying, the metal oxide catalyst component is calcined at a temperature of 400°C to 800°C for 2 to 6 hours. For example, the metal oxide catalyst component can be calcined at temperatures of 400°C to 800°C, such as 425°C to 775°C, 450°C to 750°C, 475°C to 725°C, 500°C to 700°C, 525°C to 675°C, 550°C to 650°C, 575°C to 625°C, about 550°C, or about 600°C. The duration of calcination can be from 2 hours to 6 hours, such as 2 hours to 5 hours, 2 hours to 3 hours, 3 hours to 6 hours, 4 hours to 6 hours, or 4 hours. After calcination, the composition of the mixed metal oxide catalyst components is determined and reported in mmol of the metals identified above (e.g., nickel, gallium, and optionally lanthanum) as previously disclosed above, based on 100 g of phase-pure zirconium oxide (simplified to stoichiometry of ZrO2).

[0034] In embodiments, the metal oxide catalyst component can be prepared by mixing a nickel precursor (such as nickel nitrate, nickel acetate, or nickel oxide), a gallium precursor (such as gallium nitrate, gallium hydroxide, hydrated gallium oxide, or gallium oxide), and optionally a lanthanum precursor (such as lanthanum nitrate, lanthanum carbonate, basic lanthanum carbonate, or lanthanum oxide) with zirconium oxide powder or slurry. According to some embodiments, the zirconium oxide particles comprise zirconium oxide particles having a crystalline structure. In embodiments, the zirconium oxide particles comprise zirconium oxide particles having a monoclinic crystal structure. In one or more embodiments, the zirconium oxide particles consist substantially of or comprise only of crystalline zirconium oxide particles, and in some embodiments, the zirconium oxide particles consist substantially of or comprise only of monoclinic zirconium oxide particles. In embodiments, the zirconium oxide particles have the BET surface area disclosed above. The powder or slurry can be vigorously mixed at high temperatures, such as room temperature (approximately 23°C) to 100°C. After the powder or slurry has been sufficiently mixed, the metal oxide catalyst component can be dried and calcined at a temperature of 400°C to 800°C for 2 to 6 hours, as discussed above. After calcination, the composition of the mixed metal oxide catalyst components is determined and reported in mmol of the metals identified above (e.g., nickel, gallium, and optionally lanthanum) as previously disclosed above, based on 100 g of phase-pure zirconium oxide (simplified to stoichiometry of ZrO2).

[0035] As discussed herein, in some embodiments, elements other than nickel oxide, gallium oxide, and zirconium oxide (e.g., rare earth oxides such as lanthanum oxide) may be present in the metal oxide catalyst component containing phase-pure zirconium oxide, nickel oxide, and gallium oxide. Such elements may be introduced into the phase-pure zirconium oxide before, during, or after the introduction of nickel and gallium precursors into the composition. Sometimes, such elements are added to guide and stabilize the crystallization of the zirconium oxide phase (e.g., Y-stabilized or cubic ZrO2 or La-stabilized tetragonal ZrO2). For example, in embodiments, the metal oxide catalyst component includes lanthanum. In other cases, additional elements from the group consisting of rare earth, alkali metals, and / or transition metals are co-deposited with the nickel and gallium precursors, or introduced only if a mixed composition comprising nickel oxide, gallium oxide, and zirconium oxide has already been prepared first.

[0036] In one or more embodiments, after the metal oxide catalyst component has been prepared, for example, by the methods disclosed above, the metal oxide catalyst component prepared according to this disclosure is mixed with a microporous catalyst component and an optional binder (as discussed herein) to form a single catalyst. In embodiments, the microporous catalyst component is selected from molecular sieves having 8-MR pore openings and having a framework type selected from the group consisting of: CHA, AEI, AFX, ERI, LEV, LTA, UFI, RTH, EDI, GIS, MER, RHO, and combinations thereof, which correspond to the nomenclature conventions of the International Zeolite Association. It should be understood that in embodiments, both aluminosilicate and aluminosilicate frameworks can be used. Some embodiments may include tetrahedral aluminosilicates, ALPO (such as, for example, tetrahedral aluminosilicates), SAPO (such as, for example, tetrahedral aluminosilicates), and silica-only framework silicates. In some embodiments, the microporous catalyst component may be aluminosilicate with a chalcogenide (CHA) framework type. Examples of these aluminosilicates may include, but are not limited to: CHA embodiments selected from aluminosilicate-34 (SAPO-34) and SSZ-13; and AEI embodiments, such as SAPO-18; and ERI embodiments, such as SAPO-17. For example, the microporous catalyst component includes aluminosilicate-34 (SAPO-34). Combinations of microporous catalyst components having any of the above framework types may also be used. It should be understood that, depending on the desired product, the microporous catalyst component may have different membered ring pore openings. For example, depending on the desired product, microporous catalyst components with 8-MR to 12-MR pore openings may be used. However, for the production of C2 to C5 hydrocarbons, microporous catalyst components with 8-MR pore openings are used in the embodiments.

[0037] For methods of preparing shaped mixed catalysts, the metal oxide catalyst component and the microporous catalyst component of the shaped mixed catalyst provided herein can be mixed together in any suitable manner to achieve homogeneous mixing of all components prior to any further processing (e.g., extrusion). The metal oxide catalyst component and the microporous catalyst component can initially be mixed in powder form to achieve homogeneity in a suitable dry mixer, such as a ribbon or plow mixer. Optionally, a binder can be added to the metal oxide catalyst component and the microporous catalyst component to form a paste, thereby preparing the shaped mixed catalyst of this disclosure. For embodiments, based on the total weight of the shaped mixed catalyst, the shaped mixed catalyst formed from the paste can have a binder concentration ranging from 5 wt% to 30 wt%, 10 wt% to 30 wt%, 15 wt% to 30 wt%, 20 wt% to 30 wt%, 5 wt% to 25 wt%, 10 wt% to 25 wt%, 15 wt% to 25 wt%, 20 wt% to 25 wt%, or 20 wt%.

[0038] As provided herein, the binder may comprise alumina, zirconium oxide, or mixtures thereof. For embodiments, the binder discussed herein may be prepared as a colloidal solution, suspension, or gel comprising a binder precursor comprising an oxide or hydroxide of aluminum, an oxide or hydroxide of zirconium, or mixtures thereof. As discussed herein, the binder may be prepared as a colloidal solution, suspension, or gel by peptizing a binder precursor comprising an oxide or hydroxide of aluminum with an acidic solution. In embodiments, the acidic solution used for peptization may be an organic carboxylic acid solution. In embodiments, the acidic solution used for peptization may be a nitric acid solution. The binder precursor or peptized binder precursor may be added to a mixture of a metal oxide catalyst component and a microporous catalyst component, and mixed in a suitable heavy-duty industrial mixer capable of processing paste formulations. Alternatively, the dried premixed metal oxide catalyst component and microporous catalyst component may be fed directly into the feed screw of a screw extruder along with the binder precursor or peptized binder precursor composition, and mixed directly in the screw extruder. The paste can then be extruded into the desired shape using any suitable extrusion method to produce a shaped mixed catalyst. Examples of shapes for shaped mixed catalysts include granular, spherical, or near-spherical.

[0039] In the implementation scheme, based on the total weight of the molded mixed catalyst, the metal oxide catalyst component may account for 40.0% to 85.0% by weight of the molded mixed catalyst. For example, the metal oxide catalyst component may account for 45.0% to 85.0% by weight, 50.0% to 85.0% by weight, 55.0% to 85.0% by weight, 60.0% to 85.0% by weight, 65.0% to 85.0% by weight, 70.0% to 85.0% by weight, 75.0% to 85.0% by weight, or 75.0% to 85.0% by weight. In some embodiments, the metal oxide catalyst component comprises 40.0 wt% to 80.0 wt%, 40.0 wt% to 75.0 wt%, 40.0 wt% to 70.0 wt%, 40.0 wt% to 65.0 wt%, 40.0 wt% to 60.0 wt%, 40.0 wt% to 55.0 wt%, 40.0 wt% to 50.0 wt%, or 40.0 wt% to 45.0 wt%. In some embodiments, the metal oxide catalyst component comprises 45.0 wt% to 80.0 wt% of the shaped mixed catalyst, such as 50.0 wt% to 80.0 wt%, 55.0 wt% to 80.0 wt%, 60.0 wt% to 80.0 wt%, 65.0 wt% to 75.0 wt%, 65.0 wt% to 70.0 wt%, 45.0 wt% to 65.0 wt%, 50.0 wt% to 60.0 wt%, or 45.0 wt% to 55.0 wt%. In some embodiments, the metal oxide catalyst component accounts for 50.0% to 80.0% of the shaped mixed catalyst, such as 50.0% to 75.0% by weight, 50.0% to 70.0% by weight, 60.0% to 80.0% by weight, 60.0% to 75.0% by weight, or 60.0% to 70.0% by weight.

[0040] The metal oxide catalyst component and the microporous catalyst component can be mixed in a mass ratio of 1:10 to 10:1, 1:10 to 9:1, 1:10 to 8:1, 1:10 to 5:1, 1:10 to 4:1, 1:10 to 3:1, 1:8 to 8:1, 1:8 to 7:1, 1:8 to 6:1, 1:8 to 5:1, 1:8 to 4:1, 1:5 to 8:1, 1:5 to 7:1, 1:5 to 6:1 or 1:5 to 5:1.

[0041] After the prepared metal oxide catalyst component is mixed with the microporous catalyst component, an optional binder can be added to produce a paste. The binder can hold the metal oxide catalyst component and the microporous catalyst component together. The paste can be extruded to produce a shaped mixed catalyst. The shaped mixed catalyst can be formed by any suitable shaping method.

[0042] In one embodiment, the shaped mixed catalyst has a particle size of 0.5 mm to 6.0 mm, such as 0.5 mm to 5.5 mm, 0.5 mm to 5.0 mm, 0.5 mm to 4.5 mm, 0.5 mm to 4.0 mm, 0.5 mm to 3.5 mm, 0.5 mm to 3.0 mm, 0.5 mm to 2.5 mm, 0.5 mm to 2.0 mm, or 0.5 mm to 1.5 mm. In another embodiment, the shaped mixed catalyst has a particle size of 1.0 mm to 6.0 mm, such as 1.0 mm to 5.5 mm, 1.0 mm to 5.0 mm, 1.0 mm to 4.5 mm, 1.0 mm to 4.0 mm, 1.0 mm to 3.5 mm, 1.0 mm to 3.0 mm, 1.0 mm to 2.5 mm, 1.0 mm to 2.0 mm, or 1.0 mm to 1.5 mm. In the embodiments, the shaped mixed catalyst has a particle size of 1.5 mm to 3.0 mm, such as 1.8 mm to 3.0 mm, 2.0 mm to 3.0 mm, 2.2 mm to 3.0 mm, 2.5 mm to 3.0 mm, 2.8 mm to 3.0 mm, 1.5 mm to 2.8 mm, 1.8 mm to 2.8 mm, 2.0 mm to 2.8 mm, 2.2 mm to 2.8 mm, 2.5 mm to 2.8 mm, 1.5 mm to 2.5 mm, 1.8 mm to 2.5 mm, 2.0 mm to 2.5 mm, 2.2 mm to 2.5 mm, 1.5 mm to 2.2 mm, 1.8 mm to 2.2 mm, 2.0 mm to 2.2 mm, 1.5 mm to 2.0 mm, 1.8 mm to 2.0 mm, or 1.5 mm to 1.8 mm. The particle size can be substantially the shortest size of the catalyst particles. For example, when the molded mixed catalyst has a hollow cylindrical or annular shape, the particle size is the thickness of the hollow cylinder wall. When the molded mixed catalyst has a spherical shape, the particle size is the diameter of the sphere. The particle size of this molded mixed catalyst can be controlled by selecting the extrusion die diameter and measured using dynamic image analysis methods.

[0043] Various binders are considered suitable. For example, binders may include alumina, zirconium oxide, or both. In embodiments, the binder may include pure alumina. In embodiments, the binder may include pure zirconium oxide. When the binder includes alumina, the alumina binder may be hydrated alumina. Hydrated alumina compositions may be prepared from bohemitic precursors with water and optionally a colloidal solvent. The binder may be mixed with both the metal oxide catalyst component and the microporous catalyst component. After mixing the binder with the metal oxide catalyst component and the microporous catalyst component (e.g., to form a paste), the mixture (e.g., the paste) may be extruded, dried, and calcined, as discussed herein. Upon calcination, the binder can form alumina and bind the metal oxide catalyst component and the microporous catalyst component together to provide mechanical strength for extruded mixed catalysts. Without being bound by any particular theory, other commonly used binders, such as SiO2 and TiO2, may lead to catalyst activity poisoning or a significant loss of olefin selectivity. Mixing two catalyst components into a single catalyst body is not straightforward. Although the physical mixture of the formed metal oxide catalyst component and the formed microporous catalyst component (i.e., without the formation of a single catalyst body) can achieve the required pressure drop on the reactor, catalytic performance such as olefin selectivity and carbon conversion is significantly reduced.

[0044] Binders including alumina, zirconium oxide, or both can blend metal oxide catalyst components and microporous catalyst components into a single catalyst body, thereby improving C2 to C5 hydrocarbon yields and carbon conversion. Forming the metal oxide catalyst and microporous catalyst separately and combining them into a physical mixture cannot achieve the C2 to C5 and carbon conversion rates obtained using shaped mixed catalysts as disclosed and described herein.

[0045] In embodiments, the optional binder may be a colloidal solution, suspension, or gel of the binder precursor. The binder precursor may include oxides or hydroxides of aluminum, oxides or hydroxides of zirconium, or mixtures thereof. In one embodiment, the binder precursor may include pure alumina, (pseudo)boehmite, or gibbsite, or mixtures thereof. In one embodiment, the binder precursor is aluminum hydroxide oxide, such as boehmite or pseudoboehmite. In other embodiments, the binder precursor may include pure zirconium oxide, hydrated zirconium oxide, zirconium hydroxide, ammonium zirconium carbonate, zirconium acetate, or mixtures thereof.

[0046] For embodiments, the binder can be prepared into a colloidal solution, suspension, or gel by solubilizing the binder precursor in an acidic solution. Examples of acidic solutions used to solubilize the binder precursor may include nitric acid, as is known in the art. Alternatively, examples of solubilizing the aluminum binder precursor include the use of an organic carboxylic acid solution, as discussed in U.S. Provisional Application No. 85691-US-PSP entitled “A PROCESS FOR PREPARING C2 TO C5 HYDROCARBONS WITH A FORMEDHYBRID CATALYST,” which is incorporated herein by reference in its entirety. In summary, for embodiments, the aluminum binder is prepared into a colloidal solution, suspension, or gel by solubilizing the aluminum binder precursor in an organic carboxylic acid solution. The organic carboxylic acid solution is selected from the group consisting of acetic acid solutions, formic acid solutions, oxalic acid solutions, propionic acid solutions, and combinations thereof. For colloidal solutions, suspensions, or gels, the aluminum binder precursor can be mixed with an organic carboxylic acid solution at temperatures ranging from 20°C to 60°C, 20°C to 50°C, or 20°C to 30°C to induce gelation. The duration of gelation as provided above can be 0.1 hours to 24 hours, 0.1 hours to 12 hours, 1 hour to 12 hours, 1 hour to 6 hours, 1 hour to 3 hours, or 1 hour to 2 hours. For embodiments, the binder (e.g., alumina) can have an [organic carboxylic acid] / [Al] concentration ratio of 0.005 to 0.1, 0.01 to 0.1, 0.01 to 0.05, or about 0.035. For the implementation scheme, the total solids content of the colloidal solution, suspension or gel of the binder precursor and the organic carboxylic acid solution can be 20% to 50% by weight, 30% to 50% by weight, 20% to 40% by weight, 30% to 40% by weight, or 35% by weight, based on the total weight of the colloidal solution, suspension or gel.

[0047] In the implementation scheme, the adhesive may have a 100m 2 / g to 400m 2 / g、125m 2 / g to 400m 2 / g, 150m 2 / g to 400m 2 / g, 100m 2 / g to 200m 2 / g、125m 2 / g to 200m 2 / g, 150m 2 / g to 200m 2 / g, 100m 2 / g to 175m 2 / g、125m 2 / g to 175m2 / g, 150m 2 / g to 175m 2 / g, 100m 2 / g to 150m 2 / g、125m 2 / g to 150m 2 / g, or 100m 2 / g to 125m 2 / g of surface area.

[0048] For embodiments, the method of this disclosure includes reducing and / or shaping a mixed catalyst at temperatures of 450°C to 750°C, 450°C to 650°C, 450°C to 600°C, 500°C to 750°C, 500°C to 650°C, or 500°C to 600°C in a hydrogen-containing atmosphere. For embodiments, the reduction and / or shaping of the mixed catalyst in a hydrogen-containing atmosphere can be carried out for periods of 0.5 hours to 10 hours, 3 hours to 10 hours, 4 hours to 10 hours, 5 hours to 10 hours, 2 hours to 8 hours, 4 hours to 8 hours, 5 hours to 7 hours, or 6 hours. For embodiments, the hydrogen-containing atmosphere can include pure hydrogen (purity level exceeding 99.9% v / v) or hydrogen and inert gas in a mixture of 1% hydrogen / inert gas (v / v) to 99.9% hydrogen / inert gas (v / v). For embodiments, the inert gas can be selected from the group consisting of argon, nitrogen, and combinations thereof. Unbound by any particular theory, it is believed that the reduction of the catalyst leads to greater dispersion of nickel and gallium and promotes the interaction between Ni and Ga, resulting in high hydrogenation activity for C2 to C5 alkenes and subsequently high and stable selectivity for C2 to C5 alkanes.

[0049] For the embodiments described herein, the mixed catalyst and / or shaped mixed catalyst may be reduced and / or shaped relative to the reactor in a hydrogen-containing atmosphere, either in situ, outside the reactor, or a combination of both. For example, the mixed catalyst and / or shaped mixed catalyst may be reduced and / or shaped outside the reactor according to the methods described above, followed by passivation of the shaped mixed catalyst with air or a mixture of air and an inert gas at a temperature below 100°C. For the embodiments described herein, the air may include atmospheric air, and the inert gas is as defined herein. Passivation at a temperature below 100°C may include temperatures in the ranges of 20°C to below 100°C, 25°C to 95°C, 30°C to 80°C, or 40°C to 60°C.

[0050] For the implementation scheme, in addition to reducing the mixed catalyst and / or shaped mixed catalyst outside the reactor, the mixed catalyst and / or shaped mixed catalyst may also be re-reduced in situ (undergo re-reduction) within a temperature range that is the same as or different from the temperature range used for reducing the mixed catalyst and / or shaped mixed catalyst in a hydrogen-containing atmosphere as discussed herein. For example, the mixed catalyst and / or shaped mixed catalyst may be re-reduced in situ (undergo re-reduction) within a temperature range of 450°C to 750°C. The implementation scheme may also include reducing the mixed catalyst and / or shaped mixed catalyst outside the reactor, and re-reducing the shaped mixed catalyst in the reactor at a temperature of 300°C to 500°C. The in-situ re-reduction of the mixed catalyst and / or shaped mixed catalyst may be carried out in a hydrogen-containing atmosphere as defined herein for a time of 0.5 to 10 hours. The temperature used for re-reduction of the mixed catalyst and / or shaped mixed catalyst can be in the range of 300°C to 450°C, 300°C to 400°C, 300°C to 350°C, 350°C to 500°C, 400°C to 500°C, or 450°C to 550°C, in addition to the 300°C to 550°C range in the reactor. In an alternative embodiment, the method of this disclosure includes re-reducing the mixed catalyst and / or shaped mixed catalyst outside the reactor, and the mixed catalyst or shaped mixed catalyst is not re-reduced when loaded into the reactor.

[0051] Mixed catalysts can be used in methods for converting carbon in a carbon-containing feed stream into C2 to C5 hydrocarbons in the reaction zone of a reactor. Such methods will be described in more detail below.

[0052] According to the embodiments, a feed stream is fed into the reaction zone of the reactor, the feed stream comprising hydrogen (H2) and a carbonaceous gas selected from carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. In some embodiments, H2 gas is present in the feed stream in an amount from 10 volume percent (vol%) to 90 vol%, based on the combined volume of H2 gas and the gas selected from CO, CO2, and combinations thereof. The feed stream is contacted in the reaction zone with a shaped mixed catalyst as disclosed and described herein. The mixed catalyst and / or shaped mixed catalyst comprises: a metal oxide catalyst component including nickel oxide, gallium oxide (optionally lanthanum oxide), and zirconium oxide, a microporous catalyst component, and optionally a binder for shaping the mixed catalyst.

[0053] It should be understood that for feed streams containing CO as a carbon-containing gas, the activity of mixed catalysts and / or shaped mixed catalysts will be higher, and the activity of mixed catalysts and / or shaped mixed catalysts will decrease when the majority of the carbon-containing gas in the feed stream is CO2. However, this does not mean that the mixed catalysts and / or shaped mixed catalysts disclosed and described herein cannot be used in methods in which the feed stream includes CO2 as all or most of the carbon-containing gas.

[0054] Under reaction conditions sufficient to form a product stream comprising C2 to C5 hydrocarbons, the feed stream is brought into contact with a shaped mixed catalyst in the reaction zone. According to one or more embodiments, the reaction conditions include a temperature range within the reaction zone of 350°C to 480°C, such as 375°C to 450°C, 400°C to 450°C, 350°C to 425°C, 375°C to 425°C, 400°C to 425°C, 350°C to 400°C, or 375°C to 400°C.

[0055] In the implementation scheme, the reaction conditions include at least 1 bar (100 kPa) within the reaction zone, such as at least 5 bar (500 kPa), at least 10 bar (1,000 kPa), at least 15 bar (1,500 kPa), at least 20 bar (2,000 kPa), at least 25 bar (2,500 kPa), at least 30 bar (3,000 kPa), at least 35 bar (3,500 kPa), at least 40 bar (4,000 kPa), at least 45 bar (4,500 kPa), and so on. Pressure of at least 50 bar (5,000 kPa), at least 55 bar (5,500 kPa), at least 60 bar (6,000 kPa), at least 65 bar (6,500 kPa), at least 70 bar (7,000 kPa), at least 75 bar (7,500 kPa), at least 80 bar (8,000 kPa), at least 85 bar (8,500 kPa), at least 90 bar (9,000 kPa), at least 95 bar (9,500 kPa), or at least 100 bar (10,000 kPa). In other embodiments, the reaction conditions include 5 bar (500 kPa) to 100 bar (10,000 kPa) within the reaction zone, such as 10 bar (1,000 kPa) to 95 bar (9,500 kPa), 15 bar (1,500 kPa) to 90 bar (9,000 kPa), 20 bar (2,000 kPa) to 85 bar (8,500 kPa), and 25 bar (2,500 kPa) to 80 bar (8,500 kPa). Pressures ranging from 8,000 kPa, 30 bar (3,000 kPa) to 75 bar (7,500 kPa), 35 bar (3,500 kPa) to 70 bar (7,000 kPa), 40 bar (4,000 kPa) to 65 bar (6,500 kPa), 45 bar (4,500 kPa) to 60 bar (6,000 kPa), or 50 bar (5,000 kPa) to 55 bar (5,500 kPa). In some embodiments, the pressure inside the reaction zone is 20 bar (2,000 kPa) to 60 bar (6,000 kPa).

[0056] According to the implementation plan, the gas hourly space velocity (GHSV) in the reaction zone is from 500 per hour to 12,000 per hour, such as 500 to 10,000 per hour, 1,200 to 12,000 per hour, 1,500 to 10,000 per hour, 2,000 to 9,500 per hour, 2,500 to 9,000 per hour, 3,000 to 8,500 per hour, 3,500 to 8,000 per hour, 4,000 to 7,500 per hour, 4,500 to 7,000 per hour, 5,000 to 6,500 per hour, or 5,500 to 6,000 per hour. In some implementations, the GHSV in the reaction zone is 1,800 to 3,600 h / h, such as 2,000 to 3,600 h / h, 2,200 to 3,600 h / h, 2,400 to 3,600 h / h, 2,600 to 3,600 h / h, 2,800 to 3,600 h / h, 3,000 to 3,600 h / h, 3,200 h / h to 3,600 h / h, or 3,400 h / h to 3,600 h / h. In some embodiments, the GHSV within the reaction zone is 1,800 to 3,400 rpm, such as 1,800 to 3,200 rpm, 1,800 to 3,000 rpm, 1,800 to 2,800 rpm, 1,800 to 2,600 rpm, 1,800 to 2,400 rpm, 1,800 to 2,200 rpm, or 1,800 to 2,000 rpm. In some embodiments, the GHSV within the reaction zone is 2,000 to 3,400 rpm, such as 2,200 to 3,200 rpm, 2,400 to 3,000 rpm, or 2,600 to 2,800 rpm.

[0057] In the implementation scheme, the use of the mixed catalysts and / or shaped mixed catalysts disclosed and described herein, along with the process conditions disclosed and described herein, can improve carbon conversion. Within the scope of the disclosed methods, the conversion of a feed containing carbon oxides and hydrogen can be carried out in a series of reactors, wherein water byproducts are knocked out intermediately by means of, for example, phase separation, membrane separation, or some type of water-selective absorption or adsorption method. Further continuously guiding the partially converted and anhydrous effluent to subsequent reactors and repeating this technical operation will have the overall effect of improving the yield of C2 to C5 hydrocarbons.

[0058] In embodiments, using the mixed catalysts and / or shaped mixed catalysts disclosed and described herein, and the process conditions disclosed and described herein, the C2-C5 alkane selectivity / C2-C5 olefin selectivity ratio of the method may be greater than or equal to 5, 5 to 240, 5 to 240, 40 to 240, 50 to 240, 60 to 240, 70 to 240, 5 to 80, 5 to 70, 5 to 60, about 5 to 50, or about 5 to 40. In embodiments, using the shaped mixed catalysts disclosed and described herein, and the process conditions disclosed and described herein, the C2-C5 hydrocarbons primarily comprise C2-C5 alkanes.

[0059] Example

[0060] The following examples illustrate features of this disclosure but are not intended to limit the scope of this disclosure. For each of the following examples (EX) and comparative examples (CE), the microporous catalyst component was prepared as follows: Silicate aluminophosphate-34 (SAPO-34) was synthesized according to a literature procedure (Lok, BM; Messina, CA; Patton, RL; Gajek, RT; Cannan, TR; Flanigen, EM Crystalline silicoaluminophosphates. U.S. Patent 4,440,871A, 1984). When calcined SAPO-34 was used, the material was calcined in air using the following procedure: heated to 600°C at a heating rate of 2°C / min, held at 600°C for 4 hours (h), and cooled to 25°C over the 4 hours.

[0061] Comparative Example A (CE A)

[0062] Gallium-containing metal oxide catalyst components supported on zirconium oxide were prepared by a wet impregnation method. Impregnation solutions of gallium(III) nitrate hydrate (Ga(NO3)3∙xH2O), nickel(II) nitrate hexahydrate (Ni(NO3)2·6H2O), and lanthanum(III) nitrate hexahydrate (La(NO3)3∙6H2O) at concentrations of 0.7 mol / L, 0.21 mol / L, and 0.21 mol / L in deionized water were prepared. 10 g of ZrO2 support (manufactured by Daichi Kigenso, trade code Z3186, >90% monoclinic phase as determined by XRD, pore volume = 0.59 mL / g as determined by deionized water) was weighed and placed in a glass vial. Then, 5.7 mL of the Ga, Ni, and La impregnation solutions were added dropwise to the support while continuously shaking. After impregnation, the metal oxide catalyst component was dried overnight at 85°C in a forced convection oven and calcined in a muffle furnace using the following procedure: heating from 25°C to 550°C at a heating rate of 3°C / min, and holding at 550°C for 4 hours. After calcination, the catalyst was re-sieved to a size of less than 200 mesh (less than 75 μm) to remove larger agglomerated particles.

[0063] Powder was prepared by mixing 10 g of the aforementioned metal oxide catalyst component with 2.28 g of uncalcined SAPO-34 for 10 minutes using a mortar and pestle. Separately, pseudoboehmite (AlOOH, 79% Al2O3, manufactured by Sasol Limited, trade name Catapal D) was dissolved in water using HNO3 (65 wt% H2O solution) at a [HNO3] / [Al] ratio of 0.035 and a total solids content of 35 wt%. The dissolved pseudoboehmite mixture was added to the dried powder to form a paste, aiming for a pseudoboehmite concentration of 24 wt% based on total solids (Catapal D, SAPO-34, and MMO). The paste was then mixed using a mortar and pestle for at least 10 minutes until an extrudable paste was obtained. The paste was transferred to a ceramic pan and dried overnight at 85°C to form a dried precursor. The dried precursor was heated from 25°C to 600°C in a static muffle furnace at a heating rate of 2°C / min and held at 600°C for 4 hours to form a shaped mixed catalyst of CEA. After calcination, CEA was pulverized and sieved to 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0064] Comparative Example B (CE B): Reduction in hydrogen at 400°C

[0065] Prior to testing, the same catalyst as in CEA was reduced at atmospheric pressure in pure hydrogen (99.9% purity) at 400°C for 6 hours.

[0066] Example 1 of the present invention (EX 1): Reduction in hydrogen at 500°C

[0067] Prior to testing, the same catalyst as in CEA was reduced at atmospheric pressure in pure hydrogen (99.9% purity) at 500°C for 6 hours.

[0068] Example 2 of the present invention: Reduction in hydrogen at 600°C

[0069] The same catalyst as in CEA was reduced at atmospheric pressure in a 5% H2 / Ar (v / v) mixture at 600°C for 1 hour, followed by passivation at 30°C for 30 minutes in a 1% O2 / He (v / v) mixture. The passivated catalyst was loaded into a reactor and reduced again at atmospheric pressure in hydrogen at 500°C for 6 hours prior to testing.

[0070] Example 3 of the present invention: Reduction in hydrogen at 700°C

[0071] The same catalyst as in CEA was reduced at atmospheric pressure in a 5% H2 / Ar (v / v) mixture at 700°C for 1 hour, followed by passivation at 30°C for 30 minutes in a 1% O2 / He (v / v) mixture. The passivated catalyst was loaded into a reactor and reduced again at atmospheric pressure in hydrogen at 500°C for 6 hours prior to testing.

[0072] Example 4 of the present invention: Reduction in hydrogen at 600°C without further reduction.

[0073] The same catalyst as in CEA was reduced at atmospheric pressure in a 5% H2 / Ar (v / v) mixture at 600°C for 1 hour, followed by passivation in a 1% O2 / He (v / v) mixture at 30°C for 30 minutes. The passivated catalyst was then loaded into a reactor for catalytic testing.

[0074] Comparative Example C (CE C): Reduction in carbon monoxide at 500°C

[0075] Prior to testing, the same catalyst as in CEA was reduced in carbon monoxide at atmospheric pressure and 500°C for 6 hours.

[0076] Comparative Example D (CE D): Reduction at 500°C in a H2:CO (3:1) mixture.

[0077] Prior to testing, the same catalyst as in CEA was reduced at atmospheric pressure in a mixture of H2:CO (3:1) at 500°C for 6 hours.

[0078] Comparative Example E (CE E): Reduced in H2 at 800℃

[0079] The same catalyst as in CEA was reduced at atmospheric pressure in a 5% H2 / Ar (v / v) mixture at 800°C for 1 hour, followed by passivation at 30°C to 45°C for 30 minutes in a 1% O2 / He (v / v) mixture. The passivated catalyst was loaded into a reactor and reduced again at atmospheric pressure in hydrogen (99.9% purity) at 500°C for 6 hours prior to testing.

[0080] Catalytic performance data

[0081] The shaped mixed catalyst was tested in a Hastelloy C276 fixed-bed reactor system (7.7 mm inner diameter) under the following conditions: 420 °C, H2 / CO = 3 or H2 / CO = 6, p = 40 bar, GHSV = 3600 hr -1 .

[0082] Before contact with the synthesis gas, the catalyst was heated to the aforementioned reaction temperature and pressure under nitrogen (N2). The reactor effluent composition was obtained by gas chromatography, and the conversion and carbon-based selectivity were calculated using the following equations:

[0083] X CO (%) = [(η) CO，进 – η CO，出 ) / η CO，进 ] · 100; and (1)

[0084] S j (%) = [α j · η j，出 / (η CO，进 – η CO，出 )] · 100,(2)

[0085] Where Χ CO Defined as CO conversion rate (%), η CO，进 The molar inlet flow rate of CO (µmol / s), η CO，出 S is the molar outlet flow rate of CO (µmol / s). j Defined as the carbon-based selectivity (%) for product j, α j η is the number of carbon atoms in product j. j，出 denoted as the molar outlet flow rate (µmol / s) of product j. All data were collected under steady-state conditions after a run time of at least 40 hours (TOS).

[0086] The results of the catalytic tests are shown in Table 1 below. The reported values ​​are the average TOS between 100 and 150 hours for H2:CO = 3, and the average TOS between 175 and 225 hours for H2:CO = 6.

[0087] Table 1. Catalyst performance. For H2:CO=3, the average TOS is between 100 and 150 hours, and for... H2:CO=6 is the average value between 175 and 225 hours of TOS, tested under the following conditions: 420℃, p = 40 bar, GHSV = 3600hr -1 .

[0088]

[0089] As can be observed in Table 1, the bifunctional catalyst formulations of EX 2-4 reduced in hydrogen at high temperatures (i.e., 600 °C and 700 °C) exhibit significantly lower initial methane selectivity and lower steady-state C2-C5 olefin selectivity at comparable levels of total CO conversion and hydrocarbon productivity. A loss of activity was observed when the reduction temperature in H2 was increased to 800 °C.

[0090] It should be noted that one or more of the following claims utilize the term "where or inwhich" as a transitional phrase. For the purpose of defining this technology, it should be noted that this term is introduced in the claims as an open-ended transitional phrase used to introduce a description of a series of characteristics of the structure, and should be interpreted in a manner similar to the more commonly used open-ended prepositional phrase "comprising." For the purpose of defining this invention, the transitional phrase "consisting of..." may be introduced in the claims as a closed prepositional phrase that limits the scope of the claims to the listed components or steps and any naturally occurring impurities. For the purpose of defining this invention, the transitional phrase "substantially constitutes..." may be introduced in the claims to limit the scope of one or more claims to the stated elements, components, materials, or method steps and any non-stated elements, components, materials, or method steps that do not substantially affect the novelty of the claimed subject matter. The transitional phrases “composed of” and “substantially composed of” can be interpreted as open-ended transitional phrases, such as subsets of “comprising” and “including”, such that any use of an open-ended phrase to introduce a list of elements, components, materials, or steps should be interpreted as also disclosing a list of elements, components, materials, or steps using the closed terms “composed of” and “substantially composed of”. For example, a statement “comprising” a composition of components A, B, and C should be interpreted as also disclosing a composition “composed of components A, B, and C” and a composition “substantially composed of components A, B, and C”. Any quantitative values ​​expressed in this application can be considered to include open-ended embodiments conforming to the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments conforming to the transitional phrases “composed of” and “substantially composed of”.

[0091] As used in the specification and appended claims, unless the context clearly indicates otherwise, the singular forms “a,” “an,” and “the” include plural references. The verb “comprising” and its homologous forms should be interpreted as referring to an element, component, or step in a non-exclusive manner. The referenced element, component, or step may exist, be used, or be combined with other elements, components, or steps not expressly referenced.

[0092] It should be understood that any two quantitative values ​​assigned to a characteristic may constitute a range for that characteristic, and all combinations of ranges formed by all stated quantitative values ​​of a given characteristic are considered in this disclosure. The subject matter of this disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of one or more embodiments does not necessarily imply that the component or feature is necessary for a particular embodiment or any other embodiment. Furthermore, it will be apparent to those skilled in the art that various modifications and changes may be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

1. A method for preparing C2 to C5 hydrocarbons, the method comprising: A feed stream containing hydrogen and carbon-containing gases selected from the group consisting of carbon monoxide, carbon dioxide and mixtures thereof is introduced into the reaction zone of the reactor; as well as In the presence of a mixed catalyst, the feed stream is converted into a product stream containing C2 to C5 hydrocarbons in the reaction zone, wherein the mixed catalyst comprises: The metal oxide catalyst component includes nickel oxide, gallium oxide, and zirconium oxide. Microporous catalyst component, wherein the microporous catalyst component is a molecular sieve having 8-MR (membered ring) pore openings; and The mixed catalyst is reduced in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C.

2. The method according to claim 1, wherein the mixed catalyst is a physical mixture of the metal oxide and the microporous catalyst component.

3. The method of claim 1, wherein the mixed catalyst is a molded mixed catalyst containing a binder, the binder comprising alumina, zirconium oxide, or a mixture thereof.

4. The method of claim 3, wherein the binder is prepared as a colloidal solution, suspension or gel of a binder precursor, the binder precursor comprising an oxide or hydroxide of aluminum, an oxide or hydroxide of zirconium or a mixture thereof.

5. The method according to any one of claims 3 to 4, wherein the shaped mixed catalyst has a particle size of 0.5 mm to 6 mm.

6. The method according to any one of claims 3 to 5, wherein the metal oxide catalyst component accounts for 40.0% to 85.0% by weight of the shaped mixed catalyst based on the total weight of the shaped mixed catalyst.

7. The method according to any one of claims 3 to 6, the method comprising reducing the shaped mixed catalyst outside the reactor and passivating the shaped mixed catalyst with air or a mixture of air and an inert gas at a temperature below 100°C.

8. The method according to any one of claims 3 to 7, the method comprising reducing the shaped mixed catalyst outside the reactor and further reducing the shaped mixed catalyst in the reactor at a temperature of 450°C to 750°C.

9. The method according to any one of claims 3 to 7, the method comprising reducing the shaped mixed catalyst outside the reactor and further reducing the shaped mixed catalyst in the reactor at a temperature of 300°C to 500°C.

10. The method according to any one of claims 3 to 7, wherein the method comprises reducing the shaped mixed catalyst outside the reactor, and the shaped mixed catalyst is not reduced again when loaded into the reactor.

11. The method according to any one of claims 1 to 10, wherein the metal oxide catalyst component further comprises rare earth oxides.

12. The method according to any one of claims 1 to 11, wherein the microporous catalyst component comprises silica aluminophosphate-34 (SAPO-34).

13. The method according to any one of claims 1 to 12, wherein the hydrogen atmosphere comprises pure hydrogen or a mixture of hydrogen and inert gas having a hydrogen / inert gas (v / v) mixture of 1% to 99.9% (v / v).

14. The method according to any one of claims 1 to 13, wherein during the conversion, the temperature within the reaction zone is from 350 degrees Celsius (°C) to 480 degrees Celsius.

15. The method according to any one of claims 1 to 14, wherein the C2 to C5 hydrocarbons mainly comprise C2 to C5 alkanes.

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