Cobalt-molybdenum-manganese catalysts for fischer-tropsch synthesis processes

Abstract

The present disclosure related generally to a supported Fischer-Tropsch catalysts and Fischer-Tropsch processes for preparing non-oxygenated and oxygenated hydrocarbons using the same. The catalyst materials described herein include a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount from 0.5 to 10 wt%, based on the total weight of the catalyst material; and optionally, manganese, present in an amount from 0.1 to 10 wt%; based on the total weight of the catalyst material.

Description

COBALT-MOLYBDENUM-MANGANESE CATALYSTS FOR FISCHER-TROPSCHSYNTHESIS PROCESSES1 Field

[0001] The present disclosure relates generally to Fischer-Tropsch catalyst materials, processes for making the same, and Fischer-Tropsch synthesis processes using the Fischer-Tropsch catalyst materials described herein.2. Technical Background

[0002] The conversion of synthesis gas (i.e. , a mixture of carbon monoxide and hydrogen, also known as syngas) into non-oxygenated and oxygenated hydrocarbons by Fischer-Tropsch synthesis has been known for decades. The growing importance of alternative energy sources has resulted in renewed interest in Fischer-Tropsch (FT) synthesis as it allows a direct route to high-quality fuels and feedstock chemicals.

[0003] Fischer-Tropsch synthesis processes are known for producing hydrocarbons, both non-oxygenated (e.g., alkanes and alkenes) and oxygenated (e.g., alcohols and aldehydes), that can be useful in fuels and can also serve as valuable feedstock chemicals. The hydrocarbon fuel derived from Fischer-Tropsch synthesis processes is typically better able to meet increasingly stringent environmental regulations compared to conventional refinery-produced fuels, as Fischer-Tropsch-derived fuels typically have lower contents of sulfur, nitrogen, and aromatic compounds, which contribute to the emission of potent pollutants such as SO2, NOX, and particulates. Products derived from Fischer-Tropsch synthesis processes often burn more completely compared to the petroleum-derived equivalent, thereby potentially reducing some aspects of the environmental impact of such a fuel. Olefins, alcohols, and other oxygenates obtained may also be used as reagents in other processes, such as in the synthesis of lubricants. In particular, Cs+ oxygenates (e.g., alcohols) are of interest for use as base-oil reactants, lubricants, chemical intermediates, or in the larger molecular manufacture of surfactants, detergents, fragrances and cosmetics.

[0004] Typical Fischer-Tropsch synthesis processes aim to minimize methane production and optimize for longer hydrocarbon chains by using catalysts with extended life “windows” of operation. The catalyst life “window” is defined as the temperature over which a catalyst can run before a process is shut-down due to a plant ceiling temperature. Over the life of a catalyst, the temperature used to conduct the Fischer-Tropsch synthesis process may increase to maintain a desired conversion. While increasing the operating temperature can maintain the performance of such catalysts, it can also increase selectivity for less desirable side products, such as methane. As such, having catalysts with high activity at lower temperatures for a given conversion can extend the catalyst life “window” of operationand reduce methane production. Currently, cobalt-based catalysts are the primary type of catalysts used in Fischer-Tropsch synthesis processes; they generally yield linear paraffins as primary products. However, they typically suffer from increased methane production at high operating temperature. Additionally, there is a growing need for increased oxygenate production with Fischer-Tropsch synthesis processes. As such, there is a need to provide improved cobalt-based Fischer-Tropsch catalysts for C5+ non-oxygenated and oxygenated hydrocarbon selectivity with less methane production.SUMMARY

[0005] In one aspect, the present disclosure provides a catalyst material for Fischer- Tropsch synthesis processes. The Fischer-Tropsch catalyst material includes: a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount of 0.5 to 10 wt%, based on the total weight of the catalyst material; and optionally manganese, present in an amount of 0.1 to 10 wt%, based on the total weight of the catalyst material.

[0006] In another aspect, the present disclosure provides a process for performing a Fischer-Tropsch synthesis process, the process comprising contacting a catalyst material as described herein with a feed stream comprising H2 and CO under conditions sufficient to provide a product stream comprising C5+ non-oxygenated and oxygenated hydrocarbons.BRIEF DESCRIPTION OF FIGURES

[0007] The accompanying drawings are included to provide a further understanding of the processes of the disclosure, and are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, and sizes of various elements may be distorted for clarity. The drawings illustrate one or more embodiment(s) of the disclosure and together with the description serve to explain the principles and operation of the disclosure.

[0008] FIG. 1 is a schematic of a process for performing a Fischer-Tropsch synthesis process as described herein.

[0009] FIG. 2 is a schematic of a process for performing a Fischer-Tropsch synthesis process as described herein.

[0010] FIG. 3 is a schematic of a process for performing a Fischer-Tropsch synthesis process as described herein.

[0011] FIG. 4 is a schematic of a process for performing a Fischer-Tropsch synthesis process as described herein.DETAILED DESCRIPTION

[0012] The present disclosure is concerned with cobalt-based catalyst materials and processes for their use in converting CO and H2 to non-oxygenated and oxygenated hydrocarbons via the Fischer-Tropsch synthesis process.

[0013] The present inventors have noted that the overall conversion of CO to nonoxygenated and oxygenated hydrocarbons in Fischer-Tropsch synthesis processes can be limited by the formation of side products such as methane and other C2-C4 hydrocarbon products. While methane can be converted to CO and / or CO2 (e.g., via a steam methane reforming reaction or a partial-oxidation reaction) and recycled as part of the feed to the Fischer-Tropsch synthesis. However, conversion of methane as typically requires the installation of additional equipment, which may be undesirable for a given Fischer-Tropsch synthesis plant. Additionally, the formation of methane can limit the hydrogen efficiency of the Fischer-Tropsch synthesis, which is also undesirable, particularly when using hydrogen produced from electrolysis (e.g., so-called “green” hydrogen). While C2-C4 products can be useful in their own right, they are not applicable for liquid fuels (e.g., diesel, jet, etc.) and thus are typically a lower-value product. These side products can provide for an overall limit on the conversion of feedstock carbon to C5+ hydrocarbons, which are the generally-desired Fischer-Tropsch synthesis products.

[0014] The present inventors have found that molybdenum acts as a promoter in cobaltbased Fischer-Tropsch catalysts, lowering the methane selectivity and increasing the C5+ non-oxygenated hydrocarbon selectivity of the catalyst, particularly increasing the long chain non-oxygenated hydrocarbon (e.g., Cs-Ci6 non-oxygenated hydrocarbon) selectivity. As used herein, a “promoter” is a component that improves the performance of the Fischer- Tropsch catalyst in some advantageous way, such as increasing the catalytic activity, increasing the CO selectivity, or extending the catalyst lifetime, without reference to any particular mechanism for such effect. Accordingly, in various embodiments, the disclosure provides Co / Mo Fischer-Tropsch catalyst materials that exhibit improved selectivity for long- chain non-oxygenated hydrocarbons, processes of making the same, and Fischer-Tropsch synthesis processes using the same.

[0015] Additionally, the present inventors found that the inclusion of a molybdenum promoter in a Co / Mn catalyst can provide improved long-chain non-oxygenated hydrocarbon selectivity and lower methane selectivity while maintaining the high oxygenated hydrocarbon selectivity provided by a Co / Mn Fischer-Tropsch catalyst. This combination of improvedlong-chain non-oxygenated hydrocarbon selectivity and lower methane selectivity is not observed in Co / Mn or Co / Mo catalyst materials. Accordingly, without being bound by theory, the present inventors hypothesize that the combination of Co, Mn, and Mo provide a synergy to improve long-chain non-oxygenated selectivity, maintain oxygenated hydrocarbon selectivity, and lower methane selectivity that would not have been expected based on the performance of catalysts that included these metals individually.

[0016] Accordingly, the present disclosure provides cobalt-based Fischer-Tropsch catalysts with low methane selectivity and high catalyst activity for both C5+ non-oxygenated and oxygenated hydrocarbons, processes of making the same, and Fischer-Tropsch synthesis processes using the same with increased selectivity for oxygenated hydrocarbons.

[0017] Fischer-Tropsch Catalyst Materials

[0018] In one aspect, the present disclosure provides a supported Fischer-Tropsch catalyst material comprising: a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount of 0.5 to 10 wt%, based on the total weight of the catalyst material; and optionally manganese, present in an amount from 0.1 to 10 wt%, based on the total weight of the catalyst material.

[0019] As described above, the Fischer-Tropsch catalyst materials of the present disclosure are supported catalyst materials. In various embodiments as described herein, the support material makes up at least 70 wt%, e.g., at least 75 wt%, or at least 80 wt% at least 85 wt%, or at least 90 wt% of the catalyst material, based on the total weight of the catalyst material.

[0020] In various embodiments as described herein, the support material is a titanium oxide support material. As used herein, a “titanium oxide” support material is a support material that presents at least a surface layer (e.g., at least 50 microns in thickness) that is at least 50 wt% titanium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the titanium oxide support material includes at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide. In some such embodiments, at least a surface layer of the titanium oxide support material includes at least 90 wt% titanium oxide. For example, in some embodiments, at least a surface layer of the titanium oxide support material includes at least 95 wt% titanium oxide or at least 98 wt% titanium oxide. In various examples, the titanium oxide support material contains titanium oxide substantially throughout, e.g., at least 50 wt% of the titanium oxide support material is titanium oxide on an oxide basis. For example, in various embodiments, the titanium oxide support material includes at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide. For example,in various embodiments, the titanium oxide support material includes at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide. In some embodiments, the titanium oxide support may further include additional metals or metal oxides.

[0021] In various embodiments as described herein, the support material is a cerium oxide support material. As used herein, a “cerium oxide” support material is a support material that presents at least a surface layer (e.g., at least 50 microns in thickness) that is at least 50 wt% cerium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the cerium oxide support material includes at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide. In some such embodiments, at least a surface layer of the cerium oxide support material includes at least 90 wt% cerium oxide. For example, in some embodiments, at least a surface layer of the cerium oxide support material includes at least 95 wt% cerium oxide or at least 98 wt% cerium oxide. In various examples, the cerium oxide support material contains cerium oxide substantially throughout, e.g., at least 50 wt% of the cerium oxide support material is cerium oxide on an oxide basis. For example, in various embodiments, the cerium oxide support material includes at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide. For example, in various embodiments, the cerium oxide support material includes at least 90 wt% cerium oxide, e.g., at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide. In some embodiments, the cerium oxide support may further include additional metals or metal oxides.

[0022] In various embodiments as described herein, the support material is an aluminum oxide support material. As used herein, an “aluminum oxide” support material is a support material that presents at least a surface layer (e.g., at least 50 microns in thickness) that is at least 50 wt% aluminum oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the aluminum oxide support material includes at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide. In some such embodiments, at least a surface layer of the aluminum oxide support material includes at least 90 wt% aluminum oxide. For example, in some embodiments, at least a surface layer of the aluminum oxide support material includes at least 95 wt% aluminum oxide or at least 98 wt% aluminum oxide. In various examples, the aluminum oxide support material contains aluminum oxide substantially throughout, e.g., at least 50 wt% of the aluminum oxide support material is aluminum oxide on an oxide basis. For example, in various embodiments, the aluminum oxide support material includes at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide. For example, in various embodiments, the aluminum oxide support material includesat least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide. In some embodiments, the aluminum oxide support may further include additional metals or metal oxides.

[0023] In various embodiments as described herein, the support material is a zirconium oxide support material. As used herein, a “zirconium oxide” support material is a support material that presents at least a surface layer (e.g., at least 50 microns in thickness) that is at least 50 wt% zirconium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the zirconium oxide support material includes at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide. In some such embodiments, at least a surface layer of the zirconium oxide support material includes at least 90 wt% zirconium oxide. For example, in some embodiments, at least a surface layer of the zirconium oxide support material includes at least 95 wt% zirconium oxide or at least 98 wt% zirconium oxide. In various examples, the zirconium oxide support material contains zirconium oxide substantially throughout, e.g., at least 50 wt% of the zirconium oxide support material is zirconium oxide on an oxide basis. For example, in various embodiments, the zirconium oxide support material includes at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide. For example, in various embodiments, the zirconium oxide support material includes at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide. In some embodiments, the zirconium oxide support may further include additional metals or metal oxides.

[0024] In various embodiments as described herein, the support material is a zinc oxide support material. As used herein, a “zinc oxide” support material is a support material that presents at least a surface layer (e.g., at least 50 microns in thickness) that is at least 50 wt% zinc oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the zinc oxide support material includes at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide. In some such embodiments, at least a surface layer of the zinc oxide support material includes at least 90 wt% zinc oxide. For example, in some embodiments, at least a surface layer of the zinc oxide support material includes at least 95 wt% zinc oxide or at least 98 wt% zinc oxide. In various examples, the zinc oxide support material contains zinc oxide substantially throughout, e.g., at least 50 wt% of the zinc oxide support material is zinc oxide on an oxide basis. For example, in various embodiments, the zinc oxide support material includes at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide. For example, in various embodiments, the zinc oxide support material includes at least 90 wt%zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide. In some embodiments, the zinc oxide support may further include additional metals or metal oxides.

[0025] In various embodiments as described herein, the support material is a mixed oxide support material. These can be provided, for example, by admixture of multiple of the oxides above and formation into a support material that includes those oxides. For example, in some embodiments, the mixed oxide support material is a mixture of two or more metal oxides, such as titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In some embodiments, at least a surface layer of the support material includes at least 50 wt% total of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In some embodiments, at least a surface layer of the mixed oxide support material includes at least 60 wt% total, e.g., at least 70 wt% total, or at least 80 wt% total of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In some embodiments, at least a surface layer of the mixed oxide support material includes at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In various examples, the mixed oxide support material contains the oxides substantially throughout, e.g., at least 50 wt% total of the mixed oxide support is two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In various embodiments, the mixed oxide support material includes at least 60 wt% total, e.g., at least 70 wt% total, or at least 80 wt% total of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In various embodiments, the mixed oxide support material includes at least 90 wt% total, e.g., at least 95 wt% total, or at least 98 wt% total of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In some embodiments, the mixed oxide support material may further include additional metals or metal oxides.

[0026] The present inventors have found that titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide can provide good performance in the absence of substantial amounts of other metals in the support material. For example, in various embodiments of the disclosure as described herein, the support material does not include additional metals in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt%, or in excess of 0.5 wt%, on an oxide basis.

[0027] However, the inventors have noted that in many cases performance can be desirably affected by the inclusion of other metals in the support material. Accordingly, in other embodiments as described herein, the support material includes at least one additional metal. In various embodiments, the total amount of the at least one additional metal in the support material is in the range of 0.5-20 wt%, e.g., 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%,or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.

[0028] Support materials suitable for use herein can be provided with a range of pore volumes. The person of ordinary skill in the art will select a pore volume appropriate for a desired catalytic process. For example, in various embodiments as described herein, the pore volume is at least 0.15 mL / g, e.g., at least 0.30 mL / g. In various embodiments as described herein, the support material, prior to impregnation, has an average pore diameter in the range of 10 to 500 Angstroms, e.g., in the range of 15 to 100 Angstroms, or in the range of 20 to 80 Angstroms, or in the range of 25 to 60 Angstroms. The BET surface area is suitably from 2 to 1000 m2 / g, e.g., in the range from 10 to 600 m2 / g, or in the range from 15 to 300 m2 / g, or in the range from 30 to 150 m2 / g. For example, in some embodiments, wherein the support material is a titanium oxide support, the titanium oxide support may be a low surface area (LSA) support (e.g., having a BET surface area in the range of 30 to 60 m2 / g or 45 to 55 m2 / g). In other embodiments, wherein the support material is a titanium oxide support, the titanium oxide support may be a high surface area (HSA) support (e.g., having a BET surface area in the range of 80 to 100 m2 / g or 90 to 100 m2 / g). In some embodiments, wherein the support material is a zirconium oxide support, the support material has a BET surface area in the range of 30 to 60 m2 / g or 45 to 55 m2 / g. In other embodiments, wherein the support material is a zirconium oxide support, the support material has a BET surface area in the range of 80 to 100 m2 / g or 90 to 100 m2 / g. In some embodiments, wherein the support material is an aluminum oxide support, the support material has a BET surface area in the range of 200 to 700 m2 / g, e.g., in the range of 200 to 600 m2 / g or 200 to 500 m2 / g. In other embodiments, wherein the support material is a cerium oxide, the support material has a BET surface area in the range of 5 to 50 m2 / g, e.g., in the range of 5 to 40 m2 / g or 5 to 30 m2 / g. In other embodiments, wherein the support material is a zinc oxide, the support material has a BET surface area in the range of 5 to 50 m2 / g, e.g., in the range of 5 to 40 m2 / g or 5 to 30 m2 / g. The BET surface area, pore volume, pore size distribution and average pore radius may be determined from the nitrogen adsorption isotherm determined at 77K using a Micromeritics TRISTAR 3000 static volumetric adsorption analyzer. A procedure which may be used is an application of British Standard methods BS4359: Part 1 : 1984 'Recommendations for gas adsorption (BET) methods' and BS7591 : Part 2: 1992, 'Porosity and pore size distribution of materials' - Method of evaluation by gas adsorption. The resulting data may be reduced using the BET method (over the pressure range 0.05-0.20 P / Po) and the Barrett, Joyner & Halenda (BJH) method (for pore diameters of 20-1000 Angstroms) to yield the surface area and pore size distribution respectively.

[0029] Suitable references for the above data reduction methods are Brunauer, S, Emmett, P H, & Teller, E, J. Am. Chem. Soc. 60, 309, (1938) and Barrett, E P, Joyner, LG & Halenda P, J. Am. Chem. Soc., 73, 373, (1951).

[0030] As described above, the supported Fischer-Tropsch catalyst materials of the disclosure include cobalt. For the purposes of this disclosure, the amount of cobalt present is calculated as a weight percentage of cobalt atoms in the catalyst material based on the total weight of the catalyst, regardless of the form in which the cobalt may be present. The cobalt may be present in the catalyst in a variety of forms; most commonly, cobalt is principally present as metal oxide, metal, or a combination thereof (e.g., substantially metal oxide before catalyst activation by reduction, and substantially metallic after). In various embodiments of the present disclosure as described herein, cobalt is present in the catalyst material in an amount in the range of 5 to 25 wt%, based on the total weight of the catalyst material. For example, in various embodiments, cobalt is present in the range of 5 to 20 wt%, e.g., in the range of 5 to 18 wt%, or 5 to 15 wt%, or 5 to 12 wt%, or 5 to 10 wt%, based on the total weight of the catalyst material. In various embodiments of the present disclosure as described herein, cobalt is present in the catalyst material in an amount in the range of 6 to 25 wt%, e.g., in the range of 6 to 22 wt%, or 6 to 20 wt%, or 6 to 18 wt%, or 6 to 15 wt%, or 6 to 12 wt%, or 6 to 10 wt%, based on the total weight of the catalyst material. In some embodiments, cobalt is present in the catalyst material in an amount in the range of 8 to 25 wt%, e.g., in the range of 8 to 22 wt%, or 8 to 20 wt%, or 8 to 18 wt%, or 8 to 15 wt% or 8 to 12 wt%, or 8 to 10 wt%, based on the total weight of the catalyst material.

[0031] As described above, the supported Fischer-Tropsch catalyst materials of the disclosure also include molybdenum. The present inventors note that the inclusion of molybdenum as a promoter can advantageously improve the long-chain non-oxygenated hydrocarbon (e.g., Cs-Ci6 non-oxygenated hydrocarbon) selectivity and lower the methane selectivity exhibited by the Fischer-Tropsch catalyst. The lower methane selectivity from the inclusion of molybdenum is particularly advantageous during the end-of-life operation of cobalt-based Fischer-Tropsch catalysts, as it can extend the life “window” of the catalyst.

[0032] The molybdenum may be present in the catalyst in a variety of forms at a variety of stages in a Fischer-Tropsch synthesis process; most commonly, molybdenum is principally present as metal oxide, metal, or a combination thereof (e.g., substantially metal oxide before catalyst activation by reduction, and substantially metallic after).

[0033] In various embodiments of the present disclosure as described herein, molybdenum is present in the catalyst material in an amount in the range of 0.5 to 10 wt%, based on the total weight of the catalyst material. For example, in various embodiments,molybdenum is present in the range of 0.5 to 8 wt%, e.g., in the range of 0.5 to 6 wt%, based on the total weight of the catalyst material. In some embodiments, molybdenum is present in the catalyst material in an amount in the range of 0.8 to 10 wt%, e.g., in the range of 0.8 to 8 wt%, or 0.8 to 6 wt%. In various embodiments of the present disclosure as described herein, molybdenum is present in the catalyst material in an amount in the range of 1 to 10 wt%, e.g., in the range of 1 to 8 wt%, or 1 to 6 wt%. In various embodiments, molybdenum is present in the catalyst material in an amount in the range of 1.5 to 10 wt%, e.g. in the range of 1.5 to 8 wt%, or 1.5 to 6 wt%.

[0034] The present inventors have determined that suitable Fischer-Tropsch catalysts can be formed from one or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide as a support material, with cobalt and molybdenum included in / on the catalyst. The person of ordinary skill in the art would appreciate that the amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, and molybdenum can be quantified on a metallic basis, regardless of the form in which these metals may be present. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of metals in the catalyst material (i.e. , on a metallic basis), i.e. , without inclusion of oxygen or non-metallic counterions in the calculation. Accordingly, in various embodiments of the present disclosure as described herein, the total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, on a metallic basis. In various embodiments, the total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, and molybdenum in the catalyst material is at least 98 wt%, e.g., at least 99 wt%, on a metallic basis. For example, in some particular embodiments, the total amount of titanium, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of cerium, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of aluminum, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of zirconium, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of zinc, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis.

[0035] In various embodiments of the present disclosure as described herein, manganese is not present in a significant amount in the catalyst material. For example, in some embodiments, a manganese content of the catalyst material is less than 0.1 wt%, e.g.,less than 0.05 wt%, or less than 0.01 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst material does not include manganese.

[0036] However, as described above, the supported Fischer-Tropsch catalyst materials of the disclosure may also include manganese. The inclusion of manganese has been found to increase oxygenated hydrocarbon selectivity. The manganese may be present in the catalyst in a variety of forms; most commonly, manganese is principally present as metal oxide, metal, or a combination thereof (e.g., substantially metal oxide before catalyst activation by reduction, and a combination of metallic and oxidic manganese after). In various embodiments of the present disclosure as described herein, manganese is present in the catalyst material in an amount in the range of 0.1 to 10 wt%, based on the total weight of the catalyst material. For example, in various embodiments, manganese is present in the range of 0.1 to 8 wt%, or 0.1 to 6 wt%, based on the total weight of the catalyst material. In various embodiments of the present disclosure as described herein, manganese is present in the catalyst material in an amount in the range of 0.5 to 10 wt%, e.g., in the range of 0.5 to 8 wt%, or 0.5 to 6 wt%, based on the total weight of the catalyst material In some embodiments, manganese is present in the catalyst material in an amount in the range of 1 to 10 wt%, e.g., in the range of 1 to 8 wt%, or 1 to 6 wt%, based on the total weight of the catalyst material. In some embodiments, manganese is present in the catalyst material in an amount in the range of 2 to 10 wt%, e.g., in the range of 2 to 8 wt%, or 2 to 6 wt%, based on the total weight of the catalyst material. In some embodiments, manganese is present in the catalyst material in an amount in the range of 3 to 10 wt%, e.g., in the range of 3 to 8 wt%, or 3 to 6 wt%, based on the total weight of the catalyst material. In some embodiments, manganese is present in the catalyst material in an amount in the range of 4 to 10 wt%, e.g., in the range of 4 to 8 wt%, or 4 to 6 wt%, based on the total weight of the catalyst material.

[0037] When both manganese and molybdenum are present in the catalyst material, the manganese and molybdenum can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of manganese to molybdenum present in the catalyst material is at least 0.1 :1 (i.e. , calculated using weights of the metals themselves). For example, in various embodiments, the weight ratio of manganese to molybdenum is at least 0.5:1 , or at least 1 :1. In various embodiments of the present disclosure as described herein, the weight ratio of manganese to molybdenum present in the catalyst material is at most 20:1. For example, in various embodiments, the weight ratio of manganese to molybdenum is at most 15: 1 , or at most 10: 1. In various embodiments, the weight ratio of manganese to molybdenum present in the catalyst material is in the range of 0.1 : 1 to 20: 1. For example, the weight ratio of manganese to molybdenum is in the range of 0.5:1 to 20:1 , or 1:1 to 20:1, or 0.1 :1 to 15:1, or 0.5:1 to 15:1 , or 1:1 to 15:1,or 0.1 :1 to 10:1 , or 0.5:1 to 10:1, or 1:1 to 10:1. In particular, the present inventors have found that when there is too much molybdenum present in the catalyst material, the oxygenated hydrocarbon selectivity provided by the manganese is no longer observed. In other words, to maintain the oxygenated hydrocarbon selectivity of the catalyst material, the amount of manganese present in the catalyst material is greater than the amount of molybdenum present in the catalyst. For example, the weight ratio of manganese to molybdenum is in the range of 1 : 1 to 20: 1 , or 1 : 1 to 15:1 , or 1 : 1 to 10:1.

[0038] In various embodiments as described herein, the cobalt and molybdenum as present in the catalyst material in a weight ratio of at least 0.5:1. For example, in various embodiments, the cobalt and molybdenum are present in a weight ratio of at least 1:1, at least 2:1, or at least 5:1. In various embodiments as described herein, the cobalt and molybdenum are present in the catalyst material in a weight ratio in the range of 0.5:1 to 25:1, e.g., in the range of 0.5:1 to 20:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 1:1 to 25:1, or 1:1 to 20:1, or 1 :1 to 15:1, or 1 :1 to 10:1.

[0039] The present inventors have determined that suitable Fischer-Tropsch catalysts can be formed from one or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide as a support material, with cobalt in combination with manganese and molybdenum included in / on the catalyst. The person of ordinary skill in the art would appreciate that the amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese, and molybdenum can be quantified on a metallic basis, regardless of the form in which these metals may be present. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of metals in the catalyst material (i.e., on a metallic basis), i.e., without inclusion of oxygen or non-metallic counterions in the calculation. Accordingly, in various embodiments of the present disclosure as described herein, the total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, on a metallic basis. In various embodiments, the total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese and molybdenum in the catalyst material is at least 98 wt%, e.g., at least 99 wt%, on a metallic basis. For example, in some particular embodiments, the total amount of titanium, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of cerium, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of aluminum, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallicbasis. In other embodiments, the total amount of zirconium, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis. In other embodiments, the total amount of zinc, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%, or at least 99 wt%, on a metallic basis.

[0040] As described above, the catalyst materials of the present disclosure include a substantial amount of a plurality of titanium, cerium, aluminum, zirconium, cobalt, molybdenum, and optionally manganese (e.g., at least 90% on a metallic basis). As such, in some embodiments of the present disclosure, other metals are not present in a significant amount in the catalyst material. For example, in some embodiments, the catalyst material does not include a substantial amount of copper, nickel, or iron. In some embodiments as described herein, a copper content of the catalyst material is less than 0.1 wt% copper, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst. In some embodiments as described herein, a nickel content of the catalyst material is less than 0.1 wt% nickel, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst. In some embodiments as described herein, an iron content of the catalyst material is less than 0.1 wt% iron, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst material does not include copper. In some embodiments as described herein, the catalyst material does not include nickel. In some embodiments as described herein, the catalyst material does not include iron.

[0041] In some embodiments of the present disclosure, the catalyst material does not include a substantial amount of a lanthanide metal or oxide. In various embodiments as described herein, a lanthanide metal or metal oxide content of the catalyst material is less than 0.1 wt% lanthanide metal or metal oxide, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst material does not include a substantial amount of lanthanum. For example, in various embodiments, a lanthanum content of the catalyst material is less than 0.1 wt% lanthanide metal or metal oxide, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.

[0042] As described above, the supported catalyst material includes cobalt, molybdenum, and optionally manganese. Depending on the method of synthesis, these species, which will typically be principally present in metallic form and / or oxide form, can be disposed at a variety of different places on the support material. For example, they can be in the pores of the support material and on the outer surface of the support material. They may be found substantially throughout the support, e.g., as when a large volume of impregnationliquid is used, or only in a surface layer of the support, e.g., when the impregnation liquid does not permeate into the entirety of the support, such as when using an incipient wetness technique.

[0043] Without intending to be bound by theory, it is believed that the active form of cobalt in the Fischer-Tropsch catalyst material is typically in a substantially metallic form (i.e. , as cobalt(O)). As described below, cobalt may be present substantially in an oxide form after catalyst preparation and during shipment and storage. As described below, it is typically desirable to activate the catalyst material by contacting it with a reducing gas, e.g., hydrogen gas, to convert a substantial fraction of the cobalt present in an oxide for to a metallic form. The person of ordinary skill in the art will appreciate that there are a variety of techniques for measuring the amount of metallic cobalt in the catalyst material, such as temperature-programmed reduction (“TPR”) or X-ray diffraction (“XRD”). In various embodiments as described herein, the amount of metallic cobalt in the catalyst material is determined by temperature-programmed reduction (“TPR”). In various embodiments as described herein, the Fischer-Tropsch catalyst material is an activated catalyst, wherein at least 50 mol% of the cobalt present in the catalyst material is in the form of cobalt(O), e.g., at least 60 mol%, or at least 70 mol%. The amount of cobalt(0) present in the catalyst material may be determined by TPR, as described herein. The catalyst materials of the disclosure will typically be activated in situ in a reactor system, by treatment with reducing gas such as hydrogen. This can be in a separate process step and / or as part of an induction phase of the Fischer-Tropsch synthesis. However, the person of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of cobalt forms in its catalyst materials, as these can be active or can be conveniently transformed to active forms.

[0044] The molybdenum will typically be provided in oxide form after catalyst preparation and during shipment and storage. The present inventors contemplate that it is possible that some of the molybdenum present in oxide form is converted to a metallic form during the activation of the cobalt species. However, the person of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of molybdenum forms (e.g., in a metallic form, an oxidic form, an alloy form with the cobalt and optionally manganese, or combinations thereof) in its catalysts, as these can provide a promoting effect or can be conveniently transformed into forms that will.

[0045] The manganese, when present, will typically be provided in oxide form after catalyst preparation and during shipment and storage. The present inventors contemplate that it is possible that some of the manganese present in oxide form is converted to a metallic form during the activation of the cobalt species. However, the person of ordinaryskill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of manganese forms (e.g., in a metallic form, an oxidic form, an alloy form with the cobalt and molybdenum, or combinations thereof) in its catalysts, as these can provide a promoting effect or can be conveniently transformed into forms that will.

[0046] The person of ordinary skill in the art will appreciate that the catalyst materials of the disclosure can be provided in many forms, depending especially on the particular form of the reactor system in which they are to be used, e.g., in a fixed bed or as a fluid bed. The supports themselves can be provided as discrete bodies of material, e.g., as porous particles, pellets or shaped extrudates, with cobalt, molybdenum, and optionally manganese provided thereon to provide the catalyst material. However, in other embodiments, a catalyst of the disclosure can itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It can be formed of, e.g., a metal or metal oxide, and can itself be provided in a number of forms, such as particles, pellets, shaped extrudates, or monoliths. Of course, as would be understood by the person of ordinary skill in the art, other embodiments may be possible.

[0047] As discussed above and demonstrated below, the present inventors have determined that the performance of the catalyst materials of the disclosure is improved by the use of manganese and molybdenum. In particular, it has been found that the inclusion of molybdenum can increase the selectivity for forming long-chain non-oxygenated hydrocarbons. As used herein, long-chain non-oxygenated hydrocarbons as used herein refers to linear and branched non-oxygenated hydrocarbons (e.g., alkanes and alkenes) having at least 8 carbon atoms. In various embodiments, the catalyst material exhibits a long-chain non-oxygenated hydrocarbon selectivity of at least 15%, e.g., at least 18%, or at least 20%, when tested in the FT performance test described below. In various embodiments, the catalyst material exhibits a long-chain non-oxygenated hydrocarbon selectivity that is at least 70% greater, e.g., at least 80% greater, or at least 90% greater, than a long-chain non-oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a Cs-Ci6 non-oxygenated hydrocarbon selectivity of at least 15%, e.g., at least 18%, or at least 20%, when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a Cs-Ci6 non-oxygenated hydrocarbon selectivity that is at least 70% greater, e.g., at least 80% greater, or at least 90% greater, than a Cs-Ci6 non-oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below. For example, in some embodiments, thecatalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity of at least 4%, e.g., at least 6%, or at least 8%, or at least 10%, when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity that is at least 100% greater, e.g., at least 110% greater, or at least 120% greater, than a Cn+ non-oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity that is at least 250% greater, e.g., at least 300% greater, or at least 350% greater, than a Cm- non-oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below. In various embodiments, the catalyst material exhibits a C5+ non-oxygenated hydrocarbon selectivity of at least 20%, e.g., at least 30%, or at least 40%, when tested in the FT performance test described below. For example, for a catalyst material of the disclosure having 10 wt% Co, 5 wt% Mn and 1 wt% Mo on a titanium dioxide support, an “otherwise identical” catalyst material lacking molybdenum would have 10 wt% Co and 5 wt% Mn on the titanium dioxide support.

[0048] The present inventors have also found that the methane selectivity exhibited by a catalyst material can be advantageously lowered by including molybdenum in the catalyst material. For examples, in various embodiments of the present disclosure as described herein, the catalyst material exhibits a methane selectivity of no more than 20%, e.g., no more than 18%, or no more than 15%, when tested in the FT performance test described below. In some embodiments, the catalyst material exhibits a methane selectivity that is at least 25% less, e.g., at least 35% less, or at least 45% less, or at least 55% less, or at least 65% less, than a methane selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below.

[0049] The catalyst materials of the present disclosure can advantageously improve conversion at a given set of conditions. In various embodiments, the catalyst material exhibits a CO conversion of at least 15%, e.g., at least 20% or at least 25% when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a CO conversion that is at least 20% greater, e.g., at least 25% greater, or at least 30% greater, than a CO conversion exhibited by an otherwise identical catalyst lacking the molybdenum, when tested in the FT performance test described below.

[0050] The present inventors have determined that while the combination of molybdenum and manganese improve the performance of the catalyst material as describedabove, these improvements do not come at the expense of lowering the oxygenated hydrocarbon selectivity exhibited by the catalyst material. In various embodiments, the catalyst material exhibits an oxygenated hydrocarbon selectivity of at least 8%, e.g., at least 10%, or at least 12%, when tested in the FT performance test described below. For example, in some embodiments, the catalyst material exhibits a C2-C8 alcohol selectivity of at least 8%, e.g., at least 10%, or at least 12%, when tested in the FT performance test described below. For example, the catalyst material exhibits an oxygenated hydrocarbon selectivity that is at least 80%, e.g., at least 85%, or at least 90%, of an oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below. In some embodiments, the catalyst material exhibits a C2-C8 alcohol selectivity that is at least 80%, e.g., at least 85%, or at least 90%, of an oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum (e.g., a Co / Mn catalyst material), when tested in the FT performance test described below.

[0051] While the improved performance of the catalyst materials of the disclosure can be demonstrated in a variety of manners, for the performance metrics described here the following FT test procedure is used: 1 g of catalyst material in substantially oxidic form (i.e. , at least 99% in oxidic form) is loaded into a tubular test reactor with a 4 mm internal diameter, having an inlet, an outlet, and temperature control. The catalyst material is activated at 300 °C under flow of 100% H2 at atmospheric pressure and a gas hourly space velocity (GHSV) of 5,000 h'1for 15 hours. The GHSV value is based on the volume of catalyst material in the reactor tube; any portion of the reactor unfilled with catalyst material is not counted as part of the reactor volume here. The temperature is reduced to 130 °C, and then a flow of a 2:1 molar mixture of H2:CO with 20 mol% N2 at 30 barg and GHSV of 2,300 IT1is provided while ramping the temperature to 240 °C at 1 °C per minute. The composition of the feed stream from the inlet and the product stream from the outlet are analyzed through online gas chromatography; data are reported at steady state at the reported reaction temperature. CO conversion is calculated as a percentage of the amount of CO present in the product stream compared to the CO from the inlet.

[0052] Preparing Catalyst Materials

[0053] The catalyst materials of the disclosure can be prepared in a variety of fashions, including those relying on the impregnation and co-precipitation techniques as known in the art.

[0054] For example, another aspect of the present disclosure provides for a method of making the catalyst materials as described herein. The method includes providing a supportmaterial (e.g., a titanium oxide support material, a cerium oxide support material, an aluminum oxide support material, a zirconium oxide support material, a zinc oxide support material, or a mixed oxide support material including a mixture of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide); contacting the support material with one or more liquids each including one or more cobalt-containing compounds, one or more molybdenum-containing compounds, and / or one or more manganese-containing compounds dispersed in a solvent; allowing the solvent(s) to evaporate to provide a catalyst precursor; and calcining the catalyst precursor. The person of ordinary skill in the art will appreciate, of course, that other methods can be used to make the catalyst materials described herein.

[0055] In some embodiments of the present disclosure as described herein, contacting the support material with the liquid includes adding the liquid in an amount about equal to (i.e., within 25% of, or within 10% of) the pore volume of the support. In other embodiments, contacting the support with the liquid includes adding the liquid in an amount greater than the pore volume of the support. For example, in some embodiments, the ratio of the amount of liquid to the amount of support material on a mass basis is in the range of 0.75:1 to 5:1 , e.g., in the range of 0.9:1 to 3:1. In some embodiments, contacting the support material with the liquid provides a slurry.

[0056] In various embodiments of the present disclosure as described herein, allowing the solvent to evaporate is conducted at ambient temperature. In various embodiments, allowing the solvent to evaporate is conducted at an elevated temperature for a drying time. The person of ordinary skill in the art would be able to select appropriate apparatuses or instruments to allow the solvent to evaporate, and such apparatuses or instruments are not particularly limited. Additionally, the person of ordinary skill in the art would understand that the elevated temperature that will allow the solvent to evaporate depends on the boiling point of the solvent. As such, the person of ordinary skill in the art would be able to select an appropriate elevated temperature. For example, in some embodiments, the elevated temperature is in the range of 50 to 150 °C, e.g., in the range of 50 to 120 °C, or 50 to 100 °C, or 100 to 150 °C, or 100 to 120 °C. In some embodiments, the drying time is in the range of 1 to 48 hours, e.g., in the range of 10 to 36 hours, or 12 to 24 hours. For example, in particular embodiments, the drying time is about 24 hours. In some embodiments, allowing the solvent to evaporate is conducted under vacuum and at an elevated temperature for a drying time, as described herein. In some embodiments, allowing the solvent to evaporate is conducted in a stirring drybath at an elevated temperature, for example, in the range of 30 to 100 °C.

[0057] In some embodiments of the present disclosure as described herein, calcining the catalyst precursor is conducted in a furnace for a calcining time and at a calcining temperature. For example, in some embodiments, the calcining time is in the range of 0.5 to 24 hours, or 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours. In some embodiments, the calcining temperature is in the range of 100 to 600 °C, e.g., in the range of 120 to 500 °C.

[0058] As described above, the method of making the catalyst material as described herein includes contacting the support with one or more liquids each including one or more cobalt-containing compounds, one or more molybdenum-containing compounds, and / or one or more manganese-containing compounds dispersed in a solvent. The cobalt-, molybdenum-, and manganese-containing compounds are not particularly limited and the person of ordinary skill in the art would be able to choose appropriate compounds that are soluble in the solvent. For example, in some embodiments of the disclosure as described herein, the cobalt- and manganese-containing compounds may be selected from metal salts (e.g., nitrates and acetates). For example, in some embodiments of the disclosure as described herein, the molybdenum-containing compounds may be selected from metal oxides (e.g., ammonium molybdate). The solvent is also not particularly limited, and the person of ordinary skill in the art would be able to choose an appropriate solvent that can be absorbed by the support. For example, in some embodiments of the disclosure as described herein, the solvent is water. As the person of ordinary skill in the art will appreciate, these metal species can be conveniently provided in the same liquid, so that only one step of contacting the support with liquid is required. However, other schemes are possible.

[0059] In another aspect, the present disclosure provides a catalyst as described herein made by the methods as described herein.

[0060] Fischer-Tropsch Synthesis Processes

[0061] Another aspect of the present disclosure provides a process for performing a Fischer-Tropsch synthesis process. As described above, the process includes contacting a catalyst material as described herein with a feed stream comprising H2 and CO under conditions sufficient to provide a product stream that comprises C5+ non-oxygenated and oxygenated hydrocarbons. An example of such a process is shown schematically in FIG. 1. In FIG. 1, the process 100 includes contacting a catalyst material 123 with feed stream 121 in a Fischer-Tropsch reaction zone (e.g., reactor 120) to provide product stream 122 which includes C5+ non-oxygenated and oxygenated hydrocarbons.

[0062] The Fischer-Tropsch catalyst materials as described herein are suitable for use in the Fischer-Tropsch synthesis processes described herein. The person of ordinary skill inthe art will appreciate that the Fischer-Tropsch catalyst materials of the disclosure can be provided in many forms, depending especially on the particular form of the reactor system in which they are to be used, e.g., in a fixed bed or as a fluidized bed. The person of ordinary skill in the art will select an appropriate form of the Fischer-Tropsch catalyst material for the particular reactor system.

[0063] As discussed above, without intending to be bound by theory, it is believed that the active form of cobalt in the Fischer-Tropsch catalyst material is typically in a substantially metallic form (i.e. , as cobalt(O)). For example, in various embodiments as described herein, in the catalyst material that is contacted with the feed stream at least 50 mol% of the cobalt is present as metallic cobalt, e.g., at least 60 mol%, or at least 70 mol%, or at least 80 mol% of the cobalt. The amount of metallic cobalt present in the catalyst may be determined by TPR, as described herein.

[0064] It can be desirable to activate the catalyst material by contacting it with a reducing gas, e.g., hydrogen gas, to convert a substantial fraction of the cobalt present in an oxide for to a metallic form. Thus, in various embodiments as described herein, the process further comprises, before contacting the catalyst material with a feed stream comprising H2 and CO, activating the catalyst material by contacting the catalyst material with a reducing gas stream comprising H2 for a time and at a temperature sufficient to provide at least 50 mol% of the cobalt, e.g., at least 60 mol%, or at least 70 mol%, in the catalyst material in metallic form. The amount of metallic cobalt present in the catalyst may be determined by TPR, as described herein. The source of the H2 used for the reducing gas stream is not particularly limited. For example, in various embodiments as otherwise described herein, the process includes separating at least a portion of H2 from the feed stream and contacting it with the Fischer-Tropsch catalyst material to activate the Fischer-Tropsch catalyst. For example, in the process of FIG. 1, stream 125 separates H2 and conducts it to reactor 120. This separation need not be continuous; rather, it need only be performed for a time desirable to provide reducing gas to the Fischer-Tropsch catalyst for activation. Of course, as would be understood by the person of skill in the art, other sources of H2 may be used to provide reducing gas to the Fischer-Tropsch catalyst for activation.

[0065] The composition of the reducing gas stream is not particularly limited. For example, in various embodiments as described herein, the reducing gas stream further comprises an inert gas. In some embodiments, the inert gas is nitrogen. In various embodiments, the inert gas is present in the reducing gas stream in an amount no more than 50 mol%. The activation of the catalyst material can be performed in the substantial absence of carbon monoxide. For example, in various embodiments as described herein, the reducing gas stream comprises no more than 1 mol% carbon monoxide, e.g., no morethan 0.5 mol%, or no more than 0.1 mol%, or no more than 0.05 mol%, or no more than 0.01 mol% carbon monoxide.

[0066] The activation conditions for contacting the catalyst material with the reducing gas stream is not particularly limited and the person of ordinary skill in the art can determine appropriate reducing conditions to provide a desirable amount of cobalt(O) in the activated catalyst.

[0067] For example, in various embodiments, the Fischer-Tropsch catalyst material is contacted with the reducing gas stream at an activation temperature in the range of 200 to 600 °C, e.g., in the range of 200 to 500 °C, or 200 to 400 °C, or 250 to 600 °C, or 250 to 500 °C, or 250 to 400 °C. In various embodiments as described herein, the Fischer-Tropsch catalyst material is contacted with the reducing gas stream at an activation pressure in the range of 0 to 50 barg, e.g., in the range of 0 to 40 barg, or 0 to 30 barg, or 0 to 20 barg, or 0 to 10 barg. In some embodiments, the activation pressure is at about ambient pressure. In various embodiments as described herein, the Fischer-Tropsch catalyst material is contacted with the reducing gas stream at an activation gas hourly space velocity in the range of 1 ,000 to 10,000 IT1, e.g., in the range of 2,000 to 8,000 IT1, or in the range of 4,000 to 6,000 IT1. In various embodiments as described herein, the Fischer-Tropsch catalyst material is contacted with the reducing gas stream for an activation time in the range of 1 to 48 hours, e.g., in the range of 1 to 24 hours, or in the range of 4 to 24 hours, or in the range of 8 to 20 hours.

[0068] As used herein, a “feed stream” is used to mean the total material input to a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single inlet or multiple inlets. For example, H2 and CO of the feed stream can be provided to the Fischer-Tropsch catalyst material in a single physical stream, or in multiple physical streams. Similarly, a “product stream” is used to mean the total material output from a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single outlet or multiple outlets.

[0069] As described above, the feed stream contains both H2 and CO (e.g., provided in a single physical stream or multiple physical streams). In various embodiments as otherwise described herein, the molar ratio of H2 to CO in the feed stream is at least 0.1 :1 , e.g., at least 0.5:1 . In some embodiments, the molar ratio of H2 and CO in the feed stream is at least 0.9:1 , e.g., at least 1 :1 or at least 1.5:1. In some embodiments, the molar ratio of H2 to CO in the feed stream is no more than 20:1 , e.g., no more than 15:1 or no more than 10:1. In some embodiments, the molar ratio of H2 to CO in the feed stream is no more than 6:1 , e.g., no more than 4:1 or no more than 3:1. For example, in some embodiments, the molar ratioof H2 to CO in the feed stream is in the range of 1 :1 to 6:1 , e.g., in the range of 1.5:1 to 3:1.The person of ordinary skill in the art can provide a desired ratio of H2 to CO in the feed stream, based on the disclosure herein, that provides a desirable conversion and selectivity.

[0070] In some embodiments as described herein, the feed stream further comprises CO2. For example, in various embodiments, the feed stream further comprises CO2 in a total amount of up to 30 mol% CO2, or up to 25 mol% CO2, or up to 20 mol% CO2. In some embodiments, the feed stream further comprises CO2 in a total amount in the range of 5-30 mol% (e.g., in the range of 5-25 mol% or 5-20 mol%).

[0071] In some embodiments of the disclosure as otherwise described herein, the feed stream further comprises one or more inert gases. For example, in some embodiments, the feed stream further comprises nitrogen, and / or argon. Methane (e.g., recycled from the product stream) can also be present as an inert. In some embodiments, it can be desirable to perform the Fischer-Tropsch synthesis process in the presence of a significant amount of inerts (i.e. , components that are not H2, CO, or CO2). For example, in various embodiments, the feed stream includes up to 80 mol% of one or more inerts, e.g., in the range of 3-80 mol%, or 5-80 mol%, or 10-80 mol%, or 15-80 mol%, or 30-80 mol% of one or more inerts. In various embodiments, the feed stream includes up to 70 mol% inerts, up to 60 mol% inerts, or up to 50 mol% inerts, e.g., 3-70 mol%, or 5-70 mol%, or 10-70 mol%, or 15-70 mol%, or 30-70 mol%, or 3-60 mol%, or 5-60 mol%, or 10-60 mol%, or 15-60 mol%, or 30-60 mol%, or 3-50 mol%, or 5-50 mol%, or 10-50 mol%, or 15-50 mol%, or 30-50 mol% inerts. In some embodiments of the disclosure as otherwise described herein, C2+ hydrocarbons. For example, in various embodiments, the feed stream includes no more than 10 mol%, no more than 5 mol%, or no more than 1 mol% C2+ hydrocarbons.

[0072] The process includes contacting the Fischer-Tropsch catalyst material as described herein with the feed stream as described herein. In various embodiments of the process as otherwise described herein, the feed stream is not contacted with a catalyst material comprising iron (e.g., a second catalyst material not described herein). For example, in various embodiments, the contacting comprises contacting only one type of catalyst material (e.g., as otherwise described herein) with the feed stream. As described above, in various embodiments, the Fischer-Tropsch catalyst does not include substantial amounts of iron.

[0073] As described above, the process includes contacting a Fischer-Tropsch catalyst material with a feed stream comprising H2 and CO. The person of ordinary skill in the art will select appropriate reaction conditions (e.g., temperature and pressure) in conjunction with the feed stream and catalyst material compositions to provide the desired Fischer-Tropschproducts. In some embodiments of the disclosure as described herein, the contacting of the Fischer-Tropsch catalyst material with the feed stream is conducted at a temperature in the range of 150 to 280 °C. For example, in various embodiments, the contacting is conducted at a temperature in the range of 150 to 260 °C, or 150 to 250 °C, or 175 to 280 °C, or 175 to 260 °C, or 175 to 250 °C, or 190 to 280 °C, or 190 to 260 °C, or 190 to 250 °C, or 200 to 280 °C, or 200 to 260 °C, or 200 to 250 °C.

[0074] The present inventors note that methane selectivity can undesirably increase with higher temperatures. In such situations, it can be advantageous to lower the applied temperature of the Fischer-Tropsch synthesis. Advantageously, the catalyst materials of the disclosure can have high conversion even at more moderate temperatures. Accordingly, in some embodiments as described herein, the contacting of the Fischer-Tropsch catalyst material with the feed stream is conducted at a temperature in the range of 150 to 240 °C. For example, in various embodiments, the contacting is conducted at a temperature in the range of 150 to 230 °C, or 150 to 220 °C, or 175 to 240 °C, or 175 to 230 °C, or 175 to 220 °C, or 190 to 240 °C, or 190 to 230 °C, or 190 to 220 °C, or 200 to 240 °C, or 200 to 230 °C, or 200 to 220 °C, or 220 to 240 °C. Operating at lower temperatures can advantageously increase catalyst lifetime as well as increase the lifetime of the reactor system in which it is used.

[0075] Of course, the person of ordinary skill in the art will appreciate that the efficiency of the Fischer-Tropsch catalyst material can be relatively lower, for example, during the start- of-life and end-of-life operation of the Fischer-Tropsch catalyst material. Nevertheless, the present inventors have found that the catalyst materials as described here can maintain the temperature of the Fischer-Tropsch synthesis during these operations to provide a desirable non-oxygenated and oxygenated hydrocarbon selectivity. For example, in some embodiments as described herein, the contacting of the Fischer-Tropsch catalyst material with the feed stream is conducted at a temperature in the range of 240 to 280 °C at the start- of-life and / or end-of-life operation.

[0076] In some embodiments of the disclosure as described herein, the contacting of the Fischer-Tropsch catalyst material with the feed stream is conducted at a pressure of at least 1 barg, e.g., at least 5 barg, or at least 10 barg. In some embodiments of the disclosure as described herein, contacting is conducted at a pressure in the range of 10 to 60 barg, e.g., in the range of 10 to 50 barg, or 20 to 50 barg, or 25 to 50 barg, or 10 to 40 barg, or 20 to 40 barg, or 25 to 40 barg, or 10 to 35 barg, or 20 to 35 barg, or 25 to 35 barg.

[0077] The Fischer-Tropsch synthesis processes described herein can be performed at a variety of gas hourly space velocity (GHSV) values, as would be appreciated by the personof ordinary skill in the art. As such, the GHSV for contacting the Fischer-Tropsch catalyst material with the feed stream is not particularly limited. For example, in various embodiments of the present disclosure, the contacting of the Fischer-Tropsch catalyst material with the feed stream is conducted at a GHSV in the range of 100 to 100,000 IT1, or 100 to 50,000 IT1, or 100 to 40,000 IT1, or 100 to 30,000 IT1, or 100 to 20,000 IT1, 500 to 100,000 IT1, or 500 to 50,000 IT1, or 500 to 40,000 IT1, or 500 to 30,000 IT1, or 500 to 20,000 IT1, 1 ,000 to 100,000 IT1, or 1 ,000 to 50,000 IT1, or 1 ,000 to 40,000 IT1, or 1 ,000 to 30,000 IT1, or 1 ,000 to 20,000 IT1. In various embodiments of the present disclosure, the contacting is conducted at a GHSV in the range of 500 to 15,000 IT1, e.g., in the range of 500 to 15,000 IT1, or 500 to 10,000 IT1, or 500 to 8,000 IT1, or 500 to 5,000 IT1, or 1 ,000 to 15,000 IT1, or 1 ,000 to 10,000 IT1, or 1 ,000 to 8,000 IT1, or 1 ,000 to 5,000 IT1, or 2,000 to 15,000 IT1, or 2,000 to 10,000 IT1, or 2,000 to 8,000 IT1, or 2,000 to 5,000 IT1. The person of ordinary skill in the art will appreciate that the full range of space velocities described above may not be available for a given Fischer-Tropsch synthesis process, depending on the details of the particular process at hand.

[0078] The present inventors have determined that the catalyst materials described here can provide desirably oxygenated hydrocarbon selectivity and desirably low methane selectivity at commercially relevant conversion rates. As used herein, a “conversion” is a molar fraction of a species that is reacted as a result of contacting the feed stream with the catalyst material to form the product stream, be it to desirable products or undesirable species. In various embodiments of the present disclosure as described herein, contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed at an oxides of carbon (e.g., CO and CO2) conversion of at least 20%, e.g., at least 24%, or at least 30%. For example, in some embodiments, contacting the Fischer- T ropsch catalyst material with the feed stream to provide the product stream is performed with a CO conversion of at least 20%, e.g., at least 25%, or at least 30%. The person of ordinary skill in the art will, based on the disclosure herein, operate at a degree of conversion that provides a desirable product, and can change process parameters (e.g., activation conditions, reaction temperature, space velocity) to influence the degree of conversion. And of course, in other embodiments, e.g., when in a stacked-bed, the CO conversion may be even higher than described here.

[0079] C5+ non-oxygenated hydrocarbons are the generally-desirable products ofFischer-Tropsch synthesis, and as such, the Fischer-Tropsch synthesis processes of the present disclosure can have a desirable level of C5+ non-oxygenated hydrocarbon selectivity. As used herein, a “selectivity” for a given reaction product is the weight fraction of the carbon monoxide of the feed stream that is converted to a given reaction product (here, C5+ non-oxygenated hydrocarbons) out of the entire product stream. For example, in various embodiments, contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed with a C5+ non-oxygenated hydrocarbon selectivity of at least 20%, e.g., at least 25%, or at least 30%. As used herein, the term “nonoxygenated hydrocarbons” encompasses alkanes and olefins. For example, in some embodiments, contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed with a C5+ non-oxygenated hydrocarbon selectivity of at least 20%, e.g., at least 25%, or at least 30%. Moreover, in various embodiments as described herein, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C5+ non-oxygenated hydrocarbon selectivity of no more than 60%, e.g., no more than 50%, or no more than 40%. For example, in some embodiments, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C5+ non-oxygenated hydrocarbon selectivity of no more than 60%, e.g., no more than 50%, or no more than 40%.

[0080] As discussed above, the Fischer-Tropsch catalyst materials of the present disclosure advantageously can have relatively good selectivity for oxygenated hydrocarbons. As used for oxygenated hydrocarbons, a “selectivity” for a given reaction product is the molar fraction of the carbon monoxide of the feed stream that is converted to a given reaction product (here, oxygenated hydrocarbons) out of the entire product stream. As used herein, the term “oxygenated hydrocarbons” as used herein encompasses alcohols and aldehydes, and other oxygen-substituted alkanes or olefins. For example, in various embodiments, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with an oxygenated hydrocarbon selectivity of at least 8%, e.g., at least 10%, or at least 12%. In some embodiments, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C2-C8 alcohol selectivity of at least 8%, e.g., at least 10%, or at least 10%.

[0081] As discussed above, the Fischer-Tropsch catalyst materials of the present disclosure advantageously can have relatively good selectivity for long-chain nonoxygenated hydrocarbons (e.g., Cs-C alkanes). As used for long-chain non-oxygenated hydrocarbons, a “selectivity” for a given reaction product is the weight fraction of the carbon monoxide of the feed stream that is converted to a given reaction product (here, long-chain alkyls) out of the entire product stream. For example, in various embodiments, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a long-chain non-oxygenated hydrocarbon selectivity of at least 15%, e.g., at least 18%, or at least 20%. In various embodiments, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a Cs-Ci6 non-oxygenatedhydrocarbon selectivity of at least 15%, e.g., at least 18%, or at least 20%. In some embodiments as described herein, contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a Cn+ non-oxygenated hydrocarbon selectivity of at least 4%, e.g., at least 6%, or at least 8%, or at least 10%.

[0082] As discussed above, the present inventors note that the inclusion of manganese and molybdenum in the catalyst materials described herein allows the catalyst materials to provide oxygenated hydrocarbons during Fischer-Tropsch synthesis at reasonable CO conversions with low methane production. For example, in various embodiments of the present disclosure as described herein, contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed with a methane selectivity of no more than 20%, e.g., no more than 18%, or no more than 15%. It can also be desirable to limit the formation of other light hydrocarbon products, such as C2-C4 hydrocarbons. For example, in various embodiments, contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed with a C2-C4 hydrocarbon selectivity of no more than 40%, e.g., no more than 35%, or no more than 30%.

[0083] As discussed above, the product stream comprises oxygenated hydrocarbons. Additionally, the Fischer-Tropsch catalysts of the present disclosure can have high C5+ nonoxygenated hydrocarbon selectivity, and thus C5+ non-oxygenated and oxygenated hydrocarbons can comprise a substantial portion of the product stream. However, the person of ordinary skill in the art will appreciate that additional components may also be present in the product stream. The product stream will typically include water, which itself is a by-product of the Fischer-Tropsch synthesis reaction. Methane, and one or more light hydrocarbons (i.e., C1-C4 hydrocarbons) can also be present as well as secondary products of the converted carbon monoxide. And of course, the product stream will typically include any inert gases from the feed stream as well as any unreacted hydrogen and carbon monoxide. The person of ordinary skill in the art will be familiar with methods to separate various components of the product stream, for example, for provision as ultimate products of the process or for recycle to the feed. Some particular process architectures are described below.

[0084] As an example of the processes described herein, FIG. 2 depicts process 200 in a schematic view, wherein the process includes contacting catalyst material 223 with feed stream 221 in a Fischer-Tropsch reaction zone (e.g., reactor 220) to provide product stream 222 which includes C5+ non-oxygenated and oxygenated hydrocarbons. FIG. 2 further includes recycle stream 236, which allows for at least a portion of various components of product stream 222 (e.g., H2, CO, and / or inerts) to be separated and recycled back to the feed stream 221.

[0085] Another example of the processes described herein are shown schematically in FIG. 3. In the embodiment of FIG. 3, process 300 includes contacting catalyst material 323 with feed stream 321 in a Fischer-Tropsch reaction zone (e.g., reactor 320) to provide product stream 322 which includes C5+ non-oxygenated and oxygenated hydrocarbons.FIG. 3 further includes providing heat exchanger 330 to exchange heat between the product steam 322 and the feed stream 321. FIG. 3 also includes steam generation zone 332 for heat exchange with the product steam 322. As described herein, various components of product stream 322 can be separated and used in other streams or processes. For example, in FIG. 3, water is separated from product stream 322 to provide a watercontaining stream 334. FIG. 3 further includes recycle stream 336, which allows for at least a portion of various other components of product stream 322 (e.g., H2, CO, and / or inerts) to be separated and recycled back to the feed stream 321. As described in more detail below, FIG. 3 also includes providing a hydroprocessing reactor 350 to convert at least a portion of product stream 322 into a hydroprocessed product stream 352. FIG. 3 also includes providing at least a portion of the water-containing stream 334 to an electrolyzer 360 to provide a H2-containing stream 334. At least a portion of the H2-containing stream 334 can be provided to feed stream 321.

[0086] FIG. 4 depicts process 400 in a schematic view of the processes as described herein, wherein the process includes contacting catalyst material 423 with feed stream 421 in a Fischer-Tropsch reaction zone (e.g. reactor 420) to provide product stream 422 which includes C5+ non-oxygenated and oxygenated hydrocarbons. FIG. 4 further includes recycle stream 436, which allows for at least a portion of various components of product stream 422 (e.g., H2, CO, and / or inerts) to be separated and recycled back to the feed stream 421. Additionally, at least a portion of the product stream 422 can be separated to provide a CO2- containing stream 460. The CO2-containing stream 460 can be conducted to CO generation zone 462 to provide a CO-containing stream 464.

[0087] FIG. 4 also includes separating at least a portion of product stream 422 to provide a light hydrocarbon stream 450. As described in more detail below, at least a portion of the light hydrocarbon stream 450 can be conducted to partial oxidation (pOX) reaction zone 452 to provide pOX stream 454. FIG. 4 also includes various power generation zones. As described in more detail below, at least a portion of the light hydrocarbon stream 450 can be provided to an electrical generator 470 to provide electricity stream 472 or a heat generator 480 to provide heat stream 482. The heat stream 482 can provide heat to feed stream 421 via heat exchanger 490.

[0088] The various gaseous components of the product stream, e.g., hydrogen, carbon monoxide, and carbon dioxide may be used in other feeds of the process as describedherein. As such, in some embodiments as described herein, at least a portion of hydrogen, carbon monoxide, and carbon dioxide of the product stream is included in the feed stream. It can be desirable to recycle hydrogen from the product stream, for example, to the feed stream. Since hydrogen efficiency is vital when using H2 made from renewable energy sources, it can be especially desirable to recycle H2 to the feed stream. For example, in the process 200 of FIG. 2, at least a portion of H2 of the product stream 222 can be recycled to the feed stream 221 via the recycle stream 236. In the process 300 of FIG. 3, at least a portion of H2 of the product stream 322 can be recovered to the feed stream 321 via the recycle stream 336. In the process of FIG. 4, at least a portion of H2 of the product stream 422 can be conducted to the feed stream 421 via the recycle stream 436. In various embodiments, at least 25%, e.g., at least 50% of H2 of the product stream is recycled to the feed stream. In various embodiments, at least 75%, e.g., at least 90% of H2 of the product stream is recycled to the feed stream.

[0089] Similarly, it can be desirable to recycle CO of the product stream, for example, to the feed stream. Since CO is the carbon source for Fischer-Tropsch synthesis, it can be especially desirable to recycle CO to the feed stream. For example, in the process 200 of FIG. 2, at least a portion of CO of the product stream 222 can be recycled to the feed stream 221 via the recycle stream 236. In the process 300 of FIG. 3, at least a portion of CO of the product stream 322 can be recovered to the feed stream 321 via the recycle stream 336. In the process of FIG. 4, at least a portion of CO of the product stream 422 can be conducted to the feed stream 421 via the recycle stream 436. In various embodiments, at least 25%, e.g., at least 50% of carbon monoxide of the product stream is recycled to the feed stream. In various embodiments, at least 75%, e.g., at least 90% of carbon monoxide of the product stream is recycled to the feed stream.

[0090] As with hydrogen and carbon monoxide, it can be desirable to recycle carbon dioxide of the product stream, for example, to the feed stream. For example, in the process 200 of FIG. 2, at least a portion of CO2 of the product stream 222 can be recycled to the feed stream 221 via the recycle stream 236. In the process 300 of FIG. 3, at least a portion of CO2 of the product stream 322 can be recovered to the feed stream 321 via the recycle stream 336. In various embodiments, at least 25%, e.g., at least 50% of carbon dioxide of the product stream is recycled to the feed stream. In various embodiments, at least 75%, e.g., at least 90% of carbon dioxide of the product stream is recycled to the feed stream.

[0091] In many cases, hydrogen, carbon monoxide, and carbon dioxide of the product stream will be recycled.

[0092] Moreover, when one or more inerts are used in the process steps, it can be desirable to recycle these. For example, in various embodiments, the process includes recycling at least a portion of inerts of the product stream to the feed stream. For example, in the process 200 of FIG. 2, at least a portion of the inerts of the product stream 222 can be recycled to the feed stream 221 via the recycle stream 236. In the process 300 of FIG. 3, at least a portion of inerts of the product stream 322 can be recovered to the feed stream 321 via the recycle stream 336. In the process of FIG. 4, at least a portion of inerts of the product stream 422 can be conducted to the feed stream 421 via the recycle stream 436. In various embodiments, at least 25%, e.g., at least 50% of inerts of the product stream is recycled to the feed stream. In various embodiments, at least 75%, e.g., at least 90% of inerts of the product stream is recycled to the feed stream. In various embodiments, a purge stream can be incorporated with the recycle stream to prevent uncontrolled accumulation of inerts in the recycle stream (not shown here).

[0093] As described above, the product stream also comprises light hydrocarbons, i.e. , C1-C4 hydrocarbons, and these may be further separated to provide a light hydrocarbon stream. Light hydrocarbons, while often not a desired portion of a Fischer-Tropsch product to be used as a fuel or a lubricant, can themselves be useful for a number of purposes. Accordingly, in various embodiments, the process further includes separating at least a portion of C1-C4 hydrocarbons from the product stream to provide a light hydrocarbon stream. For example, in the process 400 of FIG. 4, at least a portion of the C1-C4 hydrocarbons from the product stream 422 are separated to provide a light hydrocarbon stream 450.

[0094] As would be understood by the person of skill in the art, the product stream will also include water. In various embodiments, the process further comprises separating at least a portion of water from the product stream. This is shown schematically in FIG. 3. Here, the process 300 also optionally includes separating at least a portion of water (e.g., at least 50%, at least 75%, or at least 90%) from the product stream 322 to provide watercontaining stream 334.

[0095] The carbon dioxide of the product stream can also be used as a source of carbon monoxide for the process described herein. For example, in some embodiments of the disclosure as described herein, the process further includes reacting at least a portion of the carbon dioxide of the product stream in a CO generating zone to convert carbon dioxide to carbon monoxide, and including a least a portion of the carbon monoxide from the CO generating zone in the feed stream. The conversion method of carbon dioxide to carbon monoxide is not particularly limited. For example, a reverse water-gas shift or a conversion by a solid oxide electrochemical cell can be used. This is shown schematically in FIG. 4.Here, at least a portion of the CO2 of the product stream 422 is separated and conducted to CO generating zone 462 via CO2-containing stream 460. The CO generating zone 462 converts CO2 to CO, and at least a portion of the CO is provided to feed stream 421 via CO- containing stream 464.

[0096] As described above, the product stream may also include light hydrocarbons that may be recycled to the feed stream. There are other uses for the light hydrocarbon stream. For example, in some embodiments, the process further comprises at least partially oxidizing at least a portion of the C1-C4 hydrocarbons of the light hydrocarbon stream in a partial oxidation reaction zone to provide a partial oxidation (pOX) stream comprising carbon monoxide e.g., a CO- and / or CO2-containing partial oxidation (pOX) stream, and including at least a portion of the pOX stream in the feed stream. An example of such a process is shown schematically in FIG 4. Here, the process 400 includes oxidizing at least a portion of the light hydrocarbon stream 450 in a partial oxidation (pOX) reaction zone 452 to provide a CO- and / or CO2 containing pOX stream 454, and providing at least a portion of the pOX stream 454 to feed stream 421.

[0097] Moreover, the light hydrocarbon stream can be burned to provide heat energy, which can be used to heat various process streams, or to generate electricity. Accordingly, in various embodiments, the process includes burning at least a portion of the light hydrocarbon stream to provide energy, e.g., heat energy or electrical energy. For example, in the process 400 of FIG. 4, a portion of light hydrocarbon stream 450 is burned in a power generation zone (here, in an electrical generator 470), to generate electricity stream 472. In various embodiments, the heat energy may be used to provide the needed heat for the Fischer-Tropsch synthesis process. For example, in the process 400 of FIG. 4, a portion of the light hydrocarbon stream 450 is burned in a power generation zone (here, in a heat generator 480), to generate heat stream 482. The heat stream 482 is conducted to a heat exchange zone 490 to heat feed stream 421.

[0098] Heat can be exchanged from the product stream to provide heat to, for example, a feed stream or a steam generation zone. For example, in various embodiments, the process further comprises exchanging heat between at least a portion of the product stream and at least a portion of the feed stream, thereby cooling at least a portion of the product stream and heating at least a portion feed stream. In the process 300 of FIG. 3, heat is exchanged between at least a portion of the product stream 322 and the feed stream 321 in heat exchange zone 330, thereby cooling the product stream 322 and heating the feed stream 311. The person of ordinary skill in the art will appreciate that a wide variety of heat exchangers can be used for this purpose.

[0099] Of course, any excess heat in the product stream can be additionally or alternatively used for other purposes. For example, in various embodiments the process further comprises exchanging heat between at least a portion of the product stream and a steam generation zone, thereby cooling at least a portion of the product stream and providing heat to the steam generation zone. This is shown in FIG. 3. Here, after heat exchange with feed stream 321 , the product stream 322 is conducted to steam generation zone 332 to cool the product stream 322 and provide heat to the steam generation zone 332. Steam can be generated from the heat provided, and electricity can be generated from the steam (not shown here).

[0100] As noted above, the Fischer-Tropsch synthesis process provides a product stream that includes oxygenated hydrocarbons (e.g., C2-C8 oxygenated hydrocarbons). Accordingly, in various embodiments, one or more products are provided from at least a portion of oxygenated hydrocarbons of the product stream. Similarly, the Fischer-Tropsch synthesis process provides a product stream that includes C2-C8 alcohols. Accordingly, in various embodiments, one or more products are provided from at least a portion of C2-C8 alcohols of the product stream. The oxygenated hydrocarbons and alcohols can be used as the basis of a variety of base-oil reactants, lubricants, and fine chemical intermediates.

[0101] As noted above, the Fischer-Tropsch synthesis process provides a product stream that also includes C5+ non-oxygenated hydrocarbons (e.g., unsubstituted hydrocarbons like alkanes and alkenes).

[0102] Accordingly, in various embodiments, one or more products are provided from at least a portion of C5+ non-oxygenated hydrocarbons of the product stream. The C5+ nonoxygenated hydrocarbons can be used as the basis of a variety of fuels, e.g., gasoline, diesel, aviation fuel. Other products, like waxes and lubricants, can also be made. And alkenes and oxygenated hydrocarbons can be used as feedstocks in a variety of other processes.

[0103] The person of ordinary skill in the art will use conventional post-processing techniques to convert the C5+ non-oxygenated hydrocarbon-containing product to desirable products such as desirable fuels. For example, in various embodiments, the process further includes hydroprocessing at least a portion of C5+ non-oxygenated hydrocarbons of the product stream. As the person of ordinary skill in the art will appreciate, hydroprocessing is a treatment of the hydrocarbon stream with hydrogen in the presence of a suitable catalyst. A wide variety of hydroprocessing techniques are known and the person of ordinary skill in the art will apply them here. For example, in the process 300 of FIG. 3, the product stream322 is hydroprocessed in hydroprocessing reactor 350 to provide a hydroprocessed product stream 352.

[0104] As described above, CO is a substantial input to the process as described herein. The person of ordinary skill in the art will appreciate that CO can be provided from a variety of sources, e.g., gasification, reforming, or electrochemical CO2 reduction. Moreover, as described above, CO can be recycled to the feed stream from the product stream; and / or can be provided by reaction of the light hydrocarbon stream, e.g., by partial oxidation or reforming (e.g., steam reforming and / or autothermal reforming).

[0105] As described above, H2 is also a substantial input to the processes as described herein. Advantageously, the present inventors have recognized that H2 can come from renewable or otherwise environmentally responsible sources. In some embodiments, at least part of the H2 of the feed stream and / or the reducing stream is from a renewable source. For example, in various embodiments, at least part (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the feed stream and / or the reducing stream can be so-called “green” hydrogen, e.g., produced from the electrolysis of water operated using renewable electricity (such as wind, solar, or hydro-electric power). In some embodiments, at least part (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the feed stream and / or the reducing stream may be from a so-called “blue” source, e.g., from a natural gas reforming process with carbon capture. Of course, other sources of H2 can be used in part or in full. For example, in some embodiments, at least part (e.g., at least 25%, at least 50%, or at least 75%) of the H2 of the feed stream and / or the reducing stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.

[0106] The present inventors have noted that electrolysis of water is a desirable way to provide hydrogen to the claimed processes. Accordingly, in some embodiments, the process includes providing at least a portion of H2 of the feed stream and / or the reducing stream from the electrolysis of water. In some embodiments, the electrolysis of water is performed using at least partially electricity from a renewable source, e.g., to provide so- called “green hydrogen.” However, the present inventors have noted that electricity can be generated as part of the claimed process, e.g., using heat exchange from the product stream, or by burning light hydrocarbons as described above. In some embodiments, the electrolysis of water is performed using at least partially electricity generated according to the processes as described herein. For example, in the process 300 of FIG. 3, water separated from the product stream 322 is conducted to an electrolyzer 360 via watercontaining stream 334. Water can be electrolyzed in electrolyzer 360 by using electricity generated from a power generation zone (not shown here). H2 generated from theelectrolysis of water can be provided to feed stream 321 via ^-containing stream 362. In some embodiments, at least a portion of the O2 generated from the electrolyzer 360 can be provided to a partial oxidation reaction zone (not shown here).

[0107] As described above, CO2 can be an input to the processes as described herein. CO2 can be captured from the environment generally or more directly from processes that form CO2 (especially in difficult-to-abate sectors). This can make the eventual hydrocarbon product substantially carbon-neutral or of lower carbon intensity. Accordingly, in some embodiments of the disclosure as described herein, at least a portion of the CO2of the feed stream is from a renewable source. In some embodiments, at least part (e.g., at least 25%, at least 50%, or at least 75%) of the CO2of the feed stream is from direct air capture. In some embodiments, at least part (e.g., at least 25%, at least 50%, or at least 75%) of the CO2 of the feed stream is from a manufacturing plant such as a bioethanol plant (e.g., CO2produced fermentation), a steel plant, or a cement plant.EXAMPLES

[0108] The Examples that follow are illustrative of specific embodiments of the process of the disclosure, and various uses thereof. They are set forth for explanatory purposes only, and are not to be taken as limiting the scope of the disclosure.

[0109] Example 1. Preparing Co / Mo and Co / Mo / Mn Catalysts

[0110] To prepare the TiC>2Co(10)Mn(5)Mo(1) catalyst as described herein, a solution of cobalt, manganese, and molybdenum were prepared by dissolving 24.66g g of cobalt nitrate hexahydrate, 12.33 g of manganese acetate tetrahydrate, and 2.47 g of ammonium molybdate in 13 mL of deionized water. The solution of cobalt, manganese, and molybdenum were added to 100 g of P25 titanium dioxide. The amount of titanium dioxide added is based on the amount of the water on a mass basis so that the mass ratio of watersupport is 1 :4. The slurry was then stirred at room temperature for 4 hours. Excess water was then evaporated using a stirring drybath at a temperature of 60 °C. The resulting catalyst precursor powder was then dried for 24 hours at 90 °C in a drying oven. Co / Mo and Co / Mn catalyst precursors were also prepared following the description above without the addition of manganese acetate tetrahydrate or ammonium molybdate, respectively. Other catalysts were prepared in the same way with varying amounts of manganese acetate tetrahydrate and ammonium molybdate. For example, 2.47 g, 12.33 g, and 24.66 g of ammonium molybdate was used to prepare catalysts containing 1 wt%, 5 wt%, and 10 wt% of Mo, respectively.

[0111] That catalyst precursor powder was then subjected to calcination by evenly spreading out the powder in a crucible. The crucible is placed in a calcination furnace andthe temperature is increased from ambient to 120 °C at a rate of 10 °C per minute. The temperature was then held at 120 °C for 1 hour, and then increased from 120 °C to 500 °C at a rate of 2 °C per minute. The temperature was held at 500 °C for 4 hours, and then cooled to ambient temperature. The resulting catalysts were then tested for its viability for Fischer-Tropsch reactions.

[0112] Example 2. Fischer-Tropsch Catalyst Performance of Co / Mn and Co / Mn / Mo Catalysts

[0113] Catalysts prepared by methods as described herein were tested for their catalyst performance for Fischer-Tropsch synthesis processes. The catalysts tested were titania supported catalysts that include cobalt at 10 wt%, manganese at 5 wt%, and molybdenum at 0 wt%, 1 wt%, 5 wt%, and 10 wt%. Prior to performing the Fischer-Tropsch reaction, the catalysts were activated with 100% H2 at 300 °C, atmospheric, and a GHSV of 5,000 hr1for 15 hours.

[0114] The Fischer-Tropsch synthesis processes were completed in a 16 fold high throughput reactor with common gas fees to all 16 catalyst liners, common pressure, and individual temperatures. The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. Table 1 reports the catalytic performance of each catalyst tested and the temperature of the Fischer- Tropsch synthesis process. All trials were conducted at a GHSV of 1,500 hr1and with 18% N2. In Table 1 , Trials 1-3 were conducted with a H2:CO ratio of 1.8:1 at 30 barg. In Table 2, Trials 4-7 were conducted with a H2:CO ratio of 1.2:1 at 30 barg. In Table 3, Trials 8-11 were conducted with a H2:CO ratio of 1.2:1 at 42 barg. In Tables 1, 2 and 3 below, the amount of cobalt, manganese, and molybdenum present in the catalyst are shown in parenthesis. These numbers are in weight percent and based on the total weight of the catalyst. For example, TiO2Co(10)Mn(5) corresponds to a catalyst with 10 wt% Co, 5 wt% Mn, and 85 wt% TiO2.

[0115] Table 1. GHSV = 1,500 hr1, H2:CO ratio of 1.8, 30 barg

[0116] Table 2. GHSV = 1,500 hr1, H2:CO ratio of 1.2, 30 barg

[0117] Table3. GHSV = 1,500 hr1, H2:CO ratio of 1.2, 42 barg

[0118] From Table 1 , 2, and 3, it can be seen that the inclusion of both manganese and molybdenum to cobalt provide increased long chain alkyl (i.e. , Cs-Ci6 alkyl and Cn+ alkyl) selectivity and reduced methane selectivity. Further, the inclusion of molybdenum to a Co / Mn Fischer-Tropsch catalyst improves the activity of the catalysts, as CO conversion increases even when running the Fischer-Tropsch synthesis process at a lower temperature. These improvements in catalyst improvements do not come at the expense of oxygenated hydrocarbon selectivity, which still remains high even after the inclusion of molybdenum in the catalyst.Embodiment 1. A Fischer-Tropsch catalyst material comprising: a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount of 0.5 to 10 wt%, based on the total weight of the catalyst material; and optionally manganese, present in an amount of 0.1 to 10 wt%, based on the total weight of the catalyst material.Embodiment 2. The Fischer-Tropsch catalyst material of embodiment 1, wherein the support makes up at least 70 wt%, e.g., at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt% of the catalyst material, based on the total weight of the catalyst material.Embodiment 3. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is a titanium oxide support material.Embodiment 4. The Fischer-Tropsch catalyst material of embodiment 3, wherein at least a surface layer of the titanium oxide support material comprises at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, on an oxide basis.Embodiment 5. The Fischer-Tropsch catalyst material of embodiment 3, wherein at least a surface layer of the titanium oxide support material comprises at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, on an oxide basis.Embodiment 6. The Fischer-Tropsch catalyst material of any of embodiments 3-5, wherein the titanium oxide support material comprises at least 50 wt% titanium oxide, e.g., at least 60 wt% titanium oxide, or at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, on an oxide basis.Embodiment 7. The Fischer-Tropsch catalyst material of any of embodiments 3-5, wherein the titanium oxide support material comprises at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, on an oxide basis.Embodiment 8. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is a cerium oxide support material.Embodiment 9. The Fischer-Tropsch catalyst material of embodiment 8, wherein at least a surface layer of the cerium oxide support material comprises at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, on an oxide basis.Embodiment 10. The Fischer-Tropsch catalyst material of embodiment 8, wherein at least a surface layer of the titanium oxide support material comprises at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, on an oxide basis.Embodiment 11. The Fischer-T ropsch catalyst material of any of embodiments 8-10, wherein the cerium oxide support material comprises at least 50 wt% cerium oxide, e.g., at least 60 wt% cerium oxide, or at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, on an oxide basis.Embodiment 12. The Fischer-Tropsch catalyst material of any of embodiments 8-10, wherein the cerium oxide support material comprises at least 90 wt% cerium oxide, e.g., at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, on an oxide basis.Embodiment 13. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is an aluminum oxide support material.Embodiment 14. The Fischer-Tropsch catalyst material of embodiment 13, wherein at least a surface layer of the aluminum oxide support material comprises at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide, on an oxide basis.Embodiment 15. The Fischer-Tropsch catalyst material of embodiment 13, wherein at least a surface layer of the aluminum oxide support material comprises at least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide, on an oxide basis.Embodiment 16. The Fischer-Tropsch catalyst material of any of embodiments 13-15, wherein the aluminum oxide support material comprises at least 50 wt% aluminum oxide, e.g., at least 60 wt% aluminum oxide, or at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide, on an oxide basis.Embodiment 17. The Fischer-Tropsch catalyst material of any of embodiments 13-15, wherein the aluminum oxide support material comprises at least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide, on an oxide basis.Embodiment 18. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is a zirconium oxide support material.Embodiment 19. The Fischer-Tropsch catalyst material of embodiment 18, wherein at least a surface layer of the zirconium oxide support material comprises at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide, on an oxide basis.Embodiment 20. The Fischer-Tropsch catalyst material of embodiment 18, wherein at least a surface layer of the zirconium oxide support material comprises at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide, on an oxide basis.Embodiment 21. The Fischer-Tropsch catalyst material of any of embodiments 18-20, wherein the zirconium oxide support material comprises at least 50 wt% zirconium oxide, e.g., at least 60 wt% zirconium oxide, or at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide, on an oxide basis.Embodiment 22. The Fischer-Tropsch catalyst material of any of embodiments 18-20, wherein the zirconium oxide support material comprises at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide, on an oxide basis.Embodiment 23. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is a zinc oxide support material.Embodiment 24. The Fischer-Tropsch catalyst material of embodiment 23, wherein at least a surface layer of the zinc oxide support material comprises at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide, on an oxide basis.Embodiment 25. The Fischer-Tropsch catalyst material of embodiment 23, wherein at least a surface layer of the zinc oxide support material comprises at least 90 wt% zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide, on an oxide basis.Embodiment 26. The Fischer-Tropsch catalyst material of any of embodiments 23-25, wherein the zinc oxide support material comprises at least 50 wt% zinc oxide, e.g., at least 60 wt% zinc oxide, or at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide, on an oxide basis.Embodiment 27. The Fischer-Tropsch catalyst material of any of embodiments 23-25, wherein the zinc oxide support material comprises at least 90 wt% zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide, on an oxide basis.Embodiment 28. The Fischer-Tropsch catalyst material of embodiment 1 or embodiment 2, wherein the support material is a mixed oxide support material having at least a surface layer comprising at least 60 wt% total of two or more of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, and zinc oxide, e.g., at least 70 wt%, or 80 wt% total, on an oxide basis.Embodiment 29. The Fischer-Tropsch catalyst material of any of embodiments 1-28, wherein the support material does not include additional metals in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt%, or in excess of 0.5 wt%, on an oxide basis.Embodiment 30. The Fischer-Tropsch catalyst material of any of embodiments 1-28, wherein the support material includes at least one additional metal.Embodiment 31. The Fischer-Tropsch catalyst material embodiment 30, wherein a total amount of the at least one additional metal in the support material is in the range of 0.5 to 20 wt%, e.g., 1 to 20 wt%, or 2 to 20 wt%, or 0.5 to 15 wt%, or 1 to 15 wt%, or 2 to 15 wt%, or0.5 to 10 wt%, or 1 to 10 wt%, or 2 to 10 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, on an oxide basis.Embodiment 32. The Fischer-Tropsch catalyst material of any of embodiments 1-31, wherein the support material has a pore volume of at least 0.15 mL / g., e.g. at least 0.30 mL / g.Embodiment 33. The Fischer-Tropsch catalyst material of any of embodiments 1-32, wherein the support material has an average pore radius in the range of 10 to 400 Angstroms, e.g., in the range of 15 to 100 angstroms, or in the range of 20 to 80 Angstroms, or in the range of 25 to 60 Angstroms.Embodiment 34. The Fischer-Tropsch catalyst material of any of embodiments 1-33, wherein the support material has a BET surface area in the range of 2 to 1000 m2 / g, e.g., in the range of 10 to 600 m2 / g, or 15 to 300 m2 / g, or 30 to 150 m2 / g.Embodiment 35. The Fischer-Tropsch catalyst material of any of embodiments 1-34, wherein cobalt is present in the catalyst material in an amount in the range of 5 to 20 wt%, e.g., in the range of 5 to 18 wt%, or 5 to 15 wt%, or 5 to 12 wt%, or 5 to 10 wt%, based on the total weight of the catalyst material.Embodiment 36. The Fischer-Tropsch catalyst material of any of embodiments 1-34, wherein cobalt is present in the catalyst material in an amount in the range of 6 to 25 wt%, e.g., in the range of 6 to 22 wt%, or 6 to 20 wt%, or 6 to 18 wt%, or 6 to 15 wt%, or 6 to 12 wt%, or 6 to 10 wt%, based on the total weight of the catalyst material.Embodiment 37. The Fischer-Tropsch catalyst material of any of embodiments 1-34, wherein cobalt is present in the catalyst material in an amount in the range of 8 to 25 wt%, e.g., in the range of 8 to 22 wt%, or 8 to 20 wt%, or 8 to 18 wt%, or 8 to 15 wt%, or 8 to 12 wt%, or 8 to 10 wt%, based on the total weight of the catalyst material.Embodiment 38. The Fischer-Tropsch catalyst material of any of embodiments 1-37, wherein molybdenum is present in the catalyst material in an amount in the range of 0.5 to 8 wt%, e.g., in the range of 0.5 to 6 wt%, based on the total weight of the catalyst material.Embodiment 39. The Fischer-Tropsch catalyst material of any of embodiments 1-37, wherein molybdenum is present in the catalyst material in an amount in the range of 1 to 10wt%, e.g., in the range of 1 to 8 wt%, or 1 to 6 wt%, based on the total weight of the catalyst material.Embodiment 40. The Fischer-Tropsch catalyst material of any of embodiments 1-37, wherein molybdenum is present in the catalyst material in an amount in the range of 1.5 to 10 wt%, e.g., in the range of 1.5 to 8 wt%, or 1.5 to 6 wt%, based on the total weight of the catalyst material.Embodiment 41. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein a total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, on a metallic basis.Embodiment 42. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein a total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, and molybdenum in the catalyst material is at least 98 wt%, e.g., at least 99 wt%, on a metallic basis.Embodiment 43. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein manganese is present in the catalyst material in an amount in the range of 0.1 to 8 wt%, e.g., in the range of 0.1 to 6 wt%, based on the total weight of the catalyst material.Embodiment 44. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein gallium is present in the catalyst material in an amount in the range of 0.5 to 10 wt%, e.g., in the range of 0.5 to 8 wt%, or 0.5 to 6 wt%, based on the total weight of the catalyst material.Embodiment 45. The Fischer-Tropsch catalyst material of any of embodiments 2-44, wherein manganese is present in the catalyst material in an amount in the range of 1 to 10 wt%, e.g., in the range of 1 to 8 wt%, or 1 to 6 wt%, based on the total weight of the catalyst material.Embodiment 46. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein manganese is present in the catalyst material in an amount in the range of 2 to 10 wt%, e.g., in the range of 2 to 8 wt%, or 2 to 6 wt%, based on the total weight of the catalyst material.Embodiment 47. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein manganese is present in the catalyst material in an amount in the range of 3 to 10 wt%, e.g., in the range of 3 to 8 wt%, or 3 to 6 wt%, based on the total weight of the catalyst material.Embodiment 48. The Fischer-Tropsch catalyst material of any of embodiments 1-40, wherein manganese is present in the catalyst material in an amount in the range of 4 to 10 wt%, e.g., in the range of 4 to 8 wt%, or 4 to 6 wt%, based on the total weight of the catalyst material.Embodiment 49. The Fischer-Tropsch catalyst material of any of embodiments 1-48, wherein the manganese and molybdenum are present in the catalyst material in a weight ratio of at least 0.1 :1 (e.g., at least 0.5:1, or at least 1:1).Embodiment 50. The Fischer-Tropsch catalyst material of any of embodiments 1-48, wherein the manganese and molybdenum are present in the catalyst material in a weight ratio of at most 20:1 , e.g., at most 15:1, or at most 10:1.Embodiment 51. The Fischer-Tropsch catalyst material of any of embodiments 1-49, wherein the manganese and molybdenum are present in the catalyst material in a weight ratio in the range of 0.1:1 to 20:1 , e.g., in the range of 0.5:1 to 20:1, or 1 :1 to 20:1 , or 0.1:1 to 15:1, or 0.5:1 to 15:1 , or 1 :1 to 15:1, or 0.1 :1 to 10:1, or 0.5:1 to 10:1 , or 1:1 to 10:1.Embodiment 52. The Fischer-Tropsch catalyst material of any of embodiments 1-51 , wherein the cobalt and molybdenum are present in the catalyst material in a weight ratio of at least 0.5:1 (e.g., at least 1:1, at least 2:1, or at least 5:1).Embodiment 53. The Fischer-Tropsch catalyst material of any of embodiments 1-52, wherein the cobalt and molybdenum are present in the catalyst material in a weight ratio in the range of 0.5:1 to 25:1 , e.g., in the range of 0.5:1 to 20:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1, or 1 :1 to 25:1, or 1 :1 to 20:1 , or 1 :1 to 15:1, or 1:1 to 10:1.Embodiment 54. The Fischer-Tropsch catalyst material of any of embodiments 1-53, wherein a total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese, and molybdenum in the catalyst material is at least 90 wt%, e.g., at least 95 wt%, on a metallic basis.Embodiment 55. The Fischer-Tropsch catalyst material of any of embodiments 1-53, wherein a total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese, and molybdenum in the catalyst material is at least 98 wt%, e.g., at least 99 wt%, on a metallic basis.Embodiment 56. The Fischer Tropsch catalyst material of any of embodiments 1-55, wherein the catalyst material does not include a substantial amount of copper, nickel, or iron.Embodiment 57. The Fischer-Tropsch catalyst material of any of embodiments 1-56, wherein a copper content of the catalyst material is less than 0.1 wt% copper, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.Embodiment 58. The Fischer-Tropsch catalyst material of any of embodiments 1-57, wherein a nickel content of the catalyst material is less than 0.1 wt% nickel, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.Embodiment 59. The Fischer-Tropsch catalyst material of any of embodiments 1-58, wherein an iron content of the catalyst material is less than 0.1 wt% iron, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.Embodiment 60. The Fischer-Tropsch catalyst material of any of embodiments 1-59, wherein the catalyst material does not include copper.Embodiment 61. The Fischer-Tropsch catalyst material of any of embodiments 1-60, wherein the catalyst material does not include nickel.Embodiment 62. The Fischer-Tropsch catalyst material of any of embodiments 1-61, wherein the catalyst material does not include iron.Embodiment 63. The Fischer-Tropsch catalyst material of any of embodiments 1-62, wherein the catalyst material does not include a substantial amount of a lanthanide metal or metal oxide.Embodiment 64. The Fischer-Tropsch catalyst material of any of embodiments 1-63, wherein a lanthanide metal or metal oxide content of the catalyst material is less than 0.1 wt% lanthanide metal or metal oxide, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.Embodiment 65. The Fischer-Tropsch catalyst material of any of embodiments 1-64, wherein the catalyst material does not include a substantial amount of lanthanum.Embodiment 66. The Fischer-Tropsch catalyst material of any of embodiments 1-65, wherein a lanthanum content of the catalyst material is less than 0.1 wt% lanthanide metal or metal oxide, e.g., less than 0.05 wt% or 0.01 wt%, based on the total weight of the catalyst.Embodiment 67. The Fischer-Tropsch catalyst material of any of embodiments 1-66, wherein the cobalt present in the catalyst material is substantially in oxide form (i.e. , in the form of cobalt oxide).Embodiment 68. The Fischer-Tropsch catalyst material of any of embodiments 1-66, wherein the catalyst material is an activated catalyst, and at least 50 mol% of the cobalt, e.g., at least 60 mol% or at least 70 mol%, is in the form of Co(0).Embodiment 69. The Fischer-Tropsch catalyst material of any of embodiments 1-68, wherein the catalyst material exhibits a long-chain non-oxygenated hydrocarbon (e.g., Cs- Cie non-oxygenated hydrocarbon) selectivity of at least 15%, e.g., at least 18%, or at least 20%, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 70. The Fischer-Tropsch catalyst material of any of embodiments 1-69, wherein the catalyst material exhibits a long-chain non-oxygenated hydrocarbon (e.g., Cs- Cie non-oxygenated hydrocarbon) selectivity that is at least 70% greater, e.g., at least 80% greater, or at least 90% greater, than a long-chain alkyl selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 71. The Fischer-Tropsch catalyst material of any of embodiments 1-70, wherein the catalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity of at least 4%, e.g., at least 6%, or at least 8%, or at least 10%, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 72. The Fischer-Tropsch catalyst material of any of embodiments 1-71 , wherein the catalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity of at least 100% greater, e.g., at least 110% greater, or at least 120% greater, than a long-chainalkyl selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 73. The Fischer-Tropsch catalyst material of any of embodiments 1-72, wherein the catalyst material exhibits a Cn+ non-oxygenated hydrocarbon selectivity of at least 250% greater, e.g., at least 300% greater, or at least 350% greater, than a long-chain alkyl selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 74. The Fischer-Tropsch catalyst material of any of embodiments 1-73, wherein the catalyst material exhibits a C5+ non-oxygenated hydrocarbon selectivity of at least 20%, e.g., at least 30%, or at least 40%, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 75. The Fischer-Tropsch catalyst material of any of embodiments 1-74, wherein the catalyst material exhibits a methane selectivity of no more than 20%, e.g., no more than 18%, or no more than 15%, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 76. The Fischer-Tropsch catalyst material of any of embodiments 1-75, wherein the catalyst material exhibits a methane selectivity that is at least 25% less, e.g., at least 35% less, or at least 45% less, or at least 55% less, or at least 65% less, than a methane selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.Embodiment 77. The Fischer-Tropsch catalyst material of any of embodiments 1-76, wherein the catalyst material exhibits a CO conversion of at least 15%, e.g., at least 20% or at least 25%, when tested in the FT performance test described in the specification.Embodiment 78. The Fischer-Tropsch catalyst material of any of embodiments 1-77, wherein the catalyst material exhibits a CO conversion that is at least 20% greater, e.g., at least 25% greater, or at least 30% greater, than a CO conversion exhibited by an otherwiseidentical catalyst lacking the molybdenum, when tested in the FT performance test described below.Embodiment 79. The Fischer-Tropsch catalyst material of any of embodiments 1-78, wherein the catalyst material exhibits an oxygenated hydrocarbon (e.g., C2-C8 alcohol) selectivity of at least 8%, e.g., at least 10%, or at least 12%, determined on a molar basis, when tested in the FT performance test described below.Embodiment 80. The Fischer-Tropsch catalyst material of any of embodiments 1-79, wherein the catalyst material exhibits an oxygenated hydrocarbon (e.g., C2-C8 alcohol) selectivity that is at least 80%, e.g., at least 85%, or at least 90%, of an oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a molar basis, when tested in the FT performance test described in the specification.Embodiment 81 . A process for performing a Fischer-Tropsch synthesis, the process comprising contacting a catalyst material according to any of embodiments 1-80 with a feed stream comprising H2 and CO under conditions sufficient to provide a product stream comprising C5+ non-oxygenated and oxygenated hydrocarbons.Embodiment 82. The process according to embodiment 81 , wherein H2 and CO are present in the feed stream in a molar ratio of at least 0.1 :1 , e.g., at least 0.5:1.Embodiment 83. The process according to embodiment 81 , wherein H2 and CO are present in the feed stream in a molar ratio of at least 0.9:1 , e.g., at least 1.1 :1 , or at least 1.5:1.Embodiment 84. The process according to any of embodiments 81-83, wherein H2 and CO are present in the feed stream in a molar ratio of no more than 20:1 , e.g., no more than 15:1 , or no more than 10:1.Embodiment 85. The process according to any of embodiments 81-83, wherein H2 and CO are present in the feed stream in a molar ratio of no more than 6:1 , e.g., no more than 4: 1 , or no more than 3: 1.Embodiment 86. The process according to embodiment 81 , wherein H2 and CO are present in the feed stream in a molar ratio in the range of 1 :1 to 6:1 , e.g., in the range of 1.5:1 to 3:1.Embodiment 87. The process according to any of embodiments 81-86, wherein the feed stream further comprises CO2, in a total amount up to 30 mol% CO2, e.g., up to 25 mol% CO2, or up to 20 mol% CO2.Embodiment 88. The process according to any of embodiments 81-87, wherein the feed stream further comprises CO2, in a total amount in the range of 5-30 mol%, e.g., in the range of 5-25 mol%, or 5-20 mol%.Embodiment 89. The process according to any of embodiments 81-88, wherein the feed stream further comprises one or more inerts, e.g., CH4, N2, or Ar, in a total amount up to 80 mol% of one or more inerts, e.g., up to 70 mol%, or up to 60 mol%, or up to 50 mol%.Embodiment 90. The process according to any of embodiments 81-88, wherein the feed stream further comprises one or more inerts, e.g., CH4, N2, or Ar, in a total amount in the range of 3-80 mol%, e.g., 5-80 mol%, or 10-80 mol%, or 15-80 mol%, or 30-80 mol%, or 3-70 mol%, or 5-70 mol%, or 10-70 mol%, or 15-70 mol%, or 30-70 mol%, or 3-60 mol%, or 5-60 mol%, or 10-60 mol%, or 15-60 mol%, or 30-60 mol%, or 3-50 mol%, or 5-50 mol%, or 10-50 mol%, or 15-50 mol%, or 30-50 mol% inerts.Embodiment 91 . The process according to any of embodiments 81-90, wherein the feed stream does not include a substantial amount of C2+ hydrocarbons (e.g., no more than 10 mol%, no more than 5 mol%, or no more than 1 mol%).Embodiment 92. The process according to any of embodiments 81-91 , wherein the feed stream is not contacted with a catalyst material comprising iron.Embodiment 93. The process accordingly to any of embodiments 81-92, wherein the contacting comprises contacting only one type of catalyst material (e.g., as described according to any of embodiments 1-65) with the feed steam.Embodiment 94. The process according to any of embodiments 81-93, wherein the contacting is conducted at a temperature in the range of 150 to 280 °C, e.g., in the range of150 to 260 °C, or 150 to 250 °C, or 175 to 280 °C, or 175 to 260 °C, or 175 to 250 °C, or 190 to 280 °C, or 190 to 260 °C, or 190 to 250 °C, or 200 to 280 °C, or 200 to 260 °C, or 200 to 250 °C.Embodiment 95. The process according to any of embodiments 81-93, wherein the contacting is conducted at a temperature in the range of 150 to 240 °C, e.g., in the range of 150 to 230 °C, or 150 to 220 °C, or 175 to 240 °C, or 175 to 230 °C, or 175 to 220 °C, or 190 to 240 °C, or 190 to 230 °C, or 190 to 220 °C, or 200 to 240 °C, or 200 to 230 °C, or 200 to 220 °C, or 220 to 240 °C.Embodiment 96. The process according to any of embodiments 81-95, wherein the contacting is conducted at a pressure in the range of 10 to 60 barg, e.g., in the range of 10 to 50 barg, or 20 to 50 barg, or 25 to 50 barg, or 10 to 40 barg, or 20 to 40 barg, or 25 to 40 barg, or 10 to 35 barg, or 20 to 35 barg, or 25 to 35 barg.Embodiment 97. The process according to any of embodiments 81-96, conducted at a GHSV in the range of 500 to 15,000 IT1, e.g., in the range of 500 to 15,000 IT1, or 500 to 10,000 h’1, or 500 to 8,000 IT1, or 500 to 5000 IT1, or 1 ,000 to 15,000 IT1, or 1 ,000 to 10,000 h’1, or 1 ,000 to 8,000 IT1, or 1 ,000 to 5000 IT1, or 2,000 to 15,000 IT1, or 2,000 to 10,000 IT1, or 2,000 to 8,000 IT1, or 2,000 to 5,000 IT1.Embodiment 98. The process according to any of embodiments 81-97, wherein contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed at a CO conversion of at least 20%, e.g., at least 25%, or at least 30%.Embodiment 99. The process according to any of embodiments 81-98, wherein contacting the Fischer-Tropsch catalyst material with the feed stream to provide the product stream is performed is performed at a C5+ non-oxygenated hydrocarbon selectivity of at least 20%, e.g., at least 25%, or at least 30%, as determined on a weight basis.Embodiment 100. The process according to any of embodiments 81-99, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C5+ non-oxygenated hydrocarbon selectivity of no more than 60%, e.g., no more than 50%, or no more than 40%, as determined on a weight basis.Embodiment 101. The process according to any of embodiments 81-100, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with an oxygenated hydrocarbon (e.g., C2-C8 alcohol) selectivity of at least 8%, e.g., at least 10% or at least 12%, as determined on a molar basis.Embodiment 102. The process according to any of embodiments 81-101, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a long-chain non-oxygenated hydrocarbon (e.g., Cs-Ci6 non-oxygenated hydrocarbon) selectivity of at least 15%, e.g., at least 18%, or at least 20%, as determined on a weight basis.Embodiment 103. The process according to any of embodiments 81-102, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C11+ non-oxygenated hydrocarbon selectivity of at least 4%, e.g., at least 6%, or at least 8%, or at least 10%, as determined on a weight basis.Embodiment 104. The process according to any of embodiments 81-103, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a methane selectivity of no more than 20%, e.g., no more than 18%, or no more than 15%, as determined on a weight basis.Embodiment 105. The process according to any of embodiments 81-104, wherein contacting the Fischer-Tropsch catalyst with the feed stream to provide the product stream is performed with a C2-C4 hydrocarbon selectivity of no more than 40%, e.g., no more than 35%, or no more than 30%, as determined on a weight basis.Embodiment 106. The process according to any of embodiments 81-105, further comprising recycling at least a portion of H2 of the product stream to the feed stream.Embodiment 107. The process according to any of embodiments 81-106, further comprising recycling at least a portion of CO of the product stream to the feed stream.Embodiment 108. The process according to any of embodiments 81-107, further comprising recycling at least a portion of CO2 of the product stream to the feed stream.Embodiment 109. The process according to any of embodiments 81-108, further comprising recycling at least a portion of inerts of the product stream to the feed stream.Embodiment 110. The process according to any of embodiments 81-109, further comprising separating at least a portion of C1-C4 hydrocarbons of the product stream to form a light hydrocarbon stream.Embodiment 111. The process according to any of embodiments 81-110, further comprising at least partially oxidizing at least a portion of the light hydrocarbon stream to provide a partial oxidation (pOX) stream comprising carbon monoxide e.g., a CO- and / or CO2-containing partial oxidation (pOX) stream, and including at least a portion of the pOX stream in the feed stream.Embodiment 112. The process according to any of embodiments 81-111 , further comprising burning at least a portion of the light hydrocarbon stream to provide energy, e.g., heat energy or electrical energy.Embodiment 113. The process according to embodiment 112, wherein the heat energy is used to heat the feed stream.Embodiment 114. The process according to any of embodiments 81-113, wherein one or more products are provided from at least a portion of C5+ non-oxygenated hydrocarbons of the product stream.Embodiment 115. The process according to embodiment 114, wherein the one or more products are selected from fuels (e.g., gasoline, diesel fuel, aviation fuel), lubricants and waxes.Embodiment 116. The process according to any of embodiments 81-115, further comprising hydroprocessing at least a portion of C5+ non-oxygenated hydrocarbons of the product stream.Embodiment 117. The process according to any of embodiments 81-116, wherein one or more products are provided from at least a portion of oxygenated hydrocarbons of the product stream.Embodiment 118. The process according to any of embodiments 81-117, wherein one or more products are provided from at least a portion of C2-C8 alcohols of the product stream.Embodiment 119. The process according to embodiments 117 or 118, wherein the products are selected from base-oil reactants, lubricants, and fine chemical intermediates.Embodiment 120. The process according to any of embodiments 81-119, wherein at least part of the H2 of the feed stream is from a renewable source.Embodiment 121. The process according to any of embodiments 81-120, wherein at least a portion of the hydrogen of the feed stream is green hydrogen.Embodiment 122. The process according to any of embodiments 81-120, wherein at least a portion of the hydrogen of the feed stream is blue hydrogen.Embodiment 123. The process according to any of embodiments 81-122, wherein at least a portion of the hydrogen of the first feed stream or the second feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.Embodiment 124. The process according to any of embodiments 81-123, further comprising providing at least a portion of H2 to the first feed stream and / or the second feed stream by electrolysis of water.Embodiment 125. The process of embodiment 124, wherein the electrolysis of water is performed using at least partially electricity from a renewable source.Embodiment 126. The process of embodiment 124 or 125, wherein the electrolysis of water is performed using at least partially electricity generated from steam made by heat exchange from the first product stream and / or the second product stream, or by burning a light hydrocarbon stream (e.g., methane from biogas).

[0119] The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention inmore detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and / or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0120] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0121] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0122] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0123] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitionalphrase “consisting of’ excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0124] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0125] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0126] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0127] Some embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0128] Furthermore, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Othermodifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.

Claims

We claim:

1. A process for performing a Fischer-Tropsch synthesis, the process comprising contacting a Fischer-Tropsch catalyst material with a feed stream comprising H2 and CO under conditions sufficient to provide a product stream comprising C5+ non-oxygenated and oxygenated hydrocarbons, wherein the Fischer-Tropsch catalyst material comprises: a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount of 0.5 to 10 wt%, based on the total weight of the catalyst material; and optionally manganese, present in an amount of 0.1 to 10 wt%, based on the total weight of the catalyst material.

2. The process of claim 1 , wherein manganese is present in the catalyst material in an amount in the range of 3 to 8 wt%, based on the total weight of the catalyst material.

3. The process of claim 1 or claim 2, wherein the support material is a titanium oxide support material, a cerium oxide support material, an aluminum oxide support material, a zirconium oxide support material, or a zinc oxide support material.

4. The process of any of claims 1-3, wherein the support material is a titanium oxide support material.

5. The process of any of claims 1-4, wherein cobalt is present in the catalyst material in an amount in the range of 8 to 15 wt%, based on the total weight of the catalyst material.

6. The process of any of claims 1-5, wherein molybdenum is present in the catalyst material in an amount in the range of 1 to 10 wt%, based on the total weight of the catalyst material.

7. The process of any of claims 1-6, wherein the manganese and molybdenum are present in the catalyst material in a weight ratio in the range of 0.5:1 to 20:1.

8. The process of any of claims 1-7, wherein a total amount of titanium, cerium, aluminum, zirconium, zinc, cobalt, manganese, and molybdenum in the catalyst material is at least 95 wt%, on a metallic basis.

9. The process of any of claims 1-8, wherein cobalt is present in the catalyst material in an amount in the range of 8 to 15 wt%, based on the total weight of the catalyst material, molybdenum is present in the catalyst material in an amount in the range of 1 to 10 wt%, based on the total weight of the catalyst material, and manganese is present in the catalyst material in an amount in the range of 3 to 8 wt%, based on the total weight of the catalyst material.

10. The process of any of claims 1-9, wherein the catalyst material exhibits a long-chain non-oxygenated hydrocarbon (e.g., Cs-Ci6 non-oxygenated hydrocarbon) selectivity that is at least 80% greater, than a long-chain alkyl selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.

11. The process of any of claims 1-10, wherein the catalyst material exhibits a Cn+ nonoxygenated hydrocarbon selectivity of at least 250% greater, than a long-chain alkyl selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.

12. The process of any of claims 1-11, wherein the catalyst material exhibits a methane selectivity that is at least 25% less than a methane selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a weight basis, when tested in the FT performance test described in the specification.

13. The process of any of claims 1-12, wherein the catalyst material exhibits an oxygenated hydrocarbon (e.g., C2-C8 alcohol) selectivity that is at least 80% of an oxygenated hydrocarbon selectivity exhibited by an otherwise identical catalyst lacking the molybdenum, determined on a molar basis, when tested in the FT performance test described in the specification.

14. The process according to any of claims 1-13, wherein contacting the Fischer- Tropsch catalyst with the feed stream to provide the product stream is performed with a Cn+ non-oxygenated hydrocarbon selectivity of at least 4%, as determined on a weight basis.

15. A Fischer-Tropsch catalyst material comprising: a support material; cobalt, present in an amount of 5 to 25 wt%, based on the total weight of the catalyst material; molybdenum, present in an amount of 0.5 to 10 wt%, based on the total weight of the catalyst material; and manganese, present in an amount of 0.1 to 10 wt%, based on the total weight of the catalyst material, wherein manganese and molybdenum are present in the catalyst material in a weight ratio in the range of 0.5:1 to 20:1.

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