A process for preparing c2 to c5 hydrocarbons with a formed hybrid catalyst

Abstract

A process for preparing C2 to C5 hydrocarbons includes introducing a feed stream including hydrogen gas 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 including C2 to C5 hydrocarbons in the reaction zone in the presence of a formed hybrid catalyst. The formed hybrid catalyst includes a metal oxide catalyst component comprising gallium oxide and zirconia, a microporous catalyst component that is a molecular sieve having 8-MR (Membered Ring) pore openings, and a binder including alumina, where the alumina binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution.

Description

A PROCESS FOR PREPARING C2 TO C5 HYDROCARBONS WITH A FORMED HYBRID CATALYSTTECHNICAL FIELD

[0001] The present disclosure relates to processes that efficiently convert various carbon- containing streams to C2 to C5 hydrocarbons. In particular, the present disclosure relates to preparation of hybrid catalysts and application of process methods to achieve a high carbon conversion and high yield of desired products.Background

[0002] For a number of industrial applications, hydrocarbons are used, or are a starting material used, to produce plastics, fuels, and various downstream chemicals. Such hydrocarbons include C2 to C5 olefins, such as ethene, propene, butenes and pentenes (also commonly referred to as ethylene, propylene, butylenes and pentylenes respectively) or C2 to C5 paraffins, such as ethane, propane, butanes and pentanes. A variety of processes for producing these lower hydrocarbons have been developed, including petroleum cracking and various synthetic processes.

[0003] Synthetic processes for converting feed carbon to desired products, such as hydrocarbons, are known. Different types of catalysts have been explored, as well as different kinds of feed streams and proportions of feed stream components.

[0004] Many of these synthetic processes have low carbon conversion and much of the feed carbon either does not get converted and exits the process in the same form as the feed carbon or is converted to CO2. In addition, these synthetic processes can have low stability over time and the catalyst rapidly loses its activity for carbon conversion or selectivity to desirable products. Accordingly, a need exists for processes and catalytic systems that improve C2 to C5 hydrocarbon production, especially as time on stream increases.SUMMARY

[0005] Embodiments of the present disclosure address these and other needs by preparation of formed hybrid catalysts and processes using such a catalyst. A formed hybrid catalyst includes 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 peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution. The metal oxide catalyst component and the microporous catalyst component are mixed and then formed into a paste using the binder. The paste is then extruded to produce the formed hybrid catalyst. The formed hybrid catalyst can be used in a process for preparing C2 toC5 hydrocarbons by the direct conversion of a feed stream comprising hydrogen gas and a carbon-containing gas, such as syngas, to the C2 to C5 hydrocarbons. The metal oxide catalyst component and the microporous catalyst component operate in tandem so that the formed hybrid catalyst is able to directly and selectively convert a feed stream comprising hydrogen and carbon-containing gas, such as syngas, to C2 to C5 hydrocarbons.

[0006] According to one or more aspects of the present disclosure, a process for preparing C2 to C5 hydrocarbons includes introducing a feed stream including hydrogen gas 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 including C2 to C5 hydrocarbons in the reaction zone in the presence of a formed hybrid catalyst. The formed hybrid catalyst includes a metal oxide catalyst component including gallium oxide and zirconia, a microporous catalyst component that is 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 peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution.

[0007] According to one or more other aspects of the present disclosure, a process for preparing a formed hybrid catalyst includes mixing a metal oxide catalyst component and a microporous catalyst component, where the metal oxide catalyst component includes gallium oxide and zirconia, and the microporous catalyst component includes 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, where the binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum, with an organic carboxylic acid solution, and extruding the paste to produce the formed hybrid catalyst. The formed hybrid catalyst can undergo drying and subsequent calcination.

[0008] Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows and the claims.

[0009] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.DETAILED DESCRIPTION

[0010] Reference will now be made in detail to embodiments of methods for preparing the formed hybrid catalyst and to processes for forming C2 to C5 hydrocarbons from a feed stream comprising hydrogen gas and a carbon-containing gas. As used herein, “a carbon-containing gas” refers to a gas selected from carbon monoxide, carbon dioxide, and mixtures thereof. As used herein, “synthesis gas” or “syngas” refers to a gas comprising hydrogen gas and a carbon- containing gas.

[0011] For the embodiments, a process for preparing C2 to C5 hydrocarbons includes introducing a feed stream including hydrogen gas 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 including C2 to C5 hydrocarbons in the reaction zone in the presence of a formed hybrid catalyst. The formed hybrid catalyst includes a metal oxide catalyst component including gallium oxide and zirconia, a microporous catalyst component that is a molecular sieve having 8-MR pore openings, and a binder comprising alumina, where the alumina binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution.

[0012] As used herein, “C2 to Cs hydrocarbons” include C2 to C5 olefins and / or C2 to C5 paraffins and subsets of these carbon ranges, such as C2 to C4 hydrocarbons, including C2 to C4 olefins and / or C2 to C4 paraffins, where “C2 to C5 hydrocarbons” as used herein can be replaced by anyone one of C2 to C5 olefins, C2 to C5 paraffins, C2 to C4 hydrocarbons and / or C2 to C4 olefins. The “C2 to C5 hydrocarbons” can also include both linear and branched alkanes and alkenes.

[0013] In embodiments, the metal oxide catalyst component comprises gallium oxide. As used herein, “gallium oxide” refers to gallium in various oxidation states. In embodiments, gallium oxide can be deposited on the surface of zirconia or be in solid solution with zirconia. In other embodiments, gallium oxide may include, but is not limited to, Ga2C>3, GaO(OH), and GasOv / OH). Gallium oxide can also include polymorphs of Ga2O3, such as monoclinic ( - Ga2O3), rhombohedral (a-Ga2O3), defective spinel (y-Ga2O3), cubic (5-Ga2O3), or orthorhombic (s-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 comprising gallium in homogenous oxidation states.

[0014] The use of formed hybrid catalysts is known in the field of hydrocarbon products, such as diesel, or aromatics. However, many known formed hybrid catalysts are inefficient for forming C2 to C5 hydrocarbons, both for C2 to C5 paraffins and for C2 to C5 olefins, from a feed stream comprising hydrogen gas and a carbon-containing gas, because they exhibit a low feed carbon conversion and / or deactivate quickly as they are used, such as, for example, by having an increase in methane production, which leads to a low C2 to C5 hydrocarbon productivity and low stability for a given set of operating conditions over a given amount of time. Known formed hybrid catalysts for the production of C2 to C5 paraffins exhibit an increase in C2 to C5 olefin selectivity as function of time on stream. In contrast, formed hybrid catalysts disclosed and described herein exhibit a substantially higher and more stable C2 to C5 paraffin selectivity at comparable overall CO conversion and hydrocarbon productivity levels as compared to hybrid catalysts where the binder for the metal oxide catalyst component and the microporous catalyst component was peptized using nitric acid as opposed to being peptized with an organic carboxylic acid solution according to the present disclosure. The preparation and composition of such formed hybrid catalysts used in embodiments is discussed below.

[0015] As a summary, formed hybrid catalysts closely couple independent reactions on each of the two independent catalysts in a single catalyst particle. In the first step, a feed stream comprising hydrogen gas (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, for example, syngas, is converted into an intermediate(s) such as oxygenated hydrocarbons. In the subsequent step, these intermediates are converted into a product stream comprising hydrocarbons (mostly short chain hydrocarbons, such as, for example C2 to C5 hydrocarbons). The continued formation and consumption of the intermediate oxygenates formed in the first step by the reactions of the second step ensures that there is no thermodynamic limit on conversions.

[0016] In embodiments, the formed hybrid catalyst has a particle size from 0.5 millimeter (mm) to 6.0 mm, such as from 0.5 mm to 5.5 mm, from 0.5 mm to 5.0 mm, from 0.5 mm to 4.5 mm, from 0.5 mm to 4.0 mm, from 0.5 mm to 3.5 mm, from 0.5 mm to 3.0 mm, from 0.5 mm to2.5 mm, from 0.5 mm to 2.0 mm, or from 0.5 mm to 1.5 mm. In embodiments, the formed hybrid catalyst has a particle size from 1.0 mm to 6.0 mm, such as from 1.0 mm to 5.5 mm, from 1.0 mm to 5.0 mm, from 1.0 mm to 4.5 mm, from 1.0 mm to 4.0 mm, from 1.0 mm to 3.5 mm, from 1.0 mm to 3.0 mm, from 1.0 mm to 2.5 mm, from 1.0 mm to 2.0 mm, or from 1.0 mm to1.5 mm. In embodiments, the formed hybrid catalyst has a particle size from 1.5 mm to 3.0 mm,such as from 1 .8 mm to 3.0 mm, from 2.0 mm to 3.0 mm, from 2.2 mm to 3.0 mm, from 2.5 mm to 3.0 mm, from 2.8 mm to 3.0 mm, from 1.5 mm to 2.8 mm, from 1.8 mm to 2.8 mm, from 2.0 mm to 2.8 mm, from 2.2 mm to 2.8 mm, from 2.5 mm to 2.8 mm, from 1.5 mm to 2.5 mm, from 1.8 mm to 2.5 mm, from 2.0 mm to 2.5 mm, from 2.2 mm to 2.5 mm, from 1.5 mm to 2.2 mm, from 1.8 mm to 2.2 mm, from 2.0 mm to 2.2 mm, from 1.5 mm to 2.0 mm, from 1.8 mm to 2.0 mm, or from 1.5 mm to 1.8. The particle size may be essentially the shortest dimension of the catalyst particle. For example, when the formed hybrid catalyst has a hollow cylinder or a ring shape, the particle size is the thickness of the hollow cylinder wall. When the formed hybrid catalyst has a spherical shape, the particle size is the diameter of the sphere. The particle size of the formed hybrid catalyst may be controlled by choice of the extrusion die diameter and measured by dynamic image analysis methods.

[0017] In one or more embodiments, the metal oxide catalyst component may comprise zirconia, where the zirconia acts as a metal oxide support. The term “metal oxide support” may refer to a support material that supports the other components of the metal oxide catalyst component, for example, gallium oxide and optionally nickel oxide and a rare earth oxide (e.g., lanthanum oxide). In some embodiments, the zirconia of the metal oxide catalyst component may comprise micropores. The term “micropores” may refer to the pores of a material where one or more pores are less than 2 nm in diameter. In some embodiments, the zirconia of the metal oxide catalyst component may comprise mesopores. The term “mesopores” may refer to the pores of a material where one or more pores are 2-50 nm in diameter. In some embodiments, the zirconia of the metal oxide catalyst component may comprise macropores. The term “macropores” may refer to the pores of a material where one or more pores are greater than or equal to 80 nm in diameter.

[0018] For the various embodiments, the zirconia can have a macroporosity fraction that is less than 0.3. The term “macroporosity fraction” may refer to the macroporous pore volume of the zirconia over the total pore volume of pores of the zirconia with a size below 500 nm. In order to test the macroporosity fraction, mercury porosimetry testing may be used where the porosity of the zirconia is measured by immersing the material in mercury and applying controlled pressure to the system so that mercury can penetrate into the pores of the material. Based on the pressure it takes to force the mercury into certain pores of the zirconia, the pore diameter and pore volume may be calculated. Correlating the pore diameter and the associated pressure can be achieved using Formula I below, where D is the diameter of the zirconia pore, Pis the pressure it takes for mercury to penetrate the zirconia pore, y is the surface tension of the mercury, and 0 is the contact angle between the zirconia and the mercury:(Formu ila I)

[0019] For the embodiments, the zirconia can have a macroporosity fraction that is less than 0.3, such as having a macroporosity fraction of 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 from 0.05 to 0.25, from 0.10 to 0.25, or from 0.10 to 0.20. In embodiments, the macroporosity fraction may be from 0.05 to 0.25, from 0.05 to 0.20, from 0.05 to 0.15, or from 0.0 to 0.10. In embodiments, the macroporosity fraction may be from 0.10 to 0.30, from 0.15 to 0.30, from 0.20 to 0.30, or from 0.25 to 0.30.

[0020] Tn embodiments, the metal oxide catalyst component comprises gallium oxide and zirconia (ZrCh). In additional embodiments, the metal oxide catalyst component comprises gallium oxide, nickel oxide and zirconia (ZrC ). In embodiments, the metal oxide catalyst component can also comprise a rare earth oxide. As used herein, “rare earth oxide” refers to an oxide comprising a rare earth element, which includes scandium, yttrium, and elements having an atomic number from 57 to 71, such as but not limited to, samarium, gadolinium, dysprosium, lanthanum, cerium, and neodymium. For example, in additional embodiments the metal oxide catalyst component comprises gallium oxide, nickel oxide, lanthanum oxide and zirconia (ZrC ).

[0021] As used herein, the zirconia used in embodiments disclosed and described herein in the metal oxide catalyst component of the formed hybrid catalyst is “phase pure zirconia”, which is defined herein as zirconia to which no other materials have intentionally been added during formation. Thus, “phase pure zirconia” includes zirconia with 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, for example, hafnium (Hf). Accordingly, as used herein “zirconia” and “phase pure zirconia” are used interchangeably unless specifically indicated otherwise.

[0022] Without being bound by any particular theory, it is believed that the high surface area of zirconia allows the gallium oxide catalyst, and optionally the nickel oxide and the rare earth oxide, acting as part of formed hybrid catalyst to convert carbon-containing components to C2 to C5 hydrocarbons. It is believed that the gallium oxide, and optionally the nickel oxide and the rare earth oxide, and the zirconia help to activate one another, which results in improved yield for C2 to C5 hydrocarbons.

[0023] Tn embodiments disclosed herein, the composition of the metal oxide catalyst component is designated by a millimole (mmol) to weight ratio of the gallium metal, and optionally the nickel metal and the rare earth metal, to the pure zirconia (accounting for ZrOz stoichiometry). In one or more embodiments, the composition of the metal catalyst component is designated by mmol of gallium per 100 grams (g) of zirconia. According to embodiments, the metal oxide catalyst component includes from 5 mmol gallium to 80 mmol gallium per 100 g of zirconia, such as 10 mmol gallium to 80 mmol gallium per 100 g of zirconia; 15 mmol gallium oxide to 80 mmol gallium per 100 g of zirconia; 20 mmol gallium to 80 mmol gallium per 100 g of zirconia; 25 mmol gallium to 80 mmol gallium per 100 g of zirconia; or 30 mmol gallium to 80 mmol gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 5 mmol gallium to 75 mmol gallium per 100 g of zirconia, such as from 5 mmol gallium to 70 mmol gallium per 100 g of zirconia, from 5 mmol gallium to 65 mmol gallium per 100 g of zirconia, from 5 mmol gallium oxide to 60 mmol gallium per 100 g of zirconia, or from 5 mmol gallium to 55 mmol gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 10 mmol gallium to 75 mmol gallium per 100 g of zirconia, such as from 15 mmol gallium to 70 mmol gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 5 mmol gallium per 100 g of zirconia to 50 mmol gallium to 100 g zirconia, such as from 10 mmol gallium per 100 g of zirconia to 45 mmol gallium to 100 g zirconia, from 15 mmol gallium per 100 g of zirconia to 40 mmol gallium to 100 g zirconia, from 20 mmol gallium per 100 g of zirconia to 35 mmol gallium to 100 g zirconia, from 25 mmol gallium per 100 g of zirconia to 30 mmol gallium to 100 g zirconia, from 50 mmol gallium per 100 g of zirconia to 80 mmol gallium to 100 g zirconia, from 55 mmol gallium per 100 g of zirconia to 75 mmol gallium to 100 g zirconia, or from 60 mmol gallium per 100 g of zirconia to 70 mmol gallium to 100 g zirconia.

[0024] In embodiments disclosed herein, metal oxide catalyst component can further include other metal oxides, as discussed herein. For example, the metal oxide catalyst component can further include a nickel oxide and a rare earth oxide. For the embodiments disclosed herein, the composition of the metal oxide catalyst component is designated by a mmol to weight ratio of the nickel oxide metal to the pure zirconia (accounting for ZrO: stoichiometry). In one or more embodiments, the composition of the metal oxide catalyst component is designated by mmol of nickel per 100 grams (g) of zirconia. According to embodiments, the metal oxide catalyst component includes from 6 mmol nickel to 20 mmol nickel per 100 g of zirconia, such as 7mmol nickel to 20 mmol nickel per 100 g of zirconia, 8 mmol nickel to 20 mmol nickel per 100 g of zirconia, 10 mmol nickel to 20 mmol nickel per 100 g of zirconia, 12 mmol nickel to 20 mmol nickel per 100 g of zirconia, or 15 mmol nickel to 20 mmol nickel per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 6 mmol nickel to 18 mmol nickel per 100 g of zirconia, such as from 6 mmol nickel to 16 mmol nickel per 100 g of zirconia, from 6 mmol nickel to 15 mmol nickel per 100 g of zirconia, from 6 mmol nickel to 12 mmol nickel per 100 g of zirconia, or from 6 mmol nickel to 10 mmol nickel per 100 g of zirconia. In some embodiments, the metal catalyst component includes from 7 mmol nickel to 18 mmol nickel per 100 g of zirconia, such as from 8 mmol nickel to 18 mmol nickel per 100 g of zirconia, from 10 mmol nickel to 18 mmol nickel per 100 g of zirconia, from 12 mmol nickel to 18 mmol nickel per 100 g of zirconia, or from 14 mmol nickel to 18 mmol nickel per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 10 mmol nickel per 100 g of zirconia to 18 mmol nickel to 100 g zirconia, such as from 12 mmol nickel per 100 g of zirconia to 18 mmol nickel to 100 g zirconia, from 14 mmol nickel per 100 g of zirconia to 18 mmol nickel to 100 g zirconia, or from 16 mmol nickel per 100 g of zirconia to 18 mmol nickel to 100 g zirconia.

[0025] For the embodiments disclosed herein, examples of the rare earth oxide include, but are not limited to, lanthanum oxide. For the embodiments disclosed herein, the composition of the metal oxide catalyst component is designated by a mmol to weight ratio of the lanthanum oxide metal to the pure zirconia (accounting for ZrCF stoichiometry). In one or more embodiments, the composition of the metal oxide catalyst component is designated by mmol of lanthanum per 100 grams (g) of zirconia. According to embodiments, the metal oxide catalyst component includes, when present, from 1 mmol lanthanum to 40 mmol lanthanum per 100 g of zirconia, , 5 mmol lanthanum to 40 mmol lanthanum per 100 g of zirconia, 10 mmol lanthanum to 40 mmol lanthanum per 100 g of zirconia, or 15 mmol lanthanum to 40 mmol lanthanum per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 1 mmol lanthanum to 35 mmol lanthanum per 100 g of zirconia, such as from 1 mmol lanthanum to 30 mmol lanthanum per 100 g of zirconia, from 1 mmol lanthanum to 25 mmol lanthanum per 100 g of zirconia, from 1 mmol lanthanum to 20 mmol lanthanum per 100 g of zirconia, or from 1 mmol lanthanum to 15 mmol lanthanum per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 1 mmol lanthanum to 35 mmol lanthanum per 100 g of zirconia. In some embodiments, the metal oxide catalyst component includes from 1 mmol lanthanum per 100 g of zirconia to 30 mmol lanthanum to 100 g zirconia, such as from 1mmol lanthanum per 100 g of zirconia to 25 mmol lanthanum to 100 g zirconia, from 2 mmol lanthanum per 100 g of zirconia to 20 mmol lanthanum to 100 g zirconia, from 5 mmol lanthanum per 100 g of zirconia to 15 mmol lanthanum to 100 g zirconia, from 5 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia, from 5.50 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia, from 6 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia, from 7 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia, from 8 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia, or from 9 mmol lanthanum per 100 g of zirconia to 10 mmol lanthanum to 100 g zirconia.

[0026] In view of the above, one method for making the gallium oxide and zirconia metal oxide catalyst component of the formed hybrid catalyst is by incipient wetness impregnation. In such a method, an aqueous mixture of a gallium precursor material, which, in embodiments, may be gallium nitrate (Ga(NO3)3) is added to zirconia powder in a dosed amount (such as dropwise) while stirring and mixing the zirconia particles. In other embodiments, the gallium oxide may be deposited or distributed on the zirconia oxide by chemical vapor deposition (CVD) method. However, the method for making the gallium oxide and zirconia metal oxide catalyst component of the formed hybrid catalyst is not particularly limited and any method that can apply a fine layer of gallium oxide on the surface of zirconium oxide can be used according to embodiments. It should be understood that the total amount of gallium precursor that is mixed with the zirconia particles will be determined on the desired target amount of gallium in metal oxide form in the catalyst component.

[0027] In addition, in view of the above one method for making the gallium oxide, nickel oxide, rare earth oxide (e.g., lanthanum oxide) and zirconia metal oxide catalyst component of the formed hybrid catalyst is also by the incipient wetness impregnation approach. In such a method, an aqueous mixture of a gallium precursor material, which, in embodiments, may be gallium nitrate (Ga(NO3h); a nickel precursor material, which, in embodiments, may be nickel nitrate (Ni NCh ); a lanthanum precursor material, which, in embodiments, may be lanthanum nitrate (La(NO3)3) are added to zirconia powder in a dosed amount (such as dropwise) while stirring and mixing the zirconia particles. In other embodiments, the gallium oxide, nickel oxide and lanthanum oxide may be deposited or distributed on the zirconia oxide by CVD method. However, the method for making the gallium oxide, nickel oxide, lanthanum oxide and zirconia metal oxide catalyst component of the formed hybrid catalyst is not particularly limited and any method that can apply a fine layer of gallium oxide, nickel oxide and lanthanum oxide on thesurface of zirconium oxide can be used according to embodiments. It should be understood that the total amount of gallium precursor, nickel precursor and lanthanum precursor that is mixed with the zirconia particles will be determined on the desired target amount of the gallium, nickel and lanthanum in metal oxide form in the catalyst component.

[0028] As discussed previously, according to some embodiments, the particles include zirconia particles having a crystalline structure. In embodiments, the zirconia particles include zirconia particles having a monoclinic structure. In one or more embodiments, the zirconia particles consist essentially of or consist of crystalline zirconia particles, and in some embodiments, the zirconia particles consist essentially of or consist of monoclinic zirconia particles. According to some embodiments, the zirconia particles have a BET surface area that is greater than or equal to 5 meters squared per gram (m2 / g), such as greater than 10 m2 / g, greater than 20 m2 / g, greater than 30 m2 / g, greater than 40 m2 / g, greater than 50 m2 / g, greater than 60 m2 / g, greater than 70 m2 / g, greater than 80 m2 / g, greater than 90 m2 / g, greater than 100 m2 / g, greater than 110 m2 / g, greater than 120 m2 / g, greater than 130 m2 / g, or greater than 140 m2 / g. According to some embodiments, the maximum BET surface area of the zirconia particles is 150 m2 / g. Accordingly, in some embodiments, the BET surface area of the zirconia particles is from 5 m2 / g to 150 m2 / g, from 10 m2 / g to 150 m2 / g, from 20 m2 / g to 150 m2 / g, such as from 30 m2 / g to 150 m2 / g, from 40 m2 / g to 150 m2 / g, from 50 m2 / g to 150 m2 / g, from 60 m2 / g to 150 m2 / g, from 70 m2 / g to 150 m2 / g, from 80 m2 / g to 150 m2 / g, from 90 m2 / g to 150 m2 / g, from 100 m2 / g to 150 m2 / g, from 110 m2 / g to 150 m2 / g, from 120 m2 / g to 150 m2 / g, from 130 m2 / g to 150 m2 / g, or from 140 m2 / g to 150 m2 / g. In some embodiments, the BET surface area of the zirconia particles is from 5 m2 / g to 140 m2 / g, such as from 5 m2 / g to 130 m2 / g, from 5 m2 / g to 120 m2 / g, from 5 m2 / g to 110 m2 / g, from 5 m2 / g to 100 m2 / g, from 5 m2 / g to 90 m2 / g, from 5 m2 / g to 80 m2 / g, from 5 m2 / g to 70 m2 / g, from 5 m2 / g to 60 m2 / g, from 5 m2 / g to 50 m2 / g, from 5 m2 / g to 40 m2 / g, from 5 m2 / g to 30 m2 / g, from 5 m2 / g to 20 m2 / g, or from 5 m2 / g to 10 m2 / g. In some embodiments, the BET surface area of the zirconia particles is from 10 m2 / g to 140 m2 / g, from 20 m2 / g to 130 m2 / g, from 30 m2 / g to 120 m2 / g, from 40 m2 / g to 110 m2 / g, from 50 m2 / g to 100 m2 / g, from 60 m2 / g to 90 m2 / g, or from 70 m2 / g to 80 m2 / g.

[0029] For the embodiments, once the gallium precursor (and optionally the nickel precursor and the rare earth precursor) and zirconia particles are adequately mixed, the metal oxide catalyst component may be dried at temperatures less than 200 degrees Celsius (°C), such as less than 175 °C, less than 150 °C, less than 100 °C, or about 85 °C. Subsequent to the drying, the metal oxide catalyst component is calcined at temperatures from 400 °C to 800 °C for a time of2 to 6 hours. For example, the metal oxide catalyst component can be calcined at temperatures from 400 °C to 800 °C, such as from 425 °C to 775 °C, from 450 °C to 750 °C, from 475 °C to 725 °C, from 500 °C to 700 °C, from 525 °C to 675 °C, from 550 °C to 650 °C, from 575 °C to 625 °C, about 550 °C, or about 600 °C. The duration of the calcining can be 2 to 6 hours, such as from 2 to 5 hours, from 2 to 3 hours, from 3 to 6 hours, from 4 to 6 hours, or 4 hours. After calcining, the composition of the mixed metal oxide catalyst component is determined and reported as a mmol amount of the above identified metal(s) (e.g., gallium, and optionally nickel and lanthanum referenced per 100 g of phase pure zirconia (simplified to the stoichiometry of ZrCh) as previously disclosed above.

[0030] In embodiments, the metal oxide catalyst component may be made by mixing powders or slurries of a gallium precursor (such as gallium nitrate, gallium hydroxide, hydrous gallium oxide or gallium oxide), optionally a nickel precursor (such as nickel nitrate, nickel acetate or nickel oxide) and lanthanum precursor (such as lanthanum nitrate, lanthanum carbonate, lanthanum hydroxycarbonate or lanthanum oxide), and zirconia. According to some embodiments, the zirconia particles include zirconia particles having a crystalline structure. In embodiments, the zirconia particles include zirconia particles having a monoclinic structure. In one or more embodiments, the zirconia particles consist essentially of or consist of crystalline zirconia particles, and in some embodiments, the zirconia particles consist essentially of or consist of monoclinic zirconia particles. The zirconia particles may, in embodiments, have the BET surface areas disclosed above. The powders or slurries may be vigorously mixed at high temperatures such as from room temperature (approximately 23 °C) to 100 °C. After the powders or slurries have been adequately mixed, the metal oxide catalyst component may be dried and calcined at temperatures from 400 °C to 800 °C for a time of 2 to 6 hours, as discussed above. After calcining, the composition of the mixed metal oxide catalyst component is determined and reported as a mmol amount of gallium (and optionally nickel and lanthanum) in reference to 100 g of phase pure zirconia (simplified to the stoichiometry of ZrCF) as disclosed above.

[0031] As discussed herein, elements other than gallium oxide and zirconia may, in some embodiments, be present in the metal oxide catalyst component containing phase pure zirconia and gallium oxide (e.g., nickel oxide and lanthanum oxide). Such elements may be introduced to the phase pure zirconia before, during or after introducing gallium precursor to the composition. Sometimes such elements are added to direct and stabilize the crystallization of zirconia phase (e.g., Y-stabilized tetragonal or cubic ZrCF or La-stabilized tetragonal ZrCF). For example, inembodiments the metal oxide catalyst component includes nickel and lanthanum. In other instances, additional elements from the group of rare earth, and / or transition metals are codeposited with gallium precursor or introduced only when the mixed composition including gallium oxide and zirconia has been prepared in the first place.

[0032] In one or more embodiments, after the metal oxide catalyst component has been prepared such as, for example, by the methods disclosed above the metal oxide catalyst component is mixed with a microporous catalyst component, and a binder, as prepared according to the present disclosure, to form a single catalyst. The microporous catalyst component is, in embodiments, selected from molecular sieves having 8-MR pore openings and having a framework type selected from the group consisting of the following framework types: CHA, AEI, AFX, ERI, LEV, LTA, UFI, RTH, EDI, GIS, MER, RHO, and combinations thereof, the framework types corresponding to the naming convention of the International Zeolite Association. It should be understood that in embodiments, both aluminosilicate and silicoaluminophosphate frameworks may be used. Some embodiments may include tetrahedral aluminosilicates, ALPOs (such as, for example, tetrahedral aluminophosphates), SAPOs (such as, for example, tetrahedral silicoaluminophosphates), and silica-only based tectosilicates. In certain embodiments, the microporous catalyst component may be silicoaluminophosphate having a Chabazite (CHA) framework type. Examples of these may include, but are not necessarily limited to: CHA embodiments selected from silicoaluminophosphate-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 comprises silicoaluminophosphate-34 (SAPO-34). Combinations of microporous catalyst components having any of the above framework types may also be employed. It should be understood that the microporous catalyst component may have different membered ring pore opening depending on the desired product. For instance, microporous catalyst component having 8-MR to 12-MR pore openings could be used depending on the desired product. However, to produce C2 to C5 hydrocarbons, a microporous catalyst component having 8-MR pore openings is used in embodiments.

[0033] For the process of preparing the formed hybrid catalyst, the metal oxide catalyst component and the microporous catalyst component of the formed hybrid catalyst, as provided herein, may be mixed together by any suitable means to achieve homogenous mixing of all the components prior to extrusion. The metal oxide catalyst component and the microporous catalyst component can be initially mixed as powders to achieve homogeneity in suitable dry mixer, such as a ribbon or plow mixer. The binder is added to the metal oxide catalyst component and themicroporous catalyst component to form a paste. For the embodiments, the formed hybrid catalyst formed from the paste can have a concentration of the binder in a range of 5 to 30 wt.%, from 10 to 30 wt.%, from 15 to 30 wt.%, from 20 to 30 wt.%, from 5 to 25 wt.%, from 10 to 25 wt.%, from 15 to 25 wt.%, from 20 to 25 wt.% or 20 wt.% based on the total weight of the formed hybrid catalyst.

[0034] As provided herein, the binder is prepared, as discussed herein, as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum, with an organic carboxylic acid solution. The peptized binder precursor can be added to the mixture of the metal oxide catalyst component and the microporous catalyst component and mixed in a suitable heavy duty industrial mixer capable of handling thick paste formulations. Alternatively, the dry pre-mixed metal oxide catalyst component and the microporous catalyst component can be fed directly into the feeding screws of a screw extruder along with the peptized binder precursor composition and mixed directly in the screw extruder. The paste can then be extruded into a desired shape by any suitable extrusion method to produce the formed hybrid catalyst. Examples of shapes include pellets, spherical, or near-spherical.

[0035] In embodiments, the metal oxide catalyst component may include from 40.0 weight percent (wt.%) to 85.0 wt.% of the formed hybrid catalyst based on the total weight of the formed hybrid catalyst. For example, the metal oxide catalyst component may include from 45.0 wt.% to 85.0 wt.%, from 50.0 wt.% to 85.0 wt.%, from 55.0 wt.% to 85.0 wt.%, from 60.0 wt.% to 85.0 wt.%, from 65.0 wt.% to 85.0 wt.%, from 70.0 wt.% to 85.0 wt.%, from 75.0 wt.% to 85.0 wt.%, or from 75.0 wt.% to 85.0 wt.%. In some embodiments, the metal oxide catalyst component includes from 40.0 wt.% to 80.0 wt.%, from 40.0 wt.% to 75.0 wt.%, from 40.0 wt.% to 70.0 wt.%, from 40.0 wt.% to 65.0 wt.%, from 40.0 wt.% to 60.0 wt.%, from 40.0 wt.% to 55.0 wt.%, from 40.0 wt.% to 50.0 wt.%, or from 40.0 wt.% to 45.0 wt.%. In some embodiments, the metal oxide catalyst component includes from 45.0 wt.% to 80.0 wt.% of the formed hybrid catalyst, such as from 50.0 wt.% to 80.0 wt.%, from 55.0 wt.% to 80.0 wt.%, from 60.0 wt.% to 80.0 wt.%, from 65.0 wt.% to 75.0 wt.%, from 65.0 wt.% to 70.0 wt.%, from 45.0 wt.% to 65.0 wt.%, from 50.0 wt.% to 60.0 wt.%, or from 45.0 wt.% to 55.0 wt.%. In some embodiments, the metal oxide catalyst component includes from 50.0 wt.% to 80.0 wt.% of the formed hybrid catalyst, such as from 50.0 wt.% to 75.0 wt.%, from 50.0 wt.% to 70.0 wt.%, from 60.0 wt.% to 80.0 wt.%, from 60.0 wt.% to 75.0 wt.%, or from 60.0 wt.% to 70.0 wt.%.

[0036] The metal oxide catalyst component and the microporous catalyst component may be combined with the mass ratio of from 1:10 to 10:1, from 1:10 to 9:1, from 1: 10 to 8:1, from 1:10to 5:1 , from 1 :10 to 4:1 , from 1 :10 to 3:1 , from 1 :8 to 8:1 , from 1 :8 to 7:1 , from 1 :8 to 6:1 , from 1:8 to 5:1, from 1:8 to 4:1, from 1:5 to 8:1, from 1:5 to 7: 1, from 1:5 to 6:1, or from 1:5 to 5:1.

[0037] After the metal oxide catalyst component has been prepared and combined with a microporous catalyst component, the binder is added to produce a paste. The binder may be capable of holding the metal oxide catalyst component and the microporous catalyst component together. The paste may be extruded to produce the formed hybrid catalyst. The formed hybrid catalyst may be formed by any suitable shaping process.

[0038] In embodiments, the binder may include alumina, including pure alumina. For the embodiments, the alumina binder may be a hydrous alumina. A hydrous alumina composition may be prepared from bohemitic precursors with water and peptizing agent. The binder may be mixed with 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 the paste), the mixture (e.g., paste) may be extruded, dried, and calcined, as discussed herein. After calcination, the binder may form aluminum oxide and bind the metal oxide catalyst component and the microporous catalyst component together to provide mechanical strength to extrude the formed hybrid catalyst. Without being bound by any particular theory, other typically employed binders, such as SiO and TiO . may lead to poisoning of the catalyst activity or significant loss in hydrocarbon selectivity. The combination of the two catalyst components into a single catalyst body is not trivial. While a physical mixture of the formed metal oxide catalyst component and the formed microporous catalyst component (i.e., not formed into a single catalyst body) may achieve the required pressure drop over the reactors, the catalytic performance, such as hydrocarbon selectivity, and carbon conversion, drops dramatically.

[0039] The binder including alumina, can combine the metal oxide catalyst component and the microporous catalyst component into a single catalyst body to improve C2 to C5 hydrocarbon yields and carbon conversion. Individually forming both metal oxide catalyst and microporous catalyst and combining them as a physical mixture is not able to obtain C2 to C5 and carbon conversion that are obtained with a formed hybrid catalyst as disclosed and described herein.

[0040] In embodiments, the binder is a colloidal solution, suspension, or gel of a binder precursor. The binder precursor may include oxides or hydroxides of aluminum. 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 pseudo-boehmite.

[0041] For the embodiments, the binder is prepared as a colloidal solution, suspension, or gel by peptization of the binder precursor with an organic carboxylic acid solution. The organic carboxylic acid solution is selected from the group consisting of an acetic acid solution, a formic acid solution, an oxalic acid solution, a 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 in the range from 20 to 60 °C, from 20 to 50 °C or from 20 to 30 °C for the peptization. The duration of the peptization can be from 0.1 to 24 hours, from 0.1 to 12 hours, from 1 to 12 hours, from 1 to 6 hours, from 1 to 3 hours or from 1 to 2 hours. For the embodiments, the binder (e.g., alumina) may have a [organic carboxylic acid] / [Al] concentration ratio (molar, M, concentration ratio) of from 0.005 to 0.1, from 0.01 to 0.1, from 0.01 to 0.05 or about 0.035. For the embodiments, a total solids content of the colloidal solution, suspension, or gel of the binder precursor with the organic carboxylic acid solution can from 20 to 50 wt.%, from 30 to 50 wt.%, from 20 to 40 wt.%, from 30 to 40 wt.% or 35 wt.% based on the total weight of the colloidal solution, suspension, or gel.

[0042] In embodiments, the binder may have a surface area of from 100 m2 / g to 400 m2 / g, from 125 m2 / g to 400 m2 / g, from 150 m2 / g to 400 m2 / g, from 100 m2 / g to 200 m2 / g, from 125 m2 / g to 200 m2 / g, from 150 m2 / g to 200 m2 / g, from 100 m2 / g to 175 m2 / g, from 125 m2 / g to 175 m2 / g, from 150 m2 / g to 175 m2 / g, from 100 m2 / g to 150 m2 / g, from 125 m2 / g to 150 m2 / g, or from 100 m2 / g to 125 m2 / g.

[0043] In some embodiments, the process of the present disclosure can further include reducing the formed hybrid catalyst in a hydrogen-comprising atmosphere at a temperature of 450 to 750 °C, of 450 to 650 °C, of 450 to 600 °C, of 500 to 700 °C, of 500 to 650 °C or of 500 to 600 °C. For the embodiments, reducing the formed hybrid catalyst in the hydrogencomprising atmosphere can take place for a time from 0.5 to 10 hours, from 3 to 10 hours, from 4 to 10 hours, from 5 to 10 hours, from 2 to 8 hours, from 4 to 8 hours, from 5 to 7 hours, or 6 hours. For the embodiments, the hydrogen-comprising atmosphere can include pure hydrogen (purity level exceeding 99.99 % v / v) or a hydrogen and an inert gas in a 1% hydrogen / inert (v / v) to a 99.9% hydrogen / inert (v / v) mixture. For the embodiments, the inert gas can be selected from the group consisting of argon, nitrogen, and combinations thereof. Without being bound to a particular theory, it is believed that reduction of the catalyst leads to a higher dispersion of nickel and gallium, and facilitates the interaction between Ni and Ga, leading to high hydrogenation activity for C2 to C5 olefins, and subsequently high and stable C2 to C5 paraffin selectivity.

[0044] The formed hybrid catalyst may be used in methods for converting carbon in a carbon- containing feed stream to C2 to C5 hydrocarbons. Such processes will be described in more detail below.

[0045] According to embodiments, a feed stream is fed into a reaction zone, the feed stream comprising hydrogen (H2) gas and a carbon-containing gas selected from carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. In some embodiments, the H2 gas is present in the feed stream in an amount of from 10 volume percent (vol%) to 90 vol%, based on combined volumes of the H2 gas and the gas selected from CO, CO2, and combinations thereof. The feed stream is contacted with a formed hybrid catalyst as disclosed and described herein in the reaction zone. The formed hybrid catalyst includes a metal oxide catalyst component comprising gallium oxide (optionally nickel oxide and lanthanum oxide) and zirconia, a microporous catalyst component, and a binder.

[0046] It should be understood that the activity of the formed hybrid catalyst will be higher for feed streams containing CO as the carbon-containing gas, and that the activity of the formed hybrid catalyst decreases as a larger portion of the carbon-containing gas in the feed stream is CO2. However, that is not to say that the formed hybrid catalyst disclosed and described herein cannot be used in methods where the feed stream includes CO2 as all, or a large portion, of the carbon-containing gas.

[0047] The feed stream is contacted with the formed hybrid catalyst in the reaction zone under reaction conditions sufficient to form a product stream comprising C2 to C5 hydrocarbons. The reaction conditions include a temperature within the reaction zone ranging, according to one or more embodiments, from 350 °C to 480 °C, from 375 °C to 450 °C, from 400 °C to 450 °C, from 350 °C to 425 °C, from 375 °C to 425 °C, from 400 °C to 425 °C, from 350 °C to 400 °C, or from 375 °C to 400 °C.

[0048] In embodiments, the reaction conditions include a pressure inside the reaction zone of at least 1 bar (100 kilopascals (kPa), 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), 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 a pressure inside the reaction zone is from 5 bar (500 kPa) to 100 bar (10,000 kPa), such as from 10 bar (1,000 kPa)to 95 bar (9,500 kPa), from 15 bar (1 ,500 kPa) to 90 bar (9,000 kPa), from 20 bar (2,000 kPa) to 85 bar (8,500 kPa), from 25 bar (2,500 kPa) to 80 bar (8,000 kPa), from 30 bar (3,000 kPa) to 75 bar (7,500 kPa), from 35 bar (3,500 kPa) to 70 bar (7,000 kPa), from 40 bar (4,000 kPa) to 65 bar (6,500 kPa), from 45 bar (4,500 kPa) to 60 bar (6,000 kPa), or from 50 bar (5,000 kPa) to 55 bar (5,500 kPa). In some embodiments, the pressure inside the reaction zone is from 20 bar (2,000 kPa) to 60 bar (6,000 kPa).

[0049] According to embodiments, the gas hourly space velocity (GHSV) within the reaction zone is from 500 per hour ( / h) to 12,000 / h, such as from 500 / h to 10,000 / h, from 1,200 / h to 12,000 / h, from 1, 500 / h to 10,000 / h, from 2,000 / h to 9, 500 / h, from 2, 500 / h to 9,000 / h, from 3,000 / h to 8, 500 / h, from 3, 500 / h to 8,000 / h, from 4,000 / h to 7, 500 / h, from 4, 500 / h to 7,000 / h, from 5,000 / h to 6, 500 / h, or from 5, 500 / h to 6,000 / h. In some embodiments the GHSV within the reaction zone is from 1,800 / h to 3,600 / h, such as from 2,000 / h to 3,600 / h, from 2,200 / h to 3,600 / h, from 2,400 / h to 3,600 / h, from 2,600 / h to 3,600 / h, from 2,800 / h to 3,600 / h, from 3,000 / h to 3,600 / h, from 3,200 / h to 3,600 / h, or from 3,400 / h to 3,600 / h. In some embodiments, the GHSV within the reaction zone is from 1,800 / h to 3,400 / h, such as from 1,800 / h to 3,200 / h, from 1,800 / h to 3,000 / h, from 1,800 / h to 2,800 / h, from 1,800 / h to 2,600 / h, from 1,800 / h to 2,400 / h, from 1,800 / h to 2,200 / h, or from 1,800 / h to 2,000 / h. In some embodiments, the GHSV within the reaction is from 2,000 / h to 3,400 / h, such as from 2,200 / h to 3,200 / h, from 2,400 / h to 3,000 / h, or from 2,600 / h to 2,800 / h.

[0050] In embodiments, using formed hybrid catalysts disclosed and described herein along with the process conditions disclosed and described herein, the carbon conversion may be improved. Within the process ranges disclosed, the conversion of the feed containing carbon oxides and hydrogen can be carried out in a series of rectors with an intermediate knock-out of water by-product by the means of e.g., phase separation, membrane separation, or some type of water-selective absorptive or adsorptive process. Further directing the partially converted and water-free effluent to the subsequent reactor in series and repeating this manner of technological operations will have an overall effect of enhancing the C2 to C5 hydrocarbon yield.

[0051] For the present embodiments, the selectivity of the formed hybrid catalyst can be tailored to favor the relative production of C2-C5 paraffin to C2-C5 olefin or the relative production of C2-C5 olefin to C2-C5 paraffin. For the embodiments, one approach to tailoring this selectivity is through the exclusion or the inclusion of nickel oxide in the metal oxide catalyst component of the formed hybrid catalyst. When the nickel oxide is present in the metal oxide catalyst component of the formed hybrid catalyst the process for preparing C2 to C5hydrocarbons has an increased selectivity for C2-C5 paraffin over C2-C5 olefin (e.g., a C2-C5 paraffin selectivity / C2-C5 olefin selectivity ratio of greater than or equal to 1.9). Similarly surprising is when nickel oxide is excluded from the metal oxide catalyst component (e.g., only gallium oxide used) of the formed hybrid catalyst the process for preparing C2 to C5 hydrocarbons has an increased selectivity for C2-C5 olefin over C2-C5 paraffin (e.g., a C2-C5 olefin selectivity / C2-C5 paraffin selectivity ratio of greater than or equal to 1.9). So, in embodiments where the selectivity for C2-C5 paraffin is desired (e.g., nickel oxide is present in the metal oxide catalyst component of the formed hybrid catalyst), using formed hybrid catalysts disclosed and described herein along with the process conditions disclosed and described herein, the process may have C2-C5 paraffin selecti vity / Cb-C olefin selectivity ratio of greater than or equal to 1.9, from 1.9 to 240, from 1.9 to 80, from 1.9 to 71, from 3 to 240, from 3 to 80, from 3 to 71, from 5 to 240, from 5 to 80, from 5 to 71, from 71 to 240, from 71 to 80, from 1.9 to 5, or about 1.9 to 3. In embodiments, using formed hybrid catalysts disclosed and described herein along with the process conditions disclosed and described herein, the C2-C5 hydrocarbons predominantly comprises C2-C5 paraffins.

[0052] In addition to improved selectivity, yield, and conversion at extended times on stream, using formed hybrid catalyst according to embodiments also provides these benefits across a wider range of process conditions (temperature, pressure, flow rate, etc.) in the reaction zone of a reactor. For example, the formed hybrid catalyst according to embodiments disclosed and described herein can allow lower reaction temperatures to be used while still providing high conversion, selectivity, yield, and low oxygenate selectivity over time on stream.EXAMPLES

[0053] The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. For each of the following examples (EX) and comparative examples (CE), the microporous catalyst component was prepared as follows: silicoaluminophosphate-34 (SAPO-34) was synthesized per literature procedures (Lok, B. M.; Messina, C. A.; Patton, R. L.; Gajek, R. T.; Cannan, T. R.; Flanigen, E. M. Crystalline silicoaluminophosphates. U.S. Patent 4,440,871 A, 1984) and was used in uncalcined e.g., templated) form.Inventive Example 1 (EX 1)

[0054] A metal oxide catalyst component comprising gallium, nickel and lanthanum on zirconia was prepared by an incipient wetness impregnation method. An impregnation solution 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) with a concentration of respectively 0.7 mol / L, 0.21 mol / L and 0.21 mol / L in DI water was prepared. 10 g of ZrCL support (manufactured by Daichi Kigenso, product code Z3186, >90% monoclinic phase by XRD, pore volume = 0.59 mL / g measured by DI water) was weighed and placed into a glass vial. After that, 5.7 mL of the Ga, Ni and La impregnation solution was added dropwise to the support while constantly shaking / mixing. After impregnation, the metal oxide catalyst component was dried at 85 °C in a forced convection oven overnight and calcined in a muffle furnace using the following program: from 25 °C to 550 °C at a heating rate of 3 °C / min held at 550 °C for 4 hours. After calcination the metal oxide catalyst component was re-sieved to smaller than 200 mesh size (smaller than 75 pm) to remove larger agglomerated particles.

[0055] The powder was prepared by mixing 10 g of the metal oxide catalyst component described above with 2.28 g of uncalcined SAPO-34 for 10 min using a mortar and pestle. Separately, pseudo-boehmite (A1OOH, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using HCOOH (95wt.% in H2O) at a [HCOOH] / [A1] ratio of 0.035, and a total solid content of 35wt.%. The peptized pseudo-boehmite mixture was added to the dried powders to form a paste, targeting a pseudo-boehmite concentration of 24 wt.% on total solids basis (Catapal D, SAPO-34 and MMO). The paste was subsequently mixed for at least 10 minutes using the mortar and pestle until an extrudable paste was obtained. The paste was transferred to a ceramic dish and dried at 85 °C overnight to form a dried precursor. The dried precursor was heated from 25 °C to 600 °C at a heating rate of 2 °C / min in a static muffle furnace and held at 600 °C for 4 hours to form the formed hybrid catalyst of EX 1. After calcination, EX 1 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm) for testing. Inventive Example 2 (EX 2)

[0056] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, with the following differences. The pseudo-boehmite (A1OOH, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using glacial acetic acid (CH3COOH, >99 wt.%) at a [CH3COOH] / [A1] ratio of 0.035, and a total solid content of 35 wt.%. After calcination, EX 2 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm) for testing.Inventive Example 3 (EX 3)

[0057] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. The formulation was also prepared as described above forEX 1 , with the following differences. After calcination, EX 3 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm), and it was reduced at 600 °C for 1 h in 5%H2 / Ar mixture at atmospheric pressure, followed by passivation at 30 - 45 °C in 1%02 / He mixture for 30 min. The passivated catalyst was loaded in the reactor and re-reduced at 300 °C for 6 h in hydrogen at atmospheric pressure prior testing.Inventive Example 4 (EX 4)

[0058] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 2. The formulation was also prepared as described above for EX 2, with the following differences. After calcination, EX 4 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm), and it was reduced at 600 °C for 1 h in 5%H2 / Ar mixture at atmospheric pressure, followed by passivation at 30 - 45 °C in 1%02 / He mixture for 30 min. The passivated catalyst was loaded in the reactor and re-reduced at 300 °C for 6 h in hydrogen at atmospheric pressure prior testing.Inventive Example 5 (EX 5)

[0059] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, with the following differences. The pseudo-boehmite (A100H, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using oxalic acid (C2H2O4, >99 wt.%) at a [C2H2O4] / [A1] ratio of 0.035, and a total solid content of 35 wt.%. After calcination, EX 5 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm) for testing.Inventive Example 6 (EX 6)

[0060] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. The powder was also prepared as described above for EX 1, with the following differences. The pseudo-boehmite (A100H, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using propionic acid (CH3CH2COOH) at a [CH3CH2COOH] / [A1] ratio of 0.035, and a total solid content of 35 wt.%. After calcination, EX 6 was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm) for testing.Comparative Example A (CE A)

[0061] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. A hybrid catalyst was prepared as described above for EX 1, with the following differences. The pseudo-boehmite (A100H, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using HNO3 (65 wt.% in H2O) at a[HNO3] / [A1] ratio of 0.035, and a total solid content of 35 wt.%. After calcination, CE A was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm) for testing.Comparative Example B (CE B)

[0062] A metal oxide catalyst component comprising gallium supported on zirconia was prepared as described above for EX 1. A hybrid catalyst was prepared as described above for EX 1, with the following differences. The pseudo-boehmite (A100H, 79% AI2O3, manufactured by Sasol Limited, tradename Catapal D) was peptized in water using HNO3 (65 wt.% in H2O) at a [HNO3] / [A1] ratio of 0.035, and a total solid content of 35 wt.%. After calcination, CE B was crushed and sieved to 40 mesh (400 pm) to 80 mesh (177 pm), and it was reduced at 600 °C for 1 h in 5%H2 / Ar mixture at atmospheric pressure, followed by passivation at 30 - 45 °C in 1% O2 / He mixture for 30 min. The passivated catalyst was loaded in the reactor and re-reduced at 300 °C for 6 h in hydrogen at atmospheric pressure prior testing.Catalytic Performance Data

[0063] Testing of the hybrid catalysts was performed in a Hastelloy C276 fixed bed reactor system (7.7mm internal diameter) under the following conditions: 420 °C, H2 / CO = 3 or H2 / CO = 6, p=40 barg, GHSV = 3600 hr1.

[0064] Prior to contact with syngas, the catalyst was heated under nitrogen (N2) to reaction temperature and pressure noted above. The reactor effluent composition was obtained by gas chromatography and the conversion and carbon based selectivities were calculated using the following equations:Xco (%) = [(T|co, in - T]co, out) / i]co. in] • 100; and (1)Sj (%) = [aj • T|j. out / (T|CO. in - T|co. out)] • 100, (2)

[0065] where Xco is defined as the CO conversion (%), r|co, in is defined as the molar inlet flow of CO (pmol / s), r|co, out is the molar outlet flow of CO (pmol / s), Sj is defined as the carbon based selectivity to product] (%), aj the number of carbon atoms for product], ip,out is the molar outlet flow of product j (pmol / s). All data was collected under steady state conditions, after at least 40 hours time on stream (TOS).

[0066] The results of the catalytic testing are shown in Table 1 below. The reported conversion values are the averaged conversion levels between 100 and 150 h TOS for H2:CO = 3 and between 175 and 225h TOS for H2:CO = 6.Table 1

[0067] 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 show substantially lower C2-C4 olefin selectivity at comparable overall CO conversion and hydrocarbon productivity levels as compared to the bifunctional catalyst formulations of CE A formulated with nitric acid. Without being bound to any particular theory, it is believed that the positive impact of utilizing an organic carboxylic acid as peptization agent, as discussed herein, is related to lower mobility of metal oxide components during the formulation of the hybrid catalyst, including the formed hybrid catalyst, exemplified by the lower solubility of organic nickel-salts compared to nickel nitrate as shown in Table 2.Table 2

[0068] It is noted that one or more of the following claims utilize the term “where” or “in which” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” For the purposes of defining the present technology, the transitional phrase “consisting of’ may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recitedcomponents or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of’ may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of’ and “consisting essentially of’ may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of’ and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of’ components A, B, and C as well as a composition “consisting essentially of’ components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of’ and “consisting essentially of.”

[0069] As used in the Specification and appended Claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced.

[0070] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter of the present 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 essential to the particular embodiment or to any other embodiment. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter.

Claims

CLAIMSWhat is claimed is:

1. A process for preparing C2 to Cs hydrocarbons comprising: introducing a feed stream comprising hydrogen gas 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 hybrid catalyst, the formed hybrid catalyst comprising: a metal oxide catalyst component comprising gallium oxide and zirconia; a microporous catalyst component that is a molecular sieve having 8-MR (Membered Ring) pore openings; and a binder comprising alumina, wherein the alumina binder is prepared as a colloidal solution, suspension, or gel by peptization of a binder precursor comprising oxides or hydroxides of aluminum with an organic carboxylic acid solution.

2. A process for preparing a formed hybrid catalyst, the process comprising: mixing a metal oxide catalyst component and a microporous catalyst component, wherein: the metal oxide catalyst component comprises gallium oxide and zirconia; and the microporous catalyst component comprises a molecular sieve having 8-MR(Member Ring) pore openings; adding a binder 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 peptization of a binder precursor comprising oxides or hydroxides of aluminum, with an organic carboxylic acid solution; and extruding the paste to produce the formed hybrid catalyst.

3. The process of claim 2, wherein the paste is calcined after extruding.

4. The process of any of claims 1 to 3, wherein the metal oxide catalyst component further comprises a nickel oxide and a rare earth oxide.

5. The process of any one of claims 1 to 4, wherein the zirconia has a macroporosity fraction that is less than 0.3.

6. The process of any one of claims 1 to 5, wherein the metal oxide catalyst component comprises from 40 weight percent (wt.%) to 85 wt.% of the formed hybrid catalyst based on the total weight of the formed hybrid catalyst.

7. The process of any one of claims 1 to 6, wherein the microporous catalyst component comprises silicoaluminophosphate-34 (SAPO-34).

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

9. The process of any one of claims 1 to 8, wherein the binder includes a metal selected from aluminum and zirconium, and wherein the binding solution has a [organic carboxylic acid] / [aluminum] concentration ratio of 0.005 to 0.1.

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

11. The process of any one of claims 1 to 10, wherein the formed hybrid catalyst has a particle size of from 0.5 mm to 6 mm.

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

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

14. The process of claim 13, wherein a temperature within the reaction zone during the converting is from 350 °C (Celsius) to 480 °C.

15. The process of any one of claims 1 to 14, wherein the C2-C5 hydrocarbons predominantly comprises C2-C5 paraffins.

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