Method for preparing C2 to C5 hydrocarbons using the resulting mixed catalyst

Abstract

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 formed mixed catalyst. The formed mixed catalyst comprises: a metal oxide catalyst component comprising gallium oxide and zirconium oxide, a microporous catalyst component as a molecular sieve having 8-MR (membered ring) pore openings, and an alumina binder, wherein the alumina binder is prepared as a colloidal solution, suspension, or gel by solubilizing a binder precursor comprising aluminum oxide or hydroxide with an organic carboxylic acid solution.

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 and the application of process methods to achieve high carbon conversion rates and high yields of desired products. 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 olefins such as ethylene, propylene, butene, and pentene (often also referred to as ethylene, propylene, butene, and pentene, respectively), or 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 a hybrid catalyst and methods for using such a catalyst. The hybrid catalyst comprises a combination of a metal oxide catalyst component, a microporous catalyst component, and a binder. The binder is prepared as a colloidal solution, suspension, or gel by solubilizing a binder precursor containing an aluminum oxide or hydroxide with an organic carboxylic acid solution. The metal oxide catalyst component and the microporous catalyst component are mixed using the binder and then formed into a paste. The paste is then extruded to produce the hybrid catalyst. The hybrid catalyst can be used in methods for producing C2 to C5 hydrocarbons by directly converting a feed stream containing hydrogen and carbon-containing gases, such as syngas, into C2 to C5 hydrocarbons. The metal oxide catalyst component and the microporous catalyst component are operated in series, enabling the hybrid catalyst to directly and selectively convert a feed stream containing hydrogen and carbon-containing gases, such as syngas, into C2 to C5 hydrocarbons.

[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 formed mixed catalyst. The formed mixed catalyst comprises: a metal oxide catalyst component comprising gallium oxide and zirconium oxide, a microporous catalyst component as a molecular sieve having 8-MR (membered ring) pore openings, and a binder comprising alumina. The alumina binder is prepared as a colloidal solution, suspension, or gel by solubilizing a binder precursor comprising aluminum oxide or hydroxide with an organic carboxylic acid solution.

[0007] According to one or more other aspects of this disclosure, a method for preparing a hybrid catalyst includes: mixing a metal oxide catalyst component and a microporous catalyst component, wherein the metal oxide catalyst component comprises gallium oxide and zirconium oxide, and the microporous catalyst component comprises a molecular sieve having 8-MR pore openings; adding a binder to the mixture of the metal oxide catalyst component and the microporous catalyst component to form a paste, wherein the binder is prepared as a colloidal solution, suspension, or gel by solubilizing a binder precursor comprising an aluminum oxide or hydroxide with an organic carboxylic acid solution; and extruding the paste to produce the hybrid catalyst. The resulting hybrid catalyst may undergo drying and subsequent calcination.

[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 the mixed catalysts and methods for forming C2 to C5 hydrocarbons from a feed stream containing hydrogen and carbon-containing gases. 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] According to one embodiment, 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 formed mixed catalyst. The formed mixed catalyst comprises: a metal oxide catalyst component comprising gallium oxide and zirconium oxide, a microporous catalyst component as a molecular sieve having 8-MR pore openings, and a binder comprising alumina, wherein the alumina binder is prepared as a colloidal solution, suspension, or gel by solubilizing a binder precursor comprising aluminum oxide or hydroxide with an organic carboxylic acid solution.

[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 C4 hydrocarbons, including C2 to C4 alkenes and / or C2 to C4 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 C4 hydrocarbons and / or C2 to C4 alkenes. “C2 to C5 hydrocarbons” may also include straight-chain and branched alkanes and alkenes.

[0013] In embodiments, the metal oxide catalyst component includes gallium oxide. As used herein, "gallium oxide" refers to gallium in various oxidation states. In 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 Ga₅O₇(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 may be in different oxidation states. Gallium oxide is not limited to gallium comprising a uniform oxidation state.

[0014] The use of such hybrid catalysts is known in the field of hydrocarbon products such as diesel or aromatic compounds. However, many known hybrid catalysts are inefficient for both the formation of C2 to C5 alkanes and the formation of C2 to C5 olefins from feed streams containing hydrogen and carbon-containing gases, because they exhibit low feed carbon conversion and / or rapid deactivation, for example by increasing methane production, resulting in low C2 to C5 hydrocarbon productivity and stability over a given time under a given set of operating conditions. Known hybrid catalysts for the production of C2 to C5 alkanes exhibit increasing C2 to C5 olefin selectivity over time. In contrast, the hybrid 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 hybrid catalysts in which the binder for the metal oxide catalyst component and the microporous catalyst component is soluble in nitric acid rather than in an organic carboxylic acid solution as disclosed herein. The preparation and composition of such mixed catalysts used in the implementation scheme are discussed below.

[0015] In summary, the resulting hybrid catalyst tightly couples independent reactions on each of the two independent catalysts within a single catalyst particle. 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 via the reaction in the second step ensures that there are no thermodynamic limitations on the conversion.

[0016] In one embodiment, the formed 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 formed 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 formed 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 formed mixed catalyst has a hollow cylindrical or annular shape, the particle size is the thickness of the hollow cylinder wall. When the formed mixed catalyst has a spherical shape, the particle size is the diameter of the sphere. The particle size of the formed mixed catalyst can be controlled by selecting the extrusion die diameter and measured using dynamic image analysis methods.

[0017] In one or more embodiments, the metal oxide catalyst component may comprise 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., gallium oxide and optionally nickel oxide and rare earth oxides (e.g., lanthanum oxide)) are supported. In some embodiments, the zirconium oxide of the metal oxide catalyst component may comprise 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 comprise 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 comprise 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]

[0020] In one or more embodiments, the 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 comprises gallium oxide and zirconium oxide (ZrO2). In another embodiment, the metal oxide catalyst component comprises gallium oxide, nickel oxide, and zirconium oxide (ZrO2). In another embodiment, the metal oxide catalyst component may also comprise rare earth oxides. As used herein, "rare earth oxide" means 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 comprises gallium oxide, nickel oxide, lanthanum oxide, and zirconium oxide (ZrO2).

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

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

[0024] In the embodiments disclosed herein, the composition of the metal oxide catalyst component is expressed as millimoles (mmol) / weight ratios of gallium metal and optionally nickel metal and rare earth metal relative to pure zirconium oxide (considering ZrO2 stoichiometry). In one or more embodiments, the composition of the metal catalyst component is expressed as mmol of gallium per 100 grams (g) of zirconium oxide. According to embodiments, the metal oxide catalyst component comprises 5 mmol to 80 mmol of gallium per 100 g of zirconium oxide, such as 10 mmol to 80 mmol of gallium per 100 g of zirconium oxide; 15 mmol to 80 mmol of gallium per 100 g of zirconium oxide; 20 mmol to 80 mmol of gallium per 100 g of zirconium oxide; 25 mmol to 80 mmol of gallium per 100 g of zirconium oxide; or 30 mmol to 80 mmol of gallium per 100 g of zirconium oxide. In some embodiments, the metal oxide catalyst component comprises 5 mmol to 75 mmol gallium per 100 g zirconium oxide, such as 5 mmol to 70 mmol gallium per 100 g zirconium oxide, 5 mmol to 65 mmol gallium per 100 g zirconium oxide, 5 mmol to 60 mmol gallium per 100 g zirconium oxide, or 5 mmol to 55 mmol gallium per 100 g zirconium oxide. In some embodiments, the metal oxide catalyst component comprises 10 mmol to 75 mmol gallium per 100 g zirconium oxide, such as 15 mmol 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.

[0025] In the embodiments disclosed herein, the metal oxide catalyst component may also include other metal oxides as discussed herein. For example, the metal oxide catalyst component may also include nickel oxide and rare earth oxides. For the embodiments disclosed herein, the composition of the metal oxide catalyst component is expressed as a mmol / w ratio of nickel metal relative to pure zirconium oxide (considering the stoichiometry of ZrO2). In one or more embodiments, the composition of the metal oxide catalyst component is expressed as mmol of nickel per 100 g (g) of zirconium oxide. According to embodiments, the metal oxide catalyst component comprises 6 mmol to 20 mmol of nickel per 100 g of zirconium oxide, such as 7 mmol to 20 mmol of nickel per 100 g of zirconium oxide, 8 mmol to 20 mmol of nickel per 100 g of zirconium oxide, 10 mmol to 20 mmol of nickel per 100 g of zirconium oxide, 12 mmol to 20 mmol of nickel per 100 g of zirconium oxide, or 15 mmol to 20 mmol of nickel per 100 g of zirconium oxide. 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 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.

[0026] 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 lanthanum per 100g zirconium oxide to 30 mmol lanthanum per 100g zirconium oxide, such as 1 mmol lanthanum per 100g zirconium oxide to 25 mmol lanthanum per 100g zirconium oxide, 2 mmol lanthanum per 100g zirconium oxide to 20 mmol lanthanum per 100g zirconium oxide, 5 mmol lanthanum per 100g zirconium oxide to 15 mmol lanthanum per 100g zirconium oxide, 5 mmol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide, 5.50 mol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide, 6 mmol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide, 7 mmol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide, 8 mmol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide, or 9 mmol lanthanum per 100g zirconium oxide to 10 mmol lanthanum per 100g zirconium oxide.

[0027] In view of the above, a method for preparing the gallium oxide and zirconia metal oxide catalyst components of the formed mixed catalyst is carried out by initial wet impregnation. In this method, while stirring and mixing zirconia particles, a gallium precursor material (in an embodiment, this may be an aqueous mixture of gallium nitrate (Ga(NO3)3)) is added to the zirconia powder in a dosage (such as dropwise). In other embodiments, gallium oxide may be deposited or distributed on the zirconia oxide by chemical vapor deposition (CVD). However, the method for preparing the gallium oxide and zirconia metal oxide catalyst components of the formed mixed catalyst is not particularly limited, and any method that can apply a fine layer of gallium oxide to the zirconia surface can be used according to the embodiments. It should be understood that the total amount of gallium precursor mixed with the zirconia particles will be determined based on the desired target amount of gallium in the form of metal oxide in the catalyst component.

[0028] Furthermore, in view of the above, a method for preparing the gallium oxide, nickel oxide, rare earth oxide (e.g., lanthanum oxide), and zirconium oxide metal oxide catalyst components of the formed mixed catalyst 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 gallium oxide, nickel oxide, lanthanum oxide, and zirconium oxide metal oxide catalyst components of the formed mixed catalyst 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 amounts of gallium, nickel and lanthanum in metal oxide form in the catalyst composition.

[0029] As previously discussed, according to some embodiments, the particles comprise zirconia particles having a crystalline structure. In 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.

[0030] For the implementation scheme, once the gallium precursor (and optionally the nickel and rare earth precursors) and zirconium oxide particles are sufficiently 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 a temperature 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 calcination duration 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 as mmol per 100g of phase-pure zirconium oxide (simplified to the stoichiometry of ZrO2) for the metals identified above (e.g., gallium and optionally nickel and lanthanum), as previously disclosed above.

[0031] In some embodiments, the metal oxide catalyst component can be prepared by mixing gallium precursors (such as gallium nitrate, gallium hydroxide, hydrated gallium oxide, or gallium oxide), optionally nickel precursors (such as nickel nitrate, nickel acetate, or nickel oxide), and lanthanum precursors (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 some 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 some 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 as the amount of gallium (and optionally nickel and lanthanum) in mmol relative to 100 g of phase-pure zirconium oxide as disclosed above (simplified to stoichiometry of ZrO2).

[0032] As discussed herein, in some embodiments, elements other than gallium oxide and zirconium oxide may be present in the metal oxide catalyst component containing phase-pure zirconium oxide and gallium oxide (e.g., nickel oxide and lanthanum oxide). Such elements may be introduced into the phase-pure zirconium oxide before, during, or after the introduction of the gallium precursor into the composition. Sometimes, such elements are added to guide and stabilize the crystallization of the zirconium oxide phase (e.g., Y-stabilized tetragonal or cubic ZrO2 or La-stabilized tetragonal ZrO2). For example, in embodiments, the metal oxide catalyst component includes nickel and lanthanum. In other cases, additional elements from the group of rare earth and / or transition metals are co-deposited with the gallium precursor or introduced only when a mixed composition comprising gallium oxide and zirconium oxide has already been prepared first.

[0033] 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 a binder 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, the CHA embodiments selected from aluminosilicate-34 (SAPO-34) and SSZ-13; and the AEI embodiments, such as SAPO-18; and the ERI embodiments, such as SAPO-17. For example, the microporous catalyst component comprises 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, a microporous catalyst component having 8-MR to 12-MR pore openings may be used. However, for the production of C2 to C5 hydrocarbons, a microporous catalyst component having 8-MR pore openings is used in the embodiments.

[0034] For methods of preparing the formed mixed catalyst, the metal oxide catalyst component and the microporous catalyst component of the formed mixed catalyst, as provided herein, can be mixed together in any suitable manner to achieve homogeneous mixing of all components prior to 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. A binder is added to the metal oxide catalyst component and the microporous catalyst component to form a paste. For embodiments, the formed 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% based on the total weight of the formed mixed catalyst.

[0035] As presented herein, binders, as discussed herein, are prepared as colloidal solutions, suspensions, or gels by the solubilization of a binder precursor containing an aluminum oxide or hydroxide with an organic carboxylic acid solution. The solubilized binder precursor can 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 handling thick paste formulations. Alternatively, the dried premixed metal oxide catalyst component and microporous catalyst component can be fed directly into the feed screw of a screw extruder along with the solubilized 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 the resulting mixed catalyst. Examples of shapes include pellets, spheres, or near-spherical shapes.

[0036] In the embodiments, based on the total weight of the formed mixed catalyst, the metal oxide catalyst component can account for 40.0% to 85.0% by weight of the formed mixed catalyst. For example, the metal oxide catalyst component can 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 formed 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 formed 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.

[0037] 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.

[0038] After preparing a metal oxide catalyst component and mixing it with a microporous catalyst component, a binder is added to prepare a paste. The binder enables the metal oxide catalyst component and the microporous catalyst component to be held together. The paste can be extruded to produce the resulting mixed catalyst. The resulting mixed catalyst can be formed by any suitable forming method.

[0039] In embodiments, the binder may include alumina, including pure alumina. For embodiments, the alumina binder may be hydrated alumina. Hydrated alumina compositions may be prepared from bohemitic precursors with water and 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 the extruded mixed catalyst. 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 a physical mixture of the formed metal oxide catalyst component and the formed microporous catalyst component (i.e., without forming 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.

[0040] Alumina-based binders can combine metal oxide catalyst components and microporous catalyst components into a single catalyst body to improve C2 to C5 hydrocarbon yields and carbon conversion. Forming either the metal oxide catalyst or the microporous catalyst separately and combining them into a physical mixture does not yield the C2 to C5 and carbon conversion rates achieved using the mixed catalysts as disclosed and described herein.

[0041] In one embodiment, the binder is a colloidal solution, suspension, or gel of a binder precursor. The binder precursor may include aluminum oxide or hydroxide. In one embodiment, the binder precursor may include pure alumina, (pseudo)boehmite, or gibbsite, or mixtures thereof. In one embodiment, the binder precursor is an aluminum hydroxide oxide, such as boehmite or pseudoboehmite.

[0042] For the embodiments described, the binder is prepared as a colloidal solution, suspension, or gel by the peptization of a binder precursor in an organic carboxylic acid solution. The organic carboxylic acid solution is selected from the group consisting of acetic acid solution, formic acid solution, oxalic acid solution, propionic acid solution, and combinations thereof. For the colloidal solution, suspension, or gel, the binder precursor can be mixed with the organic carboxylic acid solution at a temperature ranging from 20°C to 60°C, 20°C to 50°C, or 20°C to 30°C for peptization. The duration of peptization can be from 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 the embodiments described, the binder (e.g., alumina) can have an [organic carboxylic acid] / [Al] concentration ratio (molar M 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, based on the total weight of the colloidal solution, suspension or gel, the total solids content of the binder precursor and the organic carboxylic acid solution in the colloidal solution, suspension or gel 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.

[0043] In the implementation scheme, the adhesive may have a thickness of 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 175m 2 / 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.

[0044] In some embodiments, the method of this disclosure may further include reducing the mixed catalyst formed in a hydrogen-containing atmosphere at temperatures of 450°C to 750°C, 450°C to 650°C, 450°C to 600°C, 500°C to 700°C, 500°C to 650°C, or 500°C to 600°C. For embodiments, the reduction of the mixed catalyst in a hydrogen-containing atmosphere may be carried out for a time 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 may include pure hydrogen (purity level exceeding 99.99% 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 may 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.

[0045] The resulting mixed catalyst can be used in methods for converting carbon in a carbon-containing feed stream into C2 to C5 hydrocarbons. Such methods will be described in more detail below.

[0046] According to the embodiments, a feed stream comprising hydrogen (H2) and a carbonaceous gas selected from carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof is fed into the reaction zone. In some embodiments, H2 gas is present in the feed stream at an amount from 10 volume percent (vol%) to 90 vol%, based on the combined volume of the H2 gas and the gas selected from CO, CO2, and combinations thereof. The feed stream is contacted in the reaction zone with a mixed catalyst formed as disclosed and described herein. The formed mixed catalyst comprises a metal oxide catalyst component including gallium oxide (optionally nickel oxide and lanthanum oxide) and zirconium oxide; a microporous catalyst component; and a binder.

[0047] It should be understood that the activity of the resulting mixed catalyst will be higher for a feed stream containing CO as a carbon-containing gas, and the activity of the resulting mixed catalyst 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 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.

[0048] Under reaction conditions sufficient to form a product stream comprising C2 to C5 hydrocarbons, the feed stream is contacted with the formed 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.

[0049] 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).

[0050] 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.

[0051] In the implementation scheme, the use of the mixed catalysts and 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.

[0052] In embodiments of the invention, the selectivity of the formed mixed catalyst can be adjusted to favor the yield of C2-C5 alkanes relative to C2-C5 olefins or the yield of C2-C5 olefins relative to C2-C5 alkanes. In one embodiment, one method of adjusting this selectivity is by excluding or including nickel oxide in the metal oxide catalyst component of the formed mixed catalyst. When nickel oxide is present in the metal oxide catalyst component of the formed mixed catalyst, the selectivity for C2-C5 alkanes in the method for preparing C2-C5 hydrocarbons is higher than the selectivity for C2-C5 olefins (e.g., the C2-C5 alkanes selectivity / C2-C5 olefins selectivity ratio is greater than or equal to 1.9). Similarly, surprisingly, when nickel oxide is excluded from the metal oxide catalyst component of the formed mixed catalyst (e.g., using only gallium oxide), the selectivity for C2-C5 olefins in the method for preparing C2-C5 hydrocarbons is higher than the selectivity for C2-C5 alkanes (e.g., the C2-C5 olefins selectivity / C2-C5 alkanes selectivity ratio is greater than or equal to 1.9). Therefore, in embodiments where a selectivity for C2-C5 alkanes is desired (e.g., nickel oxide is present in the metal oxide catalyst component of the formed mixed catalyst), the mixed catalyst and process conditions disclosed and described herein are used, and the method may have a C2-C5 alkane selectivity / C2-C5 olefin selectivity ratio greater than or equal to 1.9, 1.9 to 240, 1.9 to 80, 1.9 to 71, 3 to 240, 3 to 80, 3 to 71, 5 to 240, 5 to 80, 5 to 71, 71 to 240, 71 to 80, 1.9 to 5, or about 1.9 to 3. In embodiments, the C2-C5 hydrocarbons primarily comprise C2-C5 alkanes, using the mixed catalyst and process conditions disclosed and described herein.

[0053] In addition to improved selectivity, yield, and conversion during long-term operation, the use of a hybrid catalyst formed according to the embodiments also provides these benefits over a wider range of process conditions (temperature, pressure, flow rate, etc.) in the reactor's reaction zone. For example, a hybrid catalyst formed according to the embodiments disclosed and described herein can allow the use of lower reaction temperatures while still providing high conversion, selectivity, yield, and low oxygen-containing compound selectivity over time.

[0054] Example

[0055] 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: SAPO-34 (Lok, BM; Messina, CA; Patton, RL; Gajek, RT; Cannan, TR; Flanigen, EM Crystalline silicoaluminophosphates. U.S. Patent 4,440,871A, 1984) was synthesized according to a literature procedure and used in an uncalcined (e.g., template-containing) form.

[0056] Embodiment 1 of the present invention (EX 1)

[0057] Metal oxide catalyst components comprising gallium, nickel, and lanthanum 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 / mixing. 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 metal oxide catalyst component was re-sieved to a size of less than 200 mesh (less than 75 μm) to remove larger agglomerated particles.

[0058] 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 HCOOH (95 wt% H2O solution) at a [HCOOH] / [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 the mixed catalyst EX 1. After calcination, EX 1 was crushed and sieved to 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0059] Embodiment 2 of the present invention (EX 2)

[0060] The metal oxide catalyst component comprising gallium supported on zirconium oxide was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, but with the following differences. Pseudoboehmite (AlOOH, 79% Al2O3, manufactured by Sasol Limited, trade name Catapal D) was dissolved in water using glacial acetic acid (CH3COOH, >99 wt%) at a [CH3COOH] / [Al] ratio of 0.035 and a total solids content of 35 wt%. After calcination, EX 2 was crushed and sieved from 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0061] Embodiment 3 of the present invention (EX 3)

[0062] The metal oxide catalyst composition comprising gallium supported on zirconium oxide was prepared as described above for EX 1. The formulation was also prepared as described above for EX 1, but with the following differences. After calcination, EX 3 was crushed and sieved to 40 mesh (400 μm) to 80 mesh (177 μm), and reduced at atmospheric pressure in a 5% H2 / Ar mixture at 600 °C for 1 hour, followed by passivation at 30 °C–45 °C for 30 minutes in a 1% O2 / He mixture. The passivated catalyst was loaded into a reactor and further reduced at atmospheric pressure in hydrogen at 300 °C for 6 hours prior to testing.

[0063] Embodiment 4 of the present invention

[0064] The metal oxide catalyst composition comprising gallium supported on zirconium oxide was prepared as described above for EX 2. The formulation was also prepared as described above for EX 2, but with the following differences. After calcination, EX 4 was crushed and sieved to 40 mesh (400 μm) to 80 mesh (177 μm), and reduced at atmospheric pressure in a 5% H2 / Ar mixture at 600 °C for 1 hour, followed by passivation at 30 °C–45 °C for 30 minutes in a 1% O2 / He mixture. The passivated catalyst was loaded into a reactor and further reduced at atmospheric pressure in hydrogen at 300 °C for 6 hours prior to testing.

[0065] Embodiment 5 of the present invention

[0066] The metal oxide catalyst component comprising gallium supported on zirconium oxide was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, but with the following differences. Pseudoboehmite (AlOOH, 79% Al2O3, manufactured by Sasol Limited, trade name Catapal D) was dissolved in water using oxalic acid (C2H2O4, >99 wt%) at a [C2H2O4] / [Al] ratio of 0.035 and a total solids content of 35 wt%. After calcination, EX 5 was crushed and sieved from 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0067] Embodiment 6 of the present invention (EX 6)

[0068] The metal oxide catalyst component comprising gallium supported on zirconium oxide was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, but with the following differences. Pseudoboehmite (AlOOH, 79% Al2O3, manufactured by Sasol Limited, trade name Catapal D) was dissolved in water using propionic acid (CH3CH2COOH) at a [CH3CH2COOH] / [Al] ratio of 0.035 and a total solids content of 35% by weight. After calcination, EX 6 was crushed and sieved from 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0069] Compare Example A (CE A)

[0070] As described above for EX 1, a metal oxide catalyst component comprising gallium supported on zirconium oxide was prepared. A mixed catalyst was also prepared as described above for EX 1, but with the following differences. 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%. After calcination, CEA was crushed and sieved to 40 mesh (400 μm) to 80 mesh (177 μm) for testing.

[0071] Comparative Example B (CE B)

[0072] As described above for EX 1, a metal oxide catalyst composition comprising gallium supported on zirconium oxide was prepared. A mixed catalyst was also prepared as described above for EX 1, but with the following differences. 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%. After calcination, CE B was crushed and sieved to 40 mesh (400 μm) to 80 mesh (177 μm), and reduced at atmospheric pressure in a 5% H2 / Ar mixture at 600 °C for 1 hour, followed by passivation at 30 °C–45 °C for 30 minutes in a 1% O2 / He mixture. The passivated catalyst was loaded into a reactor and further reduced at atmospheric pressure in hydrogen at 300 °C for 6 hours prior to testing.

[0073] Catalytic performance data

[0074] The 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 .

[0075] 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:

[0076] X CO (%) = [(η) CO，进 – η CO，出 ) / η CO，进 ] · 100; and (1)

[0077] S j (%) = [α j · η j，出 / (η CO，进 – η CO，出 )] · 100,(2)

[0078] 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 α is defined as the carbon-based selectivity (%) for product j. 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).

[0079] The results of the catalytic tests are shown in Table 1 below. The reported conversion values ​​are average conversion levels between 100 and 150 hours TOS for H2:CO = 3, and between 175 and 225 hours TOS for H2:CO = 6.

[0080]

[0081] As can be observed in Table 1, the bifunctional catalyst formulations of EX 1 and EX 2, formulated with organic acids such as formic acid, acetic acid, oxalic acid, and propionic acid, exhibit significantly lower C2-C4 olefin selectivity at comparable overall CO conversion and hydrocarbon productivity levels, compared to the bifunctional catalyst formulation of CEA prepared with nitric acid. Without being bound by any particular theory, it is believed that the positive effects of utilizing organic carboxylic acids as colloidal solvents, as discussed herein, are related to the lower mobility of the metal oxide component during the formulation of mixed catalysts (including the resulting mixed catalysts), as illustrated in Table 2 by the lower solubility of organonitrile salts compared to nickel nitrate.

[0082]

[0083] It should be noted that one or more of the following claims utilize the terms "where" or "in which" as transitional phrases. 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 term "comprising." For the purpose of defining this invention, the transitional phrase "consisting of..." may be introduced in the claims as a closed prepositional term, limiting 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 composed of..." 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”.

[0084] 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.

[0085] 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 the formed mixed catalyst, the feed stream is converted into a product stream containing C2 to C5 hydrocarbons in the reaction zone, the formed mixed catalyst comprising: A metal oxide catalyst component, wherein the metal oxide catalyst component comprises gallium oxide and zirconium oxide; Microporous catalyst component, wherein the microporous catalyst component is a molecular sieve having 8-MR (membered ring) pore openings; as well as A binder containing alumina, wherein the alumina binder is prepared as a colloidal solution, suspension or gel by solubilizing a binder precursor containing an aluminum oxide or hydroxide with an organic carboxylic acid solution.

2. A method for preparing a mixed catalyst, the method comprising: The mixture comprises a metal oxide catalyst component and a microporous catalyst component, wherein: The metal oxide catalyst component comprises gallium oxide and zirconium oxide; and The microporous catalyst component comprises a molecular sieve with 8-MR (membered ring) pore openings; A binder is added to the metal oxide catalyst component and the microporous catalyst component to form a paste, wherein the binder is prepared as a colloidal solution, suspension, or gel by a binder precursor comprising aluminum oxide or hydroxide reacting with an organic carboxylic acid solution; and The paste is extruded to produce the resulting mixed catalyst.

3. The method according to claim 2, wherein the paste is calcined after extrusion.

4. The method according to any one of claims 1 to 3, wherein the metal oxide catalyst component further comprises nickel oxide and rare earth oxides.

5. The method according to any one of claims 1 to 4, wherein the zirconium oxide has a macroporosity fraction of less than 0.

3.

6. The method according to any one of claims 1 to 5, wherein the metal oxide catalyst component accounts for 40 to 85% by weight of the formed mixed catalyst, based on the total weight of the formed mixed catalyst.

7. The method according to any one of claims 1 to 6, wherein the microporous catalyst component comprises silica aluminophosphate-34 (SAPO-34).

8. The method according to any one of claims 1 to 7, wherein the organic carboxylic acid solution is selected from the group consisting of acetic acid solution, formic acid solution, oxalic acid solution, propionic acid solution, and combinations thereof.

9. The method according to any one of claims 1 to 8, wherein the binder comprises a metal selected from aluminum and zirconium, and wherein the binder solution has an [organic carboxylic acid] / [aluminum] concentration ratio of 0.005 to 0.

1.

10. The method according to any one of claims 1 to 9, wherein the formed mixed catalyst has a concentration of the binder in the range of 5% to 30% by weight, based on the total weight of the formed mixed catalyst.

11. The method according to any one of claims 1 to 10, wherein the formed mixed catalyst has a particle size of 0.5 mm to 6 mm.

12. The method according to any one of claims 1 to 11, further comprising reducing the formed mixed catalyst in a hydrogen-containing atmosphere at a temperature of 450°C to 750°C.

13. The method of claim 12, wherein the hydrogen-containing atmosphere comprises pure hydrogen or hydrogen and an inert gas in a mixture of 1% hydrogen / inert gas (v / v) to 99.9% hydrogen / inert gas (v / v), wherein the inert gas is selected from nitrogen, argon, and combinations thereof.

14. The method of claim 13, wherein during the conversion, the temperature within the reaction zone is from 350°C to 480°C.

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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